“UBWS ON THE WLYMER: mm WWRW! - STYRE‘EI- Mforfhobognodfidyi WEAK $TATE' COLL”! Edward Rem Gaffe" 1948 M495 ~‘n a; 111-?" ,fi urn-I‘M- Date A" \J‘I Ann‘s- t '71 i This is to certify that the thesis entitled {NYE ?,fiT “fir“? -""‘l"" v' ' V ' ‘7" "'1""Y‘\'\'r7‘\" ~mvv’~~ ‘f . ' I . . x 5- ...I .-s~'c _A._..~_..: 1~’¢..44.A J ‘*Ol..~44--4. /~-U&-‘u- presented by ,_7. f) ‘ - If! 1 . 'arii . mmr‘t 1:21 rot’t has been accepted. towards fulfillment of the requirements for ‘f ‘. . 3 ’ 'q' degree in OWNS”?! 1/(W%XM Major professor EN,“ rV “ vv-w I 5 OJ STUDIES ON THE HETEROPOLYMER: MALEIC ANHYDRIDE-STYRENE By EDWARD ROBERT GARRETT A THESIS Submitted to the School of Graduate Studies of Michigan State College of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Chemistry 1948 754/ ‘ €139 ACKNOWLEDGMENT The writer wishes to express his appreciation to Dr. Ralph L. Guile for his counsel and guidance and to Dr. R.C. Huston and Dr. F.R. Duke for their helpful assistance. lo \4 . z.“ .,. :2: * a 9' a (VP- V». l” git; CONTENTS IntrOduCtion o o o o o o o 0 Historical . . . . . . . . Experimental 0 o o o o o o 0 Part I (COpolymerization TeChniqueS) o o o 0 Part II (COpolymerization Rate). Part III (Aqueous Potentiometric TitrationS) o o o 0 Part IV (Titrations of Different Molar Ratio) . . . Part V (Anhydrous Potentio- metric Titrations). . Part VI (Elementary Analyses) . Discussion . . . . . . . . Part I (COpolymerization Techniques). . . . Part II (Copolymerization Rate). Part III (Aqueous Potentiometric Titrations) . . . Part IV (Titrations of Different Molar Ratio) . . . Part V (Anhydrous Potentio- metric Titrations). . General Discussion . . . . Conclusions . . . . . . . . Literature Cited . . . . . . page no. 1 2 18 19 24 35 135 156 142 149 167 169 177 179 INTRODUCTION Styrene and maleic anhydride in all pro- portions were reported to always form a hetero- polymer with a 1:1 composition. Since accurate data on this fact, the rate of reaction, the exact structure of the polymer and prOperties of the polymer were lacking or inadequately proven by publisned data an investigation to determine these by use of precise analytical techniques was desirable and is the subject of this thesis. HISTORICAL Literature on the detailed study of the copolymerization process and 00polymer structure is of comparatively recent date and thus has not been adequately reviewed; in fact more than half of the accumulated data on the subject that is suitable for a true scientific study has been in publication for less than a year.15'18’ 20 The patent literature for a decadez-lo has abounded in recipes but these give little inkling of the true nature of cepolymers. Because of this fact, it has been deemed advisable to devote more space in this thesis to a review of the existing lit- erature than is usual in order to acquaint the reader with the problems and methods of attack in this new field. In the following historical discussion, special reference has been given to c0polymers with prOperties analogous to the maleic-anhydride - styrene heterOpolymer. It was recognized at an early date that the polymer product of cOpolymerization possesses prOperties that differ from a mixture of the homopolymerization products of each separate monomer. The term "heterOpolymerization" was prOposed by Wagner-Jaureggl in 1950 to include those additive \ heteropolymers of two different monomers, one of which showed no tendency to polymerize by itself. _In these studies, maleic-anhydride (m.a.) was used as representative of the latter class of monomers. Representatives of the ethylenic class in additive heteropolymerization included stilébene, benzal fluorene, 1,4 diphenyl butene-l and dimethyl maleate. These non catalyzed reactions were carried out in refluxing solvents; the polymerization of maleic-anhydride and stilvbene in boiling xylene. This product has an average molecular weight of 4200 and from the data of elementary analysis it appeared that with a reactant ratio of 2:1 (stil-— bene: m.a.), the heterOpolymer was 1:1; with a reactant ratio of 1:1, the heterOpolymer was .95:1. It was suggested by Wagner-Jauregg1 that the amorphous, white, infusible xylene insoluble polymer consisted of an alternating series of hydrocarbon and maleic-anhydride units linked thru the reaction of the individual double bonds: l—H H H H - c - c - c - c - K / \ I L... 0 Similarly a 1:1 reactant ratio (m.a.:benza1 fluorene) gave a 1:1 c0polymer, whereas a 2:1 reactant ratio resulted in a 1:.9 00polymer. Wagner-Jaureggl proposed that the tendency for an excess of m.a. could be explained on the premise of a chain ending with m.a. in these instances. Analogous results that tended to confirm this premise were obtained from the heterOpolymer of m.a. with 1,4 diphenyl butene-l which gave lower molecular weight polymers. Mass polymerization of styrene with maleic anhydride was also carried out but no significant data obtained. 2 have c0polymerized maleic V033 and Dickhauser anhydride and various ethylenic compounds in mass and solution by both heat and peroxide catalyst. They produced a m.a. -styrene heteropolymer by heat catalyzed mass polymerization that yielded a resin insoluble in benzene but soluble in acetone and dilute aqueous alkali. Using acetone asla solvent, a heat catalyzed soluble polymer was also obtained which could be precipitated by alcohol and had the same solubility prOperties. These polymerizations were greatly accelerated by the use of peroxide catalysts. The resultant products were capable of esterification during and after the polymerization process to yield esterified c0polymers possessing different solubility prOperties than the original heterOpolymer. The copolymer underwent the other usual reactions of carboxyl containing compounds. '7' For some time the m.a.-ethylenic hydrocarbon heteropolymer was considered as a phenomenon apart from true co-polymerization due to the stoichiometric prOportions of the constituents in the polymer as evidenced by the studies of Wagner-Jauregg1 and the unique prefix "hetero" applied. Wall11 in his first theoretical develOpment of relative reactivities of monomers in copolymerization ignored any Specificity of attack of one type of monomer free radical upon an other of a different kind; such specificity may .be considered extreme in the m.a. cases cited. His differential equation for the rate of c0polymerization was based solely on the first order rate hypothesis for the disappearance of each monomer and is: (1) :Eil . km: [”1] : fig d [M2] kM2 [M2] [M2] whereEdfl and E; are the concentrations of un- reacted monomer; where at. is the relative reactiv- ity of the two monomers in the copolymerization, a quotient of the rate constants for the individual polymerizations kM1,(rate constant of polymerization Mljand kM2,(rate constant of polymerization M2) respectively. When 9L -_- 1, the polymer composition will be the same as the monomer reaction mixture. When aL./ l, the polymer composition will be prOportional to, but not the same as, the reaction mixture. Mayo and Lewisle studied the 00polymerization of styrene and methyl methacrylate and, attempting to utilize the above equation, found that Oh varied with the [MH/ [Ma ratio. They also stated that this equation could not account for the specificity of the several maleic anhydride heteropolymers to occur in a stoichiometric ratio as indicated by Wagner-Jaureggl. The differential equation of c0polymerization as prOposed by Mayo and Lewis12 and based on the work of Norrish and Brookmanls is formulated thusly: Consider the two monomers M1 and M2 that co- polymerize and the two kinds of free radicals that form the growing ends of the polymer molecules M10 and M2; The reactions that occur are: ' (2) M10 -1- M1 _k;_> M1- (:5) My + M2 k2 9 M2. (4) M2- 4- M2 kg 9 M2- (5) M2. Jr M1 kg 9 Ml. The rates of disappearance of M1 and M2 alone are: (5) -d E1111 / (it I k1 Mg Elll’]'+k4 EQEZJ <7) -d E12] / at = k2 [Mai $111+ k5 @élfidzil and thus: (8) d [M1] i k1 [Mil Ell 9+1“ [M1] E1251 (1 [M21 k2 Eda] E’Iljtl'ksfiflél. E121 -7- Assuming a steady state where Mlo type radicals are converted to M2; type radicals at a rate equal to which M2; type radicals are converted to M1. type radicals we have: M 1:2 (3123911 = k4 Eh] 5‘23 a] __ ["11 M k2 M2 k l l l . Thus: d M3] 3 12% 1M1. {11:4 1312] M2 11:49:11 [‘23 as] 2 1(2 2 1:411 M2 3% 2 34-34112 2) And multiplying numerator and denomina by [Ida / k4 E12] we have: 2 3:11: filfl-thzl 114:1. am ma + 2;; ea am a] :5: [ +[1 k4 Bali-E11 and (11) fl = E1 . r1 731111.92] d [M21 [M21 ”2 ["2 +E'Ifl In equation (11), r 1 and r2 are termed the monomer reactivity ratids; r1 is the ratio of the rate constants for the reaction of M1 type radical with M1 and M2 respectively while r2 is the ratio for the reaction of M2 type radical with M2 and M1 respectively. The simple Wall11 equation (1) states that rate of monomer consumption in the polymer depends solely on relative concentrations of unreacted monomer 1.9. collision probability. It does not consider any possible specificity of attack of one free radical monomer on a molecule of the other kind, which con- sideration is included in the Mayo and Lewisl2 equation (11). If r1r2 s 1, M10 is just as apt to attack M1 (or M2) as M20 is to attack M1 (or M2) and thus we can expect the "ideal" copolymer of Walll4, purely random and dependent on feed ratios entirely. But if r1r2 : 0, then either M1 or M2 will not react with itself and if r1 - O and r2 is very small, M1 exclusively attacks M2 and M2 has extreme preference for M1 and thus we have the "alternating" type polymerls’l6 prOposed by Wagner- Jaureggl. If the rlrg product has intermediate values, there is a variation in degree between the alternating and random effects. A product greater than unity indicates that the 00polymer has the greatest tendency not to c0polymerize but to homepolymerize. The Mayo and Lewis techniquelz:15'2O in- volved precipitation of the copolymer, solvent extraction of monomer, drying and elementary analysis. This data, coupled with the yield data at precipitation, allowed them to calculate the monomer concentration at the time of polymerization cessation. These values of flag and [M2] plus the Gail o andfiwa 0 values, the monomer concen- trations at the start of the reaction, were sub- stituted into an integrated form of equation (ll)4. For a particular reaction (i.e. specific molar ratios at start and specific yield), a series of r1 and r2 values satisfied this integrated equation. When these values were plotted on rectangular coordinates r1 vs. r2, they gave a straight line as per the linear differential equation (11). Another reaction is necessary, using another initial monomer ratio and yield to determine another linear plot. The point of intersection theoretically definesa unique point giving the values of r1 and r2 for the c0polym- erization. In general, however, several such reactions are made and the center of the focal area is chosen as the closest approximation to the r1 and r2 values. 4 Wall1 in a further theoretical study along the 1 lines of Mayo and Lewis- states that if rl (or r2) is equal to zero, there is a marked tendency to form a 1:1 c0polymer "azeotrOpe" which cannot have this composition exactly as no such copolymer can -10- have a composition with maleic anhydride greater than .5 due to the latter's inability to react with itself. He calculates that the "azeotrope" of an analogous system would contain .474 mole fraction as a maximum i.e. when the m.a. monomer mole fraction is initially greater or equal to .5. For a .25 mol fraction of m.a., his theoretical system predicts a mol fraction of m.a. in the copolymer of .45. This theoretical deve10pment also brings Wall14 to the conclusion that if such a c0polym- erization is carried out with an excess of styrene, the first polymer formed will be close to the azeotrOpe but the last polymer formed will be pure styrene. He states, however, that we cannot assume that polymer chains would not have intermediate compositions. In the light of the Mayo and Lewis12 copblymer equation (11), Bartlett and Nozacki21 have studied an azeotropic c0polymer with a marked tendency toward a 1:1 composition. The yield of the peroxide catalyzed c0polymer is determined at different intervals and the c0polymer constitution of maleic anhydride and allyl acetate is determined by analysis of the remaining monomers using a specific unsaturation analytical technique. It is interesting to note that they effected a self-polymerization of maleic anhydride in these studies. The rate of c0polymerization is -11- greater than either homepolymerization of the monomers and resulted in a molecular weight of 40,000 with high peroxide catalyst concentration and a lower molecular weight with decreased per- oxide concentration. They note that the copolym- erization showed great sensitivity to air in- hibition. With as high as 58:1 molar ratio of reactants (allyl acetate: m.a.) Bartlett and Nozackizl showed that the monomers entered into the c0polymer mole for mole. However, with a m.a. excess over .8 mole fraction in the monomer mixture, they con- cluded that a definite tendency existed to have a greater mole fraction of m.a. in the c0polymer. Their stated experimental error of 10% does not allow this assertion to be too valid. No characteristic abnormalities in vapor pressures, mutual solubilities and viscosities of mixtures of monomers showing tendency toward 1:1 c0polymerization were evident although concentrated mixtures of such monomers as still- bene, styrene, 1,1 diphenyl ethylene gave decided colors when mdxed in solution with m.a. These compounds all contain aromatic groups and all tend to 1:1 copolymersl. Bartlett and Nozacki21 suggested that resonant structures and polarities may allow the co-monomers to act as electron donors and acceptors respectively. Thus polar -12- chromOphoric intermediates may occur that facili- tate the "alternating tendencies " in the c0polymer. In a series of recent publicationsle’le’zO more detailed attention has been given to the alternation tendency in c0polymerization. The relative reactivity ratios have indicated a qual- itative relation between an increasing tendency of monomers to alternate with styrene and the tendency of substituents on olefinic carbons to accept electrons from double bonds15. However, this relationship is not quantitative and other effects must be postulated to account for the observed relative alternation tendencies, such as specific resonance interactions between certain radicals and monomer, perhaps even involving actual electron transfer. Steric effects may also in- hibit or abet alternation. Mayo, Lewis and Wallingl6 have established a donor-acceptor series which is, in a sense, a rel- ative measure of electrOphilicity (electronegativity). From the position of these radical groups in the series, alternation tendencies may be predicted. If two monomers are close together they will be "ideal" or random c0polymers (e.g. styrene-buta- diene). However, the position of the monomers in an activity series must also be considered, since the further apart they lie in this latter series the more the reactive monomer will predominate in -15... the cepolymer (e.g. styrene-vinyl acetate). It can be noted that these copolymerizations will fit the simple equation (1) of Wall11 and the copolymer constitution will depend solely on the feed ratio of the monomers. With two monomers well separated in the donor acceptor series, they will tend to alternate. If neither monomer polymerizes easily by itself (e.g. stillbene-m.a.) or if they lie close together in the average activity series (e.g. styrene-acrylonitrile) the tendency toward a 1:1 c0polymer is high. Since polarity considerations do not fully account for all alternation tendencies, cis and trans forms of various monomers were c0polymerizedl7. In general the cis form (e.g. maleate ester with styrene) was less reactive than the trans form (e.g. fumarate ester with styrene) due to the non ceplanar configuration of the cis form which decreases the ability of resonance to stabilize the activated complex. Thus, it became apparent that steric inhibition of resonance, when resonance can occur, affects the relative reactivities of geometrical isomers. The comparison of c0polymerizations of various substituted styrenes with methyl methacry- late18 gave relative reactivity values for various substituents on the styrene radical. On comparison with the absorption spectra of these styrenes mixed with maleic anhydride, an excellent correlation -14- is found with the intensity of the color formation. This lends credence to the intermediate complex postulate which may facilitate alternation and, in general, increased rates of c0polymerization over homepolymerization. In this regard, a radical-ion resonant hybrid is postulated which may act.as the chromophoret PCB-CH; CH-C-O H / ‘C-Cao L .1 L .1 Further work along these lines has been conducted by the same schoolz0 utilizing monomers that tend toward complete alternation. A ter- polymerization system was utilized of substituted alpha methylstyrenes and maleic anhydride. In this regard, the competing of two different alpha methyl styrenes to alternate with maleic anhydride served as an index to the effect of the substituent on the reactivity of the alpha methyl styrene. The terpolymeration equation is greatly simplified when the monomer reactivity ratios are essentially zero: (12) dEMg k1 ‘ mil [a k2 a Elementary analysis of the c0polymers demonstrated that the increased reactivity of the styrenes -15- paralleled their tendencies to form colored molecular complexes with conjugated carbonyl sys- tems. This serves as additional evidence that the alternating tendency arises from the presence of resonant structures in the previously postulated radical-ion. Thus it seems possible that the mechanism.of alternation depends on the attack of a radical on the molecular complex i.e. polar resonance forms. Alfrey and Lavin22 have conducted a study of maleic anhydride-styrene c0polymerization based on their derivation of the 00polymerization equation: (13) b/a u B/A ‘flan—té— G‘s—ta where in terms of equations (2 through 5) (14) at a kg/kl @ . k3/k4 and B is [htyrenel and A is [maleic anhydride} . b/a is the ratio of monomer components in the c0poly- mer (styrene: m.a.) From equations (10) and (11) it is apparent that: (15) 0C : 1/1‘1 (151$ : 1/1‘2 If we assume that there is no tendency for an m.a. radical to attack an m.a. molecule then: (17)(_B 3 0 and equation (13) simplifies to: (18) a b . 1+1A‘ . A/B Alfrey and Lavin22 in an industrial laboratory . conducted these polymerizations in benzene solvent -15- with peroxide catalysis and when precipitation of the cepolymer was first noted, it was filtered, thrice refluxed with benzene and vacuum dried. Yield was determined and the polymer dissolved in .2N NaOH. The maleic anhydride content was analyzed by electro- metric titrations, which data is not given in the paper. This procedure was used at different molar ratios of styrene-maleic anhydride and the¢flLvalues calculated by means of equation (18) since a/b, A and B were known. The at. value was 24 t 5 i.e. r1~.025 indi- cating that a styrene radical prefers an m.a. molecule 25 times more than it prefers a styrene molecule. The data in this paper is meager and only the per cent monomer in the reaction mixture, percentage composition of the 00polymer, per cent yield at time of precipi- tation has been given. No experimental data or tech- niques are published. Katchalsky and Spitnikzs provide data and curves in their study of potentiometric titrations of carboxyl containing polymer. In their study of the polymeric acid polymethacrylic acid they found that the pH of the solutions fulfills a modification of the Henderson- Hasselbalch equation: 1-IXL 0L where the exponent n has to be introduced as an empirical (19) pH - pK -n log factor. 0L,is the fraction of carboxyls that have -17- dissociated. Katchalsky and Spitnik also mention that polydibasic acids, as in the case of the c0polymer polyallyl acetate - maleic acid, act in themselves as dibasic acids and conform to the polymeric acid conditions for each distal part of the titration curve in their agreement with equation (19). No data or curves are offered to . substantiate this point. E KP ER I PATENT AL -18- -19- PART I COMPARISON OF SOLUTION COPOLVMFRIZATION TECHNIQUES REACTION A Materials: The benzene was c.p., thiOphene free. Eastman technical maleic anhydride was used without further purification. The benzoyl peroxide was Eastman. Tertiary butyl catechol inhibitor was removed from Eastman styrene by washing twice with aqueous 10% NaOH and twice with distilled water. The uninhibited styrene was of a straw yellow color, uD a 1.5468 at 20° 0 whereas the colorless inhibited styrene index of refraction was 1.5448 at 23° c. The handbook value was 1.5449 uD at 20°, indicating that polymeric impurities appear in caustic uninhibited styrene. Equipment: A 500 ml 3 necked flask with thermometer, reflux condenser and stirrer attachments was sus- pended in a water bath heated on a hot plate. Recipe: 500 ml benzene 10.4 g maleic anhydride (.106 mole) 9.8 g styrene (.094 mole) .l g benzoyl peroxide Procedure: Benzoyl peroxide was dissolved in benzene and added to the reaction flask with stirring. Maleic anhydride was added and stirred until dissolu- tion and then the styrene was added through the condenser. Observations: Time Minutes 0 15 2O 25 27 45 65 70 80 81 82 85 90 Temp. Reaction 25° C 70 55 80 72 81.5 85 84 81.5 82.5 85 88 Temp. bath 92° 90 98 100 100 100 100 -20- Remarks Heating begun Solution appears milky. Heating bath removed Replaced heating bath Reflux stated. Removed water bath No great exothermality involved in reaction. Replaced heating bath Solution is greatly turbid. Reflux rate appears slower Viscous white solution More viscous, splatters on sides of flask Motor speed of stirrer increased to maximum Removed water bath from flask -21- REACTION B Materials: The materials used were the same as Reaction A except that c.p. acetone was substituted for the benzene. Equipment: A 500 ml 5 necked flask with thermometer, reflux condenser, and stirrer attachments was used. In addition, the flask was fitted with a gas inlet tube under the surface of the solution leading from a nitrogen tank purified through 10% pyrogallol and a trap. Recipegs: 150 ml acetone 12.5 g styrene (.12 mole) 15.5 g maleic anhydride (.158 mole) .O4g benzoyl peroxide Procedure: Benzoyl peroxide was dissolved in acetone and added to the reaction flask with stirring. Maleic anhydride was added and stirred until dissolution and then the styrene was added through the condenser. Prior to monomer addition nitrogen gas was bubbled through 10% pyrogallol and under the surface of the solvent providing a nitrogen atmosphere for the reaction. Observations: Time Temp. Temp. Remarks Minutes Reaction Bath 0 20° - Heating in water bath begun 15 45 - Reflux started. Removed bath 20 40 - No exothermality noted. Replaced bath 25 57 - Refluxed from 400 up to 570, temp. rose quite swiftly. 55 62 78° - Clear slightly yellow solution 65 65 85 80 65 82 85 65.2 82 145 64.6 86 - Solution is definitely viscous 150 - Removed water bath, added 150 ml acetone and re- fluxed for 7 more hours. Summary and Comparison of Experimental Observations of Polymers A and B. 1. No apparent exothermality or reaction violence was indicated with the volume of solvent required by the recip6324’25. 2. With benzene solvent (A) the reaction temperature was comparatively consistent at 800 C and the polymer precipitated as a granular white powder while With the acetone solvent (B) the reaction temperature did not appear consistent. 5. Polymer B was less easily worked and washed than Polymer A as the latter needs but to be fl.ltered, benzene washed and dried. The former tends to coagulate as an unworkable sticky mass on being precipitated out of its acetone solvent with water. Qualitatively, it -25- appears to have a much greater excess of dissolved styrene. This latter polymer was broken up and washed in benzene which tended to remove some of its gelatinous, sticky nature. 4. Both polymers were dried at 400 C for five weeks. The total yield of (A) was 85.1%, of (B) 15%. 5. Weighed samples of the polymers were dissolved in acetone and titrated to phenolphthalein endpoint with aqueous alkali. By this method, the acid num- ber28 of (A) was 8.5 and of (B) 545.5. The value for B corresponds to a maleic anhydride - styrene ratio in the heterOpolymer of 1:2 whereas the value for A indicates 15.4 gram styrene in the c0polymer whereas the initial amount of styrene was only 9.8 grams. These results show that new titration techniques were necessary. -24- PART II STUDIES ON THE RATE OF COPOLYMERIZATION STUDY A Materials: The materials were the same as Reaction A, Part I except that Dow specially distilled unhibited styrene was used without further purification. Equipment: The reaction was carried out in a 1 liter round bottom three necked flask, equipped with a thermometer, vacuum sampler, reflux condenser, stirrer with mercury seal and heating mantle. All the glass equipment was fitted with ground joints. Recipe: 615.2 grams benzene 22.881 grams maleic anhydride (.255 mole) 24.266 grams styrene (.251 mole) .2555 gram benzoyl peroxide Procedures: 1. The Polymerization: Benzene solvent was heated to reflux temperature 80°C. Maleic anhydride was washed into the solvent by a portion of the benzene. Similarly, the styrene and benzoyl peroxide were washed into the reaction mixture by a portion of the benzene. 2. Sampling and polymer treatment: Samples of the reaction mixture were taken periodically in tared 50 m1 erlenmeyers and the polymer frozen in the benzene solvent until it could be filtered through tared asbestos-matted gooch crucibles. The c0polymer was washed several times with benzene, dried for one week at 80°C, and weighed (see Table I). -25.. 5. Method of determination of unreacted monomer: The filtrate and benzene washings of a c0polymer sample were titrated with standard bromine in glacial acetic acid to test for unsaturation by the direct bromine titration method developed by Uhlrig and Levin27. Validity of this method was based on preliminary work by Morgan26 who preposed that although maleic anhydride did not undergo bromine addition alone, it did so in styrene mixtures. (See Table 2). '4. Comparative molecular weight determinations: Although no empirical constant was available for this copolymer to correlate viscosity in acetone solvent with molecular weight by Staudinger's viscosity method29’50, it was believed relative values could be obtained by this method. (See Table 5). 5. Analysis of polymer constitution: Due to the relative stability of the anhydride linkage to direct caustic titration as evidenced in Part I, the dried polymer samples were dissolved in acetone and treated with a probable excess of standard aqueous NaOH, brought to the boiling point, cooled and titrated with standard acid to a phenolphthalein endpoint. The entire gooch crucible with its con- tents was introduced into the acetone solvent. (See Table 4). -25- Observations: Cloudiness due to polymer formation was first noted at 7 minutes after monomer addition to reaction flask. The reaction was conducted for five hours. Due to the asbestos used in the gooch crucible, the extent of polymer dissolution during the titrations could not be followed al- though it appeared that different samples gave differing clarity in the titrated solutions. There was difficulty in determining the endpoint with phenolphthalein indicator due to the slow change in indicator color. No. of Sample 1 tom-JOUIWiCfiN P’ F‘ F’ F’ CfltOl-‘O PART II STUDY A Table l DETERMINATION or % POLYMERIZATION BY AMOUNT OE FRECIPITATED POLYMER Time Minutes 5.85 18.55 18.55 42.45 42.45 68.17 68.17 100.75 100.75 171.67 171.67 250.00 250.00 Net Wt 0 Sample 25.861 19.021 25.787 17.714 19.189 11.487 19.157 24.890 22.924 24.267 21.219 18.090 27.450 Reaction Weights Benzene 615.2 22.88 M.A. Benzoyl Peroxide Styrene .2555 662.5805g (as per procedure 2) Net wt. Polymer .0015 .1720 .2551 .7001 .7949 .6476 .9817 1.4881 1.5551 1.5142 1.5542 1.5028 1.9008 Ig (.2555 mole) 8 24.266g#(.2555 mole) % Polymer in Sample .006 .904 1.071 5.94 4.14 5.64 5.15 5.98 5.85 6.24 6.58 7.21 6.95 Total Weight of Monomers: 47.147g -27- %Monomer Polym- erized .008 12.7 12.8 55.5 59.1 79.2 72.0 84.0 81.9 87.5 89.6 101.0 97.2 % Monomers in Initial Reaction Mixture: 7.12% -28- PART II STUDY A Table 2 DETERMINATION or % POLYMERIZATION BY BROMINE TITRATION OE UNSATURATION (as per procedure 5) sample Br Grams Unreact Net wt. Total % (ml Brg ed Mon- sample Mon. Unreact Polym- omer-wt in ed Mon- eriza- Sample omer tion 1 25.5 1.555g 1.022g 25.861 1.845g 55.4 44.6 2 17.2 1.042 .764 19.021 1.554 56.4 45.6 5 24.7 1.500 1.000 25.787 1.69 59.0 41.0 4 5.7 .545 .255 17.714 1.262 20.0 80.0 5 5.7 .224 .164 19.189 1.568 12.0 88.0 6 .7 .042 .051 11.487 .818 5.8 96.2 7 2.2 .155 .098 19.157 1.562 7.2 92.8 8 .7 .042 .051 24.890 1.772 1.8 98.2 9 1.7 .105 .076 22.924 1.655 4.7 95.5 10 1.2 .075 .054 24.267 1.750 5.1 96.9 11 .8 .049 .056 21.219 1.512 2.4 97.6 12 .5 .018 .015 18.090 1.289 1.0 99.0 15 .4 .024 .018 27.450 1.959 .7 99.5 METHOD OF CALCULATION: (1) 1 m1 Brg a 60.59 mg/ml = (2) M.W. styrene = 104 .0606g Br2/m1 M.W. 1“.vo = 98 average 101 (5) M.W. Brg a 159.8, therefore 159.8ng33 3 1.5g Br2 per 101g Mon. (1 g. Monomer (4) g Brg consumed . 1.5 : g. unreacted Monomer. (5) 7.12% of sample wt. = g. monomer in sample. (6) G. unreacted monomer/Total g Mon. in sample ° 100 a unreacted monomer. (7) 100 - % unreacted monomer - % Polymerization. -29- PART II STUDY A Table 5 VISCOSIMETER MEASUREMENT (a) Size Ostwald Viscosimeter used: 100 Solvent: Acetone Molarity of Polymer: .02N Temperature: 20.000 3 .05 (.2020g polymer / 100 ml) The molecular weight of each monomer in the 00polym- er was assumed to be the average of the molecular weights of styrene and maleic anhydride i.e. 101.126g = 1 mole. This assumes a 1:1 relation. Sample Efflux Time Deviation Reproducibility Seconds from Pure solvent efflux Blank 26.25 0 t .05 5 29.7 5.45 i .05 7 28.9 2.65 i .05 9 29.8 5.55 i .1 11 29.5 5.05 t .2 15 28.4 2.15 i .1 Final 28.6 2.55 t .08 (b) All data is the same as (a) except that a size 50 Ostwald Viscosimeter was used. Sample Efflux time Deviation Reproducibility Seconds from Pure solvent efflux . Blank 11600 O " .3 5 165.7 47.7 30.00 7 165.7 47.7 3 .15 9 164.1 48.1 3 .15 11 160.7 44.7 10.00 PART II Table 4 -50- STUDY A DETERMINATION 0E MALEIC ANHYDRIDE CONTENT OF COPOLYMER BY AQUEOUS TITRATION WITH PHENOL- Sample 1* 12 a In used. ** In used. PHTHALEIN INDICATOR (as per procedure 5) 5.00 55.00 45.4 90.0 80.0 125.0 125.0 100.0 m1 NaOH ml HCl 1.75 41.60 22.4 41.2 50.0 4.50 2.50 7.00 samples 1 through samples 4 through METHOD OF CALCULATION: (1) M1 0 n s Mequ. wts. Net Mequ Wt. M.A. % m.a. in wt. M.A. in Cepolymer COpolymer .545 .017 - 1.67 .082 47.6 2.52 .125 48.8 4.97 .245 54.7 5.10 .250 58.6 12.52 .604 40.6 12.54 .615 40.6 9.50 .465 55.7 5, .lO22N NaOH and .0952NHC1 12, .1022N NaOH and .1026N HCl (2) Mequ. wts. of NaOH used - mequ. wts. HCl used = mequ. wts Maleic Anhydride (5) M.w. of M.A. = 98.06, therefore meq. wt. of N.A. is .049 (4) # mequ. wts. of M.A. 0 .049 = wt. M.A. cepolymerized (5) Wt. M. . copolymerized Wt. sample ° 100 = % M.A. 00polymerized in sample. r..\ \x \L .. .\ \c \r h. AKMLNANQI .- u. u) .. e .. 1.1. \\ h.)rflun \1‘. xk » x 1.1. | 1% u... 54.56%, .3»..an .\ 11. \ 11x x \/,. L.-1511-11-11.---...-.-1.1..- -1- . -- 6.. 5 III \\| 1. 2.1 x i... ..a \MH. J...»- 3516).. L. L . .NHN \- 155.1. .. 1 L5. N111”? Firm-k? \ .L. L 1! >1.111 4.1.1 (1.1 L. “0%.. 1\\b h..F.. 5535.“ \ng ‘ .s a; . ‘ MJUNVAXKN k 5.1 1.51.“...211; mVA...KN< 1. 5.1-R. «H... mm.“ 5.5.1.551 $1.651. .I..I.IIIIIIII. .Il'.lllltl'| Ill'allulll’t."!'| Ill. . In. ‘71! ll '71-‘10.“ .1.’ 1‘ _. e 5 L.-._,.L 6.. _ - A... L... 1..-M... 4.111111% 1W J. \5 L136 854.. .3 5L...- 5.5 53-4 #1 :1. _ -.-1_1.11....4 . @Lflmfiufi - .1 , 5 1 L .. 15 1.. .. L 5 1L 5 m...- WHJQLL 155.5155. - ...50\.R 95. \\§1L551LML.1...\ 1..-b1. .1- 9M11-1VL1HNm 61%.; @5555 55.5 5mm 16.555515. 1.5.5.5. 56.511551. ‘l’- ‘1 -ILIIirl' .NL. $055515~5N55551 L. .155 .1- -11 -I In M L 1. .I I. II Lu: -1... 1| 1|. 1| II 111 1.1 11.1 1... -X 11 .1. .1... .11 11. ..I 1 > K5 Ema 0.515.555.” . x \I . X 6.3155335. 0511 \ I.» III X \ \\>\..L\LV5.P\UI¥1\.\ILMIH5W\ \ viz} \ x GGLN $051,555.56.“ I- l1.-.. ‘ Ill '1'!" ‘1!!! 1 -1111; .1 11".-.‘Il.1l. .I‘.’ -V' ‘t...’ PAW 1W1... 6 WWW-S 55555.”. 5555 5.55555 NM.-.- 5AII5HH1155T- $5 15W. 1mm flLLMLMm-x. VQWIW 5.4. L“ 1516.011--- 555.55.. -51.. STUDY B Materials, equipment, recipe and procedure No.(l) were the same as in Study A. Procedure No.(2) was modified so that filter crucibles were used instead of asbestos matting in gooches (see Table 5). The crucible polymer samples were vacuum dried (5mm at 80° C) for 12 hours. Procedures hos. (5) and (4) were not used due to the fact that they did not provide significant data in , -.\ / Study A. Procedure No. (4) was used on the filtrate /? from the weighed reaction samples to determine the amount of maleic anhydride not in the precipi- tated polymer. Observations: Cloudiness due to polymer formation was first noted at 6 1/3 minutes after monomer addition to the reaction flask and the total reaction time was 2 hours. PART II STUDY B Table 5 DETERMINATION OF % POLYMERIZATION BY No. of Sample (OGJQOCfirhCfiNI-J H l4 l4 I4 +4 9- u N) P’ o 15 (as per procedure 2) Time Minutes 4.5 6.0 8.6 9.6 11.7 14.2 18.8 20.4 50.6 54.8 46.5 58.5 65.0 85.5 114.5 % Monomer in Initial Reaction Mixture: 7.12% Net wt Reaction Sample 11.595 5.790 16.277 10.652 19.560 15.470 15.122 17.055 21.560 15.150 17.00 25.99 18.025 22.145 21.565 AMOUNT OF PRECIPITATED POLYMER Net wt. Polymer .0005 .0001 .0428 .1542 .1622 .2785 .5644 .7716 .5542 .8561 1.4125 .9696 1.4455 1.5716 % Polymer in Sample .005 .002 .265 .568 .687 1.05 1.84 2.14 5.58 4.06 4.92 5.45 5.58 6.54 6.57 -52- % Polym- erization .004 .005 5.8 5.4 10.00 15.5 26.8 51.10 52.1 59.0 71.6 79.1 78.5 95.0 92.7 Sample QCDQOCflI-P-NH F’ k' F‘ F’ F‘ a. on an +4g<3 15 PART II STUDY B Table 6 DETERMINATION OF MALEIC ANHYDRIDE CONTENT OF COPOLVMER BY AQUEOUS TITRATION 0F UNREACTED NONOMERS WITH PHENOLPHTHALEIN INDICATOR (as per procedure 5) m1 NaOH m1 HCl Unreacted Unreacted Monomer % Monomer in grams 61.95% 15.65 7.12 .812 25.00 11.50 7.12 .270 45.00 2.20 6.75 .719 89.5 2.20 6.45 1.259 56.00 4.10 6.07 .959 50.00 9.60 5.28 .800 49.0044 9.00 4.98 .852 45.00 9.00 5.54 .765 25.00 4.00 5.06 .402 25.00 2.20 2.20 .574 25.00 '2.70 1.69 .459 25.00 10.00 1.74 .514 25.00 12.50 .58 .129 25.00 18.00 .75 .161 % Samples 1 through 7; ** Samples 8 through 15; -35- % M.A. in Polymer 60.1 72.6 71.5 65.1 82.9 74.6 77.9 77.8 75.4 71.1 76.1 78.0 56.6 82.0 .1027N NaOH and .lO26N H01 .0970N NaOH and .1026 N H01 _54_ METHODS OF CALCULATION: 1. (ml NaOH used 0 Normality NaOH) - (ml H01 used ° Normality HCl) : net meq. wts. M.A. in sample's unreacted monomer. I 2. Net meq. wts. M.A. ' Meq. wt. M.A. (.049) = grams M.A. in sample's unreacted monomer. 5. % monomer in initial reaction mixture (7.12%) - % Polymer in sample = % Unreacted monomer in sample. 4. % Unreacted monomer in sample - wt. of sample - grams unreacted monomer in sample. . unreacted M.A. in sam 19 _ 5. 100 e g p - A M.A. in g. unreacted monomer in sample (polymer. 1.. HI? I 5.9.85.2. sixth/r. 5.. .. .3 a. 4.... \.>\Fknw\ \. ...\.\t .4. r# U - N14-.. - a n \. tum .. {whiiwtw 0‘ \tdvlehl“ . OIIIKI. - ”Ipb .1 I.II1IIIIII|IOQI.II;EQIIII. .IIII..II.-l-IID|IO.-u .4 .III..l.I;‘IwIII-Illt.v.'l"‘g.Ii'nl1‘...‘ I? Ul.-l‘u-.lill. ( ,\ . . x . - VIII» _ 9 xv. \. K » «Ilia-«III rVC \hwo._ \\ h... \u I C. QI\. R Lab)“ \‘I‘I‘IIIIIII 1‘. rk.plw hrL» \LIKLlr LR!" m .J . x - .33, . .81. . .a I . It ml II My. . l | u. . .. v . . 1/ . Lurks»- .. 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IIISIII I’vrvIoO'i 105' III! -55- PART III AQUEOUS POTENTIOMETRIC TITRATIONS OF THE HETEHOPOLYMER: MALEIC ANHYDRIDE-STYRFNE General Method of Preparation of C0polymer Samples for Titration: The weighed c0polymer samples 1 through 11, 15 and 14 were taken from the final product of Study A, Part II, (1:1 molar ratio of reactants), the re- sult of a five hour reaction. Samsle 12 was from Study B, Part II, same molar ratio. The amorphous, powdery material was weighed on tared watch glasses and washed with C.P. acetone into covered 400 ml beakers. Sufficient acetone was added to effect solution of the material. Standard alkali was added to the acetone solution with constant stirr- ing and decided turbidity resulted. (N.B.: In the cases of samples 1 and 2, a definite precipitate occurred.) The solution samples were boiled on the hot plate until the acetone odor could not be dis- cerned and at which time the solution generally became transparent. The solution sample was potentio- metrically titrated several times with standard acid, than standard alkali, etc., using the glass electrode. Comments on the particular quantitative treatment of each sample as well as remarks on the titrations will be found in the tables correSponding to the specific samples (Tables I through XIV). Samples 1 through 14 were washed with cold ben- zene and dried at 85° C under 5 mm vacuum. Sample 5 was exposed to the carbon dioxide of the air for one week before being potentiometrically titrated (Table V). Samples 6 and 7 were potentiometrically titrat- ed with an indicator, brom cresol purple, being used. (Tables VI and VII). In Samples 9 and 10, weighed amounts of pure maleic anhydride were dissolved prior to the potentio- metric titrations. (Tables ix and X). Samples 10 through 14 were refluxed twice with benzene and were also dried at 110°C, 14mm pressure. (Tables X through XIV). Samples 15 and 14 were also dried at 155°C (Tables XIII and XIV). ‘ TABLE I POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYNER SAMPLE #1: Initially dissolved in 100 m1. .0970N NaOH. weight: 1.000gram Titration A: .1141N H01 Equipment: Beckman Portable Titration B: .097N NaOH p3 meter, standard outside glass electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with B202 catalyst, washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hours at 85°C, 5 mm pressure. Weighed sample dissolved in 100-150 ml. acetone. 100 m1 .097N NaOH added quickly. Some sticky string-like precipitate noted, which did not dissolve on the boiling off of the acetone. TITRATION A Total m1 M1. .1141N pH Remarks solution HCl 100 O 11.55 Pink to phth. 100.5 0.5 . 11.52 101.5 1.5 11.51 102.5 2.5 11.50 104.0 4.0 11.48 106.0 6.0 11.47 108.0 8.0 11.57 110.0 10.0 11.25 111.0 11.0 11.18 112.0 12.0 11.09 TITRATION A (continued) 158.5 58.5 8.38 clear Total m1 M1. .1141N pH Remarks solution HCl 115.0 15.0 11.01 114.0 14.0 10.92 115.0 15.0 10.85 116.0 16.0 10.76 117.5 17.5 10.61 119.0 19.0 10.48 120.5 20.5 10.55 121.5 21.5 10.22 125.0 25.0 10.12 124.5 24.5 9.98 126.0 26.0 9.78 127.0 27.0 09.65 128.0 28.0 9.57 129.0 29.0 9.48 150.0 50.0 9.55 150.5 50.5 9.28 151.0 51.0 9.18 phth. pink 151.6 51.6 9.10 lightening 152.5 52.5 9.08 155.5 55.5 8.99 154.5 54.5 8.88 faint pink 155.6 55.6 8.77 156.5 56.5 8.66 157.5 57.5 8.52 extremely faint 158.0 58.0 8.48 trace Of pink -39- TITRATION A (continued) 152.5 52.5 5.08 Total m1 Ml .1141N pH Remarks solution HCl 159.0 59.0 8.55 Shreds ppt. still here 140.0 40.0 ' 8.20 As HCl hits solution, noted cloudiness, dis- appears on stirring. 140.5 40.5 8.15 141.0 41.0 8.07 141.5 41.5 8.00 142.0 42.0 7.92 142.5 42.5 7.87 145.0 45.0 7.72 Suds developed on stirring 145.5 45.5 7.68 144.0 44.0 7.57 144.5 44.5 7.42 145.0 45.0 7.55 145.5 45.5 7.21 146.0 46.0 7.05 146.5 46.5 6.89 147.0 47.0 6.69 147.5 47.5 6.51 148.0 48.0 6.58 148.5 48.5 6.22 149.0 49.0 6.05 With steady stirring the pH reading held constant. 150.0 50.0 5.69 On halting stirring, the galvanometer needle 150.5 50.5 5.55 tended to backtrack toward alkaline side. 151.0 51.0 5.40 151.5 51.5 5.28 Total ml solution 155.5 154.6 155.6 157.0 158.5 160.0 162.0 164.0 166.0 169.0 175.0 177.0 180.0 181.0 182.0 185.0 184.5 186.0 188.0 190.0 192.0 194.0 196.0 198.0 200.0 202.0 204.0 208.0 225.0 -40- TITRATION A (continued) M1 .1141N HCl 55.5 54.6 55.6 57.0 58.5 60.0 62.0 64.0 66.0 69.0 75.0 77.0 80.0 81.0 82.0 85.0 84.5 86.0 88.0 90.0 92.0 94.0 96.0 98.0 100.0 102.0 104.0 108.0 125.0 pH 4.89 4.77 4.65 4.52 4.42 4.52 4.22 4.15 4.08 5.96 5.76 5.48 5.10 5.00 2.89 2.81 2.68 2.59 2.45 2.55 2.26 2.19 2.11 2.08 2.00 1.97 1.92 1.88 1.70 Remarks cloudiness seems to persist at this point Cloudiness obviously persists Almost Opaque -41- TITRATION B Total m1 Ml .097N Ml .097N NaOH pH Remarks solution NaOH used corresponds 15.: 25254.2 225.0 0 O 1.7 24° 245.0 20 17 1.94 250.0 25 21.25 2.02 255.0 50 25.5 2.12 260.0 55 29.75 2.25 265.0 40 54.0 2.42 270.0 45 58.2 2.57 272.0 47 59.92 2.68 Cloudiness 275.0 48 40.8 2.74 AIiggiiggne 275.5 48.5 41.2 2.77 Faint haze 274.0 49 41.6 2.81 275.0 50 42.5 2.88 277.5 52.5 44.6 5.00 280.0 55 46.7 5.22 282.5 57.5 48.8 5.45 285.0 60.0 50.95 5.62 287.5 62.5 55.1 5.75 290.0 65.0 56.1 5.85 295.0 70.0 59.5 5.96 298.0 75.0 62.0 4.04 501.0 76.0 64.6 4.19 505.0 80.0 68.0 4.42 507.0 82.0 69.6 4.59 509.0 84.0 71.4 4.82 511.0 86.0 75.1 5.22 515.0 88.0 74.8 5.89 -42- TITRATION B (continued) Total m1 ml .097N m1 .097N NaOH pH Remarks solution NaOH used corresponds to following # m1 .1141N NaOH 514.0 89.0 75.6 6.41 515.0 90.0 76.5 6.75 516.0 91.0 77.5 7.06 517.0 92.0 78.2 7.51 518.0 95.0 79.0 7.52 519.0 94.0 79.8 7.69 520.0 95.0 80.8 7.88 521.0 96.0 81.5 7.98 522.0 97.0 82.4 8.10 525.0 98.0 85.5 8.21 524.0 99.0 84.1 8.50 Machine corrected 525.0 100.0 85.0 8.58 Pink tinge of 526.0 101.0 85.8 8.5 gIIght pink 527.0 102.0 86.7 8.62 528.0 105.0 87.6 8.71 550.0 105.0 89.5 8.9 Decided pink 552.0 107.0 91.0 9.07 555.0 110.0 95.5 9.52 558.0 115.0 95.1 2.55 541.0 116.0 98.6 9.79 545.0 120.0 102.0 10.08 550.0 125.0 106.2 10.40 555.0 150.0 110.5 10.7 560.0 155.0 114.8 10.81 565.0 140.0 119.0 11.0 575.0 150.0 127.5 11.18 - .. :kl-Mth-wllmib- .... - ... m...16».N-......kk-.. ... ... 1..ka «fink-M4. warn-r» ...p... ....i. 4.... Rh! -..-.4». .. .a .1 _ . \v .- n... . .u. -. . ... . .- w \m\...L-u Ty.“ ErnQN-DU .... w... 44 - 413...... “4.1.4! . L. .. N%L-.N% k\\ b \-.o.m 4.. .44‘. 4.. ”1......n ... 4.5 -t L.- \\A.m.m \mhkb 1.1.4.5..» tab» 44.14....- 5334. 4.4.4.. Men-.44.. \~ 51 PK 5“ \ at .3 m. .x x KNN. 1,. ”WWI-m..-- __... 4x 1N ... ...-I .. ...-«ELF... 1..-...... 44.44 x. +- 4.3- 404...... ...-4.... {III III! P Ill-«ER NP. 4.44. ......- . 44.4. 4.4.41.4“ ...-4.1149711... {1../171l- mlalllfiu-AéoqQkkw-ETSN. ., .. 1(1-1 .... a ....- .a. at- a. a... 4. .....- ...... .. ...... .. -45- TABLE II POTENTIOMETRIC TITRATIONS 0F MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE #2: Initially dissolved in 75 m1 _.O97N NaOH wt: 1.003. Titration A: .ll4lN HCl Equipment: Beckman Portable pH meter Titration B: .097N NaOH Standard outside glass electrode Titration C: .ll4lN HCl COMMENTS: Heteropolymer prepared from 1:1 molar ratio of reactants with 3202 catalyst, washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hrs. 85°C, 3 mm pressure. Weighed sample dissolved in 100-150m1 acetone. 75 ml .097N NaOH added quickly. Some sticky string-like ppt. noted, which did not dissolve on the boiling off of acetone. TITRATION A Total ml ml .1141N pH Remarks solution HCl 75.0 0 9.52 23° Shreds of white material in solution 78.0 5 9.28 80.0 5 9.10 85.0 8 8.85 86.0 11 8.42 Pink lightening..solution slightly cloudy 89.0 14 8.11 92.0 17 7.61 93.9 18 7.59 Slow in coming to ' equilibrium 94.0 19 7.17 ' 95.0 20 6.91 96.0 21 6.62 98.0 23 5.97 Appears to lather well 99.0 24 5.69 Total ml solution 100.0 101.0 102.0 103.0 104.0 106.0 109.1 112.0 114.0 116.0 117.0 118.0 119.0 120.0 121.0 122.0 123.0 124.0 125.0 126.0 127.0 128.0 129.0 130.0 131.0 131.5 132.0 13H5.0 m1 TITRATION A (continued) .1141N HCl 25 26 27 28 29 31 34.1 37 39 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 56.5 57 58 pH 5.42 5.20 5.02 4.89 4.78 4.60 4.40 4.28 4.19 4.12 4.08 4.02 3.98 3.94 3.91 3.88 3.83 3.78 3.72 3.68 3.60 3.52 3.45 3.37 3.23 3.18 3.13 3.01 Remarks -44- Total ml solution 134.0 136.0 137.0 137.5 138.0 138.5 139.0 139.5 140.0 140.5 141.0 141.5 142.0 142.5 143.0 143.5 144.0 144.5 145.0 145.5 146.0 147.0 148.0 149.0 150.0 151.0 152.0 160.0 ml -45... TITRATION A (continued) .1141N HCl 59 61 62 62.5 63 63.5 64 64.5 65 65.5 66 66.5 67 67.5 68 68.5 69 69.5 70 70.5 71 72 75 74 75 76 77 85 pH 2.90 2.70 2.62 2.58 2.52 2.49 2.43 2.41 2.38 2.32 2.29 2.29 2.25 2.22 2.18 2.15 2.14 2.12 2.10 2.08 2.07 2.02 1.98 1.98 1.94 1.89 1.88 1.74 Remarks Corrected pH meter Slightly more cloudy Hazier Definite cloudiness Can barely see electrode Electrode no longer seen White, no translucence -45- TITRATION B Total m1 ml .097N NaOH ml .097N NaOH pH Remarks solution used corresponds to following # ml .1141N NaOH 160.0 0 0 1.74 170.0 10 8.5 1.92 172.0 12 10.2 1.98 174.0 14 11.9 2.02 176.0 16 13.6 2.08 177.0 17 14.43 2.12 178.0 18 15.30 2.18 179.0 19 16.17 2.22 180.0 20 17.00 2.22 Corrected pH 182.0 22 18.7 2.31 meter 183.0 23 19.55 2.36 184.0 24 20.4 2.42 185.0 25 21.23 2.48 Lightening 186.0 26 22.1 2.52 187.0 27 22.97 2.62 187.5 27.5 23.4 2.62 Clear 188.0 28 23.8 2.65 191.0 31 26.38 2.88 195.0 35 29.77 3.19 197.0 37 31.45 3.32 199.0 39 33.17 3.48 201.0 41 34.83 3.59 205.0 45 38.5 3.75 210.0 50 42.5 3.94 216.0 56 47.6 4.1 220.0 60 51.0 4.2 225.0 65 55.2 4.52 TITRATION B (continued) Total m1 m1 .097N NaOH ml solution 230.0 235.0 237.0 238.0 240.0 242.0 245.0 250.0 255.0 260.0 70 75 77 78 80 82 85 90 95 100 used corresponds .097N NaOH to following # ml .1141N NaOH 59.5 63.75 65.5 66.3 68.0 69.7 72.2 76.5 80.8 85.0 pH 5.33 7.02 7.40 7.58 7.88 8.12 8.42 8.88 9.29 9.68 -47- Remarks Light pink -48- TITRATION C Filtered Sample #2 at this point to remove insolubles. Let stand for 3 days. 317.0 57 3.50 Total ml m1 .ll4lN pH Remarks solution HCl 260.0 0 9.32 263.0 3 9.12 266.0 6 8.88 269.0 9 8.58 272.0 12 8.22 Phth cleared 274.0 14 7.98 276.0 16 7.64 278.0 18 7.17 279.0 19 6.88 280.0 20 6.62 281.0 21 6.34 282.1 22.1 6.08 283.0 23 5.88 284.0 24 5.65 285.0 25 5.48 287.0 27 ' 5.13 290.0 30 4.82 294.0 34 4.58 298.0 38 4.41 302.0 42 4.29 306.0 46 4.15 310.0 50 3.99 313.0 53 3.80 315.0 55 3.65 316.0 56 3.58 -49- TITRATION C (continued) Total ml m1 .1141N pH Remarks solution HCl 319.0 59 3.31 321.0 61 3.17 324.0 64 2.98 325.0 65 2.90 Stood 48 hours 325.0 65 2.80 Corrected pH meter 328.0 68 2.67 551.0 71 2.55 Let stand 1% hr., no ppt. 334.0 74 2.35 335.0 75 2.30 337.0 77 2.23 Let stand 40 min., no ppt. 337.0 77 2.23 338.0 78 2.19 Appears more cloudy 339.0 79 2.12 340.0 80 2.09 Let stand 15 hours, 540.0 80 2.52 slight ppt. settled 343.0 83 2.25 346.0 86 2.20 349.0 89 2.17 352.0 92 2.12 357.0 97 2.03 360.0 100 2.00 Seems a bit more cloudy Allowed to stand 7 hours. Considerable amount ppt. on bottom of beaker but supernatant liquid still cloudy. Let stand 15 hours, great deal ppt. settled but supernatant iquid not clarified, added reagent HCl and let stand. Reagent HCl fully ptd. and clarified supernatant liqu d. l\..\ - .. . . .. . . - .. . hgtfl‘i QN. !\1/ erhmkr-Mflxw (...! R13. ...-......“ ..\ “J kWh-muffin. hrxherx004§1> 5.1.4.. Rx . rm.\V\,\\cx,n-. Mu 11..\.m....y\.......> -.\......\s3.1\ .04.. 44...... ...... ””3134. .33.. 1.1".'{ 6' PI: '11.. .... ..l.l.:u'k. If. ..- l.r.. 33‘5"? mm“? 3...-.14.... 4.44.- :41395140 3‘ T444344 .Nxbfixvxfi \Mm. PDFVQ¢1§§M 4.4.x...451,\\ mm... xxx. ‘ {i1'u so... -50- TABLE III POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE #3: Initially dissolved in 75 ml. .097N NaOH. wt.: 1.0000g. Titration A: .114lN HCl Equipment: Beckman Portable pH meter Titration B: .097N NaOH Standard outside glass electrode Titration C: .1141N HCl COMMENTS: Heteropolymer prepared from 1:1 molar ratio of reactants with BzOg catalyst and washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hours at 850 0., 3 mm pressure. Weighed sample dissolved in 100-150 ml acetone. 75 ml. .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. TITRATION A Total ml ml .1141N pH Remarks solution HCl 75.0 0 9.39 260 77.0 2 9.21 79.0 4 9.02 81.0 6 8.82 83.0 8 8.61 85.0 10 8.39 87.0 12 8.15 88.0 13 8.03 89.0 14 7.91 90.0 15 7.75 91.0 16 7.61 91.5 16.5 7.50 92.0 17 7.39 92.5 17.5 7.28 93.0 18 7.18 93.5 18.5 7.09 -51.. TITRATION A (continued) 150.0 55 5.52 Total ml m1 .1141N pH Remarks solution HCl 94.0 19 6.92 94.5 19.5 6.77 95.0 20 6.62 95.5 20.5 6.48 96.0 21 6.28 96.5 21.5 6.11 97.0 22 5.92 97.5 22.5 5.75 98.0 25 5.58 98.55 25.55 5.42 99.05 24.05 5.51 99.5 24.5 5.21 100.0 25 5.11 101.0 26 4.95 102.0 27 4.82 105.0 28 4.72 105.0 50 4.58 107.0 52 4.45 109.0 54 4.52 111.0 56 4.25 114.0 59 4.12 117.0 42 4.02 120.0 45 5.94 122.0 47 5.86 125.0. 50 ' 3.72 127.0 52 5.59 129.0 54 5.42 Total ml solution 151.0 151.5 152.0 152.5 155.0 154.0 155.0 156.0 156.5 157.0 157.5 158.0 158.5 159.5 140.0 140.5 141.0 141.5 142.0 142.5 145.0 145.5 144.0 144.5 145.0 146.05 147.0 150.0 ml TITRATION A (continued) .1141N H01 56 56.5 57 57.5 58 59 60 61 61.5 62 62.5 65 65.5 64.5 65 65.5 66 66.5 67 67.5 68 68.5 69 69.5 70 71.05 72 75 pH 5.21 5.15 5.10 5.02 2.99 2.88 2.78 2.68 2.62 2.59 2.52 2.49 2.47 2.40 2.55 2.51 2.27 2.25 2.22 2.20 2.18 2.15 2.12 2.11 2.08 2.05 2.01 1.94 Remarks -52- Some stringy ppt. More definite ppt. Can no longer see electrode -53- TITRATION B Total m1 ml .097N ml .097N NaOH pH Remarks solution NaOH used corresponds to following # m1 .1141N NaOH 150.0 0 0 1.94 154.0 4 5.4 2.07 157.0 7 5.95 2.15 159.0 9 7.65 2.22 161.0 11 9.56 2.52 162.0 12 10.20 2.58 Lightening 165.0 15 11.05 2.41 Clears more on 165.5 15.5 11.48 2.45 253236251; all 164.5 14.5 12.52 2.50 in solution 166.0 16 I 15.6 2.58 167.0 17 14.45 2.65 Washed electrode 167.0 17 14.45 2.73 ¥§t§t§3§’§%13¥2? 168.0 18 15.5 2.82 169.0 19 16.15 2.89 170.0 20 17.0 2.98 171.0 21 17.85 5.06 172.0 22 18.7 5.15 175.0 25 19.55 5.25 174.0 24 20.4 5.51 175.0 25 21.24 5.41 176.0 26 22.1 5.48 177.0 27 22.95 5.55 179.0 29 24.65 5.62 181.0 51 26.55 5.72 185.1 55.1 29.75 5.85 189.0 59 55.15 5.92 195.0 45 56.55 4.02 -54.. TITRATION B (continued) Total m1 m1 .097N m1 .097N NaOH pH solution NaOH used corresponds to following # ml .1141N NaOH Remarks 197.0 47 59.95 4.18 200.0 50 42.5 4.29 205.0 55 45.1 4.47 205.0 55 46.9 4.68 208.0 58 49.5 5.02 210.0 60 51.0 5.47 211.55 61.55 52.2 5.97 212.0 62 52.7 6.14 215.0 65 55.6 6.56 214.0 64 54.4 6.88 215.0 65 55.2 7.15 216.0 66 56.1 7.54 218.0 68 57.7 7.66 220.0 70 59.5 7.91 225.0 75 62.1 8.22 226.0 76 64.6 8.52 250.0 80 68.0 8.88 254.0 84 71.4 9.18 258.24 88.24 75 9.50 TITRATION C Total m1 ml .1141N pH Remarks solution H01 258.24 0 9.45 241.24 5 9.20 244.24 6 8.92 247.24 9 8.62 250.24 12 8.55 252.25 14 8.10 254.24' 16 7.82 257.24 19 7.52 259.24 21 6.75 260.24 22 6.52 260.74 22.5 6.08 261.24 25 5.88 261.74 25.5 5.69 262.25 24.01 5.51 265.24 25 5.28 264.24 26 5.09 266.24 28 4.82 268.24 50 4.66 272.24 54 4.41 277.24 59 4.21 282.24 44 4.07 288.24 50 5.82 290.24 52 5.72 292.24 54 5.49 295.24 55 5.49 Adjusted pH meter 294.24 56 5.52 295.24 57 5.22 296.24 58 5.12 -55- TITRATION C (continued) Total m1 m1 .1141N pH Remarks solution H01 297.24 59 5.05 298.24 60 2.98 299.24 61 2.89 500.54 62.1 2.79 501.24 65 2.77 505.24 65 2.62 Corrected PH meter-- 303.24 65 2.55 let stand one hour 504.24 66 2.52 506.24 68 2.48 508.24 70 2.42 510.24 72 2.52 512.24 74 2.50 514.24 76 2.26 516.24 78 2.22 518.24 80 2.18 520.24 82 2.15 Opalescent? 522.24 84 2.12 More Opalescent 524.24 86 2.09 526.24 88 2.07 Definitely more cloudy 529.24 91 2.05 On standing clouds up moreso. 529.24 91 2.08 giggngdggnutes' cant 896 529.24 91 1.88 After 1% hours 552.24 94 1.82 555.24 97 1.79 558.24 100 1.75 After rechecking against A buffer, pH reads 2.07 \U. L \ ... I [1»: .. . . ...}. W ... I \ f. . . . .4... xx ..1 . . _ .. . .. . a... \....x. , .. . . .4 . ... .1 H..\\. .n .1 . '. l.!..l.l.h n. .7. 7‘. N. c .\I tfitu'ri‘l n 4 . -r. 1 1. I -..»..lvllgi - .\l|llvt . ..... 71-411». .7. if 1|-..Iilnwrllllli.t‘. \ ‘1 I V 5 k A! \ 1\ h \ \ s1 \ V . \ L pr IVE-Vrnli \‘vul ‘ o l . . . . . 1 1 tr. .krlr l {k 1.. . . . 6 . - .. . . - F .. . -4119... ...A. ~ . . . . fir). 1r . ..r . .1 . . . . . ll.-lll Ill‘ll ’III] 887‘s] ‘ ’7 . ... 4 IO. . . . .. I... . s. . / .. . s \ \5. 1. x x 1 ... . .. ~ . .. «\K . : ...VJ..¢.M. INDIA! \r‘ k. (1 .. \ . \ a . . n ... W n I ix f. 1 \Q. -. . . .w .. .... \... 1 ...... .... ...... / \. Tukxo; . ... ...... rv .. . .. .. .. .-.. .. S... 4......H6..Ll L- ......rolnr - n D . p a 0 V x k1 . .. . . .\ . . . I . . f7‘!‘.¥ll{ifhl' .I"! <2.-. . A.“ v..l1 l ol'lufnl . I.|o||l.¢ .. 4 I... ..1 .rllnllovllu ‘L’.+.I|7l. 1" 1.1.)..- h t.) kb|i\\\\\l§.vh“§l§1 5.1%-. {WP—gr LIVU :34.K1r......ilh._..7|....l.....|fi...a.u1tv...m..t.4§..~. ........ .... LL13; .. ..-. z .. ,../.o .. .9..- -n.v.l.11..1.1m1w$...1.. ... 5 \u. 1....V.. . .....- . .1... 141 .52... 11,1“. ...... ............. 1...... «i. ll- 1. 1......131; 3 ... La... 21 (:47... .\.,1......m,:.1.....-.........: 1|- . - .-. null 'IVM‘. Rik: ....x .. .. |\Ns~kk ......im. . _ ..a . It'lv v.0!!! ..l. . vb .. .1. 51...}. $1.1M. Kid 8 8. 11.115 0 7 TABLE -57- POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE SAMPLE #4: Titration A Titration B Titration C Titration D Titration E STYRENE HETEROPOLYMER Initially dissolved in 75 ml .1141N HCl .097N NaOH .1141N HCl .097N NaOH .1141N HCl Equipment: .097N NaOH wt.: 1.0000g. Beckman Portable pH meter Standard outside glass electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with B202 catalyst and washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hrs. at 85°C, 5mm pressure. Weighed sample dissolved in loo-150ml acetone. 75 ml .097N NaOH added slowly. Total ml solution 75.0 79.0 85.0 87.0 91.05 93.0 94.0 95.0 96.0 97.0 98.0 99.0 100.0 102.0 TITRATION A ml .1141N H01 0 4 8 12 16.05 18 19 20 21 22 23 24 25 27 pH 9.17 8.78 8.57 7.91 7.27 6.83 6.61 6.58 6.11 5.80 5.52 5.29 5.11 4.84 All ppt. dissolved on the boiling off of acetone. Remarks Total ml solution 105.0 109.0 113.0 117.0 121.0 125.0 127.0 129.0 131.0 132.0 133.0 134.0 135.0 137.0 139.0 140.0 140.0 142.0 142.0 143.0 144.0 145.0 146.0 147.0 147.0 149.0 150.0 ml -58- TITRATION A (continued) .1141N HCl 30 34 38 42 46 50 52 54 56 57 58 59 60 62 64 65 65 67 67 68 69 70 71 72 72 74 '75 pH 4.58 4.35 4.20 4.09 3.94 3.75 3.62 3.48 3.29 3.14 3.03 2.95 2.84 2.68 2.50 2.42 2.38 2.22 2.19 2.12 2.25 2.21 2.17 2.11 1.92 1.88 1.80 Remarks Rinsed off electrodes, allowed to stand..no ppt. Allowed to stand, slight ppt. Seems more cloudy Some ppt. settled Definite ppt. Allowed to stand Opaque, but will not settle Allowed to stand 2 hours, some settled but still ‘milky supernatant liquid. -59- TITRATION B ' Total ml ml .097N ml .097N NaOH pH solution NaOH used corresponds Remarks to following # ml .1141N NaOH 150.0 0 O 1.81 153.0 3 2.55 1.89 156.0 6 5.1 2.00 ‘ lowed to stand 159.0 9 7.65 2.37 Still not clear 160.0 10 8.5 2.38 161.0 11 9.35 2.34 Still settles 162.0 12 '10.2 2.45 Let stand 162.0 12 10.2 2.37 20 min. later still settles 163.0 13 11.05 2.40 164.0 14 11.9 2.45 164.0 14 11.9 2.38 after 2% hrs. still settles 166.0 16 13.6 2.47 Allowed to stand 167.0 17 14.45 2.52 Apparently less Opaque, clearing somewhat in 45 min. 168.0 18 15.3 2.58 Clearing further 40 min. later clear as usual 169.0 19 16.13 2.69 170.0 20 17.0 2.78 171.0 21 17.83 2.78 Adjusted pH meter 172.0 22 18.7 2.82 174.0 24 20.4 3.01 175.0 25 21.23 3.09 176.0 26 22.1 3.19 Adjusted pH meter 176.0 26 22.1 3.47 177.0 27 22.97 3.52 179 .0 29 24.65 3.67 18]..O 31 26.35 3.75 -50- TITRATION B (continued) Total m1 m1 .097N m1 .097N NaOH pH Remarks solution NaOH used corresponds to following # ml .1141N NaOH 185.0 35 29.77 3.89 189.0 39 34.13 4.00 193.0 43 136:6 4.09 197.0 47 39.97 4.20 200.0 50 42.5 4.29 Adjusted pH meter 204.0 54 45.9 4.42 208.0 58 49.3 4.71 213.0 63 53.6 5.64 215.0 65 55.25 6.41 217.0 67 57.0 7.02 221.0 71 60.4 7.71 223.0 73 62.1 7.98 225.0 75 63.8 8.18 227.0 77 65.4 8.48 229.0 79 67.1 8.58 231.0 81 68.9 8.70 233.0 83 70.6 8.87 239.0 89 75.6 9.31 241.0 91 77.4 9.42 245.0 95 80.75 9.72 247.0 97 82.4 9.87 249.04 99.04 84.2 10.01 250.0 100 85.0 10.08 254.0 104 88.3 10.33 255.0 105 89.3 10.41 257.0 107 91.0 10.51 259.0 109 92.6 10.61 262.0 112 95.2 10.77 269.0 119 101.1 11.00 -6l- TITRATION C 317.1 48.1 5.30 Total m1 m1 .1141N pH Remarks solution HCl 269.0 0 11.0 272.0 3 10.89 274.0 5 10.80 276.0 7 10.69 278.0 9 10.58 279.0 10 10.51 280.0 11 10.42 281.0 12 10.38 282.0 13 10.29 283.0 14 10.20 284.0 15 10.12 285.0 16 10.03 286.0 17 9.98 287.0 18 9.89 288.0 19 9.81 289.0 20 9.72 291.0 22 9.58 294.0 25 9.31 297.0 28 9.05 300.0 31 8.79 303.0 34 8.49 306.0 37 8.15 309.0 40 7.79 311.0 42 7.50 313.05 44.05 7.02 315.0 46 6.3 316.0 47 5.88 -62.. TITRATION 0 (continued) Total m1 m1 .1141N pH Remarks solution HCl 318.05 49.05 5.23 319.0 50 5.08 320.0 51 4.90 321.0 52 4.79 323.0 54 4.59 326.0 57 4.41 330.0 61 4.22 335.0 66 4.09 340.0 71 3.92 344.0 75 3.78 347.0 78 3.59 350.0 81 3.48 353.0 84 3.12 355.0 86 3.00 357.0 88 2.86 359.0 90 2.74 362.0 93 2.62 365.0 96 2.51 369.0 100 2.38, 2.33 373.0 104 2.32 378.0 109 2.15 384.0 115 2.08 396.0 127 1.98 Allowed to stand--- Definitely becoming Opaque. -63- TITRATION D Total ml m1 .097N m1 .097N NaOH pH Remarks solution NaOH used corresponds to following # m1 .1141N NaOH 396.0 0 0 1.97 401.0 5 4.25 1.98 406.0 10 8.5 2.02 Clearing? 411.0 15 12.75 2.09 416.0 20 17 2.16 Clearing. 421.0 25 21.25 2.21 Allowed to stand 426.0 30 25.55 2.28 Not clearing more 431.0 35 29.75 2.37 435.0 39 33.15 2.49 Practically 440.0 44 37.4 2.62 clear 446.0. 50 42.5 2.89, 292 448.0 52 44.2 3.10 450.0 54 45.9 3.23 452.0 56 47.6 3.39 454.0 58 49.2 3.57 456.0 60 51.0 3.68 458.0 62 52.7 3.74 463.0 67 56.9 3.9 468.0 72 61.2 4.01 473.0 77 65.4 4.15 478.0 82 69.7 4.32 483.0 87 73.9 4.65 488.0 92 78.3 5.42 489.0 93 79 5.75 1490.0 94 79.9 6.16 491.0 95 80.7 6.52 492.0 96 81.6 6.87 -54- TITRATION D (continued) Total ml m1 .097N m1 .097N NaOH pH solution NaOH used correSponds to following # 496.0 100 85.0 7.61 501.0 105 89.3 8.19 506.0 110 93.5 8.68 511.0 115 97.8 9.03 516.0 120 102.0 9.39 517.0 121 102.9 9.45 518.0 122 103.8 9.51 520.0 124 105.9 9.68 523.0 127 108.0 9.83 524.0 128 108.9 9.91 525.0 129 109.8 9.975 527.0 131 111.2 10.08 529.0 133 113.0 10.20 531.0 135 114.8 10.29 533.0 137 116.4 10.39 536.0 140 119 10.51 Total ml solution 555.0 541.0 542.0 545.0 544.0 545.0 548.0 550.0 552.0 554.0 ‘ 555.0 558.0 550.0 552.0 554.0 555.0 568.0 570.0 572.0 574.0 575.0 577.0 578.0 579.0 581.0 586.0 595.0 TITRATION ml .1141N HCl 0 5 6 7 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 41 42 43 45 50 60 E pH 10.51 10.23 10.18 10.12 10.04 9.90 9.78 9.61 9.43 Remarks 9.28, 9.50, 9.29 9.12 8.98 8.78 8.60 8.38 8.16 7.92 7.68 7.29 6.78 5.92 5.56 5.27 5.03 4.72 4.42, 4.45, 4.48 4.09 -55- -66... TITRATION E (continued) Total ml ml .1141N pH Remarks solution HCl 601.0 65 3.92 611.0 75 3.41 616.0 80 3.09 618.0 82 3.00 620.0 84 2.90 624.0 88 . 2.77 628.0 92 2.63 632.0 96 2.57 636.0 100 2.48 641.0 105 2.40 646.0 110 2.32 651.0 115 2.27 Still clear . NE . .. ...thuN.:Lme\A4m 55L. -.5.\ 1&54mmmt%4h4mk ........4... ...--.LfiXPLb... .. WW 3.r.\......r...4.... 4\...........\..... / ...- _ l / M . 4.5.... 454... 545.455. 4.559.545 5.... XMSR “54.)va 454 mw-// . / _ émflpm 54.5.5.1.-. .....m... // / . {.5531 E. H.453..- UN / . M4455. $544.5 {m.fimxkiar 44,445.45... LI {‘7‘ 4S4 n44.54432.4 4.5.44.5... fishkflfixx .7! .. H5555 E4451 4.2 545.41.044-54. H5354... 444.....5... 5.. 334 ...... a. ...-_.---...4.-4m-54.. .w H.454... H5845? R4, {5.542.455 ......ik4m 74.51.».3 i -# a. LLM .. _ . 07......1 , w../.4_fis.1kn\..\LNLm MAW)LL\....._J ... . [I I .. ‘ 4... . . ... . ,9. ~ _ .1. .f .. t. .5 5M. 54.4.1.5...Nw5 , /. w _ m m 5.. quwQufitLLu .Q- Dfi [44.5.4434 45444.0“ .WHMWP Illlllv A... ll... l1 \.4 4...: ..e. RP 54...... 44.4.44: 84.3.4.4. K14...4....._ All)- ..I ......II F. F r l. I. -- ..V..\4...4...:...:..L..b....... H-154..- 5......44444 -4... H.325! .... .. .v .5.; ..... .55 L 445...... .545... -455... ......A............ .. ...... -..... ....m.........-...-.,.. 44..-...2 £3.44 44.4 5.4 .....- - .... 1. 1 A N45 4.\ “44... .4; #4.... .5....“ NW —#’Iu_ fir. II..I. NE I‘ll" Ill-q". O -67- TABLE V POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE #5: Initially dissolved in 100 ml .097N NaOH. wt.: 1.0000 gram Titration A: .ll4lN 301 Equipment: Beckman Portable pH Titration B: .097N NaOH meter. Standard outside glass Titration C: .1141N HCl electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with Bz02 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 85°C., 3 mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 ml .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. Exposed one week to 002 of air. TITRATION A Total m1 ml .1141N pH solution H01 100 '0 10.32 102 2 10.20 104 4 10.03 106 6 9.92 108 8 9.81 110 10 9.68 112 12 9.52 114 14 9.39 116 16 9.22 118 18 9.09 120 20 8.91 123 23 8.63 126 26 8.52 Total ml solution 130 135 155 137 139 140 141 142 144 146 148 150 TITRATION A (continued) ml .1141N H01 30 53 35 57 59 40 41 42 44 46 48 50 pH 7.90 7.48 7.15 6.88 6.52 6.58 6.19 6.02 5.58 5.15 4.89 4.69 -68.. TITRATION B 100 ml distilled water added before titration. Total ml solution 250 252 254 256 257 258 259 260 261 262 265 265 268 271 275 280 285 290 294 296 298 500 502 504 508 ml .097N NaOH (OGJQCDI-hmo 10 11 12 15 15 18 21 25 50 55 40 44 46 48 50 52 54 58 m1 m1 .097N NaOH used corresponds to following # O 1.7 5.4 5.1 5.95 6.8 7.64 8.5 9.4 10.2 11.05 12.72 15.29 17.85 21.22 25.5 29.75 54.0 57.4 59.1 40.8 42.5 44.15 45.9 49.5 pH 4.71 4.88 5.11 5.51 5.80 6.15 6.55 6.89 7.19 7.41 7.61 7.91 8.25 8.55 8.87 9.24 9.61 9.95 10.22 10.54 10.47 10.55 10.66 10.75 10.90 -59- Total ml solution 510 512 514 516 518 521.5 525 m1 TITRATION B (continued) .097N NaOH ml .097N NaOH used corresponds to following # ml .1141N NaOH 60 51.0 62 52.7 64 54.4 66 56.1 68 57.8 71.5 60.75 75 65.7 -70- 10.98 11.02 11.08 11.12 11.15 11.21 11.27 -71- TITRATION C Total m1 m1 .1141N pH solution HC1 525 O 11.27 550 5 11.14 555 8 11.09 555 10 11.00 557 12 10.95 559 14 10.85 541 16 10.75 545 18 10.65 545 20 10.52 547 22 10.41 549.5 24.5 10.26 552 27 10.05 555 50 9.81 560 55 9.40 565 40 9.02 570 45 8.51 575 48 8.27 575 50 7.88 577 52 7.58 580 55 6.79 581 56 6.45 582 57 6.08 584 59 5.42 585 60 5.22 589 64 4.72 591 66 4.57 595 68 4.45 595 70 4.52 ...). \.\..4 4., ..... .Q .44.... .... ...... 1 .\ \v‘fl . .. ...\.\.\..~...\.. ..-. .... .4 \ .. Ht\.. \ILFILJIF1IIYLITNP in 4V- K. 3“ “Riva-K111 $.14 ‘4 ..L. .Hlt.\ 7.4 In”! 'I! 1I.‘(P..4..4..?\.~.\.\.§1F1‘11\4'141“4k§-1‘ QUM git"! I'I’L \INI‘ ‘Wfishn 11.5.! x \ ..s... K .. . . Til/bl LIL. \mNHm thwtku 44.). .NVWAIK. ‘1 / \P\......\ .44 r .v. ...... . . \\. ... ...\ \.......... . . \4 \1.I . \.. , //4 41414441111044? 191 11.....k1. ’Pt. 4: .94.. if ’1 i: ....O ht‘rb‘k’1ii/ 3:143 ._’Ap 1.400% a}. 44M} ii Ewkku’. «”115W '4“ It.“ \muo}! VI‘I \NX. .\.v.I I ../. / .1/1 MINI\\N¥\54 ..4 ”H4143... ......r (”YEPVEKI I. Iv (..i...1ul..14.444h.ix1 ... w ... ‘ L1 4......\ r118wiL'r1-\Lr.144444444f411&4r \Kfibiikglt? 1......fi1111444 4“,...19444M14'4RMI \. .. J x .1 V . xi ‘l . J . . t 4 I, u .' 42.4. . \ \ .. . A .. 4 DEX. 4* \l).\ 4 .... .41. J.‘\\’l1L\.4..-41.\V14f\lql. \ -5445 4.- I 4.; (1‘41 . 44.x... 5.4.". .14 1..! 11' 4 . 1. 4 \ avr11... ....Io. \ \(‘r . . U. .. ...Im‘r: \V... .'.&L. ‘1'!»‘1‘11 A: $2114.14VIHW. T 4&5... -..\.br.r4.\.\...... . ..th RN.” 4...... .. -..- {98.1. ...: 5 q . . :. ...... c .... .4 \QO :5 m Q 0.41.14h11n4411 1444444411.. 4.1..41. .\.. 4— .... 4 ..J\ . . .. 5 NW; “Junk”; “.4’I‘L II\.M\J..I I\XH “1.1443\}|-'Q ~1K1‘4o..4\.fl\fl.Fat1l.P|\l.ll.iDILlN1 4 4. J u .. . v. . \‘44 . ......LHL. 44:... \4 R. ...... . 2.6%. .44“... Mia... .llllw p. T. .. ...... 3...-...,\_ m. .... E 1x... :4... it... A. ...... .... 1951-1144111}; urn-17.14.11,".LII'1R‘4II“ I1 I‘III‘ . .. . . .. . .4 K1 n . 1‘. .4 1...... 1N...\ A‘\ .‘.I .\ 4 .\. k. .I‘. . \ ..‘x . 4 . v n _ ‘. .‘k. ......Iy) I II 1' $ 1111414101}! . .11-idglurz‘i 4:; g 1.1! .1 .1 \i ...... k... .... p... ...... r1... ... .r. ...... .T. an R5 4+. .\........ .. TABLE VI POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 6: Initially dissolved in 100 ml .097N NaOH. wt.: 1.000g COMMENTS: Heteropolymer prepared from 1:1 molar ratio of reactants with B202 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 850 G, 3mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 ml .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. Diluted to 275 ml with dist. HOH. Titration of alkaline solution with Brom cresol purple as indicator. 15 drOps Total ml ml .1141N pH Remarks solution H01 275 0 9.78 purple 285 10 9.19 " 290 15 8.81 " 295 20 . 8.37 " 300.5 25.5 7.69 " 303 28 7.19 Ilighter..still purple 305 30 6.82 " " " 306 31 6.69 " " " 307 32 6.53 lighter..still purple 308 33 6.43 " " ‘ " 309 34 6.31 " " " 310 35 6.22 311 36 6.12 light purple 312 37 6.03 313 38 5.93 314 39 5.85 slight purplish tint 315 40 5.73 dirty brown tint 316 41 5.62 amber 317 42 5.52 yellow Total ml solution 518 519 520 325 -75- TABLE VI (continued) .1141N pH Remarks HCl 45 5.4 44 5.29 45 5.18 50 4.69 a . W EEKEMKFKZNREEEE: SM REEE:%ELK: 2m-.. .. $9.5... /:.:_.. ICL TEN“ ......H \waxifi aw./ W . ENJLLM.) ItintNNlV: kmfiKkNm \...\\.N...: :1\_\r\ when! [fill->05“ “AUX O . . . ”mix. Nun. H. 4 / , NEE Eu LN: -mm»\\.\mfidt fill-II? ,4 WEE QUE it n 35...“... 1.9» :2... r \r .. \E 9 >343,” .K 961).... hunEXEE 4, NEE EL...» T\...--..\..:.M..:mm..~.m..wwm..--: . PEPE? View .-.: ...-.-ébhmgh / . Hows? R 423;: IE» rut. PM, ::+ i: TY) I f. \ ’— “:3" .... -: «mfi .... -..Elml. N... 3. 3%.”. 44.1...4 . ..XN hi..LrL..._:‘?|r. \ I::¢$Sr.u..\~.b ...-E, pa . ......»E Kt-.. win? Alli... IMAL_$...;> E? K \TIR 5x. 1:: x will- Kr ‘ . . . s.‘ . \ x . \v‘; . .. ‘_ I. 4‘. Nu. ... I I I!" . .313}..- t... -. : ..::\< EN: :1 4. x . .0 ..\-.\ \I H. . .. \ 1‘ .\s.x\ W . x. I. w I‘l! ..fi k .‘id $ ...... R‘. ‘1 Id" “'1'. .LIII’ . lir\'h ‘l‘tl-I Ilul l": ‘1. Lti.il 'u‘l ..:::::Z....tr.:...:. .3... ....n-:§.£.. EL d E... -lli Ki. .... E... .... .... ...... -67- TABLE V POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE ngRENE HE‘I‘EROPOLYMER SAMPLE #5: Initially dissolved in 100 ml .097N NaOH. wt.: 1.0000 gram Titration A: .ll4lN HCl Equipment: Beckman Portable 93 Titration B: .097N NaOH meter. Standard outside glass Titration C: .ll4lN HCl electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with B202 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 85°C., 5 mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 ml .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. Exposed one week to C02 of air. TITRATION A Total m1 ml .1141N pH solution HCl 100 0 10.52 102 2 10.20 104 4 10.03 106 6 9.92 108 8 9.81 110 10 9.68 112 12 9.52 114 14 9.39 116 16 9.22 118 18 9.09 120 20 8.91 125 23 8.63 126 26 8.52 Total ml solution 130 133 135 137 159 140 141 142 144 146 148 150 TITRATION A (continued) ml .1141N H01 50 35 35 57 59 4O 41 42 44 46 48 50 pH 7.90 7.48 7.15 6.88 6.52 6.58 6.19 6.02 5.58 5.15 4.89 4.69 -68- TITRATION B 100 ml distilled water added before titration. Total ml solution 250 252 254 256 257 258 259 260 261 262 265 265 268 271 275 280 285, 290 294 296 298 500 502 504 508 m1 .097N NaOH comqouuszoo 10 11 12 15 15 18 21 25 50 55 40 44 46 48 50 52 54 58 ml ml used corresponds to following # O 1.7 5.4 5.1 5.95 6.8 7.64 8.5 9.4 10.2 11.05 12.72 15.29 17.85 21.22 25.5 29.75 54.0 57.4 59.1 40.8 42.5 44.15 45.9 49.5 pH 4.71 4.88 5.11 5.51 5.80 6.15 6.55 6.89 7.19 7.41 7.61 7.91 8.25 8.55 8.87 9.24 9.61 9.95 10.22 10.54 10.47 10.55 10.66 10.75 10.90 -59- Total ml solution 510 512 514 516 518 521.5 525 m1 TITRATION B (continued) .097N NaOH m1 .097N NaOH used corresponds to following # ml .ll4lN NaOH 60 51.0 .62 52.7 64 54.4 66 56.1 68 57.8 71.5 60.75 75 65.7 -70- 10.98 11.02 11.08 11.12 11.15 11.21 11.27 -71- TITRATION C Total ml ml .1141N pH solution HCl 525 0 11.27 550 5 11.14 555 8 11.09 555 10 11.00 557 12 10.95 559 14 10.85 541 16 10.75 545 18 10.65 545 20 10.52 547 22 10.41 549.5 24.5 10.26 552 27 10.05 555 50 9.81 560 55 9.40 565 40 9.02 570 45 8.51 575 48 8.27 575 50 7.88 577 52 7.58 580 55 6.79 581 56 6.45 582 57 6.08 584 59 5.42 585 60 5.22 589 64 4.72 591 66 4.57 595 68 4.45 595 70 4.52 ...Kb....-L\¥6..Q1.h\}1:r.h1N. 6.x..‘m..11.1.r.1..1111..u\1 NA\.W o... .5“?! AV...“ s.) x .. . \ Lilimfik 0.111: wmbtblul‘i $5..\:1KK)ID\KM~11PI5I.&IJ.1K» .\N\KMMEU. 1.1. ..NJXKL. .u. . K K .. ‘1 1 . .. . E .1 .\ v. .. ... \x..._.\....14...x E“ .7...“ .. . \1\\\. . %\ . K. . $551K...) 9.1.1... ,. Lunar-.1114.” :- 5E1151£h25h111h}.\m.kikxbifblefl #11:... .1..\. INKNR.1QK1311.\..¢H ... hi»~1§..n.t.1r..5 ...... -1“.th . _ ‘5 c 1 1‘ ..u 13%149 1 .5. ... ..Ir1... .kKhIL 6.1%... ..1.w..1 .... . 1.1.1.15.-- fins..- \Ueb v 1.1.1.1"...1: .. x . 1.11”... .11w.\...115r 1.MH»\..N 3.1%.... “11F1351M11itfixk. 1.1.1.“. 1.1.1....“ .1\. 1:555:151r5551l5551035 .. .5 4| N15 Em... ...1.K...L L- 1erm1kxt11 -1. RN H 1...... t- :2. 8.66. \.\\0 Elm 1151.. 011.511 ‘1 1 6 4.1%.. .1-.. 6mm... - 1 1K1: Lam... 16.48.. .4. 1...... .I - . ' ' 5 1 . \ \.\........ . .511. .. . . I 1...... 1. x... \f‘. ..‘1‘.1H~. . \...1N... 5 5 5 1 .1114- 11.0111 1 4.. 511 its, . TABLE VI POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 6: Initially dissolved in 100 ml .097N NaOH. wt.: 1.00Ug COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with 8202 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 85° G, 3mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 ml .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. Diluted to 275 ml with dist. HOH. Titration of alkaline solution with Brom cresol purple as indicator. 15 drOps Total ml ml .1141N pH Remarks solution H01 275 O 9.78 purple 285 10 9.19 " 290 15 8.81 " 295 20 . 8.37 " 500.5 25.5 7.69 " 503 28 7.19 lighter..still purple 505 50 6.82 " " " 506 31 6.69 " " " 507 52 6.53 lighter..still purple 508 33 6.43 " " . " 309 54 6.51 " " " 310 35 6.22 311 56 6.12 light purple 512 37 6.05 313 58 5.93 514 39 5.85 slight purplish tint 315 40 5.73 dirty brown tint 316 41 5.62 amber 317 42 5.52 yellow -73- TABLE VI (continued) Total ml ml .1141N pH Remarks solution H01 318 43 5.4 519 44 5.29 320 45 5.18 525 50 4.69 -75... TABLE VI (continued) Total m1 ml .1141N pH Remarks solution HCl 518 43 5.4 519 44 5.29 520 45 5.18 325 50 4.69 -74- TABLE VII POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 7: Initially dissolved in 100 ml .097N NaOH wt.: 1.0000 gram COMMENTS: Heteropolymer prepared from 1:1 molar ratio of reactants with B202 catalyst and washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hours at 85°C, 5 mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 m1 .097N NaOH added very slowly. A11 ppt. dissolved on the boiling off of acetone. Diluted to 525 ml with distilled HOB. Brom Cresol Purple, Indicator. Total m1 ml .ll41N pH Remarks solution H01 525 0 9.68 555 10 9.1 545 20 8.25 550 25 7.57 555 50 6.62 556 51 6.5 557 . 52 6.41 558 55 6.52 Faint purple 560 55 6.12 562 57 5.98 Amber 564 59 5.79 566 41 5.6 568 45 5.59 570 45 5.17 572 47 4.98 575 50 4.72 578 55 4.55 584 59 4.29 -75- TABLE VIII POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 8: Initially dissolved in 100 m1 .097N NaOH. wt.: 1.0000g Titration A: .1141N HCl Equipment: Beckman Portable pH meter Titration B: .097N NaOH Standard outside glass electrode COMMENTS: Heter0polymer prepared from 1:1 molar ratio of reactants with 8202 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 85°C, 5 mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 m1 .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. Added .5525 g. C.P. Maleic-Anhydride to above solution. Heated on steam bath until dissolved. TITRATION A Total ml ml .1141N pH Remarks solution H01 100 O 5.60 101 l 5.52 104 4 5.41 110.05 10.05 5.02 115 15 4.67 120 20 . 4.58 125 25 4.17 130.05 50.05 4.01 Quite a bit of foan 135 55 5.88 dissolved 002 140 40 5.67 145 45 5.48 145 45 5.50 147 47 5.15 149 49 5.01 150 50 2.91 Total ml solution 152 154 156 158 160 162 164 167 170 175 180 182 184 186 -75- TITRATION A (continued) m1 .1141N pH Remarks HCl 52 2.79 54 2.69 56 2.59 58 2.49 60 2.41 62 2.52 64 2.27 67 2.19 Cloudy 70 2.10 Thick ppt. 75 2.00 80 1.95 82 1.89 84 1.87 86 1.82 Removed sample. Heated on steam bath to drive out C02. Balled up into a sticky mass. -77- TITRATION B Total ml m1 .097N ml .097N NaOH pH Remarks solution NaOH used corresponds to following # ml .1141N NaOH 186 O 0 2.01 Hard ball ppt. 196 10 8.5 2.18 206 20 17.0 2.58 216 50 25.5 2.72 226 40 54.0 4.2 - Galvonometer needle drifting to lower reading 226 40 54.0 2.88- After standing 16 hrs. almost dissolved 251 45 58.22 5.15- Allowed to stand 4 hrs. all in solution. 254 48 40.8 5.55 256 50 42.5 5.45 258 52 44.2 5.52 241 55 46.7 5.7 244 58 49.5 5.81 247 61 51.8 5.91 251 65 ‘55.2 4.07 254 68 57.8 4.12 257 71 60.5 4.22 261 75 65.7 4.57 266 80 67.9 4.60 270 84 71.4 4.88 J \ .4 1%. \v ‘x x . \MV\‘.I- ‘1 \ 11.! \ 0‘ 44 \ 4 . Iv.|. . K. . - .. _ .. . .... . ....i ....... l . ... Flt; (I... A .13 KIN-Bu. V: )‘Lk .. v. .I\ b." I\ ) .439. .\.P NIKLA .55 fl ¢h\\.o.\..\ ...F-E.WIJ4 a 8,! 044‘.‘Iis.tuslnl\twll\‘..‘§'iralbo.b. l\ . . 4 \ IN {II-h ... L. . \rr . . . .1 . .4 .. _ ..4- .. \- ‘ ... I. . u. I J . . . . I .l . . - a . . 18‘ .- . . .. .. . \. . .. . .. . . . . . .. x . .. . L \41 \- l. .1 4. .. . I . . . . 4 4 . 4 x \ \ . .4 .. K N 4.. . . .. 4 .4 . v 4 4 8 N ‘— 4 .\.\ r IIIIs'D.-t.l\ll.ul.!).1. ’It 41." t. ...? :. III-101! .1V‘l, D 11.19.. .... .. .. ...ILCuI-4ul. ['8. 137:2]. .-r‘l‘ .r... 4.7.3,... ... . ...-u If an (flit-’11,..Itr- wily-It’ll“? n9? . \ ...-4 afl 4. A4 4 . .\ 4‘ RE... \\.4.. . .4 m\-.\\ .I‘ . \s . 4.9.21.4 .. l. \. .494... mu...- 23.... ...- .... .4 our!!! 9‘. D- 1..... ..[ll‘l’tll n.“ in! 'f. r 1:411 I!!! livi- I'f' 1|. 1’1. 1018;11) piil- .vPI‘lIll-v I0 ’3... \uii'11 xii-... s. 9.39-.... .99. 9...“..9 N...- [...-E- ...-2.99“.”- . \99-9 \WQQ Ebb-t- ...-._.... ...-.... / 29...... K ...-9 S9...» ...-8:999 / own-kamsfi .9. .- ..- 3;) )ID 8155! x a :xmkfiLK-Hu {:ib-szr NR“ n m\ “.....H\ H ER >..Om\1 8..! 7m... x... I / E\\ 4..._n.. K..)RK» |\_ c L %t\.LN.. .LVIQPEU? (AK IN- a3h.N..\.. ._ 9. ..., . m4. 4...... ... [M\ // kill. \\ N..4.I\.$m-‘D.'LW-Wz\g\t W“!~l.!~..lln.tl(. viur‘tlhm-HV; .... .4 ”1...! . /,/ . a . u . .N 4; ”NI-J...- W9... .7/ 1\ b9... 9 ......»o R... .. 1.1.5 4.. 9K...” ...... . 9. 4|. ‘rlll'ln. I18... ...! twig-Ll .f/ 47 .../fl Flu-Pm” 0 . . all-III!!! EQKEW W ...... .9...“- r | |..|. W J . V. \1..4.-V xx . .- . .-. _. . ...-K.....EA \ . .1 t Eyrlcflib I 4\ ‘ sfil . I! .:.".l Ill... ‘ ill-Iv Q39. .m- ...--..er -_ .9. 9... ...... 9...... 9.29-x 1..-AMH- ...-ii.» A... -..-.... 5499-9... nix K-.-1-999991. \A- .- - 9. 9 .9. 9. .9..- .9 .9 9 9 9 -78- TABLE IX POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 9: Initially dissolved in 100 ml .097N NaOH. wt.: 1.0000 gram Titration A: .ll4lN H01 Equipment: Beckman Portable pH meter Titration B: .097N NaOH Standard outside glass electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with B202 catalyst and washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hours at 85° C, 5 mm pressure. Weighed sample dissolved in 100-150 ml acetone. 100 ml .097N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone. Added .1554 g. C.P. Maleic-Anhydride to above solution. Heated on steam bath until dissolved. TITRATION A Total ml ml .1l4lN pH Remarks solution H01 100 0 7.49 105 5 7.00 110 10 6.51 115 15 6.15 120 20 5.82 125 25 5.48 150 ' 50 5.00 155 55 4.58 140 40 4.29 145 45 4.16 150 50 5.97 155 55 5.79 160 60 5.52 165 65 5.10 Total ml solution 167 169 171.5 174 177 179 181 185 185 187 ml -79- TITRATION A (continued) .1141N HC1 67 69 71.5 74 77 79 81 83 85 87 pH 2.92 2.77 2.60 2.48 2.32 2.25 2.18 2.12 2.07 2.01 Remarks Little cloudy ppt. Good ppt. Total ml solution 187 197 207 212 214 216 218 220 222 224 227 232 237 242 247 252 254 256 258 260 262 266 270 272 274 276 m1 TITRATION .097N NaOH 10 2O 25 27 29 31 33 35 37 4O 45 50 55 60 65 67 69 71 73 75 79 83 85 87 89 ml ml B used corresponds to following # .1141N NaOH 0 8.5 17.0 21.22 22.95 24.62 26.35 28.03 29.75 31.43 34.0 39.25 42.5 46.75 51.0 55.3 57.0 58.7 60.4 62.1 63.7 67.2 70.6 72.3 74.0 75.7 pH 2.01 2.29 2.70 3.00 3.12 3.31 3.42 3.52 3.62 3.72 3.79 3.94 4.00 4.22 4.49 4.89 5.11 5.31 5.54 5.68 5.81 6.13 6.49 6.87 7.13 7.42 -80- Remarks Clear . n\.l.\ \. ‘ .\\ | --..-.bflrbvux. - ‘1‘5 {an 1..]: ”I n! ill .l I)‘ \II . s... .. .... .... .o' L...\... \ ...... . wA. -. «Nix ...Qxfikwmssxasm ._....Nx. .... ...... 5. ...- \\h..mr. .\ \..~..!x.5.... {...hukxm‘n ..N\V‘\H.\nw.i HUN“. 3. - . a. -, , .. . - IQ! ,// ......Huw. WALK”... ......uu...i.. .lANwH: WA am“: . “Ami. .{I.&:At}wf: akhwirNXNVLfimbxle {finch \. \NAMH.‘ . e ....\p...._ \m .... i: ... SAN... Mm. .. x. x K..? ..M...i.\w..mbu.mw._m.w.k ’ «W. . Q . v .. . ... s ,p a C ... ill . \J ..x ‘5. . h 5.1.-.. .\...\........>....... ...- (m. .HN..x.k........:r....r.- Rana swab... . c M. A... .....2. 1....3 3... AA... AF. . A m». Illa: 1.-..W SM \meh... .f.\.,.\ T III I NMHNME bk .5... «I KARL. A .-.- ...N I. AH»... Nut! «...rk .ln U0 «\x “if ‘IIII ‘0‘" W. A}. Q Aishmflxfimimx NW5... k..-§5«ikw. Eng $55.... .. x... ..x\ x... \N.\ .....- 3... NR. ANN HA... ... -mM..-.. .. ..-..Io. (DIVIV -.l QEARV . 1!.I\II In". I .5. U ERR. ..x MN.\\_. 2. ...me 3...“. . 555K. 2. hnsQQ x5. I-‘.~: \....1\ .-....E..- WNQKCA. 1.53.3 ‘W’F. NFL-[klhkvh\q'|1 . laIHMI.‘ PLIPWN \u\‘\\. .....\Vfi\vl\r. .\.n.\.M\...fl 5.: . sI-I.“u. 'p \.~..\\\.\c..’\ fi'l I.OI'I-‘ ...-ID §§b-:nax A. .0... \...Q in! It: ctr)- ._\.Mm+ .:\R.? ..tkfltoufikttilt LI w s3. mm...\\¢\-,NAW.-m§NMhAm III... .....M. n; 5%.? .. 5.55th I III .. . . ..§ 3.. o . . \. .I-u.:. v: Q Nfiwfl ‘ A»--- .. km ...... .NWN G . -82- TABLE X POTENTIOMETRIC TITRATIONS 0F MALEIC-ANHYDQIDE STYRENE HETEROPOLYMER SAMPLE # 10: Initially dissolved in 75 ml .0923N Na0H* wt.: 1.0007 gram Titration A: .1141N HCl Equipment: Beckman Portable Titration B: .0923N NaOH pH meter..Standard outside Titration C: .114lN HCl glass electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with Bz02 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 85°C, 5mm pressure. Weighed sample dissolved in 100-150ml acetone. Added 75 ml .0925 N NaOH. Material washed by refluxing 2 hours twice with fresh C.P. benzene. Dried in an Aberhalden drying pistol at 1100 C at 14 mm pressure for two days. % An apparent error in caustic normality was evident. TITRATION A Total ml ml .1141N pH Remarks solution HCl 75 O 9.10 79 4 8.72 83 8 8.28 87 12 7.79 91 16 7.15 95 18 6.68 94 19 6.51 95 20 6.28 96 21 6.00 97 22 5.72 98 25 5.49 99 24 5.22 Total ml solution 100 101 103 105 109 11:5 117 121 125 128 130 132 155 134 135 157 139 141 m1 TITRATION .1141N HCl 25 26 28 50 54 38 42 46 50 55 55 57 58 59 6O 62 64 66 A (continued) pH 5.02 4.89 4.66 4.50 4.27 4.10 5.97 5.92 3.62 5.42 5.22 3.02 2.90 2.81 2.71 2.52 2.52 2.18 Remarks ppt persists -85- Total ml solution 141 144 147 150 152 154 156 158 166 171 176 181 186 191 195 195 197 199 201 206 211 216 220 225 250 255 259.05 241 ml TITRATION .0925N NaOH (003010 11 13 15 17 25 so 35 4o 45 50 52 54 56 58 so 65 7o 75 79 84 89 94 98.05 100 B Correction to ml of .1141N NaOH 0 2.45 4.86 7.28 8.90 10.51 12.15 15.77 20.22 24.25 28.55 52.55 56.5 40.4 42.1 45.7 45.5 46.9 48.6 52.6 56.7 60.7 65.9 67.9 72.0 76.1 79.5 80.9 pH 2.17 2.51 2.50 2.72 2.91 5.10 5.58 5.48 5.79 5.91 4.02 4.22 4.52 5.28 5.82 6.48 7.00 7.57 7.62 8.16 8.58 8.97 9.21 9.58 9.87 10.15 10.57 10.45 -84- Remarks Clear -85- TITRATION C Total ml m1 .1141N pH Remarks solution HCl 241 0 10.45 251 10 9.74 261 20 8.94 271 50 7.92 276 55 7.12 278 57 6.61 279 58 6.55 280 59 6.08 281 40 5.81 282 41 5.58 285 42 5.55 284.05 45.05 5.12 285 44 4.98 288 47 4.61 291 50 4.41 501 60 4.01 506 65 5.85 511 70 5.59 513 72 3.42 515 74 5.27 517 76 5.09 519 78 2.95 521 80 2.79 525 82 2.68 526 85 2.52 551 90 2.52 556 95 2.21 541 100 2.09 Ppt., but not fully even on standing 24 hours 0 -86- TABLE XI POTENTIOMETRIC TITRATIONS 0F MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 11: Initially dissolved in 100 ml .0925N Na0H* wt.: 1.0012 gram Titration A: .1141N HCl Equipment: Beckman Portable pH meter Titration B: .0925N NaOH Standard outside glass electrode Titration C: .114lN HC1 COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with 3202 catalyst and washed with cold benzene. Dried at atm. pressure and 80° one week, dried 24 hours at 85°C, 5 mm pressure. Weighed sample dissolved in 100-150 ml acetone. Added 100 m1 .0925N NaOH. Material washed by refluxing 2 hours twice with fresh C.P. benzene. Dried in an Aberhalden drying pistol at 110°C at 14 mm pressure for 2 days. * An apparent error in caustic normality was evident. TITRATION A Total ml ml .1141N pH Remarks solution H01 100 0 10.0 102 2 9.98 104 4 9.77 106 6 9.65 108 8 9.52 110 10 9.59 115 15 9.02 120 20 8.65 125 25 8.15 150 50 7.51 155 55 6.72 156 56 6.58 157 57 6.42 -87- TITRATION A (continued) Total ml ml .1141 pH Remarks solution HC1 158 58 6.51 140 40 6.09 141 41 5.97 145 45 5.59 145 45 5.19 150 50 4.57 160 60 4.09 165 - 65 5.92 170 70 5.72 175 75 5.55 176 76 5.25 177 77 5.17 178 78 5.05 179 79 2.97 180 so ' 2.85 181 81 2.72 182 _ 82 2.65 185 85 2.42 186 86 2.58 Very slight ppt. On standing 24 hrs., solution is clear. Total ml solution 188 194 197 200 205 206 209 212 215 219 225 228 255 258 240 242 244.1 247 250 255 258 268 278 285 286 288 ml TITRATION B .0925N NaOH 0 6 9 12 15 18 21 24 27 51 55 40 45 50 52 54 56.1 59 62 65 70 80 90 95 98 100 Correction to ml of .1141N NaOH 0 4.86 7.28 9.79 12.15 14.58 17.0 19.41 21.85 25.07 28.55 52.55 56.41 40.4 42.1 45.7 45.5 47.75 50.2 52.7 56.7 64.7 72.8 76.8 79.5 80.9 pH 2.08 2.57 2.59 2.79 2.98 5.17 5.52 5.52 5.72 5.97 4.08 4.24 4.57 5.22 5.67 6.21 6.72 7.25 7.65 7.95 8.58 9.09 9.72 10.00 10.18 10.28 -88.. ~89- TITRATION C Added 10 drOps Brom Cresol Purple to solution. Total ml ml .1141N pH Remarks solution H01 288 0 10.28 295 5 9.92 298 10 , 9.57 508 20 8.78 518 50 7.72 525 55 6.80 525 57 6.51 Lightened considerably 526 58 6.08 About clear 527 59 5.81 Clear (yellowish) 529 41 5.58 555 45 4.70 558 50 4.51 548 60 5.99 555 65 5.81 558 70 5.58 565 75 5.18 568 80 2.8 575 85 2.59 578 | 90 2.41 588 100 2.20 TABLE XII POTENTIOMETHIC TITRATIONS 0F MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 12: Initially dissolved in 50 m1 .0925N NaOH* wt.: .4145 gram Titration A: .1141N HC1 Equipment: Beckman Portable Titration B: .0925N NaOH pH meter, Standard outside Titration C: .1141N HC1 glass electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio with B202 catalyst and refluxed with benzene for 20 hours. Dried at atm. pressure and 80° one week, dried 24 hours at 85°C, 5 mm pressure. Weighed sample dissolved in 100-150 ml acetone. Added 50 m1 .0925N NaOH and 10 ml distilled HOH. * An apparent error in the caustic normality is evident. TITRATION A Total ml ml .1141N pH Remarks solution HCl 65 0 10.68 67 2 10.58 69 4 10.09 71 6 9.92 75 8 9.58 75 10 9.25 77 12 8.91 79 14 8.50 81.05 16.05 8.00 82 17 7.72 85 18 7.58 84 19 6.97 85 20 6.61 86 21 6.50 Total ml solution 87 89 91 95 96 99 102 104 105 106 107 108. 110 115 115 ml TITRATION A (continued) .1141N HCl 22 24 26 28 51 54 57 59 40 41 42 45 45 48 50 pH 6.02 5.58 4.79 4.47 4.18 5.93 3.59 5.19 2.99 2.79 2.55 2.50 2.52 2.15 2.02 Remarks Milky Ppt. noted -91- -92- TITRATION B Total m1 ml .0925N Correction pH Remarks solution NaOH to m1 of .1141N NaOH 215 O O 2.19 Added 100ml dist. HOH 219 4 5.4 2.52 225 8 6.48 2.59 226 11 8.9 2.92 228.1 15.1 10.6 5.28 229 14 11.55 5.42 250 15 12.15 5.60 255 20 16.18 5.98 240 25 20.22 4.52 245 28 22.65 4.69 245 50 24.28 5.19 246 51 25.1 5.59 247 52 25.9 6.05 248 55 26.72 6.62 249 54 27.52 7.17 250 55 28.55 7.58 252' 57 29.97 8.2 TITRATION C Total ml ml solution 252 255 256 .1141N HC1 0 5 4 pH 8.2 6.82 6.18 -95- ................................. Added 100 ml distilled HOH 556 557.5 559 6.28 5.57 5.08 5.95 5.09 2.94 2.86 -94- TABLE XIII POTENTIOMETRIC TITRATIONS 0F MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 15: Initially diasolved in 50 ml .1000N,NaOH wt.: .6055 gram Titration A: .1141N HCl Equipment: Beckman Portable Titration B: .1000N NaOH pH meter, Standard outside' Titration C: .1141N HCl glass electrode Titration D: .IOOON NaOH COMMENTS: -Heteropolymer prepared from 1:1 molar ratio of reactants with B202 catalyst and washed with cold benzene. Dried at atm. pressure and 800 one week, dried 24 hours at 8500, 5mm pressure. Weighed sample dissolved in 100- 150 m1 acetone. Added 50 m1 .1000N NaOH. Material washed by refluxing 2 hours twice with fresh C.P. benzene. Dried in an Aberhalden drying pistol at 110° C at 14 mm pressure for two days. Dried at 155° for two days. TITRATION A Total m1 m1 .1141N pH Remarks solution H01 100 O 10.19 107 7 9.22 110 10 8.80 115 15 8.27 115 15 7.78 116.5 16.5 7.27 118 18 6.52 119 19 6.08 120 20 5.62 121 21 5.51 Total ml solution 122 124 127 152 157 158 159 141 142 145 144 145 146 148 150 m1 TITRATION A (continued) .1141N HC1 22 24 27 52 57 58 59 41 42 45 44 45 46 48 50 pH 5.04 4.7 4.40 4.09 5.68 5.49 5.44 5.15 2.99 2.82 2.70 2.59 2.49 2.51 2.19 Remarks Slight ppt. Definite ppt. -95.. -96- TITRATION B Total m1 ml .1000N Correction pH solution NaOH to ml .1141N NaOH 152 2 1.75 2.27 154 4 5.50 2.48 155 5 4.58 2.47 156 6 5.26 2.55 157 7 6.15 2.62 158 8 7.01 2.72 159 9 7.88 2.88 160 10 8.77 5.05 161 11 9.65 5.22 162 12 10.52 5.55 165 15 11.59 5.48 164 14 12.28 5.57 165 15 15.14 5.65 172 22 19.28 5.99 177 27 25.65 4.51 180 50 26.28 4.62, 4.76 182 52 28.05 5.15 185 55 28.95 5.47 184 54 29.80 5.80 185.1 55.1 50.78 6.52 186 56 51.57 7.00 187 57 52.4 7.58 189 59 54.2 7.88 190 40 55.05 7.98 191 41 55.95 8.15 195 45 57.7 8.50 195 45 59.42 8.79 197 47 41.15 9.05 Total ml solution 199 201 205 204 205 206 207 208 209 210 211 215 215 218 225 226 228 250 251 252 255 254 255 TITRATION 0 m1 .1141N HCl 2 £003th 10 11 12 15 14 16 18 21 26 29 51 55 54 55 56 57 58 pH 8.75 8.4 8.01 7.81 7.52 7.21 6.72 6.17 5.62 5.25 4.98 4.61 4.40 4.19 5.84 5.62 5.42 5.15 5.01 2.91 2.78 2.69 2.61 -97- -98- TITRATION D Total m1 ml .1000N Correction pH solution NaOH to m1 .1141N NaOH 257 2 1.75 2.72 259 4 5.50 2.92 241 6 5.26 5.18 242 7 6.15 5.29 245 8 7.01 5.41 244 9 7.88 5.5 250 15 15.14 5.87 255 20 17.52 4.09 260 25 21.9 4.52 262 27 25.65 4.89 265 28 24.55 5.15, 5.19 264 29 25.41 5.59 265 50 26.28 6.02 266 51 27.17 6.60 267 52 28.05 7.00 268 55 28.95 7.52 269.5 54.5 50.21 7.70 271 56 51.57 8.2 275 58 55.50 8.58 275 40 55.02 8.67 280 45 59.42 9.25 285 50 45.80 9.85 \o to. ...-V 4: *7" ._., .2. 01.:- LQ..QV\ . , l ... \I'I.“LLE~..H. . .....rL.\- NL.‘4...I\IQC. ..S .P‘lcy. .(.A\JIP\U1II\.—r fi‘WFWan."\1h-by.i §Tl\.1l. s; «0| .hht‘kr.’kk \lX-N kph-.31.!Vrut :5“!¥-N...\... I. s. 1..-MON: //. RM...» {rut ....Tnkdc \IHL..ULW${ ,y/ .0. 1% Fla. .(RMLH‘ .... 5.1?NPI LRINKRCOil‘bN19KNCk“HNp%.t¥H..N.\WW.P “Mtg! (fowl... {War-p.22. w. / v.35... \\.\ 514M? \............2_...TN\.. / Ilia-2.13.1:"II! l'lnl'f‘lgétt‘ltlnt. / m.a.-2.222...- 2.-.... 2.8.9.585 (If. “was: LNEI‘NILyiyE +6.13... ......\\ 12!“: , / . Sgt-ah 11.218323.-- ...... .22.... ha? / .4 ES...» 2 J 5 VC .. .Lu J L. - \ ik‘hl‘fltkrte\u!pl (’Wraiitfhi 1. ‘ . .' . . .. .. u I x . .‘r. . rll‘flhn. ”mt, ...!LI (.5., “.141. .I .... .‘HNLW.’ NI... finWH'WJH-IIIWIW z» r bib}? EM... .. .. 4 . 1.. .-llfll-.l.ycf {JwV.1y........:..0.!?I.I!..i .. \2- . Hath... .... \..o.\...-.‘. nl‘lullli’ 1:1-It’ll? Q... 9-. In‘ .lS): :I‘Qu.’ f‘b'?l ’3 - A. ._. .. 25.22....3. \u‘. v t 2. .5 . ._ . . spitting... .51.»... {MO.'E.1!L1|¥I1\L ...! CVKBLLKNF 12H) ‘ MN.- "--m~mm~m.- i... v 3x22122222, .23m.v.25,52.38.225.44,2-343.214.422 it... .27 ., ...- I: -8 4...... ......» .-m..-...\.2.2-2222.a L283... 2.51-41.. .2152. y/ .41 .9. 11!- , 2- JV \._. ”a: ..N «U..WF\'§.. {IRbux ..Hlkkn‘xr I\.§. “if“... ‘211W3WI III 211-25v ; i. ..2 22222.22... 2.222 2.22 2.2.2.2.... 22.. x2... 22... 23222.1--- n1'.l.‘l;¢"“’l'.’ l ‘l gflt‘!‘ 0.1!-.." . 2. 3 .23 u. as. .2. 2 .5. ...M. 2.2 2.23... -... -... ... 2., 4 ... -99- TABLE XIV POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 14: Initially dissolved in 50 ml .lOOON NaOH wt.: .6712 gram. Titration A: .ll4lN HCl Equipment: Beckman Portable Titration B: .lOOON NaOH pH meter, Standard outside Titration C: .ll4lN HCl glass electrode COMMENTS: Same as Table XIII . TITRATION A Efiiiiifli mchill4lN pH 100 o 9.32 105 5 8.67 110 10 7.72 112 12 7.08 114 14 6.33 115 15 6.08 116 16 5.80 117 17 5.52 118 18 5.28 119 19 5.08 121 21 4.72 124 24 4.42 130 30 4.09 134 34 3.88 136 36 3.48 138 38 3.22 139 39 3.16 140 40 3.01 142 42 2.71 143 43 2.59 150 50 2.08 Total ml solution 154 158 160 161 162 163 164 166 171 176 181 186 189 191 195 197 TITRATION B ml .lOOON NaOH 10 11 12 13 14 21 26 31 36 59 41 45 47 NaOH 3.50 7.01 8.77 9.65 10.52 11.39 12.28 14.03 18.42 22.80 27.17 51.57 34.2 65.96 59.42 41.22 Correction to ml .1141N pH 2.25 2.59 2.79 2.92 5.05 3.18 5.29 5.48 3.71 5.87 4.20 5.09 6.48 7.22 -100- 8.02 8.57 Total ml solution 199 201 202 203 204 205 206 207 208 210 216 221 221 223 225 227 229 230 231 232 233 235 237 TITRATION C m1 .1141N HC1 (OCDQGO‘Inh-N) 10 11 13 19 24 24 26 28 30 32 33 34 35 36 38 40 pH 8.02 7.65 7.49 7.22 6.70 6.17 5.70 5.24 5.01 4.63 4.18 3.91 3.72 3.62 3.48 3.28 3.08 2.91 2.81 2.71 2.62 2.48 2.35 Let stand 16 hours -101- 1;.) I1. \x..... Q1 .1. .... ..sN.....\. ... |1||u| 1. ”LhIL‘ t..l.l.|r||l. :fv.\ will :1an... :1»: ID. i‘ V‘II I455 .I‘IL-lnl.l 1:) 53.11%... \ mg. (W\w\tmmm».,nm. \ .X. \m... \ . .. 1n.w-n..M.m ...... . . ...»?x H [If V. . l/ . .....-LFHQ» 7.2.3 ...... .... / J/w/X , . ...A ll ' / '0 III: In”: I'- A In! III. .'/ III! [I I’ll I! 0.3.31: 1 El‘lfih!‘ shy: ...-Ll. Ami \AV.. 3.» by. - grit-‘35,: 6". ..‘Ln- .3!“ \\.. ‘3... 1.. ............\.\...: .. . H‘s .ll‘lcli. :5; unit... .‘3|(. .3. 3.?!1 ..‘4 ’11.! at. .‘l‘ .... I“. V/ ,. |. . \k..\ k N .\Q ..ln . 3-.! 4.2.3011 .r.. 45;. P... NM... \m ......rx Kb. 3.....» Mm... - fimfizfi .k .. \) gnu; -. Hynvm1wrx/l4 1:11.... .1... . 3...... ...xx... I)..- \\.V.~....:..I.-.\.\r ... .5... x. > “.i.nn .. \KA. \ \ \grkf\| .. ....ux... N...» \ \ l .§."{i \m. 4...... .--.Krrbavwwf 5%? Just»? _ mm. .Nw. \_ 91. 5F No... IV quA INII FIE: o. V:..u:fl\7 x... .. 3.314- 10."-I".Y:|p|t‘| av ./L, .1-.. ...hw: : ... MW .6 1%. I I‘ .\ . .4. .Ir It'll. ...!" Ell... -102- PART IV ANALYSIS OF THE MALEIC ANHYDRIDE-STYRENE HETEROPOLYMER PREPARED FROM DIFFERENT MOLAR RATIOS OF REACTANTS BY MEANS OF POTENTIOMETRIC TITRATIONS Materials: Eastman Styrene was vacuum distilled and the fraction distilling at 41-45°C, l4-16mm, r12Oo 1.5446, was used immediately after distillation. This is a standard method of styrene purification but determination of the freshly distilled styrene purity by the direct bromine titration of the double bond of Uhlrig and Levin27 gave a % styrene purity value of 95.2%. By the mercuric acetate unsaturation method as described by Mihina31 a % styrene value of 94.2% purity of freshly distilled styrene was obtained. In all probability, these methods, which depend on quantitative addition to the styrene double bond, are not adequate. Eastman maleic anhydride was redistilled at 80mm Hg pressure, 155°C. 100% purity was certi- fied by titration with anhydrous methanolic sodium hydroxide of weighed maleic anhydride samples dissolved in anhydrous acetone to phenol- phthalein endpoint corresponding to half neutraliza- tion of the anhydride, according to the method of Moran and Siegelsz. Nitrogen gas was passed through alkaline pyrogallol and under the surface of the solvent prior to and during the reactions so that the -lO5- c0polymerization took place in the absence of oxygen. The other materials were the same as used in the reactions of Studies A and B, Part II. Procedures: The polymerization procedure was effected as per Part II, Study A, Procedure 1. The copolymer samples were prepared for potentiometric titration by the methods developed in Part III. STUDY A ' 1:1 (Styrene: Maleic anhydride) molar ratio of reactants: (Samples 15 and 16, Tables XV and XVI). Recipe: 24.2970 g styrene (.2333 mole) 22.8810 5 maleic anhydride (.2333 mole) 615.2 grams benzene .2333 g benzoyl peroxide Total time of polymerization: 6 hours. Treatment of 00polymer and Potentiometric titration data: See tables XV and XVI for Samples 15 and 16 respectively. STUDY B 3:1 (Styrene:Maleic anhydride) molar ratio of reactants: (Samples 17 and 18, Tables XVII,XVIII). Recipe: 36.8004 g styrene (.3500 mole) 11.4431 3 maleic anhydride (.1167 mole) 615.2 grams benzene .2333 grams benzoyl peroxide Total time of polymerization: 6% hours. Treatment of 00polymer and Potentiometric titration data: See Tables XVII and XVIII for Samples 17 and 18. -lO4- STUDY C 1:3 (Styrene-Maleic anhydride) molar ratio of reactants: (Samples 19 and 20, Tables XIX and XX). Recipe: 12.1536 g styrene (.1167 mole) 34.3161 3 M.A. (.3500 mole) 615.2 grams benzene .2333 g benzoyl peroxide Total time of polymerization: 8 hours Treatment of 00polymer and potentiometric titration data: See Tables XIX and XX for samples 19 and 20 respectively. -105- TABLE XV POTENTIOMETRIC TITRATIONS OF MALEIC:§NHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 15: Initially dissolved in 100 ml .0975N NaOH wt.: 1.0000 gram Titration A: .0949N HCl Equipment: Fischer Line Titration B: .0975N NaOH Operated pH meter, Standard Titration 0: .0949N HCL outside glass electrode COMMENTS: Heteropolymer prepared from 1:1 molar ratio of reactants and washed with hot benzene. Polymer extracted ‘in soxhelets by benzene for three weeks and vacuum dried at 3 mm pressure, 1400 C for three weeks. 100 ml .0975N NaOH added very Slowly. A11 ppt. dissolved on the boiling off of acetone, but was slightly cloudy. Temperature of titrations 28°C. TITRATION A Total m1 ml .0949N pH solution H01 115.5 ' .5 10.42 116.0 1.0 10.41 117.0 2.0 10.57 118.0 5.0 10.52 119.0 4.0 10.28 120.5 5.5 10.19 122.0 7.0 10.11 124.0 9.0 10.01 126.0 11.0 ' 9.9 128.0 15.0 9.78 129.0 14.0 9.75 151.0 16.0 9.63 132.5 . 17.5 9.50 -106- TITRATION A (continued) Total ml ml .0949N pH Total ml ml .0949N pH solution HCl solution HC1 154.0 19.0 9.45 177.0 62.0 4.81 155.5 20.5 9.5 179.0 64.0 4.67 157.0 22.0 9.22 182.0 67.0 4.55 138.5 25.5 9.1 185.0 70.0 4.45 140.0 25.0 9.08 188.0 75.0 4.55 141.5 26.5 8.91 191.07 76.07 4.22 145.0 28.0 8.83 194.0 79.0 4.12 144.5 29.5 8.7 197.0 82.0 4.02 146.0 51.0 8.58 200.0 85.0 5.90 147.5 52.5 8.47 205.0 88.0 5.72 149.0 54.0 8.56 205.0 90.0 3.6 151.0 56.0 8.11 207.0 92.0 5.48 152.5 57.5 8.00 209.0 94.0 5.52 154.0 59.0 7.81 210.0 95.0 5.22 155.0 40.0 7.69 211.0 96.0 5.20 156.0 41.0 7.59 212.5 97.5 5.10 157.0 42.0 7.44 215.5 98.5 5.00 158.0 45.0 7.50 215.0 100.0 2.91 159.0 44.0 7.15 216.5 101.5 2.80 160.0 45.0 7.01 217.75 102.75 2.72 161.0 46.0 6.90 219.0 104.0 2.62 162.0 47.0 6.78 222.0 107.0 2.5 165.0 48.0 6.7 225.5 110.5 2.4 164.0 49.0 6.57 229.0 114.0 2.5 165.0 50.0 6.46 251.0 116.0 2.51 175.1 60.1 4.95 255.0 120.0 2.25 -107- TITRATION B Total m1 ml .0975N Correction pH solution NaOH to ml .0949N NaOH 235 0 0 2.25 241 6 6.16 2.42 246 11 11.3 2.58 251 16 16.42 2.8 255 20 20.53 3.0 259 24 24.63 3.21 261 26 26.7 3.32 263 28 28.75 3.5 265 30 30.81 3.68 266 31 31.82 3.75 267 32 32.83 3.82 268 33 33.88 3.88 271 36 36.98 4.01 276 41 42.1 4.18 280 45 46.2 4.3 285 50 51.3 4.5 295 60 61.6 5.24 297 62 63.7 5.61 298 63 64.7 5.89 299 64 65.7 6.12 300 65 66.7 6.42 301 66 67.75 6.74 302 67 68.8 7.00 303.5 68.5 70.35 7.25 305 70 71.9 7.50 307 72 73.9 7.80 310 75 77.0 8.16 -108- . ‘ TITRATION C Total m1 ml .0949N pH Total m1 m1 .0949N pH solution H01 solution H01 310 0 8.15 363 53 3.42 312 2 7.88 364 54 3.38 315 5 7.52 365 55 3.31 317 7 7.22 367 57 3.2 318 8 7.1 368 58 3.11 319 9 6.79 369 59 3.08 320 10 6.59 371 61 3.01 321 11 6.29 374 64 2.9 322 12 6.02 378 68 2.78 323 13 5.78 383 73 2.7 324 14’ 5.51 389 79 2.57 325 15 5.3 395 85 2.48 326 16 5.2 328 18 4.99 331 21 4.79 334 24 4.6 339 29 4.48 345 35 4.3 350 40 4.15 355 45 3.9 357 47 3.81 359 49 3.7 360 50 3.62 362 52 3.5 R Q. /’ Vern heist: PE. i... . . . . o . DIRK. .... szHKuE he we on Karma ...rx 10.1”: \H K052..- is.“ .e\a\VQ\t\. - .... “1&5. MW. 9. .v\ . -0 . 04.. .95....41). mu“ \.. \ De 5. #3... b. Q ,6 3E" he om t t .038 >4 5.2! .3sz ..IIII. . EESRP Tull. -ul-..v.§h.. EFIEEIII:4 t t KT. EfrlybihnkL ”ENDL- g l - . . _ .. .PILVLF\4 1...}... HEEK. ....prao. aim. 5.3811361 R9? .51..» .355... “5.54- charrPPm mp -109- TABLE XVI POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 16: Polymer sample treatment same as in Table XV. TITRATION A Total ml ml .0949N pH Total ml ml .0949N pH solution H01 solution H01 174 0 11.15 234 60 5.07 176 2 11.10 237 63 4.83 180 6 10.98 240 70 4.52 184 10 10.78 249.1 75.1 4.39 188 14 10.52 252 78 4.30 193 19 10.20 257 83 4.15 196 22 10.01 262 88 3.95 199 25 9.81 267 93 3.62 202 28 9.59 269 95 3.5 205 31 9.36 271 97 3.35 208 34 9.10 272 98 3.29 211 37 8.86 273 99 3.21 214 40 8.6 274 100 3.15 217 43 8.32 276 102 3.02 220 46 8.00 278 104 2.95 222 48 7.67 281 107 2.8 224 50 7.20 285 111 2.63 225 51 6.98 226 52 6.67 227 53 6.38 228 54 6.10 229 55 5.85 230 56 5.6 231 57 5.42 232 58 5.30 Total ml solution 290 295 297 298 299 300 301 302 303 304 305 310 315 320 325 329 334 335 337 339 340 342 343 344 345 347 351 ml TITRATION B .O975N NaOH 5 10 12 13 14 15 16 17 18 19 2O 25 3O 35 40 44 49 50 52 54 55 57 58 59 60 62 66 Correction to ml NaOH 5.13 10.27 12.33 13.36 14.38 15.40 16.42 17.47 18.49 19.52 20.55 25.7 30.8 35.96 41.15 45.2 50.3 51.35 53.4 55.45 56.5 58.6 59.6 60.6 61.6 63.7 67.75 .0949N -llO- pH 2.81 3.09 3.20 3.28 3.32 3.38 3.48 3.51 3.59 3.68 3.72 4.00 4.15 4.30 4.48 4.62 4.95 5.02 5.28 5.68 6.00 6.6 6.88 7.10 7.28 7.6 8.12 Total ml solution 354 357 359 360 361 362 363 364 366 368 371 375 380 386 391 396 399 401 403 405 407 409 411 413 ml TITRATION C .0949N NaOH 3 6 8 9 10 11 12 13 15 17 20 24 29 35 40 45 48 50 52 54 56 58 6O 62 pH 7.83 7.40 7.02 6.75 6.4 6.1 5.82 5.58 5.2 '4.98 4.75 4.55 4.4 4.23 4.1 3.9 3.72 3.6 3.48 3.36 3.23 3.12 3.05 3.00 -111- P....mp. kt. ‘3 ..1k...«....04.\hvrn|& .‘ 1|V.H11MN1\5.?P1\>D\I-mwnE01rbMRE...Hxhwm-Wo w «I 1.- 1.0.0 1d..p0\-IL_-,1...t 0.1150100- . I n I .1. 3551.345. ml .08-...... ....- ‘ .I'II“ 5- .5 .5 .5 ...... 10...... 51.4.9035 \ .1... .,_..\......,.. 5..- ..Uu. KK1 \ )Ri...‘ B “NW-9.01 1 . \ . -‘ .I . .. 1.. .. . .. ... .. . I... \a .1 .. ._.... ...s..1.\....._.thkb.b.t.1. ; ... .n “\mkmh Nob; MN... 1. NF N1-..“ .01.th .. RC. “\r\t-\ 1.2». mm. 40.00 Wk. \5. .. - \S .1. ... ..1. 53..de ..\ \0 143......1. . .3 ... 1.1.5. H5150»... \UEIH: 0110151.. ...1... L\~.4s\ \\.. 111-0.711.“. -..._....._.-..-.P m .1qu». 1WQLMLE In -qufivawp ML «(Ir-RH]... 13.9 n. C 1N... \3015 ....m. ,/x .. .-. ....fl/ r0»... 11.5.4.1 -ll2- TABLE XVII POTENTIOMETRIC TITRATIONS of MALEIC-ANHYDRIDE STYRENE HETEROPOLYME SAMPLE # 17: Polymer sample treatment same as Table XV. COMMENTS: Heteropolymer was prepared from 1:5 (Maleic-An- hydride - Styrene) molar ratio of reactants with Bz02 catalyst and washed with hot benzene. Polymer extracted in soxhelets by benzene for three weeks and vacuum dried at 5 mm pressure, 1400 C for three weeks. 100ml .0975N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone and the solution was clear. TITRATION A Total ml ml .0949N pH solution H01 140 0 11.15 145 5 10.92 150 10 10.65 160 20 10.00 164 24 9.75 167 27 9.52 170 50 9.28 175 53 9.05 176 36 8.8 178 58 8.68 180 40 8.48 182 42 8.29 184 44 8.05 186 46 7.80 188 48 7.52 189 49 7.35 190 50 7.18 Total ml solution 191 192 195 194 195 196 197 198 199 200 202 204 207 211 216 222 227 251 255 235 257 258 259 240 244 248 250 TITRATION A (continued) ml .0949N HCl 51 52 53 54 55 56 57 58 59 60 62 64 67 71 76 82 87 91 95 95 97 98 99 100 104 108 110 pH 7.00 6.85 -115- Total ml solution 255 257 258 259 260 261 262 265 264 265 267 271 274 278 285 289 295 298 500 501 502 505 504 505 506 508 510 514 TITRATION m1 .0975N NaOH <0QO 10 ll 12 15 14 15 17 21 24 28 55 59 45 48 5O 51 52 55 54 55 56 58 6O 64 B correction to ml .0949N NaOH 5.15 7.19 8.22 9.24 10.27 11.29 12.55 15.56 14.58 15.40 17.47 21.54 24.6 28.7 55.78 40.1 44.2 49.5 51.55 52.4 55.4 54.4 55.45 56.5 57.5 59.6 61.6 65.7 pH 2.8 2.9 2.95 5.01 5.09 5.17 5.22 5.50 5.58 5.45 5.61 5.9 4.05 4.22 4.58 4.58 4.75 5.1 5.59 5.58 5.85 6.15 6.51 6.82 7.00 7.40 7.72 8.17 -114- Total ml solution 516 518 520 522 525 524 525 TITRATION C ml .0949N HC1 {0030145 10 11 12 15 14 15 l7 19 26 51 57 42 46 48 5O 52 54 60 65 66 70 pH 8.05 7.8 7.5 7.12 6.96 6.72 6.44 6.12 5.82 5.6 5.41 5.17 4.95 4.61 4.48 4.28 4.07 5.82 5.70 5.52 5.40 5.28 5.12 2.97 2.82 2.7 2.58 -115- h) a. x... . 1 1.4.. 4. . . 1.1.... e... ._. . Km” n ., . . . Nb. Nu R315“; “.th .61 Q .Dimknhiwb .. KL.“ \ h . ... “ Jab l S on“. finsk . n a --1/ m. EH ,m,\3.\flh.. x. fibnfiw / q bath .\ .. s - . REE fl . II I \/ Illlvwwuamflxsk \wn h». bm LB}; 9 Link SEEN lullzw m.» - Ar. ...! 5%. firbfi. ._ as; R. fink Dunk Tu .. II I! .... ...: Iv “£43663be 0 .. ht? b h .6136 5... {AM “flown”?! .... .... 1W by. in: km: 6.6 65 1 .6 hp. @- .fip as Sp hp 16 SAMPLE # 18: TABLE XVIII STYR8NE HETEEQPOLVMER ~116- POTENTIOMETRIC TITRATIONS OF MALEIC-ANHYDRIDE Polymer sample treatment and COMMENTS are the same as Table XVII. Total m1 ml .0949N H01 so1ution 1174 179 184 189 194 199 204 209 214 218 221 225 225 226 227 228 229 250 251 252 255 254 O 5 10 15 20 25 5O 55 40 44 47 49 51 52 55 54 55 56 57 58 59 6O TITRATION A pH 11.05 10.98 10.78 10.52 10.28 9.98 9.7 9.5 8.91 8.5 8.12 7.89 7.58 7.55 7.09 6.88 6.68 6.42 5.95 5.92 5.80 5.68 256 258 241 244 247 252 257 261 264 266 268 270 272 274 277 280 284 meter Total m1 ml .0949N solution HC1 62 64 67 70 adjusted 75 78 85 87 90 92 94 96 98 100 105 106 110 pH 5.45 5.02 4.78 4.92 4.58 4.4 4.22 4.08 5.9 5.75 5.58 5.45 5.29 5.10 2.95 2.78 2.62 TITRATION .0975N Total m1 ml solution NaOH 289 5 292 8 294 10 \296 12 298 14 500 16 502 18 507 25 515 29 519 55 524 40 528 44 551 47 555 49 554 50 555 51 556 52 557 55 558 54 559 55 540 56 541 57 542 58 544 60 B Correction to m1. NaOH 5.15 8.22 10.27 12.55 14.58 16.42 18.49 25.6 29.78 55.96 41.15 45.2 48.25 50.5 51.55 52.4 55.4 54.4 55.45 56.5 57.5 58.6 59.6 61.6 .0949N pH 2.8 5.0 5.11 5.22 5.41 5.59 5.71 4.00 4.25 4.42 4.60 4.78 5.00 5.2 5.59 5.6 5.9 6.19 6.50 6.75 6.98 7.2 7.59 7.72 -117- Total ml solution 547 549 550 551 552 555 554 556 559 564 571 577 582 587 591 595 594 596 599 402 409 TITRATION ml .0949N HC1 5 5 6 7 8 9 10 12 15 20 27 55 58 45 47 49 50 52 55 58 65 C pH 7.52 6.97 6.72 6.45 6.12 5.85 5.6 5.28 4.99 4.71 4.48 4.5 4.1 5.81 5.52 5.41 5.55 5.21 5.02 2.90 2.65 -118- 447/ B/ httmbth. £3.50ka In!!!“ NH»... v4-4.4.5» .L....n.n\x.1 \aMKLuI III.-. 4...\_....N...\.r..4 4.... 4. ..h:4.t1.wy-HI..IL...&w..4 . 4.5....” V/ . 4 . . .... ..-u // Irmmhhvrhz- 4.... . \\6 I444... .41 44 4.4.6 04.. k .440 \44. 44 Hm h \ .. W . ELIMNESRV mm. / ,, . . bx... 4.4.44 444.... 1.44.8.4... .4........... 44.4 4N8I4 . . 4.4.4.4.. I/ @444“ L50 (M44440 .4 Mug 4 m . / IF 4/ \QN. \«Rmr 4.4.4hm V02. QR”... WLFx 04H .xNN... bow... /I...4 / // M“ Mafiwabhwb 6.44 44me 5.9:--- .. \Nx Illlllw \454.WE.% DR nh.D«tmRI.WK.4 INN]... ._.IIIIIIIIV 47 Tianfldeinminnm. \1I1QTIIIIII I... I... I. 4502.44.44.44 m. 85.»..[4 Rag! l ..I L. 44 44.. 4.. .. .4 4.4.» 4.4 .4. 4.4- 4.4... .... 4... -119- TABLE XIX POTENTIOMETRIC TITRATIONS 0F MALEIC ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # l9: Initially dissolved in 100 ml .0975N NaOH wt.: 1.0000 gram Titration A: .0949N HCl Equipment: Fischer Line Titration B: .0975N NaOH Operated pH meter, Standard Titration C: .0949N HC1 outside glass electrode COMMENTS: HeterOpolymer was prepared from 5:1 (Maleic Anhydride - Styrene) molar ratio of reactants with B202 catalyst and washed with hot benzene. Polymer extracted in soxhelets by benzene for three weeks and vacuum dried at 5mm pressure, 140° C for one week. 100 ml .O975N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone and the solution was clear. TITRATION A Total ml ml .0949N pH solution H01 135 O 10.78 157 2 10.68 140 5 10.49 145 10 10.19 150 15 9.89 155 20 9.55 158 25 9.55 161 26 9.12 164 29 8.92 167 52 8.7 170 35 8.48 ~120- TITRATION A (continued) Total ml ml .0949N pH Total ml ml .0949N pH solution HCl solution H01 174 59 8.10 255 100 5.27 176 41 7.9 255 101 5.2 178 45 7.52 257 102 5.15 180 45 7.31 258 105 5.09 181 45 7.11 240 105 5.00 182 - 47 6.98 245 108 2.89 185 48 6.78 245 110 2.80 154 f 49 5.59 185 50 6.59 155 51 6.18 197 52 5.00 188 55 5.80 189 54 5.68 190 55 5.5 192 57 5.22 195 50 4.98 199 54 4.77 204 59 4.52 210 75 4.58 217 82 4.19 222 97 4.00 225 91 5.81 229 94 5.55 251 95 5.51 253 98 5.38 TITRATION B Total ml ml .0975N Correction pH solution NaOH to ml. .0949N NaOH 250 5 5.15 5.00 255 8 8.22 5.10 255 10 10.27 5.22 257 12 12.55 5.59 259 14 14.58 5.5 261 16 16.42 5.61 265 18 18.49 5.72 266 21 21.54 5.91 270 25 25.7 4.1 275 50 50.8 4.25 281 56 56.98 4.59 286 41 42.1 4.52 290 45 46.2 4.72 295 48 49.5 4.88 295 50 51.55 5.09 297 52 55.4 5.50 299 54 55.45 5.61 500 55 56.5 5.85 501 56 57.5 6.02 502 57 58.6 6.50 505 58 59.6 6.55 504 59 60.6 6.75 505 60 61.6 7.00 506.5 61.5 65.2 7.25 508 65 64.7 7.55 510 65 66.7 7.79 512 67 68.8 8.01 515 70 71.9 8.25 Total ml solution 515 520 522 524 525 526 527 528 529 550 551 555 555 558 542 548 555 560 565 570 575 578 580 582 585 591 595 TITRAT ml ION C .0949N HC1 O 5 7 9 10 11 12 15 14 15 16 18 20 25 27 55 4O 45 50 55 60 65 65 67 7O 76 80 pH 8.50 7.89 7.62 7.55 7.11 6.98 6.78 6.55 6.29 6.08 5.81 5.47 5.18 4.92 4.7 4.5 4.52 4.2 4.02 5.79 5.52 5.58 5.29 5.2 5.1 2.92 2.84 -122- \) ~ 1 \( .... €\ hbhg1 -.. .-.‘I‘l- .Illl( N\\th\1k.\\l|k.d 1 L6950 7’}: u‘i'iifi‘ ii. \>\ \QNJLKL .PVQAl ..llllv 619.153.11.111 L11..- .1111; m1. 1 1.. 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L19 NT ub RD MB L0 NE» RD LT. fl ban bk TABLE XX POTENTIOMETRIC TITRATIONS OF NALEIC ANHYDRIDE STYRENE HETEROPOLYMER SAMPLE # 20: Initially dissolved in 100 m1 .0975N NaOH wt.: 1.000 gram Titration A: .0949N HCl Equipment: Fischer Line Titration B: .O975N NaOH Operated pH meter, Standard Titration C: ..O949N HCl outside glass electrode COMMENTS: HeterOpolymer was prepared from 5:1 (Maleic Anhydride-Styrene) molar ratio of reactants with B202 catalyst and washed with hot benzene. Polymer extracted in soxhelets by benzene for three weeks and vacuum dried at 3mm pressure, 140° C for one week. 100 ml .O975N NaOH added very slowly. All ppt. dissolved on the boiling off of acetone and the solution was clear. TITRATION A Total m1 m1 .0949N pH solution H01 146 O 10.80 156 10 10.22 166 20 9.60 172 26 9.19 178 52 8.78 183 57 8.35 187 41 7.95 190 44 7.51 1927 46 7.17 194 48 6.81 195 49 6.6 TITRATION A Total m1 ml solution 196 197 198 199 201 206 216 226 232 236 240 245 246 248 250 256 HC1 50 51 52 53 55 60 70 80 86 90 94 97 100 102 104 110 .0949N (continued) pH 6.41 6.2 6.0 5.78 5.42 4.92 4.48 4.21 4.02 5.85 5.60 3.41 5.25 5.15 5.04 2.85 -124- ~125- TITRATION B Total ml ml .0975N Correction pH solution NaOH to ml .0949N NaOH 256 O 0 2.85 261 5.13 3.00 264 8 8.22 3.10 266 10 10.27 3.20. 268 12 12.33 3.32 270 14 14.38 3.45 276 20 20.55 3.80 286 30 30.8 4.20 296 40 41.15 4.47 302 46 47.25 4.7 306 50 51.35 4.99 309 53 54.4 5.3 311.5 55.5 57.0 5.75 313 57 58.6 6.15 314.5 58.5 59.1 6.50 316.5 60.5 62.1 6.98 319 63 64.7 7.39 322 66 67.75 7.70 326 70 71.9 8.15 TITRATION C Total ml ml solution 551 556 558 559 540 541 542 546 556 566 576 581 586 589 591 595 596 406 .0949N H01 5 10 12 15 14 15 16 20 50 40 50 55 60 65 65 67 70 80 pH 7.79 7.10 6.68 6.40 6.20 5.95 5.72 5.1 4.55 4.28 5.99 5.72 5.45 5.5 5.18 5.10 5.02 2.8 -126- R . 40 n, 4 . $ \ \ .\ . . ._ x \ - . x .. . -... 4. . . . . . .. w ‘1. ‘5‘.“ K x \\ o I .1 4.45 4 . . \\ x~ ‘ ‘5 ‘ . .. v‘ n. 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I. 5‘. . .... r . . . ..4. . . I... It. _v. .v'IMtfi L _ / x.) .4... .. .. .\ .. .. .. ... “N, .w‘ n .1 4 3...... z\. ~ In!" a)" ‘naév.-.’ ..‘u 41051.3..I 1|.ll I v!¥"ll’ to. CI tit ‘ \ ‘ . . 4. .4 4... 41.4.. I‘ ’ .. ‘ b? ...I'-“ rfilJ \n - I . .... 44 I Y .y N IV) \a\ \1. . . ..\4 “K .:\.r. .....x. ”VI. Wk! . \ /. / x . . .. iJPL ... .I-I’! I‘ll n I. u . ..I 4‘. 4 . . 4.. 4 .. . 4 . I/ . ,l . . t . . . . . ..I J blwx .. J .4». .. v. .0. ....» N»\._.\.. \2 t ) \xx _ L . . x ._.V ...... .8» \w... \w... . .4441 ...} I .4..... \ . 4. 4.. 3. . - Fifh.» 10‘. I, . It .1” 1 -Illtllll 11-444.44.448... 44.. 44.- . 4-: ....i... V/ . l. 44.4.4. ..\.. 5MP \4xflrii-..!-..i§&{-.4 4.44 \.4 SL1; ...xl. di .14- WT! ll 1.1.3.- {I III .IV\\\ Lin-9.--.»lrxhtelr: IBKLlutlthlo.!rF.‘4«. . -..“! .. ., .... . . . ...l nl [I 1w ..N {p101 I...” U: . LMJQ va. , . \fb 1 WI}, . ...\ 9 x... ”Kg \44\_.HV 4x44...“ ..v mw . 4 1.0.0. 4| 4- -4. 5. 4A -4 ... 4. - , -.- 4- . n II .o k:.h.’rn|L..!r ll. .1 ‘ (.-...- .. .-- .. 3- -... -- . va i .... I-.. a.“ -127- PART V ANHYDROUS POTENTIOMETRIC TITRATIONS OF THE HETEROFOLYMER: MALEIC ANHYDRIDE-STYRENE Treatment of the copolymer samples for Anhydrous Potentio- metric Titration: The heterOpolymer product from Study A, Part II was used. The treatment of the polymer and potentiometric titration data is given in Tables XXI, XXII and XXIII, corresponding to samples 21,22 and 23 reapectively. Table XXIV is a blank titration of the pure solvent. The procedure was based on the anhydrous titration of mono-esters of monomeric anhydrides with standard alcoholic caustic as prOposed by Moran and Siegelse. The copolymer sample was dissolved in 250 ml acetone and potentiometrically titrated. Phenolphthalein indicator was also used as per the method of Moran and Siegel but due to polymer precipitation and indicator absorption by the polymer, no acute endpoint was dis- cernable. TABLE XXI POTENTIOMETRIC TITRATIONS OF MALEIC ANHYDRIDE-STYRWNE HETEROPOLYMERS WITH ABSOLUTE METHANOLIC NaOH IN ANHYDROUS ACETONE MEDIA SAMPLE # 21: Initially dissolved in 250 ml anhydrous acetone wt.: 1.0062 gram Titration: .0949N Methanolic NaOH Equipment: Beckman Portable pH meter, Standard outside glass electrode COMMENTS: HeterOpolymer prepared from 1:1 molar ratio of reactants with 8202 catalyst and washed with cold benzene. Dried at atm. pressure and 800 C one week, dried 24 hours at 85° G, 3mm pressure. Added 1 ml absolute methyl alcohol. ml .0949N Correction pH Remarks NaOH to ml .1141N NaOH 1 .83 4.9 3 drOps phth. 2 1.66 6.39 Clouding up 3 2.49 7.59 4 3.32 7.19 5 4.16 7.38, 7.29 6 4.98 7.52, 7.48 7 5.82 7.62, 7.58 8 6.65 7.6 , 7.58 9 7.48 7.68, 7.61 13 10.80 8.15, 6.42 After 15% hrs., still turbid. ‘ No ppt., but not 14 11-52 6°48 transparent 16 13.3 6.68 18 14.96 7.03 m1. TABLE XXI (continued) .0949N Correction NaOH to ml .1141N 20 22 24 26 28 30 32 34 36 38 40 42 44 48 50 52 54 57 59.15 61 63 65 NaOH 16.61 18.30 19.95 21.6 23.25 24.95 26.6 28.25 29.92 31.6 33.25 34.9 36.6 39.9 41.6 43.2 44.9 47.4 49.2 50.7 52.3 54 pH 7.19 7.41 7.6 7.76 7.93 8.08 8.20 8.32 8.44 8.58 8.68 8.79 8.92 9.3 9.58 10.2 10.58 10.58 10.48 10.42 10.35 10.48 Remarks -129- Slight pinkish cast Phth shows pink F‘ \b \ ..x ..\.. v..by. ..A V * h? H .3 \\ . [£7be t6 ».U\ \.‘Nflik I. AL lxmernha k ‘H\.}....b..l.l.r ..N-‘ln‘l \-..x. ”\..n .... .... . x \ ffil'rh.‘ Irrlr. Kl.» ..Lisirll .\ ., ... .I.I-I”nlil" A; x . . \..... a .. ... e . .. --. .. \/ L» K\ L K In IL Nrfl. \Lx K} \M \H L “JR. L Hfltlvl-rAN ..K....NV.\|H \ 9: wk ml / .. EVrNuh . .N MEI»... a / b4 ....4.....1....... .- \Vbxlt E-K\u. K413. r u..\.....;.w... MW! ..kafihfibs 2 ._.4 ......S .4 ..n as a. an t .6 4 .. I\lk..l\tvk.u.l\ \1\!\.\\;\.... .-. \.. .4... .. .. (Lutlklriiri . xx) Alhukfu.‘ af\\\\. {\..‘A’O \\. .fl...\..._ \.u.. \' .. .u I x 2‘ ..x. ~ .. l. . . ..r PL...» 50.1.8. i. IL *{Ae’ Ii! 4.0%. .. .ILI..- ...lv...ovt3¢q...n Iru. . \v - .\.\A\\\\. n 431...... !\\»\: . h. MUN Wm-.- . -444 -130- TABLE XXII SAMPLE # 22: Same as TABLE XXI. COMMENTS: Same as TABLE XXI. ml. .0949 Correction pH Remarks NaOH to ml .1141N NaOH 0 0 1.85 2 1.66 7.8 Cloudy 4 3.33 8.23 6 4.98 8.07 8 6.64 8.10 Galv. jumpy when trying to read pH 12 9.98 8.19 15 15.5 8.20 **(D1fficult to see any phth color 20 16.6 8.38 even by adding sev. drOps on spot plate. 2 2 . . 2 However phth drop 5 O 78 8 6 atop sol. in beaker 50 24.9 8.79 pink. Also, aqueous diluted anhydrous 35 29.1 9.11 samples in spot plate are pink.) 40 33.21 9.38 45 37.4 9.76 47 39.05 9.82 Neg. to spot plate 49 40.7 10.12 50 41.6 10.32, 10.18 Neg. 51 42.5 10.67, 10.42 " 52 43.2 10.88, 10.73 " 53 44.1 10.98, 10.95 * " 54 44.8 10.98 " 55 45.7 10.93 " 59 49 10.82 4* " 64 53.2 10.72 " 70 58.2 10.62 ” 81 67.3 10.52 " * Glass stirrer affects pH..From here, measured without glass rods in solution. - I V Ilcl ' \ .1 \ . K .x I. a . s \ \. ... . \ - 4 . . I . \ ~r... . . . . 1| v \ u. ...-I ! . .. uu\. \ II In!!! It- .. 0. 4 .Ikli ._ ll . \ \ .. . . In x. . 3‘. . . . \ . _ v n.l..?: {QB-4a .. {AD}. \.. I. ldr- xx x \ . \\ ... \ \ \ .\ . .1 o d. .l .I.. y 1 .t.:§l 9 4.4! '.I.V‘ll.lla1 I\ .\ . . -.\ .4 . .... . . \.. 1c . 1 .\ . V A QI. ‘0 I .n 0. .~ I h ..J-( Ill... ..l\a. . III. . .. . _ .\ I _ s a v.' ...! -.. I~....'.|IJ-‘.‘. A ..u . \f 2.. III ... artillfl‘ .5.! y \ \ .t . 1p: \ It .12... . I‘QI‘I‘ \ 4 .A I ~ ‘l‘ r. . 0 . ulv ~. . N . . . x. I I U \ KN. ... .\t\u¢....\..x? \ . _ ..v _ Pf, ... \Iu \1 \x.\\. A ~ VI b ‘ KL * .\ ..w o h .. x. .. .. . . \x. \. . . . . v . . \ .4 . \‘ .. III‘. l‘ll.l‘ 4.. .. ., \. N r. it . \ . . . . . . . ~\~.v.\.. . .... .- ..-:E , . ‘IILII . . 4 . . n l . \ \ \ ..\ I.-u'05i.llI| I. ‘ll’l.ll-- u, til 1. y In. D |’. . A .J 1 .II - III!" . _ . .-.. -------i--,-n --.. 1_-_____ I | fifi. UH. Vx...\_\ A44»... ..v. ._. . .... .w. ..I... ..LN.K..R£P. -L. I .. \ K . - . .. I I u“. n‘ . .l. X . . . \v I. ... \ U \..? . . k. . . 0. ., . .. . \ \ . . \ . . ~. I a \\ . \ . . a .... . 5| n . . ., irletu‘,r I- ... . Q h. . .. \\. \ \... . . u.\~ o .\ \. \. h .l .l. I. I‘luvli.l. :. II.‘\.I- " ... 0 . \, I! s .1 ‘ ‘\4 _ .I -, " 0 l 1 I l.‘ I.’ I 'll ’ Di . am an a... .--. a . -. . Q 15....» 4. .. -l31- TABLE XXIII SAMPLE # 23: Same as TABLE XXI. COMMENTS: Same as TABLE XXI. wt. 1.0040 gram ml. .0949N Correction pH Remarks NaOH to ml .1141N NaOH 1 .83 6.0 10 8.3 8.08 20 16.62 7.7 30 24.9 8.52 40 33.22 9.02 45 37.4 9.32 (Spot test: 47 39.05 9.52 SBLBIIQSS to 1 dr0p 48 39.9 9.59 Slight pink to spot 49 40.7 9.72 Liigle more pink 50 41.6 9.81 Definite pink 51 42.4 10.02 52 43.2 10.05 53 44.1 10.37 54 44.9 10.69 55 45.7 10.67 56 46.6 10.62 Slight pink 58 48.2 10.62 " " 60 49.8 10.52 65 54 10.51 70 58.2 10.28 85 70.6 10.15 100 83.1 10.12 \...) I. . . . \ \\ .. I. \.. .. . 6.4.... . 41...; \... .. . \ u\. i. . J I \ 1 . . I. B: . .\ 1. III ”JIM. \.DQI . \. ”\.. Air. ..\.\ L \ ...I‘. . . WI; II ..‘1\V.—.x v 00‘]. I I- A I \..c\.\| \.X.\...‘\L .or \oK......V..\I.u,. I .KK.....-. K 9x319 ...). .L.I§.thn.1!o.‘.u o . .....III 9. ..5‘... t. u.... or. .4 . . . : ...xfi......\..\. ....x--. «PW. . . . I r. l R ..n.h. I. . .1. 5‘0. ‘uvD.-‘.tb :1 \. \I .. . u .H . . .. \ x J \ \.I‘ J N o . ..I . XII . I -. . «I‘ . . \ ‘\ \\.\ . rflplh4\ . \ x. I). u o [2“..- ‘I. It .IIV‘. Q} ...”. \. URI-k 4... :..~ . . \ ch. 4 .0. .‘ :I V. .x s . \ . x ‘ \ x) .03.... . .....x... . 7 .. .t . . .--. . . s . . x . N u. . 3". (99:1).0 .. .. .l 1..~ . ., .... g F Ah. ~ . . 0’ A. . ‘1 \. iXuN-K P. . 1‘ . I . \|( \ t .‘l .lls LI I. o l‘rn- I IFKLIII‘I'IWHM’F. III." u.h—Ib.l..l.m. 1“. K“ I‘ \. .4 4 4 rLIIIIl...’ ....» I J n . 4 . . . _ . ‘ 1 V y .. \. i .A ‘ w. I I. ..l .u .I III-I-I It». I . --., an .1. ..II.II-'.|...O... I! .. .v \J . .. \ .H M‘s . . I . l . I I ...P 1...!) .III.’ Lu”. b“...N\. (A.\..,\ .. . .- .. .. .» ....L. ) \ ILL\ ?L_rl\|||l 1.. i0“- ”Lithi- .K“. I x Z ...? 4 {44. _. . x 4. \ .. ...... : . - fun. ...I.).:..-I.V.!r . I; ....Isv hirlbb .4 . K . 4 . . ...-5-59.»... ... 0.. II.» '1‘; \‘\\».C.... rt; 1 I I I i I . _ u- burr... \ .\:t\_-........._!\ ......t. \..... .. . 1.. II‘l.-ul.lll*¢Kh.oiII If K. \..m TE. .II Ir". t‘o.‘. I ‘1. .30‘I .‘II‘I 4m 44 4.4. . 4 .41 .. 3 bio 44. 44 -132- TABLE XXIV BLANK POTENTIONETRIC DETERMINATION OF ACETONE 250 ml C.P. acetone was used. pH of NaOH in abs. methyl alcohol: 10.25 m1. .0949N Correction pH NaOH to ml .ll4lN NaOH 1 .83 9.78 1.2 .998 9.85 1.5 1.25 10.09 2.0 1.66 10.3 3.0 2.49 9.98 4.0 3.32 9.85 6.0 4.98 9.79 10.0 8.5 9.79 20.0 16.62 9.88 50.0 24.9 9.95 40.0 33.22 9.93 ,.\ .....k. 1, M \ LIE-pvt"; \\\V\ A‘I...\. -\ \..1 .-. aLILI‘I'iKnrH..gL!h1h-I\q’w*rh .hl hr \rvLI D I... .I. I... . Nxxx..\.tn..fl r ‘F I. a. \-. Mix- .... . II..) 1...; \....- .& \mv\uunwm _n\w. x. .. V. . .L...:&. ...r A133...) Q‘J...‘ It??? LIIIIIU..\.vI-Vunllf.~ I . ‘. . \ \ v i lyi‘ 1‘? ti. 5.. /\3 ...N4 P'\.:\ III. ..IlmlL-LI’ILSI .‘3lltt ..‘..\ .LQ ir. L'huIl-oslvnn t; :ial'. Hwy. \ \«s. 13.5“ ’ .. A.h....- . _ x. r... . N\\\ .n.:,. J \.... _\\q ‘0 U... ..IIII' 3. .m u \ Iii... . . II.II I... 1'1... .I"" r '- L. 4.2.}. -155- PART VI ELEMENTARY ANALYSIS OF HETEROPOLYMRR PRODUCTS FROM DIFFERENT MOLAR RATIO OF REACTANTS (a) 1:1 (Styrene: Maleic anhydride) molar ratio of reactants: This is the product prepared under Part IV, Study A. Macro quantitative organic analysis. Sample Sample co HOH % C % HOH weight weiggt weight 1 .14933 .5846g .0700g 70.92 5.25 2 .1565g .5514g .0622g 70.2 5.10 average: 70.57% 5.18% (b) 5:1 (Styrene: Maleic anhydride) molar ratio of reactants: This is the product prepared under Part IV, Study B. Micro Quantitative methods of organic analysis were used: Sample Sample co HOH p c % HOH weight weiggt weight - 1 9.655mg 25.454mg 4.591 71.8 5.29 2 9.122mg 25.994mg 4.565 71.7 5.51 -154- DISCUSSION -155- PART I COMPARISON OF SOLUTION COPOLYHFHIZATION TECHNIQUES To facilitate the study of the heterOpolymer maleic anhydride-styrene, it was necessary to compare several standard proceduresgzhg5 for preparation of the c0polymer by solution polymerization methods using benzoyl peroxide as a catalyst. These pro- cedures demonstrated that benzene (Reaction A) as a reaction medium possessed certain advantages over acetone (Reaction B) in that: a more consistent reaction temperature (BO-810C) was maintained; an insoluble copolymer results which can be readily filtered from the benzene solvent, separating it from the soluble monomers and any byproduct polystyrene. Whereas the copolymer B (acetone solvent) is precipi- tated by the addition of the non solvent water as a gelatinous, adhesive mass with the pronounced odor of styrene, the 00polymer A (benzene solvent) is a granular white powder that is readily washed by benzene and apparently tends not to be solvated with monomers or solvent. Reaction A (benzene solvent) also gave the greater product yield indicating the greater reaction rate and the course of the reaction could be followed visually from the extent of the precipitation. Because of these facts, all further c0polymer prepa- rations were carried out in benzene solvent and these studies are limited to 00polymer prepared in that manner 0 The solution of weighed polymer samples in acetone and titration with standard alkali to phenol- phthalein endpoint yielded inconsistent results and this titration technique was deemed unsatisfactory. PART II STUDIES ON THE RATE OF COPOLVWFRIZATION In order to investigate the reproducibility of the c0polymerization technique, studies A and B (Experimental, Part II) were conducted to determine reaction rate and to develOp quantitative techniques for following the course of the reaction and 00poly- mer properties. The per cent polymerization data as determined from the extent of polymer precipitation is the more consistent in Study B (see Table 5 and Figure 2) than in Study A (see Table l and Figure 1), due to the fact that in the former case the sampling tech- niques were being perfected and there was a difference in the time of sampling of the several samples listed as being drawn at the same reaction time. This sample time was actually only applicable to the first sample of the pair in Study A. With realization of this fact, it is apparent that the rate of reaction is reproducible within experimental error for the 00polym- erization with molar ratio of reactants 1:1. The standard induction period is seven minutes. -137- From kinetic theory, we have for a first order reaction: (20) 2% 3 *kt where X is the molar con- dt centration of the reactant and k the rate constant. This expression integrates into: (21) log x -.-. ~k/2.503 t + c which is in the form of the linear equation: (22) log x a At + c where A is the slepe of the line determined from the plotting of the time of reaction in seconds as abscissa against log x as ordinate and from which: (25) k g -2.503A Now, if we assume that the styrene and maleic anhydride enter into the c0polymer mole for mole we may consider for the purpose of this discussion that the "monomer" is a styrene-maleic anhydride unit, its molar concentration at any time being the same as the molar concentration of styrene or maleic anhydride. (The assumption of the copolymer composition is 1:1 as a legitimate approximation will be validated further in the discussion.) Using the data compiled in Table 5 (Part II, Study B) we may tabulate the log of the molar concentration of "monomer" vs. the reaction time in seconds as in Table 7. -158- PART II STUDY B Table 7 DETERMINATION OF REACTION RATE CONSTANT Sample Seconds Weight Moles ‘ log Time Unreacted Unreacted E'monomerfl Monomers "monomer" O 0 47.1470 .2552 -.4774 1 270 47.1450 .2551 -.4776 2 560 47.1455 ‘ .2552 -.4774 5 515 45.5554 .2245 -.4945 4 575 44.6011 .2206 -.5017 5 700 42.4525 .2098 -.5255 6 850 59.9555 .1975 -.5496 7 1125 54.5116 .1707 -.6128 8 1225 52.4845 .1607 -.6590 9 1855 22.5854 .1117 -.7970 10 2080 19.5505 .0956 -.8645 11 2780 15.5897 .0662 -1.0241 12 5500 9.8558 .0458 -1.2054 15 5780 10.2509 .0506 -1.1409 METHODS OF CALCULATION} (see data in Table 5, Part II, Study B). l. 100% - % polymerization = % monomers unreacted. 2. % monomers unreacted . “initialwwt. of monomers g ’MOlecular weight of "monomer“ number of moles of unreacted "monomer" 5. number of moles of unreacted Vmonomer"/ volume of solution in liters (.7 liter) a molar concentration of unreacted "monomer". 4. Initial wt. of monomers: 47.1470g. Molecular wt. of m.a.-styrene unit: 202.2. 5.5.; ’1 1../-.- LS... —.'.- .. “...... a . ,1 . g. . [I , ’ ,JL... ,’/¢‘_/-— J. A“ 2‘77 4A 1 I .-..» ._....) -"’ r- . ‘ «.0 F. ,1. y x’!,' “r d n*.‘--A 1“ ;‘ ~. "' --‘.:~’ 'L/L 71”” I? ff. 4 J (1. l ‘-' EI'ON- ...-f “A. :L x ,. .x . .l.:\v: .11) an” '- \ \ ...»:1.‘ 1w“. s\..11l )\\\.\\\ ....xrn .\, n. :. 1 , In... 1. u . 1 ‘1 ., 1.. ‘1 \ i . ... a . . .....\w. an. \ .... .3. ... >1}; .1. v.1 ..11... ... .. m \ \x. a x. .\ mx. ‘ ‘ '11 I)" ‘1. d. .flflkty ital-($150. 1| hummer...) .. .....r ‘ \K- | ...V ..x ..x .. ... x ....r:\ \..LJ . .v .11. .‘L‘a 1. \o I)! 111m: 11“ .. khan-(.1 I11liI|1lL 1.1! '1' .IIVIchnIIQQ!‘ sill-I I.’\.h§.1i.tb i t \... H 11 1‘\D . 3. \al1 . - “be .5.. ...... LXJ \...u .. ....1 x: V...” . ‘.. I’p.b(\W'|l..-Ig.\mos1‘\ .u.1o...l\.‘.1lunlla\)‘\-IHH. \ufiL1quwwvlnL KL ...: 1 1.1 .1:.\.\.?l\ ...... m: ._ ..:. V....,..-............1 IJ . .5 H. 1. ., .. ‘ it... 5.1.2.1.: . , 1 1. I. l. . ‘- 1.5.0va .11l‘lp11il K.. 2 n. a. ...: “I “”4 \ _. w ... ~ In!!! I'IIJ'IIII ll /, . ...: .3. ---: :- . / .hum L. \(xuu . NM”... 1.1.5 Ami 1‘ 1-\P.r.“:ux1.rluq:. -.....111 1. .V!)III\..WI\.IM\I.U.IL ’.i1|l .{l111f4 -l59- The plotting of this data in Figure 22 gives an excellent straight line demonstrating the validity of the data and that the reaction rate is first order with respect to styrene or maleic anhy- dride under the conditions of the c0polymerization. Since the SIOpe (A) of the line is -.00025, we have from equation (25) that the reaction rate constant (k) is 5.5 . 10‘4 sec‘l. We may justify a minimum reaction time of five hours yielding complete c0polymerization for all reaction mixtures with molar concentration of "monomer" less than that of the Part II studies (.5555 M in "monomer"), providing they give a 1:1 c0polymer composition or the same cepolymer comp- osition that resulted from these studies. Consider an initial [fimonomeri] of 1/5 at 420 seconds (i.e. 7 minute induction period) and a final [fmonomeri] = X at 18000 seconds ( 5 hours total reaction time). Then we may set up the expression: (24) X 18000 dX : -k dt 420 1/3 and integrating between the limits: (25) log 5x = -(5.3 . 10'4) (18000 - 420) . -4.05 2.503 whence X ( ["monomer'fl after five hours of reaction time) is [300005] and thus the % unreacted "monomer" is .Ol%. (See Figure l for experimental verification.) ~140- Morgan26 prOposed that maleic anhydride did not undergo bromine addition alone but did so in styrene mixtures, the amount of bromine addition being equivalent to the amount of styrene and maleic anhydride in the mixture. An attempt was made to apply this principle (Part II, Study A, Table 2) using the direct bromine titration method of Uhlrig and Levin?7 on the unreacted monomer in the sample filtrates. Apparently under the con- ditions of the bromine titrations, addition to the monomers' ethylenic bonds did not completely occur. From Figure 1, it can be seen that a maximum of 60% of the monomers added bromine. The results are not exceptionally quantitative and the endpoint is a fading one. We may interpret Figure l as indicat- ing that maleic anhydride still maintains its non- hdogen adding preperties even mixed with styrene under the conditions of these titrations and that the bromine addition to styrene was practically complete with some substitution or addition being effected on the maleic anhydride. In an attempt to correlate relative molecular weight values with extent of reaction, the viscosity method of Staudinger was usedzg’so. As given in Table 5 (Part II, Study A) there is no apparent relation between the viscosities as considered proportional to time of solution efflux and the extent of the reaction. In fact the deviations between samples are outside the reproducibility possible. Dissolution of weighed polymer samples in acetone, addition of excess alkali, distilling off the acetone, cooling and back titration with standard acid to phenolphthalein endpoint provided the data in Table 4 (Part II, Study A). As is evidenced from Figure 1 this data is more consistent than the analogous polymer analyses by titration of Part I indicating that these more drastic treatments probably fractured the anhydride linkages of the cepolymer to a much greater extent. Yet Figure 1 indicates that 00polymer composition is an erratic function of reaction time from the results of these analyses. In order to estimate the validity of these titrations, the unreacted monomers (Study B) remain- ing in the sample filtrate were treated as was the 00polymer above, after distilling off the benzene. 0n titrating with standard acid to phenolphthalein endpoint, the data of Table 6 was plotted on Figure 2. Inconsistency of results is more obvious in this Figure. Reproducibility is not apparent and no correlation of copolymer composition with reaction time exists. The huge discrepancies in cepolymer com osition as deter- ~142- mined by the two methods, where c0polymer analyses in Study A (Figure 1) average 415 m.a. in the co- polymer and where by the monomer analysis of Study B (Figure 2) the m.a. in the 00polymer averages 75%, readily show that phenolphthalein as a neutra- lization indicator with 00polymers, a common indust- rial practicega, is not reliable. PART III ASUEOUS FOTENTIOMETRIC TITRXTIONS OF THE RETERO- POLYMER: MALEIC ANHYDRIDE-STYREHE As was previously discussed, analysis of hetero- polymer composition by aqueous titration to phenol- phthalein endpoint was invalid due to the indicator endpoint not coinciding with the pH of acid polymer neutralization. A series of samples from the final product of Study A, Part II (1:1 molar ratio of reactants) were potentiometrically titrated under varying conditions in order to characterize the titration curve of the heteropolymer. In the plotting of the titration curves the ml. of titer of the several acid and base titrations on the one sample have been calculated and plotted so as to be equivalent to the same normality so that these curves may be prOperly compared. The zero point on the abscissa is arbitrarily chosen as corresponding to the pH of the solution just prior to the initial titration A. The several curves on each Figure represent the titrations of the same sample in different solution volumes, the decreasing order -145- of concentration being for curves A, B, C, D, E. In general, the dark vertical line on the graphs represents the point where the pH of the solution is due to the free acid heterOpolymer alone in the presence of NaCl that never exceeds .05 molar. At this point any excess acid or base is completely neutralized as computed from the milliliters and normalities of the standard titrating solutions used. For purposes of recognition the tables of potentiometric data are all numbered with roman numerals. The standard alkali was added to the acetone solution of Sample 1 at a fast enough rate to shock precipitate a portion of the c0polymer in the form of hard shreds which did not completely dissolve on the distilling off of the acetone or in the time of heating allowed for the caustic sol- ution of the sample. Thus Figure 5 (data in Table I) does not represent a quantitative amount of sample. This difficulty was avoided in future samples by slow addition of standard alkali with constant stirring to the acetone solution of the 00polymer and subsequent adequate heating time to effect complete solution in the aqueous alkali. From analysis of Figures 5 through 17 it is apparent that a point of inflection exists at a pH of 6.25 where d pH/d ml is a maximum. From ~144- neutralization theory this is recognized as the stoichiometric point of neutralization of a carboxyl and conceivably may represent neutrali- zation of all the carboxyls in the c0polymer or merely half of them. If we consider the latter to be the case, we may calculate the amount of maleic anhydride in the sample by considering the amount of titer used between the two stoichiometric points, CH 6.25 and arrowed vertical line, as being equivalent to one half the carboxyls. The results of such cal- culations are tabulated in Table 8 for some titrations of Part III. -145- PART III Table 8 CALCULATION OF NOLAR RATIO OF CO-MONOMERS IN HETEROPOLYHER FROM POTSNTIONETRIC TITWATION CURVES Sample Fig. Tit- ml. of molar ratio Avg. molar No. No. ration stoich- in polymer ratio for iometric (m.a.:sty.) sample titer 2 4 A 41.80 .95:l B 59.65 .85:1 0 42.50 .96:1 .91:1 5 5 A 42.60 .97:l B 41.60 .92:1 C 45.40 .92:1 .94:1 4 6 A 44.75 1.00:1 B 45.90 1.07 l C 45.90 1.05°1 D 45.90 1.05 l E 45.90 1.05:1 1.05:1 15 10 A 25.0 .92.1 B 24.3 ' .87°1 C 24.5 .87 l D 24.5 .87 .88:1 14 11 B 27.7 .89 l C 27.7 .89°l .89:l average: .91:1 The normality of the titer is .1l4lN. -146- METHODS OF CALCULATION(f0r Table 8) 1. (From Figures of the potentiometric curves): ml. reading from abscissa at free acid hetero- polymer (vertical line) - ml. reading from abscissa at pH 6.25 = ml. of stoichiometric titer for half the carboxyls. 2. ml. of stoichiometric titer ° titer normality . millimoles of m.a. unit in the sample. 5. millimoles m.a. unit ° .09806 a wt. m.a. units in sample. 4. wt. of sample - wt. m.a. units 3 wt. styrene units in sample. 5. wt. of styrene units/ .1041 = millimoles styrene units in sample. 6. millimoles m.a. units/ millimoles styrene units - molar ratio in polymer. The average molar ratio of the samples listed is .91:1. The % Carbon in such a polymer would be: 100 ° (m.wt. of total C in .91 m.a.i‘total C m.wt. in 1 styrene) / (.91 mol. wt. m.a. 1' mol. wt. styrene) = 45.72 4‘ 96.08 . 89.25 1‘ 104.14 100 = 72.1% The % H in such a polymer would be: 100 . (m.wt. of total H in .91 m.a. +~total H m.wt. in l styrene) / (.91 mol. wt m.a.‘+ mol. wt. styrene) a 1.855 + 8.064 89.25‘+‘104.14 . 100 = 5.12% -147- If the titer actually corresponded to all the carboxyls in the heter0p01ymer, then we would have one half the number of maleic anhydride units and the molar composition of the 00polymer would be .455:l (m.a.: styrene). The % C in such a polymer would be: 100 - (m. wt. of total 0 in .455 m.a.‘+‘ total C m. wt. in l styrene) / (m.wt. of .455 m.a. 1‘ total m.wt. of l styrene) = 21.82—P96.08 44.7+104.14 . 100 . 79.2% The % H in such a polymer would be: 100 ° (m.wt. of total H in .455 nuaJvftotal H m.wt. in l styrene) / (m.wt. of .455 nuaweftotal m.wt. of 1 styrene) : .917‘+ 8.064 44.7 +104.l4 ° 100 . 5.04% Macro quantitative analysis of the elements of a 00polymer prepared from 1:1 molar ratio of reactants as listed in Part VI conclusively shows that the .91:1 ratio in the 00polymer is the correct one and thus we can conclude that the heter0polymer acts as dibasic acid and the above discussed stoichiometric titer corresponds to the neutralization oncarboxyls only. In general, Figures 5 through 17 demonstrate a reasonable coincidence of the titration curves in the buffer regions and a divergence above a pH of 10 and below a pH of 5.5 when the molar concentrations of the heter0polymer vary widely. It is to be expected of weak acids that acidity in the free acid state will ~148- depend on concentration and acidity in the buffer region be relatively independent of it. The secondary carboxyl is apparently so weak that no inflection point could be obtained above a pH of 7 and since the extent of heteropolymer salt hydroly- sis would depend on concentration, the divergence above a pH of 10 at different molar concentrations is easily understood. (See Figures 5 and 5). Figure 5 (Sample 1) obviates the unreliability of phenolphthalein indicator as a means of stoichio- metric analysis. The phenolphthalein color change at a pH of 8.2 is well on the buffer portion of the curve correSponding to the second carboxyl neutrali- zation and thus would also give an indefinite and fading endpoint. In several of the samples (see Figures 4,9,10, 11 and 12) the first acid titration of the alkali dissolved sample gave a stoichiometric titer value in excess of that from subsequent titrations on the same sample; the distinctive point of inflection at- a pH of 6.25 was not well apparent. The initial alkali solution of sample 5 (See Figure 7) was allowed to stand exposed to the air for a period of a week and this phenomenon occurred to show that the cause of error in the other first titrations was due to solution of carbon dioxide from the air in the caustic solution of the polymer. -149- The alkaline solutions of samples 6 and 7 were titrated with standard acid using brom cresol purple as indicator (see Tables VI and VII). Using this indicator With the back titration technique, the calculated stoichiometry of the heteropolymer is valid within 2%%. The stoichiometric titer from potentiometric titrations is approximately 40 ml while 58 m1 is the stoichiometric titer for one carboxyl using the indicator. To the first alkalire solution of samples 8 and 9 were added weighed amounts of maleic anhydride. The resultant curves (Figures 8 and 9) show that the buffer portion of the curves in the lower pH range is similar to that of the heterOpolymer acid alone. Analysis of the data for the samples 10, 11 and 12 (see Tables X, XI and XII) show discrepancies between the stoichiometric titers from acid and base titrations that can only be accounted for by erroneous caustic normality. Since a different standard base was only used for these three samples, this conclusion is justified. PART IV ANALYSIS OF THE HALRIC ANFYDRIDE-STYRRNE HETEROPOLYMERS PREPARED FROM DIFFERENT MOLAR RATIOS OF REACTANTS Utilizing the benzene solvent c0polymerization techniques develOped in Part II, three 00polymer ~150- products were prepared from different molar ratios of reactants. The potentiometric titrations tech- niques developed in Part III were then applied to weighed samples of each. Using the methods of calculation of Part III, Table 8, the compositions of these 00polymers are tabulated in Table 9. These 00polymer products differed from those of Part III in that they were benzene extracted for several weeks and then vacuum dried for a least one week to remove any possibly occluded monomeric maleic anhydride or contaminating polystyrene so that .such intense treatment would insure the true cOpOly- mer product. PART IV Table 9 CALCULATION OF MOLAR RATIO OF CO-MONOWFRS IN HETEROPOLYMERS PREPARED FROM DIFFERENT MOLAR RATIOS OF REACTANTS Sample Fig. Tit- ml. of polymer Avg. Avg. No. No. ration stoich- comp. for for iometric (m.a.:sty)sample Reactant titer Ratio 1:1 Molar Ratio of Reactants (m.a.: styrene) 15 12 A* - - (* exposed to C02 of B 48.75 .882:1 air. ** pH C 48.75 .882:1 .882:1 machine off) l6 15 A 49.25 .899:1 .890:l (mole fraction B 49.25 .899:1 m.a. a .471) C 49.25 .899:1 .899:1 1:5 Molar Ratio of Reactants (m.a.: styrene) 17 14 A 48.15 .846:1 B 47.55 .845:l C 47.55 .845:1 .849:1 (mole fraction C 47.65 .846:1 .846:1 5:1 Molar Ratio of Reactants (m.a.: styrene) 19 16 A 52.15 1.001:1 51.05 .961:1 50.10 .928:l .955:1 20 17 52.15 1.001:1 .975:1 (mole fraction 52.15 l.001:1 m.a. : .494) C) (3 3’ C) tn 51.05 .961:1 .987:1 -152- It can be noted from Table 9 that the 00polymer composition is not greater than 1:1 (m.a.:styrene) notwithstanding the molar ratio of reactants and thus the argument presented under the discussion of Part II as to total polymerization having occurred with a reaction time in excess of five hours is valid in regard to these 00polymeriza- tions which were conducted with a total reaction time over 6 hours. Z‘Ialll4 has predicted the instantaneous comp- osition of this heter0polymer prepared from different reactant ratios from a theoretical kinetic study. Alfrey and Levin22 have analytical- ly determined the c0polymer com osition of the first products formed from polymerization with different molar ratios of reactants. For purposes of compari- son, these data are tabulated in Table 10. -155- EWTIV Table 10 -4 I COMPARATIVE DATA: MOLE % NONOTER IN REACTION MIXTURE VS MOLE % IN COPOLYMER Monomers in Reaction Composition of COpolymer Mixture Alfrey Walll4 This Paper Mol % Mol % & Lavin22 m.a. sty. Molz M01 % M01 % M01 % M01% :01 % m.a. sty. m.a. sty. m.a. sty. + - 9909 01 " " 5O 50 "’ - 95 5 49.9 5001 - - - - 75 25 - - 48.9 51.1 49.4 50.6 50 50 48.9 51.1 47.4 52.6 47.1 52.9 25 75 - - 44 56 45.9 5401 1607 8503 4500 5500 ~ - - u 9.1 90.9 42.4 57.6 - - - - 5.0 95.0 58.9 61.1 - - - - It should be realized that the copolymer compositions reported in this paper are not the instantaneous result of a given molar ratio of reactants as with Wall and Alfrey & Lavin, but rather the ultimate product of a total polymerization of a given molar ratio of reactants. These data are plotted in Figure 25 and show excellent agreement within experimental error. We would expect the curve plotted through the points representing the data of this paper to lie «s,— l,- ...—.3 —---~ .-_ A...“ . —.._ r3 /L’—,v’.'l {7 [IF 3 4...- 5. H13 i" '\ ,- v ._.-u -‘ Iv . 4"»... _-,_. n 1 N7 !y LC ‘ngor’ . r‘- :4. :- ”‘3 / '7 L” ' I; 1,] A” . "|\II||‘I||I|II \‘lb ‘h‘l ‘l |\lq \.LOtlllill \x.-\.. in... us x| \ lx“!i‘\|\l\| _ ‘l - "Oll- ..OIII| I‘ll I-il‘i \.. .\ l\. . \\\\I\ \ \I‘. I‘ll ‘4\|~.. \ .. ..\ ‘ 'I |v|ul\‘| t. ..\\ \ \\ \ O IIIIII I - \J 3 4. » ) .... a F r\ Wu.\,mr:1®llihkrnl \«r s. . ‘Y J. \9 1c) 3 . .. . . .. :2 I a a -E- KNEE. rl in}... m. _.> . 1‘ - 9 ii: .9 . rehfirxm... ,Y t . , . ,. 2 D --.i . I»- .32: be t, . Iv‘ \w . ) . y w ~ V . u \- \~ \ x. ‘5. . . VI.‘ 6 II 4 NR. X‘. x)\ _ . D , a K... \ :\; \.C an... ,. u . .7. .xCh Hm _ . . . t i . ¥.IIILK. . rlli’l IIE‘».D .I’I il‘ikrl. .4 | ... .7 [2" .r I“ I.. \. .. ~\| \l. \. V ‘\ . .% “My (er ON $4.. L4K . _ . - . _ Bk ..-»-mE:bwag Lthuhb.) \9V.\sNQW_....3.-.\g ....‘\.,...._rv\..o...r Nu 'Il'lvhl‘i‘ln“ ~154- below the curve plotted from the data of Alfrey and Levin. The smaller the mol percent maleic anhydride in the initial reacting monomers, the greater should be the discrepancy of the two curves which should tend to approach and cross each other as the mol % maleic anhydride increases. The unbroken curve A corresponding to the points of the thesis data repre- sents this comparison. The broken curve B correspond- ing to the points of the thesis data represents a similar comparison with the theoretical predictions of Wall. If we define the primary disassociation constant of the free heterOpolymer acid as: (26) Ka (or K) : (iii 0 lHMA‘I [Hgm where Elgmg is the molar concentration of all maleic acid units in the copolymer, EIMAE) is the molar concentration of all mono-ionized maleic acid units in the c0polymer and [Eli is the molar concentration of hydrogen ions. Then by taking the logarithm of the reciprocals of both sides of this equation we have: (27) log l/K : log 1/ [133 + log gfl or (28) pH ll "U N I |--' O 09 pK-log (1 -d\ )/a( where‘a( is the fraction of mono-ionized maleic or (29) pH -155- acid units in the Henderson-Hasselbalch equation. If our definition(26) is valid, our potentiometric data should conform to the linear equations (28) and (29). Katchalsky and Spitnik25 have attempted to apply the Henderson-Hasselbalch equation (29) to potentiometric data from the titrations of the poly- meric acids polymethacrylic and polyacrylic and have found it necessary to modify it to the form: (1’90)sz pK-nlog(1-0‘W as the 310pe of the lines determined by plotting pH vs log (1 - cl ‘)fifor these polymeric acids was not equal to unity. -l56- PART IV STUDY A Table 11 TABULATION OF DATA FOR DETERMINATION OF pK VALUE OF HETEROPOLYHER Copolymer produced from.molar ratio of reactants 1:1 (m.a.: styrene) is of .89:1 composition. From weight of polymer sample (Table XV) and mole fraction of m.a. in copolymer (Table 9) there are .004624 moles of m.a. in the polymer sample. pH liters [C] ml. [HMA‘] [Hngg log 1 -aL titer ‘:2T" sol'n added to free acid 5.51 .524 .01428 46 .01549 .00079 1.2520 4.99 .528 .01410/ 42 .01320 .0009 1.0664 4.79 .351 .01598 39 .01121 .00277 .5071 4.6 .334 .01585 33 .01024 .00531 .4329 4.48 .539 .01565 51 .00870 .00495 .2449 4.50-.545 .01541 25 .00590 .00651 .0255 5.90 .555 .01505 15 .00416 .0088? -.5288 5.50 .562 .01278 8 .00242 .01056 -.6516 5.20 .567 .01261 5 .00142 .01119 -.8965 The representative potentiometric titration data for this table was taken from Table XV, Sample 15, Titration C. —157- PART IV STUDY B Table 12 TABULATION OD DATA FOR DETERNINATION OF pK VALUE OF HETEROPOLYMER Copolymer produced from molar ratio of reactants 1:5 (m.a.: styrene) is of .85:1 composition. From weight of polymer sample (Table XVII) and mole fraction of m.a. in COpolymer (Table 9) there are .0045175 moles of m.a. in the polymer sample. pH liters soln 5.09 .260 5.50 .265 5.61 .267 5.90 .271 4.22 .278 4.58 .285 4.58 .289 4.75 .295 5.1 .298 5.59 .500 5.85 .502 [C] .01758 .01718 .01692 .01667 .01625 .01596 .01565 .01542 .01516 .01506 .01496 ml. [HMA‘] E42141] log 1 -aL titer “0(- added to free acid 6 .00274 .01444 -.7218 10 .00592 .01500 -.5206 14 .00519 .01148 -.5447 21 .00745 .00882 -.0745 26 .00902 .00694 .1158 52 .01085 .00480 .5554 56 .01200 .00542 .5452 41 .01542 .00174 .8872 45 .01547 .0C109 1.1078 45 .01454 .00042 1.5595 The representative potentiometric titration data for this table was taken from Table XVII, Sample 17, Titration B. ~158- PART IV STUDY C Table 15 TABULATION OF DITA FOR DETERNIN4TION OF pK VALUE 01? HETEROPOLYI’EER COpolymer produced from molar ratio of reactants 5:1 (m.a.: styrene) is of .98:1 composition. From.weight of polymer sample (Table XIX) and mole fraction of m.a. in COpolymer (Table 9) there are .0050401 moles of m.a. in the polymer sample. pH liters [0] ml EMA") E1 Ma log 1 wk soln titer 2 ':ZTF' added to free acid 5.59 .257 .01961 4 .00177 .01784 -1.0054 5.61 .261 .01951 8 .00524 .01607 - .6954 5.91 .266 .01895 15 .00489 .01406 - .4587 4.25 .275 .01855 22 .00788 .01045 - .1226 4.59 .281 .01794 28 .00976 .00818 .0861 4.52 .286 .01762 54 .01164 .00598 .2895 4.72 .290 .01758 58 .01281 .0045? .4477 4.88 .295 .01720 41 .01566 .00554 .5865 5.09 .295 .01709 45 .01414 .00295 .6807 5.50 .297 .01697 45 .01471 .00226 .8155 5.61 .299 .01685 47 .01525 .00161 .9765 The representative potentiometric titration data for this table was taken from Table XIX, Sample 19, Titration B. -159- METHODS OF CALCULATION in Tables ll, 12 and 15. LC] .-.- Total molar concentration of all m.a. units in sample ; moles m.a. in polymer sample liters of solution 2. [hafHMAi] = molar concentration of the mono salt of m.a. units in heteropolymer = ml of alkali titer adied to free acid . norm. of alkali liters of solution 5. [EMA] = 10‘13H (i. e.L [gig -[HMAj due acid disassocia- tion) HENa HMAj 4' [03 :nnEHMAj- =E12MAJ : log 1 -“' @2141 “'2'" .5.. ‘1‘ {V k~su1~\\ .\\ K \ \ s .. N. N\ \ x) \ u‘ n \ ”\.. .. . IV ... "V‘ r.‘ ... D.) D I u . \.. .| N. \ . I\.\ ‘ko ‘ . . \‘ IAN\I.I.I4 ...IIA.\.I . III. ..I\.\1\W... \. ..\.\H..... W . :1 3.6.- m: ..‘Iltvrd .1- ....\l!.!ll.l.(\f.9n|rfi ll. \11“..I.L.I .5”!- 6. ..\u.‘.. I.“ blur. .1.-.u.m...\tm.t...lt\‘. lhIIrvnr- .‘Si'-y!f.la‘l;~i-.l 59$! \ Ii .5..\l-1 5.70-ll u a n 1 . . llb)...L[at.|.rdr-n.. . (‘0!)- sJIln-sllvt ‘ 1.17.. '1’? 'rrll .10.. tr15353igltgiz 2 1 \- . tin! bansb ......x... .... K... x. ....H bx “5.. C. I . m.a.: ...,“ \... v. (0. .. ,H N; \ 5 %\..\~ g. .. u . ._.... ......x x I“! \I o 2 fl 1 ..S . . I\ .IKVIMI"; . L . o . A\ O -160- In Tables ll, 12 and 15 are tabulated pH vs log ‘HgMfl (i.e. log (l-OCA ) for representative [Hm-j potentiometric data from the three different molar ratios of reactants studied in Part IV. In Figure 24 pH is plotted as the ordinate against log (1 -725) as abscissa for the potentiometric titration data from Studies A, B and C. Excellent agreement with the linear nature of equation (50) is obtained and since the possible experimental limits of the slope (n) of the lines drawn through the points are .9 to 1.1, we may take our resultant lepe (n) equal to unity in confirmation of equations (28) and (29). These results justify our definition (26) for our heteropolymer acid. Since the intercept of the linear equation (29) is the pH value i.e. when the log function is equal to zero, the pK of the Study A COpolymer (1:1 molar ratio of reactants) and the pK of the Study B COpolymer (1:5 molar ratio of reactants, m.a.: styrene) are the same within ex- perimental error and equal to 4.18. This latter value is the same as the succinic acid pH for the primary carboxyls disassociation constant. This item is worthy of note as the COpolymerized maleic acid units are actually substituted succinic acids in the COpolymer. The pH value of 4.58 for the Study C COpolymer (5:1 molar ratio of reactants, -161- m.a.: styrene) is higher notwithstanding the fact that mole fraction of m.a. in the copolymer mole- cule is actually the greater. When the free acid heterOpolymer is dissolved in a neutral aqueous medium with no extraneous base present we have in the definition of the primary carboxyl disassociation constant (26): that (51) (Eff): [HMAj and thus: - l (32) 1 .. E12145] - K 1?] 2 where in a weak acid[H2MIg may be equated to the total molar concentration of all m.a. units and taking the logarithm of both sides of the equation, we have: (55) 2pH -.- pK+log 1/ E2145 3 pK + pLLA This is a linear equation with the unit lepe justified in the above discussion. Table 14 TABULATION OF 2pH VS pMA ASED ON pH AND VOLUHE -162- OF FREE ACID HETEROPOLVEER SAMPLES FOR UNPURIFIED Sam- ple 15 14 MATERIAL (Data in Part III) 4 II 5 III 6 IV 10 XIII 11 XIV Fig.Table pH 2.48 2.48 5.00 2.45 2.45 2.78 2.5 2.5 2.75 2.95 2.74 2.74 2.81 2.81 2.55 2.55 2.74 ml. 105 ° soln Total moles H MA n sample' 158.5 4.7140 185 524 159 4.7846 164 500 159 5.0170 164 559 619 144 2.7926 158 255 258 144 5.1606 157 251.5 [52M 5.4040 2.548 1.455 5.442 2.926 1.595 5.609 5.059 1.597 .811 1.959 1.767 1.199 1.175 2.195 2.015 1.565 4.96 4.96 6.00 Avg. pMA 1.5509 1 08‘572 1.7975 1.4785 1.8548 2.0910 1.7525 1.9259 1.6776 1.8649 (A) (B) -165- Table 15 J TABULATION OF 2pH VS pMA BASED ON pH AND VOLUM‘ 1L 1 OF FREE ACID HETEROPOLVMER SAVILES FOR EATERIAL IN ‘J J) TFu PREIENCR OF SODIUM.AOID MALEATE 8 FREI FALEIC ACID (Data in Part III) Sam- Fig. Table pH ml 105 - [BBMA] 2pH Avg ple soln Total pMA moles . 102 HQMA in sample In the presence of sodium acid maleate 8 8 VIII 2.72 155 4.74 5.1 5.54 1.59 2.72 222 2.1 9' 9 IX 2.62 171 4.74 2.8 5.54 1.59 2.62 206 2.5 In presence of maleic acid 8 8 VIII 1.85 184 8.54 4.55 5.70 1.54 9 9 IX 2.07 185 6.50 5.40 4.14 1.46 In (B) the total moles of HQMA in sample now includes the moles of true maleic acid added. 54 24 84 -164- Table 16 TABULATION OF 2pH VS pMA BASED ON pH AND VOLUME OF FREE ACID HETEROPOLYMmR SANFLES a FOR PURIFIED MATERIAL PREPARED FROM DIFFERENT NOLAR RATIO OF REACTANTS (Data in Part IV) Sam- React- Fig.Table pH ml 10:5 ° [HgMé] 2pH Avg ple ant soln total 2 pMA Ratio moles . 10 m.a.: H2MA in sty. sample 15 1:1 12 XV 2.75 217 4.6264 2.152 5.5 1.7028 2.75 251 1.845 5.05 569 1.254 6.1 1.9017 16 1:1 15 XVI 2.98 275 4.6758 1.700 5.96 1.7857 2.98 295 1.595 5.07 411 1.157 6.14 1.9442 17 1:5 14 XVII 2.87 245 4.5515 1.865 5.74 1.7456 2.87 256 1.770 5.04 572 1.218 6.08 1.9145 18 1:5 15 XVIII 2.95 277 4.5220 1.652 5.90 1.7979 2.95 291 1.554 5.07 598 1.156 6.14 1.9446 19 5:1 16 XIX 5.11 258 4.8495 2.042 6.22 1.7056 5.11 255 1.917 5.50 580 1.276 6.60 1.8942 20 5:1 17 XX 5.08 249 4.9142 1.974 6.16 1.7165 5.08 265 1.869 5.20 591 1.257 6.40 1.9006 -l65- METHODS OF CALCULATIONS IN TABLES 14, 15 & l6 : [H2143 MA in sample are obtained from the 1. Moles HQMA in Sample liters of solution The moles of H2 determined copolymer compositions (see Tables 8 and 9) See appropriate table of potentiometric data for liters of solution and weight of sample. 2. In calculations of samples 8, 9 Table 15 (B) the moles of maleic acid added to the solution of the sample is included in the [hQMA] . 5. pMA : 10gl_1__ [HZMA] 4. pH of free heteropolymer acid is obtained from vertical line of the apprOpriate figure. In Tables 14, 15 and 16 we have tabulated 2pH vs. pMA as determined from the pH and volume of the solutions of free heterOpolymer acid, which data comes from the potentiometric titration tables. The data from these tables is plotted in Figure 25 with 2pH as the ordinate and pMA as the abscissa. Thus on the basis of equation (55) only one point is theoretically necessary to graph the linear function by drawing a line through the point with a slope of unity. For purposes of ascertaining the validity of the data, several points are plotted for each sample r'.-\ -. 1 , “I “I 4 L-.'.:-.".'."/ C-”7~'."..-~..-'x‘. 2,4...— "- 75" /‘ h“ —4-—— . ....._ -- *- -....- .‘e—ang-m vsw‘ 0 fiw' “' “'5' _ “'V" ' " ' I "~"""'", /‘1 . C A s ‘ ‘ ’ A ‘~ A 51H (AWIIJ I ; 2. C.‘1-...£L.J§...L‘ifii 2' A/ 1 AU" -~."/V’//'..'.V [.f’fi'm" z” / Hf “r r I ,' fiA”’~Ié;-I/L ;:_/‘_,-_ ."//' .. If"; g / i “w" . / f» e -‘ " 7 «- ; 1.? e‘ a1"__/‘V._"/:"-.-;Z{'_e‘** /’ in I v " . ’ ._.. _' - ‘ A.‘ " r ’ ' Ali-... 1 -..r;- . p ...—.70....“ r\ l4 s Q ‘Q X \ . ._.—-_.... ...—._.. \ l \ I 9 \ \ / O ,/ / O :3} rmrv (I / O ‘5;— -- o-‘J‘fi‘ I I -‘QL" “‘“4 // 1/ j / ‘ ,/ / (D . 4' J, .r 1.0 / l I 4 / f ,’ r) U" “T” ’ ‘LT ‘1“ ”IF ”T" T n if) It") ‘0‘ ‘ ‘ ’9" 5mm a 591-: .351 Ii ; 4.1; 4.1.4!» __ . 1...... D fflfi/‘A 9‘3 New; ; x" x,- avg :_; M... 'IH -"c‘C 1"? 8‘ " 3 [9(1"! ._ 5:11.”, .. Tee/1 )1, fix ....» A & (ID/‘4 a... .3 l7 ()- :0 " E'JIC "\ V 2:: “-..—- A— ..'._— ) ..LA -a—L-_-A—D’ ”9' "’8‘ 5r v -~-—L—u i.“- d-v--‘cv ,M """"‘ ’L" Lew-u: 3' (263 '- I. I 4x.» " ) A a + I: \ ... I: "’5. ”(3.4;1/3 9‘"- L? -166- set and a focal point chosen to determine the drawn line and it can be readily seen from the figure that the data for a particular set of samples gives con- sistent agreement with equation (55). The conclusions drawn from Figure 24 are substantiated by Figure 25 in that the pK value of 1:1 and 1:5 c0polymers (molar ratio of reactants; m.a.: styrene) is 4.18 and the pK value from the 5:1 c0polymer is decidedly higher (4.5). It may seem contradictory that the weaker heterOpolymer acid (5:1) is the richer in maleic acid composition and to afford further comparison the data for samples 2,5,4, 15 and 14 were tabulated in Table 14 and plotted in the figure. These polymer samples did not undergo any extensive purification treatment to remove contaminating monomers and it can be presumed that they may possess a slight excess of occluded monomeric maleic anhydride. The variations in the extent of such occlusions may be surmised by the greater inconsistency of this data with the linear plot of equation (55) through a focal point. The samples 8 and 9 tabulated in Table 15 B had known amounts of maleic anhydride monomer added and this monomer was treated as actual m.a. in the COpolymer in the tabulation for the purpose of comparative plotting in Figure 25. Thus it is obvious that occluded maleic acid increases the sample acidity and lowers that pK value. The data -167- of Table 15A when plotted in the figure also show that when the primary carboxyl of the occludaimaleic acid monomer is neutralized the free heterOpolymer acid will have the ostensible pK value in the presence of monosodium maleate that it would have in the ab- sence of monosodium maleate. PART V ANHYDROUS DOTENTIOMETRIC TITRATIONS OF ANHYDRIDE HETEROPOLYMER WITH METHANOLIC CAUSTIC Moran and Siege152 have shown that in anhydrous solutions organic anhydrides form the mono-ester of primary alcohols with the speed of an ionic reaction and that titration of the anhydride with alcoholic alkali in acetone solvent gives the stoichiometric value for one carboxyl. The data of Tables XXI, XXII and XXIII for samples 21, 22 and 25 represents an attempt to apply this principle to a polymeric anhydride. From their respective potentiometric titration curves in Figures 18, 19 and 20 it will be noted that d pH/ d ml (rate of change of pH with milliliters of titer) occurs at a maximum during the methanolic alkali titration until a peak pH is reached, from.which point the pH slowly decreases to a constant reading. Considering this rate of change maximum as a stoichiometric point for neutralization of one half the potential carboxyls of the anhydride units of the heteropolymer we have the tabulations of Table 17 -168- which demonstrate that the heterOpolymer composition (ma.a: styrene) is .95:1 by this method. PART V Table 17 CALCULATION OF MALEIC ANHYDRIDE-STYRFEE RATIO IN THE HETEROPOLYMRR BASD’ON IOTBNTIOHETRIC TITRATIONS IN NON AQUEOUS KEDIA (ACETONE) WITH ALCOHOLIC NaOH M1. of .1141N methanolic NaOH used to neutralize a monocarboxyl of all anhydride units is calculated from inflection point where de/ dml is a maximum. Sam- Table Fig. m1. of Net weight Ratio ple .1141N m1 sample m.a.: sty. NaOH grams in polymer 21 XXI 18 45 42 1.0062 .90:1 22 XXII 19 45 42 1.0020 .95:1 25 XXIII 20 44 45 1.0040 .97:1 Acetone Blank XXIV 21 1 average: .95:1 This .95:1 result agrees well with the copolymer product compositions tabulated in Table 8 for Samples 2,5,4 whose average is .94:l. Those polymer samples were from the same lot as these used in the anhydrous titrations. It is demonstrated that the methods of anhydrous potentiometric titrations are applicable to heteropolymers and give data equal to that of aqueous -169- titrations. It provides the clinching argument for the dibasic nature of the COpolymer. Due to the fact that the depolymer precipitates during the titration and adsorbs phenolphthalein indicator, the indicator method is not too valid with these anhydrous titra- tions. GENERAL DISCUSSION The similarity of the acid units in the hetero- polymer to individual succinic acid molecules goes beyond the coincidence of pK values in that the potentiometric curves exhibit no point of inflection for the neutralization of the second carboxyl. This lack‘of inflection point is characteristic of the titration curve for succinic acid. In contrast to 25 polymeric acids (poly- Katchalsky and Spitnik's acrylic and polymethacrylic) the calculated pK values are independent of polymer concentration in the ranges investigated, as would be expected of the mono- molecular succinic acid. Introduction of an empirical factor "n" into the Henderson-Hasselbalch equation is not necessary in our heteropolymer as it was with these other polymeric acids since the intercession of at least one ethyl benzene molecule between sub- stituted succinic acids apparently allows each sub- stituted succinic, for all practical purposes, to act independently of another. The greater pK value, or -170- weaker acid characteristics, for the heterOpolymer prepared from a molar excess of maleic anhydride is not readily understood. Perhaps different mechanisms of termination provide different end groups in the polymer molecule when styrene is in molar insufficiency since the latter may possibly react with the polymer radical whereas maleic anhy- dride cannot do so in excess of a 1:1 molar com- position of the copolymer. To fully clarify this phenomenon it is sug- gested that future work be carried out on the potentiometric analysis of other polymeric acids. Katchalsky and Spitnik23 have studied polyacrylic acid: . -’ H H H H C - C - C - C - H I H l COOH COOH Jn with carboxyls alternating with methylene groups. This paper treats a linear molecule: H H H H -4 C - c - c - c - \ l l C5H5 COOH coon 1 ._J n with pairs of carboxyls alternating with a substituted ethylene. For a fully "homologous" series, we may study the COpolymer of acrylic acid (using ester or nitrile as starting material) and maleic acid (using the anhydride as starting material): ~171- H H H H * -e c - c - c - c 4- H 0 I a COOH COOH COOH L - ..n This provides a linear molecule with three carboxyls alternating with a methylene. Polymaleic acid21 would be the ultimate of the "homologous" series: H H H H - c - c - c - c \ | l | COOH COOH COOH COOH n From the previous detailed discussion, we may conclude that the pH value of the heteropolymer for most intermediate molar ratios of reactants is independ- ent of polymer size. This confirms the observations of Katchalsky and Spitnik on their polymeric acids. The COpolymer compositions determined in this thesis for differing molar ratios of reactants confirm the data of Alfrey and Levin and the theoretical pre- dictions of Wall in that with increased reactant maleic anhydride, the COpolymer constitution tends to approachfl:1. ’With lessening amounts of maleic anhy- dride, the COpolymer constitution has a predominance of styrene units. This situation is readily comprehended inthe light of the concept first prOposed by Bartlett and Nozackigl and recently embellished by Mayo, Lewis, Walling et a116'18’20. The polymerizing unit in these types of "alternating" COpolymers (i.e. heterOpolymers) is a polar "radical-ion" or resonant complex formed from -172- a stoichiometric ratio of the co-monomers i.e. 1:1 and that it is this complex which actually acts as the monomeric unit. Since maleic anhydride itself will not readily c0polymerize whereas styrene will, it is to be expected that the molar ratio in the polymer composition can never exceed 1:1 (m.a.: styrene). This concept readily serves as a mechanical model for the mathematical predictions of Wall14 based on Mayo and Lewis' differential equat- ions12 of c0polymerization. The application of anhydrous potentiometric titrations of heteropolymer with alcoholic alkali indicates that monoesterificetion of the anhydride units of the heterOpolymer readily occurs. This affords an easy method of preparation of hemi-esterified maleic anhydride-styrene heteropolymer that may possess desirable prOperties. Specific prOperties of the maleic anhydride- styrene heteropolymer have also been characterized. The polymer is alkali soluble and the free acid polymer is soluble in water alone. It provides excellent buffering action in the acid range 5.5 - 4.5 pH and lathers well, possessing diapersive prOperties that indicate its possible use as a feasible detergent in acid pE's, i.e. the unusual phenomenon of an acidic soap. The polymer is very ~175- readily soluble in acetone both in the free acid and anhydride form. On refluxing with absolute methyl alcohol with the probable formation of the di-ester, it forms a compound readily soluble in methanol. The free acid heteropolynmr is soluble in acetone and water mixtures of all compositions. However addition of alkali will precipitate out the partial heterOpolymer acid salt which will again dissolve on distilling off the acetone. Subsequent addition of acetone will again precipitate the salt but freeing of the heterOpolymer acid by strong acid will again make it miscible with acetone- water mixtures. In the studies of Part III samxles, special note was taken of the pH values when precipitation of the heteropolymer first appeared and disappeared. The former values are the more valid since equilibrium is more easily achieved under the conditions of pre- cipitation than under those of dissolution. These pH's for the different titrations are tabulated in Table 18' and show that the pH of polymer precipitation for a 1:1 molar ratio of reactants heteropolymer is independent of heteropolymer concentration. ~174- Table 18 pH OF INITIAL FOLYHER PRECIFITAWION & DISAPPEARANCE (Data from Part III) Sample Titra- pH ppt. first pH ppt. tion noted disappears l A 2.4 B 2.6 2 A 2.2 B 2.4 C 2.4 3 A 2.15 B 2.4 C 2.15 4 A 2.15 B 2.5 C 2.15 D 2.5 E 2.25 8 A 2.2 9 A 2.25 B 2.7 10 A 2.18 B 2.5 C 2.1 11 A 2.5 B c 2.2 12 A 2.2 C 2.15 15 A 2.13 -175- The data from samples 8 and 9 also show that occluded or additional monomolecular maleic anhydride does not affect the pH of precipitation. Analysis of the Remarks in the correspondinw potentiometric titration tables (for example, see Table II, sample 2, Titration C) shows that increased precipitation occurs only with lessening pH. For weak monomolecular acids, however, it woufl be expected that the greatest amount of precipitation in an acid pH would occur at one value if sufficient time for equilibrium is allowed even with the further addition of strong acid. This phenomenon is directly attributable to the buffering effect of the precipitating weak acid on the solution. Allowing more than sufficient equilibrium times, this phenomenon of precipitation at constant pH did not occur with the heteropolymer acid. Now, from our def- inition of the primary disassociation constant (26) of the heteropolymer acid we have: (34)_3g__ g IHMA-l = 10'4-2 . 10’2=1:1oo [H‘l [32m] 10‘2 '2 Thus we may consider that on a probability basis only one out of every hundred carboxyls in the heteropolymer can be ionized when precipitation initial- ly occurs. If we disregard a prOportionality factor dependent on chain length and consider for the purposes of this discussion that it takes one ionized carboxyl ~176- per polymer molecule to hold that molecule in solution, it is obvious that on a probability distribution of ionized carboxyls that more of the smaller polymer molecules would tend to be in the uncharged portion that tends to precipitate. Thus the smaller polymer molecules would tend to precipitate first and it may be estimated on the basis of the above calculated ratio that the approximate molecular weight of the fraction of polymer molecules that first precipitate is 100 ° (m.wt. of unit or 200) : 20,000. If total precipitation is considered to be affected at a pH of 1.5 a similar calculation gives the approximate molecular weight of the finally precipitated fraction i.e. the very last portion to precipitate as 40,000. In this regard, it is interesting to note that Bartlett and NozackiZl have determined the molecular weight of the copolymer allyl acetate-maleic anhydride as produced by benzoyl peroxide catalysis as averafing 40,000. The COpolymer is similar in nature to the one of this paper in that it tends to a 1:1 molar ratio of copolymer composition. Future work may show exact correlation between molecular fractions precipitated at various pH's and their molecular weight. It may also provide a method of molecular fractionation of carboxyl-containing high polymers and shed light on the general theory of electrolytes. l. -177- CONCLUSIONS The rate of c0polymerization of a 1:1 molar ratio of maleic anhydride and styrene in re- fluxing benzene when catalyzed by .495% (of monomer weight) benzoyl peroxide is first order with respect to styrene, maleic anhydride or a homOpolymerizing "radical-ion" complex where k : Q? - 10'4 sec'l. The copolymerizations can be duplicated. Half the carboxyls of the free acid heterOpolymer are neutralized at a pH of 6.25. Thus phenol- phthalein is an unreliable indicator for neutra- lization whereas brom cresol purple gives a stoichiometric approximation of 2%%. A quantitative analytical method for COpolymer com osition is pro- vided by potentiometric titration. Mono esters of heterOpolymer acids can be easily formed by addition of primary alcohols to the heterOpolymer anhydride in acetone solvent. Thus anhydrous potentiometric titrations with methanolic NaOH provide a good analytical method of determining the maleic anhydride content of the copolymer. The heterOpolymer acid conforms to the Henderson- Hasselbalch ezuation: pH = pK - log .l_i§; ‘Niflfl no slope other than unity being necessary to introduce into the linear equation. 5. -178- The theoretical predictions of Hall and the data of Alfrey and Levin on COpolymer composition resulting from different molar ratios of reactants are confirmed. A 1:1 (m.a.: styrene) molar ratio of reactants yield a .89:1 heterOpolymer molar composition; a 1:5 ratio yield a .85:1 polymer; and 5:1 ratio yields a .98:1 polymer. The heterOpolymenaprepared from a 1:1 and a 1:5 molar ratio of reactants (m.a.: styrene) give titration curves and pKl value (4.18) coincidental with succinic acid, one of the recurring units of the copolymer. Heteropolymers formed from increas- ing amounts of maleic anhydride tend to have higher pKl values viz: The product of a 5:1 (m.a.:styrene) molar ratio of reactants has a pKl of 4.4. Heteropolymer acid with greater number of maleic acid units comoosition has less acidic prOperties than a mixture of a heterOpolymer composed of a lesser number of such units and pure maleic acid. Secondary carboxyls of the heteropolymer are very weak acids and their salts readily hydrolizable. There is no inflection point in the titration curve of the secondary carboxyl. The pH of initial precipitation of the acid hetero- polymer is 2.2. On the basis of a theoretical develop- ment, the approximate molecular weight of the portion precipitating at a pH of 2.2 is predicted to be 20,000. -179- LITERATURE CITED 1. Wagner-Jauregg,T., Ber., 65, 5215 (1950). 2. Voss,A. and Dickhauser E. German patents: 540,101 (1950); 44,566 (1952) 0.4., 26 1815 ( 952). British—Patent 5(6,479 (1951) U.S. Patent 2,047,598 (1956). li—‘Ulu 5. Arnold, H.W., Brubaker, M.M. and Dorough,G.L., U.S. Patent 2,500,556 (1942). . 2.1. du Pont, British Patent 549,682 (1942). .. Cerhart, H.L., U.S. Patent 2,297,551 (1945). 4 5 6. Van Nelsen, U.S. Patent 2,297,059 (1945). 7. Swan,D.R., U.S. Patent 2,299,189 (1945). 8 o StOOpSfl‘Yel 0 81171 1381118011, 1../01“.. , U.S. Patent 2.594,74O (1944). 9. D'alelio, G., U.S. Patent 2,540,110 (1944). 10. Halbig,P., Matthias,F. and Treibs A., U.S. Patent 2,544,065 (1944). 11. Wall,F.T., J. Am. Chem. Soc., 65, 1862 (1941). 12. Mayo, F.R., and Lewis, F.M., J. Am. Chem. Soc., 66, 1594 (1944). 15. Norrish, R.G.W., and Brookman, E.F., Proc. Roy. Soc., (London) 171A, 147 (1959). 14. Wall,F.T., J. Am. Chem. Soc., 66, 2050 (1944). 15. Lewis, F.M., Walling,C., et al, J. Am. Chem. Soc; 19, 1519 (1948). 16. Mayo, F.R., Lewis, F.M., and Walling,c., J. Am. Chem. Soc. 19, 1529 (1948). 1'70 Le‘flis’ FOB-’10, and 1119370, FoRo, J0.Amo Chem. SOC. :72, 1555 (1948). 18. Walling,C., Briggs, E.R., Wolfstirn,K.B. and Mayo, F.R., J.Am.Chem. Soc. 29, 1557 (1948). 19. Lewis, F.M., and Nayo,F.R. Ind. Eng. Chem.,Ana1.Ed. 11, 154 (1945) -180- 20. Walling,0., Seymour,D. and ”olfstirn ,K. B., 21. Bartlett,P.D., and Nozacci, K., OJ. Am. Chem. 22. Alfrey,T., and Levin ,E., J. Am. Chem. Soc., 67, 2044 (1945). 25. Ha tchalsky, A., and Spitni k ,P., J. Poly Sci, II, 452 (1947). 24. D'Alelio, G. F. "Experimente l Plastics 8: Synthetic Resins" J. Uiley 8 Sons, Inc. N.Y. 1945 Expt. 66, Part B, Pg 115,(1945) 25. Guile ,R.L., and Huston, R. C., "Revis sed Lab. Manual of Synthetic Plastics and Hesinous Materials" 1944, Expt. 44, Pg 94 26. Morgan, H.D., B.S. Thesis, Michigan State College (1945) 27. Uhlrig,K., and Levin ,H., Ind. Eng. Chem., Ana1.Ed., 15,90 (1941). 28. Simonds, H.R. and Ellis,C., "Handbook of Plastics" D.Van Nostrand 00., Inc., N. Y. (1945) pg. 742-755. 29. Staudinger, H. and Hauer, 1., "Die Hochmolehularen Organischen Verbindungen", Springer, Berlin 192 2 p. 1179. 50. Yang, P.T., M.S. Thesis, Michigan State College (19. 51. Mihina,J.S., M.S. Thesis, Michigan State College (1 4 ) 52. Moran,M.K., and Siegel, E.F., J. Am. Chem. Soc. E9, 1457 (1947). c. 615% 21 QM vow-"V ABSTRACT 1 (“Y-4151 51m Application of the method of continuous variations to benzene solutions of para substituted styrenes with maleic anhydride proves the formation of a 1:1 complex, heretofore surmised, and indicates further interaction of the complex with styrene in at least two observable cases (p-chlorostyrene and styrene). \ Generally applicable methods have been developed to prove the simultaneous existence and composition of several complexes in solution when the method of continuous variations fails. These methods have been applied. Constants have been evaluated on the basis of these theories allowing the prediction of the Optical density of such complexes at all wave lengths (com- plexes of maleic anhydride with styrene, p-chloro- styrene, p-methylstyrene, p-methoxystyrene and p-di- methylaminostyrene. True equilibrium and Beer's law have been demon- strated for the instantaneous formation of the complexes. Comparison of solutions of the same concentration in the substituted styrene and anhydride to spectrOphoto- metrically compare complex stability is not warranted. The kinetics of the interaction of p-dimethylamino- styrene and p-methoxystyrene with maleic anhydride have been studied and interpreted. It has been shown that other complexes are formed. The observed kinetics have been correlated with structure and alternating tendencies in copolymerization. ‘ "35‘11 c') " (’7' 4 r AJO "10 4113 K" 1 34555651. T541 206049 G25 » Garrett Studies on the ‘ 1a 4' w 7% ) reterOpolymer: taler 5 anhydride-styrene. 31293 024L\6