711' *1” ‘r‘H WNW \ L 1 I“ 137 108 HTHS THE EFFECT OF MECHANICAL AGITATION ON THE EMULSION POLYMERIZATION OF STYRENE CA?ALYZED BY POTASSWM PERSULFATE Thesis far m Degree 9% M. S. :‘ViECHiGAN STATE CG‘LLEGE S. R. Simmmaskhfim W49 L1 This is to certify that the thesis entitled 'Iffect of lechanical Agitation on the lmulsion Polymerization of Styreno' presented by S. R. Shunmukhan has been accepted towards fulfillment of the requirements for H.S. , Chemistry degree m JWQ/M Major professor Date “a! 27. 19"‘9 0-169 THE EFFECT OF MECHANICALEAGITAUION ON THE EMUESION POLYMEHIZAUION OF'STYRENE OATALYZED BY POTASSIUM PERSULFATE By s. R. SHUNMUKHAM A THESIS 'SUBMITTED TO THE GRADUATE SCHOOL OF MICHIGAN STATE COLLEGE OF AGRICULTURE AND APPUIED SOIENCEIIN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE 0F MASTER OF SCIENCE DEPARTMENT OF CHEMISTRY I949) T547. ,1? 5 56 Z gfi‘ - ‘.Y""."'T 7‘T1’LT-"T’m ‘Q“‘¢L‘IV Ail—lfif...’ vu.‘.- 1,. .l h - -. ,- 7-: :- r.‘Tt ‘ Vt? -‘ z- . 1 .r‘ ;He WTLtur m_shes to dpuhouleube his doe; appreciation and gratitude to Doctor Ralph L. Guile for his suggestions and "uidance in the planning and devolOpmert o [‘5 cf- :T' I‘"” U] prcject. I") - 17989 .lti.--- "‘ \vw‘fi‘ «taxi-t '. '0 \ , ‘ I ,3 Pages L4 l~rm*fl-T~rfir'~-1-r~' it--. v__..._\.‘ (.1 fr . s A, . <« " 1* "l , 9‘3“ 5“": ’y " ' ‘ ’. r ‘Lfi. ' 1“ r‘ u; Lam}; factors 3612.13.01]? exiiinion 1019.331 .2: _.-;« z: 0.» at 3x») 110. have been there}: '31?“ :LJ an} (5::‘30 asive drzfia are 3V1“? 13.1336: concerning ’ ”n ‘ I" ' ’1. (- n "" . " \~!“I', 4 T , I’ The effect 0; ma hinical a itatiOJ on the e vision “AW’HEF‘_a (“l- rJ. O .‘ r. v ' A - -"~ :- -""1;-“ . . fl ‘r f‘ ' D r. “L '2" has been KICJITlOI'luCI Irm. not SI."_»'.Il.C‘Co It) lacs- 0:. .nortnati on about ohm -. 1 .1 1,-- n "in. - - -..-‘ n- 5:9 VaTlv.tl3.;e, 7-4:, :.as 1 e "u “flange? I :I :1 Jam CPI.»;-..~:1 L'f U._L_L"‘ PM .w‘ .., M. : run: ,1; h .L\,rC/.Jtl {-(Jr;nk.‘i.) ”14.4.-- “.0 .4-..“ or Il‘pallini‘ JI-LeSSO . h uv 1 . I' ~ ,- 4- -' ~v- +1- A .- . "’ ~ ‘4- 1 .1... This. 1.01 k 18 an attezsgw to she»: ossiI : 1.9.1 01 mice 0 ita'tiozz in the ex.“ 1111011 polymerization —l -..c led type and, rate C?" Ir;;e<:‘:iz3.1":irra]. a field. \\ ITS” RI CAL «Ld-v - The polymerization of styrene was first observed in 1839 and since that time its polymerization has been studied more extensively than any other single monomer. Today, styrene is still one of the most MI nortant monomers and polystyrene in various forms, as well as the copolymers of styrene are of wide commercial importance. Extensive literature exists on polymerization of styrene in bulk and in solution by light, neat, and other catalysts. I ‘ In 1915 a patent by Til-:entscher1 described for the first time a meth— od of polymerizi.ng uns at rated monomers neon 5115;31 :ded in aqueous emulsion. This method, d e +0 certai; features, namely the ease of temge'ature con- trol, the hi.h molecular weirhrc of the products formed, and the introduc— tion of a namser of new cortrolling factors in the polymeric' ation reaction, became of widespread use in the production of polymers. Emulsim npolymeri zation d c to the heterogenity of the system and the many variables affecting rate and molecular weight of the polymers formed presents a complex problem. Extensive work has been carried out on the process y corms rcial concerns in the production.of usrketatle products. Considerable theoretical and experimental work has also been D reported but many of the variacle s that affect the reaction have only been mentioned. It still remains impossible to predict the reac ion rat and molecular weights of the polymers from system.to system or within a given system when one of the many variables is changei. T 02 ' f o 1 o Earx and Rafi give a list of ingreoients necess for the emulsion polymerization as: Basic phase or emulsion medium, the main nor orer, additional monomers, cmnlsif 31h: agent or agerts, stabilizer, refltatcr of surface tension, catalyst, chain regulator. The more important of those are none nor, catalyst and emulsifying agent. [\J The catalysts in emulsion )— 1h'fi~,$-n.\ rsl‘X‘L . ' f~ rm, fiw’l'j 1"? ? J ‘r‘\ erc 4‘ a 1| - J.’ v 1.1!. 1.....',-‘;. (13.01,). -'.-_ U U~D‘«;i.i.-‘_;’ 0'. [2.19 dd. v-1 soluble type such as hydro; en peioxide or salts of the peraeids. Of the latter type potassiur: persulfate is most " idel y used. Price and Ho: cff3 have shown that the rate of polymerization is deve1dort on the sqlare root of the pe rsxlfate concentration and that the concertra tion of 1eisulLat decreasts le jn1;ly toriards the end of the _ . t . _ reaction, but the mecha raism of the deco:t1pos ition of the persulfate catalyst and its cort1r1|1on with the monomer to produce an active nu clEs in an emulsion polymerization is not clearly understood. The emulsif3 in3 agents are usually soaps or sulfonated aliphatic alcohols. The polymers formed can he coagulated hy ttc nonsolvents 51ch as alcohol, ether, etc. 1 L. .J- ° 1'. . h .. .. S -. V. v. 4.1...» v. r .oaenstein, main and ccllaho1atozs’ :epolted ULQV emulsion pcl3'meri» zation of styrene takes place in the aqueous phase. If a layer of sty— rene, approximately 1 e.m. think is placed in a test tube on the top of a dilute potassium persulfate or hydrogen peroxide solution and allowed to star d for several days, the aqueous jnase slowly becomes cloudy. Substances more soluble in water such as, methacrylic esters, vinyl— acetate etc., cause cloudi n-ss more rapidly. These fae+ s indicate that the polymerization takes place in the aqueous phase. Active centers pro- duced by the interaction of the monomer and the potassium pcrsulfate catalyst in water, can gron'in the aqueous phase without being in dir»ct contact with the liquid monomer. In lth, Vinogard and his collaborators6 ohserved the behavior of small dre1lets of styrene in the aqueou us solution of peroxides under the microscope. They found that the radius of these glotules decreases 7 roughly in proportion to the time of imnsmr ion and that further the poly- 3 mer in the absence of soap is slo ml forged in the aqueous phase outside of the droplet If soae solati ons are used instead of pare tater this situation 7 C \ C0 8...! 3 F04 H) H. O 9 C+ '._.J <4 Iyling and Harrington reported that acryloni— trile polymerizes rapidly if it is in direct contact with water containing soap and catalyst 8 ale was that C) An important observation made, by Kolthoff, Povey and at a given xygen concentration the length of the induction perioe are the lisa~noarii,e of oxygen in the system is essentially independent of the soap concentration. This indicaiee that the acti atiou reaction dnring the inhibition period, tikes place prepofiierantly in the "truly" The extensive studie sof Harkins, KacRain and their collaborator39'13 on the sol 1b-lization 01° hydrocarbons in soap solutions in the absence and presence of jeroxidi_c initiators provided a great deal of clarifyinr information and helped to develop the present picture of the course of an emulsion polymerization. Hess ani his co orkers obtained a nuxr -er of remarkable diffraction oatterns from concentrated soap solutions, which indicate the presence lamellar micelles. In order to explain the accelerating influence of soap on the rate of the polymerization, it is now 1:3m1med that l1n Iellar *- \ J; A H O K \ I ‘43) ~33 s...) 0') mi: 31Jes not only exist in cone trated oap sol1tion but also in the dilute (lfi-Bfi) soap solutions. These micelles contain solubilized monomers and, because of the low soap to water ratio, are highly swollen with water. They permit, therefore, a free diffusion of water solible initiator. It: 8 thus concluded that these micelles are the pri-eipal c o o .17 3; 1:, 1001 for the formation of active centers.*"’1“fit/ {b As the activation energy of the initiation o; st'zsne in the emul- b sion polymeri: tion by potassium persultate was found to be 17,300 CIals.. er moleg’é’l6 "‘3 which is about 8,000 calories less than that in bulk or solutionp ml mieri sation, it is anioaren 1t ti: at the activation of the double bond by potassium persulfate inside of a soao nicelle re“ than in the bulk and solution “olvmwrirat‘on It is assumed that the orientation and polymeriz vati on of the monomer molecules within the soap micelles are (at least partly) responsible for this drop of activation enervv ari at tie same time resconsible for an increase in he average UV 0 '? VA A. ’ . V A . I‘- r- r". \. . " ‘p N “3‘“: ’1‘ degree 0; pOljm:llZaolOH by decrea31n5 the aCCessitilitf oi the arohins l7 chains for chain terminators. Rainard1 reported that there is a maximum ()0 to the interaction ‘etveen soap and pers 13m? e, and since the yield maxim.;i occnzs in approximately the sa me re'ion, he concluded that the reaction product of soap and persulfate is capable of initiating polymer- ization. In the emulsion polymerization, soap not only brings the mono- mer into the aqueous phase to establis sh a close contact with the activa- ting radical, but also stabilizes the latex to prevent olymer particles from coalescing. _::D J. The molecu Jar‘w hts of the polymer at different stages of the reaction is significant in tne study of mechanism and rate 0. reaction. The relation of rate of conversion to the avera a molecular ight was studied by Siggia, Hohenstein and iia r1: .5 It was found that the molecular weight of the 3013maer form,d, during the period immedia eJy after the te— 3inning of the p risition i comparatively low. This is due to the deactivation by inhibitor. FoJ_lowing the initi 11 phase, the molecular weiwht increases at a steady rate to reach a maximum. Finally the mole~ cular weight necrease s dn.e to a decrea se in monomer concentration and an chain breaking deeonposition prodic liny methods have been marl to det ermine the m"Jacular reichi of the llAu’_L..l Hg U'L oolymer, the most important bein 'Osmotic', 'Vi5(m minctric', 'Jltra- centrifugal', and 'Ti nt Scattc cring'. Use of any of tnese meth o_Js re— snlts in average molecxlar weights rather th n absolute values. The 'Viscosc Ml otric' ,tuci for reasons of simolicity of €113 :ient nd ocera- p tion is widely used. 11 Standinger develoried an expres sion for molecular W91 I I I I _ Viscositv which ha: rcnc; ilJ. been emoloyed in calculatinc average mole— the validitv U U) ,4. O cular'weiehts. Theie is a great deal of controversy at of the Standinser's equation and be nv correction factors h; ve been ap— I“ The average moleofll ar usicht of the polymer at any stage is fa rly 7+ (—4- "5‘ p cons t nt, a fee t has been e<~loinei bv Schulz as being due to a con— stant rat 50 of chain propa 3ations to chain terminations throncbou, the D 4.1 (" ' 21 4.1 1 course Oi the >ol"*eriiation. omlth * has shown shat the average molecu— la" weight of a polymer is related to the ratio of monomer to regulator. 1 This I a. Emulsion polymerisatiors generally have an induction LCTiQ is the interval during which the activated monomers are reacting with components in the system until the latter are Six mantially neutralized. After that, the chain propa3ation reaction becomes the ma; or re :.ction. One type of inhibition is due to tab is traces of st1.:il~ izcr sleft in the monomer. Then the emulsion is agitated these stabil— Ho zers in the monomer diffuse into the aqueous phase and react with the 2o oo o! . “)‘JJ'L activated monomers. m his goes on until their concentration (stain ml zers) reaches a low value, after nhicht he formation of long .0 I chain polymers basins. The rate 0“ polymerization increases as the in- Another type of inhibition is due to traces of orvcen.“/ .. . O . F.) Vinowarc, -rilettc,16 and P'nHeL-i3 h(ve p01 inted out that the excli- m1 J. ’. sion of oxygen reduces an induction ceriod. iOiDhlbitiOD period is th time necessary to Foild u: a concentration of active nuclei sufficient .,‘°1 r ..,. 4.. - ,+° to BStubllSfl a steely-soate raoicdl concentration. 9 '5 .:. .t .. . . ,4. . .-- a: i .‘4. ,.. . o - . :reitegkioh‘7 polymeligel styrene uoins a ni.ro;en atmoskqere to prevent oxygen inhibition, and in this laboratory use of a nitP03en at- .L mosphere, or lacm of oxygen, has been found essential for the d glica ion P . . Oi resglts. Lfl‘f‘f )I ‘fflk J4-.--J'.l l—J‘:[$’L R.Oa~\(3‘ 11+ (.0 l . S tyreue 2. Pot as si_nfl :ers :lfate 3. Hvdr 0 en peroxifle h. "Jolloidal" iodine 7. “133001—3: 8. L‘thanol (95 ) n _ ' ‘r‘l ' .3 9. al:.in1m Ciioriae Styrene: The stvrene was obtained from Dow Chemical Company. It was purified hy vacuum distillation from a three—neck flask with ground glass joints under a nitrogen atmosphere,a afte rthe air in the distilla— .4. ion flfjk had been re ..... ovei ty flvs“‘n' the system'w;th nitro en Thejka;tion boiling at hBOC/l m.m. and havih n3 an index of refraction of 1.3;20r as used. The styrene was used immediately or stored under an atmosohere of nitrogen gas in a refrigerator for no longer than a week tefore use. Potassium persulfate: The gotassium persulfate used as a catalyst was Herck C. P. grade, which was rec z'ystallised from water and the same lot of recrystallized material was used throu3hout this work. Hydrogen peroxide: Hydrogen peroxide used was Baker and Adamson C. P. grade. "Colloidal" iodih me: The catalyst "Colloidal" iodine was 1repared by ‘1 dissolvin3 l 31. of iodine crystals in 20 ml. of aqueous sou ium hvdrox ide solution containing 0.36 gm. of the alkaii and the sodium hydroxide was cu . . - . . . then naetralised to litmus by 563 hydrochloric sold. The solution was made up to the mark in a 100 ml. volumetric flask. _ o ‘ t ‘ “'9 'f‘ T‘ 1’ -~ ~ cm - n Clodiurn hisultite: o. r. 3rade W33 used. " N f j "' (r ' 'L V‘ H 1‘ “ A .V ‘, Avvg. 1" “n. c~ -‘. 1' 4‘ r fifi Larsaptan: Dooecml Lercanoan from thfpltg Cneuleii Co fiaLJo Grale )5. Dujonol—G: The Diponol-G used as an emulsifying a ant was a sulfonated derivative of lauryl alcohol nroduCed by Du Pont Company. Ethanol: The ethanol used to coagulate tie polymer‘was commercial 953 grade. 1 Aluminum chloride: The aluminum caloride used to coagulate the oolvmer was a technical grade. wa+er1 All water used was distilled under a nitrogen atmosohere from an . alkaline permanganate solution as follows: Fifty ml. of alkaline potas- sium perman3anate solution (300 gm. potassium hydroxide, 8 3m. potassium permanganate per liter of solution) and 2300 ml. of distilled water wer refluxed under a nitr03en athsphere for 30 minutes. The wnter'was then distilled under a nitrogen atmosghere, the first 200 ml. distarded and the freshly distilled water collected was kept under a nitrogen atmosphere until used. T‘ ~ "T‘V‘A‘q'fi‘ m ' quLI—lu: 1-1.; The c"»er;nxr1al emulsion polymerizations were carried out in a four 13‘ neck: flask, eqm L,tpted wit glass joints. Lhe flask was fitted with a 9 p1 G) c f' thermometer, a nitrogen i tube, a vacuum samrl r, and a mercury sealed I" :4 stirrer operated by a var Te speed motor. The fl ask was immersed in a constant temperature water bath kept at LOOC t 1.000. The same stirrer ) flask, and fittings were used throufkout these eruer1m-nts. The nitrogen used in these eXferi m s was cylinder nitrogen, nassei through two 503 ml. bottles conta'ning 5% solution of fwyr :allic acid in "I o 0 . l e lOt aqueous notasSium hydra Mid , to rem ve traces of oxygen. Tne gas was passed into the reacti on flask ahove the polymerizing reaction The latter part of the experiments were cari ied out in a ceppm tank constant temperature water be h {opt rt LOOC t 1.00C. A rocking motor was used to shake the reaction hottle under water. The speed of shaki was also adjustable. The reaction fleck was a ASO ml. bottle having a pharmaceutical rubber closure. The polymerization in the reaction bottle was car; ied out uno ler a nitrogen airosoher and samples were taken out by means of a hVT oderzric syrin3e through the ruhher closure. A Cannon - I‘enske - Ostwald viscosity pipette was use dto deter mine the spec cific viscosity of 311M101 mer solution PlQCED 17.35 Part I The Effect 0 Stirring on the Emillsion rolrreriuation of Styrene under a nitro en Atmosphere Catalyzed by Potassium Pe walfate Experiment 1 m1 -ne reac ction Is lash was flusied with purified nitrogen "a To the f L. U} . o o . reaction flask imner:e in a water bath at LG C t 1.0 C were added 51X cenated and distilled 1m ter and 6.h 3m. ‘0 hlndred a1d forty ml. of deoziy of Duponol—G. The contents were stirred by the mechanical stirrer until the tem- perature of the mixture in the reaction flask was hOOC f 1.000. The stirrine was continued and 0.178 gm. of potassium hers; lfate was added. fter five minutes 80 grams of styrene were added and the time of addition was recorded. The stirring F15 COflllled for another five minutes to com— plete the emulsion and then discontinue-d. In the so called"non—stirred" reactions stirring was always discontinued at this point but in studying stirred systems it was maintained throu3ho‘t t e reaction at a consta.r1t rate. The beginning of the polymerization was determined by vacuum samiling very smalla iolnts of the reaction mi"t11re int alcohol every'ten minutes. Is soon as a cloudiness was obse-¢ed, the reaction mixture was vacuum sempled at kioxn time intervals into orev501sly wei3hed (13m.) asleimcyer flasks cont.1n1n 50 m1. of 95$ alcohol and 0.001 5“. of aluminum chlori , . The amount of samole was determined by weight dif- ference and sahgline was continued until the reaction was nearly comnlet . .J r1 inc olvrcr in e: eh sa ole was coagulated by the addition of three times the sa1w11e 01 use of 95% ethyl alcohol. The precipitated mixture was centrif uged and the clear s eruataat 11 .4 J. ‘ ' ""lL 111d V.as r1mo"ei hy dec anta- 'r1s with alcohol to renove traces 0) $1) C1 0 a. 31 o a o 5.. *4 C‘- r.) "3 tion. The oolyner wa J. l 9 o o I O“ ‘ .' . of ennlSifier and then dried in a drVin: room at 100 r. Tne cried L rolymor was weighed and the percentage polymerization (percent polymer formed) was calculated as follows: S polymerization = 100 x Weight of Polymer in Samjle x Height of Sa:;le Total tight 0 :i Lt of ”tvreu: Ysed \J 0 Experiment 2 The reaction was carried out under the same conditions and in a manner identical with that used in experiment 1 with the excegtion that the reaction was stirred at a rate of 360 revolutions per minute through- out the entire polymerization. Egmfimmfij This experiment was carried out under the sane conditions and in a manner identical with that used in experiment 1 with the exception that the reaction was stirred at a rate of 720 revolutions per minute through— out the entire polymerization. (‘1; Duplicates T"ere carried out for experiments 1 and 2. Part II The Fffect of Snazing on the Emulsion Polymerization under Nitrogen Atmosphere of Styrene Catalyzed by Potassium Persul fate \ xperiment h To the reaction tottle (3 DEC ml. bottle having a pharmaceutical rubber closure) were added 320 ml of deoxygenated distilled v.ai:er, 3.2 gm. of Duponol-G and 0. 09 gm. of potassium pe rsulfate. Deoxygenated nitrogen gas was bubbled throu3h the reaction w mt re and then hO gm. of styrene were added while the buthling of nitre3en through the reaction mixture was continued. The. the bottle was quickly closed and the time recorded. 139 reaction fla.s x was immediately placed in the shaker m011nted in the copper tar_< constant tenderature water bath kept at hOOC and shaken at a rate of SO shakes per minute. A similar sampling technique to that described in experin ment 1 wa employed for all bottle experiments except that sarplin through the rubber closure. It was necessary'to step too shakin? aid remove the bottle durin Htle time necessary for sampling. The so called 'hon—shaked'reactions were sometimes carried out for convenience in the H CO reaction flask do cribed in experiment 1. In this ase stirriig wa used to prepare the emulsion but stirring was discontinued within five minute0 after addingt h styrene. When a bottle technique was employed the bottle was shaken vi3orously for five minu+es after adding the sty- re.e in order to prepare a suitable emulsion of the monoaer in the aque- us phase. hwtzr nfi1iY‘ ATW4 Q .m» . . - . . I“ “L ‘. ‘I “ . 4" -"3‘ ‘9 4". ' ~¢ ."’ ‘L' ' ‘ . ‘L. A polymerization redoulon was carried out nesyin3 all the coneitions r ‘. -- .1: ‘ . F 7‘ ‘ “ ‘- . » I'V‘ . f" ‘ the same as in exieiiment h ezcflyt the rate of shaming mas increased to ' I BIO sha .:es oer minute. - EK5e1dmmuzt A polymerization reaction was carried out under the same conditions L. used in ergerimcnt L eteegt the rate of shaking was 600 shahes per min- Duplicates were carried out for experiments h and S. "N *- 1 ‘ ~_‘ 5 f” h‘_' -. 1 in 3 W. I 3 a r tart ll: Tue Eipect oi aha 1n3 on the WmdjolOn ulv~ow1~ation unle“ a "'4. , ' a s..- ._ 0 m4» ,. '1 J. \‘v .. ad b- ‘-\-.,4 ~33 «t_. T .3: nitrogen afih081“:19 oi ~tgrele nat1433u y a 3: ex DJF»H$ - iodine- g 223e1riment 7 A polymerisation Tar attem ted iiwrer s milur conditions (not stigrztmi) 1:9 e=:‘_rir;e rfi. l irit ve_th {lie '70?" :si‘;m “v3r37ilf'i‘3 re:laced by 0.091 3 ":olloidal” ioiin? w .- '1 7., 'er' .. iv.“ ., .-_,q “9+ “0 gerymoriu: o11.h o se'xcu a- er 0) L6 hours so the attempt to — -~ -: -,- - - ‘4 . r3 . . v a war . . uolrmerize under tLGSQ convitions has discortinced. J. is -,,, exoeriment 3 A I a O [_ ‘.‘\ 7 VV «‘5‘ )4- ‘f‘fi fl " 1 .3 - Ojkdrn.'.nl ‘ .1 . ‘.—.OIa xr‘) . V3-1 at; . .’ ' n4- . as caiiied a.“ ander Similar conditions to ex- perinent 7 tut with 3.00 I sod'um bisulfite in addition to 0.301 X 1“! y _I' Q L... I ma, l— J-laln e . 4..L~'_v.1 ’ / L' A rolymerivation TV“S cariied out under similsr C“ ‘itions to e: C 1 periment 3 except that the bottle technique was employed and the reaction hottle was shahen at the rate of 3L0 shakes oer minute. ....' .- 1 n ( "f‘ir': ‘n- A 5r a t O r,‘ 1: ('VO’ ' Part IV The F”feet of Shikir: on tLe :mtlsion LOlymGliidthJ of St A u .T. ‘ «wr‘ A . 1 ‘v r‘ r V T h ’ ‘- ‘ . —‘ ‘ ‘1 n" . 4' ’ under h1t10¢ch $tmOQ3AGT€ Catalyzed by lotassinm iersaiiete and in the _ L. ' m ‘ an. ~,n- T.’ .rv--. q Freewhee of a Cuiin iransfvr “bent - Dede 31 “eradyteh A pol"meri:ation reaction similar to exgeriment l was carried out except that it contaired 0.001 K dodecyl mercegten. Experiment 11 A POIYWGFJHfltion was carried out under similar COWditions to ex- periment 10 except that the bottle tsehniQue was employed and the reaction bottle was shaken at the rate of 3h0 shakes ger minute. Part V The Effect of Oxygen on the Emulsion Folynerigstion of Suvrene A polymerization reaction similar to experiment 1 was carried out but a nitrogen atm sphere was used only for the first three hours and then an oxygen atmosphere was used for the rest of the reaction. Experiment 13 "\ “~ 1. y-'. ‘1. ~] .‘L . fi- . i ‘. .' .W\ s 1‘ -‘ fl 1 \' ~~ n polyreiisstion leaction similar to eAQeriient 1 nos eeziied Out )3; but 0.001 R hy.rogen eroxide was used in addition to the 0.001 K potas- (7 é . \r‘ ~~ {‘1‘ Slum tersnliete. Part VI svera3e Ho1eculer Uei3ht Determinations m‘ ' ’ v ‘~ ‘ " ‘ I . " “ V' ‘ , ' :1 "" ‘ ' . ‘ V lee average HUlGCH1dF we1511tsof tne psirwoc tore detenuined hf Into 100 m1. volumetric tiasss were placed 0.10 gm. of polystyrene Slfljlfiu. Ten mi11i 1i ers of toluen: were add d to these flasks xfiiee 1 (~lo3) overr1"ot to di 1336 17s the “Olymers. V O 4 were placed in a hot roo. y 4- , ,. x m ,1. '3 On .... s. " 4.4 .. "H: 3 Then one flas s tore cooled to 10 u and she SOLUULONS s :e neue UP to the mark by aiiinr more toluene Ten ii11iliters of the solutions were ransfsrreu int: {he Vizrcri‘* Sifstio 12‘ ghe efflux time of the solutions megsirod at 2003. In a :.fi:l‘" fashion the :fflzx tive of tge solJeot was else de— térniuei. The average molecular wei3ht: ane c11231Mfl from Staui nger's 1" ~ I“ .- 7"} O a. - A! I’m v A 0' PI :3 H [.4 O ( P Cm : molar concentration of the oolvstyrele hareu on a recurriz- 5rou — 10h. L) - Time of r - m a p ei so1n+ion at 2093 -i;ne: o; e r)? - - ,. r3 _f‘~ ux of solvent at ¢0~C t“) "‘3 The average molecular weights of the polymer samples were also . - . or a cal ulsted fing th Kemp and :eter‘s 0*u1tion.~99JO ~ ~3 rP:-~¢‘ -- Dr r - --~ -.‘ - . v~ »- ,' . e mole<2u1ar TW—a»uts here Jutufmlflcd on 111 si H‘chafit sanoles ,t H... H: ,, e 1.,.,, -V, -~, . ., , from the var1.ous GJdlafljfl sretu s livesti5 ted and the O *1 (D U) >_ “J (+ (.0 (4- T {in 3..) C ,re determined on solvnor solutions ‘ U _v _‘ f) O I~" "'3 VJ. C) 1 s *4. (O C) U L.) l...)- 1'!" .:_’. C. L ‘4 «4 T) h . - . . - L 4,. ,, rm- . .0 orent concentrauions for some dexléso A olot 01 s .. ..—-L r .' .. :- 4. :4 L 9..- m . aiust CancengJ-LOQS site; a stra;;0t line one interee t (1' .3‘ (D H' :3 f‘ "5 Ho :3 1’) H. C) (j H. U) C) O L. ’4 O f the gclymer. (Graph V) =ie Viscositie of several polymer samples were cenerninod ‘5...tl\lll-’l1!ll i 1| (to -‘Iti'zll"u‘ a. III: .p . I|..:‘.(llvn“‘1. \f’!!!’ I. . :- nn-OI . 1. |V,.¢1|I IIIVO(‘vE I ‘.I\OU....1~1I}§1£ .P".I l“ . C mmkbxiz 2. wwfk 00$ 005 300 com 003 00m ooN 00H r n- i;l;n| l .1“! -it l||illrll-l----||l!l1|.|z.ll||.lt I..!L.‘|||i--ll|ll|.l.. 19-1:317 _ _ C O \\I\III0 \o \\.. \. g \o \\ o..\ . o .3. \\ \u .7 I \ O O 6 \o .o...\\\ \ M \ fi : . .\ \\ . M. 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KN w 3:339 C: «00.3 39: 33$ 5. .mumrmfiu I .7763 0.23% .380on xwwfil ./\- E001310n PQlJmeladL;OU 0; otVTgDC O \ltv', 670,000 ‘ la, ‘3 ’f‘ trv' t 100. -‘l L "at“ 5‘, I“ 0 . 1 0.097 X ' I. 1‘ T" "'4- 'XVO ..‘0 Nil. 1di1fier K”;3 SKA 7-1-1 000 210,000 ,000 319,000 139,00. I v h00,000 330,000 #09 gnn F, I. .2 \p ( 0 Q .‘.) L-J \ T“ .L.’ ujliéate (Tonfi.) Polymcrization «.4 7) 63 AV . ‘. r -... ~nncific “3 *"'1ors: Yak: of st1rr1*: 360 flux/win. Ismaining confiitions were the safe as in atfirmwmyl. 'Tiunu I‘0?;*.r ‘1'31tu 0:1 :LV. 7?. :t. in‘trt) Q Sfaldffignr Kemp and Peter 120 3 233 13 LI,QOO EL? 20 233,0L0 2T 33 2L0,003 325 L3 337,??? 235,000 C) ’1 0\ LA) C9L,000 212,000 / J2" O\ O C ‘J L) \ r l i) 5.4 x. ‘3 ~29 k.) \J'L \ L 11 'r--' O < ‘0 \ 0 k») U a b) 3 \O ,7 ‘0 \a L) Q 5 J (D Q L) )1 ‘1) \J) ha 'A 3 ~§ x.-__. .-., . -.‘. . ’. I.-. . , . . .' \ $1.. 3.1:. ., -.’_' ‘.._,_... .-/ Iv ' QKJ —' ~ JV‘, 6n ‘2 . .. ’1 1"." W" H—‘v' .‘ A] 1"?) “5:1 Tlnhjjdxx‘r) , “a".iT-" u;.)q-u.‘_ V- 5;;gg 1h;g groi1ww figs a stiflg 3* f‘e Cffcct Of mCCLJCijgl agiiu on fie C1113'3; Ciyws‘ii'+;:n OT S‘;ICCC a stun? vi 305 o; nrfli iCI 5311 ii :fl 13"1'”’ * “V ‘.:.L C 2 "1“ 0: ‘1?“'C ‘ L“““U;;19‘q* ‘“17r3751 3+: szfifisv1 1‘0 Only ‘HC *fju a-” ~'+‘ CT 1:35 “‘17 LgiiuiiCW was varicw Crd thfii a- inflicgtcj. TZC 51117 t“ Coniifi on: WCCC ? WLLCC “C*C“C“ “"“D (9 : a ““TOTLL“W“ijtmiflgi’:ffitj 2:C7t D.jor03—3 l: CJ'“”“*““*~”P ‘asod CC 1?? 'CICOHU 3K 1%,CT‘CJyst (Potassium rCrsulf:flc) at a Concentrati Cf P.C31 N C3594 3? the C;“acvs :2139, a nit*o:an et4mr “Fro, 13' the of fiCCYfgliiirf EAL“? ani xcnut‘r. 1h Sui-‘“d rC'cfion 1? :13C r 1.735 (a ilcgwaw {LP‘Qvgjuadt ’-17 +319 =Ci_crfixreri: . TC" EEC C7 C of CCnrénfche C? iis‘u-:1cr uhO Charact :1sLics O the ’mu_lsion polymeriz 7atio“ that have seen snnwn to TC aiiucth are C sificd 33%110m7: T. T‘s -1230f10fl pCrioi 2. ”5C CVCC1I? PSiO Cf Cénvorsinv Cf nahcmcr iwio folymcr CC? C tiwn. 3. TYI? tiflill ERICLII’ <3f fif‘ IW“:‘ C :uFrC3; 'tC-. 5:110 IQCZICH‘*' at, fkc: CL yletion of the polJmCri 1on r action. h. The intrirm ic visc»sity of the ”ClymCr sclufiicn. S. The CKCV‘"C "‘O'Lle'“C wei.‘kt of VhC jolywer. l. The induétion Cerioi: It 01C 19 seen £20m gr7Jh I 313% i“g ,1.110“ Lerior without stirring in 51wost "9C0. 1751.111 the reaction is "firm“; at the: r313 01" «1’3 “‘1’0311113 3-1 rfihwfig, the ivducticn p3r:?oi is i11crca5Cl to 2 h011r151Lq w.cn tFC r: i“':TC 720 revolL.t ions Cor miLl 0 .-. «I ,~‘. . ‘ -. a ~~r ‘. . Aw |~ yeiic1 is LLCerofi to 3 hullb. ltC, .7~.\. . )4— 7+ 1 “PC m7" W777Cr why't'e izid‘zction ceriod ‘\ . Awu '. n \ Q- - fi . - - . ' . ‘. ~ ' *\ I‘ - ' V‘" ‘ ‘u‘ 4‘7: . ," " ' ’v .P\ . 1‘ . ‘. rate of Stii W1 ' is ;rchaoci, inra - nan as there is a .reater 3o531u1] ty . - s.) V L ('9‘ I o o _ ‘ ‘1 ‘ ‘ A v ‘1‘ I '..‘ r., e n - 1_ _' of the collisions of activateo MQQONKT A.C]Gl 1'31nst the monomer CO molecule to tuild up long chain polymers. This effect may be due to two ..-. F eters. Tiret’" the "Li“rins acts to destr v or proverb fory;ation of active nuclei. Secondlv, when the rate of stirring is increased, the amownt 71° imr‘lr‘ t .2613 ' i ...-L I l 2. The CVCrall rate of conversion of monoser into polymer per unit V ‘ . . —. x“: «r- wnen tne rate of Stlillhg (“F LJ. F5 3 ca ’-3 (D ('1 H O *3 (D 0 f4) 7" IT .3 J J 1 13 p+o I“ J 3 b—S .‘ 0' (v 0 r- (3 C u the rate at which the moromer is converted i110 polyxer in this case is 1 m1 3 a . .. w 4. 1 . tnc slcaest. 1Jl> fact 8 .wests that the s H D '3 \ ) O (“f T ’7.) ‘3 do C O W O O 1.". a D ‘5 I ,1 F]. O :1“ 0 It 53 the fozna“ tion of active inclei and or— om:r into oolvme: decreases in stirred svstsms. The slooe of the curve, when the stirrinC rate is only 360 revolutions per minute, is greater w! "L than that when the stirring .ete is 720 revolutior ‘ sper minute. The ...14..: .. m. ' - .. ~ ~ ~ stigiiiq effect 1: sti ll noticeable but to a leesei thri The 513 C if the curve in tfi e C4se of non-stirred svstem is the Creates t of she three, which indie mt sthat the convrrsion of monomer into polymer per unit time is the 7r3atest in reaeifi ions carried owt with minimum amount of agi,ation. 3. The total anount of mcr ncl conrerted irto polymer at H“e coy- -~..4.- v - =7 plction o the polymerization reaction: The total amount of m homer converted intt :oly.ner at the end of the reaction decreases with the A increase in agitation (graphs I and II). Thi is is esgeeially tree when the rate of stirring is 720 revolutions oer min ate ar d the reaction stoos then only 20 percent of monomer is converted into polymer. inis can he Ctglained on the assumption that all LhC catalyst has been used us in forming active nuclei some of which have been destroyed hy incrcasin agitation. inerefore, there would not be eroagh ca tal; st to activate more monomers so that ~--e conversion ould he conjlcted. It has heen ohscrved in this laboratory that polymerisation rggtions when only nartiallyc n111te~ 1 ill continue to polymerize on further ad- dition of catalyst. Therefore, it is uro‘chle that if 311fficient catalvst is preserzt the ina.l convex sion.will be inie q1endent of the rate of stir- ring. Stirring effects will be observed only when low concentrations of h. The intrin ic viscosin tv: he intrinsic viscosities of the U H- d styrene ;ol;rers are ottair-ed by determin. the specific viscosities (73?) at three diffe rent cone ntrations and plottinCr against toe concen— trations. Straight and parallel lines are obtained. The interCepts of these linCs on th: ordinate of 7%? are the intrinsic viscosities of the pol;'mers. (Graph V) The in trin.ic Viscositics of the 101VWO"C of the non—stirred system 8. w -e greater than that of the stiIred svstem. This agrees with the fact that thea vera e molecnlsi 1r weight of the former is ng mt than the atter. (Experimenhsl and 2) p. The average molecular weight: The average molecular 1veights of samples from a typical emulsion oolvr""1,ation have been slwozn to resain fairly constant and at a maximum value for the system between LO and 603 polymerization.Comi1arisons can be made, therefore, at a17r0t1mrt ly 503 conversion between the average molecular weights of polymer produced under different conditions. Average molecular'weights are lower in the ' .y a 3,, a , .. . stirred aud shah n sysueus covers .. a. ' ‘ . ”4: molecular 'ei5nts 1n the non-s-1r average molecular weights of the tens n he n" V