A sruov OF THE copoummzmou AND commas as iTACONlC mama»: AND swam: ' Thesis §or the Dog". of Ph. D. MECHGAN STATE UNPVERSWY Jchn Conshnfine Drougas 1959 nay-2513 (3.1,. 0-169 Date This is to certify that the thesis entitled A STUDY OF THE COPOLYMERIZATION AND COPOLYMERS 0F ITACONIC ANHYDRIDE AND STYRENE presented by JOHN CONSTANTINE DROUGAS has been accepted towards fulfillment of the requirements for Ph 0 D 0 degree in Chemi Stry W -/’ , /II , ” / // :1 L,l ' (/l -. cow“ -:\ L . \ ' Major professor April 2, 1959 LIBRARY Michigan State University a 50- {n . ’ A STUDY OF THE COFOLYMERIZATION.AND COPOLYMERS OF ITACONIC.ANHXDRIDE.AND STYRENE By John Constantine Drougas A THESIS Submitted to the School for Advanced Graduate Studies of Michigan State University of Agriculture and .Applied Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1959 "r ACKNOWLEDGMENT The author expresses his sincere appreciation to Doctor Ralph.L. Guile, under whose direction this investigation was accomplished, for his inspiration, guidance, patience, and understanding which made this thesis possible. He also wishes to make known his debt to Doctor .Andrew Timnick for his aid in instrumentation, and for his helpful suggestions. .Appreciation is also extended to the Archer- Daniels-Midland Company, Minneapolis, Minnesota, whose Fellowship Program provided personal financial assist- ance during the academic years 1956-1958. \ --l\-I\-.I\I\I\I\ ‘7s "“’ ‘ ii To my Mother and Father iii A STUDY OF THE COPOLYMERIZATION AND COPOLYMERS OF ITACONIC ANHYDRIDE AND swam: By John C onstantine Dr ou gas AN ABSTRACT Submitted to the School for Advanced Graduate Studies of Michigan State University of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry Year 19 59 // '/ I’x/ "/ ( / , Approved ‘ié"; I" E/ (’2 .,.( .r',\./ L ’. . 1/ / ' ' ' ' ' ' ' / 4 —444 fivfir—fiffi ABSTRACT Itaconic anhydride and styrene were cepolymerized by benzoyl peroxide to form COpolymers of varying compositions. The reactivity ratios for this copolymerization were determined in two solvents. In benzene r2 (itaconic anhydride) = 0.78, rl-(styrene) = 0,015, and in tetrahydrofuran r2 = 0.60, rip: 0.10. Values determined for the copolymerization in tetrahydrofuran are probably more accurate because of the homogeneous nature of the polymerization but polymerization in benzene yields copolymers that are easier to work with and at a faster rate. The itaconic anhydride-styrene copolymers were shown to have a highly alternating structure and arranged in a head-to-tail manner. The dibasic acid nature of the itaconic anhydride-styrene segment in the copolymer was established both by potentiometric and high-frequency titrations. Apparent values of pKlI and pKzs are_5.7 and 8.8 respectively. Monoester derivatives were prepared and were shown by high-frequency titrations in all cases to be a mixture of two different monoesters. Apparent values of pKl" and pKz" for the monomethyl ester are 6.3 and 7.9 reSpectively. . Diester derivates of the copolymer were prepared. An optically active derivative was produced from the copolymer and the copolymer was converted to a network polymer which exhibited ion- exchange properties. The monoethyl and dimethyl ester derivatives of the copolymer do not undergo hydrolysis in aqueous sodium hydroxide at 250C in about twenty—five hours. vi TABLE OF CONTENTS INTRODUCTION..... ...... .............................. ....... ..... 1 HISTORICALIOOOOOOOO0.00.0.0.00.00.0000.0.000.000.0000000900000000 2 MGENTSOOOOOOOOOOOO. 000000 00.00.0000,.OOOOOOOOOOOOO'OOOOO'OOOOOO 11, PART I mPWALOOOIOOOOOOOOOOO0.0...'OOOOOOOOOOOOOOOOO0.0.0.0.000... 9 A. Evaluation of Monomer Reactivity Ratios in Benzene......... 9 B. ENaluation of Monomer Reactivity Ratios in Tetrahydrofuran. 19 DISCUSSIONOOOOOO...OOOOOOOOQOCOCOOOOOOOOO00.0....000.00.000.00... 26 PART II EXPERIMENTAL...” ....... .. ......... . ......... 5-3 A. Preparation of Itaconic Anhydride-Styrene Copolymers. ...... 53 B. High Frequency and Potentiometric Titration Procedures for the Itaconic Anhydride-Styrene Copolymers............... 56 0. Determination of Apparent pKl' and pK2i Values. ..... ....... 7h D. Preparation of Monoester Derivatives of the Itaconic \ Anhydride-Styrene Copolymers...... ...... ........ ..... ... 78 1. By Reaction with.Alcohols. ....... . ....... . ...... ...., 78 2. By Reaction with Dimethyl Sulfate........... ........ . 79 E. Titration of the Monoester Derivatives of the Itaconic Anhydride-Styrene Copolymers. . .............. . ...... ..... 80 F. Preparation of Diester Derivatives of the Itaconic Anhydride-Styrene Copolymers............................ 9h 1. Preparation of the Dimethyl Ester of Poly 61:39 (itaconic anhydride co styrene).......... ..... ....... 9h 2. Preparation of the Methyl Ethyl Diester of Poly S7:h3 (itaconic anhydride co styrene)...................... 97 3. Preparation of a Partial Diethyl Ester of Poly 61:39 (itaconic anhydride co styrene)...................... 98 h. Attempted Preparation of a Diester Using Absolute Alcohol and Gaseous Hydrogen Chloride Catalyst....... 101 G. Titration of the Diesters.................................. 102 H. Preparation and Titration of the Homopolymer-Polyitaconic Anhydride 107 Vii TABLE OF CONTENTS - Continued 1. Preparation of Polyitaconic Anhydridc................ 2. Titration of Polyitaconic Anhydride.................. I. Titration of Mixtures...................................... l. Mixture of Poly 61:39 titaconic anhydride co styrene) and the monoetnyl ester of Poly 61:39 (itaconic aniydride co styrene)...................... 2. Mixture of Poly 61:39 (itaconio anhydride co styrene) and itaconic anhydride...................... 3. Mixture of Monoethyl ester of Poly 61:39 \itaconic anhydride oo styrene) and itaconic anhydride......... J. Titration of Some Libasic Acids............................ K. Derivatives of the Itaconic Anhydride-Styrene Copolymer.... 1. Preparation of an Optically Active Derivative of Poly 61:39 titaconic anhydride co styrene)........... 2. Preparation of a Network Polymer..................... L. Stability to hydrolysis 1. Stability to fiydroiysis of the Mono 3 Poly 61:39 itaconic anhyfiride c: s ne). 2. Stability to Hydrolysis of the Dimethyl Ester o: Poly 61:39 \itaconic anhydride co styrene) U) F1 (1 '1 U H 0000000000. Page 10 7 10 7 108 109 13A 13A 135 136 oo' 1) M. Infrared Speotra........................................... 1 DISCUSSION....................................................... SUMMARY........................... ..... .. ..... ................... [JTTPATURE c1733................. ...... ... ........ ............... APPENDIX................................. ..... ................... viii 1h? 16A 166 169 II III VI VII VIII IX LIST OF TABLES Page Determination of Itaconic Anhydride by Reaction with MorphOlineOOOOOO’COOOOQOOOOO...0.0.00.00000000000000PDOOOOQ 8 Reactivity Ratio Data for Itaconic Anhydride-Styrene Copolymerization in Benzene............ ...... .............. 1h Reactivity Ratios in Benzene............................... 15 Reactivity Ratio Data for Itaconic Anhydride-Styrene Copolymerization in Tetrahydrofuran......... ..... ... ...... . 21 Reactivity Ratios in Tetrahydrofuran. ...... ................ 22 First Order Reaction Rate Constants......... ....... ........ hS Data for the Preparation of Itaconic Anhydride-Styrene copolmerSo00000009000000.0000000000oooooovooooovoooooooooo 55 Apparent pK' Values for the Itaconic Anhydride-Styrene COpOlymerSOOOOOOOOCIODC.0.0.0.....OCOOOO'OOOQOOOO00.0.0000, w Summary of the Titration Data for the Itaconic Anhydride— Styrene Copolymers......................................... 61 .Apparent pKi Values for the Monoester Derivatives of the Itaconic Anhydride-Styrene Copolymers.. .......... .......... 83 Summary of the Titration Data for the Monoesters of the Itaconic Anhydride-Styrene Copolymers...................... 8h XI Summary of the Titration Data for the Diesters of the Itaconic.Anhydride—Styrene Copolymers..... ...... ........... 103 XII Data for the Titration in Figure 27................ ........ 110 XIII Data for the Titration in Figure 28......... ..... .......... 113 XIV Data for the Titration in Figure 29. ..... ... ..... .......... 116 XV Data for the Titration in Figure 30.... ..... ... ........ .... 119 XVI pK Values of Some Dibasic Acids......... ............ ....... 12h ‘LIST OF TABLES - Continued TABLE Page iXVTI Summary of the Titration Data for Some Dibasic Acids....... 12S 3(1TIII Data Plotted in Figure 7................... ......... ....... 169 XIX Data Plotted in Figure 8............. ............. ......... 170 XX Data Plotted in Figure 9 .............. .............. ....... 171 XXI This Data is Plotted in Figure 9A and is for the Titration Shown in Figure 9.... .... ...... .......................... 172 )(XII Data Plotted in Figure 10................... ....... ........ 173 )(JCIII Data Plotted in Figure 11..................... ..... ........ 17h )(XIV This Data is Plotted in Figure 11A and is for the Titration Shown in Figure 11....................... .......... ........ 17S XXV Data Plotted in Figure 12.................................. 176 )(XVI Data Plotted in Figure 13.................................. 177 3()CVII Data Plotted in Figure 1h..................... ...... ....... 178 XXVIII DataPlot-tedinFigure 15 ....... 179 3(XIX This Data is Plotted in Figure 15A and is for the Titration Shown in Figure 15....... ..... . .. ..... ................... 180 XXX Data Plotted in Figure 16.. . ..................... ....... 181 )(XXI This Data is Plotted in Figure 16A and is for the Titration ShowninFigure 16. ..... . .......... ................ .182 XXXII Data Plotted inFigure 17 ..... ........................ 183 XXXIII Data Plot-ted in Figure 18..... .................. . .......... 18D mIVDataPlottedinFigure19..... ....... 185 XXXVData PlottedinFigure 2o............... ........... ..... 186 XXXVI Data Plotted in Figure 21 ...... 187 XXXVI]: DataPlotted in Figure 22188 rhh'h _, LIST or TABLES — Continued TABLE Page )C)C}CVIII Data Plotted in Figure 23.......... ....... ................. 189 JKJCXIX Data Plotted in Figure 2b.. . .... ....... .. . ....... 190 XL Data Plotted in Figure 25.................................. 191 XLI Data Plotted in Figure 26 ....... ... ..... ................... 192 )CLII Data Plotted in Figure 27................ ........ .......... 193 }CILIII Data Plotted in Figure 28...................... ...... ...... 19h XLIV Data Plotted in Figure 29......... ....... .................. l95 XLV Data Plotted in Figure 30.................................. 196 )CLVI Data Plotted in Figure 31.................................. 197 )CIQVII Data Plotted in Figure 32.............. ...... .............. 198 JCILXTIII Data Plotted in Figure 33............ ....... . ........ . 199 3(LIX Data Plotted in Figure 3h................... ....... ..... . 200 L Data Plotted in Figure 35................. ......... .. . 201 L1 Data Plotted in Figure 36.... ............. . ...... .... . 202 LII Data Plot-ted in Figure 37 .. ........ . .............. . 203 11111 Data Plotted in Figure 38.. ..... ........... ...... .......... 20h ILIV Stability to Hydrolysis of the Monoethyl Ester of Poly 63:37 (itaconic anhydride co styrene)......... ..... ........ 205 LV Stability to Hydrolysis of the Dimethyl Ester of Poly 63:37 (itaconic anhydride co styrene)... ................ . ........ 206 xi IFIGURE 7. 9A. ll. LIST OF FIGURES Reactivity ratios for the copolymerization of itaconic anhydride with styrene in benzene.................. ..... .. Copolymer composition curve... .......... ..... ........ ..... Reactivity ratios for the COpolymerization of itaconic anhydride with styrene in benzene, by the method of Fjllemanand ROSSQOOOOOOQDOI0.00.000...'O'OOOOOOOOOOOOOOOOO Reactivity ratios for the copolymerization of itaconic anhydride with styrene in tetrahydrofuran................. Copolymer composition curve.............. ..... ., ..... ..... Reactivity ratios for the copolymerization of itaconic anhydride with styrene in tetrahydrofuran, by the method or Enema]. arld ROSSOOOOOOOOOOQOOOOOOOI.OOOOOODOOOOO'OOOO'O High frequency and potentiometric displacement titration curves for the disodium salt of Poly S7:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HC1........... High frequency and potentiometric displacement titration curves for the disodium salt of Poly S7:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HC1...... ..... High frequency and potentiometric diSplacement titration curves for the disodium salt of Poly S7:h3 (itaconic anhydride co styrene) titrated with 0.1286N-Hc1........... -CI. Plot of pH vs. log 1 a for the titration of Poly. 57zh3 (itaconic anhydride co styrene), from the data for the titratiOndlFigo 90010000'00000000000000900 ooooooo o oooooo High frequency and potentiometric displacement titration curves for the disodium salt of Poly S7:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HCl........... High frequency and potentiometric displacement titration curves for the disodium salt of Poly SS:hS (itaconic anhydride co styrene) titrated with 0.1286N~HC1........... Page 16 17 18 23 2h 25 62 63 6h 65 66 67 LIST OF FIGURES - Continued IFIGURE 11A. 12. 13. 15. 15A. 16. 16A. .179 18. 19. Plot of pH vs. log -l—-&-— for the titration of Poly 55: 1.5 (itaconic anhydride co styrene), from the data for the titration in Fig. 11...................................... High frequency and potentiometric displacement titration curves for the disodium salt of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N—HCl........... High frequency and potentiometric diSplacement titration curves for the disodium salt of Poly 61:39 (itaconic anhydride co styrene) titrated with 0.09666N-HCl.......... High frequency and potentiometric diSplacement titration curves for the disodium salt of Poly 61:39 (itaconic anhydride co styrene) titrated with 0.03883N~H01.......... High,frequency and potentiometric displacement titration curves for the disodium salt of Poly 50:50 (maleic anhydride co styrene) titrated with 0.1286N-HC1.. ..... .... Plot of pH vs. log 1 g for the titration of Poly 50:50 (maleic anhydride co styrene), from the data for the titrationjnhgo 1500 00.0.0000 ooooooooovooooqpooooovo High frequency and potentiometric displacement titration curves for the sodium salt of the monomethyl ester of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N—H01............................................... Plot of pH vs. log 1 for the titration of the ane- methyl ester of Poly 57: D3 (itaconic anhydride co styrene) from the data for the titration in Fig. 16. ............. High frequenoy and potentiometric displacement titration curves for the sodium salt of the monoethyl ester of Poly 57: A3 (itaconic anhydride co styrene) titrated with 0. 1286N-H01.... ..................... ....... ..... ........ High frequency diaplacement titration curve for the sodium salt of the monoethyl ester of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N—HC1........... High frequency and potentiometric displacement titration curves for the sodium salt of the monobenzyl ester of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N—HCl............................................... xiii Page 68 69 7O 71 72 73 85 86 87 88 89 LIST OF FIGURES - Continued IIIGURE 20. 21. 22. 23. 2h. 25. 26. 270 28. 29. Page High frequency and potentiometric diSplacement titration curves for the sodium salt of the mono-2~methyl-1-butyl ester of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HC1................................. 90 High frequency and potentiometric displacement titration curves for the sodium salt of the monoethyl ester of Poly 61:39 (itaconic anhydride co styrene) titrated with 0.03883N~HC1.............................................. 91 High frequency and potentiometric displacement titration curves for the sodium salt of the monomethyl ester of Poly 61:39 (itaconic anhydride co styrene) titrated with 0097).).LLN‘HC]. 92 High frequency and potentiometric displacement titration curves for the sodium salt of the monomethyl ester of Poly 50:50 (maleic anhydride co styrene) titrated with 0.1286N-HCl............................................... 93 High frequency and potentiometric titration curves for the methyl ethyl diester of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HCl..................... 10h High frequency and potentiometric titration curves for the dimethyl ester of Poly 61:39 (itaconic anhydride co styrene) titrated with 0.097th-HC1....................... 105 High frequency and potentiometric titration curves for the partial diethyl ester of Poly 61:39 (itaconic anhydride co styrene) titrated with 0,097ADN—HCl.....,.............. 106 High frequency and potentiometric diSplacement titration curves for a mixture of the sodium salts of Poly 61:39 (itaconic anhydride co styrene) and the monoethyl ester of Poly 61:39 (itaconic anhydride co styrene) titrated with 0.09666N~HC1.............. ..... . ............ ......... 111 High frequency and potentiometric displacement titration curves for a mixture of the sodium salts of Poly 61:39 (itaconic anhydride co styrene) and itaconic anhydride titrated With 0.09666N—HC1................................ 11h High frequency and potentiometric displacement titration curves for a mixture of the sodium salts of Poly 61:39 (itaconic anhydride co styrene) and itaconic anhydride titrated with 0.03883N‘HCl................................ 117 xiv TLIST OF FIGURES - Continued IVIGURE 30. 31. 32. 33. 3h. 35. 36. 37. 38. 39. 110 0 Page High frequency and potentiometric displacement titration curves for a mixture of the sodium salts of the monoethyl ester of Poly 61:39 (itaconic anhydride co styrene) and itaconic anhydride titrated with 0.09666N-HC1............. 120 High frequency and potentiometric displacement titration curves for the disodium salt of itaconic anhydride titrated With 001286NqHC100000000000000000000000,?!0'0'000 126 High frequency and potentiometric displacement titration curves for the disodium salt of polyitaconic anhydride titrated With.001286NHH01000000000000000000000000000000000 127 High frequency and potentiometric diSplacement titration curves for the disodium salt of itaconic acid titrated With0.1286N-HClOOOOOOIOQO'.0.0.9.0.0....IOO'OOOOOOOIOOOOQ128 High frequency and potentiometric displacement titration curves for the disodium salt of unsymmetrical dimethyl succinic acid titrated with 0.097th—HC1.................. 129 High frequency and potentiometric displacement titration curves for the disodium salt of methyl succinic acid t’itrat‘ed Wit'h O OO97MLN~HClO O I O O I O O O O Q 0 O O O O l O O O O O O O O O ..... O 130 High frequency and potentiometric displacement titration curves for the disodium salt of succinic acid titrated With 00097th-HC100000000000 ooooo 000 ccccc 00000000000000000 131 High frequency and potentiometric displacement titration curves for a mixture of the disodium salts of benzoic and salicylic acids titrated with 0.097th-H01................ 132 High frequency diSplacement titration curve for a mixture of sodium acetate and sodium propionate titrated with 0.097th-HC100000000.9.0.0...000.000000000.000009000000000 133 Infrared spectrum of polyitaconic anhydride mull with hexaChlorObut'adieneOOOO0.900 O'QIOIOOOOO O'OOOQOOOOOOOO'OOOO 139 Infrared Spectrum of Poly 61:39 (itaconic anhydride co Styrene) mUll With hexaCthTObUtadienego ooooooo 00000000000 lbo Infrared Spectrum for the monoethyl ester of Poly 61:39 (itaconic anhydride co styrene) mull with hexachloro~ but‘adieneCCO.......C.‘.....O....'......'.... ...... 0.00....lh-l XV LIST OF‘FTGUHES = Continued IFIGURE h2. h3. h5. h6. h7. MB. Page Infrared spectrum for the monobenzyl ester of Poly 57zh3 (itaconic anhydride co styrene) mull with hexachloro- butadien80000000000000000000000000000000000000000090000000111,2 Infrared Spectrum for the mononopol ester of Poly 61:39 (itaconic anhydride co styrene) mull with hexachloro- but’adieneOOOOCOOOOQO'OOOOOO'OOOOQO'OO'OO'O'QOOO'OOQ'OOOOQ. M3 Infrared spectrum for the dimethyl ester of Poly 61:39 (itaconic anhydride co styrene) in hexachlorobutadiene, . . . lhh Infrared Spectrum for the dimethyl ester of Poly 61:39 (itaconic anhydride co styrene) mull with hexachloror but’adiene..'.........O0.0D.'......Q....l......O........... m5 Infrared Spectrum for the partial diethyl ester of Poly 61:39 (itaconic anhydride co styrene) in hexachloro— butadiene0919000090090900I.0......OOOIOOOOQOIOOOO'OOOOCOOO M6 Infrared Spectrum of styrene in hexachlorobutadiene....... 1h? Infrared spectrum of hexachlorobutadiene versus salt plat'eqoqo000000000000000000090000 000000000000000000 0000000 1.14.8 I N ‘PRO DUO T ION ,. I. I" ,. IN TRODUC TION The copolymers and copolymerization of itaconic anhydride and styrene have been the subject of a number of investigations in this laboratory (1,2,3). The study was originally initiated because of the availability of itaconic anhydride and the research in this laboratory and elsewhere on the apmarently Similar copolymerization and copdlymers of maleic anhydride and styrene (h,S,6). The purpose of this investi- gation was to determine the reactivity ratios of each of the monomer radicals, to analyze the copolymers for composition and structure, and to prepare derivatives of the copolymers. This thesis also reports, we believe for the first time, the study of a high frequency titration applied to polymeric polyelectro- lytes, an analytical technique made necessary by the limitations of potentiometric titrations when applied to polycarboxylic acids. HIS TORICAL HISTORICAL Styrene has been Shown to be a useful monomer in many copolymer- izations (7,8,9). Itaconic acid, an unsaturated dibasic acid has the structure necessary for the preparation of high-molecular weight thermoplastic materials by polycondensation reactions. These linear products can crosslink through the residual unsaturation. In pnactice however, vinyl type monomers such as styrene or dimethyl itaconate are deymerized with the polycondensation product, in order to improve the physical properties of the resulting thermosetting resin. The diesters of itaconic acid formed from saturated monohydric alcohols may be polymerized with peroxide catalysts to form thermoplastic homo- polymers. They may also be copolymerized with other vinyl type monomers to yield useful, transparent plastics. Copolymers of itaconic acid or its derivatives with various unsaturated compounds have been found to be excellent viscosity improvers for lubricating oils (10,11). Copolymers prepared using diallyl itaconate as one of the com- ponents are claimed to be useful as ion exchange resins (12,13). .Diesters of itaconic‘acid formed from saturated monohydric alcohols may be copolymerized with monomers such.as divinyl benzene. Saponification of these copolymers forms an ion exchange resin. Itaconic acid and some of its derivatives may be copolymerized 'with aCrylonitrile, vinyl chloride and other vinyl monomers to form pmlymers useful as textile fibers (lh,lS). Copolymers of itaconic acid diesters with styrene or one of the methacrylates yield clear, water-white materials with excellent optical properties which should be useful for the manufacture of lenses and other tranSparent plastic products (16,17). Copolymers of itaconic anhydride and vinyl acetate are useful as soil conditioners (l8,l9). A swrch of the literature has indicated that no extensive study of the copolymerization of styrene and itaconic anhydride has been made . REAGENTS l. Benzene Thiophene-free benzene was obtained from the stockroom and Shaken for one-half hour with concentrated sulfuric acid. The process was repeated twice with fresh portions of acid. The benzene was then placed over sodium and distilled. The fraction boiling at 80-8100 was used. 2. Tetrahydrofuran . The tetrahydrofuran obtained from the stockroom was purified by treatment with potassium hydroxide, followed by distillation over lithium aluminum hydride. The fraction boiling at 65-6600 was used. 3. Methyl Alcohol Absolute methanol was placed in a one-liter flask fitted with a large reflux condenser. To this was added 10 g. of magnesium turnings and the mixture refluxed for three hours. The dry alcohol was distilled from the magnesium hydroxide and magnesium methoxide, that part boiling at 6h.S-6SOC was used in this work. h. Ethyl.Alcohol. The above procedure was applied to absolute ethanol and the fraction boiling at 71.1; to 7h.6°C was selected for use in these experiments. 5. Styrene Commercially available styrene was washed with three successive portions of a 10% sodium hydroxide solution to remove the inhibitor, The styrene was then washed with water until the washings were neutral to litmus. The styrene was then stored over anhydrous sodium sulfate for 2—3 days, and distilled under reduced pressure in a nitrogen atmos- phere. The sample was free of polymer as indicated by the lack of a precipitate on the addition of methanol. The refractive index of the material used was 11:50 -1.53uo, and the boiling point was 3e—37°c at 30 mm. pressure. 6. Unsymmetrical Dimethylsuccinic Acid This material was purchased from K & K Laboratories, Inc., Long Island City, 1, N. Y. 7. Methylsuccinic Acid This was obtained from Aldrich Chemical Co., Inc., Milwaukee, 10, 'Wisconsin. 8. Succinic, Salicylic, Benzoic, Prqpionic, and Acetic Acids These were of a C. P. Grade available in this laboratory. 9. Itaconic Anhydride A mixture of 50 g. (0.39 mole) itaconic acid and 100 ml. acetyl chloride was heated under reflux for one hour, during which time the itaconic acid dissolves. Heating was continued for about fifteen minutes beyond this point. The acetyl chloride-acetic acid mixture was then distilled under reduced pressure (water aspirator 25 mm.) under a nitrogen atmoSphere. Two 60 ml. portions of toluene were added consecutively and removed. During the distillation of the toluene and acetic acid mixtures the temperature was kept below 8000 by means of a water bath. This was a critical temperature above which decomposition and polymerization occurred. The syrupy residue was transferred to an Erlenmeyer flask and 100 ml. anhydrous ethyl ether were added. Approximately 32 g. of itaconic anhydride, m.p. 68-6900 crystallizes. Concentration of the ethereal solution yielded an additional 8.5 g. of crude anhydride, m.p. 6376600. About four hours are required for this preparation. The preparation should be continuous up to the point where the ether is added. The crude itaconic anhydride was recrystallized twice from c.p. chloroform to give a constant melting product, m.p. 68-68.SOC. A good yield of itaconic anhydride was 90% based on itaconic acid. Itaconic anhydride may be prepared from itaconic acid with thionyl chloride (21), phosphorous pentoxide (22), acetyl chloride (23), or acetic anhydride (2h). Itaconic acid is chiefly produced by the sub- merged culture fermentation of a glucose media by "Aspergillus terreus." A laboratory method of preparation consists in the rapid distillation of citric acid (25). Determination of Itaconic Anhydride_by Reaction with Morpholine The procedure used was similar to that of Johnson and Funk (57). A standard (0.8552N) HCl methanolic solution was prepared by the addition of 6N—HCl to a one liter volumetric flask and diluting to the mark with methanol. The HCl should be standardized daily against standard NaOH using phenolphthalein indicator. An approximately 0.5N-methanolic solution of morpholine was pre-~ pared by adding hh ml. of redistilled morpholine to a one liter reagent bottle and diluting to one liter with methyl alcohol. The bottle was fitted with a two hole rubber stopper. A 50 ml. pipette was inserted in the one hole so that the tip dipped below the solution of the morpholine. A short piece of glass tubing was inserted through the second hole and a rubber bulb was attached to it. A methyl yellow—methylene blue mixed indicator was prepared by dissolving 1 g. of methyl yellow and 0.1 g. of methylene blue in 125 ml. of methanol. Procedure: A 50 ml. aliquot of morpholine was added to each of two 250 ml. glass—stoppered flasks. An accurately weighed sample (0.5 g.) of itaconic anhydride was introduced into one of the flasks. About one hour was allowed for the solution of the itaconic anhydride and then h drops of the indicator solution were added to each flaSk. The solutions were then titrated with standardi ed HCl to the disappear— ance of the green color. The morpholine consumed is represented by titration difference between the blank and sample and this is a measure of the anhydride. The amount of acid originally present in the sample may be determined when the morpholine procedure is used in conjunction with others which measure total acid and anhydride. The results are summarized in the following table. TABLE IA DETERMINATION OF ITACONIC ANHYDRIDE BY REACTION WITH MORPHOLINE .: —-I —_ f.“ .- ——-:——._‘I-l - a, — Sample Weight % Ml. 0.8522 N-HCl Ml. 0.8522 N-HCl Percent Itaconic Anhydride“ For Sample For Blank Itaconic g Anhydride 0 .5312 38 .22 LLB .82 100.9 0.50h3 38.60 t3.82 99.1 0.5261 38.36 15.81 99.1], Sample Calculation: Percent _ (ml: HCl Blank-ml. HCl Sample)(N-HCl) x %%§5- Itaconic Anhydride " x 100% Sample‘Weight *The itaconic anhydride used for these experiments was a sample whichO had been recrystallized several times from chloroform. M.p. 68-68.5 C. PART I A. Evaluation of Monomer Reactivity Ratios in Benzene. B. Evaluation of Monomer Reactivity Ratios in Tetrahydrofuran. EXPERIMENTAL make a total comonomer charge of 0.233 mole. EXPERLWTAL A. E\ra1uation of Monomer Reactivity Ratios in Benzene A series of copolymerizations of itaconic anhydride and styrene were carried out in benzene at molar ratios of itaconic anhydride/ styrene of 10/90. 20/80. 25/75. 110/60, 50/50. 65/35, 75/25, 85/15, 95/5. A typical procedure for the reactions follows. The copolymerization was carried out in a five hundred milliliter, three-neck, round bottom flask with standard taper ground glass joints. The flask was fitted with a reflux condenser, a nitrogen inlet tube and a mechanical stirrer. The polymerization mixture was protected from moisture by a calcium chloride tube and kept under a nitrogen atmosphere. The flask was charged with three hundred and fifty milliliters (307.6 g.) of benzene and the desired amount of itaconic anhydride was added. To dissolve the itaconic anhydride the mixture was heated, with stirring, at the reflux temperature of benzene (80°C) mintained by use of an oil bath. Approximately thirty minutes were required for the solution of the itaconic anhydride. A sufficient- a-~""1<>u_nt of styrene comonomer was then added to the reaction flask to The benzoyl peroxide catalyst, 0.1166 g., was added and the time recorded. When the. desired per cent of polymerization was obtained, in about fourteen "51111-1: es, the contents of the flask were transferred to a large test tube and immersed in a. dry-ice acetone mixture for several minutes to lO quench the reaction. The solid copolymer was filtered off with suction and washed with several portions of hot benzene. Finally the solid copolymer was dried at h-5 mm. pressure at 5600 for twenty-four hours and weighed. Per cent polymerization was calculated as follows: weight of polymer x 100 Per cent polymerization = total monomer weight The samples from the various copolymerization reactions were submitted for carbon-hydrogen analyses, the results of which were used to calculate the mole per cent of itaconic anhydride in the copolymer. The data for these experiments are listed in Table I. The mole frac- tion of itaconic anhydride was calculated from the per cent carbon as shown by analysis. A sample calculation follows: Assume a sample of copolymer of 100 g. Let x = g. itaconic anhydride in sample Then (loo-x) = g. styrene in sample Itaconic anhydride contains 53.6% carbon. Styrene contains 92.3% carbon. Therefore 0.536 x + O.923(100-x) = per cent carbon. The copolymerization equation dIM J M! rlMl 4» Ma 3: 9 (1) dfiiie] M2 reMz ‘5 M1 can be arranged to the form M m M In1 M2 7 4o . 4 11 where 3 H I — mole per cent styrene in the monomer charge. 3' to II mole per cent itaconic anhydride in the monomer charge. m1 = mole per cent styrene in the copolymer. mole per cent itaconic anhydride in the copolymer. 5 to II Substitution in equation (2) for the values of M1, M2, m1, and m2 was made for the various reactions. There resulted a series of teat-ions which would give straight line graphs when rl is plotted against r2. Assumed values of rl (from --0.1 to +0.1) were substituted in equation (2) to give a corresponding value of r2. A sample calculation is given below u31ng reaction No. I in Table I. mgr-34.2. in£(l+_.1. r1)-1 M2 _m1 M2 r2=%[m (l+%rl)-l] 3 = 0.135 r—u’ Ho ’1 H ll 0 \0 "5 [0 r1 = +0.1 5 r2 = 8.356 ‘8 0086 '1 r1 = -0.13r2 Only two substitutions of r1 in equation (2) were required to obtain two values of r2 which would determine the straight line. However, tI'll-"ese values of r1 were used so that the third point on the straight line could serve as a check on the calculations. The values of r1 VeI‘Sus r2 were plotted for each of the copolymer compositions and the resulting series of straight lines is shown in Fig. l. 12 The rl - r2 values were now used, along with the monomer compo- sition, to calculate the theoretical composition of the increment of polymer formed at a specified monomer composition. These values are Shown in the last column of Table I. The equation used to make these calculations is (3) F2 = (r2f22 + flf2)/(r2f22 + 21‘11"2 + rlflg) where F2 = mole fraction of monomer M2 in the increment of copolymer formed at a given stage in the polymerization. f2 = mole fraction of monomer M2 in the monomer charge. f1 = mole fraction of monomer M1 in the monomer charge. r2 = ratio of the rate constants of M: with monomer M2 and M; with monomer M1. r1 = ratio of the rate constants of M1 with monomer M1 and ’i with monomer M2. M2 is itaconic anhydride. M1 is styrene. A plot of the mole fraction (F2) of itaconic anhydride in the co- Poly‘mer versus the mole fraction of itaconic anhydride (f1) in the monomer mixture is shown in Fig. 2. The method of Fineman and Ross (20) was also used in the analysis of the copolymerization data to evaluate rl and r2. In their method equation d [M ] M1 r M. + M m (l) 1 g: __= . u—Lhu—v-Z— = —-1—' _ . TIM—J M2 r2M2 + M1 ( m2 for low conver81ons) may be rewritten as: f = F rJF + 1 r2 + F where f = EJ' and F = mg 3L: (0 and by rearranging the terms one obtains: f (f 1) — rl f r2 .A plot of (F/f) (f - l) as ordinate and (FZ/f) as abscissa is a straight line whose slope is rl and whose intercept is ~r2. are plotted in Fig. 3. 13 The data Table II lists the values of the reactivity ratios as determined by the copolymerization equation (2) and the method of Fineman and Ross. .poofispopop hamsofismho mooao> matey map was ooflpflmoasoo Hosooos one Eopm popmHSoHoo ms ooflmpaqso oflooompfl mo coapownm cacao .mfimhamdo cowomphnlsOnnoo he posesnopop Hoshfioaoo one oH opflppmnso oesoompfi Mo soapomgm oHozo .oosfimppo posaaoa mo infloz.mnp no women seemposcCo peso Home .owpmeo one SH ooflnphnos owoooopfi oofipomnm ofiozs III I [l I I [l t l oad.o dcm.o cm.r Na.rm m.m omd.o HN.H as.am d m:w.o was.o mo.m am.ao N.: omm.o mc.m rH.mN r Hos.o ao~.o :O.m ma.mo m.: mes.o No.0 mm.ma S wo~.o maa.o oo.m mo.ao m.a Hmc.o as.r Nd.ca c cmc.o smo.o da.m rd.co d.a oom.o oa.ma mo.ma m adm.o cac.o oo.m oc.oo H.c 00:.0 mm.aa m:.oa : csm.o mmm.o :m.m wa.os H.m omN.o mH.®H :Nm.o m dam.o omm.o cm.m dm.0s a.m ada.o or.da amm.m N ama.o e_MOMao sc.m ma.ma N.H ooa.o sm.am mac.m a soapomwm awesomnm Paco pom Paco pom psoo mom soapompm .w .w .02 p mac: 0 mac: smwonphm Gonnwo sofimhosuoo s oaoz encampm oofihphaqa ccpstcaso o cascccea hlll I. LII! I L'lwi . [IlliufluflunuflulItIilIIMHHHMHHHHHHHHHHHHHHHHH MZMszm 2H ZOHB¢NHmmquomoo mzmmwamrmmwmmwmz<.UHZOUHBO¢Hm H mqmdy TABLE II REACTIVITY RATIOS IN BENZENE 15 .fi ‘- a. By rl - r2 plots: Itaconic.Anhydride 0.780 Styrene 0.015 r1 r2 = 0.011 b. By the method of Fineman and Ross: Itaconic Anhydride 0.750 Styrene 0.008 16 mg m+ H+ 0 HI l .csossch ca eschew are: ceases? casccfia so sowswfiscsaacaoc cap sow ceases aeasapcccm A .wfi HI mm.o u Aopflapaeom OHooospHv ms mfio.o u Aocohaymv Ha I as \\\\\A\ o as Mole fraction itaconic anhydride in copolymer Benzene Solvent I l l I ll l l l 0.1 0.2 0.3 0.h 0.5 0.6 0.7 0.8 0.9 f2 Mole fraction itaconic anhydride in monomer mixture Fig. 2. Copolymer composition curve. 1.0 17 18 .mmom was essoqfim no tonnes map an “commode SH moosasm gees opflhpaaod oflooompe mo soapsmflaoexaoooo mop pom weapon hpfisaposom .m .mfim {we S 2 ca fl 3 as s o a N L _ _ _ _ _ _ _ a T A‘IA . . b --"'--""'-'I"---' ' --.---0J O Aopflhpaeso oesoompflv was u mw.ou u Paooaopow Accommemv as u woo.o u macaw B. Evaluation of Monomer Reactivity Ratios 19 t in Tetrahydrofuran \ l I The copolymerizations were carried out at the reflux temperature ; of tetrahydrofuran (6500.). The experimental procedure is the same 7 as that used in benzene. .After the reaction mixture was removed from the dry-ice acetone bath, the following steps were necessary: a..Addition of anhydrous diethyl ether to precipitate the copolymer. This apmeared to be the only non-solvent yielding a good precipitate. It was necessary that the non-solvent be anhydrous to prevent the hydrolysis of the anhydride ring. b. Centrifugation and filtration to isolate the copolymer. Due to the finely divided nature of the copolymer, it was necessary to centrifuge the reaction mixture for about ten minutes. .After decanting off most of the liquid, the re- mainder was removed by filtration. c. The copolymer was then dried at h-5 mm. at 5600. for twenty-four hours and weighed. The samples were then submitted for carbon-hydrogen analysis. The data for these experiments are found in Table III. The values of rl and r2 were determined as previously described and these were plotted as shown in Fig. h. The composition of the increment of polymer formed at a Specified monomer composition was calculated using equation (3) and the values appear in the last column of Table III. The plot of mole fraction (F2) of itaconic anhydride in the copolymer versus the mole fraction of itaconic anhydride (f2) in the monomer mixture is shown in Fig. 5. 2O The method of Fineman and Ross (20) was also used to evaluate r1 and r2 and Fig. 6 shows a plot of the data. Table IV lists the values of the reactivity ratios as determined by the copolymerization equation and the method of Fineman and Ross. 21 .pofisnopop mamoofleona meander Np .. as one. our. soapwmoasoo aoEosos one. spam popdfiooaoo mm opfippsEss oesoooflu mo 530.95 oHoZp .mfimhaoso Swopphclsonpoo c3 pofishopop 9953800 on... 5” operands 3:003.“ mo 8309M oHozo dosages... hoiaoa mo Emacs mg. no women Scamnoaaoo ..Eoo home .ownfio map E.” eagerness oasooofi 830on cacao [Ill 1 [I'll Pl bl! A [I A I [it E :rc.o mms.o H:.m rm.Nc m.m omw.o mc.m wa.NN a oce.o cec.o mm.m mc.cc o.ma ame.o as.m ad.ca c Hem.c dwm.o we.m aw.me w.w ccm.c ca.Na mc.ma m mom.o mmm.o o~.m ad.o~ H.d cos.o mm.sa m:.oa : ems.o . mms.o mo.c No.sa d.s omN.o ma.sa Nm.o m was.o om:.o no.6 ea.sa H.m ada.o or.da NN.m N Nam.o . mcm.o Nm.c we.as m.d ooa.o :m.HN ac.N a 111:! 830me 85.0me peso pom pooo pom Show pom sochme .w 1 4.4m II .0211 U 362 0 mac: flowchprnm H8930 :Ofimpobnoo .m oHoz odofinpm mpfinphnnd consasoaco o caeccon 7| t [A l I t it |' tlllllll zéaomahéeme 2H ZOHE¢NHmEQomoo EHEBmIMQHmEmZas 0HZOU etc. As in all chain reactions, the overqall polymerization involves two other processes: 1) chain initiation, which depends on,a reaction which introduces free radicals into the system, and 2) chain termin- ation, in which the termdnal radical on a growing chain is deactivated. The number of reactions required to represent the copolymerization of two or more monomers increases geometrically with the number of monomers entering into reaction. The types of chain radicals to be considered is equal to the number of monomers present, and the reaction characteristics of a chain radical are determined almost entirely by the terminal monomer unit, the structure of those before it in the chain being of little importance. In the copolymerization of two monomers, two chain radicals must be distinguished. .Addition of the two monomers to each of the radical species introduces four simul- taneously occurring propagation reactions. 33 If the chains are long, the composition of the copolymer and the arrangement of units along the chain are determined almost entirely by the relative rates of the various chain propagation reactions. However, the rate of polymerization depends not only on the rates of the propagation steps but also on the termination reactions. Three dif~ ferent chain~terminating reactions between pairs of radicals should be considered. The chain propagating reactions occurring when two monomers M1 and M; are present may be written as: a) M? + Ml iii, M} b) M; + M2 £13., M: c) M; + M2 1.323, M; (1) Mg + M1 .1532, M: ‘Where Mi and M: represent chain radicals having monomer residues M1 and M2 as the terminal, free~radical~bearing units. Radicals of type M): are formed by initiation of the monomer in (a) and by reaction.(cD above. These radicals, Mi, are destroyed by reaction (b) and by termination reactions. .At the steady state, the rates of appearance and disaprearance of these radicals are practically equal. If it is assumed that the chains are long, only the above reactions need be considered since the interest lies in the relative concentrations of the two types of chain radicals. The steady state condition in this approximation reduces to e) k2. mi] [M1] = 1.12 [mi] [M2] The rates at which monomer M1 and M? are used are 3h f) 39%;!— .-= kn [Mi] [Mi] + k1,, [Mi] [M1] 91314.2}. dt = kiz [Mai] [M21 + 1:22 [Mi] [M2] Solving equation (e) for one of the radical concentrations, substitut- ing this value in (f) and (g) to eliminate one of the radicals, and dividing (f) by (g) we obtain: diM 1 [M J rliMiJ/[Ma] + 1 h) dlMgl a (mil) ( mil/34217 re) The quantity dm11/dng given by equation (h) represents the ratio of the two monomers in that increment of copolymer formed when the ratio of unreacted monomers is [M1]/ [M2]. Therefore by letting d _ % a '34 and rearranging one arrives at the previously used 2 2 equation (2) M m M g ....2. ...a —.‘L .. (2) r2 M2 ["11 (l + M2 r1) 1] where r] and r2 are monomer reactivity ratios defined by 1‘i = kll/ k 12 1'2 "" k22/k21 rl represents the ratio of the rate constants for the reaction of a radical M; with monomer ML and with monomer M23 r2 similarly expresSes the relative reactivity of an M: radical toward an M2 monomer compared with an M1 monomer. The unreacted monomer ratio changes as the polymerization continues, and this gives rise to a continually changing composition of the polymer being formed at each instant. mmfi— - _ -..- 35 The compositions of the monomer feed and of the polymer formed may be expressed as mole fractions instead of mole ratios as indicated earlier. If Fl represents the fraction of monomer M1 in the increment of copolymer formed at a given instant in the polymerization then, d [ML] 1) F1= d(fiVIJTIM2l) = l-F2 and if f1 and f2 represent the mole fractions of unreacted monomers in the feed then, [M] (1M1! + IMEI) J) f1 = I I-J I H) N Substituting (i) and (j) in dmln M d M..] M2 ' r2M2 + Ml ‘, (1) there results equation (3): (3) F2 = (refez + f1f2)/T2f22 + Zflfz + rlflz) The composition of the increment of polymer formed at a specified monomer composition can be readily calculated using equation (3) and the determined reactivity ratios rl and r2. Figures 2 and 5 represent a plot of the mole fraction of itaconic anhydride in the copolymer versus the mole fraction of itaconic anhydride in the monomer mixture. .Also plotted on these graphs are the mole fractions of itaconic an- hydride in the copolymer as determined from the carbon-hydrogen analysis. These data are listed in the last two columns of Tables I and III and Be an inspection of these and the graphs shows that the theoretical mele fractions agree very well with the actual values. It can.be seen that the mole fraction F2 will not usually equal f2; and thus F2 and f2 will change as the polymerization progresses. If the two radicals display the same preference for one of the monomers over the other then kll/kie ‘3 kel/kzz or rlvr2 = l. The broken line in Fig. 2 and 5 represents the case in whichk11 = klg and k22 = kgl, that is, the two monomers are equally reactive with each radical. In this case r1 = r2 = l and F2 = f2, that is, the polymer composition is equal to the monomer composition. In the case where the monomer feed contains a mole fraction of 0.h in itaconic anhydride, the copdlymer will contain the same mole fraction in itaconic anhydride. wall (33) first indicated the close analogy between the copokymer- monomer mixture composition relationships and vapor-liquid equilibria in binary systems. wall introduced the term ideal copolymerization for the case where rlorz = l, in analogy to the vapor-liquid equilibria for ideal liquid mixtures. In this case the two radicals disphay the same preference for one of the monomers over the other, and as before kil/kle = kZI/k22 or I‘l'I'2 ‘3 l 37 Equations (1) and (3) in this caSe reduce to k) $171 = r1 [Mll/[MEJ and 1) F2 = rgfjhgfg + fl) The monomer reactivity ratio r1 in equation (k) corresponds to the ratio of the vapor pressures (PIG/P20) of the pure components of the ideal mixture, and Fl and f1 to the mole fractions of component 1 in the vapor and liquid at equilibrium. When rl > 1 the polymer ("vapor") is richer in M1 than is the monomer feed; thus the residual mole fraction f1 Irnist diminish as the polymerization (distillation) proceeds. For r1 < l the reverse is true. In an ideal polymerization the sequence of monomer units must be random. The probability of the occurrence of an M1 unit immediately following an M1 unit is the same as for an M1 unit to follow an M2 unit. The probability of either unit at any place in the chain is always equal to its mole fraction in an ideal copolymer. This applies to the increment of copolymer formed over a narrow range of conversion and not to the total product. The total product consists of increments of polymer formed at progressively changing monomer ratios. If the two radicals show different selectivities in their selection of monomers then rlvr2 = 1. If rl'r2 > 1, the tendency for radicals of D a given kind to regenerate themselves is greater than their tendency for alternation. Such a copolymer would contain groups of like units 38 in greater abundance than in a random copolymer and this tendency in- creases as the product of rl'r2 increases. In the as yet unknown case where both k12 and k21 are zero, the two monomers might polymerize simultaneously yielding a mixture of two polymers rather than a co- polymer containing both units. There appears to be no known example of a free radical propagated copolymerization for which rlor2 >-l. The product rlvr2 is almost always less than unity. .Actually cross monomer additions predominate over additions of a like monomer. In the specific case for the copolymerization of itaconic anhydride and styrene in benzene the rlvr2 product is 0.011 and for the same copolymerization in tetrahydrofuran the rlorz product is 0.058. The small values for rl and r2 correspond to very small rate constants for reactions (a) and (c) on page 33. This condition leads to a copolymer in which the monomer units alternate with near perfect regularity along the chain, and the itaconic anhydride-styrene co- polymers are believed therefore to have highly alternating structures. In figures 2 and 5 the curve crosses the broken line which represents F2 = f2. .At the point of intersection the composition of polymer being formed coincides with that of the monomer mixture and polymerization proceeds without change in composition. ‘wall (33) designates these critical mixtures as "copolymerization azeotropes." Letting F2 = f2 in equation (3) we obtain for the critical concen- tration (f2)c = (1 ‘ r1)/(2 ”'r2 - r1) 39 In.benzene (f2)c 0.61 calculated 0.77 from graph. (f2)o In tetrahydrofuran (f2)c = 0.76 calculated (f2)c = 0.73 from graph. The value of (f2)c lies within the permissible range only if both r1 and r2 are greater than unity or less than unity. If one of the reactivity ratios is greater than unity while the other is less than unity, no critical composition exists. .As the polymerization continues, the compositions f2 and F2 depart increasingly from that of the azeotrope. The final increment of polymer formed when pdlymerization is complete would consist entirely of the pure polymer of M1 or M2. If the monomer reactivity ratios are much less than unity the mix- ture is strongly azeotropic. The copplymer composition approximates that of the azeotrope over a wide range in f2, and the two units tend to alternate regularly along the chain. The itaconic anhydride-styrene copolymer exhibits a strong tendency towards alternation. In the determination of the parameters rl and r2, all the pro- cedures depend on careful analysis of the copolymers formed from a series of monomer mixtures at varying concentrations. Since the con- centration changes with conversion it is necessary to limit the copolymerization to a conversion to polymer that represents a very small fraction of the monomer mixture. If the monomer mixture is not carried to a low per cent polymerization then the average composition of the copolymer produced over a finite range of conversion must be [to oalculated. This can be done by the method of Skeist (3h). Let [M] = [M1] + [M2]. The number of moles of M1 polymerized out of a total of -d[M] moles of monomers converted to polymer is ~F1dEM]. Meanwhile f1 changes by dfl and the number of moles of unreacted M1 changes from flflM] to (f1 + df1)([M] + d[M]). The decrease in moles of M1 must equal the moles appearing in the newly formed polymer r1[M] - (£19. df1)([M] ... d[M1) = ~FldLM] dDVIJ/[M] = dfl/(Fl - f1) This may be converted to the integral form from the initial feed composition (f1)O to some value f1 f1 ([MJ/[M]o) ‘3 (4-1») dfl/(Fl " f1) For the values of r1 and r2, Fl-may be calculated as a function of f1 through the use of equation (3). The integration may then be performed graphically to give the degree of conversion. Through.a repetition of this process for chosen values of f1, it is possible to construct the relationship between fl and the degree of conversion. The calculations required by this method are indeed laborious and for this reason the experiments were designed to eliminate these calculations. .All polymer- izations used for the evaluation of reactivity ratios were carried out to a low per cent conversion. The method selected for this investigation to evaluate rl and r2 is the most widely used (37) and consists in substituting the copdlymer and monomer compositions for a single copolymerization in equation (2), Lil and plotting rl verSus r2. This was done for each of several co- polymerizations. If there were no experimental error, all of the lines would intersect at. the same point, the coordinates of which are the proper values of rl and r2. However, an average point of intersection had to be determined which represented the best experimental pair of r1 and r2 values. Theoretical composition curves (Figs. 2 and 5) calculated from r1 and r2 values determined in this way are seen to agree very well with the experimentally observed copolymer composition throughout the range of monomer composition. It appears therefore, that one is justified in concluding that the theoretical treatment is correct and that the same rate constant ratios apply at all compositions. For the copolymerization of itaconic anhydride and styrene in benzene, r1 (styrene = M1) is 0.015. This means that the styrene radical is about sixty-seven times more reactive towards the itaconic anhydride monomer than it is towards the styrene monomer. In the same system, r2 (itaconic anhydride = M2) has been shown to be 0.780. This means that the itaconic anhydride radical is one and three-tenths times more reactive towards the styrene monomer than towards the itaconic anhydride monomer. For the copolymerization of itaconic anhydride and styrene in tetrahydrofuran rl is 0.1 indicating that the styrene radical is ten times more reactive towards the itaconic anhydride monomer than towards the styrene monomer. In this solvent, r2 is 0.6 showing that the itaconic anhydride radical is about one and seven-tenths times more reactive towards the styrene monomer than it is towards the itaconic anhydride monomer . h2 In both cases r1 and l/r2 are lees than unity and greater than unity respectively. This indicates that both radicals prefer different monomers, and lends further evidence to the belief that the itaconic anhydride-styrene copolymer has a highly alternating structure. The temperature effect on the monomer reactivity ratio is fairly small. In the limited number of cases examined with accuracy (36) the ratio nearly always changes towards unity as the temperature increases. This indicates that a difference in activation energy is responsible, at least in part, for the difference in rate of the competing reactions. The reactivity ratios rl and r2 are fundamental constants for the free radical polymerization of the two monomers and are expected to be independent of the polymerizing conditions. The fundamental nature of r1 and r2 values to describe the free radical copolymerization of two monomers is obvious from the theoretical considerations. However the constancy of the rl-r2 values for a specific co- polymerization in a variety of solvents with a variety of free radical catalysts and temperatures has not been systematically studied. Variations in the rl-r2 values might be expected for variations in the type of copolymerization, that is, free radical, cationic, or anionic. Variations would also be expected when comparing polymer- izations having different reaction sites. Copolymerization where polymerization occurs in solution might differ from a copolymerization where polymerization occurs on the sur- face of the polymer or solid catalyst which might in turn differ from copolymerization where polymerization occurs at a liquid-liquid interface. 1L3 This must be expected because of the individual and separate solu- bilities of any two monomers in solvents (precipitated polymer included) and the individual and separate adsorption of the two monomers by the polymer or catalytic surface. A different ratio of monomers at a reaction site than the ratio added to the reaction will result in copolymers which when used to evaluate an rl-r2 pair experimentally will give an apparent value only. A strict comparison of the reactiVity ratios for the copolymer- ization of itaconic anhydride with styrene in the two solvents used in this investigation is not, therefore, entirely justified. As previously mentioned, the growing copolymer precipitates as it is being formed in benzene but remains in solution in tetrahydrofuran. Polymer thus precipitated may act as an auxilliary site of reaction. The values of r1 and r2 determined in tetrahydrofuran should be closer to the funda~ mental values than those determined in benzene. In view of the above mentioned physical difference between the copolymerization in tetrahydrofuran and the copolymerization in benzene it is indeed striking that the valuesof rl and r2 obtained in the course of this investigation are so close. The values of rl in benzene and tetrahydrofuran differ by a factor of only seven, while the values of r2 in the two solvents are almost identical. It seems even more significant that the reactivity ratios agree as Well as they do in the two different polymerizing media, when one notices the considerable variations observed in the two solvent systems with regard to molecular weights and reaction rates. The weight average molecular weights, Eh; were determined by Kangas (35) making use of light scattering phenomena from dilute solu- tions of the polymers. The light scattering measurements on the itaconic anhydride-styrene copolymer were made in acetone. The following values were obtained: —- Solvent Catalyst ‘Mw Benzene Benzoyl Peroxide 156,000 Tetrahydrofuran Benzoyl Peroxide 50,000 A primary factor affecting the molecular weight of a polymer as it is being formed during reaction is chain transfer. The amount of chain transfer depends on the nature of the particular solvent and has been shown to affect the degree of polymerization (h9). The more chain transfer the lower the molecular weight of the polymer formed. Chain transfer is at a minimum in benzene as compared to a large variety of solvents. .Although no work has been reported on chain transfer in tetrahydrofuran it would be predicted that transfer re- actions would be considerably greater in this solvent than in benzene, a phenomenon that could easily account for the difference in the observed molecular'weights. The copolymerization of itaconic anhydride and styrene has been shown (35) to be about twenty times faster in benzene than in tetra- hydrofuran. The values are given in Table V. In order to explain the difference in the rates of polymerization as observed in the two solvents, the following arguments are presented. An increase in the over-all rate of polymerization may be affected by: LLS TABLE V FIRST ORDER REACTION RATE CONSTANTS mm"— W Copolymerization System __‘.— ———v——— 'q f 7% fi—v—v _—__f -1 k (Sec. ) from Styrene from I..A, Solvent Catalyst Concentration Concentration -4 -4 Benzene Benzoyl 1.6 x 10 2.0 x 10 Peroxide -6 -6 Tetrahydrofuran Benzoyl 9.6 x 10 8.3 x 10 Peroxide [[6 a) An increase in active centers. b) An increase in propagation steps. c) A decrease in termination reactions. The increase in the rate of polymerization in benzene nay be attributed to an increase in active centers, due to an induced decompo- sition of the benzoyl peroxide catalyst. The benzoyl peroxide catalyst has been shown to undergo an induced decomposition in certain solvents (BB-ho). A second possible explanation for an increase in active centers and hence an increased rate for the polymerization in benzene solvent may be due to the action of the dead or precipitated polymer acting as a co-catalyst with benzoyl peroxide. This co-catalytic effect has been proposed by Bengough and Norrish (h6) to explain certain of their observations in studies on the polymerization of vinyl chloride. In the presence of a solvent for the polymer, such as tetrahydro- furan, the polymerization proceeds at a somewhat constant rate which decreases in the late stages of the reaction. Dead polyvinylchloride has been shown to act as a co-catalyst with benzoyl peroxide in the polymerization of vinyl chloride. In the absence of benzoyl peroxide the dead polymer does not catalyze the polymerization. It is suggested that the co-catalytic effect of the dead polymer is caused by an increase in the number of centers of polymer growth in the reacting System. These new centers arise from chain transfer reactions between growing polymer chains and molecules of dead polymer resulting in the accumulation of stabilized centers of polymer growth on the surface of h? the solid polymer. The revivified polymer grows by addition of monomer until it is finally terminated by chain transfer with monomer, with the production of a mobile free radical. Only in the case of the polymerization in benzene does the co- polymer of itaconic anhydride and styrene precipitate and therefore only in this case can a co—catalytic effect be expected. A decrease in the rate of termination will also account for an increase in the over—all rate of polymerization since any given radical will propagate longer and for a given concentration of active nuclei more monomer will be converted to polymer in a given time. A related dependence of the rate of termination, kt’ on the medium has been observed by Norrish and Smith (hl) working with methyl methacrylate, and by Burnett and Melville (h2) with vinyl acetate. Rates in poor solvents are high due to a decrease in kt‘ This decrease in kt accounts for the increased rate in polymerization. Actually pre- cipitation of the polymers appears to be responsible for the effect since the growing radicals become imbedded in precipitated droplets, presumably of very small size. This effect causes the suppression of the termination reaction owing to the isolation of the chain radical in one droplet from that in another. This is common in systems yielding polymer which is not soluble in the reaction mixture (D3). It is closely related to the fast rates observed in emulsion polymerizations, which are explained on the basis of a decrease in kt caused by reaction environment. 1L8 Precipitation of the itaconic anhydride-styrene copolymer from benzene as it was being formed would result in conditions leading to a decrease in kt and consequently a higher over-all rate. This is not the case for the copolymerization of itaconic anhydride and styrene in tetrahydrofuran from which the copolymer does not precipitate as it is being formed. A consideration of the structural unit of the styrene—itaconic anhydride polymer molecule is essential at this point. If the growing polymer radical, M:, were to attack a styrene monomer two product radicals might be formed. They are: M: + CH2 = CH Mx-CHz-CH- V Mx-CH-CH; II (b) I (a) Process (a) should be more favorable since the product radical would have more opportunity for resonance due to the adjacent phenyl ring. Three quinoid resonance structures may be written for the substituted benzyl radical obtained during the course of polymerization: Mx—CH2~CH Mx-CHz-CH Mx-CHg-CH [fills—s [>9 C“ The relative rates of these processes should depend on the stability of the product radicals I and II. In II, the phenyl ring is situated on the beta carbon atom and thus is unavailable for participation L9 in resonating structures involving the odd electron. Thus I is more probable than II. A comparison of bond strengths in methane and toluene (Ml) indicates that a benzyl radical. as in I is favored by resonance stabilization in the amount of 20 to 25 kcal. per mole. The product radical II is a (B-phenylethyl radical analog which should have approxi- mately the same stability as an ethyl or methyl radical. Thus process (a) should be favored over (b) by an energy difference of about 20 to 219 kcal. per mole. Resonance stabilization in the transition state f or the monomer addition step will be less than the energy of the product radical, but the activation energy for (a) should be less than that- for‘ (b) by about 8 to 10 kcal. per mole which should be enough to cause I to form to the almost complete exclusion of II. If the growing polymer radical attacks the itaconic anhydride man :omer two possible structures would result: M -CH "C' X 2/\I III o=c Ch2 'c) I l Mx-+Ch.=C-—Ch3 o—c=o I I O=C C-O / \O Mx~ c—cr2 /\... IV 0=C bhg Id) I I ' O—C=O The product radical III could have the following resonance stmct-u res: MX-CHE-C—CHE MX- . u I or C ‘ C C a O \‘O” \. 1’ C) :1: C) m H l (7—00 0—0 H O In monomers having the C = 0 group conjugated with the carbon- carbon double bonds, the above resonance structures describe states of higher energy than those for the radical styrene. thus their resonance energy is smaller. From resonance considerations III would be more stable, and although the resonance stabilizations are less than phenyl they are by no means negligible. The stabilization of the monomer by substituents must also be considered. The additional resonance structures which are introduced by the presence of the substituent contain fewer bonds than are present in the structure normally written for the monomer; thus these represent higher energy states. Resonance stabilization by the substituent is therefore much less in the monomer than in the corresponding radical. In styrene, the resonance stabilization due to conjugation amounts to about 3 kcal. per mole. The effect of a conjugating substituent in the monomer may be summed up by observing that its influence is much greater in the product radical than in the monomer. In the activated complex which is in an intermediate state between reactants and product. resonance stabiliration is appreciably greater than in the monomer reactant, but less than in the product radical. The substituent there- fore lowers the activation energy of the reaction and increases the reactivity of the monomer. The conclusion to be drawn is that the more reactive monomers give the least reactive radicals. and the least reactive monomers the most reactive radicals. 51 Thus from the previous discussion of reactivity ratios it can be seen that the propagation constant for the more reactive styrene with a styrene radical turns out to be less than that for the less reactive itaconic anhydride monomer with the more reactive itaconic anhydride radical, since this lacks appreciable resonance stabilization. Successive and alternate addition of monomer molecules in accord- ance with the preferred processes (a) and (c) will produce the following polymer chain oCh'2-CI—L-CH, S— c —- CH2“GH"CH2 — c —— CHa’Ch / \ / \ o .-= 0 CH2 = 0 CH2 (A) I I I I - p This structure has the units oriented in the same direction and is designated as the head-to-tail or l,3-structure. In each monomer the -CH2~ is designated as the head. At the other extreme there is the head-to-head, tail-to-tail, or 1,2 - l,h- structure _ 7 fl? oCH2~CH - c\- CH,—- CP2-CH o\~ CH2-— CHE-CH -/C\- on, B) 02C / CH 2 0:0 CH2 c=c CH2 ‘ I I l l l I o----c-.-.oL o—c=o o-c=o A p The head-to-head structure is impossible based on resonance con- siderations. .Another factor which may favor the head-to-tail arrange“ ment is the steric hindrance offered by the phenyl radical as it 52 approaches the anhydride ring. .A model compound was constructed and this was indeed evident, since it was impossible to construct a unit with a head-to-head arrangement. A few of the possible configurations which the polymer chain may have when the units are arranged in a head-to-tail construction have been illustrated Ipage 29). From the previous consideration the structures of the monomers are such as to greatly favor head~to-tail arrangement to the almost complete exclusion of any head-to-head, (tail-to-tail) configuration. Similar lines of reasoning have been and can be applied to many vinyl type homo and hetero copolymerizations. This reasoning has been confirmed in abundant instances by various workers (h7,h8,h9). Detailed analysis of many polymers and some co- polymers has failed to reveal one substantiated case of head-to-head \tail-to~tail) structure. The subject is reviewed in detail by Marvel IIIS). Until direct evidence to the contrary is obtained. the formula for the unit of the itaconic anhydride styrene copolymer will be considered a head-to-tail structure as illustrated in A: t 'I ’Cno-CHHCI‘I, " C _'_’ Clio-CH-‘CI'E - 3 — CIi.--CH' ... ... / \ -. 2 / \ z o = I: Ch, c = ; Ch, I I I I C - k. c O b L. _ v = K: n PART II Preparation and Analysis of Itaconic Anhydride--Styrene Copolymers and Their Ester Derivatives A. Preparation of Itaconic Anhydride-Styrene Copolymers. Titration of Itaconic Anhydride-Styrene Copolymers. Determination of Apparent pK' Values. Preparation of Monoester Derivatives of the Itaconic Anhydride- Styrene Copolymers. 1. By Reaction with Alcohols. 2. By Reaction with Dimethyl Sulfate. Titration of the Monoester Derivatives of the Itaconic Anhydride- Styrene Copolymers. Preparation of Diester Derivatives of the Itaconic Anhydride-Styrene Copolymers. l. Dimethyl Ester of Poly 61:39 (itaconic anhydride co styrene). 2. Methyl Ethyl Diester of Poly 57:h3‘(itaconic anhydride co styrene). 3. A Partial Diethyl Ester of Poly 61:39 (itaconic anhydride co styrene). h. Attempted Preparation of a Diester Using Absolute Alcohol and Gaseous Hydrogen Chloride Catalyst. Titration of the Diester Derivatives of the Itaconic Anhydride- Styrene Copolymers. Preparation and Titration of the Homopolymer-Polyitaconic Anhydride. 1; Preparation of Polyitaconic Anhydride. 2. Titration of Polyitaconic Anhydride. Titration of Mixtures l. Itaconic Anhydride-Styrene Copolymer and a Monoethyl Ester Derivative. 2. Itaconic Anhydride-Styrene Copolymer and Itaconic Anhydride 3. Monoethyl Ester Derivative and Itaconic Anhydride. Titration of Some Dibasic.Acids. Itaconic Acid ‘Unsymmetrical DimethylSuccinic Acid Methylsuccinic Acid Salicylic Acid-Benzoic Acid Mixture Propionic AcidoAcetic Acid Mixture K. Derivatives of the Itaconic Anhydride~Styrene Copolymer. 1. Preparation of an Optically Active Monoester Derivative of Poly 61:39 (itaconic anhydride co styrene). 2. Preparation of a Network Polymer. L. Stability to Hydrolysis. 1. Stability to Hydrolysis of the Monoethyl Ester of Poly 61:39 (itaconic anhydride co styrene). 2. Stability to Hydrolysis Of the Dimethyl Ester Of Poly 61:39 (itaconic anhydride co styrene). M. Infrared Spectra. EXPERIMENTAL T S 3 Q'd-o—OJC SEQ ...; 2 DEW) ___> 20.4.2002 m- .-= CH —--—9 M-CHg-CH' M—CHz-CH- CH2 .. 0- CH2 M-CHz-CH-CHz—C' F ' I '—9 / \ o= c\ [c = o 0:? (EH2 o o — C = o M~CH ~CH-CHc-C- CH H " " , 2 ~ \ + 2‘0 a M»CH2-CH-CH2;C\- CHE-CH ‘IM'; ‘SHB / I“? ‘9“ o—C=o ‘ O—C-=O \ \ .. _J A. Preparation of Itaconic Anhydride-Styrene Copolymer. Sh A. Preparation of Itaconic Anhydride-Styrene Copolymer§_ The copolymerization was carried out in a one-liter, three—neck, round bottom flask with standard taper ground glass joints. The flask was fitted with a reflux condenser, a nitrogen inlet tube and a mechani- cal stirrer. The polymerization mixture was protected from moisture by a calcium chloride tube and kept under a nitrogen atmosphere. The flask was charged with 625 ml. of thiophene-free benzene and the desired quantity of itaconic anhydride. To dissolve the itaconic anhydride the mixture was heated, with stirring, at the reflux temperature of benzene (80°C) maintained by use of an oil bath. Approximately thirty minutes were required for the solution of the itaconic anhydride. To the resulting solution was added the styrene and 0.233 g. of benzoyl peroxide dissolved in 75 ml. of benzene. At the end of the reaction, the solid copolymer was removed by filtering with suction, dried, and weighed. The copolymer was purified by exhaustive extraction with benzene in a Soxhlet extractor for ten days, and then dried under vacuum in a drying pistol at the reflux.temperature of acetone. The copolymer was then analyzed for carbon and hydrogen. The data on the various copolymers prepared are summarized in Table VI. 55 l L Amthhvm oo mpwhphndw oasoowpflv meannaeea deededea u .a .H .2. \I meumm sane m.mm H.em N.oe H.m ne.o N.nH mm.n Amdmphpm oo mpflpphnqm aflooompfiv mnuem_aaod m.pm H.dm :.dn o.nd m.pfi N.:N H.0m Aommphnm no testament eaeoedpav mnuem sand e.nm m.®m n.de 1.10 :.mm N.nm H.0N Amcohhpm no mcflnphAQm ofidoompflv am an sand m.Hn m.mn n.en e.ee m.mm N.:N H.0N - -nm 4 my -rl m mm. .HoEmHoooo S.” .HmEmHoooo cH pogoooo go 3.3 pmsmHodoo pasta“: chafing pmpwcwflmmm mpsmswmm .4.H mpsmswmms.¢.H qfl magnum sflnmstom mesonoz Luanda: smeaHoaoo pnmoamm pswommm pcmonmm psmoumm CH mqmpmpm CH mpflpvhgq4 can: ofiaoompH an at: all {1" 56 . HighLFrequenpy and Potentiometric Titration Procedures for the ItacoWyflride—Stygene Copolymers e titrations were followed with a pH meter and a high frequency ter at the same time. a hydrogen ion concentration was measured on a line operated pH meter equipped with glass reference and saturated calomel ies. a high frequency titrimeter which was used is one originally i by Johnson and Timnick (SO) and later modified by Lai, Mortland, 110k (51). a titrations were performed with the titration apparatus operated negacycles per second. Oscillator tube grid current change was 1 during the course of the titration. To follow this change a Dmeter set-up had been designed to follow the potentialmdrop related to the grid current flow change across a resistor which lected in series with the grid leak resistor. The potential drop this added measuring resistor was compensated with a potentiometer. ant reSponse is expressed throughout this study in terms of by potentiometer dial units. 7k % ”CH2 '/C'{ H‘Cl‘ 3 —CH2 — c - CH2 Preparation 0 = C CH2 . . __ I \ | Of sample r | | titration O — C ?H2 - C = O Na 0 c = o | 1_ + H-O c = o O Na I 57 accurately weighed sample (approximately 0 .2 g.) of the finely copolymer was dis solved in acetone. To this solution was added quantity of standard sodium hydroxide and the solution was on a steam bath to drive off the acetone. There resulted a clear In of the disodium salt of the copolymer. When the odor of 2 was gone, the sample was quantitatively transferred to the xylene cell of the high frequency titrimeter. ‘Ihe sample was Lluted with distilled water to a volume of about 180 ml. The odes of the potentiometer were placed in the solution and pro- was made for mechanical stirring of the solution during the ion. A glass stirrer was used. he standard HCl solution was added from a 50 ml. buret in 1 ml. Lents. In the titrations where the HCl tit-rant was added in O .5 .crements, a 10 ml. buret'was used. After each addition of tit-rant, two minutes were allowed for the reaction to reach equilibrium. 1 reading of the potentiometer and the potentiometer dial reading a high frequency titrimeter were simultaneously recorded. hen the copolymer was converted to the free acid form a precipitate userved in the titration cell. Several increments of tit-rant were beyond this point to insure the completeness of the titration and he purpose of plot-ting the data. Figures 7 through 11; represent plots of the data obtained in the .tion of the itaconic arfi1ydride-styrene copolymers. Figure 15 is >t of the data for the titration of the maleic anhydride-styrene Lymer. The data are summarized in Table VIII. 58 CI .gures 9A, 11A, and 15A represent plots of pH versus log 1 > calculate apparent pK' values. 1e data used in plotting all the figures in this thesis are in the Appendix. .1 adding sodium hydroxide to the copolymer there result two ylate ions: CH2 “/C\" __1§ng"0}1‘a - CH2 -/0 - o = 0 CH2 \ I I O = (.3 (EH2 O-C=O Na‘O" p—eo Type II O_Na+ PKa' Type I The apparent pKt values are shown in Table VII. The method used Iculate pK' values is shown in C, page 7h. F‘or reference, the carboxylate groups were labeled Type I and II and considered to have corresponding pKli and pKEt values ctively. Type .I was assigned to that particular carboxylate group, ased on structural considerations it is believed to be the stronger Type I carboxylate is attached to a methylene group and is Ler removed from the polymer backbone, whereas Type II is attached disubstituted carbon atom and is directly attached to the polymer >one. For these reasons Type I carboxylate is probably a stronger and it is believed to be more easily solvated . Whenever necessary, the end points determined from the high- lency titration curves were used to locate accurately the end ts on the pH titration curves so that apparent pKi values could be 59 xi. The use of the high frequency end points to locate >metric end points was especially necessary in locating amy sodium hydroxide, an end point which was completely hidden in entiometric titration curve. ice in all cases the calculated pK- values agreed very well with sad directly from the pH titration curve, only a limited number values were calculated. meanpaeea saddest 0. a a. 0 a. d 0. 0 0000. 0 m. 00 *3 0.0 0.0 0.d 0.0 020.0 0.00 0H --- I- a. 0H 0. a 0000. 0 0. m0 2 --- .I m. 0 00 800.0 H. mm 00 0.0 hum 0.0 0.m 008.0 dam S I... u-.. mé m.m m00m.o m.wm 9H 06 9m 0.0 Tm :8m.o mém m n} .3 0.0 0.0 0000.0 0.00 0 --- --- do 0.0 22.0 0.00 N. .mvfi 2 mu .m mm .H 0.3 . w .HmEmHoQo o no 952 pofimagfico mmsdg ma . @550 mg. 9:353 sun mfiBfiwmm mpsmfia 089m unapoma‘a comm cognac? Mg mflgfimm 24; yamopmmu £0 a: 61 .000000000 000000000 0000020 .smmohpmmtsonamo u 0:0 mmpflpphndd.oficnowp_ n .0..0* 000.0 000.0 000.0 000.0 000.0 000.0 0 0 000.0 000.0 0.00 0000.0 .00 0mm.0 mom.0 000.0 mwm.0 m0m.0 mum.0 0 0 m0m.0 m:m.0 0.00 0000.0 00 00m.0 000.0 000.0 000.0 000.0 000.0 0 0 000.0 000.0 0.00 0000.0 00 000.0 000.0 mom.0 00m.0 000.0 00m.0 0 0 000.0 000.0 H.0m 0m00.0 NH 000.0 000.0 000.0 mmo.fl 000.0 000.0 000.0 mmm.0 000.0 000.0 H.0m 0000.0 0H 000.0 000.0 Ham.0 Hmm.0 mHm.0 Hmm.0 0 0 0:0.H 000.0 0.0m m000.0 QH 000.0 000.0 000.0 000.0 000.0 000.0 0 0 000.0 000.0 0.00 0000.0 0 000.0 000.0 000.0 000.0 000.0 000.0 mam.0 mam.0 000.0 000.0 0.0m 0000.0 0 000.0 000.0 000.0 000.0 000.0 000.0 000.0 000.0 000.0 000.0 0.00 0000.0 0 mwth0d¢emuo qoflpwapfia pooch .00000 coach .poamo pd:o@..00000 .000: .0002 goshaoooo .w Honssz sang wasps 5000 mpsms ..mmmnll .0002 «000: 0000< 00000000 00 00008000 000003. mpswflm -000 .40 -000 .00 00000080000 00000000000 0002 000800 0002 0002 .4; 0.000.000 0000000 .006: 00.0.0.0 .0000: 00.090. 0.0 0&0 0 080.0 . .0. 0.00003 62 .00:I200~0.0 £003 0000n00p Amnmhmpm 00 00000000020 000000000 m000m 0000 00 0000 55000000 0:0 000 00>050 000000000 0:0E00000000 Amv 0000050000000 0G0 000.002000000 £000 .0 .000 000 0a 00 00 00 00 00 00. m0 00 00 0 0 m m 0 0 _ _ _ _ _ _ _ ... _ _ _ _ _ 000 O 0 l l 000 m l O O I CON. 0 O 0 l I 000 O x m I I 000 O O 0 I. o 1: 000 N I . I 000 O 0 w ..I .0'! I 003 0 l . . 000 00 1 000 0 00! . 000 o .9... o 00! m 000 Empeeu 19m Dial Reading 801 799 797 795 793 791 789 787 785 783 779 777 775 773 771 769 63 —-]2 -?ll -—'10 Fig. 80 l l l l I h 6 8 10 12 1h 16 18 2o 22 2h ml HCl High frequency'CA) and potentiometric (B) displacement titratian _ - _ curves for the disodium salt of Poly 57:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HCl. Dial Reading 800 790 780 770 760 750 7110 6b O A r—13 ‘— O - --l2 0 __ -»ll — -1o 0 I O O — o .. —9 O O ,0 _. ' , —8 O. ._ ‘ 0 __ 7 o O O — . '. —6 0 ° 0 .— . —§ __ 0 - h o B -— ‘- —3 0". 2 I I I l I 1 l l I I 2 u 6 8 1o 12 1h 16 18 19 2o 22 ml HCl Fig. 9. High frequency (A) and potentiometric (B) dispLacement titration curves for the disodium salt of Poly S7:h3 (itaconic anhydride co styrene) titrated with 0.1286N-HCl. 65 .m .wfim c0 0000000000 000 00.0 .0000 0:0 E000 $0500.00 00 - 0.000000% 00:83: 00$ .38 .00 00002000 000 .80 I00 000 .9, mg 00 098 1a .000 0 .II mo .0 ... 0 0 0.0+ 0.0-. 0.0.. 4.0+ 0.9- 0 0.0. :0. 0.0.. 0.0. 0.0.. 0.0.. 13”.. 0.0. 0 _ _ _ _ _ _ _ _ _ _ _ _ _ 66 .000az0000.0 0003 00000000 00000000 00 000000000 000000000 mgupm 0000 00 0000 00000000 000 000 000050 000000000 000500000000 Amy 00000500020000 000 A ma mo poem .4HH .maa d UIH N.H+ o.Hi @.0+ 0.0+ 1.0+ N.o+ o N.o. 3.0. 0.0- m.o- o.H- N.H. _ _ _ _ _ _ _ _ _ _ _ _ r moH o.H u macaw 1.m N. m "3..“va II© AV 0 law a [um m w.fi u macaw 9w .....me la 0 uuoa Dial Reading 802 800 798 796 79b 82 790 788 786 78h 782 780 778 776 —-12 l \fl l I l I l I l *1 2 3 h 5 6 7 8 9 ml HCl Fig. 12. High frequency (A) and potentiometric (B) disphacement titration curves for the disodium salt of Poly S7:h3 (itaconic anhydride co styrene) titrated With 0.1286N-HC1. 69 Dial Reading 8h2 8hO 838 836 83h 832 830 828 826 82h 822 820 818 70 ~18 r-13 —l2 O A. C -—I ‘— O -i O O — O O .0 I '—I o O c—I . . . B —§ 0 O'. I I I I I I I I ml HCl Fig. 13. High frequency (A) and potentiometric (B) displacement titration curves for the disodium salt of Poly 61:39 (itaconic anhydride co styrene) titrated with 0.09666N-HCl. 71 Hom HE P“: CHI HHI O C II' o < o o O O . O C \ 6 1m Q . O O .Smémnwmoé 8.8 8853 $888 8 823.83 38033 smug has ..8 £8 5888 at (an 358 838.33 a 955083ch Amv 39me03ngko 28 SC mocwsomnm «~me 4:“ .wfim mmm I mmw I 4% I. m% I own I Rm I mmw I mmw I 03 I Hmm ll mmn I mmm BUIPBGH 119m 72 mm ma Hum HE OH II HH ll NH I1 mall 4:; .Homlzmwmaé fig 63.339 Amqmbnpm 0.0 69362396 4 33.95 om“0m buom mo pawm sowoomfio 93 pom $550 53.8de prmEmomHQmHU pmv cunnpmsofiqmpoa and 33 honmdompm gwfim .mH .wwm amp I 95 I mam I $8 I 6% I 93 I omn I mmm I :mw I omn I mmw BUIpeeH IB'FCI 73 .mH .mafi 0H codpmupdp may now 8980 map 509% .Ammmhhpm oo moapomgsw oamawsv om. om AHom Mo moawwnpdp map pom .ILPIw moH mb mm Mo pon .ama U a; 0.? 0.? 0.? 0.9 0.0+ 0.0... 0.0; 0 0.0. 0.? 0.0. 0.0- 04.. NA. _ _ _ _ _ a _ _ _ _ _ _ _ _ mod .0: m.H u macaw ®.m ".mm mg 7h C. Determination of Apparent pKlf and ng' Values If we define the primary dissociation constant of the free copolymer acid as: . + I - _ H x HIA J <1) Ka~ Limin— where [HQLAI is the molar concentration of all itaconic acid segments in the copolymer, IHIA? is the molar concentration of all mono-ionized itaconic acid segments in the copolymer and [HP] is the molar concen- tration of hydrogen ions .‘ Taking the logarithm of the reciprocals of both sides of equation (1) we have: ;_ 1 _ I Mng (2) log K — log THT] I— log TH—LT-T or (3) pK = pH + 10% [Eiié] Rearranging (3) gives ()4) pH = pK - log [BI-}E% or \5) pH = pK - 10g (1 _ a) 75 where a is the fraction of mono-ionized itaconic acid segments. If equation (1) is valid, the potentiometric data should conform to the linear equations (h) and (S). Katchalsky and Spitnik (52) have attempted to apply the Henderson-Hasselbach equation -5- to potentio- 'metric data from the titrations of the polymeric acids polymethacrylic acid and polyacrylic acid and have found it necessary to modify it to the form (6) pH = pK ~ n log L;:El- g as the slope of the lines determined by a plot of pH versus log (l_él22. for these polymeric acids was not equal to unity. Garrett and Guile.(53) presented the first conclusive evidence as to the polydicarboxylic nature of the maleic anhydride-styrene copolymer. The calculations presented here are similar to those used by these authors. (I A plot ol'the data of pH vs log 1 from aqueous titrations is given in Figures 9A, 11A, 15A, and 16A. The slope(n) of the curve for the apparent pKII is close to unity. For secondary carboxyls Garrett and Guile (53) have shown that if a correction is made for activity by a procedure similar to that of Katchalsky and Spitnik (52), the slope approaches two. Since titration curves of the primary carboxyls show no deviation in slope and are similar to univalent acid titrations, pKl' is a measure of the "fundamental" as well as the "practical" dissociation constant and each of the primary carboxyls may be considered to dissociate independently of the ionization of the others. 76 The lepes of the secondary titration curves are 1.7, 1.8, and 1.8. The values approach the predicted value of 2 and do not appear to vary. Previous work (53) revealed a difficulty in measuring pKzi, and it is felt that the difficulty was due to the use of too high a concen- tration. The present work appears to indicate that the difficulty has been overcome by using more dilute solutions in the titrations and apparent pKé' values for the ionization of the secondary carboxyl have been found for the maleic anhydride-styrene and itaconic anhydride- styrene copolymers. In the case of the monoester derivatives, the slope for the primary and secondary carboxylates approaches unity. As expected, this indicates the monobasic acid character of these substances. 77 Method of Calculation for Date Plotted in Figures 9A, 11A, 15A, 16A 1. [G] = Total molar concentration of all IA units in sample = 2. 3. moles IA in copolymer sample liters of solution INa+HIA-] = molar concentration of the monosodium salt of the IA units in the copolymer = ml. of acid titer added x norm. of acid liters of solution [c] - [Hm-1= [HELIX] or [c] - [If] = [HIA‘] F " _ h. Log IHIA J = log i;*-£Q' for primary carboxyl-pK1' 5. Log TEEK=j = log £;*:-£Q- for secondary carboxyl-pKz| 78 D. Preparation of Monoester Derivatives of the Itaconic Anhydride~Styrene Copolymers 1. By Reaction with Alcohols "CI-12 "/C\~ CH2 '- OH "' CH2 "/C\-‘ 0 a ? CH2 0 ==p fHE .2!Ei.ep o— c = o ' o —c = o vCH — C - CH - CH - CH“ — C — 2 / \ 2 c. / \ =I <82 0 =I IH2 H-O C = O RrO C = O O-R O-H Type II . Type I ng" I pKlII A weighed sample (approximately 0.2 g.) of the itaconic anhydride— styrene copolymer was placed in a 250 ml. flask equipped with a reflux condenser. To the flask was added a quantity (from 5 to 15 ml.) of the desired alcohol and the mixture brought to reflux. The copolymer dissolved on reaction with the alcohol. Reflux was continued for several hours after solution to insure complete reaction (1). In some cases the monoester derivative was isolated before titra- tion, and this was accomplished in one of two ways. 1. The excess alcohol was removed under reduced pressure. 2. Water was added to the alcohol solution of the monoester resulting in the formation of a precipitate. The monoester derivative was then removed by filtration, washed with ether, and dried under reduced pressure. 79 The approximate times required to dissolve a 0.2 g. sample of poly S7zh3 (itaconic anhydride co styrene) in 5 ml. of the correSponding alcohol at.reflux were as follows: Alcohol Tim§_in Hours Temperatuge OC Benzyl 0.5 200 Methyl 3 6h Ethyl 5 78 n-Butyl 6 117 2-Methyl-l-butanol 13 130 2. By Reaction with Dimethyl Sulfate ~'CH - C - CH - CH - CH - C r O 2 C/ \CH 2 02 C/ \CH = a 2:: '{1 I_ I (7' l_ 4' | 2 \1) \\H3)BSO4 0 Na. 0 a o 0 Na = o + I + . I- I- (2) H O‘Na ' 0 Na ~CH2 “/C\ '_ CH2 " CH "' CH2 - C '- 0 .... 9H2 0 =53 IH2 OCH3 q = 0 0H 9 = 0 0H OCH3 A finely ground sample (0.5 g.) of Poly 61:39 (itaconic anhydride co styrene) was placed in a 250 ml. three-necked flask fitted with a dropping funnel, mechanical stirrer and a reflux condenser. The required amount of sodium hydroxide to form the disodium salt, (Sh ml. 0.10hh N) was added to the flask and the stirrer started. About one hour was required for the solution of the itaconic anhydride-styrene copolymer. When solution was complete, 0.6 ml. of dimethyl sulfate was added through the dropping funnel. 'When the addition of the dimethyl sulfate 80 was completed the reaction was heated to reflux and maintained at that temperature for three hours. A precipitate was formed during the course of the reaction. The precipitate was separated by filtering with suction and washed with HCl. The solid product was then washed with distilled water until the washings were free of chloride ion. The acid-ester copolymer was then subjected to an exhaustive extraction with water to remove any sodium sulfate that may have been occluded during the precipitation of the product. A Soxhlet extraction apparatus was used and the extraction was continued for h8 hours. A sample of the acid-ester copolymer was then ignited in a Vycor crucible and a trace of ash remained. The ash was probably sodium sulfate. In many cases it is virtually impossible to remove inorganic salts from a polymer. This same difficulty was encountered when a catalytic quantity of sulfuric acid was used to aid esterification. E. Titration of the Monoester Derivatives of the Itaconic Anhydride-Styrene Copolymers ~CH- — CH -CH-CH-C- 2 / \ 2 2 H-O C = 0 R-O C = 0 Preparation t-R t-H of sample —G. C - CH. - C CH - C - H2 1’ ‘\ ~ H 2 1’ 0 = C CH = C CH + - . I, I 2 I I 2 H_Cl 1?, Na 0 C = 0 R-O C = 0 Back titra ion ng' O-R O-Nal PKlI -CH-C —CH-CH-CH-C-; 2 / \ 2 2 / \ 0 = 0 CH2 0 = C CH2 H'0 = O R-O C = 0 81 An accurately weighed sample of the monoester derivative of the itaconic Emhydride-styrene copolymer was dissolved in 10 ml. of acetone followed by addition, in the cold, of a known amount of standard sodium hydroxide. The clear solution was then ready for titration. In the instances where the monoester derivative was not isolated the procedure was as follows: ~CH2 _ C c/ \c c/ \c ROH 2) O = I, 'H‘? O = I |H2 Preparation of O—— C = O O — C = O monoester -CH2 /C - CH”, ~ CH - CH2 _/C\ O = ('3 CH2 0 = ('3 (EH2 NaOH _ - _ _ _ Preparation HO C—O . R0 C—O ofsample b-R (St 0 = CH2 0 =2 (I) (EH2 H Cl 3 Na+o‘ ('3 = o R—O ('3 = 0 Back titration o-R 0"sz O = C CH2 0 = C CH2 I I I & H-0 ('3 == 0 R-O l = O O-R O-H To an accurately weighed sample of the copolymer was added 20 ml. of the desired alcohol and the mixture heated until solution was obtained. The excess methyl or ethyl alcohol was removed on a steam bath. The solid monoester derivative was dissolved in 10 ml. of acetone, 82 heating on the steam bath when necessary. The solution was then cooled to room temperature and a known amount of standard sodium hydroxide was added. The clear solution was then ready for the back titration with standard hydrochloric acid. Figures 16 through 23 represent plots of data obtained in the titration of the monoester derivatives of the copolymers. The data are summarized in Table X. In the reaction of an alcohol with the anhydride segment of the copolymer two isomeric monoesters result. Both isomers are evident in all the high-frequency titration curves of the monoester derivatives. The apparent pK' values for the monoester derivatives are tabulated in Table TX. The method used to calculate pK' values is shown in C, page 7h. 2321: r of // 83 meateaaqa oamamz, IP ) II II w.a m.m Haapm ooom.o om.n: *mm II II o5 No 63me Amado 2.3 mm II II m.n a.o Haapm amao.o om.0a Hm II II N.a H.a HapapIHIHaapszm momm.o ma.fia ON II II :.n a.a Hamatm NnHm.o mfi.ma ma II II N.@ m.o aagbm ammm.o 44.00 pa m.a H.o ©.a m.o shape mNoN.o 34.00 Na w.a :.o a.» m.o asapmz mamm.o am.mo 0H imam Lama rmxm Lama pmpmmosoz .m nmshaomoo Amnszz popdfidodmo mood“; Md 9550 mm 50mm m9? .3353 5” 9:85 magma hapooflnm Comm mmsdIS ma mfimfimm Iwmm .Hmpmooaoz I‘ pamonma pamamz mmmmfigomoo EmImamag OHZOUELH Mme mo EHE<>HMHQ mmBmmozoS mam. mom and»; $3 Egan: NH mama 8h fl 1‘] mm 00 00.9 00.9 900.0 000.0 00.9 00.9 00.00 0000.0 00 00 mm 03.0 03.0 R00 R00 00.0 000.0 00.00 3000.0 00 00 00 000.0 000.0 099.0 000.0 000.0 000.0 00.00 0000.0 90 00 00 00.9 “000.0 090.0 000.0 00.0 00.9 00.90 0000.0 00 90 00 00.9 00.9 000.0 000.0 00.0 00.9 09.00 0090.0 09 00 00 00.9 09.9 000.0 000.0 00.0 00.9 00.00 0000.0 09 am 00 000.0 900.0 000.0 900.0 00.0 000.0 00.00 0000.0 09 00 90 00.9 00.9 000.0 000.0. 00.0 00.9 00.00 0000.0 09 HH 0909. II H 0905 002905000. 083.0993. S 0809. H 0909 .0002 .0002 909530000 ma .m 900,552 909009902 900000082 900002902 509% 00990530 9001000082. 9000000902 00000. .0082 0.2908000 900.00 029.02 0900.02 pd0o9mm pd00902 mo .0002 90P000no2 mo .0002 .0002 2002 2002 Inco2 0000902 0HQEMm 00000000 00>t0m00 . 000003 .00900 90000 .000: 90000 ‘ 222mg. Ill édomoo éemImmHmDME/E OHzoo¢eH. 22.2. .20 awn—.3982 22.2. mom 0.2.42 289.0252. M22. mo Mmgbm 85 2a .900Iz 0009.0 0993 00909999 20009000 00 009900000 090000090 manpm 29cm 90 90900 92290Eocos 099 Mo 9900 509000 029 909 009950 009909999 900500092090 Amv 09990509990900 090 A O=C CH2 1 | Preparation +l_ | back | l O -- C = Q of sample Na 0 ? = O titration H-O C = O O 108 A sample of the polyitaconic anhydride was dissolved in acetone. To the solution was added a quantity of standard sodium hydroxide and the solution was heated on a steam bath to drive off the acetone. The resulting solution was then titrated with standard hydrochloric acid as previously described. The titration data are plotted in Fig. 32 and listed below. Sample NaOH NaOH Calc'd. Found Meqs. 'Weight Required Added Meqs. Acid from g. Megs._ Meqs4_ Acid Titration pK:t pKa' 0.0997 1.780 1.760 1.750 1.675 5.1 7.1 I. Titration of Mixtures These species are present in the mixtures titrated: Poly 61:39 (itaconic anhydride co styrene) ~CH—C- -CH2-C- 2 / \ NaOH / \ o = c 'CH2 ————> o = Ic ('ng 0—C=0 o'Na"‘c-=o pKz‘ o‘Na+ PKl' Monoethyl ester of Poly 61:39 (itaconic anhydride co styrene) «CH2 — c —CH2-CH—CH2 — c / \ NaOH 0 = c CH 0 = c CH | I 2 I \ 2 > O-Csz OH -CH2 - c - CHg-CH-CHQ - c - ./ \\ ,I \. o = C CH2 0 = 0 CH2 I- + I I \ ONaC'l-O 0-C2H5Cl3=0 ng o-ch5 o‘Naf 109 Itaconic Anhydride I I .9, I I 0 = C C = 0 C a 0 C = 0 ‘\ /' I- 1- 0 O Na o Na pK=’ sz‘ l. Mixture of Poly 61:39 'itaconic anhydride co styrene) and the monoethyl ester of Poly 61:39 “itaconic anhydride co styrene). There are four acid species in this mixture and therefore four types of carboxylate ions are involved in the back titration. The titration curve should yield four neutralitation breaks and Fig. 27 does show four breaks, 'a—d). a. The break at about 11.8 ml. HCl could be the neutralization of one—half of the disodium salt of the copolymer. The theoretical value is 11.6 ml. HCl. b. The break at 19 ml. Cl could be the monosodium salt of the copolymer and the neutrali-ation of one type of carboxylate of the mono- ethyl ester derivative. The theoretical value is 19 ml. 31. c. lfle break at 28 ml. HCl could be the neutrali~ation of both types of carboxylate of the copolymer and one type of carbo ylate of the mono- ethyl ester. The theoretical value is 3C .1. Hi1. d. The break at 36.7 ml. HCl represents the free acid form of the four carboxylate species. It represents the neutrali ation of the second type of carboxylate of the monoethyl ester derivative. The theoretical value is 36.7 ml. HCl. 110 A2 oomo.ov Hem .H5 :.mm u Az oomo.ov Hum .He :.ma u momz mo .meoe 0mm.m ADV momz Mo .mems omN.H Adv m.w 4.0 w.m m.m soapwppfle mecflm Scam moodm> Mg pnchmma¢ 0.x m.m m.od m.© ccfipmnpfia casprz Scam mmofim> gm pochmmg< _¢ea .mxa .mea .Hea omN.N 0mm.m p.05 ooaN.o Ana oom.m 0mm.m mam.a omN.H w.mo ooo~.o Aav mHthmq< mno scam deflpmapfly scam .momz .mvmz amexHoQoo :H .w mocdpmnsn pomsmmm .<.H pdcsmmm .¢ .H Umpc< confisvmm pqoswmm .¢.H magswm a8 .252 H38. as 58: H.305 moms momz $83.1. 3mg: paws: .Amthhpm oo Imwflncandw ofldoompflv mmufio hHom Mo pmpmm fihcpmoonz ADV pom Acumempm oo mcflnbhgcw oflqoompfiv mmuap zHom Adv l mm mmDUHm 2H ZOHEdeHH mmH mom ¢H¢Q HHN mamdy PI’ 111 mm NH] ma II d... .Homrzooomo.o npfiz vmpmnpflp Amccympm oo mcflnphng oficcompflv mmnao hHom no pmpmm ahnpmocos on» one Amomthm oo mafiawzncd aflooompav mmuao_haom mo mpfiwm ssfluom mop Ho caspxfis w you mmbmso dofipmaeflp pcmsmomdumfic Amv oflgpmeOHpncpom cow A¢u_moccnvmnm swam .wm .mflm mum II 0mm II «mm II 4mm .I 08 II 2mm I 9.3 II man I as l 93 II can .I.omn II_mmw T 4mm Iuomn Empeeu I'BTCI 2. Mixture of Poly 61:39 (itaconic anhydride co styrene) and itaconic anhydride. There are four acid species in.this mixture and therefore four types of carboxylate ions are involved in the back titration. The titration curve should yield four neutralization.breaks and Fig. 28 shows five breaks, (e-i). e. The break at 6.h m1. HCl could be the neutralization of one type of carboxylate of the disodium salt of the copolymer. The theoretical value is 5.6 m1. HCl. f. The break at 11.8 could be the neutralization of all the carboxylate in the polymer which is now in the free acid form. The theoretical end point is at 11.3 ml. HCl. The breaks at g and h are unexplainable in relation to the expected stoichiometry of the titration. i. The end point at 29.h m1. HCl represents the free acid form of all the species. The theoretical end point is at 30.0 ml. H01. 113 A2 ooao.ov Hum .He ~.ma u momz an .meme mmw.fi ADV A2 oomo.ov Hum .He m.HH u momz on .mwms aao.H Amv m.o m.: m.n N.m unflpmmpfle cfiwqflm seem mosam> mm pcchwmm< mo.©~ mm.:~ mm.HHH mo.mw uoflpmnpfle caspxflz Scam moodmb mg pfimhmmgo .wea imam .mea .Hea mmm.H mmw.H NHOH.O n 0mm.m Nam.m mmo.H mmO.H m.mo memo.o m mwmhamo<_muo Scam Heapmppfia Scam .momz .mdmz nmshaomoo ca .w mocwpmnom newswmm .<.H pcmsmmm .<.H emcee emphasmm pfimfiwmm .<.a maaewm co new: Hapoa mo .mwmz fleece moaz momz pemocmm pamamz. pswflmg. .mcflnpm£Qm cacoowpfl ADV Ugo Amcmhhpm no mcwpphgqm cacoowpfiv mmuao AHom.Amv i '5‘ “III [lul‘ 11" I! i mm mmbch 2p ZOHH¢MBHB HEB mom ¢H¢d HHHN mqm¢y I4 H mm an 5 mm 3 ma 3 a m _ _ _ _ _ _ _ _ m \/ H I .Hom 2038.0 :33 xx / I 0mm cmpgfip camera? 028pr 9.8 Amcmfinpm oo ocfinaafiw 030033 mmfimo renew Mo madam Ede—”com 93 Mo masons .m 90% $53 53.239 m I #558333 Amv 02553593 9.8 A3 homage.“ CHme .3 .mfim .I amp 0 m I I own 0 I . l J o D .. mom a... d m I o o I new In ... o AoI 0 I co. m 0 II 8m I O N 0 I now 0 w I O I 0N3 . O m I I N5 . O O OH I I in O Entpeeu tam 115 Mixture of Poly 61:39 (itaconic anhydride co styrene) and itaconic anhydride. ' There are four acid Species in this mixture and therefore four types of carboxylate ions are involved in the back titration. The titration curve should yield four neutralization breaks and Fig. 29 does show four breaks (j-m). This is.a repetition of the titration in Fig. 28, but at a lower concentration of the two substances. Note: In the previous titration of the same mixture at a higher concen- tration, five breaks were observed and only four were expected. Since the acid functions in the mixture are not titrated independently of each other, the observed effect might be attributed to concentration. It would be expected that in dilute solutions there is less interaction between carboxylate groups than in concentrated solutions. j. The neutralization break at 3 m1. H01 could be the half neutralization of the ccpolymer. The theoretical end point is at 3 m1. H01. k. The break at 6 m1. H01 could be the complete conversion of the copolymer to the free acid. The theoretical end point is at 5.9 ml. H01. 1. The break at 12.8 ml. H01 should be the conversion of all the ccpolymer to the free acid and the neutralization of one-half of the anhydride salt. The theoretical end point is at 10.7 ml. H01. m. The end point at 15.5 ml. H01 represents the free acid form of all the Species. The theoretical end point is at 15.5 ml. H01. 116 .§ 958.8 Sn .2 new I. momz .meos mend 3v .Az mammo.ov Hum .fis m.m u momz .mcme wmm.o Adv m.@ m.: n.w ~.m defipwhpfls cchHm 50cm mmsdm> zm pcchmmd< fi~.mg ~m.m~ fio.oaw mm.wg coHpMHpfiE cospxaz some mosam> mo pompodd< .de .mxa .NMQ .de mmm.o mem.o memo.o ADV HQ©.o Hop.o wmm.o mmm.o N.m© mo~o.o Adv mflmhaoc<.mno Seam anaemapfle Scum .mvoz .mooz nmEhHomoo ca .w .mwddpmcsm cqmsmmm .<.H pgmgwmm .<.H emeea emcaaemm pemswmm .<._ maceom on .memz Hmpoe co .memz emcee moaz momz pemocmm pawflmz. cameos. mcfinphccw oflcnompfl Acv com Accoempm oo moflmpaccw cacoompflv mmnao hand Adv III II III III II III I l II 'III I am mmbbwm zw ZOHB¢mEHE HEB mom ¢H4Q >Hx mqmde ll? Hum as we ma 4H ma NH HH OH a w a o m a m _ _ _ 0 . .HomI2mwmmo.o spas empmnaap meaceeaea oaeooapa pom Amcmbnpm oo 32oz? 380.33 mmuao know Ho moLme Edfioom one. mo ongofie .w .89 $550 mafipgflp pdmfimomadmfio Am: ofippmfioficopom cow 3; Ravage.“ CHme .3 .ma II.o:n II.dqn I. mdn I 93 II.::w T as .I.©:n BU‘FP'EQH "[9130 118 3. Mixture of Monoethyl ester of Poly 61:39 Iitaconic anhydride co styrene) and itaconic anhydride. There are four acid species in this mixture and therefore four types of carboxylate ions are involved in the back titration. The titration curve should show four breaks and Fig. 30 does reveal four breaks, .n-q). n. The neutralization break at 6.7 m1. H01 might represent the complete neutralization of the carboxylate functions in the monoester derivative. The theoretical end point is at h.8 m1. H01. o. The break at 10.3 ml. H01 could be the free acid form of one- half of the anhydride. The theoretical end point is at 9.h m1. H01. p. The break at 1h.6 ml. H01 might be the complete conversion of the monoester derivative to the free acid and the monosodium salt of the anhydride. The theoretical end point is at 1L.2 m1. HCl. q. The break at 23 m1. HCl represents the free acid form of all the carboxylate Species. The theoretical end point is at 23.6 ml. H01. 119 .Az oomo.ov Hoe .fie n.nfi momz .mams mHQ.H ADV .Az ooao.ov Hum .H2 w.: mowz .mams a©:.o Adv m.o m.: w.m :.© cofipmnpfle mech Each mmofim> 2Q pqmadmm< mm.©H mc.zu fiN.OHH am.wg cofipwppfle mhcprz Scam mm5Ho> go pcmndmg< .oMQ .mxm .vmm .mxg maw.a man.H Omoa.o c mmm.m mmm.m 502.0 ~©:.o n.o~ mqoa.o w mammamc¢.mIo Snow coflpmhpfie Scam .mvoz .momz noeaaomoo ca .w mocdpmcsm newsmmm .a.H cqoewmm .a.H emcee emcaaeom pamsmmm .<.a mfiaeam on .memz among an .memz Hmong mowz momz pemocoa pcmamz. cameos mowhpmccw cacoowpw ADV use Amdophpm oo mcflhohccw ofldoompfiv mmuflo mHom mo ampmm Hhcpmocoz Adv ill ‘. om mmbwwm 2H onaamBHE MIR mom ¢H¢d >x mqmdfi . .Hoszooomod coup.» @3ng 03025. 3.8082.” 38 Accoezpm 00 332ch 3.8033 mmuao buom Ho 9030 Hthoocoe 93 Mo madam £363 93 mo 3.503: .m 120 mm com 3550 83.293 pamEmomHmmflc Amv 33983593 one A3 honmgwnm cwwm .om .mfim Hem d: um mm mm Hm ma 5“ ma flu in m N. m m H T _ _ _ r r L _ _ L _ _ _ N l we m I :3 a I omm I m ll .3. \ wmw O C s. C III 0 0 com a I a. .. . New .0. O O O .. o m .1 .. Jpn O m I won oTL new HHI 05 O O Bremen tram 121 J. Titration of Some Dibasic Acids O=C C==O CH3—C ---'CH2 _5 I I I H O-H O = ? g = O H-O O-H Itaconic Acid Unsymmetrical Dimethylsuccinic Acid \ I I 0 =e f= 0 0 =9 Cr 0 H-O O-H H-O O-H Methylsuccinic Acid Succinic Acid An accurately weighed sample was dissolved in water. For the direct titrations, the volume was adjusted to about 180 ml., with distilled water, and the sample titrated directly with standard sodium hydroxide. The procedure for the titrations has been described in B. For the back titrations, a known amount of standard sodium hydroxide was added to the solution of the acid in water. The volume was then adjusted to 180 ml., with distilled water, and the sample titrated with standard hydrochloric acid. I—L— 122 It was desired to use a quantity of acid equivalent to the anhydride content of the copolymer. In some cases this amount of acid was satisfactory for titration, but in some instances a larger sample was required. The back titrations, (displacement titrations), were carried out for two reasons. The first was to see how the observed pK‘ values of the back titrations agreed with the literature pK values determined by direct titration of the free acid. By back titration is meant the initial‘ formation of the sodium salt by adding the known amount of the standard sodium hydroxide to the acid sample and titrating with standard hydro- chloric acid to the free acid form of the species. The second reason was to see if the pK8 values determined by the titrations_for any of these acids resembled the observations made for the itaconic acid segment in the copolymer. Analysis of this titration data indicates: 1. That direct titrations and back titrations are in most cases equivalent. 2. The itaconic acid segment in the copolymer has a structure resembling that of a substituted succinic acid. Much difficulty was encountered in the tirration of itaconic acid which in View of the excellent purity of the sample of itaconic anhydride used was unexplainable. In this connection it should be noted that the itaconic anhydride segment cannot have the original double bond of itaconic anhydride, but is similar to a substituted succinic anhydride. 123 No particular difficulties were noted in the titration of the succinic acids. The acetic acid~propionic acid mixture and the benzoic acid- salicylic acid mixture were titrated to determine if the high—frequency titrimeter could resolve each of these two acid species and show two breaks in the titration curve. The ratio of the ionization constants of acetic and propionic acids is 1.3. It was impossible to observe two breaks in the high-frequency titration curve, and this is probably due to the fact that they are very similar in acidity. The ratio of the ionization constants of salicylic and benzoic acids is 16.8. The high-frequency titration curve for this mixture shows two breaks. This is the first known instance of the titration, in aqueous medium, of a mixture of acids with such a low ionization constant ratio. The titration data for these experiments are listed in Table XVII. The following table includes the pK values observed for the back titrations, the literature values for the pK values of the direct titrations and some observed pK values for direct titrations. 12h pmnsmwoe pom nun w.m nun m.m Uflom OHHhOHHdm poHSmme pod 1:: m.: In: H.: ofiow OHONnmm :.m H.: ©.m m.: m.m H.: oflom ofiqfloosm m.© «.4 1.0 m.: 3.0 m.: snow seafloosmaanpmeae .samq: wondmmos pod ofinwaflwbmcd ©.m N.: taco OfidflooSmthpmz m.m w.m b.m m.m m.© m.: oflom oflqocpr _~ma _Hma was Hag .mma .Hma mocwpmgsm emsmwmno .a:mmmmmmmmwm macapmnpaa seam mmmmswppwe p oopflm I III III 509% mosHm> Umbhomno mmHo< DamamHo mzom mo manna» ma H>x mqmpzo deflowuofiy quamoddnmflc Amy oflpmenHHGOyno paw n<1 hocmsoopm swfi: .wm .afia Hom HE cm ma 0H 4H NH 0H s o g m o _ _ _ _ p L _ _ _ _ own New isms own new U\w NHL T is lubwn lumen GE 1910 Butpe 131 Joni/3430.0 :35 @3339 Snow ofifioosm .Ho 3% £360me 93 no.“ noise 53.2.pr pdosooqfinmap Amv ofihpmsogcmpoa 93 34v Avocados.“ gwflm .bm .mfim Hum HE mm mm Hm H H H mH HH _ _ _ _ _ _ _ _ _m OHI En Immm Izmm Ipmm Immn I Now I102 I002 Emma I’BTCI 132 mm .Homuzfiaoé fies 8353 aged oHHsHHam E... 3028 Ho mpHam savage as Ho 233: a. .Hom 8550 83459.3 pdmfimodflmfiv Amv 393503593 38 33 hodmsvonm nmfim . pm .mfim Hum HE mm mm :N mm om wH 0H 4H NH OH 3 J m o _ _ _ _ _ _ _ _ _ _ _ _ _ as H I I 0mm m l l .Nmm m I I Hmm : I I 03 m l I nmm b I I 08 N. I I won 3 I I :3 m I I new OHI I now HHI Tog gunmen 1813a .. .—.- -~-..-—.—-.—'1r . 133 Hum HE .Homlfifimod noun: 89.8013 39830.3 £368 . . and mmeod an m mo 23%.? .m mom 25:0 acunpmppfip .ynmfimofldmfiw moggmpm nwfim .nm wWoE II Nmm I mmw In mmm I. 03 I 33 I mom I :3 I men I won T Sn gamma 19m 13h K. Derivatives of the Itaconic.Anhydride—Styrene Copolymer 1. Preparation of an Optically.Active Derivative of Poly 61:39 (itaconic anhydride co styrene). €H2”OH ~CH - C - CH -CH - C - O = $3 lCH2 + -X- 0 = C.) Cin O -- C = O ---€>- H-0 9 = O Copolymer * O - CH2 - CH2 (-) Nopol * An optically active monoester derivative of the itaconic anhydride-‘ styrene copolymer was prepared by the reaction of an optically active primary alcohol with the anhydride segment of the copolymer to form a monoester. The optically active primary alcohol selected was 6,6-dimethyldi- cyclo—(l,l,3)-hept-2~ene-2-ethanol, having the common name, nopol. The optical rotation of pure nopol is IGJSS = "36.50 (10 cm. tube). Nopol is formed by the action of B~pinene and formaldehyde (56). Regardless of the source of fi-pinene, it occurs as the optically pure levo form. A weighed sample of the copolymer was dissolved in tetrahydrofuran. A weighed quantity of nopol sufficient to form a monoester was added to the reaction flask. A reflux condenser was attached to the flask and the mixture refluxed for four hours. The solution was cooled and on the addition of water a precipitate was formed. The precipitate was filtered with suction, washed with ether and dried in a drying pistol 135 at the reflux temperature of acetone. The supernatant showed no optical rotation. A 1.0hh9 g. sample of the monoester'was dissolved in tetrahydro- furan and the volume of the solution made up to 50 ml. in a volumetric flask. A 10 cm. polarimeter tube was filled with the solution and the rotation was measured with a Rudolph Polarimeter Model 80. The observed rotation was --O.772O and the specific rotation was calculated to be 22 o IPGJD "‘ 3.69 o A 1.0059 g. sample of the monoester was dissolved in acetone and the solution made up to a volume of 50 ml. in a volumetric flask. The observed rotation was -l.266O and the specific rotation was calculated to be [0152 = -6.293. 2. Preparation of a Network Polymer In a 250 ml. three-neck flask fitted with a reflux condenser, a mechanical stirrer, and a thermometer were placed h g. of Poly 61:39 (itaconic anhydride co styrene) and 50 g. of ethylene glycol. On heat- ing the copolymer went into solution and further heating to 17000 the solution began to gel. The gel appeared in about thirty minutes. Heating was continued for one hour after the appearance of the gel. The gel was then removed from the flask with some difficulty and washed thoroughly with ether. The solid product was then dried in vamuo. The solid derivative was insoluble in a variety of solvents, indicating that a network polymer had formed. The solid copolymer was finely ground in an agate mortar. To a 0.2762 g. sample of the fine powder were added 2.0880 megs. of NaOH and 136 the suspension was allowed to sit for thirty minutes. The suspension 'was then filtered off and washed with several portions of water. The supernatant was then titrated with standard HCl and 1.3815 meqs. of NaJH'were present. Thus 0.7065 meqs. of NaOH were used by the sample. To the residue was then added 1.9h88 meqs. of HCl and after allowing the suspension to sit for thirty minutes the residue was filtered and washed thoroughly. The supernatant was titrated with standard HaOH and 1.2319 meqs. of HCl were present. Thus 0.7169 meqs. of HCl were used by the sample. It was calculated that 22.5% of all the carboxyl groups in the sample were free. and thus 77.5% of the carboxyl groups were esterified or cross-linked. L. Stability to Hydrolysis 1. Stability to Hydrolysis of the Monoethyl Ester of Poly 61:39 {Itaconic Anhydride co Styrene). l...) A inely ground sample 70.l2~2 g.) of the monoethyl ester derivative “'3 U ,_+. was weighed into a conductance cell. he cell were added 3 ml. of ethyl also ol to effect solution of the copolymer and also a quantity of conductance water. The cell was allowed to reach a temperature ’\ ..v" equilibrium of 25 t C._ L in an oil bath. A ten percent excess of 0.10th~Ea0H was then added and the time recorded. The c:ll was filled to a volume of about 25 ml. The resistance readings were taken over a 2 \J‘I hour period and are recorded in I ble XLTV. The data indicate that practically no hydrolysis has taken place at 25 t .l’f. for 25 tours. 137 2. Stability to Hydrolysis of the Dimethyl Ester of Poly 61:39 (Itaconic Anhydride co Styrene). A finely ground sample (0.0962 g.) of the dimethyl ester was weighed into the conductance cell. The dimethyl ester of the copolymer was not found to be completely soluble in any suitable solvent. A mixture of 5 ml. of ethanol and acetone was added to the cell and some of the di- ester dissolved and some remained suspended in the system. A quantity of conductance water was added and the cell placed in an oil bath at 250 i 0.190 to reach equilibrium. A ten percent excess of 0.10th-Na0H ‘was added, the volume adjusted to about 25 ml. and the time recorded. The resistance readings were taken over a 31 hour period and are recorded in Table XLV. The data indicate that practically no hydrolysis has taken.place at 25 i 0.1OC. for 31 hours. M. Infrared Spectra Infrared Spectra were obtained for polyitaconic anhydride, poly 61:39 (itaconic anhydride co styrene), the monoethyl ester of poly 61:39 (itaconic anhydride co styrene), the monobenzyl ester of poly 57:h3 (itaconic anhydride co styrene), the mononopol ester of poly 61:39 (itaconic anhydride co styrene), the dimethyl ester of poly 61:39 (itaconic anhydride co styrene), the partial diethyl ester of poly 61:39 (itaconic anhydride co styrene), styrene, and hexachlorobutadiene. The spectrum of styrene was determined in.hexachlorobutadiene, and the spectrum of hexachlorobutadiene was obtained versus a salt plate. The Spectrum of the dimethyl ester of poly 61:39 (itaconic anhydride 138 co styrene) was obtained in solution in hexachlorobutadiene and also as a mull with this solvent. The remainder of the spectra were obtained as mulls with hexa- chlorobutadiene. The instrument used in all cases was the Perkin4Elmer double beam recording Spectrophotometer. The infrared Spectra are shown in Figures 39 through h8. 139 .ocmflpgsnonoflowxmg any HHS: mama? 350.358 Mo €30.0QO 62.23 .mm .mfim 3890...”: 5” fimcmambws 9 NH fl OH a m N. o m s m b L _ _ _ _ _ _ _ _ . trots spasm spas is: $5830 00 03923.20 3:00.33 mmuao buom mo 55.3080 023de .0: .mfim 2890.“: nun gadgets; ma NH .3 OH m m m o m m _ _ _ _ _ _ _ _ b r . 0533590903088: uotsstursuazq, lhl MH NH 0590.“: 5.. £35353 H 0H m m N 0 m _ r _ _ _ _ P .0n0flvadnonodgowun0n fin? .32: $000,030 00 0303.? 0.200.093 an"? Enom mo 900.00 thp0ofiofi .23 now 85.5030 0090.53 .H: .wfim motssmsuazg, m .0q0ficmpsnon0Hgodx0g npfiz Hans A0g0ahpm 00 00Havznc0 oflcoompflv mznwm aflom mo A0900 ahwa0noccs 0:0 00% Esnpo0am 00ndfiHnH .N: .mfih mcbpofiz ca gpwc0a0>03 mH NH HH OH m m w 0 m J m _ _ r _ _ _ _ _ _ _ h uctsstmsuaqL lh3 0009002 09 :pmq0fi0903 4H ma NH HA 0H m m w c _ _ _ _ _ 0909033090200090: £393 .905 3909990 00 009900300 0.990033 mmuaw buom .90 90.900 Hogoqodoe 093 90.9 9599900990 009.09de .m: .9959, 110153 spusrrazl A0909hp0 00 00H90h£90 oficoompfiv mmun hHom mo 90900 thp0efi0 0gp 909 Ed9po0m0 00909HqH 000909: 0H npwn0H0>03 mH NH _ HH _ OH _\ m _ w _ w . .090900950090H00020n ca oj owuoflhm uotsstmsunam 5 mm 000909: 09 npwq0H0>03 MH NH HH OH m m N o m J m _ _ _ _ h‘ _ P0 — — F — .000900puno90H900R0: npfiz in:E A0009990 00 00H909§00 ofidoodpflv mmuHm hHom 90 90900 Hh£p0sH0 0gp 909.20990000 0090999H .m: .mam uoxsstmsueal lh6 :H .000900950090H90020g 99 A0909990 00 009909990 09000099V mmuHo hHom 90 90900 thp090 H099900 099 909 E09900m0 00909999 .0: .m9m 0009092 09 £9w90H0>03 99 NH 99 09 m m N. 0 m J _ _ _ _ _ _ uctsstmsumum 09090095009020.8903 99 0909990 .90 5.0990090 00909.95 090 909: 99 £9m90H0>03 09 m m 9 0 m _ _ _ _ _ _ 0N: OWE UO'FS spasm; r-fl lh8 NH .090Hm 9H00 000909 000900959090H£00x05 90 50990000 00909959 000909: 09 59w50H0>03 99 09 m m _ _ . _ _ . 9 0 m .3 .099 ji unisstmsueum DISCUSSION lh9 A copolymer of itaconic anhydride~styrene can be prepared from the monomers with the use of almost any free radical catalyst. Benzoyl peroxide was used as the catalyst in these preparations since it is readily available in high purity. .A copolymer of itaconic anhydride-styrene may be prepared in'benzene or tetrahydrofuran. Benzene-was used as a reaction medium because it possesSed certain advantages in that: l).An insoluble copolymer results which can be readily filtered from the benzene solvent, thus separating it from the soluble monomers. 2) The copolymer produced was a granular white powder. 3) The method gave a greater product yield in a reasonable time due to a faster reaction rate. A) The course of the reaction could be followed by the extent of precipitation. The use of tetrahydrofuran as a reaction medium offers several disadvantages. l) The ccpolymer produced is soluble and must be precipitated by the addition of the non-solvent ether. 2) This precipitated product was a gelatinous, adhesive mass, difficult to wash, extract, and purify. The copolymers prepared and used for this portion of the work (data tabulated in Table VI) were prepared in benzene using a benzoyl peroxide catalyst. The monoester derivatives were prepared by reaction of the itaconic anhydride—styrene copolymer with the desired alcohol. Moran and Siegel (55) have shown that in anhydrous solutions organic anhydrides form the monoester of primary alcohols with the speed of ionic reactions. This 'work supports the views expressed by Moran and Siegel. The reaction of the itaconic anhydride-styrene copolymer with alcohol was indeed rapid. The approximate times required for reaction with various alcohols are listed on page 79. By using a larger quantity of alcohol, or inert solvent, these times may be shortened. The monoesters of the copolymer were isolated by precipitation with the non—solvent water or by distilling the excess alcohol under reduced pressure. If a large quantity of a monoester derivative is desired, isolation by precipitation with water is preferable since it is rapid and yields a white granular powder which can be easily handled. This investigation has also revealed that no hydrolysis of the monoester derivative occurs under these conditions, see page 136. A monomethyl ester was prepared from the disodium salt of the itaconic anhydride~styrene copolymer by reaction with dimethyl sulfate. This experiment was carried out for two reasons. The first was to determine if the copolymer could be esterified starting from the acid form. The second reason was to determine if this esterification produced two isomeric acid esters aStmam3produced in the reaction of the copolymer with an alcohol. The high-frequency titration curve, Fig. 22, indicates that two isomeric acid esters are produced by the esterification with dimethyl sulfate. The pK values for this monoester derivative having an anhydride content of 63.276” are: MIMI-6.2, pK2"=-S.o. The pK values 151 for the monoester derivative prepared by reaction with methanol for the copolymer having an anhydride content of 56.3% are: pKf“=6.3, ngh=7.9. lhus it appears that the two monoesters prepared by different methods are identical. As shown on page 78 , two isomeric acid esters result when an alcohol reacts with the itaconic anhydride segment of the copolymer. The evidence obtained from the high-frequency titration curves for all the monoester derivatives indicates that both acid ester isomers are present. LePeletier de Rosanbo (59), isolated two isomeric ethyl esters on reacting unsymmetrical dimethylsuccinic anhydride with sodium ethylate. The values reported are: 0 CH3 0 0 CH3 0 u I u _ , 1 _ u I u H50 Z-o-c-c —c-o Na and Na c -C-—C", -c-o--c,uE CH3 hos}; CH3 514% The percent of each type of acid ester isomer agrees very well with those reported in this thesis for the isomers obtained by the reaction of the itaconic anhydride segment of the copolymer with an alcohol. The data are tabulated in Table VIII. Farmer and Kracovski (60} isolated two isomeric ethyl esters on reacting unsymmetrical dimethylsuccinic anhydride with ethyl alcohol. The preparation of the diester derivatives was accomplished by the reaction of diazomethane with the monoester derivative. With the exception of the ha7ardous nature of this reagent, this method of preparation appears to be the most favorable at this time. The excess diazomethane presents no problem and there is no impurity to contaminate 152 the copolymer. One limitation of this procedure is that it does not lend itself to the preparation of diester derivatives in large quantities. No more than 0.2 mole of diazomethane should be produced at any one time, due to the explosive nature of the reagent. The carbon-hydrogen analysis of the diester derivative prepared with dizaomethane agrees well with the calculated value. One attempt to prepare a diethyl ester derivative by reaction with diazoethane resulted in a partial diester derivative, as shown by carbon-hydrogen analysis. The partial diester precipitated as formed and this might account for the incomplete esterification. Some of the free carboxyl groups were probably imbedded in the precipitated product and were thus unavailable for esterification. Numerous attempts to prepare a diester derivative employing gaseous hydrogen chloride or sulfuric acid as catalysts failed. In all cases the monoester derivative was obtained as indicated by carbon-hydrogen analyses and the high-frequency titration curves. The use of sulfuric acid as a catalyst in the preparation of diester derivatives is not recommended. It was found impossible to purify the copolymer and get it free of sulfur. The inability to remove solid catalysts from the product limited the use of preparative procedures involving these catalysts. In the case where gaseous hydrogen chloride was passed into the reaction vessel, it was Lound that it could be removed by the addition of benzene to the reaction flask and distilling under reduced pressure. The product isolated was f ee of chloride. 153 The preparation of the optically active monoester derivative of the itaconic anhydride~styrene copolymer was accomplished by reacting the copolymer with the optically active primary alcohol, nopol. The optical activity was measured in acetone and tetrahydrofuran. The Specific rotation in acetone was [al;2= -6.293 and in.tetrahydrofuran [algza ~3.69O. The observed difference in the specific rotation may be due to a difference in solvation and association in the respective solvents. The analysis of the copolymers to determine the composition depends on the determination of the itaconic anhydride segment in the copolymer. The itaconic anhydride-styrene copolymer was dissolved in acetone and a known quantity of standard sodium.hydroxide was added to the solution. On heating on a steam bath, the itaconic anhydride segment was completely hydrolyzed to the disodium salt and the acetone was boiled off. An attempt was made to titrate the itaconic acid segment using phenolphthalein as an indicator, but in all cases the amount of itaconic acid found did not correspond to the theoretical quantity present. Thus it appears that the indicator may be adsorbed on the copolymer. The phenophthalein indicator was observed to change from pink to colorless not at the usual pH range of 6-9, but anywhere in the range of pH ll to 6. The use of a line operated Beckman.pH meter to titrate the acid segment was then attempted. The titration curve obtained by plotting pH versus ml. of titer revealed the dibasic nature of the itaconic acid segment, but the end points were not very sharp and were not always too close to the theoretical values. A second and major difficulty with 15h the potentiometric titration is the inability of the instrument to locate the excess sodium hydroxide. The titration of the acid segment depends on the addition of a known excess of base to completely hydrolyze the anhydride. Thus the method used to determine the dibasic acid must also be capable of detecting the excess base. Another difficulty encountered with the use of a potentiometer occurs when the polymer begins to precipitate. 'When the disodium salt is converted to the free acid form of the copolymer, a precipitate appears. This precipitate tends to adhere to the electrode surface and may lead to inconsistent results. It was found that a sample weight of copolymer not larger tha 0.3 g. should be used in order to obtain two reasonably good neutralization ‘breaks in the potentiometric titration curve. Previous (5) potentiometric titration work with the maleic anhydride-styrene copolymer was performed using 1 g. samples. The pH titration curves did not show a second neutralization point under these conditions. The potentiometric titra- tion of the maleic anhydrideestyrene copolymer was reinvestigated and it was found that the second inflection point does appear in the pH curve, Figure 15, under the conditions of the titration. The availability of a high frequency titrimeter presented an interesting possibility to adapt this instrument to solutions of polyelectrolytes. Electrometric methods of analysis include those methods based on the response of electrodes immersed in a solution to concentration changes of ionic species in solution; the reactions at electrodes in contact with electrolyte solution; the passage of electricity through 155 electrolyte solutions, or some other measurable change in electrical properties. High~frequency titration is a relatively new addition to electrometric methods (61,62). In high~frequency titrations, the vessel containing the solution to be titrated is placed between the plates of a condenser or in a field of the coil of the tank circuit of an oscillator operating in the megacycle frequency range. Discussions of the theory of the high- frequency method have been published (63,6h,65,66). The distinct advantage of the high-frequency titration method lies in.the fact that the "electrodes" do not come into contact with the solution. Contamination of the solution by immersed electrodes or the desensitization of electrodes by adsorption of substances onto the electrodes immersed in solution is thus eliminated. Preliminary work indicated that the excess of sodium hydroxide could be determined. Thus it was decided to use the high-frequency titrimeter and the pH meter simultaneously. The high—frequency titra- tion end points were used to check and detect the end points determined from the potentiometer. The potentiometer readings were desired for the determination of apparent pK' values. The data for the titration of the itaconic anhydride-styrene copolymers are tabulated in Table VIII, and plotted in Figures 7 to 15. In all instances where there was an excess of sodium hydroxide added this was determined quite accurately. The total milliequivalents of the itaconic acid segment as determined from titration are equal in.most cases to the theoretical milliequivalents as calculated from the composition of the itaconic anhydride-styrene 156 copolymer. In some instances the milliequivalents of one type of carboxylate determined by titration do not agree too well with the calculated milliequivalents for the same type of carboxylate. However, the total milliequivalents of the two types of carboxylate determined by high~frequency titration agree very well with the total theoretical milliequivalents of carboxylate. The advantage of the highefrequency titration method in determining composition of copolymers is that it is rapid and the accuracy is very good under the conditions used in this investigation. The use of the high-frequency titration method was valuable in the determination of the monoester derivatives. The excess sodium hydroxide was easily located, and the quantity of the monoester-acid segment readily calculated. A more striking advantage is the ability to determine, with the use of the high-frequency titrimeter, the two isomeric acid esters which are obtained on reacting the itaconic anhydride segment of the copolymer 'with an alcohol. The problem of proving the existence of two isomeric acid esters when a simple unsymmetrical anhydride is reacted with an alcohol is complicated. The isolation of the two isomers and their purification is tedious. In a copolymer, where isolation and recrystallization become impossible, it has been clearly demonstrated, in this investigation, that it is possible not only to show that two isomeric esters are formed when the anhydride reacts with an alcohol, but also to determine 15 7 the amount of each type of acid ester formed with the use of the high“ frequency titrimeter. A look at the titration curves of the monoesters, Figures 16—23, shows two distinct breaks beyond the sodium hydroxide excess. The minimum in the high-frequency titration curve represents the excess of sodium hydroxide. The data for the titration of the monoesters are tabulated in Table X. The table shows that the anhydride ring opens to give almost equivalent amounts of the two isomeric acid esters. The observed and theoretical milliequivalents of the acid segment agree very well in most cases. Special attention is called to Fig. 22 which represents the titra- tion of the monomethyl ester of the itaconic anhydride-styrene copolymer prepared by the action of dimethyl sulfate. The high-frequency titration curve indicates that there are two isomeric acid-esters present. Thus the esterification of the anhydride segment with alcohol and the action of dimethyl sulfate on the disodium salt of the itaconic acid segment both lead to two isomeric acid esters. The apparent pKl‘ and pKz' values for the itaconic anhydride- styrene copolymers and for the maleic anhydride-styrene copolymer are shown in Table VII. In most cases the agreement of the pK‘ values read directly from the graph agree well with each other. The ng‘ value reported for the titration shown in Fig. 10 appears to be low compared to the others in the table. A possible explanation 157A may lie in the fact that this titration was a little different from the others in that only one- rialf of the sodium hydroxide necessary to hydro lyze all the anhydride segments was added. The reason for adding one— half of the required sodium hydroxide was to see if the high-frequency titration curve showstwo breaks, since the following structures are possible when the sodium hydroxide is added. —CHo - C? - CH9 -(HI- CEO- —CHe-C ‘— CH -CH - CHg- C - l /. \\ ~ ~ ,rc \\ 2Na01;a ~ ,I \\ 2 ‘ ./ \x O = C CH2 0 = C Ch 2 C = C CH2 C = C CH2 I I l I l I I O -- C = O (D ——.C = O H-O C = O H—O C = C ,3 O-Na o'ua‘ pKt' PKf ~CH° - — CF? - CH - CE- — C . CH; C - CH. - CH - CH, - C - “ ,/ \\ " /’ \\.=£%hg, ./ ‘\ ‘ ‘ /’ ‘\ O = C CH; O = t CH~ C — C CH2 0 = C CH: $ I I I _ I- I I- I -—- C - O (3 -—- C = O .a O C = O n C E = C l 2\ ij' O-_ pKB! C- Ch- C ~ CH - C“ - CE- — C - n H -CI - C — - CH - CL — C - / \ ~ / \ 2.IaOr-.i / \ / \ I I I l I- I I I ‘ O -—- C e C O -—- C - C We C C a O H-C S = O pK,I c-e ID 0‘ 3) phli A look at Fig. 10 reveals two breaks in the nigh—frequency titration curve and it is felt that reaction I3) took place when the sodium hydroxide was addet. Thus it appears that the titration resem ble 3 that of a monobasic acid or the acid species :f toe monoester derivative. "i lhe pKI values for this titration are o: the order of magnitude of thos- determined for the monoe st r derivatives as Shown in able IX. A — v 158 The pK' values reported for the titrations shown in Figs. 13 and 11; are somewhat higher than for the other listed values. -These titrations invcflved more dilute solutions. No systematic study has been done as ;yet to determine if the concentration affects the apparent pK' values of a polyelectrolyte. - The apparent pK' values for the monoester derivatives are shown in Table IX. A look at Fig. 16A shows that the plot of pH versus Ilog l ; 3 gives a slope approaching unity for the primary and secondary carboxyls. It appears that the monoester derivatives are acting as monobasic acids and one carboxylate ionizes independently of the other. The titration curves for the diester derivatives are shown in Figures 2h and 25. The high—frequency and potentiometric titration curves indicate the titration of a strong acid (HCl) and strong base (NaOH). In this case there is only a minimum in the high-frequency curve which represents the sodium hydroxide added. There is no free carboxylate in the copolymer. The milliequivalents of sodium hydroxide found by titration are identical to the quantity added. The titration and elemental analysis data indicate the presence of a diester. Figure 26 represents the titration of the partial diethyl ester prepared in the diaZoethane reaction. The carbon-hydrogen analysis of this sample indicates that the diester was not completely formed. A look at Fig. 26 indicates a break in the high-frequency titration curve beyond the sodium hydroxide excess represented by the minimum in the curve. The second break represents the carboxylate which was not esterified. Once again it becomes obvious that the high-frequency titrimeter is a valuable tool in determining composition of copolymers 159 or their derivatives. Since it was possible to detect two acid Species in the itaconic anhydride~styrene copolymer, in the monoester derivatives of the copolymer, and itaconic acid itself, it was felt that mixtures of these species should be investigated. In a mixture of any of these two species it was expected that four breaks would be found in the high-frequency titration curves. This indeed was the case in the instances studied, with one exception. Fig. 28 represents the titration of a mixture of poly 61:39 (itaconic anhydride co styrene) and itaconic anhydride. The high-frequency titration curve shows five breaks and only four are expected. A repetition of this titration using more dilute solutions is shown in Fig. 29. In this instance only four breaks are seen in the high-frequency titration curve. Since no systematic study has been conducted dealing with concen- tration effects in mixtures it is impossible to explain the presence of a fifth break in the case of the more concentrated solution. In the discussion of each titration in VIII, it was necessary to assume that each of the species was titrated independently of the others present. This is probably not the case, but the observations for the individual breaks agree well with the theoretical values. With this assumption, the five breaks in Fig. 28 can be explained. The total milliequivalents of all acid Species in each of the titrations of the mixtures agree well with the calculated values. The apparent pKI values listed for each of the titration mixtures were read directly from the pH curve making use of the assumption that each carboxylate Species is titrated independently. It appears impossible 160 to calculate the apparent pKI values for this mixture. The pK' values of the mixtures were read for the purpose of comparison with those determined for the separate titration of the particular substance. It might be mentioned at this point that it appears that the composition of polyamines might be determined with the use of the high- frequency titrimeter. The titration curves for a number of monomeric dibasic acids and polyitaconic acid are plotted in Figures 30 to 38. The data for the titrations are tabulated in Table XVII. An interesting instance is a comparison of the titration curve of itaconic acid Figures 31 and 33 and polyitaconic acid Figure 32. The high-frequency titration curve for the monomeric itaconic acid shows a curved effect whereas the high-frequency titration curve for the polyitaconic acid is a straight line. The curved nature of the high- frequency titration curves for monomeric dibasic acids is quite prevalent in all the work done in this laboratory. Only the titration curve of methylsuccinic acid, Figure 36, is a straight line. The milliequivalents of acid found by titration agree well with the theoretical millieouivalents of acid present. Fig. 37 is a plot of a mixture of ben oic and salicylic acids. The determination of these two acids in aqueous solution was surprising. It represents the first time that a mixture of two acids with a ratio of ionization constants of about 17 has been determined in aqueous solution using the high-frequency titrimeter. It was impossible to resolve a mixture of acetic and propionic acid. The ratio of the ionisation constants of these two acids is about 1.3. No extensive study has been made to determine the limits for the high-frequency titrimet er . The hydrolysis of the monoethyl ester and of the dimethyl ester was followed conductometrically. The data indicate that the monoethyl ester was not hydrolyzed at 25 i O.13C. for 25 hours. The dimethyl ester does not show any hydrolysis at 25 i 0.13C. for 31 hours. The hydrolyses were conducted at 253C and in aqueous solution to simulate the conditions for the titrations of the monoester and diester derivatives which were done at Itxmt temperatures and in aqueous basic solution. Thus it is concluded that no hydrolysis occurred during the titration of the monoester and diester derivatives. The conclusion often found expressed is that the difficulty encountered in forming a diester derivative was due to a reversible hydrolysis with the small quantity of water formed in the esterification. This conclusion is no longer tenable. The difficulty encountered in preparing diesters by a catalytic method is attributed to a steric factor and the equilibrium nature of the esterification reaction. The infrared spectra of various copolymer derivatives appear in Figures 39 to h8. The bands for carbonyl groups as a class are the most stable in position, 5.h5—W.SO r” In the region of 5-7 F these are the strongest in the spectrum 67). This was found to be true in the copolymers investigated, the two absorption bands for the anhydride linkage, 5.38 and 5.62 r were reasonably constant . The 0.2 ,4 separation between these two bands «é/I was approximately constant in each case. I _1 C\ ”U The shift to higher frequencies for the carbonyl containing anhydrides followed the correlation that this shift was due to ring strain in the five membered ring. The band at 8.3 F in the Spectrum of polyitaconic anhydride and that at about 8.2‘r,in.the copolymer's spectra were attributed to the C—O-C stretching vibration. The band was shifted in the copolymer and this was probably due to hindrance to stretching by the phenyl groups in the proximity of the five membered ring (68). The absorptions characteristic to esters arise from C=O and C-0- linkages. These appear approximately in the regions 5.73 to 5.&3’1. The spectra of the esterified copolymers had a common band at about 5.8-5.9 r” This absorption band was shifted from the normal region of ester C=O and this may be due to the unsymmetrical groups adjacent to the carbonyl carbon. In the copolymer. the absorption band at about lh.25 r,was attributed to the contribution of the phenyl ring. Through the corre- lation from open chain vibrations (683 in long chain molecules with methylene groups along the chain a strong band was observed in the region of lh’l. In this work it was found at lh.2 ,4. This band is attributed to a roCking mode of the CH3 group. The band at lh.2’¢ shifted to higher wavelengths with no correlation in the relative amounts k.) f the contributing struCtures. An excellent region for the identification of the carboxylic acid in the monoester derivatives lies in the range -3.5 r" The separation of these bands from the absorptions o; the C-H Stretching vibrations was great enough to prevent any confusion. In the diester preparations. 163 Figures hh and h5, this broad band attributed to the carboxylic acid residue has disappeared. No quantitative evaluation of the linkages involved in the ccpolymer and its derivatives was made.. However, the characteristic linkages present were sufficient to give a qualitative identification. If a suitable solvent were available, a quantitative determination of the amount of anhydride or its derivatives could be made, thus serv- ing as another tool for the analysis of copolymer composition. 16h SUMMARY 1. Itaconic anhydride and styrene have been copolymerized in benzene and tetrahydrofuran solvent using benzoyl peroxide as a catalyst. 2. The reactivity ratios for the copolymerization of these two monomers are: In benzene r2 (itaconic anhydride) = 0.78 and r1 (styrene) = 0.015. In tetrahydrofuran r2 = 0.60 and r1 = 0.10. 3. The copolymer produced in benzene precipitates as it is being formed and is an easily workable white granular powder. h. The copolymer produced in tetrahydrofuran must be precipitated by a nonmsolvent and is a gelatinous, adhesive mass which is difficult to purify. S. The itaconic anhydride-styrene copolymer has a highly alternat- ing structure and the units are arranged in a head-to—tail manner. 6. The high-frequency titration apparatus is a useful tool in the titration of polycarboxylic acids. 7. The composition of the itaconic anhydride styrene copolymers has been determined by carbon—hydrogen analysis and by high-frequency titration. 8. The potentiometric and high~frequency titrations indicate that the itaconic anhydride segment of the copolymer is a dibasic acid. The apparent pKl' and ngt values are 5.7 and 8.8 reSpectively. 9. Monoester derivatives of the copolymer were prepared by reaction of a primary alcohol with the anhydride segment of the copolymer. 165 10. The high-frequency titration curves show the monoester deriva- tive to be a mixture of two isomeric acid esters. Apparent values of ij}‘and pKz" for the monomethyl ester are 6.3 and 7.9 respectively. - ll. Diester derivatives of the copolymer have been prepared by reaction with diazomethane. 12. An optically active monoester derivative has been prepared by reaction of the anhydride segment of the copolymer with an optically active alcohol. 13. The itaconic anhydride-styrene copolymer has been converted to a network polymer exhibiting ion-exchange properties. 1h. The monoethyl and the dimethyl ester derivatives of the copolymer do not undergo hydrolysis in aqueous sodium hydroxide at 2530 in twenty-five hours. 15. The high-frequency titration procedure was applied to the maleic anhydride~styrene copolymer. The apparent values of pKl' and pKz' are h.8 and 9.9 reSpectively. . - l6. Itaconic anhydride was polymerized to produce a homopolymer, polyitaconic anhydride. LITERATURE CITED LITERATURE CITED Curtice, G. M., M. S. Thesis, Michigan State University .1955). Guile, R. L., G. M. Curtice and J. Drougas, presented 1313t A. C. S. Meeting, {1957). Kangas, D..A., M. S. Thesis, Michigan State University \1958). Byrne, R. E., M. S. Thesis, Michigan State University a19h9). Garrett, E. R., M. S. Thesis, Michigan State University \l9h8l. Alfrey, T. Jr., and Lavin, E., J. Am. Chem. Soc., 61, 20hh fl9h5). Lecher, H., U. S. Patent No. 1,780,873. Norrish, R. G. W., and E. F. Brookman, Proc. Roy. Soc. London, A163, 205 1937). Boundy, R. h., and R. F. Boyer, "Styrene, Its Polymers, Copolymers and Derivatives,” A. C. S. Monograph, Reinhold Publishing Corp. U. S. Patent No. 2,5h2,5h2 ,1951). U. 5. Patent No. 2,616,8h9 {1952). U. 3. Patent No. 2,3uo,110 .19UU). . U. 3. Patent N2. 2,3uc,111 .19uu). . U. S. Patent No. 2,366,h95 \19h5). U. 3. Patent No. 2,531,h08 .1950). U. S. Patent N». 2,279,882 \19U2). U. 3. Patent No. 2.279,885 19h23. U. S. Patent No. 2,625.529 £1952). U. S. Patent No. 2.625,h71 Kl952). Fineman, M., and s. 1:. Ross, J. Polymer Sci., 5..- 259 .1950. . Meyer, H., Monatsh. 33, L22 19013. 33. 3h. 35. 36. 3?. 38. lb? Bakunin, Garz. Chim. Tta1., 0, 361 ,1900). Anschutz and Petri. Ber.. 13, 1539 \1800). I \ Fittig and Boch. Ann.. 331. 17; '190L). Shriner, R. L.. S. G. Ford and L. J. Roll. "Organic Synthesis," Collective Volume If, John Wiley Co._, 19‘3, p. 368. Carothers, w. H., Trans. Faraday Soc.. 32, 39 {1936\. Carothers. W. H., Chem. Revs., g, 333 1931). Carothers, W. 3.. J. Am. Chem. Soc.. 51, 25hd 1929). Staudinger. H. and W. H. Kohlscnutter, Ber., 6Q, 2091 {19311. I- J .O / \JJ Staudinger, H. and W. Frost, Ber., 68. 2351 5) . Taylor, H. S., and J. R. Bates, J. Am. Chem. Soc.. g2; 2L 38 .193/). Staudinger, H., Die hochmoloi:u1aren organischen Verb indungen, Julius Springer, Berlin, 1032. p. 151. Wall, F. T.. J. Am. Chem. Soc._, pp, 2050 19-2.). Skeist, I., J. Am. Chem. Soc.. 6‘. 1751 .1913} Kangas. D. A.. M. S. Tn;sis, Michigan State University. .1958). Lewis. F. M.. C. Walling. e1 ‘1 _ ._ I Q J. IL-m a CIJDIR 0 83C 0 .. 70 .. _L'J:19 . 191+ _') a May—3 " F n F O | and C o 1Na1.;ing q Cli'jrr- 0 ROE-S O ‘ 3" I.‘ Q L9: . 1930 \ o Hine, J.. "Ph3sica1 Crgani: C endstryu h12_' in xi.‘ I McGraw-Li 11 19561, pp. Bartlett, P. L., and K. Iozaki. J. Am. Chem. Soc.. 62, 2299 lQL/I. Bartlett, P. E.. and R. Altsciul, J. Am. Cu-sm. Soc.. 52. :12 1915). Norrish. R. G. W.. and F. R. Smith, Laiure. -QC. 336 _;;x). Burnett. G. M.. and H. W. Melville. Proc. Roy. Soc. london), Alic. MES .l9h’l. Bengough, :0. r '. ' \ A200. 301 l950). ~ ~- ~ " ~ ; - - . ~a « - 3- —:- ~-; S7warc. M.. J. tgem. PLJ3.. -0. 12” _?,:1, .LE-. nevs.. at, Tao--3 o '1 ‘ '. '5 - o '0 ~- -\ \‘Kfl ' T: Marvel. .. S.. ”The Chemistry 3‘ Largt M -e:u-;s." er. by R. _. Burn and C. Grumrit. rtorsci‘nco Pub__s-ers. Iew :rn. Len}. Chapt. VIE. A6. U7. ha. A9. 50. 51. 5?. 63. 6h. 65. 66. 67. 168 Bengough, W. 1., and R. G. W. Norrish, Proc. Roy. Soc. tLondon), A200, 301 {1950). Standinger, H., and A. Steinhofer, Ann., 51/, 35 a1935). Marvel, C. S., §:_a1,, J. Am. Chem. Soc., 61, 32hl -1939). Gregg, R. A., and F. R. Mayo, Faraday Soc. Discussions, 2, 328 (19h7). Johnson, A. H., and A. Timnick, Anal. Chem., 28. 889 \1956). Lai, T. M., M. M. Mortland, and A. Timnick, Soil Sci., §;, 359-68 I1957). Katchalsky. A.. and P. Spitnik, J. Poly. Sci., ll, A32 I19LI). Garrett, E. R., and P. L. Guile, J. Am. Chem. Soc., 133 A533 {1951). Org. Syn., C:1l. Vol. II, p. A61. Org. Syn., Coll. Vol. III, p. 2AA. Bain, J. P., J. Am. Chem. Soc.,368, 638 .19h6). Johnson. J. 3.. and FUnk, G. L., 21, lh6h .1955). Moran, M. K.. and Siegel, E. F., J. Am. Chem. Soc.. gg, 2318-2323 :1926). LePeletier de Rosanbo. C. M.. Ann. Chim., 12, 335 -l923). ,- . Farmer, E. M.. J. Kracouski. J. Am. Chem. Soc.. :8, 2310-2323 1926). Blake, G. G., J. Sci. Instr.. 22. 17h 19h5). Jensen, F. W.. Parrack. A. 1.. Ind. Eng. Chem. Anal. Ed. 591-599 .19hé). . 3;, \JL r\) \J Blaedel, W. J., et 31.. Anal. 3nem., 2‘_ l21C—l2hh l9- Fujiwara, 8., S. Hayashi. Anal. Chem., 2’. 239-2Ll 1951). J. L. Hall. Anal. Chem., 2;, 123c-1210 1952). . . - . . . — -- _' I .—I Reilley. C. n.. W. E. McCurcy, Anal. Chem., 2~, .6-93 .1953). Randall, H. M.. I. Fuson. et a1,, "Infrared Determination of Organic Structures." 0. van Iostranc, Inc., 19h9. Bellamy. L. W.. "Infrared Spectra of Complex Molecules, Methuen, London. 1953. H m If 169 TABLE XVIII (Data Plotted in Figure 7) Dial Reading pH 0 816.5 12.05 1 815.5 12.02 2 813.5 11.99 3 813 .0 11.95 A 811.7 11.88 5 810.0 11.85 6 808.5 11.78 7 806.5 11.72 8 80h.0 11.65 9 801.8 11.55 10 800.0 11.88 11 797.2 11.22 12 795.1; 10-98 13 793.0 10.h9 lh 793-8 9.75 15 795-9 9.12 16 796.5 8.hh 17 798.9 7.22 18 800.0 6.32 19 800.9 5.75 20 802.5 b.90 21 80h.8 3.71 precipitate 22 810.0 3.22 23 813.0 2.99 28 816.0 2.8M 170 TABLE XIX (Data Plotted in Figure 8) 4“ M1. H01 Dial Reading pH 0 768.5 11.05 1 766.0 10.83 2 765.0 10.58 3 765.0 10.31 A 766.0 10.0h 5 768.0 9.77 6 769.8 9.88 7 772.6 9.21 8 775-0 8.92 9 778.3 8.56 10 780.2 8.12 11 783.0 7.h8 12 78h.8 6.98 13 785.3 . 6.62 in 786.5 6.35 15 787.5 6.15 16 789.0 5.92 17 790.3 5.68 18 791.5 S.h0 19 792.5 5.03 20 793 .8 hth 21 797.6 3.89 precipitate 22 802.5 3.05 23 806.2 2.83 ————-——.~ —— ——_—-—— ——. TABLE XX (Data Plotted in Figure 9) WWW Ml. H01 Dial Reading pH 0 750.0 10.08 1 751.3 9-78 2 752-5 9.50 3 758.7 9.23 A 757.5 8.92 5 760.0 8.59 6 763.3 8.19 7 765.7 7.62 8 767.7 7.08 9 769.7 6.63 10 771.0 6.32 11 772.8 6.09 12 77h.0 5.90 13 775.5 5-63 1h 777.0 5.29 15 779.0 b.87 16 781.0 h.05 17 787.0 3.28 precipitate 18 793.3 2.95 19 799.0 2.77 20 803.0 2.63 21 806.8 2.55 22 808.5 2.h7 __T TABLE XXI 172 THIS DATA IS PLOTTED IN FIGURE 9A AND IS FOR THE TITRATION .’ SHOWN IN FIGURE 9 . . Liters of M1. HCl —r pH Solution [0] Added [IA=] [BIA—J logfilhéfgo 9.78 0.181 0.00576 1 0.00505 0.00071 0.8521 9.50 0.182 0.00573 2 0.00832 0.00181 0.8861 9.23 0.183 0.00570 3 0.00360 0.00210 0.2380 8.92 0.188 0.00567 8 0.00289 0.00278 0.0166 8.59 0.185 0.00568 5 0.00216 0.00388 -0.2072 8.19 0.186 0.00561 6 0.00187 0.00818 ~0.8898 7.62 0.187 0.00558 7 0.00077 0.00881 —0.7959 7 .08 0 .188 0.00555 8 0 .00009 0 .00586 -1 .9598 [HIA'] [HQIA] 6.63 0.189 0.00552 9 0.00892 0.00060 0.9138 6.32 0.190 0.00588 10 0.00820 0.00128 0.5160 6809 0.191 0.00585 11 0.00350 0.00195 0.2539 5.90 0.192 0.00583 12 0.00283 0.00260 0.0370 5.63 0.193 0.00580 13 0.00215 0.00325 -0.l795 5.29 0.198 0.00537 18 0.00186 0.00391 ~0.8278 8.87 0.195 0.00535 15 0.00082 0.00858 —0.7876 8.05 0.196 0.00532 16 0.00023 0.00517 —1.3518 173 TABLE XXII (Data Plotted in Figure 10) Dial Reading pH 3v 0 735.0 8.55 I; 1 737.8 7.80 i: 2 780v; 7 '05 3 783 -3 6 .55 8 785 .5 e .15 5 787 .5 5 .78 " 6 789 .9 5 .38 7 751—5 8.85 8 756 .2 3 .82 9 767 .5 3 .10 10 778.8 2.88 precipitate 11 787.0 2.72 12 798.8 . 2.58 13 800.0 2.50 18 808 .O 2 .83 15 807.0 2.35 TABLE XXIII (Data Plotted in Figure 11) ————- ,._.___ —— fi—-—————— 178 Ml. HCl Dial Reading pH 0 792.9 11.25 1 789.5 11.13 2 786.8 10.98 3 783.8 10.69 8 782.5 10.39 5 782.5 10.08 6 783.3 9.75 7 788 5 9.88 8 787.0 9.12 9 788.8 8.75 10 791.8 8.33 11 793.5 7.75 12 795.5 7.12 13 796.8 6.68 18 797.6 6.38 15 798.7 6.15 16 799.8 5.92 17 800.5 5.68 18 801.7 5.30 19 802.8 8.88 20 808.0 8.12 21 808.3 3.38 precipitate 22 813.2 3.12 23 818.0 2.92 TABLE XXIV 175 THIS DATA IS PLOTTED IN FIGURE 11A AND IS FOR THE TITRATION SHOWN IN FIGURE 11 Liters of M1. HCl pH Solution [0] Added [18:] [HIA‘J 10g 1 g a l ! 9.75 0.186 0.005500 1.8 0.008533 0.000967 0.6709 9.88 0.187 0.005870 2.8 0.003820 0.001650 0.3685 9.12 0.188 0.005881 3.8 0.003116 0.002325 0.1271 8.75 0.189 0.005812 8.8 0.002819 0.002993 -0.0925 8.33 0.190 0.005388 5.8 0.001730 0.003658 «0.3287 7.75 0.191 0.005356 6.8 0.001088 0.008308 -0.6139 7.12 0.192 0.005327 7.8 0.000371 0.008956 -1.1261 [H1A'] [H218] 0.005300 8.8 0.005005 0.000295 1.2296 l 0.005273 9.8 0.008320 0.000953 0.6568 A 0.005286 10.8 0.003636 0.001610 0.3537 . 0.005219 11.8 0.002959 0.002260 0.1170 0.005192 12.8 0.002293 0.002899 -0.1019 0.005167 13.8 0.001632 0.003535 -0.3357 0.005181 18.8 0.000981 0.008160 —0.6275 l 0.005115 15.8 0.000330 0.008785 -1.1616 TABLE XXV (Data Plotted in Figure 12) 176 ML. HC1 Dial Reading pH 0 776.8 11.08 1.0 776.2 10.58 2.0 778.3 10.05 2.5 780.0 9.77 3-0 782.3 9-88 3.5 783.6 9.07 8.0 785.2 8.36 5.0 788.0 7.10 5.5 789-8 6.73 6.0 790.2 6.32 6.5 791.0 5.87 7.0 792.0 5.38 7.5 792-8 8.67 8.0 795.5 3.68 precipitate 8.5 800.0 3.25 9.0 805.3 3.03 9.5 809.7 2.86 10.0 813.8 2.76 10.5 817.8 2.68 11.0 822.0 2.59 i TABLE XXVI (Data Plotted in Figure 13) M1. H01 Dial Reading pH 0 825.7 11.13 1 822.7 10.93 2 820.2 10.53 3 818.6 9.98 8 820.2 8.60 5 821.8 6.37 6 822.8 8.28 7 830.0 2.90 8 836.7 2.61 9 882 .7 2 .82 H 0 887.7 2.30 TABLE XXVI I (Data Plotted in Figure 18) 178 Ml. HCl Dial Reading pH 0 822.8 10.50 1 822.5 10.35 2 822.5 10.20 3 822.5 10.00 8 822.5 9.75 5 822.6 9.50 6 822.8 9.15 7 823.0 8.53 8 823.6 7.63 9 828.0 6.95 10 828.8 6.55 11 825.2 6.15 12 825.5 5 .85 13 825.8 5.85 18 826.8 8.85 15 827.6 3.95 16 830.3 3.52 17 833.2 3.28 18 835.7 3.12 19 838.8 2.98 20 881.0 2.88 TABLE XXVIII (Data Plotted in Figure 15) ML. H01 Dial Reading pH 0 838.7 10.95 1 838.7 10.78 2 835.2 10.53 3 836.5 10.28 8 838.5 9.92 5 880.7 9.58 6 883 .8 9 .18 7 885.5 8.58 8 887 .8 7 .83 9 888.8 6.29 10 889.8 5-58 11 851.5 5.03 12 852.0 8.67 13 852.8 8.80 18 858.8 8.20 15 855.5 8.02 16 858.0 3.75 17 861.0 3 .38 18 868.5 3.05 19 867.5 2.80 20 871.0 2.68 THIS DATA IS TABLE XXIX 180 PLOTTED IN FIGURE 15A AND IS FOR THE TITRATION SHOWN IN FIGURE 15 Liters of M1. HCl pH Solution [C] Added [MA=] [HMA-I log 1 ; a 10.78 0.181 0.005898 1 0.000710 0.008788 0.8286 10.53 0.182 0.005868 2 0.001813 0.008051 0.8578 10.28 0.183 0.005838 3 0.002108 0.003326 0.1981 9.92 0.188 0.005805 8 0.002796 0.002609 -0.0301 9.58 0.185 0.005376 5 0.003876 0.001900 —0.2623 9.18 0.186 0.005387 6 0.008188 0.001199 -0.5800 8.58 0.187 0.005318 7 0.008818 0.000508 —0.9800 888'] [HQMA] 7.83 0.188 0.005290 8 0.005108 0.000182 1.8882 6.29 0.189 0.005262 9 0.008800 0.000862 0.7079 5.58 0.190 0.005238 10 0.003700 0.001538 0.3828 5.03 0.191 0.005207 11 0.003008 0.002199 0.1361 8.67 0.192 0.005179 12 0.002320 0.002859 —0.0907 8.80 0.193 0.005153 13 0.001688 0.003509 -0.3293 8.20 0.158 0.005126 18 0.000972 0.008158 ~0.6308 8.02 0.195 0.005100 15 0.000308 0.008792 —1.1921 TABLE XXX (Data Plotted in Figure 16) 181 Ml. HCl Dial Reading pH 0 819.5 11.98 1 818.2 11.95 2 817.0 11.92 3 816.2 11.85 8 813.5 11.82 5 811.5 11.75 6 808.5 11.65 7 805.8 11.56 8 803.8 11.83 9 800.5 11.25 10 798.0 10.95 11 796.8 10.35 12 796.8 9.82 13 798-5 8.85 18 800.0 7.85 15 802.8 7.89 16 803.2 7.22 17 808.0 7.02 18 808.8 6.72 19 805.2 6.26 20 806.9 5.37 21 810.5 3.68 22 815.9 3.22 23 820.0 2.99 28 828.0 2.88 11 1 . 1 1 1 .171 F i 182 I r TABLE XXXI THIS DATA IS PLOTTED m FIGJRE 16A AND Is FOR THE TITRATION SHOWN IN FIGURE 16 Liters of m. HCl _ Type I 1 _ a pH Solution [C] Added IHIA I [HQLA] log a 8 .85 0 .193 0.002728 0.7 0 .00 2262 0.000866 0 .6861 7 .85 0 .198 0 .002718 1.7 0 .001587 0.001127 0 .1886 7 .89 0 .195 0 .002 700 2 .7 0.000920 0.001780 —0 . 2867 7.22 0.196 0.002686 3.7 0.000258 0.002828 -0.9739 Type II [HIA‘H [H218] 7.02 0.197 0.002673 8.7 0.002278 0.000395 0.7610 6 .72 0 .198 0.00 2659 5 .7 0.001616 0 .001083 0 .1900 6.26 0.199 0.002686 6.7 0.000963 0.001683 —0.2825 5.37 0 .200 0.002633 7 .7 0.000315 0.002318 -0.8671 TABLE XXXII (Data Plotted in Figure 17) 183 M1 . HCl Dial Reading pH 0 821.2 11.86 1 819.0 11.86 2 817.8 11.80 3 816.5 11.35 8 815.0 11.32 5 813.0 11.25 6 811.2 11.18 7 808.7 11.12 8 806.7 11.02 9 808.8 10.90 10 801.5 10.73 11 799-3 10.50 12 797.2 10.10 13 796.3 9-13 18 797.7 8.01 15 799-3 7.80 16 800 .5 7 .12 17 801 .6 6 .82 18 803 .O 6 .83 19 808 .0 5 .63 20 805.0 8.37 21 809.3 3.10 22 818.9 2.69 23 819.0 2.89 28 822.0 2.35 , TABLE XXXIII (Data Plotted in Figure 18) 188 M1. HCl Dial Reading pH 0 818.1 12.28 1 816.1 12.28 2 818.1 12.18 3 811.7 12.11 8 808.6 12.02 5 805 .6 11.92 6 802.9 11.85 7 799.6 11.76 8 795.9 11.68 9 793.2 11.87 10 790.1 11.17 11 788.0 10.67 12 788.7 9.66 13 790.5 8.80 18 792.6 8.21 15 798.8 7.87 16 795.8 7.63 17 797.8 7.80 18 798.8 7.13 19 .800.0 6.63 20 801.2 5.79 21 808.8 3.82 precipitate 22 810.0 3.33 23 816.8 3.08 28 820.5 2.98 TABLE XXXIV (Data Plotted in Figure 19) 185 Ml. H01 Dial Reading 0H 0 822.8 11.98 1 822.8 11.91 2 819.1 11.86 3 817.0 11.80 8 818.8 11.75 5 812.0 11.67 6 809.6 11.59 7 808.3 11.86 8 803.8 11.29 9 801.5 11.03 10 799.9 10.60 11 800.1 10.12 12 802.8 9.65 13 803.6 9.13 18 805.8 8.70 15 807.2 8.31 16 808.9 8.00 17 811.8 7.68 18 812.8 7.29 19 813.9 6.89 20 815.7 6.87 21 816.8 5.66 22 818.5 3.98 23 823.1 3.35 28 827.1 3.11 25 830.3 2.98 TABLE XXXV (Data Plotted in Figure 20) 186 Ml. HCl Dial Reading pH 0 833.8 12.08 1 832.5 12.05 2 831.9 12.02 3 831.0 11.98 8 829.9 11.92 5 829.0 11.86 6 827.2 11.82 7 825.5 11.75 8 823.5 11.68 9 820.5 11.60 10 818.0 11.88 11 815.2 11.38 12 812.5 11.12 13 809.9 10.75 18 808.5 10.12 15 809-0 9-39 16 810.8 8.78 17 812.8 8.18 18 818.8 7.52 19 815.6 6.72 20 816.5 5.65 21 820.0 3.75 22 826.2 3.25 23 830.5 3.08 28 .833-5 2.89 XXXVI (Data Plotted in Figure 21) 187 M1. HCl Dial Reading pH 0 816.0 9.80 1 816.8 8.96 2 817.2 8.10 3 817.8 7.86 8 818.0 6.80 5 818.8 6.15 6 820.0 8.00 7 823.8 3.88 8 827.3 3.22 9 830.5 3.08 10 838.0 2.96 TABLE XXXVII (Data Plotted in Figure 22) 188 Dial Reading pH 0 870.8 11.86 1 869.0 11.82 2 867.7 11.37 3 866.2 11.32 8 868.8 11.27 5 863.8 11.22 6 861.7 11.13 7 860.3 11.06 8 859.0 10.98 9 857.8 10.83 10 855.8 10.66 11 858.5 10.80 12 853.8 9.98 13 858.2 9.87 18 855.2 8.97 15 856.3 8.82 16 857.0 7.80 17 857.8 7.28 18 858.5 6.75 19 858.8 6.88 20 859.1 6.12 21 859.8 5.75 22 860.8 5.05 23 862.3 3.73 28 866.0 3.10 25 869.6 2.82 26 871.8 2.67 27 878.8 2.55 TABLE XXXVIII (Data Plotted in Figure 23) 189 Ml. HCl Dial Reading pH 1 882 .3 11.22 2 880 .8 11.05 3 839 .0 10.82 8 838.8 10.52 5 839 .0 10 .13 6 880.8 9 .70 7 881.6 9 .09 8 883 .5 7.88 9 885.8 7.00 10 886.8 6.50 11 888 .5 6.18 12 889 .7 5 .85 13 851.0 5 .59 18 852.0 5.28 15 853.0 8.93 16 858.0 8.50 17 856.0 3.86 18 859 .3 3 .28 19 862.8 2.88 20 866.0 2.68 21 869 .0 2 .52 TABLE XXXIX (Data Plotted in Figure 28) 190 Dial Reading pH 0 868.3 12.83 1 862.3 12.82 2 860.8 12.82 3 859.5 12.80 8 858.5 12.38 5 857.3 12.36 6 856.2 12.35 7 855.0 12.33 8 853.5 12.33 9 852.8 12.31 10 851.0 12.27 11 889.9 12.23 12 888.8 12.20 13 887.2 12.15 18 885.5 12.12 15 888.2 12.08 16 882.9 11.93 17 881.5 11.80 18 880.2 11.56 19 839.0 11.05 20 839.0 8.00 21 880.5 8.15 22 885.2 3.05 23 850.8 2.72 28 858.5 2.55 N U'l 858.7 2.88 ___,w 191 TABLE XL (Data Plotted in Figure 25) Dial Reading pH 0 888.8 12.78 1 887.5 12.78 2 -886.5 12.77 3 885.5 12.77 8 888.3 12.73 5 883.2 12.73 6 882.2 12.70 7 880.7 12 68 8 879.2 12 65 9 878.2 12 62 10 876.5 12 58 11 875.5 12 55 12 878.7 12 53 13 873.7 12 88 18 872.5 12 87 15 871.5 12 83 16 870.8 12 38 17 868.7 12 28 18 867.8 12 23 19 866.7 12 16 20 865.5 12 08 21 868.3 11 88 22 863.0 11 58 23 862.3 10 88 28 862.3 5 28 25 865.6 3 73 26 870.0 3 38 27 873.3 3 22 28 876.0 3.08 29 879.2 2 98 30 881.8 2.90 TABLE XLI (Data Plotted in Figure 26) M1. H01 Dial Reading 0 880.7 1 878.0 2 877.0 3 876.2 8 875.0 5 878.0 6 873.2 7 872.0 8 870.6 9 869.6 10 868.8 11 867.0 12 865.7 13 868.8 18 863.3 15 861.8 16 860.8 17 859.0 18 857.8 19 857.0 20 857.0 21 857.5 22 858.2 23 858.8 28 862.5 3.88 25 865.5 3.18 26 869.0 2.98 27 872.5 2.83 28 878.8 2.75 TABLE XLII (Data Plotted in Figure 27) Dial Reading 0 803.7 1 803.3 2 802.5 3 801.5 8 812.8 5 818.3 6 820.3 7 822.6 8 828.0 9 826.8 10 828.8 11 830.5 12 832.0 13 _833.8 . 18 835.0 . 15 836.8 8.63 16 838.5 8.80 17 839.7 8.18 18 881.0 7.91 19 882.1 7.67 20 882.8 7.87 21 883 .3 7 .27 22 888.2 7.07 23 885.1 6.89 28 885.9 6.68 25 886.7 6.52 26 887.5 6.37 27 888.5 6.18 28 889.0 6.02 29 889.7 5.88 30 850.0 5.68 31 850.5 5.50 32 851.2 5.38 33 851.6 5.18 38 852 .0 8.89 35 852.0 8.56 36 852.8 8.02 37 858.5 3.81 38 856.5 2.98 39 858.8 2.78 80 860 8 2.63 81 862.7 2.53 82 868.3 2.83 TABLE XLIII (Data Plotted in Figure 28) 198 Ml. HCl Dial Reading pH 0 865.8 11.85 1 863.8 11.39 2 862.3 11.30 3 860.0 11.19 8 858.7 11.08 5 857.8 10.88 6 856.6 10.58 7 856.3 10.18 8 856.3 9.70 9 857.3 9.25 10 858.3 8.78 11 859.3 8.10 12 860.0 7 20 13 860.2 6.68 18 861.0 6.33 15 861.2 6.08 16 861.5 5.83 17 862.0 5.63 18 862.0 5.83 19 862.5 5.23 20 862.5 5.02 21 862.5 8.80 22 862.8 8.58 23 862.8 8.36" 28 863.2 8.15 25 863.8 3.98 26 868.0 3.78 27 868.8 3.58 28 865.8 3.38 29 866.2 3.18 30 867.8 2.90 31 869.7 2.72 32 871.7 2.57 33 873.6 2.83 38 875.8 2.38 35 877.3 2.25 TABLE XLIV (Data Plotted in Figure 29) Dial Reading pH 0 837.7 10.85 1 837.7 10.25 2 837.3 9.95 3 . 837 .3 9 .58 8 837.5 8-73 5 837.5 7.55 6 838 .0 6.95 7 838.0 6.55 8 838.2 6.22 9 838.2 5.90 10 838.2 5.60 11 838.8 5.23 12 838.8 8.88 13 838.7 8.80 18 839-5 3.98 15 880.8 3.67 16 882.5 3.82 17 888.0 3.28 18 886.8 3.10 19 887.7 2.97 20 850 .5 2 .88 TABLE XLV (Data Plotted in Figure 30) 196 Dial Reading pH 0 858.0 11 72 1 852.8 11 60 2 852.8 11.32 3 852.8 10.82 8 853 .5 9 .86 5 855.8 9.09 6 856.8 8.35 7 858.2 7.88 8 858.8 7.50 9 859.5 7.23 10 860.8 6.97 11 860.8 6 72 12 861.2 6.85 13 861.5 6.17 18 862.0 5 88 15 862.2 5.58 16 862.2 5.28 17 862.5 5.00 18 863.0 8.77 19 863.0 8.53 20 863.3 8.28 21 863.6 8.08 22 868.0 3.78 23 865.0 3.80 28 867.2 2.98 25 870.5 2.72 26 873.5 2.52 27 876.7 2.38 28 880.0 2.28 29 882.8 2.19 TABLE XLVI (Data Plotted in Figure 31) m. HCl Dial Reading pH 0 803 .8 10.55 1 803 .5 10.23 2 802.8 9 .80 3 802 .8 8.95 8 803 .O 7.18 5 803.5 6.68 6 803 .8 6.86 7 808.8 6.13 8 808.8 5.87 9 808.8 555 10 805.0 5.20 11 805.9 8.87 12 806.8 8.51 13 807 .9 8.20 18 809 .O \ 3 .80 TABLE XLVII (Data Plotted in Figure 32) 198 M1. H01 Dial Reading pH 0 789.2 9.30 1 791.2 8.72 2 793.7 7-78 3 798.7 7-15 8 796.6 6.78 5 797.8 6.53 6 799-5 6.28 7 800.8 6.05 8 801.5 5.79 9 802.8 5.89 10 803.5 5.10 11 805.0 8.60 12 806.5 8.10 13 810.0 3.55 18 818.8 3.18 15 821.0 2.86 16 826.6 2.69 17 830.5 2.58 18 833.8 2.87 19 835.8 2.39 20 837.2 2.32 TABLE_XLVIII (Data Plotted in Figure 33) 199 fiWF Dial Reading PH 0 818.8 10.80 1 811.8 9-97 2 811.8 6.88 3 811.8 5.98 8 812.3 5.66 5 812 .3 5.80 6 812.3 5.18 7 813.8 8.93 8 818.3 8-65 9 815.0 8.80 10 815.2 8.15 11 815.2 3.85 12 816.8 3.68 13 819.5 3-80 18 822.3 3.18 15 827.6 2.98 16 531.7 2.80 17 836.0 2.66 TABLE XLIX (Data Plotted in Figure 38) 200 M1. HCl Dial Reading pH 0 883.3 9.32 1 883 .3 7 .03 2 883.3 6.58 3 883.5 6.28 8 883-5 5.97 5 888.2 5.60 6 888.6 5.08 7 885.5 8.62 8 886.5 8.80 9 887.8 8.08- 10 889.2 3.78 11 851.8 3.52 12 855.8 3 .27 13 859.7 3 .08 18 863.7 2.93 15 867 .7 2 .82 16 871.3 2.73 TABLE L (Data Iietted in Figure 35) 201 Ml. H01 Dial Reading pH 0 858.8 9.53 1 858.2 6.56 2 858.2 6.13 3 858.8 5.87 8 858.8 5.66 5 858.7 5.88 6 858.7 5.28 7 858.8 5 .08 8 858.8 8.88 9 859.3 8.68 10 859.8 8.50 11 860.5 8.32 12 861.2 8.16 13 862.2 3.98 18 863.0 3.78 15 868.2 3.62 16 866.8 3.80 17 869 .0 3 22 18 872.3 3.05 19 875.3 2 -93 20 877.7 2.83 TABLE LI (Data Plotted in Figure 36) M1. H01 Dial Reading pH 0 850.2 6.88 1 850.0 6.08 2 850.2 5.87 3 850.2 5.68 8 850-3 5-53 5 850.3 5.80 6 850.3 5.28 7 850.3 5-18 8 850.3 5.02 9 850.8 8.89 10 850.8 8.77 11 850.8 8.68 12 851.8 8.53 13 851.8 8.81 18 851.8 8.28 15 852.8 8.18 16 852.8 8.08 17 853.8 3.90 18 858.0 3.78 19 858.8 3.68 20 855 .8 3 .88 21 857.3 3.32 22 858.8 3.13 23 860.7 2.97 28 863.0 2.80 25 865.2 2.68 26 867.3 2.58 27 869.0 2.50 TABLE LII (Data Plotted in Figure 37) 203 Ml. H01 Dial Reading pH 0 858.8 2 .37 1 855.8 2.83 2 853.3 2'51 3 851.5 2258 8 889.9 2.67 5 889.0 2.77 6 888.5 2.86 7 888.5 2.96 8 888.5 3.07 9 888.5 3.18 10 889.0 3.30 11 889.5 3.81 12 850.2 3.53 13 851.2 3.65 18 852.0 3.78 1; 852 .8 3 .90 16 853.8 8.05 17 855.0 8.21 18 856.0 8.80 19 856.7 8-67 20 857.8 5-18 21 859.2 9.50 22 862.3 10.32 23 865.2 10.56 28 868.3 10.72 25 871.0 10.83 26 873.8 10.92 27 875.6 11.00 TABLE LIII (Data Plotted in Figure 38) 208 M1. H01 Dial Reading pH 0 852.2 10.05 1 852.5 6.58 2 852.8 5.97 3 852.8 5.71 8 853.3 5-52 5 853.5 5.80 7 858.0 5.18 8 858.5 5.12 9 858.5 5.08 10 855.0 8.97 11 855.2 8.88 12 855.5 8.83 13 855.9 8.77 18 855.9 .71 15 856.8 8.67 16 856.6 8.61 17 856.8 8.56 18 857.8 8.88 19 857.8 8.83 20 857.8 8.37 21 858.0 8.29 22 858.8 8.28 28 859.0 8.09 25 859.3 8.03 26 859.3 3.92 27 859.7 3.83 28 860.2 3.72 29 860.7 3.58 30 861.7 3.82 31 862.6 3.23 32 863.6 3.02 33 865.8 2.88 38 867.0 2.70 35 868.3 2.58 STABILITY ’ID HIDROLYSIS OF THE MONOETHYL ESTER OF POLY 63: 37 TABLE LIV (ITACONIC ANHYDRIDE CO STYRENE) 205 Time in Minutes Resistance in Ohms 10 15 20 33 88 63 78 93 108 123 138 153 183 333 393 853 1083 1203 1503 88. 88 88 88 11" O) ...-.... O\O\O\O\O\O\O\O\O\ TABLE LV STABILITY TO HYDROLYSIS OF THE DIMETHYL ESTER OF POLY 63:37 (ITACONIC ANHYDRIDE 00 STYRENE) 206 Time in Minutes Resistance 0 32.2 2 32.2 8 32.2 7 32.2 10 32.2 15 32.2 22 32.2 27 32.2 82 32.2 57 32.1 72 32.1 87 32.1 127 32.1 297 32.1 357 32.0 817 32.0 1867 31.9 1850 31.9 my 1.1an C'LBICIJ 0.!“ “781111717117!MMHIUMMIEIII'“