The Microstructure of Poly(Isobutylene-co-p-Methylstyrene) by NMR Spectroscopy

Abstract

The microstructure of isobutylene-para-methylstyrene (IB-pMeSt) copolymers was studied by NMR spectroscopy. ¹H- and ¹³C-NMR spectra were used to obtain overall copolymer compositions. ¹³C-NMR signals were assigned in terms of triad monomer sequences, and triad distributions were obtained over a wide copolymer composition range. According to statistical tests, the IB-pMeSt copolymerization cannot be described by zero- (Bernoullian) or first-order Markov models because reactivity ratios r _IB and r _pMeSt were found to change with the monomer feed composition. Additional insight into the microstructure of IB-pMeSt copolymers was gained by calculating sequence numbers, run numbers, and sequence lengths from triad distributions. Further, the Kelen-Tüdös plot showed a distinct curvature indicating that the Kelen-Tüdös method, applied over the entire monomer feed composition range, cannot give meaningful reactivity ratios for this monomer pair. Evidently the simple two-parameter Mayo-Lewis model is inadequate to describe the IB-pMeSt copolymerization system.     

Synthesis and characterization of fused‐thiophene containing naphthalene diimide n‐type copolymers for organic thin film transistor and all‐polymer solar cell applications

Naphthalene diimide copolymers are attractive n‐type materials due to their high electron affinities, high electron mobilities, and exceptional stability. Herein, we report a series of NDI‐fused‐thiophene based copolymers with each copolymer differing in the number of fused thiophenes in the donor monomer. Increasing the number of fused‐thiophene moieties within an NDI‐copolymer backbone is shown to not only enable tuning of the electronic structure but also improve charge mobilities within the active layer of organic field‐effect transistors. Electron mobilities and on/off ratios as high as 0.012 cm² V^?1 s^‐1 and I_on/I_off > 10⁵ were measured from n‐channel thin‐film transistors fabricated using NDI‐xfTh copolymers. Bulk heterojunction solar cell devices were also fabricated from the NDI‐xfTh copolymer series in blends with poly(3‐hexylthiophene) (P3HT) with PNDI‐4fTh ‐ based devices yielding the largest J_sc (0.57 mA cm^?2) and fill factor (55%) in addition to the highest measured PCE for this series (0.13%). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4061–4069     

Acrylonitrile–4-vinylpyridine copolymers effect of comonomer sequence distribution on properties

Acrylonitrile–,4-vinylpyridine copolymers were prepared in chloroform solution at 60°C with AIBN as initiator. Copolymer compositions were determined from their 15.01-MHz ¹³C-NMR spectra. Reactivity ratios of r_AN = 0.093 and r_4VP = 0.32 were calculated by the Kelen and Tudos method. The run number, number-average sequence lengths, and monomer sequence distributions were also calculated. The T_g values of the copolymers, their dye uptake, and degree of alkaline hydrolysis were influenced by the overall copolymer composition but particularly by the monomer sequence distribution in the copolymers.     

Temperature‐induced aggregation of the copolymers of N‐isopropylacrylamide and sodium 2‐acrylamido‐2‐methyl‐1‐propanesulphonate in aqueous solutions

A series of random copolymers of N‐isopropylacrylamide (NIPAM) and sodium 2‐acrylamido‐2‐methyl‐1‐propanesulphonate (AMPS) was synthesized by free‐radical copolymerization. The content of AMPS in the copolymers ranged from 1.1 to 9.6 mol %. The lower critical‐solution temperature (LCST) of copolymers in water increased strongly with an increasing content of AMPS. The influence of polymer concentration on the LCST of the copolymers was studied. For the copolymers with a higher AMPS content, the LCST decreased faster with an increasing concentration than for copolymers with a low content of AMPS. For a copolymer containing 1.1 mol % of AMPS the LCST dropped by about 3 °C when the concentration increased from 1 to 10 g/L, whereas for a copolymer containing 9.6 mol % of AMPS the LCST dropped by about 10 °C in the concentration range from 2 to 10 g/L. It was observed that the ionic strength of the aqueous polymer solution very strongly influences the LCST. This effect was most visible for the copolymer with the highest content of AMPS (9.6 mol %) for which an increase in the ionic strength from 0.2 to 2.0 resulted in a decrease in the LCST by about 27 °C (from 55 to 28 °C), whereas for the copolymer containing 1.1 mol % of AMPS the LCST decreased only by about 6 °C (from 37 to 31 °C) when the ionic strength increased from 0.005 to 0.3. The reactivity ratios for the AMPS and NIPAM monomer pairs were determined using different methods. The values of r_AMPS and r_NIPAM obtained were 11.0–11.6 and 2.1–2.4, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2784–2792, 2001     

A polarity‐activation strategy for the high incorporation of 1‐alkenes into functional copolymers via RAFT copolymerization

A new synthetic methodology for the preparation of copolymers having high incorporation of 1‐alkene together with multifunctionalities has been developed by polarity‐activated reversible addition‐fragmentation chain transfer (RAFT) copolymerization. This approach provides well‐defined alternating poly(1‐decene‐alt‐maleic anhydride), expanding the monomer types for living copolymerizations. Although neither 1‐decene (DE) nor maleic anhydride (MAn) has significant reactivity in RAFT homopolymerization, their copolymers have been synthesized by RAFT copolymerizations. The controlled characteristics of DE‐MAn copolymerizations were verified by increased copolymer molecular weights during the copolymerization process. Ternary copolymers of DE and MAn, with high conversion of DE, could be obtained by using additive amounts (5 mol %) of vinyl acetate or styrene (ST), demonstrating further enhanced monomer reactivities and complex chain structures. When ST was selected as the third monomer, copolymers with block structures were obtained, because of fast consumption of ST in the copolymerization. Moreover, a wide variety of well‐defined multifunctional copolymers were prepared by RAFT copolymerizations of various functional 1‐alkenes with MAn. For each copolymerization, gel permeation chromatography analysis showed that the resulting copolymer had well‐controlled M_n values and fairly low polydispersities (PDI = 1.3–1.4), and ¹H and ¹³C NMR spectroscopies indicated strong alternating tendency during copolymerization with high incorporation of 1‐alkene units, up to 50 mol %. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3488–3498, 2008     

Copolymers of 7-Methoxy-2-Acetyl Benzofuryl Methylmethacrylate With Styrene: Synthesis,Characterization, Reactivity Ratios and Determination of Kinetic Parameters With Thermogravimetric Analysis

The 7-methoxy-2-acetyl benzofuryl methylmethacrylate (MABMM) monomer was synthesized by reacting 7-methoxy-2-bromo acetyl benzofurane with sodium methacrylate in acetonitrile solvent at 70°C in the presence of triethylbenzylammoniumchloride (TEBAC). The monomer was characterized by FTIR, ¹H-and ¹³C-NMR spectral studies. Reactivity ratios for the copolymers 7-methoxy-2-acetyl benzofuryl methylmethacrylate (MABMM)-co- styrene (ST) are reported. Copolymers were prepared by free radical polymerization using 2,2′-azobisisobutyronitrile (AIBN) as an initiator at 70°C in 1,4-dioxane solution. FTIR, ¹H-and ¹³C-NMR spectral studies and gel permeation chromatography (GPC) were used the copolymer characterization. The monomer compositions in the copolymer were determined by elementel analyses and the reactivity ratios (ri) were calculated applying diverse linear methods, namely Finemann-Ross (FR) and Kelen-Tüdös (KT) and the nonlinear error invariable model method of a computer program RREVM. By using the latter pr°Cedure, the values of the reactivity ratios were estimated as 2.74 and 0.69 for the system MABMM (1) and ST (2), respectively. These values suggest the formation of nearly-alternating copolymers in the systems. Molecular weights were determined by gel permeation chromatography (GPC). The polydispersity indices of the polymers determined using suggest a strong tendency for chain termination by disproportionation. The glass transition temperature of the polymers were investigated by Shimadzu DSC-60 and the apparent thermal decomposition activation energies (E_d) were calculated by the Ozawa method using the Perkin-Elmer TGA thermobalance, respectively. Tg increases when the concentration of polar monomer (MABMM) in the copolymer increases. It was observed that thermal stabilities of copolymers increased with increasing of MABMM content in copolymers.     

Propagation Mechanism of Radical Copolymerization of Sulfur Dioxide and Vinyl Chloride

Radical copolymerization of sulfur dioxide and vinyl chloride (VC) has been studied by the comparison of the composition of copolymers obtaining from different reaction conditions, i.e., reaction temperatures, feed compositions, and total monomer concentrations. The composition of VC in copolymer is independent of comonomer composition except at high concentration of VC in feed; it increases with increasing reaction temperature or decreasing total monomer concentration. At lower temperature, the composition of copolymer becomes independent of total monomer concentration. The overall rate of polymerization is proportional to [VC]^1,7 and [SO₂]^0.5. These results were compared with those obtained in our previous study on the SO₂-styrene copolymerization. A propagation mechanism for radical copolymerization of SO₂ and VC is also proposed.     

Water-soluble copolymers. III. Dextran-g-poly(acrylamides) control of grafting sites and molecular weight by Ce(IV)-induced initiation in homogeneous solutions

Model graft copolymers were synthesized by grafting acrylamide onto dextran (M_w = 500,000) utilizing an initiation method in which a Ce(IV)/HNO₃ solution was added to the dextran solution in order to allow coplexation prior to monomer addition. Three synthetic reaction parameters were optimized on the basis of conversion and solution viscosity: monomer concentration, dextran concentration, and nitric acid concentration. Molar ratios of [Ce(IV)]/[dextran] were changed systematically to affect the number and length of the acrylamide grafts. The number of grafting sites and graft chain lengths, determined by selective hydrolysis of the carbohydrate backbone, were in good agreement with those theortically predicted from knowledge of initiation efficiency and monomer conversion. Rheological studies of the model graft copolymers were conducted in aqueous solutions as a function of temperature, added salt, and copolymer concentration.     

Radical Copolymerization of Fluorine Ring-Substituted 2-Phenyl-1,1-dicyanoethylenes with 4-Fluorostyrene: Synthesis and Characterization

Novel copolymers of trisubstituted ethylene monomers, fluorine ring-substituted 2-phenyl-1,1-dicyanoethenes, RC₆H₄CH[dbnd]C(CN)₂ (where R is 2-F, 3-F, and 4-F) and 4-fluorostyrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR. High T _g of the copolymers, in comparison with that of poly(4-fluorostyrene) indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decomposed in two stages in the range 210–600°C.     

Surfactant‐free synthesis of amphiphilic copolymer of poly(styrene‐co‐acrylamide) in aqueous emulsion with the assistance of ultrasound

The hydrophilic monomer acrylamide (AM) and hydrophobic monomer styrene (St) have been directly copolymerized in a surfactant‐free aqueous emulsion with the assistance of powerful ultrasound. Fourier Transform Infrared spectrocopy (FT‐IR), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC) measurements revealed that copolymers of AM and St were obtained. Elemental analysis was used to calculate the composition of the copolymer. Size exclusion chromatography (SEC) measurement showed that the molecular weight (M_w) of the copolymer is 1.86 × 10⁵ g/mol and the polydispersity index (PDI( = 2.31. The self‐assembly behavior in different solvents was investigated utilizing laser light scattering (LLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM); the copolymer film showed amphiphilicity, as measured by contact angle goniometry. Copyright © 2008 John Wiley & Sons, Ltd.     

Copolymers of methyl methacrylate and fluoroalkyl methacrylates: Effects of fluoroalkyl groups on the thermal and optical properties of the copolymers

Fluoroalkyl methacrylates, 2,2,2‐trifluoroethyl methacrylate ( 1 ), hexafluoroisopropyl methacrylate ( 2 ), 1,1,1,3,3,3‐hexafluoro‐2‐methyl‐2‐propyl methacrylate ( 3 ), and perfluoro t‐butyl methacrylate ( 4 ) were synthesized. Homopolymers and copolymers of these fluoroalkyl methacrylates with methyl methacrylate (MMA) were prepared and characterized. With the exception of the copolymers of MMA and 2,2,2‐trifluoroethyl methacrylate ( 1 ), the glass transition temperatures (T_gs) of the copolymers were found to deviate positively from the Gordon‐Taylor equation. The positive deviation from the Gordon‐Taylor equation could be accounted for by the dipole–dipole intrachain interaction between the methyl ester group and the fluoroalkyl ester group of the monomer units. These T_g values of the copolymers were found to fit with the Schneider equation. The fitting parameters in the Schneider equation were calculated, and R² values, the coefficients of determination, were almost 1.0. The refractive indices of the copolymers, measured at 532, 633, and 839 nm wavelengths, were lower than that of PMMA and showed a linear relationship with monomer composition in the copolymers. 2 and MMA have a tendency to polymerize in an alternating uniform monomer composition, resulting in less light scattering. This result suggests that the copolymer prepared with an equal molar ratio of 2 and MMA may have useful properties with applications in optical devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4748–4755, 2008     

Quasiliving Carbocationic Polymerization. XII. Forced Ideal Copolymerization of lsobutylene with Styrene

Forced ideal carbocationic copolymerization of isobutylene/styrene systems has been achieved by continuous addition of mixed monomer feeds to 2-chloro-2,4,4-trimethylpentane/TiCl₄ in n-hexane/methylene chloride charge by keeping the input rate equal to the overall rate of copolymerization. The composition of the copolymers was identical to that of the feeds over the entire monomer concentration range. The number-average molecular weight of the copolymers increased almost linearly with the amount of consumed monomers at higher isobutylene concentrations in the feed. The molecular weight increase was less pronounced at higher styrene concentration because more methylene chloride had to be used in the solvent system to keep the copolymer in solution. The micro-structure of the copolymers is uniform as determined by gel permeation chromatography (UV plus RI) and ¹³C-NMR spectroscopy According to these studies, true copolymers have formed. The probability of triads in the copolymer has been determined.     

Novel Copolymers of Styrene. 9. Methyl and Methoxy Ring-Substituted 2-Cyano-3-phenyl 2-propenamides

Novel electrophilic trisubstituted ethylene monomers, methyl and methoxy ring- substituted 2-cyano-3-phenyl-2-propenamides, RPhCH=C(CN)CONH₂, where R is 2,3-dimethyl, 2,4-dimethyl, 2,5-dimethyl, 2-(3-methoxyphenoxy), 2-(4-methoxyphenoxy), 3-(4-methoxyphenoxy), 4-(4-methylphenoxy), 2,3-methylenedioxy were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (5.8–33.8 wt%), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene and Some Halogen Ring-substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₃CH═C(CN)₂ (where R is 2-bromo,3-bromo, 3-chloro, 2,3-dichloro, 2-chloro-6-fluoro, 2,6-difluoro, 3,4-difluoro, and 3,5-difluoro) and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR, GPC, DSC, and TGA. High T _g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 200–800°C range.     

Influence of multiple stimuli on the lower critical solution temperature of new cationic poly(N‐acryloyl‐N′‐ethylpiperazine‐co‐N‐isopropylacrylamide) solutions

New multi‐stimuli responsive cationic copolymers based on N‐acryloyl‐N′‐ethyl piperazine (AcrNEP) and N‐isopropylacrylamide (NIPAM) were prepared by thermal free‐radical solution polymerization in dioxane at 75 °C. The chemical composition of the copolymers was determined by ¹H NMR spectroscopy and was found that the copolymers were slightly rich in NIPAM content than that of AcrNEP. The reactivity of the two monomers for the copolymerization reaction was evaluated by the extended Kelen‐Tüdös method. The distribution of monomer sequence in the copolymer chain was estimated using the terminal copolymerization model. The maximum tendency to alternation (～ 70%) was at 60 mol % of AcrNEP in the monomer feed. The copolymers were readily soluble in water at room temperature at all compositions and exhibited well‐defined lower critical solution temperature (LCST) phenomenon. The influence of various stimuli such as pH, temperature, simple inorganic salts, and surfactants on the LCST of the copolymers was studied in detail. Simple inorganic salts such as sodium chloride, sodium bromide, and sodium sulfate showed a salting‐out effect while sodium iodide showed a salting‐in effect. The salting‐out coefficient of the salts were calculated using the Sestchenow method, and the salting trend followed the order SO₄^2? > Cl^? > Br^? > I^?. The divalent salt was more effective in lowering the LCST than the monovalent salts. The cationic surfactant hexadecyl trimethylammonium bromide at concentrations above the critical micelle concentration caused a gradual increase in the LCST of the copolymer solutions. The intrinsic viscosity and light scattering behavior of the copolymers in water and in sodium chloride solutions were studied in detail. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1175–1183     

Synthesis and characterization of novel poly(ester carbonate)s based on pentaerythritol

Novel poly(ester carbonate)s were synthesized by the ring‐opening polymerization of L ‐lactide and functionalized carbonate monomer 9‐phenyl‐2,4,8,10‐tetraoxaspiro[5,5]undecan‐3‐one derived from pentaerythritol with diethyl zinc as an initiator. ¹H NMR analysis revealed that the carbonate content in the copolymer was almost equal to that in the feed. DSC results indicated that T_g of the copolymer increased with increasing carbonate content in the copolymer. Moreover, the protecting benzylidene groups in the copolymer poly(L ‐lactide‐co‐9‐phenyl‐2,4,8,10‐tetraoxaspiro[5,5]undecan‐3‐one) were removed by hydrogenation with palladium hydroxide on activated charcoal as a catalyst to give a functional copolymer, poly(L ‐lactide‐co‐2,2‐dihydroxylmethyl‐propylene carbonate), containing pendant primary hydroxyl groups. Complete deprotection was confirmed by ¹H NMR and FTIR spectroscopy. The in vitro degradation rate of the deprotected copolymers was faster than that of the protected copolymers in the presence of proteinase K. The cell morphology and viability on a copolymer film evaluated with ECV‐304 cells showed that poly(ester carbonate)s derived from pentaerythritol are good biocompatible materials suitable for biomedical applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45:1737 –1745, 2007     

Novel Copolymers of Styrene and Alkoxy Ring‐Substituted 2‐Phenyl‐1,1‐dicyanoethylenes

Electrophilic trisubstituted ethylene monomers, ring‐substituted 2‐phenyl‐1,1‐dicyanoethylenes, RC₆H₄CH?C(CN)₂ (where R is 2‐methoxy, 3‐methoxy, 4‐methoxy, 4‐ethoxy, 4‐propoxy, and 4‐butoxy), were synthesized by piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T _g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 290–450°C range.     

Novel Copolymers of Vinyl Acetate and Alkyl Ring‐Substituted 2‐Phenyl‐1,1‐dicyanoethylenes

Electrophilic trisubstituted ethylene monomers, alkyl ring‐substituted 2‐phenyl‐1,1‐dicyanoethylenes, RC₆H₄CH?C(CN)₂ (where R is 2‐methyl, 3‐methyl,4‐methyl, 4‐ethyl, 4‐isopropyl, 4‐butyl, and 4‐t‐butyl), were synthesized by piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and vinyl acetate were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C‐NMR, GPC, DSC, and TGA. High T_g of the copolymers, in comparison with that of polyvinyl acetate, indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 190–700°C range.     

Flexibilized styrene‐N‐substituted maleimide copolymers. I. Multiblock copolymers prepared from styrene‐maleimide telechelics and polytetrahydrofuran

Telechelic copolymers of styrene and different N‐substituted‐maleimides (SMIs) with a molecular weight of 2000–8000 g/mol were synthesized using the starved‐feed‐reactor technique and were nearly bifunctional when the monomer feed had a high styrene concentration. The COOH‐terminated rigid SMI blocks were polycondensated with OH‐terminated poly(tetrahydrofuran) (PTHF) blocks, with a molecular weight of 250–1000 g/mol, which are the flexible parts in the generated homogeneous multiblock copolymer. The entanglement density, which is closely related to the toughness of materials, increased in these flexible SMI copolymers (ν_e = 5.2 · 10²⁵ m⁻³) compared to the unflexibilized ones (ν_e = 2.4 · 10²⁵ m⁻³). The glass transition temperature of these flexibilized, single‐phase multiblock copolymers was still high enough to qualify them as engineering plastics. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3550–3557, 2000     

Novel Copolymers of Styrene. 7. Chlorine Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel trisubstituted ethylenes, chlorine ring-substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₃CH?C(CN)CONH₂ (where R is 2,3-dichloro, 2,4-dichloro, 2,6-dichloro, 3,4-dichloro, 2-chloro-5-nitro, 4-chloro-3-nitro, 5-chloro-2-nitro) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution in the presence of a radical initiation (AIBN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. Thus, the order of relative reactivity (1/r1) and the tendency toward alternation of monomer units in the copolymer for the monomers is 2-Cl-5-NO₂ (3.09) > 5-Cl-2-NO₂ (1.88) > 4-Cl-3-NO₂ (0.97) > 2,6-Cl₂ (0.93) > 3,4-Cl₂ (0.31) > 2,4-Cl₂ (0.30) > 2,3-Cl₂ (0.22). High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3.5–5.0 wt%), which then decomposed in the 500–800°C range.