Free‐radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio

Free‐radical copolymerizations of vinyl acetate (VAc = M₁) and other vinyl esters (= M₂) including vinyl pivalate (VPi), vinyl 2,2‐bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) with fluoroalcohols and tetrahydrofuran (THF) as the solvents were investigated. The fluoroalcohols affected not only the stereochemistry but also the polymerization rate. The polymerization rate was higher in the fluoroalcohols than in THF. The accelerating effect of the fluoroalcohols on the polymerization was probably due to the interaction of the solvents with the ester side groups of the monomers and growing radical species. The difference in the monomer reactivity ratios (r₁, r₂) in THF and 2,2,2‐trifluoroethanol was relatively small for all reaction conditions and for the monomers tested in this work, whereas r₁ increased in the VAc‐VF6Pi copolymerization and r₂ decreased in the VAc‐VPi copolymerization when perfluoro‐tert‐butyl alcohol was used as the solvent. These results were ascribed to steric and monomer‐activating effects due to the hydrogen bonding between the monomers and solvents. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 220–228, 2000     

Determination of the reactivity ratios of methyl acrylate with the vinyl acetate,vinyl 2,2-dimethyl-propanoate,and vinyl 2-ethylhexanoate

The course of composition drift in copolymerization reactions is determined by reactivity ratios of the contributing monomers. Since polymer properties are directly correlated with the resulting chemical composition distribution, reactivity ratios are of paramount importance. Furthermore, obtaining correct reactivity ratios is a prerequisite for good model predictions. For vinyl acetate (VAc), vinyl 2,2-dimethyl-propanoate also known as vinyl pivalate (VPV), and vinyl 2-ethylhexanoate (V2EH), the reactivity ratios with methyl acrylate (MA) have been determined by means of low conversion bulk polymerization. The mol fraction of MA in the resulting copolymer was determined by ¹H-NMR. Nonlinear optimization on the thus-obtained monomer feed–copolymer composition data resulted in the following sets of reactivity ratios: r_MA = 6.9 ± 1.4 and r_VAc = 0.013 ± 0.02; r_MA = 5.5 ± 1.2 and r_VPV = 0.017 ± 0.035; r_MA = 6.9 ± 2.7 and r_V2EH = 0.093 ± 0.23. As a result of the similar and overlapping reactivity data of the three methyl acrylate–vinyl ester monomer systems, for practical puposes these data can be described with one set of reactivity data. Nonlinear optimization of all monomer feed–copolymer composition data together resulted in r_MA = 6.1 ± 0.6 and r_VEst = 0.0087 ± 0.023. © 1994 John Wiley & Sons, Inc.     

Alternating copolymers of hexafluoroisobutylene with vinyl trifluoroacetate and vinyl pentafluorobenzoate

Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r₁ (HFIB) = 0, r₂ (VPFB) = 0.373, and r₁r₂ = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average T_gs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the T_g of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of T_gs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Mn2(CO)10‐induced controlled/living radical copolymerization of vinyl acetate and methyl acrylate: Spontaneous formation of block copolymers consisting of gradient and homopolymer segments

The controlled/living radical polymerization of vinyl acetate (VAc) and its copolymerization with methyl acrylate (MA) were investigated in bulk or fluoroalcohols using manganese complex [Mn₂(CO)₁₀] in conjunction with an alkyl iodide (R? I) as an initiator under weak visible light. The manganese complex induced the controlled/living radical polymerization of VAc even in the fluoroalcohols without any loss of activity. The R? I/Mn₂(CO)₁₀ system was also effective for the copolymerization of MA and VAc, in which MA was consumed faster than VAc, and then the remaining VAc was continuously and quantitatively consumed after the complete consumption of MA. The ¹H and ¹³C NMR analyses revealed that the obtained products are block copolymers consisting of gradient MA/VAc segments, in which the VAc content gradually increases, and homopoly(VAc). The use of fluoroalcohols as solvents increased the copolymerization rate, controllability of the molecular weights, and copolymerizability of VAc. The saponification of the VAc units in poly(MA‐grad‐VAc)‐block‐poly(VAc) resulted in the corresponding poly(MA‐co‐γ‐lactone)‐block‐poly(vinyl alcohol) due to the intramolecular cyclization between the hydroxyl and neighboring carboxyl groups in the gradient segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1343–1353, 2009     

Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)2

The radical polymerization of vinyl acetate (VAc) is moderated by iron(II) acetylacetonate (Fe(acac)₂) by the organometallic route (OMRP), as well as by degenerative transfer polymerization (DTP) when in the presence of excess radicals, through the formation of thermally labile organometallic Fe^III dormant species. The poly(vinyl acetate) (PVAc)‐Fe^III(acac)₂ dormant species has been isolated in the form of an oligomer and characterized by ¹H NMR, EPR, and IR methods, and then used as a single‐component initiator for the OMRP of VAc. The degree of polymerization of this isolated oligomeric species demonstrates the limited ability of Fe(acac)₂, relative to the Co(acac)₂ congener, to rapidly trap the growing PVAc radical chain. Control under OMRP conditions is improved by the presence of Lewis bases, especially PMe₂Ph. On the other hand, iron(II) phthalocyanine inhibits the radical polymerization of VAc completely. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3494–3504     

Radical copolymerization behavior of a highly fluorinated cyclic olefin with vinyl ether

The copolymerization of a highly fluorinated cyclic monomer, octafluorocyclopentene (OFCPE, M₁), with ethyl vinyl ether (EVE, M₂) was investigated with a radical initiator in bulk. Despite the poor homopolymerizability of each monomer, the copolymerization proceeded successfully, and the molecular weights of the copolymers reached up to more than 10,000. Incorporation of the OFCPE units into the copolymer led to an increase in the glass‐transition point. The copolymer composition was determined from ¹H NMR spectra and elemental analysis data. The molar fraction of the OFCPE unit in the copolymer increased and approached but did not exceed 0.5. The monomer reactivity ratios were estimated by the Yamada–Itahashi–Otsu nonlinear least‐squares procedure as r_1,OFCPE = ?0.008 ± 0.010 and r_2,EVE = 0.192 ± 0.015. The reactivity ratios clearly suggest that the copolymerization proceeds alternatively in the case of an excessive feed of OFCPE. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1151–1156, 2002     

Synthesis and reactivity ratios of regioisomeric vinyl‐1,2,3‐triazoles with styrene

The free radical reactivity ratios between styrene and different vinyl‐1,2,3‐triazole regioisomeric monomers in 1,4‐dioxane at 65 °C have been established using nonlinear least square method. The results obtained for the reactivity ratio between regioisomers show exceptionally different polymerization behavior, highlighting the effects of the electronic and steric factors of these regioisomeric monomers. The experimental results highlight the effects of the electronic and sterics on the copolymerization behavior. In case of 1,4‐vinyl‐triazoles, it was found that without the steric effects, the reactivity is very similar to that of styrene and forms random copolymers. However, it was found that 1,5‐vinyl‐triazoles are more reactive than 1,4‐vinyl triazoles. In the case of styrene‐co‐1,4‐vinyl‐1,2,3‐triazoles, the reactivity ratios were calculated to be r_styrene: r_{1‐octyl‐4‐vinyl‐triazole} = 1.97:0.54, r_styrene : r_{1‐benzyl‐4‐vinyl‐triazole} = 1.62:0.50, and r_styrene: r_{1‐methyl‐4‐vinyl‐triazole} = 0.90:0.87. On the other hand, reactivity ratios for styrene‐co‐1,5‐vinyl‐1,2,3‐triazoles were found to be r_styrene: r_{1‐octyl‐5‐vinyl‐triazole} = 0.13:0.66 and r_styrene: r_{1‐benzyl‐5‐vinyl‐triazole} = 0.34:0.49. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3359–3364     

Synthesis and characterization of epoxy functionalized cooligomers based on chlorotrifluoroethylene and allyl glycidyl ether

The synthesis of functionalized fluorocooligomers based on chlorotrifluoroethylene (CTFE) and allyl glycidyl ether (AGE) under radical copolymerization is presented. The compositions of comonomers in the cooligomers were determined by three different analyses viz: from ¹H and ¹⁹F NMR spectroscopy by using 1,3‐bis(trifluoromethyl) benzene as the external standard, epoxy equivalent weight value, and elemental analyses. The compositions determined by three methods were matching reasonably well and showed that the resulting poly(CTFE‐co‐AGE) cooligomers exhibit a tendency for alternation. The distribution of the monomers in the cooligomers was proposed based on the assessment of the reactivity ratios, r_i, of both comonomers. These values were determined from the kinetics of radical copolymerization of CTFE with AGE from Fineman‐Ross, Kelen‐Tudos, and extended Kelen‐Tudos methods which led to the assessment of the average reactivity ratios as: r_CTFE = 0.20 ± 0.03 and r_AGE = 0.15 ± 0.08 at 74 °C. The lower M_n values substantiated the formation of cooligomers rather than copolymers. The formation of cooligomers was attributed to the chain transfer to AGE (by hydrogen abstraction from AGE) from the allylic transfer. The poly(CTFE‐co‐AGE) cooligomers were soluble in most of the common organic polar solvents. An optimization of cooligomer yields was investigated by using ethyl vinyl ether as a third comonomer and from different initiators. The thermal stabilities of the cooligomers, obtained by thermal gravimetric analysis, showed a 5% weight loss at temperatures over 225 °C under air. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3587–3595, 2010     

Kinetics of radical copolymerization of [1‐(fluoromethyl)vinyl]benzene with chlorotrifluoroethylene

The synthesis of [1‐(fluoromethyl)vinyl]benzene (or α‐(fluoromethyl)styrene, FMB) and its radical copolymerization with chlorotrifluorethylene (CTFE), initiated by tert‐butyl peroxypivalate (TBPPi) are presented. The allyl monomer [H₂C = C(CH₂F)C₆H₅] was obtained by electrophilic fluorodesilylation of trimethyl(2‐phenylprop‐2‐en‐1‐yl)silane in 93% yield. A series of seven copolymerization reactions were carried out starting from initial [CTFE]₀/([FMB]₀ + [CTFE]₀) molar ratios ranging from 19.6 to 90.0 mol %. The molar compositions of the obtained poly(CTFE‐co‐FMB) copolymers were assessed by means of ¹⁹F nuclear magnetic resonance spectroscopy. Statistic copolymers were produced with molar masses ranging between 13,800 and 25,600 g/mol. From the Kelen and Tudos method, the kinetics of the copolymerization led to the determination of the reactivity ratios, r_i, of both comonomers (r_CTFE = 0.4 ± 0.2 and r_FMB = 3.7 ± 1.8 at 74 °C) showing that FMB is more reactive than CTFE as well as other halogenated or nonhalogenated monomers involved in the radical copolymerization with CTFE. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3843–3850, 2007     

Syntheses of Vinyl Sulfoxide/Vinyl Acetate-Type Copolymers

The homopolymerization of a series of alkyl vinyl sulfoxides (CH₂[dbnd]CHSOR; R = CH₃ (MVSO), C₂H₅ (EVSO), t-C₄H₉ (BVSO)) and their copolymerization with vinyl acetate (VAc) with 2,2′-azobisisobutyronitrile (AIBN) as initiator at 60°C was attempted. MVSO was found to homopolymerize radically, but EVSO and BVSO were not. Poly-MVSO is soluble in chloroform, methanol, DMSO, and water, but insoluble in acetone and benzene. MVSO and EVSO were found to copolymerize with VAc, but BVSO was not. The copolymerization parameters obtained for both systems were as follows; r₁(MVSO) = 2.23, r₂ (VAc) = 0.09, and r₁(EVSO) = 3.40, r₂ (VAc) = 0.11, respectively. MVSO/vinyl alcohol (VA) copolymers were obtained through the saponification of MVSO/VAc copolymers by sodium hydroxide in methanol. The solubility of MVSO/VAc and of MVSO/VA copolymers toward various solvents was examined, and it was observed that the sulfoxide comonomer has a tendency to give amphiphilicit to poly(vinyl acetate) and poly(vinyl alcohol). The 24 mol% MVSO containing VAc copolymer is soluble in both benzene and water.     

Effect of solvent on the copolymerization of ethylene and vinyl acetate

The ethylene (M₁)–vinyl acetate (M₂) copolymerization at 62°C and 35 kg/cm² with α,α′-azo-bisisobutyronitrile as initiator has been studied in four different solvents, viz., tert-butyl alcohol, isopropyl alcohol, benzene, and N,N-dimethylformamide. The experimental method used was based on frequent measurement of the composition of the reaction mixture throughout the copolymerization reaction by means of quantitative gas chromatographic analysis. Highly accurate monomer reactivity ratios have been calculated by means of the curve-fitting I procedure. The observed dependence of the r values on the nature of the solvent is surprisingly large and can be correlated with the volume changes (= excess volumes) observed on mixing vinyl acetate (VAc) with the relevant solvent. An increased hydrogen bonding or dipole–dipole interaction through the carbonyl moiety of the acetate side group of VAc, induces a decreased electron density on the vinyl group of VAc, which in turn leads to a decreased VAc reactivity. The differences among the overall rates of copolymerization in the various solvents can be interpreted in terms of a variable chain transfer to solvent and the rate of the subsequent reinitiation by the solvent radical. In the case of benzene, complex formation is believed to play an important part.     

Poly(vinyl acetate‐co‐dibutyl maleate) latex films in the presence of grafted and post‐added poly(vinyl alcohol)

We describe the synthesis and characterization of a series of poly(vinyl acetate‐co‐dibutyl maleate) [P(VAc‐DBM)] latex particles (monomer molar ratio 10.6:1). One set of samples [high‐M and M_250k SDS‐P(VAc‐DBM), gel content 50% and 0%] was prepared in the presence of an anionic surfactant sodium dodecyl sulfate. The other two sets of samples [high‐M and M_250k PVOH–P(VAc‐DBM)] were prepared in the presence of poly(vinyl alcohol) (PVOH). These polymers differ in gel content (50 and 0%) and the extent of PVOH grafting (30 and 15%). Polymer diffusion across cell boundaries in the latex films was monitored by fluorescence resonant energy transfer (ET) experiments. First, we examined M_250k samples in the presence of grafted and post‐added PVOH. The presence of post‐added PVOH (5%) causes a small but detectable retardation on the rate of polymer diffusion, whereas the presence of grafted PVOH (degree of grafting: 15%) significantly promotes the polymer diffusion rate. For the high‐M P(VAc‐DBM), the presence of post‐added PVOH also retards the polymer diffusion. Strikingly, the presence of grafted PVOH (degree of grafting: 30%) in the high‐M PVOH‐P(VAc‐DBM) promotes the polymer diffusion to such an extent that the diffusion was complete in the freshly prepared films. Our data also suggest that under our experimental conditions, the rate of P(VAc‐DBM) diffusion increases with an increase of the degree of PVOH grafting. To confirm these results, we carried out fluorescence microscopy experiments to monitor the fate of PVOH in these latex films and found that in newly formed PVOH–P(VAc‐DBM) films, the PVOH was either uniformly distributed in the P(VAc‐DBM) matrix or the domains were too small to be resolved (i.e., < 0.5 μm). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5005–5020, 2004     

Copolymerization of N-Vinylcarbazole and Vinyl Acetate via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization

Summary: The reversible addition–fragmentation chain transfer (RAFT) random copolymerization of N-vinylcarbazole (NVC) and vinyl acetate (VAc) was carried out using s-benzyl-o-ethyl dithiocarbonate (BED) as the chain transfer agent and 2,2′-azoisobutyronitrile (AIBN) as the initiator in 1,4-dioxane solution at 70 °C. The polymerization showed the characteristics of ‘living’ free radical polymerization behaviors: first order kinetics, linear relationships between molecular weight and conversion, and narrow polydispersity of the polymers. The reactivity ratios of NVC and VAc were calculated via the Kelen–Tudos (KT) and non-linear error in variable (EVM) methods and showed as r₁ = 1.938 ± 0.191, r₂ = 0.116 ± 0.106. The thermal behavior of the copolymers with different content of NVC and VAc was investigated by DSC and TGA. The results showed that the introduction of a VAc segment into copolymer significantly reduced the T_g of the NVC homopolymers. FT-IR spectra, fluorescence spectra, and cyclic voltammetric behavior of these copolymers were also measured and compared with those of NVC homopolymers. The copolymers showed similar oxidative behavior to the NVC homopolymer. However, there was only one reductive potential peak shown for the copolymers at about 0.058 V.     

Inductive effect of substituents on the dipole moment of α-substituted vinyl methyl ether

Dipole moments of several α-substituted vinyl methyl ethers R(OMe)C:CH₂; R = Me, Et, i-Pr, t-Bu, cyclopropyl, vinyl, Ph) have been determined by the Halverstadt-Kumler method in benzene solution at 293 K. The square of the total dipole moment μ_r was found to be a linear function of the Taft's inductive constant σ_r^*: μ_r²/D²=(0.619±0.033)+(1.092±0.10) σ_r^*. The inductive contribution of the substituent R on the total dipole moment may be expressed by the equation μ_j/D = ?0.52 σ^* + 0.25. This is in good agreement with the corresponding equation for the dipole moments of alkyl-substituted ethenes: μ_i/D = ?0.58 σ^* + 0.28 (based on dipole moments obtained by PCILO calculations).     

Reactivity ratios and microstructure determination of vinyl acetate–alkyl acrylate copolymers by NMR spectroscopy

(Vinyl acetate)/(ethyl acrylate) (V/E) and (vinyl acetate)/(butyl acrylate) (V/B) copolymers were prepared by free radical solution polymerization. ¹H-NMR spectra of copolymers were used for calculation of copolymer composition. The copolymer composition data were used for determining reactivity ratios for the copolymerization of vinyl acetate with ethyl acrylate and butyl acrylate by Kelen-Tudos (KT) and nonlinear Error in Variables methods (EVM). The reactivity ratios obtained are r_v = 0.03 ± 0.03, r_E = 4.68 ± 1.70 (KT method); r_v = 0.03 ± 0.01, r_E = 4.60 ± 0.65 (EV method) for (V/E) copolymers and r_v ? 0.03 ± 0.01, r_B ? 6.67 ± 2.17 (KT method); r_v = 0.03 ± 0.01, r_B = 7.43 ± 0.71 (EV method) for (V/B) copolymers. Microstructure was obtained in terms of the distribution of V- and E-centered triads and V- and B-centered triads for (V/E) and (V/B) copolymers respectively. Homonuclear ¹H 2D-COSY NMR spectra were also recorded to ascertain the existence of coupling between protons in (V/E) as well as (V/B) copolymers. © 1995 John Wiley & Sons, Inc.     

Copolymerization of Allilidene Diacetate with Vinyl Acetate

Abstract

The monomer reactivity ratios for vinyl acetate (VAc)-allilidene diacetate (ADA) copolymerization have never been obtained. The composition of VAc-ADA copolymers was determined by NMR spectroscopy, measuring CH protons corresponding to ADA at 3.1τ and VAc at 5.1τ. The monomer reactivity ratios were evaluated; r₁ = 1.34 ± 0.05 and r₂ = 0.48 ± 0.03, where M₁ = ADA and M₂ = VAc. From these values the Q and e values for ADA were calculated: Q = 0.047 and e = 0.44 by taking Q = 0.026 and e = ?0.22 for VAc. The H value [1] for copolymerization of ADA, VAc, and vinyl chloride (VC) is 0.87.     

Comparative study of electrostatic binding vs. complexation of Cu2+ ions with water‐soluble polymers containing styrene sulphonic acid and/or maleic acid units or their sodium salt forms

The interaction of Cu²⁺ ions with the homopolymer poly(styrene sulfonic acid) (PSSH), as well as with the copolymers of maleic acid (MAc) with styrene sulfonic acid (SSH) or vinyl acetate (VAc), was investigated in dilute aqueous solution through turbidimetry, potentiometry, viscometry, and spectrophotometry in the visible region. Cu²⁺ ions were introduced either through neutralization with Cu(OH)₂ of the acid form of the (co)polymers (PSSH, P(SSH‐co‐MAc) and P(VAc‐co‐MAc)) or through mixing of the sodium salt form of the (co)polymers (PSSNa, P(SSNa‐co‐MANa) and P(VAc‐co‐MANa)) with CuSO₄. Turbidimetry, potentiometry, and spectrophotometry revealed that the first carboxylic group of MAc or both carboxylate groups of MANa are involved in the complexation with Cu²⁺ ions when neutralization with Cu(OH)₂ or mixing with CuSO₄ are applied, respectively. The increased values of the reduced viscosity observed mainly at the first stages of neutralization of P(VAc‐co‐MAc) with Cu(OH)₂ indicate that interchain polymer‐Cu²⁺ complexation takes possibly place. Finally, the spectrophotometric behavior observed upon neutralization of P(SSH‐co‐MAc) with Cu(OH)₂ or mixing of P(SSNa‐co‐MANa) with CuSO₄ revealed that the strength of counterion binding by the sulfonate groups is, in fact, comparable with the complexation of Cu²⁺ ions with the carboxylate groups of MAc. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1149–1158, 2008     

Grafting of polycaprolactone onto poly(ethylene‐co‐vinyl alcohol) and application to polyethylene‐based bioerodable blends

Poly(ethylene‐co‐vinyl acetate) (EVA) powders containing 10 and 20 wt % of vinyl acetate (VAc) units was saponified in ethanol/KOH solution in a heterogeneous manner. Intermolecular interaction between vinyl alcohol(VOH) units in the produced poly(ethylene‐co‐vinyl alcohol) (EVOH) promoted the crystallization of intervening segments composed of ethylene units. Ring opening polymerization of caprolactone (CL) in the presence of EVOH gave EVOH‐g‐PCL graft copolymers with relatively short chain branches. Even though the graft copolymerization was carried out in a homogeneous solution, all the VOH units were not equally reactive for the PCL grafting. And the unreacted VOH units decreased very slowly with the graft copolymerization time. EVOH‐g‐PCL decreased the domain size of the dispersed phase in low density polyethylene (PE)/biodegradable master batch (MB) blends, and thus increased their tensile properties significantly. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2561–2569, 2002     

Studies of the polymerization of diallyl compounds. XXVII. Copolymerization of diallyl tartrate with several vinyl monomers

The radical copolymerization of diallyl tartrate (DATa) (M₁) with diallyl succinate (DASu), diallyl phthalate (DAP), allyl benzoate (ABz), vinyl acetate (VAc), or styrene (St) was investigated in order to disclose in more detail the characteristic hydroxyl group's effect observed in the homopolymerization of DATa. In the copolymerization with DASu or DAP as a typical diallyldicarboxylate, the dependence of the rate of copolymerization on monomer composition was different for different copolymerization systems and unusual values larger than unity for the product of monomer reactivity ratios, r₁r₂, were obtained. In the copolymerization with ABz or VAc (M₂), the r₁ and r₂ values were estimated to be 1.50 and 0.64 for the DATa/ABz system and 0.76 and 2.34 for the DATa/VAc system, respectively; the product r₁r₂ for the latter copolymerization system was found again to be larger than unity. In the copolymerization with St, the largest effect due to DATa monomer of high polarity was observed. Solvent effects were tentatively examined to improve the copolymerizability of DATa. These results are discussed in terms of hydrogen-bonding ability of DATa.