Effect of solvent for vinyl acetate polymerization on microstructure of poly(vinyl alcohol)

The solution polymerization of vinyl acetate was carried out in several solvents at 0 to 100°C, using 2,2′-azobisisobutyronitrile as initiator. For the resulting poly(vinyl alcohol) (PVA), iodinecoloration, 1,2-glycol structure and tacticity were observed. The pentad tacticity of PVA was estimated from its methine carbon spectra by means of ¹³C-FTNMR spectrometer. Iodine-coloration ability of PVA varied markedly with the type of polymerization solvent and decreased in the following order: phenol > aq. phenol > methyl alcohol > ethyl acetate > DMSO, ethylene carbonate. The syndiotactic fraction in PVA also decreased with polymerization solvent in the same order as that of iodine coloration, while 1,2-glycol content of PVA was not almost affected by polymerization solvent except for phenol and aq. phenol. In solution polymerization performed, effect of polymerization temperature on tacticity was less than that of solvent.     

Preparation of block copolymers from occluded vinyl acetate macroradicals

Stable vinyl acetate macroradicals were produced by polymerization in a nonviscous poor solvent, a viscous good solvent and a viscous poor solvent. These macroradicals were then allowed to react with a second vinyl monomer to produce block copolymers. The formation of block copolymers was monitored for rate and yield data. The block copolymers produced were poly(vinyl acetate-b-methyl methacrylate), poly(vinyl acetate-b-acrylic acid), poly(vinyl acetate-b-vinylpyrrolidone), poly(vinyl acetate-b-acrylonitrile), poly(vinyl acetate-b-styrene), and poly(vinyl acetate-b-methyl acrylate). The block copolymers were characterized by yield, precipitation in selected solvents, pyrolysis gas chromatography, and differential scanning calorimetry.     

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     

Effect of solvent on radical polymerization of vinyl benzoate

Absolute rate constants of the vinyl benzoate polymerization have been measured by use of the intermittent illumination method in various aromatic solvents and ethyl acetate at 30°C. The determination of absolute rate constants showed that effects of solvent on the polymerization rate of vinyl benzoate were mainly ascribed to the variation of k_p values with solvents rather than that of k_t values. The k_p values for solvents used increased in the order: benzonitrile < ethyl benzoate < anisole < chlorobenzene < benzene < fluorobenzene < ethyl acetate. There was an eightfold difference between the largest and the smallest values The large variation among k_p values was explained neither by the copolymerization through solvents nor the chain transfer to solvents, but by a reversible complex formation between the propagating radical and aromatic solvents. This explanation was supported by a correlation between k_p values and calculated delocalization stabilizations for the complexes.     

Poly(vinyl alcohol) obtained through polymerization of some vinyl esters

Bulk and/or solution polymerizations of a series of vinyl esters, e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, and vinyl benzoate were conducted. Iodine-coloration, 1,2-glycol structure, molecular weight, and tacticity (triad and pentad) were measured for the resulting poly(vinyl alcohol)s (PVAs). The iodine-coloration abilities of PVAs, derived from poly(vinyl ester)s that were obtained through bulk polymerization at 60°C, depended on the starting monomer, increasing in the following order: vinyl benzoate < vinyl acetate < vinyl propionate < vinyl butyrate < vinyl pivalate. In solution polymerizations of vinyl propionate and vinyl butyrate, it was revealed that the tacticity of the derived PVAs apparently depended on the type and amount of polymerization solvent employed, as found previously in the case for vinyl acetate. The iodine-coloration of these PVA samples varied in the same order as their syndiotactic content, while no relationship was observed toward their 1,2-glycol content. The probabilities of the syndiotactic propagation at 60°C were estimated as 0.49 (benzoate), 0.54 (acetate), 0.55 (propionate), 0.56 (butyrate), and 0.60 (pivalate), respectively.     

Chain transfer constants for vinyl monomers polymerized in methyl oleate and methyl stearate

Chain transfer constants were obtained for styrene, methyl methacrylate, methyl acrylate and vinyl acetate, polymerized in methyl oleate and methyl stearate at 60°C. Transfer constants increased in the order: methyl methacrylate < styrene < methyl acrylate ? vinyl acetate in both solvents. Average values of the transfer parameters were: for methyl oleate, Q_tr = 2.04 × 10^?4, e_tr = 1.08; for methyl stearate, Q_tr = 0.373 × 10^?4, e_tr = 1.01. Indication that polar species predominate in the transition state is supported by the observed order of reactivity. The usual rate dependence appeared to be followed by all of the monomers except vinyl acetate, which was retarded, severely in methyl oleate. Transfer in methyl oleate was about 5.8 times greater than that found in methyl stearate for these four monomers. The internal allylic double bond of methyl oleate had about the same reactivity in transfer as had the terminal unsaturation in N-allylstearamide at 90°C. Rough estimates were obtained of the monomer transfer constants for the long side-chain homologs of these four monomers from the respective monomer transfer constants and the experimental transfer constants, corrected for transfer to the labile groups of the solvent. It was concluded that the rate of polymerization would determine in large measure the degree of polymerization for the reactive 18-carbon homologs but that the molecular weight of poly(vinyl stearate) and (oleate) will be regulated primarily by transfer to monomer.     

Effect of solvent on the rate constants in solution polymerization. Part II. Vinyl acetate

Measurements were made of the value of the lumped kinetic constant k_p/k of vinyl acetate in different solvents and with different initiators. This quantity was evaluated using the well‐known conversion vs. time approach in dilute solutions using both azo‐bis‐isobutyronitrile and benzoyl peroxide (AIBN and BPO), and two different solvents (toluene and ethyl acetate) at 60°C. As was found for butyl acrylate in Part 1 of this series, it was found that the value of the lumped rate constant depends very strongly on the concentration of monomer in solution, decreasing as the solution becomes more and more dilute. However, unlike butyl acrylate, vinyl acetate is much more susceptible to changes in the solvent type, with toluene acting as a severe retarding agent of polymerization. The results of the present study suggest that at least two separate effects of solvent exist simultaneously in the case of vinyl acetate polymerization, and that both of them must be taken into account when attempting to model this type of system. The number‐ and weight‐average molecular weights of the different polymers were also measured, and excellent agreement was found between the measurements and model predictions. A linear relationship was shown to exist between the value of the lumped constant and the square root of the number‐average chain length. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 589–601, 1999     

Radiation induced graft polymerization of multi-walled carbon nanotubes for superhydrophobic composite membrane preparation

Highly soluble multi-walled carbon nanotubes (MWNTs) were prepared by radiation-induced free radical graft polymerization of vinyl acetate (VAc) onto pristine MWNT surfaces. High resolution transmission electron microscopy (HR-TEM), Fourier transform infrared (FTIR) spectroscopy, and micro-Raman spectroscopy were used to confirm that poly(vinyl acetate) (PVAc) had been successfully grafted onto the surface of the MWNTs. The effects of experimental parameters on the degree of grafting (DG) of PVAc were also investigated, including adsorbed dose, dose rate, initial monomer concentration, and solvents. The grafted MWNTs (MWNTs-g-PVAc) exhibited good solubility in common organic solvents at high mass fraction. In addition, a superhydrophobic composite membrane could be readily fabricated by vacuum filtration of MWNTs-g-PVAc onto a supporting membrane, as was confirmed by water contact angle testing and visualization by scanning electron microscopy.     

Thermodynamic properties of some concentrated polymer solutions

Solubilities of several solvents were measured in four molten polymers by using an isobaric vapor-pressure apparatus. Solvent concentration ranged from 0.5 to 15 wt-%. The systems polyisoprene–benzene and polyisobutylene–benzene were studied at 80.0°C; polyisobutylene–cyclohexane was studied at 100.0°C; ethylene–vinyl acetate copolymer (EVA)–cyclohexane, EVA–isooctane, and poly(vinyl acetate)–isooctane were studied at 110.0°C. Of six polymer–solvent systems studied, all except poly(vinyl acetate)–isooctane appear to exhibit hysteresis in a single sorption–desorption cycle starting with dry polymer. The desorption curves of solvent activity plotted versus solvent weight fraction show an inflection point, suggesting localized adsorption of solvent molecules. Experimental data were analyzed with a theory which takes into account adsorption of solvent by polymer in addition to differences in free volumes and intermolecular forces. The theory gives a semiquantitative representation of the experimental data.     

Structure–property relationships of poly(vinyl alcohol). I. Influence of polymerization solvents and temperature on the structure and properties of poly(vinyl alcohol) derived from poly(vinyl acetate)

The solubility properties of poly(vinyl alcohol) (PVA) vary with the method of preparation of the poly(vinyl acetate) (PVAc) from which it is derived. PVAc was prepared with free-radical catalysts over a range of temperatures from ?78 to 90°C. with solvents of varying chain-transfer ability. The corresponding PVA samples varied in their resistance to dissolution in water. Their high-resolution proton nuclear magnetic resonance spectra showed on differences in tacticity. Data on 1,2-diol content showed only minor differences. Hence, the increase in resistance of PVA to dissolution in water arising from changes in chain-transfer activity of the solvent used in vinyl acetate polymerization is largely attributable to a decrease in molecular weight, and the increase in resistance of PVA to dissolution in water arising from a decrease in the temperature of the vinyl acetate polymerization is largely attributable to a decrease in both long and short branches. Evidently, with polar polymers having small side groups, tacticity is not the only factor influencing property variation; that is, variations in stereoregularity influence more the crystallinity of the sample as measured by density or x-ray methods than the ultimate crystallizability under conditions of mechanical and thermal treatment. In this regard polar polymers having small side groups differ from nonpolar polymers.     

Grafting of Polymer Brushes from Xanthate-Functionalized Silica Particles

Monodisperse silica particles (SiPs) were surface-modified with a newly designed silane coupling agent comprising a triethoxysilane and an alkyl halide, namely, 6-(triethoxysilyl)hexyl 2-bromopropionate, which was further treated with potassium O-ethyl dithiocarbonate (PEX) to immobilize xanthate molecules on the particle surfaces. Surface-initiated macromolecular design via interchange of xanthates (MADIX) polymerization of vinyl acetate (VAc) was conducted with the xanthate-functionalized SiPs. The polymerization was well controlled and produced SiPs coated with poly(vinyl acetate) (PVAc) with a well-defined target molar mass and a graft density of about 0.2 chains nm⁻². Dynamic light scattering and TEM measurements revealed that the hybrid particles were highly dispersible in good solvents without any aggregation. The PVAc brushes were hydrolyzed with hydrochloric acid to produce poly(vinyl alcohol) brushes on the SiP surfaces. In addition, the number of xanthate molecules introduced on the SiP surfaces could be successfully controlled by adjusting the concentration of PEX. Thus, the SiPs have two functionalities: xanthates able to act as a MADIX chain-transfer agent and alkyl bromide initiation sites for atom transfer radical polymerization (ATRP). By using these unique bifunctional particles, mixed polymer brushes were constructed on the SiPs by MADIX of VAc followed by ATRP of styrene or methyl methacrylate.     

Solvent effects in the free radical copolymerization of vinyl acetate and methyl methacrylate

A study was made of the effects of five solvents on the compositions of copolymers of vinyl acetate (VA) and methyl methacrylate (MMA) produced by free radical polymerization from feeds rich in VA. The MMA content was reduced significantly by propanol, unaffected by benzene and ethyl acetate and increased by acetonitrile and acetone. The effects observed for propanol, acetonitrile and acetone all reached a maximum at a solvent to monomer molar ratio of about 7:1. Experiments showed that neither monomer physical aggregation nor monomer carbonyl polarization phenomena could explain completely the observed effects. A complete explanation probably requires several factors including some associated with polymer radical reactivity.     

The effect of solvents on the radiation-induced polymerization of ethyl and isopropyl vinyl ethers

The radiation-induced cationic polymerization of ethyl and isopropyl vinyl ethers was studied in a variety of solvents. The propagation rate constants were estimated and found to vary widely with the nature of the solvent. In particular, a good linear relationship existed between the logarithms of the rate constants and the reciprocal of the dielectric constants. The lowest rates were those of the highest dielectric constant solvents. These results have been interpreted in terms of the Laidler and Eyring theory of ion-molecule reactions. Isopropyl vinyl ether polymerizes much faster than ethyl vinvl ether, although the rates approach the same value at infinite dielectric constant. In contrast, “free” carbenium ion polymerizations initiated by stable carbenium ion salts in methylene chloride solution had similar values for both monomers. A comparison is made between the rate constants obtained with both methods of initiation.     

High-pressure polymerization of vinyl chloride

The radical polymerization of vinyl chloride was investigated at 60°C under high pressure up to 5000 bar in benzaldehyde, benzonitrile, toluene, heptane, cyclohexane, and dioxane as solvent. In benzaldehyde and benzonitrile, the polymerizations were depressed by increased pressure. This unusual behavior was explained by the solvent participation and the effect of pressure on the propagating radicals. The crystallinities of polymer obtained in all solvents decreased with increasing pressure, as judged by the absorbance ratio of the infrared spectra. However the effects of pressure on the absorbance ratio of the polymer obtained in benzaldehyde and benzonitrile were not identical with those in the other solvents. These facts also suggest that both solvents play a special role for the solvent participation in the propagating step.     

Regioselective oxidative polymerization of 1,5-dihydroxynaphthalene catalyzed by bilirubin oxidase in a water–organic solvent mixed solution

Bilirubin oxidase (EC1.11.1.7) was used to catalyze the oxidative polymerization of 1,5-dihydroxynaphthalene to its polymer in a mixed solvent composed of dioxane, ethyl acetate, and acetate buffer. In an aqueous solution, the enzymatic oxidative polymerization hardly occurred and resulted in negligible yield mainly due to the poor solubility of 1,5-dihydroxynaphthalene. In the mixed solvent the conversion proceeded with a yield of ca. 70%. The polymer yield was studied with respect to reaction time and solvent components. Elemental analysis, UV-visible, fluorescent, and FT-IR spectroscopic analyses, proton NMR and electrochemical studies, and solubility in various organic solvents revealed that 1,5-dihydroxynaphthalene is polymerized by the C? C coupling. The molecular weight of the polymeric products solubilized with DMF varied from low molecular weight product to high molecular weight polymer. From the chromatographic studies, the organic solvent–insoluble residue was suggested to be highly polymerized material. Based on these findings a possible mechanism for enzymatic polymerization of 1,5-dihydroxynaphthalene is presented: less stable intermediates produced enzymatically from 1,5-dihydroxynaphthalene undergo coupling and polymerization to ortho-1,5-dihydroxynaphthalene polymer, thereby resulting in a regioselective polymerization of 1,5-dihydroxynaphthalene. © 1993 John Wiley & Sons, Inc.     

ESR study on radical polymerization and its application to microemulsion systems

Well-resolved electron spin resonance (ESR) spectra of propagating radicals of vinyl and diene compounds were observed in a single scan by a conventional CW-ESR spectrometry without the aid of computer accumulation and the specially designed cavity and cells. Although solvents which could be used for ESR measurements were restricted to nonpolar solvents, such as benzene, toluene, and hexane, new information on dynamic behavior and reactivity of the propagating radicals in the radical polymerization of vinyl and diene compounds were obtained. Thus, values of propagation rate constants (k_p) for vinyl and diene compounds were determined by an ESR method. Some of the k_p values were in a fair agreement with those obtained by a pulsed laser polymerization (PLP) method. Furthermore, polymer chain effect on apparent k_p was clearly observed in the radical polymerization of macromonomers and in the microemulsion polymerization. In ESR measurement on inclusion polymerization system, important information on the origin of the 9-line spectrum observed in the radical polymerization of methacrylate propagating radicals was obtained.     

Stereocontrol in radical polymerization

The stereospecific radical polymerization of vinyl esters, methacrylates, and alpha-substituted acrylates was studied. Fluoroalcohols, as a solvent, have remarkable effects on the stereoregularity of the radical polymerizations of vinyl acetate, vinyl pivalate, and vinyl benzoate, affording polymers rich in syndiotacticity, heterotacticity, and isotacticity, respectively. This method was successfully applied to the polymerization of methacrylates to give syndiotactic polymers. The steric repulsion between the entering monomer and the chain-end monomeric unit bound by the solvent through hydrogen bonding is important for the stereochemical control in these systems. Lewis acid catalysts, such as lanthanide trifluoromethanesulfonates and zinc salts, were also effective for the stereocontrol during the radical polymerization of methyl methacrylate, to reduce the syndiotacticity and alpha-(alkoxymethyl)acrylates to synthesize isotactic and syndiotactic polymers. Radical polymerization of the methacrylates bearing a bulky ester group, such as the triphenylmethyl methacrylate derivatives, gave highly isotactic polymers, as in the case of anionic polymerization. In addition, the control of one-handed helical conformation was attained in the radical polymerization of 1-phenyldibenzosuberyl methacrylate using chiral neomenthanethiol or cobalt(II) complexes as an additive.     

A novel synthetic procedure of vinylacetamide and its free radical polymerization

The pyrolysis of N-(α-methoxyethyl) acetamide, which was obtained by one-step reaction of acetamide, acetaldehyde, and methanol, gave N-vinylacetamide (NVA) in a good yield. The polymerizability and copolymerizability of NVA were studied. Free radical polymerization was carried out in the presence of radical initiator or by γ-ray irradiation. The monomer reactivity ratios of NVA were estimated in the copolymerization with acrylamide, vinyl acetate, and methyl methacrylate. The solvents were found to influence the monomer reactivity ratio. NVA showed a typical copolymerizability as nonconjugated vinyl monomer, and Q and e values were obtained in DMF as 0.16 and ?1.57, respectively.     

Catalytic action of metallic salts in autoxidation and polymerization. IX. Polymerization of methyl methacrylate with sodium hexanitrocobaltate(III) in mixed solvent of acetone and water

Polymerization of methyl methacrylate with some cobalt (III) complexes was carried out in various solvents and in mixed solvents of acetone and water or alcohols. Sodium hexanitrocobaltate(III) was found to be an effective initiator in mixed solvent of water and acetone. The kinetic study on the polymerization of methyl methacrylate with Na₃[Co(NO₂)₆] in a water-acetone mixed solvent gave the following over-all rate equation: R_p = 8.04 × 10⁴ exp{ ?13,500/RT} [I]^1/2[M]² (mol/1.?sec). The effects of various additives on polymerization rate and the copolymerization curve with styrene suggest that polymerization proceeds via a radical mechanism. The dependence of the polymerization rate on the square of monomer concentration and the spectroscopic data were indicative of the formation of a complex between initiator and monomer.     

Efficient lipase-catalyzed kinetic resolution of 4-arylmethoxy-3-hydroxybutanenitriles: application to an expedient synthesis of a statin intermediate

The kinetic resolution of 4-arylmethoxy-3-hydroxybutanenitriles was investigated by lipase-catalyzed transesterification in organic solvents. A high enantioselectivity was obtained via reaction with vinyl acetate in a mixed solvent (n-heptane/acetonitrile 1:1), which was catalyzed by the lipase from Artgribacter sp. A better selectivity was demonstrated when the number of substituents on the aryl ring increased. (S)-4-Arylmethoxy-3-hydroxybutanenitriles can be obtained with enantiomeric excesses of up to 98.0% by this method. Furthermore we have developed a novel route to synthesize tert-butyl (S)-6-benzyloxy-5-hydroxy-3-oxohexanoate, a key intermediate for the preparation of HMG-CoA reductase inhibitors (statins).