Novel cyano-containing copolymers of vinyl esters for piezoelectric materials

The synthesis of a series of novel cyano-containing copolymers is described. Alternating copolymers of acrylonitrile with vinyl esters are obtained by increasing the electrophilic character of the nitrile monomers by complexation with zinc chloride. Copolymers of methyl and ethyl α-cyanoacrylates with vinyl esters are prepared using radical initiators in the presence of 7% acetic acid as inhibitor for anionic polymerization. The copolymers of methyl α-cyanoacrylate with the vinyl esters have T_g's above 140°C. Methyl vinylidene cyanide (MVCN) copolymerizes spontaneously with para-substituted styrenes to yield copolymers with high inherent viscosities and high T_g (160°C) and the copolymer of MVCN with vinyl acetate is also synthesized. The pyroelectric constants p for these polymers were measured and the values of p for the copolymers of vinyl acetate with methyl β,β-dicyanoacrylate, methyl α-cyanoacrylate, or MVCN were in the same range as the well-studied vinylidene cyanide/vinyl acetate copolymer. A higher concentration of dipoles generally results in higher T_g's and higher pyroelectric coefficients. © 1992 John Wiley & Sons, Inc.     

Thermal stability of copolymers of vinyl acetate and methyl acrylate

The thermal degradation of a series of copolymers of vinyl acetate and methyl acrylate and the two homopolymers poly(vinyl acetate) and poly(methyl acrylate) obtained using Ce(IV) as initiator has been investigated using differential thermal analysis (DTA) and thermogravimetry (TGA) in dynamic nitrogen. The kinetic parameters E, n, and A have been obtained following several methods of thermogravimetric analyses. The stability increases as the methyl acrylate content in the copolymer composition increases. The incorporation of 5 mol % of vinyl acetate in the copolymer produces a marked decrease in stability compared to the homopolymer poly(methyl acrylate). There is evidence for an intramolecular lactonization process in vinyl acetate—methyl acrylate copolymers.     

Azanorbornenes in radical polymerization reactions

Activity of azanorbornenes: N-benzyl-2-azanorborn-5-ene, (2-azanorborn-5-en-2-yl)methyl acetate, and N-allyl-2-azanorborn-5-ene in radical homo-and copolymerization with vinyl monomers and sulfur dioxide was studied.     

Synthesis of poly(vinyl acetate) block copolymers by successive RAFT and ATRP with a bromoxanthate iniferter

Poly(vinyl acetate)-b-polystyrene, poly(vinyl acetate)-b-poly(methyl acrylate) and poly(vinyl acetate)-b-poly(methyl methacrylate) block copolymers with low polydispersity (M(w)/M(n) < 1.25) were prepared by successive reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) employing a bromoxanthate iniferter (initiator-transfer agent-terminator).     

Modulated Differential Scanning Calorimetry Analysis of Interphases in Multi-Component Polymer Materials

A modulated-temperature differential scanning calorimetry (M-TDSC) method for the analysis of interphases in multi-component polymer materials has been developed further. As examples, interphases in a polybutadiene-natural rubber (50:50 by mass) blend, a poly(methyl methacrylate)-poly(vinyl acetate) (50:50 by mass) structured latex film, a polyepichlorohydrinpoly(vinyl acetate) bilayer film, and polystyrene-polyurethane (40:60 by mass) and poly(ethyl methacrylate)-polyurethane (60:40 by mass) interpenetrating polymer networks were investigated. The mass fraction of interphase and its composition can be calculated quantitatively. These interphases do not exhibit clear separate glass transition temperatures, but occur continually between the glass transition temperatures of the constituent polymers. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hyperbranched polymers with maleic functional groups as radical crosslinkers

The crosslinking performance of the unsaturated hyperbranched polyester poly(allyloxy maleic acid‐co‐maleic anhydride) (MAHP) was investigated with copolymerizations of three different monomers: styrene, vinyl acetate, and methyl methacrylate. Both styrene and vinyl acetate afforded interpenetrating‐polymer‐network copolymer gels. The gels exhibited crosslink density gradients through the polymer matrices on a macroscopic level, and density maximums were concentrated around the MAHP moieties. The heterogeneity of the gels is briefly discussed in terms of a modified two‐phase model, where one phase consists of an elastic part of low crosslinking density and the other phase consists of an inelastic dendritic part with a highly condensed bond density. Unlike the two‐phase model developed by Choquet and Rietsch, the modified two‐phase model takes into account that both phases swell in good solvents. Unlike copolymerizations employing styrene or vinyl acetate, the copolymerization of MAHP with methyl methacrylate afforded noncrosslinked starbranched copolymers that consisted of a MAHP core from which long poly(methyl methacrylate) branches were protruding. The different behaviors of the copolymerizations of the three monomers used in this study can rationally be explained by their different reactivity ratios with maleic end groups of MAHP. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 964–972, 2001     

Bestimmung des Vinylacetat-Gehaltes in EVA Copolymeren: Möglichkeiten und Grenzen der Anwendung MS-gekoppelter Analysenmethoden

Ethylene vinyl acetate copolymers were investigated by means of simultaneous thermal analysis (STA) and pyrolysis gas chromatography (Py-GC). Both devices are coupled to a mass spectrometer (MS). STA-MS revealed that the calibration with poly(vinyl acetate) leads to sufficient accuracy in relation to the vinyl acetate (VA) content, because of the linear calibration plot.Quantitative determination of VA by means of Py-GC-MS was carried out at both 500 and 700°C. The calibration plot in this method was linear provided that the mass of VA did not exceed a critical value.This revised version was published online in November 2005 with corrections to the Cover Date.     

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.     

THE COMPATIBILITY OF BLENDS OF POLY(VINYL CHLORIDE) OR CHLORINATED POLY(VINYL CHLORIDE) WITH POLY(METHYL METHACRYLATE)

IR spectral shifts of carbonyl vibrational absorption for ethyl acetate, which acts analogically as the structural unit of poly(methyl methacrylate), in cyclohexane, chloroform, chlorinated paraffins, poly(vinyl chloride) and chlorinated poly(vinyl chloride) were measured. The results suggest that there are specific interactions between the carbonyl groups and the chlorinated hydrocarbons which could be responsible for the apparent compatibility of poly(vinyl chloride)—poly(methyl methacrylate) and chlorinated poly(vinyl chloride)—poly(methyl methacrylate) blends. Additionally, the effects of the preparation mode of blend films on phase separation and observed compatibility are discussed.     

Studies on ceric–thiol-initiated aqueous vinyl polymerization with particular reference to end groups in poly(methyl methacrylate)

Ceric-thiol systems are good initiators for the acid aqueous polymerization of some water-soluble Vinyl monomers although not for styrene (in aqueous emulsion) and vinyl acetate. Thiols used are 2-mercaptoethanol, thioglycolic acid, 2-mercaptoethylamine hydrochloride, and L -cysteine hydrochloride. The polymerization proceeds through a radical mechanism. End-group analysis of poly(methyl methacrylate) obtained by initiation with various ceric-thiol systems has been carried out using Palit's dye testes. Hydroxyl, carboxyl, and amine end groups (to the extent of about one per polymer molecule) were incorporated in poly(methyl methacrylate)s obtained by initiation with 2-mercaptoethanol, thioglycolic acid, and 2-mercaptoethylamine hydrochloride, respectively, each in combination with Ce⁴⁺ ions; both amine and carboxyl end groups were obtained using C⁴⁺/L -cysteine hydrochloride initiator system. From the end-group results, the initiating species have been identified and the initiation mechanism prooposed. The probable termination mechanism also has been discussed.     

Kinetic Study of the Accelerating Effect of Coal-burning Additives on the Combustion of Graphite

The relationship between copolymer composition and transition temperatures was studied by means of differential scanning calorimetric analysis and dynamic mechanical spectroscopy. Six samples of ethylene vinyl acetate (EVA) copolymers containing from 5 to 40 mass per cent of vinyl acetate (VA) were studied. The differential scanning calorimetric analysis revealed that each EVA copolymer displays two endothermic peaks (T_m1 and T_m2 ) in the melting zone. Dynamic mechanical spectroscopy was used to determine the primary relaxation temperature (T_α ) for EVA copolymers. This latter characteristic is relatively insensitive to the level of vinyl acetate contained in the copolymer and is influenced by the pulsation frequency ω, also named the angular frequency. This revised version was published online in July 2006 with corrections to the Cover Date.     

Δχ effects on the miscibility of polymer blends

The Δχ effect on the miscibility of polymer blends prepared by solution-casting has been investigated using the mixture of poly(methyl methacrylate)(PMMA) with poly(vinyl acetate) (PVAc). The PMMA/PVAc blends have been prepared by casting from eleven different solutions. The Δχ effect of the solution–cast PMMA/PVAc blends was discussed in terms of Hansen's specified solubility parameters. It was found that the miscibility of the blends could be defined mainly by the solubility parameter contributed by the hydrogen–bonding of a solvent.     

Polymerization of methyl methacrylate and vinyl acetate initiated by the manganese carbonyl-1,2-epoxy-4,4,4-trichlorobutane system

Polymers containing epoxy groups at the ends of macromolecules and in side radicals are prepared through polymerization of methyl methacrylate and vinyl acetate in the presence of the manganese carbonyl-1,2-epoxy-4,4,4-trichlorobutane system. The presence of reinitiation is revealed; it leads to an appreciable increase in the molecular masses of poly(methyl methacrylate) and poly(vinyl acetate) as compared to polymers synthesized in the presence of 2,2′-azo-bis(isobutyronitrile) and 1,2-epoxy-4,4,4-trichlorobutane.     

Fluorocyclopropanes. IV. Copolymers of perfluorocyclopropene

Perfluorocyclopropene undergoes free-radical copolymerization with ethylene, isobutylene, cis- and trans-2-butene, vinyl acetate, methyl vinyl ether, vinyl chloride, styrene, acrylonitrile, tetrafluoroethylene, vinyl fluoride, and vinylidene fluoride. The copolymerization proceeds most readily with electron-rich olefins such as methyl vinyl ether (to yield a 1:1 copolymer), but conditions were found to give copolymers with electron-deficient olefins such as tetrafluoroethylene and vinylidene fluoride. Copolymers with methyl vinyl ether, tetrafluoroethylene, vinyl fluoride, and vinylidene fluoride were examined in detail. Evidence is presented that the perfluorocycloproply ring is incorporated intact into the copolymer and can be subsequently isomerized to a perfluoropropenyl unit by heating at 200–300°C.     

Hydrophilic membranes based on poly(vinyl methyl ether-crosslinked-polystyrene) semi-interpenetrating networks

Microporous membranes were prepared from poly(vinyl methyl ether - crosslinked-polystyrene) (PVME-cross-PS) semi-IPN's by extraction of poly(vinyl methyl ether) (PVME) with water. Membrane morphology and properties are fixed during the process of swelling, phase separation, PVME extraction and vitrification which occurs upon immersing the samples in water. The membranes are characterized by swelling (water uptake), the relative amounts of free and bound water, and their permselectivity towards KCI solution.     

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.     

Radical reactions involving esters of fumaric acid—III. Chain transfer processes

Model compounds have been used in studies at 60° in connection with transfer to polymer during the copolymerization of vinyl acetate with esters of fumaric acid. Succinate esters were used to simulate the fumarate ester units and ethyl acetate the vinyl acetate units in the copolymers. The succinate esters are much more reactive than ethyl acetate in transfer reactions with polyvinyl acetate radicals. Methyl isobutyrate and methyl propionate were also examined to assess the difference in reactivity in transfer of tertiary and secondary hydrogen atoms. It is concluded that branching is a very important reaction in the preparation of high conversion copolymers of fumarate esters with vinyl acetate.     

Aggregation and protein binding of sodium maleate copolymers with varying hydrophobicities

Copolymers of sodium maleate with methyl methacrylate, styrene, or vinyl acetate have been synthesized and studied in aqueous NaCl solutions of various ionic strengths. The polymers are polyelectrolytes with varying hydrophobicities, and their solution properties have been studied using static and dynamic light scattering. Copolymers containing methyl methacrylate or styrene were shown to aggregate in water upon increasing salt concentration. Copolymers of sodium maleate and vinyl acetate do not associate with increasing ionic strength. The binding of bovine serum albumin and cytochrome C to the sodium maleate copolymers was also investigated by light scattering. It was observed that cytochrome C forms complexes with the copolymers containing methyl methacrylate or vinyl acetate whereas albumin does not bind to any of the copolymers studied. Copyright © 2004 John Wiley & Sons, Ltd.     

Compatibility studies on solutions of polymer blends by viscometric and ultrasonic techniques

Detailed viscometric and ultrasonic velocity studies have been conducted on solutions of blends of poly(methyl methacrylate) with poly(vinyl acetate), poly(vinyl chloride) with poly(vinyl acetate) and poly(methyl methacrylate) with polystyrene over an extended range of concentrations and temperatures in toluene, chlorobenzene and toluene respectively. The plots of both absolute viscosity and ultrasonic velocity vs composition deviate from linearity according to the degree of compatibility of polymer blends, at all concentrations and temperatures. The curves for compatible systems are linear. These investigations offer an entirely new approach to the study of the compatibility of polymer blends.     

Iron powder and tin/tin chloride as new reducing agents of Meerwein arylation reaction with unexpected recycling to anilines

Abstract

Simple and rapid route for Meerwein arylation reaction using iron powder or a mixture of tin/tin chloride has been developed. In the presence of iron powder, different aryl diazonium salts reacted with methyl vinyl ketone, acrylates, and isopropenyl acetate. Production of oximes was detected as the main product with acrylates or in a mixture with β-aryl methyl ketones in the case of methyl vinyl ketone. The in situ produced HNO₂ from an excess of NaNO₂/HCl was trapped by alkyl aryl radical to form oximes in the E configuration form. The presence of tin/tin chloride mixture in the reaction of the aryl diazonium salts with methyl vinyl ketone produced Michael products along with β-aryl methyl ketones. The predicted α-aryl methyl ketones from the reaction of isopropenyl acetate with the diazotized anilines were obtained using iron or tin/tin chloride mixture.