2-chloroethyl Vinyl Ether Research Articles

Synthesis of dihydroxy terminated poly(chloroethyl vinyl ether)s by “living” cationic polymerization: evidences for side reactions and their control

AbstractThis paper reports on the synthesis of dihydroxy terminated poly(chloroethyl vinyl ether)s (PCEVE) via bifunctional living cationic polymerization. The bifunctional chain initiator is obtained by reacting malonaldehyde bis(diethyl acetal) with trimethylsilyl iodide (TMSI) to form the corresponding di‐α‐iodo ether derivative. The polymerization of chloroethylvinyl ether is then triggered by ZnCl2. The direct transformation of active ends into aldehyde terminals, as well as their derivatization into hydroxy groups, is described. The synthesis of high molar mass ditelechelics by bifunctional polymerization provides evidence for the occurrence of a monofunctional side initiation. The latter has been attributed to the hydrolysis of TMSI by adventitious water, which leads to the in situ formation of hydrogen iodide. In order to trap hydrogen iodide, the influence of different additives, bulky amines, metals and alkylaluminiums, was investigated. Therefore, in the presence of alkylaluminiums, it is possible to obtain a clean bifunctional polymerization up to relatively high molar mass ditelechelic PCEVE (M̄n = 33000 g/mol, M̄w/M̄n = 1.11).

Multifunctional Coupling Agents for Living Cationic Polymerization. 5. Synthesis of Amphiphilic Tetraarmed Star Poly(vinyl ethers) by Coupling Reactions with Tetrafunctional Silyl Enol Ether

Amphiphilic tetraarmed star poly(vinyl ethers), where each arm carries alkyl (hydrophobic) and alcohol (hydrophilic) pendant groups, have been synthesized by the coupling reaction of AB-block living poly(vinyl ethers) (4; arm chain) with a tetrafunctional silyl enol ether 1, C[CH 2 OC 6 H 4 -p-C(OSiMe 3 )=CH 2 ] 4 . The living arm chaise 4 were prepared by the sequential living cationic polymerization of an alkyl vinyl ether (CH 2 =CHOR 1 ; R 1 =iBu, CH 2 CH 2 Cl) and a fuctionalized vinyl ether (CH 2 =HOCH 2 -CH 2 R 2 ; R 2 =OCOCH 3 , OSi t BuMe 2 ) with hydrogen chloride/zinc chloride initiating system in methylene chloride at -15 o C. The treatment of 4 with the silyl enol ether 1 led to tetraarmed block copolyiners 5. The yield of 5 (93-73%) depended on the structure and the polymerization sequence of the monomer pair for the arm chain 4. The best result (93% yield) was obtained with the AB-block polymer of 2-chloroethyl vinyl ether (R 1 =CH 2 CH 2 Cl; CEVE) and 2-acetoxyethyl vinyl ether (R 2 =OCOCH 3 ; AcOVE) where CEVE has polymerized first. Separate coupling experiments with the homopolymers of these vinyl ethers showed that the coupling yield was higher for monomers with less bulky pendant groups. Subsequent quantitative deprotections of the acetoxy of tert-butyldimethylsilyl groups in 5 into hydroxyl groups gave the amphiphilic tetraarmed polymers 6. By changing the polymerization sequence of the monomer pair, the hydrophilic polyalcohol segments could be placed either inside or outside the tetraarmed structure. For pairs of such inner- and outer-alcohol versions with identical segmental compositions, solubility and arm-chain conformation (by 1 H NMR) were compared

Controlled Synthesis of Bicyclic "Eight-Shaped" Poly(chloroethyl vinyl ether)s

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTControlled Synthesis of Bicyclic "Eight-Shaped" Poly(chloroethyl vinyl ether)sMichel Schappacher and Alain DeffieuxCite this: Macromolecules 1995, 28, 8, 2629–2636Publication Date (Print):April 1, 1995Publication History Published online1 May 2002Published inissue 1 April 1995https://doi.org/10.1021/ma00112a006RIGHTS & PERMISSIONSArticle Views221Altmetric-Citations52LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (2 MB) Get e-Alerts Get e-Alerts

Nature and concentration of active species in cationic polymerization of vinyl ethers: A kinetic investigation

AbstractThe Kinetics of the polymerization of isopropyl vinyl ether, isobutyl vinyl ether (IBVE) and chloroethyl vinyl ether initiated by HI in CH2Cl2, in the presence and in the absence of tetrabutylammonium iodide as common anion salt, were investigated. The polymerizations proceed directly through the carbon–iodide termini without any necessary electrophilic activator. As previously observed with cyclohexyl vinyl ether, it was found that the addition of small amounts of salt, (0·5–10% with respect to initial [HI], depending on the monomer) drastically reduces the polymerization rate and leads to living‐type polymerizations. Higher amounts of salt have no influence on the polymerization rate which remains constant over a broad range of [NBu4I]/[HI] ratios. This general behaviour, observed for the all vinyl ethers, suggests a common ion salt effect and therefore an ionic polymerization mechanism involving ion pairs and free ions. In the absence of salt, both ion pairs and free ions of higher reactivity participate in the propagation, whereas only ion pairs contribute to the propagation in the presence of a common ion salt. According to this scheme, the living character of the polymerization is assumed to result from a propagation reaction governed by undissociated ionic species. The validity and the implications of this reaction scheme, in terms of active centre concentrations, are also discussed.

Characterization of Alternating Copolymers of Vinyl Ethers

Abstract Copolymerization of methyl 2-cyano-3-phenyl-2-propenoate (MCP) and 2-phenyl-1,1-dicyanoethene (PDE) with ethyl, n-butyl, i-butyl, 2-chloroethyl, and phenyl vinyl ethers in broad ranges of comonomer ratios always produces copolymers of an equimolar composition. The alternating structure of these copolymers was established by elemental analysis and by infrared, 1H− and 13C-NMR spectroscopy. Microstructure analysis of the copolymer of PDE and phenyl vinyl ether, as deduced from 1H and NOESY 13C-NMR data, demonstrated the formation of alternating monomer structures with different orientations of the monomer units. Additional characterization of the copolymers was carried out by DSC and TGA. The order of decreasing T g values, ethyl > phenyl > 2-chloroethyl >i-butyl >n-butyl vinyl ether, is the same for both MCP and PDE.

Curable copolymers of isobutylene and acrylic ester

Curable copolymers of isobutylene and acrylic ester were successfully synthesized by incorporation of a third monomer into alternating copolymers of isobutylene and acrylic ester by means of complexed copolymerization catalysed with alkylboron halide. As the third monomer, acrylic ester including an unsaturated bond in the ester group (AEU), such as crotyl acrylate, or vinyl monomer including a chlorine atom (CVM), such as 2-chloroethyl vinyl ether, was effectively incorporated. The terpolymers containing AEU (AIDM) were easily vulcanized with sulfur. The terpolymers containing CVM (AICM) were sufficiently well cured with polyamine. The cured products of both AIDM and AICM had excellent properties in terms of oil resistance, water resistance and others. The blend of AIDM and ethylenepropylenediene rubber was satisfactorily co-vulcanized with sulfur.

Synthesis, characterization, and polymerization of propenyl ether analogues

AbstractA series of aromatic monomers bearing cationically polymerizable propenyl groups were prepared and characterized using the readily available starting materials: isoeugenol and o‐allyl phenol. Monomers with both propenyl and vinyl ether functional groups were also synthesized by the reaction of these starting materials with chloroethyl vinyl ether. The reactivity of the resulting monomers in photoinitiated cationic polymerization was studied using differential scanning photocalorimetry and photogel point measurements. Their thermal properties were determined using thermogravimetric analysis. © 1994 John Wiley & Sons, Inc.

Living Cationic Polymerization of α-Methylstyrene. 2. Synthesis of Block and Random Copolymers with 2-Chloroethyl Vinyl Ether and End-Functionauzed Polymers†

Abstract Both AB and BA block copolymers of α-methylstyrene (αMeSt) and 2-chloroethyl vinyl ether (CEVE) were synthesized by the sequential living cationic polymerization initiated with the HCl-CEVE adduct (1a)/SnBr4 system in CH2Cl2 at -78°C. αMeSt-CEVE (AB) block copolymers with narrow molecular weight distributions ([Mbar]w/[Mbar]n ∼ 1.15) were obtained when αMeSt was polymerized first, followed by addition of CEVE to the resulting αMeSt living polymer solution. The reverse order of monomer addition, from CEVE to αMeSt, also led to a BA-type block copolymer. In the polymerization of a mixture of the two monomers, almost random copolymers were obtained. Living polymerizations of αMeSt were also induced with functional initiating systems, HCl-functionalized vinyl ether adducts (1b-1d)/SnBr4, to give end-function-alized poly(αMeSt)s with a methacrylate, an acetate, or a phthalimide terminal.

Functionalizable polyurethane networks based on hydroxymodified poly(chloroalkyl vinyl ether)s. 1

This paper describes the synthesis of polyurethane networks based on partly hydroxymodified poly(chloroethyl vinyl ether)s and examines the possibility to introduce various amounts of hydroxy groups in the network. Poly(chloroethyl vinyl ether)s are prepared by living-type cationic polymerization initiated by the HI/ZnCl2 system. Introduction of hydroxyl groups along the chain, in controlled amount, is then achieved in a two-step process involving the reaction of a fraction of the pendant chloride groups with a carboxylic salt, followed by alkaline hydrolysis. Finally the corresponding polyurethane networks- with or without remaining hydroxy functions- are obtained by reaction with hexamethylene diisocyanate in different proportions. Preliminary study of the mechanical properties of the networks are also reported.

Synthèse de polymères hautement fluorés amorphes et à Tg élevées: copolymérisation de maléimides fluorés avec des éthers vinyliques

We have prepared and characterized (by 1H NMR and MS methods) N-4-(2'- F-hexylethoxy)phenylmaleimide and N-4-(2'- F-hexylethylthio)phenylmaleimide. The behaviour of these fluorinated maleimides (FM) towards various vinyl ethers (2-chloroethylvinyl ether, benzylvinyl ether) in radical copolymerization has been studied. Generally, maleimides and vinyl ethers lead to alternated copolymers but, in this case, the copolymer was not alternated. The thermal behaviour of the copolymers has been evaluated and their thermal decomposition explained.

Resine acetylante: Synthese, polymerisation et etude de selectivite

The synthesis and the characterization of a resin called “acetylative” able to transfer its acetyl groups to amine or alcohol functions are described. The resin is a crosslinked copolymer of a maleimic monomer bearing an acetylated pyrazole heterocycle which provides the properties, and of divinylbenzene. The synthesis and the polymerization of the monomer and its copolymerization with 2-chloro ethyl vinyl ether are described and so are the thermal properties. Then, the behaviour of the resin with respect to several alcohol or amine functions is discussed.

Living Cationic Polymerization of α-Methylstyrene. 2. Synthesis of Block and Random Copolymers with 2-Chloroethyl Vinyl Ether and End-Functionalized Polymers

Living Cationic Polymerization of α-Methylstyrene. 2. Synthesis of Block and Random Copolymers with 2-Chloroethyl Vinyl Ether and End-Functionalized Polymers

Preparation and properties of poly(alkyl vinyl ether‐2‐ethyl‐2‐oxazoline) diblock copolymers

AbstractA method for the synthesis of well‐defined poly(alkyl vinyl ether–2‐ethyl‐2‐oxazoline) diblock copolymers with hydrolytically stable block linkages has been developed. Monofunctional poly(alkyl vinyl ether) oligomers with nearly Poisson molecular weight distributions were prepared via a living cationic polymerization method using chloroethyl vinyl ether together with HI/ZnI2 as the initiating system and lithium borohydride as the termination reagent. Using the resultant chloroethyl ether functional oligomers in combination with sodium iodide as macroinitiators, 2‐ethyl‐2‐oxazoline was polymerized in chlorobenzene/NMP to afford diblock copolymers. A series of poly(methyl vinyl ether–2‐ethyl‐2‐oxazoline) diblock materials were found to have polydispersities of ≈ 1.3–1.4 and are microphase separated as indicated by two Tg's in their DSC thermograms. These copolymers are presently being used as model materials to study fundamental parameters important for steric stabilization of dispersions in polar media. © 1993 John Wiley & Sons, Inc.

Living cationic polymerization of .alpha.-methylstyrene initiated with a vinyl ether-hydrogen chloride adduct in conjunction with tin tetrabromide

The first example of living cationic polymerization of α-methylstyrene was achieved with an initiating system that consist of the HCl-adduct of 2-chloroethyl vinyl ether [1a: CH 3 CH(OCH 2 CH 2 Cl)Cl] and SnBr 4 in CH 2 Cl 2 at -78°C. The number-average molecular weight of the polymers increased in direct proportion to monomer conversion up to 110 000 (DP n =1000) and agreed with the calculated values assuming that one polymer chain forms per 1a molecule. Throughout the reaction, the molecular weight distribution of the polymers stayed very narrow (M w /M n ∼1.1)

Novel vinyl ether thermosetting resins

The divinyl ether of diallylbisphenol A (VEABA) was investigated as a candidate for advanced composite matrix resin. VEABA was readily prepared in over 90% yield from a condensation reaction between diallyl bisphenol A and chloroethyl vinyl ether using a phase transfer catalyst. Since vinyl ethers are electron-rich monomers, they are polymerized by cationic initiators. The VEABA polymer possesses properties comparable to polymers produced from epoxy resins based on the diglycidyl ether of bisphenol A, except for much lower moisture absorption and a slightly lower glass transition temperature. Since the VEABA monomer is a low viscosity liquid, it is a good candidate for filament winding, resin transfer moulding and pultrusion fabrications for advanced composites.

The propagation rate-constants of the cationic polymerization of some alkenes in nitrobenzene—IV. Not the real kp+

The cationic polymerization of several alkenes, including vinyl ethers (VE), by carbenium and carboxonium salts in nitrobenzene had given propagation rate-constants which were interpreted by us as being the k p + as defined by the equation − dm dt = k p + · [P n +] · m, where [P n +] is the concentration of unpaired, uncomplexed propagating cations. The purpose of the present paper is to show that our own work contains evidence, not understood and neglected at the time, indicating that this is not correct. An interpretation has been devised which is compatible with all the facts, including the very low values of the rate-constants (now called k p +A), the bimodal DPD of the poly(2-chloroethylvinyl ethers), and the antibatic correlation between the k p +A and the enthalpy of polymerization for three hydrocarbons and two VE. This is based on the idea, introduced by others, that the propagating carbenium ions cationate the solvent, Sv, giving the ions P nSv +, i.e. P nON +(O)C 6H 5, which are in equilibrium with the P n +. The observed k p +A are weighted means of the propagation rate-constants of the two propagating species. A propagation mechanism for the P nSv + has been suggested which resembles closely that for pseudocationic polymerizations [8].

Model copolymerization reactions: Evidence against stereochemical effects of donor-acceptor complexation in reactions of simple alkyl radicals with n-phenylmaleimide and donor olefins

Reductive demercuration of alkylmercuric bromides with NaBD 4 was used to generate the 1-butyl and t-butyl radicals in mixtures of N-phenylmaleimide (NPM) and either of the donor olefins 2-chloroethyl vinyl ether (CEVE) or tetrathiafulvalene (TTF). In each case, the major products of the reaction were derived from simple addition of the radical to NPM followed by transfer of a deuterium atom to the initial adduct. There were no differences in the stereochemistries of the products formed from reaction mixtures of widely varying monomer compositions. These results show that transfer of the deuterium atom to the radical center is unaffected by electron donor-acceptor (EDA) complexation and argue against important stereochemical consequences of EDA complexation in radical copolymerization.

Synthesis of poly vinyl ethers with pendant non-linear optical azo dyes

Two vinyl ether polymers with pendant 4′-amino-4-nitroazobenzene dyes were synthesized with different lengths of spacer from the main chain. The synthesis involved polymerization of 2-chloroethylvinyl ether with HI/I 2 to give a polymer of M n 13200 and M w/ M n 1.23. The azo-dye molecules were attached to this polymer backbone by a Williamson ether synthesis route using a propyl or hexyl alcohol derivative of the azo dye. High loading of the dyes (> 75%) was achieved as measured by visible spectrophotometry, elemental analysis and 1H-NMR. The polymers exhibit high solubility in a range of solvents and thermal stability up to 200° in air. Liquid crystal (nematic) behaviour is observed for these polymers on cooling from the isotropic melt phase.

相間移動触媒法を用いる高分子の化学修飾と機能性高分子の合成

Chemical modification of polymers containing pendant chlorine was investigated using phase transfer catalysis, which is a very simple and convenient method for polymer synthesis as well as organic syntesis. The reactions of polymers containing chlorine such as poly (chloromethylstyrene), poly (epichlorohydrin), and poly (2-chloroethylvinyl ether) with various nucleophilic reagents composed from alkalimetal salts were carried out under three different reaction systems, solid-liquid, liquid-liquid, and solid-liquid-solid systems in the presence of phase transfer catalysts (PTCs). The reactions were strongly influenced by the kind of PTC, concentration, concentration of reagent, reaction solvent, and the combination of PTC and nucleophilic reagent. From these results, it was found that the reactions proceeded smoothly to give the corresponding polymers under mild conditions.Synthesis of some functional polymers such as photosensitive polymers, multi-functional polymers, and solar energy storage polymers with pendant norbornadiene moieties was performed using PTC based on the above information.

Derivatization of hydroxyl into α‐chloro ether: application to the synthesis of block copolymers from hydroxy‐telechelic polymers

AbstractIt has been recently shown that a‐halogeno ether, when activated by a weak Lewis acid such as ZnX2, may be used as initiator for the living cationic polymerization of vinyl ethers. A route to the a‐halogeno ether function is the action of dry hydrogen halide on an alcohol in the presence of an aldehyde or a cyclic acetal. The quantitative preparation of α‐chloro ethers by this route, as well as the use of such compounds to initiate the “living” cationic polymerization of vinyl ethers, was examined. This procedure was then applied to hydroxy‐telechelic polybutadiene to give a macro‐initiator with α‐chloro ether terminal groups. The latter was used to initiate the polymerization of vinyl ethers. The synthesis of poly(butadiene‐block‐ethyl vinyl ether) and poly(butadiene‐block‐2‐chloroethyl vinyl ether) is reported, as well as the preparation of other copolymers by chemical modification of the chloroethyl vinyl ether units.