2-chloroethyl Vinyl Ether Research Articles

Design of new polymer architectures by combination of anionic and cationic living polymerization techniques

AbstractThe grafting of polystyryl lithium onto poly(chloroethyl vinyl ether) chains has been investigated. The reaction proceeds cleanly and quantitatively thus allowing the synthesis of comblike polymers. Since the dimensions of the polystyrene branches and of the poly(chloroethyl vinyl ether) backbone can be controlled by living polymerizations, both the length and the number of branches of the graft copolymers can be tuned. The latter behave as star polymers. The possibility to initiate a new cationic polymerization of chloroethyl vinyl ether from polystyrene branches bearing acetal termini in order to prepare the corresponding stars with poly(chloroethyl vinyl ether‐b‐ styrene) branches is also examined.Finally access to hyperbranched polymers of controlled architecture and dimensions by deactivation of a second amount of polystyryl lithium onto the last blocks of poly(chloroethyl vinyl ether) is also reported.

Synthesis of amphiphilic block copolymers by polymer analogous modification of poly(2-chloroethyl vinyl ether)-block-poly(isobutyl vinyl ether)

Amphiphilic block copolymers were prepared starting from poly(2-chloroethyl vinyl ether)-block-poly(isobutyl vinyl ether) (PCEVE-b-PIBVE) via polymer analogous reaction. The chlorine function in the hydrophobic poly(2-chloroethyl vinyl ether) segment was substituted by polar groups to achieve block copolymers containing a hydrophilic poly(vinyl ether) segment. This procedure allows the synthesis of tailor made amphiphilic block copolymers.

Synthesis of amphiphilic block copolymers by polymer analogous modification of poly(2-chloroethyl vinyl ether)-block-poly(isobutyl vinyl ether)

Amphiphilic block copolymers were prepared starting from poly(2-chloroethyl vinyl ether)-block-poly(isobutyl vinyl ether) (PCEVE-b-PIBVE) via polymer analogous reaction. The chlorine function in the hydrophobic poly(2-chloroethyl vinyl ether) segment was substituted by polar groups to achieve block copolymers containing a hydrophilic poly(vinyl ether) segment. This procedure allows the synthesis of tailor made amphiphilic block copolymers.

Synthesis of ABC-triblock copolymers for light emitting diodes

In this paper we report on the synthesis and characterization of ABC-triblock copolymers poly(N-vinylcarbazole)-block-poly(4-(1-pyrenyl)butyl vinyl ether)-block-poly(2-[4-(2-phenyl-1,3,4-oxadiazolyl)phenyloxy]ethyl vinyl ether) 15. The ABC-triblock copolymers were synthesized by sequential living cationic polymerization of N-vinylcarbazole 11, 4-(1-pyrenyl)butyl vinyl ether 10 and 2-chloroethyl vinyl ether 3. In a second step, the reactive pendant chloro groups of the poly(2-chloroethyl vinyl ether) segment of the block copolymers were substituted with 2-(4-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole 6 to form fully functionalized ABC'-triblock copolymers. The molecular weight of the block copolymers varied from M n = 4800 to 14000. The thermal behavior is discussed with respect to the block copolymer composition and compared with corresponding polymer blends. LED characteristics of a single layer device for one of the block copolymers are presented as an example.

Chemoselective Synthesis of Diamines with Cationically Polymerizable Groups and Polyimides Synthesis

Abstract Functional diamines with cationically polymerizable groups were successfully prepared in one-step by the chemoselective reaction of 4,4′-diamino-3,3′-dicarboxydiphenylmethane (1) using 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU). The reaction of 1 with propargyl bromide (2a), 2-chloroethyl vinyl ether (2b), and 2-bromomethyl-1,4,6-trioxa-spiro[4.4]nonane (2c) using DBU proceeded chemoselectively under mild conditions without any protection of the amino group to produce the corresponding diamines (3a-3c) in high yields.

Vinyl monomers bearing chromophore moieties and their polymers. V. Synthesis and fluorescence behavior of a vinyloxy monomer bearing electron-accepting chromophore moiety,N-(2-(vinyloxy)ethyl)-1,8-naphthalimide, and its polymer

A vinyloxy monomer bearing electron-accepting chromophore, N-(2-(vinyloxy)ethyl)-1,8-naphthalimide (VOENI), was synthesized by reaction of potassium 1,8-naphthalimide with 2-chloroethyl vinyl ether. VOENI can be homopolymerized by cationic initiation and copolymerized with maleic anhydride (MAn) under radical initiation. The fluorescence behaviors of VOENI and its polymers were investigated. It has been found that the fluorescence intensity of the VOENI monomer is much lower than that of its polymers at the same chromophore concentration. This means that a “structural self-quenching effect” (SSQE) has been also observed in the vinyloxy monomer consisting of an electron-accepting chromophore, which has opposite electronic structure in comparison with acrylates bearing electron-donating chromophores as we have reported previously. The SSQE is attributed to the charge-transfer interaction between the electron-accepting chromophore and the electron-donating double bond in the same molecule. The fluorescence quenching of 1,8-naphthalic anhydride and P(VOENI-co-MAn) by ethyl vinyl ether (EVE), dihydrofuran, triethylamine (TEA), etc. evidences that the electron-rich vinyloxy group does act as an important role in the SSQE of VOENI. C60 can also quench the fluorescence of the polymers, and an upward deviation from the linearity of the Stern–Volmer plot was observed showing that C60 acted as a powerful electron donor to quench the fluorescence of the copolymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1111–1116, 1998

Block copolymers from isobutyl vinyl ether and 2-chloroethyl vinyl ether

Scope and limitation of the vinyl ether block copolymerization of isobutyl vinyl ether (IBVE) and 2-chloroethyl vinyl ether (CEVE) initiated by CH3CHIOR/ZnI2 were studied. These polymerizations exhibit the characteristics of a living polymerization. Di- and triblock copolymers were synthesized by sequential monomer addition (IBVE, CEVE). The poly(2-chloroethyl vinyl ether) (PCEVE) segment in those block copolymers is of particular interest because of the possibility to modify this segment by nucleophilic substitution of the chlorine. This strategy allows the synthesis of tailor made amphiphilic block copolymers.

Block copolymers from isobutyl vinyl ether and 2-chloroethyl vinyl ether

Block copolymers from isobutyl vinyl ether and 2-chloroethyl vinyl ether

Block copolymers from isobutyl vinyl ether and 2-chloroethyl vinyl ether

Block copolymers from isobutyl vinyl ether and 2-chloroethyl vinyl ether

Electroinitiated polymerization of 2-chloroethylvinyl ether

The electroinitiated polymerization of 2-chloroethylvinyl ether via controlled potential conditions has been achieved. The kinetics of the polymerization were determined by cyclic voltammetry at different temperatures in dichloromethane (DM) and acetonitrile (AN). The post-polymerization kinetics were followed with a similar technique. It was found that polymerization was twice as fast in DM as in AN. In DM, both the polymerization and the post-polymerization rates increased with decreasing temperature, whereas in AN the reverse behavior was observed.

New comblike copolymers of controlled structure and dimensions obtained by grafting by polystyryllithium onto poly(chloroethyl vinyl ether) chains

AbstractThe grafting reaction of polystyrene branches onto poly(chloroethyl vinyl ether) (PCEVE) chains, based on the deactivation of polystyryl (PS) carbanionic ends onto chloroethyl ether functions has been investigated. The selectivity of the coupling is very high and allows the almost complete substitution of the chloride group of the CEVE units by PS chains with molar masses up to 15 000. The main side reaction observed is the deactivation of some PS chains, at the very beginning of the reaction. It is attributed mainly to impurities present in the PCEVE solution. Since the PCEVE polymer backbone and the PS grafts can be prepared by both living cationic and anionic polymerization, it is possible to synthesize poly(CEVE‐g‐styrene) copolymers possessing both a backbone with controlled dimensions and an adjustable number of branches having precise length and narrow molar mass distribution. The synthesis and the characteristics of comblike poly[(chloroethyl vinyl ether)‐g‐styrene]s are described.

Living Cationic Isomerization Polymerization of β-Pinene. 2. Synthesis of Block and Random Copolymers with Styrene or p-Methylstyrene

Block copolymers of β-pinene with styrene (St) or p-methylstyrene (pMeSt) were prepared by the sequential living cationic polymerizations initiated with the HCl adducts of styrene (1b: HCl−St) or 2-chloroethyl vinyl ether (1a: HCl−CEVE), respectively, in the presence of isopropoxytitanium trichloride [TiCl3(OiPr)] and tetra-n-butylammonium chloride (nBu4NCl) in CH2Cl2 at −40 °C. As for the β-pinene−St pair, both AB and BA block copolymers (M̄w/M̄n ∼ 1.3) were obtained by this method. With pMeSt, the addition of β-pinene to the living pMeSt polymers gave block copolymers with narrow molecular weight distributions (MWDs) (M̄w/M̄n ∼ 1.2), whereas the reverse order of addition led to block copolymers with broad MWDs (M̄w/M̄n ∼ 1.9). In the polymerization of a mixture of β-pinene and St, the former was consumed faster to give tapered copolymers. In contrast, β-pinene and pMeSt were copolymerized nearly at the same rate to give random or statistical copolymers.

Field-portable solid-phase microextraction/fast GC system for trace analysis

A commercially available SRI gas chromatograph (model 9300B) has been adapted to enable the use of solid phase microextraction (SPME) as the sample preparation and introduction technique for fast GC separations in the field. SPME utilizes a small-diameter fused silica fiber coated with a polymeric stationary phase for extraction of organic analytes from aqueous or gaseous matrices. The analytes extracted are thermally desorbed in the injector of a gas chromatograph. Modifications to the instrument included a new injector and modifications to the PID detector. The injector enables very fast fiber heating rates (∼4000 °C/s), which produce narrow injection bands suitable for fast GC. Separation of BTEX (100 ppb each compound) within 15 s has been demonstrated with FID and PID detection. The precision of the results was very good. Separation of purgeables (trichlorofluoromethane, 1,1-dichloroethene, dichloromethane, 1,1-dichloroethane, trichloromethane, tetrachloromethane, trichloroethene, 1,2-dichloropropane, 2-chloroethyl vinyl ether, 1,1,2-trichloroethane, tetrachloroethene, dibromochloromethane, chlorobenzene; 200 ppb each compound) was accomplished in 2 min with good precision with the use of a dry electrolytic conductivity detector (DELCD). The instrument was tested in the field in the analysis of trichloroethylene in soil extracts. PID was used for detection because its dynamic range is better as compared to DELCD. Almost 500 samples were analyzed in 10 days without major problems. © 1997 John Wiley & Sons, Inc. Field Analyt Chem Technol 1: 277–284, 1997

Living Cationic Isomerization Polymerization of β-Pinene. 1. Initiation with HCl−2-Chloroethyl Vinyl Ether Adduct/TiCl3(OiPr) in Conjunction with nBu4NCl

The first example of living cationic isomerization polymerization of β-pinene was achieved with an initiating system that consists of the HCl−2-chloroethyl vinyl ether adduct [1a; CH3CH(OCH2CH2Cl)Cl] and isopropoxytitanium trichloride [TiCl3(OiPr)] in the presence of tetra-n-butylammonium chloride (nBu4NCl) in CH2Cl2 at −40 and −78 °C. The number-average molecular weight of the polymers (Mn ≤ 5 × 103) increased in direct proportion to monomer conversion, and the molecular weight distribution of the polymers was relatively narrow (Mw/Mn ∼ 1.3). The living nature of the polymerization was further demonstrated by monomer-addition experiments. A similar living polymerization was also feasible with the HCl−styrene adduct or 1-phenylethyl chloride [1b; CH3CH(Ph)Cl] in conjunction with TiCl3(OiPr) and nBu4NCl. 1H NMR analysis of the polymers from 1a showed that 1a serves as an initiator and generates poly(β-pinene) chains consisting of the 1-(2-chloroethoxy)ethyl head group, a tert-chloride tail group, and is...

Photoinitiated cationic polymerization with triarylsulfonium salts

Triarylsulfonium salts Ar3S+MXn− with complex metal halide anions such as BF4−, AsF6−, PF6−, and SbF6− are a new class of highly efficient photoinitiators for cationic polymerization. In this article we describe several synthetic routes to the preparation of these compounds along with their physical and spectroscopic properties. Mechanistic studies have shown that when these compounds are irradiated at wavelengths of 190–365 nm carbon-sulfur bond cleavage occurs to form radical fragments. At the same time the strong Brϕnsted acid HMXn, which is the active initiator of cationic polymerization that takes place in subsequent “dark” steps, is also produced. A study of the parameters that affect the photolysis of triarylsulfonium salts is reported with a measurement of the absolute quantum yields. The cationic polymerizations of four typical monomers—styrene oxide, cyclohexene oxide, tetrahydrofuran, and 2-chloroethyl vinyl ether—with triarylsulfonium salt photoinitiators are described.

Influence of various proton traps on the bifunctional cationic polymerization of chloroethyl vinyl ether mediated by α‐iodo ether/zinc dichloride

AbstractThe synthesis of relatively high molar mass telechelic poly(chloroethyl vinyl ether)s (PCEVE) via bifunctional initiation of the “living” cationic polymerization of CEVE was examined in the absence and in the presence of various proton traps. In the absence of a proton trap, a monofunctional initiation involving hydrogen iodide (HI), formed by partial hydrolysis of trimethylsilyl iodide (TMSI) by adventitious water, occurred concurrently to the main bifunctional process. The addition of sterically hindered aromatic amines leads to complete inhibition of the polymerization due to the formation of a complex between the aromatic amines and ZnCl2. In the presence of trialkylaluminium as HI trapping agent, monofunctional initiation is totally suppressed and a clean bifunctional polymerization takes place. Telechelic PCEVE of DPn up to 300 with narrow molar mass distribution were synthesized. However, in the presence of these additives, a slow ligand exchange between AIR3 and ZnCl2 takes place, decreasing the rate of polymerization. For polymers with high DPn (>300), the increasing amount of trialkylaluminium required to totally suppress the formation of monofunctional polymer results in a chain coupling process during the deactivation step. This reaction limits the clean synthesis of high molar mass bifunctional PCEVE.

From Linear Side-chain Functionalized Poly(vinyl ether)s to Functional Macrocycles

This paper deals with the synthesis of functional polymers of controlled chain dimensions and architecture from poly(chloroalky1 vinyl ether)s. The living polymerization of chloroalkyl vinyl ethers initiated by HX/ZnX2 systems, and the chemical substitution of the pendant chlorines by various organic functions and groups, in order to generate specific polymer properties are first discussed. Also based on the living character of the polymerizations, the preparation of poly(chloroethyl vinyl ether) with monomacrocyclic and plurimacrocyclic architectures as well as their characterization are then reported. Some evidence for specific host–guest interactions between large organic molecules and polymacrocycles is also presented.

New Chemical Modification of Polymers with Pendant Chloromethyl Groups Using 1,8-Diazabicyclo-[5.4.0]-7-undecene

The esterification reaction of poly[(p-chloromethyl)styrene] (PCMS) with benzoic acid and acetic acid proceeded very smoothly to give the corresponding polymers with pendant ester residues using 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as an organic base even at 30°C in aprotic polar solvents such as N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone, and dimethyl suloxide (DMSO). The reaction of poly(2-chloroethyl vinyl ether) (PCEVE) and poly(epichlorohydrin) (PECH) with benzoic acid in the presence of DBU in DMF also gave corresponding polymers with pendant benzoate moieties. However, the reactivities of PCEVE and PECH were lower than that of PCMS. Furthermore, the reaction of PCMS with N-protected amino acids such as Boc-L-alanine, Cbz-L-alanine, and Bz-DL-alanine afford corresponding polymers with pendant amino acid residues in high conversions using DBU in DMSO. From these results, it was concluded that DBU is the extremely useful organic base for the esterfication reaction of the pendant chloromethyl groups in the polymers with carboxylic acids under mild reaction conditions.

Multifunctional Coupling Agents for Living Cationic Polymerization. 7. Synthesis of Amphiphilic Tetraarmed Star Block Polymers with α-Methylstyrene and 2-Hydroxyethyl Vinyl Ether Segments by Coupling Reactions with Tetrafunctional Silyl Enol Ether

By the polymer coupling reaction with a tetrafunctional silyl enol ether [1; C{CH2OC6H4C(OSiMe3)CH2}4], amphiphilic tetraarmed star polymers (6) with α-methylstyrene−2-hydroxyethyl vinyl ether (αMeSt−HOVE) block arm chains have been synthesized: C{CH2OC6H4COCH2−[CH(OCH2CH2OH)CH2]n−[C(CH3)(C6H5)CH2]m−}4. The synthesis consisted of the following steps: (i) the sequential living cationic polymerization of αMeSt and 2-[(tert-butyldimethylsilyl)oxy]ethyl vinyl ether (SiVE) into an αMeSt−SiVE living block copolymer (4); (ii) the coupling of four chains of 4 with the quencher 1 into a tetraarmed polymer (5); and (iii) the transformation of the poly(SiVE) segment into the poly(HOVE) chain by the fluoride-catalyzed deprotection. In step i the living polymerization was carried out at −78 °C in methylene chloride with a binary initiating system comprising tin tetrabromide and the hydrogen chloride adduct of 2-chloroethyl vinyl ether. After step iii, the tetraarmed amphiphile 6 (αMeSt/HOVE = 27/27 in n in each arm)...

Synthèse et caractérisation des polymères porteurs de groupements pyrazoles—III: Les derives vinyliques

The copolymerizations of N-methyl maleimide (NMM) with three vinyl ethers bearing 2-pyridine carbinol, mono and bipyrazole were investigated. The synthesis by phase transfer catalysis of 2-chloroethyl vinyl ether with the corresponding alcohols were performed in moderate yield. Copolymerization with various feed compositions were carried out in order to check the alternance. Although the initial rate of copolymerization was higher for the stoichiometric compositions used, the copolymers contain in each case more than 70% of NMM. Thus, contrary to expected results, the copolymers were not alternated. T g values of these copolymers are in the 100–160 °C range and increase with NMM content. Moreover, the TGA measurement showed the decomposition started from about 250 °C, the middle part being at 300 °C, and from 500 °C a total decomposition occurred.