Butyl Vinyl Ether Research Articles

Synthesis of block copolymers by combination of cationic and initer polymerization system

Trityl terminated poly(butyl vinyl ether) was obtained by the polymerization of butyl vinyl ether with triphenylcarbonium tetrafluoroborate-thiolane initiator system. In this system, thiolane was used to prevent both hydride abstraction of trityl cation and chain transfer of growing chain of butyl vinyl ether cation. Trityl terminated polymers served as thermal initer for the polymerization of methyl methacrylate which proceeded via a quasi-living radical mechanism. This procedure makes it possible to prepare block copolymers.

Polymerization of n-Butyl Vinyl Ether Photoinitiated by the Initiator System Poly(methyl phenyl silane)/N-Ethoxy-2-methylpyridinium Iodide/ZnI2/Benzaldehyde

Polymerization of n -Butyl Vinyl Ether Photoinitiated by the Initiator System Poly(methyl phenyl silane)/ N -Ethoxy-2-methylpyridinium Iodide/ZnI 2 /Benzaldehyde

Thermally induced radical promoted cationic polymerization using a novel N‐allyloxypyridinium salt

AbstractA system consisting of a novel N‐allyloxypyridinium salt and a radical initiator is highly appropriate for the thermal initiation of cationic polymerizations. Radicals formed upon the thermolysis (at 70°C) of initiators as 2,2′‐azoisobutyronitrile or benzoyl peroxide add to the double bond of the pyridinium salt N‐[2‐(ethoxcarbonyl)allyloxy]‐α‐picolinium hexafluoroantimonate (1). Subsequently, the pyridinium salt is fragmented yielding pyridinium‐type radical cations, species able to initiate cationic polymerizations. In the case of the radical initiator phenylazotriphenylmethane (triphenylmethaneazobenzene), the polymerization is extremely rapid, since additionally the triphenylmethyl cation formed by electron transfer initiates the polymerization. The initiation capability of the system described was demonstrated for a number of monomers, such as cyclohexene oxide, butyl vinyl ether and the bifunctional 3,4‐epoxycyclohexylmethyl 3′,4′‐cyclohexanecarboxylate. With the latter, an insoluble polymer network was readily obtained.

Ring‐opening polymerization of cyclobutane adducts of tetracyanoethylene and vinyl ethers with quaternary ammonium halides

AbstractRing‐opening polymerizations of cyclobutane adducts of tetracyanoethylene (TCNE) and vinyl ethers (VE) with quaternary ammonium halides are described. The polymerization of the cyclobutane adduct 5a of TCNE and ethyl vinyl ether (EVE) was carried out with 10 mol‐% of tetrabutylammonium iodide (TBAI) in N,N‐dimethylacetamide (DMAc) at ambient temperature to afford the alternating copolymer of TCNE and EVE with high molecular weight in good yield without contamination by TBAI. Under the optimum conditions, the cyclobutane adducts of TCNE and a variety of VEs such as butyl vinyl ether, isobutyl vinyl ether, 2,3‐dihydrofuran, and 3,4‐dihydro‐2H‐pyran were polymerized to yield similar polymers. On the basis of the fact that the polymer molecular weight increased rapidly at the initial stage and slowly even after the consumption of all monomers, we propose that the iodide ion of TBAI initiates the anionic chain polymerization of the cyclobutane adduct to afford an iodide‐substituted macroanion 6, which is subjected to intermolecular nucleophilic substitution with each other in a step reaction manner. This intermolecular reaction of 6 was further confirmed by a model reaction of cyclobutane with chloromethyl methyl ether in the presence of chloride ion.

Stereospecific cationic polymerization of mesomorphic vinyl ethers characterized by 13C-n.m.r., d.s.c. and X-ray diffraction

Abstract Butylvinyl ether, 4-ethoxyphenyl 4-[4-(vinyloxy)butyloxy]benzoate and 4-ethoxyphenyl 4[11-(vinyloxy)-undecyloxy]benzoate have been polymerized using boron trifluoride diethyl etherate and tin tetrachloride as cationic initiator. Polymers produced at different temperatures and with different solvents exhibited different stereoregularities. Dyad resonances were assigned from the β-methylene absorption in a decoupled 13 C nuclear magnetic resonance spectrum, assuming that the polymerization proceeded according to the first-order Markovian trial. The liquid crystalline side-chain polymers were characterized by differential scanning calorimetry, hot-stage polarized light microscopy and X-ray diffraction in order to study the influence of tacticity on mesomorphism and organization. The polymers based on 4-ethoxyphenyl 4[11-(vinyloxy)undecyloxy]benzoate with different tacticities exhibited the same interdigitated smectic A and B structures. Recorded differences in isotropization temperatures could be attributed to differences in molar mass.

Pulse radiolysis of vinyl monomers, in the pure state and with added pyrene

Pulse radiolysis studies have been used to investigate the early phenomena in the radiolysis of acrylic acid, methyl acrylate, butyl vinyl ether, propionic acid, methyl acetate and butyl ether; the latter three solvents were used as model compounds for these vinyl monomers. The triplet state, radical cation, radical anion, and free radical of pyrene (cyclohexadienyl type) were observed to various degrees in the radiolysis of pyrene in these monomers. In acrylic acid, where the free radical and the cation dominate, the monomer polymerizes efficiently, whereas in butyl vinyl ether, where the anion dominates, polymerization does not occur. The behavior of methyl acrylate lies between that of acrylic acid and butyl vinyl ether. However, the high intensity of the electron pulses creates a high concentration of radicals leading to a short lifetime of the radical which in turn leads to a much smaller yield of polymerization. The mechanism of polymerization under high energy radiation is found to be free radical in nature.

Photosensitized cationic polymerization using allyl sulfonium salt

AbstractThe cationic polymerization of cyclic ethers such as cyclohexane oxide (CHO) and vinyl monomers such as butyl vinyl ether (BVE) and N‐vinylcarbazole (NVC) is initiated upon irradiation at λ 380 nm in CH2Cl2 solution containing an allylic sulfonium salt, namely, 2‐ethoxycarbonyl‐2‐propenylthiophenium hexafluoroantimonate (1) (EMT+SbF6−), and one of the following compounds: benzophenone, anthracene, thioxanthone, perylene or phenothiazine. Electron transfer and hydrogen abstraction mechanisms were proposed for the initiation step. Stable cation radicals of phenothiazine were also prepared, and the cationic polymerization of butyl vinyl ether was initiated by these cation radicals.

Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for Butyl Vinyl Ether, 1,2-Dimethoxyethane, Methyl Glycolate, Bicyclo[2.2.1]hept-2-ene, 5-Vinylbicyclo[2.2.1]hept-2-ene, trans-Azobenzene, Butyl Acrylate, Di-tert-butyl Ether, and Hexane-1,6-diol

Ideal-gas enthalpies of formation of butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol are reported. Enthalpies of fusion were determined for bicyclo[2.2.1]hept-2-ene and trans-azobenzene. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for each compound studied. Liquid-phase densities along the saturation line were measured for bicyclo[2.2.1]hept-2-ene. For butyl vinyl ether and 1,2-dimethoxyethane, critical temperatures and critical densities were determined from the dsc results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, and di-tert-butyl ether. Group-additivity parameters or ring-correction terms useful in the application of the Benson group-contribution correlations were derived.

Temperature‐responsive swelling and deswelling of the copolymers from vinyl ether of ethylene glycol and butyl vinyl ether

AbstractLinear and crosslinked copolymers of a vinyl ether of ethylene glycol (2‐hydroxyethyl vinyl ether, (1)) and butyl vinyl ether (2) are synthesized by α‐irradiation polymerization. It is shown that the linear copolymers exhibit a phase separation phenomenon in dependence of the temperature due to the destruction of hydrogen bonds and the enhancement of hydrophobic interaction in aqueous solution. The processes of reversible swelling or shrinking upon temperature change are demonstrated for polymer networks.

Synthesis of new polymers containing α‐(trifluoromethyl)‐acrylate units

AbstractFree radical polymerization of both α‐(trifluoromethyl)acrylic acid (TFMAA) and its methyl ester MTFMA is shown to be possible in the presence of bis(4‐tert‐butylcyclohexyl) peroxycarbonate (Percadox) as initiator and dioxane or THF as solvent. Also it is shown that copolymers of TFMAA with α‐olefins (1‐decene, 2‐methyl‐1‐hexene) and of methyl α‐(trifluoromethyl)acrylate (MTFMA) with vinyl ethers (butyl, 2‐ethylhexyl, and menthyl vinyl ether) can be simply obtained with AIBN as initiator; these copolymers have a predominantly alternating structure.

Interpolymer complexes of (co)poly(vinyl ethers) of glycols and poly(carboxylic acids)

AbstractThe complex formation reaction of poly(vinyl ethers) of ethylene glycol (1), poly(vinyl ether) of diethylene glycol (2), copolymers of vinyl ether of ethylene glycol and vinyl butyl ether (3a–3c) with poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) was studied by conductimetric, viscometric and spectroturbidimetric methods in aqueous solution. It is shown that 1 and 2 do not form polycomplexes with PAA. While an introduction of hydrophobic vinyl butyl ether fragments into the structure of 1 enhances the complexation processes with respect to poly(carboxylic acids), the composition of the polycomplexes is independent of the mixing order of interacting components, temperature and composition of the copolymers. An addition of organic solvents to the aqueous solution of the polycomplexes leads to the cooperative destruction of polycomplex particles. An analysis of IR spectra of the polycomplex films shows the existence of COOH dimers, hydrogen bonds between hydroxyl groups and carboxylic groups as well as ester bonds.

Initiation of cationic polymerization of n‐butyl vinyl ether by stable cation radicals of substituted phenothiazines

Abstract3,7‐Diethyl‐ 10‐phenylphenothiazine (DEPPT), a phenothiazine derivative whose 3,7‐ and 10‐positions are blocked, was synthesized. Potentiostatic electrolysis of DEPPT in acetonitrile (ACN) in the presence of 0.1M of LiClO4 at 0.7 V (vs. Ag/Ag/Cl) yielded the stable cation radical of DEPPT (DEPPT+·) which was characterized by cyclic voltammetry, UV‐visible spectroscopy, and ESR spectrometry. Stable cation radicals of 10‐phenylphenothiazine and 3,7‐diethyl‐10‐methylphenothiazine were also prepared. The cationic polymerization of n‐butyl vinyl ether was initiated by these cation radicals, including DEPPT·+. The electron transfer mechanism for the initiation step, which we proposed previously, was supported by the fact that DEPPT·+ was capable of initiating the polymerization; dimerization of DEPPT·+ by releasing protons is precluded because 3,7‐ and 10‐positions are all blocked. © 1994 John Wiley & Sons, Inc.

A new simple synthesis of 1,3‐dideuterated malondialdehyde (3‐hydroxy[1,3‐2H2]‐2‐propenal)

AbstractA synthetic route for obtaining 1‐butoxy‐1,3,3‐triethoxy[1,3‐2H2]propane a stable diacetal of the malondialdehyde, is described. The synthesis involves the condensation of deuterated butylvinyl ether with deuterated triethyl orthoformate in the presence of montmorillonite clay K‐10. The deuteration of butyl vinyl ether was accomplished via the intermediary formation of a stannane derivative which was quantitatively metallated by n‐butyllithium and then treated with 2H2O. From the diacetal the 1,3‐dideuterated malondialdehyde was obtained by a short treatment with acid ion exchange resin.

Living Cationic Polymerization of tert-Butyl Vinyl Ether by Organoaluminum Halides in the Presence of Added Bases

Living cationic polymerization of tert-butyl vinyl ether (TBVE) was achieved by the 1-(isobutoxy)ethyl acetate (1)/Et1.5AlCl1.5 initiating system in the presence of THF in hexane at −20°C. The polymers had a very narrow molecular weight distribution (M̅w/M̅n≤1.1), and M̅n increased directly proportional to the monomer conversion. On the other hand, under conditions suitable for the living polymerization of isobutyl vinyl ether (e.g., 1/EtAlCl2 initiating system, methyl acetate as added base, temperatures higher than 0°C), non-living polymers of TBVE with a broader molecular weight distribution were obtained. For the living polymerization of such a highly reactive monomer as TBVE, combinations of added bases having stronger basicity, weaker Lewis acid activators, and low temperature turned out to be indispensable. Using this system, the high molecular weight poly(TBVE) with a narrow molecular weight distribution was also obtained (M̅n=1.1×105, M̅w/M̅n=1.11). The tert-butyl groups of the poly(TBVE) were quantitatively deprotected (99.9%) by bubbling HBr gas, to yield poly(vinyl alcohol). To elucidate the polymerization characteristics of TBVE, neo-pentyl vinyl ether and three isomers of butyl vinyl ethers (n-butyl vinyl ether, isobutyl vinyl ether, and sec-butyl vinyl ether) were polymerized, and polymerization behavior is discussed on the basis of the sterical structures of side alkyl groups.

DDQ-mediated formation of carboncarbon bonds: Oxidation of imines

The reaction of imines with alkynes and alkenes, in the presence of 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), to give quinoline derivatives is described. The mechanism of the annulation is discussed, and evidence supporting a non-concerted pathway, at least when the alkene is butyl vinyl ether, is reported. Preliminary information is also given about solid adducts of imines with DDQ, which do not seem to be involved in the reaction path leading to quinolines, and should account for the dependence of product yields on the position of substituents on the starting imines.

Acylketene [4+2] cycloadditions: divergent de novo synthesis of 2,6-dideoxy sugars

The synthetic methodology demonstrated herein provides a divergent, de novo synthetic pathway to 2,6-dideoxy carbohydrates. Pyranone 2, which was prepared by [4+2] cycloaddition of the acylketene generated from dioxinone 1 with butyl vinyl ether, was converted in a straightforward manner to arabino-hexopyranosides olivoside 11 and oleandroside 12, and branched sugars olivomycoside 14 and chromoside B 15, with near complete control of relative stereochemistry at the three newly introduced stereogenic centers. Olivoside 11 proved to be a pivotal intermediate for elaboration to the ribo, lyxo, and xylo families of 2,6-dideoxy carbohydrates

Radiation induced terpolymerization of tetrafluoroethylene with propylene and n‐butyl vinyl ether in bulk

AbstractTerpolymerization of tetrafluoroethylene (TFE) with propylene (P) and n‐butyl vinyl ether (NBVE) induced by γ‐rays at room temperature at dose rate 5 × 105 rad/h and P/NBVE molar ratio from 49/1 to 10/40 was carried out. An alternating copolymerization between TFE and two α‐olefins was found to take place in this system, so that 50 mole % of TFE containing terpolymer is always formed at various monomer compositions. The terpolymer composition can be explained successfully by the treatment by a complex mechanism. The complex reactivity ratios of rI (TFE–complex) and rII (TFE‐NBVE complex) were calculated to be 0.5 and 0.6, respectively, assuming a complex mechanism. The polymerization rate and molecular weight increase with NBVE concentration in the monomer mixture. Colorless transparent rubber‐like polymers were obtained at each monomer composition. The glass transition temperature sharply decreases with NBVE concentration in the terpolymer but the thermal and chemical resistances of the terpolymer slightly decrease. Considering these results together with the mechanical properties it has been concluded that the 45/48/7 terpolymer of TFE/P/NBVE molar ratio is good as a practical elastomer useful at relatively low temperatures.

Viscosity studies of liquid boundary layers by the blow-off method

Since viscosity is a structure-sensitive property, the peculiar structure of the boundary layers of liquids can be detected by their viscosity, measured after the ‘blow-off’ method developed at an earlier date. The measurements given (for non-volatile liquids) show that for non-polar liquids the viscosity remains strictly constant right down to the solid wall. The contrary is true for polar liquids or solutions of polar substances. In these cases viscosity changes, often in the nature of a jump, are observed upon approaching the solid wall to within 10-6-10-5 cm; in the case of vinylbutyl ether polymer, to within 5·10-4 cm.

Synthesis and characterization of poly(alkyl vinyl ether)/poly(ϵ-caprolactone) diblock copolymers

This paper reports the synthesis and characterization of hydroxyl functionalized poly(butyl vinyl ether) oligomers, and block copolymers comprised of poly(butyl vinyl ether) and poly(ϵ-caprolactone). Using the HI/ZnI2 initiating system in toluene at −20°C, monofunctional poly(butyl vinyl ether) oligomers of predicted molecular weights precisely terminated with aldehyde or primary hydroxyl endgroups have been prepared. Furthermore, the primary hydroxyl end functionality has been utilized to initiate ring opening polymerization of ϵ-caprolactone in the presence of stannous octanoate as the catalyst. This ring opening reaction provides an entry into new poly[(butyl vinyl ether)-block-poly(ϵ-caprolactone)] copolymers.

Synthesis of a Model Triblock for Novel Thermoplastic Elastomers

Abstract Thus far, we have been successful in preparing novel diblock and triblock copolymers comprised of poly(methyl methacrylate) and poly(butyl vinyl ether). Future work will focus on studying the morphology of both the diblock and triblock copolymers. Moreover, we are also interested in synthesizing triblocks with long poly(butyl vinyl ether) segments and short PMMA segments, since these polymers have the potential for exhibiting good elastomeric properties.