Butyl Vinyl Ether Research Articles

Electroinitiated cationic polymerization of ethyl and i‐butyl vinyl ethers

AbstractThe electroinitiated cationic polymerization of ethyl and i‐butyl vinyl ethers has been studied under various experimental conditions using NaB(C6H5)4 as background electrolyte.Differring from other electrolytes with higher oxidation potentials, the NaB(C6H5)4 allows appreciable current intensities and the polymerizations can occur at moderate rates.The monomer to polymer conversion presents a slightly sigmoidal shape as a function of the quantity of electricity and at a fixed quantity of electricity is independent from the current intensities.The molecular weights of the polymers are substantially controlled by chain transfer to monomers and solvents: the relative chain transfer constants are reported.The reaction temperature affects remarkably the molecular weights while the influence of dielectric constant of the reaction medium is negligible.An interpretation is given of the effect of NaB(C6H5)4 electrolyte on the initiation mechanism and on the resulting conditions of polymerization.

Synthesis of secondary silicon-containing acetylenic alcohols of the thiophene series

New silicon-containing acetylenic alcohols of the thiophene series have been obtained by the reaction of trialkylsilylacetylenylmagnesium bromides with 2-thiophenealdehydes. Their addition to butyl vinyl ether has given the corresponding acetals.

Electroinitiated cationic polymerization of n‐butyl vinyl ether

Die Makromolekulare ChemieVolume 139, Issue 1 p. 293-296 Kurzmitteilung Electroinitiated cationic polymerization of n -butyl vinyl ether Giuliano Mengoli, Giuliano Mengoli From the Laboratorio di Polarografia ed Elettrochimica Preparativa del Consiglio Naz. le delle Ricerche in Padova, P.tta Conciapelli, 8/11, 35100 Padova, ItalySearch for more papers by this authorGraziano Vidotto, Graziano Vidotto From the Laboratorio di Polarografia ed Elettrochimica Preparativa del Consiglio Naz. le delle Ricerche in Padova, P.tta Conciapelli, 8/11, 35100 Padova, ItalySearch for more papers by this author Giuliano Mengoli, Giuliano Mengoli From the Laboratorio di Polarografia ed Elettrochimica Preparativa del Consiglio Naz. le delle Ricerche in Padova, P.tta Conciapelli, 8/11, 35100 Padova, ItalySearch for more papers by this authorGraziano Vidotto, Graziano Vidotto From the Laboratorio di Polarografia ed Elettrochimica Preparativa del Consiglio Naz. le delle Ricerche in Padova, P.tta Conciapelli, 8/11, 35100 Padova, ItalySearch for more papers by this author First published: 27 November 1970 https://doi.org/10.1002/macp.1970.021390123Citations: 14AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume139, Issue127 November 1970Pages 293-296 RelatedInformation

Role of complex-formation in the copolymerization of maleic anhydride and vinylbutyl ether

Role of complex-formation in the copolymerization of maleic anhydride and vinylbutyl ether

Synthetic Studies Starting from β-Cyanopropionaldehyde. IV. Reactions of β-Cyanoacrolein

Abstract The reactions of β-cyanoacrolein or its dimethyl acetal were investigated. Various new compounds were prepared by the application of several basic reactions, namely, oxidation, reduction, addition, and others. Moreover, β-cyanoacrolein was found to react as a dienophile or as a diene in Diels-Alder reactions. In the reaction with butadiene, isoprene, and 1, 3-pentadiene, cyanotetrahydrobenzaldehyde derivatives were obtained. When ethyl vinyl ether or butyl vinyl ether was used as a dienophile, dihydropyran derivatives were prepared; this pyran was hydrolyzed with dilute hydrochloric acid to 2-cyanoglutar aldehyde.

Effect of Polymer Structure on Crosslinking Efficiency and Molecular Chain Scission/Crosslinking Ratio in a Dicumyl Peroxide‐Sulfur Vulcanizing System

AbstractMolecular chain scission (p), crosslinking (q), and crosslinking efficiency (Z) were determined by sol‐gel technique for several poly(vinyl alkyl ethers) in a dicumyl peroxidesulfur vulcanization system. For isomeric poly(vinyl butyl ethers), p, q, and Z decreased as follows: n‐butyl > isobutyl > sec‐butyl. However, the ratio), p/q, was essentially unchanged. Lengthening the n‐alkyl group from ethyl to n‐butyl did not significantly change p, q, or Z values. Increasing the length from n‐butyl to n‐octyl almost doubled the Z value and halved the p value. The data for poly(vinyl n‐butyl ether) and poly(1‐heptene) indicate that replacement of the ether group by the methylene group did not appreciably affect the Z value; however, p was significantly increased. Poly(propylene oxide), in which the ether linkage is in the backbone of the polymer chain, had the highest p/q and the lowest Z values among these polymers. An analysis of the data shows that both p and q values are quite low. The infrared spectra of the low‐molecular‐weight, soluble portion of poly(propylene oxide) obtained by curing showed the presence of carbonyl, carbon‐carbon double bond and hydroxyl groups.

Cationic stereospecific polymerization of t‐butyl vinyl ether

AbstractThe stereospecific polymerization of t‐butyl vinyl ether (tBVE) in polar and non‐polar solvents was studied. The steric structure of poly‐t‐butyl vinyl ether (PtBVE) was examined by IR spectra of and polyvinyl alcohol derived from (PtBVE). The syndiotactic part in PtBVE increased with increasing polarity of a solvent in low temperature polymerization. Methylene chloride containing a small amount of nitro‐compounds was the most suitable solvent for preparation of syndiotactic polymers. BF3·O(C2H5)2 had a tendency to promote both polymerizations giving isotactic as well as syndiotactic structure. Raising of polymerization temperature caused formation of atactic structures from both isotactic and syndiotactic sides.

NMR study of polymers of ethyl, isopropyl, and tert‐butyl vinyl ethers

AbstractThe high resolution NMR spectra of poly(vinyl ethyl, isopropyl, isobutyl, and tert‐butyl ethers), yields, upon examination at 60 and 100 Mcycles/sec., and under the conditions of decoupling, information concerning the various tactic forms present. The spectra are complicated by the number of overlapping resonances to the extent that an unambiguous assignment of the three triad forms could not be made. For poly(vinyl isobutyl ether) the resonances of the α proton decoupled from the β protons exhibits three components which are tentatively assigned to the central monomer units in heterotactic, isotactic, and syndiotactic configurations, with increasing field strength, respectively.

Reactions of carbon tetrachloride with unsaturated compounds in presence of dicyclohexyl peroxydicarbonate or oxidation-reduction systems

1. The oxidation-reduction system benzoyl peroxide-dimethylaniline initiates the addition of carbon tetrachloride to alkyl vinyl ethers and the telomerization of allyl acetate with carbon tetrachloride at 25–30dg. 2. The oxidation-reduction system benzoyl peroxide-(p-tolylsulfonyl)methanol-iron triacetylacetonate initiates the telomerization of allyl acetate with carbon tetrachloride at 30–32dg. 3. Dicyclohexyl peroxydicarbonate initiates the addition of carbon tetrachloride to butyl vinyl ether at 30° and the telomerization of allyl acetate, allyl chloride, and 1-octene with carbon tetrachloride at 55–60dg.

Stereospecific polymerization of butyl vinyl ether at room temperature in presence of the sulfuric acid-aluminum sulfate complex

1. Stereoregular polymers of butyl vinyl ether were prepared in 80–95% yield at room temperature in presence of the sulfuric acid—aluminum sulfate complex; they had a molecular weight of 9.5 · 105 and contained a fraction that was insoluble in butanone at 20°. 2. An investigation was made of the effects of polymerization time and temperature, monomer concentration, and amount of catalyst on the polymerization of butyl vinyl ether in presence of the sulfuric acid-aluminum sulfate complex. 3. The sulfuric acid—aluminum sulfate complex has a low sensitivity to impurities in the monomer and solvent and is an extremely promising catalyst from the point of view of the technology of the production of stereoregular polymers of butyl vinyl ether.

New polymers of vinyl ethers

1. A new, previously undescribed homogeneous catalyst was prepared for the stereospecific polymerization of vinyl ethers at room temperature. 2. Polymers prepared from butyl vinyl, isobutyl vinyl, cyclohexyl vinyl, and decahydro-2-naphthyl vinyl ethers in good yields in presence of this catalyst were characterized by their viscosities, molecular weights, solubilities, and x-ray diagrams. 3. Study of a heterogeneous catalyst system consisting of TiCl4, LiC3H7, and Al(i-C4H9)3 made it possible to find a modification which promoted the formation of vinyl ether polymers of high viscosity at room temperature. 4. The butyl vinyl ether and isobutyl vinyl ether polymers isolated had higher viscosities and molecular weights than previously known polymers of these ethers and had the properties of stereoregular polymers.

High Pressure Copolymerization of Styrene and Vinyl Acetate, and Styrene and n- Butyl Vinyl Ether

スチレンと酢酸ビニルおよびスチレンとn-ブチル・ビニル・エーテルとのラジカル高圧重合をベンゼン溶液中で50℃,1～1000kg/cm2で行なったが,加圧によ'る共重合比への影響は認めることができなかった。しかし両コポリマーの分子量および共重合速度は圧力とともにかなり増大した。このことは共重合に関する四つの生長段階の速度定数(k11,k12,k21,k22)が圧力によって同じように増加することを意味していると思われる。すなわちΔV11≠=ΔV12≠ , ΔV22≠=ΔV21≠であろう。ただしΔVij≠は活性末端がモノマーiなるラジカルにモノマーブが反応するときの活性化体積である。酢酸ビニルおよびn-1ブチル・ビニル・エーテルの単独高圧ラジカル重合では,圧力によって重合度はかなり増加するが,その重合の活性化体積はともに約-2cc/molであって,メタクリル酸エステルやスチレンのそれに比較してきわめて大きい(約1ケタ)。スチレンとの共重合において,非共役型ビニル・モノマーとでは,共重合比は圧力によってほとんど変化せず,またこの非共役型ビニル・モノマーの単独重合速度は圧によってあまり影響をうけない。

Copolymerization of vinyl chloroacetate with vinyl ethers and with styrene

1. Vinyl chloroacetate was synthesized by the method of indirect vinylation. 2. Copolymers of vinyl chloroacetate with vinyl ethers (ethyl vinyl, butyl vinyl, and phenyl vinyl ethers) were synthesized. In some cases the content of vinyl ether units in these copolymers attained 80–90 moles percent. 3. Copolymers of vinyl chloroacetate with styrene were synthesized.

Stereogular polymers of methyl, iso‐butyl and tert‐butyl vinyl ethers

AbstractDevelopment of new catalysts allowed the synthesis of more highly stereoregular poly(methyl vinyl ethers) (PMVE). PMVE properties are markedly dependent on the degree of stereoregularity. Infrared is employed to establish an index of stereoregularity. This index is correlated with nuclear magnetic resonance spectra, density, stiffness, and tensile properties. A method of characterizing a catalyst system by the stereoregularity distribution obtained in the polymer product is presented.Data is also presented for stereoregular polymers of iso‐butyl and tert‐butyl vinyl ethers.

The decomposition of azoisobutyric acid dinitrile in vinylbutyl ether

1. We have studied the decomposition of azoisobutyric acid dinitrile by heating it with vinylbutyl ether. 2. We have shown the formation of compounds (CH32C=CH-N=N-C(CH3)2CN, isobutylene azoisobutyronitrile, which permits the conclusion of a split of the dinitrile of azoisobutyric acid with formation of the foflowing radicals: $$\begin{array}{*{20}c} \hfill {CH_3 CH_3 } \\ \hfill { \setminus / } \\ \hfill {C \cdot } \\ \hfill | \\ \hfill {CN} \\ \end{array} and\begin{array}{*{20}c} \hfill {CH_3 CH_3 } \\ \hfill { \setminus / } \\ \hfill {C - N:} \\ \hfill | \\ \hfill {CN} \\ \end{array}$$ 3. We have shown the formation of a low mofecular weight polymer which is evidently a compound of the type R-M-M-R, R-M-M-M-R, etc., where M is the monomer link.

Vinyl compounds in the diene synthesis

1. Under the conditions studied, in the reaction of cyclohexyl, phenyl, and butyl vinyl ethers and also of ethyl vinyl suifide with isoprene the process goes both by the diene-synthesis scheme, and also by the copolymerization of the vinyl ethers with isoprene. 2. The adducts, which are new methylcyclohexene derivatives, were prepared and characterized, New copolymers of vinyl ethers with isoprene containing up to 70 moles per cent of the vinyl ether were isolated, and also a copolymer of ethyl vinyl suifide-with isoprene containing 16 moles per cent of ethyl vinyl suifide was isolated. 3. Diene condensation with isoprene occurs most readily in the case of phenyl vinyl ether, and copolymerization with isoprene occurs most readily in the case of cyclohexyl vinyl ether.

The cationic polymerization of t‐butyl vinyl ether at low temperature and the conversion into polyvinyl alcohol of poly‐t‐butyl vinyl ether

AbstractThe stereospecific polymerization of t‐butyl vinyl ether (tBVE) catalyzed by BF3·O(C2H5)2 in homogeneous system is studied. The stereoregular polymer is obtained at low temperature in solvents of low dielectric constant. In homogeneous polymerization, a more highly stereoregular polymer can be obtained than in heterogeneous polymerization, but in the heterogeneous system the polymer having a higher molecular weight is formed. These results are approximately the same as in the case of isobutyl vinyl ether. As one of the characteristics of tBVE polymerization, the stereoregularity of the polymer is greatly affected by its solubility in the solvent used.Polyvinyl alcohol (PVA) and polyvinyl acetate (PVAc) can be obtained from the isotactic and atactic poly‐t‐butyl vinyl ether. The infrared spectra of isotactic PVAc are the same as those of the atactic PVAc, while there are some differences between the isotactic and atactic PVA so obtained. In the case of isotactic PVA contrary to that of atactic PVA the crystalline band near 1140 cm−1 is very week even after heating.

Di‐isotactic polymers of cis‐ and trans‐β‐chloro‐vinyl ethers and factors determining their steric configurations

AbstractSome cis‐ and trans‐β‐chlorovinyl alkyl ethers were polymerized in a stereospecific way, and crystalline polymers.The steric structures of poly(cis‐) and poly(trans‐β‐chloro vinyl butyl ethers) are different one from another, and more precisely of the erythro and threo di‐isotactic type respectively. These results demonstrate a steric polymerization mechanism, which is identical in both forms, with a cis opening of the double bond.Moreover some aspects of the stereospecific polymerization mechanism of mono‐olefinic monomers are discussed. Beside the type of opening of the double bond (cis or trans), determining the steric ratios inside each monomeric unit, also the mode of attack of the monomer to the chain is considered here. It can take place on one or on the other of the two enantiomer faces (D or L) of the monomer in a constant or in an alternated way. Such a steric attack determines the structural relationships between subsequent monomeric units.

The role of ferric chloride in the polymerization of vinyl butyl ether

The mechanism of polymerization of vinyl alkyl ethers has been discussed in Shostakovskii's monograph [1]. According to the monograph the polymerization of vinyl alkyl ethers is brought about by the action of an electrophilic agent, usually hydrogen chloride, and always involves the formation of an oxonium-ion complex. Shostakovskii used ferric chloride as a catalyst for the polymerization of vinyl butyl ether but even in this case he considered that polymerization is brought about by hydrogen chloride, which in his opinion is formed by the hydrolysis of ferric chloride [2]. This interpretation is not in accord with the facts and does not explain the extremely small expenditure of catalyst. For this reason an attempt was made in the present investigation to define by experimental means the role of ferric chloride in the polymerization of vinyl butyl ether and the effect of hydrogen chloride on this reaction.

Reactions of unsaturated and macromolecular compounds

1. A study was made of the copolymerization of methyl acrylate with butyl vinyl ether in presence of various amounts of initiator. 2. Increase in the initiator content of the reaction mixture results in reduction of the molecular weight of the copolymer, but does not affect its composition and yield. 3. The nature of the initiator has no effect on the compositions and yields of copolymers of methyl acrylate and butyl vinyl ether.