茂钛对乙烯基单体的催化聚合 VIII.二氯二茂钛催化乙烯基单体聚合机理的证明

本文以UV和'HNMR跟踪方法研究了二氯二茂钛(Cp2TiCl2)在二甲亚砜中的光化学反应,用自旋捕获技术来捕获Cp2TiCl2催化丙烯腈单体聚合体系中所生成的自由基。UV和'HNMR跟踪结果表明,Cp2TiCl2逐渐分解并生成环戊二烯,ESR测定表明,用自旋捕获剂PBN和BNO都捕获到了环戊二烯自由基,进一步证明了Cp2TiCl2催化乙烯基单体聚合反应是一种自由基机理。     

Cationic polymerization of vinyl compounds in the presence of tetra-n-butylammonium salts

The effects of salts were examined in cationic polymerization of vinyl compounds. Cationic polymerization of styrene was carried out at 0°C, with acetyl perchlorate, stannic chloride, stannic chloride–trichloroacetic acid and boron trifluoride etherate as catalysts. Tetra-n-butylammonium perchlorate, fluoroborate and iodide were used as salts. The presence of small amounts of the salts changed both the polymerization rate and the molecular weight of polymer considerably. The consideration of various effects led to the conclusion that the results are explicable principally on the basis of counterion exchange. To confirm this, the copolymerization of 2-chloroethyl vinyl ether with γ-methylstyrene was investigated at ?78°C. The copolymer composition curve when stannic chloride was used as catalyst was changed and coincided with that of polymer obtained with acetyl perchlorate catalysis when the perchlorate salt was added. This supports the concept of counterion exchange.     

Non-ideality in vinyl polymerization—VIII: Retarded polymerization of methyl methacrylate in presence of p-benzoquinone initiated by azobisisobutyronitrile

Detailed kinetic analysis of AIBN-initiated polymerization of methylmethacrylate in presence of p-benzoquinone has been reported. Primary radical transfer, whereby a primary radical transfers its radical reactivity to a transfer agent, has been considered along with macroradical transfer. It is found that the former process is quite appreciable in the system and must be allowed for to arrive at accurate values of transfer constants. Values of transfer constants for both primary radicals and macroradicals towards benzoquinone, and characteristic constants for degradative chain transfer and primary radical transfer have been evaluated applying the mathematical treatment developed previously. The mode of termination of macroradicals by fairly stable microradicals formed as a result of transfer has also been discussed.     

Regioselectivity of reductive-coupling reaction of alkynes in the presence of titanocene and zirconocene dichloride

A series of (Z,Z)-tetraaryl-1,3-butadiene has been synthesized stereospecifically and regioselectively by acidolysis of five-membered Ti, Zr metallocycles formed from asymmetrically substituted alkynes. The structures of these products have been proved by physical and chemical methods.     

Cp2TiCl2及Cp2ZrCl2存在下炔烃还原偶联反应的区域选择性

经五元钛、锆杂环,由非对称炔烃,区域选择性地合成了一系列立体专一的(Z,Z)-四芳基-1,3-丁二烯,并通过物理、化学方法证明了产物结构.     

Studies of the polymerization of diallyl compounds. XI. Polymerization of styrene in the presence of diallyl compounds

Radical polymerization of styrene in the presence of various diallyl compounds was carried out at 60°C, with the use of 2,2′-azobisisobutyronitrile as an initiator. The chain transfer constant C_s of the styryl radical to diallyl compounds was determined graphically by solving the Mayo equation. The C_s values of diallyl esters are quite small compared to those of diallyl acetals. The polymerization mechanism of styrene in the presence of diallyl compounds was also discussed in connection with the results obtained previously.     

Mechanism of the controlled radical polymerization of styrene and methyl methacrylate in the presence of dicyclopentadienyltitanium dichloride

The mechanism of the controlled radical polymerization of styrene and methyl methacrylate in the presence of dicyclopentadienyltitanium dichloride (Cp₂TiCl₂) was studied using quantum chemical calculations and electron spin resonance spectroscopy. It was established that the reduction of Cp₂TiCl₂ to Cp₂TiCl during the macromolecule synthesis occurs through the living polymerization mechanism, which adjusts the growth of a polymeric chain. The geometrical structures of the molecular complexes between a growing macroradical and Cp₂TiCl₂ and transition states of radical inhibition steps were optimized and the thermodynamic and kinetic parameters of the elementary reactions were estimated for several feasible directions of the process. On this basis, the observed kinetic features of vinylic monomer polymerization with participation of organic compounds of titanium are discussed. Copyright © 2004 John Wiley & Sons, Ltd.     

Stereochemistry at titanium in the sulfur dioxide insertion reaction of titanocene compounds

The insertion reaction of SO₂ has been studied for the two diastereoisomeric forms of η⁵-C₅H₅-η⁵-C₅H₄ CHMePhTi(C₆F₅)CH₃. The reaction is regioselective and stereospecific. Arguments that it involves a retention at the titanium atom are given.     

Studies on diacetylenic vinyl compounds. VI. ESR studies on the polymerization of diacetylene containing acrylate and methacrylates

A number of diacetylene containing acrylate and methacrylates have been synthesized and the interaction between their propagating radicals and the diacetylene groups was studied by ESR spectroscopy. In the case of polymerization at 70°C using AIBN as an initiator, the propagating radicals of methacrylates are temporarily trapped with the diacetylenes with rapid exchange of the electron, thus showing strong signals of the propagating radicals. Gamma irradiation of the frozen state produces a blue color in samples, and the ESR signals were found to be those of uninteracted acrylate and methacrylates. From a comparison of spectral widths, there seems to exist an intramolecular interaction between the radicals and the diacetylene group at the frozen state. © 1992 John Wiley & Sons, Inc.     

Studies of the polymerization of diallyl compounds. XII. Cyclocopolymerization of dimethallyl phthalate with vinyl acetate

Dimethallyl phthalate was copolymerized with vinyl acetate at 60°C with the use of benzoyl peroxide as an initiator. The rate and degree of copolymerization increased with an increase in the mole fraction of vinyl acetate. The residual unsaturation of the copolymer was nearly constant, regardless of the feed molar ratio. The monomer reactivity ratios (MRR) were obtained on the basis of the copolymer composition equation in which the intramolecular cyclization reaction was considered: γ₁ = 1.08 (MRR of the uncyclized radical), γ₂ = 0.99 (MRR of vinyl acetate radical), γ_c = 0.73 (MRR of the cyclized radical). The difference between γ₁ and γ_c is discussed.     

Studies of the polymerization of diallyl compounds. XXVII. Copolymerization of diallyl tartrate with several vinyl monomers

The radical copolymerization of diallyl tartrate (DATa) (M₁) with diallyl succinate (DASu), diallyl phthalate (DAP), allyl benzoate (ABz), vinyl acetate (VAc), or styrene (St) was investigated in order to disclose in more detail the characteristic hydroxyl group's effect observed in the homopolymerization of DATa. In the copolymerization with DASu or DAP as a typical diallyldicarboxylate, the dependence of the rate of copolymerization on monomer composition was different for different copolymerization systems and unusual values larger than unity for the product of monomer reactivity ratios, r₁r₂, were obtained. In the copolymerization with ABz or VAc (M₂), the r₁ and r₂ values were estimated to be 1.50 and 0.64 for the DATa/ABz system and 0.76 and 2.34 for the DATa/VAc system, respectively; the product r₁r₂ for the latter copolymerization system was found again to be larger than unity. In the copolymerization with St, the largest effect due to DATa monomer of high polarity was observed. Solvent effects were tentatively examined to improve the copolymerizability of DATa. These results are discussed in terms of hydrogen-bonding ability of DATa.     

Studies on the analytical chemistry of iodonium compounds. Part VIII

Summary Procedures are described for the titration of 10–200 mg of diphenyliodonium cation with sodium tetraphenylborate, and a turbidimetric procedure for 10–200g of the cation.

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Zusammenfassung Die maßanalytische Bestimmung von 10 bis 200 mg Diphenyljodoniumkation wurde beschrieben; ebenso eine nephelometrische Methode für 10 bis 200g.

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Part VII: Mikrochim. Acta [Wien]1970, 1125.     

On suspension polymerization of vinyl chloride. Polymerization of vinyl chloride in the presence of epoxidized oil

A study has been made on the suspension polymerization of vinyl chloride in the presence of epoxidized cottonseed oil. Inclusion of the additive into the polymer chain was proved by i.r. spectrophotometry. The effects of epoxidized cottonseed oil on polymerization rate and K-value were slight, but plasticizer absorption by the polymer was reduced. Thermogravimetric curves of the product have been obtained, and show that epoxidized cottonseed oil improves the thermostability of the polymer.     

Effects of trivalent phosphorus compounds on vinyl polymerizations—VII. A nonstationary state radical polymerization of methylmethacrylate in the presence of phenyldichlorophosphine

In the radical polymerization of methylmethacrylate in the presence of p-phenyldichlorophosphine, the initial rate and degree of polymerization increased with polymerization time. They first decreased with increase in the phosphine concentration but increased with further increase in the phosphine concentration. Termination was first order with respect to the initiator. The degree of polymerization was independent of the initiator concentration, but dependent on the conversion. The polymer contained no phosphorus units regardless of the phosphine concentration. The ESR spectra of system showed existence of a phosphorus radical. In order to explain these characteristics of the polymerization, it is proposed that there may be a nonstationary state in which the polymer radicals are regenerated during the polymerization from the phosphoranyl radicals.     

Effects of trivalent phosphorus compounds on vinyl polymerization. III. Anionic polymerization of acrylonitrile with triethyl phosphite

The polymerization of acrylonitrile catalyzed by triethyl phosphite was studied. It was found that the order with respect to the monomer concentration varies from two to three, depending on the polymerization temperature. From the results obtained for the molecular weight of the polymer and the phosphorus content in the polymer, it was thought that the zwitterion formed by the addition of triethyl phosphite to acrylonitrile is responsible for the initiation of polymerization. The following equation was suggested for the rate of the polymerization: