Copolymerization of Vinyl Monomers with Different Water Solubilities in the Presence of Manganese Sulfonate Complexes

Mixed-ligand Mn(III) complexes were prepared from manganese tris(acetylacetonate) and alkyl- benzenesulfonic acid, and their surface activity and initiating power with respect to polymerization of vinyl monomers differing in reactivity and water solubility were studied.     

Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with vinyl acetate

The free-radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with vinyl acetate in bulk and organic solvents has been studied. Copolymerization is shown to produce random copolymers. The kinetic features of the process are examined, and the relative activities of the monomers are estimated. 2,2-Diallyl-1,1,3,3-tetraethylguanidinium chloride is involved in copolymerization with vinyl acetate via both double bonds to give rise to pyrrolidinium structures.     

Hybrid copolymerization of cyclic and vinyl monomers

In this work,we report the hybrid copolymerization of various cyclic monomers and vinyl monomers.Our studies demonstrate that 1-tert-butyl-4,4,4-tris-(dimethylamino)-2,2-bis[tris(dimethylamino) phophoranyliden-amino]-2 5,5-catenadi(phosphazene) (t-BuP 4) can catalyze the hybrid copolymerization of caprolactone (CL),lactide (LA) or cyclic carbonate ester with acrylate or methyl acrylate.However,the polymerization of cyclosiloxane with vinyl monomers yields two corresponding homopolymers,and the polymerization of lactone with acrylonitrile (AN) produces only polyacrylonitrile.Clearly,the extent of matching of activity between a monomer and an active center determines whether or not there is hybrid copolymerization.     

60Co-initiated copolymerization of styrene with vinyl acetate

The kinetic behavior of the ⁶⁰Co-initiated copolymerization at 25°C of styrene with vinyl acetate at 1100 and 2000 rad/hr was studied. As in the case of thermal and photochemical copolymerizations of these monomers, the growing chains are particularly rich in styrene units, and the overall rate is affected by a diluent effect due to the vinyl acetate monomer. However, in the case of the radiation copolymerization, this effect is partially counterbalanced by an increase of the initiation rate with the vinyl acetate concentration; the polymerization rate curve shows a maximum at a vinyl acetate molar fraction of 0.25. This effect is due to the very different free radical yields of these two monomers. The experimental results may be understood on the basis of a kinetic scheme which involves an energy transfer process from the excited vinyl acetate molecules to the styrene monomer and a termination reaction of the growing chains by very short styrene radicals when the mixture is rich in vinyl acetate.     

Sequence distributions of vinyl chloride-vinyl acetate and vinyl chloride-vinyl propionate copolymers

¹³C-NMR spectroscopy was used in a detailed study of vinyl chloride-vinyl acetate and vinyl chloride-vinyl propionate copolymers. The NMR spectra of the methylene carbon region showed three split peaks whose intensities changed with composition of the copolymers. These peaks were assigned to diad sequences and the observed diad concentrations were in good agreement with the calculated concentrations in terms of the random copolymerization theory. For the methine carbon spectra of vinyl acetate or vinyl propionate units in the copolymers the degree of splitting of the signal was improved by the addition of tris(1,1,1,2,2,3,3-heptafluro-7,7-diemthyl-1,4,6-octanedinata)-praseodymium as a shift reagent. Four peaks assigned to the methine carbon were interpreted in terms of triad sequence distribution and tacticity.     

聚苯乙烯大单体与乙酸乙烯酯的共聚及其接枝共聚物的表征

研究了聚苯乙烯大单体与乙酸乙烯酯的溶液聚合,结果表明,接枝效率随引发剂用量、聚合温度及小单体与大单体的投料比的增加而增加,随大单体的分子量增加而减少,而随单体浓度的变化呈现一最大值。共聚过程中大单体的转化率开始较小单体的增加快,后期变慢。用萃取法纯化的接枝共聚物经GPC、IR、~1H-NMR及PGC等表征,并算得平均接枝数为4—7。透射电镜表明接枝共聚物中存在微观相分离。     

Grafting onto Wool. XXVII. Graft Copolymerization of MixeD Vinyl Monomers by Use of Ceric Ammonium Nitrate as Redox Initiator

In order to ascertain the effect of a donor monomer, vinyl acetate (VAc), on the graft copolymerization of acceptor monomers, ethyl acrylate (EA) and butyl acrylate (BA), grafting of mixed vinyl monomers (EA + VAc) and (BA + VAc) was carried out on Himachali wool in aqueous medium using ceric ammonium nitrate (CAN) as a redox initiator. Graft copolymerization was carried out at different temperatures for various reaction periods. Percent grafting and percent efficiency were determined as functions of 1) concentration of mixed vinyl monomers, 2) concentration of CAN, 3) concentration of HNO₃ 4) temperature, and 5) reaction time. VAc, the donor monomer, was found to decrease percent grafting of EA and BA onto wool.     

Synthesis of functional polyolefins using cationic bisphosphine monoxide-palladium complexes

The copolymerization of ethylene with polar vinyl monomers, such as vinyl acetate, acrylonitrile, vinyl ethers, and allyl monomers, was accomplished using cationic palladium complexes ligated by a bisphosphine monoxide (BPMO). The copolymers formed by these catalysts have highly linear microstructures and a random distribution of polar functional groups throughout the polymer chain. Our data demonstrate that cationic palladium complexes can exhibit good activity for polymerizations of polar monomers, in contrast to cationic α-diimine palladium complexes (Brookhart-type) that are not applicable to industrially relevant polar monomers beyond acrylates. Additionally, the studies reported here point out that phosphine-sulfonate ligated palladium complexes are no longer the singular family of catalysts that can promote the reaction of ethylene with many polar vinyl monomers to form linear functional polyolefins.     

聚苯乙烯大单体与乙酸乙烯酯的共聚及其接枝共聚物的表征

 研究了聚苯乙烯大单体与乙酸乙烯酯的溶液聚合,结果表明,接枝效率随引发剂用量、聚合温度及小单体与大单体的投料比的增加而增加,随大单体的分子量增加而减少,而随单体浓度的变化呈现一最大值。共聚过程中大单体的转化率开始较小单体的增加快,后期变慢。用萃取法纯化的接枝共聚物经GPC、IR、¹H-NMR及PGC等表征,并算得平均接枝数为4—7。透射电镜表明接枝共聚物中存在微观相分离。     

醋酸乙烯—二乙烯基苯共聚反应动力学

根据文献查得的Ｑ，ｅ值，计算了醋酸乙烯－二乙烯基二元共聚的竞聚率，预测其共聚的可能性。以甲苯为汽油为致孔剂，采用悬浮聚合方法合成该二元大孔共聚物。红外光谱分析跟踪共聚反应过程中乙酰氧基和苯环相对比例的变化，并测定共聚反应过程中比表面积，孔率和平均孔径的变化。     

Polymerization and copolymerization studies on vinyl fluoride

The polymerization of vinyl fluoride has been studied in the temperature range of 0–50°C. with the aid of different types of initiators. Ziegler-Natta systems based on vanadyl acetylacetonate and AIR(OR)Cl compounds showed good activity. Enhanced reaction rates and higher polymerization degrees were achieved with boron alkyls (and, to a lesser degree, Cd, Zn, and Be alkyls) activated by oxygen. With either types of initiator, the main features and the kinetic parameters of the polymerization were determined. In all cases, the polymerization is considered to be of the free-radical type, though some properties (crystallinity, melting temperature) of the polymer are shown to be markedly improved over the previously described high-pressure polymer. This is chiefly ascribed to an improved degree of chemical regularity of the chains. The copolymerization of vinyl fluoride in the presence of the cited initiators was studied with a number of monomers. The values of the copolymerization parameters allow us to obtain Q (0.010 ± 0.005) and e (?0.8±0.2) values and to discuss the reactivity of vinyl fluoride in radical chain propagation.     

Copolymerization of vinyl acetate with ethyl α-cyanocinnamate

Trisubstituted ethylene, ethyl α-cyanocinnamate, is readily copolymerized with vinyl acetate by a conventional radical initiator. Terminal, penultimate, and “complex” copolymerization models were applied by using the data of composition of the copolymers obtained in bulk and by copolymerization in benzene, ethyl acetate, and chloroform. The model based on the participation of the monomer complexes describes satisfactorily the deviation from the terminal copolymerization model. The proton NMR analyses of the monomer mixtures indicate that the interaction between the monomers leads to the formation of weak monomer complexes. Kinetic studies of the initial rate dependence on the total monomer concentration and monomer feed composition enabled us to evaluate the degree of participation of the free uncomplexed monomers and the monomer complex in the propagation reactions. The contribution of the complexed monomers in the propagation stages increases with the increase in total monomer concentration. The initial rate of the copolymerization is proportional to the square root of the initiator concentration, thus confirming the bimolecular termination of the macrochains. The rate constants of the addition reactions of the complex and free monomers were evaluated from the kinetic studies. The quantitative kinetic treatment provided information regarding the relative weight of the termination reaction and indicated that the termination in the system occurs predominantly by the cross-termination reaction between two growing polymer radicals with different kinds of monomer units at the ends. Additional information on the termination in this system was obtained from viscosity measurements.     

SYNTHESIS OF MACROPOROUS COPOLYMER OF VCA AND DVB

The reactivity ratios of vinyl acetate(VAc) and divinyl benzene (DVB) were calculated from the Q and e values.The possibility of the copolymerization of these two monomers was predicted and the copolymerization was carried out by suspension polymerization technique in the presence of pore producing agent (toluene and gasoine).The relative ratio of acetoxy group and benzene ring in the copolymer were monitored by IR measurement during the polymerization.The variation of pore properties,such as spectific surface area,porosity and average pore diameter,with polymerization time were determined.The copolymers at various polymerization time were alcoholyzed and thus the variation of the hydroxyl group content with polymerization time was studied.     

Copolymerization studies of vinyl chloride and vinyl acetate with ethylene using a transition-metal catalyst

Since the advent of Ziegler-Natta polymerization of ethylene, attempts have been made to extend coordination polymerization to commercially important monomers with polar functionality. In this study we examined the copolymerization of perdeuterated vinyl chloride (VC) and perdeuterated vinyl acetate (VA) with ethylene using a tridentate Fe(II) dichloride pyridine diimine metal catalyst. The resulting ethylene oligomers were examined by GC/MS and 2H NMR spectroscopy. It was shown that VC was inserted once for every approximately 180 ethylene monomers and VA was inserted once for every approximately 350 ethylene monomers. VC and VA behave as comonomers for coordination/insertion polymerizations with ethylene. However, we find that insertion with either monomer leads to termination of the growing chain via beta-elimination processes. The deuterium atoms are exclusively located at the olefin terminus for each of the monomers.     

SYNTHESIS OF MACROPOROUSCOPOLYMER OF VCA AND DVB

1.INTRODUCTIONVinylacetate(VAc)isacommonandcheapmonomeLUsuallyitisusedtopreparelinearhomopolymerorcopolymeLHowever,becauseoftheusefulestergrouppresentinVAc,italsoat'tractsthegreatinterestsofsomescientistswhoworkintheareaoffunctionalpolymers.Recently,alotofreporthaveappearedusingVAcasamainmonomertopreparecrosslinkedpolymersII~sl.ThesereportsmainlyfocustheinterestsonthesynthesisandapplicationoftheVAccontainingcrosslinkedpolymers.Noreportshavebeenfoundtostudythekineticsofthesynthesisofc…     

Peculiarities of N-vinylpyrrolidone copolymerization with vinyl acetate in the presence of tributylborane and 1,4-benzoquinone

Copolymerization of N-vinylpyrrolidone with vinyl acetate in the presence of tributylborane and 1,4-benzoquinone has been investigated. The curves of copolymer composition and relative reactivity of monomers were obtained. An introduction of tributylborane in the monomer mixture leads to the formation of complex with N-vinylpyrrolidone. Molecular weight of the copolymers and the rate of the copolymerization decreases with the addition of tributylborane and 1,4-benzoquinone compare to conventional copolymerization initiated by dicyclohexyl peroxydicarbonate. The curve of the copolymer composition acquires an S-shape. Triad composition of the copolymers differs from the theoretical values. The reason for the observed pheno mena is realization of the effect of preferential solvation (bootstrap-effect).

     

Hyperbranched polymers with maleic functional groups as radical crosslinkers

The crosslinking performance of the unsaturated hyperbranched polyester poly(allyloxy maleic acid‐co‐maleic anhydride) (MAHP) was investigated with copolymerizations of three different monomers: styrene, vinyl acetate, and methyl methacrylate. Both styrene and vinyl acetate afforded interpenetrating‐polymer‐network copolymer gels. The gels exhibited crosslink density gradients through the polymer matrices on a macroscopic level, and density maximums were concentrated around the MAHP moieties. The heterogeneity of the gels is briefly discussed in terms of a modified two‐phase model, where one phase consists of an elastic part of low crosslinking density and the other phase consists of an inelastic dendritic part with a highly condensed bond density. Unlike the two‐phase model developed by Choquet and Rietsch, the modified two‐phase model takes into account that both phases swell in good solvents. Unlike copolymerizations employing styrene or vinyl acetate, the copolymerization of MAHP with methyl methacrylate afforded noncrosslinked starbranched copolymers that consisted of a MAHP core from which long poly(methyl methacrylate) branches were protruding. The different behaviors of the copolymerizations of the three monomers used in this study can rationally be explained by their different reactivity ratios with maleic end groups of MAHP. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 964–972, 2001     

The interaction of vinyl monomers and poly (ethylene terephthalate) in the presence of various initiators produces a physical mixture,not a graft copolymer

The interaction between poly(ethylene terephthalate) and four vinyl monomers, methacrylic acid, methyl methacrylate, styrene, and vinyl acetate, has been studied using hydrogen peroxide, benzoyl peroxide, azobisisobutyronitrile, and cobalt acetylacetonate as initiators. The ease of addition of the monomer to the polymer follows the solubility of the monomer in the polymer film. No chemical interaction occurs between the PET film and the monomer; rather, the monomer is homopolymerized within the film and forms a semi-interpenetrating network so that the two homopolymers cannot be separated unless the PET matrix is destroyed. © 1995 John Wiley & Sons, Inc.     

Copolymerization of N-Substituted Maleisoimides with Vinyl Acetate

Abstract

N-Substituted maleisoimides have been polymerized [1,2] and copolymerized with readily polymerizable vinylic monomers, such as acrylonitrile and vinyl acetate [3]. However, the homopolymerization or copolymerization of N-substituted maleisoimides is not reported in the literature. Attempts to homopolymerize N-substituted maleisoimides free radically have failed completely 141. During such attempts, however, none of the maleisoimides used suffered isomerization to the corresponding imides. This paper reports the free-radical copolymerization of three N-substituted maleisoimides with vinyl acetate.     

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Switchable polymerization provides the opportunity to regulate polymer sequence and structure in a one‐pot process from mixtures of monomers. Herein we report the use of O₂ as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)Co^III?R [Salen=N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine; R=alkyl] to the ring‐opening copolymerization (ROCOP) of CO₂/epoxides. Critical to this process is unprecedented monooxygen insertion into the Co?C bond, as rationalized by DFT calculations, leading to the formation of (Salen)Co^III?O?R as an active species to initiate ROCOP. Diblock poly(vinyl acetate)‐b‐polycarbonate could be obtained by ROCOP of CO₂/epoxides with preactivation of (Salen)Co end‐capped poly(vinyl acetate). Furthermore, a poly(vinyl acetate)‐b‐poly(methyl acrylate)‐b‐polycarbonate triblock copolymer was successfully synthesized by a (Salen)cobalt‐mediated sequential polymerization with an O₂‐triggered switch in a one‐pot process.