Stereochemistry of the radical polymerization of vinyl pentafluorobenzoate

The free-radical polymerization of vinyl pentafluorobenzoate (VPBz) was carried out under various conditions in order to compare its stereochemistry to that of the vinyl benzoate (VBz) polymerization using similar conditions. Contrary to the stereochemistry of the radical polymerization of VBz, VPBz favors syndiotactic propagation. The poly(VPBz) obtained in hexafluoroisopropanol (HFIP) with nBu₃B-air at −30 °C has a triad syndiotacticity (rr) of 52% which achieved the highest syndiotacticity reported for the radical polymerization of vinyl esters. The stereochemistry difference for the VPBz polymerization was ascribed to the electron-withdrawing effect of the fluorine on the aromatic ring. The solvent effect of enhancing the rr specificity in HFIP may be related to the hydrogen-bonding between HFIP and VPBz or the growing species. It was also found that the glass transition temperatures (T_g) of the VPBz polymers apparently increased with an increase in their diad syndiotacticities (r): the T_g of poly(VPBz) with r=72% was 79 °C, which was 25 °C higher than that of poly(VPBz) with r=56% obtained in toluene.     

Controlled free‐radical polymerization of vinyl chloride

Owing to the importance of poly(vinyl chloride) (PVC) as the second‐largest plastic in volume after the polyolefins and above styrene polymers, the control of the free‐radical polymerization of vinyl chloride (VC) is of high industrial and academic interest. But still the term “controlled” polymerization is not yet clearly defined. Often it is used for quasi‐living polymerizations with equilibrium reactions in the initiation and/or termination step or for the control of the molecular weight distribution (MWD), but it can also be applied to several structural aspects such as stereochemistry, branching, or special technical properties. In the present article, the control of chain growth and chain transfer is discussed. It has been well known for many years that the propagation step in the VC polymerization is terminated to a large degree by the rather frequent and temperature‐dependent chain transfer of the growing macromolecules to the monomer. Therefore, the degree of polymerization is strongly governed by the polymerization temperature. However, this transfer step does not result in a controlled or a narrow MWD. By means of free‐radical nitroxide‐mediated polymerization of VC in suspension, PVC with a narrower MWD can be obtained also at higher polymerization temperatures. The resulting PVC with nitroxide end groups can act as a macro‐initiator for various monomers, resulting in two‐block copolymers, which are, e.g., interesting compatibilizers in blends with PVC. J. VINYL ADDIT. TECHNOL., 11:86–90, 2005. © 2005 Society of Plastics Engineers     

Probing the reaction kinetics of vinyl acetate free radical polymerization via living free radical polymerization (MADIX)

Living free radical polymerization technology (macromolecular design via the interchange of xanthates (MADIX)) was applied to give accesses to chain length and conversion dependent termination rate coefficients of vinyl acetate (VAc) at 80 °C using the MADIX agent 2-ethoxythiocarbonylsulfanyl-propionic acid methyl ester (EPAME). The kinetic data were verified and probed by simulations using the PREDICI^® modelling package. The reversible addition-fragmentation transfer (RAFT) chain length dependent termination (CLD-T) methodology can be applied using a monomer reaction order of unity, since VAc displays significantly lower monomer reaction orders than those observed in acrylate systems (ω(VAc, 80 °C)=1.17±0.05). The observed monomer reaction order for VAc is assigned to chain length dependent termination and a low presence of transfer reactions. The α value for the chain length regime of log(i)=1.25−3.25 (in the often employed expression ) reads 0.09±0.05 at low monomer to polymer conversion (10%) and increases significantly towards larger conversions (α=0.55±0.05 at 80%). Concomitantly with a lesser amount of midchain radicals, the chain length dependence of k_t is significantly less pronounced in the VAc system than in the corresponding acrylate systems under identical reaction conditions. The RAFT(MADIX)-CLD-T technique also allows for mapping of k_t as a function of conversion at constant chain lengths. Similar to observations made earlier with methyl acrylate, the decrease of k_t with conversion is more pronounced at increased chain lengths, with a strong decrease in k_t exceeding two logarithmic units from 10 to 80% conversion at chain lengths exceeding 1800.     

Controlled radical copolymerization of vinyl acetate and dibutyl maleate by iodine transfer radical polymerization

Iodine transfer radical homo‐ and copolymerization of vinyl acetate (VAc) with dibutyl maleate (DBM) were carried out in the presence of ethyl iodoacetate (EtIAc) and 2,2′‐azobis(isobutyronitrile) (AIBN) as chain transfer agent and initiator, respectively, at 60 °C. Molecular weight and its distribution and (co)polymer structure (i.e. copolymer composition and chain end groups) were analysed using gel permeation chromatography and ¹H NMR spectroscopy, respectively. Homo‐ and copolymerization reactions proceed via a controlled characteristic with predetermined molecular weight and relatively narrow molecular weight distribution. The presence of DBM in the reaction mixture decreases the consumption rate of EtIAc as well as the polymerization rate. This is attributed to the effect of DBM on the transfer constant to the EtIAc and probably on the iodine exchange rate constant between the growing chains. The effect of the concentration of AIBN, EtIAc and overall monomers on the conversion, molecular weight and its distribution was studied. Simultaneously high conversion and molecular weight with a relatively narrow molecular weight distribution can be achieved only when equimolar and intermediate concentration of EtIAc and AIBN is used in the reaction mixture. End‐group analysis by ¹H NMR reveals that iodinated VAc end groups in the (co)polymer chains are unstable, resulting in aldehyde end groups. Thermogravimetric analysis shows that the thermal stability of the VAc‐based polymer increases on incorporating DBM units into the copolymer chains. © 2013 Society of Chemical Industry     

Reverse iodine transfer polymerization of vinyl acetate and vinyl benzoate: synthesis and characterization of homo‐ and copolymers

Homo‐ and copolymers of vinyl esters including vinyl acetate (VAc) and vinyl benzoate (VBz) were synthesized via the reverse iodine transfer radical polymerization technique. Polymerization was carried out in the presence of iodine as the in situ generator of the transfer agent and 2,2′‐azobis(isobutyronitrile) as the initiator at 70 °C. Reverse iodine transfer radical homopolymerization of VAc and VBz led to conversions of 76 and 57%, number‐average molecular weights of 8266 and 9814 g mol^?1 and molecular weight distributions of 1.58 and 1.49, respectively. The microstructure of the synthesized polymers was investigated in detail using gel permeation chromatography, ¹H NMR, ¹³C NMR and distortionless enhancement of polarization transfer (135° decoupler pulse) techniques. Relatively narrow molecular weight distribution and controlled and predictable trend of molecular weight versus conversion were observed for the synthesized polymers, showing that reverse iodine transfer radical homo‐ and copolymerization of VAc and VBz proceeded with controlled characteristics. Results of molecular weight and its distribution along with the ¹H NMR spectra recorded for homo‐ and copolymers indicated that side reactions can occur during the course of polymerization with a significant contribution when VAc, even in a small amount, was present in the reaction mixture. This can result in polymer chains with aldehyde dead end and broadening of the molecular weight distribution. © 2015 Society of Chemical Industry     

Free radical polymerization of vinyl acetate in the presence of liquid polysulfides

The free radical polymerization of vinyl acetate in the presence of a liquid polysulfide H(SCH₂CH₂OCH₂OCH₂CH₂S)_nH (thiocol) was investigated from the point of view of reaction mechanism and characterization of the resulting copolymers. It was shown that, besides the thiol end groups that were consumed very rapidly, the disulfide groups within the thiocol chain were also involved in chain transfer processes. The chain transfer constant of the thiocol S–S groups in the polymerization reaction was estimated from their rate of consumption versus the rate of monomer consumption (C_T = 0.89). The resulting copolymers, made up of randomly distributed thiocol sequences and PVAc blocks, were characterized by ¹H NMR, GPC, DSC and TGA measurements. The copolymers displayed only one glass transition each, which decreased as the PVAc block length decreased, while their thermal stability was lower than that of both thiocol and PVAc. The molecular weight of the copolymers increased with VAc conversion as a consequence of the insertion of PVAc blocks within the thiocol chain.     

Thermal characterization of poly(vinyl chloride) samples prepared by living radical polymerization: Comparison with poly(vinyl chloride) prepared by free radical polymerization

Poly(vinyl chloride) (PVC) samples were synthesized by a living radical polymerization (LRP) method and compared with commercial PVC prepared by the conventional free radical polymerization (FRP). The differences were assessed, for the first time, in terms of viscosimetry parameters and thermal analysis. The LRP method used to prepare the PVC‐LRP samples is the only one available to obtain this polymer free of structural defects, being of commercial interest in a view of preparing a new generation of PVC‐based polymer with outstanding performance. The polymerization temperature selected (35°C) to prepare the LRP samples is currently used in the industry to prepare PVC‐FRP grades with moderate to high molecular weight. Since the thermal stability is a direct consequence of the polymer structure, this study is of vital importance to understand the potential of new PVC‐LRP. The thermoanalytical measurements demonstrate an enhanced thermal stability of PVC‐LRP when compared with its FRP counterpart. The PVC‐LRP sample with very low molecular weight reveals a higher thermal stability than the most stable PVC‐FRP sample. It is the first report dealing with thermal analysis of PVC prepared by LRP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Photochemically initiated free radical promoted living cationic polymerization of isobutyl vinyl ether

A new photoinitiating system for living cationic polymerization of vinyl ethers such as isobutyl vinyl ether (IBVE) has been reported. The photoinitiating system comprises free radical photoinitiators such as 2,2-dimethoxy-2-phenyl acetophenone (DMPA), benzophenone or thioxanthone, together with an onium salt, such as diphenyliodonium chloride and zinc bromide. In the first step, photochemically generated free radicals are oxidized to the corresponding carbocations which subsequently react with vinyl ether monomer to yield an adduct. In the presence of zinc salt, this adduct initiates living cationic polymerization of IBVE.     

原子转移自由基聚合机理及其应用

原子转移自由基聚合(ATRP)是目前研究的热点之一。该文介绍了ATRP的反应机理及其应用。     

The free radical polymerization of vinyl monomers in the presence of carbon black

The polymerization of vinyl monomers has been carried out in the presence of furnace blacks using initiators such as 2,2′-azobisisobutyronitrile (AIBN) and benzoyl peroxide (Bz₂O₂) in nitrogen or oxygen atmosphere. The results indicate that free radicals form by the decomposition of initiators reacting with carbon blacks to give active sites on their surface which then capture either the free radicals or the growing polymer radicals. Using the monomers with negative e values, such as styrene and vinyl acetate, a marked retardation was observed in Bz₂O₂-initiated polymerization in the presence of furnace blacks, while a moderate inhibition was found in the polymerization initiated by AIBN. The polymerization reaction using Bz₂O₂ was found to be very sensitive to oxygen in the presence of furnace blacks and the involvement of oxygen was found to promote grafting onto the surface of carbon black by the growing polymer radicals, consequently giving polymer-grafted particles while hindering the formation of homopolymers. Furthermore, the reaction of Bz₂O₂ with the surface of furnace blacks in oxygen atmosphere has been studied in carbon tetrachloride at 45°C. The resulting carbon blacks show an increase in the number of surface quinone groups with an increase in reaction time.     

Non-ideal kinetics in vinyl polymerization primary radical termination and chain transfer to solvent in benzoyl peroxide initiated polymerization of vinyl acetate in benzene

The kinetics of vinyl acetate polymerization initiated by benzoyl peroxide in benzene at 60°C have been studied. Deviation of the rate of polymerization from kinetic orders of 0.5 in initiator and 1.0 in monomer is discussed in terms of primary radical termination and chain transfer to solvent.     

The effect of radical desorption on the particle size distribution in vinyl acetate emulsion polymerization

The effect of free radical desorption is studied by using a mathematical model of particle size distribution in continuous emulsion polymerization. By comparing the theoretical prediction with experimental data, the value of D_o for the vinyl acetate (VAc) system is best chosen as 0.19 × 10^?7 cm²/h. The effect of radical desorption as well as mean residence time on the absolute particle size distribution, total concentration of polymer particles, conversion, and average number of radicals per polymer particle are analyzed by the model proposed.     

Free radical polymerization with long chain branching: continuous polymerization of vinyl acetate in t-butanol

Vinyl acetate was polymerized in a continuous stirred tank reactor (CSTR) at 60°C in t-butanol solution. Mean residence times ranged from 1.35 to 7.2 hr; steady state conversions ranged from 15 to 61%. Molecular weights $\text{M}$_n and $\text{M}$_w were measured and interpreted in terms of a kinetic model developed from batch studies and the state of local mixing in the reactor. Good macroscopic mixing was confirmed by tracer studies and measurements of conversion vs time during the start-up period and at steady state. The molecular weights obtained at high conversions agreed more closely with predictions based upon a locally segregated state than with those based on complete molecular mixing. However, calculations based on agitation and diffusion rates raised serious questions about the validity of the segregation model for this polymerization. Other factors, some chemical and some related to the agitation, may be important, but the problem of predicting molecular structure remains unresolved.     

Reactivity and mechanism in the cationic polymerization of isobutyl vinyl ether

The cationic polymerization of isobutyl vinyl ether initiated by triphenyl methyl and tropylium hexachloroantimonates, and by triphenyl methyl tetrafluoroborate, has been studied in detail. Initiation was rapid and complete, termination was shown to be insignificant, polymerization half lives were of the order of 5–10 s and reaction rates were measured by an adiabatic calorimetric technique. Catalyst concentrations employed were sufficiently low that essentially complete dissociation into free ions is indicated by ion-pair dissociation constants, and this permits estimation of the rate coefficient for propagation by free cations (k_p). At 0°C in methylene dichloride k_p ∼ 5 × 10³ M⁻¹ s⁻¹, in substantial agreement with values obtained by radiation induced polymeirzation of bulk monomer. Molecular weights of the poly(isobutyl vinyl ether) samples fell in the range 2000–5000 on account of monomer transfer processes. Detailed mechanisms for initiation, propagation, transfer and termination reactions are considered.     

Controlled synthesis of poly(vinyl acetate) by traditional radical emulsion polymerization

A new redox initiation system, potassium persulfate/N,N‐dimethylethanolamine, was used to initiate traditional radical emulsion polymerization of vinyl acetate at low temperature. Polymers were characterized using gel permeation chromatography, scanning electron microscopy and dynamic light scattering. The results showed that poly(vinyl acetate) with high molar mass and small dispersity (?) was successfully synthesized. © 2016 Society of Chemical Industry     

Synthesis and radical polymerization of novel vinyl monomers having the imidazoline and pyrimidine moiety

Summary Alkylation of the methylene bridged tetrahydropyrimidine derivatives by chloromethylstyrene produces the bridged bis(4-vinylbenzyl)-1,4,5,6,-tetrahydropyrimidinium salts in high yields. Similar procedures are used to prepare 2-imidazolinium derivatives. The quaternary salts which support functional side groups of potential biomedical interest are characterized by means of spectroscopic methods. These monomers are readily polymerized free radically in solution of dimethyl formamide at moderate temperatures. The soluble and insoluble polymers containing 2-imidazolinium and 1,4,5,6-tetrahydropyrimidinium salts were found to exhibit antibacterial activites againstEscherichia coli.     

Steric effect in the free radical polymerization of vinyl ethers containing electron-deficient olefin groups

Summary o-(2-Vinyloxyethoxy)benzylidenemalononitrile (3a), methyl o-(2-vinyloxyethoxy)benzylidenecyanoacetate (3b), 1,3-di-(2'-dicyanovinyl)-5-methyl-2-(2'-vinyloxyethoxy)benzene (4a), methyl 1,3-di-(2'-carbomethoxy-2'-cyanovinyl)-5-methyl-2-(2'-vinyloxyethoxy)benzene (4b), 2,3,4-tri-(2'-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl 2,3,4-tri-(2'-vinyloxyethoxy)benzylidenecyanoacetate (5b), 2,4,6-tri-(2'-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl 2,4,6-tri-(2'-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of o-(2-vinyloxyethoxy) benzaldehyde (1a), 2-(2'-vinyloxyethoxy)-5-methylisophthaldehyde (1b), 2,3,4-tri-(2'-vinyloxyethoxy)benzaldehyde (2a), 2,4,6-tri-(2'-vinyloxyethoxy)benzaldehyde (2b) with malononitrile or methyl cyanoacetate, respectively. Vinyl ether compounds 3a–b and 5a–b were polymerized readily by free radical initiators to give optically transparent swelling poly(vinyl ethers) 7a–b and 9a–b. Compounds 4a–b and 6a–b did not polymerize by radical initiators due to the steric hindrance. Polymers 7a–b and 9a–b were not soluble in common organic solvents such as acetone and DMSO due to crosslinking. Polymers 7a–b and 9a–b showed a thermal stability up to 300°C in TGA thermograms. Received: 1 December 1999/Revised version: 14 February 2000/Accepted: 16 February 2000     

乙烯基化合物乳液聚合的研究

研究了多种因素对乙烯基化合物乳液聚合的影响,发现十二烷基苯磺酸钠的乳液化学稳定性远不如十二烷基硫酸钠。分析证明,聚甲基丙烯酸甲酯胶乳粒子由于具有极性,粒子粒径及分布除受乳化剂浓度影响外,主要受粒子合并控制,受温度的影响则不明显。用计算机精确控制的量热反应器检测所得的动力学数据表明,易水溶性（极性）单体均相（水相）成核显著,难水溶性单体则甚微。     

Studies on the initiation mechanism of persulfate/aliphatic secondary amine system in vinyl polymerization

Persulfate/aliphatic secondary amine initiation systems were studied. Secondary amines were discovered to be excellent accelerators for the polymerization of acrylic monomers in aqueous solution initiated by persulfate. The rate of acrylamide polymerization and the overall activation energies were determined respectively. The active intermediates of the secondary amine species formed during the initiation reaction were detected by ESR technique to be dialkylamino radicals(R₂N·). From the results the initiation mechanism was proposed.     

Metal-complex compounds as components of initiating systems for the controlled radical polymerization of vinyl monomers

The effect of initiating systems based on substituted and unsubstituted metallocenes; polynuclear macrocyclic semi- and clathrochelates of Fe(II); and metal complexes of Ti(IV), Zr(IV), Fe(III), and Co(III) porphyrins on the free-radical polymerization of MMA and styrene is analyzed. Experimental data are systematized, general relationships are ascertained, and specific features of the process related to the structure of metal-complex compounds and the nature of initiators and monomers are revealed.