Anionic polymerization of styrene: Integration with styrene monomer production

Anionic polymerization and ethylbenzene dehydrogenation were carried out in the laboratory using continuous reactor designs and conditions typical of current commerical processes. The dehydrogenator was operated at 43–55% conversion with continuous distillation of the ethylbenzene/styrene mixture to remove byproducts that would interfere with the subsequent anionic polymerization. The anionic polymerization was carried out using a reactor of the CSTR type which operated at > 99% conversion of styrene. The volatiles were recovered from the polymer syrup and recycled back to the dehydrogenator. During 4 months of continuous operation the integrated process showed no detrimental buildup of impurities which affected the anionic polymerization or dehydrogenation. The polystyrene produced had excellent color, clarity, thermal stability, and polydispersity (M_w/M_n = 2.1–2.4). The ability to control weight average molecular weight was within a range of 20,000 using an on-line GPC in concert with a colorimeter.     

Anionic polymerization of styrene in triglyme-benzene mixtures

Living anionic polymerization of styrene was kinetically investigated in triglyme-benzene mixtures. At low concentrations of triglyme the overall propagation rate constant, k_p, was much larger than at the same concentration of monoglyme (DME) in DME-benzene mixtures. The Szwarc-Schulz plot did not have negative slopes for lithium and sodium salts at triglyme contents of 5～20vol%, and no contribution of free anions to the propagation was observed for the sodium salt. The sodium ion pair was more highly reactive than the lithium ion pair; thus at 25°C, the ion pair rate constant, k′_p, for the lithium salt was 43, 102, 135 and 165 M^?1sec^?1 at triglyme concentrations of 5, 10, 15, and 20%, respectively, while that for the sodium salt was 410, 920, and 1460 M^?1sec^?1 in 5, 10, and 15% triglyme, respectively. The dissociation constant, K, for the lithium salt was 2·4×10^?11, 1·9×10^?10 and 1·3×10^?9 M in 10, 15, and 20% triglyme, respectively and the free ion rate constant, k″_p, was 2～2·5×10⁴ M^?1sec^?1 for the lithium salt.     

Anionic polymerization of styrene: The search for an industrial process

Anionic polymerizations were carried out in the laboratory using a CSTR reactor design and conditions typical of current commercial mass polystyrene plants. Polystyrene having excellent color and polydispersity was produced. Polymer quality, styrene conversion, and molecular weight control were all linked to use of polymerization feed of consistently high purity and polymerization in the 90–110°C temperature range. The results of this study clearly show that high quality polystyrene can be made utilizing anionic polymerization chemistry in existing well mixed mass polystyrene reactors of the CSTR design. The key to the successful practice of this technology is the ability to produce consistently high purity polymerization feed.     

磁场引发苯乙烯分散聚合反应的研究

本文采用苯乙烯的分散聚合反应体系为研究对象,在无外加温度、压力及其它物理手段的前提下,直接利用磁场在室温条件下引发苯乙烯的分散聚合反应,成功制备出了聚苯乙烯微球。研究结果表明,交变磁场作用引发苯乙烯分散聚合生成了聚苯乙烯,其重均分子量Mw=96856,数均分子量Mn=13162。所制备的聚苯乙烯微球的粒径为1—2μm,恒定磁场条件下制备的聚苯乙烯微球重含有部分不成形的杂质,而交变磁场条件下制备的聚苯乙烯微球的球形度规整,表面光滑,无缺陷和杂质。     

Measurements on the temperature dependence of the cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst

Summary The cationic polymerization of styrene in CH₂Cl₂ with CF₃SO₃H as catalyst and at low monomer concentrations shows, at –15°C, –45°C and –60°C, the same formal dependence on monomer concentration. The dependence on the catalyst concentration is approximately but not exactly of a third order.The unimodal molecular weight distributions at [M]_o<0.2 mol·1^–1 become broader with decreasing polymerization temperature and increasing monomer concentration and change to bimodal or trimodal distributions at [m]_o>0.2 mol·1^–1. The addition of (Bu)₄N⁺CF₃SO₃ ^– to the polymerization system shows that the two higher molecular peaks are produced by free ions. The activation energy of the total reaction is found to be 3.5 kcal·mol^–1.I thank Prof. G. V. Schulz for interesting discussions and the possibility to work in his group, G. Greschner for a computer program and the Alexander von Humboldt Stiftung for their financial help.     

Anionic polymerization of 2-haloethyl methacrylates

The anionic polymerizations of 2-chloroethyl methacrylate (1), 2-bromoethyl methacrylate (2), and 2-iodoethyl methacrylate (3) were carried out in THF at −78 °C with 1,1-diphenyl-3-methylpentyllithium in the presence of LiCl. The polymerizations proceeded in a controlled manner to quantitatively afford polymers with predictable molecular weights and narrow molecular weight distributions. Under similar conditions, the anionic block copolymerizations by the sequential addition of methyl methacrylate (MMA) followed by 1, 2, and 3 generated the corresponding diblock copolymers with well-defined structures. On the other hand, in the block copolymerization by the reverse addition of monomer, a well-defined diblock copolymer, poly(1)-block-PMMA, could be synthesized only by the sequential addition of 1 followed by MMA, whereas the block copolymerizations using 2 and 3 were not successful because of instabilities of the propagating chain-end anions derived from 2 and 3. The side reactions which occurred during the polymerization were discussed.     

The electroinitiated polymerization of styrene: Part 2

Electrolysis of a solution of styrene and sodium borofluoride in dimethyl acetamide gives rise to polystyrene at the cathode. The polymerization occurs by an anionic mechanism initiated by solvated electrons produced during electrolysis. Kinetics in a single compartment cell and a divided compartment cell show differences. Acceleration occurs in the cathode compartment of the divided cell giving rise to high current efficiencies. Evidence is given for the presence of an electrolytic termination reaction occurring in the single cell.     

邻仲丁基4,6-二硝基苯酚(DNBP)对苯乙烯热聚合阻聚行为研究

用折光指数法考察了90~120℃下邻仲丁基4,6-二硝基苯酚(DNBP)对苯乙烯热聚合的阻聚效果,并从温度和质量浓度(0.02%~1%)两个方面进行研究。实验结果表明,随着温度的升高,阻聚效果逐渐变弱;随着阻聚剂浓度的增加,阻聚效果逐渐变强;温度对于阻聚过程的影响要强于浓度对其的影响;温度为120℃,DNBP浓度超过0.1%时,可以产生表面意义上的诱导期。     

Anionic polymerization initiated by lamellar compounds of LiC12: 1. Kinetics of the polymerization of styrene and isoprene — initiator efficiency

The polymerizations of styrene and isoprene initiated by LiC₁₂ in cyclohexane are far slower than those observed in homogeneous media. The initiator's efficiency is estimated from a determination of the polymer molecular weight at differents reaction steps. Keeping in mind the monomer diffusion inside the graphite layers and in allowing some assumptions, some of the propagation rate constants were estimated. These values are much lower than those found in homogeneous polymerization. Temperature speeds up the reaction. The initiator's efficiency depends on the rate at which the graphite separates under the conjugated action of temperature and polymer growth.     

The stabilization effect of mixed-surfactants in the emulsion polymerization of styrene

Summary The emulsion polymerization of styrene was performed at 50°C with a mixture of anionic and nonionic surfactants using different surfactant concentrations. In the single-surfactant systems, a proportional relationship was observed between the total particle surface area per cm³ of aqueous solution at 90% conversion (TS) and the amount of surfactant used for each polymerization. For mixed-surfactant systems an additivity was established between the TS value and surfactant composition. The study of the particle size data from low to high conversion showed that the particle number changed with conversion.     

Anionic polymerization of ethylene oxide with cryptates as counterions: 2

A kinetic study of the anionic polymerization of ethylene oxide has been made in tetrahydrofuran at 20°C, with the cryptate Cs⁺ + [TC] as counterion, [TC] being a spheroidal macrotricyclic ligand. Conductance measurements have been made on THF solutions of ?₄BCs + [TC]. Ionic associations higher than cryptated ion pairs are negligible for living end concentrations lower than 3 × 10^?4 moll^?1. k_± and the alkoxide ion pair dissociation constant K_D were determined from both sets of kinetic data obtained with and without added salt knowing the value of k_? from kinetic data performed with K⁺ + [222] as counterion. Free alkoxide ions are about twenty times more reactive than cryptated caesium ion pairs.     

Anionic polymerization of vinylsilanes

Summary The anionic polymerization of dimethylphenylvinylsilane with sec-butyllithium/N,N,N,N-tetramethylethylenediamine (TMEDA) was investigated. The polymerization proceeded up to 100% yield and afforded the polymer having isomerized-structure units. The polymerization was accompanied by chain transfer reaction to the monomer and the polymerization rate in the presence of TMEDA was much lower than in the absence of TMEDA.     

Anionic polymerization of acrylates

Summary The article presents preliminary results of the anionic polymerization of 2-ethylhexyl- and butyl acrylates initiated by ester enolate in the presence of Li 3-methylpentoxide-3. Compared with the Li t-butoxide which has been widely used earlier, this alkoxide is a more efficient stabilizer of active centers. Under selectively chosen reaction conditions, polymerizations of both monomers proceed quantitatively with a small extent of the selftermination event at-40 and-20°C producing polymers with narrow MWD's.     

溶剂对甲基丙烯酸甲酯与苯乙烯高温聚合的影响

利用引发剂,在高温下引发甲基丙烯酸甲酯(MMA)与苯乙烯(St)聚合,研究了w(甲苯)对聚合过程及产品结构的影响。结果表明,溶剂的存在能够显著影响MMA与St的共聚合。随着w(甲苯)增加,聚合物中w(St)随之增加;w(甲苯)=5%～20%,反应转化率减小,聚合物相对分子质量增加;w(甲苯)20%,反应转化率减小趋势变慢,聚合物相对分子质量降低。     

The effect of temperature and solvent on the polymerization of 2-propenylfuran

Summary 2-Propenylfuran was polymerized by trifluoroacetic acid in various solvents. The reactions were accomplished over the temperature range of -78 to 70°C depending on the solvent used. The kinetics of the polymerization in CCl₄ at 0°C was second order. It was observed that the 2,5-disubstituted furan moiety in the chain grows as the dielectric constant of the solvents decreases and that the percentage of alkylated furan ring in the polymer increases with temperature independently from the solvent used. Both findings are explained by considering the possibility of 2-propenylfuran to propagate either by the C-5 position of the furan ring or by the vinyl bond.     

Syndiotactic-specific polymerization of styrene: catalyst structure and polymerization mechanism

The mechanistic investigation of syndiotactic-specific polymerization of styrene is reviewed, mainly with reference to the research work carried out at the University of Salerno. NMR analysis of the stereochemical structure of s-PS macromolecules, in some cases suitably labelled, provided valuable information concerning the regiochemistry of polyinsertion, the type of addition to the monomer double bond, and the model of stereospecific propagation. Kinetic studies and spectroscopic investigation of the catalytic systems suggested a cationic Ti(III) complex with a strongly π-co-ordinated benzyl-type growing chain as the true active species. This revised version was published online in June 2006 with corrections to the Cover Date.     

Thermal polymerization of styrene

An experimental investigation of the kinetics of bulk thermal polymerization of styrene in the temperature range of 200°–230°C is reported. Conversions and molecular weight averages were measured by gel permeation chromatography. At elevated temperatures, oxygen in the polymerization mixture appears to have negligible effect on the rate of polymerization and the molecular weights of the polymer. Experimental evidence suggests that the molecular weight development of the polymer is strongly influenced by transfer reactions.     

Microemulsion polymerization of styrene

Summary Heats of polymerization of three carbazolyl-containing epoxides 9-(2,3-epoxypropyl)carbazole, 1,2-epoxy-6-(9-carbazolyl)-4-oxahexane and 3,6-dibromo-9-(2,3-epoxypropyl) carbazole have been determined on the differential microcalorimeter DAK 1-1A (USSR). The influence of the structure of monomers upon the values of polymerization heat is discussed.