溴化苯乙烯/苯乙烯/丙烯腈乳液聚合试验条件探索

以过硫酸钾为引发剂,十二烷基硫酸钠为乳化剂,叔十二烷基硫醇为链转移剂,通过乳液法对溴化苯乙烯、苯乙烯、丙烯腈进行共聚得到溴化苯乙烯-丙烯腈共聚物.考察了引发剂、乳化剂、链转移剂的添加量,反应温度,反应时间,水和单体比例等对聚合反应收率的影响.研究表明：较适宜的反应条件为反应温度80℃,反应时间6h,水与单体质量比4∶1,引发剂质量为单体总质量的0.4％,乳化剂质量为单体总质量的4％,叔十二烷基硫醇为单体总物质的量的2％;上述条件下的产物收率高,相对分子质量4万左右,热分解温度高于350℃.     

Effects of water solubility of acrylonitrile on vinylidene chloride/acrylonitrile/styrene suspension polymerization

The water solubility of acrylonitrile (AN) and its effects on vinylidene chloride/acrylonitrile/styrene (VDC/AN/St) suspension copolymerization were investigated in this study. It shows that the VDC/St ratio and the presence of suspending agent have no obvious influences on AN phase partition between the monomer and aqueous phases, whereas the water solubility of AN increases as temperature increases. Polymerization in the aqueous phase occurs extensively with azobis(isobutyronitrile) (AIBN) as initiator, whereas with lauryl peroxide (LPO) as initiator, polymerization in the aqueous phase is negligible. Theoretical analysis and experimental results indicate that transport of the monomer molecule is possible during polymerization. Both VDC and AN transfer from the monomer phase to the aqueous phase when AIBN is used as initiator. AN transfers from the aqueous phase to the monomer phase for the polymerization system initiated by LPO. Sodium nitrite (NaNO₂), but not sodium sulfide (Na₂S), can be used to effectively inhibit polymerization in water and exerts less influence on the polymerization in the monomer phase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1431–1438, 2001     

Effect of acrylonitrile water solubility on the suspension copolymerization of acrylonitrile and styrene

Effect of acrylonitrile water solubility on the suspension polymerization of acrylonitile and styrene was investigated. It was found that the copolymer composition produced in the suspension polymerization of acrylonitrile and styrene was significantly different from that in the bulk polymerization at the same monomer feed ratio, since acrylonitrile is partially soluble in water. To predict accurately and then control the copolymer composition in the suspension polymerization, a model to calculate the copolymer composition was proposed based on considering the phase partition of actylonitrile between monomer and aqueous phases. The results calculated by the model are in agreement with the experimental data. The real reactivity ratios in monomer phase used in the model are the same as that in the bulk polymerization, but the apparent reactivity ratios used in the classical theory for the suspension polymerization vary significantly with water/oil ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4270–4274, 2006     

Synthesis and thermoanalysis of emulsion terpolymers of N‐phenylmaleimide,styrene, and acrylonitrile

Terpolymers of N‐phenylmaleimide (PMI), styrene, and acrylonitrile (AN) were synthesized by emulsion polymerization. The thermal properties of terpolymers at different PMI and AN feed contents were investigated by differential scanning calorimetry, torsional braid analysis, thermogravimetric analysis, and a Vicat softening point test. The results showed the glass‐transition temperature and decomposition temperature of the terpolymers increased with increasing PMI feed content. Furthermore, the Vicat softening point of the terpolymers rose with PMI feed content. The weight‐ and number‐average molecular weights (M̄_w and M̄_n) of the terpolymers were also determined by gel permeation chromatography. The results showed that the M̄_w and M̄_n of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. The mechanical properties (tensile strength and impact strength) of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1067–1073, 2001     

Reverse atom transfer radical polymerization of acrylonitrile

FeCl₃ coordinated by succinic acid was used as the catalyst for the first time in azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile (AN). N,N‐dimethylformamide (DMF) was used as a solvent to improve the solubility of the ligand. A FeCl₃ to succinic acid ratio of 0.5 not only gives the best control of molecular weight and its distribution but also provides rather rapid reaction rate. Effects of different solvents on polymerization of AN were also investigated. The rate of the polymerization in DMF is faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agrees reasonably well with the theoretical molecular weight in DMF. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 64.8 kJ mol^?1. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 32–36, 2006     

Encapsulation of aluminum flakes by dispersion polymerization of styrene in a nonaqueous system with reactive surfactants

Dispersion polymerization of styrene in ethanol was carried out to encapsulate aluminum flakes. The effects of three reactive surfactants, two anionic and one nonionic, were investigated. It was confirmed prior to encapsulation that these surfactants did not polymerize by themselves but did promote polymerization of styrene. The capsules obtained were characterized with respect to the morphology and mean size. The encapsulating efficiency of the polymer of the wall material, the wall thickness, and the molecular weight distribution were measured. The effects of the concentrations of styrene monomer and reactive surfactants on these characteristics were determined and discussed. Aluminum flakes were coagulated to form secondary particles and they were covered with fine polymer particles, which were precipitated in the continuous phase. To improve encapsulation, the auxiliary addition of nonionic surfactant was attempted. By controlling those concentrations, capsules covered with polymer layer were prepared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 675–683, 2001     

Mini-emulsion formation and polymerization of styrene

The morphology of an anionic emulsifier/long chain fatty alcohol complex and its change during the formation process were studied. The main factors affecting the morphology, such as various types of anionic emulsifiers and fatty alcohols, their molar ratios and the addition of styrene, were investigated. It was discovered that the rod-like particles of the complex had a length of 0.1 -0-2 μm and diameter of 0.01-0.02 μm. A model of a rod-like particle or molecular aggregate was proposed. Both water-soluble and oil-soluble initiators were used to study the kinetics of styrene mini-emulsion polymerization and polystyrene latex size characteristics.     

氧化还原体系引发苯乙烯乳液聚合

以不同的过氧化物引发剂分别与硫酸亚铁组成氧化还原引发体系,引发苯乙烯的乳液聚合,研究反应温度和还原剂用量等对聚合的影响.采用气相色谱、三检测体积排除色谱、动态光散射对单体转化率、聚苯乙烯的相对分子质量及其分布和乳胶粒径进行了分析.结果表明:升高温度或增加还原剂用量均会使聚合物的相对分子质量增大,聚合反应速率加快,与常规...     

丁二烯丙烯腈聚合过程中间产物性能研究

采用兰州石化公司生产的丁腈橡胶N41乳液聚合配方,考察了聚合反应单体转化率随反应时间的变化,测定了生胶的结合丙烯腈含量、分子质量及其分布、玻璃化转变温度、微凝胶含量和门尼黏度等性能,结果表明:随着转化率的升高,生胶结合丙烯腈含量降低,耐寒性能变好,门尼黏度、相对分子质量及其分布指数升高,当转化率达到86%时,生胶的门尼黏度达到产品指标上限。     

Dispersing behaviour of droplets in suspension polymerization of styrene in a loop reactor

Suspension polymerization of styrene was performed using a loop reactor. The dispersing behaviour of the droplets in the course of the reaction was observed. The mean droplet diameter was determined by the energy level at the impeller region. Moreover, the final particle size distribution and mean particle size were also determined after an elapsed time of 1-2 hrs. An expression which correlated the final mean particle size with the operating conditions, such as the mixing conditions at the impeller region and the initial physical properties of the suspension system, was derived. The deposition of polymers on the reactor wall was found to be prevented due to the high fluid velocity.     

Synthesis,characterization and kinetics of terpolymerization of acrylonitrile,N-vinyl pyrrolidone and styrene

Synthesis of a series of novel terpolymers, consisting of two electron-donating monomers, viz. N-vinyl pyrrolidone (N-VP) (heterocyclic polar monomer) and styrene (Sty) (non-polar monomer), with one electron-accepting polar monomer, i.e. acrylonitrile (AN), using α,α'-azobisisobutyronitrile as radical initiator and benzene as diluent at 60°C, has been extensively surveyed. Besides the synthesis, an attempt has been made to study the kinetics and various properties of the terpolymers, such as softening temperature and chemical resistance. The system follows non-ideal kinetics and the kinetic equation for the present system can be written as This non-ideality can be explained on the basis of significant initiator-dependent termination through primary radicals and degradative chain transfer to acrylonitrile monomer. The overall energy of activation is 72.4 kJ mol^?1 and k_p²/k_t is 0.26 × 10^?3 litre mol^?1 s^?1. The effects of various additives such as imidazolium-p-chlorophenacylide (ICPY) and ZnCl₂ were also studied. ICPY functions as a chain transfer agent (C^tr = 0.43 × 10^?4), whereas ZnCl₂ accelerates the rate of reaction. IR spectroscopy was used to confirm the structure of the terpolymers.     

苯乙烯精馏阻聚剂性能分析及阻聚措施

苯乙烯是一种重要的有机化工原料,也是最基本的芳烃化学品。苯乙烯在生产过程中极易发生聚合,增加了装置的物耗损失,影响装置的安全稳定生产。本文对乙苯脱氢制苯乙烯、碳八抽提苯乙烯两种苯乙烯生产工艺进行了简单介绍,对苯乙烯自由基聚合以及自引发聚合两种聚合反应机理进行研究,对2,4-二硝基苯酚、2,6-二硝基-对甲苯酚、4,6-二硝基-2-仲丁基苯酚、真阻聚剂4种苯乙烯阻聚剂的物化性质、毒性、使用效果进行比较,提出了真阻聚剂与2,4-二硝基苯酚以及真阻聚剂与4,6-二硝基2-仲丁基苯酚的协同阻聚方案,并提出了降低苯乙烯在工艺系统中的停留时间、维持工艺操作温度稳定、减少系统漏氧量、随系统苯乙烯浓度变化及时调节阻聚剂用量等有效的阻聚措施,从而降低聚合物生成,减少阻聚剂消耗,降低装置物耗,增加装置的经济效益。     

Radical polymerization of acrylonitrile initiated by α-picolinium p-chlorophenacylid

The radical polymerization of acrylonitrile (AN) with α-picolinium p-chlorophenacylid (α-PCPY) as initiator using carbon tetrachloride as inert solvent was investigated at 50°C. The polymerization follows ideal kinetics: the exponent values calculated for the initiator and monomer were found to be 0.5 and unity, respectively. A free radical mechanism with bimolecular termination was confirmed by the inhibiting effect of hydroquinone, a radical quencher. The rate of polymerization was a direct function of initiator (α-PCPY) concentraction, monomer (AN) concentration and temperature. The overall activation energy calculated was 56 kJ/mol. The polymerization was favoured by polar solvents and retarded by non-polar solvents.     

Effect of plant gums on thermal polymerization of acrylonitrile

The effect of some plant gums on the polymerization of acrylonitrile (AN) using ceric ammonium nitrate (CAN) as an initiator in the presence of air (containing 21% oxygen) was studied. The induction period and percent conversion were determined. The induction period in the presence of gum was comparatively lower than that under a N₂ atmosphere. The rate of polymerization has a 1.5‐power dependence on the monomer concentration and the rate is sufficiently high at moderate temperature. The rate also increased with an increasing initiator concentration and reaches a maximum value of 93% at 0.72 × 10^?2 mol L^?1 of CAN. The activation energy was found to be 6.4 kcal mol^?1. Both the molecular weight and density of the polyacrylonitrile (PAN) prepared in the presence of gum were higher than those of PAN prepared in the absence of the gum. The PAN produced in the presence of the gum was thermostable than that prepared in its absence. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3596–3600, 2002     

原子转移自由基法合成乙丙橡胶接枝物中的热聚合研究

采用原子转移自由基聚合法(ATRP)合成了三元乙丙橡胶与苯乙烯的接枝共聚物(EPDM-g-St),动力学研究表明聚合过程为“活性”聚合。在接枝聚合过程中发现了明显的苯乙烯热聚合现象。对接枝聚合中得到的均聚苯乙烯进行表征的结果表明,苯乙烯在ATRP接枝体系中的热聚合过程在一定程度上受到ATRP机理的控制;升高温度和延长反应时间使得热聚合更为显著。     

Effects of surfactants on acrylonitrile polymerization initiated by a Cr(VI)–cyclohexanone redox system: A kinetic study

The polymerization of acrylonitrile (AN) was kinetically studied with a Cr(VI)–cyclohexanone (CH) redox system as an initiator from 25 to 45° C in the presence of a surfactant. The rate of polymerization and the percentage of the monomer conversion increased as the concentration of the anionic surfactant [sodium dodecyl sulfate (SDS)] increased above its critical micelle concentration. However, the cationic surfactant (cetyltrimethylammonium bromide) reduced the rate considerably at higher concentrations, whereas the nonionic surfactant (TX‐100) had no effect on the rate. The effects of the Cr(VI), CH, AN, and H⁺ concentrations and the ionic strength on the rates were also examined. The presence of 0.015M SDS reduced the overall activation energy of the polymerization by 5.55 kcal/mol with respect to that in the absence of the surfactant. With increasing SDS concentration, the viscosity‐average molecular weight also increased. A suitable mechanistic scheme was proposed for the polymerization process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1147–1153, 2004     

基于均匀设计的苯乙烯分散聚合反应研究

本文基于均匀设计方法对苯乙烯的分散聚合反应进行了试验设计,并通过回归分析,建立了聚苯乙烯粒子相关性能参数(聚苯乙烯粒子分子量、粒径大小及分布)和各变量(单体浓度、稳定剂用量、引发剂用量和反应介质溶度参数)之间的回归方程。根据回归方程进行了分散聚合反应的配方优化,得到了约束条件下的苯乙烯分散聚合反应配方,实测值与预测值比较结果表明,回归方程的预测值与优化配方制备的PS粒子的各项性能实测值存在一定的偏差(相对偏差在15%以内),但仍对试验配方设计有一定的指导作用。     

Thermodynamic correlation of partial and saturation swelling of styrene-acrylonitrile copolymer particles by styrene and acrylonitrile monomers

The possibility of thermodynamic correlation of partial and saturation swelling of styrene-acrylonitrile (SAN) copolymer particles by styrene (St) and acrylonitrile (AN) monomers is investigated. The unknown Flory-Huggins interaction parameters involved in the thermodynamic swelling equations are estimated by fitting the equations to the experimentally observed monomer concentrations. It is shown that the concentration of each monomer in SAN copolymer particles predicted by using the thermodynamic swelling equations with the parameters and constants estimated in this study agrees fairly well with that observed experimentally over a wide range of experimental conditions. The validity and utility of the parameters and constants estimated from saturation swelling are also demonstrated by showing that the experimental results for partial swelling of SAN copolymer particles by AN monomer dissolved in the aqueous phase agree with those predicted by the thermodynamic equation for partial swelling. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 931–939, 1997     

Microemulsion polymerization of styrene using developed redox initiation system and study of rheological properties of obtained latices

Microemulsion polymerization of styrene was kinetically studied using a potassium persulfate (KPS)/P‐methyl benzaldehyde sodium bisulfite (MeBSBS) adduct as the developed redox pair initiation system. The rate of microemulsion polymerization of styrene was found to be dependent on the initiator, emulsifier, and monomer to the powers of 1.4, −0.77, and 0.83, respectively. The apparent Arrhenius activation energy (E_a) estimated for the microemulsion polymerization system was 6.5 × 10⁴ J/mol. Also, the morphological parameters were studied at different initiator concentrations. The rheological measurements for the prepared microemulsions were carried out to investigate the effect of the preparation parameters on the rheological behavior of the polystyrene microemulsions. The rheological flow curves of the polystyrene microemulsion latices prepared at different temperatures were carried out, and we found that the plastic viscosity and Bingham yield values of the flow curves increased with an increasing reaction temperature. That may be due to the cage effect of the prepared polymer particles, which trapped the medium molecules. The plastic viscosity increased with increasing emulsifier concentration while the Bingham yield value decreased. For the polystyrene microemulsion prepared in the presence of different initiator concentrations, the plastic viscosity and Bingham yield increased with increasing initiator concentration. This trend was found to be the same for the microemulsion latices prepared in the presence of different monomer concentrations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1240–1249, 2000     

A kinetic study on bulk thermal polymerization of styrene

The kinetics of bulk thermal polymerization of styrene over the range of 100–200 °C has been studied based on three stage polymerization model (TSPM) in this paper. TSPM plots showed that the whole polymerization course only exhibits two stages, low conversion stage and gel effect stage, which is consistent with TSPM as the reaction temperature is higher than the glass transition temperature of polystyrene. It was found that the critical conversion, x₁, for the transition from low conversion stage to gel effect stage is independent of the reaction temperature and approximately equal to 0.5. In addition, the apparent reaction rate constants obtained from TSPM plots could be correlated to temperature by Arrhenius equation. Expressions predicting number-average molecular weight were also derived according to TSPM. Using the expressions to treat experimental data available in the literature, it was found that number-average molecular weight is independent of the conversion and relative to the reaction temperature at low conversion stage. However, it varies with the conversions at gel effect stage and the variations are more obvious as the reaction temperature rises.