新型过氧化物引发剂引发氯乙烯悬浮聚合动力学

研究了新型过氧化物引发剂过氧化新癸酸 1,1 二甲基-3-羟基丁基酯(Lup 610)在51.3与56.8℃以及过氧化新庚酸叔丁酯(Lup 701)和过氧化新戊酸叔己酯(HPV)在61.8℃单一引发剂引发氯乙烯悬浮聚合动力学,并采用模型计算结果绘制转化率 时间曲线,取与实验数据符合最好的f值作为引发剂的引发效率,求得引发剂Lup 610在51.3与56.8℃的引发效率分别为0.80与0.75,引发剂Lup 701和HPV在61.8℃下的引发效率分别为0.55和0.50。研究了上述引发剂与过氧化二碳酸二(2-乙基己酯)、过氧化新癸酸叔丁酯在各温度下复合引发剂引发氯乙烯悬浮聚合的动力学,与模型值相比较,发现两者能很好吻合。     

氯乙烯聚合用引发剂的研究

在研究单一引发剂分解动力学的基础上,提出复合引发剂分解动力学模型,并结合ＶＣＭ聚合动力学,为恒速聚合的复合引发体系的配方设计提供指导。     

复合引发剂存在下的氯乙烯聚合动力学

Kinetic models for the rate constants of vinyl chloride polymerization in the presence of initiator mixtures were proposed. They may be used to design the initiator recipes for the vinyl chloride polymerization with uniform rate at different temperatures at which various grades of poly(vinyl chloride) will be prepared.     

新型引发剂在氯乙烯悬浮聚合中的应用试验

通过试验,对过氧化新戊酸叔己酯与偶氮二异庚腈两种引发剂在氯乙烯悬浮聚合中的应用进行了比较.结果表明:过氧化新戊酸叔己酯的反应活性和相对分子质量比偶氮二异庚腈略低,水溶性略大;在相同条件下,过氧化新戊酸叔己酯的残留率高;在用量(物质的量)相同的条件下,二者使用效果相当.     

缩短氯乙烯悬浮聚合时间的动力学研究

研究了有机过氧化物引发剂引发氯乙烯悬浮聚合的过程和影响因素,给出了不同温度、不同引发体系的聚合动力学试验数据和聚合时间-转化率、聚合时间-转化速率曲线．讨论了不同引发体系对PVC树脂质量的影响。试验结果表明：采用适宜的复合有机过氧化物引发剂可缩短聚合时间1h,提高聚合釜的生产能力。     

氯乙烯悬浮聚合复合引发剂体系的中试研究

提出了生产3种牌号PVC树脂的复合引发剂配方。中试结果表明:采用悬浮法生产S-700、S-1000和S-1300 PVC树脂时宜分别采用Tx-36和Tx-23、EHP和Tx-99、Tx-99和Tx-23复合过氧化物引发剂体系,聚合时间可控制在3.2~3.8 h,反应过程平稳,反应速率快,生产的PVC树脂质量优良。     

引发剂对氯乙烯微悬浮聚合转化率和聚氯乙烯粒径分布的影响

分别采用水溶性过硫酸铵(APS)和油溶性偶氮二异庚腈(ABVN)引发剂进行氯乙烯(VC)微悬浮聚合,并与APS引发的VC乳液聚合以及ABVN引发的VC悬浮聚合情况进行比较,考察了引发剂类型对聚氯乙烯(PVC)乳胶粒子粒径分布和增塑糊流变特性的影响。结果表明:引发剂浓度相同时,VC微悬浮聚合转化率大于悬浮聚合,而小于VC乳液聚合;APS引发微悬浮聚合得到的PVC乳胶粒子存在数目较多的纳米级粒子,而ABVN引发微悬浮聚合得到的PVC基本不存在纳米级粒子;引发剂和分解产生的初级自由基在水相/油相/胶束中的分配和成核机理不同是导致上述差异的主要原因。ABVN引发微悬浮聚合得到的PVC树脂成糊后呈剪切增稠特性,而APS引发微悬浮聚合得到的PVC树脂成糊后呈剪切变稀特性,且糊黏度较大。     

氯乙烯悬浮聚合过程引发体系优化

在氯乙烯悬浮聚合过程机理模型的基础上,建立了复合引发体系的优化模型,并进行了二元引发体系的优化研究,得到了不同引发剂配比下的最大聚合速率等高线和临界转化率时的聚合时间等高线。结果可以用来指导复合引发剂的配方设计,有助于聚合热的均匀释放、聚合釜冷却能力的充分利用和聚合釜生产率的提高。     

新型高效引发剂过氧化二碳酸二（十六烷酯）在氯乙烯悬浮聚合中的工业性应用

1 前言 随着聚氯乙烯工业的迅速发展,越来越迫切地需要综合性能优良的引发剂,即活性高,放热均匀,易贮运。在我国的氯乙烯悬浮聚合中,普遍使用的高效引发剂为EHP(过氧化二碳酸—2乙基己酯)。EHP虽然活性高,放热均匀,但它在常温下为液体,易分解,保存和运输较难。许多聚氯乙烯生产     

聚合引发剂有机过氧化物

有机过氧化物可用作聚合引发剂。本文介绍了有机过氧化物的特性、在聚合中的引发作用、品种的选择,以及对聚合物性能的影响。     

Continuous dosing of fast initiator during vinyl chloride suspension polymerization: Polymerization rate and PVC properties

Continuous dosing of a fast initiator during the suspension polymerization of vinyl chloride has been carried out in a pilot‐scale reactor. The kinetics course of this polymerization and the particle features of the resulting grains were discussed and compared to the conventional polymerization with the same conversion and maximum reaction rate. It was found for the system used that a suitable dosage trajectory allows the reaction rate to remain constant during polymerization. This decreases the polymerization time up to 53% compared with the conventional suspension polymerization, while the molecular weight distribution and molecular weight of the final grains remained almost unchanged. SEM micrographs revealed that PVC grains prepared using this polymerization process had irregularly shaped, uneven particle surfaces and larger particle sizes. The grains also featured high porosity with loosely aggregated smaller primary particles that led to low levels of residual unreacted monomer. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44079.     

Experimental investigation of vinyl chloride drop behavior during suspension polymerization

The effects of some polymerization conditions on poly(vinyl chloride) (PVC) particles produced by the suspension polymerization process were studied on a laboratory scale. The different stages of vinyl chloride suspension polymerization were investigated experimentally by using an on-line sample withdrawal technique during reaction. It was found that the method of addition of initiator has a great effect on the PVC particle uniformity as well as the size distribution. Furthermore, when the initiator was predispersed in the continuous phase, some latex particles were formed. The effect of the type of stabilizer was also studied with two different types of PVA [partially hydrolyzed poly(vinyl acetate)]. It was found that by changing the stabilizer, the particle size, the porosity, and the morphology could change. When H80 (PVA with a degree of hydrolysis of 80% and a molecular weight of 259,000) stabilizer was used, the rigidity of the PVC particles was weak. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 127–134, 1997     

无机添加剂对氯乙烯悬浮聚合的影响

研究了添加未改性和表面改性的无机热稳定剂和CaCO3对氯乙烯悬浮聚合过程的影响,发现采用硅烷和铝酸酯改性无机热稳定剂和采用硬脂酸改性CaCO3,可以达到良好的表面有机改性效果．改性剂最佳质量分数为1．0％左右;热稳定剂对聚合起延缓作用,使一定压降(AP)时的聚合时间增加5～120min、转化率下降3．6％～17．5％;但经表面改性后,对聚合的延缓作用减弱;CaCO3使聚合△P提前10～20min,使一定△P时的聚合转化率下降2．4％～17．5％,但对实际聚合速率的影响不大。     

Influences of some polymerization conditions on particle properties of suspension poly(vinyl chloride) resin

Effects of polymerization temperature, conversions, and nonionic surfactant on the particle properties of suspension poly(vinyl chloride) (PVC) resins were investigated. It was shown that polymerization temperature has no significant influences on the mean particle size of PVC resin, and that the cold plasticiser absorption (CPA) of resin decreases linearly with the increase of polymerization temperature. Agglomeration of VCM droplets finishes before 20% conversion, and the mean particle size keeps almost constant at later stages of the polymerization process, but the CPA continues decreasing with the increase of conversion. Scanning Electron Microscopy (SEM) micrographs show that the degree of agglomeration of primary particles increases with polymerization temperature and conversion. Addition of nonionic surfactant to the VCM suspension system, as a secondary suspending agent, has a great influence on the particle properties of PVC resin. The particle size and CPA increase as the concentration of nonionic surfactant increases. The nonionic surfactant with a greater HLB value is more effective in raising the mean particle size, but is less effective in raising the CPA. It is considered that the added nonionic surfactant would be absorbed faster on the VCM/water interface than the poly(vinyl alcohol) (PVA), which was used as the primary suspending agent. Because the colloid protection ability of the nonionic surfactant is less than that of PVA, droplets become less resistant to coalescence, and the mean particle size of the final PVC resin increases consequently. The increase of porosity is caused by the combined effects of increased coalescence of VCM droplets and the nonionic surfactant's steric effect inside the droplets. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1544–1552, 2002