Modelling of addition polymerization processes — Free radical,ionic, group transfer,and ziegler–natta kinetics

A brief review of addition polymerization processes is presented with a summary of the key characteristics classified by kinetic mechanism (free-radical, anionic, cationic, group transfer, or Ziegler–Natta), phase behavior, and reactor type. A practical approach to modelling in the industrial R & D environment is discussed in terms of a CAD package for polymerization processes.     

Effects of processing conditions on the curing of a vinyl ester resin

The effects of temperature, initiator, and accelerator levels on the curing of an epoxy bisphenol‐A vinyl ester resin Derakane® 411‐45 (formulated with styrene) were investigated by gel‐time and exotherm‐peak measurements on bulk samples. It was observed that the gel time was reduced as the initiator or accelerator ratio increased. Except at higher contents of the accelerator, a small kinetic plateau was seen in the gel curve and a shift of the maximum exotherm toward high temperatures in the DSC curves. This was explained by the dual role played by the accelerator species. A regression analysis of all gel‐time data showed a dependence of 3/2 order in the accelerator and first order in the initiator concentrations. Thus, for this polymerization initiation system, the gel time can be predicted for any initiator and cobalt levels and at any temperature within the ranges studied. The effect of the initiator on the unreacted styrene and vinyl ester was also examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1146–1154, 2002; DOI 10.1002/app.10403     

Radiation polymerization of acrylonitrile in a viscous system with styrene

Radiation polymerization of acrylonitrile in a viscous system with styrene was performed at ambient temperature by using γ‐rays. It is found that the overall rate of polymerization was accelerated after critical conversion due to the gel effect. As the molar fraction of styrene in monomer feed (f_St) is increased, both the total polymer conversion and molar fraction of acrylonitrile in the copolymer feed (F_AN) were decreased. The monomer reactivity ratios for acrylonitrile and styerne were determined to be r₁ (AN) = 0.25 and r₂ (St) = 2.0, respectively. The copolymers obtained were characterized by Fourier transformed infrared spectra (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), ¹H‐NMR, and pyrolysis mass spectrometry (PMS). It was found that the slight addition of styrene to acrylonitrile strongly changes crystallinity, morphology, and thermal decomposition of the resulting polymer. ¹H‐NMR measurment of AN/St copolymer showed the appearance of aromatic proton signals and shifted the resonance of the methylene proton to lower chemical shifts. The mass spectra of AN/St copolymers showed fragments of pyrolysates corresponding to oligonitriles with styrene end groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 268–275, 2002; DOI 10.1002/app.10324     

高分子量阴离子型聚丙烯酰胺的制备

介绍了聚丙烯酰胺的品种、性能及用途；研究了以丙烯酸为共聚单体，采用反相乳液聚合制备高分子量阴离子型聚丙烯酰胺胶乳的原理和方法；分析讨论了原料纯度、乳化剂和引发剂种类及操作条件等因素对产品性能的影响．     

气相聚合流化床内静电与结片现象的研究进展

综述了气相聚合流化床内静电及结片现象的研究进展,对流化床内结片现象进行了描述,将静电与流化床的壁面结片现象关联,并从流化床流体力学行为与静电生成速率的关系出发对静电的生成机理进行了论述。通过对流化床内静电分布分析,确定了流化床内静电积累和消散的位置。提出了流化床内静电检测、静电产生机理、静电信号与工业流化床中结片现象关联等有待继续研究的方向和领域。     

离子液体催化C_5馏分中二烯烃的聚合反应

合成了多种基于1-丁基-3-甲基咪唑阳离子的离子液体,并作为裂解C5馏分中混合二烯烃聚合反应的介质。考察了离子液体种类、反应温度、反应时间和添加Lew is酸对混合二烯烃聚合反应的影响。实验结果表明,以硝酸根为阴离子的离子液体对混合二烯烃的聚合反应具有一定的阻聚作用;以六氟磷酸根为阴离子的离子液体能明显促进混合二烯烃的聚合反应,提高二聚物的含量;添加Lew is酸(质量分数为1%的ZnCl2)的离子液体对混合二烯烃的聚合反应具有更明显的促进作用,其效果仅次于酸性氯铝酸类离子液体,反应温度以30℃以下为宜,温度过高将促使二聚物进一步聚合,形成三聚物乃至多聚物,降低二聚物的含量。     

Photoinitiated cationic polymerization using a novel phenacyl anilinium salt

A novel phenacyl anilinium salt, N-phenacyl, N,N-dimethylanilinium hexafluoroantimonate, (PDA), has been synthesized and used as photoinitiator for cationic polymerization of cyclohexene oxide (CHO), butyl vinyl ether (BVE) and N-vinyl carbazol (NVC). Plausible mechanism of the photoinitiation involves the decay of the excited PDA with both heterolytic and homolytic cleavages of carbon-nitrogen bond. Thus, phenacylium cations formed directly or subsequent intermolecular electron transfer, respectively, initiate the polymerization.     

PVA平均聚合度波动因素分析及优化控制

针对聚乙烯醇 (PVA)聚合反应过程中 ,平均聚合度波动的实际问题 ,在对聚合反应工艺、反应机理进行理论分析的基础上 ,找出了影响平均聚合度波动的主要因素 ,并逐一分析了对平均聚合度影响的情况 ,在理论和实验基础上找出了在多品种PVA生产中各主要因素变化对平均聚合度变化的规律 ,提出了包括运用先进仪表控制手段在内的优化控制措施和处理办法     

种子乳液共聚法制备含氢聚甲基硅氧烷/丙烯酸酯织物涂层剂

以丙烯酸丁酯 ( BA)、丙烯酸乙酯 ( EA)、含氢聚甲基硅氧烷 ( PHMS)、甲基丙烯酸甲酯 ( MMA)、丙烯腈( AN)为主单体 ,丙烯酸 ( AA)等为功能单体 ,N 羟甲基丙烯酰胺 ( NMA)等为交联剂 ,采用种子乳液共聚法制备了自交联织物涂层剂。经实验确定最佳反应条件为 :m( BA) / m( EA) / m( PHMS) / m( MMA) / m( AN) =6 .8/0 .5 / 0 .7/ 1 .2 / 0 .8,AA、交联剂、乳化剂和引发剂的用量分别为单体总质量的 3%、4 %、4 %和 0 .3% ,种子和外壳的反应温度分别为 78℃和 82℃ ,反应时间分别为 4 h和 6 h。应用实验结果表明 ,乳液胶膜拉伸强度可达2 .1 3MPa,涂层织物抗静水压可达 6 .85 k Pa,透湿量 ( 2 4 h)达 5 6 1 5 g/ m2。     

丙烯酰胺-二甲基二烯丙基氯化铵反相微乳液体系的制备及表征

采用石油醚为连续相、失水山梨糖醇酐单油酸酯(Span80)和聚氧乙烯失水山梨醇单硬脂酸酯(Tween80)为复合乳化剂、正己醇为助乳化剂,建立了丙烯酰胺(AM)和二甲基二烯丙基氯化铵(DMDAAC)反相微乳液体系。使用Zeta电位/粒度/相对分子质量分析仪对该体系的形成及聚合过程中乳胶粒子粒径及其分布进行了测试。实验结果表明,当体系达到微乳液状态时,体系主要由10~100nm的单体微珠及少量粒径小于10nm的胶束组成;随聚合过程的进行,胶束消失,乳胶粒子体积增大。乳胶粒子体积的增大主要是通过扩散和碰撞两种机理完成的。最佳的复合乳化剂亲水-亲油平衡值为8.045,复合乳化剂在油相中的质量分数为33%,助乳化剂在油相中的质量分数为1.6%。在此条件下达到微乳液状态时的水相增容体积最大。