The influence of monomer types on the colloidal stability in the miniemulsion copolymerization involving alkoxysilane monomer

Unlike conventional emulsion polymerization, monomer droplet nucleation becomes dominant in miniemulsion polymerization, offering the miniemulsion polymerization a great advantage over conventional emulsion polymerization when incorporating alkoxysilane monomer, which can easily undergo premature hydrolysis and condensation reactions, into polymer latex. The extensive premature hydrolysis and condensation can lead to the issue of the colloidal instability. In this article, the influence of monomer types on the colloidal stability in the miniemulsion co-(or ter-)polymerization was investigated when incorporating alkoxysilane monomer into styrene or acrylate latex. In the cases of butyl acrylate (BA)/γ-methacryoxypropytrimethoxysilane (MPMS), BA/methyl methyacrlate (MMA)/MPMS, and BA/styrene (St)/MPMS miniemulsion polymerization, nearly no coagulum was observed. The obtained latex had a long shelf life. However, the coagulum was formed in the late stage of MMA/MPMS and St/MPMS miniemulsion copolymerization. The shelf life of the corresponding latex was short. The selection of the main monomer, which can fast consume alkoxysilane comonomer, was critical to obtain the stable latex. In this way, the alkoxysilane groups were completely buried in particles thus the coagulation caused by condensation reactions derived from the alkoxysilane hydrolysis among particles was suppressed.     

超低聚合度PVC树脂的生产状况及应用

介绍了超低聚合度PVC树脂的生产状况、应用领域及聚合时应注意的问题,并比较了国内与国外超低聚合度PVC树脂的基本物性.     

超临界烯烃聚合

论述了超临界流体对烯烃聚合的影响，总结了超临界聚合技术的研究与应用。认为：在单体临界点以上进行的超临界聚合技术的研究开发已比较成熟；而新近开发的超临界流体介质中的烯烃取合技术更为重要，可以充分发挥超临界技术的优点，提高聚合产率，并能制备性能特殊的取合物。特别是采用超临界CO2为介质的聚合过程，为实现烯烃聚合的绿色生产奠定了基础。     

Polyamide‐6‐b‐polybutadiene block copolymers: Synthesis and properties

Polyamide‐6 (PA6)/polybutadiene (PB) block copolymers were synthesized with macroactivators (MAs) based on hydroxyl‐terminated polybutadiene functionalized with diisocyanates and having three N‐acyllactam chain‐growing centers per molecule. Two different diisocyanates, hexamethylene diisocyanate and isophorone diisocyanate, were applied as precursors for the MAs. The sodium salt of ε‐caprolactam was chosen as an initiator. The influence of the MA type and concentration on the anionic ring‐opening polymerization of ε‐caprolactam at 180°C was studied. A large percentage of the gel fraction in the copolymers was estimated, indicating crosslinked macromolecules. The structure and phase behavior of the copolymers were investigated with differential scanning calorimetry, wide‐angle X‐ray scattering, thermogravimetric analysis, and dynamic mechanical thermal analysis. In the copolymers, only the PA6 chains crystallized, and the crystallinity depended on the PB content. Different glass‐transition temperatures for the PB blocks and PA6 blocks were observed, indicating microphase separation in the copolymers. The mechanical properties of the copolymers were studied by notched impact testing and hardness measurements. The impact strength increased linearly with the soft component concentration up to 10 wt % and reached values six times higher than those of the PA6 homopolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 711–717, 2003     

In situ formation and compounding of polyamide 12 by reactive extrusion

The anionic polymerization of lauryllactam was initiated at 270°C using sodium hydride as an initiator and N,N′‐ethylene‐bisstearamide (EBS) as an activator (NaH:EBS molar ratio of 2). Polymerization occurred in less than 2 min and was successfully performed in an internal mixer and a twin‐screw extruder with corotating intermeshing screws (Werner & Pfleiderer ZSK 25). The content of residual monomer, as determined by thermogravimetric analysis, was lower than 0.5 wt %. Molecular weight, as measured by size exclusion chromatography, was governed by the lauryllactam:NaH molar ratio calculated on a M_n of 25 kg/mol at a constant NaH:EBS molar ratio of 2. Blends were prepared in situ by polymerization of lauryllactam solutions of various polymers. When poly(ethylene‐co‐butylacrylate) (Lotryl®; Atofina) was dissolved in lauryllactam, rubber‐toughened polyamide 12 blends were obtained. Mechanical properties of the injection‐molded polymers were examined by stress–strain as well as notched Charpy impact tests at different temperatures. Blend morphologies were imaged by scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 344–351, 2003     

有机硅改性丙烯酸乳液性能的研究

采用含乙烯基官能团的有机硅单体与甲基丙烯酸酯、丙烯酸酯和丙烯酸羟基酯等单体通过种子乳液聚合方法进行共聚,合成了有机硅改性丙烯酸酯共聚乳液,考察了有机硅单体用量对乳液机械稳定性、热稳定性、电解质稳定性和冻融稳定性的影响,同时还考察了乳液胶膜的机械性能和吸水率改进。     

聚乳酸-聚氨酯微球的合成及其形态的研究

以低相对分子质量生物可降解D，L-聚乳酸(D，L-PLA)二醇和六亚甲基二异氰酸酯(HDI)为原料、1，4-丁二醇(BD)为扩链剂及聚乙烯基吡咯烷酮(PVP)为悬浮剂，通过悬浮聚合法初步合成了一种新型聚氨酯微球(PUMS)。用扫描电子显微镜(SEM)考察了BD的含量对微球表面形态的影响，通过激光粒度分析仪讨论了搅拌速率和PVP浓度对微球粒径及其分布的影响，用傅立叶变换红外光谱(FTIR)粒度分析仪对微球的化学结构进行了表征。结果表明，合成的微球的平均粒径随搅拌速率和PVP浓度的增加而减少，粒径分布变宽；当搅拌速率为400r／min，PVP质量分数为1．5％时。微球的平均粒径约47μm，粒径分布最窄。约在10～90μm；微球表面有孔，但随着BD含量的增加，微球表面变得相对粗糙，孔数减少，孔径减小，直至孔消失。     

乳液聚合中单体醋酸乙烯酯与保护胶体聚乙烯醇的接枝反应研究

研究了以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,聚乙烯醇与单体的接枝反应。探讨了引发剂用量、聚合反应温度、保护胶体聚合度等因素对接枝反应的影响。     

Adsorption of block copolymers at latex surface and their utilization in emulsion polymerization

Amphiphilic block copolymers have been investigated for their utilization in emulsion polymerization of butyl methacrylate. Special attention has been paid to the adsorption mechanism of the block copolymers from systematic measurements of equilibrium adsorption isotherms. A series of well-defined water-soluble amphiphilic block copolymers, composed of poly(butyl methacrylate) and poly(sodium methacrylate) blocks, were synthesized by anionic polymerization of butyl methacrylate and tert-butyl methacrylate followed by the thermal deprotection of the tert-butyl ester groups and final hydrolysis. The number density of emulsion polymer particles N_P varied as [copolymer]^α, α lying between 0.44 and 0.73 according to the hydrophilic content of the copolymers. In contrast with SDS taken as a reference emulsifier, the adsorption of the copolymers was very strong and this provided quite an efficient stabilization of the polymer particles during emulsion polymerization, even at low concentrations (<10⁻⁴ mol L⁻¹) and low coverages (<10% of the interfacial area).     

羧基偏氯乙烯丁苯胶乳粒子的相态结构和应用性能

以过硫酸铵为引发剂，十二烷基硫酸钠为乳化剂，采用种子聚合工艺，合成了偏氯乙烯质量分数为２３％～４３％的羧基偏氯乙烯丁苯胶乳。通过电镜观察到所合成的胶乳粒子具有核－壳结构。通过测定胶闰子表面层的羧基数量，研究了羧基的分布，结果表明，羧酸种类对羧基在胶乳粒子中及在聚合体系中的分布有重要影响，该胶乳作为地毯背衬粘合剂，具有粘合力高，极限氧指数高的特点，是一种较好的阻燃性粘合剂。