The effect of segment length on some properties of thermoplastic poly(ester–siloxane)s

A series of novel thermoplastic elastomers, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) (PBT) as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reactions of dimethyl terephthalate and methyl esters of carboxypropyl‐terminated poly(dimethylsiloxane)s (M?_n = 550–2170 g mol^?1) with 1,4‐butanediol. The lengths of both the hard and soft segments were varied while the weight ratio of the hard to soft segments in the reaction mixture was maintained constant (57/43). The molecular structure, composition and molecular weights of the poly(ester–siloxane)s were examined by ¹H NMR spectroscopy. The effectiveness of the incorporation of the methyl‐ester‐terminated poly(dimethylsiloxane)s into the copolymer chains was verified by chloroform extraction. The effect of the segment length on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as the degree of crystallinity and hardness properties of the synthesized TPESs, were studied. Copyright © 2003 Society of Chemical Industry     

二-(4-羟基丁基)四甲基二硅氧烷的合成研究

采用一步法以二甲基二氯硅烷、四氢呋喃和金属镁粉为原料,在碘乙烷和单质碘催化下合成二-(4-羟基丁基)四甲基二硅氧烷。产物温合物减压过滤,以除去镁盐。滤液无需蒸馏提纯,而直接水解,干燥,减压蒸馏,收集71℃/1333Pa馏份。还探讨和优化合成条件:四氢呋喃与二甲基二氯硅烷之摩尔比应大于3.5;Grignard反应停止后应继续加热回流1小时;蒸馏时系统压力为1333Pa。     

两性乳化剂体系对有机硅改性丙烯酸酯乳液合成的影响

采用新型琥珀酸类两性乳化剂(A1)与非离子乳化剂壬基酚聚氧乙烯醚(CA407)复配体系,合成了有机硅γ-甲基丙烯酰氧基丙三甲氧基硅烷(A174)改性的丙烯酸酯乳液。系统研究了两性乳化剂体系与非离子乳化剂复配比例、用量及乳化剂在种子乳液与预乳液中分布比例(R/F)E对乳液聚合及其性能的影响。研究表明:乳化剂配比m(A1)∶m(CA407)=30∶70时,乳液聚合稳定性及抗电解质稳定性较好;乳化剂用量越大,乳胶粒径越小,粒径分布越宽,乳液黏度越大,涂膜吸水率也越大;乳化剂在种子乳液与预乳液中的分布比例主要影响乳液聚合的稳定性。同时通过TEM乳胶粒形态分析及DSC涂膜的玻璃化转变温度分析认为,A174主要在乳液聚合时分布在乳胶粒表面,易水解交联。     

有机硅改性丙烯酸酯核-壳结构压敏胶聚合物乳液的研制

采用种子乳液聚合的方法制备了一种新型具有核/壳结构的有机硅改性丙烯酸酯压敏胶聚合物乳液,讨论了多官能团有机硅氧烷功能性单体、核壳单体结构、乳化剂、引发剂以及聚合温度等因素对压敏胶聚合物乳液性能的影响。     

The Influence of Diphenyl Siloxane on Morphology and Physical Properties in the Poly(Imide Siloxane)(PIS) Copolymer

Various numbers of diphenyl-siloxane groups were incorporated in α,ω-bis(aminopropyl)polydimethylsiloxane (APPS) to prepare α,ω-bis(aminopropyl)-polydimethyldiphenylsiloxane (APPPS) oligomers of three different number-average molecular weights(Mn = 547,772,1210 g mol⁻¹).These APPPS oligomers were than used, together with 3,3′,4,4′-bezonphenone tetracarboxylic dianhydride (BTDA) and 2-2′-bis[4-(3-aminophenoxy)phenyl] sulfone (m-BAPS), to synthesize a series of APPPS containing poly(imide siloxane) (PIS) copolymers. Microstructural studies showed that at certain APPPS content, a critical microphase separation point existed, beyond which, microphase separation began to develop. This critical point of microphase separation was found to be affected by the Mn of the APPPS oligomers (8.0, 4.3 and 2.1 mol% for Mn of 547, 772 and 1,210 g mol⁻¹, respectively). Diphenyl-siloxane significantly improved compatibility between polyimide and polysiloxane segments. Physical studies showed that the introduction of diphenyl siloxane changed the thermal stabilities and mechanical properties of the PIS copolymers. These findings have potential applications for design purposes in engineering polymers.     

Controlled destruction of residual crosslinker in a silicone elastomer for drug delivery

In drug delivery systems that use silicone elastomers as a diffusion matrix for the active drug, it is common to crosslink the material by the hydrosilylation reaction. In this platinum‐catalyzed reaction, vinyl groups on a polymer add to the methyl siloxane hydride (MHS) groups on a low molecular mass crosslinker. With an excess of crosslinker, a fast curing is achieved and a fully crosslinked material is formed. Unreacted MHS groups were shown to remain in the elastomer after curing because of the excess crosslinker. In this work, a simple procedure was developed to eliminate the unreacted MHS groups from the final product. We found that storage of the product at +40°C and 75% relative humidity for a few weeks will effectively destroy the residual MHS groups in the elastomer. The effects of varying levels of humidity, oxygen, and temperature on this postcuring procedure were studied. The amount of MHS groups was measured with NMR and IR spectroscopy. We also found that the hardness of the material increased by approximately 25% as a consequence of this postcuring treatment. This increase is probably due to a secondary crosslinking reaction between MHS and silanol groups. Heat treatment at higher temperatures led to an even further increase in the hardness and compression modulus. Because no MHS groups remained in the elastomer when this heat treatment was started, it is apparent that another secondary crosslinking reaction is occurring, probably silanol condensation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2254–2264, 2002     

含二苯甲酮基的有机硅光引发体系

在UV照射下,用含巯基的有机硅化合物与聚甲基乙烯基硅氧烷加成硫化虽有专利报道,但该反应体系是以二苯甲酮类化合物作为光敏剂。当我们进行这方面研究时,发现二苯甲酮与有机硅氧烷预聚物相容性差,从而影响光加成反应的速度。为了改善光敏剂与有机硅预聚物的相容性,本文合成了具二苯甲酮基团的环状有机硅氧烷及其高聚物作为光敏剂。我们的合成路线是用硅氢加成反应,制备了文献没有报道的具二苯甲酮侧基的环状硅氧烷,然后将其与八甲基环四硅氧烷一起进行开环聚合,得到了具有二苯甲酮侧基的聚有机硅氧烷,其反应过程如下:     

高支化含无机粒子的巯基硅氧烷溶胶的制备及结构表征

用溶胶-凝胶法制备了一种新型的多功能巯基硅氧烷溶胶,其结构用1H-NM R,FT-IR和M S进行了表征,巯基硅氧烷溶胶的无机粒子粒径大小与分布用小角度光散射仪(SALS)进行了测定。这种新型巯基硅氧烷溶胶能够提高改性亚麻籽油体系自由基聚合速率。     

有机硅-丙烯酸酯水分散液的合成及表征

以端乙烯基硅氧烷齐聚物(NS)、甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为原料,通过乳液共聚合,制备了有机硅-丙烯酸酯二元共聚水分散液。考察了不同单体配比对水分散液及成膜物性能的影响。通过动态光散射仪、透射电子显微镜等对水分散液进行了表征,发现共聚物乳胶粒子粒径较小,均在30nm～60nm范围;水分散液成膜物透明、光滑、力学性能好。当共聚物中有机硅含量达到10%(质量分数,下同)时,成膜物对水的接触角已超过100°,接近纯有机硅的接触角,表明端乙烯基硅氧烷齐聚物的引入赋予了薄膜良好的表面拒水性能。