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     

蒙脱土-有机硅复合改性硅烷化聚氨酯密封胶

采用2,4-甲苯二异氰酸酯、聚醚多元醇、蒙脱土、有机硅(α,ω-二羟基聚二甲基硅氧烷)和硅烷偶联剂为原料,制备了有机蒙脱土/聚醚多元醇复合物(OMMT/330N)-有机硅复合改性的硅烷化聚氨酯(SPU)密封胶。通过广角X射线衍射、透射电子显微镜和傅里叶变换红外光谱手段表征了蒙脱土在复合材料中的分散情况,表征结果显示,有机蒙脱土以平均层间距不小于4.12nm的宽分布分散在SPU基体中。同时对密封胶的力学性能进行测试,测试结果表明,经OMMT/330N-有机硅复合改性的SPU密封胶具有性能互补效果,当添加质量分数为5%(基于330N)的OMMT和8%的有机硅时,复合改性的SPU密封胶的拉伸强度和断裂伸长率比纯SPU密封胶提高了65.8%和71.6%。     

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。     

氟化硅氧烷改性环氧树脂的制备与性能

首先,以全氟(2-甲基-3-氧杂己基)氟化物(六氟环氧丙烷二聚体)和N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(KH792)为原料制备一种氟化硅氧烷,用FTIR和1HNMR表征其结构.然后,将氟化硅氧烷与聚醚胺共同固化环氧树脂DGEBA(双酚A型二缩水甘油醚),测试了改性环氧树脂复合材料的性能.结果表明,与未改性环氧树脂相比,加入氟化硅氧烷使含氟量1％(以DGEBA质量计)改性环氧树脂复合材料的表面静态水接触角由72.0°增至103.2°,表面能由(42.08±2.17)mN/m降至(20.55±1.45)mN/m,40 d吸水率由1.75％降至1.38％,有效提高了材料的疏水性;介电常数由3.83降低至3.63;材料热分解5％温度由339℃升高至347℃;拉伸及弯曲力学性能分别提高了8.5％及7.7％.含氟量为1％时,改性环氧树脂复合材料的综合性能最佳,差式量热扫描和动态力学性能测试结果表明,少量改性剂可以促进环氧树脂的固化反应,提高固化度和交联密度;当氟化硅氧烷添加量增加时,材料内部发生显著的微相分离并导致性能逐渐下降.     

Synthesis and characterization of aromatic copolyesters containing siloxane linkages in the polymer backbone

A new series of aromatic copolyesters containing siloxane linkages were prepared by the melt polymerization of bisphenol A (BPA) with eugenol end‐capped siloxane (EuSi), diphenyl terephthalate (DPT), and diphenyl isophthalate (DPI) in varying ratio in the temperature range 220–290°C under reduced pressure in the presence of dibutyl tin dilaurate (DBTL) catalyst. The siloxane copolyesters prepared were characterized by FTIR, ¹H‐NMR spectroscopy, solution viscosity, thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction. The effect of incorporation of eugenol end‐capped siloxane was studied on the properties of BPA/DPI/DPT copolyesters. The glass‐transition temperature of copolyester was decreased from 184 to 70°C by incorporation of 20% of eugenol end‐capped siloxane. All copolyesters were found to be soluble in commonly used aprotic polar solvents and had film‐forming properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3222–3228, 2006     

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.     

Oligomer and Polymer Formation in Hexamethylcyclotrisiloxane (D<Subscript>3</Subscript>) – Hydrosilane Systems Under Catalysis by tris(pentafluorophenyl)borane

Summary Reactions of hexamethylcyclotrisiloxane, D₃, with 1,1,3,3-tetramethyldisiloxane, ^HMM^H, 1,1,1,3,3-pentamethyldisiloxane, ^HMM, phenyldimethylsilane and phenylmethylsilane catalyzed by tris(pentafluorophenyl)borane were studied. These reactions lead to ring opening of D₃ by the SiH reactant producing open chain oligomers with hydrosilane functionality at one or both chain ends. The reactivity of the hydrosilanes toward D₃ decreases in the series: PhMeSiH₂ > ^HMM^H > PhMe₂SiH > ^HMM. Competitive self-oligomerization of ^HMM^H and ^HMM also occurs. Primary products of these processes are able to enter into reactions with the SiH and D₃ reactants; some also undergo cyclization. Thus, consecutive and competitive processes lead to a series of various oligohomologues. Gas chromatography in conjunction with chemical ionization mass spectroscopy permitted identification of structure and determination of the basic directions of these oligomerization processes. Polysiloxanes of higher molecular weight may be also formed in some of these systems. The reactions, which occur in the systems studied, are rationalized on the basis of the mechanism involving the hydride transfer from silicon to trivalent boron. This includes the transient formation of tertiary trisilyloxonium borate which decomposes by the hydride transfer to one of the silicon atoms of the trisilyloxonium center. Footnote: This paper is dedicated to Professor Ian Manners in recognition of his significant contributions to the field of organometallic polymers.