聚甲基环戊二烯基硅烷及其共聚物的合成与表征

用钠试剂法合成了甲基环戊二烯基二氯硅烷,采用钠缩合法将其均聚,并分别与二甲基二氯硅烷、二苯基二氯硅烷、甲基苯基二氯硅烷及甲基正丁基二氯硅烷进行共聚反应,合成了5种聚硅烷。并用IR、UV、^1H NMR、GPC和荧光光谱对它们进行了表征。     

甲基苯乙基二氯硅烷和甲基环己基二氯硅烷的合成

利用改进了的铂催化剂的硅氢化反应,合成了符合反马氏规则加成的甲基苯乙基二氯硅烷和甲基环己基二氯硅烷。使用紫外灯照射和提高反应温度等手段使甲基环己基二氯硅烷的反应时间大大缩短。两者的产率分别达87%和91%。用IR谱等方法分析了该催化剂可能为含有醛、醚的P_t(Ⅱ)络合物。     

聚甲基氢硅烷及其共聚物的合成及发光性能的研究

以甲基二氯硅烷,二甲基二氯硅烷,二苯基二氯硅烷及甲基乙烯基二氯硅烷为原料,采用钠缩合法合成了聚甲基氢硅烷及聚甲基氢硅烷与聚二甲基硅烷,聚二苯基硅烷和聚甲基乙烯基硅烷的共聚物,并用IR,UV,1HNMR,GPC进行了表征。     

二茂铁高温催化合成甲基苯基二氯硅烷的研究

以二茂铁为催化剂先驱体、氯苯与甲基氢氯硅烷为反应物,采用气相缩合法合成了甲基苯基二氯硅烷。研究了二茂铁用量对甲基苯基二氯硅烷含量的影响。气质分析表明:产物中主要含甲基三氯硅烷、苯、氯苯、甲基苯基二氯硅烷、联苯等。适量添加二茂铁能显著提高产物中甲基苯基二氯硅烷的含量,添加10 g二茂铁(占原料质量的0.88%)时,产物中甲基苯基二氯硅烷的质量分数达到20.73%,比未加二茂铁时提高了16.77个百分点;但不宜过多,否则管式反应器会发生严重堵塞。     

甲基苯基二氯硅烷的合成及应用研究进展

概述了甲基苯基二氯硅烷的合成方法,着重介绍了以甲基苯基二氯硅烷为原料制备硅树脂、硅油、硅橡胶的方法,以及产品的种类、性能、主要用途.     

聚甲基四苯基苯硅烷的合成及非线性光学性质的研究

在甲苯中，将甲基四苯基苯二氯硅烷与金属钾反应，或甲基四苯基苯二氯硅烷分别与甲基乙烯基二氯硅烷、甲基苯基二氯硅烷、二甲基二氯硅烷和二苯基二氯硅烷按摩尔比１∶１混合，再与金属钾反应，合成了聚硅烷１、２、３、４和５，分别用元素分析、ＩＲ、ＵＶ、１ＨＮＭＲ和ＧＰＣ作了表征，并测得它们的非线性谐波极化率Ｘ（３）的值分别为８．６×１０－１２、７．９×１０－１２、９．１×１０－１２、６．５×１０－１２和９．３×１０－１２ｅｓｕ。     

光照法合成甲基苯基二氯硅烷的研究

本文研究了甲基二氯硅烷,苯和氯在紫外光照射下,各种因素对合成甲基苯基二氯硅烷影响规律。中试阶段甲基苯基二氯硅烷的单程收率为54-59％,选择性为53-62％。     

甲基二氯硅烷的化学反应及其综合利用

简述了甲基二氯硅烷的硅氢化反应、热缩合反应、水解反应和醇解反应，及其重要反应产物甲基氯丙基二氯硅烷、甲基乙烯基二氯硅烷、甲基三氟丙基二氯硅烷、甲基苯基二氯硅烷、甲基含氢环体和含氢硅油的制备和应用。     

提高有机硅甲基(氢)二氯硅烷收率研究成果通过化工部鉴定

吉化公司研究院开发成功的提高有机硅甲基(氢)二氯硅烷收率研究成果,于8月1日正式通过化工部科技司组织的专家技术鉴定。 甲基(氢)二氯硅烷是有机硅合成工业的重要原料中间体,用它可以制备出用途广泛的硅橡胶、硅油、硅树脂等系列产品。近年来,我国的甲基氯硅烷生产一直徘徊在年产5000吨水平,但是市场需求一直以年     

β-氰乙基聚硅烷的合成与性质研究

以甲基二氯硅烷、丙烯腈为原料，通过硅氢加成反应合成了β-氰乙基甲基二氯硅烷；然后采用钠缩合法将其分别与甲基苯基二氯硅烷和二苯基二氯硅烷共聚，制得了两种二元共聚硅烷——聚（β-氰乙基甲基-甲基苯基）硅烷[P1]、聚（β-氰乙基甲基-二苯基）硅烷[P2]。并用IR、UV、^1HNMR、GPC和荧光光谱进行了表征。结果表明，β-氰乙基甲基二氯硅烷的反应活性与甲基苯基二氯硅烷相仿，低于二苯基二氯硅烷；此外，P2具有部分枝状聚硅烷的性质，Stoks位移达到80nm，荧光发射峰位于412nm，可能是少量枝化点的引入造成P2具有部分枝状聚硅烷的特征。     

The importance of organosilane polymer photo-oxidation in resist pattern fabrication

The siloxane structure formed in photo-oxidized poly(methylphenylsilane) and poly(methylpropylsilane) is evaluated to clarify its effect on resist sensitivity. It is produced by 17–35 mol% where exposure energy corresponds to the resist sensitivity. This structure change enhances polymer solubility with the developer. Photo-oxidation reaction is found to be an important factor for fabricating organosilane polymer resist patterns.     

Synthesis,characterization, and thermal studies of polyamides and polyimides containing two silarylene units in the main chain

Polyamides (PAs) and polyimides (PIs) containing two silarylene units were synthesized and characterized by their spectroscopic properties. Bis(4‐aminophenyl)methylphenylsilane was employed as a unique diamine, whereas acid dichloride and dianhydride monomers contained combinations of methyl and phenyl groups bonded to the silicon atom. The PAs were obtained in dimethylformamide solutions, and the PIs were prepared by thermal cyclization of the respective poly(amic acid)s (PAAs). The yields were low (32–51%), and the inherent viscosities for PAAs were slightly higher than the PA values. The low inherent viscosities were indicative of oligomeric species. The thermal stability was also evaluated by thermogravimetric analysis and differential scanning calorimetry analysis. In both series, the glass‐transition temperatures increased with the replacement of methyl groups by aromatic rings according to the lower mobility of the polymeric chain. On the other hand, an increase in the aromatic content also increased the thermal stability of the PAs and PIs, and this was registered through their thermal decomposition temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of polysilane-acrylamide copolymers by photopolymerization and their application to polysilane-silica hybrid thin films

Various polysilane-acrylamide block copolymers have been prepared from photopolymerization of acrylamide-type monomers using poly(methylphenylsilane) (PMPS) as a macro-photo-radical initiator. The acrylamide block in the copolymers improved the hydrophilic property of PMPS. These PMPS-acrylamide block copolymers have been applied to formation of PMPS-silica hybrid thin films via sol-gel reaction. Homogeneous and transparent PMPS-silica hybrid thin films were obtained from a few PMPS-acrylamide block copolymers. It was found for these hybrid thin films based on hydrogen bonding formation between amide group and silanol group. The surface properties of hybrid thin films were evaluated by water contact angle measurement, scanning electron microscope (SEM), and atomic force microscope (AFM) images.     

N-丁基马来酰亚胺/丙烯酸丁酯的共聚研究

研究了N-丁基马来酰亚胺与丙烯酸丁酯的溶液共聚,考察了原料配比、反应温度和溶剂极性等因素对共聚反应的影响,并用IR、DTA和特性粘数[η]等对共聚产物进行了表征。     

Synthesis,structure and behavior of new polycaprolactam copolymers based on poly (ethylene oxide)–poly (propylene oxide)–poly (ethylene oxide) macroactivators derived from Pluronic block copolymers

Novel series of poly (CL–co–Pluronic) polymers were successfully synthesized in situ by ring-opening polymerization (ROP) of ε-caprolactam (ε-CL). The copolymerization was activated by new type macroactivators (MAs) based on hydroxyl-terminated poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) [PEO-PPO-PEO] triblock copolymers, known under the trade name Pluronic^®. Toluene-2,4-diisocyanate (TDI) was used to obtain the isocyanate-terminated Pluronic prepolymers. The corresponding MAs were synthesized in situ with an N-carbamoyllactam structure. As an initiator of the copolymerization processes was used sodium lactamate (NaCL). To confirm the influence over the copolymerization process, microstructure, composition and molecular weight of the polymeric products two new types MAs based on Pluronic (P123 and F68) have been varied from 2 to 10 wt.% (vs. the monomer ε-CL). The structure of the both Pluronic based macroactivators (MAs) and accordingly obtained two series poly (CL-co-Pluronic) polymers were confirmed by ¹H NMR and FT-IR analyses. Additionally, the structure, molecular weight, physicomechanical behavior, thermal stability and morphology of the new synthesized poly (CL–co–Pluronic) polymers have been investigated by Differential Scanning Calorimetry (DSC), Wide-Angle X-ray Diffraction (WAXD), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM) analysis.     

Effects of co‐hard segments on the microstructure and properties thermoplastic poly(ether ester) elastomers

A thermoplastic poly(ether ester) elastomer (TPEE) is composed of polyester hard segments and polyether soft segments. Polyester and polyether segments are often homopolymer segments. This work aims at incorporating poly(butylene phthalate (PBP) as co‐hard segments in the hard segments of poly(butylene terephthalate) (PBT)‐b‐poly(tetramethylene oxide) (PTMO) thermoplastic elastomer, and investigating structures and properties of the resulting materials, denoted as (PBT‐co‐PBP)‐b‐PTMO. (PBT‐co‐PBP)‐b‐PTMO was synthesized from dimethyl terephthalate (DMT), dimethyl phthalate (DMP), PTMO (M_n = 1000 g/mol), and 1,4‐butanediol (BDO). The crystallinity of (PBT‐co‐PBP)‐b‐PTMO first decreased and then increased with increasing PBP content from 5% to 10% due to a decrease in the average sequence length of the PBT hard segments. Its elongation at break was increased by 200–350%. When the mass fractions of PBT and PBP were 42% and 8%, respectively, the (PBT‐co‐PBP)‐b‐PTMO showed the best performance in terms of permanent deformation, strength, and hardness whose values were 30%, 25 MPa, and 37 D, respectively. All the synthesized copolymers had good thermal stability with a decomposition temperature of 400°C or so. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43337.     

Synthesis and characterization of highly branched poly(anhydride‐co‐glycol) with glycerin as branching agent

A novel branched poly(anhydride‐co‐glycerol) was synthesized by introducing glycerin into a poly(sebacic anhydride‐co‐ethylene glycol) system via melt condensation without catalyst. The nuclear magnetic resonance spectroscopy (NMR) analysis showed that the reaction between the hydroxyl group on glycerin and the sebacic anhydride pre‐polymer was completed without any hydroxyl group remaining. In addition, with more glycerin introduced, intramolecular chain reaction became more remarkable. This resulted in the production of more cyclic chains and lower molecular weight species that hinder the crystal growth of sebacic anhydride chain segments. This in turn decreases melting temperature of sebacic anhydride chain segments in these synthesized materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 886–893, 2003     

Synthesis and photopolymerization of acrylic acrylate copolymers

Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). ¹³C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002     

Poly(α-methylstyrene)–poly(dimethylsiloxane) block copolymers

Block copolymers were synthesized by the condensation of dihydroxyl-terminated poly-(α-methylstyrene) oligomers and bisdimethylamino-terminated poly(dimethylsiloxane) oligomers. Manipulation of block molecular weight produced copolymers ranging in composition from 21% to 73% poly(dimethylsiloxane). Compression moldablity was found to be good. Physical properties were dependent upon siloxane content, varying from high modulus, low elongation to low modulus, high elongation materials. High siloxane-content compositions exhibited elastomeric properties due to the two-phase morphology of these systems. Glass transition temperatures were observed as low as ?120°C for the poly(dimethylsiloxane) block and as high as + 140°C for the poly(α-methylstyrene) block. Even higher poly(α-methylstyrene) transition temperatures may be possible by using higher molecular weight oligomers.     

PEN-PET共缩聚动力学研究

研究了PEN-PET共缩聚动力学以及添加膜用二氧化硅的影响 ,首次得出了该反应体系的活化能数据。在小试研究的基础上进行了工业化试产 ,得到了合格的共聚酯切片