甲基硅羟基封端硅树脂的合成及固化性能

将甲基三氯硅烷和二甲基二氯硅烷分别与二苯基二羟基硅烷反应得到1,1,5,5-四氯-1,5-二甲基-3,3-二苯基三硅氧烷(A)和1,1,5,5-四甲基-1,5-二氯-3,3-二苯基三硅氧烷(B)。按一定比例将(A)和(B)水解缩合得到完全是甲基硅羟基封端树脂(Ⅰ)。将甲基三氯硅烷和甲基三乙酰氯基硅烷分别处理一般共水解法硅封端树脂可得到另外两种甲基硅羟基封端树脂(Ⅱ)和(Ⅲ),将树脂Ⅰ、Ⅱ、Ⅲ与一般共水解法得到的具有相同R/Si和Ph/R(R代表甲基和苯基)的树脂(Ⅳ、Ⅴ、Ⅵ)进行固化试验,结果表明,甲基-硅羟基封端树脂(Ⅰ—Ⅲ)的固化速度为共水解法制得的以苯基硅羟基封端树脂(Ⅳ—Ⅵ)固化速度的两倍以上。     

γ-（甲基丙烯酰氧基）丙基二甲基氯硅烷的合成

利用自制的催化剂C,通过甲基丙烯酸烯丙酯和二甲基氯硅烷的硅氢加成反应制备了γ-(甲基丙烯酰氧基)丙基二甲基氯硅烷。与经典的Speier催化剂相比,自制催化剂具有更高的催化活性,显著地降低了反应温度,且缩短了反应时间,同时考察了反应条件对催化剂活性和反应结果的影响。     

聚苯基硅氧烷/聚丙烯酸酯复合乳液的合成与性能

本文以二苯基二甲氧基硅烷(DPDMS)和γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)合成了具有微交联结构的聚硅氧烷乳液,并以此为种子乳液再与丙烯酸酯类单体聚合,合成了稳定且性能优良的聚硅氧烷/聚丙烯酸酯复合乳液.用激光粒度分析仪、FTIR、DMA等进行了表征.结果表明,硅氧烷被有效的接枝到了聚丙烯酸酯分子链中;硅氧烷的加入,使聚合物的储能模量,损耗模量增大,玻璃化温度提高,加入量为10％时,Tg由50.5℃升高到57.2℃;加入20％的硅氧烷涂膜吸水率由13.8％降低到6.8％.     

紫外光固化聚多氟烷氧丙基甲基硅氧烷的研究

本文报道几种紫外光敏有机硅单体:(γ-甲基丙烯酰氧)丙基甲基二甲氧基硅烷,1,3,5,7-四(γ-甲基丙烯酰氧丙基)四甲基环四硅氧烷和1,3-双(甲基丙烯酰氧甲基)-1,1,3,3-四甲基二硅氧烷的合成,以及它们与αH,αH,ωH-全氟烷氧丙基甲基环四硅氧烷的开环共聚反应,制备了一系列新型光敏聚多氟烷氧丙基甲基硅氧烷.并初步研究了在紫外光辐照下,这类光敏聚多氟烷氧丙基甲基硅氧烷的化学结构对固化速度的影响.     

含乙二醇低聚体间隔臂的胆酸酯及其甲基丙烯酸衍生物的制备与表征

通过在胆酸羧基端修饰乙二醇低聚体间隔臂,合成了一系列乙二醇低聚体胆酸酯及其甲基丙烯酸衍生物:3'-氧杂-5'-羟基胆酸戊酯,3',6'-二氧杂-8'-羟基胆酸辛酯,3',6',9'-三氧杂-11'-羟基胆酸十一酯,3'-氧杂-5'-甲基丙烯酰氧基戊基-3α,7α,12α-三甲基丙烯酰氧基胆酸酯,3',6'-二氧杂-8'-甲基丙烯酰氧基辛基-3α,7α-12α-三甲基丙烯酰氧基胆酸酯,3',6',9'-三氧杂-11'-甲基丙烯酰氧基十一烷基-3α,7α,12α-三甲基丙烯酰氧基胆酸酯.利用红外光谱研究了含乙二醇低聚体间隔臂胆酸酯分子间的氢键与其物理性质间的关系.结果表明,随着间隔臂链长的增加,胆酸酯中氢键的受体基团由以胆酸24位酯羰基氧和间隔臂上醚键氧为主过渡到以间隔臂上醚键氧为主,醚键氧作为受体形成氢键极大限制了胆酸甾环骨架的运动,影响了其分子骨架的有序排列,使该类胆酸酯的物理形态从固体粉末变为粘稠液体.DSC的测定结果显示,随间隔臂链长的增加,舍乙二醇低聚体间隔臂的胆酸酯甲基丙烯酸衍生物功能单体的玻璃化转变温度下降.初步预计该类单体的聚合转化率会随间隔臂链长的增加有所增加.     

Langmuir-Blodgett方法构建聚合物仿细胞外层膜结构涂层

以盖玻片为基质,采用Langmuir-Blodgett(LB)方法制备含磷酰胆碱基团的两亲性无规共聚物聚(2-甲基丙烯酰氧基乙基磷酰胆碱(MPC)-甲基丙烯酸十八烷基酯(SMA)-γ-甲基丙烯酰氧丙基三甲氧基硅(TSMA)(简称PMST)的单层、双层和三层薄膜.薄膜的表面亲疏水性和表面形貌分别用动态接触角(DCA)和原子力显微镜(AFM)进行测试.结果表明,PMST在盖玻片表面形成了致密的膜层,薄膜的致密程度随层数而增加.在水中前进/后退测试DCA过程中,聚合物薄膜在气相/水相界面存在基团的迁移取向,且膜层内会发生交联.双层膜具有仿细胞外层膜结构,单层和三层膜具有反细胞外层膜结构;双层膜的亲水性比单层和三层膜的要好.     

响应面法优化双羟丙基封端聚硅氧烷的微波合成工艺研究

采用微波辐射法合成双羟丙基封端聚硅氧烷,将响应面分析法应用于1,3-双(3-三甲硅氧基丙基)四甲基二硅氧烷的合成工艺,通过Box-Behnken中心组合实验,考察原料摩尔配比、反应时间、微波辐射温度和催化剂加量四个因素对1,3-双(3-三甲硅氧基丙基)四甲基二硅氧烷收率的影响,得到最佳微波合成工艺参数并建立多元回归数学模型。结果表明:微波合成最佳反应条件n(2-烯丙基三甲基硅氧烷)/n(1,1,3,3-四甲基二硅氧烷)=2.4∶1,反应时间103 min,微波温度95℃,催化剂加量19 mg/kg,得到产物收率可达94.46%。以优化条件下制备的1,3-双(3-三甲硅氧基丙基)四甲基二硅氧烷为原料,制备出了双羟丙基封端聚硅氧烷,目标产物转化率可达90.5%。采用IR、1HNMR、GC对产品结构进行了表征。     

丙烯酸β-羟基γ-(邻乙酰氧基苯甲酰氧基)丙酯的合成及其聚合

<正> 将近来发现具有抗血小板凝聚效应的阿斯匹林进行高分子化的研究迄今尚少报告,我们曾合成了酯基上带有邻-乙酰氧苯甲酰氧基的丙烯酸酯类;甲基丙烯酸β-(乙酰水杨酰氧)乙酯;甲基丙烯酸β-(乙酰水杨酰氧)丙酯及丙烯酸β-(乙酰水杨酰氧)乙酯,本文合成了在酯基上兼有羟基和邻-乙酰氧基苯甲酰氧基的丙烯酸酯;甲基丙烯酸     

1,3,5,7-四异氰氧基乙基-1,3,5,7-四甲基环四硅氧烷合成及结构表征

以丙烯酸和1,3,5,7-四甲基环四硅氧烷(D4H)等为初始原料,经酯化、硅氢加成反应制得1,3,5,7-四(三甲基硅氧羰丙基)-1,3,5,7-四甲基环四硅氧烷(2),水解2制得1,3,5,7-四羧丙基-1,3,5,7-四甲基环四硅氧烷(3),3经Staudinger反应和Curtius重排反应制得1,3,5,7-四异氰氧基乙基-1,3,5,7-四甲基环四硅氧烷(4).反应总收率为14.5%,化合物结构经1H NMR,29Si NMR,IR,MS和HRMS确证.     

1,3-双[3-(1-甲氧基-2-羟基丙氧基)丙基]封端聚硅氧烷的合成

以1,3-双[3-(1-甲氧基-2-羟基丙氧基)丙基]四甲基二硅氧烷和八甲基环四硅氧烷(D4)为原料,通过阳离子催化开环聚合制备了1,3-双(3-(1-甲氧基-2-羟基丙氧基)丙基)封端聚硅氧烷,研究了反应温度,反应时间,催化剂种类及加入量对于聚合反应的影响,结果表明,最佳反应条件为:反应温度65℃,反应时间24h,浓硫酸作为催化剂加入量为反应物质量的0.3%,此时反应拥有最高的转化率。通过红外光谱与核磁共振光谱对产物进行了表征。     

Gas-phase reactivity of the O=P(OCH3)2 + phosphonium ion towards alpha,beta-unsaturated esters in a quadrupole ion trap

Ion-molecule reactions between the O=P(OCH3)2 + phosphonium ions and eight alpha,beta-unsaturated esters (methyl acrylate, ethyl acrylate, methyl crotonate, ethyl crotonate, methyl 3,3-dimethylacrylate, ethyl 3,3-dimethylacrylate, methyl methacrylate and ethyl methacrylate) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH3)2 + phosphonium ions, formed by electron ionization from neutral trimethyl phosphite, were found to react with alpha,beta-unsaturated esters to give an adduct [RR'C=CR'COOR', O=P(OCH3)2]+, which lose spontaneously a molecule of trimethyl phosphate (R'=CH3) or dimethyl ethyl phosphate (R'=C2H5). An ion corresponding to a protonated trialkyl phosphate is also observed when substituent R'=H. To confirm the experimental results, and to elucidate the mechanism for the formation of the ionic species, a theoretical study using the density functional theory (DFT) approach was carried out. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH3)2 + and methyl acrylate is described.     

Stabilising effect of monomers,homopolymers and copolymers of vinyl derivatives of sterically hindered amines on the photo-oxidation of polypropylene

Vinyl derivatives of sterically hindered amines, N-(2,2,6,6-tetramethyl-4-piperidyl)methacrylamide, 2,2,6,6-tetramethyl-4-piperidyl acrylate and methacrylate and 1,2,2,6,6-pentamethyl-4-piperidyl acrylate and methacrylate were prepared. Monomers, homopolymers and copolymers with dodecyl methacrylate (DMA) and octadecyl acrylate (ODA) were tested as stabilisers of the photo-oxidation of polypropylene film. The copolymers exhibited higher efficiency and lower extractability. The photostabilising efficiency increased in the order: homopolymer < monomer < copolymer with DMA < copolymer with ODA.     

Development of Carbazole and Bipyridine Copolymers as Novel Photovoltaic Materials

Summary: A novel acrylate polymer with a carbazole pendant group and bipyridine derivatives as side chains was synthesized, in which derivatives of bipyridine as electro-optic chromophores and carbazole as photoconductive moiety were covalently linked to the acrylate backbone. 2–(Carbazol-9-yl)ethyl methacrylate (CEM) and methacrylic 2-[5-(2-{5,5′-dimethyl-6′-[2-(5-pentylthiophen-2-yl)vinyl]-3,3′-bipyridin-6-yl}vinyl)thiophen-2-yl]ethyl methacrylate (BiPy) were synthesized and then copolymerized to give 99:1, 98:2, 92:8 (mol/mol) CEM/BiPy copolymers. Films of the copolymers blended with poly(3-octylthiophene) (P3OT) or poly(3-decylthiophene) (PDT) and sandwiched between the transparent ITO and Al electrode were examined for photovoltaic properties.     

SYNTHESIS OF BIOCOMPATIBLE ACRYLIC POLYMERS HAVING ASPIRIN-MOIETI

 Several new monomers, β-(acetylsalicylyloxy)ethyl methacrylate, β-(acetylsalicylyloxy)propyl methacrylate, β-(acetylsalicylyloxy)ethyl acrylate, β-hydroxy-Υ-(acetylsalicylyloxy)propyl methacrylate,β-hydroxy-Υ-(acetylsalicylyloxy)propyl acrylate have been synthesized from aspirin with corresponding hydroxyalkyl or glycidyl acrylates, and then polymerized by free radical initiator.     

High pressure phase behavior and modeling of CO2–propyl acrylate and CO2–propyl methacrylate systems

High pressure phase behavior are obtained for CO₂–propyl acrylate system at 40, 60, 80, 100 and 120 °C and pressure up to 161 bar and for CO₂–propyl methacrylate systems at 40, 60, 80, 100 and 120 °C and pressure up to 166 bar. The solubility of propyl acrylate and propyl methacrylate for the CO₂–propyl acrylate and CO₂–propyl methacrylate systems increases as the temperature increases at constant pressure. The CO₂–propyl acrylate and CO₂–propyl methacrylate systems have continuous critical mixture curves that exhibit maximums in pressure at temperatures between the critical temperatures of CO₂ and propyl acrylate or propyl methacrylate. The CO₂–propyl acrylate and CO₂–propyl methacrylate systems exhibit type-I phase behavior with a continuous mixture critical curve.The experimental results for CO₂–propyl acrylate and CO₂–propyl methacrylate systems are modeled using both the statistical associating fluid theory (SAFT) and Peng–Robinson equations of state. A good fit of the data are obtained with SAFT using two adjustable parameters for CO₂–propyl acrylate and CO₂–propyl methacrylate systems and Peng–Robinson equation using one and two adjustable parameter for CO₂–propyl acrylate and CO₂–propyl methacrylate system.     

X-ray diffraction investigation of siloxanes. I. Effects of organic substituents at the silicon atoms on the structure of acyclic trisiloxane-1,5-diols and on formation of different hydrogen bond systems

The molecular and crystal structure of four acyclic trisiloxane compounds, which differ in substituents at the silicon atoms (Ph-phenyl, mPh-methoxyphenyl, 2mPh-dimethoxyphenyl), was investigated by X-ray diffraction analysis. Due to intermolecular hydrogen bonding between the oxygen atoms of the diol fragments, the crystal structure of 1,1,5,5-tetramethyl-3,3-diphenyl-1,3,5-trisiloxane-1,5-diol (C₁₆H₂₄O₄Si₃) (I) is a double chain architecture with hydrogen-bonded dimeric motifs of C(8)R ₄ ⁴ (12) type in graph set representation. In 1,1,5,5-tetramethyl-3,3-(2-methoxybenzo)-1,3,5-trisiloxane-1,5-diol (C₁₈H₂₈O₆Si₃) (II) and 1,1,5,5-tetramethyl-3,3-(2,6-dimethoxybenzo)-1,3,5-trisiloxane-1,5-diol (C₂₀H₃₂O₈Si₃) (III), a double chain structure with a graph set R ₃ ³ (8)D ₃ ³ (10) is formed. In contrast to I–III, 1,1,3,3,5,5-hexaphenyl-1,3,5-trisiloxane-1,5-diol (C₃₆H₃₂O₄Si₃) (IV) has an intramolecular hydrogen bond S(8). The independent molecules are joined by O-H...O intermolecular hydrogen bonds into centrosymmetrical dimers; the system of hydrogen bonds in general may be described as S(8)R ₄ ⁴ (8).     

Humidity sensitive properties of alkoxysilane-crosslinked polyelectrolyte using sol-gel process

New trialkoxysilyl group-containing copolymers for humidity-sensitive polyelectrolytes were prepared by copolymerization of [2-(methacryloyloxy)ethyl]trimethyl ammonium chloride (METAC), 3-(trimethoxysilyl)propyl methacrylate (TSPM) and 2-ethylhexyl acrylate (2-EHA). They were self-crosslinkable copolymers composed of different contents of METAC/TSPM/2-EHA = 4/1/5 and 4/2/4. The resistance varied from 10(7) to 10(3)[capital Omega] between 20% RH and 95% RH, which was required for a humidity sensor operating at ambient humidity. Temperature dependence, hysteresis, response time, water durability and long-term stability at high temperature and humidity were also measured and estimated.     

Synthesis of Liquid Crystalline Polymers with Side Chains

The present paper covers the synthesis and characterization of several intermediate products, monomer, and polymers. 3-{ 2-[ 4-( 4-Nitrophenylazo ) phenoxy] ethyloxycarbonyl} propanoyloxy (2-hydroxy) propyl acrylate (4) was prepared by the ring-opening reaction of glycidyl acrylate with the monoester of succinic acid (3). The polymers (5) with different molecular weights were prepared by the free-radical polymerization. The polymers (5) had liquid crystalline behavior without decomposition as revealed by DSC, optical microscope.     

纳米SiO_2/聚丙烯酸酯复合乳液的制备与表征

根据核壳乳液聚合理论,以经过硅烷偶联剂表面改性的纳米SiO2为种子,采用适当的乳液聚合工艺,制备了纳米SiO2/聚丙烯酸酯复合乳液,并表征了其性能.结果表明,纳米SiO2经过改性后,硅烷偶联剂接枝在其表面;以其为种子制备的复合乳液具有核壳结构,其热稳定性有所提高.     

A rational synthesis of polyacrylates with discogenic side groups

The ferric chloride mediated oxidative coupling of 3,3 ,4,4-tetrahexyloxybiphenyl with 2-hexyloxyanisole followed by demethylation gave 3,6,7,10,11-pentahexyloxy-2-hydroxyor triphenylene. Reaction with tert -butyldimethylsilyl-protected 6-bromohexanol, removal of the protecting group, and condensation with acryloyl chloride methacryloyl chloride gave acrylate and methacrylate monomers with hexamethylene 'spacers'. Alternatively, reaction of 3,6,7,10,11-pentahexyloxy-2-hydroxytriphenylene with 2-(2-chloroethoxy)ethanol followed by acryloyl chloride or methacryloyl chloride gave acrylate and methacrylate monomers with diethylenoxy 'spacers'. Both of the poly(acrylate) homopolymers and the poly(methacrylate) homopolymer with the diethylenoxy 'spacer' gave columnar liquid crystal phases. This is contrary to the current perception that the methacrylate polymer backbone is too inflexible to be incorporated in columnar phases.