聚氰丙基甲基硅氧烷-聚脲嵌段共聚物的结构和性能

本文以氨丙基封端聚(氰丙基,甲基)硅氧烷(CH_2)_3CN:CH_3=1:5),MDI和EDA为原料,采用DMAC单一溶剂合成了一系列高软段分子量(Mn=3000～9000)和高硬段含量(7～30%wt)的多嵌段共聚物。产物为透明热塑性弹性体,具有良好的成膜性能和宽阔的使用温区,其杨氏模量比相应的聚二甲基硅氧烷-聚脲显著提高。通过FT-IR,WAXD,DSC,DMA等证明其硬段为近程有序结构,氰丙基与聚脲硬段有氢键作用,这一作用力使两相相溶性提高,“界面厚度”增加。氰丙基的引入和硬段含量的增加对材料相结构和力学性能有显著影响。     

聚硅氧烷聚脲嵌段共聚物的TEM及SAXS研究

采用透射电子显微镜与小角X光散射分别研究了不同软、硬段分子量及软段极性对聚硅氧烷聚脲多嵌段共聚体系微相结构的影响。结果表明,增加软段分子量及硬段含量有利于聚硅氧烷与聚脲的相分离。将极性氰丙基引入聚硅氧烷后两相混合度明显改善,同时聚脲硬段粒径减小并趋于均一。在聚氰丙基甲基硅氧烷基体中增加聚脲含量及其分子量,则两相界面厚度也随之增大。     

氨基聚硅氧烷对改性环氧树脂的形态与性能的影响

将带有Ｎ－（β－氨乙基）－γ－氨丙基侧基的聚二甲基硅氧烷与环氧树脂共混,制备了聚硅氧烷改性环氧树脂固化物。研究了氨基聚硅氧烷的氨基含量对改性环氧树脂的形态和性能的影响。结果表明,改性环氧树脂固化物的形态与性能主要依赖于氨基聚硅氧烷的氨基含量,在环氧树脂中引入适宜氨基含量的氨基聚硅氧烷,可在一定程度上降低其模量,提高其柔性,并可明显改善环氧树脂的表面性能。     

近晶型聚硅氧烷侧链液晶的合成与表征

以烯丙基溴、对羟基苯甲酸、对氰基苯酚为主要原料合成了液晶基元对-烯丙氧基苯甲酸对-羟基苯氰酯,通过硅氢化加成反应将其接枝到聚甲基氢硅氧烷主链上,合成了一种新型的聚硅氧烷侧链液晶.通过傅里叶变换红外光谱仪(FT-IR)、氢核磁共振仪(1H-NMR)、差示扫描量热仪(DSC)、热台偏光显微镜(POM)和X-射线衍射仪(XR...     

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.     

聚硅氧烷键合离子液体的合成及色谱性能

提出了一种基于聚硅氧烷键合离子液体(PSOIL)的气相色谱固定相的方法, 即首先合成γ-氯丙基聚硅氧烷, 然后通过氯丙基与甲基咪唑的反应合成了聚硅氧烷负载的离子液体, 并对其色谱性能及分离选择性进行了评价.     

用二氧化硅为载体的聚-γ-氰丙基和聚-γ-氨丙基硅氧烷的钯络合物对醛和酮的催化加氢

<正> 许多过渡金属络合物能够在温和的条件下催化烯烃的均相加氢,但是只有少数络合物能够催化醛酮的均相加氢。 从前我们曾报道过二氧化硅为载体的聚-γ-氰丙基硅氧烷-钯络合物(简称Si-CN-Pd)和聚-γ-氨丙基硅氧烷-钯络合物(Si-NH_2-Pd)能够作为烯烃的加氢催化剂。最     

聚四氟乙烯、有机硅复合改性聚氨酯/环氧树脂共混聚合物的合成及其低表面能特性

以甲苯-2,4-二异氰酸酯(TDI)、聚醚二元醇为主要原料制得—NCO封端的预聚体,按一定比例和环氧树脂E-51混合均匀;另用氨乙基氨丙基甲基二甲氧基硅烷、八甲基环四硅氧烷(D4)合成一系列分子量不同的氨基聚硅氧烷,用多元胺作固化剂,并以聚四氟乙烯(PTFE)粉末为填料,合成一系列由PTFE、有机硅共同改性的聚氨酯/环氧树脂共混聚合物。测试了其力学性能、表面接触角、吸水率,同时进行了扫描电镜(SEM)以及表面电子能谱(ESCA)分析。结果表明:所制得的共混聚合物具有很低的表面能和良好的综合性能,PTFE和氨基聚硅氧烷对降低聚氨酯/环氧体系的表面能具有明显的复合效应。     

聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物的合成与催化性能

γ-氨丙基三乙氧基硅烷与丙烯腈反应，得到γ-(β-氰乙基)胺丙基三乙氧基硅烷。后者用气相法二氧化硅固载，再与氯亚铂酸钾反应，合成了聚γ-(β-氰乙基)胺丙基硅氧烷铂配合物。研究了它对不饱和烃与三乙氧基硅烷的硅氢加成反应的催化特性。     

端环氧基聚硅氧烷对环氧模塑料的改性

引入端环氧基聚硅氧烷对环氧封装材料的低应力化作用，将聚硅氧烷直接与环氧树脂及固化剂共混，由于聚硅氧烷不能完全键事到脂基体上，模塑料出现表面渗油，将端环氧基聚二甲基硅氧烷首先与不环氧树脂首先与环氧树脂的固化剂－酚醛树脂预反应形成嵌段共聚物，然后再与环氧树脂混合，解决了渗油，使聚硅氧烷在环氧树脂中的分布更均匀，相区尺寸更小，在环氧树脂固化物中，聚硅氧烷微区尺寸依赖于预反应条件、聚硅氧烷嵌段链长和聚硅氧     

Studies on thermal, mechanical and morphological behaviour of caprolactam blocked methylenediphenyl diisocyanate toughened bismaleimide modified epoxy matrices

Diglycidyl ether of bisphenol A epoxy resin (DGEBA, LY 556) was toughened with 5%, 10% and 15% (by wt) of caprolactam blocked methylenediphenyl diisocyanate (CMDI) using 4,4′-diaminodiphenylmethane (DDM) as curing agent. The toughened epoxy resin was further modified with chemical modifier N,N′-bismaleimido-4,4′-diphenylmethane (BMI). Caprolactam blocked methylenediphenyl diisocyanate was synthesized by the reaction of caprolactam with methylenediphenyl diisocyanate in presence of carbon tetrachloride under nitrogen atmosphere. Thermal properties of the developed matrices were characterized by means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), heat distortion temperature (HDT) and dynamic mechanical analysis (DMA). Mechanical properties like tensile strength, flexural strength and impact strength were tested as per ASTM standards. The glass transition temperature (T_g) and thermal stability were decreased with increase in the percentage incorporation of CMDI. The thermomechanical properties of caprolactam blocked methylenediphenyl diisocyanate toughened epoxy resin were increased by increasing the percentage incorporation of bismaleimide. The values of impact strength for epoxy resin were increased with increase in the percentage concentration of CMDI. The homogeneous morphology of CMDI toughened epoxy resin and bismaleimide modified CMDI toughened epoxy resin system were ascertained from scanning electron microscope (SEM).     

聚硅氧烷聚脲多嵌段共聚物中氢键的研究

采用多种手段研究了聚硅氧烷与聚脲嵌段共聚物中所存在的各类氢键．特别探讨在聚硅氧烷软段中引入极性氰丙基对体系成氢键能力的影响和两相间相互作用力的情况结果表明，在软段分子中引入极性氰丙基有利于增加聚硅氧烷分子与聚脲链段的相互作用，这一相间作用力使两相间界面层厚度随着硬段分子量的增加而加宽，并发现在聚硅氧烷聚脲嵌段共聚物中硬段的聚集形态随溶液浓度改变变化不大，其中氢键随着温度升高而下降．     

STUDY ON SEGMENTED POLYURETHANE WITH MIXED SOFT SEGMENTS OF POLYCHLOROMETHYL METHYL SILOXANE AND POLYTETRAMETHYLENE OXIDE

Two series of polyurethanes based on mixed polychloromethyl methyl siloxane and poly-tetramethylene oxide in different weight fractions were synthesized. The phase separation ofsamples was studied using DSC and dynamic mechanical property analysis. The results showedthat the introduction of chloromethyl group into polysiloxane increased its polarity and henceimproved the miscibilities with polytetramethylene oxide and polyurethane hard segment.Particularly, in the case of N-methyldiethanolamine extended materials, the surface and tensileproperties of these samples can be adjusted by various ratios of two soft segments.     

Synthesis of new siloxane urethane block copolymers and their properties

Siloxane urethane block copolymers were prepared with siloxanes as the soft segment. Films were cast from a variety of solvents. Solvent has an effect on the segregation of soft and hard segments. Surface studies, including ESCA, EDS, and FT-IR, show well segregated block copolymers with enhanced siloxane on the surface. DSC studies show a low mp (-44°C) for the soft segment and a T_g for the hard segment above room temperature. These materials show higher thermal stability compared to polyether urethane block copolymers. These copolymers also show relatively good resistance to exposure to oxygen plasma and show improved flame retardancy compared to nonsiliconated, polyether polyurethane block copolymers. © 1994 John Wiley & Sons, Inc.     

Thermal,mechanical, and morphological properties of soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks (IPNs)

A series of interpenetrating polymer networks (IPNs) based on epoxy (EP) resin and polyurethane (PU) prepolymer derived from soybean oil-based polyols with different mass ratios were synthesized. The structure, thermal properties, damping properties, tensile properties, and morphology of soybean oil-based PU/EP IPNs were characterized by Fourier-transform infrared spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), universal test machine, and scanning electron microscopy (SEM). DSC and DMA results show that the glass transition temperature of the soybean oil-based PU/EP IPN decreases with the increase of PU prepolymer contents. Soybean oil-based PU/EP IPNs have better damping properties than that of the pure epoxy resin. The tensile strength and modulus of PU/EP IPNs decrease, while elongation at break increases with the increase of PU prepolymer contents. SEM observations reveal that phase separation appears in PU/EP IPNs with higher PU prepolymer contents.     

Synthesis and thermal characterization of phosphorus containing siliconized epoxy resins

Siliconized epoxy matrix resin was developed by reacting diglycidyl ethers of bisphenol A (DGEBA) type epoxy resin with hydroxyl terminated polydimethylsiloxane (silicone) modifier, using γ-aminopropyltriethoxysilane crosslinker and dibutyltindilaurate catalyst. The siliconized epoxy resin was cured with 4, 4-diaminodiphenylmethane (DDM), 1,6-hexanediamine (HDA), and bis (4-aminophenyl) phenylphosphate (BAPP). The BAPP cured epoxy and siliconized epoxy resins exhibit better flame-retardant behaviour than DDM and HDA cured resins. The thermal stability and flame-retardant property of the cured epoxy resins were studied by thermal gravimetric analysis (TGA) and limiting oxygen index (LOI). The glass transition temperatures (T_g) were measured by differential scanning calorimetry (DSC) and the surface morphology was studied by scanning electron microscopy (SEM). The heat deflection temperature (HDT) and moisture absorption studies were carried out as per standard testing procedure. The thermal stability and flame-retardant properties of the cured epoxy resins were improved by the incorporation of both silicone and phosphorus moieties. The synergistic effect of silicone and phosphorus enhanced the limiting oxygen index values, which was observed for siliconized epoxy resins cured with phosphorus containing diamine compound.     

主链型液晶聚硅氧烷聚氨酯的合成及性质

合成了主链型联苯类及氧化偶氯苯类液晶聚硅氧烷聚氨酯弹性体，采用红外光谱，示差扫描量热，动态粘弹谱及带热台偏光显微镜等方法对聚合物进行了表征，讨论了它们的结构与性能．研究结果表明，这一系列多嵌段聚氨酯多数是向列型的液晶高分子聚合物，液晶相的形成同嵌段聚氨酯样品的软硬段相互作用有着密切的联系     

有机硅改性环氧树脂的合成与性能研究

用氨基硅油和双酚A型环氧树脂为原料合成一种新型的环氧树脂。研究了不同反应时间、不同反应温度以及不同氨基硅油含量对改性环氧树脂性能的影响,用热重法对改性树脂的耐热性进行了表征。结果表明,用工业产的氨基硅油合成的改性环氧树脂同样具有良好的韧性和耐热性。     

Epoxy-modified, unsaturated polyester hybrid networks

Hybrid polymer networks (HPNs) based on unsaturated polyester resin (UPR) and epoxy resins were synthesized by reactive blending. The epoxy resins used were epoxidised phenolic novolac (EPN), epoxidised cresol novolac (ECN) and diglycidyl ether of bisphenol A (DGEBA). Epoxy novolacs were prepared by glycidylation of the novolacs using epichlorohydrin. The physical, mechanical, and thermal properties of the cured blends were compared with those of the control resin. Epoxy resins show good miscibility and compatibility with the UPR resin on blending and the co-cured resin showed substantial improvement in the toughness and impact resistance. Considerable enhancement of tensile strength and toughness are noticed at very low loading of EPN. Thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were employed to study the thermal properties of the toughened resin. The EPN/UPR blends showed substantial improvement in thermal stability as evident from TGA and damping data. The fracture behaviour was corroborated by scanning electron microscopy (SEM). The performance of EPN is found to be superior to other epoxy resins.