氨基改性聚醚硅油的合成、结构表征及应用

在Pt催化剂的作用下，利用含氢硅油与烯丙基缩水甘油醚、烯丙基聚氧乙烯聚氧丙烯醚的硅氢化加成反应合成聚醚／环氧硅油中间体，然后分别用吗啉、乙二胺、N,N-二甲基丙二胺、N-氨乙基哌嗪等氨解开环，制得了一系列氨烃基改性聚醚硅油AMPES，对其进行了结构表征和应用。结果表明：增加含氢硅油的数均分子量，提高硅含量，可改善AMPES的柔软性，而对织物的吸湿性影响不大。     

聚醚聚季铵盐反相破乳剂的合成与破乳性能评价

通过将环氧醚和甲基醚分别加到含氢硅油的基本骨架上,合成环氧醚甲基醚共改性硅油中间体。通过环氧氯丙烷和正二丁胺亲核加成反应得到聚-2-羟基丙基二丁基氯化铵,与有机交联剂多乙烯多胺交联得到聚季铵盐。再将共改性硅油与聚季铵盐进行环氧开环反应,得到聚醚聚季铵盐水包油型反相破乳剂。利用FTIR和1H NMR分析了聚醚季铵盐型水包油型反相破乳剂的结构,考察了破乳条件对破乳性能的影响。实验结果表明,在适宜的破乳条件(破乳剂用量100 mg/L、破乳时间4 h、破乳温度为65℃)下,使用聚醚季铵盐型水包油型反相破乳剂的除油率94.9%,破乳后污水含油量为25.8 mg/L,破乳性能优于聚醚季铵盐破乳剂。     

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。     

高效有机硅消泡剂的研制与应用

以二甲基硅油、疏水气相二氧化硅制成的硅膏和聚醚改性硅油为主要成份,Span-60、Twen-60为乳化剂,采用高速剪切乳化搅拌方式将水相在油相中进行乳化,制备出高效乳液型有机硅消泡剂。研究了各主要成分的含量及乳化温度对消泡剂性能的影响,得到的最佳配方为:硅膏的质量分数分别为12%,聚醚改性硅油4%,HLB值为9.5的复配乳化剂6%。制备的有机硅消泡剂的稳定性及消泡抑泡性能较好,适用范围广。     

氨基硅油的合成

本文用丙烯胺与含氢硅油加成法合成了氨中和当量为６００—１４００的氨基改性硅油。在研究了反应温度，滴胺时间，催化剂用量，投料比及持续保温反应时间等五个条件的改变对产品的影响基础上，得出最佳反应条件。     

机械力化学法疏水改性高岭土

以含氢硅油为表面改性剂,用机械力化学法改性高岭土.研究了影响高岭土疏水改性效果的相关因素,并对改性后高岭土进行了IR,BET,TEM和接触角等表征.结果表明,含氢硅油改性剂的加入量对高岭土疏水性能影响很大,存在一个最佳值.当油料比为1:30时,改性高岭土粉体粒度较小,分散均匀,改性后高岭土对水的接触角可达155.98 °.此接触角数值远超过改性剂含氢硅油本身和水的接触角,对这一现象进行了深入讨论.     

聚硅氧烷/钛溶胶光催化复合膜的制备与表征

在锐钛型钛溶胶颗粒或粉体TiO2存在下,进行端乙烯基硅油与含氢硅油的原位硅氢加成反应,制得聚硅氧烷/TiO2复合膜,实现TiO2在立体交联膜中的分散及与聚硅氧烷基体的有效复合.通过红外分析、电镜观察、拉伸实验和紫外-可见光透过测试,对聚硅氧烷的组成和交联结构、复合膜的形态结构及其拉伸和光学性能进行表征和分析.发现原料硅油的扩链处理和SiO2的补强作用有助于提高反应的过程稳定性及复合膜的拉伸性能.亲水性的粉体TiO2在成膜过程中易发生进一步的大规模团聚,这在膜表面构筑微纳结构的同时会劣化膜材的力学、光学性能.溶胶-凝胶法自制钛溶胶颗粒表面残留有部分未脱除的有机基团,这使其具有一定的亲油性和较好的有机相容性,因而钛溶胶颗粒可在有机介质和聚硅氧烷膜中达到初级粒子形式的均匀稳定分散.上述形态结构,可使相应复合膜具有更佳的拉伸性能和紫外屏蔽/可见光透过性能,并有望在保持复合膜高耐老化性的同时具有高效的光催化性能.     

丙二醇嵌段聚醚改性有机硅复配消泡剂的研制

研制了一种高效聚醚改性有机硅消泡剂,考察了白炭黑硅膏、乳化剂以及注水量对消泡剂复配的影响,确定了在室温下消泡剂复配的最适用条件:聚醚接枝聚硅氧烷与硅膏用量质量比为5∶5,聚醚接枝聚硅氧烷与水的质量比为1∶2~3,HLB值范围在8.5~9.5的乳化剂用量为消泡剂总量的4~6%。     

聚硅氧烷/液晶复合膜的制备及其血液相容性研究

以含氢硅油和乙烯基硅油为基质,在氯铂酸催化下与胆甾醇油烯基碳酸酯液晶共混交联成一定强度的聚硅氧烷／液晶复合膜。借助偏光显微撞观察了不同液日含量在材料表面的状态,通过动态凝血实验、血小板粘附与变形实验、溶血实验等研究材料表面形态与血液相容性的关系。结果表明,含液晶２０％、３０％的液晶膜具有优良的抗凝血性能。     

聚硅氧烷皮肤组织黏接材料的设计合成与性能表征

设计开发了以聚硅氧烷材料为基础的皮肤组织黏接剂, 其主要由硅氧烷预聚体、 含氢硅油交联剂和卡斯特催化剂等多组分构成. 在卡斯特催化剂作用下, 预聚体和交联剂室温下在皮肤表面原位快速固化, 其中聚硅氧烷预聚体的苯甲醛侧基与皮肤组织中广泛存在的胺基通过醛胺缩合反应实现共价黏接. 本文系统研究了聚硅氧烷预聚体的聚合度、 侧基含量及交联剂的用量等参数对该黏接剂性能的影响, 得到了最大剪切黏接强度为77.6 KPa、 室温条件下100 s内即可形成稳定黏接的组织黏接材料. 该材料还具有良好的力学相容性、 生物安全性和结构稳定性, 可满足皮肤黏接剂的基本要求, 具有较好的应用前景.     

Properties of ABA and BA polysiloxane amphiphiles modified by polyether

To investigate the effect of content of polyether (F400) grafted on the properties of polysiloxane amphiphiles, polyether was grafted on the polysiloxane by hydrosilylation reaction with H₂PtCl₆ catalyst. The modified polysiloxanes were divided into two types; moreover, the ratio of polyether and polysiloxane was 1:1 or 1:2. The first one was similar to the conventional surfactant structure that is BA polysiloxane amphiphile, which own one hydrophobic chain and one hydrophilic group. Another one was ABA polysiloxane amphiphile, which possess one hydrophobic chain and two hydrophilic groups at the terminal. In our work, we compared the property of modified polysiloxanes with various contents of polyether in aqueous solution at room temperature to analyze the impact of polyether content on siloxane surfactants. The conclusion was that siloxane amphiphiles possess good solubility, high surface activity, and excellent spreading property.     

Hydrophilicity Modification of Addition-cured Room Temperature Vulcanization Silicone Rubber

Allyl terminated polyether was used to improve the hydrophilicity of addition-cured room temperature vulcanization silicone rubber. With the increasing of the polyether, both the hydrophilicity and water absorbed of the vulcanizates were increased. The mechanical properties were also improved by adding the polyether. The result showed that 1.5wt% of the polyether provided the silicone rubber with proper hydrophilicity.     

Preparation and Properties of the Emulsions of the Polysiloxane Material Modified with Tertiary Amino Side Chain

A series of the polysiloxane materials modified with tertiary amino groups were synthesized. FTIR, ¹H NMR were used to characterize the polysiloxane structure. The emulsions of the modified polysiloxanes are prepared. Some surface properties of the polysiloxane materials with tertiary amino groups as resins were discussed. The results show that the polysiloxane materials modified with tertiary amino side chains had good flexibility and the repellency to water. With increasing the amino value of the polysiloxanes, the flexibility of the fabrics treated with the emulsion was improved. After the samples treated with the polysiloxanes, the thermal yellowing of the polysiloxane had emerged. The whiteness of fabrics treated with the polysiloxane decreased. The K/S of the yellow fabrics treated with the modified polysiloxanes had not obvious change, the K/S of the red and blue fabrics treated with the modified polysiloxanes slightly decreased. The shapes of the reflectance spectra curves of the dyed fabrics treated without and with the modified polysiloxanes had not noticeable change.     

一种低代超支化聚醚的合成、表征及表面活性研究

以十二胺、丙烯酸甲酯和乙二胺为原料,甲醇为溶剂,采用发散合成法合成一种低代超支化分子骨架.采用1H NMR对分子骨架的结构进行了表征.在此基础上,以低代骨架为起始剂,分别与环氧乙烷、环氧丙烷加成制备了一种超支化聚醚,测定了它的表面张力、浊点,同时计算出了它的HLB值.结果表明:骨架的分子结构与所设计的结构相符,合成的聚醚具有典型表面活性剂的性质.     

Synthesis of linear and hyperbranched sugar‐grafted polysiloxanes using N‐hydroxysuccinimide‐activated esters

A straightforward method for the preparation of polysiloxanes grafted with carbohydrate side groups is described. Two kinds of backbones have been functionalized, namely one‐dimensional, linear polysiloxanes, and hyperbranched poly(siloxysilane)s based on cyclotetrasiloxanes. The method enables us to keep a good integrity of the polysiloxane backbone. The introduction of intermediate activated esters as side groups on the polysiloxane backbone ensures a complete homogeneity of the reaction medium during sugar grafting in dimethyl sulfoxide, and consequently an easy grafting with the unprotected amino sugar. Solubility of the resulting polysiloxanes has been tested in various solvents. The sugar‐grafted polysiloxanes are good candidates for applications such as silicone formulations, hydrophilic silicone elastomers, interactions with metallic nanoparticles, and suspension stabilization, or as starting point for the design of more complex polysiloxanes for molecular recognition. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3607–3618     

Impacts of filler covalent and non‐covalent modification on the network structure and mechanical properties of carbon–silica dual phase filler/natural rubber

The carbon–silica dual phase filler (CSDPF) was modified by bis (3‐triethoxy‐silylpropyl) tetrasulphane (Si69) and 1‐allyl‐3‐methyl‐imidazolium chloride (AMI), respectively. The natural rubber (NR) vulcanizates filled with modified CSDPF were fabricated through mechanical mixing followed by a high‐temperature cure process. The impacts of filler surface modification on the curing characters, crosslinked junctions, network structure, and mechanical properties of NR vulcanizates were investigated. The results showed that the Si69 interacted with CSDPF through covalent bond, while the interaction between AMI and CSDPF was hydrogen bond. Both modifications increased the cure rate of CSDPF/NR compounds as well as the crosslinked degree, compared with those of pristine CSDPF/NR compound. The modifications improved the dispersion of CSDPF in NR matrix. The covalent modification by Si69 caused a limited movement of NR chains in the CSDPF surface, which contributed to a greater tensile modulus of Si69‐modified CSDPF/NR. However, the higher content of mono‐sulfidic crosslink and the poorer content of strain‐induced crystallization in the NR matrix led to a slight increase of tensile strength and tear strength of Si69‐modified CSDPF/NR, compared with those of CSDPF/NR. The tensile modulus of AMI‐modified CSDPF/NR had a lower value due to a faster polymer chain motion on the CSDPF surface. However, the tensile and tear strength of AMI‐modified CSDPF/NR increased significantly because of the increase of mono‐sulfidic crosslink, strain‐induced crystallization, and the existed hydrogen bond between CSDPF and NR. Copyright © 2015 John Wiley & Sons, Ltd.     

Aryl-group substituted polysiloxanes with high-optical transmission,thermal stability,and refractive index

Polysiloxanes are an important class of polymers for optoelectronic applications. Novel polysiloxanes with high-refractive index (RI) based on phenanthrenyl-substituted monomers are prepared by a polycondensation reaction starting from various substituted dialkoxysilanes as monomers. The substitution patterns on the Si atom are systematically changed to vary the properties of the linear polymers as well as the final cured material. The two monomers with polycyclic aromatic side groups 9-phenanthrenylmethyldimethoxysilane and 9-phenanthrenylphenyldimethoxysilane are synthesized and fully characterized, including their single crystal X-ray structures. Linear polysiloxanes with variations in hydride, methyl, vinyl, phenyl, and phenanthrenyl side group content are prepared by acid- and base-catalyzed polycondensation reactions. Both Si H and Si vinyl substituted polymers with molecular weights up to 30 kDa and adjustable RI's from 1.52 to 1.63 are obtained and the thermally cured by Pt-catalyzed hydrosilylation reactions. Polysiloxane resins are obtained with high-RI's, optical transmittance above 95% and thermal stabilities up to 420°C. Long-term thermal stability tests show transmittance values above 85% even after 60 days of thermal treatment at 180°C.     

Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources

Oligomeric polyether polyols were obtained through the acid‐catalyzed ring‐opening polymerization of epoxidized methyl oleate and the subsequent partial reduction of ester groups to give primary alcohols. The oligomers were characterized with titration, spectroscopic techniques (Fourier transform infrared and nuclear magnetic resonance), matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, size exclusion chromatography, and differential scanning calorimetry. Depending on the degree of reduction, polyols of different hydroxyl content values were obtained and were reacted with 4,4′‐methylenebis(phenyl isocyanate) to yield polyurethanes. These materials, which were characterized by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis, could behave as hard rubbers or rigid plastics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 634–645, 2006     

硅改性密封剂的进展

简要地回顾了硅改性聚醚和硅改性聚氨酯密封剂的出现和发展 ,对硅改性聚醚和硅改性聚氨酯的制备作了简要的介绍 ,并对硅改性密封剂的配方、性能和应用作了进一步阐述。