【作者】 宋秘钊；

【导师】 张廷有；

【作者基本信息】 四川大学 ， 皮革化学与工程， 2004， 博士

【摘要】 许多专家认为21世纪是有机硅世纪，是有机硅全面发展的时代。有机硅产品以技术密集和应用多样性为特色，应将应用技术研究提高到应有的高度。很多有机硅产品升级换代的动力来自用户。我国只有大路品种，规格也少，只有千方百计地开发新产品，才有与国外公司分享市场的能力。而要做到这一点，就必须大力开展有机硅的应用基础研究，本课题正是基于这一点而开展的应用基础研究。欲研制侧链含烃羧基硅油、烃羧酸高碳醇酯基硅油以及烃羧基和烃羧酸高碳醇酯基双亲硅油。含长链酯烃基的烃羧酸高碳醇酯基硅油具有优良的润滑性、憎水性、防污性、可涂印性及与有机材料的相容性。硅油主链上带的烃羧基具有反应活性，可作为树脂和涂料的改性剂，改善它们的成型性、脱模性、耐热性及润滑性等。烃羧基硅油可用于织物柔软整理剂、抛光剂、脱模剂和皮革防水等。含烃羧基和烃羧酸高碳醇酯基的双亲硅油除了具有烃羧基硅油和烃羧酸高碳醇酯基硅油的性能外，必将带来一些新的功能。 论文实验的主要内容包括：(1)采用硅氢加成反应，合成烃羧酸甲酯基硅油、烃羧酸高碳醇酯基硅油、以及烃羧酸甲酯基和烃羧酸高碳醇酯基双官能团硅油，得到较成熟的合成工艺；纯化所得到的合成物，并进行结构鉴定，确定其硅氢加成方式。(2)采用碱催化水解或选择性碱催化水解的方式分别将烃羧酸甲酯基硅油与烃羧酸甲酯基和烃羧酸高碳醇酯基双官能团硅油水解得到烃羧基硅油，以及烃羧基和烃羧酸高碳醇酯基双亲硅油，得到较成熟的水解工艺。(3)比较所合成的各种改性硅油的乳化性能及影响因素，比较所合成的各种改性硅油的有机相容性，为它们的应用奠定基础。(4)测定各种改性硅油和用它四川大学博士学位论文们处理的织物的表面能，为它们的应用服务。主要的实验方法和结果如下: 提高甲基丙烯酸甲酷和聚甲基氢硅氧烷之间的硅氢加成反应温度可大大缩短反应时间，转化率可达90%以上。正交实验结果表明，各影响因素顺序是:催化剂用量>反应时间>物料比>反应温度。结合影响硅氢加成反应转化率的各单因素实验，以及各反应因素对甲基丙烯酸甲醋均聚物形成量的影响，确定反应较佳条件是:反应温度140℃，催化剂的用量为反应物质量的60 x 10一6，反应时间30h，物料比为1.5。反应产物的IR和IH一MR图谱分析表明，甲基丙烯酸甲酷与聚甲基氢硅氧烷之间的硅氢加成反应产物主要是旦一1，2加成产物，而在其IR和‘H一NMR图谱分析中未出现。一1，2加成和1，4一加成产物结构所具有的特征吸收峰和化学位移。 烃梭酸甲酷基硅油水解制备烃梭基硅油的反应可在碱催化条件下进行。其正交实验结果表明，各影响因素顺序是:碱的质量分数>反应温度>反应时间。通过对影响其水解反应的各个因素的进一步研究可知，烃梭酸甲醋基硅油水解反应的较佳条件可确定为:碱的质量分数为12%，时间80min，温度90℃，水解率可达90%以上。 丙烯酸高碳醇酷与聚甲基氢硅氧烷之间硅氢加成反应的正交实验结果表明，各因素的影响顺序为:催化剂用量>反应温度>反应时间>物料比>溶剂量。结合影响该硅氢加成反应转化率的各单因素实验，确定较佳的硅氢加成反应条件是:温度 130一140℃，催化剂用量为反应物质量的60xl护，时间12h，反应的物料比为1.2左右，转化率可达95%以上。 采用本论文的合成路线，以大分子的丙烯酸高碳醇醋单体直接接枝聚甲基氢硅氧烷的改性方式是可行的。通过对反应产物的IR和’H一MR分析可知，该硅氢加成反应的产物主要是p一1，2加成产物，而在IR和’H一NMR图谱中未发现它们a一1，2加成产物和1，4一加成产物(顺式+反式)的特征吸收峰和化学位移。 由于甲基的位阻，甲基丙烯酸甲醋和聚甲基氢硅氧烷之间的硅氢加成反应明显难于丙烯酸高碳醇醋和聚甲基氢硅氧烷之间的硅氢加成反应;丙烯酸高碳醇酷接枝到聚硅氧链上后，对其后续甲基丙烯酸甲醋和聚甲基氢硅氧烷之间的硅氢加成反应有屏蔽作用。基于以上两点，将甲基丙烯酸甲醋和丙烯酸高碳醇四川大学博士学位论文醋依次与聚甲基氢硅氧烷进行硅氢加成反应，得到烃梭酸甲酷基和烃梭酸高碳醇酷基双官能团聚硅氧烷。通过调整甲基丙烯酸甲醋和丙烯酸高碳醇醋的物料比以及它们与聚甲基氢硅氧烷进行硅氢加成反应的时间，可得到烃梭酸甲酷基和烃梭酸高碳醇酷基双官能团聚硅氧烷，其转化率可达90%以上。经IR和，H一NMR分析后表明，甲基丙烯酸甲醋和丙烯酸高碳醇醋两种单体的接枝方式均为p一1，2加成，在其xR和’H一NMR图谱中未观察到a一l，2加成和一，4一加成 (顺式十反式)方式。 碱催化水解烃梭酸甲酷基和烃梭酸高碳醇酷基双官能团聚硅氧烷时，可选择性地水解聚硅氧烷链上接枝的甲基丙烯酸甲酷基而保留丙烯酸高碳醇醋基，得到烃梭基和烃梭酸高碳醇醋基双亲硅油。当烃梭酸甲醋基比烃梭酸高碳醇酷基摩尔比约为1:1时，以质量分数为18%的碱，温度90℃，时间110min的条件水解，烃梭酸甲醋基水解率可达到83.0%左右。烃梭酸高碳醇酷基的量和比例增加，则水解难度有所提高，水解率有所下降。 因引入聚硅氧烷链上基团的结构和数量的不同，致使硅油的最佳乳化HLB值更多还原

【Abstract】 Many experts have predicted that 21st century is the century of siiicone and the times for it to development in an all-round way. Siiicone characterizes by intensive technology and varied application. It is very important to advance the research application technology to keep pace with the time. The motive power for upgrading siiicone products usually derives from consumers. Adding variety to limited siiicone products is urgent to compete with foreign companies in China at present, in which basic application research plays key role.Samples were synthesized, including carboxyalkyl siiicone (PHMS-g-AA), siiicone grafted by long chain alkyl acylate(PHMS-g-LCAA), and siiicone grafted with carboxyalkyl and long chain alkyl acylate(PHMS-g-AA-LCAA). Siiicone grafted by long chain alkyl acylate characterizes by lubrication, waterproof, anti-soil, and compatibility with other organics. Because of its reactivity, the carboxyalkyl of siiicone chain can be the modifier of resin and paint to improve their mouldability, demouldability, heat resistance, and lubricity. Carboxyalkyl siiicone can be used as softener and finishing agent for textile, glossing agent, and waterproofing agent for leather. Siiicone grafted with carboxyalkyl and long chain alkyl acylate will have some auxiliary function, except that of carboxyalkyl siiicone and siiicone grafted by long chain alkyl acylate.The main content in this paper includes, (1) the sophisticated synthetic method of silicone grafted with methyl methacrylate(PHMS-g-MMA), PHMS-g-LCAA and silicone grafted with methyl methacrylate and long chain alkyl acrylate (PHMS-g-MMA-LCAA) were obtained. The synthetic products were purified and identified to confirm their adding manner of hydrosilylation. (2) sophisticated synthetic method of PHMS-g-AA, and PHMS-g-AA-LCAA was obtained by hydrolysing PHMS-g-MMA and PHMS-g-MMA-LCAA selectively catalysed by alkali. (3) to establish base for application, the emulsibility of varied modified silicone and the influence factors, and compatibility with other organics were studied. (4) the surface energy of varied modified silicone and textile treated with varied modified silicone were determined to serve application.The main experiment methods and results are as follows:The reaction that between methyl methacrylate(MMA) and polymethylhydrosiloxane(PHMS) can be operated under high temperature to greatly shorten the reaction time, and the reaction conversion rate can reach 90%. The result of orthogonal experiment shows that the sequence of different kinds of influence factors is that catalyst levels > reaction time > material ratio > reaction temperature. Considering the effect from varied factors and the amount of polymethyl methacrylate on conversion rate, the reaction condition is, reaction temperature 140 catalyst levels 60 10-6 times of reactant mass, reaction time 30h, and solvent dosage 0. 8 times of reactant mass, and material ratio 1.5. The IR and ’H-NMR spectrum of the reaction product show that the absolute majority of reaction products of hydrosilylation between methyl methacrylate(MMA) and polymethylhydrosiloxane(PHMS) is 1,2 addition product, and there are no characteristic absorption peak and chemical shift of 1,2 and 1,4 - addition product.PHMS-g-MMA was hydrolyzed to PHMS-g-AA by catalyzing with alkali. The result of orthogonal experiment shows that the sequence of different kinds of influence factors is mass fraction of alkali > reaction temperature > reaction time.The best reaction condition is that mass fraction of alkali 12%, reaction time 80min, reaction temperature 90, considering the effect from varied factors on hydrolyzing reaction of PHMS-g-MMA.The orthogonal experiment of the hydrosilylation between long chain alkyl acrylate(LCAA) and polymethylhydrosiloxane shows that the sequence of different kinds of influence factors is catalyst dosage > reaction temperature > reaction time > material ratio, considering varied influence factors on the conversion rate of hydrosilylation, the best reaction condition is reaction temperature 130-140更多还原