稀土固体超强酸催化D4和D_4~H开环共聚合制备二甲基含氢硅油  

Preparation of Methyl Hydrogen Silicone Fluids via Ring-Opening Copolymerization of D4 with D_4~H Catalyzed with Rare Earth Solid Super Acid

作　　者：刘佳[1] 邵倩[1] 杨雄发[1] 曹诚[1] 陈忠红[1] 来国桥[1] 

机构地区：[1]杭州师范大学有机硅化学及材料技术教育部重点实验室,浙江杭州310012

出　　处：《高分子材料科学与工程》2015年第4期11-16,共6页Polymer Materials Science & Engineering

基　　金：浙江省自然科学基金资助项目(Y4080264;LY14E030008);浙江省公益性技术应用研究计划(2012C23089;2013C31079)

摘　　要：二甲基含氢硅油是制备二甲基硅橡胶不可缺少的原料,其性能对硅橡胶性能有较大影响。针对二甲基含氢硅油传统制备方法存在的缺点,本文中采用高活性、便于处理、能重复利用、低腐蚀性的稀土固体超强酸SO42-/Ti O2/Ln3+催化八甲基环四硅氧烷(D4)与1,3,5,7-四氢-1,3,5,7-四甲基环四硅氧烷(D4H)开环共聚合,制备了二甲基含氢硅油。系统考察了共聚合反应的规律,并探索了所得产物在加成型硅橡胶制备中的应用。结果表明,用SO42-/Ti O2/Nd3+做催化剂,[SO42-]=1.85 mol/L,[Nd3+]=0.05 mol/L时,在80℃聚合60 min,获得的二甲基含氢硅油收率为87.9%,相对分子质量为4.23×104,相对分子质量分布指数为3.07。当单体按照D4H/(D4H+D4)=30%,共聚单体与封端剂摩尔比为178.5∶1时,所得硅橡胶性能最佳。Hydrogen silicone fluids generally served as cross-linking reagents for addition type liquid silicone rubber,which was widely used due to excellent performance. There are some disadvantages for hydrogen silicone fluids prepared by the traditional method. Here a convenient method for preparation of methyl hydrogen silicone fluids was explored:ring-opening copolymerization of octamethylcyclosiloxane( D4) with 2,4,6,8-tetramethylcyclotetrasiloxane( D4H) catalyzed with SO42-/Ti O2/Ln3 +. Features of the ring opening copolymerization were examined in detail. The reuse performance of the catalysts and the fabrication of the products for silicone gel were also investigated. The results exhibit that when the ring opening copolymerization is catalyzed by SO42-/Ti O2/Nd3 +with [SO42-]= 1. 85 mol/L,[Nd3 +]=0. 05 mol/L at 80 ℃ for 60 min,the product obtained is with yield = 87. 9 %,珚Mn= 4. 23 × 104,PDI = 3. 07. The silicone rubber has optimal performances when the methyl hydrogen silicone fluid is synthesized under the condition of D4H/( D4H+ D4) = 30% and n( D4H+ D4)/n( MM) = 178. 5∶ 1.

关 键 词：稀土固体超强酸 二甲基含氢硅油 开环聚合 硅橡胶 

分 类 号：O634.41[理学—高分子化学]