线型二甲基硅氧烷低聚物的制备

doi:10.11944/j.issn.1000-0518.2015.05.140326

摘要/Abstract

摘要：

以八甲基环四硅氧烷(D₄)、六甲基二硅氧烷(MM)为原料, 采用固体超强酸(SA)TiO₂/SO42-为催化剂合成线型二甲基硅氧烷四聚体(MD₄M), 通过均匀设计实验和单因素实验分别研究了反应时间、反应温度、相对分子质量调节剂MM量和催化剂添加量对反应转化率和MD₄M含量的影响, 结果表明, 当D₄与MM的摩尔配比为0.75:1, 反应温度为100 ℃, 反应时间为7 h, 催化剂(SA)用量为反应物总质量的2%时, D₄开环聚合制备线型二甲基硅氧烷低聚物的反应转化率为87%, 其中MD₄M的收率为16.8%, 较硫酸催化体系提高了1.6%, 催化剂SA循环套用3次以上, 催化活性基本不变, 采用准均相体系建立了固体超强酸非均相催化D₄开环聚合的宏观动力学模型。

关键词: 固体超强酸, 二甲基硅氧烷低聚物, 动力学

Abstract:

Linear dimethyltetrasiloxane(MD₄M) was synthesized using octamethylcyclotetrasiloxane(D₄) and hexamethyldisiloxane(MM) as raw materials and solid super acid(SA) TiO₂/SO42- as catalyst. The influence of reaction time, reaction temperature, amount of relative molecular mass modifier(MM) and catalyst dosage on the degree of polymerization and the content of the product was studied by uniform design experiments and single factor experiments. Experiment results showed that the optimum reaction conditions are as follows:the molar ratio of octamethylcyclotetrasiloxane to hexamethyldisiloxane) is 0.75:1, the catalyst loading is 2%(mass fraction) of the total reactants, the reaction temperature is 100 ℃ and the reaction time is 7 h. The reaction conversion is 87% and the yield of MD₄M is 16.8% which is 1.6% more than the sulfuric acid system. The catalyst(SA) can be recycled more than 3 times without the loss of its catalytic activity. The macro-kinetics model of the ring-opening polymerization of D₄ with solid super acid as the heterogeneous catalyst was also created using the quasi-homogeneous system.

Key words: solid super acid, dimethyltetradesiloxane, dynamics

中图分类号:

曹都, 夏勇, 姚洪涛, 祁争健, 孙宇, 李丰富. 线型二甲基硅氧烷低聚物的制备[J]. 应用化学, 2015, 32(5): 527-534.

CAO Du, XIA Yong, YAO Hongtao, QI Zhengjian, SUN Yu, LI Fengfu. Synthesis of Linear Oligomer of Dimethyltetrasiloxane[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 527-534.

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