1,3-bis([(1-methoxy-2-methyl-1-propenyl)oxy])-1,1,3,3-tetramethyldisiloxane

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,3-bis([(1-methoxy-2-methyl-1-propenyl)oxy])-1,1,3,3-tetramethyldisiloxane
• 英文别名: 1,3-bis(1,1-dimethyl-2-methoxy-2-ethenoxy)-1,1,3,3-tetramethyldisiloxane；1,3-bis(1-methoxy-2-methyl-1-propenyloxy)-1,1,3,3-tetramethyldisiloxane；(1-methoxy-2-methylprop-1-enoxy)-[(1-methoxy-2-methylprop-1-enoxy)-dimethylsilyl]oxy-dimethylsilane
• 化学式: C₁₄H₃₀O₅Si₂
• 分子量: 334.56
• InChiKey: AJMLCOLIOWQBLF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,3-bis([(1-methoxy-2-methyl-1-propenyl)oxy])-1,1,3,3-tetramethyldisiloxane 、 三苯碳四(五氟苯基)硼酸盐 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  Dinuclear Silylium-enolate Bifunctional Active Species: Remarkable Activity and Stereoselectivity toward Polymerization of Methacrylate and Renewable Methylene Butyrolactone Monomers

  摘要：

  Novel dinuclear silylitun-enolate active species, consisting of an electrophilic silylium catalyst site and a nucleophilic silicon enolate initiating site that are covalently linked as single molecules, and their unique polymerization characteristics and kinetics are reported. Such unimolecular, bifunctional propagating species are conveniently generated from activation of ethyl- and oxo-bridged disilicon enolate (i.e., disilyl ketene acetal, di-SKA) compounds with [Ph3C] [B(C6F5)(4)]. Both the ethyl- and oxo-bridged dinuclear species are much more active for the polymerization of methyl methacrylate (MMA) than the mononuclear SKA-based active species, exhibiting an approximate rate enhancement by a factor of 12 and 44, respectively. The oxo-bridged silylium-enolate species is considerably more active and controlled than the ethyl-bridged one, with their differences being even more pronounced in polymerizing a renewable monomer, gamma-methyl-alpha-methylene-gamma-butyrolactone. The polymerization by the oxo-bridged silylium-enolate active species follows first-order kinetics in both monomer and silylium catalyst concentrations, indicating a unimolecular propagation mechanism which involves an intramolecular delivery of the polymeric enolate nudeophile to the monomer activated by the silylium ion electrophile being placed in proximity in the same catalyst molecule. Highly stereoregular poly(methyl methacrylate) (PMMA), with a syndiotacticity up to 92% rr, can be produced in quantitative yield using the oxo-bridged propagator at low temperature.

  DOI：

  10.1021/ja2053573
• 作为产物：
  描述：

  1,1,3,3-四甲基二硅氧烷 、 甲基丙烯酸甲酯 在 三(五氟苯基)硼烷 1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯 作用下， 反应 5.5h， 以79.1%的产率得到1,3-bis([(1-methoxy-2-methyl-1-propenyl)oxy])-1,1,3,3-tetramethyldisiloxane
  参考文献：
  名称：

  Preparation of silyl ketene acetals and disilyl ketene acetals

  摘要：

  公开号：

  EP1471069B1

文献信息

• Controlled or High-Speed Group Transfer Polymerization by Silyl Ketene Acetals without Catalyst
  作者：Jiawei Chen、Ravikumar R. Gowda、Jianghua He、Yuetao Zhang、Eugene Y.-X. Chen

  DOI：10.1021/acs.macromol.6b01654

  日期：2016.11.8

  Group transfer polymerization (GTP) is an important ambient-temperature living polymerization method using silyl ketene acetal (SKA) or related initiators. Although several different GTP systems have been developed for polymerizing acrylic monomers, they all require the use of a catalyst to activate the SKA initiator, commonly believed to be ineffective on its own. Now, this work shows that, in fact

  基团转移聚合（GTP）是使用甲硅烷基乙烯酮缩醛（SKA）或相关引发剂的一种重要的室温活性聚合方法。尽管已经开发了几种用于聚合丙烯酸单体的不同的GTP体系，但它们都需要使用催化剂来活化SKA引发剂，通常认为它本身是无效的。现在，这项工作表明，实际上，中性SKA单独取决于极性施主溶剂（例如DMF）中的甲基丙烯酸甲酯（MMA）之类的丙烯酸单体的受控或极快聚合，具体取决于SKA和螯合侧链的核数组上Si。在的情况下的单SKA诸如Me 2 C = C（OME）OSiMe 3，MMA的在DMF中GTP相对较慢（几个小时完成），但被控制，并且非常有效，与制造PMMA中号Ñ值接近那些[M] / [I]之比，低的基础上预测Đ值（≤1.2）和高启动效率（≥80％）。与之形成鲜明对比的是，通过羰基，二茂铁基或双萘基桥连接的di-SKA，以及在Si上带有供体螯合甲氧基侧基的单SKA，介导了极快的聚合反应（几秒钟即可完成），极高的周转频率，高达1