十六烷基三甲氧基硅烷合成及结构表征

以α-十六烯、三甲氧基硅烷为原料,加入铂催化剂和一种液态位阻胺助催化剂,采用硅氢加成方法,合成十六烷基三甲氧基硅烷,分别用气质联用仪和核磁共振波谱仪对产物进行了分析和结构表征。考察了催化剂用量、助催化剂用量、反应温度以及预混合时间对反应的影响。结果表明,在反应温度30~80℃、预混合时间20m in、催化剂和助催化剂用量分别为5 mg/kg和70μL/kg的条件下,反应2 h,产品得率为84%,并且所得产品全部为β加成产物。     

Functionalization of polymethylhydrosiloxane gels with an allyl ureido benzocrown ether derivative: Complexation properties

Crosslinked polymethylhydrosiloxane (PMHS) thin films prepared by sol–gel polycondensation have been functionalized by Pt‐catalyzed hydrosilylation of SiH groups with an allyl ureido crown ether precursor. To this purpose, both 4′‐allylurea‐benzo‐15‐crown‐5 ( 1 ) and 1‐allyl‐3‐propyl‐urea ( 2 ) were synthesized and characterized. We have shown that competitive side‐reactions occurred following hydrosilylation due to the hydrolysis of part of the SiH groups resulting in the formation of new crosslinks Si(CH₃)O_3/2 as shown by solid‐state ²⁹Si‐NMR. This is explained by the deactivation of the Pt catalyst toward hydrosilylation by amide groups. For thin films (～ 1 μm) prepared on silicon wafers, a quantitative method based on FT‐IR transmission spectroscopy was used to measure the crosslinking density of the network, and the percentage of functionalization (SiC %) following hydrosilylation. The results are discussed in relation to the mesh size of the network, and the diffusion of alkenes and water molecules within lightly crosslinked PMHS gels obtained by varying the amount of triethoxysilane crosslinker (mol %) from 15 to 1%. The self‐organization properties of ureido groups by H‐bonding were studied by FT‐IR for the functionalized thin films. The complexation properties of the crown ether 1 ‐functionalized thin films were evidenced by using FT‐IR following diffusion‐reactions of NaSCN and KSCN salts in CHCl₃ : MeOH solvent mixtures within thin films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

改性阳离子树脂配合铂催化苯乙烯硅氢加成反应

研究了改性阳离子树脂配合铂催化剂的制备及其催化苯乙烯与甲基二氯硅烷硅氢加成反应,反应在连续式多相催化反应器中进行。由阳离子树脂、乙醇氨和氯铂酸制备的改性阳离子树脂配合铂是一个催化活性和β–加成选择性高、热稳定性好的固体催化剂。考察了温度、催化剂用量、加料速率等因素对苯乙烯与甲基二氯硅烷硅氢加成反应的影响。在加料速率为6.7mL/h、催化剂用量为2g、反应温度为70℃条件下反应,甲基二氯硅烷单程转化率达到98.42%,β-加成产物的选择性为99.23%,反应连续进行21h后催化剂性能仍保持稳定。     

环已基甲基二甲氧基硅烷的研究进展

介绍了环已基甲基二甲氧基硅烷的几种合成方法：格氏试剂法、硅氢加成法和有机碱金属法，并对其工艺方法作了比较，认为从技术可行性及稳定性上看，选择无溶剂格氏试剂法生产环已基甲基二甲氧基硅烷较好。     

支链聚醚原油破乳剂的合成与表征

以聚氧乙烯聚氧丙烯环氧基醚和聚氧乙烯聚氧丙烯甲基醚为支链,聚硅氧烷为主链,在异丙醇溶剂下,以氯铂酸为催化剂,通过硅氢加成反应,合成出聚醚聚硅氧烷类原油破乳剂。得到较佳的合成条件为:n(环氧醚)∶n(甲基醚)=1∶1,n(硅氢键)∶n(双键)=1∶1.15,反应温度105℃,反应时间5 h,催化剂用量30μg/g(相对于反应物总质量)和溶剂用量40%(以原料总质量计),在该条件下转化率达到92.62%,并通过FTIR和1HNMR对产物的分子结构进行了表征,谱图分析证明合成了预期产物。表面张力仪测定了其临界胶束质量浓度为0.7 g/L,最低表面张力24.2 mN/m。该破乳剂在破乳温度70℃,用量为100 mg/L条件下,对延长石油永平原油的脱水率达到88.42%,具有较好的破乳性能。     

P(i-BuNCH2CH2)3N的合成及用作过渡金属催化剂配体的应用

以三-(2-氨基乙基)胺和异丁醛的醛胺缩合物与HMPT/PCl3为原料合成了一种有机非离子超强碱P(i-BuNCH2CH2)3N,产物经1HNMR、13CNMR、31PNMR和GC-MS测定表征。含氮二环磷碱与Pt(DVDS)组成的催化体系,能高效高立体选择性地催化端基炔烃的硅氢加成反应,含氮二环磷碱及其改性的催化剂经31PNMR表征。     

Synthesis of phosphazene-substituted polysiloxanes

Phosphazene-substituted polysiloxanes have been synthesized via a hydrosilylation reaction of allyl derivatives of cyclophosphazenes with polymethylhydrosiloxanes. It turned out that a proper choice of both the spacer between the phosphazene group and the double bond and the position of the phosphazene group at the spacer is important for the preparation of soluble polysiloxanes with a high content of phosphazene units.     

长链烷基改性苯基含氢硅油的制备与表征

采用溶液聚合法,根据硅氢加成反应原理,以1-十二烯和苯基含氢硅油为原料、异丙醇为溶剂、氯铂酸为催化剂,制备长链烷基改性苯基含氢硅油。采用FTIR和1H NMR技术对试样的结构进行表征,并采用正交实验确定了产物合成的最佳工艺条件。表征结果显示,苯基含氢硅油与1-十二烯发生了接枝反应,长链烷基成功接枝到了聚硅氧烷链上。实验结果表明,在反应时间5.0 h、反应温度115℃、催化剂加入量30μg/g、n(Si—H)∶n(C-C)=1∶1.10、1-十二烯的滴加时间25 min的最佳工艺条件下,Si—H键的转化率高达82.25%。产物长链烷基改性苯基含氢硅油为油溶性单体,且相对分子质量较高,具有较好的破乳效果。