Synthesis,Characterization and Catalytic Hydrosilylation Activity of [60] Fullerene n-Propylamine Platinum,Rhodium Complex

Fullerene n propylamine platinum,rhodium complex have been prepared from C 60 via amination with n propylamine, then reacting respectively with potassium chloroplatinite or rhodium chloride. The two noble metal complexes can effectively catalyze hydrosilylation of olefins with triethoxysilane. The Pt complex exhibits high regioselectivty for styrene, nearly 100% branched product is obtained.

SYNTHESIS AND CATALYTIC BEHAVIOR OF POLYSILOXANESUPPORTED FULLERENE PLATINUM OR RHODIUM COMPLEXES

Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes have been prepared from C-60 via amination with omega-decenylamine, followed by hydrosilylation with triethoxysilane and immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensation with polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride in acetone respectively under argon atmosphere. It was found that the four noble metal complexes are effective catalysts for the hydrosilylation of olefins with triethoxysilane. The regioselectivity of platinum complexes for styrene increases remarkably by introducing C-60 moiety. Factors influencing catalytic activity and the mechanism have been investigated.

SILICA-BOUND CROWN ETHERS PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.

CROWN FUNCTIONALIZED LINEAR POLYSILOXANE PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silanol-terminated polydimethylsiloxane to give the title crownfunctionalized linear polysiloxane. It was found that the polysiloxane could be coordinated withplatinum salt to form platinum complex, which could catalyze the hydrosilylation of olefins withtriethoxysilane efficiently.

4-Selena-7-thiaoctyl Polystyrene-supported Platinum Complex as Hydrosilylation Catalyst

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(η^(2)C_(60))Pt (PPh_3)_2 as the Catalystfor the Hydrosilylation of Olefins

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Effect of Aminoaromatic Acids as Additives on the Activity and Selectivity of the Platinum-catalyzed Hydrosilylation of Alkenes

A series of aromatic acids has been tested as additives for the platinum-catalyzed hydrosilylation of styrene with triethoxysilane. Both excellent conversion of styrene and selectivity in favor of the ,β-adduct were achieved using aminobenzoic acids as additive. Moreover, the use of 4-aminobenzoic acid led to significantly superior enhancement in both catalytic activity and selectivity among the tested aminobenzoic acids. Indeed, 100% conversion of styrene and 98.4% selectivity in favor of the β-adduct were obtained. Additionally, hydrosilylations of various alkenes with a variety of platinum catalysts have also been tested, and in each case the conversion of substrate and the selectivity of the β-adduct were promoted by using 4-aminobenzoic acid as additive.

SYNTHESIS OF POLYSILOXANE-SUPPORTED SELENAETHER PLATINUM COMPLEX AND ITS CATALYTIC PROPERTY FOR HYDROSILYLATION OF OLEFINS

A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquinoxane, and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosilylation with triethoxysilane, followed by immobilized on fumed silica, and then reacting with potassium chloroplatinite under nitrogen atmosphere in acetone. It was found that the platinum complex can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The effects of the nature of the substrate, the amount of complex used, and the reaction temperature on the catalytic activity were investigated.

SYNTHESIS AND CATALYTIC HYDROSILYLATION PROPERTY OF POLYSILOXANE-SUPPORTED MERCAPTOSELENAETHER PLATINUM OR RHODIUM COMPLEX

Silica-bound mercaptoselenaether-containing silsesquioxane and its platinum or rhodium complex were synthesized from gamma-(2,3-epithiopropyl) propyltrimethoxysilane via ring-opening reaction with bis(2-hydroxyethyl) selenide, followed by hydrolysis and immobilization on fumed silica, and then reacting with potassium chloroplatinite or rhodium chloride in acetone under nitrogen atmosphere. It was found that two noble metal complexes can catalyze the hydrosilylation of olefins with triethoxysilane effectively. The influences of temperature, the amount of complex used, the nature of olefin on catalytic activity were investigated.

NETWORK CROWN ETHER POLYMERS WITH CENTRIC FUNCTIONAL GROUPS．Ⅱ．SYNTHESIS OF NETWORK CROWN ETHER POLYMER WITH PENDANT SULFIDE SIDE CHAIN AND ITS PLATINUM COMPLEX

Network crewn ether polymer with pendant sulfide side ohain in the networkstructure units has been synthesized via ring- opening copolymerization of β-ethylthioethyl glycidyl ether and diethylene glycol bisglycidyl ether. A kind of active catalyst suitable for this reaction was suggested. The title polymer was found tobe a good ligand for platinous chloride, and the platinous complex could catalyze thehydrosilylation of olefins with triethoxysilane efficiently.

A NEW TYPE OF CROWN FUNCTIONALIZED POLYSILOXANE AND ITS PLATINUM COMPLEX

A new type of crown functionalized polysiloxane, in which the crown moieties were incorporated into main chain, and its platinum complex were synthesized. The polysiloxane was synthesized from 3, 16-dihydroxy-1- thia - 5, 8, 11, 14- tetraoxacycloheptadecane via etheritication with ω-chloroundecene, followed by hydrosilylation with triethoxysilane, cohydrolysis with D_4, sequentially. Treating the polysiloxane with potassium cholroplatinite, the title complex was obtained. It was found that the platinum complex exhibited high catalytic activity in the hydrosilylation of olefins with triethoxysilane.

NETWORK CROWN ETHER POLYMERS WITH CENTRIC FUNCTIONAL GROUP (Ⅳ) SYNTHESIS OF NETWORK CROWN ETHER POLYMER WITH PENDANT DIETHYLAMINO THIAALKYL GROUP AND ITS PLATINUM COMPLEX

The title polymer was prepared from 5-diethylamino-3-thia-pentyl glycidyl ether anddiethylene glycol bisglycidyl ether via ring-opening copolymerization. It was found that thisreaction could be catalyzed by sodium, but not Lewis acid. The obtained polymer can coordinatewith platinum compound, and the platinum complex is a new kind of catalyst for thehydrosilylation of olefins with triethoxysilane.

Studies On A Selena-aza-crown Ether: Synthesis and Catalytic Behavior In Hydrosilylation

The synthesis of a new type of selena aza crown ether 6 (4 nitrobenzyl) 1,4,7,10 selenatriazacyclododecane (L) derivated from phenylalanine , and its platinum(Ⅱ) complex was described. The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.

Silica－supported Polysiloxane with Selenacrown Ether Moieties and Its Platinum Complex

he present paper covers syntheses of the first functionalized selenacrownether, allyloxymethyl-1-selena-4, 7 , 10, 13, 16-pentaoxacyclooctadecane, and its im-mobilized product, silica-supported polypropyloxymethyl- 1-selena-18-C- 6 siloxane.It was found that the immobilized selenacrown ether could coordinate with platinumsalt and the platinum complex was a new type of polymeric hydrosilylation catalyst.The polymer catalyst exhibited a high catalytic activity for the hydrosilylation ofolefins with triethoxysilane in the temperature range of 60 to 110℃. The turnovernumber could amount to more than 100,000 in one run.

SYNTHESIS AND CATALYTIC ACTIVITY OF PLATINUM COMPLEX OF ACRYLATE TERPOLYMER WITH Se, N BIDENTATE LIGAND

Acrylate terpolymer- bound Se, N bidentate ligand was synthesized fromthe side chain chlorine of copolymer and β- dimethylamino -β - hydroxyl diethyl selenoether. The polymer - supported platinum complex exhibited highcatalytic activity in the hodrosilylation of olefins with triethoxysilane.

C_(60)乙二胺衍生物铂配合物的合成及其催化硅氢化性能

Ｃ６０与乙二胺反应，再与氯亚铂酸钾配位，得到了一种以Ｃ６０衍生物为基的Ｐｔ（Ⅱ）配合物，并研究了其在烯烃与三乙氧基硅烷的硅氢加成反应中的催化性能．结果表明，该配合物为硅氢加成反应的高效催化剂，并对苯乙烯有独特的催化性能，以近１００％的区域选择性得到α－加成产物．

有机硅工业中的铂催化剂研究进展

铂催化硅氢加成反应，广泛用于含Ｓｉ—Ｃ单体的制备及聚合物的交联。本文综述了铂催化剂的组成、表征、抑制剂的作用及铂催化剂催化机理。

硅氢反应合成有机硅蜡

在铂络合物催化剂的作用下,以高碳数烯烃化合物和含氢硅油为原料,利用硅氢加成反应合成有机硅蜡。研究了原料配比、催化剂用量、反应时间、反应温度对Si—H键转化率和产物运动粘度的影响,确定最佳反应条件为:烯键与硅氢健摩尔比n(C=C)∶n(Si—H)=1.12∶1、铂催化剂用量3.2μg/g、反应温度130℃、反应时间8 h。并对合成产物的分子结构进行了红外、核磁表征,结果表明长链烷基已被接枝到聚硅氧烷主链中。

4A分子筛固载铂催化剂催化乙炔硅氢加成反应

研究了4A分子筛固载铂催化剂的制备及其催化乙炔与三乙氧基硅烷硅氢加成反应的反应规律,考察了反应温度、原料配比、催化剂铂含量、乙炔流量等对反应的影响。结果说明4A分子筛固载铂催化剂对乙炔与三乙氧基硅烷硅氢加成反应具有较好的催化活性,并且反应条件温和,催化剂回收利用3次仍具有较高的活性。

长链α-烯烃的硅氢加成反应研究

以聚三氟丙基乙烯基甲基硅氧烷为保护剂制备了102白色担体负载的铂络合物催化剂,用于催化长链α-烯烃与甲基二氯硅烷的硅氢加成反应。考察了铂催化剂用量、反应温度、不同长链烯烃原料、催化剂回收利用等因素对长链烷基甲基二氯硅烷收率的影响,结果表明,102白色担体负载的铂络合物催化剂对该硅氢加成反应具有较高的活性和稳定性,在常温下无需加热,无诱导期即可发生加成反应。在密闭体系中,1-十二烯烃与甲基二氯硅烷的摩尔比为1∶1.1,铂络合物与甲基二氯硅烷的摩尔比为6.5×10-5∶1时,十二烷基甲基二氯硅烷的收率可达88%;敞开体系中,相同条件下,十二烷基甲基二氯硅烷的收率可达77%。催化剂重复使用8次不失活。