Novel platinum–thiol catalytic system was constructed by the combination of platinum (Pt) catalysts (Karstedt's catalyst (KC) and chloroplatinic acid hexahydrate (CPA)) and thiol-containing compounds ((3-mercaptopropyl)trimethoxysilane (SM), (3-mercaptopropyl)triethoxysilane (SE), 1,6-hexanedithiol (HDT) and 1-octadecanethiol (OT)). It was found that Pt-thiol catalytic system could remarkably enhance the organic-to-inorganic conversion of polydimethylsiloxane (PDMS) and methylvinylpolysiloxane (Vi-PDMS) at elevated temperature. Under optimal condition, the ceramic yield of KC/SE/Vi-PDMS with 50 ppm Pt (KC) and 0.5 phr SE at 1000 °C was dramatically improved from 0.6 wt% to 54.4 wt% in comparison with Vi-PDMS. FTIR, Raman spectroscopy, XPS and XRD revealed that amorphous free carbon-containing SiOC ceramics were formed after thermal treatment of KC/SE/PDMS and KC/SE/Vi-PDMS at 1000 °C for 60min. And during organic-to-inorganic conversion of Vi-PDMS under high temperature, Pt-thiol catalytic system can efficiently retain C in the inorganic network of SiOC ceramics with existence of vinyl. TG, TG-FTIR and viscosity test results suggested that Pt-thiol system might enhance radicals coupling of Vi-PDMS chains and suppress unzipping decomposition or random scission, which resulted in the high capacity of organic-to-inorganic conversion of KC/SE/Vi-PDMS at elevated temperature.

新型铂-硫醇催化体系是由铂（Pt）催化剂（Karstedt催化剂（KC）和六水合氯铂酸（CPA））和含硫醇的化合物（（3-巯基丙基）三甲氧基硅烷（SM），巯基丙基）三乙氧基硅烷（SE），1,6-己二硫醇（HDT）和1-十八烷硫醇（OT））。发现在高温下，Pt-硫醇催化体系可以显着提高聚二甲基硅氧烷（PDMS）和甲基乙烯基聚硅氧烷（Vi-PDMS）的有机合成。在最佳条件下，与Vi-PDMS相比，在1000°C下具有50 ppm Pt（KC）和0.5 phr SE的KC / SE / Vi-PDMS的陶瓷产率从0.6 wt％显着提高到54.4 wt％。FTIR，拉曼光谱，XPS和XRD表明，在1000°C下对KC / SE / PDMS和KC / SE / Vi-PDMS进行60min热处理后，形成了无定形的无碳含SiOC陶瓷。在高温下Vi-PDMS有机-无机转化过程中，Pt-硫醇催化体系可以有效地将C保留在具有乙烯基的SiOC陶瓷的无机网络中。TG，TG-FTIR和粘度测试结果表明，Pt-硫醇体系可能增强Vi-PDMS链的自由基偶联并抑制解链分解或随机断裂，从而导致KC / SE /的有机物-无机物转化能力高。 Vi-PDMS在高温下。Pt-硫醇催化体系可以有效地将C保留在具有乙烯基的SiOC陶瓷的无机网络中。TG，TG-FTIR和粘度测试结果表明，Pt-硫醇体系可能增强Vi-PDMS链的自由基偶联并抑制解链分解或随机断裂，从而导致KC / SE /的有机物-无机物转化能力高。 Vi-PDMS在高温下。Pt-硫醇催化体系可以有效地将C保留在具有乙烯基的SiOC陶瓷的无机网络中。TG，TG-FTIR和粘度测试结果表明，Pt-硫醇体系可能增强Vi-PDMS链的自由基偶联并抑制解链分解或随机断裂，从而导致KC / SE /的有机物-无机物转化能力高。 Vi-PDMS在高温下。