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不同官能团对室温硫化硅橡胶制备过程中α-胺基酮肟硅烷水解动力学速率的影响

Impacts of Different Functional Groups on the Kinetic Rates of α-Amine Ketoximesilanes Hydrolysis in the Preparation of Room Temperature Vulcanized Silicone Rubber.

作者信息

Xu Huihui, Liu Zihou, Liu Qingyang, Bei Yiling, Zhu Qingzeng

机构信息

Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.

College of Biology and the Environment, Nanjing Forestry University, Nanjing 210037, China.

出版信息

Materials (Basel). 2018 May 13;11(5):790. doi: 10.3390/ma11050790.

Abstract

α-Amine ketoximesilanes are proven to be effective crosslinkers in the preparation of ketone-oxime one-component room temperature vulcanized (RTV) silicone rubber without the use of toxic metal catalyst. This work aimed to investigate the hydrolysis kinetic of α-amine ketoximesilanes, which is vitally important for the preparation of RTV silicone rubber. Five kinds of α-amine ketoximesilanes, namely α-(N,N-diethyl)aminomethyltri(methylethylketoxime)silane (DEMOS), α-(N,N-di-n-butyl)aminomethyltri(methylethylketoxime)silane (DBMOS), α-(N-n-butyl)aminomethyltri(methylethylketoxime)silane (n-BMOS), α-(N-cyclohexyl)aminomethyltri(methylethylketoxime)silane (CMOS) and α-(β-aminomethyl)aminomethyltri(methylethylketoxime)silane (AEMOS), were successfully obtained and confirmed using Fourier transform infrared spectrometer (FT-IR) and hydrogen-1 nuclear magnetic resonance ( ¹H NMR). Kinetics of hydrolysis reactions were measured by FT-IR and conductivity. Our results illustrated that the kinetic constant rates ranged from 12.2 × 10 s to 7.6 × 10 s, with the decreasing order of DEMOS > n-BMOS > DBMOS > CMOS > AEMOS at the given temperature and humidity. Better performances of thermal stability could be achieved when using the α-amine ketoximesilanes as crosslinkers in the preparation of RTV silicon rubber than that of RTV silicone rubber with the use of methyltri(methylethylketoxime)silane (MOS) as a crosslinker and organic tin as a catalyst.

摘要

α-胺酮肟硅烷被证明是制备酮肟型单组分室温硫化(RTV)硅橡胶的有效交联剂,且无需使用有毒金属催化剂。本工作旨在研究α-胺酮肟硅烷的水解动力学,这对RTV硅橡胶的制备至关重要。成功制备了五种α-胺酮肟硅烷,即α-(N,N-二乙基)氨基甲基三(甲乙酮肟)硅烷(DEMOS)、α-(N,N-二正丁基)氨基甲基三(甲乙酮肟)硅烷(DBMOS)、α-(N-正丁基)氨基甲基三(甲乙酮肟)硅烷(n-BMOS)、α-(N-环己基)氨基甲基三(甲乙酮肟)硅烷(CMOS)和α-(β-氨基甲基)氨基甲基三(甲乙酮肟)硅烷(AEMOS),并使用傅里叶变换红外光谱仪(FT-IR)和氢-1核磁共振(¹H NMR)进行了确认。通过FT-IR和电导率测量水解反应动力学。我们的结果表明,在给定温度和湿度下,动力学常数速率范围为12.2×10⁻⁶ s⁻¹至7.6×10⁻⁶ s⁻¹,其递减顺序为DEMOS > n-BMOS > DBMOS > CMOS > AEMOS。在制备RTV硅橡胶时,使用α-胺酮肟硅烷作为交联剂比使用甲基三(甲乙酮肟)硅烷(MOS)作为交联剂和有机锡作为催化剂的RTV硅橡胶具有更好的热稳定性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8df/5978167/df9aa76551d4/materials-11-00790-sch001.jpg

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