丙二醇对四甲氧基硅烷水解缩聚行为的影响

doi:10.11902/1005.4537.2021.229

中国腐蚀与防护学报

2022, Vol. 42

Issue (5): 717-723 DOI: 10.11902/1005.4537.2021.229

研究报告

本期目录 | 过刊浏览

丙二醇对四甲氧基硅烷水解缩聚行为的影响

陈小涵, 周金赫, 胡吉明(

)

浙江大学化学系杭州 310027

Influence of Propylene Glycol on Hydrolytie Polyconden-sation of Tetramethoxysilane

CHEN Xiaohan, ZHOU Jinhe, HU Jiming(

)

Department of Chemistry, Zhejiang University, Hangzhou 310027, China

全文: PDF(3684 KB) HTML

摘要:

1,2-丙二醇沸点184.8 ℃、闪点107.2 ℃,能与水和乙醇混溶且安全无毒,是一种绿色环保型溶剂,可能是目前常用硅烷处理液中高乙醇含量导致高安全风险的解决方案之一。本文采用质子核磁共振 (¹H NMR) 和MALDI-TOF质谱技术对4种不同水解环境下四甲氧基硅烷的水解缩聚动力学进行了研究,主要考察丙二醇的影响。结果显示,在溶液中水含量较低或中性环境下,丙二醇的加入显著提高硅烷的水解和缩聚速度；当溶液中的水含量较高且酸性环境下,由于硅烷本身的水解和缩聚速度较高,其受丙二醇的影响变得不再明显。

关键词 ：四甲氧基硅烷, 丙二醇, 溶剂, 水解, 缩聚

Abstract：

Propylene glycol has many merits, such as high boiling point (184.8 ℃), high flash point (107.2 ℃), nontoxicity and can be miscible with water and ethanol. These make propylene glycol be an environment-friendly and safe solvent that may be a promising alternative to commonly used ethanol or methanol solvent in silanization solution. In this paper, the kinetics of hydrolytie polycondensation of tetramethoxysilane in four environments with different water content and pH value with the addition of propylene glycol were systematically investigated by means of proton nuclear magnetic resonance (¹H NMR) and MALDI-TOF mass spectrometry. The results showed that the addition of propylene glycol remarkably promoted the rate of hydrolytie polycondensation of silane in low water content or neutral environment, however the above effect caused by propylene glycol can be ignored due to the high rates of hydrolytie polycondensation of silane itself when the water content is higher or the pH of solution is relatively lower.

Key words： tetramethoxysilane propylene glycol solvent hydrolyzation polycondensation

收稿日期: 2021-09-02

ZTFLH:

TG172

基金资助:国家自然科学基金(52071283)

通讯作者: 胡吉明 E-mail: kejmhu@zju.edu.cn

Corresponding author: HU Jiming E-mail: kejmhu@zju.edu.cn

作者简介: 陈小涵,女,1998年生,硕士生

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引用本文:

陈小涵, 周金赫, 胡吉明. 丙二醇对四甲氧基硅烷水解缩聚行为的影响[J]. 中国腐蚀与防护学报, 2022, 42(5): 717-723.
Xiaohan CHEN, Jinhe ZHOU, Jiming HU. Influence of Propylene Glycol on Hydrolytie Polyconden-sation of Tetramethoxysilane. Journal of Chinese Society for Corrosion and protection, 2022, 42(5): 717-723.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.229 或 https://www.jcscp.org/CN/Y2022/V42/I5/717

表1 硅烷溶液组分

图1 不同水解时间后TMOS-1和TMOS-2溶液的1H NMR及甲醇峰的积分面积 (相对于丙酮内标)

图2 不同水解时间后TMOS-1和TMOS-2溶液的Maldi-Tof质谱图

图3 不同水解时间后TMOS-a和TMOS-b溶液的1H NMR和甲醇峰的积分面积

图4 不同水解时间后TMOS-a和TMOS-b溶液的Maldi-Tof质谱图

图5 pH为7时样品凝胶化所需时间

图6 不同水解时间后TMOS-Y和TMOS-YB溶液的1H NMR及甲醇峰的积分面积

图7 不同水解时间后TMOS-Y和TMOS-YB溶液的Maldi-Tof质谱图

图8 水解1和1.5 h后TMOS-e和TMOS-eb溶液的1H NMR及甲醇峰的积分面积

图9 不同水解时间后TMOS-e和TMOS-eb溶液的Maldi-Tof质谱图

图10 pH为4时样品凝胶化所需时间

1	Twite R L, Bierwagen G P. Review of alternatives to chromate for corrosion protection of aluminum aerospace alloys [J]. Prog. Org. Coat., 1998, 33: 91 doi: 10.1016/S0300-9440(98)00015-0
2	Osborne J H, Blohowiak K Y, Taylor S R, et al. Testing and evaluation of nonchromated coating systems for aerospace applications [J]. Prog. Org. Coat., 2001, 41: 217 doi: 10.1016/S0300-9440(01)00132-1
3	Child T F, van Ooij W J. Application of silane technology to prevent corrosion of metals and improve paint adhesion [J]. Trans. IMF, 1999, 77: 64 doi: 10.1080/00202967.1999.11871249
4	Petrunin M A, Gladkikh N A, Maleeva M A, et al. The use of organosilanes to inhibit metal corrosion. A review [J]. Int. J. Corros. Scale Inhib., 2019, 8: 882
5	Aramaki K. Prevention of iron corrosion at scratched surfaces in NaCl solutions by thin organosiloxane polymer films containing octylthiopropionate [J]. Corros. Sci., 2000, 42: 2023 doi: 10.1016/S0010-938X(00)00037-8
6	Liu L, Hu J M, Zhang J Q, et al. Progress in anti-corrosive treatment of metals by silanization [J]. J. Chin. Soc. Corros. Prot., 2006, 26: 59
6	刘倞, 胡吉明, 张鉴清等. 金属表面硅烷化防护处理及其研究现状 [J]. 中国腐蚀与防护学报, 2006, 26: 59
7	Beccaria A M, Chiaruttini L. The inhibitive action of metacryloxypropylmethoxysilane (MAOS) on aluminium corrosion in NaCl solutions [J]. Corros. Sci., 1999, 41: 885 doi: 10.1016/S0010-938X(98)00161-9
8	Bexell U, Grehk T M. A corrosion study of hot-dip galvanized steel sheet pre-treated with γ-mercaptopropyltrimethoxysilane [J]. Surf. Coat. Technol., 2007, 201: 4734 doi: 10.1016/j.surfcoat.2006.10.014
9	Cabral A, Duarte R G, Montemor M F, et al. Analytical characterisation and corrosion behaviour of bis-[triethoxysilylpropyl]tetrasulphide pre-treated AA2024-T3 [J]. Corros. Sci., 2005, 47: 869 doi: 10.1016/j.corsci.2004.07.024
10	Zhu D Q, van Ooij W J. Corrosion protection of AA 2024-T3 by bis-[3-(triethoxysilyl) propyl]tetrasulfide in neutral sodium chloride solution. Part 1: corrosion of AA 2024-T3 [J]. Corros. Sci., 2003, 45: 2163 doi: 10.1016/S0010-938X(03)00060-X
11	Wang J, Wu L K, Zhou J H, et al. Construction of a novel painting system using electrodeposited SiO₂ film as the pretreatment layer [J]. Corros. Sci., 2013, 68: 57 doi: 10.1016/j.corsci.2012.10.033
12	Liu Y H, Jin X H, Hu J M. Electrodeposited silica films post-treated with organosilane coupling agent as the pretreatment layers of organic coating system [J]. Corros. Sci., 2016, 106: 127 doi: 10.1016/j.corsci.2016.01.032
13	Liu Y H, Xu J B, Zhang J T, et al. Electrodeposited silica film interlayer for active corrosion protection [J]. Corros. Sci., 2017, 120: 61 doi: 10.1016/j.corsci.2017.01.017
14	Zhu D Q, vanOoij, W J. Corrosion protection of metals by water-based silane mixtures of bis-[trimethoxysilylpropyl]amine and vinyltriacetoxysilane [J]. Prog. Org. Coat., 2004, 49: 42 doi: 10.1016/j.porgcoat.2003.08.009
15	Zhu D Q, van Ooij W J. Enhanced corrosion resistance of AA 2024-T3 and hot-dip galvanized steel using a mixture of bis-[triethoxysilylpropyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine [J]. Electrochim. Acta, 2004, 49: 1113 doi: 10.1016/j.electacta.2003.10.023
16	Harada Y, Girolami G S, Nuzzo R G. Growth kinetics and morphology of self-assembled monolayers formed by contact printing 7-octenyltrichlorosilane and octadecyltrichlorosilane on Si(100) wafers [J]. Langmuir, 2004, 20: 10878
17	Yuan W, van Ooij W J. Characterization of organofunctional silane films on zinc substrates [J]. J. Colloid Interface Sci., 1997, 185: 197 doi: 10.1006/jcis.1996.4604
18	Subramanian V, van Ooij W J. Silane based metal pretreatments as alternatives to chromating: shortlisted [J]. Surf. Eng., 1999, 15: 168 doi: 10.1179/026708499101516407
19	Wang Y M, Puomi P, van Ooij W J. Effect of substrate cleaning solution pH on the corrosion performance of silane-coated cold-rolled steel [J]. J. Adhes. Sci. Technol., 2007, 21: 935 doi: 10.1163/156856107781393901
20	Yang L X, Feng J, Zhang W G, et al. Experimental and computational study on hydrolysis and condensation kinetics of γ-glycidoxypropyltrimethoxysilane (γ-GPS) [J]. Appl. Surf. Sci., 2010, 257: 990 doi: 10.1016/j.apsusc.2010.07.102
21	Yang Y Q, Liu L, Hu J M, et al. Improved barrier performance of metal alkoxide-modified methyltrimethoxysilane films [J]. Thin Solid Films, 2012, 520: 2052 doi: 10.1016/j.tsf.2011.10.041

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