含巯基聚硅氧烷改性环氧树脂的制备及性能

doi:10.19491/j.issn.1001-9278.2022.07.004

中国塑料 ›› 2022, Vol. 36 ›› Issue (7): 21-29.DOI: 10.19491/j.issn.1001-9278.2022.07.004

含巯基聚硅氧烷改性环氧树脂的制备及性能

谭立钦¹^,²^,³^,⁴^,⁵, 刘伟区¹^,⁵(), 梁利岩¹^,⁵(), 王硕¹^,⁵, 冯志强¹^,⁵, 林家明¹^,⁵

^1.中国科学院广州化学研究所，广州 510650
^2.广东省电子有机聚合物材料重点实验室，广州 510650
^3.中国科学院新型特种精细化学品工程实验室，广州 510650
^4.国科广化韶关新材料研究院，广东韶关 512400
^5.中国科学院大学，北京 101408

收稿日期:2022-03-16 出版日期:2022-07-26 发布日期:2022-07-20
通讯作者: 刘伟区（1963—），男，研究员，主要从事功能化树脂材料研究，liuwq@gic.ac.cn
梁利岩（1974—），男，研究员，主要从事热固性功能高分子材料研究，lyliang@gic.ac.cn
E-mail:liuwq@gic.ac.cn;lyliang@gic.ac.cn
基金资助:
责任心强，工作热情，积极支持期刊发展

Preparation and performance of epoxy resin modified with mercaptan polysiloxane

TAN Liqin¹^,²^,³^,⁴^,⁵, LIU Weiqu¹^,⁵(), LIANG Liyan¹^,⁵(), WANG Shuo¹^,⁵, FENG Zhiqiang¹^,⁵, LIN Jiaming¹^,⁵

^1.Guangzhou Institute of Chemistry，Chinese Academy of Sciences，Guangzhou 510650，China
^2.Guangdong Provincial Key Laboratory of Organic Polymer Materials for Electronics，Guangzhou 510650，China
^3.CAS Engineering Laboratory for Special Fine Chemicals，Guangzhou 510650，China
^4.CASH GCC Shaoguan Research Institute of Advanced Materials，Shaoguan 512400，China
^5.University of Chinese Academy of Sciences，Beijing 101408，China

Received:2022-03-16 Online:2022-07-26 Published:2022-07-20
Contact: LIU Weiqu, LIANG Liyan E-mail:liuwq@gic.ac.cn;lyliang@gic.ac.cn

摘要/Abstract

摘要：

以双酚A环氧树脂（E51）为基料、聚醚胺（D?230）为固化剂、含巯基聚硅氧烷（PMMS）为改性剂，分别经过简单物理混合和化学改性的方法，制备了一系列聚硅氧烷改性环氧树脂（E51⁃D⁃PMMS）固化物。通过衰减全反射红外（ATR?FTIR）和X射线衍射仪（XRD）表征了固化物的结构特征；通过拉伸测试和冲击实验、扫描电子显微镜（SEM）、接触角测量（CA）、动态热力学分析（DMA）及中性盐雾实验探究了改性固化物的力学性能、热稳定性、防腐性能等。结果表明，化学改性的E51?D?PMMS固化物的综合物理化学性能优于简单物理改性的，当PMMS含量为1 %（质量分数，下同）时，改性固化物的拉伸强度为74.63 MPa，较改性前提高了13.5 %，断裂伸长率提高了40.2 %，冲击强度提高了43.7 %；水接触角从改性前的72.8 °增至100.3 °，表面能从39.4 J/m²降至17.4 J/m²，吸水率下降了44 %，耐水性能大大增强；其防腐性能和玻璃化转变温度（T_g）也有一定的提升。

关键词: 巯基, 聚硅氧烷, 环氧树脂, 力学性能, 耐水性, 防腐性能

Abstract:

In this article， a series of polysiloxane epoxy composites were prepared through physical mixing and chemical modification methods using epoxy resin （E51） as a base material， amino?terminated polyoxypropylene （D?230） as a curing agent， and mercaptan polysiloxane （PMMS） as a modifier. The chemical structure of the cured epoxy resins were characterized using attenuated total reflection infrared spectroscope and X?ray diffractometer， and their mechanical properties， thermal stability and anti?corrosion performance were investigated through tensile and impact tests， scanning electron microscopy， contact angle measurement， dynamic thermomechanical analysis， and neutral salt spray test. The results indicated that the cured epoxy resins exhibited better comprehensive properties that the conventional epoxy resin. The cured epoxy resins containing 1 wt% PMMS obtained tensile strength of 74.63 MPa， which was 13.5 % higher than that before modification. Compared to neat pure E51， the polysiloxane epoxy resins showed an increase in elongation at break by 40.2 % and in impact strength by 43.7 %. The contact angle of the cured epoxy resins increased from 72.8 ° to 100.3 °， their surface energy decreased from 39.4 J/m² to 17.4 J/m²， their water absorption rate decreased by 44 %， and their water resistance was enhanced greatly. In addition， their anti?corrosion performance and T_g were also improved.

Key words: mercapto, polysiloxane, epoxy resin, mechanical property, water resistance, corrosion resistance

中图分类号:

TQ323.5

谭立钦, 刘伟区, 梁利岩, 王硕, 冯志强, 林家明. 含巯基聚硅氧烷改性环氧树脂的制备及性能[J]. 中国塑料, 2022, 36(7): 21-29.

TAN Liqin, LIU Weiqu, LIANG Liyan, WANG Shuo, FENG Zhiqiang, LIN Jiaming. Preparation and performance of epoxy resin modified with mercaptan polysiloxane[J]. China Plastics, 2022, 36(7): 21-29.

图/表 11

图1 E51?D?PMMS固化物的制备路线

Fig.1 Preparation route of the cured polysiloxane epoxy resin

样品编号	E51 含量	D230 含量	PMMS 含量	SO 含量	DMAP 含量
E51	25	7.78	0	0	0
E51⁃D⁃PMMS⁃1 %	25	7.78	0.25	0	0.01
E51⁃D⁃PMMS⁃3 %	25	7.78	0.75	0	0.03
E51⁃D⁃PMMS⁃5 %	25	7.78	1.25	0	0.05
E51⁃D⁃PMMS⁃7 %	25	7.78	1.75	0	0.07
E51⁃SO⁃1 %	25	7.78	0	0.25	0
E51⁃PMMS⁃1 %	25	7.78	0.25	0	0

表1 E51?D?PMMS固化物的投料比 (g)

Tab.1 Feeding ratio of the cured polysiloxane epoxy resin

图2 E51、PMMS与E51?D?PMMS?1 %固化物的FTIR谱图

Fig.2 FTIR spectra of neat cured E51， PMMS and E51?D?PMMS?1 %

图3 E51与E51?D?PMMS?1 %的XRD谱图

Fig.3 XRD patterns of neat cured E51 and E51?D?PMMS?1 %

图4 E51?D?PMMS固化物的力学性能

Fig.4 Mechanical properties of the cured polysiloxane epoxy resin

图5 E51?D?PMMS固化物断裂面的SEM照片

Fig.5 SEM of fracture surface of the cured polysiloxane epoxy resin

图6 E51?D?PMMS固化物的水接触角和乙二醇接触角

Fig.6 Water contact angle and ethylene glycol contact angle of the cured polysiloxane epoxy resin

图7 E51?D?PMMS固化物的表面能和吸水率

Fig.7 Surface energy and water absorption of the cured polysiloxane epoxy resin

图8 E51?D?PMMS固化物的900 h盐雾试验图

Fig.8 900 h salt spray test of the cured polysiloxane epoxy resin

图9 E51和E51?D?PMMS?1 %固化物的tan δ曲线

Fig.9 tan δ of neat cured E51 and E51?D?PMMS?1 % composites

样品	T_g /℃	储能模量/MPa
样品	T_g /℃	-50 ℃	25 ℃
E51	75.0	3 326	2 702
E51⁃D⁃PMMS⁃1 %	74.6、94.3	3 922	2 924

表2 E51和E51?D?PMMS?1 %固化物的DMA数据

Tab.2 DMA data of neat cured E51 and E51?D?PMMS?1 %

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含巯基聚硅氧烷改性环氧树脂的制备及性能

Preparation and performance of epoxy resin modified with mercaptan polysiloxane

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