抗水解三硅氧烷表面活性剂的研制
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摘要
以七甲基三硅氧烷和甲基烯丙基聚醚、炔二醇醚为原料,通过硅氢加成反应合成了2种表面活性剂:甲基烯丙基聚醚改性三硅氧烷SE-429和炔二醇醚改性三硅氧烷SE-640。考察了催化剂种类及用量、温度对反应的影响,确定了较佳的反应条件为:催化剂选用烯丙基铂配合物、催化剂用量为0.02%、温度为110～120℃。研究了产物的表面张力、铺展面积、临界胶束浓度(CMC)、动态表面张力(DST)以及抗水解稳定性。结果表明,这2种三硅氧烷表面活性剂质量分数为0.1%的水溶液表面张力均小于21 mN/m,储存360 d后表面张力增幅分别为78.6%和28.2%,低于常规的烯丙基聚醚改性三硅氧烷SE-90(201.5%);SE-429的CMC为40.7 mg·L,铺展面积与SE-90接近;SE-640水溶液不形成胶束,表面张力能更快达到平衡。两者具有优良的表面活性和抗水解稳定性。
Two kinds of organo modified trisiloxane surfactants(i.e.methyl allyl polyether modified trisiloxane of SE-429 and acetylenicdiolether modified trisiloxane of SE-640) were synthesized,respectively,by hydrosilylation of 1,1,1,3,5,5,5-heptamethyltrisiloxane with 2-methyl allyl polyether and acetylenicdiolalkoxylate.The effect of the types and amount of catalyst,and the temperature on the reaction were investigated.The optimized reaction conditions are as follows:the mass fraction of catalyst(allyl complex platinum) is 0.02%,the reaction temperature is 110-120℃.The surface tension,the spreading area,critical micelle concentration(CMC),dynamic surface tension(DST) and the hydrolysis resistance of the trisiloxane surfactants are investigated.Results show that the surface tension of aqueous solutions(0.1% w/w) is less than 21 mN/m.In addition,the amplitude of surface tension aging in 360 days is 78.6% and 28.2%,respectively,lower than that of conventional allyl polyether modified trisiloxane surfactants SE-90(201.5%).The CMC of SE-429 is 40.7 mg/L,whose spreading area is close to that of SE-90.The aqueous solution of SE-640 cannot form micelle,and its surface tension reaches equilibrium faster than those of SE-90 and SE-429.The property analysis reveals that both the trisiloxane surfactants have excellent surface activity and hydrolysis resistance.
Two kinds of organo modified trisiloxane surfactants(i.e.methyl allyl polyether modified trisiloxane of SE-429 and acetylenicdiolether modified trisiloxane of SE-640) were synthesized,respectively,by hydrosilylation of 1,1,1,3,5,5,5-heptamethyltrisiloxane with 2-methyl allyl polyether and acetylenicdiolalkoxylate.The effect of the types and amount of catalyst,and the temperature on the reaction were investigated.The optimized reaction conditions are as follows:the mass fraction of catalyst(allyl complex platinum) is 0.02%,the reaction temperature is 110-120℃.The surface tension,the spreading area,critical micelle concentration(CMC),dynamic surface tension(DST) and the hydrolysis resistance of the trisiloxane surfactants are investigated.Results show that the surface tension of aqueous solutions(0.1% w/w) is less than 21 mN/m.In addition,the amplitude of surface tension aging in 360 days is 78.6% and 28.2%,respectively,lower than that of conventional allyl polyether modified trisiloxane surfactants SE-90(201.5%).The CMC of SE-429 is 40.7 mg/L,whose spreading area is close to that of SE-90.The aqueous solution of SE-640 cannot form micelle,and its surface tension reaches equilibrium faster than those of SE-90 and SE-429.The property analysis reveals that both the trisiloxane surfactants have excellent surface activity and hydrolysis resistance.
引文
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[15]张殿龙,屈文山,李哲.炔二醇类双子表面活性剂的表面活性和铺展性能研究[J].印染助剂,2016,33(4):15-17.
[2]李祥洪.三硅氧烷表面活性剂[J].有机硅材料,2004,18(1):32-34.
[3]黄良仙,郝丽芬,袁俊敏,等.农用有机硅表面活性剂的制备及应用研究新进展[J].有机硅材料,2010,24(1):59-64.
[4]KNOCHE M,TAMURA H,BUKOVAC M J.Performance and stability of the organosilicon surfactant L-77:effect of p H,concentration,and temperature[J].J Agric Food Chem,1991,39(1):202-206.
[5]SNOW S A,FENTON W N,OWEN M J.Synthesis and characterization of zwitterionic silicone sulfobetaine surfactants[J].Langmuir,1990,6(2):385-391.
[6]SAKUTA K,GUNMA-KEN.Water-base agrochemical composition containing polyether-modified silicon:US,6300283[P].2001-10-09.
[7]POLICELLO G A,LEATHERMAN M D,PENG WQ,et a1.Hydrolysis resistant organomodified trisiloxane surfactants:US,2007197394A1[P].2007-08-23.
[8]吴建芬,邵均林,赵柯,等.聚醚改性三硅氧烷的合成工艺研究[J].有机硅材料,2012,26(5):316-319.
[9]汪瑜华,李瑶,佘慧玲,等.三硅氧烷和四硅氧烷乙氧基化物的合成和性能[J].有机硅材料,2005,19(1):5-7.
[10]龚红升,胡文斌,廖列文,等.非离子型聚醚改性三硅氧烷表面活性剂的合成表征及性能[J].化工学报,2015,66(6):2181-2188.
[11]余龙飞,郑小珊,李欢玲,等.聚醚改性聚硅氧烷的合成及其在水性涂料消泡剂中的应用[J].有机硅材料,2013,27(5):333-338.
[12]李光亮.有机硅高分子化学[M].北京:科学出版社,1998:27-35.
[13]张墩明,张宇峰.烯丙基硅(氧)烷铂配合物硅氢加成催化剂的研究[J].精细化工,2000,17(2):82-85.
[14]顾强,李干佐,沈强.乙氧基炔二醇类表面活性剂应用性能与机理的研究进展[J].精细化工,1999,16(增刊):37-40.
[15]张殿龙,屈文山,李哲.炔二醇类双子表面活性剂的表面活性和铺展性能研究[J].印染助剂,2016,33(4):15-17.