磷酸酯型聚醚改性三硅氧烷的制备及界面性能
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摘要
以烯丙基聚氧乙烯醚(FAE-10)和1,1,1,3,5,5,5-七甲基三硅氧烷(HTSO)为原料,在H_2Pt Cl6催化下,经硅氢加成反应先合成末端带羟基的聚醚改性三硅氧烷(TPETS),再与H_3PO_4进行酯化反应,制得一种磷酸酯型聚醚改性三硅氧烷(PTSS)。用正交试验对其酯化反应条件进行了优化,用红外光谱(IR)对PTSS的结构进行了表征,并对PTSS的临界表面张力、临界胶束浓度、发泡性能等进行了测定。结果表明,PTSS酯化反应的优化条件为:反应温度80℃、反应时间4 h、n(TPETS)∶n(H_3PO_4)=1∶1.1。PTSS的临界表面张力(γ_(cmc))为21.9 m N/m,临界胶束浓度(cmc)为5.0×10~(-4)g/m L。质量分数为0.1%的PTSS水溶液发泡力为3.03,5 min稳泡性为0.590。对煤油和苯的乳化力分别为131和304 s。
A new kind of phosphate polyether modified trisiloxane(PTSS) was synthesized by the esterification reaction of hydroxyl-terminated polyether modified trisiloxanes(TPETS) with phosphoric acid(H_3PO_4).TPETS was prepared by hydrosilylation of 1,1,1,3,5,5,5-heptamethyltrisiloxane(HTSO) with allyl polyoxyethylene ether(FAE-10) using chloroplatinic acid as the catalyst. The esterification reaction conditions of PTSS synthesis were optimized using orthogonal experiment. The structure of PTSS was characterized by infrared spectra(IR). The properties of PTSS, such as critical surface tension(γcmc), critical micelle concentration(cmc), foaming properties and emulsifying ability were measured. The results showed that the optimum conditions of the esterification reaction for the PTSS: reaction temperature 80 ℃, reaction time 4 h, n(TPETS): n(H_3PO_4) =1:1.1.And the γ_(cmc)of PTSS solution was 21.9 m N/m, the cmc of PTSS solution was 5.0×10~(-4)g/m L. The foaming power of 0.1% PTSS(mass fraction) solution was 3.03 and foam stability after 5 min was 0.590. The emulsifying ability of 0.1% PTSS solution were 131 and 304 s for kerosene and benzene, respectively.
A new kind of phosphate polyether modified trisiloxane(PTSS) was synthesized by the esterification reaction of hydroxyl-terminated polyether modified trisiloxanes(TPETS) with phosphoric acid(H_3PO_4).TPETS was prepared by hydrosilylation of 1,1,1,3,5,5,5-heptamethyltrisiloxane(HTSO) with allyl polyoxyethylene ether(FAE-10) using chloroplatinic acid as the catalyst. The esterification reaction conditions of PTSS synthesis were optimized using orthogonal experiment. The structure of PTSS was characterized by infrared spectra(IR). The properties of PTSS, such as critical surface tension(γcmc), critical micelle concentration(cmc), foaming properties and emulsifying ability were measured. The results showed that the optimum conditions of the esterification reaction for the PTSS: reaction temperature 80 ℃, reaction time 4 h, n(TPETS): n(H_3PO_4) =1:1.1.And the γ_(cmc)of PTSS solution was 21.9 m N/m, the cmc of PTSS solution was 5.0×10~(-4)g/m L. The foaming power of 0.1% PTSS(mass fraction) solution was 3.03 and foam stability after 5 min was 0.590. The emulsifying ability of 0.1% PTSS solution were 131 and 304 s for kerosene and benzene, respectively.
引文
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[2]毛桃嫣.新型阳离子三硅氧烷表面活性剂的无溶剂合成及性能研究[D].南宁:广西大学,2013.
[3]陈耀彬,罗儒显.三硅氧烷表面活性剂的合成、性能及应用[J].日用化学工业,2010,40(4):287-292.
[4]李祥洪.三硅氧烷表面活性剂[J].有机硅材料,2004,18(1):32-34.
[5]RANDAL M H.Silicone surfactants:new developments[J].CurrentOpinion in Colloid&Interface Science,2002,7(5/6):255-261.
[6]黄良仙,安秋凤,杨军胜,等.聚醚改性三硅氧烷表面活性剂的合成及其界面性能[J].精细石油化工,2010,27(4):19-22.
[7]CHURAEV N V,ERSHOV A P,ESIPOVA N E,et al.Application of atrisiloxane surfactant for removal of oils from hydrophobic surfaces[J].Langmuir,2001,17(5):1 349-1 352.
[8]POLICELLO G A,LEATHERMAN M D,PENG W Q,et al.Hydrolysisresistant organomodified trisiloxane surfactants:WO,2008111928[P].2008-09-18.
[9]黄良仙,黄洁.非离子型三硅氧烷表面活性剂制备和表征[J].陕西科技大学学报,2010,28(3):40-43.
[10]LEATHERMAN M D,POLICELLO G A,PENG W Q,et al.Hydroly-sis resistant organomodified trisiloxane ionic surfactants:US,2009176893[P].2009-07-09.
[11]黄良仙,丁洋,黄洁.阴离子型三硅氧烷表面活性剂合成及其性能[J].应用化学,2011,28(6):722-726.
[12]黄良仙,安秋凤,李献起,等.阳离子型三硅氧烷表面活性剂合成及性能[J].精细化工,2010,27(7):642-645.
[13]张国栋,韩富,张高勇.新型三硅氧烷表面活性剂合成与界面性能[J].化学学报,2006,64(11):1 205-1 208.
[14]O′LENICKJR.Phosphated silicone polymers:US,5070171[P].1991-12-03.
[15]O′LENICKJR.Silicone alkyl phosphate esters:US,6175028[P].2001-01-16.
[16]黄良仙,顾玲,杨百勤,等.磷酸酯型有机硅表面活性剂制备及其表面活性[J].日用化学工业,2008,38(2):87-90.
[17]王学川,王固霞,宋世鹏.聚醚改性硅氧烷磷酸酯的合成[J].中国皮革,2007,36(3):57-60.
[18]王学川,丁建华.有机硅磷酸酯加脂剂的制备及性能研究[J].陕西科技大学学报,2008,26(4):42-44.
[19]李欢玲.聚醚改性硅氧烷磷酸酯盐的合成与应用[D].上海:华南理工大学,2010.
[20]刘亨昌.磷酸酯表面活性剂合成及结构与性能的研究[D].石家庄:河北科技大学,2012.
[21]黄良仙,李顺琴,李婷.聚醚氨基改性三硅氧烷的制备及性能[J].印染助剂,2014,31(6):21-26.
[22]黄良仙,李顺琴,李婷.端基型氨基聚醚有机硅表面活性剂的合成及性能[J].印染助剂,2014,31(11):24-28.
[23]崔盂忠,任万忠,李竹云.双子型有机硅表面活性剂及其制备方法和用途:中国,102343235A[P].2012-02-08.