磷酸酯型三硅氧烷表面活性剂的合成及应用性能
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摘要
在H_2PtCl6催化下,1,1,1,3,5,5,5-七甲基三硅氧烷(HTSO)和烯丙基聚氧乙烯醚(FAE-10)经硅氢加成反应先制得端羟基聚醚改性三硅氧烷(TPETS),再与H_3PO_4进行酯化反应,合成了一种磷酸酯型三硅氧烷表面活性剂(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、临界胶束浓度以及在农药中的应用性能等进行了测定.结果表明:酯化反应的优化条件为n(TPETS)∶n(H_3PO_4)=1∶1.1、反应温度80℃、反应时间4h.PTSS的临界胶束浓度(cmc)为5.0×10~(-4) g/mL,临界表面张力(γ_(cmc))为21.9 mN/m.在41%草甘麟异丙胺盐水剂和36%甲基硫菌灵悬浮剂各1 000倍稀释药液中添加质量分数为0.1%的PTSS后,可使其农药稀释液的表面张力(γ)分别由54.83mN/m和45.48mN/m降至20.38mN/m和17.40mN/m;可使其在银杏树叶、七叶树叶、梧桐叶、塑料薄膜上的铺展面积分别增大4~8倍和2~4倍.
Hydroxyl-terminated polyether modified trisiloxanes(TPETS)was prepared by hydrosilylation of 1,1,1,3,5,5,5-heptamethyltrisiloxane(HTSO)with allyl polyoxyethylene ether(FAE-10)in the presence of chloroplatinic acid.A new kind of phosphate trisiloxane surfactants(PTSS)was synthesized by the esterification reaction of TPETS with phosphoric acid(H_3PO_4).The esterification reaction conditions of PTSS synthesis were optimized using orthogonal test.The structure of PTSS was characterized by infrared spectra(IR).The critical surface tension(γ_(cmc))and critical micelle concentration(cmc)of PTSS solution were measured.And its application was investigated in pesticide.Experimental results were showed as follows.Optimum conditions of the esterification reaction for the PTSS are that reaction temperature is 80℃,reaction time is 4h,n(TPETS)∶n(H_3PO_4)=1∶1.1.Theγcmc of PTSS solution is 21.9mN/m,the cmc of PTSS solution is 5.0×10~(-4) g/mL.When PTSS solution was added with 0.1% into glyphosate isopropylamin 41% AS and thiophanatemethyl 36% SC diluted to 1 000 times with water,the surface tension of glyphosate isopropylamin solution and thiophanate-methyl solution decreased from 54.83 mN/m and 45.48mN/m to 20.38mN/m and 17.40mN/m,respectively.It′s the spreading area on the ginkgo leaves,horse chestnut leaves,french phoenix tree leaves and plastic film is increased 4~8times and 2~4times,respectively.
Hydroxyl-terminated polyether modified trisiloxanes(TPETS)was prepared by hydrosilylation of 1,1,1,3,5,5,5-heptamethyltrisiloxane(HTSO)with allyl polyoxyethylene ether(FAE-10)in the presence of chloroplatinic acid.A new kind of phosphate trisiloxane surfactants(PTSS)was synthesized by the esterification reaction of TPETS with phosphoric acid(H_3PO_4).The esterification reaction conditions of PTSS synthesis were optimized using orthogonal test.The structure of PTSS was characterized by infrared spectra(IR).The critical surface tension(γ_(cmc))and critical micelle concentration(cmc)of PTSS solution were measured.And its application was investigated in pesticide.Experimental results were showed as follows.Optimum conditions of the esterification reaction for the PTSS are that reaction temperature is 80℃,reaction time is 4h,n(TPETS)∶n(H_3PO_4)=1∶1.1.Theγcmc of PTSS solution is 21.9mN/m,the cmc of PTSS solution is 5.0×10~(-4) g/mL.When PTSS solution was added with 0.1% into glyphosate isopropylamin 41% AS and thiophanatemethyl 36% SC diluted to 1 000 times with water,the surface tension of glyphosate isopropylamin solution and thiophanate-methyl solution decreased from 54.83 mN/m and 45.48mN/m to 20.38mN/m and 17.40mN/m,respectively.It′s the spreading area on the ginkgo leaves,horse chestnut leaves,french phoenix tree leaves and plastic film is increased 4~8times and 2~4times,respectively.
引文
[1]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].广西:广西大学,2013.
[2]温福山,孔祥双,王维,等.一种新型阳离子三硅氧烷表面活性剂的合成及其表面性能[J].应用化学,2014,31(10):1 216-1 221.
[3]Randal M H.Silicone surfactants:New developments[J].Current Opinion in Colloid&Interface Science,2002,7(5-6):255-261.
[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]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.
[6]Churaev N V,Ershov A P,Esipova N E,et al.Application of a trisiloxane surfactant for removal of oils from hydrophobic surfaces[J].Langmuir,2001,17(5):1 349-1 352.
[7]Policello G A,Leatherman M D,Peng W Q,et al.Hydrolysis resistant organomodified trisiloxane surfactants[P].WO:2008111928,2008-09-18.
[8]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.
[9]黄良仙,黄洁,李献起,等.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(自然科学版),2010,28(3):40-43,59.
[10]Leatherman M D,Policello G A,Peng W Q,et al.Hydrolysis resistant organomodified trisiloxane ionic surfactants[P].US:2009176893,2009-07-09.
[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]张国栋,韩富.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.
[13]黄良仙,安秋凤,李献起.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.
[14]O′lenickjr.Phosphated silicone polymers[P].US:5070171,1991-12-03.
[15]O′lenickjr.Silicone alkyl phosphate esters[P].US:6175028,2001-01-16.
[16]黄良仙,顾玲.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]李欢玲.聚醚改性硅氧烷磷酸酯盐的合成与应用[D].广州:华南理工大学,2010.
[18]王学川,丁建华,强涛涛,等.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(自然科学版),2008,26(4):42-44.
[19]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.
[20]刘亨昌.磷酸酯表面活性剂合成及结构与性能的研究[D].河北:河北科技大学,2012.
[21]田欣,董文增.烷基磷酸酯中单、双酯含量的测定[J].印染助剂,2000,17(3):19-20.
[22]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[P].CN:102343235A,2012-02-08.
[23]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.
[2]温福山,孔祥双,王维,等.一种新型阳离子三硅氧烷表面活性剂的合成及其表面性能[J].应用化学,2014,31(10):1 216-1 221.
[3]Randal M H.Silicone surfactants:New developments[J].Current Opinion in Colloid&Interface Science,2002,7(5-6):255-261.
[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]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.
[6]Churaev N V,Ershov A P,Esipova N E,et al.Application of a trisiloxane surfactant for removal of oils from hydrophobic surfaces[J].Langmuir,2001,17(5):1 349-1 352.
[7]Policello G A,Leatherman M D,Peng W Q,et al.Hydrolysis resistant organomodified trisiloxane surfactants[P].WO:2008111928,2008-09-18.
[8]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.
[9]黄良仙,黄洁,李献起,等.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(自然科学版),2010,28(3):40-43,59.
[10]Leatherman M D,Policello G A,Peng W Q,et al.Hydrolysis resistant organomodified trisiloxane ionic surfactants[P].US:2009176893,2009-07-09.
[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]张国栋,韩富.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.
[13]黄良仙,安秋凤,李献起.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.
[14]O′lenickjr.Phosphated silicone polymers[P].US:5070171,1991-12-03.
[15]O′lenickjr.Silicone alkyl phosphate esters[P].US:6175028,2001-01-16.
[16]黄良仙,顾玲.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]李欢玲.聚醚改性硅氧烷磷酸酯盐的合成与应用[D].广州:华南理工大学,2010.
[18]王学川,丁建华,强涛涛,等.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(自然科学版),2008,26(4):42-44.
[19]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.
[20]刘亨昌.磷酸酯表面活性剂合成及结构与性能的研究[D].河北:河北科技大学,2012.
[21]田欣,董文增.烷基磷酸酯中单、双酯含量的测定[J].印染助剂,2000,17(3):19-20.
[22]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[P].CN:102343235A,2012-02-08.
[23]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.