含磷氮原子有机硅聚合物的制备及性能研究
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摘要
以八甲基环四硅氧烷、氨基硅烷偶联剂等为原料,通过开环聚合反应制备了氨基硅油中间体(AS),再用AS与苯基膦酰二氯进行亲核取代反应合成含磷氮原子的有机硅聚合物(PSiNP)。用红外光谱(IR)、核磁共振氢谱(1HNMR)、热重分析对PSiNP进行结构和性能表征,研究了反应温度、反应时间、溶剂种类以及投料比n(NH2)∶n(PCl)对处理织物阻燃性和柔软性的影响。结果表明:合成PSiNP较佳条件为反应温度10℃,反应时间1 h,溶剂苯,n(NH2)∶n(PCl)=2.0∶1.0。未处理织物、AS处理织物、PSiNP处理织物的弯曲刚度分别为403、168、195 mN;燃烧时间分别为7.47、8.10、9.34 s;600℃残余量分别为5.9%、6.3%、7.5%。
Amino silicone oil(AS) was prepared by ring-opening polymerization using octamethylcyclotetrasiloxane, amino silane coupling agent as raw materials. The organosilicon polymer(PSiNP) containing phosphorus and nitrogen atoms was synthesized by nucleophilic substitution of AS and phenylphosphonic dichloride. The structure and properties of PSiNP were characterized by infrared spectroscopy(IR), ~1 HNMR and thermogravimetric analysis. Effects of reaction temperature, reaction time, solvent type and feed ratio [n(NH2)∶n(PCl)] on the flame retardancy and softness of fabrics after finishing were studied. The results showed that the optimum conditions for synthesis of PSiNP were as follows: reaction temperature 10 ℃, reaction time 1 h, solvent benzene, n(NH_2)∶n(PCl)=2.0∶1.0. The bending stiffness of untreated fabrics, AS treated fabrics and PSiNP treated fabrics were 403, 168 and 195 mN, the burning time was 7.47, 8.10 and 9.34 s, and the residual at600 ℃ was 5.9%, 6.3% and 7.5%, respectively.
Amino silicone oil(AS) was prepared by ring-opening polymerization using octamethylcyclotetrasiloxane, amino silane coupling agent as raw materials. The organosilicon polymer(PSiNP) containing phosphorus and nitrogen atoms was synthesized by nucleophilic substitution of AS and phenylphosphonic dichloride. The structure and properties of PSiNP were characterized by infrared spectroscopy(IR), ~1 HNMR and thermogravimetric analysis. Effects of reaction temperature, reaction time, solvent type and feed ratio [n(NH2)∶n(PCl)] on the flame retardancy and softness of fabrics after finishing were studied. The results showed that the optimum conditions for synthesis of PSiNP were as follows: reaction temperature 10 ℃, reaction time 1 h, solvent benzene, n(NH_2)∶n(PCl)=2.0∶1.0. The bending stiffness of untreated fabrics, AS treated fabrics and PSiNP treated fabrics were 403, 168 and 195 mN, the burning time was 7.47, 8.10 and 9.34 s, and the residual at600 ℃ was 5.9%, 6.3% and 7.5%, respectively.
引文
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[3] LONGJIAN Y E,QIAN L J,WANG L,et al.Research progress in silicon flame retardants[J].China Plastics,2009,23(11):7-14.
[4]石延超,王建国.有机磷阻燃剂的合成及在阻燃高分子材料中的应用研究进展[J].高分子材料科学与工程,2016,32(5):167-175.
[5]王然,王晓春,杨中开.有机硅阻燃处理剂研究进展[J].天津纺织科技,2010,191(3):11-13.
[6] QIAN Yong,WEI Ping,JIANG Pingkai,et al.Synthesis of a novel hybrid synergistic flame retardant its application in PP/IFR[J].Polymer Degradation and Stability,2011,96:1 134-1 140.
[7]窦午红,刘月东,刘文涛,等.新型P-N-Si无卤阻燃剂的合成及其在棉纤维中的应用[J].合成化学,2016,24(2):107-111.
[8]刘学钢.DMC或D4与氨基硅氧烷本体聚合制备氨基硅油[J].精细与专用化学品,2005,13(6):6-8.
[9]陈秀林.纺织上氨基改性硅油的合成及乳化[J].广东化工,2005,32(9):22-25.
[10]张壮,孙永强,史修启,等.氨基硅油微乳液的制备及性能研究[J].天津工业大学学报,2010(6):42-46.
[11]黄良仙,张乐,李丹杰,等.系列季铵盐型有机硅双子表面活性剂的制备及性能比较[J].陕西科技大学学报,2015,33(3):73-78.
[12]黄良仙,李婷,李顺琴,等.磷酸酯型氟硅表面活性剂的制备及性能研究[J].印染助剂,2016,33(6):27-31.
[13]赵雪,朱平,展义臻,等.阻燃纺织品的性能测试方法及发展动态[J].染整技术,2007,29(5):38-54.
[14]乔欣.纺织品阻燃性能测试[J].非织造布,2010,18(2):23-26.
[15]杨丽,周逸潇,韩新宇,等.阻燃剂阻燃机理的探讨[J].天津化工,2010,24(1):1-4.
[16]王晓明.柠檬酸抗皱处理对真丝织物耐洗性影响研究[J].染整技术,2005,27(5):5-8.
[17] QUN L I,MENG X Y,GENG C Y,et al.Studies on bulk polymerization of amino-silicone oil and its application on the wool fabric[J].Textile Auxiliaries,2003,20(6):10-13.
[18]李云燕,胡传荣.实验设计与数据处理[M].第二版.北京:化学工业出版社,2008:132-136.
[19]卢涌泉,邓振华.实用红外光谱解析[M].第一版.北京:电子工业出版社,1989:210-219.
[20] WU C S,LIU Y L,CHIU Y C,et al.Thermal stability of epoxy resins containing flame retardant components:an evaluation with thermogravimetric analysis[J].Polymer Degradation&Stability,2002,78(1):41-48.
[21]叶春生,陈连喜,白向鸽,等.阻燃型含硅环氧树脂体系的研究进展[J].山西化工,2009,29(3):33-37.