侧链型碳硼烷氟硅聚合物的合成及性能研究
发布时间：2018-10-30 19:33
【摘要】：氟硅聚合物具有良好的耐化学介质性能和耐燃油性能,但是与有机硅聚合物相比,耐热性能明显降低,为了提高氟硅聚合物的耐热性能,可以向氟硅聚合物的侧链上引入耐热基团提高其耐热性。碳硼烷是一种拟芳香族化合物,具有高度稳定性,因此将碳硼烷引入氟硅聚合物的侧链中可以提高其耐热性能,可以扩大氟硅聚合物在耐高温方面应用范围,如耐高温胶黏剂和耐高温密封剂等。本文分别采用阴离子开环聚合法和阳离子开环聚合法,分别制备了侧链型碳硼烷硅氧烷聚合物、侧链型碳硼烷氟硅聚合物和氟硅聚合物。主要研究内容如下:1.以1- (4-羟基苯基)-m-碳硼烷和烯丙基溴为原料,成功制备了 1-(4-丙烯氧基苯基)-m-碳硼烷化合物,通过FT-IR、1H-NMR、13C-NMR表征方式对其结构进行分析,结果证明1- (4-丙烯氧基苯基)-m-碳硼烷化合物的合成。同时也探究了反应时间和反应物摩尔配比对目标产物的产率的影响并且找到合成1- (4-丙烯氧基苯基)-m-碳硼烷化合物最佳反应条件。2.以七甲基环四硅氧烷和1- (4-丙烯氧基苯基)-m-碳硼烷为原料,成功制备了 1- (4-七甲基环四硅氧烷丙氧基苯基)-m-碳硼烷单体,通过FT-IR、1H-NMR、13C-NMR表征方式对其结构进行分析,结果证明1- (4-七甲基环四硅氧烷丙氧基苯基)-m-碳硼烷化合物的合成。同时也探索了反应时间、反应温度和原料摩尔配比对目标产物的产率影响并且找到合成1- (4-七甲基环四硅氧烷丙氧基苯基)-m-碳硼烷单体的最佳反应条件。3.采用浓硫酸催化的阳离子开环聚合法制备了侧链碳硼烷硅氧烷聚合物P1,并且研究了催化剂量、四氢呋喃用量、反应温度和反应时间对分子量及其分布的影响,并且对其结构进行表征;采用浓硫酸催化的阳离子开环聚合法制备了 3种聚合物分别为P2、P3和P4,并且对其结构进行了表征;采用四甲基氢氧化铵催化的阴离子开环聚合法制备了 3种不同含氟量的氟硅聚合物P5、P6和P7,并且对其结构进行了表征。4.在氟硅聚合物中,随着含氟量的增加,聚合物的耐热性能就越低;在氮气条件下侧链型碳硼烷硅氧烷聚合物和侧链型碳硼烷氟硅聚合物热性能与碳硼烷连接方式有关系。连接碳硼烷到硅氧烷主链上的碳链越短,碳硼烷基团对主链的屏蔽效果越明显,耐热性能就越高。
[Abstract]:Fluorosilicon polymer has good chemical resistance and fuel resistance, but compared with silicone polymer, the heat resistance of fluorosilicon polymer is obviously lower. In order to improve the heat resistance of fluorosilicon polymer, Heat-resistant groups can be introduced into the side chain of fluorosilicon polymers to improve their heat resistance. Carboborane is a pseudo aromatic compound with high stability. Therefore, introducing carboborane into the side chain of fluorosilicon polymer can improve its heat resistance and expand its application in high temperature resistance. Such as high-temperature adhesive and high-temperature sealant. In this paper, side chain carboborane siloxane polymer, side chain carboborane fluorosilane polymer and fluorosilicon polymer were prepared by anion ring-opening polymerization and cationic ring-opening polymerization respectively. The main contents are as follows: 1. 1- (4-propenyl phenyl) -m- carboborane was prepared by using 1- (4-hydroxyphenyl) -mcarboborane and allyl bromide as raw materials. The structure of 1- (4-propenoxy phenyl) -m- carboborane was characterized by 13C-NMR, and the results showed that 1- (4-propenyl phenyl) -m- carboborane was synthesized. At the same time, the effects of reaction time and molar ratio of reactants on the yield of the target product were investigated and the optimum reaction conditions for the synthesis of 1- (4-propenoxy phenyl) -m- carboborane were found. 2. The 1- (4-heptylcyclotetrasiloxane prooxyphenyl) -mcarboborane monomer was successfully prepared from heptomethylcyclotetrasiloxane and 1- (4-propenoxyphenyl) -mcarboborane by FT-IR,1H-NMR,. The structure of 1- (4-heptylcyclotetrasiloxane prooxy phenyl) -m- carboborane was characterized by 13C-NMR and the results showed that 1- (4-heptylcyclotetrasiloxane) -m- carboborane was synthesized. At the same time, the effects of reaction time, reaction temperature and molar ratio of raw materials on the yield of the target product were investigated and the optimum reaction conditions for the synthesis of 1- (4-heptylcyclotetrasiloxane prooxy phenyl) -m-carboborane monomer were found. The side chain carboborane siloxane polymer P1 was prepared by cationic ring-opening polymerization catalyzed by concentrated sulfuric acid. The effects of the amount of catalyst, the amount of tetrahydrofuran, the reaction temperature and reaction time on the molecular weight and its distribution were studied. And its structure was characterized. Three kinds of polymers were prepared by cationic ring-opening polymerization catalyzed by concentrated sulfuric acid, and their structures were characterized. Three fluorosilicon polymers P _ 5N _ 6 and P _ 7 with different fluorine contents were prepared by anion ring-opening polymerization catalyzed by tetramethylammonium hydroxide and their structures were characterized. In fluorosilicon polymer, the heat resistance of the polymer is lower with the increase of fluorine content, and the thermal properties of side chain carboborane siloxane polymer and side chain carboborane fluorosilane polymer are related to the connection mode of carboborane. The shorter the carbon chain connecting carboborane to the siloxane main chain, the more obvious the shielding effect of the carbborane group to the main chain, and the higher the heat resistance.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.5
本文编号：2300955
[Abstract]:Fluorosilicon polymer has good chemical resistance and fuel resistance, but compared with silicone polymer, the heat resistance of fluorosilicon polymer is obviously lower. In order to improve the heat resistance of fluorosilicon polymer, Heat-resistant groups can be introduced into the side chain of fluorosilicon polymers to improve their heat resistance. Carboborane is a pseudo aromatic compound with high stability. Therefore, introducing carboborane into the side chain of fluorosilicon polymer can improve its heat resistance and expand its application in high temperature resistance. Such as high-temperature adhesive and high-temperature sealant. In this paper, side chain carboborane siloxane polymer, side chain carboborane fluorosilane polymer and fluorosilicon polymer were prepared by anion ring-opening polymerization and cationic ring-opening polymerization respectively. The main contents are as follows: 1. 1- (4-propenyl phenyl) -m- carboborane was prepared by using 1- (4-hydroxyphenyl) -mcarboborane and allyl bromide as raw materials. The structure of 1- (4-propenoxy phenyl) -m- carboborane was characterized by 13C-NMR, and the results showed that 1- (4-propenyl phenyl) -m- carboborane was synthesized. At the same time, the effects of reaction time and molar ratio of reactants on the yield of the target product were investigated and the optimum reaction conditions for the synthesis of 1- (4-propenoxy phenyl) -m- carboborane were found. 2. The 1- (4-heptylcyclotetrasiloxane prooxyphenyl) -mcarboborane monomer was successfully prepared from heptomethylcyclotetrasiloxane and 1- (4-propenoxyphenyl) -mcarboborane by FT-IR,1H-NMR,. The structure of 1- (4-heptylcyclotetrasiloxane prooxy phenyl) -m- carboborane was characterized by 13C-NMR and the results showed that 1- (4-heptylcyclotetrasiloxane) -m- carboborane was synthesized. At the same time, the effects of reaction time, reaction temperature and molar ratio of raw materials on the yield of the target product were investigated and the optimum reaction conditions for the synthesis of 1- (4-heptylcyclotetrasiloxane prooxy phenyl) -m-carboborane monomer were found. The side chain carboborane siloxane polymer P1 was prepared by cationic ring-opening polymerization catalyzed by concentrated sulfuric acid. The effects of the amount of catalyst, the amount of tetrahydrofuran, the reaction temperature and reaction time on the molecular weight and its distribution were studied. And its structure was characterized. Three kinds of polymers were prepared by cationic ring-opening polymerization catalyzed by concentrated sulfuric acid, and their structures were characterized. Three fluorosilicon polymers P _ 5N _ 6 and P _ 7 with different fluorine contents were prepared by anion ring-opening polymerization catalyzed by tetramethylammonium hydroxide and their structures were characterized. In fluorosilicon polymer, the heat resistance of the polymer is lower with the increase of fluorine content, and the thermal properties of side chain carboborane siloxane polymer and side chain carboborane fluorosilane polymer are related to the connection mode of carboborane. The shorter the carbon chain connecting carboborane to the siloxane main chain, the more obvious the shielding effect of the carbborane group to the main chain, and the higher the heat resistance.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.5
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