【摘要】：氟硅聚合物具有良好的耐化學(xué)介質(zhì)性能和耐燃油性能,但是與有機(jī)硅聚合物相比,耐熱性能明顯降低,為了提高氟硅聚合物的耐熱性能,可以向氟硅聚合物的側(cè)鏈上引入耐熱基團(tuán)提高其耐熱性。碳硼烷是一種擬芳香族化合物,具有高度穩(wěn)定性,因此將碳硼烷引入氟硅聚合物的側(cè)鏈中可以提高其耐熱性能,可以擴(kuò)大氟硅聚合物在耐高溫方面應(yīng)用范圍,如耐高溫膠黏劑和耐高溫密封劑等。本文分別采用陰離子開(kāi)環(huán)聚合法和陽(yáng)離子開(kāi)環(huán)聚合法,分別制備了側(cè)鏈型碳硼烷硅氧烷聚合物、側(cè)鏈型碳硼烷氟硅聚合物和氟硅聚合物。主要研究?jī)?nèi)容如下:1.以1- (4-羥基苯基)-m-碳硼烷和烯丙基溴為原料,成功制備了 1-(4-丙烯氧基苯基)-m-碳硼烷化合物,通過(guò)FT-IR、1H-NMR、13C-NMR表征方式對(duì)其結(jié)構(gòu)進(jìn)行分析,結(jié)果證明1- (4-丙烯氧基苯基)-m-碳硼烷化合物的合成。同時(shí)也探究了反應(yīng)時(shí)間和反應(yīng)物摩爾配比對(duì)目標(biāo)產(chǎn)物的產(chǎn)率的影響并且找到合成1- (4-丙烯氧基苯基)-m-碳硼烷化合物最佳反應(yīng)條件。2.以七甲基環(huán)四硅氧烷和1- (4-丙烯氧基苯基)-m-碳硼烷為原料,成功制備了 1- (4-七甲基環(huán)四硅氧烷丙氧基苯基)-m-碳硼烷單體,通過(guò)FT-IR、1H-NMR、13C-NMR表征方式對(duì)其結(jié)構(gòu)進(jìn)行分析,結(jié)果證明1- (4-七甲基環(huán)四硅氧烷丙氧基苯基)-m-碳硼烷化合物的合成。同時(shí)也探索了反應(yīng)時(shí)間、反應(yīng)溫度和原料摩爾配比對(duì)目標(biāo)產(chǎn)物的產(chǎn)率影響并且找到合成1- (4-七甲基環(huán)四硅氧烷丙氧基苯基)-m-碳硼烷單體的最佳反應(yīng)條件。3.采用濃硫酸催化的陽(yáng)離子開(kāi)環(huán)聚合法制備了側(cè)鏈碳硼烷硅氧烷聚合物P1,并且研究了催化劑量、四氫呋喃用量、反應(yīng)溫度和反應(yīng)時(shí)間對(duì)分子量及其分布的影響,并且對(duì)其結(jié)構(gòu)進(jìn)行表征;采用濃硫酸催化的陽(yáng)離子開(kāi)環(huán)聚合法制備了 3種聚合物分別為P2、P3和P4,并且對(duì)其結(jié)構(gòu)進(jìn)行了表征;采用四甲基氫氧化銨催化的陰離子開(kāi)環(huán)聚合法制備了 3種不同含氟量的氟硅聚合物P5、P6和P7,并且對(duì)其結(jié)構(gòu)進(jìn)行了表征。4.在氟硅聚合物中,隨著含氟量的增加,聚合物的耐熱性能就越低;在氮?dú)鈼l件下側(cè)鏈型碳硼烷硅氧烷聚合物和側(cè)鏈型碳硼烷氟硅聚合物熱性能與碳硼烷連接方式有關(guān)系。連接碳硼烷到硅氧烷主鏈上的碳鏈越短,碳硼烷基團(tuán)對(duì)主鏈的屏蔽效果越明顯,耐熱性能就越高。
[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.
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.5

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