胺基化线型聚苯乙烯的合成及其性能研究
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摘要
功能高分子材料具有广泛用途,其中胺基化聚苯乙烯因其带有可以质子化的氨基,可广泛应用于生物医用高分子、高分子催化剂载体及水处理吸附树脂等众多领域。
本文采用三种合成路线制备了线型胺基化聚苯乙烯,并对聚合物的结构和性能进行了研究。
(1)以浓HN03／浓H2SO4混合酸为硝化试剂对自制线型聚苯乙烯(PS)进行硝化制备了聚对硝基苯乙烯(PPNS),然后将PPNS还原为聚对氨基苯乙烯(PPAS)。用红外光谱仪(FT-IR)、核磁共振波谱仪(NMR)、热重分析仪(TGA)和差示扫描量热仪(DSC)对聚合物进行了表征。考察了反应温度、时间和混合酸配比对硝化反应的影响以及还原剂的种类和用量对还原反应的影响。结果表明：PS的苯环上引入了硝基制备了PPNS, PPNS被还原为PPAS; PPNS和PPAS均分两个阶段热分解,且PS、PPNS PPAS热稳定性依次降低。PPNS的玻璃化转变温度(Tg)随硝化率的增加而升高。升高反应温度、延长反应时间以及增加混合酸中硫酸的体积,硝化率均提高。降低PS的分子量以及提高还原剂的用量,PPAS的水溶性提高。
(2)以氯乙酰氯为酰基化试剂,AlCl3为催化剂,合成了聚对氯乙酰基苯乙烯(PS-Acyl-Cl),然后以乙二胺(EDA)为胺基化试剂对PS-Acyl-Cl进行胺基化反应得到聚对(a-氨基乙基胺)乙酰基苯乙烯(PS-Acyl-EDA)。利用FT-IR、TGA和DSC对聚合物结构及性能进行了研究,考察了反应条件对氯乙酰化反应及胺基化反应的影响。结果表明：制备了PS-Acyl-Cl和PS-Acyl-EDA。它们均分为两个阶段热分解；随着氯乙酰基取代度的增加,PS-Acyl-Cl的热稳定性降低,但Tg升高。
(3)采用1,4-丁二醇、甲醛、三氯化磷为原料制备了氯甲基化试剂——1,4-二氯甲氧基丁烷,以其为氯甲基化试剂,Lewis酸为催化剂,制备了聚对氯甲基苯乙烯(PS-Meyl-Cl)并对其进行胺基化反应得到聚对(氨基乙基胺)甲基苯乙烯(PS-Meyl-EDA)。利用FT-IR、TGA对聚合物结构及性能进行了研究,考察了反应条件对氯甲基化反应以及胺基化反应的影响。结果表明：制备了PS-Meyl-Cl和PS-Meyl-EDA,它们均分为两个阶段热分解；随着氯甲基取代度的增加,PS-Meyl-Cl热稳定性降低。综合考虑各种影响因素,确定了制备PS-Meyl-Cl及PS-Meyl-EDA的较佳反应条件。
Functional polymer has a wide range of applications. Amino-polystyrene which can be protonated with its amino, can be widely used in biomedical polymers, polymer-support catalyst and water treatment and many other fields.
In this dissertation, amino-polystyrene was prepared by three synthesis routes, respectively.
(1) Poly(p-nitrostyrene) (PPNS) was prepared by nitration of linear PS using the mixture of nitric acid and sulfuric acid as nitrating agents, and finally PPNS was reduced to poly(p-aminostyrene) (PPAS). The resultant polymers were characterized by means of Fourier transform infrared spectrometer (FT-IR), nuclear magnetic resonance (NMR) spectrometer, thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC), respectively. The effects of reaction temperature, reaction time and mixed acid composition on nitration and the kind and amount of reducing agent on reduction were studied. The results show that the nitro groups are incorporated into benzene rings of PS and PPNS is reduced to PPAS. Both PPNS and PPAS have two decomposing stages. The thermal stability of PS, PPNS and PPAS rank in descending order. The glass transition temperature (Tg) of PPNS increased with increasing rate of nitration, and the Tg of PPAS is also high. The rate of nitration increased with increasing reaction temperature, reaction time and volume of sulfuric acid in acid mixture. With reducing the molecular weight of PS and increasing the amount of reducing agent, the water solubility of PPAS increased.
(2) The linear poly(p-chloroacetyl styrene)(PS-Acyl-Cl) was prepared by Friedel-Crafts acetylation of linear PS using chloroacetyl chloride and aluminium trichloride as chloroacetylation reagent and catalyst, respectively. Then PS-Acyl-Cl was aminated to poly(p-(a-amin o-ethylamino)acetyl styrene)(PS-Acyl-EDA) using ethylene diamine (EDA) as aminating agent. The resultant polymers were characterized by FT-IR, TGA and DSC. The effects of reaction conditions on chloroacetylation and amination were studied. The results show that chloroacetyl groups are introduced into benzene rings of PS and the amination is successful. Both PS-Acyl-Cl and PS-Acyl-EDA have two decomposing stages. And the thermal stability of PS-Acyl-Cl decreased and Tg of PS-Acyl-Cl increased with increasing substitution value of chloroacetyl groups.
(3) 1,4-Bis(chloromethoxy)butane was synthesized using 1,4-butanediol, formaldehyde and phosphorus trichloride as raw material. The poly(p-chloromethyl styrene)(PS-Meyl-Cl) was performed using 1,4-Bis(chloromethoxy)butane and Lewis acid as the chloromethylation reagent and catalyst, respectively. Then PS-Meyl-Cl was aminated to poly(p-(amio-e thylamino)methyl styrene) (PS-Meyl-EDA) using EDA as aminating agent. The resultant polymers were characterized by FT-IR and TGA. The effects of reaction conditions on chloromethylation and amination were studied. The results show that the chloromethyl groups are intrduced into benzene rings of PS and the amination is successful. Both PS-Meyl-Cl and PS-Meyl-EDA have two decomposing stages. And the thermal stability of PS-Meyl-Cl decreased with increasing substitution value of chloromethyl groups. Considering various factors, the optimum reaction conditions for chloromethylation are determined.
本文采用三种合成路线制备了线型胺基化聚苯乙烯,并对聚合物的结构和性能进行了研究。
(1)以浓HN03／浓H2SO4混合酸为硝化试剂对自制线型聚苯乙烯(PS)进行硝化制备了聚对硝基苯乙烯(PPNS),然后将PPNS还原为聚对氨基苯乙烯(PPAS)。用红外光谱仪(FT-IR)、核磁共振波谱仪(NMR)、热重分析仪(TGA)和差示扫描量热仪(DSC)对聚合物进行了表征。考察了反应温度、时间和混合酸配比对硝化反应的影响以及还原剂的种类和用量对还原反应的影响。结果表明：PS的苯环上引入了硝基制备了PPNS, PPNS被还原为PPAS; PPNS和PPAS均分两个阶段热分解,且PS、PPNS PPAS热稳定性依次降低。PPNS的玻璃化转变温度(Tg)随硝化率的增加而升高。升高反应温度、延长反应时间以及增加混合酸中硫酸的体积,硝化率均提高。降低PS的分子量以及提高还原剂的用量,PPAS的水溶性提高。
(2)以氯乙酰氯为酰基化试剂,AlCl3为催化剂,合成了聚对氯乙酰基苯乙烯(PS-Acyl-Cl),然后以乙二胺(EDA)为胺基化试剂对PS-Acyl-Cl进行胺基化反应得到聚对(a-氨基乙基胺)乙酰基苯乙烯(PS-Acyl-EDA)。利用FT-IR、TGA和DSC对聚合物结构及性能进行了研究,考察了反应条件对氯乙酰化反应及胺基化反应的影响。结果表明：制备了PS-Acyl-Cl和PS-Acyl-EDA。它们均分为两个阶段热分解；随着氯乙酰基取代度的增加,PS-Acyl-Cl的热稳定性降低,但Tg升高。
(3)采用1,4-丁二醇、甲醛、三氯化磷为原料制备了氯甲基化试剂——1,4-二氯甲氧基丁烷,以其为氯甲基化试剂,Lewis酸为催化剂,制备了聚对氯甲基苯乙烯(PS-Meyl-Cl)并对其进行胺基化反应得到聚对(氨基乙基胺)甲基苯乙烯(PS-Meyl-EDA)。利用FT-IR、TGA对聚合物结构及性能进行了研究,考察了反应条件对氯甲基化反应以及胺基化反应的影响。结果表明：制备了PS-Meyl-Cl和PS-Meyl-EDA,它们均分为两个阶段热分解；随着氯甲基取代度的增加,PS-Meyl-Cl热稳定性降低。综合考虑各种影响因素,确定了制备PS-Meyl-Cl及PS-Meyl-EDA的较佳反应条件。
Functional polymer has a wide range of applications. Amino-polystyrene which can be protonated with its amino, can be widely used in biomedical polymers, polymer-support catalyst and water treatment and many other fields.
In this dissertation, amino-polystyrene was prepared by three synthesis routes, respectively.
(1) Poly(p-nitrostyrene) (PPNS) was prepared by nitration of linear PS using the mixture of nitric acid and sulfuric acid as nitrating agents, and finally PPNS was reduced to poly(p-aminostyrene) (PPAS). The resultant polymers were characterized by means of Fourier transform infrared spectrometer (FT-IR), nuclear magnetic resonance (NMR) spectrometer, thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC), respectively. The effects of reaction temperature, reaction time and mixed acid composition on nitration and the kind and amount of reducing agent on reduction were studied. The results show that the nitro groups are incorporated into benzene rings of PS and PPNS is reduced to PPAS. Both PPNS and PPAS have two decomposing stages. The thermal stability of PS, PPNS and PPAS rank in descending order. The glass transition temperature (Tg) of PPNS increased with increasing rate of nitration, and the Tg of PPAS is also high. The rate of nitration increased with increasing reaction temperature, reaction time and volume of sulfuric acid in acid mixture. With reducing the molecular weight of PS and increasing the amount of reducing agent, the water solubility of PPAS increased.
(2) The linear poly(p-chloroacetyl styrene)(PS-Acyl-Cl) was prepared by Friedel-Crafts acetylation of linear PS using chloroacetyl chloride and aluminium trichloride as chloroacetylation reagent and catalyst, respectively. Then PS-Acyl-Cl was aminated to poly(p-(a-amin o-ethylamino)acetyl styrene)(PS-Acyl-EDA) using ethylene diamine (EDA) as aminating agent. The resultant polymers were characterized by FT-IR, TGA and DSC. The effects of reaction conditions on chloroacetylation and amination were studied. The results show that chloroacetyl groups are introduced into benzene rings of PS and the amination is successful. Both PS-Acyl-Cl and PS-Acyl-EDA have two decomposing stages. And the thermal stability of PS-Acyl-Cl decreased and Tg of PS-Acyl-Cl increased with increasing substitution value of chloroacetyl groups.
(3) 1,4-Bis(chloromethoxy)butane was synthesized using 1,4-butanediol, formaldehyde and phosphorus trichloride as raw material. The poly(p-chloromethyl styrene)(PS-Meyl-Cl) was performed using 1,4-Bis(chloromethoxy)butane and Lewis acid as the chloromethylation reagent and catalyst, respectively. Then PS-Meyl-Cl was aminated to poly(p-(amio-e thylamino)methyl styrene) (PS-Meyl-EDA) using EDA as aminating agent. The resultant polymers were characterized by FT-IR and TGA. The effects of reaction conditions on chloromethylation and amination were studied. The results show that the chloromethyl groups are intrduced into benzene rings of PS and the amination is successful. Both PS-Meyl-Cl and PS-Meyl-EDA have two decomposing stages. And the thermal stability of PS-Meyl-Cl decreased with increasing substitution value of chloromethyl groups. Considering various factors, the optimum reaction conditions for chloromethylation are determined.
引文
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