含氟聚氨酯弹性体的制备和性能研究
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摘要
聚氨酯弹性体(PUE)由于具有优良的机械性能、良好的加工性能和优异的其它性能,在日常生活和其他领域得到了广泛的应用。但是由于科技的发展,人们对材料的要求越来越高,使得聚氨酯弹性体的原来的一些不足显示出来了,限制了它的进一步应用。含氟聚氨酯弹性体(FPUE)作为作为一类新型功能型高分子材料,由于氟元素的引入,使聚合物材料具有优异的表面性能、化学稳定性等一些独特的性能,弥补了原来普通PUE的不足。本文通过合成两种含氟二元胺,以此为扩链剂制备了一系列的含氟聚氨酯弹性体,并对所制备的FPUE进行了研究。
(1)以邻氯三氟甲苯、对苯二酚和双酚A为原料合成了两种芳香族含氟二元胺：1,4-二(4-氨基-2-三氟甲基苯氧基)苯(BAFB)和2,2-二[4-(4-氨基-2-三氟甲基苯氧基)苯基]丙烷(BAFPP)。用红外光谱(FTIR)和核磁共振谱(1H-NMR、19F-NMR)对合成的BAFB和BAFFP,进行结构表征,结果表明合成的产物与预期设计的完全一致。
(2)分别以BAFB和BAFPP为扩链剂合成含氟聚氨酯弹性体(FPUE-Ⅰ、FPUE-Ⅱ)。
以DDL系列聚醚多元醇、PTMEG2000和聚酯2000为软段与甲苯二异氰酸酯(TDI)反应制备一系列的聚氨酯预聚体,再分别以BAFB和BAFPP为扩链剂合成FPUE-Ⅰ和FPUE-Ⅱ。聚氨酯弹性体的合成采用两步法：第一步是选择异氰酸酯指数R=2合成异氰酸根封端的聚氨酯预聚体；第二步是弹性体的制备,将预聚体和扩链剂分别溶解在一定量的溶剂中,再将二者混合经扩链和交联得到一系列含氟聚氨酯弹性体。同时为了对比还使用了传统的扩链剂MOCA采用同样的方法制备了普通的聚氨酯弹性体。
以红外光谱仪(FTIR)、光电子能谱仪(XPS)、热失重分析仪(TGA)、微型燃烧量热仪(MCC)、表面接触角测试、吸水率测试和力学性能测试等对制备的含氟聚氨酯弹性体和普通的聚氨酯弹性体进行结构和性能研究。结果表明：BAFB和BAFPP确实与—NCO基团封端的聚氨酯预聚体发生了反应,氟基团被成功地引入到聚氨酯弹性体中去；由于氟元素的引入及其在表面富集作用,使得FPUE具有良好的疏水性和较低的表面张力,同时FPUE具有良好的耐热性能、阻燃性能和力学性能。
(3)分别以MOCA和BAFPP为扩链剂对比研究了聚氨酯弹性体固化动力学。
以PTMEG2000型聚氨酯预聚体为第一组份,扩链剂(MOCA和BAFPP)为第二组分通过动态扭振法得到聚氨酯弹性体等温固化曲线。通过计算两个体系的固化表观活化能E。和固化反应速率常数k,研究了体系的固化特征。结果表明：预聚体/BAFPP体系固化反应的活化能为37.41kJ/mol低于聚氨酯预聚体/MOCA体系固化反应活化能46.98kJ/mol。BAFPP的扩链反应同MOCA扩链反应均为一级固化反应。
Due to their excellent mechanical and processing propertites and other advantages, polyurethane elastomers(PUE) have been widely appilied in our daily lives and many other fields. However, with the development of science and people's higher and newer requirements. Riginal PUE materials have shown insufficiency and their use has been limited. Fluorinated Polyurethane Elastomers(FPUE), as a species of novel functional macromolecule materials, owing to the introduction of fluorinate, have excellent surface properties, excellent resistance to chemicals and other unique qualities. So FPUE have mitigated the above mentioned shortages of PUE.In this study, two species of aromatic fluorinated diamines were synthesized and two diamines were used as chain extender to prepare a series of fluorine containing polyurethane elastomers(FPUEs) with different fluorine contents. The structure and properties were measured.
(1) Two species of aromatic fluorinated diamines 1,4-bis(4-amino-2-trifluofometh-yloxyphenyl)benzene(BAFB) and 2,2-bis[4-(4-amino-2-trifluoromehyloxyphenyl) phen-yl]propane(BAFPP), were synthesiszed based on 2-chlorobenzotrifluoride, p-dihydroxy-benzene and Bisphenol A. Their structure and properties were determined by FTIR, NMR(1H-NMR、19F-NMR). The results showed that the structure of BAFB and BAFPP met our expectation.
(2) Preparation of fluorine-containing polyurethane elastomers(FPUE-Ⅰ, FPUE-Ⅱ) chain extended by BAFB and BAFPP.
FPUE(FPUE-Ⅰ, FPUE-Ⅱ)were prepared with the chain extender(BAFB and BAFPP) and polyurethane prepolymers, which prepared with TDI, DDL, PTMEG2000 and polyester2000. FPUE were prepared by a two-step method. In the first step, isocyano-capped polyurethane prepolymers were synthesized with isocyano index 2, and in the second step, the prepolymers and chain extender were dissolved in a certain amount of solvent, and then mixed two parts are mixed to prepare FPUE. At the same time, PUE with the conventional chain-extender MOCA was prepared to be compared with the new elastomers.
The structures and properties of FPUEs were analyzed with the measurements of FTIR, contact angle measurement, XPS, TGA, MCC and tensile tests. The results showed that fluorine was successfully incorporated into the polyurethane chains whose terminal group is-NCO with BAFB and BAFPP reacting to prepolymers. FPUE showed a good hydrophobic property and lower surface tension due to the introduction of fluorine and its increase on the air-side of the surface for materials. At the same time these polymers exhibited good thermal stability, good flammability properties and mechanical properties.
(3) The curing kinetics of PUE and FPUE was prepared with MOCA and BAFPP as chain extender was assessed.
Isothemal curing curves of polyurethane elastomers were made by the dynamic torsional vibration method, in which prepolymer of PTMEG-2000 was the first components and the chain extender(MOCA and BAFPP) was the second components. Apparent activation energy Ea and reaction rate constant k were calculated. The results showed that the Ea of prepolymer/BAFPP is lower than the prepolymer/MOCA. Simultaneously, the crosslinking reaction of polypolmer/BAFPP is a first order reaction, which is the same as the crosslinking reaction of polypolmer/MOCA. Figure 39; table 22; reference 55;
(1)以邻氯三氟甲苯、对苯二酚和双酚A为原料合成了两种芳香族含氟二元胺：1,4-二(4-氨基-2-三氟甲基苯氧基)苯(BAFB)和2,2-二[4-(4-氨基-2-三氟甲基苯氧基)苯基]丙烷(BAFPP)。用红外光谱(FTIR)和核磁共振谱(1H-NMR、19F-NMR)对合成的BAFB和BAFFP,进行结构表征,结果表明合成的产物与预期设计的完全一致。
(2)分别以BAFB和BAFPP为扩链剂合成含氟聚氨酯弹性体(FPUE-Ⅰ、FPUE-Ⅱ)。
以DDL系列聚醚多元醇、PTMEG2000和聚酯2000为软段与甲苯二异氰酸酯(TDI)反应制备一系列的聚氨酯预聚体,再分别以BAFB和BAFPP为扩链剂合成FPUE-Ⅰ和FPUE-Ⅱ。聚氨酯弹性体的合成采用两步法：第一步是选择异氰酸酯指数R=2合成异氰酸根封端的聚氨酯预聚体；第二步是弹性体的制备,将预聚体和扩链剂分别溶解在一定量的溶剂中,再将二者混合经扩链和交联得到一系列含氟聚氨酯弹性体。同时为了对比还使用了传统的扩链剂MOCA采用同样的方法制备了普通的聚氨酯弹性体。
以红外光谱仪(FTIR)、光电子能谱仪(XPS)、热失重分析仪(TGA)、微型燃烧量热仪(MCC)、表面接触角测试、吸水率测试和力学性能测试等对制备的含氟聚氨酯弹性体和普通的聚氨酯弹性体进行结构和性能研究。结果表明：BAFB和BAFPP确实与—NCO基团封端的聚氨酯预聚体发生了反应,氟基团被成功地引入到聚氨酯弹性体中去；由于氟元素的引入及其在表面富集作用,使得FPUE具有良好的疏水性和较低的表面张力,同时FPUE具有良好的耐热性能、阻燃性能和力学性能。
(3)分别以MOCA和BAFPP为扩链剂对比研究了聚氨酯弹性体固化动力学。
以PTMEG2000型聚氨酯预聚体为第一组份,扩链剂(MOCA和BAFPP)为第二组分通过动态扭振法得到聚氨酯弹性体等温固化曲线。通过计算两个体系的固化表观活化能E。和固化反应速率常数k,研究了体系的固化特征。结果表明：预聚体/BAFPP体系固化反应的活化能为37.41kJ/mol低于聚氨酯预聚体/MOCA体系固化反应活化能46.98kJ/mol。BAFPP的扩链反应同MOCA扩链反应均为一级固化反应。
Due to their excellent mechanical and processing propertites and other advantages, polyurethane elastomers(PUE) have been widely appilied in our daily lives and many other fields. However, with the development of science and people's higher and newer requirements. Riginal PUE materials have shown insufficiency and their use has been limited. Fluorinated Polyurethane Elastomers(FPUE), as a species of novel functional macromolecule materials, owing to the introduction of fluorinate, have excellent surface properties, excellent resistance to chemicals and other unique qualities. So FPUE have mitigated the above mentioned shortages of PUE.In this study, two species of aromatic fluorinated diamines were synthesized and two diamines were used as chain extender to prepare a series of fluorine containing polyurethane elastomers(FPUEs) with different fluorine contents. The structure and properties were measured.
(1) Two species of aromatic fluorinated diamines 1,4-bis(4-amino-2-trifluofometh-yloxyphenyl)benzene(BAFB) and 2,2-bis[4-(4-amino-2-trifluoromehyloxyphenyl) phen-yl]propane(BAFPP), were synthesiszed based on 2-chlorobenzotrifluoride, p-dihydroxy-benzene and Bisphenol A. Their structure and properties were determined by FTIR, NMR(1H-NMR、19F-NMR). The results showed that the structure of BAFB and BAFPP met our expectation.
(2) Preparation of fluorine-containing polyurethane elastomers(FPUE-Ⅰ, FPUE-Ⅱ) chain extended by BAFB and BAFPP.
FPUE(FPUE-Ⅰ, FPUE-Ⅱ)were prepared with the chain extender(BAFB and BAFPP) and polyurethane prepolymers, which prepared with TDI, DDL, PTMEG2000 and polyester2000. FPUE were prepared by a two-step method. In the first step, isocyano-capped polyurethane prepolymers were synthesized with isocyano index 2, and in the second step, the prepolymers and chain extender were dissolved in a certain amount of solvent, and then mixed two parts are mixed to prepare FPUE. At the same time, PUE with the conventional chain-extender MOCA was prepared to be compared with the new elastomers.
The structures and properties of FPUEs were analyzed with the measurements of FTIR, contact angle measurement, XPS, TGA, MCC and tensile tests. The results showed that fluorine was successfully incorporated into the polyurethane chains whose terminal group is-NCO with BAFB and BAFPP reacting to prepolymers. FPUE showed a good hydrophobic property and lower surface tension due to the introduction of fluorine and its increase on the air-side of the surface for materials. At the same time these polymers exhibited good thermal stability, good flammability properties and mechanical properties.
(3) The curing kinetics of PUE and FPUE was prepared with MOCA and BAFPP as chain extender was assessed.
Isothemal curing curves of polyurethane elastomers were made by the dynamic torsional vibration method, in which prepolymer of PTMEG-2000 was the first components and the chain extender(MOCA and BAFPP) was the second components. Apparent activation energy Ea and reaction rate constant k were calculated. The results showed that the Ea of prepolymer/BAFPP is lower than the prepolymer/MOCA. Simultaneously, the crosslinking reaction of polypolmer/BAFPP is a first order reaction, which is the same as the crosslinking reaction of polypolmer/MOCA. Figure 39; table 22; reference 55;
引文
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