MDI合成聚氨酯型不饱和树脂及其性能
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摘要
本文以二苯基甲烷二异氰酸酯(MDI)、丙烯酸羟乙酯和自制的二元醇为原料制备了分子内同时含有酯键和氨基甲酸酯键的不饱和树脂,内聚能较大的氨基甲酸酯键能进一步增强分子间作用力,使不饱和树脂表现出优异的力学性能和热稳定性。研究了聚氨酯型不饱和树脂浇注体的拉伸强度、弯曲强度、冲击强度、热分解温度以及玻璃化转变温度与分子结构的关系,并研究了分别以甲基丙烯酸甲酯和苯乙烯为交联剂时不饱和树脂的力学性能。结果表明:R_1(邻苯二甲酸酐)∶R_2(马来酸酐)为1∶1,甲基丙烯酸甲酯为交联剂的聚氨酯型不饱和树脂(UPPU)的力学性能最优,拉伸强度、弯曲强度、冲击强度分别为81MPa、153MPa、26kJ/m2,是通用型不饱和树脂的1.4、1.4、3.8倍;玻璃化转变温度随着马来酸酐比例的增加而提高。
An unsaturated polyester polyurethane resin(UPPU)was synthesized from diphenyl-methanediisocyanate(MDI),hydroxyethyl acrylate and homemade diol,containing not only ester bond but also urethane bond in molecular skeleton.The whole process expectedly endowed the UPPU with excellent mechanical properties and preferable thermal stability.Relationships among mechanical properties(such as tensile strength,flexural strength,impact strength),thermal stability(such as heat distortion temperature and the glass transition temperature)and the molecular structures of the unsaturated polyester as well as crosslinker were studied.It is revealed that the mechanical properties of UPPU with R1∶R2(o-phthalic anhydride and maleic anhydride)monomer ratio of 1∶1,in the presence of hydroxyproyl methacry as the crosslinker,are the best.with the tensile strength,flexural strength and impact strength of 81 MPa,153 MPa and 26 kJ·m-2,respectively.And the thermal stability of UPPU increases with the content increment of maleic anhydride.
An unsaturated polyester polyurethane resin(UPPU)was synthesized from diphenyl-methanediisocyanate(MDI),hydroxyethyl acrylate and homemade diol,containing not only ester bond but also urethane bond in molecular skeleton.The whole process expectedly endowed the UPPU with excellent mechanical properties and preferable thermal stability.Relationships among mechanical properties(such as tensile strength,flexural strength,impact strength),thermal stability(such as heat distortion temperature and the glass transition temperature)and the molecular structures of the unsaturated polyester as well as crosslinker were studied.It is revealed that the mechanical properties of UPPU with R1∶R2(o-phthalic anhydride and maleic anhydride)monomer ratio of 1∶1,in the presence of hydroxyproyl methacry as the crosslinker,are the best.with the tensile strength,flexural strength and impact strength of 81 MPa,153 MPa and 26 kJ·m-2,respectively.And the thermal stability of UPPU increases with the content increment of maleic anhydride.
引文
[1]沈开猷.不饱和聚酯树脂及其应用[M].北京:化学工业出版社,1988,1~23.
[2]杨睿,潘安徽,赵世琦.不饱和聚酯树脂的增韧和降收缩—种兼具增韧和降收缩效果的新型添加剂[J].材料科学与工程学报,2000,18(z1):156~158.
[3]冯钦邦.气相二氧化硅改性不饱和聚酯树脂研究[D].华南理工大学硕士学位论文,何慧,吴春蕾,广州,2015.12.
[4]杨睿,潘安徽,赵世琦.不饱和聚酯树脂的原位同时增韧和降收缩研究[J].高分子材料科学与工程,2003,19(4):140~143.
[5]A.B.Cherian,L.A.Varghese,E.T.Thachil.Epoxymodified,Unsaturated Polyester Hybrid Networks[J].European Polymer Journal,2007,43(4):1460~1469.
[6]陈一虹,黄剑莹,等.聚氨酯丙烯酸酯的合成和性能研究[J].厦门大学学报(自然科版),2006,45(3):370~374.
[7]刘晓暄,杨建文,黄劲涛,陈用烈.光固化聚氨酯丙烯酸酯涂层的固化动力学及其光稳定化研究[J].功能高分子学报,2001,14(4):387~392.
[8]林金娜,曾幸荣,等.可UV固化的超支化聚氨酯丙烯酸酯的合成与表征[J].材料科学与工程学报,2008,26(1):27~31.
[9]王贵友,胡春圃.聚氨酯/丙烯酸酯类树脂互穿网络的结构形态与力学性能研究——网络间化学键的影响[J].高分子学报,1999,(1):24~30.
[10]徐朝华,尹顺,等.可UV固化超支化聚氨酯丙烯酸酯的制备及性能研究[J].高校化学工程学报,2014,(1):156~164.
[11]肖文清,涂伟萍.光固化超支化聚氨酯丙烯酸酯的合成及其固化膜性能[J].高校化学工程学报,2009,23(2):240~245.
[12]Digar M.L.,Hung S.L.,et al.Studies on Cross-linked Polyurethane Acrylate-based Electrolyte Consisting of Reactive Vinyl/divinyl Diluents[J].Polymer,2002,43(5):1615~1622.
[13]Kaewpirom S.,Kunwong D.Curing Behavior and Cured Film Performance of Easy-to-clean UV-curable Coatings Based on Hybrid Urethane Acrylate Oligomers[J].Journal of Polymer Research,2012,19(11):1871~1878.
[14]李扬俊,单志,杨二钘,邵慧菊.聚氨酯型不饱和聚酯树脂的合成及其性能的研究[J].塑料工业,2012,40(1):13~19.
[15]Chattopadhyay D.K.,Webster D.C.Thermal Stability and Flame Retardancy of Polyurethanes[J].Progress in Polymer Science,2009,34(10):1068~1133.
[2]杨睿,潘安徽,赵世琦.不饱和聚酯树脂的增韧和降收缩—种兼具增韧和降收缩效果的新型添加剂[J].材料科学与工程学报,2000,18(z1):156~158.
[3]冯钦邦.气相二氧化硅改性不饱和聚酯树脂研究[D].华南理工大学硕士学位论文,何慧,吴春蕾,广州,2015.12.
[4]杨睿,潘安徽,赵世琦.不饱和聚酯树脂的原位同时增韧和降收缩研究[J].高分子材料科学与工程,2003,19(4):140~143.
[5]A.B.Cherian,L.A.Varghese,E.T.Thachil.Epoxymodified,Unsaturated Polyester Hybrid Networks[J].European Polymer Journal,2007,43(4):1460~1469.
[6]陈一虹,黄剑莹,等.聚氨酯丙烯酸酯的合成和性能研究[J].厦门大学学报(自然科版),2006,45(3):370~374.
[7]刘晓暄,杨建文,黄劲涛,陈用烈.光固化聚氨酯丙烯酸酯涂层的固化动力学及其光稳定化研究[J].功能高分子学报,2001,14(4):387~392.
[8]林金娜,曾幸荣,等.可UV固化的超支化聚氨酯丙烯酸酯的合成与表征[J].材料科学与工程学报,2008,26(1):27~31.
[9]王贵友,胡春圃.聚氨酯/丙烯酸酯类树脂互穿网络的结构形态与力学性能研究——网络间化学键的影响[J].高分子学报,1999,(1):24~30.
[10]徐朝华,尹顺,等.可UV固化超支化聚氨酯丙烯酸酯的制备及性能研究[J].高校化学工程学报,2014,(1):156~164.
[11]肖文清,涂伟萍.光固化超支化聚氨酯丙烯酸酯的合成及其固化膜性能[J].高校化学工程学报,2009,23(2):240~245.
[12]Digar M.L.,Hung S.L.,et al.Studies on Cross-linked Polyurethane Acrylate-based Electrolyte Consisting of Reactive Vinyl/divinyl Diluents[J].Polymer,2002,43(5):1615~1622.
[13]Kaewpirom S.,Kunwong D.Curing Behavior and Cured Film Performance of Easy-to-clean UV-curable Coatings Based on Hybrid Urethane Acrylate Oligomers[J].Journal of Polymer Research,2012,19(11):1871~1878.
[14]李扬俊,单志,杨二钘,邵慧菊.聚氨酯型不饱和聚酯树脂的合成及其性能的研究[J].塑料工业,2012,40(1):13~19.
[15]Chattopadhyay D.K.,Webster D.C.Thermal Stability and Flame Retardancy of Polyurethanes[J].Progress in Polymer Science,2009,34(10):1068~1133.