新型形状记忆功能高分子材料的研制
摘要
本论文采用化学交联法和辐照交联法对聚乙烯(PE)、乙烯-醋酸乙烯酯共聚物(EVA)和聚己内酯及其共混物(PCL/EVA)进行改性,制备具有形状记忆功能的高分子材料。通过形状记忆性能测试、凝胶含量测定、光学显微镜等仪器以及DSC 和DMTA等热力学分析手段,研究了工艺参数对形状记忆性能的影响,分析了材料的动态力学性能,在此基础上进一步深入探讨了该功能材料的组成、结构和形状记忆性能之间的关系。
研究了引发剂用量、辐照剂量、凝胶含量、拉伸比、结晶、共混物的组成比以及交联点间平均分子量等与材料的形状记忆行为及其机理的关系。热致型形状记忆高分子材料的响应温度基本对应于未交联材料的熔点,较之低5～10℃左右,主要受结晶的影响。形状回复率及其回复速率、回复应力主要受引发剂用量、辐照剂量、凝胶含量以及交联点间平均分子量的影响。形状固定率受结晶、引发剂用量和辐照剂量的影响。材料的使用性能主要与结晶度有关。拉伸比对形状记忆性能影响不大。交联点间平均分子量是决定材料形状记忆性能的本质因素,相对于凝胶含量更能准确表征形状记忆高分子材料的记忆性能。可通过控制交联引发剂用量或辐照剂量来制备性能优异的形状记忆高分子材料。
In this paper polyethylene(PE), ethylene-vinyl acetate copolymers(EVA) and poly(ε-caprolactone) - ethylene-vinyl acetate copolymers blends(PCL/EVA) were crosslinked by dicumyl peroxide(DCP) or γ-ray, and shape-memory polymers were prepared. Some macroscopic and microscopic factors, which influence the shape-memory properties, processability and mechanism, were studied by mensuration of memory properties & gel content, optical microscope, Differential Scanning Calorimeter and Dynamical Mechanical Thermal Analysis.
It is found that the shape-memory behavior and mechanism has great relationship with the content of DCP, the irradiation dose, the content of gel, the strain ratio, crystallinity and the average molecular weight between the cross-linkage point (Mc). The recovery temperature is corresponding to the melting point of the polymer that isn’t crosslinked; the recovery temperature is 5～10℃ below the melting
temperature of the polymer and is influenced by crystallinity. The shape recovery rate, recovery speed and recovery stress are mainly affected by the content of DCP, the irradiation dose, the content of gel and Mc. The influence of crystallinity,the content of DCP and the irradiation dose on shape fixity rate is prominent. The crystallinity has great influence on the service performance. The strain ratio has little influence on the shape memory properties. The average molecular weight between the cross-linkage point is a determining factor influencing the shape memory properties and can accurately character the shape memory properties relative to gel content. The shape memory polymers with excellent properties can be prepared by controlling the content of DCP or the dose of irradiation.
研究了引发剂用量、辐照剂量、凝胶含量、拉伸比、结晶、共混物的组成比以及交联点间平均分子量等与材料的形状记忆行为及其机理的关系。热致型形状记忆高分子材料的响应温度基本对应于未交联材料的熔点,较之低5～10℃左右,主要受结晶的影响。形状回复率及其回复速率、回复应力主要受引发剂用量、辐照剂量、凝胶含量以及交联点间平均分子量的影响。形状固定率受结晶、引发剂用量和辐照剂量的影响。材料的使用性能主要与结晶度有关。拉伸比对形状记忆性能影响不大。交联点间平均分子量是决定材料形状记忆性能的本质因素,相对于凝胶含量更能准确表征形状记忆高分子材料的记忆性能。可通过控制交联引发剂用量或辐照剂量来制备性能优异的形状记忆高分子材料。
In this paper polyethylene(PE), ethylene-vinyl acetate copolymers(EVA) and poly(ε-caprolactone) - ethylene-vinyl acetate copolymers blends(PCL/EVA) were crosslinked by dicumyl peroxide(DCP) or γ-ray, and shape-memory polymers were prepared. Some macroscopic and microscopic factors, which influence the shape-memory properties, processability and mechanism, were studied by mensuration of memory properties & gel content, optical microscope, Differential Scanning Calorimeter and Dynamical Mechanical Thermal Analysis.
It is found that the shape-memory behavior and mechanism has great relationship with the content of DCP, the irradiation dose, the content of gel, the strain ratio, crystallinity and the average molecular weight between the cross-linkage point (Mc). The recovery temperature is corresponding to the melting point of the polymer that isn’t crosslinked; the recovery temperature is 5～10℃ below the melting
temperature of the polymer and is influenced by crystallinity. The shape recovery rate, recovery speed and recovery stress are mainly affected by the content of DCP, the irradiation dose, the content of gel and Mc. The influence of crystallinity,the content of DCP and the irradiation dose on shape fixity rate is prominent. The crystallinity has great influence on the service performance. The strain ratio has little influence on the shape memory properties. The average molecular weight between the cross-linkage point is a determining factor influencing the shape memory properties and can accurately character the shape memory properties relative to gel content. The shape memory polymers with excellent properties can be prepared by controlling the content of DCP or the dose of irradiation.
引文
[1] Andreas Lendlein, Steffen Kelch. [J]. Shape-memory Polymers. Angewandete Chemie International Edition. 2002. 41(12): 2034～2057
[2] 谭树松. [J]. 形状记忆合金研究的最新进展及应用. 功能材料, 1991, 22(3): 185～190
[3] Ota S. [J]. The heat shrinkage properties of polyethylene. Radiat. Phys. Chem., 1981, 18: 81～84
[4] 詹茂盛,方义,王瑛. [J]. 形状记忆功能高分子材料的研究现状. 合成橡胶工业, 2000,23(1): 53～57
[5] 张福强. [J]. 形状记忆高分子材料. 高分子通报, 1993,(1): 34～42
[6] Masahiro Irie. Developments and applications of shape memory polymers[M]. First Edition.Tokyo: Co Ltd, 1989,1023～1027
[7] 加藤顺. 功能性高分子材料[M]. 第一版. 北京: 中国石化出版社, 1987, 130～134
[8] Ishihars K. [J]. Photoinduced swilling contuol of amphiphilic azoaromatic polymer membrane. Journal of Polymer Science Polymer Chemistry Edition, 1984, 22(1): 121～128
[9] Irie M. [J]. Reversible photostimulated dilation of polyacrylamede gels having triphenylmethane leuco derivarives. Macromolecules, 1986, 19(10): 2476～2480
[10] Irie M. [J]. Reversible solution viscosity change of poly(methacrylic acid) having spirobenzopyran side groups ibid. Photoresponsive polymers, 1979, 12(6): 1176～1180
[11] Menju A. [J]. Reversible solution viscosity change of poly(methacrylic acid) having spirobenzopyran pendant groups in metnanol. Macromolecules, 1981,14(3): 755～758
[12] 石田正雄. [J]. 形状记忆树脂. 配管技术, 1989, 31(8): 112
[13] 白子文,张旭琴,韩雪岗. [J]. 形状记忆聚氨酯. 合成橡胶工业, 1999, 22(3): 184～188
[14] 林俊一. [J]. ポリウレタン系形状记忆プラスチックの开发. ペラスチツクス, 1989, 40(7):66～71
[15] Nojiri A, Shiina N, Nkae H. US, US3965054. 1976
[16] Kiyono H, Ishimoto A, Noda Y. US, US4213925. 1980
[17] Shinshara Y, Takahasshi T, Yamagachi K. US, US3562367. 1971
[18] Sims G L, Sirithongtaworn W. [J]. Azodicarbonamide and sodium bicarbonate blengs as blowing agents for crosslinked polyethylene foam. Gellular Polymers, 1997, 16(4): 271～283
[19] 祝梦林. [J]. 形状记忆材料的开发与应用. 石家庄化工, 1992, (2): 16～18
[20] 谢荣化主编. 塑料购销手册[M]. 第一版. 北京: 中国物资出版社,1994, 32～37
[21] 林俊一.[J]. 聚氨酯塑料.塑料工业,1989,(6):169～173
[22] 杜仕国.[J]. 形状记忆高分子材料的研究进展.功能材料, 1995, 26(2): 107～112
[23] Hayashi S, Shirai Y. [J]. Development of polymers slasticty memory material. Mitsubishi Technical Bulletin, 1988, 184: 213～219
[24] Anda Norihiko. The meterials heating recovery [P]. 日本公开特许公报(日文), 昭 59-227 438. 1984
[25] 傅玉成.[J]. 形状记忆材料的实验研究.高分子材料科学与工程, 1991, 7(2): 99～100
[26] 谭树松.[J]. 形状记忆合金研究的最新进展及应用.化工科技时代, 1991,(5): 17～21
[27] 唐牛正失, 平田明良.[J]. スチレソ -ズタヅエソ共重合树脂.プラスチヘテスエヅ, 1989,(6): 173～178
[28] Noda yoichiro. The foams of shaping recovery[P]. 日本公开特许公报(日文), 昭 60-36 538. 1985
[29] Li Fengkui, Zhu Wei, Zhang Xian, Zhao Chuntian, Xu Mao. [J]. Shape Memory Effcet of Ethtylene-Vinyl Acetate Copolymers. Journal of Applied Polymer Science, 1999, 71: 1063～1070
[30] 王诗任, 徐修成, 詹茂盛. [J]. 微交联EVA的形状记忆特性研究. 功能高分子学报, 1999, 12(2): 132～134
[31] 杨俊华. [J]. 形状记忆树脂. 化工新型材料, 1991, (8): 19～25
[32] 朱光明.形状记忆聚合物及其应用[M].第一版.北京:化学工业出版社,2002,233～241
[33] 山口章三郎.[J]. プラスチツクの形态记忆.化学工业, 1983,34(10): 58～63
[34] 王诗任,吕智,赵伟岩,徐修成,李冰泉. [J]. 热致形状记忆高分子的研究进展. 高分子材料科学与工程, 2000, 16(1): 1～4
[35] 朱光明,梁国正. [J]. 具有形状记忆功能的高分子材料. 化工新型材料, 2002, 30(2): 20～23
[36] 喻春红,陈强,沈健. [J]. 热致感应型形状记忆聚合物. 大学化学, 2000, 15(4): 33～38
[37] 李凤奎,张贤,候建安. [J]. 具有热致形状记忆功能的热塑性多嵌段聚氨酯. 高分子学报, 1996, (4): 462～467
[38] 白井良记. 三菱重工技报[P], 1988, 25(3): 236
[39] M. IRIE. Shape Memory Materials [M]. First Edition. Cambridge, UK: Cambridge University Press, 1998, 203～219
[40] 张欢琴. [J]. 形状记忆聚氨酯弹性体的开发及应用. 化工新型材料, 1997, (3): 32～33
[41] Berstedt B H. [J]. On the Effects Very Low Levels of Long Branching on Rheological Behavior in Polyethylene. Journal of Applied Polymer Science,1985,30(9):3751～3765
[42] Andreopoules A G, Kampouris EM. [J]. Mechanical Properties of Crosslinked Polyethylene. Journal of Applied Polymer Science, 1986,31(4): 1061～1068
[43] Suwanda D, Balde ST. [J]. The Reactive Modification of Polyethylene: Mathematical Modeling. Polymer Engineering and Science, 1993, 33(16): 1592～1605
[44] 龚方红,俞强,李锦春,林明德. [J]. LDPE交联物结构的研究. 高分子材料科学与工程,2000,16(2):140～143
[45] 王正洲,瞿保钧,范维澄,徐云华. [J]. 聚乙烯的交联技术进展. 高分子材料科学与工程,2001,17(1):7～9
[46] Dole M. Chemical & Engineering News. 1948, 26: 2289
[47] Lawton E J. Bueche A M, Balwit J S. Nature, 1953, 172: 76
[48] 罗延龄,赵振兴. [J]. 高分子辐射交联技术及研究进展. 高分子通报,1999,(4):88～99
[49] 王硕,魏国峰,刘宏吉. [J]. 交联聚乙烯的生产技术及应用. 弹性体,1999,9(4):55～59
[50] Kumer S. Thermally Recoverable Crosslinked Polyethylene. Journal of Applied Polymer Science, 1997,64(5): 823
[51] Salyer I.O., Kenyon A.S.. [J]. Structure and Property Relationships in Ethylene-Vinyl Acetate Copolymers. Journal of Polymer Science: Part A-1, 1971, 9(11): 3083～3103
[52] 程曾越. 通用树脂实用技术手册 [M]. 第一版. 北京:中国石油化工出版社,1999,139～145
[53] D’Alelio G.F., Haberli R., Pezdirtz G.F.. Journal of Macromolecular Science Chemistry, 1968, A2(3): 501
[54] 周其凤,胡汉杰. 高分子化学[M]. 第一版. 北京:化学工业出版社,2001,47
[55] 吴培熙,张留城. 聚合物共混改性[M]. 第一版. 北京:中国轻工业出版社出版,1996,18
[56] Brandrup.J. Polymers Handbook [M]. Fourth Edition. NEW YORK:A Wile Intrescience Publication,1995,V/13
[57] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000, 59～60
[58] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,172～173
[59] Minkova L. [J]. Polym Degrad Stab, 1987, (18): 189
[60] Thomas S. Radiat Phys Chem, 1986, 28(3): 283
[61] 张福强,张平平. [J].形状记忆树脂的性能及其应用. 工程塑料应用,1994,22(2):51～55
[62] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,37
[63] 王诗任,徐修成,过梅丽,詹茂盛,王瑛. [J].EVA形状记忆效应的综合评价和分析. 高分子材料科学与工程,2000,16(5):78～80
[64] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,135
[65] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,150
[66] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,136
[2] 谭树松. [J]. 形状记忆合金研究的最新进展及应用. 功能材料, 1991, 22(3): 185～190
[3] Ota S. [J]. The heat shrinkage properties of polyethylene. Radiat. Phys. Chem., 1981, 18: 81～84
[4] 詹茂盛,方义,王瑛. [J]. 形状记忆功能高分子材料的研究现状. 合成橡胶工业, 2000,23(1): 53～57
[5] 张福强. [J]. 形状记忆高分子材料. 高分子通报, 1993,(1): 34～42
[6] Masahiro Irie. Developments and applications of shape memory polymers[M]. First Edition.Tokyo: Co Ltd, 1989,1023～1027
[7] 加藤顺. 功能性高分子材料[M]. 第一版. 北京: 中国石化出版社, 1987, 130～134
[8] Ishihars K. [J]. Photoinduced swilling contuol of amphiphilic azoaromatic polymer membrane. Journal of Polymer Science Polymer Chemistry Edition, 1984, 22(1): 121～128
[9] Irie M. [J]. Reversible photostimulated dilation of polyacrylamede gels having triphenylmethane leuco derivarives. Macromolecules, 1986, 19(10): 2476～2480
[10] Irie M. [J]. Reversible solution viscosity change of poly(methacrylic acid) having spirobenzopyran side groups ibid. Photoresponsive polymers, 1979, 12(6): 1176～1180
[11] Menju A. [J]. Reversible solution viscosity change of poly(methacrylic acid) having spirobenzopyran pendant groups in metnanol. Macromolecules, 1981,14(3): 755～758
[12] 石田正雄. [J]. 形状记忆树脂. 配管技术, 1989, 31(8): 112
[13] 白子文,张旭琴,韩雪岗. [J]. 形状记忆聚氨酯. 合成橡胶工业, 1999, 22(3): 184～188
[14] 林俊一. [J]. ポリウレタン系形状记忆プラスチックの开发. ペラスチツクス, 1989, 40(7):66～71
[15] Nojiri A, Shiina N, Nkae H. US, US3965054. 1976
[16] Kiyono H, Ishimoto A, Noda Y. US, US4213925. 1980
[17] Shinshara Y, Takahasshi T, Yamagachi K. US, US3562367. 1971
[18] Sims G L, Sirithongtaworn W. [J]. Azodicarbonamide and sodium bicarbonate blengs as blowing agents for crosslinked polyethylene foam. Gellular Polymers, 1997, 16(4): 271～283
[19] 祝梦林. [J]. 形状记忆材料的开发与应用. 石家庄化工, 1992, (2): 16～18
[20] 谢荣化主编. 塑料购销手册[M]. 第一版. 北京: 中国物资出版社,1994, 32～37
[21] 林俊一.[J]. 聚氨酯塑料.塑料工业,1989,(6):169～173
[22] 杜仕国.[J]. 形状记忆高分子材料的研究进展.功能材料, 1995, 26(2): 107～112
[23] Hayashi S, Shirai Y. [J]. Development of polymers slasticty memory material. Mitsubishi Technical Bulletin, 1988, 184: 213～219
[24] Anda Norihiko. The meterials heating recovery [P]. 日本公开特许公报(日文), 昭 59-227 438. 1984
[25] 傅玉成.[J]. 形状记忆材料的实验研究.高分子材料科学与工程, 1991, 7(2): 99～100
[26] 谭树松.[J]. 形状记忆合金研究的最新进展及应用.化工科技时代, 1991,(5): 17～21
[27] 唐牛正失, 平田明良.[J]. スチレソ -ズタヅエソ共重合树脂.プラスチヘテスエヅ, 1989,(6): 173～178
[28] Noda yoichiro. The foams of shaping recovery[P]. 日本公开特许公报(日文), 昭 60-36 538. 1985
[29] Li Fengkui, Zhu Wei, Zhang Xian, Zhao Chuntian, Xu Mao. [J]. Shape Memory Effcet of Ethtylene-Vinyl Acetate Copolymers. Journal of Applied Polymer Science, 1999, 71: 1063～1070
[30] 王诗任, 徐修成, 詹茂盛. [J]. 微交联EVA的形状记忆特性研究. 功能高分子学报, 1999, 12(2): 132～134
[31] 杨俊华. [J]. 形状记忆树脂. 化工新型材料, 1991, (8): 19～25
[32] 朱光明.形状记忆聚合物及其应用[M].第一版.北京:化学工业出版社,2002,233～241
[33] 山口章三郎.[J]. プラスチツクの形态记忆.化学工业, 1983,34(10): 58～63
[34] 王诗任,吕智,赵伟岩,徐修成,李冰泉. [J]. 热致形状记忆高分子的研究进展. 高分子材料科学与工程, 2000, 16(1): 1～4
[35] 朱光明,梁国正. [J]. 具有形状记忆功能的高分子材料. 化工新型材料, 2002, 30(2): 20～23
[36] 喻春红,陈强,沈健. [J]. 热致感应型形状记忆聚合物. 大学化学, 2000, 15(4): 33～38
[37] 李凤奎,张贤,候建安. [J]. 具有热致形状记忆功能的热塑性多嵌段聚氨酯. 高分子学报, 1996, (4): 462～467
[38] 白井良记. 三菱重工技报[P], 1988, 25(3): 236
[39] M. IRIE. Shape Memory Materials [M]. First Edition. Cambridge, UK: Cambridge University Press, 1998, 203～219
[40] 张欢琴. [J]. 形状记忆聚氨酯弹性体的开发及应用. 化工新型材料, 1997, (3): 32～33
[41] Berstedt B H. [J]. On the Effects Very Low Levels of Long Branching on Rheological Behavior in Polyethylene. Journal of Applied Polymer Science,1985,30(9):3751～3765
[42] Andreopoules A G, Kampouris EM. [J]. Mechanical Properties of Crosslinked Polyethylene. Journal of Applied Polymer Science, 1986,31(4): 1061～1068
[43] Suwanda D, Balde ST. [J]. The Reactive Modification of Polyethylene: Mathematical Modeling. Polymer Engineering and Science, 1993, 33(16): 1592～1605
[44] 龚方红,俞强,李锦春,林明德. [J]. LDPE交联物结构的研究. 高分子材料科学与工程,2000,16(2):140～143
[45] 王正洲,瞿保钧,范维澄,徐云华. [J]. 聚乙烯的交联技术进展. 高分子材料科学与工程,2001,17(1):7～9
[46] Dole M. Chemical & Engineering News. 1948, 26: 2289
[47] Lawton E J. Bueche A M, Balwit J S. Nature, 1953, 172: 76
[48] 罗延龄,赵振兴. [J]. 高分子辐射交联技术及研究进展. 高分子通报,1999,(4):88～99
[49] 王硕,魏国峰,刘宏吉. [J]. 交联聚乙烯的生产技术及应用. 弹性体,1999,9(4):55～59
[50] Kumer S. Thermally Recoverable Crosslinked Polyethylene. Journal of Applied Polymer Science, 1997,64(5): 823
[51] Salyer I.O., Kenyon A.S.. [J]. Structure and Property Relationships in Ethylene-Vinyl Acetate Copolymers. Journal of Polymer Science: Part A-1, 1971, 9(11): 3083～3103
[52] 程曾越. 通用树脂实用技术手册 [M]. 第一版. 北京:中国石油化工出版社,1999,139～145
[53] D’Alelio G.F., Haberli R., Pezdirtz G.F.. Journal of Macromolecular Science Chemistry, 1968, A2(3): 501
[54] 周其凤,胡汉杰. 高分子化学[M]. 第一版. 北京:化学工业出版社,2001,47
[55] 吴培熙,张留城. 聚合物共混改性[M]. 第一版. 北京:中国轻工业出版社出版,1996,18
[56] Brandrup.J. Polymers Handbook [M]. Fourth Edition. NEW YORK:A Wile Intrescience Publication,1995,V/13
[57] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000, 59～60
[58] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,172～173
[59] Minkova L. [J]. Polym Degrad Stab, 1987, (18): 189
[60] Thomas S. Radiat Phys Chem, 1986, 28(3): 283
[61] 张福强,张平平. [J].形状记忆树脂的性能及其应用. 工程塑料应用,1994,22(2):51～55
[62] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,37
[63] 王诗任,徐修成,过梅丽,詹茂盛,王瑛. [J].EVA形状记忆效应的综合评价和分析. 高分子材料科学与工程,2000,16(5):78～80
[64] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,135
[65] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,150
[66] 金日光,华幼卿. 高分子物理[M]. 第二版. 北京:化学工业出版社,2000,136
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