常压辉光放电等离子装置的建立和引发接枝改性PE纤维的研究
|
摘要
本课题提出并建立了常压辉光放电等离子(APGDP)发生装置。它采用平板金属电极结构,在频率0-40kv高压激励下,可在He/C7F16、He、He/丙酮气体中产生大面积、均匀稳定的辉光放电。并利用常压等离子体引发接枝技术,分别采用亲水性单体和疏水性单体对PE纤维进行了表面改性处理。
本课题通过常压等离子体引发接枝技术,分别采用亲水性单体和疏水性单体对PE纤维进行了表面改性处理。通过对接枝不同单体后PE纤维表面单体接枝率的计算和表面接触角以及表面自由能的测量,系统的研究了常压等离子体引发接枝因素(放电电压、处理时间、接枝率等)对纤维接枝率、接触角和自由能的影响,并利用接触角测量仪、扫描电镜、红外光谱、核磁共振谱等仪器对接枝单体后纤维的表面的化学组成及表面结构进行了表征分析。
通过常压等离子体引发亲水性和疏水性两种处理效果截然相反的单体在PE纤维表面的接枝,对常压等离子体引发亲水性单体和疏水性单体接枝聚合影响接枝效果的规律进行了分析和总结。
An atmospheric-pressure glow discharge plasma reactor is brought forward and developed in this thesis. The glow discharge can be driven of 0-40kv supply. The electrodes are two parallel metal plates. Many kinds of working gasses such as He/ C7F16、He、He/acetone can be used. The measurement provide sufficient evidence to demonstrate that is a really stable and homogeneous glow discharge at atmospheric pressure.
In this paper, the surface of PE fiber was modified by plasma-induced graft reaction. Treating effect, grafting principle of hydrophilic monomer and hydrophobic monomer grafting induced by plasma onto the PE fiber was studied.
Through the related measurement of surface contact angle, grafting rate and surface tension of PE fiber, the involved treatment parameters were studied systematically including plasma power, treating time, monomer types etc. Moreover, IR, NMR and SEM were used to characterize the surface properties of the samples such as chemical composition and morphological structure.
The paper summarized the principle and mechanism of hydrophilic monomer and hydrophobic monomer grafting induced by atmospheric-pressure glow discharge plasma.
本课题通过常压等离子体引发接枝技术,分别采用亲水性单体和疏水性单体对PE纤维进行了表面改性处理。通过对接枝不同单体后PE纤维表面单体接枝率的计算和表面接触角以及表面自由能的测量,系统的研究了常压等离子体引发接枝因素(放电电压、处理时间、接枝率等)对纤维接枝率、接触角和自由能的影响,并利用接触角测量仪、扫描电镜、红外光谱、核磁共振谱等仪器对接枝单体后纤维的表面的化学组成及表面结构进行了表征分析。
通过常压等离子体引发亲水性和疏水性两种处理效果截然相反的单体在PE纤维表面的接枝,对常压等离子体引发亲水性单体和疏水性单体接枝聚合影响接枝效果的规律进行了分析和总结。
An atmospheric-pressure glow discharge plasma reactor is brought forward and developed in this thesis. The glow discharge can be driven of 0-40kv supply. The electrodes are two parallel metal plates. Many kinds of working gasses such as He/ C7F16、He、He/acetone can be used. The measurement provide sufficient evidence to demonstrate that is a really stable and homogeneous glow discharge at atmospheric pressure.
In this paper, the surface of PE fiber was modified by plasma-induced graft reaction. Treating effect, grafting principle of hydrophilic monomer and hydrophobic monomer grafting induced by plasma onto the PE fiber was studied.
Through the related measurement of surface contact angle, grafting rate and surface tension of PE fiber, the involved treatment parameters were studied systematically including plasma power, treating time, monomer types etc. Moreover, IR, NMR and SEM were used to characterize the surface properties of the samples such as chemical composition and morphological structure.
The paper summarized the principle and mechanism of hydrophilic monomer and hydrophobic monomer grafting induced by atmospheric-pressure glow discharge plasma.
引文
[1] 王保刚,腾翠青等.高强度、高模量聚乙烯纤维的表面改性[J].纤维复合材料,1997,(4):17
[2] 田晓伟.UHMWP 纤维表面改性技术的研究进展[J].纤维复合材料,2006,(4):60
[3] 顾庆超,杨昌正.高分子材料开发现状与展望[J]科技与经济.2002,2:44～48
[4] 张燕,顾彪等.常压辉光放电等离子体对化纤及其它聚合物材料的表面研究进展[J].合成纤维,2006,(7):7
[5] 马志领,赵文革.高分子材料科学与工程,2002,18(1):44～46.
[6] 李青.材料表面改性技术[J]石油化工腐蚀与防护.1997,14(1):46～52
[7] 邓建元.高分子材料的表面改性新技术[J]化工新型材料,1997,5:17～21
[8] 顾彪,陈茹.辉光放电等离子体对聚丙烯纤维的表面改性[J].高分子通报,2003,(2):51
[9] 郭锴,李军,伊敏.大学化学,1999,14(3):7～12
[10] Sing P P.Prog.Polym.Sci,1992,17:37
[11] 李朝顺等,化学与粘合.1994:(3):45
[12] 佐藤弘三,“涂膜の接着(Ⅺ)”,高分子加工(日).1994,43(6):34
[13] 牛家嵘,顾振亚.利用微波低温空气等离子体引发聚乙烯薄膜接枝丙烯酸的研究[J] .合成纤维,2004,(4):6
[14] Behnisch I, et al. J. Appl Polym. Sci,1993,49:117
[15] 杨万泰,尹梅贞,邓建元等.高分子通报,1999,1:60～65.
[16] Oster G,ShibataO.J.Polym.Sci,1957,26:233
[17] 陈陈陈.低温等离子体化学及其应用[M].北京:科学出版社,2001.234
[18] Ikada Y.Radiat Phys Chem.,1992,39(6):509
[19] Behnisch I,et al. J. Appl Polym.Sci,1993,49:117
[20] 刘晓冬(Liu Xiaodong).高分子材料科学与工程(Polymer Materials Science and Engineering),1996,(2):106
[21]耿奎士(Geng Kuishi).合成树脂及塑料(Synthetic Resin& Plastics),1993,10(2):52
[22]Garbassi F et al. Polymer Surfaces John Willy & Sono Ltd.1994
[23] 赵化侨.等离子体化学及其应用[J].大学化学,1994,9(4):1—8 [24] Doguel.L,MermilliodN,et al,Vide Sci.Tech.Appl.[J],1995,275:149
[25] 金士九等.高强聚乙烯纤维的冷等离子体改进[J].应川化学,1990,13(2):85
[26] Mantel M,Rabinovich Y L,Wightman J P.A study of hydrophobic interaction between stainless steel and silanated dlass surface using atomic force microscopy[J].Journal of colloid and interface,1995,170:203～214
[27]Mattson B,et al.J. Appl Polym.Sci,1993,50:1247
[28]Iwata H,et al.J.Membr.Sci,1990,55:119
[29]徐秀娟,陈冬芝,郑军.真丝织物低温等离子体拒水拒油整理研究[J]现代纺织技术,2005,4:1～3
[30] Hirotsu T.Water-ethanol separation by pervaporation through the plasma graft polymerizedmembranes[J],J.Appl.Polym.Sci.1987,34:1159
[31] Takehisa Y,Shinihi N,etal.J.P.05,237:352
[32] Hideto M.,Masaaki T.Acs.Symp.Ser[J],1996,642:252
[33] A.H. Josihi,etal. Grafting of Cellophe Films Using Magnetron-Enhanced Plasma Polymerization[J].J.Appl.Polym.Sci,1997,63(6):737
[34] 胥伟清,林晓等.原生态聚丙乙烯等离子体处理接枝甲基丙烯酸甲酯[J]应用化学,1994,11(4):74
[35] 日野常稔,根金嗣男,日本接脊协会志(日文),[J].1978,14:133
[36]李刚,孙秋石等.等离子体引发甲基丙烯酸缩水甘油酯在聚丙烯膜上的的价值反应及肝素的固定化[J].高分子学报,1997,(5):589
[37] Yamada K,Haraguchi T,et al,JP:08120013
[38] Kang F. T , Tan K. L , Surface Modification And Founca Tionalization ol-Polymerization of PolytelratluoroLithylene Film [J].Macromolecules,1996,29 (21):6872
[39] 王雪梅,沈宁徉,盛京.等离子体引发聚合及其研究进展.河北化工,2001,2:9～13
[40] Bergbreiter D E. Prog Polym.Sci,1994,19:526
[41] Chan C M. Polymer Surface Modification and Characterization Carl Harsor Verlag.1994
[42] Krentsel et al. J.Appl Polym.Sci,1994,32:1839
[43] Ren Z L,et al. Seni Gakkaishi,1991,47:635
[44] 张瑞峰(Zhang Ruifeng),等.塑料工业(Plastics Industry),1993,(4):37
[45] Badey J P,et al. Polym.1994,35:2472
[46] Behnisch I,et al.J. Appl Polym.Sci.,1993,49:117
[47] Hollander A,et al.J.Appl Polym.Sci,1993,49:1857
[48] Garbassi F,et al.Polymer Surfaces John Willy & Sono L td.1994
[49] Gao S L,et al.J.App Polym.Sci,1993,47:2093
[50]M itchenko Y I,et al. J.Appl Polym.Sci,1990,41:2561
[51] Inagaki N,et al.J.Appl.Polym,Sci,1992,46:595
[52] 陈陈莹(Chen Jieying).南京大学学报(自然科学)(Journal of Nanjing University),1995,31 (专辑):251
[53] 马立群.难粘高分子材料的表面处理技术[J].化学与粘合,1999,1:23～25
[54] Yu Z J,Kang E T,Neoh K G,et al.Surface passivation of epoxy resin with a covalently adhered poly(tetrafluoroethylene) layer[J].Surf Coatings Technol,2001,138:48～55
[55] Traub H L,Herlinger P H,Oppermann W.Die Angewandte Makromolekulare Chemie,1995,230(4055):179
[56] 路建美,程振平,朱秀林,朱健,周炜萍.等离子体引发丙烯酸聚合[J]胶体与聚合物,1999,1:13～17
[57] 郭雅琳.低温等离子体引发丙烯酸在亚麻上的接枝聚合[J]大连轻工业学院学报,2004,23(3):212～216
[58] 陈宋辉,刘长生.聚丙烯微波辐照固相接枝改性研究[J]化学与生物工程,2006,23(10):25～28
[59] 任忠海,郭雅琳,刘德钧,刘学.等离子体引发丙烯酸在亚麻织物上的接枝聚合[J].辐射研究与辐射工艺学报.2004,22(4):205～209
[60] 周文英,杜泽强.PE/UPR 玻璃钢界面粘接研究[J].中国胶粘剂,2004,(5):52～54
[61] 程时远,陈艳军,王康丽.含氟丙烯酸酯三元共聚物乳液的研究[J] .高分子学报,2002,(5):560～564
[62] 敖玲,刘裕明等.冷等离子体对聚酯表面改性时效性的研究[J] .中央民族大学学报,997(2):134
[63] 李斌,陈文广,王晓工,周其庠.紫外光引发 LDPE 膜接枝含氟丙烯酸酯的研究[J]高分子学报,2002,6:786～791
[64] 周春晓,陈国强.含氟单体接枝真丝的性能研究[J]印染助剂,2006,23(10):20～24
[65] 雷景新,廖霞,李强,高峻.含氢硅油表面接枝改性 PET 织物的拒水性能[J]功能高分子学报,2000,13:317～321
[66] 邢铁玲,陈国强.烯类硅氧烷单体对家蚕丝的接枝改性[J]印染助剂,2004,21(4):46～50
[67] 幸松民,王一璐.有机硅合成工艺及产品应用[M].北京:化学工业出版社,2000,5.
[68] 章基凯(ZHANG Ji-kai).有机硅材料(Organo silicone Materials).北京:中国物资出版社(Beijing: Goods and Materials Press of China),1999
[69] 李巧娟,谢大荣.低密度聚乙烯与有机硅共混和接枝改性对性能的影响研究[J]绝缘材料 2004,4:17～19
[2] 田晓伟.UHMWP 纤维表面改性技术的研究进展[J].纤维复合材料,2006,(4):60
[3] 顾庆超,杨昌正.高分子材料开发现状与展望[J]科技与经济.2002,2:44～48
[4] 张燕,顾彪等.常压辉光放电等离子体对化纤及其它聚合物材料的表面研究进展[J].合成纤维,2006,(7):7
[5] 马志领,赵文革.高分子材料科学与工程,2002,18(1):44～46.
[6] 李青.材料表面改性技术[J]石油化工腐蚀与防护.1997,14(1):46～52
[7] 邓建元.高分子材料的表面改性新技术[J]化工新型材料,1997,5:17～21
[8] 顾彪,陈茹.辉光放电等离子体对聚丙烯纤维的表面改性[J].高分子通报,2003,(2):51
[9] 郭锴,李军,伊敏.大学化学,1999,14(3):7～12
[10] Sing P P.Prog.Polym.Sci,1992,17:37
[11] 李朝顺等,化学与粘合.1994:(3):45
[12] 佐藤弘三,“涂膜の接着(Ⅺ)”,高分子加工(日).1994,43(6):34
[13] 牛家嵘,顾振亚.利用微波低温空气等离子体引发聚乙烯薄膜接枝丙烯酸的研究[J] .合成纤维,2004,(4):6
[14] Behnisch I, et al. J. Appl Polym. Sci,1993,49:117
[15] 杨万泰,尹梅贞,邓建元等.高分子通报,1999,1:60～65.
[16] Oster G,ShibataO.J.Polym.Sci,1957,26:233
[17] 陈陈陈.低温等离子体化学及其应用[M].北京:科学出版社,2001.234
[18] Ikada Y.Radiat Phys Chem.,1992,39(6):509
[19] Behnisch I,et al. J. Appl Polym.Sci,1993,49:117
[20] 刘晓冬(Liu Xiaodong).高分子材料科学与工程(Polymer Materials Science and Engineering),1996,(2):106
[21]耿奎士(Geng Kuishi).合成树脂及塑料(Synthetic Resin& Plastics),1993,10(2):52
[22]Garbassi F et al. Polymer Surfaces John Willy & Sono Ltd.1994
[23] 赵化侨.等离子体化学及其应用[J].大学化学,1994,9(4):1—8 [24] Doguel.L,MermilliodN,et al,Vide Sci.Tech.Appl.[J],1995,275:149
[25] 金士九等.高强聚乙烯纤维的冷等离子体改进[J].应川化学,1990,13(2):85
[26] Mantel M,Rabinovich Y L,Wightman J P.A study of hydrophobic interaction between stainless steel and silanated dlass surface using atomic force microscopy[J].Journal of colloid and interface,1995,170:203～214
[27]Mattson B,et al.J. Appl Polym.Sci,1993,50:1247
[28]Iwata H,et al.J.Membr.Sci,1990,55:119
[29]徐秀娟,陈冬芝,郑军.真丝织物低温等离子体拒水拒油整理研究[J]现代纺织技术,2005,4:1～3
[30] Hirotsu T.Water-ethanol separation by pervaporation through the plasma graft polymerizedmembranes[J],J.Appl.Polym.Sci.1987,34:1159
[31] Takehisa Y,Shinihi N,etal.J.P.05,237:352
[32] Hideto M.,Masaaki T.Acs.Symp.Ser[J],1996,642:252
[33] A.H. Josihi,etal. Grafting of Cellophe Films Using Magnetron-Enhanced Plasma Polymerization[J].J.Appl.Polym.Sci,1997,63(6):737
[34] 胥伟清,林晓等.原生态聚丙乙烯等离子体处理接枝甲基丙烯酸甲酯[J]应用化学,1994,11(4):74
[35] 日野常稔,根金嗣男,日本接脊协会志(日文),[J].1978,14:133
[36]李刚,孙秋石等.等离子体引发甲基丙烯酸缩水甘油酯在聚丙烯膜上的的价值反应及肝素的固定化[J].高分子学报,1997,(5):589
[37] Yamada K,Haraguchi T,et al,JP:08120013
[38] Kang F. T , Tan K. L , Surface Modification And Founca Tionalization ol-Polymerization of PolytelratluoroLithylene Film [J].Macromolecules,1996,29 (21):6872
[39] 王雪梅,沈宁徉,盛京.等离子体引发聚合及其研究进展.河北化工,2001,2:9～13
[40] Bergbreiter D E. Prog Polym.Sci,1994,19:526
[41] Chan C M. Polymer Surface Modification and Characterization Carl Harsor Verlag.1994
[42] Krentsel et al. J.Appl Polym.Sci,1994,32:1839
[43] Ren Z L,et al. Seni Gakkaishi,1991,47:635
[44] 张瑞峰(Zhang Ruifeng),等.塑料工业(Plastics Industry),1993,(4):37
[45] Badey J P,et al. Polym.1994,35:2472
[46] Behnisch I,et al.J. Appl Polym.Sci.,1993,49:117
[47] Hollander A,et al.J.Appl Polym.Sci,1993,49:1857
[48] Garbassi F,et al.Polymer Surfaces John Willy & Sono L td.1994
[49] Gao S L,et al.J.App Polym.Sci,1993,47:2093
[50]M itchenko Y I,et al. J.Appl Polym.Sci,1990,41:2561
[51] Inagaki N,et al.J.Appl.Polym,Sci,1992,46:595
[52] 陈陈莹(Chen Jieying).南京大学学报(自然科学)(Journal of Nanjing University),1995,31 (专辑):251
[53] 马立群.难粘高分子材料的表面处理技术[J].化学与粘合,1999,1:23～25
[54] Yu Z J,Kang E T,Neoh K G,et al.Surface passivation of epoxy resin with a covalently adhered poly(tetrafluoroethylene) layer[J].Surf Coatings Technol,2001,138:48～55
[55] Traub H L,Herlinger P H,Oppermann W.Die Angewandte Makromolekulare Chemie,1995,230(4055):179
[56] 路建美,程振平,朱秀林,朱健,周炜萍.等离子体引发丙烯酸聚合[J]胶体与聚合物,1999,1:13～17
[57] 郭雅琳.低温等离子体引发丙烯酸在亚麻上的接枝聚合[J]大连轻工业学院学报,2004,23(3):212～216
[58] 陈宋辉,刘长生.聚丙烯微波辐照固相接枝改性研究[J]化学与生物工程,2006,23(10):25～28
[59] 任忠海,郭雅琳,刘德钧,刘学.等离子体引发丙烯酸在亚麻织物上的接枝聚合[J].辐射研究与辐射工艺学报.2004,22(4):205～209
[60] 周文英,杜泽强.PE/UPR 玻璃钢界面粘接研究[J].中国胶粘剂,2004,(5):52～54
[61] 程时远,陈艳军,王康丽.含氟丙烯酸酯三元共聚物乳液的研究[J] .高分子学报,2002,(5):560～564
[62] 敖玲,刘裕明等.冷等离子体对聚酯表面改性时效性的研究[J] .中央民族大学学报,997(2):134
[63] 李斌,陈文广,王晓工,周其庠.紫外光引发 LDPE 膜接枝含氟丙烯酸酯的研究[J]高分子学报,2002,6:786～791
[64] 周春晓,陈国强.含氟单体接枝真丝的性能研究[J]印染助剂,2006,23(10):20～24
[65] 雷景新,廖霞,李强,高峻.含氢硅油表面接枝改性 PET 织物的拒水性能[J]功能高分子学报,2000,13:317～321
[66] 邢铁玲,陈国强.烯类硅氧烷单体对家蚕丝的接枝改性[J]印染助剂,2004,21(4):46～50
[67] 幸松民,王一璐.有机硅合成工艺及产品应用[M].北京:化学工业出版社,2000,5.
[68] 章基凯(ZHANG Ji-kai).有机硅材料(Organo silicone Materials).北京:中国物资出版社(Beijing: Goods and Materials Press of China),1999
[69] 李巧娟,谢大荣.低密度聚乙烯与有机硅共混和接枝改性对性能的影响研究[J]绝缘材料 2004,4:17～19