膨体聚四氟乙烯医用膜材料开发研究
|
摘要
膨体聚四氟乙烯（EPTFE）具有独特的结构和性能，生物相容性良好，非常
适合作脏器修补材料和整形外科材料。而且随着医学的进步，各种高难度手术
的普及和人们生活水平的提高，对其需求量越来越大，但目前所用EPTFE产
品多依赖进口，且价格昂贵，给病人带来很大的经济负担。因此研制出与进口
产品性能相当EPTFE材料不仅具有重要的理论意义，而且会产生明显的经济
效益。
本文采用多向拉伸高温烧结法制备膨体聚四氟乙烯膜，并根据拉伸成孔原
理，在国内，首次成功地研制出一台可用于中试生产的多向拉伸试验仪，设计
了结构和控制性能独特的拉伸装置、控温装置。所研制的样机综合性能优良，
达到了设计要求。利用此多向拉伸试验仪，经过将一定配比的PTFE和助挤剂
的混合、研磨、模压、压延、干燥、拉伸、烧结、冷却过程，制备出了外观洁
白、柔软、富弹性的EPTFE。具体的较佳制备工艺可表示如下：
1 分散聚四氟乙烯树脂（PTFE）分子量必须足够大才能保证膜制品的拉伸
强度达到要求，且粒子尺寸尽可能小，以使助挤剂能较好地浸润。
2 PTFE_1与助挤剂的配比为每100gPTFE中加入20～30ml助挤剂；
3 配料在30～40MPa下模压成板，要求升降速度缓慢并保压；
4 30～40℃下双辊压延，折叠4～6次，进行预拉伸取向；
5 压延片材在80～90℃下干燥48h，除去助挤剂；
6 拉伸温度为170℃，拉伸倍率为4倍时的机械性能最好；
7 在360℃烧结，烧结时间为10～20分钟，327℃之前升温速度60℃/h，327
℃之后20℃/h
8 空气中淬火处理。
所制备的EPTFE多孔膜拉伸强度为7.76MPa，断裂伸长率为94.61％，空
隙率为68％，孔径为1.11～4.44μm，与进口Gore-Tex产品性能相当，但价格
远比其低。动物毒性试验的结果表明我们所制备的EPTFE材料组织相容性好，
无毒性，深入的动物试验正在进行中。
Expanded Polytetrafluoroethylene(EPTFE) has particular network structure and
stable chemical property which make it useful for hazarded heard repairing. In recent
years ,the requirement for it is increasing quickly. But the products we use are mainly
imported. Its high price give the sick hard load. So, it抯 very important not only in
theories but also in economical practice to produce EPTFE with good property in
China.
According to the multi-stretching theory, We have designed and produced a
special machine for EPTFE membrane production which has been installed heating
control device, oven, sample-fixed device and etc.. On the basis of success of multi-
stretching machine, the results prove that it can be used for studying and preparing the
EPTFE membrane.It can meet the demands of hazarded heart repairing.
EPTFE membrane can be produced by mixing PTFE resin and liquid lubricant,
then grinding, molding, calending,drying, stretching, sintering and quenching.
The optimum conditions could be concluded as following:
1 Dispersion PTFE resin should be chosen from high MW PTFE;
2 Optimum composition was lOOg PTFE plus 20挆3Oml liquid lubricant;
3 The plate is produced by molding under 30?OMPa;
4 The plate is calended at 30~400C and folded for 4?-6 times;
5 The slice is dried at 80?00C;
6 The slice is stretched for 400% at 17000;
7 The slice is sintered at 36000 for 10~?0 mm; The heating rate was 60扖/h
before 32700 and 200C/h after 32700;
8 The EPTFE membrane is quenched in air.
The EPTFE membrane tensile strength is up to 7.76MPa, elongation at break is
up to 94.61%, porosity is up to 68%, the size of pore is up to l.11?.44i?m. So, the
complex property can catch up with the Gore-Tex membrane,but its price is much low
than Gore-Tex membrane.The EPTFE membrane can be used for animal organism
(such as rabbit and rat) repairing which has be proved by Shao Shao Run Hospital.
The results show that the membrane has no toxicity and good compatibility with the
organism of the sample animals.
适合作脏器修补材料和整形外科材料。而且随着医学的进步，各种高难度手术
的普及和人们生活水平的提高，对其需求量越来越大，但目前所用EPTFE产
品多依赖进口，且价格昂贵，给病人带来很大的经济负担。因此研制出与进口
产品性能相当EPTFE材料不仅具有重要的理论意义，而且会产生明显的经济
效益。
本文采用多向拉伸高温烧结法制备膨体聚四氟乙烯膜，并根据拉伸成孔原
理，在国内，首次成功地研制出一台可用于中试生产的多向拉伸试验仪，设计
了结构和控制性能独特的拉伸装置、控温装置。所研制的样机综合性能优良，
达到了设计要求。利用此多向拉伸试验仪，经过将一定配比的PTFE和助挤剂
的混合、研磨、模压、压延、干燥、拉伸、烧结、冷却过程，制备出了外观洁
白、柔软、富弹性的EPTFE。具体的较佳制备工艺可表示如下：
1 分散聚四氟乙烯树脂（PTFE）分子量必须足够大才能保证膜制品的拉伸
强度达到要求，且粒子尺寸尽可能小，以使助挤剂能较好地浸润。
2 PTFE_1与助挤剂的配比为每100gPTFE中加入20～30ml助挤剂；
3 配料在30～40MPa下模压成板，要求升降速度缓慢并保压；
4 30～40℃下双辊压延，折叠4～6次，进行预拉伸取向；
5 压延片材在80～90℃下干燥48h，除去助挤剂；
6 拉伸温度为170℃，拉伸倍率为4倍时的机械性能最好；
7 在360℃烧结，烧结时间为10～20分钟，327℃之前升温速度60℃/h，327
℃之后20℃/h
8 空气中淬火处理。
所制备的EPTFE多孔膜拉伸强度为7.76MPa，断裂伸长率为94.61％，空
隙率为68％，孔径为1.11～4.44μm，与进口Gore-Tex产品性能相当，但价格
远比其低。动物毒性试验的结果表明我们所制备的EPTFE材料组织相容性好，
无毒性，深入的动物试验正在进行中。
Expanded Polytetrafluoroethylene(EPTFE) has particular network structure and
stable chemical property which make it useful for hazarded heard repairing. In recent
years ,the requirement for it is increasing quickly. But the products we use are mainly
imported. Its high price give the sick hard load. So, it抯 very important not only in
theories but also in economical practice to produce EPTFE with good property in
China.
According to the multi-stretching theory, We have designed and produced a
special machine for EPTFE membrane production which has been installed heating
control device, oven, sample-fixed device and etc.. On the basis of success of multi-
stretching machine, the results prove that it can be used for studying and preparing the
EPTFE membrane.It can meet the demands of hazarded heart repairing.
EPTFE membrane can be produced by mixing PTFE resin and liquid lubricant,
then grinding, molding, calending,drying, stretching, sintering and quenching.
The optimum conditions could be concluded as following:
1 Dispersion PTFE resin should be chosen from high MW PTFE;
2 Optimum composition was lOOg PTFE plus 20挆3Oml liquid lubricant;
3 The plate is produced by molding under 30?OMPa;
4 The plate is calended at 30~400C and folded for 4?-6 times;
5 The slice is dried at 80?00C;
6 The slice is stretched for 400% at 17000;
7 The slice is sintered at 36000 for 10~?0 mm; The heating rate was 60扖/h
before 32700 and 200C/h after 32700;
8 The EPTFE membrane is quenched in air.
The EPTFE membrane tensile strength is up to 7.76MPa, elongation at break is
up to 94.61%, porosity is up to 68%, the size of pore is up to l.11?.44i?m. So, the
complex property can catch up with the Gore-Tex membrane,but its price is much low
than Gore-Tex membrane.The EPTFE membrane can be used for animal organism
(such as rabbit and rat) repairing which has be proved by Shao Shao Run Hospital.
The results show that the membrane has no toxicity and good compatibility with the
organism of the sample animals.
引文
[1] 蓝立文主编．功能高分子材料，西北工业大学出版社，1995年6月．
[2] 关键，顾宜．工程塑料应用，2001，29(2) ，33-39
[3] 金关泰主编．高分子化学的理论和应用进展，中国石化出版社，1995年3月
[4] D.J.Lyman,L.C.Metcalf,D.Albo.Jr.D.T.Richads J.lamb, TASAIO, 1974,20,474-479
[5] M.Suzuki.Y.Tamata,H,Iwata,Y,Ikada,Physicochem,Aspect,Polym,Surf,(Proc,Int,Symp,1981)
[6] Bauser,Herbert et al.,Polym.Sci,Technol.(Plenum Press) 1983,23,297-309
[7] A.Chapiro.Eur.Polym.J., 1983,19(10-11) ,859
[8] B.D.Ratner.ACS.Symp.Ser. 1981,162,371
[9] DJ.Lyman et al., TASAIO, 1969,14,250
[10] E.Nyilas et al.,TASAIO 1969,20,480
[11] H.Jacobs & S.W.Kij,Pharm.Sci. 1986,75,172
[12] R.S.Wilsom,ET AL., Techniques of Biocompatibility Testing (1989) .
[13] K.D.Park,T.Okano,C.Nojiri,S.W.Kim.Prepr,of 3rd.World Biomaterials Congress.Kyoto 571(1988)
[14] H.Miyake,H.Handa,Y.Yonekawa,W.Kaki,Y.Naruo,S.Yamagata.Y.Ikada et al.,microsurgery 1984,5,144
[15] 许健南主编．塑料材料，轻工业出版社．1999年1月
[16] T.Akutsu.W.J.Kolff,TASAIO, 1958,4,230,
[17] K.Atsumi,I,Fujimasa et al.Jpn.Artif.Organs, 1986,14,1264
[18] 杨子彬等，生物医学工程学杂志1987，4(3) ，157
[19] W.C.Devries.L.J.Anderson,L.D.F.L.Ioice,Anderson,E.H.Hammond.R.K.JARVIK,w.j.Kolff,N Engl.J.Med.310,237(1984) .
[20] L.D.Ioyce.W.C.Devries,W.L.Hasting,D.B.Oisen.R.K.Jarvik,W.J.Kolff,TASAIO, 1983,29,81-85
[21] 刘国惠，化学通报．1992． 7． 21-26，转6
[22] Scigala,R., wlochowicz,A., Arch,nauki Mater, 1988,9(4) ,285-299．
[23] Haneda,Tsuguo,Takahashi,Juzo,robunshi Ronbunshu, 1983 ,40(8) ,467-473．
[24] JPn 01,758,534
[25] JPn 07,278,331
[26] Hashida,shigetaki.JPn.03,197,122
[27] Hashida,shigetae. JPn.0l,247,432
[28] Japan.Kokai74118 761
[29] JPn. 0782399
[30] JPn,0341;130
[31] JPn,Kokai Tokkyo koho 79 97 686
[32] Japan Kokai 7619069
[33] Dkuda,Yasuhiro JPn,Kokai T; JP,04 ,35,35,34
[34] Ep 0,403901 A2
[35] Ep 402901
[36] Eur. Pat. 433787
[37] CA 2031808
[38] Japan.Kokai 7442,773
[39] Japan. 64-78823
[40] CN, 1107383
[41] Japa Kokai 74117568．
[42] JP.02284633
[43] US.4973609
[44] JPn.Kokai.Tokkyo yoho 79111,569
[45] FR 25594 92
[46] J.P 02284,634
[47] JPn,Kokai Tokkyo koho 7985 267．
[48] Japan. 73300533
[49] JP 01 92 244
[50] JP 07,233,273
[51] US. 4743252
[52] US. 5100422
[53] US. 5104 400
[54] Kraniler.Thane PCT.US. 9307563
[55] US．49 7369
[56] US．4208745
[57] Hirabayashi，K，Saitoh，E．，J．biomater．Pes．1992U(H)1433-1447
[58] 刘国惠，上海化工，1996，3，1-3
[59] 钱知勉，有机氟工业2000，2，25-28
[60] 浙江省科技发展对策研究中心，决策与参考1997． 2． 20
[61] 王文广，有机氟工业，1991，1，18
[62] 王文广，有机氟工业，1998，2，8-12
[63] 潘昭青，赵华民，张勒等，塑料工业1983，(2) ，29-43
[64] 汪萍．现代塑料加工应用，1995，7(3) ，45-49
[65] 汪萍．现代塑料加工应用，1995，7(1) ，37-39
[66] 陆洪畴，沈静逸．塑料，1984，1，26-31
[67] F．J．Rahl，M．A，Evanco，R．T. Fredericks，and A．C．Relmschuessel，J．Polym．Sci．1972，A-2，10，1337
[68] R．W．Gore，U．S．Patent，3，953，556
[69] Taketo kitamura，Ken-Ichi Kuruada，Polym．Eng．Sci．1999，39(11) ，2256-2263
[70] Vivier,Herve；Marie，Noeue；J．membr．Sci．1989，46(1) ，81-91
[71] Taketo Kitamura，Shohei Okake，Polym．Eng．Sci．，2000，40(3) ，908-817
[72] 罗晃，王敏．塑料，1991，20(2) ，5-8
[73] 王进华．有机氟工业，2000，3，21-23
[74] 贺季堂．有机氟工业，1991，5-6，74
[75] Scigala,R．；Wlochowicz，A．，Arch．Nauki Mater．1988，9(4) ，285-299
[76] 何曼君主编，高分子物理，复旦大学出版社，1990年10月，P80．
[2] 关键，顾宜．工程塑料应用，2001，29(2) ，33-39
[3] 金关泰主编．高分子化学的理论和应用进展，中国石化出版社，1995年3月
[4] D.J.Lyman,L.C.Metcalf,D.Albo.Jr.D.T.Richads J.lamb, TASAIO, 1974,20,474-479
[5] M.Suzuki.Y.Tamata,H,Iwata,Y,Ikada,Physicochem,Aspect,Polym,Surf,(Proc,Int,Symp,1981)
[6] Bauser,Herbert et al.,Polym.Sci,Technol.(Plenum Press) 1983,23,297-309
[7] A.Chapiro.Eur.Polym.J., 1983,19(10-11) ,859
[8] B.D.Ratner.ACS.Symp.Ser. 1981,162,371
[9] DJ.Lyman et al., TASAIO, 1969,14,250
[10] E.Nyilas et al.,TASAIO 1969,20,480
[11] H.Jacobs & S.W.Kij,Pharm.Sci. 1986,75,172
[12] R.S.Wilsom,ET AL., Techniques of Biocompatibility Testing (1989) .
[13] K.D.Park,T.Okano,C.Nojiri,S.W.Kim.Prepr,of 3rd.World Biomaterials Congress.Kyoto 571(1988)
[14] H.Miyake,H.Handa,Y.Yonekawa,W.Kaki,Y.Naruo,S.Yamagata.Y.Ikada et al.,microsurgery 1984,5,144
[15] 许健南主编．塑料材料，轻工业出版社．1999年1月
[16] T.Akutsu.W.J.Kolff,TASAIO, 1958,4,230,
[17] K.Atsumi,I,Fujimasa et al.Jpn.Artif.Organs, 1986,14,1264
[18] 杨子彬等，生物医学工程学杂志1987，4(3) ，157
[19] W.C.Devries.L.J.Anderson,L.D.F.L.Ioice,Anderson,E.H.Hammond.R.K.JARVIK,w.j.Kolff,N Engl.J.Med.310,237(1984) .
[20] L.D.Ioyce.W.C.Devries,W.L.Hasting,D.B.Oisen.R.K.Jarvik,W.J.Kolff,TASAIO, 1983,29,81-85
[21] 刘国惠，化学通报．1992． 7． 21-26，转6
[22] Scigala,R., wlochowicz,A., Arch,nauki Mater, 1988,9(4) ,285-299．
[23] Haneda,Tsuguo,Takahashi,Juzo,robunshi Ronbunshu, 1983 ,40(8) ,467-473．
[24] JPn 01,758,534
[25] JPn 07,278,331
[26] Hashida,shigetaki.JPn.03,197,122
[27] Hashida,shigetae. JPn.0l,247,432
[28] Japan.Kokai74118 761
[29] JPn. 0782399
[30] JPn,0341;130
[31] JPn,Kokai Tokkyo koho 79 97 686
[32] Japan Kokai 7619069
[33] Dkuda,Yasuhiro JPn,Kokai T; JP,04 ,35,35,34
[34] Ep 0,403901 A2
[35] Ep 402901
[36] Eur. Pat. 433787
[37] CA 2031808
[38] Japan.Kokai 7442,773
[39] Japan. 64-78823
[40] CN, 1107383
[41] Japa Kokai 74117568．
[42] JP.02284633
[43] US.4973609
[44] JPn.Kokai.Tokkyo yoho 79111,569
[45] FR 25594 92
[46] J.P 02284,634
[47] JPn,Kokai Tokkyo koho 7985 267．
[48] Japan. 73300533
[49] JP 01 92 244
[50] JP 07,233,273
[51] US. 4743252
[52] US. 5100422
[53] US. 5104 400
[54] Kraniler.Thane PCT.US. 9307563
[55] US．49 7369
[56] US．4208745
[57] Hirabayashi，K，Saitoh，E．，J．biomater．Pes．1992U(H)1433-1447
[58] 刘国惠，上海化工，1996，3，1-3
[59] 钱知勉，有机氟工业2000，2，25-28
[60] 浙江省科技发展对策研究中心，决策与参考1997． 2． 20
[61] 王文广，有机氟工业，1991，1，18
[62] 王文广，有机氟工业，1998，2，8-12
[63] 潘昭青，赵华民，张勒等，塑料工业1983，(2) ，29-43
[64] 汪萍．现代塑料加工应用，1995，7(3) ，45-49
[65] 汪萍．现代塑料加工应用，1995，7(1) ，37-39
[66] 陆洪畴，沈静逸．塑料，1984，1，26-31
[67] F．J．Rahl，M．A，Evanco，R．T. Fredericks，and A．C．Relmschuessel，J．Polym．Sci．1972，A-2，10，1337
[68] R．W．Gore，U．S．Patent，3，953，556
[69] Taketo kitamura，Ken-Ichi Kuruada，Polym．Eng．Sci．1999，39(11) ，2256-2263
[70] Vivier,Herve；Marie，Noeue；J．membr．Sci．1989，46(1) ，81-91
[71] Taketo Kitamura，Shohei Okake，Polym．Eng．Sci．，2000，40(3) ，908-817
[72] 罗晃，王敏．塑料，1991，20(2) ，5-8
[73] 王进华．有机氟工业，2000，3，21-23
[74] 贺季堂．有机氟工业，1991，5-6，74
[75] Scigala,R．；Wlochowicz，A．，Arch．Nauki Mater．1988，9(4) ，285-299
[76] 何曼君主编，高分子物理，复旦大学出版社，1990年10月，P80．