改性聚氧乙烯基金属复合材料的制备与形态结构研究
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摘要
本文分别从化学改性-多官能团异氰酸酯与聚氧乙烯的加成反应和物理共混-甲基丙烯酸甲酯与甲基丙烯酸的共聚物与聚氧乙烯溶液复合出发，提高聚氧乙烯的耐水性，以使低温下具有极强结晶能力、易溶于水的聚氧乙烯可以作为“溶液还原法”制备聚合物基金属复合材料的基体。
本文通过实验，用以上两种方法制备了可以满足电化学还原过程要求的聚氧乙烯基体。并通过溶解实验对化学改性聚氧乙烯的耐水性做了表征，通过偏光显微镜对共混体系结晶情况的检测证实了共混对PEO结晶的抑制作用。经比较及实际实验，本文确定了两种情况下制备合乎要求的溶胀阴极膜(SCF)所需的条件，并对制备过程作了优化。
对化学改性的SCF，本文采用直接渗析的方式，以之作为基体利用溶液还原法制备了聚合物基金属复合膜，通过比较分析了影响电化学还原过程的基本因素，例如温度、阴极过电位、预干燥程度等；对制得的聚合物基金属复合膜(PMCF)用透射电子显微镜(TEM)做了形貌结构的表征，X射线衍射证实在聚合物复合膜内分散较好的纳米颗粒为还原沉积的纳米铜金属晶体。结合课题组以前的工作及对本体系的分析，本文针对所得到的结果，提出了一个可能的离子迁移还原沉积模式。
对共混改性聚氧乙烯基SCF，本文成功制备了聚合物基金属梯度复合膜(PMGCF)，通过实验对影响电化学还原过程及最终PMGCF形貌结构的各个因素做了分析。本文在该体系中设计了两种溶剂体系，发现水的引入有利于提高铜的沉积量，但所得形貌较为弥散；讨论了共混物的组成对PMGCF的电化学还原过程及最终复合膜内金属沉积形貌的影响，发现具有刚性分子链段的甲基丙烯酸甲酯与甲基丙烯酸的共聚物(MMA-co-MAA)组分的增加使得铜离子迁移困难，铜沉积量较少，铜结
晶优先在枝端生长，利于树枝状晶的生成;本文比较了不同介质酸度下
所制备的PMGCF的形貌，结合本课题组以前提出的“氢离子对铜离子还
原沉积的阻碍”机理进行了分析与验证。
In this paper, two methods were tried to improve property of water-fast of Polyethylene oxide (PEO). One method was carried through grafting PEO with Triisocyanate; the other is to form blend through macromolecular complex between Methyl-Methacrylate-co-Methacrylic Acid (MMA-co-MAA) and PEO. We aim to make PEO as the matrix for Polymer-based Metal Gradient Composite Film (PMGCF) through "solution reduction synthesis" . If PEO dissolves in water, Swelling Cathode Film (SCF) made by PEO will fall to pieces during the reduction procedure.
The two routes turn out to be feasible in preparing desirable modified PEO. Dissolving experiments measured water-fast property of grafted PEO, and the blend was observed by Polarized optical microscope (POM) to make sure that blending reduces crystallization capability of PEO. The conditions under which desirable PEO were prepared were optimized.
For grafted PEO, it was reduced electrochemically under the proper electrochemical conditions to synthesize Polymer-based Metal Composite Film ( PMCF) . In this paper, we analyzed the factors, which would affect electrochemical procedures through experiments, such as temperature, voltage, extent of predrying. A transmittance electronic microscope (TEM) is used to determine the micromorphological structure in the cross-section of PMCF. Nanoscale particle scattered in Polymer matrix were found under
TEM. The particles were observed through X-ray Diffraction method, to be copper nanoscale crystal. A possible model was put forward about the mechanism for the nanoscale copper crystal got in PMCF. PMGCF was prepared by the route of blend PE0. The factors, which would affect the synthesis procedure and the micromorphological structure of PMGCF, were also analyzed. In the experiments we found that: introduction of H20 in solution increases the amount of reduced copper, but the copper in PMGCF becomes more scattered; increase of MMA-co-MAA in the blend will decrease the amount of reduced copper because of rigid segment in MMA and favors the formation of branch-like crystal. Based the mechanism about bafflement of H+ to reduction of Cu+, put forward by our group, the affect of PH value of the medium to micromorphological structure of PMGCF was discussed.
本文通过实验，用以上两种方法制备了可以满足电化学还原过程要求的聚氧乙烯基体。并通过溶解实验对化学改性聚氧乙烯的耐水性做了表征，通过偏光显微镜对共混体系结晶情况的检测证实了共混对PEO结晶的抑制作用。经比较及实际实验，本文确定了两种情况下制备合乎要求的溶胀阴极膜(SCF)所需的条件，并对制备过程作了优化。
对化学改性的SCF，本文采用直接渗析的方式，以之作为基体利用溶液还原法制备了聚合物基金属复合膜，通过比较分析了影响电化学还原过程的基本因素，例如温度、阴极过电位、预干燥程度等；对制得的聚合物基金属复合膜(PMCF)用透射电子显微镜(TEM)做了形貌结构的表征，X射线衍射证实在聚合物复合膜内分散较好的纳米颗粒为还原沉积的纳米铜金属晶体。结合课题组以前的工作及对本体系的分析，本文针对所得到的结果，提出了一个可能的离子迁移还原沉积模式。
对共混改性聚氧乙烯基SCF，本文成功制备了聚合物基金属梯度复合膜(PMGCF)，通过实验对影响电化学还原过程及最终PMGCF形貌结构的各个因素做了分析。本文在该体系中设计了两种溶剂体系，发现水的引入有利于提高铜的沉积量，但所得形貌较为弥散；讨论了共混物的组成对PMGCF的电化学还原过程及最终复合膜内金属沉积形貌的影响，发现具有刚性分子链段的甲基丙烯酸甲酯与甲基丙烯酸的共聚物(MMA-co-MAA)组分的增加使得铜离子迁移困难，铜沉积量较少，铜结
晶优先在枝端生长，利于树枝状晶的生成;本文比较了不同介质酸度下
所制备的PMGCF的形貌，结合本课题组以前提出的“氢离子对铜离子还
原沉积的阻碍”机理进行了分析与验证。
In this paper, two methods were tried to improve property of water-fast of Polyethylene oxide (PEO). One method was carried through grafting PEO with Triisocyanate; the other is to form blend through macromolecular complex between Methyl-Methacrylate-co-Methacrylic Acid (MMA-co-MAA) and PEO. We aim to make PEO as the matrix for Polymer-based Metal Gradient Composite Film (PMGCF) through "solution reduction synthesis" . If PEO dissolves in water, Swelling Cathode Film (SCF) made by PEO will fall to pieces during the reduction procedure.
The two routes turn out to be feasible in preparing desirable modified PEO. Dissolving experiments measured water-fast property of grafted PEO, and the blend was observed by Polarized optical microscope (POM) to make sure that blending reduces crystallization capability of PEO. The conditions under which desirable PEO were prepared were optimized.
For grafted PEO, it was reduced electrochemically under the proper electrochemical conditions to synthesize Polymer-based Metal Composite Film ( PMCF) . In this paper, we analyzed the factors, which would affect electrochemical procedures through experiments, such as temperature, voltage, extent of predrying. A transmittance electronic microscope (TEM) is used to determine the micromorphological structure in the cross-section of PMCF. Nanoscale particle scattered in Polymer matrix were found under
TEM. The particles were observed through X-ray Diffraction method, to be copper nanoscale crystal. A possible model was put forward about the mechanism for the nanoscale copper crystal got in PMCF. PMGCF was prepared by the route of blend PE0. The factors, which would affect the synthesis procedure and the micromorphological structure of PMGCF, were also analyzed. In the experiments we found that: introduction of H20 in solution increases the amount of reduced copper, but the copper in PMGCF becomes more scattered; increase of MMA-co-MAA in the blend will decrease the amount of reduced copper because of rigid segment in MMA and favors the formation of branch-like crystal. Based the mechanism about bafflement of H+ to reduction of Cu+, put forward by our group, the affect of PH value of the medium to micromorphological structure of PMGCF was discussed.
引文
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4．郑玉斌，张善举，柯杨船等．聚合物表面金属化的研究：Ⅰ．导电性能的研究．功能高分子学报，1996，9(4)：561～564
5. Kiss G. In-situ composities: blends of isotropic polymers and thermotropic liqued crystalline polymers. Polym Eng Sci 1987(27): 410
6. Joseph J R, et al. Growth morphology and reinforcement potential of low molecular weight crystals in amorphous polymeric matrices. J Appl Polym Sci, 1968(12): 1151
7．新野正之，平进敏雄，渡边龙三．倾斜机敏材料．日本复合材料学会志，1987(13)：257
8．张联盟，袁润章．Ni_3Al对TiC的润湿性及Mo添加的影响．复合材料学报，1995，12(4)：22
9. Liu Y, Wang A, Claus R O. App Phys Lett, 1997, 71(16): 2265
10. White sides G M, Mathias J P, et al. Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures. Science, 1991, A: 203～272.
11. Higashda N, Kressler J, Yukioka S, Inoue T. Mactomo lecules, 1992(15): 529
12. Acosta P L, Jurado J R. Journal of App lied Polymer Science, 1995(57): 431～437
13. In S S, Lee J S, Kang E Y, Journal of App lied Polymer Science,1992(45): 827～836
14. In S S, Lee J S. Synthetic Metals, 1991(41～43): 675～678
15. Fernandez A M, N air P K. Polymer Films, 1992(35): 459～471
16. Dalas E, Kolas S N, Vitoratos E, Sakkopoulos S. Journal of Materials Science Letter, 1993(12): 497
17. Sakkopoulos S, Vtoratos E, Koklas S N, Dalas E. Synthetic Metals, 1995(72): 177～180
18. Burk strand JM. Journal ofhpp lied Physics, 1981(52): 4795
19. Pireaux J J. Synthetic Metals, 1994(67): 3946
20. Service R F. Science, 1995(267): 1918～1921
21. Clery D. Science, 1994(263): 1700～1702
22. Burroughes J H, Bradley D D C, Brown A R, et al. Nature,1990(347): 539
23. Gustafsson G, Cao Y, Treacy GM, et al. Nature, 1992: 357～477
24. Grem G, Ledisky G, Ullrich B, et al. Advanced Materials,1992(4): 36
25. Ggreenham N C, Moratti S C, Bradley D D C, Friend R H, Holmes A B. Nature, 1993: 365～628
26. Azzaroni R L, Logdlund M, Calderone A, Bredsa J L. Synthetic Metals, 1995(71): 2159～2162
27. Lazzaroni R, Parente V, Fredriksson C, Bredas J L.
Synthetic Metals, 1996(76): 225～228
28. Okieimen F E, Ebhoaye J E. Polymer Journal, 1992, 28 (11): 1423～1425
29. Troev K, Kisiova T, Grozeva A, Borisov G. Polymer Journal, 1993, 29(11): 1499～1504
30. Allan J R, Binnie N. Polymer Journal, 1991, 27 (10): 1035～1038
31. Day M, Cooney J D, Mackinnon M. Polymer Degradation and Stability, 1995(48): 341～349
32. Khairou K S. Polymer Degradation and Stability, 1994(46): 315～318
33. Jose-Luis S, Hughes-Dillon M K. Polymer Degradation and Stability, 1994 (46): 241～246
34. Dutton T, Wonterghen B V, Saltiel S, Chestnoy N V, Rentzepis P M, Shen T P, Rogvin D. Journal of Physical Chemistry, 1990(94): 1100
35. Nguyen A M T, Diaz A F, Advanced Materials. 1994: 11～858
36. Ziolo R F. Science, 1992: 257～279
37. Kryszewshi M, Jeszka J K. Nanostructured conducting polymer composites-superparamagnetic particles in conducting polymers. Synthetic Metals, 1998: 94～99
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