改性EVOH的制备、性能与应用研究
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摘要
本工作利用酯化反应制备了EVOH-AA(丙烯酸)和EVOH-MAH(马来酸酐)接枝型材料,并利用转矩流变仪及凝胶抽提实验研究了制备改性EVOH的条件。利用傅立叶红外光谱对接枝产物进行了表征,通过凝胶抽提实验来验证改性EVOH是否变得易于交联,将其与辐射裂解型聚合物聚乳酸(PLA)共混后辐照,通过计算进入交联网格的PLA的含量,来验证改性EVOH作为一种大分子型多官能团单体(PFM),其是否具备强化辐射交联作用,然后通过力学性能测试和热性能测试研究了这种大分子PFM和小分子PFM对EVOH和PLA共混物强化辐射交联后性能的变化,从对共混物宏观性能的影响方面,对这两种PFM的强化辐射交联效果作一个比较。此外,对于EVOH预辐照反应接枝MAH的加工条件及反应机理也进行了初步的探索。
Grafting modification is the main one of the means for preparing modified polyolefin. To carry out grafted polyolefins containing special functional groups that have polarity and reactivity can not only improve their performance deficiencies, but also add new performance, which is a simple and effective method to expand uses of polyolefin materials. In recent years, modifying the existing polyolefin to produce functional and high-performance polyolefin materials has been developing rapidly by the reactive processing technology.
Ethylene-vinyl alcohol copolymers (EVOH) are one of the three high gas-barrier materials. They are used widely in various fields such as good packing, gasoline tanks, or other materials. EVOH are expected to work as one of the soft materials for no emission of poisonous gas upon incineration and chlorine-free. However EVOH are hygroscopic and the absorbed water lowers their ability to inhibit oxygen diffusion, which is undesirable in food packaging. Introducing crosslinking bonds between polymer molecules by chemical or radiation treatments is a powerful method to reduce the hygroscopicty. But it is difficult for EVOH to cross-link, which can’t form gel below 800kGy. The radiation crosslinking of particular ethylene copolymers can markedly be enhanced by introduction of pendant radiation-sensitive functional groups and that reactive melt processing offers an attractive alternative to introduce the pendant groups. EVOH can be activated by the branched-chain groups hydroxyl and occur grafting polymerization with vinyl monomers, and functionalized EVOH may become crosslinked easily by radiation. and EVOH with vinyl monomers as its pendant group can be used as polyfunctional monomers (PFM), which may promote crosslinking as a kind of macromolecules crosslinking promoter and be potential to overcome the unfavorable factors of common PFM and to be applied blending polymers in the or modifying engineering plastics and so on. This paper studies the following elements: 1) preparation, characterization and radiation effects of functionalized EVOH by esterification grafting; 2) whether functionalize EVOH can be used as macromolecules PFM; 3) the effect of enhanced crosslinking of macromolecules PFM on the properties of EVOH/PLA (polylactic acid) blends, and to compare with the effect of the small molecule PFM 4) pre-irradiation induced graft reaction of maleic anhydride onto EVOH.
FTIR spectrum of functionalized EVOH show that peak values of neighborhood 1717cm-1 increase corresponding to C=O peak formed by esterification. Because EVOH contains a small amount of unhydrolyzed vinyl acetate unit, we found after EVOH functionalized, the ratio value increased significantly that demonstrated AA and MAH were grafted to the matrix of EVOH by calculating the ratio of the strength of the absorbed peak of -OH and C=O groups (AbsC=O/AbsO-H). The results of gel fraction of functionalized EVOH at different doses showed that EVOH-AA materials become easier to crosslink by radiation, and gel fraction can reach more than 45% after having received a radiation dose of 10kGy. but EVOH-MAH materials that were prepared only when reaction time was 5 min, 2%MAH or reaction time was 10 min, 1%MAH can elevate the gel fraction after irradiated but gel content increased less than that of EVOH-AA. For EVOH-MAH at other processing conditions, gel content changed little as the absorbed dose increased.
The results of gel extraction experiment of EA1T1/PLA blends show that the blends can form gel when EA1T1 was used as macromolecular PFM whose content was more than 5%. At the same absorbed dose, gel fraction of blends increased as the content of EA1T1 increased. However the gel content of 20% EA1T1 was more than that of 30% and 40%. The calculated results show that the content of PLA which entered the crosslinking network was more than others and EA1T1 had certain enhanced radiation crosslinking effect, and the best content is 20%. When EA2T1, Et2M1 and Et1M2 were used as macromolecular PFM, gel content of blends increased as the content of PFM, but the calculated results showed that only Et2M1 PFM was used, a little PLA entered the crosslinking network, and Et2M1 PFM had certain enhanced radiation crosslinking effect. When EA2T1 and Et1M2 was used, no or only minimal amount of PLA entered the crosslinking network and enhanced radiation crosslinking was less effective. When Et1M1 was used, whose content was not more than 50%, blends didn’t form gel at the absorbed dose below 100kGy.
The results of the properties of EVOH/PLA which were enhanced radiation-crosslinked by macromolecular show that mechanical properties EVOH/PLA did not change much, only in the 50/50 system, heat deformation temperature of the blend had been improved. The results of the properties of EVOH/PLA which were enhanced radiation-crosslinked by small molecular PFM show that when the tensile strength of blends that had 3% or 5% PFM at the absorbed dose of 30-50kGy. The heat deformation temperature had been significantly improved at the absorbed dose of 50-100kGy. But the elongation at the breaking and the impact strength didn’t change much. Compared to macromolecular cross-linking agent, small molecule PFM was more suitable for enhanced radiation-crosslinking of EVOH/PLA blend.
The analysis results of torque and gel content in the process of pre-irradiation reaction grafting of F101 show that the gel content of product increased as the MAH content and changed not much as the absorbed dose with the same content of MAH. It is deduced that reaction was mainly esterification. Infrared spectra of product confirmed that, where a new peak appeared in 1718cm-1 corresponding to C=O in the ester bonds. E171 has a similar pre-irradiation grafting process with F101, but owning the same MAH content, gel content of product is lower than F101 system. Titration results also confirmed that esterification reactions occurred in the grafting process. According to the application, MAH content was below 2% for pre-irradiation grafting of F101 and was less than 3% for E171.
Grafting modification is the main one of the means for preparing modified polyolefin. To carry out grafted polyolefins containing special functional groups that have polarity and reactivity can not only improve their performance deficiencies, but also add new performance, which is a simple and effective method to expand uses of polyolefin materials. In recent years, modifying the existing polyolefin to produce functional and high-performance polyolefin materials has been developing rapidly by the reactive processing technology.
Ethylene-vinyl alcohol copolymers (EVOH) are one of the three high gas-barrier materials. They are used widely in various fields such as good packing, gasoline tanks, or other materials. EVOH are expected to work as one of the soft materials for no emission of poisonous gas upon incineration and chlorine-free. However EVOH are hygroscopic and the absorbed water lowers their ability to inhibit oxygen diffusion, which is undesirable in food packaging. Introducing crosslinking bonds between polymer molecules by chemical or radiation treatments is a powerful method to reduce the hygroscopicty. But it is difficult for EVOH to cross-link, which can’t form gel below 800kGy. The radiation crosslinking of particular ethylene copolymers can markedly be enhanced by introduction of pendant radiation-sensitive functional groups and that reactive melt processing offers an attractive alternative to introduce the pendant groups. EVOH can be activated by the branched-chain groups hydroxyl and occur grafting polymerization with vinyl monomers, and functionalized EVOH may become crosslinked easily by radiation. and EVOH with vinyl monomers as its pendant group can be used as polyfunctional monomers (PFM), which may promote crosslinking as a kind of macromolecules crosslinking promoter and be potential to overcome the unfavorable factors of common PFM and to be applied blending polymers in the or modifying engineering plastics and so on. This paper studies the following elements: 1) preparation, characterization and radiation effects of functionalized EVOH by esterification grafting; 2) whether functionalize EVOH can be used as macromolecules PFM; 3) the effect of enhanced crosslinking of macromolecules PFM on the properties of EVOH/PLA (polylactic acid) blends, and to compare with the effect of the small molecule PFM 4) pre-irradiation induced graft reaction of maleic anhydride onto EVOH.
FTIR spectrum of functionalized EVOH show that peak values of neighborhood 1717cm-1 increase corresponding to C=O peak formed by esterification. Because EVOH contains a small amount of unhydrolyzed vinyl acetate unit, we found after EVOH functionalized, the ratio value increased significantly that demonstrated AA and MAH were grafted to the matrix of EVOH by calculating the ratio of the strength of the absorbed peak of -OH and C=O groups (AbsC=O/AbsO-H). The results of gel fraction of functionalized EVOH at different doses showed that EVOH-AA materials become easier to crosslink by radiation, and gel fraction can reach more than 45% after having received a radiation dose of 10kGy. but EVOH-MAH materials that were prepared only when reaction time was 5 min, 2%MAH or reaction time was 10 min, 1%MAH can elevate the gel fraction after irradiated but gel content increased less than that of EVOH-AA. For EVOH-MAH at other processing conditions, gel content changed little as the absorbed dose increased.
The results of gel extraction experiment of EA1T1/PLA blends show that the blends can form gel when EA1T1 was used as macromolecular PFM whose content was more than 5%. At the same absorbed dose, gel fraction of blends increased as the content of EA1T1 increased. However the gel content of 20% EA1T1 was more than that of 30% and 40%. The calculated results show that the content of PLA which entered the crosslinking network was more than others and EA1T1 had certain enhanced radiation crosslinking effect, and the best content is 20%. When EA2T1, Et2M1 and Et1M2 were used as macromolecular PFM, gel content of blends increased as the content of PFM, but the calculated results showed that only Et2M1 PFM was used, a little PLA entered the crosslinking network, and Et2M1 PFM had certain enhanced radiation crosslinking effect. When EA2T1 and Et1M2 was used, no or only minimal amount of PLA entered the crosslinking network and enhanced radiation crosslinking was less effective. When Et1M1 was used, whose content was not more than 50%, blends didn’t form gel at the absorbed dose below 100kGy.
The results of the properties of EVOH/PLA which were enhanced radiation-crosslinked by macromolecular show that mechanical properties EVOH/PLA did not change much, only in the 50/50 system, heat deformation temperature of the blend had been improved. The results of the properties of EVOH/PLA which were enhanced radiation-crosslinked by small molecular PFM show that when the tensile strength of blends that had 3% or 5% PFM at the absorbed dose of 30-50kGy. The heat deformation temperature had been significantly improved at the absorbed dose of 50-100kGy. But the elongation at the breaking and the impact strength didn’t change much. Compared to macromolecular cross-linking agent, small molecule PFM was more suitable for enhanced radiation-crosslinking of EVOH/PLA blend.
The analysis results of torque and gel content in the process of pre-irradiation reaction grafting of F101 show that the gel content of product increased as the MAH content and changed not much as the absorbed dose with the same content of MAH. It is deduced that reaction was mainly esterification. Infrared spectra of product confirmed that, where a new peak appeared in 1718cm-1 corresponding to C=O in the ester bonds. E171 has a similar pre-irradiation grafting process with F101, but owning the same MAH content, gel content of product is lower than F101 system. Titration results also confirmed that esterification reactions occurred in the grafting process. According to the application, MAH content was below 2% for pre-irradiation grafting of F101 and was less than 3% for E171.
引文
[1]唐伟家.EVOH 树脂.合成树脂及塑料,1990,(1):63-70
[2]Lagaron JM, Powell AK, Bonner G. Permeation of water, methanol, fuel and alcohol-containing fuels in high-barrier ethylene-vinyl alcohol copolymer. Polymer Testing, 2001, 20(5): 569
[3]陈昌杰,张烈银. 塑料薄膜的印刷与复合,北京:化学工业出版社,1998
[4]Mark, H.F., Bikales, N.M., Overberger, C.G et al. Encyclopedia of Polymer Science and Engineering, Wiley, New York 1989, 17:173
[5]Foster P.H. Polymer News, 1986, 11:264
[6]Ekman K, Nasman J, Sjostrom H. Preparation of Ethylene Copolymers Containing Pendant Unsaturation for Radiation Crosslinking. J Appl Polym Sci, 1993, 48:167-179
[7]Kenneth B, Ekman k, Nasman. Radiation Cross-Linking of Ethylene Vinyl Alcohol Copolymer Functionalized with m-Isopropenyl-α,α-Dimethyl Benzyl Isocyanate. J Appl Polym Sci, 1993, 50:233-242
[8]Sjostrom H, Ekman K, Turpeinen V, Pulliainen K. Cross-linkable ethylene-vinyl alcohol-acrylate polymer and method of producing the same. U S Pat Appl, 1991, 28855
[9]Park E S, Kim M N, Yoon J S. Grafting of Polycaprolactone onto Poly(ethylene-co-vinyl alcohol) And Application to Polyethylene-Based Bioerodable Blends. J Polym Sci, 2002, 40:2561-2569
[10]Park E S, Kim H S, Kim M N, Yoon J S. Soil Burial test for Poly(ethylene-co-vinyl alcohol)-graft-Polycaprolactone. J Appl Polym Sci, 2005, 96:1064-1071
[11]Maurizio T, Elena F, Paola F, et al. Modification of EVOH Copolymers with ε-Caprolactone: Synthesis and Compatibilization Effects in PE/PVC Blends. Macromol Symp, 2001, 176:233-244
[12]Jiang Hongjin, He Junpo, Liu Jieping, Yang Yuliang. Synthesis and Characterization of Poly(ethylene-co-vinyl alcohol)-graft-poly(ε-caprolactone). Polym J, 2002, 34(9):682-686
[13]Jiang Hongjin, Wu Peiyi, Yang Yuliang. Variable Temperature FTIR Study of Poly(ethylene-co-vinyl alcohol)-graft-poly( ε-caprolactone). Biomacromolecules. 2003, 4:1343-1347
[14]Pemberton L, De Jaeger R, Gengembre L. Grafting of a thin layer of poly(organophosphazene) containing succinic anhydride groups onto poly(vinyl alcohol) and poly(ethylen-co-vinyl alcohol). Polym, 1998, 39(6-7):1299-1307
[15]Choon Mee Lee, Eung Su Kim, Jin-San Yoon. Reactive Blending of Poly(L-lactic acid) with Poly(ethylene-co-vinyl alcohol). Journal of applied polymer science, 2005, 98:886-890
[16]代丽君.EVOH 梳型单离子聚合物的合成及其离子电导电性质.应用化学,2006,23(9):1014-1018
[17]代丽君.侧链为亚乙氧基结构的 EVOH 梳型聚合物的合成.化学与黏合,2005,27(3):177-179
[18]代丽君.离子交换膜金属复合材料的制备及其形貌特征.齐齐哈尔大学学报,2006,22(4):7-10
[19]张玉军,耿林,曹海林.静电纺丝技术制备 EVOH-g-SO3 无纺布膜的研究.哈尔滨工程大学学报,2006,27(5):681-685
[20]Yoshimasa Hama, Tetsuya Hirade. THE EFFECT OF IRRADIATION ON POLYETHYLENE DOUBLE-LAMINATED BY ETHYLENE VINYL ALCOHOL COPOLYMER. Radiat. Phys. Chem. 1991, 37(1):pp.59-64
[21]Grishina A.D. Dokl.Akad.Nauk SSSR, 1963, 150:809
[22]Hase H, Yamaoka H. Radiat.Effects, 1973, 19:195
[23]Ogawa S. J.Phys.Soc.Jpn, 1960, 16:1488
[24]Ohnishi S, Sugimoto S, Nitta I. J.Polym.Sci. 1960, A1, 605
[25]Wong P.K. Nature of trapped free radicals in γ-irradiated poly(vinyl alcohol) films. Polymer 1978, 19(7):785-788
[26]Ohnishi S, Ikeda Y, Sugimoto S, Nitta I. On the ESR singlet spectra frequently observed in irradiated polymers at a large dose.J.Polym.Sci. 1960, 47:503-507
[27]Ohnishi S, Ikeda Y.Kashiwagi M, Nitta I. Electron spin resonance studies of irradiated polymers I. Factors affecting the electron spin resonance spectra of irradiated polymers.Polymer 1961, 2:119-141
[28]Lawton E J, Balwit J S, Powell R.S. Paramagnetic-Resonance Studies of Irradiated High-Density Polyethylene. II. Effect of Irradiation Dose on the Radical Species Trapped at Room Temperature. J.Chem.Phys. 1960, 33:405-412
[29]柳美华,邓鹏飏,孙国恩等. 乙烯-乙烯醇共聚物(EVOH )的辐射效应研究. 辐射研究与辐射工艺学报,2006,24(6):337-340
[30]Deng Pengyang,Liu Meihua,Zhang Wanxi,Sun Jiazhen.Preparation and physical properties of enhanced radiation induced crosslinkling of ethylene-vinyl alcohol copolymer(EVOH).Nuclear Instruments and Methods in Physics Research B 2007,258:357-361
[31]J.M.Lagaron,E.Gimenez,et al.Phase morphology,crystallinity and mechanical properties of binary blends of high barrier ethylene-vinyl alcohol copolymer and amorphous polyamide and a polyamide-containing ionomer .Polymer,2001,42:7381-7394
[32]Maria J Abad , Ana Ares , et al . Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP) ethylene–(vinyl alcohol) copolymer (EVOH) . Polymer International,2005,54(4):673-678
[33]Weichuan Du,Wei Zhong,et al.Space charge distribution and crystalline structure in polyethylene blended with EVOH.European Polymer Journal 2004,40:1987–1995
[34]M. Montoya,M.J. Abad,L. Barral,C. Bernal.Mechanical and fracture behavior of polypropylene/poly(ethylene-co-vinyl alcohol) blends compatibilized with ionomer Na+.European Polymer Journal,2006,42(2):265-273
[35]Costas K.Samios,Nikos K.Kalfoglou.Compatibilization of poly(ethylene-co-vinyl alcohol) (EVOH) and EVOH / HDPE blends with ionomers.Structure and properties.Polymer,1998,39(16):3863-3870
[36]N.Artzi, M.Narkis, A.Siegmann. Review of Melt-Processed Nanocomposites Based on EVOH/Organoclay [J].Journal of Polymer Science: Part B: Polymer Physics, 2005, Vol. 43,1931–1943
[37]Llu?′s Cabedo,Enrique Gime′nez,Jose′ M. Lagaron,Rafael Gavara,Juan J. Saura. Development of EVOH-kaolinite Nanocomposites[J]. Polymer, 2004, 45, 5233–5238
[38]HAN MO JEONG,BYEONG CHOON KIM,EUN HA KIM. Structure and properties of EVOH/organoclay Nanocomposites[J]. Journal of Materials Science, 2005, 40, 3783 – 3787
[39]Thomas S. Ellis. Reverse exfoliation in a polymer nanocomposite by blending with a miscible polymer [J]. Polymer, 2003, 44, 6443–6448
[40]Kyung Min Lee, Chang Dae Han. Rheology of Organoclay Nanocomposites: Effects of Polymer Matrix/Organoclay Compatibility and the Gallery Distance of Organoclay [J]. Macromolecules, 2003, 36,7165-7178
[41]Sang-Soo Lee,Myung Hyun Hur,Hoichang Yang,Soonho Lim,Junkyung Kim. Effect of Interfacial Attraction on Intercalation in Polymer/Clay Nanocomposites[J]. Journal of Applied Polymer Science, 2006, 101, 2749–2753
[42]Sherring D C. Reaction of Polymers. Encyclopedia of Polymer Science and Engineering. Vol 14. New York: John Wiley, 1988.101-169
[43]Lambla M. Reactive processing of thermoplastic polymers. Comprehensive Polymer Sciences 1st supplement. New York: Pergamon,1993.21
[44]Liu N C, Baker W E. Reactive polymers for blend compatibilization.Adv Polym Technol, 1992, 11: 249
[45]Xanthos X, Dagli S S. COMPATIBILIZATION OF POLYMER BLENDS BY REACTIVE PROCESSING. Polym Eng Sci, 1991, 31: 929
[46]李志君,郭宝华,胡平等. PP-g-(GMA-co-St)对 PA6/ PC 共混物的反应增容作用[J].高等学校化学学报,2001,27(7) :1 244
[47]RAHMA F,FELLAHI S. Study of compatibilizers for glass fibre reinforced nylon6/ polypropylene blends. [J]. Polym Int,2000,49(6) :519
[48]童身毅,万敏,张良均. 氯化聚丙烯接枝聚乙二醇的合成与性能[J]. 合成树脂及塑料,2001 ,18 (3) :6
[49]MISHIA J K,RAYCHOUDHURG S,DAS C K. Heat-shrinkable polymer blends based on grafted low-density polyethylene and polyurethane elastomer. Part 1[J].Polym Int,2000,49(12):1615
[50]SCLAVONS M,FRANQUINET P, CARLIER V. et al.Quantification of the maleic anhydride grafted onto polypropylene by chemical and viscosimetric titrations[J].Polym,2000,41(6):1989
[51]SHU HUI QIN,KUN YUAN QIU. A new polymerizable photoiniferter for preparing poly(methyl methecrylate)macromonomer[J].Europ Polym J,2001,37(4):711.
[52]RATZSCH M, BUCKA H,IVANCHEV S S,et al. Some Peculiar features of radiation grafting of monomers of various structure and reactivities onto polyolefins. [J].J Appl Polym Sci, 2000, 77(4):711
[53]徐绍刚,孙玉凤,杨万泰等. LDPE2 丙烯酸体系光接枝表面改性的研究[J].北京化工大学学报,2000,27(4):29
[54]A.J.斯沃罗著, 陈文琇,贾海顺. 包华影译.辐射化学导论.北京:原子能出版社 1985
[55]哈鸿飞,吴季兰.高分子辐射化学-原理与应用.北京:北京大学出版社 2002
[56]蔡鹤琴,符素兰,唐彬. 剂量率等因素对聚乙烯辐照交联的影响.激光生物学,1996,5(3):903-909
[57][日]幕内惠三著.徐俊,孟永红译. 科学出版社,2003.
[58]Fengzhe Jin, Suong-Hyu Hyon, et al. Crosslinking of Poly(L-lactide) by γ-Irradiation. Macromlo.Rapid Commun. 2002, 23, 909-912
[59]Naotsugu Nagasawa, Ayako Kaneda, et al. Application of poly(lactic acid) modified by radiation crosslinking. Nuclear Instruments and Methods in Physics Research B 236(2005)611-616.
[60]Hiroshi Mitomo, Ayako Kaneda, et al. Improvement of heat stability of poly(L-lactic acid) by radiation-induced crosslinking. Polymer 46 (2005) 4695-4703.
[61]罗延龄,赵振兴. 高分子辐射交联技术及研究进展.高分子通报, 1999,12(4):88-99.
[62]马宏伟,王胜敏. 辐射交联聚乙烯热缩片的研制.塑料,1994,23(5): 37-39.
[63]高永芝,张建斌等. 酸碱滴定法测定马来酸酐接枝聚丙烯中的酸酐含量. 工程塑料应用. 2005,33(5):46-48.
[64]赵伟,王丽. ABS 接枝马来酸酐的研究. 塑料科技. 2006,05:40-42.
[65]马向东,刘大壮等. 氯化聚丙烯接枝马来酸酐接枝率的测定. 粘结. 2002,23(05):12-14.
[2]Lagaron JM, Powell AK, Bonner G. Permeation of water, methanol, fuel and alcohol-containing fuels in high-barrier ethylene-vinyl alcohol copolymer. Polymer Testing, 2001, 20(5): 569
[3]陈昌杰,张烈银. 塑料薄膜的印刷与复合,北京:化学工业出版社,1998
[4]Mark, H.F., Bikales, N.M., Overberger, C.G et al. Encyclopedia of Polymer Science and Engineering, Wiley, New York 1989, 17:173
[5]Foster P.H. Polymer News, 1986, 11:264
[6]Ekman K, Nasman J, Sjostrom H. Preparation of Ethylene Copolymers Containing Pendant Unsaturation for Radiation Crosslinking. J Appl Polym Sci, 1993, 48:167-179
[7]Kenneth B, Ekman k, Nasman. Radiation Cross-Linking of Ethylene Vinyl Alcohol Copolymer Functionalized with m-Isopropenyl-α,α-Dimethyl Benzyl Isocyanate. J Appl Polym Sci, 1993, 50:233-242
[8]Sjostrom H, Ekman K, Turpeinen V, Pulliainen K. Cross-linkable ethylene-vinyl alcohol-acrylate polymer and method of producing the same. U S Pat Appl, 1991, 28855
[9]Park E S, Kim M N, Yoon J S. Grafting of Polycaprolactone onto Poly(ethylene-co-vinyl alcohol) And Application to Polyethylene-Based Bioerodable Blends. J Polym Sci, 2002, 40:2561-2569
[10]Park E S, Kim H S, Kim M N, Yoon J S. Soil Burial test for Poly(ethylene-co-vinyl alcohol)-graft-Polycaprolactone. J Appl Polym Sci, 2005, 96:1064-1071
[11]Maurizio T, Elena F, Paola F, et al. Modification of EVOH Copolymers with ε-Caprolactone: Synthesis and Compatibilization Effects in PE/PVC Blends. Macromol Symp, 2001, 176:233-244
[12]Jiang Hongjin, He Junpo, Liu Jieping, Yang Yuliang. Synthesis and Characterization of Poly(ethylene-co-vinyl alcohol)-graft-poly(ε-caprolactone). Polym J, 2002, 34(9):682-686
[13]Jiang Hongjin, Wu Peiyi, Yang Yuliang. Variable Temperature FTIR Study of Poly(ethylene-co-vinyl alcohol)-graft-poly( ε-caprolactone). Biomacromolecules. 2003, 4:1343-1347
[14]Pemberton L, De Jaeger R, Gengembre L. Grafting of a thin layer of poly(organophosphazene) containing succinic anhydride groups onto poly(vinyl alcohol) and poly(ethylen-co-vinyl alcohol). Polym, 1998, 39(6-7):1299-1307
[15]Choon Mee Lee, Eung Su Kim, Jin-San Yoon. Reactive Blending of Poly(L-lactic acid) with Poly(ethylene-co-vinyl alcohol). Journal of applied polymer science, 2005, 98:886-890
[16]代丽君.EVOH 梳型单离子聚合物的合成及其离子电导电性质.应用化学,2006,23(9):1014-1018
[17]代丽君.侧链为亚乙氧基结构的 EVOH 梳型聚合物的合成.化学与黏合,2005,27(3):177-179
[18]代丽君.离子交换膜金属复合材料的制备及其形貌特征.齐齐哈尔大学学报,2006,22(4):7-10
[19]张玉军,耿林,曹海林.静电纺丝技术制备 EVOH-g-SO3 无纺布膜的研究.哈尔滨工程大学学报,2006,27(5):681-685
[20]Yoshimasa Hama, Tetsuya Hirade. THE EFFECT OF IRRADIATION ON POLYETHYLENE DOUBLE-LAMINATED BY ETHYLENE VINYL ALCOHOL COPOLYMER. Radiat. Phys. Chem. 1991, 37(1):pp.59-64
[21]Grishina A.D. Dokl.Akad.Nauk SSSR, 1963, 150:809
[22]Hase H, Yamaoka H. Radiat.Effects, 1973, 19:195
[23]Ogawa S. J.Phys.Soc.Jpn, 1960, 16:1488
[24]Ohnishi S, Sugimoto S, Nitta I. J.Polym.Sci. 1960, A1, 605
[25]Wong P.K. Nature of trapped free radicals in γ-irradiated poly(vinyl alcohol) films. Polymer 1978, 19(7):785-788
[26]Ohnishi S, Ikeda Y, Sugimoto S, Nitta I. On the ESR singlet spectra frequently observed in irradiated polymers at a large dose.J.Polym.Sci. 1960, 47:503-507
[27]Ohnishi S, Ikeda Y.Kashiwagi M, Nitta I. Electron spin resonance studies of irradiated polymers I. Factors affecting the electron spin resonance spectra of irradiated polymers.Polymer 1961, 2:119-141
[28]Lawton E J, Balwit J S, Powell R.S. Paramagnetic-Resonance Studies of Irradiated High-Density Polyethylene. II. Effect of Irradiation Dose on the Radical Species Trapped at Room Temperature. J.Chem.Phys. 1960, 33:405-412
[29]柳美华,邓鹏飏,孙国恩等. 乙烯-乙烯醇共聚物(EVOH )的辐射效应研究. 辐射研究与辐射工艺学报,2006,24(6):337-340
[30]Deng Pengyang,Liu Meihua,Zhang Wanxi,Sun Jiazhen.Preparation and physical properties of enhanced radiation induced crosslinkling of ethylene-vinyl alcohol copolymer(EVOH).Nuclear Instruments and Methods in Physics Research B 2007,258:357-361
[31]J.M.Lagaron,E.Gimenez,et al.Phase morphology,crystallinity and mechanical properties of binary blends of high barrier ethylene-vinyl alcohol copolymer and amorphous polyamide and a polyamide-containing ionomer .Polymer,2001,42:7381-7394
[32]Maria J Abad , Ana Ares , et al . Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP) ethylene–(vinyl alcohol) copolymer (EVOH) . Polymer International,2005,54(4):673-678
[33]Weichuan Du,Wei Zhong,et al.Space charge distribution and crystalline structure in polyethylene blended with EVOH.European Polymer Journal 2004,40:1987–1995
[34]M. Montoya,M.J. Abad,L. Barral,C. Bernal.Mechanical and fracture behavior of polypropylene/poly(ethylene-co-vinyl alcohol) blends compatibilized with ionomer Na+.European Polymer Journal,2006,42(2):265-273
[35]Costas K.Samios,Nikos K.Kalfoglou.Compatibilization of poly(ethylene-co-vinyl alcohol) (EVOH) and EVOH / HDPE blends with ionomers.Structure and properties.Polymer,1998,39(16):3863-3870
[36]N.Artzi, M.Narkis, A.Siegmann. Review of Melt-Processed Nanocomposites Based on EVOH/Organoclay [J].Journal of Polymer Science: Part B: Polymer Physics, 2005, Vol. 43,1931–1943
[37]Llu?′s Cabedo,Enrique Gime′nez,Jose′ M. Lagaron,Rafael Gavara,Juan J. Saura. Development of EVOH-kaolinite Nanocomposites[J]. Polymer, 2004, 45, 5233–5238
[38]HAN MO JEONG,BYEONG CHOON KIM,EUN HA KIM. Structure and properties of EVOH/organoclay Nanocomposites[J]. Journal of Materials Science, 2005, 40, 3783 – 3787
[39]Thomas S. Ellis. Reverse exfoliation in a polymer nanocomposite by blending with a miscible polymer [J]. Polymer, 2003, 44, 6443–6448
[40]Kyung Min Lee, Chang Dae Han. Rheology of Organoclay Nanocomposites: Effects of Polymer Matrix/Organoclay Compatibility and the Gallery Distance of Organoclay [J]. Macromolecules, 2003, 36,7165-7178
[41]Sang-Soo Lee,Myung Hyun Hur,Hoichang Yang,Soonho Lim,Junkyung Kim. Effect of Interfacial Attraction on Intercalation in Polymer/Clay Nanocomposites[J]. Journal of Applied Polymer Science, 2006, 101, 2749–2753
[42]Sherring D C. Reaction of Polymers. Encyclopedia of Polymer Science and Engineering. Vol 14. New York: John Wiley, 1988.101-169
[43]Lambla M. Reactive processing of thermoplastic polymers. Comprehensive Polymer Sciences 1st supplement. New York: Pergamon,1993.21
[44]Liu N C, Baker W E. Reactive polymers for blend compatibilization.Adv Polym Technol, 1992, 11: 249
[45]Xanthos X, Dagli S S. COMPATIBILIZATION OF POLYMER BLENDS BY REACTIVE PROCESSING. Polym Eng Sci, 1991, 31: 929
[46]李志君,郭宝华,胡平等. PP-g-(GMA-co-St)对 PA6/ PC 共混物的反应增容作用[J].高等学校化学学报,2001,27(7) :1 244
[47]RAHMA F,FELLAHI S. Study of compatibilizers for glass fibre reinforced nylon6/ polypropylene blends. [J]. Polym Int,2000,49(6) :519
[48]童身毅,万敏,张良均. 氯化聚丙烯接枝聚乙二醇的合成与性能[J]. 合成树脂及塑料,2001 ,18 (3) :6
[49]MISHIA J K,RAYCHOUDHURG S,DAS C K. Heat-shrinkable polymer blends based on grafted low-density polyethylene and polyurethane elastomer. Part 1[J].Polym Int,2000,49(12):1615
[50]SCLAVONS M,FRANQUINET P, CARLIER V. et al.Quantification of the maleic anhydride grafted onto polypropylene by chemical and viscosimetric titrations[J].Polym,2000,41(6):1989
[51]SHU HUI QIN,KUN YUAN QIU. A new polymerizable photoiniferter for preparing poly(methyl methecrylate)macromonomer[J].Europ Polym J,2001,37(4):711.
[52]RATZSCH M, BUCKA H,IVANCHEV S S,et al. Some Peculiar features of radiation grafting of monomers of various structure and reactivities onto polyolefins. [J].J Appl Polym Sci, 2000, 77(4):711
[53]徐绍刚,孙玉凤,杨万泰等. LDPE2 丙烯酸体系光接枝表面改性的研究[J].北京化工大学学报,2000,27(4):29
[54]A.J.斯沃罗著, 陈文琇,贾海顺. 包华影译.辐射化学导论.北京:原子能出版社 1985
[55]哈鸿飞,吴季兰.高分子辐射化学-原理与应用.北京:北京大学出版社 2002
[56]蔡鹤琴,符素兰,唐彬. 剂量率等因素对聚乙烯辐照交联的影响.激光生物学,1996,5(3):903-909
[57][日]幕内惠三著.徐俊,孟永红译. 科学出版社,2003.
[58]Fengzhe Jin, Suong-Hyu Hyon, et al. Crosslinking of Poly(L-lactide) by γ-Irradiation. Macromlo.Rapid Commun. 2002, 23, 909-912
[59]Naotsugu Nagasawa, Ayako Kaneda, et al. Application of poly(lactic acid) modified by radiation crosslinking. Nuclear Instruments and Methods in Physics Research B 236(2005)611-616.
[60]Hiroshi Mitomo, Ayako Kaneda, et al. Improvement of heat stability of poly(L-lactic acid) by radiation-induced crosslinking. Polymer 46 (2005) 4695-4703.
[61]罗延龄,赵振兴. 高分子辐射交联技术及研究进展.高分子通报, 1999,12(4):88-99.
[62]马宏伟,王胜敏. 辐射交联聚乙烯热缩片的研制.塑料,1994,23(5): 37-39.
[63]高永芝,张建斌等. 酸碱滴定法测定马来酸酐接枝聚丙烯中的酸酐含量. 工程塑料应用. 2005,33(5):46-48.
[64]赵伟,王丽. ABS 接枝马来酸酐的研究. 塑料科技. 2006,05:40-42.
[65]马向东,刘大壮等. 氯化聚丙烯接枝马来酸酐接枝率的测定. 粘结. 2002,23(05):12-14.