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化学进展 2015, Vol. 27 Issue (2/3): 286-296 DOI: 10.7536/PC140826 前一篇   后一篇

• 综述与评论 •

软质PVC制品中增塑剂迁移带来的问题及应对

徐杨, 熊英*, 郭少云*   

  1. 四川大学高分子研究所 高分子材料工程国家重点实验室 成都 610065
  • 收稿日期:2014-08-01 修回日期:2014-11-01 出版日期:2015-03-15 发布日期:2014-12-22
  • 通讯作者: 熊英, 郭少云 E-mail:xiongying@scu.edu.cn;nic7702@scu.edu.cn
  • 基金资助:

    国家自然科学基金重点项目(No.51133005)资助

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导出 被引次数 ( 17 | 8 )

Issues Caused by Migration of Plasticizers from Flexible PVC and Its Countermeasures

Xu Yang, Xiong Ying*, Guo Shaoyun*   

  1. State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute, Sichuan University, Chengdu 610065, China
  • Received:2014-08-01 Revised:2014-11-01 Online:2015-03-15 Published:2014-12-22
  • Supported by:

    The work was supported by the State Key Program of National Natural Science Foundation of China (No. 51133005).

聚氯乙烯(PVC)是世界第二大通用塑料,其中软质PVC制品占PVC市场份额的30%,它被广泛用于制造人造皮革、食品包装材料、电线电缆和儿童玩具等。软质PVC中使用的增塑剂主要是邻苯二甲酸二(2-乙基)己酯(DEHP),它具有与PVC相容性良好、增塑效率高、价格低廉、不影响制品的安全性和电绝缘性等诸多优点。但由于DEHP为小分子物质,且与PVC之间并无化学键合,其添加量又通常高达30 wt%~50 wt%, 因此DEHP容易迁移到外部介质中,使制品的性能劣化,同时造成环境污染。在医疗器械和儿童玩具等敏感领域,DEHP的迁移还会危害人体健康。因此,增塑剂迁移所带来的问题引起了人们的广泛关注,亟待解决。本文介绍了DEHP迁移所带来的问题及DEHP目前所面临的使用禁令和争议,全面综述了国内外近年来为解决DEHP迁移所采取的应对措施及获得的研究成果,并对各种措施的优缺点进行了总结,以期进行更深入的研究,找到更为科学和有效的解决方案。

关键词： 软质PVC, 增塑剂, DEHP, 迁移, 禁令, 争议

Polyvinyl chloride (PVC) is the world's second largest general plastic. 30% of PVC are flexible products and have been extensively used in artificial leather, food packing, electric wire, children's toys, etc. Di(2-ethylhexyl)phthalate (DEHP) is the most widely used plasticizer in flexible PVC for it's excellent performances, such as good compatibility with PVC, high plasticizing efficiency, low cost, no effect on safety and electrical insulation of products, and so on. But DEHP is a small molecule compound and is associated with PVC through secondary bond rather than chemical bond, and its content is usually as high as 30~50 wt%, thus it can easily migrate from PVC matrix into external medium, which causes deterioration of flexible PVC's properties and environmental pollution. In sensitive areas such as children's toys and medical devices, migration of DEHP can also be hazardous to human health. So migration of DEHP has aroused wide concern and is exigent to be solved. In this paper, issues caused by migration of DEHP and the current bans and controversies on its usage are introduced. Then the countermeasures and recent scientific approaches in dealing with these issues are comprehensively reviewed. In the end, advantages and disadvantages of the various approaches are summarized in order to research more in-depth and more effectively in the near future.

Contents
1 Introduction
2 Migration of DEHP and its controversies
3 Use restrictions and bans of DEHP
4 Solutions to reduce migration of plasticizers in flexible PVC
4.1 Migration resistant plasticizers
4.2 Increasing interactions between plasticizer and PVC
4.3 Surface treatment
5 Conclusion and outlook

Key words: flexible PVC, plasticizer, DEHP, migration, ban, controversy

中图分类号: 

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[1] 石万聪(Shi W C), 石志博(Shi Z B), 蒋平平(Jiang P P). 增塑剂及其应用(Plasticizer and Its Application). 北京:化学工业出版社(Peking: Chemical Industry Press), 2002. 6.
[2] Tullo A H. Chem. Eng. News, 2005, 83(46): 29.
[3] Ceresana. Market Study: Polyvinyl Chloride (3rd Edition) UC-9505, (2005-07-30). . http://www.ceresana.com/en/market-studies/plastics/polyvinyl-chloride/
[4] Chiellini F, Ferri M, Morelli A, Dipaola L, Latini G. Prog.Polym. Sci., 2013, 38(7): 1067.
[5] Gonzalez N, Fernandez-Berridi M J. J. Appl. Polym. Sci., 2006, 101(3): 1731.
[6] Garnaik B, Sivaram S. Macromolecules, 1996, 29(1): 185.
[7] Audic J, Reyx D, Brosse J. J. Appl. Polym. Sci., 2003, 89(5): 1291.
[8] Kovacic T, Mrklic Z. Thermochim. Acta, 2002, 381(1): 49.
[9] 甘景镐(Gan J G). 化学世界(Chemistry World), 1963, 10: 012.
[10] Monney L, Jamois-Tasserie M, Dubois C, Lallet P, Villa F,Renaud C. Polym. Degrad. Stabil., 2001, 72(3): 459.
[11] Jaeger R J, Rubin R J. Science, 1970, 170(3956): 460.
[12] Jaeger R J, Rubin R J. New Engl. J. Med., 1972, 287(22): 1114.
[13] Tickner J A, Schettler T, Guidotti T, McCally M, Rossi M.Am. J. Ind. Med., 2001, 39(1): 100.
[14] Doull J, Cattley R, Elcombe C, Lake B G, Swenberg J, Wilkinson C, Williams G, van Gemert M. Regul. Toxicol. Pharm., 1999, 29(3): 327.
[15] Foster P, Preuss R, Sharpe R, Toppari J. Int. J. Androl., 2006, 29(1): 155.
[16] AuBuchon J P, Estep T N, Davey R J. Blood, 1988, 71(2): 448.
[17] Meer P F, Reesink H W, Panzer S, Wong J, Ismay S, Keller A, Pink J, Buchta C, Compernolle V, Wendel S. Vox Sang., 2014, 106(2): 176.
[18] Scientific Committee on Emerging and Newly-Identified Health Risks. Opinion on the safety of medical devices containing DEHP plasticized PVC or other plasticizers on neonates and other groups possibly at risk, (2008-02-06). . http://ec.europa.eu/health/archive/ph_risk/committees/04_scenihr/docs/scenihr_o_014.pdf
[19] Hansen O G. Med. Device. Technol., 2006, 17(3): 16.
[20] European Chemicais Agency. Candidate List of Substances of Very High Concern for Authorisation, (2008-10-28). . http://echa.europa.eu/web/guest/candidate-list-table
[21] Lindstrom A. Environmentally Friendly Plasticizers for PVC: Improved Material Properties and Long-term Performance Through Plasticizer Design, (2007-02-16). . http://www.diva-portal.org/smash/get/diva2: 11561/FULLTEXT01.pdf
[22] European Chemicals Agency. Evaluation of new scientific evidence concerning DINP and DIDP in relation to entry 52 of Annex XVII to REACH Regulation (EC) No 1907/2006(final review report), (2013-08-30). . http://echa.europa.eu/documents/10162/31b4067e-de40-4044-93e8-9c9ff1960715
[23] Content S. Plast. Eng., 2013, 69(10): 48.
[24] Ito R, Miura N, Iguchi H, Nakamura H, Ushiro M, Wakui N, Nakahashi K, Iwasaki Y, Saito K, Suzuki T. Int. J. Pharm., 2008, 360(1): 91.
[25] Kastner J, Cooper D G, Maric M, Dodd P, Yargeau V. Sci. Total Envir., 2012, 432: 357.
[26] Liu Y, Zhang R, Wang X, Sun P, Chen W, Shen J, Xue G. Polymer, 2014, 55(12): 2831.
[27] Wadey B L. J. Vinyl Additive Technol., 2003, 9(4): 172.
[28] Demir A, Ulutan S. J. Appl. Polym. Sci., 2013, 128(3): 1948.
[29] Barber E D, Fox J A, Giordano C J. Xenobiotica, 1994, 24(5): 441.
[30] Tomita I, Nakamura Y, Aoki N, Inui N. Environ. Health Persp., 1982, 45: 119.
[31] Mitchell A M, Lhuguenot J C, Bridges J W, Elcombe C R.Toxicol. Appl. Pharm., 1985, 80(1): 23.
[32] Dalgaard M, Nellemann C, Lam H R, Sorensen I K, Ladefoged O. Toxicol. Lett., 2001, 122(1): 69.
[33] Gimeno P, Thomas S, Bousquet C, Maggio A, Civade C, Brenier C, Bonnet P. J. Chromatogr. B, 2014, 949: 99.
[34] Genay S, Luciani C, Decaudin B, Kambia N, Dine T, Azaroual N, Di Martino P, Barthelemy C, Odou P. Int. J. Pharm., 2011, 412(1): 47.
[35] Biedermann-Brem S, Biedermann M, Pfenninger S, Bauer M, Altkofer W, Rieger K, Hauri U, Droz C, Grob K. Chromatographia, 2008, 68(3/4): 227.
[36] Brouillet S, Fugit J. Polym. Bull., 2009, 62(6): 843.
[37] Kambia K, Dine T, Azar R, Gressier B, Luyckx M, Brunet C. Int. J. Pharm., 2001, 229(1): 139.
[38] International Organization for Standardization. ISO472-2013: Plastics—Vocabulary, (2013-01-30). http://www.iso.org/iso/home/store/catalogue_tc/catalogue_detail.htm?csnumber=44102
[39] Prud'Homme R E. Polym. Eng. Sci., 1982, 22(2): 90.
[40] Ziska J J, Barlow J W, Paul D R. Polymer, 1981, 22(7): 918.
[41] 石万聪(Shi W C), 石志博(Shi Z B), 蒋平平(Jiang P P). 增塑剂及其应用(Plasticizer and Its Application). 北京:化学工业出版社(Beijing: Chemical Industry Press), 2002. 271.
[42] 肖尧(Xiao Y), 李喜宏(Li X H), 王彪(Wang B),汤尧(Tang Y), 王成君(Wang C J). 塑料科技(Plastic Science and Technology), 2011, 39(10): 92.
[43] Li Y, Wang C, Wang G, Qu Z. Journal of Wuhan University of Technology-Materials Science, 2008, 23(1): 100.
[44] Chiu F C, Min K. Polym. Int., 2000, 49(2): 223.
[45] Rusu M, Ursu M, Rusu D. J. Thermoplast. Compos., 2006, 19(2): 173.
[46] Hakkarainen M. Polym. Degrad. Stabil., 2003, 80(3): 451.
[47] Ferruti P, Mancin I, Ranucci E, De Felice C, Latini G, Laus M. Biomacromolecules, 2003, 4(1): 181.
[48] Penco M, Sartore L, Bignotti F, Rossini M, D'Amore A, Fassio F. Macromol. Symp., 2002, 180(1): 9.
[49] Zhou J, Ritter H. Polym. Int., 2011, 60(8): 1158.
[50] Lee J H, Kim K O, Ju Y M. J. Biomed. Mater. Res., 1999, 48(3): 328.
[51] Koleske J V, Lundberg R D. J. Polym. Sci. Pol. Phys., 1969, 7(5): 795.
[52] Pena J R, Hidalgo M, Mijangos C. J. Appl. Polym. Sci., 2000, 75(10): 1303.
[53] Sunny M C, Ramesh P, George K E. J. Elastom. Plast., 2004, 36(1): 19.
[54] Sunny M C, Ramesh P, George K E. J. Appl. Polym. Sci., 2006, 102(5): 4720.
[55] Thomas N L. J. Appl. Polym. Sci., 2004, 94(5): 2022.
[56] Choi J, Kwak S. Macromolecules, 2003, 36(23): 8630.
[57] Choi J, Kwak S. Environ. Sci. Technol., 2007, 41(10): 3763.
[58] Choi W, Chung J W, Kwak S Y. ACS Appl. Mater. Inter., 2014, 6(14): 11118.
[59] 戴继湘(Dai J X), 潘春跃(Pan C Y), 喻桂朋(Yu G P). 广州化工(Guangzhou Chemical Industry), 2013, 41(12): 75.
[60] Yue L, Cao Y, Huang T, Huang L, Bai Y, Zhou Y. Aust. J. Chem., 2014, 67(1): 22.
[61] Rahman M, Brazel C S. Polym. Degrad. Stabil., 2006, 91(12): 3371.
[62] Hou L X, Wang S. Polym. Bull., 2011, 67(7): 1273.
[63] Kuo S W, Chang F C. Prog. Polym. Sci.,2011,36(12): 1649.
[64] Soong S Y, Cohen R E, Boyce M C. Macromolecules, 2006, 39(8): 2900.
[65] Soong S Y, Cohen R E, Boyce M C. Polymer, 2007, 48(5): 1410.
[66] 王宏亚(Wang H Y). 山西化工(Shanxi Chemical Industry), 1984, 3: 47.
[67] Elicegui A, Del Val J J, Bellenger V, Verdu J. Polymer, 1997, 38(7): 1647.
[68] Navarro R, Bierbrauer K, Mijangos C, Goiti E, Reinecke H. Polym. Degrad. Stabil., 2008, 93(3): 585.
[69] Navarro R, Perrino M P, Tardajos M G, Reinecke H. Macromolecules, 2010, 43(5): 2377.
[70] 孙华圳(Sun H Z), 杨坡(Yang P), 范浩军(Fan H J), 陈意(Chen Y). 高分子学报(Acta Polymerica Sinica), 2014, 2: 233.
[71] Earla A, Braslau R. Macromol. Rapid Comm., 2014, 35(6): 666.
[72] Yu B Y, Chung J W, Kwak S Y. Environ. Sci. Technol., 2008, 42(19): 7522.
[73] Chung J W, Kim S H, Jung S J, Kwak S. Eur. Polym. J., 2009, 45(8): 2164.
[74] Sreenivasan K. J. Appl. Polym. Sci., 1996, 59(13): 2089.
[75] Yu B Y, Lee A R, Kwak S. Eur. Polym. J., 2012, 48(5): 885.
[76] 林卫平(Lin W P), 钱欣(Qian X), 王旭(Wang X). 塑料工业(Plasticizer Industry), 2004, 31(12): 19.
[77] 李树材(Li S C), 左治(Zuo Z). 塑料科技(Plastic Science and Technology), 2006, 34(3): 4.
[78] Yang B H, Bai Y P, Cao Y J. J. Appl. Polym. Sci., 2010, 115(4): 2178.
[79] 石全英(Shi Q Y), 杜林雪(Du L X), 李喜宏(Li X H), 刘霞罗(Liu X L), 金山(Jin S), 刘海娇(Liu H J). 食品工业科技(Food Industry Science and Technology), 2013, 34(19): 66.
[80] 秦晓洁(Qin X J), 蒋平平(Jiang P P), 李志莹(Li Z Y), 冷炎(Ling Y), 张萍波(Zhang P B), 盛英佩(Sheng Y P). 塑料科技(Plastic Science and Technology), 2014, 7: 35.
[81] Wen X Q, Liu X H, Liu G S. IEEE T. Plasma Sci., 2010, 38(11): 3152.
[82] Ito R, Seshimo F, Haishima Y, Hasegawa C, Isama K, Yagami T, Nakahashi K, Yamazaki H, Inoue K, Yoshimura Y. Int. J. Pharm., 2005, 303(1): 104.
[83] da Silva F F, da S Aquino K A, Araujo E S. Polym. Degrad. Stab., 2008, 93(12): 2199.
[84] Baccaro S, Brunella V, Cecilia A,Costa L. Nucl. Instrum. Meth. B, 2003, 208: 195.
[85] Ito R, Seshimo F, Miura N, Kawaguchi M, Saito K, Nakazawa H. J. Pharmaceut. Biomed., 2006, 41(2): 455.
[86] Ito R, Miura N, Ushiro M, Kawaguchi M, Nakamura H, Iguchi H, Ogino J, Oishi M, Wakui N, Iwasaki Y, Saito K, Nakazawa H. Int. J. Pharm., 2009, 376(1/2): 213.
[87] Jayakrishnan A, Sunny M C. Polymer, 1996, 37(23): 5213.
[88] Lakshmi S, Jayakrishnan A. Biomaterials, 2002, 23(24): 4855.
[89] Lakshmi S, Jayakrishnan A. J. Biomed. Mater. Res. B, 2003, 65(1): 204.
[90] Lakshmi S, Jayakrishnan A. Artif. Organs, 1998,22(3): 222.
[91] Balakrishnan B, Kumar D S, Yoshida Y, Jayakrishnan A. Biomaterials, 2005, 26(17): 3495.
[92] Krishnan V K, Jayakrishnan A,Francis J D. J. Mater.Sci.: Mater. Med., 1990, 1(4): 185.
[93] Babukutty Y, Prat R, Endo K, Kogoma M, Okazaki S, Kodama M. Langmuir, 1999, 15(20): 7055.
[94] McGinty K M, Brittain W J. Polymer, 2008, 49(20): 4350.
[95] Breme F, Buttstaedt J, Emig G. Thin Solid Films,2000, 377: 755.
[96] Amberg-Schwab S, Katschorek H, Weber U, Burger A, Hansel R, Steinbrecher B, Harzer D. J. Sol-Gel Sci. Technol., 2003, 26(1/3): 699.
[97] Messori M, Toselli M, Pilati F, Fabbri E, Fabbri P, Pasquali L, Nannarone S. Polymer, 2004, 45(3): 805.
[98] Massard C, Bernard L, Cueff R, Raspal V, Feschet-Chassot E, Sibaud Y, Sautou V, Awitor K O. Prog. Org. Coat., 2012, 75(1/2): 116.
[99] Bernard L, Cueff R, Massard C, Blavignac C, Awitor K O, Chopineau J, Sautou V. J. Appl. Polym. Sci., 2014, 131(8): 40145.
[100] Barreto M C, Borris J, Thomas M, Hansel R, Stoll M, Klages C. Plasma Process. Polym., 2012, 9(11/12): 1208.
[101] Bourdeaux D, Sautou-Miranda V, Bagel-Boithias S, Boyer A, Chopineau J. J. Pharmaceut. Biomed., 2004, 35(1): 57.
[102] Bagel-Boithias S, Sautou-Miranda V, Bourdeaux D,Tramier V, Boyer A, Chopineau J. Am. J. Health-Syst. Ph., 2005, 62(2): 182.
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