DOI QR코드

DOI QR Code

노보넨 다이알킬에스터를 포함한 PVC필름의 용출성 연구

A Study on the Elution of the PVC Film Containing Norbornene Dialkylester

  • 장혜진 (상명대학교 화공신소재학과) ;
  • 박성호 (상명대학교 화공신소재학과) ;
  • 우제완 (상명대학교 화공신소재학과)
  • Jang, Hye-Jin (Department of Chemical Engineering and Materials Science, Sangmyung University) ;
  • Park, Seong-Ho (Department of Chemical Engineering and Materials Science, Sangmyung University) ;
  • Woo, Je-Wan (Department of Chemical Engineering and Materials Science, Sangmyung University)
  • 투고 : 2017.11.24
  • 심사 : 2018.01.31
  • 발행 : 2018.04.10

초록

열가소성고분자에 첨가되는 가소제는 외부로의 용출로 인해 제품의 수명을 단축시키고, 일부는 환경, 인체에 유해한 영향을 미치는 것으로 알려져 있다. 발암물질로 의심되는 프탈레이트계 가소제의 사용이 점차 금지됨에 따라 이를 대체할 수 있는 친환경 가소제에 대한 필요성이 요구되며 대부분의 물질은 수지와의 상용성이 다소 떨어지거나 단가가 높으며 구체적인 안전성 검증이 부족한 문제가 있다. 따라서, 본 연구에서는 대체 가소제 후보물질로서 우수한 물리적 물성과 독성 평가에서 안전한 화합물로 보고되어진 노보넨 다이알킬에스터 화합물 4종을 PVC 수지에 첨가하여 용출에 의한 인체 노출 가능성을 평가하고 상용가소제 DEHP, DINCH, DOTP와 비교 분석하여 대체 물질로서의 가능성을 평가하고자 하였다. 시험은 american standard test method (ASTM) 규격에 준하여 시행하였으며 결과에 따르면, 수성 용매에서 di-2-ethylhexyl-5-norbornene-2,3-dicarboxylate (DEHN), 유성용매에서 diisopentyl-5-norbornene-2,3-dicarboxylate (DIPN) 화합물이 DEHP 대비 우수하거나 동등한 수치를 나타내었다. 또한 4종의 노보넨 화합물 모두 환경에 영향을 미칠 수 있는 수준으로 평가되는 100 ppm보다 낮은 수치를 나타내었으며 이는 극성부인 노보넨 구조가 용출성에 영향을 미친 것으로 보여진다.

Plasticizers added to thermoplastic polymers are known to shorten the life of products due to the elution to outside, and some of them are harmful to our environment and human body. Since the use of phthalate plasticizers suspected of being carcinogens has been gradually prohibited, there is a need for environmentally friendly plasticizers that can replace them. Most of the substances have a low compatibility with resin, high cost and lack of safety verification. Therefore, in this study, four kinds of norbornene dialkyl ester compounds possessing excellent physical properties, which are also reported as safe compounds from the toxicity evaluation, were added to PVC resin to evaluate the possibility of human exposure by leaching, and also the potential usage as plasticizer candidates alternative to commercial ones including DEHP, DINCH and DOTP. The test was carried out according to the American standard test method (ASTM). The results showed that di-2-ethylhexyl-5-norbornene-2,3-dicarboxylate (DEHN) in aqueous solvents and diisopentyl-5-norbornene-2,3-dicarboxylate (DIPN) compounds in oil solvents were superior or equivalent to DEHP. In addition, all four norbornene compounds showed lower values than 100 ppm, which is considered to have an influence on the environment, indicating that the polar norbornene structure affects the elution.

키워드

참고문헌

  1. P. R. Graham, Phthalate ester plasticizers-why and how they are used, Environ. Health Perspect., 3, 3-12 (1973).
  2. P. H. Daniels, A brief overview of theories of PVC plasticization and methods used to evaluate PVC-plasticizer interaction, J. Vinyl Addit. Technol., 15, 219-223 (2009). https://doi.org/10.1002/vnl.20211
  3. M. Ghisari and E. C. Bonefeld-Jorgensen, Effects of plasticizers and their mixtures on estrogen receptor and thyroid hormone functions, Toxicol. Lett., 189, 67-77 (2009). https://doi.org/10.1016/j.toxlet.2009.05.004
  4. N. S. Gayathri, C. R. Dhanya, A. R. Indu, and P. A. Kurup, Changes in some hormones by low doses of di (2-ethyl hexyl) phthalate (DEHP), a commonly used plasticizer in PVC blood storage bags & medical tubing, Indian J. Med. Res., 119(4), 139-144 (2004).
  5. K. Y. Lee, M. Shibutani, H. Takagi, N. Kato, S. Takigami, C. Uneyama, and M. Hirose, Diverse developmental toxicity of di-n-butyl phthalate in both sexes of rat offspring after maternal exposure during the period from late gestation through lactation, Toxicology, 203(1), 221-238 (2004). https://doi.org/10.1016/j.tox.2004.06.013
  6. M. Rahman and C. S. Brazel, The plasticizer market: An assessment of traditional plasticizers and research trends to meet new challenges, Prog. Polym. Sci., 29, 1223-1248 (2004). https://doi.org/10.1016/j.progpolymsci.2004.10.001
  7. T. Mekonnen, P. Mussone, H. Khalil, and D. Bressler, Progress in bio-based plastics and plasticizing modifications, J. Mater. Chem. A, 1, 13379 (2013). https://doi.org/10.1039/c3ta12555f
  8. R. Navarro, M. P. Perrino, M. G. Tardajos, and H. Reinecke, Phthalate plasticizers covalently bound to PVC: Plasticization with suppressed migration, Macromolecules, 43, 2377-2381 (2010). https://doi.org/10.1021/ma902740t
  9. N. Lardjane, N. Belhaneche-Bensemra, and V. Massardier, Migration of new bio-based additives from rigid and plasticized PVC stabilized with epoxidized sunflower oil in soil, J. Polym. Res., 20, 209-219 (2013). https://doi.org/10.1007/s10965-013-0209-2
  10. A. Lindstrom and M. Hakkarainen, Environmentally friendly plasticizers for poly(vinyl chloride) - Improved mechanical properties and compatibility by using branched poly(butylene adipate) as a polymeric plasticizer, J. Appl. Polym. Sci., 100, 2180-2188 (2006). https://doi.org/10.1002/app.23633
  11. L. Coltro, J. B. Pitta, P. A. da Costa, M. A. Favaro Perez, V. A. de Araujo, and R. Rodrigues, Migration of conventional and new plasticizers from PVC films into food simulants: A comparative study, Food Control, 44, 118-129 (2014). https://doi.org/10.1016/j.foodcont.2014.03.058
  12. Y. Y. Byong, W. C. Jae, and S. Y. Kwak, Reduced migration from flexible poly(vinyl chloride) of a plasticizer containing ${\beta}$-cyclodextrin derivative, Environ. Sci. Technol., 42, 7522-7527 (2008). https://doi.org/10.1021/es800895x
  13. J. S. Park, H. C. Oh, Y. S. Park, and J. W. Woo, Synthesis of norbornene derivative using Diels-Alder reaction, Adv. Mater. Res., 421, 136-139 (2012).
  14. S. H. Park, J. S. Park, T. W. Ko, Y. S. Park, and J. W. Woo, Esterification of 5-norbornene-2,3-dicarboxylic anhydride under titanium catalyst, Adv. Mater. Res., 634-638, 642-646 (2013). https://doi.org/10.4028/www.scientific.net/AMR.634-638.642
  15. D. H. Yun, T. W. Ko, and J. W. Woo, Study on Physical Properties of PVC Involving Norbornene Dialkyl Ester, Appl. Chem. Eng., 25(6), 602-606 (2014). https://doi.org/10.14478/ace.2014.1099
  16. T. W. Ko, Norbornene Diester Derivatives : Applicability as Plasticizer and Their Hazard Assessment by QSAR Approach, PhD Dissertation, Sangmyung University, Seoul, Korea (2015).
  17. ASTM D 1239-07, Standard Test Method for Resistance of Plastic Films to Extraction by Chemicals, American Society for Testing and Materials (ASTM), Pennsylvania, USA (2007).
  18. ASTM D 5227-01, Standard Test Method for Measurement of Hexane Extractable Content of Polyolefins, American Society for Testing and Materials (ASTM), Pennsylvania, USA (2008).