高性能低致敏性天然乳胶膜的研究及工业化生产
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摘要
天然乳胶制品因含有多种致敏蛋白质而引起人体过敏性反应。目前,改善天然乳胶过敏性的实验方法,主要有物理改性、化学改性与生物改性。但截止目前,市面上仍无抗过敏性乳胶制品的生产与销售。因此,研究与探索抗过敏性乳胶制品的工业化生产变得迫在眉睫。
针对天然乳胶过敏问题,本课题研究采用工艺简单的浸渍法形成多层复合膜的乳胶制品(中间层为改性天然乳胶层,两侧为改性水性聚氨酯层)；采用天然蚕丝的丝胶对水性聚氨酯与天然乳胶进行处理。利用共混方法,把天然乳胶和丝胶进行共混,考察不同的配比对乳液性能以及所成薄膜的影响。同时,用FTIR表征手段证明丝胶成功封端水性聚氨酯。并且对改性材料进行细胞毒性、皮肤刺激、析出可溶性蛋白质等过敏表征。
研究结果显示：丝胶改性的多层膜的乳胶制品,在细胞毒性分析实验中,表明其基本无毒性。与此同时,在制备具有相同物理机械性能的制品中(耐磨性,耐油性,耐候性,耐压性,透光性与韧性等),丝胶改性的多层膜的乳胶制品将可以制备得比普通天然乳胶制品更薄,可以大大节约原材料。鉴于本实验研究中所用的主要原料为天然可再生资源以及操作中的循环回收利用,所以在将来的工业化生产中,将不会存在三废的处理问题。这些都是响应新时代对我们化工行业的要求---节能,减排,绿色,环保。
The couse of leading to latex allergy is the special proteins in natural rubber latex from three-leaf rubber tree. According to paper reports, there are some ways of solutions of latex allergy, as physical, chemical, biologic channel and so on. But until now, it does not exist a mature industrialized process of production antiallergic nature rubber latex, due to their solutions be decreasing mechanical properties of nature rubber products. All of these make the research of commercial manufacture antiallergic rubber goods to become more important and valuable than ever.
The target of antiallergic nature rubber latex product is the film of samdwich mode, with rubber latex in the middle and waterborne polyurethane, cross-linking sericin at its end functional group, in two sides. By means of characterization technique with FTIR, we proved that sericin had successfully grafted to the polyurethane prepolymer. Then through the heterocoagulation method, natural rubber latex was blended with graft copolymer to study the influence of different blending ratio on properties of latex and films. Furthermore, we made test of cytotoxicity, skin irritatin, extracted protein to characterize irritability of modified films.
The exploring results showed that:the modified nature rubber latex product was improved the antiallergic property from cell toxicity text, which is superior in comparison with nature rubber good. Under the same physical and mechamical requirement, the modified rubber film can be produced thinner than nature rubber film, which will save a lot of raw material. Due to the main raw material in this experiment was renewable natural resource and cyclic utilization, there would be not exist the waste emission problem, which would be great stimulating the development of new chemical industry era, with saving resource, low emission, green and environment-friendly new era.
针对天然乳胶过敏问题,本课题研究采用工艺简单的浸渍法形成多层复合膜的乳胶制品(中间层为改性天然乳胶层,两侧为改性水性聚氨酯层)；采用天然蚕丝的丝胶对水性聚氨酯与天然乳胶进行处理。利用共混方法,把天然乳胶和丝胶进行共混,考察不同的配比对乳液性能以及所成薄膜的影响。同时,用FTIR表征手段证明丝胶成功封端水性聚氨酯。并且对改性材料进行细胞毒性、皮肤刺激、析出可溶性蛋白质等过敏表征。
研究结果显示：丝胶改性的多层膜的乳胶制品,在细胞毒性分析实验中,表明其基本无毒性。与此同时,在制备具有相同物理机械性能的制品中(耐磨性,耐油性,耐候性,耐压性,透光性与韧性等),丝胶改性的多层膜的乳胶制品将可以制备得比普通天然乳胶制品更薄,可以大大节约原材料。鉴于本实验研究中所用的主要原料为天然可再生资源以及操作中的循环回收利用,所以在将来的工业化生产中,将不会存在三废的处理问题。这些都是响应新时代对我们化工行业的要求---节能,减排,绿色,环保。
The couse of leading to latex allergy is the special proteins in natural rubber latex from three-leaf rubber tree. According to paper reports, there are some ways of solutions of latex allergy, as physical, chemical, biologic channel and so on. But until now, it does not exist a mature industrialized process of production antiallergic nature rubber latex, due to their solutions be decreasing mechanical properties of nature rubber products. All of these make the research of commercial manufacture antiallergic rubber goods to become more important and valuable than ever.
The target of antiallergic nature rubber latex product is the film of samdwich mode, with rubber latex in the middle and waterborne polyurethane, cross-linking sericin at its end functional group, in two sides. By means of characterization technique with FTIR, we proved that sericin had successfully grafted to the polyurethane prepolymer. Then through the heterocoagulation method, natural rubber latex was blended with graft copolymer to study the influence of different blending ratio on properties of latex and films. Furthermore, we made test of cytotoxicity, skin irritatin, extracted protein to characterize irritability of modified films.
The exploring results showed that:the modified nature rubber latex product was improved the antiallergic property from cell toxicity text, which is superior in comparison with nature rubber good. Under the same physical and mechamical requirement, the modified rubber film can be produced thinner than nature rubber film, which will save a lot of raw material. Due to the main raw material in this experiment was renewable natural resource and cyclic utilization, there would be not exist the waste emission problem, which would be great stimulating the development of new chemical industry era, with saving resource, low emission, green and environment-friendly new era.
引文
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[9]卢光.天然胶乳手套蛋自质过敏问题及对策[J].橡胶工业,2001,48(4)：235-238
[10]Yapa P A J, Lionel W A. Enzyme deproteinization of Hevea latex 3. Clonal suitability for papain treatment[J]. Journal of the Rubber Research Institute of Sri Lanka,1979,56(1):41-47
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[12]Aziz N. A. A.Formulations for heat resistant chlorinated natural rubber latex films[J].Journal of Natural Rubber Research,1994,9(2):109-120
[13]Siby V,Yosuke K,Kioz M,et al.Production of soluble protein free latex by radiation process[J].Rubber Chemistry and Technology,2000,73(1):80-88
[14]Varghese S.,Katsumura Y,Makuuchi K,et al.Rubber ChemTech,2002,73;80,308
[15]唐翠芳.低过敏性高强度医用手套[J].世界橡胶工业,2002,29(1)：21-23
[16]赵科.一次性天然胶乳手套的过敏性问题及解决措施[J]橡胶工业,2004,51(11)：679-681
[17]梁金兰.马来西亚胶乳工业概况[J].世界橡胶工业,2006,33(11)：45-47
[18]陈艳,姚成.天然乳胶手套的最新发展[J].工业卫生与职业病,2004,30(3)：182-184
[19]罗卫云.21世纪国内外乳胶制品的展望[J].特种橡胶制品,2000,21(2)：60-62
[20]唐翠芳.Ansell公司开发无粉手套[J].中国橡胶,1999,(7)：30-30
[21]刘永成,邵正中,孙玉宇等.蚕丝蛋白的结构和功能[J].高分子通报.1998(3)：17-23
[22]卢神州,李明忠,王志青.丝素膜表面磺酸化研究[J].高分子材料科学与工程.2005,21(2)：296-299
[23]陈华,朱良均,闵思佳.蚕丝丝胶蛋白的利用研究[J].东华大学学报.2002,28(3)：132-136
[24]Zhu Liangjun, Mitsuo Arai, Kiyoshi Hirabayashi. Relationship between adhesive provities and structure of sericin in cocoon filaments[J].J Sefic Sci Jpn,1995,64(5):420-426
[25]Garel A., Deleage G, Prudhomme J. Structure and organization of the bombyx mori sericin gene and of the sericins deduced from the sequence of the SerDNA[J]. Insect Biochem Molec Biol,1997,27(5):469-477
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