CN108047618A - 一种矿物填充的可降解型聚乙烯醇保鲜膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种矿物填充的可降解型聚乙烯醇保鲜膜,及其制备工艺,其特征在于,以聚乙烯醇、膨润土、柠檬酸、甘油、葡萄糖酸、炭黑、聚醚胺、纳米二氧化硅、十二烷基苯磺酸钠、氢氧化钾、氧化石墨烯、碳纳米管、戊二醇、乙酸、高岭土、硅藻土、石蜡、KH550等为原料。本发明中膨润土与葡萄糖酸发生反应,与聚乙烯醇形成了分子间氢键,提高其耐水性。用聚醚胺改性炭黑、纳米二氧化硅得到具有核壳结构的增强体;氧化石墨烯(GO)与PVA之间通过氢键结合,提高PVA材料的力学性能;用十二烷基苯磺酸钠、氢氧化钾对碳纳米管进行处理,提高拉伸强度;以戊二醛为交联剂,以乙酸为催化剂,PVA可以发生分子间的缩醛化交联,提高其耐水性。
Description
技术领域
本发明涉及复合材料领域,具体涉及一种矿物填充的可降解型聚乙烯醇保鲜膜,及其制备工艺。
背景技术
随着公众生活水平的提高,人们对于食品安全及环境安全越来越重视,使得传统塑料保鲜膜备受质疑。那么,如何保证食品的安全性和货架期,同时又对环境友好,如何制备可食或可降解保鲜膜,成为了行业研究和发展的重要方向。
黄煇荣在其硕士学位论文《膨润土/PVA保鲜膜的制备及其在芒果保鲜中的应用研究》一文中,以膨润土为填充材料,以聚乙烯醇(PVA)为基材,研究膨润土及其负载化学助剂(柠檬酸)的保鲜材料对乙烯的吸附作用。将膨润土、甘油、柠檬酸加入水中,搅拌,加入聚乙烯醇,升温至90℃水浴保温,超声,排除气泡,冷却至室温,倾倒在有机玻璃板上,用刮刀涂布成膜,将膜静置在室温下24h,使水分挥发,然后再将膜置于45℃的真空干燥箱中干燥24h,制得膨润土/PVA保鲜膜。但存在力学性能、耐水性能不足。
本发明中膨润土与葡萄糖酸发生反应,得到表面有羟基修饰的材料,与聚乙烯醇形成了分子间氢键,具有良好的相容性,提高其耐水性。用聚醚胺改性炭黑、纳米二氧化硅得到具有核壳结构的增强体,改性炭黑表面的胺基与PVA 之间形成氢键,结合紧密,提高复合材料的力学性能,同时降低材料的吸湿率;纳米二氧化硅对聚醚胺起到增稠作用,在PVA薄膜中的分散性良好,提高复合膜的拉伸强度。氧化石墨烯(GO)在PVA基体中的分散性良好,两者之间通过氢键结合,GO的加入提高了PVA材料的力学性能;用十二烷基苯磺酸钠、氢氧化钾对碳纳米管进行处理,提高其分散性、拉伸强度。以戊二醛为交联剂,以乙酸为催化剂,PVA可以发生分子间的缩醛化交联,采用缩醛交联法制备了改性膜,提高其耐水性。
发明内容
本发明主要解决的技术问题是提供一种矿物填充的可降解型聚乙烯醇保鲜膜及其制备工艺,依照该工艺制作的保鲜膜可降解性、防水耐水、力学性能好,并且透湿性能好,不易内结露。
本发明所要解决的技术问题采用以下的技术方案来实现:
聚乙烯醇31-43,膨润土6-14,柠檬酸5-11,甘油3-4,葡萄糖酸3-7,炭黑4-9,聚醚胺6-10,纳米二氧化硅3-5,十二烷基苯磺酸钠2-3,氢氧化钾3-6,氧化石墨烯4-7,碳纳米管5-8,戊二醇4-6,乙酸3-5,高岭土3-6,硅藻土2-5,石蜡2-4,KH550 2-3,乙醇、H2SO4、蒸馏水。
一种矿物填充的可降解型聚乙烯醇保鲜膜的制备方法,其特征在于,按以下步骤进行:
a. 将膨润土、甘油混合,1:10-20加入蒸馏水,搅拌1-2h分散均匀,调pH为7-8,1:5-10加入柠檬酸、乙醇,升温至70-80℃恒温水浴,缓慢滴加葡萄糖酸,搅拌反应3-4h,抽滤、水洗醇洗3-5次,30-50℃真空干燥、粉碎、过100-200目筛;
b. 向炭黑中1:3-5加入H2SO4,磁力搅拌1-2h,70-80℃超声2-3h,得A液,将聚醚胺、纳米二氧化硅1:10-20分散于蒸馏水中,滴加到A液中,磁力搅拌4-8h后,60-70℃烘干,待用;
c. 将十二烷基苯磺酸钠、氢氧化钾1:15-25溶于蒸馏水中,加入碳纳米管、氧化石墨烯,升温至85-95℃超声振荡4-5h,过滤、水洗3-5次,50-60℃真空干燥;
d. 将高岭土于800-900℃煅烧3-5h,硅藻土于600-700℃煅烧4-6h,把两者混合放入高速捏合机中,升温至90-100℃,加入石蜡、KH550,混合搅拌10-20min,出料后干燥;
e. 向聚乙烯醇中1:20-30加入蒸馏水,加热至80-90℃搅拌溶解,加入a、b、c、d中所得物料及戊二醇、乙酸,超声1-2h充分混合,恒温搅拌反应1-2h,排除气泡,冷却至室温,倾倒在有机玻璃板上,用刮刀涂布成膜,将膜静置在室温下6-10h,使水分挥发,再将膜置于45-55℃的真空干燥箱中干燥5-10h,制得一种聚乙烯醇保鲜膜。
本发明的反应机理如下:
(1)膨润土与葡萄糖酸发生反应,得到表面有羟基修饰的材料,与聚乙烯醇形成了分子间氢键,具有良好的相容性,提高其耐水性。
(2)用聚醚胺改性炭黑、纳米二氧化硅得到具有核壳结构的增强体,改性炭黑表面的胺基与PVA 之间形成氢键,结合紧密,提高复合材料的力学性能,同时降低材料的吸湿率;纳米二氧化硅对聚醚胺起到增稠作用,在PVA薄膜中的分散性良好,提高复合膜的拉伸强度。
(3)氧化石墨烯(GO)在PVA基体中的分散性良好,两者之间通过氢键结合,GO的加入提高了PVA材料的力学性能;用十二烷基苯磺酸钠、氢氧化钾对碳纳米管进行处理,提高其分散性、拉伸强度。
(4)以戊二醛为交联剂,以乙酸为催化剂,PVA可以发生分子间的缩醛化交联,采用缩醛交联法制备了改性膜,提高其耐水性。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
实施例
一种矿物填充的可降解型聚乙烯醇保鲜膜,由下述重量份(g)的原料制得:
聚乙烯醇43,膨润土14,柠檬酸11,甘油4,葡萄糖酸7,炭黑9,聚醚胺10,纳米二氧化硅5,十二烷基苯磺酸钠3,氢氧化钾6,氧化石墨烯7,碳纳米管8,戊二醇6,乙酸5,高岭土6,硅藻土5,石蜡4,KH550 3,乙醇、H2SO4、蒸馏水。
一种矿物填充的可降解型聚乙烯醇保鲜膜的制备方法,其特征在于,按以下步骤进行:
a. 将膨润土、甘油混合,1:20加入蒸馏水,搅拌2h分散均匀,调pH为7-8,1:10加入柠檬酸、乙醇,升温至70-80℃恒温水浴,缓慢滴加葡萄糖酸,搅拌反应3h,抽滤、水洗醇洗3次,40-50℃真空干燥、粉碎、过100目筛;
b. 向炭黑中1:5加入H2SO4,磁力搅拌1h,70-80℃超声2h,得A液,将聚醚胺、纳米二氧化硅1:20分散于蒸馏水中,滴加到A液中,磁力搅拌4h后,60-70℃烘干,待用;
c. 将十二烷基苯磺酸钠、氢氧化钾1:25溶于蒸馏水中,加入碳纳米管、氧化石墨烯,升温至85-95℃超声振荡4h,过滤、水洗3次,50-60℃真空干燥;
d. 将高岭土于800-900℃煅烧3-5h,硅藻土于600-700℃煅烧4-6h,把两者混合放入高速捏合机中,升温至90-100℃,加入石蜡、KH550,混合搅拌10-20min,出料后干燥;
e. 向聚乙烯醇中1:25加入蒸馏水,加热至80-90℃搅拌溶解,加入a、b、c、d中所得物料及戊二醇、乙酸,超声2h充分混合,恒温搅拌反应2h,排除气泡,冷却至室温,倾倒在有机玻璃板上,用刮刀涂布成膜,将膜静置在室温下10h,使水分挥发,再将膜置于45-55℃的真空干燥箱中干燥8h,制得一种聚乙烯醇保鲜膜。
上述实施例制备的一种矿物填充的可降解型聚乙烯醇保鲜膜的性能检测结果如下所示:
拉伸强度≥65.2MPa,撕裂强度≥96.4MPa,断裂伸长率≥149.3%,常温下可延长水果货架期2-4d,冷藏下可延长水果的货架期5-8d。
Claims (2)
1.一种矿物填充的可降解型聚乙烯醇保鲜膜,其特征在于,由下述重量份的原料制得:
聚乙烯醇31-43,膨润土6-14,柠檬酸5-11,甘油3-4,葡萄糖酸3-7,炭黑4-9,聚醚胺6-10,纳米二氧化硅3-5,十二烷基苯磺酸钠2-3,氢氧化钾3-6,氧化石墨烯4-7,碳纳米管5-8,戊二醇4-6,乙酸3-5,高岭土3-6,硅藻土2-5,石蜡2-4,KH550 2-3,乙醇、H2SO4、蒸馏水。
2.根据权利要求1所述的一种矿物填充的可降解型聚乙烯醇保鲜膜的制备方法,其特征在于,按以下步骤进行:
a. 将膨润土、甘油混合,1:10-20加入蒸馏水,搅拌1-2h分散均匀,调pH为7-8,1:5-10加入柠檬酸、乙醇,升温至70-80℃恒温水浴,缓慢滴加葡萄糖酸,搅拌反应3-4h,抽滤、水洗醇洗3-5次,30-50℃真空干燥、粉碎、过100-200目筛;
b. 向炭黑中1:3-5加入H2SO4,磁力搅拌1-2h,70-80℃超声2-3h,得A液,将聚醚胺、纳米二氧化硅1:10-20分散于蒸馏水中,滴加到A液中,磁力搅拌4-8h后,60-70℃烘干,待用;
c. 将十二烷基苯磺酸钠、氢氧化钾1:15-25溶于蒸馏水中,加入碳纳米管、氧化石墨烯,升温至85-95℃超声振荡4-5h,过滤、水洗3-5次,50-60℃真空干燥;
d. 将高岭土于800-900℃煅烧3-5h,硅藻土于600-700℃煅烧4-6h,把两者混合放入高速捏合机中,升温至90-100℃,加入石蜡、KH550,混合搅拌10-20min,出料后干燥;
e. 向聚乙烯醇中1:20-30加入蒸馏水,加热至80-90℃搅拌溶解,加入a、b、c、d中所得物料及戊二醇、乙酸,超声1-2h充分混合,恒温搅拌反应1-2h,排除气泡,冷却至室温,倾倒在有机玻璃板上,用刮刀涂布成膜,将膜静置在室温下6-10h,使水分挥发,再将膜置于45-55℃的真空干燥箱中干燥5-10h,制得一种聚乙烯醇保鲜膜。
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WO2022084119A1 (en) * | 2020-10-22 | 2022-04-28 | Basf Coatings Gmbh | Coating composition comprising an alkali salt of graphene oxide and coating layers produced from said coating composition |
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