CN114013148A - 一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜及其制备方法 - Google Patents
一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及食品包装领域,具体提供了一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜及其制备方法。采用夹心结构,聚丁二酸丁二醇酯和脂质为外层,夹心层为淀粉的纳米复合材料层,夹心层厚度为整个复合膜的45%‑85%;采用这种结构的复合膜具有良好的水蒸气阻隔性能、气体阻隔性能、疏水性、柔韧性和生物降解性,可广泛用于高含水量食品、生鲜蔬菜、高含油量易氧化产品的包装,在超市购物袋以及生活用垃圾袋等领域具有广泛应用前景。
Description
技术领域
本发明涉及一种一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜及其制备方法,涉及食品包装领域。
背景技术
我国人口众多,食品的生产和消费量巨大,传统的石油基包装材料因其不可降解性,对生态环境造成的污染日益严重,亟需全降解塑料取而代之。另一方面,现有的可降解包装塑料阻隔性较差,我国因缺乏高阻隔性材料而造成的食品损失巨大,例如,仅新鲜果蔬在运输过程中,因包装材料水蒸气阻隔性较差而造成的损失可达果蔬总产量的25%左右。因此,全降解高阻隔包装材料的研发具有重要意义。
聚丁二酸丁二醇酯是被国内外广泛研究的一种全降解材料,但聚丁二酸丁二醇酯高昂的原料成本严重限制了其推广应用。淀粉具有来源广泛、成本低廉、可完全降解等优点,因此,聚丁二酸丁二醇酯与淀粉复合,可以显著降低制品的生产成本。然而,淀粉普遍存在湿敏性强的缺点,对复合膜的水蒸气阻隔效果存在不利影响,严重限制了复合膜的实际应用。
现有的技术中,发明专利CN112266529A公开了一种高性能环保包装膜及其制备方法。该薄膜是线型低密度聚乙烯、PVC树脂、聚乳酸和淀粉的复合物。该薄膜具有良好的机械性能和阻隔性能,但所用的材料中淀粉含量较低,且聚乙烯是不可降解的,对环境仍有潜在的危害。发明专利CN113201209A公开了一种可生物降解复合薄膜的制备方法。该薄膜是由聚乳酸、聚对苯二甲酸-己二酸-丁二醇酯及改性淀粉复合而成的多层膜。该薄膜淀粉含量较高且所用的淀粉大部分为疏水改性淀粉,在吹塑前需要对原淀粉进行改性,因此制备工艺复杂且机械性能差。另一方面,该薄膜中聚酯和淀粉相容性较低,在一定程度上影响了薄膜的机械性能。发明专利CN2017100485148公开了一种聚己二酸对苯二甲酸丁二酯/淀粉高阻隔复合膜及其制备方法。该专利描述的多层膜中,外层为聚己二酸对苯二甲酸丁二酯复合材料,内层为淀粉纳米复合材料层,该膜具有良好的阻氧性能。但由于聚己二酸对苯二甲酸丁二酯的杨氏模量较差,所形成的膜过于柔软,从而影响膜的广泛应用,而且聚己二酸对苯二甲酸丁二酯层的疏水性和阻水性较差,不适合在高湿环境下使用或包装高水分含量的物品。
发明内容
本发明针对现有技术存在的诸多不足之处,提供了一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜及其制备方法,为克服现有技术的缺陷,本发明提供一种一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜及其制备方法,本发明的技术方案是:
一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,所述复合膜为夹心结构,外层为聚丁二酸丁二醇酯/脂质复合材料层,夹心层为淀粉的纳米复合材料层,夹心层厚度为整个复合膜的45%-85%。
优选地,所述的聚丁二酸丁二醇/脂质复合材料层占总复合膜总厚度的15%-55%;所述的复合膜总厚度为35-300微米。
优选地,所述夹心层的组成按重量份为:改性淀粉40-85份、增塑剂15-55份、润滑剂0.3-6.5份、增容剂0.4-3.5份、纳米填料10-45份、亲水性聚合物15-55份、多元有机酸0.4-20份、生物降解聚酯4-25份和聚酯多元醇0.3-13份。
优选地,所述的改性淀粉为交联羟丙基淀粉、酸处理淀粉、棕榈酸淀粉酯、月桂酸淀粉酯、辛烯基琥珀酸淀粉酯中的一种或两种以上的混合物;所述的增塑剂是甘油、木糖醇、甘露醇、单醋酸甘油酯、柠檬酸酯、葡萄糖、果糖中的一种或两种以上的混合物;所述的润滑剂是硬脂酸锌、硬脂酸钙、单辛酸甘油酯、单油酸甘油酯、石蜡中的一种或其两种以上的混合物;所述的增容剂是马来酸酐、乙烯基三乙氧基硅烷、三异硬脂酰基钛酸异丙酯中的一种或两种以上的混合物;所述的纳米填料是纳米碳酸钙、纳米二氧化硅、有机改性蒙脱土中的一种或两种以上的混合物;所述的亲水性聚合物是甲基纤维素、聚乙烯醇、羧甲基纤维素中的一种或其两种以上的混合物;所述的多元有机酸是柠檬酸、2-羟基丁二酸、己二酸、十二碳二元酸中的一种或两种以上的混合物;所述的生物降解聚酯是聚丁二酸-己二酸丁二酯、聚己二酸对苯二甲酸丁二酯、聚丁二酸丁二醇酯、聚乳酸、聚乙内酯中的一种或两种以上的混合物;所述的聚酯多元醇是聚乙交酯二元醇、聚己内酯三元醇、聚碳酸酯二元醇中的一种或两种以上的混合物。
优选地,所述的聚丁二酸丁二醇酯/脂质复合材料层的组成按重量份计为:聚丁二酸丁二醇酯45-95份,脂质15-20份,增塑剂15-45份,其它生物降解聚酯15-30份,纳米填料20-55份,改性淀粉3-25份,加工助剂0.4-13份。
优选地,所述的增塑剂是柠檬酸三乙酯、二醋酸甘油酯、环氧甲酯、三辛酸甘油酯、环氧大豆油中的一种或两种以上的混合物;所述的脂质是蜂蜡、小烛树蜡、巴西棕榈蜡、液体石蜡、起酥油、大豆油、玉米油中的一种或两种以上的混合物;所述的纳米填料是指纳米碳酸钙、纳米二氧化硅、天然纳米纤维素、改性纳米纤维素、有机改性蒙脱土中的一种或两种以上的混合物;所述的改性淀粉是氧化淀粉、月桂酸淀粉酯、酸处理淀粉、辛烯基琥珀酸淀粉酯中的一种或其两种以上的混合物;所述的其它生物降解聚酯是聚丁二酸丁二醇酯、聚己二酸对苯二甲酸丁二酯、聚碳酸亚丙酯、聚乙内酯、聚羟基脂肪酸酯中的一种或两种以上的混合物;所述的加工助剂是指油酸酰胺、芥酸酰胺、甲苯二异氰酸酯、硬脂酸钙中的一种或其两种以上的混合物。
本发明还提供上述复合膜的制备方法,采用多层共挤流延或多层共挤吹塑的方法制备,所制备的复合膜为三层或五层结构。
优选地,所述的多层共挤流延是指采用两台挤出机和ABA型挤出流延模具制备三层膜,或者采用三台挤出机和ABCBA型挤出流延模具制备五层膜,然后采用三辊压光机或者双向拉伸装置处理薄膜。
优选地,所述的多层共挤吹塑是指采用两台挤出机和ABA型吹膜机头制备三层膜,或者采用三台挤出机和ABCBA型吹膜机头制备五层膜,复合膜从吹膜机头出来后,采用两次吹泡工艺进行后处理,其中聚丁二酸丁二醇酯/脂质复合材料层的挤出温度为125-175℃,淀粉纳米复合材料层的挤出温度为135-195℃,机头模具温度为145-190℃,后处理温度为65-130℃。
所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜中,聚丁二酸丁二醇酯/脂质复合材料层为复合膜的阻水层。脂质在吹塑或流延的过程中重结晶并定向或随机分布于复合膜的内部或表面。分布于复合膜表面的脂质结晶形成粗糙结构,基于“荷叶效应”,提高了复合膜的疏水性。分布于复合膜内部的脂质结晶增加了水蒸气透过的路径,基于水蒸气曲线路径理论,提高了复合膜的阻水性。脂质作为一种强疏水性的物质显著降低了复合膜对空气湿度的敏感性,保证了复合膜的稳定性。
本发明采用多层共挤流延或多层共挤吹塑的方法制备薄膜,将疏水性的聚酯和脂质作为外层,淀粉作为夹心层,可有效解决脂质和淀粉因极性相差较大而难以相容的问题;在聚丁二酸丁二醇酯/脂质复合材料外层中添加了一定比例的淀粉,淀粉纳米复合材料夹心层中添加了一定量的聚丁二酸丁二醇酯,可使外层和夹心层的相容性得到提高,同时外层和夹心层中的疏水性淀粉可进一步增强外层和夹心层的相容性。该膜采用夹心结构,所述的聚丁二酸丁二醇酯和脂质为外层,所述的夹心层为淀粉的纳米复合材料层,所述夹心层厚度为整个复合膜的45%-85%;采用这种结构的复合膜具有良好的水蒸气阻隔性能、气体阻隔性能、疏水性、柔韧性和生物降解性,可广泛用于高含水量食品、生鲜蔬菜、易氧化产品的包装,在超市购物袋以及生活用垃圾袋等领域具有广泛应用前景。
本发明的有益效果:
(1)适合用于高含水量、高含油量的食品包装:
所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜中,聚丁二酸丁二醇酯复合材料层表面形成微纳结晶结构,基于“荷叶效应”,膜表面具有较强的疏水性,特别适合高含水的果蔬包装的应用。具体的应用实例包括樱桃、苹果和黄瓜等含水量高、易失重食品的包装。淀粉纳米复合材料层为复合膜的阻气层,对氧气、二氧化碳等气体具有良好的阻隔性能,特别适合在需要高阻氧包装的食品中应用。具体的应用实施例包括生鲜肉和花生、核桃等含油量高、易氧化食品的包装。通过调整聚丁二酸丁二醇酯/淀粉/脂质复合材料层的组成和厚度,可满足多种不同应用的要求。
(2)设备投资少,生产成本低:
本发明与现有薄膜制备技术中添加表面活性剂来增加淀粉与脂质的相容性以及在聚酯层和淀粉层间额外增加一层粘合层或嵌段共聚物相比,本技术具有设备投资少,生产成本低,复合膜性能调整范围宽等优势,因而更易于实现全降解复合膜的推广应用。
(3)生物降解性好:
采用本发明的方法获得的复合膜具有良好的水蒸气阻隔性能、气体阻隔性能、疏水性、柔韧性和生物降解性,可广泛用于高含水量食品、生鲜蔬菜、易氧化产品的包装,在超市购物袋以及生活用垃圾袋等领域具有广泛应用前景。
附图说明
图1为实施例1中聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的表面微观形貌。
图2为实施例1中聚丁二酸丁二醇酯/淀粉/脂质三层复合膜土埋降解30天的断面微观形貌。
具体实施方式
下面结合具体实施例来进一步描述本发明,本发明的优点和特点将会随着描述而更为清楚。但这些实施例仅是范例性的,并不对本发明的范围构成任何限制。本领域技术人员应该理解的是,在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换,但这些修改和替换均落入本发明的保护范围内。
实施例1:
一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其具体组分和制备方法如下:
(1)淀粉纳米复合材料层的组成及其粒料的制备方法:将酸处理淀粉5.8Kg,聚乙烯醇2.5Kg,聚己二酸/对苯二甲酸丁二酯610g,有机改性蒙脱土620g,马来酸酐73g,硬脂酸锌185g,硬脂酸钙362g,单甘脂48g,柠檬酸92.8g,甘油2.44Kg,聚丙交酯二元醇0.53Kg,石蜡49g倒入高速混合机中,搅拌混匀;将混匀的物料在双螺杆挤压造粒机中造粒,造粒机温度110-170℃,机头温度165℃,螺杆转速150rpm,将粉料加工成直径为1-4mm的粒料。
(2)聚丁二酸丁二醇酯/脂质复合材料组成及粒料的制备方法:聚丁二酸丁二醇酯6.7Kg,蜂蜡1.4Kg,聚己二酸/对苯二甲酸丁二酯2.44Kg,乙酰柠檬酸正丁酯1.2Kg,环氧大豆油0.32Kg,纳米碳酸钙2.94Kg,辛烯基琥珀酸淀粉酯(取代度0.03)0.58Kg,单硬脂酸甘油酯0.32Kg,硬脂酸锌0.13Kg,硬脂酸钙0.16Kg,油酸酰胺0.23Kg。将聚丁二酸丁二醇酯、蜂蜡、聚己二酸/对苯二甲酸丁二酯、纳米碳酸钙、醋酸酯淀粉、硬脂酸锌、硬脂酸钙等固体原料在高速混合机中充分混匀后,在80℃的烘箱中干燥4小时。干燥后的固体原料采用双螺杆喂料机喂料,液体原料采用计量泵注入到双螺杆挤出机中,进行造粒;造粒机温度125-160℃,螺杆转速210rpm。
(3)聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的制备
聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的制备采用两台挤出机连接ABA型三层吹膜机头的方式进行吹膜。挤出机A喂聚丁二酸丁二醇酯/脂质料(内层和外层),工艺参数为:一区145℃,二区165℃,三区173℃,连接体170℃,螺杆转速100rpm,挤出机B喂淀粉料(中间层),工艺参数为:一区135℃,二区156℃,三区179℃,连接体173℃,螺杆转速300rpm,机头温度为175℃,吹胀比为3,拉伸比为3。吹出的膜泡再进行第二次吹胀,膜泡加热温度100℃,吹胀比为6,拉伸比为6。
采用以上配料和方法制备的聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的总厚度为76微米,其中外层聚丁二酸丁二醇酯/脂质的厚度为21微米,内层聚丁二酸丁二醇酯/脂质的厚度为23微米,淀粉层的厚度为32微米;膜的横向抗拉强度为15.21MPa,断裂伸长率为213.37%,杨氏模量为300.57MPa,纵向抗拉强度为16.35MPa,断裂伸长率为237.85%,杨氏模量为320.36MPa;复合膜水蒸气透过系数为0.85×10-14g•m-1•s-1•Pa-1,氧气透过系数为1.55×10-16cm2•s-1•Pa-1;表面接触角为101.2°,复合膜表面形貌扫面电镜如图1所示,在膜表面形成了不同的脂质结晶结构,这是膜基于“荷叶效应”所形成的结构。
采用本实施例制备的复合膜包装花生,以聚乙烯膜为对照,在温度50°C,湿度65%的恒温恒湿箱内加速酸败。聚乙烯膜包装的花生在存放5周后,酸价达到6.98mg/g,而复合膜包装的花生酸价为1.21mg/g。因此,聚丁二酸丁二醇酯/淀粉/脂质复合膜可显著延长花生的保质期。
实施例2:
一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其具体组分和制备方法如下:
(1)淀粉纳米复合材料层的组成及其粒料的制备方法:将酸处理淀粉6.8Kg,聚乙烯醇1.3Kg,聚碳酸亚丙酯420g,纳米二氧化硅510g,硬脂酸锌125g,硬脂酸钙243g,硅烷偶联剂KH55075g,单甘脂63g,柠檬酸89g,甘油2.43Kg,聚碳酸酯二元醇0.32Kg,二醋酸甘油酯250g,石蜡48g倒入高速混合机中,搅拌混匀;将混匀的物料在双螺杆挤压造粒机中造粒,造粒温度115-175℃,机头温度170℃,螺杆转速200rpm,将粉料加工成直径为1-4mm的粒料。
(2)聚丁二酸丁二醇酯/脂质复合材料组成及粒料的制备方法:聚丁二酸丁二醇酯5.7Kg,小烛树蜡1.2Kg,聚己二酸/对苯二甲酸丁二酯1.23Kg,聚碳酸亚丙酯1.05Kg,柠檬酸正丁酯1.2Kg,二乙酰环氧脂肪酸甘油酯0.33Kg,纳米二氧化硅2.74Kg,月桂酸酸淀粉酯0.6Kg,单硬脂酸甘油酯0.3Kg,硬脂酸锌0.15Kg,硬脂酸钙0.13Kg,芥酸酰胺0.14Kg。将聚丁二酸丁二醇酯、聚己二酸/对苯二甲酸丁二酯、聚碳酸亚丙酯、纳米二氧化硅、甲氧基淀粉、硬脂酸锌、硬脂酸钙等固体原料在高速混合机中充分混匀后,在80℃的烘箱中干燥4小时。干燥后的固体原料采用双螺杆喂料机喂料,液体原料采用计量泵注入到双螺杆挤出机中,进行造粒;造粒机温度115-175℃,机头温度160℃,螺杆转速250rpm。
(3)聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的制备
聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的制备采用两台挤出机连接ABA型三层流延模具进行挤出流延制膜。挤出机A喂聚丁二酸丁二醇酯/脂质料(上层和下层),工艺参数为:一区135℃,二区155℃,三区175℃,连接体175℃,螺杆转速120rpm,挤出机B喂淀粉料(中间层),工艺参数为:一区135℃,二区155℃,三区175℃,连接体175℃,螺杆转速360rpm,机头温度为172℃,拉伸比为3。得到的薄膜进行双向拉伸处理,双向拉伸的加热温度80℃,拉伸比为4。
采用以上配料和方法制备的聚丁二酸丁二醇酯/淀粉/脂质三层复合膜的总厚度为71微米,其中外层聚丁二酸丁二醇酯/脂质的厚度为13微米,内层聚丁二酸丁二醇酯/脂质的厚度为14微米,淀粉层的厚度为44微米;膜的横向抗拉强度为14.36MPa,断裂伸长率为216.2%,杨氏模量为294.15MPa,纵向抗拉强度为15.88MPa,杨氏模量为310.27MPa,断裂伸长率为249.12%;复合膜水蒸气透过系数为0.75×10-14g•m-1•s-1•Pa-1,氧气透过系数为1.56×10-16cm2•s-1•Pa-1;表面接触角为102.3°;复合膜180天土埋生物降解率为84.5%,图2为三层复合膜土埋30天生物降解的断面微观形貌。
采用本实施例制备的复合膜包装核桃仁,以聚乙烯膜为对照,在温度50°C,湿度65%的恒温恒湿箱内加速氧化。聚乙烯膜包装的核桃仁在存放5周后,过氧化值达到6.82mmol/kg,而复合膜包装的核桃过氧化值为1.01mmol/kg。因此,聚丁二酸丁二醇酯/淀粉/脂质复合膜可显著延长核桃仁的保质期。
实施例3:
一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其具体组分和制备方法如下:
(1)淀粉纳米复合材料层的组成及其粒料的制备方法:将羟丙基交联马铃薯淀粉(羟丙基取代度0.1)7.5Kg,聚乙烯醇1.2Kg,羧甲基纤维素0.53Kg,聚羟基脂肪酸酯820g,有机改性蒙脱土610g,马来酸酐85g,硬脂酸锌155g,硬脂酸钙310g,单甘脂57g,己二酸64g,甘油2.53Kg,三醋酸甘油酯245g,聚乙交酯二元醇0.45Kg,石蜡48g倒入高速混合机中,搅拌混匀;将混匀的物料在双螺杆挤压造粒机中造粒,造粒机温度85-170℃,机头温度165℃,螺杆转速180rpm,将粉料加工成直径为1-4mm的粒料。
(2)聚丁二酸丁二醇酯/脂质复合材料组成及粒料的制备方法:聚丁二酸丁二醇酯6.3Kg,巴西棕榈蜡1.3Kg,聚己二酸/对苯二甲酸丁二酯0.65Kg,聚羟基脂肪酸酯1.2Kg,乙酰柠檬酸正丁酯1.3Kg,三醋酸甘油酯0.22Kg,纳米二氧化硅2.83Kg,辛烯基琥珀酸淀粉酯(取代度0.02)0.6Kg,单硬脂酸甘油酯0.23Kg,硬脂酸锌0.24Kg,硬脂酸钙0.15Kg,油酸酰胺0.11Kg。将聚丁二酸丁二醇酯、蜂蜡、聚羟基脂肪酸酯、聚己二酸/对苯二甲酸丁二酯、纳米二氧化硅、辛烯基琥珀酸淀粉酯、硬脂酸锌、硬脂酸钙等固体原料在高速混合机中充分混匀后,在80℃的烘箱中干燥4小时。干燥后的固体原料采用双螺杆喂料机喂料,液体原料采用计量泵注入到双螺杆挤出机中,进行造粒;造粒机温度115-175℃,机头温度164℃,螺杆转速230rpm。
(3)聚丁二酸丁二醇酯/淀粉/脂质五层复合膜的制备
聚丁二酸丁二醇酯/淀粉/脂质五层复合膜的制备采用三台挤出机连接ABCBA型五层吹膜机头的方式进行吹膜。挤出机A喂聚丁二酸丁二醇酯/脂质料(最外层和最里层),工艺参数为一区135℃,二区150℃,三区170℃,连接体175℃,螺杆转速100rpm,挤出机B喂淀粉料(中间夹层),工艺参数为一区145℃,二区160℃,三区175℃,连接体170℃,螺杆转速360rpm,挤出机C喂聚丁二酸丁二醇酯/脂质料(中心层),工艺参数为一区135℃,二区150℃,三区170℃,连接体175℃,螺杆转速80rpm,机头温度为175℃,吹胀比为3,拉伸比为3。吹出的膜泡再进行第二次吹胀,膜泡加热温度95℃,吹胀比为4,拉伸比为4。
采用以上配料和方法制备的聚丁二酸丁二醇酯/淀粉/脂质五层复合膜的厚度为130微米,其中外层聚丁二酸丁二醇酯/脂质的厚度为15微米,内层聚丁二酸丁二醇酯/脂质的厚度为13微米,其中一层淀粉层的厚度为43微米,另一层淀粉层的厚度为45微米;中心聚丁二酸丁二醇酯/脂质层的厚度为14微米;膜的横向抗拉强度为16.36MPa,断裂伸长率为237.64%,杨氏模量为341.19MPa,纵向抗拉强度为20.35MPa,断裂伸长率为249.17%,杨氏模量为396.47MPa;复合膜水蒸气透过系数为0.65×10-14g•m-1•s-1•Pa-1,氧气透过系数为1.53×10-16cm2•s-1•Pa-1;表面接触角为105.3°。
采用本实施例制备的复合膜包装樱桃,以普通聚乙烯膜为对照,在23℃,湿度为50%的环境中存放15天。复合膜包装的樱桃腐烂率为4.8%,包装中二氧化碳的含量为25.1%;聚乙烯膜包装的樱桃腐烂率为24.6%,包装膜中二氧化碳的含量为24.4%。可见本实施例制备的复合膜保鲜性能远高于现有材料。
实施例4:
一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其具体组分和制备方法如下:
(1)淀粉纳米复合材料层的组成及其粒料的制备方法:将酸处理糯玉米淀粉7.0Kg,聚乙烯醇1.53Kg,羟丙基甲基纤维素0.34Kg,聚羟基脂肪酸酯630g,纳米碳酸钙810g,三异硬酯酸钛酸异丙酯65g,聚丙交酯二元醇0.23Kg,硬脂酸锌165g,硬脂酸钙284g,单甘脂67g,丁二酸65g,甘油2.38Kg,双乙酸甘油酯245g,石蜡57g倒入高速混合机中,搅拌混匀;将混匀的物料在双螺杆挤压造粒机中造粒,造粒机温度95-170℃,机头温度165℃,螺杆转速220rpm,将粉料加工成直径为1-4mm的粒料。
(2)聚丁二酸丁二醇酯/脂质复合材料组成及粒料的制备方法:聚丁二酸丁二醇酯5.9Kg,蜂蜡1.2Kg,聚己内酯1.2Kg,纳米二氧化硅2.42Kg,月桂酸淀粉酯0.5Kg,单硬脂酸甘油酯0.12Kg,硬脂酸锌0.23Kg,硬脂酸钙0.15Kg,油酸酰胺0.13Kg。将聚丁二酸丁二醇酯、聚己内酯、纳米二氧化硅、辛烯基琥珀酸淀粉酯、硬脂酸锌、硬脂酸钙等固体原料在高速混合机中充分混匀后,在80℃的烘箱中干燥6小时。干燥后的固体原料采用双螺杆喂料机喂料,液体原料采用计量泵注入到双螺杆挤出机中,进行造粒;造粒机温度130-175℃,机头温度165℃,螺杆转速200rpm。
(3)聚丁二酸丁二醇酯/淀粉/脂质五层复合膜的制备
聚丁二酸丁二醇酯/淀粉/脂质五层复合膜的制备采用三台挤出机连接ABCBA型五层流延模具的方式进行生产。挤出机A喂聚丁二酸丁二醇酯/脂质料(两个最外层),工艺参数为一区145℃,二区155℃,三区170℃,连接体175℃,螺杆转速100rpm,挤出机B喂淀粉料(中间夹层),工艺参数为一区145℃,二区165℃,三区175℃,连接体175℃,螺杆转速330rpm,挤出机C喂聚丁二酸丁二醇酯/脂质料(中心层),工艺参数为一区145℃,二区155℃,三区170℃,连接体175℃,螺杆转速90rpm,机头温度为175℃,拉伸比为3。得到的薄膜进行双向拉伸处理,双向拉伸的加热温度90℃,拉伸比为4。
采用以上配料和方法制备的聚丁二酸丁二醇酯/淀粉/脂质五层复合膜的总厚度为136微米,其中外层聚丁二酸丁二醇酯/脂质的厚度为16微米,内层聚丁二酸丁二醇酯/脂质的厚度为15微米,其中一层淀粉层的厚度为43微米,另一层淀粉层的厚度为47微米;中心聚丁二酸丁二醇酯/脂质层的厚度为15微米;膜的横向抗拉强度为17.37MPa,断裂伸长率为215.33%,杨氏模量为352.64MPa,纵向抗拉强度为24.84MPa,断裂伸长率233.54%,杨氏模量为411.82MPa;复合膜水蒸气透过系数为0.78×10-14g•m-1•s-1•Pa-1,氧气透过系数为1.09×10-16cm2•s-1•Pa-1;表面接触角为103.5°。
采用本实施例制备的复合膜包装樱桃,以普通聚乙烯膜为对照,在23℃,湿度为50%的环境中存放15天。复合膜包装的樱桃腐烂率为3.7%,包装中二氧化碳的含量为24.1%;聚乙烯膜包装的樱桃腐烂率为23.3%,包装膜中二氧化碳的含量为26.8%。可见本实施例制备的复合膜保鲜性能远高于现有材料。
对比例1
一种聚丁二酸丁二醇酯/淀粉复合膜,其具体组分和制备方法如下:
(1)淀粉纳米复合材料层的组成及其粒料的制备方法:将酸处理糯玉米淀粉7.0Kg,聚乙烯醇1.53Kg,羟丙基甲基纤维素0.34Kg,聚羟基脂肪酸酯630g,纳米碳酸钙810g,三异硬酯酸钛酸异丙酯65g,聚丙交酯二元醇0.23Kg,硬脂酸锌165g,硬脂酸钙284g,单甘脂67g,丁二酸65g,甘油2.38Kg,双乙酸甘油酯245g,石蜡57g倒入高速混合机中,搅拌混匀;将混匀的物料在双螺杆挤压造粒机中造粒,造粒机温度95-170℃,机头温度165℃,螺杆转速220rpm,将粉料加工成直径为1-4mm的粒料。
(2)聚丁二酸丁二醇酯复合材料组成及粒料的制备方法:聚丁二酸丁二醇酯5.9Kg,聚己内酯1.2Kg,纳米二氧化硅2.42Kg,月桂酸淀粉酯0.5Kg,单硬脂酸甘油酯0.12Kg,硬脂酸锌0.23Kg,硬脂酸钙0.15Kg,油酸酰胺0.13Kg。将聚丁二酸丁二醇酯、聚己内酯、纳米二氧化硅、辛烯基琥珀酸淀粉酯、硬脂酸锌、硬脂酸钙等固体原料在高速混合机中充分混匀后,在80℃的烘箱中干燥6小时。干燥后的固体原料采用双螺杆喂料机喂料,液体原料采用计量泵注入到双螺杆挤出机中,进行造粒;造粒机温度130-175℃,机头温度165℃,螺杆转速200rpm。
(3)聚丁二酸丁二醇酯/淀粉五层复合膜的制备
聚丁二酸丁二醇酯/淀粉五层复合膜的制备采用三台挤出机连接ABCBA型五层流延模具的方式进行生产。挤出机A喂聚丁二酸丁二醇酯料(两个最外层),工艺参数为一区145℃,二区155℃,三区170℃,连接体175℃,螺杆转速100rpm,挤出机B喂淀粉料(中间夹层),工艺参数为一区145℃,二区165℃,三区175℃,连接体175℃,螺杆转速330rpm,挤出机C喂聚丁二酸丁二醇酯料(中心层),工艺参数为一区145℃,二区155℃,三区170℃,连接体175℃,螺杆转速90rpm,机头温度为175℃,拉伸比为3。得到的薄膜进行双向拉伸处理,双向拉伸的加热温度90℃,拉伸比为4。
采用以上配料和方法制备的聚丁二酸丁二醇酯/淀粉五层复合膜的总厚度为152微米,其中外层聚丁二酸丁二醇酯的厚度为22微米,内层聚丁二酸丁二醇酯的厚度为23微米,其中一层淀粉层的厚度为40微米,另一层淀粉层的厚度为42微米;中心聚丁二酸丁二醇酯层的厚度为25微米;膜的横向抗拉强度为15.21MPa,断裂伸长率为182.79%,杨氏模量为304.57MPa,纵向抗拉强度为17.26MPa,断裂伸长率173.26%,杨氏模量为341.02MPa;复合膜水蒸气透过系数为2.67×10-11g•m-1•s-1•Pa-1,氧气透过系数为5.77×10-13cm2•s-1•Pa-1;表面接触角为87.4°。
采用本对比例制备的复合膜包装樱桃,以实施例4为对照,在23℃,湿度为50%的环境中存放15天。本对比例包装的樱桃腐烂率为15.2%,包装中二氧化碳的含量为25.9%;实施例4包装的樱桃腐烂率为3.7%,包装中二氧化碳的含量为24.1%。可见本对比例制备的复合膜保鲜性能明显低于实施例4。
以上实施例是本发明选择的具体实施方式的一种,本领域技术人员在本技术方案范围内进行的通常变化和替换应包含在本发明的保护范围内。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其特征在于,所述复合膜为夹心结构,外层为聚丁二酸丁二醇酯/脂质复合材料层,夹心层为淀粉的纳米复合材料层,夹心层厚度为整个复合膜的45%-85%。
2.根据权利要求1所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其特征在于,所述的聚丁二酸丁二醇酯/脂质复合材料层占复合膜总厚度的15%-55%;所述的复合膜总厚度为35-300微米。
3.根据权利要求1所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其特征在于,所述夹心层的组成按重量份为:改性淀粉40-85份、增塑剂15-55份、润滑剂0.3-6.5份、增容剂0.4-3.5份、纳米填料10-45份、亲水性聚合物15-55份、多元有机酸0.4-20份、生物降解聚酯4-25份和聚酯多元醇0.3-13份。
4.根据权利要求3所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其特征在于,所述的改性淀粉为交联羟丙基淀粉、酸处理淀粉、棕榈酸淀粉酯、月桂酸淀粉酯、辛烯基琥珀酸淀粉酯中的一种或两种以上的混合物;所述的增塑剂是甘油、木糖醇、甘露醇、单醋酸甘油酯、柠檬酸酯、葡萄糖、果糖中的一种或两种以上的混合物;所述的润滑剂是硬脂酸锌、硬脂酸钙、单辛酸甘油酯、单油酸甘油酯、石蜡中的一种或其两种以上的混合物;所述的增容剂是马来酸酐、乙烯基三乙氧基硅烷、三异硬脂酰基钛酸异丙酯中的一种或两种以上的混合物;所述的纳米填料是有机改性的蒙脱土、纳米碳酸钙、纳米二氧化硅中的一种或两种以上的混合物;所述的亲水性聚合物是甲基纤维素、聚乙烯醇、羧甲基纤维素中的一种或其两种以上的混合物;所述的多元有机酸是柠檬酸、2-羟基丁二酸、己二酸、十二碳二元酸中的一种或两种以上的混合物;所述的生物降解聚酯是聚丁二酸-己二酸丁二酯、聚己二酸对苯二甲酸丁二酯、聚丁二酸丁二醇酯、聚乳酸、聚乙内酯中的一种或两种以上的混合物;所述的聚酯多元醇是聚乙交酯二元醇、聚己内酯三元醇、聚碳酸酯二元醇中的一种或两种以上的混合物。
5.根据权利要求1所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其特征在于,所述的聚丁二酸丁二醇酯/脂质复合材料层的组成按重量份计为:聚丁二酸丁二醇酯45-95份,脂质15-20份,增塑剂15-45份,其它生物降解聚酯15-30份,纳米填料20-55份,改性淀粉3-25份,加工助剂0.4-13份。
6.根据权利要求5所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜,其特征在于,所述的增塑剂是柠檬酸三乙酯、二醋酸甘油酯、环氧甲酯、三辛酸甘油酯、环氧大豆油中的一种或两种以上的混合物;所述的脂质是蜂蜡、小烛树蜡、巴西棕榈蜡、液体石蜡、起酥油、大豆油、玉米油中的一种或两种以上的混合物;所述的纳米填料是指纳米碳酸钙、纳米二氧化硅、天然纳米纤维素、改性纳米纤维素、有机改性蒙脱土中的一种或两种以上的混合物;所述的改性淀粉是氧化淀粉、月桂酸淀粉酯、酸处理淀粉、辛烯基琥珀酸淀粉酯中的一种或其两种以上的混合物;所述的其它生物降解聚酯是聚丁二酸丁二醇酯、聚己二酸对苯二甲酸丁二酯、聚碳酸亚丙酯、聚乙内酯、聚羟基脂肪酸酯中的一种或两种以上的混合物;所述的加工助剂是指油酸酰胺、芥酸酰胺、甲苯二异氰酸酯、硬脂酸钙中的一种或其两种以上的混合物。
7.一种制备权利要求1至6任意一项所述的聚丁二酸丁二醇酯/淀粉/脂质高阻隔复合膜的制备方法,其特征在于,所述的复合膜采用多层共挤流延或多层共挤吹塑的方法制备,所制备的复合膜为三层或五层结构。
8.根据权利要求7所述的制备方法,其特征在于,所述的多层共挤流延是指采用两台挤出机和ABA型挤出流延模具制备三层膜,或者采用三台挤出机和ABCBA型挤出流延模具制备五层膜,然后采用三辊压光机或者双向拉伸装置处理薄膜。
9.根据权利要求7所述的制备方法,其特征在于,所述的多层共挤吹塑是指采用两台挤出机和ABA型吹膜机头制备三层膜,或者采用三台挤出机和ABCBA型吹膜机头制备五层膜,复合膜从吹膜机头出来后,采用两次吹泡工艺进行后处理,其中聚丁二酸丁二醇酯/脂质复合材料层的挤出温度为125-175℃,淀粉纳米复合材料层的挤出温度为135-195℃,机头模具温度为145-190℃,后处理温度为65-130℃。
10.根据权利要求7所述的制备方法,其特征在于,所述的多层共挤流延制备的每层膜材料厚度均匀,纵向抗拉强度大,薄膜透明性好。
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