CN113895125A - 一种防雾阻隔bopla薄膜及其制备方法 - Google Patents
一种防雾阻隔bopla薄膜及其制备方法 Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
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- 239000000203 mixture Substances 0.000 claims description 3
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明公开了一种防雾阻隔BOPLA薄膜，依次由上表层、芯层和下表层构成；芯层由以下质量百分比的原料制成：聚乳酸切片85‑95％、乙烯‑乙烯醇共聚物5‑15％；上表层、下表层由以下质量百分比的原料制成：聚乳酸切片60‑80％、聚乳酸抗粘母料20‑40％。本发明还公开了防雾阻隔BOPLA薄膜的制备方法。本发明制备的防雾阻隔BOPLA薄膜，具有优异的防雾阻隔性能，可以减少防雾阻隔添加剂的使用，物理机械性能优良。
Description
技术领域
本发明涉及聚乳酸薄膜技术领域，尤其涉及一种防雾阻隔BOPLA薄膜及其制备方法。
背景技术
聚乳酸透明性及可印刷性良好，且其基本原料——乳酸是人体固有的生理物质之一，对人体无毒无害，在食品包装市场上的应用前景广阔。聚乳酸是生物基包装材料，相比于其他石油基塑料具有许多优势，如循环性、可回收性和安全性等。
目前用PLA替代石油基塑料的做法仅适用于对阻隔性和防雾性要求较低的食品包装应用。PLA对水蒸气、氧气的阻隔性都较低且防雾性差，这可能会影响产品的质量和安全性，极大地限制了其实际应用。
发明内容
基于背景技术存在的技术问题，本发明提出了一种防雾阻隔BOPLA薄膜及其制备方法。
本发明提出的一种防雾阻隔BOPLA薄膜，依次由上表层、芯层和下表层构成；
所述芯层由以下质量百分比的原料制成：聚乳酸切片85-95％、乙烯-乙烯醇共聚物5-15％；
所述上表层、下表层由以下质量百分比的原料制成：聚乳酸切片60-80％、聚乳酸抗粘母料20-40％；所述聚乳酸抗粘母料的成分包括聚乳酸树脂和超疏水纳米SiO2，其中超疏水纳米SiO2的含量为2500-4500ppm。
优选地，所述超疏水纳米SiO2的粒径为50-100nm。
优选地，所述超疏水纳米SiO2为硅烷偶联剂改性纳米SiO2。
优选地，所述硅烷偶联剂为亚辛基环四硅氧烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、正辛基三乙氧基硅烷中的至少一种。
其中，硅烷偶联剂改性纳米SiO2可以采用常规方法制得，例如：
称取硅烷偶联剂加入混合溶剂中，在60-70℃下预水解20-40min，得到硅烷偶联剂的水解液，将所述硅烷偶联剂的水解液与纳米SiO2混合，然后加入无水乙醇，升温至沸腾，搅拌反应3-5h，反应结束后，冷却至室温，离心，将得到的沉淀物干燥，即得；优选地，所述硅烷偶联剂、纳米SiO2的质量比为1:(1-1.2)；优选地，硅烷偶联剂、混合溶剂、无水乙醇的比例为1g：(20-24)mL：(40-48)mL；优选地，所述混合溶剂由无水乙醇和0.1mol/L的HCl按体积比为1:1混合得到。
优选地，所述聚乳酸抗粘母料是将丙交酯与硅烷偶联剂改性纳米SiO2在催化剂作用下进行原位聚合制得。
优选地，所述聚乳酸抗粘母料的制备方法为：将丙交酯、催化剂和硅烷偶联剂改性纳米SiO2在惰性气氛下，在125-140℃下反应8-10h，反应结束后，将产物用三氯甲烷溶解，过滤，再用石油醚沉淀，将得到的沉淀物抽滤在45-60℃下真空干燥，即得；优选地，所述惰性气氛为氮气气氛；优选地，所述催化剂选自辛酸亚锡、氯化亚锡、锡中的至少一种，优选辛酸亚锡；优选地，所述催化剂的用量为丙交酯重量的0.7-0.9％，优选0.8％。
优选地，所述乙烯-乙烯醇共聚物的乙烯摩尔分数为40-50％。
优选地，所述聚乳酸切片的特性粘度为0.65±0.02dL/g，熔点为160-180℃，玻璃化转变温度为60-65℃。
优选地，所述上表层的厚度占薄膜总厚度的10-15％，下表层的厚度占薄膜总厚度的10-15％。
一种所述的防雾阻隔BOPLA薄膜的制备方法，包括下述步骤：
S1、将芯层的原料混合后加入主挤出机，加热熔融挤出，过滤得到芯层熔体；分别将上表层的原料、下表层的原料混合均匀，加热熔融挤出，抽真空，过滤得到上表层熔体和下表层熔体；
S2、将所述芯层熔体、上表层熔体和下表层熔体通过模头共挤出制成厚片，所述厚片依次经过纵向拉伸、横向拉伸、热定型，得到防雾阻隔BOPLA薄膜。
优选地，所述步骤S1中，芯层的原料的加热熔融挤出温度为185-195℃，上表层的原料、下表层的原料的加热熔融挤出温度为185-195℃。
优选地，所述步骤S2中，纵向拉伸的预热温度为65-80℃，拉伸温度为95-105℃，拉伸倍数为4.0-4.2倍；横向拉伸的预热温度为99-102℃，拉伸温度为103-110℃，拉伸倍数为3.0-3.4倍；热定型温度为150-170℃。
优选地，所述芯层的原料、上表层的原料、下表层的原料中，聚乳酸切片在混合前，经过干燥处理；优选地，所述干燥的温度为60-80℃，干燥时间为4-6h。
本发明的有益效果如下：
本发明提出了一种防雾阻隔BOPLA薄膜，利用改性的超疏水SiO2，使薄膜表面高度疏水化，降低薄膜表面能，提高薄膜表面对水的接触角，使水滴滑落，以达到防雾效果，同时利也起到抗粘连粒子作用，降低摩擦系数，满足收卷要求。
疏水性SiO2能够更加均匀地分散在PLA有机相中，由于位阻效应，有效增加水和氧气分子渗透和扩散路径，减少单位时间内透过薄膜分子数量，通过与具有良好阻隔性的乙烯-乙烯醇共聚物的协同作用，提高薄膜水氧阻隔性。疏水性SiO2排斥水分子，进一步减缓了水蒸气向薄膜溶解的过程。
相较于传统工艺中将防雾阻隔涂层涂覆在薄膜表面或添加多种防雾阻隔添加剂，本发明不仅减少了添加剂用量和工序步骤，且无需添加后续涂布等处理设备、降低成本，制得的BOPLA薄膜的物理机械性能指标优良，防雾阻隔性能优异，在特定环境下能够快速完全生物降解，有效消除白色污染和海洋塑料污染，绿色环保。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
下述实施例和对比例中，使用的聚乳酸切片为美国NatureWorks，Ingeo 4043D，薄膜级聚乳酸切片；使用的乙烯-乙烯醇共聚物为日本Kuraray E105B。
实施例1
一种防雾阻隔BOPLA薄膜，依次由上表层、芯层和下表层构成；
芯层由以下质量百分比的原料制成：聚乳酸切片85％、乙烯-乙烯醇共聚物15％；上表层、下表层由以下质量百分比的原料制成：聚乳酸切片60％、聚乳酸抗粘母料40％；其中聚乳酸抗粘母料的成分包括聚乳酸树脂和硅烷偶联剂改性纳米SiO2，硅烷偶联剂改性纳米SiO2的含量为4500ppm，硅烷偶联剂改性纳米SiO2的粒径为50nm，硅烷偶联剂为亚辛基环四硅氧烷。
其中，硅烷偶联剂改性纳米SiO2的制备方法为：称取5g硅烷偶联剂加入100mL混合溶液(由无水乙醇与浓度为0.1mol/LHCl按体积比为1:1混合得到)中，在65℃下预水解30min，得到硅烷偶联剂的水解液，将硅烷偶联剂的水解液与5g纳米SiO2混合，然后加入200mL无水乙醇，升温至沸腾，搅拌反应4h，反应结束后冷却至室温，离心，将得到的沉淀物在80℃下干燥24h，即得。
聚乳酸抗粘母料是将丙交酯与硅烷偶联剂改性纳米SiO2在催化剂作用下进行原位聚合制得，制备方法为：将丙交酯、催化剂辛酸亚锡和硅烷偶联剂改性纳米SiO2在氮气气氛下，在140℃下反应8h，反应结束后，将产物用三氯甲烷溶解，过滤，再用石油醚沉淀，将得到的沉淀物抽滤在50℃下真空干燥，即得，其中催化剂辛酸亚锡的用量为丙交酯重量的0.8％。
乙烯-乙烯醇共聚物的乙烯摩尔分数为44％。
聚乳酸切片的特性粘度为0.65±0.02dL/g，熔点为160-180℃，玻璃化转变温度为60-65℃。
上表层的厚度占薄膜总厚度的15％，下表层的厚度占薄膜总厚度的15％。
防雾阻隔BOPLA薄膜的制备方法包括下述步骤：
S1、将芯层的原料、上表层的原料、下表层的原料中的聚乳酸切片在70℃干燥为5h；然后，将芯层的原料混合后加入主挤出机，在185-195℃加热熔融挤出，过滤得到芯层熔体；分别将上表层的原料、下表层的原料混合均匀，在185-195℃加热熔融挤出，抽真空，过滤得到上表层熔体和下表层熔体；
S2、将芯层熔体、上表层熔体和下表层熔体通过模头共挤出制成厚片，将厚片依次经过纵向拉伸、横向拉伸、热定型，得到防雾阻隔BOPLA薄膜，其中纵向拉伸的预热温度为70℃，拉伸温度为100℃，拉伸倍数为4.1倍；横向拉伸的预热温度为100℃，拉伸温度为105℃，拉伸倍数为3.2倍；热定型温度为160℃。
实施例2
一种防雾阻隔BOPLA薄膜，依次由上表层、芯层和下表层构成；
芯层由以下质量百分比的原料制成：聚乳酸切片90％、乙烯-乙烯醇共聚物10％；上表层、下表层由以下质量百分比的原料制成：聚乳酸切片70％、聚乳酸抗粘母料30％；其中聚乳酸抗粘母料的成分包括聚乳酸树脂和硅烷偶联剂改性纳米SiO2，硅烷偶联剂改性纳米SiO2的含量为3500ppm，硅烷偶联剂改性纳米SiO2的粒径为70nm，硅烷偶联剂为乙烯基三甲氧基硅烷。
其中，硅烷偶联剂改性纳米SiO2的制备方法同实施例1。
聚乳酸抗粘母料是将丙交酯与硅烷偶联剂改性纳米SiO2在催化剂作用下进行原位聚合制得，制备方法为：将丙交酯、催化剂辛酸亚锡和硅烷偶联剂改性纳米SiO2在氮气气氛下，在125℃下反应10h，反应结束后，将产物用三氯甲烷溶解，过滤，再用石油醚沉淀，将得到的沉淀物抽滤在45℃下真空干燥，即得，其中催化剂的用量为丙交酯重量的0.7％。
乙烯-乙烯醇共聚物的乙烯摩尔分数为44％。
聚乳酸切片、聚乳酸树脂的特性粘度为0.65±0.02dL/g，熔点为160-180℃，玻璃化转变温度为60-65℃。
上表层的厚度占薄膜总厚度的15％，下表层的厚度占薄膜总厚度的15％。
防雾阻隔BOPLA薄膜的制备方法同实施例1。
实施例3
一种防雾阻隔BOPLA薄膜，依次由上表层、芯层和下表层构成；
芯层由以下质量百分比的原料制成：聚乳酸切片95％、乙烯-乙烯醇共聚物5％；上表层、下表层由以下质量百分比的原料制成：聚乳酸切片80％、聚乳酸抗粘母料20％；其中聚乳酸抗粘母料的成分包括聚乳酸树脂和硅烷偶联剂改性纳米SiO2，硅烷偶联剂改性纳米SiO2的含量为2500ppm，硅烷偶联剂改性纳米SiO2的粒径为100nm，硅烷偶联剂为正辛基三乙氧基硅烷。
其中，硅烷偶联剂改性纳米SiO2的制备方法同实施例1。
聚乳酸抗粘母料是将丙交酯与硅烷偶联剂改性纳米SiO2在催化剂作用下进行原位聚合制得，制备方法为：将丙交酯、催化剂辛酸亚锡和硅烷偶联剂改性纳米SiO2在氮气气氛下，在130℃下反应9h，反应结束后，将产物用三氯甲烷溶解，过滤，再用石油醚沉淀，将得到的沉淀物抽滤在60℃下真空干燥，即得，其中催化剂的用量为丙交酯重量的0.9％。
乙烯-乙烯醇共聚物的乙烯摩尔分数为44％。
聚乳酸切片、聚乳酸树脂的特性粘度为0.65±0.02dL/g，熔点为160-180℃，玻璃化转变温度为60-65℃。
上表层的厚度占薄膜总厚度的15％，下表层的厚度占薄膜总厚度的15％。
防雾阻隔BOPLA薄膜的制备方法同实施例1。
对比例1
对比例1与实施例1的区别仅为：芯层的原料为：聚乳酸切片100％。
对比例2
对比例2与实施例1的区别仅为：聚乳酸抗粘母料的成分包括聚乳酸树脂和纳米SiO2，纳米SiO2的含量为4500ppm，纳米SiO2的粒径为50nm；聚乳酸抗粘母料是将丙交酯与纳米SiO2在催化剂作用下进行原位聚合制得，制备方法为：将丙交酯、催化剂辛酸亚锡和纳米SiO2在氮气气氛下，在140℃下反应8h，反应结束后，将产物用三氯甲烷溶解，过滤，再用石油醚沉淀，将得到的沉淀物抽滤在50℃下真空干燥，即得，其中催化剂的用量为丙交酯重量的0.8％。
试验例
对实施例1-3和对比例1-2制得的薄膜进行性能测试，结果如表1所示：
表1薄膜性能测试结果
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)
1.一种防雾阻隔BOPLA薄膜，其特征在于，依次由上表层、芯层和下表层构成；
所述芯层由以下质量百分比的原料制成：聚乳酸切片85-95％、乙烯-乙烯醇共聚物5-15％；
所述上表层、下表层由以下质量百分比的原料制成：聚乳酸切片60-80％、聚乳酸抗粘母料20-40％；所述聚乳酸抗粘母料的成分包括聚乳酸树脂和超疏水纳米SiO2，其中超疏水纳米SiO2的含量为2500-4500ppm。
2.根据权利要求1所述的防雾阻隔BOPLA薄膜，其特征在于，所述超疏水纳米SiO2的粒径为50-100nm。
3.根据权利要求1或2所述的防雾阻隔BOPLA薄膜，其特征在于，所述超疏水纳米SiO2为硅烷偶联剂改性纳米SiO2；
优选地，所述硅烷偶联剂为亚辛基环四硅氧烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、正辛基三乙氧基硅烷中的至少一种。
4.根据权利要求3所述的防雾阻隔BOPLA薄膜，其特征在于，所述聚乳酸抗粘母料是将丙交酯与硅烷偶联剂改性纳米SiO2在催化剂作用下进行原位聚合制得。
5.根据权利要求1-4任一项所述的防雾阻隔BOPLA薄膜，其特征在于，所述乙烯-乙烯醇共聚物的乙烯摩尔分数为40-50％。
6.根据权利要求1-5任一项所述防雾阻隔BOPLA薄膜，其特征在于，所述聚乳酸切片的特性粘度为0.65±0.02dL/g，熔点为160-180℃，玻璃化转变温度为60-65℃。
7.根据权利要求1-6任一项所述的防雾阻隔BOPLA薄膜，其特征在于，所述上表层的厚度占薄膜总厚度的10-15％，下表层的厚度占薄膜总厚度的10-15％。
8.一种如权利要求1-7任一项所述的防雾阻隔BOPLA薄膜的制备方法，其特征在于，包括下述步骤：
S1、将芯层的原料混合后加入主挤出机，加热熔融挤出，过滤得到芯层熔体；分别将上表层的原料、下表层的原料混合均匀，加热熔融挤出，抽真空，过滤得到上表层熔体和下表层熔体；
S2、将所述芯层熔体、上表层熔体和下表层熔体通过模头共挤出制成厚片，所述厚片依次经过纵向拉伸、横向拉伸、热定型，得到防雾阻隔BOPLA薄膜。
9.根据权利要求8所述的防雾阻隔BOPLA薄膜的制备方法，其特征在于，所述步骤S1中，芯层的原料的加热熔融挤出温度为185-195℃，上表层的原料、下表层的原料的加热熔融挤出温度为185-195℃。
10.根据权利要求8或9所述的防雾阻隔BOPLA薄膜的制备方法，其特征在于，所述步骤S2中，纵向拉伸的预热温度为65-80℃，拉伸温度为95-105℃，拉伸倍数为4.0-4.2倍；横向拉伸的预热温度为99-102℃，拉伸温度为103-110℃，拉伸倍数为3.0-3.4倍；热定型温度为150-170℃。
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