CN112874091B - 一种耐老化、可生物降解的薄膜及其制备方法和应用 - Google Patents
一种耐老化、可生物降解的薄膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及薄膜技术领域,公开了一种耐老化、可生物降解的薄膜及其制备方法和应用,该薄膜由下至上依次包括芯层和表层;芯层包括如下质量百分比的组分:60~80%均聚PP和10~20%降解剂;表层包括如下质量百分比的组分:80~95%均聚PP和3~15%耐老化剂;降解剂包括聚乳酸、聚碳酸酯、植物纤维素、改性玉米淀粉中的至少一种。本发明薄膜具有耐老化作用,对基材和印刷颜料色泽起到保护作用;同时具有良好的抗拉强度,抗拉强度可达到110MPa左右;本发明薄膜被弃置填埋后,在适当的温湿条件下,如在温度32~38℃、相对湿度90~100%条件下可触发生物降解,可以自然降解。
Description
技术领域
本发明涉及薄膜技术领域,特别涉及一种耐老化、可生物降解的薄膜及其制备方法和应用。
背景技术
目前户外广告耗材、户外装饰、照明材料等保护膜只关注耐老化性能。耐老化的聚丙烯产品不具有可降解性。而环保方面越来越偏向于可降解材料,现有耐老化的聚丙烯不符合环保政策要求的方向。在限塑令推行的大环境下,不可降解材料的市场受到严峻考验,可降解材料的研发、推广势在必行。目前可降解材料的耐候性较差,多数应用于快消类产品,如环保餐盒、标签类产品。对于广告耗材、户外装饰类等产品,主要使用的材料以不可降解的聚烯烃类产品为主,经印刷染色的产品废弃后回收难度大,由于该类产品具有低降解性,进行填埋处理后在短时间内不能降解,对环境保护、土地使用造成一定的压力,而且该类产品使用周期长,在户外长期光照环境下,其耐老化性能有一定的要求。
发明内容
本发明目的在于提供一种耐老化、可生物降解的薄膜,以解决现有技术中所存在的一个或多个技术问题,至少提供一种有益的选择或创造条件。
为解决上述技术问题所采用的技术方案:
一种耐老化、可生物降解的薄膜,所述薄膜由下至上依次包括芯层和表层;所述芯层包括如下质量百分比的组分:60~80%均聚PP(PP表示聚丙烯)和10~20%降解剂;所述表层包括如下质量百分比的组分:80~95%均聚PP和3~15%耐老化剂;所述降解剂包括聚乳酸、聚碳酸酯、植物纤维素、改性玉米淀粉中的至少一种。
优选地,所述芯层还包括如下质量百分比的组分:0.1~0.5%引发剂和5~8%增容剂;所述表层还包括如下质量百分比的组分:2~6%抗粘结剂;所述芯层的底面设有底层,所述底层包括如下质量百分比的组分:94~98%乙丙共聚物和2~6%抗粘结剂。
优选地,所述薄膜还包括第一夹层,所述第一夹层设置在所述表层和所述芯层之间,所述第一夹层包括如下质量百分比的组分:60~95%均聚PP和5~30%降解剂。所述降解剂包括聚乳酸、聚碳酸酯、植物纤维素、改性玉米淀粉中的至少一种。设置第一夹层起到增强表层与芯层的连接作用及材料填埋时激活细菌的分解作用。
优选地,所述薄膜还包括第二夹层,所述第二夹层设置在所述底层和所述芯层之间,所述第二夹层包括如下质量百分比的组分:90~95%均聚PP和5~10%乙丙共聚物。设置第二夹层起到增强底层与芯层的连接作用。
本发明中的组分:抗粘结剂起到膜间分离、不粘连的作用,抗粘结剂可选用ABPP05CN、ABPP905A、ABPP906、AB819中的任意一种抗粘结剂;耐老化剂起到吸收紫外光转化为热辐射从而保护底层材料和油墨色泽,耐老化剂可选用光稳定剂TINUVIN770;引发剂可选用DHBP引发剂;增容剂可选用PP-g-MAH增容剂。
本发明薄膜的生物降解原理为:薄膜的组分中含有羰基和羟基等多糖类基团,作为微生物的食物来源,有利于微生物生存和繁殖;同时含有DHBP引发剂,受光照和紫外线辐射下均聚PP链上接入羰基和羟基,填埋时可供微生物侵蚀断链,最终分解为二氧化碳和水。
本发明的第二个目的在于提供上述的薄膜的制备方法,包括以下步骤:
A、将所述芯层的组分添加至主挤出机中加热成熔融状态,得到芯层熔体,将所述表层的组分加入辅助挤出机中经加热成熔融状态,得到表层熔体;
B、将所述表层熔体和所述芯层熔体共挤,得到膜片,共挤的温度为220~230℃;
C、利用压缩空气将所述膜片贴附到激冷辊上急冷形成铸片,然后经过水浴冷却,再利用橡胶辊筒及压缩空气对冷却后的铸片进行除水,激冷辊温度为20~40℃;
D、将所述铸片依次进行纵向拉伸和横向拉伸,再经过冷却、对所述底层的表面进行电晕处理、收卷、分切,即可得到所述薄膜。电晕处理起到增大底层表面张力的作用,能够增加底层与胶水、涂层、油墨等涂覆材料的结合力。
优选地,所述步骤A和所述步骤B之间,还包括步骤A1:将底层的组分、第一夹层的组分和第二夹层的组分分别加入三台不同的辅助挤出机中经加热成熔融状态,分别得到底层熔体、第一夹层熔体和第二夹层熔体。
优选地,所述步骤B为:将所述表层熔体、所述第一夹层熔体、所述芯层熔体、所述第二夹层熔体和所述底层熔体分别加入五层共挤模头中进行共挤,得到膜片,共挤的温度为220~230℃。
优选地,所述步骤D中,所述纵向拉伸的过程具体为:将所述铸片经130~140℃预热,然后纵向拉伸为厚片,拉伸温度为120~140℃,拉伸倍率为4~6倍;所述横向拉伸的过程具体为:将所述厚片经160~175℃预热,然后横向拉伸、定型,拉伸温度为150~160℃,定型温度为165~175℃。
本发明的第三个目的在于提供上述的薄膜在户外装饰材料中的应用。优选地,该薄膜可用于户外广告耗材、户外装饰、照明材料的保护膜。
与现有技术相比,本发明具有如下有益效果:
本发明薄膜设有芯层和表层;其中,芯层包括均聚PP和降解剂,表层包括均聚PP和耐老化剂,具有耐老化作用,对基材和印刷颜料色泽起到保护作用;同时具有良好的抗拉强度,抗拉强度可达到110MPa左右;本发明薄膜被弃置填埋后,在适当的温湿条件下,如在温度32~38℃、相对湿度90~100%条件下可触发生物降解,可以自然降解。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1-3中所用各原料组分的型号如下:
均聚PP:福建联合石油化工有限公司;1104K牌号聚丙烯粒料。
降解剂:美国NatureWorks公司;4032D牌号聚乳酸材料。
乙丙共聚物:佛山塑兴母料有限公司;F800EDF共聚母料。
抗粘结剂A:广东汕头贝斯特科技有限公司;ABPP905A抗粘结母料。
抗粘结剂B:舒尔曼塑料有限公司;AB05CN抗粘结母料。
增容剂:佳易容聚合物(上海)有限公司;CMG9801牌号增容剂。
引发剂:泰州市海翔化工有限公司;2,5-二甲基-2,5-双(叔丁基过氧基)已烷。
耐老化剂:巴斯夫(中国)有限公司;光稳定剂TINUVIN 770。
实施例1
一种耐老化、可生物降解的薄膜,由下至上依次包括底层、第二夹层、芯层、第一夹层和表层,所述底层包括如下质量百分比的组分:96%乙丙共聚物和4%抗粘结剂B,所述芯层包括如下质量百分比的组分:80%均聚PP、13%降解剂、0.5%引发剂和6.5%增容剂,所述表层包括如下质量百分比的组分:85%均聚PP、4%抗粘结剂、11%耐老化剂,所述第一夹层包括如下质量百分比的组分:80%均聚PP和20%降解剂,所述第二夹层包括如下质量百分比的组分:92%均聚PP和8%乙丙共聚物。
上述薄膜的制备方法:
A、将所述芯层的组分添加至主挤出机中加热成熔融状态,得到芯层熔体,将所述表层的组分加入辅助挤出机中经加热成熔融状态,得到表层熔体;
A1:将底层的组分、第一夹层的组分和第二夹层的组分分别加入三台不同的辅助挤出机中经加热成熔融状态,分别得到底层熔体、第一夹层熔体和第二夹层熔体;
B、将所述表层熔体、所述第一夹层熔体、所述芯层熔体、所述第二夹层熔体和所述底层熔体分别加入五层共挤模头中进行共挤,得到膜片,共挤的温度为220℃;
C、利用压缩空气将所述膜片贴附到激冷辊上急冷形成铸片,然后经过水浴冷却,再利用橡胶辊筒及压缩空气对冷却后的铸片进行除水,激冷辊温度为30℃;
D、将所述铸片经135℃预热,然后纵向拉伸为厚片,拉伸温度为130℃,拉伸倍率为5倍,再将所述厚片经170℃预热,然后横向拉伸、定型,拉伸温度为155℃,定型温度为170℃,再经过冷却、对所述底层的表面进行电晕处理、收卷、分切,即可得到所述薄膜。
对实施例1制得的薄膜进行耐老化、抗拉和降解测试,测得抗拉强度为112MPa,用氙灯对薄膜照射72小时后,测得抗拉强度为105MPa,仍在合格使用范围;将薄膜填埋在温度32~38℃、相对湿度90~100%的土壤中,2周后取出观察,小心去掉薄膜表面的土壤,薄膜已发生降解,膜面出现细密蚀纹,抗拉强度降低到15MPa,用手很容易撕烂,1个月左右可降解到粉碎状,5个月左右被完全降解。
实施例2
一种耐老化、可生物降解的薄膜,由下至上依次包括底层、第二夹层、芯层、第一夹层和表层,所述底层包括如下质量百分比的组分:94%乙丙共聚物和6%抗粘结剂B,所述芯层包括如下质量百分比的组分:75%均聚PP、18%降解剂、0.5%引发剂和6.5%增容剂,所述表层包括如下质量百分比的组分:84%均聚PP、6%抗粘结剂A、10%耐老化剂,所述第一夹层包括如下质量百分比的组分:70%均聚PP和30%降解剂,所述第二夹层包括如下质量百分比的组分:90%均聚PP和10%乙丙共聚物。
上述薄膜的制备方法:
A、将所述芯层的组分添加至主挤出机中加热成熔融状态,得到芯层熔体,将所述表层的组分加入辅助挤出机中经加热成熔融状态,得到表层熔体;
A1:将底层的组分、第一夹层的组分和第二夹层的组分分别加入三台不同的辅助挤出机中经加热成熔融状态,分别得到底层熔体、第一夹层熔体和第二夹层熔体;
B、将所述表层熔体、所述第一夹层熔体、所述芯层熔体、所述第二夹层熔体和所述底层熔体分别加入五层共挤模头中进行共挤,得到膜片,共挤的温度为220℃;
C、利用压缩空气将所述膜片贴附到激冷辊上急冷形成铸片,然后经过水浴冷却,再利用橡胶辊筒及压缩空气对冷却后的铸片进行除水,激冷辊温度为20℃;
D、将所述铸片经130℃预热,然后纵向拉伸为厚片,拉伸温度为120℃,拉伸倍率为4倍,再将所述厚片经160℃预热,然后横向拉伸、定型,拉伸温度为150℃,定型温度为165℃,再经过冷却、对所述底层的表面进行电晕处理、收卷、分切,即可得到所述薄膜。
对实施例2制得的薄膜进行抗拉和降解测试,测得抗拉强度为110MPa,用氙灯对薄膜照射72小时后,测得抗拉强度为104MPa,仍在合格使用范围;将薄膜填埋在温度32~38℃、相对湿度90~100%的土壤中,2周后取出观察,小心去掉薄膜表面的土壤,薄膜已发生降解,膜面出现细密蚀纹,抗拉强度降低到20MPa,用手很容易撕烂,1个月左右可降解到粉碎状,5个月左右被完全降解。
实施例3
一种耐老化、可生物降解的薄膜,由下至上依次包括底层、第二夹层、芯层、第一夹层和表层,所述底层包括如下质量百分比的组分:98%乙丙共聚物和2%抗粘结剂B,所述芯层包括如下质量百分比的组分:80%均聚PP、12%降解剂、0.5%引发剂和7.5%增容剂,所述表层包括如下质量百分比的组分:95%均聚PP、2%抗粘结剂A、3%耐老化剂,所述第一夹层包括如下质量百分比的组分:95%均聚PP和5%降解剂,所述第二夹层包括如下质量百分比的组分:95%均聚PP和%乙丙共聚物。
上述薄膜的制备方法:
A、将所述芯层的组分添加至主挤出机中加热成熔融状态,得到芯层熔体,将所述表层的组分加入辅助挤出机中经加热成熔融状态,得到表层熔体;
A1:将底层的组分、第一夹层的组分和第二夹层的组分分别加入三台不同的辅助挤出机中经加热成熔融状态,分别得到底层熔体、第一夹层熔体和第二夹层熔体;
B、将所述表层熔体、所述第一夹层熔体、所述芯层熔体、所述第二夹层熔体和所述底层熔体分别加入五层共挤模头中进行共挤,得到膜片,共挤的温度为230℃;
C、利用压缩空气将所述膜片贴附到激冷辊上急冷形成铸片,然后经过水浴冷却,再利用橡胶辊筒及压缩空气对冷却后的铸片进行除水,激冷辊温度为40℃;
D、将所述铸片经140℃预热,然后纵向拉伸为厚片,拉伸温度为140℃,拉伸倍率为6倍,再将所述厚片经175℃预热,然后横向拉伸、定型,拉伸温度为160℃,定型温度为175℃,再经过冷却、对所述底层的表面进行电晕处理、收卷、分切,即可得到所述薄膜。
对实施例3制得的薄膜进行抗拉和降解测试,测得抗拉强度为107MPa,用氙灯对薄膜照射72小时后,测得抗拉强度为101MPa,仍在合格使用范围;将薄膜填埋在温度32~38℃、相对湿度90~100%的土壤中,2周后取出观察,小心去掉薄膜表面的土壤,薄膜已发生降解,膜面出现细密蚀纹,抗拉强度降低到16MPa,用手很容易撕烂,1个月左右可降解到粉碎状,5个月左右被完全降解。
以上对本发明的较佳实施方式进行了具体说明,但本发明创造并不限于所述实施例,熟悉本领域的技术人员在不违背本发明精神的前提下还可作出种种的等同变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。
Claims (6)
1.一种薄膜,其特征在于,所述薄膜由下至上依次包括芯层和表层;所述芯层由如下质量百分比的组分组成:60~80%均聚PP、10~20%降解剂、0.1~0.5%引发剂和5~8%PP-g-MAH增容剂;所述表层包括如下质量百分比的组分:80~95%均聚PP、3~15%耐老化剂和2~6%抗粘结剂;所述芯层的底面设有底层,所述底层包括如下质量百分比的组分:94~98%乙丙共聚物和2~6%抗粘结剂;
所述薄膜还包括第一夹层,所述第一夹层设置在所述表层和所述芯层之间,所述第一夹层包括如下质量百分比的组分:60~95%均聚PP和5~30%降解剂;
所述薄膜还包括第二夹层,所述第二夹层设置在所述底层和所述芯层之间,所述第二夹层包括如下质量百分比的组分:90~95%均聚PP和5~10%乙丙共聚物;
所述降解剂为聚乳酸;所述耐老化剂为光稳定剂TINUVIN770,所述引发剂为DHBP引发剂。
2.权利要求1所述的薄膜的制备方法,其特征在于,包括以下步骤:
A、将所述芯层的组分和表层的组分分别加热成熔融状态,分别得到芯层熔体和表层熔体;
B、将所述表层熔体和所述芯层熔体共挤,得到膜片;
C、将所述膜片进行激冷形成铸片;
D、将所述铸片依次进行纵向拉伸和横向拉伸,再经过电晕,即可得到所述薄膜。
3.根据权利要求2所述的制备方法,其特征在于,所述步骤A和所述步骤B之间,还包括步骤A1:将底层的组分、第一夹层的组分和第二夹层的组分分别加热成熔融状态,分别得到底层熔体、第一夹层熔体和第二夹层熔体。
4.根据权利要求3所述的制备方法,其特征在于,所述步骤B为:将所述表层熔体、所述第一夹层熔体、所述芯层熔体、所述第二夹层熔体和所述底层熔体共挤,得到膜片。
5.根据权利要求2所述的制备方法,其特征在于,所述步骤D中,所述纵向拉伸的过程具体为:将所述铸片经130~140℃预热,然后纵向拉伸为厚片,拉伸温度为120~140℃,拉伸倍率为4~6倍;所述横向拉伸的过程具体为:将所述厚片经160~175℃预热,然后横向拉伸、定型,拉伸温度为150~160℃,定型温度为165~175℃。
6.权利要求1所述的薄膜在装饰材料中的应用。
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