CN110091564B - 一种全生物100%全降解复合膜及其加工工艺和应用 - Google Patents
一种全生物100%全降解复合膜及其加工工艺和应用 Download PDFInfo
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Abstract
本发明公开了一种全生物100%全降解复合膜及其加工工艺和应用。该全生物100%全降解复合膜为三层结构,其中外层膜由以下质量百分数的组分组成:聚乳酸80‑95%,聚对苯二甲酸‑己二酸‑丁二醇酯5‑20%;中间层由聚氨酯粘胶剂制成;内层膜由以下质量百分数的组分组成:聚对苯二甲酸‑己二酸‑丁二醇酯70‑90%,生物淀粉10‑30%;其加工工艺为:S1、外层膜制备;S2、印刷油墨;S3、内层膜制备;S4、复合;S5、熟化。本发明的全生物100%全降解复合膜可用于制备三边封平口袋、三边封自立袋、四边封袋、背封袋和开闭条自立袋,其具有能够100%完全降解,且阻隔性能优异的优点。
Description
技术领域
本发明涉及高分子材料技术领域,更具体地说,它涉及一种全生物100%全降解复合膜及其加工工艺和应用。
背景技术
塑料软包装已经逐渐成为包装行业的中流砥柱,而其中最重要的一部分就是具有阻隔性的复合膜,多用于包装各种食品、药品等。目前,工业上常用的阻隔性材料主要有乙烯-乙烯醇共聚物(EVOH)、聚偏二氯乙烯(PDVC)等,这些材料虽然阻隔性优异,但却不能生物降解。
聚乳酸(PLA)是一种具有良好机械性能和生物降解性的完全环保型生物降解材料,原料来源广泛,以玉米、小麦、木薯等淀粉为最初原料。它易被自然界中的多种微生物或动植物体内的酶分解代替,最终形成水和二氧化碳,不污染环境,被认为是最有前途的可生物降解高分子材料。此外聚乳酸的非毒性使得它可以用于直接与食品接触的包装中,可以通过通用塑料的加工方法如注塑、挤出、吸塑、吹塑、纺丝等技术加工成各种包装用材料,在各种民用、工业、农业和医疗特殊领域等广泛使用。
现有技术中,申请号为CN201410749335.3的中国发明专利文件中,公开了一种全生物降解复合材料及其制备方法和应用,包括组分:无机填料全生物降解母粒5-40份,生物降解共聚酯40-80份,聚乳酸10-40份,相容剂0.1-5份,所述的无机填料全生物降解母粒,包含组分:生物降解共聚酯20~80份,无机填料20-80份,润滑剂0.1-10份,相容剂0.1-5份,其中,所述无机填料为改性高岭土、改性白炭黑或改性蒙脱土中的一种或其组合。
现有的这种全生物降解复合材料制备包装袋时,撕裂强度和柔韧性较好,但是在包装食品和药品时,对于水蒸气和氧气的阻隔性能较差,且生物降解率不高,因此研制一种能够100%全降解,且阻隔性能好的复合膜是需要解决的问题。
发明内容
针对现有技术存在的不足,本发明的第一个目的在于提供一种全生物100%全降解复合膜,其具有100%全降解且阻隔性能好的优点。
本发明的第二个目的在于提供一种全生物100%全降解复合膜的加工工艺,其具有制备工艺简单,易于操作的优点。
本发明的第三个目的在于提供一种全生物100%全降解复合膜的应用,其具有使制备的包装袋能够100%完全降解,降解速度快且阻隔性能好的优点。
为实现上述第一个目的,本发明提供了如下技术方案:一种全生物100%全降解复合膜,复合膜为三层结构,其中外层膜由以下质量百分数的组分组成:聚乳酸80-95%,聚对苯二甲酸-己二酸-丁二醇酯5-20%;
中间层由聚氨酯粘胶剂制成;
内层膜由以下质量百分数的组分组成:聚对苯二甲酸-己二酸-丁二醇酯70-90%,生物淀粉10-30%。
通过采用上述技术方案,聚乳酸具有较强的力学强度,良好的加工性能以及突出的生物相容性,但其韧性较差,脆性较大,而聚对苯二甲酸-己二酸-丁二醇酯同样作为全生物降解材料,具有较好的韧性,将聚对苯二甲酸-己二酸-丁二醇酯与聚乳酸复合作为外层膜,合理控制聚对苯二甲酸-己二酸-丁二醇酯与聚乳酸的含量,能够加速PBAT和PLA酯键水解的速率,从而增加复合膜的降解速率,使用聚氨酯粘胶剂作为中间层,将外层膜和内层膜进行粘贴复合,聚氨酯粘胶剂具有优异的抗剪切强度和抗冲击特性,具备优异的柔韧特性,可提高复合膜的力学性能,且聚氨酯粘胶剂的生物降解性较好,内层膜采用聚对苯二甲酸-己二酸-丁二醇酯换个生物淀粉相互配合,聚对苯二甲酸-己二酸-丁二醇酯具有高耐热性、韧性和耐疲劳性,生物淀粉能在各种环境下完全降解,最终分解为二氧化碳和水,不会对环境造成任何污染,将聚对苯二甲酸-己二酸-丁二醇酯和生物淀粉混合,得到一种淀粉填充改性的生物可降解聚对苯二甲酸-己二酸-丁二醇酯,克服淀粉吸湿、脆性和难以塑化等缺点,合理控制聚对苯二甲酸-己二酸-丁二醇酯和生物淀粉的含量,加快生物降解速率;同时将聚对苯二甲酸-己二酸-丁二醇酯与聚乳酸配合制成外层膜,将聚对苯二甲酸-己二酸-丁二醇酯和生物淀粉制成内层膜,外层膜和内层膜相互配合,可有助于提高聚乳酸的阻隔性能。
进一步地,所述外层膜由以下质量百分数的组分组成:聚乳酸85-90%,聚对苯二甲酸-己二酸-丁二醇酯10-15%;
中间层由聚氨酯粘胶剂制成;
内层膜由以下质量百分数的组分组成:聚对苯二甲酸-己二酸-丁二醇酯75-85%,生物淀粉15-25%。
通过采用上述技术方案,外层膜和内层膜中原料组分的配比更加精准,使制备的复合膜生物降解速率更快,阻隔性能更好。
进一步地,所述外层膜的厚度为0.015-0.1mm,内层膜的厚度为0.03-0.15mm。
通过采用上述技术方案,外层膜和内层膜厚度适宜,使复合膜的强度、韧性、撕裂强度和阻隔性能较好。
进一步地,所述生物淀粉由以下方法制成:
(1)将甘蔗渣放入与其固液比为1:20-25且浓度为1%的氢氧化钠溶液中搅拌2h,过滤,洗涤,烘干;
(2)将氨基三乙酸用5%的氨水溶解,加入烘干的甘蔗渣和过硫酸铵,在60-65℃下反应1.5-2h,水洗并烘干,氨基三乙酸、甘蔗渣和过硫酸铵的质量比为1:(2-2.2):(0.8-1);
(3)将步骤(2)所得甘蔗渣放入浓度为20-30%的1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的混合溶液中溶解,甘蔗渣与混合溶液的固液比为1:5-8,溶解温度为80-90℃,搅拌1.5-2h,过滤,将滤液倒入与其质量比为1:(0.6-0.9):(0.5-0.8):(0.5-0.7)的玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯中,在35-45℃下混合,制成生物淀粉。
通过采用上述技术方案,甘蔗渣中含有大量的蔗渣纤维,将甘蔗渣用氢氧化钠溶液处理,可消除蔗渣纤维表面的大分子杂质,去除包覆在蔗渣纤维表面的半纤维素、木质素和硅胶等杂质,使蔗渣纤维表面润张膨化,富有光泽,使蔗渣纤维具有较好的界面粘结力,碱处理后的甘蔗渣接枝氨基三乙酸后,增加了含氧官能团,表面粗糙度提高,使得甘蔗渣与玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯的界面结合良好,在承受外界应力时,有效传递外界应力,使复合膜的拉伸性能和断裂伸长率提高,聚丙撑碳酸酯与玉米淀粉、马铃薯淀粉、甘蔗渣协同使用,再与外层膜中的聚乳酸相互配合,可提高复合膜的水蒸气和氧气的阻隔性能。
进一步地,所述聚乳酸的分子量为10-20万,聚对苯二甲酸-己二酸-丁二醇酯的分子量为6-10万。
为实现上述第二个目的,本发明提供了如下技术方案:一种全生物100%全降解复合膜的加工工艺,包括以下步骤:
S1、外层膜制备:将聚乳酸和聚对苯二甲酸-己二醇-丁二醇酯混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成外层膜;
S2、印刷油墨:在外层膜的一侧上印刷所需图案,并烘干;
S3、内层膜制备:将聚对苯二甲酸-己二醇-丁二醇酯和生物淀粉混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成内层膜;
S4、复合:在外层膜印刷图案的一侧上用温度为35-50℃的涂刷辊辊涂一层聚乙烯醇,再用温度为35-50℃的涂刷辊辊涂一层聚氨酯粘胶剂,最后通过温度为35-50℃的热辊将内层膜压合在外层膜辊涂有聚氨酯粘胶剂的一侧上,对成型的复合膜进行冷却、牵引、收卷,制成半成品复合膜;聚乙烯醇的涂覆量为(1.2-2)g/m2,聚氨酯粘胶剂的涂覆量为(1.2-1.5)g/m2;
S5、熟化:将半成品复合膜置于熟化室中,控制熟化温度为35-45℃,熟化时间为12-48h,熟化后制成成品复合膜。
通过采用上述技术方案,工艺过程简单,操作容易,在外层膜和内层膜之间涂覆聚乙烯醇,能够增加复合膜的阻隔性,同时使制备的复合膜耐撕裂、耐拉伸,而且能够完全生物降解,无环境污染。
进一步地,所述步骤S1中吹膜机的各区温度为:一区145-155℃、二区155-165℃、三区160-170℃、四区165-175℃、五区170-180℃、六区170-180℃;步骤S3中吹膜机的各区温度为:一区115-125℃、二区125-130℃、三区125-130℃、四区130-140℃、五区140-150℃、六区150-160℃。
进一步地,所述步骤S4中外层膜和内层膜的贴合压力为0.1-0.8MPa,压合时间为(0.5-1)min/mm。
进一步地,所述步骤S1、步骤S2和步骤S4中牵引速度为100-200m/min,所述步骤S4中外层膜和内层膜的放卷张力为(6-8)kg/m,半成品复合膜的收卷张力为(7-12)kg/m。
为实现上述第三个目的,本发明提供了如下技术方案:一种全生物100%全降解复合膜的应用,所述全生物100%全降解复合膜应用于制备三边封平口袋、三边封自立袋、四边封袋、背封袋和开闭条自立袋。
综上所述,本发明具有以下有益效果:
第一、由于本发明采用聚乳酸和聚对苯二甲酸-己二醇-丁二醇酯制备复合膜的外层膜,采用聚对苯二甲酸-己二醇-丁二醇酯和生物淀粉制备复合膜的内层膜,使用聚氨酯粘胶剂作为中间层,由于可生物降解的聚乳酸成膜性良好,薄膜透明性、刚度和硬度高,添加同样能够生物降解的聚对苯二甲酸-己二醇-丁二醇酯,能够赋予薄膜良好的拉伸性能,使冲击强度、韧性、耐撕裂性能和生物降解速率提高;使用聚对苯二甲酸-己二醇-丁二醇酯和生物淀粉相互配合,提高薄膜的阻隔性和生物降解率。
第二、本发明中优选采用甘蔗渣、玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯制备生物淀粉,经过处理的甘蔗渣表面性能得到改善,与聚丙撑碳酸酯的粘结力提高,将添加有甘蔗渣和聚丙撑碳酸酯的生物淀粉与聚对苯二甲酸-己二醇-丁二醇酯混合,聚丙撑碳酸酯是完全生物降解材料,气密性好,与外层膜中的聚乳酸相互配合,可提高复合膜的阻隔性能和生物降解率,蔗渣纤维能够提高复合膜的拉伸性能和耐撕裂性能。
第三、本发明的发明中,在外层膜上涂刷聚乙烯醇,聚乙烯醇是一种生物可降解高分子材料,且其阻隔性能优异,涂覆在外层膜和内层膜之间,能够增加复合膜的阻隔性。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
生物淀粉的制备例1-3
制备例1-3中甘蔗渣选自广西南宁博冠农业开发有限公司出售的粒径为2-15mm的甘蔗渣,玉米淀粉选自苏州市禾茂化工有限公司出售的型号为HM017的玉米淀粉,马铃薯淀粉选自济南大魁化工有限公司出售的货号为DKHG-MSDF-12的马铃薯淀粉,聚丙撑碳酸酯选自内蒙古蒙西高新材料股份有限公司出售的BioCO2TM100的聚丙撑碳酸酯。
制备例1:(1)将甘蔗渣放入与其固液比为1:20且浓度为1%的氢氧化钠溶液中搅拌2h,过滤,洗涤,烘干;
(2)将氨基三乙酸用5%的氨水溶解,加入烘干的甘蔗渣和过硫酸铵,在60℃下反应1.5h,水洗并烘干,氨基三乙酸、甘蔗渣和过硫酸铵的质量比为1:2:0.8;
(3)将步骤(2)所得甘蔗渣放入浓度为20%的1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的混合溶液中溶解,甘蔗渣与混合溶液的固液比为1:5,1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的质量比为1:1,溶解温度为80℃,搅拌1.5h,过滤,将滤液倒入与其质量比为1:0.6:0.5:0.5的玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯中,在35℃下混合,制成生物淀粉,聚丙撑碳酸酯的玻璃化转变温度为40℃,分子量为20万。
制备例2:(1)将甘蔗渣放入与其固液比为1:23且浓度为1%的氢氧化钠溶液中搅拌2.3h,过滤,洗涤,烘干;
(2)将氨基三乙酸用5%的氨水溶解,加入烘干的甘蔗渣和过硫酸铵,在63℃下反应1.8h,水洗并烘干,氨基三乙酸、甘蔗渣和过硫酸铵的质量比为1:2.1:0.9;
(3)将步骤(2)所得甘蔗渣放入浓度为25%的1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的混合溶液中溶解,甘蔗渣与混合溶液的固液比为1:6.5,1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的质量比为1:1.2,溶解温度为85℃,搅拌1.8h,过滤,将滤液倒入与其质量比为1:0.7:0.6:0.6的玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯中,在40℃下混合,制成生物淀粉,聚丙撑碳酸酯的玻璃化转变温度为45℃,分子量为23万。
制备例3:(1)将甘蔗渣放入与其固液比为1:25且浓度为1%的氢氧化钠溶液中搅拌2.5h,过滤,洗涤,烘干;
(2)将氨基三乙酸用5%的氨水溶解,加入烘干的甘蔗渣和过硫酸铵,在65℃下反应2h,水洗并烘干,氨基三乙酸、甘蔗渣和过硫酸铵的质量比为1:2.2:1;
(3)将步骤(2)所得甘蔗渣放入浓度为30%的1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的混合溶液中溶解,甘蔗渣与混合溶液的固液比为1:8,1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的质量比为1:1.4,溶解温度为90℃,搅拌2h,过滤,将滤液倒入与其质量比为1:0.9:0.8:0.7的玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯中,在45℃下混合,制成生物淀粉,聚丙撑碳酸酯的玻璃化转变温度为50℃,分子量为25万。
实施例
聚乳酸选自金发科技股份出售的型号Flex-262的聚乳酸,聚对苯二甲酸-己二酸-丁二醇酯选自金发科技股份出售的型号Flex-64D的聚对苯二甲酸-己二酸-丁二醇酯、聚氨酯粘胶剂选自万华化学(北京)有限公司出售的型号为6092A的聚氨酯粘胶剂,聚乙烯醇选自深圳市伯顺化工有限公司出售的牌号为2488的聚乙烯醇,玉米淀粉选自苏州市禾茂化工有限公司出售的型号为HM017的玉米淀粉,马铃薯淀粉选自济南大魁化工有限公司出售的货号为DKHG-MSDF-12的马铃薯淀粉。
实施例1:一种全生物100%全降解复合膜,包括外层膜、中间层和内层膜,外层膜和内层膜的原料配比如表1所示,内层膜中生物淀粉由制备例1制成,外层膜的厚度为0.015mm,内层膜的厚度为0.03mm,聚对苯二甲酸-己二酸-丁二醇酯的分子量为6万,聚乳酸的分子量为10万。
该全生物100%全降解复合膜的加工工艺,包括以下步骤:
S1、外层膜制备:将81%聚乳酸和19%聚对苯二甲酸-己二醇-丁二醇酯混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成外层膜;吹膜机的各区温度为:一区145℃、二区155℃、三区160℃、四区165℃、五区170℃、六区170℃,外层膜的牵引速度为100m/min;
S2、印刷油墨:在外层膜的一侧上印刷所需图案,并烘干;
S3、内层膜制备:将71%聚对苯二甲酸-己二醇-丁二醇酯和29%生物淀粉混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成内层膜;吹膜机的各区温度为:一区115℃、二区125℃、三区125℃、四区130℃、五区140℃、六区150℃,内层膜的牵引速度为100m/min;
S4、复合:在外层膜印刷图案的一侧上用温度为35℃的涂刷辊辊涂一层聚乙烯醇,再用温度为35℃的涂刷辊辊涂一层聚氨酯粘胶剂,最后通过温度为35℃的热辊将内层膜压合在外层膜辊涂有聚氨酯粘胶剂的一侧上,对成型的复合膜进行冷却、牵引、收卷,制成半成品复合膜;聚乙烯醇的涂覆量为1.2g/m2,聚氨酯粘胶剂的涂覆量为1.2g/m2,外层膜和内层膜的放卷张力为6kg/m,贴合压力为0.1MPa,压合时间为0.5min/mm,半成品复合膜的收卷张力为7kg/m;S5、熟化:将半成品复合膜置于熟化室中,控制熟化温度为35℃,熟化时间为12h,熟化后制成成品复合膜。
表1实施例1-5中外层膜和内层膜的材料组成
实施例2:一种全生物100%全降解复合膜,包括外层膜、中间层和内层膜,外层膜和内层膜的原料配比如表1所示,内层膜中生物淀粉由制备例2制成,外层膜的厚度为0.35mm,内层膜的厚度为0.06mm,聚对苯二甲酸-己二酸-丁二醇酯的分子量为8万,聚乳酸的分子量为15万。
该全生物100%全降解复合膜的加工工艺,包括以下步骤:
S1、外层膜制备:将85%聚乳酸和15%聚对苯二甲酸-己二醇-丁二醇酯混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成外层膜;吹膜机的各区温度为:一区150℃、二区160℃、三区165℃、四区170℃、五区175℃、六区175℃,外层膜的牵引速度为150m/min;
S2、印刷油墨:在外层膜的一侧上印刷所需图案,并烘干;
S3、内层膜制备:将75%聚对苯二甲酸-己二醇-丁二醇酯和25%生物淀粉混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成内层膜;吹膜机的各区温度为:一区120℃、二区130℃、三区130℃、四区135℃、五区145℃、六区155℃,内层膜的牵引速度为150m/min;
S4、复合:在外层膜印刷图案的一侧上用温度为45℃的涂刷辊辊涂一层聚乙烯醇,再用温度为45℃的涂刷辊辊涂一层聚氨酯粘胶剂,最后通过温度为45℃的热辊将内层膜压合在外层膜辊涂有聚氨酯粘胶剂的一侧上,对成型的复合膜进行冷却、牵引、收卷,制成半成品复合膜;聚乙烯醇的涂覆量为1.6g/m2,聚氨酯粘胶剂的涂覆量为1.4g/m2,外层膜和内层膜的放卷张力为7kg/m,贴合压力为0.4MPa,压合时间为0.8min/mm,半成品复合膜的收卷张力为10kg/m;
S5、熟化:将半成品复合膜置于熟化室中,控制熟化温度为40℃,熟化时间为30h,熟化后制成成品复合膜。
实施例3:一种全生物100%全降解复合膜,包括外层膜、中间层和内层膜,外层膜和内层膜的原料配比如表1所示,内层膜中生物淀粉由制备例3制成,外层膜的厚度为0.58mm,内层膜的厚度为0.09mm,聚对苯二甲酸-己二酸-丁二醇酯的分子量为10万,聚乳酸的分子量为20万。
该全生物100%全降解复合膜的加工工艺,包括以下步骤:
S1、外层膜制备:将90%聚乳酸和10%聚对苯二甲酸-己二醇-丁二醇酯混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成外层膜;吹膜机的各区温度为:一区155℃、二区165℃、三区170℃、四区175℃、五区180℃、六区180℃,外层膜的牵引速度为200m/min;
S2、印刷油墨:在外层膜的一侧上印刷所需图案,并烘干;
S3、内层膜制备:将80%聚对苯二甲酸-己二醇-丁二醇酯和20%生物淀粉混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成内层膜;吹膜机的各区温度为:一区125℃、二区135℃、三区135℃、四区140℃、五区150℃、六区160℃,内层膜的牵引速度为200m/min;
S4、复合:在外层膜印刷图案的一侧上用温度为50℃的涂刷辊辊涂一层聚乙烯醇,再用温度为50℃的涂刷辊辊涂一层聚氨酯粘胶剂,最后通过温度为50℃的热辊将内层膜压合在外层膜辊涂有聚氨酯粘胶剂的一侧上,对成型的复合膜进行冷却、牵引、收卷,制成半成品复合膜;聚乙烯醇的涂覆量为2g/m2,聚氨酯粘胶剂的涂覆量为1.5g/m2,外层膜和内层膜的放卷张力为8kg/m,贴合压力为0.8MPa,压合时间为1min/mm,半成品复合膜的收卷张力为12kg/m;
S5、熟化:将半成品复合膜置于熟化室中,控制熟化温度为45℃,熟化时间为48h,熟化后制成成品复合膜。
实施例4:一种全生物100%全降解复合膜,与实施例1的区别在于,外层膜和内层膜的原料组分、外层膜和内层膜厚度如表1所示,生物淀粉为玉米淀粉,全生物100%全降解复合膜的加工工艺与实施例1相同。
实施例5:一种全生物100%全降解复合膜,与实施例1的区别在于,外层膜和内层膜的原料组分、外层膜和内层膜厚度如表1所示,生物淀粉为马铃薯淀粉,全生物100%全降解复合膜的加工工艺与实施例1相同。
对比例
对比例1-4:一种全生物100%全降解复合膜,与实施例1的区别在于,外层膜中原料组分如表2所示。
对比例5-8:一种全生物100%全降解复合膜,与实施例1的区别在于,内层膜中原料组分如表2所示。
对比例9:以申请号为CN201210289135.5的中国发明专利文件中实施例1制备的PLA/PBAT生物降解复合材料制成的薄膜作为对照,(1)将PLA(4032D)和PBAT于80℃鼓风烘箱中干燥处理12h,碳酸钙于105℃鼓风烘箱中干燥处理6h;(2)然后取90份PLA、10份PBAT、0.04份2,2’-双(2-恶唑啉)、2.4份六亚甲基二异氰酸酯、0.6份硬脂酸钙、0.1份抗氧剂1010、10份碳酸钙于高混机中常温混合5min;(3)将得到的混合物加入到双螺杆机中挤出造粒,双螺杆机各区温度为:一区150℃、二区160℃、三区160℃、四区170℃、五区170℃、六区175℃、机头180℃;螺杆转速为200rpm,长径比L/D=40/1;(4)将步骤(3)得到的粒料于80℃鼓风烘箱中干燥处理12h;(5)将步骤(4)中干燥后的粒料加入到单螺杆机中挤出吹塑,单螺杆机各区温度为:一区120℃、二区140℃、三区160℃、四区170℃、五区170℃、六区170℃、机头165℃;螺杆转速为150rpm,长径比L/D=25/1,单螺杆挤出机的模头口径与泡管直径之比为3:1。
对比例10:以申请号为CN201210553133.2的中国发明专利申请文件中实施例1制备的可塑性淀粉改性PBAT生物全降解材料制成的薄膜作为对照,采用PBAT切片(Mw160000,MI0.5g/10min(150℃,2160g))84wt%,木薯淀粉10wt%,增塑剂总含量为6wt%,其中包括甘油2.4wt%,甲酰胺1.2wt%,尿素2.4wt%;淀粉糊化温度为85℃,双螺杆挤出速率为10r/min;可塑性淀粉与PBAT干燥时真空度为1.3KPa,干燥温度为90℃,保持9小时;熔融共混温度为115℃,挤出速率15r/min。
对比例11:一种全生物100%全降解复合膜,与实施例1的区别在于,以对比例9公开的薄膜作为外层膜,将对比例10公开的降解材料制成内层膜,按照实施例1中的方法制成复合膜。
表2对比例1-4中外层膜和对比例5-8中内层膜的原料配比
应用例:按照实施例1-5和对比例1-9中的方法制备复合膜,并通过裁剪、折叠和封边,制备成规格为650×(370+100×2)×0.045mm的包装袋,每个实施例和对比例均取100个包装袋,并按照以下标准检测各个包装袋的性能,每个实施例或对比例制得的100个包装袋检测结果取平均值,将检测结果记录于表3中。
1、拉伸强度:按照GB13022-1991《塑料薄膜拉伸性能试验方法》进行测试;
2、断裂伸长率:按照GB/T1040.3-2006《塑料拉伸性能的测定第3部分:薄膜和薄片的试验条件》进行测试;
3、水蒸气透过率:按照GB/T21529-2008《塑料薄膜和薄片水蒸气透过率的测定》进行检测;
4、氧气透过率:按照GB/T19789-2005《包装材料塑料薄膜和薄片氧气透过性试验库伦计检测法》进行检测;
5、生物降解率:HJ/T209-2005《环境标志产品技术要求包装制品》进行检测。
表3各实施例和对比例制备的复合膜制成的包装袋的检测结果
由表3中数据可以看出,由实施例1-5中制备的复合膜制成的包装袋无论是横向和纵向拉伸强度均较大,且断裂伸长率高,水蒸气透过率在7.3-11.2%之间,氧气透过率在13.6-32.4%之间,生物降解率在80天即达到67.6-76.5%,在100天时生物降解率接近100%,在110天时,全部完成100%降解,说明由本发明制备的复合膜拉起的拉伸强度和断裂伸长率好,阻隔性能高,能够100%降解,降解时间快。
对比例1因外层膜中聚乳酸含量为70%,聚对苯二甲酸-己二醇-丁二醇酯含量为30%,由检测结果可以看出,与实施例1相比,由对比例1制备的复合膜制成的包装袋力学性能下降,水蒸气透过率和氧气透过率增大,生物降解率变慢,在110天时仅达到92.2%的降解,且降解时间为120天时,降解率不变,说明聚乳酸含量降低,聚对苯二甲酸-己二醇-丁二醇酯含量增大时,复合膜的各项性能会降低。
对比例2因外层膜中聚乳酸含量为75%,聚对苯二甲酸-己二醇-丁二醇酯的含量为25%,由对比例2制成的复合膜制成的包装袋的拉伸强度、断裂伸长率、阻隔性能和生物降解率与实施例1相比明显变差,与对比例1相比,各项性能有所提高,说明增加聚乳酸含量,降低聚对苯二甲酸-己二醇-丁二醇酯含量,能够增加复合膜的拉伸强度、阻隔性能和降解率等性能。
对比例3因外层膜中聚乳酸含量为98%,聚对苯二甲酸-己二醇-丁二醇酯的含量为2%,与实施例1-5相比,聚乳酸含量增加,聚对苯二甲酸-己二醇-丁二醇酯含量降低,由检测数据可以看出,由对比例3制备的复合膜制成的包装袋,拉伸性能和断裂伸长率变差,对于水蒸气和氧气的阻隔性能降低,在110天时,包装袋的降解率仅为94.3%,说明聚乳酸含量增加,聚对苯二甲酸-己二醇-丁二醇酯含量降低时,复合膜包装袋的阻隔性能和生物降解率变差。
对比例4因外层膜中未添加聚对苯二甲酸-己二醇-丁二醇酯,由表3中数据可以看出,对比例4制备的复合膜制成的包装袋,阻隔性能、生物降解率和拉伸性能等均变差,说明聚乳酸和聚对苯二甲酸-己二醇-丁二醇酯二者相互配合,能够提高复合膜的阻隔性和生物降解率等性能。
由对比例1-4中聚对苯二甲酸-己二醇-丁二醇酯和聚乳酸的含量对比可以看出,将聚乳酸添加量控制为80-95%,聚对苯二甲酸-己二醇-丁二醇酯添加量控制为5-20%,可提高包装袋的阻隔性和生物降解率。
对比例5因内层膜中聚对苯二甲酸-己二醇-丁二醇酯添加量为60%,生物淀粉的添加量为40%,生物淀粉的含量增加,由表中数据可以看出,包装袋生物降解率与实施例1-5相差不大,但包装袋的拉伸强度、断裂伸长率和阻隔性能变差。
对比例6因内层膜中聚对苯二甲酸-己二醇-丁二醇酯的含量为65%,生物淀粉的含量为35%,对比例6制备的复合膜制成的包装袋,与实施例1制备的包装袋相比,各项性能变差,与对比例5制备的包装袋相比,各项性能有所改善,说明增加聚对苯二甲酸-己二醇-丁二醇酯含量,降低生物淀粉含量可提高复合膜的阻隔性和降解率。
对比例7因内层膜中聚对苯二甲酸-己二醇-丁二醇酯含量为95%,生物淀粉含量为5%,由检测结果可以看出,增加聚对苯二甲酸-己二醇-丁二醇酯的含量,包装袋的阻隔性能、拉伸性能和生物降解率变差。
对比例8因内层膜中未添加生物淀粉,由检测结果可以看出,未添加生物淀粉制成的包装袋,阻隔性能和生物降解率明显变差,说明生物淀粉和聚对苯二甲酸-己二醇-丁二醇酯相互配合,能够提高复合膜的阻隔性和生物降解速率。
由对比例5-8中聚对苯二甲酸-己二醇-丁二醇酯和生物淀粉的含量可以看出,内层膜中聚对苯二甲酸-己二醇-丁二醇酯的含量为70-90%,生物淀粉含量为10-30%,可提高包装袋的阻隔性和生物降解率。
对比例9和对比例10为现有技术制备的薄膜,对比例11为对比例9中薄膜作为外层膜,对比例10中薄膜作为内层膜制成的复合膜,由表中数据可以看出,对比例9、对比例10和对比例11制备的薄膜拉伸性能、断裂伸长率较好,生物降解率在120天能够接近100%,但阻隔性能较差。
本具体实施例仅仅是对本发明的解释,其并不是对本发明的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本发明的权利要求范围内都受到专利法的保护。
Claims (9)
1.一种全生物100%全降解复合膜,其特征在于,复合膜为三层结构,其中外层膜由以下质量百分数的组分组成:聚乳酸80-95%,聚对苯二甲酸-己二酸-丁二醇酯5-20%;
中间层由聚氨酯粘胶剂制成;
内层膜由以下质量百分数的组分组成:聚对苯二甲酸-己二酸-丁二醇酯70-90%,生物淀粉10-30%;
在外层膜的一侧辊涂一层聚乙烯醇;
所述生物淀粉由以下方法制成:
(1)将甘蔗渣放入与其固液比为1:20-25且浓度为1%的氢氧化钠溶液中搅拌2h,过滤,洗涤,烘干;
(2)将氨基三乙酸用5%的氨水溶解,加入烘干的甘蔗渣和过硫酸铵,在60-65℃下反应1.5-2h,水洗并烘干,氨基三乙酸、甘蔗渣和过硫酸铵的质量比为1:(2-2.2):(0.8-1);
(3)将步骤(2)所得甘蔗渣放入浓度为20-30%的1-丁基-3-甲基咪唑氯盐和1-乙基-3-甲基咪唑醋酸盐的混合溶液中溶解,甘蔗渣与混合溶液的固液比为1:5-8,溶解温度为80-90℃,搅拌1.5-2h,过滤,将滤液倒入与其质量比为1:(0.6-0.9):(0.5-0.8):(0.5-0.7)的玉米淀粉、马铃薯淀粉和聚丙撑碳酸酯中,在35-45℃下混合,制成生物淀粉。
2.根据权利要求1所述的全生物100%全降解复合膜,其特征在于,所述外层膜由以下质量百分数的组分组成:聚乳酸85-90%,聚对苯二甲酸-己二酸-丁二醇酯10-15%;
中间层由聚氨酯粘胶剂制成;
内层膜由以下质量百分数的组分组成:聚对苯二甲酸-己二酸-丁二醇酯75-85%,生物淀粉15-25%。
3.根据权利要求1所述的全生物100%全降解复合膜,其特征在于,所述外层膜的厚度为0.015-0.1mm,内层膜的厚度为0.03-0.15mm。
4.根据权利要求1所述的全生物100%全降解复合膜,其特征在于,所述聚乳酸的分子量为10-20万,聚对苯二甲酸-己二酸-丁二醇酯的分子量为6-10万。
5.一种根据权利要求1-4任一项所述的全生物100%全降解复合膜的加工工艺,其特征在于,包括以下步骤:
S1、外层膜制备:将聚乳酸和聚对苯二甲酸-己二醇-丁二醇酯混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成外层膜;
S2、印刷油墨:在外层膜的一侧上印刷所需图案,并烘干;
S3、内层膜制备:将聚对苯二甲酸-己二醇-丁二醇酯和生物淀粉混合均匀后,用双螺杆挤出机挤出,挤出的母料经吹膜机制成薄膜,经冷却、牵引、收卷,制成内层膜;
S4、复合:在外层膜印刷图案的一侧上用温度为35-50℃的涂刷辊辊涂一层聚乙烯醇,再用温度为35-50℃的涂刷辊辊涂一层聚氨酯粘胶剂,最后通过温度为35-50℃的热辊将内层膜压合在外层膜辊涂有聚氨酯粘胶剂的一侧上,对成型的复合膜进行冷却、牵引、收卷,制成半成品复合膜;聚乙烯醇的涂覆量为(1.2-2)g/m2,聚氨酯粘胶剂的涂覆量为(1.2-1.5)g/m2;
S5、熟化:将半成品复合膜置于熟化室中,控制熟化温度为35-45℃,熟化时间为12-48h,熟化后制成成品复合膜。
6.根据权利要求5所述的全生物100%全降解复合膜的加工工艺,其特征在于,所述步骤S1中吹膜机的各区温度为:一区145-155℃、二区155-165℃、三区160-170℃、四区165-175℃、五区170-180℃、六区170-180℃;步骤S3中吹膜机的各区温度为:一区115-125℃、二区125-130℃、三区125-130℃、四区130-140℃、五区140-150℃、六区150-160℃。
7.根据权利要求5所述的全生物100%全降解复合膜的加工工艺,其特征在于,所述步骤S4中外层膜和内层膜的贴合压力为0.1-0.8MPa,压合时间为(0.5-1)min/mm。
8.根据权利要求5所述的全生物100%全降解复合膜的加工工艺,其特征在于,所述步骤S1、步骤S2和步骤S4中牵引速度为100-200m/min,所述步骤S4中外层膜和内层膜的放卷张力为(6-8)kg/m,半成品复合膜的收卷张力为(7-12)kg/m。
9.一种根据权利要求1-4任一项所述的全生物100%全降解复合膜的应用,其特征在于,所述全生物100%全降解复合膜应用于制备三边封平口袋、三边封自立袋、四边封袋、背封袋和开闭条自立袋。
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