CN112143043A - 一种发泡生物降解树脂及其生产工艺 - Google Patents
一种发泡生物降解树脂及其生产工艺 Download PDFInfo
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Abstract
本发明公开了一种发泡生物降解树脂,按照重量百分比计,所述发泡生物降解树脂包含以下原料组分且各组分含量为:PLA 40~60%,热塑性淀粉10~30%,组合发泡剂8~16%,可降解辅助材料10~18%,扩链剂1~3%,以及交联剂1~3%。本发明还公开了该发泡生物降解树脂的生产工艺。本发明的发泡生物降解树脂性能良好,具有优良的耐温性、生物降解性和发泡倍率。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种发泡生物降解树脂及其生产工艺。
背景技术
聚乳酸(PLA)是一种以可再生的植物资源为原料,经过化学合成制备的生物降解高分子,聚乳酸能够同普通高分子一样进行各种成型加工,如挤出、流延成膜、吹塑、注塑、吹瓶、纤维成型等;另外,聚乳酸还具有独特的生物相容性和生物降解性,因此,作为一种生物降解高分子材料,聚乳酸已成为高分子学术界和产业界关注的热点。
聚乳酸(PLA)发泡材料能够取代石油基发泡塑料应用于包装和生活消费品领域。同时聚乳酸发泡材料的应用也受到两大问题的制约:一是室温脆性、韧性差、热稳定性差等缺点,表现为制品因冲击韧性差而不能作为缓冲材料;二是熔融温度低,普通聚乳酸的熔融温度只有150℃左右,软化温度不超过90℃,大大限制了聚乳酸发泡材料的应用。尽管聚乳酸发泡材料具有许多优良的性能,但是在加工过程中还存在一些问题,PLA属于结晶型聚合物,结晶速率较慢,耐热性不好,熔体强度不高,在发泡过程中,无法维持泡孔形态,容易出现泡孔塌陷合并,并且由于其加工的不稳定性(如热降解、氧化、水解等),容易造成分子链断裂,使熔体强度进一步降低,这些都是不利于发泡的,这些都可以通过添加发泡剂优化其工艺。
例如,申请号为CN201010150150.2的中国发明专利公开了一种全生物降解高韧性耐热型聚乳酸树脂及其制备方法,该聚乳酸树脂包括聚乳酸树脂、聚丁二酸丁二醇酯、过氧化二异丙苯和甲基丙烯酸缩水甘油酯;聚乳酸树脂的重均分子量为8~13万,聚丁二酸丁二醇酯的重均分子量为7~11万;以重量份数计,聚乳酸树脂和聚丁二酸丁二醇酯的总和为100份,其中聚乳酸树脂为70~90份,聚丁二酸丁二醇酯为10~30份;过氧化二异丙苯为0.1~1份;甲基丙烯酸缩水甘油酯为1~10份。
又如,申请号为CN201910994881.6的中国发明专利公开了一种组合发泡聚乳酸耐热阻燃改性材料和产品的制备方法,按照重量份配比称取阻燃剂、扩链剂、过氧化物、天然植物油精制的脂肪酰胺类化合物、改性剂、可降解辅助材料、聚乳酸树脂、成核剂;制备方法为将上述原料按配方在混料机中混合,混合物在双螺杆挤出机160~210℃下熔融反应挤出得到聚乳酸阻燃改性母粒,可进一步通过各种塑料加工方式,将得到的聚乳酸阻燃改性母粒和复配化学发泡剂混合后,配合超临界流体发泡剂输送装置注入复配物理发泡剂,规模化加工成产品即可。
现有的发泡PLA基本是由PLA直接与相关发泡剂等物质加工后得到的,此类的产品在稳定性和降解性能方面有待提高。本发明人基于从事此类产品设计制造多年丰富的实务经验及专业知识,并配合学理的运用,积极加以研究创新,以期创设一种发泡生物降解树脂及其生产工艺,能够改进一般现有的发泡PLA类产品,使其性能更加优越。经过不断的研究、设计,并经反复试作及改进后,终于创设出确具实用价值的本发明。
发明内容
本发明的主要目的在于针对现有技术中存在的缺点,提供一种发泡生物降解树脂。本发明的发泡生物降解树脂具有良好的韧性和稳定性,并且降解性能好,是一种环保无污染的材料。
本发明的目的及解决其技术问题是采用以下技术方案来实现的。
本发明提供了一种发泡生物降解树脂,按照重量百分比计,所述发泡生物降解树脂包含以下原料组分且各组分含量为:PLA 40~60%,热塑性淀粉10~30%,组合发泡剂8~16%,可降解辅助材料10~18%,扩链剂1~3%,以及交联剂1~3%。
前述的发泡生物降解树脂,其中,按照重量百分比计,所述发泡生物降解树脂包含以下原料组分且各组分含量为:PLA 50%,热塑性淀粉20%,组合发泡剂12%,可降解辅助材料14%,扩链剂2%,以及交联剂2%。
前述的发泡生物降解树脂,其中,所述热塑性淀粉密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%。
前述的发泡生物降解树脂,其中,所述组合发泡剂为复配化学发泡剂和复配物理发泡剂,所述复配化学发泡剂选自偶氮二甲酰胺、偶氮二甲酰胺和碳酸氢钠及柠檬酸的复配聚合物母粒、偶氮二甲酰胺和碳酸氢钠的复配聚合物母粒、改性碳酸氢钠和柠檬酸的复配聚合物母粒中的一种或两种以上的混合物;所述复配物理发泡剂为氮气、二氧化碳中的两种的混合物。
前述的发泡生物降解树脂,其中,所述可降解辅助材料选自聚己内酯、聚羟基脂肪酸酯、聚乙醇酸、木质素、淀粉、草纤维纤维素中的一种或两种以上的混合物。
前述的发泡生物降解树脂,其中,所述扩链剂为环氧官能化ADR扩链剂。
前述的发泡生物降解树脂,其中,所述交联剂选自聚乙二醇、三羟甲基丙烷、聚丙二醇缩水甘油醚中的一种。
本发明的目的及解决其技术问题还通过采用以下技术方案来实现。
本发明提供了一种发泡生物降解树脂的生产工艺,包括以下步骤:
(1)将PLA溶于有机溶剂中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA;
(2)将上述步骤得到的改性PLA、扩链剂和可降解辅助材料按照比例配置混合均匀后在50~70℃下烘8~12h,然后加入相应比例的交联剂和热塑性淀粉经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒;
(3)将上述步骤得到的生物降解树脂母粒和复配化学发泡剂在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入复配物理发泡剂,即得发泡生物降解树脂。
前述的生产工艺,其中,所述有机溶剂选自二氯甲烷或者三氯甲烷。
前述的生产工艺,其中,所述复配化学发泡剂占所述组合发泡剂总质量的70~80%,所述复配物理发泡剂占所述组合发泡剂总质量的20~30%。
借由上述技术方案,本发明至少具有下列优点:本发明在制备发泡生物降解树脂前,通过将PLA溶于有机溶剂中然后加入强酸进行PLA的改性,能够更好的与扩链剂作用,能够提高改性后的PLA力学性能,最后通过交联剂和热塑性淀粉的作用,能够改善聚乳酸的力学性能、加工性能或功能化。在另一个方面,本发明的发泡剂为组合形式的,包括复配物理发泡剂和复配化学发泡剂,与现有的发泡剂相比,本发明以复配化学发泡剂为主要发泡剂,辅以复配物理发泡剂,这样的组合方式能够使生物降解树脂发泡效果达到最优,得到的PLA发泡制品的泡孔密度明显提高,发泡倍率增加,表观密度低,泡体结构和发泡倍率优于以物理发泡剂为主要并辅以化学发泡剂的组合方式。
综上所述,本发明特殊的发泡生物降解树脂可完全降解,且韧性好。其具有上述诸多的优点及实用价值,并在同类产品和方法中未见有类似的设计公开发表或使用而确属创新,其不论在方法上或功能上皆有较大的改进,在技术上有较大的进步,并产生了好用及实用的效果,且较现有的产品具有增进的多项功效,从而更加适于实用,而具有产业的广泛利用价值,诚为一新颖、进步、实用的新设计。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例详细说明如后。
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,下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
将50份PLA溶于二氯甲烷中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA。取得到的改性PLA与2份环氧官能化ADR扩链剂和14份聚己内酯混合均匀后在60℃下烘10h,然后加入聚乙二醇2份和热塑性淀粉(密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%)20份经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒。将得到的生物降解树脂母粒和9份偶氮二甲酰胺和碳酸氢钠的复配聚合物母粒在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入3份氮气和二氧化碳的混合物,即得发泡生物降解树脂。
实施例2
将40份PLA溶于二氯甲烷中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA。取得到的改性PLA与2份环氧官能化ADR扩链剂和18份聚己内酯混合均匀后在60℃下烘10h,然后加入三羟甲基丙烷2份和热塑性淀粉(密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%)25份经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒。将得到的生物降解树脂母粒和10份改性碳酸氢钠和柠檬酸的复配聚合物母粒在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入3份氮气和二氧化碳的混合物,即得发泡生物降解树脂。
实施例3
将50份PLA溶于二氯甲烷中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA。取得到的改性PLA与3份环氧官能化ADR扩链剂和18份聚乙醇酸混合均匀后在60℃下烘10h,然后加入聚乙二醇3份和热塑性淀粉(密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%)10份经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒。将得到的生物降解树脂母粒和12份改性碳酸氢钠和柠檬酸的复配聚合物母粒在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入4份氮气和二氧化碳的混合物,即得发泡生物降解树脂。
实施例4
将60份PLA溶于二氯甲烷中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA。取得到的改性PLA与2份环氧官能化ADR扩链剂和10份淀粉混合均匀后在50℃下烘12h,然后加入聚乙二醇2份和热塑性淀粉(密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%)16份经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒。将得到的生物降解树脂母粒和7份偶氮二甲酰胺和碳酸氢钠的复配聚合物母粒在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入3份氮气和二氧化碳的混合物,即得发泡生物降解树脂。
实施例5
将40份PLA溶于二氯甲烷中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA。取得到的改性PLA与2份环氧官能化ADR扩链剂和10份聚乙醇酸混合均匀后在70℃下烘8h,然后加入三羟甲基丙烷2份和热塑性淀粉(密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%)30份经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒。将得到的生物降解树脂母粒和12份改性碳酸氢钠和柠檬酸的复配聚合物母粒在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入4份氮气和二氧化碳的混合物,即得发泡生物降解树脂。
对比实施例1
将50份PLA与2份环氧官能化ADR扩链剂和14份聚己内酯混合均匀后在60℃下烘10h,然后加入聚乙二醇2份和热塑性淀粉(密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%)20份经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒。将得到的生物降解树脂母粒和9份偶氮二甲酰胺和碳酸氢钠的复配聚合物母粒在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入3份氮气和二氧化碳的混合物,即得发泡生物降解树脂。
试验例1发泡生物降解树脂的性能测试
将实施例1-5和对比实施例1得到的发泡生物降解树脂制成注塑成型产品并进行耐温性,注塑制品发泡倍率和生物降解性能进行测定,其中注塑制品发泡倍率按照GB1033-26的方法进行表观密度的测定,然后按照发泡倍率=聚合物树脂密度/发泡后泡沫表观密度计算得到;生物降解性能按照GB/T20197、欧盟EN13432、美国暗示他们400等执行,结果见表1。
表1实施例1~5及对比实施例1的树脂性能检测汇总
由表1可以看出,本发明的PLA经过改性后得到的树脂性能良好,即具有优良的耐温性、生物降解性和发泡倍率,较之对比实施例1具有很大的提升,说明经过改性后的PLA能够更加适合与发泡剂,扩链剂等作用,从而得到性能良好的树脂材料。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的方法及技术内容作出些许的更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
1.一种发泡生物降解树脂,按照重量百分比计,所述发泡生物降解树脂包含以下原料组分且各组分含量为:PLA 40~60%,热塑性淀粉10~30%,组合发泡剂8~16%,可降解辅助材料10~18%,扩链剂1~3%,以及交联剂1~3%。
2.根据权利要求1所述的发泡生物降解树脂,其中,按照重量百分比计,所述发泡生物降解树脂包含以下原料组分且各组分含量为:PLA 50%,热塑性淀粉20%,组合发泡剂12%,可降解辅助材料14%,扩链剂2%,以及交联剂2%。
3.根据权利要求1所述的发泡生物降解树脂,其中,所述热塑性淀粉密度:1.2g/cm3,融熔指数:1-3g/10min(190℃/2.16kg),可挥发物<0.3%。
4.根据权利要求1所述的发泡生物降解树脂,其中,所述组合发泡剂为复配化学发泡剂和复配物理发泡剂,所述复配化学发泡剂选自偶氮二甲酰胺、偶氮二甲酰胺和碳酸氢钠及柠檬酸的复配聚合物母粒、偶氮二甲酰胺和碳酸氢钠的复配聚合物母粒、改性碳酸氢钠和柠檬酸的复配聚合物母粒中的一种或两种以上的混合物;所述复配物理发泡剂为氮气、二氧化碳中的两种的混合物。
5.根据权利要求1所述的发泡生物降解树脂,其中,所述可降解辅助材料选自聚己内酯、聚羟基脂肪酸酯、聚乙醇酸、木质素、淀粉、草纤维纤维素中的一种或两种以上的混合物。
6.根据权利要求1所述的发泡生物降解树脂,其中,所述扩链剂为环氧官能化ADR扩链剂。
7.根据权利要求1所述的发泡生物降解树脂,其中,所述交联剂选自聚乙二醇、三羟甲基丙烷、聚丙二醇缩水甘油醚中的一种。
8.一种发泡生物降解树脂的生产工艺,包括以下步骤:
(1)将PLA溶于有机溶剂中然后滴加硝酸溶液并在不高于60℃下进行氧化预处理,然后调节溶液pH至6~8,然后冷却至室温,蒸发掉溶剂从而得到改性PLA;
(2)将上述步骤得到的改性PLA、扩链剂和可降解辅助材料按照比例配置混合均匀后在50~70℃下烘8~12h,然后加入相应比例的交联剂和热塑性淀粉经混料机混合均匀后,加入双螺杆挤压机中,在高温高剪切共混挤压模口后拉条风冷送切粒机切粒,得到生物降解树脂母粒;
(3)将上述步骤得到的生物降解树脂母粒和复配化学发泡剂在混料机中混合,通过釆用发泡片材机组生产线或注塑机组生产线,配合超临界流体发泡剂输送装置注入复配物理发泡剂,即得发泡生物降解树脂。
9.根据权利要求8所述的生产工艺,其中,所述有机溶剂选自二氯甲烷或者三氯甲烷。
10.根据权利要求8所述的生产工艺,其中,所述复配化学发泡剂占所述组合发泡剂总质量的70~80%,所述复配物理发泡剂占所述组合发泡剂总质量的20~30%。
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