CN113637302A - 一种改性生物降解聚乳酸发泡粒子及其制备工艺 - Google Patents
一种改性生物降解聚乳酸发泡粒子及其制备工艺 Download PDFInfo
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Abstract
本发明涉及发泡粒子技术领域,且公开了一种改性生物降解聚乳酸发泡粒子,包括以下重量配比的组分:PLA20‑85%,淀粉30‑85%,成核剂1‑5%,抗氧化剂0.1‑0.3%,增容剂1‑5%,一种改性生物降解聚乳酸发泡粒子的制备工艺,通过塑性淀粉以较大的组分比引入PLA树脂,并能保证改性PLA材料综合性能满足应用需求,大大降低PLA发泡珠粒的生产成本,同时采用纳米黏土/纳米分子筛/纳米炭黑作为发泡混合成核剂,促进PLA发泡珠粒泡孔均匀,与纳米粒子进一步增强PLA与塑性淀粉之间作用力,提升发泡制备力学强度,进而采用超临界CO2和水蒸气作为混合发泡介质,成本低,制备过程无污染,操作简单,便于大规模生产,使得制备的PLA发泡粒子完全可降解,无残留,生物相容性好。
Description
技术领域
本发明涉及发泡粒子领域,具体为一种改性生物降解聚乳酸发泡粒子及其制备工艺。
背景技术
聚乳酸是一种热塑性脂肪族聚酯,具有良好的力学性能、加工性能、透明性和独特的阻隔性能。PLA主要通过丙交酯开环聚合得到,来源于可再生资源如小麦、玉米、谷物、稻杆等中的淀粉和糖类。PLA使用废弃后完全可生物降解,最终分解产物为二氧化碳和水,不会对环境产生任何污染,是被广泛关注的绿色环保材料,有望替代传统石油基塑料被广泛应用于各个领域。近年来,聚乳酸发泡材料成为发泡材料领域研究的热点,有望广泛的用于日用品和包装等领域,取代传统的石油基泡沫塑料,解决困扰多年的“白色污染”问题。
然而,PLA的分子链呈现半刚性,导致其熔体强度低、结晶速率慢,可发泡性差,成核位点少,一般需要先对PLA进行增强改性。目前提高PLA发泡能力的方法主要有如下几种:一是在PLA中加入另外一种聚合物形成聚合物共混物,第二组分加入会在一定程度上改善聚乳酸的发泡性能;二是改变PLA 分子链结构,如通过加入扩链剂和交联剂交联;三是加入填料,同时填料的加入能够增强PLA泡沫的机械性能。
但是常规改性和填料的加入可能对PLA可降解性产生不利影响,并且PLA 本身成核效果差,导致泡孔均匀性差,降低材料的力学性能,而PLA树脂较高的成本进一步减少发泡材料的应用范围。
发明内容
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种改性生物降解聚乳酸发泡粒子及其制备工艺,具备了快速降解与发泡过程异相成核和泡孔均匀性的优点,解决了常规改性和填料的加入可能对PLA可降解性产生不利影响,并且PLA 本身成核效果差,导致泡孔均匀性差,降低材料的力学性能,而PLA树脂较高的成本进一步减少发泡材料的应用范围的问题。
(二)技术方案
为实现上述可以彻底驱除甲醛的目的,本发明提供如下技术方案:一种改性生物降解聚乳酸发泡粒子,包括以下重量配比的组分:
PLA----------------------20%-85%;
淀粉------------------30%-85%;
成核剂----------------------1%-5%;
抗氧化剂------------------------0.1%-0.3%;
增容剂--------------------1%-5%。
进一步的,所述PLA20%、淀粉71%、成核剂4.9%、抗氧化剂0.1%、增容剂4%。
进一步的,所述PLA50%、淀粉45%、成核剂3%、抗氧化剂0.2%、增容剂 1.8%。
进一步的,所述PLA85%、淀粉13%、成核剂1%、抗氧化剂0.3%、增容剂 0.7%。
进一步的,所述塑性淀粉内PLA树脂占比大于其他材料。
进一步的,所述成核剂采用纳米黏土、纳米分子筛和纳米炭黑作合成。
进一步的,混合发泡介质超以临界CO2和水蒸气为主。
一种改性生物降解聚乳酸发泡粒子的制备工艺,包括以下步骤:
S1、将PLA树脂、塑性淀粉、相容剂、纳米黏土/纳米分子筛/纳米炭黑 (其中两种种或者多种)、抗氧化剂按照一定重量比通过双螺杆挤出机混合,温度175-215℃,转速40-90r/min,然后通过热切过程制备PLA共混粒料。在175-215℃温度范围内,各个组分均能够混合均匀,获得PLA增强预发泡共混材料;
S2、将一定量PLA预发泡共混粒料置于高压反应釜中,注入一定量水,作为预发泡剂,闭合反应釜后,通过超临界CO2发泡,制备低成本改性PLA 发泡粒子;
S3、其中发泡温度可取180-230℃,压力可控制在1-20MPa,发泡时间 1-20min,在该温度范围范围内,PLA熔融,超临界CO2和水蒸气可充分溶胀改性PLA,通过泄压发泡,然后冷却定型获得PLA发泡粒子。可通过发泡条件的控制实现发泡倍率的调控。
(三)有益效果
与现有技术相比,本发明提供了一种改性生物降解聚乳酸发泡粒子及其制备工艺,具备以下有益效果:
1、一种改性生物降解聚乳酸发泡粒子及其制备工艺,塑性淀粉以较大的组分比引入PLA树脂,并能保证改性PLA材料综合性能满足应用需求,大大降低PLA发泡珠粒的生产成本。
2、一种改性生物降解聚乳酸发泡粒子及其制备工艺,采用纳米黏土/纳米分子筛/纳米炭黑作为发泡混合成核剂,成核效率更高,促进PLA发泡珠粒泡孔均匀。
3一种改性生物降解聚乳酸发泡粒子及其制备工艺,纳米粒子进一步增强 PLA与塑性淀粉之间作用力,提升发泡制备力学强度。
4一种改性生物降解聚乳酸发泡粒子及其制备工艺,采用超临界CO2和水蒸气作为混合发泡介质,成本低,制备过程无污染,操作简单,便于大规模生产。
5一种改性生物降解聚乳酸发泡粒子及其制备工艺,制备的PLA发泡粒子完全可降解,无残留,生物相容性好。
附图说明
图1为本发明的原理图。
具体实施方式
下面将结合本发明的实施例,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做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例一:
请参阅图1,一种改性生物降解聚乳酸发泡粒子,包括以下重量配比的组分:
PLA----------------------20%;
淀粉------------------71%;
成核剂----------------------4.9%;
抗氧化剂------------------------0.1%;
增容剂--------------------4%。
基于一种改性生物降解聚乳酸发泡粒子对此提出了一种发泡粒子的制备工艺,包括以下步骤:
S1、将PLA树脂、塑性淀粉、相容剂、纳米黏土/纳米分子筛/纳米炭黑 (其中两种种或者多种)、抗氧化剂按照一定重量比通过双螺杆挤出机混合,温度175℃,转速40r/min,然后通过热切过程制备PLA共混粒料。在175℃温度范围内,各个组分均能够混合均匀,获得PLA增强预发泡共混材料;
S2、将一定量PLA预发泡共混粒料置于高压反应釜中,注入一定量水,作为预发泡剂,闭合反应釜后,通过超临界CO2发泡,制备低成本改性PLA 发泡粒子;
S3、其中发泡温度可取180℃,压力可控制在1MPa,发泡时间1min。在该温度范围范围内,PLA熔融,超临界CO2和水蒸气可充分溶胀改性PLA,通过泄压发泡,然后冷却定型获得PLA发泡粒子,可通过发泡条件的控制实现发泡倍率的调控。
实施例二:
请参阅图1,一种改性生物降解聚乳酸发泡粒子,包括以下重量配比的组分:
PLA----------------------50%;
淀粉------------------45%;
成核剂----------------------3%;
抗氧化剂------------------------0.2%;
增容剂--------------------1.8%。
基于一种改性生物降解聚乳酸发泡粒子对此提出了一种发泡粒子的制备工艺,包括以下步骤:
S1、将PLA树脂、塑性淀粉、相容剂、纳米黏土/纳米分子筛/纳米炭黑 (其中两种种或者多种)、抗氧化剂按照一定重量比通过双螺杆挤出机混合,温度200℃,转速60r/min,然后通过热切过程制备PLA共混粒料,在195℃温度范围内,各个组分均能够混合均匀,获得PLA增强预发泡共混材料;
S2、将一定量PLA预发泡共混粒料置于高压反应釜中,注入一定量水,作为预发泡剂,闭合反应釜后,通过超临界CO2发泡,制备低成本改性PLA 发泡粒子;
S3、其中发泡温度可取210℃,压力可控制在10MPa,发泡时间10min。在该温度范围范围内,PLA熔融,超临界CO2和水蒸气可充分溶胀改性PLA,通过泄压发泡,然后冷却定型获得PLA发泡粒子,可通过发泡条件的控制实现发泡倍率的调控。
实施例三:
请参阅图1,一种改性生物降解聚乳酸发泡粒子,包括以下重量配比的组分:
PLA----------------------85%;
淀粉------------------13%;
成核剂----------------------1%;
抗氧化剂------------------------0.3%;
增容剂--------------------0.7%。
基于一种改性生物降解聚乳酸发泡粒子对此提出了一种发泡粒子的制备工艺,包括以下步骤:
S1、将PLA树脂、塑性淀粉、相容剂、纳米黏土/纳米分子筛/纳米炭黑 (其中两种种或者多种)、抗氧化剂按照一定重量比通过双螺杆挤出机混合,温度215℃,转速90r/min,然后通过热切过程制备PLA共混粒料,在215℃温度范围内,各个组分均能够混合均匀,获得PLA增强预发泡共混材料;
S2、将一定量PLA预发泡共混粒料置于高压反应釜中,注入一定量水,作为预发泡剂,闭合反应釜后,通过超临界CO2发泡,制备低成本改性PLA 发泡粒子;
S3、其中发泡温度可取230℃,压力可控制在20MPa,发泡时间20min。在该温度范围范围内,PLA熔融,超临界CO2和水蒸气可充分溶胀改性PLA,通过泄压发泡,然后冷却定型获得PLA发泡粒子,可通过发泡条件的控制实现发泡倍率的调控。
本发明的有益效果是:塑性淀粉的引入极大降低PLA发泡粒子成本;完全可降解,无残留;纳米黏土/纳米分子筛/纳米炭黑作为混合成核剂提升PLA 发泡过程异相成核和泡孔均匀性;纳米粒子进一步增强PLA和塑性淀粉之间的作用力;超临界CO2和水蒸气作为混合发泡介质,无残留,无污染,操作简单。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (8)
1.一种改性生物降解聚乳酸发泡粒子,其特征在于,包括以下重量配比的组分:
PLA----------------------20%-85%;
淀粉------------------30%-85%;
成核剂----------------------1%-5%;
抗氧化剂------------------------0.1%-0.3%;
增容剂--------------------1%-5%。
2.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于:所述PLA20%、淀粉71%、成核剂4.9%、抗氧化剂0.1%、增容剂4%。
3.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于:所述PLA50%、淀粉45%、成核剂3%、抗氧化剂0.2%、增容剂1.8%。
4.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于:所述PLA85%、淀粉13%、成核剂1%、抗氧化剂0.3%、增容剂0.7%。
5.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于:所述塑性淀粉内PLA树脂占比大于其他材料。
6.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于:所述成核剂采用纳米黏土、纳米分子筛和纳米炭黑作合成。
7.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于:混合发泡介质超以临界CO2和水蒸气为主。
8.根据权利要求1所述的一种改性生物降解聚乳酸发泡粒子,其特征在于,该发泡粒子制作工艺,包括以下步骤:
S1、将PLA树脂、塑性淀粉、相容剂、纳米黏土/纳米分子筛/纳米炭黑(其中两种种或者多种)、抗氧化剂按照一定重量比通过双螺杆挤出机混合,温度175-215℃,转速40-90r/min,然后通过热切过程制备PLA共混粒料,在175-215℃温度范围内,各个组分均能够混合均匀,获得PLA增强预发泡共混材料;
S2、将一定量PLA预发泡共混粒料置于高压反应釜中,注入一定量水,作为预发泡剂,闭合反应釜后,通过超临界CO2发泡,制备低成本改性PLA发泡粒子;
S3、其中发泡温度可取180-230℃,压力可控制在1-20MPa,发泡时间1-20min,在该温度范围范围内,PLA熔融,超临界CO2和水蒸气可充分溶胀改性PLA,通过泄压发泡,然后冷却定型获得PLA发泡粒子。可通过发泡条件的控制实现发泡倍率的调控。
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