CN114213697B - 一种高强聚乳酸微孔泡沫材料及其制备方法 - Google Patents

一种高强聚乳酸微孔泡沫材料及其制备方法 Download PDF

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CN114213697B
CN114213697B CN202111457385.0A CN202111457385A CN114213697B CN 114213697 B CN114213697 B CN 114213697B CN 202111457385 A CN202111457385 A CN 202111457385A CN 114213697 B CN114213697 B CN 114213697B
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赵晓文
叶林
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Abstract

本发明公开一种高强聚乳酸微孔泡沫材料及其制备方法，其特点是首先通过分子设计，采用简便高效的大分子反应性加工方法将具有较低熔点及良好生物可降解性的聚合物链节引入聚乳酸分子链，制备长链支化聚乳酸基嵌段聚合物，在增加聚乳酸分子缠结程度的同时形成具有熔点差异的两相分离结构；在此基础上，利用固相热拉伸联合超临界CO2发泡技术，通过调控发泡温度(低熔点相熔点附近)远低于拉伸取向温度(介于聚乳酸相与低熔点相熔点之间)，从而使嵌段聚合物分子在取向‑发泡过程中形成并保持高度取向结晶结构而获得高强聚乳酸微孔泡沫材料。

Description

一种高强聚乳酸微孔泡沫材料及其制备方法
技术领域
本发明涉及一种高强聚乳酸微孔泡沫材料及其制备方法，属于生物可降解泡沫材料和高分子材料加工技术领域。
背景技术
聚合物泡沫材料具有质轻、比强度高、能量吸收性优异等特点而广泛应用于建筑、包装和运输等领域。目前常用的聚合物泡沫材料，如聚苯乙烯(PS)、聚丙烯(PP)等，多以石油基聚合物为基体材料，该类材料难于降解且回收困难，其过度使用引发了一系列石油化工能源危机及生态环境问题。为代替石油基聚合物泡沫材料，实现绿色可持续经济发展，生物可降解聚合物发泡材料的研究引起了广泛关注。
聚乳酸(PLA)是一种可生物降解的脂肪族聚酯，来源于玉米、木薯、高粱等可再生资源，由于其优异的力学性能、良好的生物相容性及加工性能，被认为是最有希望替代石油基聚合物的材料。然而，由于其线性分子结构和缓慢的结晶动力学，聚乳酸在加工温度下通常表现出较低的粘弹性，在发泡过程中，易发生泡孔并聚和破裂，对泡孔生长和泡孔均匀性产生不利影响。CN200310110047.5以异氰酸酯作为扩链剂，通过反应性熔融加工及高温化学发泡制备了抗拉强度为3.6～12.8MPa，断裂伸长率为3.3～5.5％的聚乳酸泡沫材料；CN202010086835.9利用纤维素纳米纤维作为成核剂以改善聚乳酸的结晶性能与熔体强度，进一步采用超临界流体作为发泡剂，通过注塑发泡成型获得密度为0.05～0.7g/cm3的聚乳酸发泡材料；CN201410691587.5以羟基戊酸酯作为增韧剂、以二异氰酸酯及丁二醇作为交联剂、以滑石粉或蒙脱石作为成核剂，采用AC发泡剂在挤出过程中对聚乳酸进行发泡，制得具有较好韧性的聚乳酸泡沫材料，其冲击韧性达3.7～6.7KJ/m2，断裂伸长率达56～91％。然而，上述普通改性方法虽能在一定程度上改善聚乳酸的发泡行为及泡沫体力学性能，但增强效果仍较为有限，难以实现其力学强度成倍提升。
发明内容
本发明的目的是提供一种高强聚乳酸微孔泡沫材料及其制备方法，其特点是以多官能团环氧化合物联合多官能团酸酐或多官能团异氰酸酯化合物作为支化改性剂，并选择熔点(Tm2)远低于聚乳酸熔点(Tm1)的生物可降解聚合物链节作为共聚单元，通过简便易行的反应性加工方法制备具有长链支化结构的聚乳酸基嵌段聚合物，在增加聚乳酸分子缠结程度的同时，形成具有熔点差异的两相分离结构；进一步采用固相热拉伸技术，通过施加拉伸应力场诱导嵌段聚合物分子形成大量取向微纤化结晶结构，随后以CO2作为发泡剂，采用超临界二氧化碳(sc-CO2)发泡技术，对其进行发泡处理，利用聚乳酸相与低熔点聚合物相两相间存在熔点差异，调控其固相热拉伸温度介于两相熔点之间(Tm2～Tm1)，而发泡温度在低熔点相的熔点(Tm2)附近，以防止拉伸取向后材料内部高熔点聚乳酸相在随后超临界CO2发泡过程中解取向的发生，保持其稳定取向结晶结构，同时发泡剂CO2又可在处于熔融态的低熔点相内形成快速溶解与扩散，进而获得具有高发泡倍率、且泡壁聚合物分子呈高度取向结晶结构的高强聚乳酸微孔泡沫材料。
本发明的目的由以下技术措施实现，其中所述原料分数除特殊说明外，均为重量份数。
高度取向微纤化聚乳酸基嵌段聚合物的制备：
将0.05～5份多官能环氧化合物、0.05～5份多官能酸酐化合物、0.05～5份多官能异氰酸酯化合物、5～40份低熔点可降解聚合物与100份聚乳酸一起加入密炼机中，于150～220℃下反应5～60min，得到具有长链支化结构的聚乳酸基嵌段聚合物；
将聚乳酸基嵌段聚合物进行压制成型，制成尺寸为30×5×1mm3的样片，压制温度为150～220℃，压制压力为5～20MPa，然后将样片固定在可控温调速的拉伸装置上，于60～120℃下恒温5～60min后进行拉伸取向，拉伸速率为5～1000mm/min，待拉伸倍率达到4-12倍后停止拉伸、冷却、卸载、取样，得到取向试样；
其中，所述多官能环氧化合物为乙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、丙三醇三缩水甘油醚、季戊四醇四缩水甘油醚、间苯二酚缩甲醛四缩水甘油醚中的任一种；
所述多官能酸酐化合物为均苯四酸二酐、3,3',4,4'-联苯四酸二酐、3,3',4,4'-二苯醚四酸二酐、3,3',4,4'-二苯甲酮四酸二酐中的任一种；
所述多官能异氰酸酯化合物为1,6-己二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、L-赖氨酸二异氰酸酯及L-赖氨酸三异氰酸酯中的任一种；
所述低熔点可降解聚合物为聚己内酯、聚乙二醇、聚对二氧环己酮、聚丁二酸丁二醇酯中的任一种。
取向微纤化聚乳酸基嵌段聚合物的发泡成型：
将取向微纤化聚乳酸基嵌段聚合物试样置于10～60℃的高压发泡釜中并向釜体内充入CO2，使釜内压力达5～18MPa并保持0.5～2h，随后快速泄压，取出样品并迅速冷却，得到高强聚乳酸泡沫。
当聚乳酸基嵌段聚合物在固相热拉伸过程中拉伸倍率达到8倍时，由本发明制备的高强聚乳酸微孔泡沫，其平均泡孔尺寸<10μm，拉伸强度及模量可分别达20～60MPa及0.1～1.5GPa。
本发明具有如下优点
本发明针对高强聚乳酸泡沫材料的制备难点，首先通过分子设计研究制备具有熔点差异两相分离结构及长链支化结构的聚乳酸基嵌段聚合物，在此基础上，利用固相拉伸联合超临界CO2发泡技术获得泡壁聚合物具有高度取向微纤化结晶结构的高强聚乳酸微孔泡沫材料，其优势如下：
·采用简便高效的大分子反应性加工方法将具有较低熔点及良好生物可降解性的聚合物链节引入聚乳酸分子链，制备长链支化聚乳酸基嵌段聚合物，构筑具有熔点差异的两相分离结构。一方面，聚乳酸相与低熔点聚合物相两相间的熔点差异有利于调控其在固相热拉伸及超临界CO2发泡加工过程中的加工温度，使其固相热拉伸温度介于两相熔点之间，而发泡温度在低熔点聚合物相的熔点附近，不仅可有效防止热拉伸取向后材料内部高熔点聚乳酸相在随后超临界CO2发泡过程中解取向的发生，保持其稳定取向结晶结构，同时发泡剂CO2又可在处于熔融态的低熔点相内形成快速扩散与溶解，提高材料内部CO2溶解度，提升泡沫发泡倍率；
·聚乳酸基嵌段聚合物长链支化结构的形成可显著增强其分子缠结程度，赋予其“应变硬化”拉伸流变特性及高熔体强度，有利于提高其在固相热拉伸取向过程中的拉伸倍率，防止材料过早断裂，实现聚合物分子高度取向；同时高熔体强度亦可提高材料在发泡过程中泡孔生长的稳定性，减少发泡过程中的泡孔破裂、塌陷，有利于促使材料形成均匀泡孔结构；
·本发明所制备的高强聚乳酸泡沫材料不存在共混、填充改性等外增强(如玻纤、碳纤、无机纳米粒子增强)材料中普遍存在的界面问题，增强效果更加显著，且密度低、质轻、方便回收，具有完全生物可降解性。
具体实施方式
下面通过实施例对本发明进行具体的描述，有必要在此指出的是本实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容对本发明做出一些非本质的改进和调整。
实施例1
将0.5份乙二醇二缩水甘油醚、0.25份均苯四酸二酐、0.25份1,6-己二异氰酸酯、10份聚己内酯与100份聚乳酸一起加入密炼机中，于170℃下反应20min，得到具有长链支化结构的聚乳酸基嵌段聚合物；将聚乳酸基嵌段聚合物进行压制成型，制成尺寸为30×5×1mm3的样片，压制温度为170℃，压制压力为10MPa，然后将样片固定在可控温调速的拉伸装置上，于70℃下恒温10min，随后进行拉伸取向，拉伸速率为10mm/min，待拉伸倍率达6时，停止拉伸、冷却、卸载、取样，得到取向试样；
将取向试样置于30℃的高压发泡釜中并向釜体内充入CO2，使釜内压力达10MPa并保持0.5h，随后快速泄压，取出样品并迅速冷却，得到高强聚乳酸泡沫。
实施例2
将1份1,4-丁二醇二缩水甘油醚、0.5份3,3',4,4'-联苯四酸二酐、0.5份4,4’-二环己基甲烷二异氰酸酯、20份聚乙二醇与100份聚乳酸一起加入密炼机中，于190℃下反应30min，得到具有长链支化结构的聚乳酸基嵌段聚合物；将聚乳酸基嵌段聚合物进行压制成型，制成尺寸为30×5×1mm3的样片，压制温度为190℃，压制压力为15MPa，然后将样片固定在可控温调速的拉伸装置上，于90℃下恒温20min，随后进行拉伸取向，拉伸速率为100mm/min，待拉伸倍率达8时，停止拉伸、冷却、卸载、取样，得到取向试样；
将取向试样置于40℃的高压发泡釜中并向釜体内充入CO2，使釜内压力达15MPa并保持1h，随后快速泄压，取出样品并迅速冷却，得到高强聚乳酸泡沫。
实施例3
将5份季戊四醇四缩水甘油醚、2.5份3,3',4,4'-二苯甲酮四酸二酐、2.5份L-赖氨酸二异氰酸酯、40份聚对二氧环己酮与100份聚乳酸一起加入密炼机中，于220℃下反应60min，得到具有长链支化结构的聚乳酸基嵌段聚合物；将聚乳酸基嵌段聚合物进行压制成型，制成尺寸为30×5×1mm3的样片，压制温度为220℃，压制压力为20MPa，然后将样片固定在可控温调速的拉伸装置上，于110℃下恒温60min，随后进行拉伸取向，拉伸速率为500mm/min，待拉伸倍率达10时，停止拉伸、冷却、卸载、取样，得到取向试样；
将取向试样置于50℃的高压发泡釜中并向釜体内充入CO2，使釜内压力达18MPa并保持2h，随后快速泄压，取出样品并迅速冷却，得到高强聚乳酸泡沫。

Claims (1)

1.一种高强聚乳酸微孔泡沫材料的制备方法， 包括高度取向微纤化聚乳酸基嵌段聚合物制备及发泡成型两个步骤；
其中，高度取向微纤化聚乳酸基嵌段聚合物的制备方法包括以下步骤：
将0.05～5份多官能环氧化合物、0.05～5份多官能酸酐化合物、0.05～5份多官能异氰酸酯化合物、5～40份低熔点可降解聚合物与100份聚乳酸一起加入密炼机中，于150～220℃下反应5～60min，得到具有长链支化结构的聚乳酸基嵌段聚合物；
将聚乳酸基嵌段聚合物进行压制成型，制成尺寸为30×5×1mm3的样片，压制温度为150～220℃，压制压力为5～20MPa，然后将样片固定在可控温调速的拉伸装置上，于60～120℃下恒温5～60min后进行拉伸取向，拉伸速率为5～1000mm/min，待拉伸倍率达到4-12倍后停止拉伸、冷却、卸载、取样，得到取向试样；
所述多官能环氧化合物为乙二醇二缩水甘油醚、1,4-丁二醇二缩水甘油醚、丙三醇三缩水甘油醚、季戊四醇四缩水甘油醚、间苯二酚缩甲醛四缩水甘油醚中的任一种；
所述多官能酸酐化合物为均苯四酸二酐、3,3',4,4'-联苯四酸二酐、3,3',4,4'-二苯醚四酸二酐、3,3',4,4'-二苯甲酮四酸二酐中的任一种；
所述多官能异氰酸酯化合物为1,6-己二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、L-赖氨酸二异氰酸酯及L-赖氨酸三异氰酸酯中的任一种；
所述低熔点可降解聚合物为聚己内酯、聚乙二醇、聚对二氧环己酮、聚丁二酸丁二醇酯中的任一种；
发泡成型方法包括以下步骤：
将取向微纤化聚乳酸基嵌段聚合物试样置于10～60℃的高压发泡釜中并向釜体内充入CO2，使釜内压力达5～18MPa并保持0.5～2h，随后快速泄压，取出样品并迅速冷却，得到高强聚乳酸泡沫。
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