CN116333472A - 一种增容改性聚乳酸/热塑性聚氨酯共混材料 - Google Patents
一种增容改性聚乳酸/热塑性聚氨酯共混材料 Download PDFInfo
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Abstract
本发明公开了一种增容改性聚乳酸/热塑性聚氨酯共混材料及其制备方法，属于聚乳酸生物降解材料技术领域。以聚乳酸二元醇、聚酯多元醇或聚醚多元醇、二异氰酸酯为合成原料，以有机金属为催化剂，合成出一种以异氰酸酯基团封端的聚乳酸聚氨酯嵌段预聚体，将其作为增容剂与聚乳酸和热塑性聚氨酯混炼，制得所述增容改性聚乳酸/热塑性聚氨酯共混材料。本发明制得的增容改性聚乳酸/热塑性聚氨酯共混材料具有高强度、高韧性以及良好的生物相容性和可加工性，而且制备工艺简单，成本较低，安全无毒，可以广泛应用于汽车配件、医疗用品、服装和包装等诸多领域。
Description
技术领域
本发明属于聚乳酸生物降解材料技术领域，具体涉及一种增容改性聚乳酸/热塑性聚氨酯共混材料及其制备方法。
背景技术
近年来，由于石油基聚合物引起的环境保护和能源危机，来源于生物质资源的聚乳酸受到了极大的关注。聚乳酸具有高强度、高硬度、高透明度、生物可降解性和生物相容性，然而聚乳酸固有的脆性、断裂伸长率和冲击强度低等缺点限制了其应用。热塑性聚氨酯具有良好的柔韧性和生物相容性，是一种理想的弹性体材料，可应用于聚乳酸的增韧改性研究。但是聚乳酸与热塑性聚氨酯的相容性较差，需要添加增容剂来对聚乳酸/热塑性聚氨酯共混材料进行增容改性。MDI、TDI等二异氰酸酯可直接作为聚乳酸/热塑性聚氨酯共混的反应增容剂，但二异氰酸酯在使用过程中会对人体产生伤害，而且共混物中残留的二异氰酸酯破坏共混材料的生物相容性。因此，迫切需要开发一种对聚乳酸/热塑性聚氨酯共混材料具有良好增韧效果且使用安全的增容剂。
发明内容
本发明的目的在于提供一种增容改性聚乳酸/热塑性聚氨酯共混材料及其制备方法，制得的增容改性聚乳酸/热塑性聚氨酯共混材料具有高强度、高韧性以及良好的生物相容性和可加工性，而且制备工艺简单，成本较低，安全无毒，应用领域广泛。
为实现上述目的，本发明采用如下技术方案：
一种增容改性聚乳酸/热塑性聚氨酯共混材料的制备方法包括以下步骤：
（1）将1-10质量份的聚酯多元醇或聚醚多元醇100-120℃脱水处理，加入0.5-5质量份的二异氰酸酯、0.01-0.02质量份的有机金属催化剂和10-40质量份的溶剂，60-100℃下反应1-3小时，得到异氰酸酯基团封端的预聚体；加入0.5-5质量份的聚乳酸二元醇反应1-3小时，60-80℃真空干燥24小时，得到聚乳酸聚氨酯嵌段预聚体；
（2）将30-60质量份的聚乳酸和5-20质量份的热塑性聚氨酯60-80℃干燥24小时，加入0.5-5质量份的聚乳酸聚氨酯嵌段预聚体，混合均匀；
（3）将步骤（2）的混合物在温度170-200℃、转速30-60 r/min下共混5-15分钟，将共混物注塑成型，制得增容改性聚乳酸/热塑性聚氨酯共混材料。
步骤（1）中的聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯多元醇、聚己内酯二元醇中的任意一种或几种；聚醚多元醇为聚丙二醇、聚四氢呋喃多元醇中的任意一种或几种；二异氰酸酯为4,4’-二环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的任意一种或几种；有机金属催化剂为有机锡、有机铋、铋锌合金催化剂中的任意一种或几种，如辛酸亚锡、二月桂酸二丁基锡、2-乙基己酸铋、新癸酸铋；溶剂为丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、氯仿中的任意一种或几种。
本发明将合成的聚乳酸聚氨酯嵌段预聚体对聚乳酸/热塑性聚氨酯进行增容改性。在进行增容过程中，根据相似相容原理，聚乳酸段可以融入到聚乳酸里，聚氨酯段可以融入到热塑性聚氨酯中，使得聚乳酸聚氨酯嵌段预聚体位于分散相和连续相的界面，有效提高聚乳酸/热塑性聚氨酯共混材料的相容性。
相对于现有的技术，本发明的有益效果在于：
（1）本发明采用聚乳酸二元醇与聚酯多元醇合成聚乳酸聚氨酯嵌段预聚体，其中既有与聚乳酸相容的聚乳酸段，又有与热塑性聚氨酯相容的聚氨酯段，可以更好地与聚乳酸/热塑性聚氨酯共混材料相似相容。
（2）本发明中二异氰酸酯的摩尔量大于聚酯多元醇和聚乳酸二元醇总摩尔量的两倍，合成的聚乳酸聚氨酯嵌段预聚体以异氰酸酯封端，异氰酸酯端基在混炼时可以进一步与聚乳酸和热塑性聚氨酯反应，在两相界面原位生成共聚物，显著改善界面相容性。
（3）本发明合成聚乳酸聚氨酯嵌段预聚体时，因为反应温度较高，过量的二异氰酸酯会与预聚体反应生成少量脲基甲酸酯而使预聚体支化，然后异氰酸酯封端的支化预聚体在混炼时会和聚乳酸和热塑性聚氨酯发生反应，产生一定程度的交联，进而提高聚乳酸/热塑性聚氨酯共混材料的力学性能和界面相容性。
（4）本发明制备的聚乳酸聚氨酯嵌段预聚体增容改性后的聚乳酸/热塑性聚氨酯共混材料具有良好的冲击强度和断裂伸长率，制备工艺简单，成本较低，安全无毒。
附图说明
图1为实施例1增容改性后的聚乳酸/热塑性聚氨酯共混材料断口的扫描电子显微镜图。
图2为对比例1的聚乳酸/热塑性聚氨酯共混材料断口的扫描电子显微镜图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
（1）将5 g的聚碳酸酯多元醇在110℃脱水后加入反应器，然后加入1.771g的4,4’-二环己基甲烷二异氰酸酯、0.01 g的二月桂酸二丁基锡、23.7 g的N,N-二甲基甲酰胺，90℃下反应2小时，得到异氰酸酯基团封端的预聚体，然后加入1 g的聚乳酸二元醇反应2小时，然后将产物倒入聚四氟乙烯的模具中，在真空60℃干燥24小时得到聚乳酸聚氨酯嵌段预聚体；
（2）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，然后取2.4 g的聚乳酸聚氨酯嵌段预聚体与烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（3）将（2）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得增容改性后的聚乳酸/热塑性聚氨酯共混材料。
对比例1
（1）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（2）将（1）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得聚乳酸/热塑性聚氨酯共混材料。
实施例2
（1）将5 g的聚碳酸酯多元醇在110℃脱水后加入反应器，然后加入1.771 g的4,4′-二苯基甲烷二异氰酸酯、0.01 g的二月桂酸二丁基锡、23.7 g的N,N-二甲基甲酰胺，90℃下反应2小时，得到异氰酸酯基团封端的预聚体，然后加入1 g的聚乳酸二元醇反应2小时，然后将产物倒入聚四氟乙烯的模具中，在真空60℃干燥24小时得到聚乳酸聚氨酯嵌段预聚体；
（2）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，然后取1.8 g的聚乳酸聚氨酯嵌段预聚体与烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（3）将（2）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得增容改性后的聚乳酸/热塑性聚氨酯共混材料。
实施例3
（1）将5 g的聚己内酯二元醇在110℃脱水后加入反应器，然后加入2.3612 g的4,4’-二环己基甲烷二异氰酸酯、0.01 g的二月桂酸二丁基锡、23.7 g的N,N-二甲基甲酰胺，70℃下反应2小时，得到异氰酸酯基团封端的预聚体，然后加入2.5 g的聚乳酸二元醇反应2小时，然后将产物倒入聚四氟乙烯的模具中，在真空60℃干燥24小时得到聚乳酸聚氨酯嵌段预聚体；
（2）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，然后取1.8 g的聚乳酸聚氨酯嵌段预聚体与烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（3）将（2）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得增容改性后的聚乳酸/热塑性聚氨酯共混材料。
实施例4
（1）将5 g的聚碳酸酯多元醇在110℃脱水后加入反应器，然后加入2.1644g的4,4’-二环己基甲烷二异氰酸酯、0.01 g的二月桂酸二丁基锡、23.7 g的N,N-二甲基甲酰胺，90℃下反应2小时，得到异氰酸酯基团封端的预聚体，然后加入1.25g的聚乳酸二元醇反应2小时，然后将产物倒入聚四氟乙烯的模具中，在真空60℃干燥24小时得到聚乳酸聚氨酯嵌段预聚体；
（2）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，然后取1.8 g的聚乳酸聚氨酯嵌段预聚体与烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（3）将（2）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得增容改性后的聚乳酸/热塑性聚氨酯共混材料。
实施例5
（1）将5 g的聚丙二醇在110℃脱水后加入反应器，然后加入1.7660g的六亚甲基二异氰酸酯、0.01 g的二月桂酸二丁基锡、37g的氯仿，60℃下反应2小时，得到异氰酸酯基团封端的预聚体，然后加入5 g的聚乳酸二元醇反应2小时，然后将产物倒入聚四氟乙烯的模具中，在真空60℃干燥24小时得到聚乳酸聚氨酯嵌段预聚体；
（2）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，然后取1.8 g的聚乳酸聚氨酯嵌段预聚体与烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（3）将（2）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得增容改性后的聚乳酸/热塑性聚氨酯共混材料。
实施例6
（1）将5 g的聚己二酸丁二醇酯二元醇在110℃脱水后加入反应器，然后加入2.7547 g的4,4’-二环己基甲烷二异氰酸酯、0.01 g的二月桂酸二丁基锡、23.7 g的N,N-二甲基甲酰胺，80℃下反应2小时，得到异氰酸酯基团封端的预聚体，然后加入5 g的聚乳酸二元醇反应2小时，然后将产物倒入聚四氟乙烯的模具中，在真空60℃干燥24小时得到聚乳酸聚氨酯嵌段预聚体；
（2）将48 g的聚乳酸和12 g的热塑性聚氨酯在60℃烘箱中烘24小时，然后取1.8 g的聚乳酸聚氨酯嵌段预聚体与烘干后的聚乳酸和热塑性聚氨酯混合均匀；
（3）将（2）中混合物一起加入扭矩流变仪的密炼室中，温度设置为180℃，转速40r/min，共混10分钟，称取10 g共混后的物料加入微型注塑机中注塑成型，制得增容改性后的聚乳酸/热塑性聚氨酯共混材料。
性能测试
对上述实施例和对比例进行力学性能的测量和扫描电子显微镜的表征，力学性能结果列于表1。
1. 对聚乳酸/热塑性聚氨酯共混材料进行了拉伸性能测试，每根样条为哑铃型，哑铃型样条的厚度是2mm，窄部分宽度是5mm，将拉力机夹具间的初始距离调至40mm，以20mm/min的速率进行拉伸性能测试。重复测定五次，取三组接近的数据计算平均值。
2. 对聚乳酸/热塑性聚氨酯共混材料进行了冲击性能测试，每个样品厚度4mm，长度80mm，宽度10mm，中间缺口深2mm，重复测定五次，取三组接近的数据计算平均值。
由表1可以看出，相对于对比例1不添加聚乳酸聚氨酯嵌段预聚体，本发明添加聚乳酸聚氨酯嵌段预聚体后，可以大幅度提升聚乳酸/热塑性聚氨酯共混材料的断裂伸长率和冲击强度，说明改善了聚乳酸与热塑性聚氨酯的界面相容性，其原因是聚乳酸聚氨酯嵌段预聚体中既含有聚乳酸又含有聚氨酯，可以分别与聚乳酸和热塑性聚氨酯相似相容，而且聚乳酸聚氨酯嵌段预聚体的异氰酸酯端基可以进一步与聚乳酸和热塑性聚氨酯反应，在两相界面原位生成共聚物，显著改善界面相容性。聚乳酸聚氨酯嵌段预聚体位于两相界面，在应力下可以在聚乳酸基质中引发多重银纹耗散能量，并防止银纹发展成破坏性裂纹，从而显著提高共混材料的韧性。
从图1和图2可以看出，对比例1的断口中有许多海岛状粗糙结构，而且断痕清晰规整，这表明聚乳酸与热塑性聚氨酯的界面相互作用较差，共混材料存在明显的微相分离。随着聚乳酸聚氨酯嵌段预聚体的添加，实施例1的断口具有一定程度的拉伸，断痕柔和且形态多样，说明聚乳酸聚氨酯嵌段预聚体对聚乳酸和热塑性聚氨酯有良好的增容作用。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (6)
1.一种增容改性聚乳酸/热塑性聚氨酯共混材料的制备方法，其特征在于：包括以下步骤：
（1）将1-10质量份的聚酯多元醇或聚醚多元醇100-120℃脱水处理，加入0.5-5质量份的二异氰酸酯、0.01-0.02质量份的有机金属催化剂和10-40质量份的溶剂，60-100℃下反应1-3小时，得到异氰酸酯基团封端的预聚体；加入0.5-5质量份的聚乳酸二元醇反应1-3小时，60-80℃真空干燥24小时，得到聚乳酸聚氨酯嵌段预聚体；
（2）将30-60质量份的聚乳酸和5-20质量份的热塑性聚氨酯60-80℃干燥24小时，加入0.5-5质量份的聚乳酸聚氨酯嵌段预聚体，混合均匀；
（3）将步骤（2）的混合物在温度170-200℃、转速30-60 r/min下共混5-15分钟，将共混物注塑成型，制得增容改性聚乳酸/热塑性聚氨酯共混材料。
2.根据权利要求1所述的方法，其特征在于：步骤（1）中的聚酯多元醇为聚己二酸丁二醇酯二元醇、聚碳酸酯多元醇、聚己内酯二元醇中的任意一种或几种；聚醚多元醇为聚丙二醇、聚四氢呋喃多元醇中的任意一种或几种。
3.根据权利要求1所述的方法，其特征在于：步骤（1）中的二异氰酸酯为4,4’-二环己基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的任意一种或几种。
4.根据权利要求1所述的方法，其特征在于：步骤（1）中的有机金属催化剂为有机锡、有机铋、铋锌合金催化剂中的任意一种或几种。
5.根据权利要求1所述的方法，其特征在于：步骤（1）中的溶剂为丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、氯仿中的任意一种或几种。
6.一种如权利要求1-5任一种方法制得的增容改性聚乳酸/热塑性聚氨酯共混材料。
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