CN102268144B - 生物可降解的聚乳酸-淀粉耐热复合材料及其制备方法 - Google Patents
生物可降解的聚乳酸-淀粉耐热复合材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种生物可降解聚乳酸-淀粉耐热复合材料及其制备方法，它由以下组分的原料按重量份数组成：天然淀粉20～80份、聚乳酸10～70份、聚乙烯醇1～10份、增塑剂1～5份、水1～10份、耐热改性剂1～5份、成核剂1～5份、相容剂1～5份、交联剂1～5份。其制备过程包括原料混合、挤出成粒、γ射线辐射等过程。本发明复合材料具有良好的力学性能，拉伸强度20～35MPa，断裂伸长率10～20%，热变形温度90～120℃；同时具有良好的环境降解性能，并且成型加工性能良好，可在普通塑料的加工设备上通过挤出、注塑、热压等方法成型为各种各样的制品。
Description
技术领域
本发明涉及高分子材料加工领域，具体地涉及一种耐热型生物可降解的聚乳酸-淀粉复合材料及其制备方法。
背景技术
大量性能优异、价格低廉的普通石化塑料制品，已严重污染了人类的生存环境，同时全球石油资源日益枯竭，使得利用可再生资源制备能够生物可降解的材料是解决环境和能源问题的必然选择，而且近年来也成为许多国家和企业研发和关注的焦点，一些生物可降解的材料不断涌现。
现有的完全生物降解材料中，来源于天然资源的聚乳酸和淀粉由于其自身的优点格外引人关注。淀粉作为天然高分子，具有来源广、价格低、可完全生物降解和再生周期短的优点，但淀粉是多羟基聚合物，本身不具备热塑性。聚乳酸是淀粉发酵衍生物，来源于可再生资源，国内外已有规模化的工业产品，作为新型的线性脂肪族聚酯，其具有良好的降解性、热塑加工性能和良好的生物相容性。但是其力学性能为质硬而韧性较差，缺乏弹性和柔性，热变形温度低，仅55～60℃，非常容易完全变形。另外生产成本也比传统塑料高，与淀粉相容性差，这也限制了它的应用。
国内外现有的聚乳酸-淀粉共混改性的报道，主要涉及力学性能的提高，对于聚乳酸的耐高温性，只有少量新闻报道，尚未见公开的技术方案。现有的一些耐热级聚乳酸及其它生物质塑料价格较高，不具有日常应用的优势，无法大规模生产。专利CN1793229A公开了一种以聚乳酸为载体、通过对聚乳酸、淀粉、无机粉体、植物纤维分别进行改性，然后在挤出机上造粒制得可完全降解的材料，克服了聚乳酸的低温脆性，也大大降低了成本，但并没有解决聚乳酸的不耐高温性的问题。专利CN101343406A以聚乳酸、淀粉为主要原料，通过改性淀粉、改性聚乳酸、并添加各种助剂，制备了耐温型聚乳酸-淀粉合金全生物降解材料，但耐温性仅提高到85℃，仍然不能用于制造饭盘、汤碗、杯子等需要耐热温度高的制品。
发明内容
本发明所要解决的技术问题是提供一种力学性能和生物降解性能优异且价格较低的耐热高分子复合材料。
本发明所要解决的另一技术问题是提供上述高分子复合材料的制备方法。
本发明的聚乳酸-淀粉生物可生物降解的耐热高分子复合材料，所述聚乳酸-淀粉耐热复合材料为白色或淡黄色固体，其拉伸强度20～35MPa，断裂伸长率10～20％，热变形温度90～120℃，由以下组分的原料按重量份数混合制备而成：天然淀粉20～80份、聚乳酸10～70份、聚乙烯醇1～10份、增塑剂1～5份、水1～10份、耐热改性剂1～5份、成核剂1～5份、相容剂1～5份、交联剂1～5份。
本发明的生物可降解的聚乳酸-淀粉耐热复合材料，其所述的天然淀粉选自玉米淀粉、高粱淀粉、小麦淀粉、大麦淀粉、黑麦淀粉、木薯淀粉、甘薯淀粉、马铃薯淀粉、竹芋淀粉、糯米淀粉、粳米淀粉、籼米淀粉、山药淀粉、绿豆淀粉、蚕豆淀粉、豌豆淀粉、豇豆淀粉、百合淀粉、西米淀粉。
优选的，所述的聚乳酸内消旋的含量重量份数低于5％，粘均分子量为10～30万。
所述的增塑剂为甘油、乙二醇、山梨醇、木糖醇、麦芽糖醇、二甘醇、聚乙二醇、脂肪酸单甘酯或尿素中的一种或多种。
所述耐热改性剂为α甲基苯乙烯基聚合物、热畸变改性剂中的一种。所述α甲基苯乙烯基聚合物如美国康普顿公司的Blendex 587S或日本宇菱通株式会社的S700N。热畸变改性剂，如美国杜邦公司的Biomax Thermal 300。
所述的成核剂选自芳基磷酸酯铝盐、黏土、云母、碳酸钙、二氧化硅、滑石、植物纤维中的一种或多种。所述芳基磷酸酯铝盐如日本旭化成公司的ADK Stab Na-21。
所述的相容剂为马来酸酐接枝共聚物，优选为苯乙烯-马来酸酐共聚物中的一种，所述苯乙烯-马来酸酐共聚物如上海事必达石化高技术有限公司的SMA。
所述的交联剂选自过氧化二异丙苯DCP、过氧化苯甲酰BPO、二叔丁基过氧化物DTBP中的一种。
本发明所述的生物可降解聚乳酸-淀粉耐热复合材料的制备方法，包括以下步骤：
(1)将20～80份的淀粉、1～10份的聚乙烯醇、1～5份的增塑剂和1～10份的水按配比加入到带有强力循环的高速混合机中，在50-70℃搅拌混合均匀，降温出料，待用；
(2)将步骤(1)所得原料、10～70份的聚乳酸、1～5份的成核剂、1～5份的耐热改性剂、1～5份的相容剂、1～5份的交联剂加入高速混合机中，在50℃-70℃混合均匀，干燥，得到混合物；
(3)将上述混合物加入到双螺杆挤出机中，在所述双螺杆挤出机的各区段温度为140～180℃，各区段真空度为0.03～0.06兆帕的条件下将上述得到的混合物挤出造粒；
(4)利用γ射线将该粒料辐射60～70KGy，即得所述生物可降解的聚乳酸-淀粉复合材料。
优选的，在所述步骤(3)中，所述双螺杆挤出机的各区段温度分别为140～150℃、150～165℃、165～170℃、170～180℃、160～170℃，模头区温度为150～160℃。
本发明制备的生物可降解聚乳酸-淀粉耐热复合材料，呈白色或淡黄色固体，具有下列特点：
a、良好的力学性能和耐热性能。其拉伸强度20～35MPa，断裂伸长率10～20％，热变形温度90～120℃。
b、生物可降解。本发明制备的生物可降解聚乳酸-淀粉耐热复合材料，12周堆肥后生物降解率为90％以上。
c、成型加工性能良好。本发明制备的生物可降解聚乳酸-淀粉耐热复合材料，熔体流动速率为5～15g/10min(190℃，2.16kg)，可在普通塑料的加工设备上通过挤出、注塑、热压等方法成型为各种各样的制品。
具体实施方式
以下结合实施例对本发明作进一步描述。
实施例1：
按重量将20份的玉米淀粉、1份的聚乙烯醇、1份的麦芽糖醇和1份的水按配比加入到带有强力循环的高速混合机中，在55℃搅拌20min，混合均匀，降温出料。
将上述所得混合物、70份的聚乳酸、1份的ADK Stab Na-21、2份的Biomax Thermal300、3份的SMA、1份的过BPO加入高速混合机中，在50℃混合均匀，干燥，得到混合物，
然后将上述混合物加入到双螺杆挤出机中，在长径比为35∶1，螺杆转速200-300转/分钟，各区段温度分别为150℃、165℃、170℃、180℃、170℃、160℃，各区段的真空度在0.03兆帕的条件下将上述得到的混合物挤出造粒，
再利用γ射线将该粒料辐射70KGy。
所得复合材料的拉伸强度为30MPa，断裂伸长率18％，热变形温度105℃，熔体流动速率为11g/10min(190℃，2.16kg)，成型加工性能良好，可在普通塑料的加工设备上通过挤出、注塑、热压等方法成型为各种各样的制品。
实施例2～16加工过程与实施例1相同，区别在于配方、加工条件及所得复合材料的性能不同，分别如下表所示：
实施例2～4表
实施例5～7表
实施例8～10表
实施例11～13表
实施例14～16表
实施例1～16所得复合材料，均按美国ASTM D6400标准所述方法对生物降解性进行了测试，测试结果表明本发明制备的生物可降解聚乳酸-淀粉耐热复合材料，12周堆肥后生物降解率均在90％以上。
Claims (7)
1.一种生物可降解的聚乳酸-淀粉耐热复合材料，其特征在于，所述聚乳酸-淀粉耐热复合材料为白色或淡黄色固体，其拉伸强度20～35MPa，断裂伸长率10～20%，热变形温度90～120℃,由以下组分的原料按重量份数混合制备而成：天然淀粉20～80份、聚乳酸10～70份、聚乙烯醇1～10份、增塑剂1～5份、水1～10份、耐热改性剂1～5份、成核剂1～5份、相容剂1～5份、交联剂1～5份；所述的聚乳酸内消旋的含量重量份数低于5%，粘均分子量为10～30万；所述耐热改性剂为α甲基苯乙烯基聚合物、热畸变改性剂中的一种。
2.根据权利要求1所述的生物可降解的聚乳酸-淀粉耐热复合材料，其特征在于，所述的增塑剂为甘油、乙二醇、山梨醇、木糖醇、麦芽糖醇、二甘醇、聚乙二醇、脂肪酸单甘酯或尿素中的一种或多种。
3.根据权利要求1所述的生物可降解的聚乳酸-淀粉耐热复合材料，其特征在于，所述的成核剂选自芳基磷酸酯铝盐、黏土、云母、碳酸钙、二氧化硅、滑石、植物纤维中的一种或多种。
4.根据权利要求1所述的生物可降解的聚乳酸-淀粉耐热复合材料，其特征在于，所述的相容剂为马来酸酐接枝共聚物中的一种。
5.根据权利要求1所述的生物可降解的聚乳酸-淀粉耐热复合材料，其特征在于，所述交联剂选自过氧化二异丙苯DCP、过氧化苯甲酰BPO、二叔丁基过氧化物DTBP中的一种。
6.一种权利要求1-5之一所述的生物可降解的聚乳酸-淀粉耐热复合材料的制备方法，其特征在于，包括以下步骤：
（1）将20～80份的淀粉、1～10份的聚乙烯醇、1～5份的增塑剂和1～10份的水按配比加入到带有强力循环的高速混合机中，在50-70℃搅拌混合均匀，降温出料，待用；
（2）将步骤（1）所得原料、10～70份的聚乳酸、1～5份的成核剂、1～5份的耐热改性剂、1～5份的相容剂、1～5份的交联剂加入高速混合机中，在50℃-70℃混合均匀，干燥，得到混合物；
（3）将上述混合物加入到双螺杆挤出机中，在所述双螺杆挤出机的各区段温度为140～180℃，各区段真空度为0.03～0.06兆帕的条件下将上述得到的混合物挤出造粒；
（4）利用γ射线将该粒料辐射60～70KGy，即得所述生物可降解的聚乳酸-淀粉复合材料。
7.根据权利要求6所述的生物可降解的聚乳酸-淀粉耐热复合材料的制备方法，其特征在于，在所述步骤（3）中，所述双螺杆挤出机的各区段温度分别为140～150℃、150～165℃、165～170℃、170～180℃、160～170℃，模头区温度为150～160℃。
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Denomination of invention: Biodegradable polylactic acid-starch thermal-resistance composite material and preparation method thereof Effective date of registration: 20200709 Granted publication date: 20130515 Pledgee: Guanggu Branch of Wuhan Rural Commercial Bank Co.,Ltd. Pledgor: WU HAN HUA LI ENVIRONMENT PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2020420000042 |
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Denomination of invention: Biodegradable polylactic acid starch heat resistant composite and its preparation method Effective date of registration: 20220722 Granted publication date: 20130515 Pledgee: Guanggu Branch of Wuhan Rural Commercial Bank Co.,Ltd. Pledgor: WU HAN HUA LI ENVIRONMENT PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2022420000230 |
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