CN103642109B - 光热协同可控降解高分子复合母料及其制备方法 - Google Patents

光热协同可控降解高分子复合母料及其制备方法 Download PDF

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CN103642109B
CN103642109B CN201310575268.3A CN201310575268A CN103642109B CN 103642109 B CN103642109 B CN 103642109B CN 201310575268 A CN201310575268 A CN 201310575268A CN 103642109 B CN103642109 B CN 103642109B
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罗学刚
李科
林晓艳
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Southwest University of Science and Technology
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Abstract

本发明公开了一种光热协同可控降解高分子复合母料及其制备方法。它的各组分重量份配比为：光热敏催化剂0.5～4份、高分子材料80～95份、抗氧剂0.1～2份、偶联剂0.025～0.2份；它是将金属氧化物混合磨细，经高温烧结制得光热敏催化剂；用偶联剂将光热敏催化剂进行表面活化；然后与抗氧剂和高分子材料预混，再经双螺杆挤出机挤出、冷却、造粒得到的。本发明产品以不同比例添加到合成高分子中可以调控降解诱导期，扩展应用范围。

Description

光热协同可控降解高分子复合母料及其制备方法
技术领域
本发明涉及高分子材料，特别涉及光热协同可控降解高分子复合母料及其制备方法。
背景技术
合成高分子如塑料已经应用到了国民经济各部门以及人民生活的各个领域，成为我们生活中不可或缺的一部分。与此同时，塑料的稳定性和耐久性也因技术进步而被持续改善，可抵御许多来自环境的影响，大量塑料废弃物使昔日“白色革命”演变成日益严重的“白色污染”。众所周知，合成高分子材料是具有一定的环境降解性，它在光、热、水、气和微生物的共同作用下可以部分降解。依据任何高分子材料的物理、化学性能的变化都归因于其自身存在的环境因素，诸如光、热、湿、化学条件及生物影响的原理，降解塑料应运而生。降解塑料是一种新型功能材料，从世界范围来看，该技术在不断发展，用途在不断开拓。根据降解机理，降解塑料可大致分为：光降解塑料、生物降解塑料、光/生物降解塑料、热氧化降解或由这4种组合而成的环境降解塑料。
目前对合成高分子降解较为成熟的是光催化降解技术，其机理是光催化剂价带上的电子受到大于其禁带宽度能量的光照射时，会被激发跃迁到导带上，并在价带上留下相应的空穴，产生的电子-空穴对一般有皮秒级的寿命，足以使光生电子和光生空穴对经由禁带，向来自溶液或气相的吸附在光降解催化剂表面的物质转移电荷，产生带负电的电子和带正电的空穴，吸附溶解在光降解催化剂表面的氧俘获电子形成·O2?，而空穴将吸附在催化剂表面，使OH-和H2O氧化成·HO，·O2-和·HO，氧化合成高分子C-C键断裂，最终实现降解。但在阳光不能直接照射的场合，如大量的垃圾填埋场、堆肥场和地膜埋土部分等的塑料废弃物，光催化降解技术受到很大的局限。如何筛选新型催化剂组分和类型，开发新的廉价合成原料，研制出环境光、温、水、气、生物等催化因子利用率高，满足使用要求，持效性长且可控，价格低廉的产品，是今后的一个发展方向。充分利用我国天然金属氧化物资源，开发光热协同可控降解高分子复合母料用于合成高分子废弃物降解和处理，有利于实现生态效益、社会效益和经济效益三者的统一，对经济与社会可持续发展有重要的应用前景和意义。
发明内容
本发明的目的是针对已有技术方案的不足，提供一种光热协同可控降解高分子复合母料及其制备方法，为高分子材料的可控降解研究和大规模市场推广扩大应用领域。
本发明的技术方案是：一种光热协同可控降解高分子复合母料，它的各组分重量配比为：光热敏催化剂0.5～4份、高分子材料80～95份、抗氧剂0.1～2份、偶联剂0.025～0.2份。
所述的光热敏催化剂是金属氧化物CuO、Mn3O4、Co3O4、NiO4、ZnO、FeO中的两种或两种以上按相同重量份配比任意组合，通过700～1300℃高温烧结2小时，高速粉碎10分钟后制得的；所述的高分子材料是聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯中的任意一种；所述的抗氧剂是抗氧剂1010、抗氧剂CA、抗氧剂DNP、抗氧剂MB中的一种或两种以上任意组合；所述的偶联剂是钛酸酯偶联剂、铝酸酯偶联剂、硅烷偶联剂中的一种或两种以上任意组合。
一种光热协同可控降解高分子复合母料制备方法，其步骤依次是：
A、光热敏催化剂制备：按相同重量份配比取两种或两种以上的金属氧化物磨细至60目并混合均匀；将粉末置于马弗炉中，在空气气氛下以2℃/min的升温速率升温到700～1300℃，保温2h，随炉体自然冷却；将烧结后的粉末置于高速粉碎机中高速粉碎10min制得；
B、配料预混：按重量份配比取光热敏催化剂0.5～4份，加入偶联剂0.025～0.2份，在高速混合机中高速混合5分钟后，再加入高分子材料80～95份和抗氧剂0.1～2份在高速混合机中高速混合15分钟；
C、熔融共混：将预混料置于双螺杆挤出机中，在140～220℃熔融共混改性1～5min；
D、挤出造粒：在口模温度130～200℃，螺杆转速为20～200转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
有益效果：合成高分子在给人类带来巨大经济利益的同时也产生了很大的潜在隐患。在光降解、生物降解、光/生物降解和热氧降解高分子技术存在诸多问题的背景下，如何研发出低成本、满足使用要求、废弃物降解过程污染最小化甚至零危害成为人们日益关心的话题。本发明利用热、光催化效应，即在热、光等因素的作用下，复合母料能有效的催化生成用于合成高分子降解的自由基，“切断”聚合的高分子链实现光热协调可控降解。其特点是光热敏催化剂用量少、成本低和易加工，其制品在贮运、使用期间应用性能均能保持合成高分子的基本理化性质，满足使用要求，使用后的高分子废弃物较容易在热、光、氧环境中降解，即使在无光照条件下，在设定的时间范围内能较快的实现降解。本发明制备的光热协同可控降解高分子复合母料以不同比例添加到聚乙烯、聚丙烯、聚苯乙烯等合成高分子中，可以调控降解诱导期，扩展应用范围。
具体实施方式
结合实施例对本发明做进—步详细说明。
光热敏催化剂制备：根据下表按相同重量份配比取金属氧化物CuO、Mn3O4、Co3O4、NiO4、ZnO、FeO中的两种或两种以上磨细至60目，混合均匀；将粉末置于马弗炉中，在空气气氛下以2℃/min的升温速率升温到700～1300℃，保温2h，随炉体自然冷却；将烧结后的粉末置于高速粉碎机中高速粉碎10min制得光热敏催化剂，随组分和烧结温度的不同而得到的光热敏催化剂具有不同的催化效果，本实施方式中编号为1～8。
光热敏催化剂制备金属氧化物相同重量份配比表
实施例1：按重量份配比取光热敏催化剂14份，加入钛酸酯偶联剂00.2份，在高速混合机中高速混合5分钟后，再加入聚乙烯80份和抗氧剂10100.1份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在140℃熔融共混改性5min。在口模温度130℃，螺杆转速为20转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例2：按重量份配比取光热敏催化剂23份，加入铝酸酯偶联剂0.15份，在高速混合机中高速混合5分钟后，再加入聚苯乙烯85份和抗氧剂10100.1份、抗氧剂MB0.1份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在160℃熔融共混改性4min。在口模温度150℃，螺杆转速为50转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例3：按重量份配比取光热敏催化剂34份，加入铝酸酯偶联剂0.1份、硅烷偶联剂0.1份，在高速混合机中高速混合5分钟后，再加入聚丙烯80份和抗氧剂CA0.1份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在180℃熔融共混改性3min。在口模温度160℃，螺杆转速为80转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例4：按重量份配比取光热敏催化剂42份，加入硅烷偶联剂0.1份，在高速混合机中高速混合5分钟后，再加入聚氯乙烯90份和抗氧剂CA1.0份、抗氧剂MB0.5份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在220℃熔融共混改性1min。在口模温度180℃，螺杆转速为100转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例5：按重量份配比取光热敏催化剂51.5份，加入钛酸酯偶联剂0.075份，在高速混合机中高速混合5分钟后，再加入聚丙烯60份、聚氯乙烯30份和抗氧剂DNP1.5份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在200℃熔融共混改性2min。在口模温度200℃，螺杆转速为200转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例6：按重量份配比取光热敏催化剂61.0份，加入铝酸酯偶联剂0.05份，在高速混合机中高速混合5分钟后，再加入聚乙烯30份、聚丙烯65份和抗氧剂MB2份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在190℃熔融共混改性3min。在口模温度200℃，螺杆转速为180转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例7：按重量份配比取光热敏催化剂70.5份，加入硅烷偶联剂0.025份，在高速混合机中高速混合5分钟后，再加入聚苯乙烯20份、聚氯乙烯75份和抗氧剂DNP1份、抗氧剂MB1份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在180℃熔融共混改性3min。在口模温度160℃，螺杆转速为140转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
实施例8：按重量份配比取光热敏催化剂80.5份，加入钛酸酯偶联剂0.025份，在高速混合机中高速混合5分钟后，再加入聚乙烯25份、聚氯乙烯70份和抗氧剂CA2份在高速混合机中高速混合15分钟。将预混料置于双螺杆挤出机中，在160℃熔融共混改性5min。在口模温度150℃，螺杆转速为160转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。

Claims (2)

1.一种光热协同可控降解高分子复合母料，其特征在于，它的各组分按重量份配比为：光热敏催化剂0.5～4份、高分子材料80～95份、抗氧剂0.1～2份、偶联剂0.025～0.2份；所述的光热敏催化剂是金属氧化物CuO、Mn3O4、Co3O4、NiO4、ZnO、FeO中的两种或两种以上按相同重量份配比任意组合，混合磨细至60目，通过700～1300℃高温烧结2小时，高速粉碎10分钟后制得的；所述的高分子材料是聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯中的任意一种；所述的抗氧剂是抗氧剂1010、抗氧剂CA、抗氧剂DNP、抗氧剂MB中的一种或两种以上任意组合；所述的偶联剂是钛酸酯偶联剂、铝酸酯偶联剂、硅烷偶联剂中的一种或两种以上任意组合。
2.一种权利要求1所述的光热协同可控降解高分子复合母料的制备方法，其步骤依次是：
A、光热敏催化剂制备：按相同重量份配比取两种或两种以上的金属氧化物磨细至60目，混合均匀；将粉末置于马弗炉中，在空气气氛下以2℃/min的升温速率升温到700～1300℃，保温2h，随炉体自然冷却；将烧结后的粉末置于高速粉碎机中高速粉碎10min制得光热敏催化剂；
B、配料预混：按重量份配比取光热敏催化剂0.5～4份，加入偶联剂0.025～0.2份，在高速混合机中高速混合5分钟后，再加入高分子材料80～95份和抗氧剂0.1～2份在高速混合机中高速混合15分钟；
C、熔融共混：将预混料置于双螺杆挤出机中，在140～220℃熔融共混改性1～5min；
D、挤出造粒：在口模温度130～200℃，螺杆转速为20～200转/分挤出、自然空气下冷却、经切粒机造粒即得到光热协同可控降解高分子复合母料。
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