CN109370146A - 一种共混改性的abs发泡材料及其制备方法 - Google Patents
一种共混改性的abs发泡材料及其制备方法 Download PDFInfo
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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Abstract
本发明公开了一种共混改性的ABS发泡材料的制备方法，包括如下步骤：(1)通过密炼机将ABS树脂、EMA、星形SBS、DCP、发泡剂、氧化锌、硬脂酸共混制备ABS/EMA/星形SBS三元预发泡共混材料；(2)将步骤(1)制得的ABS/EMA/星形SBS三元预发泡共混材料经过模压成型制得共混改性的ABS发泡材料。制得的共混改性ABS发泡材料的泡孔均匀、密度小、力学性能较好，具有良好的弹性和综合性能，可用于包装、汽车、热绝缘、建筑、缓冲衬垫、吸声降噪等领域。
Description
技术领域
本发明属于高分子发泡材料技术领域，具体涉及一种共混改性的ABS发泡材料及其制备方法。
背景技术
ABS树脂是一种韧性好、强度高、易于加工成型的热塑型高分子材料，用于制备仪表、电气、电器、机械等各种零件。ABS树脂是丙烯腈(Acrylonitrile)、1,3-丁二烯(Butadiene)、苯乙烯(Styrene)三种单体的接枝共聚物。它的分子式可以写为(C8H8)x·(C4H6)y·(C3H3N)z，但实际上往往是含丁二烯的接枝共聚物与丙烯腈-苯乙烯共聚物的混合物，其中，丙烯腈占15％～35％，丁二烯占
5％～30％，苯乙烯占40％～60％，最常见的比例是A:B:S＝20:30:50，此时ABS树脂熔点为175℃。ABS树脂的成型加工温度一般在210～230℃。
ABS泡沫性能优而质量轻，已经有相关文献[如：虞吉钧，杨永兵，岳邦毅，等.ABS微孔发泡材料的制备与性能研究[J].工程塑料应用，2012，40(1)：12-15；黄斌，张翔，蒋团辉，等.发泡母粒对ABS发泡材料泡孔结构及力学性能的影响[J].工程塑料应用，2016，44(6):36-40。
发明内容
为了增加ABS的发泡性能，本申请用乙烯-丙烯酸甲酯共聚物(EMA)改性ABS。经试验发现EMA发泡性能好，具有发泡均匀、柔软、耐高温等特性，是良好的发泡改性材料。同时为了进一步提高ABS泡沫的性能，本申请还用星形SBS改性ABS材料。星型SBS是橡胶，实验发现星型SBS也能够进一步改善ABS的冲击强度。EMA与星型SBS这两种材料对ABS发泡材料起到共混改性的效果，能够获得发泡倍率高、泡孔均匀、较好力学性能的共混改性的ABS泡沫材料，进而获得优良的力学性能、耐热性、卫生性、热绝缘性和良好的环境效应，这种发泡复合材料可在汽车、包装、热绝缘、建筑等领域发挥重要作用。
为了实现上述目的，本发明所采用的技术方案如下：
一种共混改性的ABS发泡材料的制备方法，
这种发泡材料是将ABS树脂、EMA、星形SBS、发泡剂(如AC发泡剂)及交联剂过氧化二异丙苯(DCP)、发泡助剂氧化锌、硬脂酸、抗氧剂(可以为抗氧剂1010、抗氧剂1098、抗氧剂168、抗氧剂225、抗氧剂215，其中抗氧剂225是复合抗氧剂，由质量比为1：1的抗氧剂1010和168混合而成，抗氧剂215也是复合抗氧剂，由质量比例为1：2的抗氧剂1010和168混合而成)混和(通过密炼机)，制备ABS/EMA/星形SBS三元预发泡材料，再通过模压成型发泡，制得共混改性的ABS发泡材料。
发泡配方为:
其原料组成按重量份数计。
ABS树脂69～85份，EMA 5～20份，星形SBS 5～20份，交联剂过氧化二异丙苯(DCP)0.2～0.4份，发泡剂1～6份，氧化锌0.5～2份，硬脂酸0.5～2份，抗氧剂(优选抗氧剂1010)0.3～0.6份。
具体制备工艺如下：
(1)制备ABS/EMA/星形SBS三元预发泡共混材料：将ABS树脂、EMA、星形SBS、交联剂过氧化二异丙苯(DCP)，发泡剂、氧化锌、硬脂酸、抗氧剂按照一定重量比在密炼机中密炼混合5-10min，温度140-145℃，转速30-40r/min。在这个温度范围内，EMA能够熔融，星形SBS能够软化破碎，ABS虽然不能熔融，但能够破碎，这样发泡助剂主要分散在EMA和星形SBS之中，而黏度高的ABS小颗粒能够分散在EMA和星形SBS之中。两者与ABS三者之间相容性好。因此，在本发明中，EMA和星形SBS起到载体作用，而且它们熔体强度高，发泡性能好，是改善ABS发泡性能的良好材料。控制密炼温度140-145℃，则保证AC发泡剂不分解。
(2)制备共混改性的ABS发泡材料：将ABS/EMA/星形SBS三元预发泡共混材料通过模压发泡。发泡温度范围可取190-230℃，压力可控制在1-20MPa，发泡时间5-30min。在这个温度范围内，ABS软化、熔融，与EMA和星形SBS融为一体，分散在EMA和星形SBS中的AC发泡剂分解，产生的气泡在ABS/EMA/星形SBS基体中膨胀，同时DCP分解，塑料基体部分交联，熔体强度提高，这样有利于发泡和交联的匹配。
由于采用了上述的措施，制备了泡孔均匀、密度小、力学性能较好的共混改性的ABS发泡材料。这种共混改性ABS发泡材料，具有良好的弹性和综合性能，可用于包装、汽车、热绝缘、建筑、缓冲衬垫、吸声降噪等领域。
附图说明
图1为实施例1制得的改性ABS发泡材料的泡沫结构图。
图2为实施例2制得的改性ABS发泡材料的泡沫结构图。
图3为实施例3制得的改性ABS发泡材料的泡沫结构图。
图4为对比实施例1制得的改性ABS发泡材料的泡沫结构图。
图5为对比实施例2制得的改性ABS发泡材料的泡沫结构图。
具体实施方式
本发明下面结合实施例作进一步详述：
实施例1(以下份数均为重量份)：
发泡配方为:
ABS树脂85份、EMA 6.2份、星形SBS 5.2份，交联剂过氧化二异丙苯(DCP)0.3份，AC发泡剂2份，氧化锌0.5份，硬脂酸0.5份，抗氧剂1010 0.3份。
材料的牌号或型号为：
ABS(牌号0215A)，吉林石化。EMA(牌号TC120Molding)，美国埃克森美孚公司。星型SBS(牌号4412)，燕山石化生产，苯乙烯质量含量为40％，分子量为21万。过氧化二异丙苯(DCP)，工业级。AC发泡剂，型号Dn8，上海文华化工颜料有限公司。氧化锌(ZnO)，分析纯，国药集团化学试剂有限公司。抗氧剂1010，工业级。硬脂酸，分析纯，国药集团化学试剂有限公司。
具体制备工艺如下：
(1)制备ABS/EMA/星形SBS三元预发泡共混材料：将ABS树脂、EMA、星形SBS、交联剂过氧化二异丙苯(DCP)，AC发泡剂、氧化锌、硬脂酸、抗氧剂1010按照一定重量比在密炼机中密炼混合6min，温度140℃，转速35r/min。
(2)制备共混改性的ABS发泡材料：将ABS/EMA/星形SBS三元预发泡共混材料通过模压发泡。发泡温度范围取215℃，压力控制在10MPa，发泡时间10min。
取出共混改性的ABS发泡材料。测得泡沫密度为0.30g/cm3，撕裂强度为31N/mm，泡孔平均直径约为0.25mm。见图1。
实施例2
发泡配方为:
ABS树脂76份，EMA 9份，星形SBS 9份，交联剂过氧化二异丙苯(DCP)0.5份，AC发泡剂3份，氧化锌1份，硬脂酸1份，抗氧剂225 0.5份。
材料的牌号或型号为：
ABS(牌号0215A)，吉林石化。EMA(牌号TC115Molding)，美国埃克森美孚公司。星型SBS(牌号4412)，燕山石化生产，苯乙烯含量为40％，分子量为21万。过氧化二异丙苯(DCP)，工业级。AC发泡剂，型号Dn8，上海文华化工颜料有限公司。氧化锌(ZnO)，分析纯，国药集团化学试剂有限公司。抗氧剂225，工业级。硬脂酸，分析纯，国药集团化学试剂有限公司。
具体制备工艺如下：
(1)制备ABS/EMA/星形SBS三元预发泡共混材料：将ABS树脂，EMA，星形SBS，交联剂过氧化二异丙苯(DCP)，AC发泡剂、氧化锌、硬脂酸、抗氧剂225按照一定重量比在密炼机中密炼混合9min，温度141℃，转速40r/min。
(2)制备共混改性的ABS发泡材料：将ABS/EMA/星形SBS三元预发泡共混材料通过模压发泡。发泡温度范围取230℃，压力控制在15MPa，发泡时间15min。
取出共混改性的ABS发泡材料。测得泡沫密度为0.20g/cm3，撕裂强度为22N/mm，泡孔平均直径约为0.21mm，见图2。
实施例3
发泡配方为:
ABS树脂70份，EMA 12.1份，星形SBS 12.1份，交联剂过氧化二异丙苯(DCP)0.3份，AC发泡剂4份，氧化锌0.5份，硬脂酸0.5份，抗氧剂1010 0.5份。
具体制备工艺如下：
(1)制备ABS/EMA/星形SBS三元预发泡共混材料：将ABS树脂，EMA，星形SBS，交联剂过氧化二异丙苯(DCP)，AC发泡剂、氧化锌、硬脂酸、抗氧剂1010按照一定重量比在密炼机中密炼混合7min，温度140℃，转速35r/min。
(2)制备共混改性的ABS发泡材料：将ABS/EMA/星形SBS预发泡共混材料通过模压发泡。发泡温度范围取220℃，压力控制在10MPa，发泡时间15min。
取出共混改性的ABS发泡材料。测得泡沫密度为0.16g/cm3，撕裂强度为18.2N/mm，泡孔平均直径约为0.18mm，见图3。
对比实施例1(与例3对比)
发泡配方为:
ABS树脂70份，EMA 0份，星形SBS 24.2份，交联剂过氧化二异丙苯(DCP)0.3份，AC发泡剂4份，氧化锌0.5份，硬脂酸0.5份，抗氧剂1010 0.5份。
具体制备工艺如下：
(1)制备ABS/星形SBS三元预发泡共混材料：将ABS树脂，星形SBS，交联剂过氧化二异丙苯(DCP)，AC发泡剂、氧化锌、硬脂酸、抗氧剂1010按照一定重量比在密炼机中密炼混合7min，温度140℃，转速35r/min。
(2)制备共混改性的ABS发泡材料：将ABS/星形SBS预发泡共混材料通过模压发泡。发泡温度范围取220℃，压力控制在10MPa，发泡时间15min。
取出共混改性的ABS发泡材料。测得泡沫密度为0.25g/cm3，撕裂强度为16.1N/mm。泡孔平均直径约为0.3mm，泡孔不均匀，性能较差，见图4。
对比实施例2(与例3，4对比)
发泡配方为:
ABS树脂70份，EMA 24.2份，交联剂过氧化二异丙苯(DCP)0.3份，AC发泡剂4份，氧化锌0.5份，硬脂酸0.5份，抗氧剂1010 0.5份。
具体制备工艺如下：
(1)制备ABS/EMA/星形SBS三元预发泡共混材料：将ABS树脂，EMA，交联剂过氧化二异丙苯(DCP)，AC发泡剂、氧化锌、硬脂酸、抗氧剂1010按照一定重量比在密炼机中密炼混合7min，温度140℃，转速35r/min。
(2)制备共混改性的ABS发泡材料：将ABS/EMA预发泡共混材料通过模压发泡。发泡温度范围取220℃，压力控制在10MPa，发泡时间15min。
取出共混改性的ABS发泡材料。测得泡沫密度为0.21g/cm3，撕裂强度为17.0N/mm，泡孔平均直径约为0.24mm，见图5。
Claims (4)
1.一种共混改性的ABS发泡材料的制备方法，其特征在于：所述方法包括如下步骤：
(1)制备ABS/EMA/星形SBS三元预发泡共混材料：将如下重量份的ABS树脂69～85份、EMA5～20份、星形SBS5～20份、DCP0.2～0.4份，发泡剂1～6份、氧化锌0.5～2份、硬脂酸0.5～2份、抗氧剂0.3～0.6份在密炼机中密炼混合5-10min，温度140-145℃，转速30-40r/min；
(2)制备共混改性的ABS发泡材料：将步骤(1)制得的ABS/EMA/星形SBS三元预发泡共混材料通过模压发泡，发泡温度范围为190-230℃，压力控制在1-20MPa，发泡时间为5-30min。
2.根据权利要求1所述的共混改性的ABS发泡材料的制备方法，其特征在于：所述抗氧剂为抗氧剂1010。
3.一种共混改性的ABS发泡材料，其特征在于：所述发泡材料是采用如权利要求1所述的共混改性的ABS发泡材料的制备方法制得的。
4.根据权利要求3所述的共混改性的ABS发泡材料，其特征在于：所述发泡材料的泡沫密度为0.16-0.3g/cm3，撕裂强度为18.2-31N/mm，泡孔平均直径约为0.18-0.25mm。
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Application publication date: 20190222 Assignee: Shandong Hongke Construction Project Management Co.,Ltd. Assignor: CHANGZHOU University Contract record no.: X2023980050999 Denomination of invention: A Blended Modified ABS Foam Material and Its Preparation Method Granted publication date: 20201124 License type: Common License Record date: 20231209 |