CN109280262A - 马来酸酐接枝ldpe及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种马来酸酐接枝LDPE及其制备方法和应用。马来酸酐接枝LDPE,以重量百分比计,原料包括:LDPE:90‑95phr,马来酸酐1‑5phr,过氧化物交联剂0.5‑1.0phr,抗氧剂0.2‑1phr,润滑剂0.5‑2phr。将本发明提供的马来酸酐接枝LDPE作为改性剂应用于EVA发泡中,实践证明经过添加改性剂的EVA发泡材料具有更好的填充性能,边角料的添加量明显增加,发泡材料的强度及韧性得到很大的提升。
Description
技术领域
本发明涉及EVA模压发泡,尤其涉及一种马来酸酐接枝LDPE及其制备方法和应用。
背景技术
发泡材料,是指能在物质内部气化产生气泡使之成为多孔物质的发泡的物质,如制造泡沫塑料、泡沫橡胶、泡沫树脂等等。EVA(Ethylene Vinyl Acetate)由乙烯和醋酸乙烯酯共聚而制得,是一种热塑性塑料、弹性体。具有密度低、能吸收载荷等优点与其他弹性体相比具有优异的弹性、柔韧性、耐应力开裂性、良好的可塑性和可加工性。EVA发泡材料具有优良的化学性能,被广泛应用于制造鞋材、箱包内衬、玩具用材、体育用品材料、建材、以及各类新兴应用例如电子配件和汽车内饰等。
目前EVA发泡材料行业竞争激烈,EVA边角料的填充有限,再加上EVA发泡材料的物理性能无法满意一些高性能材料的要求。
发明内容
为解决现有技术中的问题,本发明提供了一种马来酸酐接枝LDPE及其制备方法和应用,改善了EVA发泡的填充性。
技术方案:
一种马来酸酐接枝LDPE,以重量百分比计,原料包括:
LDPE:90-95phr,马来酸酐1-5phr,过氧化物交联剂0.5-1.0phr,抑制交联剂0.1-1phr,抗氧剂0.2-1phr,润滑剂0.5-2phr。
其中,所述的过氧化物交联剂为双叔丁基过氧异丙基苯或过氧化二异丙苯;引发LDPE的分子链中的自由基的产生。
所述的抗氧剂为抗氧剂168,抗氧剂1010,抗氧剂1076中的一种或多种;其作用是防止高温条件下马来酸酐的反应。
所述的润滑剂为聚乙烯蜡,酯类润滑剂,微晶石蜡中的一种或多种,其作用是增加体系的润滑性及加工性能。
所述的抑制交联剂为二苯胺或者三乙胺,防止过度交联。
本发明还提供了所述的马来酸酐接枝LDPE的制备方法,包括:将马来酸酐、过氧化物交联剂、抑制交联剂、抗氧剂、润滑剂混匀后,在双螺杆挤出机挤出的同时进行超声处理,控制超声功率为200-600W,得到马来酸酐接枝LDPE。
本发明还提供了所述的马来酸酐接枝LDPE在制备EVA发泡材料中的应用。
一种EVA发泡材料,以重量百分数计,原料包括:
EVA:20-60phr,马来酸酐接枝LDPE:10-30phr,发泡剂:1-5phr,交联剂:0.5-1.5phr,润滑剂:1.0-3.0phr,氧化锌:1-5phr,EVA发泡材料的边角料20-40phr。
其中,所述的发泡剂为:偶氮二甲酰胺;所述的交联剂为:双叔丁基过氧异丙基苯或过氧化二异丙苯;所述的润滑剂为:硬脂酸或其他酯类润滑剂。
本发明还提供了所述的EVA发泡材料的制备方法,包括:
1)称料:按照配方的配比称料;
2)密炼:将EVA、马来酸酐接枝LDPE、EVA发泡材料的边角料、润滑剂和氧化锌倒入密炼机中,未压入重锤的情况下搅拌均匀后,再进行混炼,待所有材料软化成团时再加入发泡剂和交联剂,完全混合后,再排出物料;
3)开炼:将密炼机排出物料送入开炼机开炼;
4)出片:将开炼后的物料送入出片机加工,得到料片后冷却;
5)硫化发泡:将料片送入平板硫化机进行硫化发泡处理;
6)冷却静置:将硫化好的片材放置冷却。
其中,混炼时,密炼机的水温控制在40~70℃,压缩空气压力0.7~0.9MPa,料温为105~115℃时;开炼时,开炼机前辊温度80~90℃,后辊温度70~80℃,辊距0.3~0.7mm,补炼3~5遍;出片时,冷却水温≤35℃;硫化发泡时,蒸汽压力0.7~0.75MPa。
有益效果:
本发明选用LDPE作为接枝的主材,与EVA材料更好的相容,更有益于发泡。用马来酸酐接枝LDPE加入到EVA配方里,因为马来酸酐是一种不饱和有机酸酐,LDPE和EVA混合引发交联后,EVA发泡体系也就有了不饱和有机酸酐,能够更好地捕捉体系中的边角料,因而填充性能显著增加。
添加改性剂-马来酸酐接枝LDPE的EVA发泡材料具有更好的填充性能,边角料的添加量明显增加,增加到40%时仍具有良好的性能。
马来酸酐接枝的LDPE能够很好的相容于EVA发泡体系中,而且通过添加10-30%的马来酸酐接枝LDPE后,EVA发泡的物性性能提高了很大的提高,其中拉伸强度和断裂伸长率提高15-25%,回弹率提高15-20%,压缩形变高20-30%。
具体实施方式
下面结合具体实施例,进一步阐明本发明。
实施例1~3
1、马来酸酐接枝LDPE的制备:
1)配方:一种马来酸酐接枝LDPE的制造方法,其包括如下重量百分数计的化学成分:LDPE(低密度聚乙烯):90-95phr,马来酸酐1-5phr,过氧化物交联剂0.5-1.0phr,抑制交联剂0.1-1phr,抗氧剂0.2-1phr,润滑剂0.5-2phr。
其中,LDPE为上海石化生产的牌号N150。
过氧化物交联剂为双叔丁基过氧异丙基苯或过氧化二异丙苯中的任何一种,本实施例具体使用的是过氧化二异丙苯。
抗氧剂为抗氧剂168,抗氧剂1010,抗氧剂1076中的一种或多种,本实施例具体使用的是抗氧剂1010;
润滑剂为聚乙烯蜡,酯类润滑剂,微晶石蜡中的一种或多种,本实施例中具体使用的是硬脂酸;
抑制交联剂为二苯胺或者三乙胺,本实施例具体使用的是三乙胺。
2)工艺步骤
马来酸酐接枝LDPE的制备方法为:将LDPE从双螺杆挤出机的主喂料口加入,将马来酸酐、过氧化物交联剂、抑制交联剂、抗氧剂、润滑剂经高速机混匀后,从第一侧喂料口加入,在双螺杆挤出机的反应段安装超声发生设备,在反应挤出,挤出温度为200度,挤出的同时进行超声处理,控制超声功率为200~600W,得到马来酸酐接枝LDPE(后面统称改性剂)。
2、马来酸酐接枝LDPE用于EVA发泡上
1)配方,以重量百分数计,包括:EVA:20-60phr,马来酸酐接枝LDPE:10-30phr,发泡剂:1-5phr,交联剂:0.5-1.5phr,润滑剂:1.0-3.0phr,氧化锌:1-5phr,边角料20-40phr。具体配比参见表1。
其中,马来酸酐接枝LDPE采用上述方法制备得到,包括如下重量百分数配比的化学成分:LDPE(低密度聚乙烯):93phr,马来酸酐4phr,过氧化物交联剂0.8phr,抑制交联剂0.5phr,抗氧剂0.8phr,润滑剂0.9phr
EVA为燕山石化生产的牌号18J3,醋酸含量为18%。
发泡剂为:偶氮二甲酰胺。
交联剂为:过氧化二异丙苯。
润滑剂为:硬脂酸。
氧化锌为间接法氧化锌,含锌量为99.7%。
边角料为回收的EVA发泡材料的边角料。
2)工艺步骤及条件:
1)称料:按照配方的配比,用电子天平准确地称出各材料的重量,误差在1g以下。
2)密炼:将配好的EVA、改性剂、边角料、润滑剂和氧化锌倒入密炼机中,未压入重锤的情况下搅拌均匀后,再进行混炼,密炼机的水温控制在70℃以下(40~70℃),压缩空气压力0.7~0.9MPa,料温为105~115℃时,待所有材料软化成团时再加入发泡剂和交联剂。完全混合后,再排出物料。
3)开炼:将密炼机排出物料送入开炼机开炼,前辊温度80~90℃,后辊温度70~80℃,辊距0.3~0.7mm,补炼3~5遍;
4)出片:将开炼后的物料送入出片机加工,得到料片后冷却,冷却水温≤35℃。
5)硫化发泡
将料片送入平板硫化机进行硫化发泡处理,蒸汽压力0.7~0.75MPa,模具规格为600mm*1200mm*7mm,硫化时间为12分钟。
6)冷却静置
将硫化好的片材放置冷却48小时。
7)测试物理性能。测试方法参照GB/T6344-2008,GB/T 6342,HG/T 2489-2007,GB/T6670-2008,GB/T6669-2008。
表1
表2
通过实施例和参照例的实验数据表明:添加马来酸酐接枝LDPE的EVA发泡体系边料的填充能力显著提高。通过马来酸酐接枝的LDPE能够很好的相容于EVA发泡体系中,而且通过添加10-30%的马来酸酐接枝LDPE后,EVA发泡的物性性能提高了很大的提高,其中拉伸强度和断裂伸长率提高15-25%,回弹率提高15-20%,压缩形变高20-30%。
Claims (9)
1.一种马来酸酐接枝LDPE,其特征在于,以重量百分比计,原料包括:
LDPE:90-95phr,马来酸酐1-5phr,过氧化物交联剂0.5-1.0phr,抑制交联剂0.1-1phr,抗氧剂0.2-1phr,润滑剂0.5-2phr。
2.根据权利要求1所述的马来酸酐接枝LDPE,其特征在于,所述的过氧化物交联剂为双叔丁基过氧异丙基苯或过氧化二异丙苯;所述的抗氧剂为抗氧剂168,抗氧剂1010,抗氧剂1076中的一种或多种;所述的润滑剂为聚乙烯蜡,酯类润滑剂,微晶石蜡中的一种或多种;所述的抑制交联剂为二苯胺或者三乙胺。
3.根据权利要求1或2所述的马来酸酐接枝LDPE的制备方法,其特征在于,包括:将马来酸酐、过氧化物交联剂、抑制交联剂、抗氧剂、润滑剂混匀后,在双螺杆挤出机挤出的同时进行超声处理,控制超声功率为200-600W,得到马来酸酐接枝LDPE。
4.根据权利要求3所述的马来酸酐接枝LDPE的制备方法,其特征在于,挤出温度为200-220℃。
5.根据权利要求1或2所述的马来酸酐接枝LDPE在制备EVA发泡材料中的应用。
6.一种EVA发泡材料,其特征在于,以重量百分数计,原料包括:
EVA:20-60phr,权利要求1或2所述的马来酸酐接枝LDPE:10-30phr,发泡剂:1-5phr,交联剂:0.5-1.5phr,润滑剂:1.0-3.0phr,氧化锌:1-5phr,EVA发泡材料的边角料20-40phr。
7.根据权利要求6所述的EVA发泡材料,其特征在于,所述的发泡剂为:偶氮二甲酰胺;所述的交联剂为:双叔丁基过氧异丙基苯或过氧化二异丙苯;所述的润滑剂为:硬脂酸或其他酯类润滑剂。
8.根据权利要求6或7所述的EVA发泡材料的制备方法,其特征在于,包括:
1)称料:按照配方的配比称料;
2)密炼:将EVA、马来酸酐接枝LDPE、EVA发泡材料的边角料、润滑剂和氧化锌倒入密炼机中,未压入重锤的情况下搅拌均匀后,再进行混炼,待所有材料软化成团时再加入发泡剂和交联剂,完全混合后,再排出物料;
3)开炼:将密炼机排出物料送入开炼机开炼;
4)出片:将开炼后的物料送入出片机加工,得到料片后冷却;
5)硫化发泡:将料片送入平板硫化机进行硫化发泡处理;
6)冷却静置:将硫化好的片材放置冷却。
9.根据权利要求8所述的EVA发泡材料的制备方法,其特征在于,混炼时,密炼机的水温控制在40~70℃,压缩空气压力0.7~0.9MPa,料温为105~115℃时;开炼时,开炼机前辊温度80~90℃,后辊温度70~80℃,辊距0.3~0.7mm,补炼3~5遍;出片时,冷却水温≤35℃;硫化发泡时,蒸汽压力0.7~0.75MPa。
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