CN108530786B - 一种耐老化hips发泡塑料及其制备方法 - Google Patents

一种耐老化hips发泡塑料及其制备方法 Download PDF

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CN108530786B
CN108530786B CN201810405389.6A CN201810405389A CN108530786B CN 108530786 B CN108530786 B CN 108530786B CN 201810405389 A CN201810405389 A CN 201810405389A CN 108530786 B CN108530786 B CN 108530786B
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姜丽丽
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Ningbo CanYe Plastics Co.,Ltd.
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Abstract

本发明公开了一种耐老化HIPS发泡塑料及其制备方法，所述的耐老化HIPS发泡塑料，包括如下原料：HIPS、PMMA、PVC、无机耐老化剂、有机耐老化剂、发泡剂、填料、抗氧剂、加工助剂。本发明提供一种耐老化HIPS发泡塑料及其制备方法，通过优化组分、用量，制得的产品在不降低抗冲击性能的前提下，能具有优异的耐老化性能。

Description

一种耐老化HIPS发泡塑料及其制备方法
技术领域
本发明属于聚合物技术领域，具体涉及一种耐老化HIPS发泡塑料及其制备方法。
背景技术
橡胶接枝增韧聚苯乙烯聚合物即HIPS树脂的连续本体聚合方法是以聚丁二烯橡胶或丁二烯-苯乙烯共聚物橡胶为增韧剂，按照一定的比例将增韧剂溶解在苯乙烯和/或适量的溶剂中，采用热引发或引发剂引发的方法制备的。文献（Peng F M.Polybutadienegrafting and crosslinking in high-impact polystyrene bulkthermal process.Journal of Applied Polymer Science, 1990, 40(7-8): 1289-1302.）中对本体法热引发制备HIPS树脂的聚合反应动力学作了细致的阐述。CN1609126A采用特殊结构橡胶作增韧剂，制备出微观形态呈“卵石堆砌”结构、综合力学性能优异的HIPS树脂。该树脂不仅具有一定的刚性、硬度和加工流动性，而且具有尺寸稳定、耐低温韧性和着色性好的特点，是一个综合性能相对优良的塑料品种，因而被广泛地应用于电子、电器、通讯、仪表、建材、纺织、汽车零部件以及办公机械等领域。随着塑料材料及其制品的发展、应用范围的不断扩大，对HIPS耐久性提出了更高的要求。
然而，HIPS制品在室外长期受阳光、热、氧作用后，会出现泛黄、变脆、龟裂、表面失去光泽、力学性能大大下降等现象，最终丧失使用价值。这是由于HIPS分子中的丁二烯组份所含双键在紫外线作用下，易氧化降解，导致其耐气候性较差，在储存、成型、使用过程中，随着时间的延长而发生结构变化，出现物理力学性质的劣化。制品颜色变黄是HIPS高分子中形成羰基等发色基团的结果，这就意味着高分子链的断裂和极性基团的形成，且环境温度升高则上述变化加剧，放映在冲击强度上是在老化初期强度的急剧下降。
因此，急需一种不降低抗冲击性能的前提下，能具有优异的耐老化性能的HIPS树脂组合物。
发明内容
本发明提供一种耐老化HIPS发泡塑料及其制备方法，通过优化组分、用量，制得的产品在不降低抗冲击性能的前提下，能具有优异的耐老化性能。
为解决以上技术问题，本发明采用以下技术方案：
一种耐老化HIPS发泡塑料，其特征在于，以质量份为单位，包括如下原料：HIPS，PMMA，PVC，无机耐老化剂、有机耐老化剂、发泡剂、填料、抗氧剂、加工助剂；所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按（2-4）:（0.2-0.4）:（4-8）的质量比例复配得到，所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按1:2-4质量比复合得到；所述发泡剂为偶氮二甲酰胺和中空纤维按（2-4）：1的比例添加。
进一步地，所述的耐老化HIPS发泡塑料，以质量份为单位，包括如下原料：HIPS60-80份，PMMA10-20份，PVC10-20份，无机耐老化剂3-6份，有机耐老化剂3-6份，发泡剂5-15份，填料1-3份、抗氧剂0.1-1份、加工助剂1-3份。
进一步地，所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按3: 0.3:6的质量比例复配得到。
进一步地，所述发泡剂为偶氮二甲酰胺和中空纤维按3：1的比例添加。
进一步地，所述中空纤维的中空率为30-60%的尼龙66纤维。
进一步地，所述加工助剂为硬脂酰胺类润滑剂、硅油和白矿油中的一种或几种的混合物。
进一步地，所述抗氧剂为多元受阻酚型抗氧剂。
进一步地，所述填料为滑石粉，氧化锌，硬脂酸钙，三氧化二锑中至少一种。
一种上述的耐老化HIPS发泡塑料的制备方法，其特征在于，包括以下步骤：
（1）将HIPS，PMMA，抗菌剂，复合阻燃剂、阻燃增效剂、抗氧剂、加工助剂投入到混合器中搅拌1-3分钟，得到混合原料；
（2）将步骤2的混合原料和步骤1的混炼产物投入到双螺杆挤出机中进行反应，材料在机筒内停留时间1-2min，得到反应产物，
（3）将双螺杆挤出机中的物料挤进HIPS发泡成型模具内，保压1分钟，待模具冷却后取出HIPS发泡成型件。
进一步地，所述双螺杆挤出机的各区温度如下：一区180-200℃，二区200-220℃，三区200-220℃，四区200-220℃，五区200-220℃，六区200-220℃，七区200-220℃，八区200-220℃，九区200-220℃，机头200-210℃。
本发明具有以下有益效果：
本发明的耐老化HIPS发泡塑料中以HIPS为基材，复配一定量的PMMA，PVC，对HIPS进行改性，使其在添加其它组分时，冲击性能不下降，且耐老化性能得到了协同提高。
本发明中加入特定的无机耐老化剂、有机耐老化剂。所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按一定质量比例复配得到。通过三者组分互相协同作用，铜粉电磁屏蔽效果、纳米稀土的光电效应、赤泥的遮蔽效果，从而实现了耐老化性能的提高。所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按一定质量比复合得到，对射入树脂内部及其反射的光进行吸收。通过无机和有机耐老化剂的配合，实现了冲击性能不下降，且耐老化性能得到了协同提高的效果。
本发明的发泡剂为一定比例的偶氮二甲酰胺和中空纤维实现发泡，偶氮二甲酰胺为传统发泡剂，中空纤维中的空气在挤压中排出，形成空隙，并且其本身对发泡塑料具有一定的力学增强效果，实现高效的发泡，冲击性能不下降。
本发明的耐老化HIPS发泡塑料中以HIPS为基材，复配一定量的PMMA，PVC，然后加入特定的无机耐老化剂、有机耐老化剂、发泡剂，制得的产品能具有优异的耐老化性能。
具体实施方式
为便于更好地理解本发明，通过以下实例加以说明，这些实例属于本发明的保护范围，但不限制本发明的保护范围。
下面通过更具体的实施例加以说明。
一种耐老化HIPS发泡塑料，其特征在于，以质量份为单位，包括如下原料：HIPS60-80份，PMMA10-20份，PVC10-20份，无机耐老化剂3-6份，有机耐老化剂3-6份，发泡剂5-15份，填料1-3份、抗氧剂0.1-1份、加工助剂1-3份；所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按（2-4）:（0.2-0.4）:（4-8）的质量比例复配得到，所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按1:2-4质量比复合得到；所述发泡剂为偶氮二甲酰胺和中空纤维按（2-4）：1的比例添加。
所述中空纤维的中空率为30-60%的尼龙66纤维。所述加工助剂为硬脂酰胺类润滑剂、硅油和白矿油中的一种或几种的混合物。所述抗氧剂为多元受阻酚型抗氧剂。所述填料为滑石粉，氧化锌，硬脂酸钙，三氧化二锑中至少一种。
一种上述的耐老化HIPS发泡塑料的制备方法，其特征在于，包括以下步骤：
（1）将HIPS，PMMA，抗菌剂，复合阻燃剂、阻燃增效剂、抗氧剂、加工助剂投入到混合器中搅拌1-3分钟，得到混合原料；
（2）将步骤2的混合原料和步骤1的混炼产物投入到双螺杆挤出机中进行反应，材料在机筒内停留时间1-2min，得到反应产物，所述双螺杆挤出机的各区温度如下：一区180-200℃，二区200-220℃，三区200-220℃，四区200-220℃，五区200-220℃，六区200-220℃，七区200-220℃，八区200-220℃，九区200-220℃，机头200-210℃。
（3）将双螺杆挤出机中的物料挤进HIPS发泡成型模具内，保压1分钟，待模具冷却后取出HIPS发泡成型件。
实施例1
一种耐老化HIPS发泡塑料，其特征在于，以质量份为单位，包括如下原料：HIPS70份，PMMA15份，PVC15份，无机耐老化剂5份，有机耐老化剂5份，发泡剂10份，填料2份、抗氧剂0.5份、加工助剂2份；所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按3:0.3:6的质量比例复配得到，所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按1:3质量比复合得到；所述发泡剂为偶氮二甲酰胺和中空纤维按3：1的比例添加。
所述中空纤维的中空率为50%的尼龙66纤维。所述加工助剂为硬脂酰胺类润滑剂。所述抗氧剂为多元受阻酚型抗氧剂。所述填料为滑石粉。
一种根据上述的耐老化HIPS发泡塑料的制备方法，其特征在于，包括以下步骤：
（1）将HIPS，PMMA，抗菌剂，复合阻燃剂、阻燃增效剂、抗氧剂、加工助剂投入到混合器中搅拌1-3分钟，得到混合原料；
（2）将步骤2的混合原料和步骤1的混炼产物投入到双螺杆挤出机中进行反应，材料在机筒内停留时间1-2min，得到反应产物，所述双螺杆挤出机的各区温度如下：一区180-200℃，二区200-220℃，三区200-220℃，四区200-220℃，五区200-220℃，六区200-220℃，七区200-220℃，八区200-220℃，九区200-220℃，机头200-210℃。
（3）将双螺杆挤出机中的物料挤进HIPS发泡成型模具内，保压1分钟，待模具冷却后取出HIPS发泡成型件。
实施例2
一种耐老化HIPS发泡塑料，其特征在于，以质量份为单位，包括如下原料：HIPS60份，PMMA20份，PVC10份，无机耐老化剂6份，有机耐老化剂3份，发泡剂15份，填料1份、抗氧剂1份、加工助剂1份；所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按4:0.2: 8的质量比例复配得到，所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按1:2质量比复合得到；所述发泡剂为偶氮二甲酰胺和中空纤维按4：1的比例添加。
所述中空纤维的中空率为30%的尼龙66纤维。所述加工助剂为硬脂酰胺类润滑剂、硅油和白矿油中的一种或几种的混合物。所述抗氧剂为多元受阻酚型抗氧剂。所述填料为氧化锌。
制备方法与实施例1相同。
实施例3
一种耐老化HIPS发泡塑料，其特征在于，以质量份为单位，包括如下原料：HIPS80份，PMMA10份，PVC20份，无机耐老化剂3份，有机耐老化剂6份，发泡剂5份，填料3份、抗氧剂0.1份、加工助剂3份；所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按2: 0.4:4的质量比例复配得到，所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按1:4质量比复合得到；所述发泡剂为偶氮二甲酰胺和中空纤维按2：1的比例添加。
所述中空纤维的中空率为60%的尼龙66纤维。所述加工助剂为硅油。所述抗氧剂为多元受阻酚型抗氧剂。所述填料为三氧化二锑。
制备方法与实施例1相同。
对比例1
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中缺少PMMA，PVC。
对比例2
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中缺少PMMA。
对比例3
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中抗菌剂为PVC。
对比例4
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中缺少无机耐老化剂、有机耐老化剂。
对比例5
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中缺少无机耐老化剂。
对比例6
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中所述无机耐老化剂中缺少导电铜粉末。
对比例7
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中所述无机耐老化剂中缺少纳米氧化镧。
对比例8
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中所述无机耐老化剂中缺少赤泥。
对比例9
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中所述发泡剂为偶氮二甲酰胺。
对比例10
与实施例1的制备工艺基本相同，唯有不同的是制备耐老化HIPS发泡塑料的原料中所述发泡剂为中空纤维。
将上述实施例与对比例制备得到的产品压制成板材，制成50mm×50mm的塑料样品，耐老化性能：将实施例与对比例的样品在相同功率的紫外灯下照射2500小时后，进行拉伸测试。拉伸试验的方法参见ASTM D-638标准，进行制样测试，测试结果如下。
实施例1 实施例2 实施例3 对比例1 对比例2 对比例3 对比例4 对比例5 对比例6 对比例7 对比例8 对比例9 对比例10
简支梁冲击强度ISO179（23℃）KJ/m2 48 46 45 32 38 36 46 47 47 48 47 36 49
老化后的简支梁冲击强度下降% 11% 14% 12% 18% 14% 15% 38% 27% 24% 21% 22% 24% 16%
老化后的拉伸性能下降% 12% 16% 14% 21% 16% 17% 45% 34% 28% 22% 27% 29% 18%
由上表可知：由实施例1-3和对比例1-10的数据可见，本发明的耐老化HIPS发泡塑料中以HIPS为基材，复配一定量的PMMA，PVC，然后加入特定的无机耐老化剂、有机耐老化剂、发泡剂，制得的产品能具有优异的耐老化性能。
以上内容不能认定本发明具体实施只局限于这些说明，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思前提下，还可以做出若干简单推演或替换，都应当视为属于本发明由所提交的权利要求书确定的专利保护范围。

Claims (8)

1.一种耐老化HIPS发泡塑料，其特征在于，包括如下原料：HIPS、PMMA、PVC、无机耐老化剂、有机耐老化剂、发泡剂、填料、抗氧剂、加工助剂；所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按（2-4）:（0.2-0.4）:（4-8）的质量比例复配得到，所述有机耐老化剂为四溴双酚A与邻羟基二苯甲酮按1:2-4质量比复合得到；所述发泡剂为偶氮二甲酰胺和中空纤维按（2-4）：1的比例添加。
2.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，以质量份为单位，包括如下原料：HIPS60-80份，PMMA10-20份，PVC10-20份，无机耐老化剂3-6份，有机耐老化剂3-6份，发泡剂5-15份，填料1-3份、抗氧剂0.1-1份、加工助剂1-3份。
3.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，所述无机耐老化剂为导电铜粉末，纳米氧化镧，赤泥按3: 0.3:6的质量比例复配得到。
4.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，所述发泡剂为偶氮二甲酰胺和中空纤维按3：1的比例添加。
5.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，所述中空纤维的中空率为30-60%的尼龙66纤维。
6.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，所述加工助剂为硬脂酰胺类润滑剂、硅油和白矿油中的一种或几种的混合物。
7.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，所述抗氧剂为多元受阻酚型抗氧剂。
8.根据权利要求1所述的耐老化HIPS发泡塑料，其特征在于，所述填料为滑石粉，氧化锌，硬脂酸钙，三氧化二锑中至少一种。
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