CN112223875B - 一种耐黄变老化的透明ppr管材及其制备方法 - Google Patents

一种耐黄变老化的透明ppr管材及其制备方法 Download PDF

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CN112223875B
CN112223875B CN202011047257.4A CN202011047257A CN112223875B CN 112223875 B CN112223875 B CN 112223875B CN 202011047257 A CN202011047257 A CN 202011047257A CN 112223875 B CN112223875 B CN 112223875B
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于麒
汪磊
邱桥平
杨浩佳
韩延旺
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Rifeng Enterprise Group Co Ltd
Rifeng Technology Co Ltd
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Abstract

本发明提供一种耐黄变老化的透明PPR管材及其制备方法，所述管材包括管材内层、管材中层和管材外层，所述管材内层包括以下重量份的组分：PP树脂100份、透明成核剂0.3～0.8份、抗氧剂0.1～0.5份、卤素吸收剂0.05～0.3份、爽滑剂0.1～0.4份和抗静电剂0.1～0.6份；所述管材外层的材料为EVOH，所述管材中层的材料为热熔胶。本发明的耐黄变老化的透明PPR管材通过配合管材内层和管材外层的EVOH材料，并且限定管材内层的组分，使得本发明的耐黄变老化的透明PPR管材具有优异的透明性、光泽性、机械强度、伸缩性、耐磨性、耐寒性和表面强度。

Description

一种耐黄变老化的透明PPR管材及其制备方法
技术领域
本发明涉及塑料管道领域，具体涉及一种耐黄变老化的透明PPR管材及其制备方法。
背景技术
透明PPR管材有着透明度高、雾度低等特点，用户可透过透明PPR管材表面观察到管材内部水质的卫生情况，以便及时做出判定，有利于家庭用水健康。
但是现有的透明PPR管材在长时间通热水的情况下很容易老化变黄，导致管材不再透明，用户无法清晰观察到管材内部的水质卫生情况，这极大地限制了透明PPR管材的应用。
发明内容
本发明的目的在于克服现有技术存在的不足之处而提供一种耐黄变老化的透明PPR管材及其制备方法。
为实现上述目的，本发明采取的技术方案为：一种耐黄变老化的透明PPR管材，所述管材包括管材内层、管材中层和管材外层，所述管材内层包括以下重量份的组分：PP树脂100份、透明成核剂0.3～0.8份、抗氧剂0.1～0.5份、卤素吸收剂0.05～0.3份、爽滑剂0.1～0.4份和抗静电剂0.1～0.6份；所述管材外层的材料为EVOH，所述管材中层的材料为热熔胶。
上述的耐黄变老化的透明PPR管材结合管材内层、管材中层和管材外层，并且管材内层中通过PP树脂、透明成核剂、抗氧剂、卤素吸收剂、爽滑剂和抗静电剂的搭配，透明成核剂成核效率高，能大幅度改善管材的透明度，同时成核剂无毒无味无刺激，使用更加安全放心。管材内层的抗氧剂可大幅度提高管材的抗氧化性能，降低管材的黄变指数，管材内层的卤素吸收剂、爽滑剂及抗静电剂不仅可以提高管材的加工性能和力学性能，而且这些助剂还可以不同程度地降低管材的黄变指数，使管材的耐黄变、耐老化性能更强；管材外层为EVOH材料，具有阻氧效果，对外界气体具有极好的阻隔作用，可有效地阻止外界氧气的渗入，降低管材受热氧老化的程度，降低管材的黄变指数。上述的耐黄变老化的透明PPR管材通过配合管材内层和管材外层的EVOH材料，并且限定管材内层的组分，其透明性、光泽性、机械强度、伸缩性、耐磨性、耐寒性和表面强度也都非常优异，缺少任一组分都会导致耐黄变性能降低。
优选地，所述透明成核剂为松香型聚烯烃透明成核剂。
上述的耐黄变老化的透明PPR管材添加松香型聚烯烃透明成核剂，成核效率高，能大幅度改善结晶聚烯烃树脂的性能，提高管材的透明度，同时成核剂原料源自天然松香，无毒无味无刺激，使用更加安全放心。
优选地，所述抗氧剂由抗氧剂1010、抗氧剂626和抗氧剂DSTDP组成，所述抗氧剂的重量比为抗氧剂1010：抗氧剂626：抗氧剂DSTDP＝1:0.5～1:0.5～1。
发明人通过研究发现，上述的耐黄变老化的透明PPR管材应用抗氧剂1010：抗氧剂626：抗氧剂DSTDP搭配时，能够更好的改善耐黄变老化的透明PPR管材的耐黄变性能。
优选地，所述卤素吸收剂为硬脂酸钙。
优选地，所述爽滑剂为油酸酰胺或芥酸酰胺。
优选地，所述抗静电剂为单甘酯。
发明人通过研究发现，上述的耐黄变老化的透明PPR管材将硬脂酸钙、芥酸酰胺和单甘酯搭配时，具有更好的耐黄变性能。
优选地，所述管材中间层的厚度为0.05～0.08mm。
优选地，所述管材外层的厚度为0.05～0.1mm。
本发明还提供上述任一所述耐黄变老化的透明PPR管材的制备方法，所述方法包括以下步骤：
(1)将上述任一所述耐黄变老化的透明PPR管材的管材内层按照重量配比加入在混料机中搅拌5～10min，将混合均匀的物料加入到双螺杆挤出机中进行挤出造粒，主机及模具温度设置在190～200℃，经挤出造粒后得到管材的内层料；
(2)将所述内层料、热熔胶、EVOH树脂加入到三台单螺杆挤出机中，配置三层共挤模具，内层主机温度设置在180～190℃，中间层及外层主机温度设置在190～210℃，模具温度设置在190～210℃，管材经过挤出、定型、冷却、牵引、切割后得到耐黄变老化的透明PPR管材。
本发明的有益效果在于：本发明提供了一种耐黄变老化的透明PPR管材，本发明的耐黄变老化的透明PPR管材通过配合管材内层和管材外层的EVOH材料，并且限定管材内层的组分，使得本发明的耐黄变老化的透明PPR管材具有优异的透明性、光泽性、机械强度、伸缩性、耐磨性、耐寒性和表面强度。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
实施例1
作为本发明实施例的一种耐黄变老化的透明PPR管材，所述耐黄变老化的透明PPR管材由管材内层、管材中层和管材外层组成；
所述管材内层包括以下重量份的组分：PP树脂100份、松香型聚烯烃透明成核剂0.5份(浙江万安塑料有限公司)、抗氧剂0.4份、硬脂酸钙0.2份、油酸酰胺0.3份和单甘酯0.3份；所述抗氧剂由抗氧剂1010、抗氧剂626和抗氧剂DSTDP组成，所述抗氧剂的重量比为抗氧剂1010：抗氧剂626：抗氧剂DSTDP＝1:0.75:0.5；
所述管材外层的材料为EVOH，所述管材中层的材料为热熔胶；所述管材中间层的厚度为0.06mm；所述管材外层的厚度为0.08mm。
作为本实施例的耐黄变老化的透明PPR管材的制备方法，所述方法包括以下步骤：
(1)将上述任一所述耐黄变老化的透明PPR管材的管材内层按照重量配比加入在混料机中搅拌5～10min，将混合均匀的物料加入到双螺杆挤出机中进行挤出造粒，主机及模具温度设置在190～200℃，经挤出造粒后得到管材的内层料；
(2)将所述内层料、热熔胶、EVOH树脂加入到三台单螺杆挤出机中，配置三层共挤模具，内层主机温度设置在180～190℃，中间层及外层主机温度设置在190～210℃，模具温度设置在190～210℃，管材经过挤出、定型、冷却、牵引、切割后得到耐黄变老化的透明PPR管材。
实施例2
作为本发明实施例的一种耐黄变老化的透明PPR管材，所述耐黄变老化的透明PPR管材管材内层、管材中层和管材外层；
所述管材内层包括以下重量份的组分：PP树脂100份、松香型聚烯烃透明成核剂0.5份(浙江万安塑料有限公司)、抗氧剂0.4份、硬脂酸钙0.2份、芥酸酰胺0.2份和单甘酯0.4份；所述抗氧剂由抗氧剂1010、抗氧剂626和抗氧剂DSTDP组成，所述抗氧剂的重量比为抗氧剂1010：抗氧剂626：抗氧剂DSTDP＝1:0.75:0.5；
所述管材外层的材料为EVOH，所述管材中层的材料为热熔胶；所述管材中间层的厚度为0.06mm；所述管材外层的厚度为0.08mm。
实施例3
作为本发明实施例的一种耐黄变老化的透明PPR管材，本实施例与实施例1的唯一区别为：所述管材外层的厚度为0.05mm。
实施例4
作为本发明实施例的一种耐黄变老化的透明PPR管材，本实施例与实施例1的唯一区别为：所述管材外层的厚度为0.10mm。
对比例1
作为本发明对比例的一种耐黄变老化的透明PPR管材，本对比例与实施例1的唯一区别为：所述耐黄变老化的透明PPR管材为单层，且仅由PP树脂和松香型聚烯烃透明成核剂组成。
对比例2
作为本发明对比例的一种耐黄变老化的透明PPR管材，本对比例与实施例1的唯一区别为：所述管材内层由以下重量份的组分组成：PP树脂100份、松香型聚烯烃透明成核剂0.5份(浙江万安塑料有限公司)。
对比例3
作为本发明对比例的一种耐黄变老化的透明PPR管材，本对比例与实施例1的唯一区别为：所述抗氧剂为抗氧剂1010。
对比例4
作为本发明对比例的一种耐黄变老化的透明PPR管材，本对比例与实施例1的唯一区别为：所述管材内层中不含有硬脂酸钙。
对比例5
作为本发明对比例的一种耐黄变老化的透明PPR管材，本对比例与实施例1的唯一区别为：所述管材内层中不含有油酸酰胺。
对比例6
作为本发明对比例的一种耐黄变老化的透明PPR管材，本对比例与实施例1的唯一区别为：所述管材内层中不含有单甘酯。
效果例1
对实施例1-4和对比例1-3的耐黄变老化的透明PPR管材GB/T18742.2-2017对其检测静液压强度试验及氧化诱导时间。结果如表1所示。
表1耐黄变老化的透明PPR管材的性能
Figure BDA0002707133370000051
Figure BDA0002707133370000061
由表1可知实施例1～4所示的管材耐热氧老化能力较对比例1～3要好，对比例1中的管材由于既没有添加抗氧剂也没有阻氧层，管材本身的耐老化性能最差，且高温下的静液压强度试验也无法通过。
将实施例1～4和对比例2～7的耐黄变老化的透明PPR管材完成95℃，3.5MPa，1000h静液压强度试验后的样品进行黄变指数检测。
表2耐黄变老化的透明PPR管材的耐黄变性能
Figure BDA0002707133370000062
Figure BDA0002707133370000071
管材外层为EVOH材料，具有阻氧效果，对外界气体具有极好的阻隔作用，可有效地阻止外界氧气的渗入，降低管材受热氧老化的程度，降低管材的黄变指数。耐黄变老化的透明PPR管材通过配合管材内层和管材外层的EVOH材料，并且限定管材内层的组分可以改善耐黄变老化的透明PPR管材的耐黄变性能，缺少EVOH材料、硬脂酸钙、油酸酰胺、单甘酯都会导致耐黄变性能下降，而且抗氧剂种类的搭配将抗氧剂1010、抗氧剂626、抗氧剂DSTDP搭配后，相比于单一组分的抗氧剂，也能显著提高耐黄变性能。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (5)

1.一种耐黄变老化的透明PPR管材，其特征在于，所述管材包括管材内层、管材中层和管材外层，所述管材内层包括以下重量份的组分：PP树脂100份、透明成核剂0.3～0.8份、抗氧剂0.1～0.5份、卤素吸收剂0.05～0.3份、爽滑剂0.1～0.4份和抗静电剂0.1～0.6份；所述管材外层的材料为EVOH，所述管材中层的材料为热熔胶；
所述抗氧剂由抗氧剂1010、抗氧剂626和抗氧剂DSTDP组成，所述抗氧剂的重量比为抗氧剂1010：抗氧剂626：抗氧剂DSTDP＝1:0.5～1:0.5～1；
所述卤素吸收剂为硬脂酸钙；
所述抗静电剂为单甘酯；
所述爽滑剂为油酸酰胺或芥酸酰胺。
2.根据权利要求1所述的耐黄变老化的透明PPR管材，其特征在于，所述透明成核剂为松香型聚烯烃透明成核剂。
3.根据权利要求1所述的耐黄变老化的透明PPR管材，其特征在于，所述管材中间层的厚度为0.05～0.08mm。
4.根据权利要求1所述的耐黄变老化的透明PPR管材，其特征在于，所述管材外层的厚度为0.05～0.1mm。
5.如权利要求1-4任一所述耐黄变老化的透明PPR管材的制备方法，其特征在于，所述方法包括以下步骤：
(1)将如权利要求1-4任一所述耐黄变老化的透明PPR管材的管材内层按照重量配比加入在混料机中搅拌5～10min，将混合均匀的物料加入到双螺杆挤出机中进行挤出造粒，主机及模具温度设置在190～200℃，经挤出造粒后得到管材的内层料；
(2)将所述内层料、热熔胶、EVOH树脂加入到三台单螺杆挤出机中，配置三层共挤模具，内层主机温度设置在180～190℃，中间层及外层主机温度设置在190～210℃，模具温度设置在190～210℃，管材经过挤出、定型、冷却、牵引、切割后得到耐黄变老化的透明PPR管材。
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