CN108285609A - 高熔体强度苯乙烯类树脂组合物及其制备方法 - Google Patents

高熔体强度苯乙烯类树脂组合物及其制备方法 Download PDF

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CN108285609A
CN108285609A CN201810019938.6A CN201810019938A CN108285609A CN 108285609 A CN108285609 A CN 108285609A CN 201810019938 A CN201810019938 A CN 201810019938A CN 108285609 A CN108285609 A CN 108285609A
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styrene resin
resin composite
high fondant
strength
tackifier
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CN108285609B (zh
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段浩
朱延谭
朱丛山
汤俊杰
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Fine-Blend Compatilizer Jiangsu Co Ltd
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Abstract

本发明提供了一种高熔体强度苯乙烯类树脂组合物，其包括按一定重量份数配比的如下组分：苯乙烯类树脂或苯乙烯类合金、增粘剂、抗氧剂、润滑剂。与现有技术相比，本发明具有如下的有益效果：1、本发明中作为增粘剂的无规共聚物，与苯乙烯类树脂及其合金具有热力学相容，不会发生相分离，机械性能优异；2、本发明中作为增粘剂的无规共聚物分子量适中，相对橡胶粉、高分子量的SAN粉、耐热粉等之类的树脂更易塑化，因此具有更好加工性，厚度均匀，收缩率低，不容易产生表面缺陷的问题。

Description

高熔体强度苯乙烯类树脂组合物及其制备方法
技术领域
本发明涉及一种高熔体强度苯乙烯类树脂组合物及其制备方法，属于高分子材料领域。
背景技术
ABS树脂是一种性能优异的树脂，具有优异的抗冲击性、耐热性、尺寸稳定性以及优异的染色性能，已经在电子电气、家电、汽车等领域得到了广泛的应用，适用于各种加工工艺。最常见的加工手段是注塑，此外还有挤出和吹塑等工艺。比如，汽车尾翼和扰流板通常就采用吹塑成型加工工艺制备，而冰箱内衬一般采用吸塑工艺制备。吹塑等工艺中，若材料的熔体强度不足，则容易产生胚体垂延，塌陷等现象；吸塑时发生局部过薄，甚至破裂等一系列的问题。因此，用于该种制件的ABS树脂除了要具有良好的机械性能外，还要求具有高的熔体强度和耐热性能。
耐热性可以通过耐热剂来改进，但熔体强度的提升就比较困难，改性厂家往往通过添加例如橡胶粉、高分子量的SAN粉、耐热粉之类等的低流动性的产品来提高材料的熔体强度。但是，这些方案并不能完全解决以上问题，同时还会引入其他问题，比如塑化不良、收缩过大等，还容易造成制品壁厚不均、表面产生缺陷的问题。
上述这些技术方案存在的不足大大的限制了ABS树脂在挤出、吹塑以及吸塑制品领域的广泛应用。
类似的问题在HIPS、ASA、SAN及其PC/ABS合金、PC/ASA合金中也存在。因此相关提高熔体强度的方法成为了研究的重点，关于一种工艺过程简单、物理机械性能优异、低成本的苯乙烯类树脂及其合金获得更高熔体强度的制备方法目前还未见报道。
发明内容
针对现有技术中的缺陷，本发明的目的是提供一种高熔体强度苯乙烯类树脂组合物及其制备方法。
本发明是通过以下技术方案实现的：
第一方面，本发明提供了一种高熔体强度苯乙烯类树脂组合物，其包括按重量份数计的如下组分：
作为优选方案，所述增粘剂为由芳香族乙烯基单体和丙烯腈系单体共聚而成的无规共聚物。
作为优选方案，所述增粘剂的数均分子量为200000～400000。
作为优选方案，所述增粘剂中，芳香族乙烯基单体的质量含量为50～85％，丙烯腈系单体的质量含量为10～40％。
作为优选方案，所述增粘剂中具有长支链支化结构，其中所述支链的数均分子量为10000～90000。
作为优选方案，所述芳香族苯乙烯基单体包括苯乙烯单体、α-甲基苯乙烯单体、α-氯苯乙烯单体和p-甲基苯乙烯单体中的至少一种；所述丙烯腈系单体包括丙烯腈单体和α-甲基丙烯腈单体中的一种或两种。
作为优选方案，所述苯乙烯类树脂包括ABS树脂、SAN树脂、ASA树脂和HIPS树脂中的至少一种；所述苯乙烯类合金为PC/ABS合金和PC/ASA合金中的一种或两种。
作为优选方案，所述抗氧剂为酚类抗氧剂。
第二方面，本发明还提供了一种如前述的高熔体强度苯乙烯类树脂组合物的制备方法，其包括如下步骤：
将苯乙烯类树脂或苯乙烯类合金与增粘剂、抗氧剂、润滑剂在25～90℃下混匀后，使用双螺杆挤出机在200～260℃下进行挤出造粒，得到所述高熔体强度苯乙烯类树脂组合物。
作为优选方案，所述的双螺杆挤出机的长径比大于34。
与现有技术相比，本发明具有如下的有益效果：
1、本发明中作为增粘剂的无规共聚物，与苯乙烯类树脂及其合金具有热力学相容，不会发生相分离，机械性能优异；
2、本发明中作为增粘剂的无规共聚物分子量适中，相对橡胶粉、高分子量的SAN粉、耐热粉等之类的树脂更易塑化，因此具有更好加工性，厚度均匀，收缩率低，不容易产生表面缺陷的问题；
3、本发明的作为增粘剂的无规共聚物具有长支链结构，当高分子材料具有长支链支化的分子结构时，材料将表现出应变硬化的现象，从而让材料在局部发生大应变时不发生破裂，同时还有足够的强度使得周围部分发生形变，整体均匀减薄；
4、用途广泛：对ABS，SAN，ASA，HIPS，PC/ABS合金以及PC/ASA合金均有效果；
5、工艺过程简单，成本低，降低了生产难度和投资成本，该方法制备的产品可广泛用于家电、汽车、航空等领域。具有十分广阔的应用前景和工业化价值。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1为实施例1～3和对照例1所得到的样品的拉伸流变测试结果；
图2为实施例1～3和对照例1所得到的样品的力学性能测试结果；
图3为实施例1～4和对照例1～3所得到的样品的高温拉伸性能测试结果。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
表1实施例与对照例的配方表
材料 实施例1 实施例2 实施例3 实施例4 实施例5 对照例1 对照例2 对照例3 对照例4
高胶粉180 50 50 50 50 30 50 50 50 30
AS-128L 50 50 50 50 40 50 50 50 50
PC 1100 30 30
增粘剂 10 20 30 20 10 50 70
TAF 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
1010 0.1 0.1 0.1 0.2 0.1 0.1 0.1 0.2
168 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
245 0.2
将上述配方产品经双螺杆挤出造粒，在80℃条件烘箱中烘干2h，粒子通过毛细管流变仪测试拉伸流变特性，测试结果可以参见图1。同时将粒子注塑成标准样条，进行机械性能(结果见图2)和高温拉伸测试(结果见图3)，并观察吹塑制品表面，用1-5的数字表示表面的光洁程度(结果如表2所示)，越大越好。
测试条件如下：
IZOD缺口冲击强度：按照ASTM D256标准进行测试，样条厚度为3.2mm；
弯曲模量：按照ASTM D790标准进行测试，测试速度为3mm/min；
拉伸性能：按ASTM D628标准测试，拉伸速率5mm/min；
熔融指数：按照ASTM D1238标准进行测试，测试条件为220℃*10Kg。
高温拉伸测试：按照DIN EN ISO 527-3标准进行，
由图1所示，通过实施例1～3与对照例1相比可以看出，对照例1中的ABS随着时间的推移，没有出现到一定应变后随着应变增加而粘度快速增长的现象，而实施例1的产品显示，有了一定程度的上翘的表现，可见出现了应变硬化的特征，而实施例和实施例出现了更加明显的上翘，表现出了明显的应变硬化特征。应变硬化则表明熔体粘度增加。
由图2所示，通过实施例1～3与对照例1相比，基本力学性能没有明显差异，可见本发明的方法对于苯乙烯及其合金在明显提高熔体强度的同时，对于力学性能没有副作用。
由图3所示，实施例1～5与对照例1～4的高温拉伸性能，高温拉伸性能可以最大程度上模拟在吹塑以及吸塑的工艺过程中，材料的性能。从上图可见，实施例1～3相对实施例1，以及实施例5相对对照例4高温拉伸性能都明显上升，对照例2～3的高温拉伸性能也表现优异，但是从表2数据可见，其流动性较差。综合而言，实施例1～3具有力学性能优异，加工性能好，熔体强度高的特性，同时工艺过程简单、成本低。
表2实施例与对照例的流动性与外观
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

1.一种高熔体强度苯乙烯类树脂组合物，其特征在于，包括按重量份数计的如下组分：
2.如权利要求1所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述增粘剂为由芳香族乙烯基单体和丙烯腈系单体共聚而成的无规共聚物。
3.如权利要求2所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述增粘剂的数均分子量为200000～400000。
4.如权利要求2所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述增粘剂中，芳香族乙烯基单体的质量含量为50～85％，丙烯腈系单体的质量含量为10～40％。
5.如权利要求2所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述增粘剂中具有长支链支化结构，其中所述支链的数均分子量为10000～90000。
6.如权利要求2～5中任意一项所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述芳香族苯乙烯基单体包括苯乙烯单体、α-甲基苯乙烯单体、α-氯苯乙烯单体和p-甲基苯乙烯单体中的至少一种；所述丙烯腈系单体包括丙烯腈单体和α-甲基丙烯腈单体中的一种或两种。
7.如权利要求1所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述苯乙烯类树脂包括ABS树脂、SAN树脂、ASA树脂和HIPS树脂中的至少一种；所述苯乙烯类合金为PC/ABS合金和PC/ASA合金中的一种或两种。
8.如权利要求1所述的高熔体强度苯乙烯类树脂组合物，其特征在于，所述抗氧剂为酚类抗氧剂。
9.一种如权利要求1所述的高熔体强度苯乙烯类树脂组合物的制备方法，其特征在于，包括如下步骤：
将苯乙烯类树脂或苯乙烯类合金与增粘剂、抗氧剂、润滑剂在25～90℃下混匀后，使用双螺杆挤出机在200～260℃下进行挤出造粒，得到所述高熔体强度苯乙烯类树脂组合物。
10.如权利要求9所述的高熔体强度苯乙烯类树脂组合物的制备方法，其特征在于，所述的双螺杆挤出机的长径比大于34。
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