CN103910953B - 一种耐候阻燃pvc/asa合金材料及其制备方法 - Google Patents

一种耐候阻燃pvc/asa合金材料及其制备方法 Download PDF

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CN103910953B
CN103910953B CN201410130799.6A CN201410130799A CN103910953B CN 103910953 B CN103910953 B CN 103910953B CN 201410130799 A CN201410130799 A CN 201410130799A CN 103910953 B CN103910953 B CN 103910953B
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杨桂生
杨俊�
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Hefei Genius New Materials Co Ltd
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Abstract

本发明提供一种耐候阻燃PVC/ASA合金材料及其制备方法，该合金材料是由聚氯乙烯1000份、丙烯腈‑丙烯酸‑苯乙烯共聚物200‑1000份、加工助剂10‑50份、稳定剂25‑50份、润滑剂2‑10份、抗氧剂2‑5份，经混合、挤出制备而成。过具有良好的耐候性的丙烯腈‑丙烯酸‑苯乙烯共聚物对PVC进行改性，从而提高PVC/ASA合金材料的耐候性，并且同时具有高阻燃性、高韧性与流动好、易于加工等特点，特别适合生产在户外使用的产品。

Description

一种耐候阻燃PVC/ASA合金材料及其制备方法
技术领域
本发明属于高分子改性领域，特别的涉及一种PVC/ASA合金材料及其制备方法。
背景技术
聚氯乙烯（PVC）是目前世界上应用最广泛的通用塑料，其用量排在世界第二。 PVC具有良好的物理性能和化学性能，并且具有优异的化学稳定性、阻燃性和电绝缘性，但其加工性能较差，韧性差。虽然通过添加丙烯腈-丁二烯-苯乙烯共聚物（ABS）可以增韧PVC材料，同时其PVC/ABS合金也可以替代阻燃ABS、PC/ABS等材料应用于家电、电工面板等领域。但由于ABS耐候性差，PVC/ABS合金材料不适合用于在室外的应用。而丙烯腈-丙烯酸-苯乙烯共聚物（ASA）是一种改进的ABS树脂，具有良好的耐候性，多应用于户外使用的制件，如汽车外饰、灯罩、断路器外壳、天线外罩等领域，因此将ASA代替ABS加入PVC仍有增韧作用，还能提高材料的耐候性。
发明内容
本发明的目的在于针对现有技术的缺陷，提供一种耐候阻燃的PVC/ASA合金材料及其制备方法。PVC/ASA合金材料的原料来源广且生产成本低、操作简便，并且阻燃环保，可通过欧盟ROHS、REACH等指令。
一种耐候阻燃PVC/ASA合金材料，其特征在于：由以下组分按重量份制备而成：
聚氯乙烯（PVC） 1000份
丙烯腈-丙烯酸-苯乙烯共聚物（ASA） 200-1000份
加工助剂 10-50 份
稳定剂 25-50 份
润滑剂 2-10 份
抗氧剂 2-5 份。
所述聚氯乙烯为聚合度为650-850的悬浮法聚氯乙烯。
所述加工助剂为具有核壳结构的丙烯酸酯类共聚物（MBS）。
所述稳定剂选自有机锡类稳定剂、水滑石类稳定剂、硬脂酸锌、硬脂酸钙和环氧大豆油中的至少三种。
所述润滑剂为硬脂酸、石蜡、聚乙烯蜡、氧化聚乙烯蜡中的至少一种。
所述抗氧剂选自β-（3,5-二叔丁基羟基苯基）丙烯酸十八碳酸酯（抗氧剂1076）、三-（2,4-叔丁基苯基）亚磷酸酯（抗氧剂168）、四[β-（3，5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯 （抗氧剂1010）、硫代二丙酸双十二醇酯（抗氧剂DLTDP）中的至少两种。
本发明丙烯腈-丙烯酸酯-苯乙烯类共聚物（简称ASA）中丙烯酸酯的含量为25-35%。
本发明的另一个目的是提供一种上述PVC/ ASA合金材料的制备方法，包括以下步骤：
（1）将聚氯乙烯、加工助剂、稳定剂、润滑剂和抗氧剂加入高速搅拌机中在60-80℃下混合5-10min；
（2）向（1）中混合物中加入丙烯腈-丙烯酸-苯乙烯共聚物，继续混合5-10min；
（3）将经（2）混合好的物料送入双螺杆挤出机中，物料在螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料；所述的双螺杆挤出机为带有精确的温度控制和真空排气设备的双螺杆挤出机，螺杆各区的温度设置为140-180℃。
与现有技术相比，本发明的有益效果有：
（1）由于PVC本身具有优异的阻燃性，从而赋予了PVC/ ASA合金材料良好的阻燃性；此外通过加入适量增韧剂还能提高材料的韧性，使PVC/ ASA合金材料光泽度好、韧性好且易加工的一种材料。
（2）由于丙烯腈-丙烯酸-苯乙烯共聚物（ASA）是一种改进的ABS树脂，具有良好的耐候，所以将其对PVC进行改性，从而提高了原PVC/ ABS合金材料的耐候性。按照对氙灯老化箱内材料进行100小时紫外灯照射来检测其老化后的色差ΔE，本发明的PVC/ ASA合金材料ΔE值明显小于现有技术中的PVC/ ABS合金材料，表明本发明PVC/ ASA合金材料的耐候性更为优异。
（3）本发明的PVC/ ASA合金材料可应用于户外产品或者对耐候要求高的产品，如灯罩、断路器外壳、电表箱外壳、电动工具外壳等领域。
具体实施方式
以下结合实施例对本发明作进一步说明，其目的仅在于更好理解本发明目的，而非限制本发明的保护范围。
实施例1
本例中使用的生产配方如下
PVC（齐鲁石化，S1000，聚合度750-850）， 1000份
ASA 1000份
MBS 10份
有机锡15 份
硬脂酸锌 4份
硬脂酸钙 6份
抗氧剂1076，2 份
抗氧剂168，3 份
聚乙烯蜡 5份
将上述PVC、MBS、有机锡、硬脂酸锌、硬脂酸钙、聚乙烯蜡、抗氧剂1076、抗氧剂168加入高速搅拌机中在80℃下混合10min；再将ASA加入高速搅拌机中继续在80℃下继续混合5min，然后通过精密计量的送料装置，将混合好的物料送入双螺杆挤出机中挤出、拉条、冷却后，制成粒料，螺杆各区的温度设置为155-180℃。
实施例2
PVC（齐鲁石化，S1000，聚合度750-850）， 1000份
ASA 800份
MBS 50份
有机锡15 份
硬脂酸锌 4份
硬脂酸钙 6份
环氧大豆油 10份
抗氧剂1076，2 份
抗氧剂168，3 份
氧化聚乙烯蜡，2份
将上述PVC、MBS、有机锡、硬脂酸锌、硬脂酸钙、环氧大豆油、氧化聚乙烯蜡、抗氧剂1076、抗氧剂168加入高速搅拌机中在80℃下混合10min；再将ASA加入高速搅拌机中继续在80℃下继续混合5min，然后通过精密计量的送料装置，将混合好的物料送入双螺杆挤出机中挤出、拉条、冷却后，制成粒料，螺杆各区的温度设置为150-175℃。
实施例3
PVC（齐鲁石化，S700，聚合度650-750）， 1000份
ASA 600份
MBS 35份
有机锡20 份
硬脂酸锌 5份
硬脂酸钙 8份
抗氧剂1076，1 份
抗氧剂168，2份
石蜡 3份
聚乙烯蜡 3份
将上述PVC、MBS、有机锡、硬脂酸锌、硬脂酸钙、聚乙烯蜡、石蜡、抗氧剂1076、抗氧剂168加入高速搅拌机中在80℃下混合10min；再将ASA加入高速搅拌机中继续在80℃下继续混合5min，然后通过精密计量的送料装置，将混合好的物料送入双螺杆挤出机中挤出、拉条、冷却后，制成粒料，螺杆各区的温度设置为150-175℃。
实施例4
PVC（齐鲁石化，S700，聚合度650-750）， 1000份
ASA 400份
MBS 30份
有机锡15 份
水滑石 10份
硬脂酸锌 4份
硬脂酸钙 8份
抗氧剂1076，2 份
抗氧剂168，3 份
氧化聚乙烯蜡 5份
将上述PVC、MBS、有机锡、硬脂酸锌、硬脂酸钙、水滑石、氧化聚乙烯蜡、抗氧剂1076、抗氧剂168加入高速搅拌机中在70℃下混合7min；再将ASA加入高速搅拌机中继续在80℃下继续混合8min，然后通过精密计量的送料装置，将混合好的物料送入双螺杆挤出机中挤出、拉条、冷却后，制成粒料，螺杆各区的温度设置为150-175℃。
实施例5
PVC（齐鲁石化，S700，聚合度650-750）， 1000份
ASA 200份
MBS 20份
有机锡 18 份
水滑石 10 份
硬脂酸锌 4份
硬脂酸钙 8份
环氧大豆油 10份
抗氧剂1010，1 份
抗氧剂DLTDP，1 份
硬脂酸 5份
聚乙烯蜡 5份
将上述PVC、MBS、有机锡、硬脂酸锌、硬脂酸钙、水滑石、环氧大豆油、硬脂酸、聚乙烯蜡、抗氧剂1010、抗氧剂DLTDP加入高速搅拌机中在60℃下混合5min；再将ASA加入高速搅拌机中继续在80℃下继续混合10min，然后通过精密计量的送料装置，将混合好的物料送入双螺杆挤出机中挤出、拉条、冷却后，制成粒料，螺杆各区的温度设置为140-170℃。
按本发明的制备方法制备现有的PVC/ABS合金材料作为本发明的对比例，其具体组份组成如下面对比例1与对比例2：
对比例1
PVC（齐鲁石化，S700，聚合度650-750）， 1000份
ABS 600份
MBS 35份
有机锡 20 份
硬脂酸锌 3份
硬脂酸钙 5份
抗氧剂1076，2 份
抗氧剂168，2 份
石蜡 3份
聚乙烯蜡 5份。
对比例2
PVC（齐鲁石化，S700，聚合度650-750）， 1000份
ABS 200份
MBS 15份
有机锡 20 份
硬脂酸锌 3份
硬脂酸钙 5份
抗氧剂1076，1 份
抗氧剂168，1 份
石蜡 5份
氧化聚乙烯蜡 4份。
将上述实施例1-5和对比例1-2制备的合金材料制成样条，按相关检测标准分别检测其简支梁缺口冲击强度、阻燃性、色差，其测试结果如下表1所示。
其中简支梁缺口冲击强度测试按ASTM D6110标准测试；阻燃性测试按照UL94垂直燃烧标准测试；色差测试按以下方法测试，将由实施例和对比材料注塑的100mm×60mm的方片放入氙灯老化箱内，在紫外灯下照射100小时模拟户外日照使用条件，取出后通过色差仪得到方片老化后的色差ΔE，ΔE值越大说明颜色变化越大，材料的耐候性越差。
表1 实施例性能测试结果
实施例1 实施例2 实施例3 实施例4 实施例5 对比例1 对比例2
简支梁缺口冲击强度（KJ/m2） 32 85 70 46 37 50 25
阻燃性 V1 V0 V0 V0 V0 V0 V0
色差ΔE 0.6 0.7 0.6 0.8 0.8 4.7 3.3
由表1的结果可以看到本发明制备的PVC/ASA合金材料的韧性和阻燃性均与对比例中的PVC/ABS合金材料接近，但本发明制备的PVC/ASA合金材料色差ΔE最低为0.6，而对比例为3.3-4.7，色差显著降低，说明本发明的PVC/ASA合金材料的耐候性更好。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (3)

1.一种耐候阻燃PVC/ASA合金材料，其特征在于：由以下组分按重量份制备而成：
PVC 1000份、ASA 1000份、MBS 10份、有机锡15 份、硬脂酸锌4份、硬脂酸钙 6份、抗氧剂1076 2 份、抗氧剂168 3 份、聚乙烯蜡5份；
或PVC 1000份、ASA 800份、MBS 50份、有机锡15 份、硬脂酸锌 4份、硬脂酸钙 6份、环氧大豆油 10份、抗氧剂1076 2份、抗氧剂168 3份、氧化聚乙烯蜡2份；
或PVC 1000份、ASA 600份、MBS 35份、有机锡20 份、硬脂酸锌 5份、硬脂酸钙 8份、抗氧剂1076 1 份、抗氧剂168 2份、石蜡 3份、聚乙烯蜡3份；
或PVC 1000份、ASA 400份、MBS 30份、有机锡15 份、水滑石 10份、硬脂酸锌 4份、硬脂酸钙 8份、抗氧剂1076 2 份、抗氧剂168 3 份、氧化聚乙烯蜡5份。
2.根据权利要求1所述耐候阻燃PVC/ASA合金材料，其特征在于：所述聚氯乙烯为聚合度为650-850的悬浮法聚氯乙烯。
3.一种如权利要求1所述的PVC/ ASA合金材料的制备方法，其特征在于：包括以下步骤：
（1）将PVC、MBS、稳定剂、润滑剂、抗氧剂加入高速搅拌机中在60-80℃下混合5-10min；其中稳定剂为有机锡、硬脂酸锌和硬脂酸钙的复合物，或有机锡、硬脂酸锌、硬脂酸钙和环氧大豆油的复合物，或有机锡、硬脂酸锌、硬脂酸钙和水滑石的复合物；润滑剂为聚乙烯蜡或氧化聚乙烯蜡；抗氧剂为抗氧剂1076和抗氧剂168；
（2）向（1）中混合物中加入ASA，继续混合5-10min；
（3）将经（2）混合好的物料送入双螺杆挤出机中，物料在螺杆的剪切、混炼和输送下充分的熔合，最后经过挤出、拉条、冷却后，制成粒料；所述的双螺杆挤出机为带有精确的温度控制和真空排气设备的双螺杆挤出机，螺杆各区的温度设置为140-180℃。
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