CN103421266B - 无卤阻燃高抗冲聚苯乙烯的制备方法 - Google Patents
无卤阻燃高抗冲聚苯乙烯的制备方法 Download PDFInfo
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Abstract
本发明公开了一种无卤阻燃高抗冲聚苯乙烯及其制备方法,该无卤阻燃高抗冲聚苯乙烯是由下述重量份的组分制成:高抗冲聚苯乙烯树脂100份,苯乙烯-丁二烯-苯乙烯嵌段共聚物1~15份,无卤复合阻燃剂10~30份,润滑剂0.2~2.5份,稳定剂0.3~1.6份;所述的无卤复合阻燃剂由磷酸酯、硼酸锌以及酚醛树脂按照(10~20)∶1∶(5~10)的重量比组成,所述的磷酸酯为磷酸三苯酯或者磷酸二甲苯酯。本发明的无卤阻燃高抗冲聚苯乙烯在具有较好的阻燃性能的同时,综合力学强度高、熔体流动性好、生产成本低、环保无毒的。
Description
技术领域
本发明涉及一种高分子材料及其制备方法,具体涉及一种无卤阻燃高抗冲聚苯乙烯及其制备方法。
背景技术
高抗冲聚苯乙烯(HIPS)树脂是一种通用工程塑料,因其具有较好的综合力学性能,因此被广泛应用于电子、电器配件上。
高抗冲聚苯乙烯树脂本身属于易燃、可燃材料,氧指数为17%,在燃烧时热释放速率高,热值大,火焰传播速度快,不易熄灭,有时还产生浓烟和有毒气体,这不仅会造成严重的财产损失,还会给人类的生命安全和生存环境带来极大威胁。
随着人们对健康、安全、环境及生态保护的日益重视,塑料的阻燃标准及环保标准也日益严格,材料燃烧烟气毒性和发烟性能问题越来越受到重视,要求塑料材料或制品既具有良好的阻燃性能,又要低毒化和低发烟化。
目前无卤阻燃HIPS的文献大致分为三类:
(1)由于阻燃剂的加入会降低材料的力学性能,因此,采用聚苯醚可以提高其拉伸强度等力学性能,如中国专利文献CN1521206、CN101062992A、CN101768318A、CN102477189A、CN102408659、CN102391636。但是采用聚苯醚存在两个缺点:聚苯醚的熔融流动性较差,从而影响材料的成型加工性能;聚苯醚价格较高,导致生产成本较高。
(2)中国专利文献CN101914258A公开了一种无卤阻燃HIPS树脂生产配方及其制作方法,该配方由HIPS树脂、聚氨酯树脂、热塑性弹性体树脂(SBS)、微胶囊化红磷、磷酸三甲苯酯、硼酸锌、乙撑双硬脂酸酰胺(EBS)、硬脂酸钙、硅烷偶联剂、钛白粉、抗氧剂1010、抗氧剂168、UV-770、UV-327组成。该文献采用的无卤阻燃体系中含有微胶囊化红磷,一方面,磷分解产生的气味对人体有害,另一方面,红磷的存在使得产品变红变深,不能用于其它色彩或者淡色产品的生产,如白色家电等,从而限制了其应用。
(3)中国专利文献CN101372548A公开了一种高抗冲聚苯乙烯共混物,包括高抗冲聚苯乙烯树脂、无机阻燃剂、膨胀型阻燃剂、阻燃增效剂、增韧剂、偶联剂、润滑剂、抗氧剂。其中无机阻燃剂为氢氧化镁等,膨胀型阻燃剂包括酸源、炭源和气源,其中酸源为磷酸酯等,炭源为酚醛树脂等,气源为三聚氰胺等。阻燃增效剂为硼酸锌等。该文献需要采用多种阻燃剂,其中采用的无机阻燃剂对材料的力学性能影响很大,而同时选择酸源、炭源和气源三大类的膨胀型阻燃剂不但大大增加了生产成本,而且增大了生产复杂程度。
发明内容
本发明的目的之一在于解决上述技术问题,提供一种在具有较好的阻燃性能的同时,综合力学强度高、熔体流动性好、生产成本低、环保无毒的无卤阻燃高抗冲聚苯乙烯。
本发明的另一目的则是提供上述无卤阻燃高抗冲聚苯乙烯的制备方法。
实现本发明目的之一的技术方案是:一种无卤阻燃高抗冲聚苯乙烯,它是由下述重量份的组分制成:高抗冲聚苯乙烯树脂100份,苯乙烯-丁二烯-苯乙烯嵌段共聚物1~15份,无卤复合阻燃剂10~30份,润滑剂0.2~2.5份,稳定剂0.3~1.6份。
所述的无卤复合阻燃剂由磷酸酯、硼酸锌以及酚醛树脂按照(10~20)∶1∶(5~10)的重量比组成,所述的磷酸酯为磷酸三苯酯或者磷酸二甲苯酯。
所述的润滑剂为苏州兴泰国光化学助剂有限公司生产的商品代号为TAS-2A的光亮润滑剂。
所述的稳定剂由光稳定剂与抗氧剂按照(0.1~0.8)∶(0.2~0.8)的重量比组成。其中光稳定剂为UV-9【2-羟基-4-甲氧基二苯甲酮】、UV-P【2-(2’-羟基-5’-甲基苯基)苯并三唑】、UV-328【2-(2’-羟基-3’,5’-二叔戊基苯基)苯并三唑】中的一种或者两种。抗氧剂为抗氧剂1076【四(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯】、抗氧剂2246【2,2-亚甲基双-(4-甲基-6-叔丁基苯酚)】、抗氧剂DSTP【硫代二丙酸十八碳醇酯】中的一种或者两种。
实现本发明另一目的的技术方案是:上述无卤阻燃高抗冲聚苯乙烯的制备方法,具有以下步骤:①按照配方分别称取高抗冲聚苯乙烯树脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物、磷酸酯、硼酸锌、酚醛树脂、润滑剂以及稳定剂(包括光稳定剂和抗氧剂,下同)待用;②先将步骤①称取的高抗冲聚苯乙烯树脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物、硼酸锌、酚醛树脂、润滑剂以及稳定剂倒入高速混合机中混合,直至混合所产生的摩擦热使得物料温度升高至60℃~70℃,然后将磷酸酯倒入高速混合机中继续混合1min~2min,随即出料冷却;高速混合机的工作转速为800转/分钟~1000转/分钟;③将冷却后的混合物料送入到双螺杆挤出机中熔融挤出,所挤出的条料经水槽冷却、牵引进入切粒机造粒,即得到无卤阻燃高抗冲聚苯乙烯。
上述步骤③中,双螺杆挤出机各区的温度为:T1=120℃~130℃,T2=130℃~140℃,T3=140℃~150℃,T4=150℃~160℃,T5=160℃~170℃,T6=170℃~180℃,T7=180℃~190℃,T8=170℃~180℃,T模=180℃。
本发明具有的积极效果:(1)本发明的无卤阻燃高抗冲聚苯乙烯采用磷酸酯-硼酸锌-酚醛树脂组成新型阻燃复合体系,一方面该新型阻燃复合体系不含卤素,对环境无害;另一方面还具有良好的阻燃协同作用,在保证较好的阻燃效果的同时还具有用量少、生产成本较低、综合力学性能高的特点。(2)本发明采用的TAS-2A光亮润滑剂能有效的降低无卤阻燃高抗冲聚苯乙烯的熔体流动阻力,有利于无卤复合阻燃剂均匀分散于高抗冲聚苯乙烯和苯乙烯-丁二烯-苯乙烯嵌段共聚物中,从而提高加工流动性和脱模性,降低扭矩,减小设备磨损,充模容易,降低制品不良率。(3)本发明生产配方体系简单实用,生产实施简便,生产的无卤阻燃高抗冲聚苯乙烯综合性能良好。(4)本发明的无卤阻燃高抗冲聚苯乙烯在制备过程中,将阻燃剂之一的磷酸酯待高速混合机中混合物料温度升高到60℃~70℃后再加入,且只混合1min~2min,这样可以使磷酸酯在该高温下融化,从而使得其它阻燃剂和助剂粘附于高抗冲聚苯乙烯树脂和苯乙烯-丁二烯-苯乙烯嵌段共聚物表面,进一步提高材料的阻燃性和力学性能。
具体实施方式
(实施例1)
本实施例的无卤阻燃高抗冲聚苯乙烯由下述重量份的组分制成:
100kg的高抗冲聚苯乙烯树脂,来源于镇江奇美化工有限公司;
8kg的苯乙烯-丁二烯-苯乙烯嵌段共聚物,来源于韩国LG公司;
22kg的无卤复合阻燃剂,其中磷酸三苯酯15kg、硼酸锌1kg、酚醛树脂6kg。磷酸三苯酯来源于浙江万盛化学有限公司,硼酸锌来源于济南泰星精细化工有限公司,酚醛树脂来源于太仓市康盛化工原料有限公司。
1kg的TAS-2A光亮润滑剂,来源于苏州兴泰国光化学助剂有限公司。
0.6kg的光稳定剂UV-9;
0.3kg的抗氧剂1076。
上述无卤阻燃高抗冲聚苯乙烯的制备方法具有以下步骤:
①称取100kg的高抗冲聚苯乙烯树脂、8kg的苯乙烯-丁二烯-苯乙烯嵌段共聚物、15kg的磷酸三苯酯、1kg的硼酸锌、6kg的酚醛树脂、1kg的光亮润滑剂、0.6kg的光稳定剂UV-9以及0.3kg的抗氧剂1076待用。
②先将步骤①称取的高抗冲聚苯乙烯树脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物、硼酸锌、酚醛树脂、光亮润滑剂、光稳定剂以及抗氧剂倒入高速混合机中,在900转/分钟的工作转速下混合,直至混合所产生的摩擦热使得物料温度升高至65℃。然后将磷酸三苯酯倒入该高速混合机中继续混合1min,随即出料冷却。此时磷酸三苯酯(熔点约50.52℃)融化,从而使硼酸锌、酚醛树脂、光稳定剂以及抗氧剂均匀粘附于高抗冲聚苯乙烯树脂和苯乙烯-丁二烯-苯乙烯嵌段共聚物表面。
③将冷却后的混合物料送入到双螺杆挤出机中熔融挤出,所挤出的条料经水槽冷却、牵引进入切粒机造粒(粒径约为2mm~3mm),即得到颗粒状的无卤阻燃高抗冲聚苯乙烯。
双螺杆挤出机各区的温度依次为:T1=120℃~130℃,T2=130℃~140℃,T3=140℃~150℃,T4=150℃~160℃,T5=160℃~170℃,T6=170℃~180℃,T7=180℃~190℃,T8=170℃~180℃,T模=180℃。
(实施例2~实施例4)
各实施例与实施例1基本相同,不同之处在于见表1。
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | |
高抗冲聚苯乙烯树脂 | 100kg | 100kg | 100kg | 100kg |
苯乙烯-丁二烯-苯乙烯嵌段共聚物 | 8kg | 10kg | 12kg | 12kg |
磷酸三苯酯 | 15kg | 14kg | 18kg | 12kg |
硼酸锌 | 1kg | 1kg | 1kg | 1kg |
酚醛树脂 | 6kg | 7kg | 5kg | 7kg |
TAS-2A光亮润滑剂 | 1kg | 1kg | 1kg | 1kg |
UV-9 | 0.6kg | 0.5kg | 0.6kg | 0.6kg |
抗氧剂1076 | 0.4kg | 0.4kg | 0.4kg | 0.3kg |
(应用例)
将实施例1~实施例4制得的无卤阻燃高抗冲聚苯乙烯分别加入到注射成型机注射塑料标准试样,并按国家标准对该标准试样进行试验测试其热学性能、力学性能和阻燃性,测试结果见表2。
表2
测试性能 | 性能指标 | 测试标准 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
缺口抗冲击强度/KJ·m-2 | ﹥6.0 | GB/T1043-2008 | 8.2 | 8.8 | 9.1 | 8.7 |
弯曲强度/MPa | ﹥40.0 | GB/T9341-2000 | 43.3 | 42.8 | 42.1 | 42.3 |
弯曲模量/MPa | ﹥1600 | GB/T9341-2000 | 1900 | 1870 | 1820 | 1860 |
拉伸强度/MPa | ﹥25.0 | GB/T1040-2006 | 28.5 | 27.6 | 26.7 | 26.8 |
维卡软化温度/℃ | ﹥75.0 | GB/T1633—2000 | 88.3 | 87.5 | 87.1 | 87.3 |
熔体流动速率/g·10min-1 | ﹥4.0 | GB/T3682-2000 | 8.8 | 8.2 | 8.1 | 8.5 |
氧指数/% | ﹥25.0 | GB/T2406-1993 | 26.1 | 27.6 | 27.2 | 26.4 |
Claims (5)
1.一种无卤阻燃高抗冲聚苯乙烯的制备方法,其特征在于具有以下步骤:
①按照下述配方分别称取高抗冲聚苯乙烯树脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物、磷酸酯、硼酸锌、酚醛树脂、润滑剂以及稳定剂待用;
高抗冲聚苯乙烯树脂100份,苯乙烯-丁二烯-苯乙烯嵌段共聚物1~15份,无卤复合阻燃剂10~30份,润滑剂0.2~2.5份,稳定剂0.3~1.6份;
所述的无卤复合阻燃剂由磷酸酯、硼酸锌以及酚醛树脂按照(10~20)∶1∶(5~10)的重量比组成;所述的磷酸酯为磷酸三苯酯或者磷酸二甲苯酯;
②先将步骤①称取的高抗冲聚苯乙烯树脂、苯乙烯-丁二烯-苯乙烯嵌段共聚物、硼酸锌、酚醛树脂、润滑剂以及稳定剂倒入高速混合机中混合,直至混合所产生的摩擦热使得物料温度升高至50℃~60℃,然后将磷酸酯倒入高速混合机中继续混合1min~2min,随即出料冷却;高速混合机的工作转速为800转/分钟~1000转/分钟;
③将冷却后的混合物料送入到双螺杆挤出机中熔融挤出,所挤出的条料经水槽冷却、牵引进入切粒机造粒,即得到无卤阻燃高抗冲聚苯乙烯。
2.根据权利要求1所述的无卤阻燃高抗冲聚苯乙烯的制备方法,其特征在于:所述的润滑剂为苏州兴泰国光化学助剂有限公司生产的商品代号为TAS-2A的光亮润滑剂。
3.根据权利要求1或2所述的无卤阻燃高抗冲聚苯乙烯的制备方法,其特征在于:所述的稳定剂由光稳定剂与抗氧剂按照(0.1~0.8)∶(0.2~0.8)的重量比组成。
4.根据权利要求3所述的无卤阻燃高抗冲聚苯乙烯的制备方法,其特征在于:所述的光稳定剂为UV-9、UV-P、UV-328中的一种或者两种;所述的抗氧剂为抗氧剂1076、抗氧剂2246、抗氧剂DSTP中的一种或者两种。
5.根据权利要求1所述的无卤阻燃高抗冲聚苯乙烯的制备方法,其特征在于:步骤③中,双螺杆挤出机各区的温度为:T1=120℃~130℃,T2=130℃~140℃,T3=140℃~150℃,T4=150℃~160℃,T5=160℃~170℃,T6=170℃~180℃,T7=180℃~190℃,T8=170℃~180℃,T模=180℃。
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