CN116041872B - 一种耐迁移析出、耐老化pvc电缆料组合物 - Google Patents
一种耐迁移析出、耐老化pvc电缆料组合物 Download PDFInfo
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- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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Abstract
一种耐析出、耐老化的PVC组合物,其以质量份数计包括:中高聚合度PVC树脂,100份;高功能增塑剂,40~80份。其还可进一步包括钙锌稳定剂:6~9份;加工助剂:1.0~3.0份;抗氧剂:0.5~1.0份;润滑剂:1.0~2.0份;填料:10~20份等。制备方法为:将以上物料按照配方准确称量,将物料加入到高速混合机中混合,放料至冷却机中冷却。将冷却后的物料于双螺杆挤出机中造粒,最终得到PVC组合物。所得组合物具有耐迁移析出、耐老化、耐低温、耐油性和阻燃性等性能,可广泛应用于汽车电缆、充电桩电缆等领域。
Description
技术领域
本发明涉及PVC组合物应用领域,具体涉及一种耐迁移析出、耐老化PVC电缆料组合物。
背景技术
近年来,随着线缆在细分的产品如安全防火线缆、船用线缆、通信线缆、数据线缆、伺服控制线缆、编码器线缆、充电桩线缆、深井勘测线缆、深井潜油泵线缆等对线缆提出了特殊的要求,如柔软性、耐高温、耐寒、耐磨、耐油、耐溶剂、耐水性、耐酸碱性等。PVC电缆具有柔软、耐磨、力学性能高、易加工、性价比高等优点,在车用、船用、电脑、办公、家庭等场所应用广泛。但PVC电缆由于添加的增塑剂分子量小,往往会出现增塑剂迁移到电缆表面的问题,长期析出迁移会造成电线硬化脆化,不能满足使用要求,造成安全隐患。近几年来开发的聚酯类增塑剂可以明显改善增塑剂析出的问题,析出量明显较少,但在抗析出方面仍有改进的空间。
CN109735021A公开了焊接机器人用耐高温耐油阻燃PVC电缆料及其制备方法,由以下重量份组分组成:聚合度为1300的PVC树脂50~ 100份,聚合度为2500的PVC树脂0~50份,偏苯三酸酯20~30 份,聚酯增塑剂2050 10~20份,三氧化二锑5~10份,硼酸锌8~12份,填料5~10份,氢氧化铝10~15份,钙锌热稳定剂10~15 份,抗氧剂1076 0.2~0.4份,润滑剂0.4~0.6份,加工改性剂P551J 0.8~1.2份,乙烯-醋酸乙烯-马来酸酐共聚物5~10份,聚酯弹性体20~30份,无机硅酸盐粘土1~3份。该发明所用的PVC树脂为两种聚合度差异较大的PVC树脂,这会造成能够塑化不均,降低材料的性能。乙烯-醋酸乙烯-马来酸酐共聚物的耐热性较差,还容易与加工设备内壁发生粘连,影响成型加工。CN112552617A公开了一种PVC 电缆料及其制备方法和应用,所述PVC电缆料包括如下重量份数的组分:PVC树脂10~30份,填料40~60份,乙烯-醋酸乙烯-一氧化碳和小分子增塑剂10~20份,剂DOS、DOA2~5份,POE-g-MAH、 EVA-g-MAH相容剂0.1~2份,硅烷偶联剂1~2份,硅酮润滑剂1~ 3份。该发明能够达到较高的性能,但剂DOS、DOA是小分子增塑剂,耐热性能差,容易迁移析出。
为了解决上述问题,本发明制备了一种耐迁移析出、耐老化PVC 电缆料组合物,解决了PVC电缆析出、耐热性能差的问题。
发明内容
本发明提供了一种PVC组合物,其以质量份数(下同)计包括:中高聚合度PVC树脂,100份;高功能增塑剂,40~80份。其还可进一步包括钙锌稳定剂:6~9份;加工助剂:1.0~3.0份;抗氧剂:0.5~ 1.0份;润滑剂:1.0~2.0份;填料:10~20份等。其中,所述高功能增塑剂为甲基丙烯酸甲酯、长链丙烯酸酯、丙烯腈、苯乙烯的无规共聚物,甲基丙烯酸甲酯/长链丙烯酸酯/丙烯腈/苯乙烯的质量比为 0.5~1.0/5.0~7.0/0.5~1.0/1.0~2.0;长链丙烯酸酯为丙烯酸丁酯、丙烯酸己酯、丙烯酸辛酯、丙烯酸月桂酯、丙烯酸十四酯中的一种或几种。
其中,高功能增塑剂的制备方法为:在常温下,反应釜中往100 份水中加入5~8份乳化剂油酸钾、50~70份长链丙烯酸酯、0.5~1.0 份引发剂,抽真空充氮气后,搅拌均匀,升温至60℃~70℃,引发反应,将10~20份苯乙烯、5~10份丙烯腈、5~10份甲基丙烯酸甲酯混合后,连续滴加到长链丙烯酸酯乳液中。将0.25~0.4份促进剂于升温引发后4~5小时加入。升温引发后,反应持续16~18小时,加入终止剂终止反应。将乳液经过破乳、脱水、干燥等后处理步骤获得高功能增塑剂。
中高聚合度PVC树脂优选通过悬浮法生产,平均聚合度1000-3000 之间,更优选2000-2100之间。
所述加工助剂可以为ACR类、MBS类加工助剂;所述抗氧剂为受阻酚类抗氧剂、硫代酯类抗氧剂、亚磷酸酯类抗氧剂的两种或三种复配抗氧剂;所述填料为经双长链烷基铵表面改性的有机蒙脱石,粒径为 1200目~2000目。
PVC组合物的制备方法包括:将以上物料按照配方准确称量,将物料加入到高速混合机中混合,放料至冷却机中冷却。将冷却后的物料于双螺杆挤出机中造粒,得到一种耐迁移析出、耐老化的PVC组合物。
本发明还提供了将上述的PVC组合物或所述制备方法得到的PVC 组合物用于电缆料中,尤其是汽车电缆、充电桩电缆等绝缘层的用途,其具有耐迁移析出、耐老化、耐低温、耐油性和阻燃性等性能。
本发明具有以下有益技术效果:
(1)由中高聚合度PVC树脂、高功能增塑剂,并根据需要加入稳定剂、加工助剂、抗氧剂、润滑剂、填料等共混后,通过双螺杆剪切造粒制得一种耐迁移析出、耐老化、耐低温的PVC电缆料组合物。本申请所述中高聚合度PVC树脂兼顾加工性和机械性能,比高、低聚合度配混的PVC性能好。
(2)高功能增塑剂为甲基丙烯酸甲酯、长链丙烯酸酯、丙烯腈、苯乙烯的无规共聚物。高功能增塑剂为高分子量固相增塑剂,不仅具有极佳的抗析出迁移性能,其长链丙烯酸酯链段能够够赋予PVC特种电缆的柔软性、耐热性;甲基丙烯酸甲酯、丙烯腈、苯乙烯链段能够赋予PVC相与长链丙烯酸酯链段良好的相容性、耐非极性溶剂性和良好的加工性能,保证了PVC特种电缆的最终性能。
(3)高功能增塑剂与ACR类、MBS类PVC加工助剂具有协同增效作用,共同提高PVC电缆料的耐迁移析出性能。
(4)抗氧剂1076、626、DLTDP的复合抗氧剂及双长链烷基铵表面改性的有机蒙脱石具有协同提高PVC电缆耐热氧老化的效果。
附图说明
图1是PVC电缆料组合物的增塑剂迁移性能评价示意图。从上到下为五层,上下两层为玻璃板,中间层为PMMA板(压克力片),两个待测样片层夹在玻璃板和PMMA之间,具体如图所述。测试条件为 70℃,72小时,测试由PVC软片迁移到压克力片上增塑剂的量。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合具体实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
耐迁移析出、耐老化PVC电缆料组合物的实施例和对比例各物料组分按照表1、表2的配方进行称量。其中中高聚合度PVC树脂通过悬浮法生产,平均聚合度为2000-2100(如聚合度为2050);所述高功能增塑剂为甲基丙烯酸甲酯、长链丙烯酸酯、丙烯腈、苯乙烯的无规共聚物,甲基丙烯酸甲酯/长链丙烯酸酯/丙烯腈/苯乙烯的质量份数比为0.5~1.0/5.0~7.0/0.5~1.0/1.0~2.0;高功能增塑剂的制备方法为:在常温下,反应釜中往100份水中加入5~8份乳化剂油酸钾、50~70份长链丙烯酸酯、0.5~1.0份引发剂,抽真空充氮气后,搅拌均匀,升温至60℃~70℃,引发反应,将10~20份苯乙烯、5~10份丙烯腈、5~10份甲基丙烯酸甲酯混合后,连续滴加到长链丙烯酸酯乳液中,持续滴加10小时。将0.25~0.4份促进剂于升温引发后4~5小时加入。升温引发后,反应持续16~18小时,加入终止剂终止反应。将乳液加入破乳剂破乳、离心脱水、进入干燥床干燥后获得高功能增塑剂。处理的蒙脱石为经双长链烷基铵表面改性的有机蒙脱石,粒径为1200目~2000目。
表1 PVC电缆料组合物的实施例(质量份数)
表2 PVC电缆料组合物的对比例(质量份数)
将以上物料按照配方准确称量,将物料加入到高速混合机中在 110℃下混合10分钟,放料至冷却机中冷却至30℃~40℃。将冷却后的物料于双螺杆挤出机中造粒,得到一种耐迁移析出、耐老化PVC电缆料组合物。
将制得耐迁移析出、耐老化PVC电缆料组合物开炼、热模压制样、裁样。组合物的增塑剂迁移性能的评价方法如图1所示,测试条件为 70℃,72小时,测试由PVC软片迁移到压克力片上增塑剂的量。性能如表3所示。组合物的热氧老化性能按照GB/T 8815-2008中6.12测试,热氧老化温度为115℃,老化时间是240h。
表3 PVC电缆料组合物实施例和对比例性能
由表1-3对应实施例和对比例及其效果数据可看出,高功能增塑剂可以给PVC电缆料带来优异的耐迁移性和抗热氧老化性能;而对比例1组分含有普通聚酯增塑剂,其耐迁移性和抗热氧老化性能均较差。高功能增塑剂与ACR类、MBS类PVC加工助剂具有协同增效作用,共同提高PVC电缆料的耐迁移析出性能;而对比例2含有脂肪酸酯类加工助剂,与实施例2相比,其无法与高功能增塑剂形成协同效应,耐迁移性和抗热氧老化性能均较差。抗氧剂1076、626、DLTDP的复合抗氧剂及双长链烷基铵表面改性的有机蒙脱石具有协同提高PVC电缆耐热氧老化的效果,而对比例4和对比例5未含有抗氧剂1076、626、DLTDP 的复合抗氧剂及双长链烷基铵表面改性的有机蒙脱石的组合,其热氧老化性能很差。润滑体系中,由对比例3可以看出,硬脂酸与聚乙烯蜡复配使用的耐迁移性和抗热氧老化效果不如氧化聚乙烯(AC-316A) 与聚乙烯蜡复配使用的效果。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (4)
1.一种PVC组合物,其以质量份数计由如下组分组成:
中高聚合度PVC树脂 100份,钙锌稳定剂 8份,高功能增塑剂 60份,ACR类加工助剂 2份,润滑剂AC-316A 0.5份,润滑剂PE蜡 0.3份,抗氧剂1076 0.2份,抗氧剂626 0.2份,抗氧剂DLTDP 0.1份,处理的蒙脱石 5份;
其中,所述中高聚合度PVC树脂通过悬浮法生产,平均聚合度为2000-2100;所述高功能增塑剂为甲基丙烯酸甲酯、长链丙烯酸酯、丙烯腈、苯乙烯的无规共聚物,甲基丙烯酸甲酯/长链丙烯酸酯/丙烯腈/苯乙烯的质量份数比为0.5~1.0/5.0~7.0/0.5~1.0/1.0~2.0;高功能增塑剂的制备方法为:在常温下,反应釜中往100份水中加入5~8份乳化剂油酸钾、50~70份长链丙烯酸酯、0.5~1.0份引发剂,抽真空充氮气后,搅拌均匀,升温至60℃~70℃,引发反应,将10~20份苯乙烯、5~10份丙烯腈、5~10份甲基丙烯酸甲酯混合后,连续滴加到长链丙烯酸酯乳液中,持续滴加10小时,将0.25~0.4份促进剂于升温引发后4~5小时加入,升温引发后,反应持续16~18小时,加入终止剂终止反应,将乳液加入破乳剂破乳、离心脱水、进入干燥床干燥后获得高功能增塑剂;所述处理的蒙脱石为经双长链烷基铵表面改性的有机蒙脱石,粒径为1200目~2000目。
2.如权利要求1所述的PVC组合物,其中长链丙烯酸酯为丙烯酸丁酯、丙烯酸己酯、丙烯酸辛酯、丙烯酸月桂酯、丙烯酸十四酯中的一种或几种。
3.如权利要求1或2所述的PVC组合物的制备方法,包括:将所述物料按照配方准确称量,将物料加入到高速混合机中在110℃下混合10分钟,放料至冷却机中冷却至30℃~40℃;将冷却后的物料于双螺杆挤出机中造粒,得到PVC组合物。
4.如权利要求1或2所述的PVC组合物或如权利要求3所述制备方法得到的PVC组合物用于汽车电缆、充电桩电缆绝缘层的用途。
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