CN109438877B - 离火自熄且可导电导热的阻燃塑料合金及其制备方法 - Google Patents

离火自熄且可导电导热的阻燃塑料合金及其制备方法 Download PDF

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CN109438877B
CN109438877B CN201811324705.3A CN201811324705A CN109438877B CN 109438877 B CN109438877 B CN 109438877B CN 201811324705 A CN201811324705 A CN 201811324705A CN 109438877 B CN109438877 B CN 109438877B
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周伯昕
聂祝平
丁伟伟
黄然
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Research Institute of Zhejiang University Taizhou
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Abstract

本发明公开了一种离火自熄且可导电导热的阻燃塑料合金及其制备方法,其中,离火自熄且可导电导热的阻燃塑料合金包括丙烯腈‑丁二烯‑苯乙烯三元共聚物、聚氯乙烯、石墨、氮化铝、硫醇有机锡和金属氧化物,所述阻燃塑料合金采用同向平行双螺杆挤出机进行共混挤出加工。本发明的阻燃塑料合金同时具有优异的导电性、导热性和阻燃性;流动性好,易于成型,适用于注塑、挤出等工艺,对环境友好,可以广泛使用于各类场景中。

Description

离火自熄且可导电导热的阻燃塑料合金及其制备方法
技术领域
本发明涉及一种高分子聚合物及其制备方法,尤其涉及一种离火自熄且可导电导热的阻燃塑料合金及其制备方法。
背景技术
各种各样的阻燃塑料合金材料已用于生活的方方面面,包括运输工具的内装饰、各类电器的屏蔽材料和包装袋等。
这样的塑料合金材料除了具有适当的电性能,还必须大幅保留它们的初始性能,以在多年的使用中具有有效的使用性能,并严格满足国家安全标准的要求。
阻燃剂是在抑制或抵抗火势蔓延的聚合物中使用的化学品。含有卤族元素的部分化合物首先被发现可以提高聚合物的阻燃性。但含卤化合物的生产过程伴有较为严重的污染,因此随着环保标准的提升,产能和价格均出现了较大的限制。
随后,一种不含卤素的膨胀型无机填料,例如羟基化合物,开始被作为阻燃剂添加到塑料合金中。上述填料在200至600℃的温度下吸热膨胀并发生分解,释放出惰性气体,通过降低燃烧部位的温度、隔绝氧气而实现阻燃。但为了实现高级别的阻燃效果,必须使用大量填料才能满足要求,由此带来的缺点是塑料合金的加工性和机械性能严重下降。
此外,在塑料合金中添加磷或含磷的化合物也可以实现高阻燃性。然而,上述磷或含磷的化合物易发生自燃或具有极强的吸水性,且吸水后摩擦系数急剧下降,加工性能较差,长期以来无法被大量应用于阻燃塑料合金的生产。更进一步,上述含有磷或含磷化合物的阻燃塑料合金,在起火-熄灭过程中会出现明显的滴落现象,不能满足较为严格的阻燃要求。
随着电气技术的发展,在一些应用场景中,部分电气部件要求材料同时具备导电、导热的特性,以实现静电屏蔽和散热的需求,同时需要离火自熄的阻燃等级以满足安全要求。但截止目前,无论以何种形式进行改性,在同一高分子材料上同时具有导电、导热和离火自熄的阻燃特性的技术手段及产品尚未见报道。
CN201010576777.4公开了一种PVC-ABS-EVA材料及其制备方法,其公开的材料不具备导电、导热特性,也不具备阻燃效果。CN200910058605.5公开了一种低电阻导电塑料的制备方法,其公开的材料不具备导热特性和阻燃效果。CN201410506348.8公开了一种导热塑料及其制备方法,其公开的材料不具备导电特性。
发明内容
本发明的目的是为解决目前同一高分子材料上不能同时具有导电、导热和离火自熄阻燃特性的技术问题。
为了解决上述技术问题,第一方面,本发明提供一种离火自熄且可导电导热的阻燃塑料合金,包括如下组分:
Figure GDA0002696380290000021
所述阻燃塑料合金的体积电阻率为1000Ωm-10000Ωm;导热系数为3-5W/mK;阻燃等级为离火自熄。
进一步地,所述丙烯腈-丁二烯-苯乙烯三元共聚物中丁二烯的含量为22-24wt%。
进一步地,所述丙烯腈-丁二烯-苯乙烯三元共聚物的熔体质量流动速率在5kg及200℃条件下为0.5-9g/10min。
进一步地,所述聚氯乙烯为经悬浮法聚合而成的疏松型聚氯乙烯,聚合度为700-720。
进一步地,所述石墨为鳞片型石墨,粒径为100-150μm。
进一步地,所述氮化铝为六方氮化铝,粒径为6-8μm。
进一步地,所述硫醇有机锡是质量比为20:80的硫醇一甲基锡和硫醇二甲基锡的混合物。
第二方面,本发明提供一种离火自熄且可导电导热的阻燃塑料合金的制备方法,采用第一方面中的组分及配比,包括如下步骤:
8、离火自熄且可导电导热的阻燃塑料合金的制备方法,其特征在于,采用第一方面中的组分及配比,包括如下步骤:
(1)将聚氯乙烯置于混合机中慢速搅拌,并缓缓加入硫醇有机锡;
(2)保持低速混合,并依次将石墨、氮化铝、金属氧化物和丙烯腈-丁二烯-苯乙烯三元共聚物加入步骤(1)形成的混合物中,充分混合均匀;
(3)将步骤(2)形成的混合物投入同向平行双螺杆挤出机中进行挤出造粒加工,即获得所述离火自熄且可导电导热的阻燃塑料合金。
进一步地,所述同向平行双螺杆挤出机的长径比为44:1。
进一步地,所述挤出造粒加工的温度为130-180℃。
本发明的阻燃塑料合金同时具有优异的导电性、导热性和离火自熄的阻燃性;流动性好,易于成型,适用于注塑、挤出等工艺,对环境友好,可以广泛使用于各类场景中。
具体实施方式
现在结合实施例对本发明作进一步详细的说明,本发明的应用并不局限于下面的实施例,对本发明所做的任何形式上的变通都将落入本发明的保护范围。
实施例1:
一种离火自熄且可导电导热的阻燃塑料合金,包含以下组分:
组分名称 质量百分比(%)
丙烯腈-丁二烯-苯乙烯三元共聚物 20
SG-8型聚氯乙烯 45
磷片石墨 20
六方氮化铝 7
硫醇有机锡 3
氧化铝 5
依次将SG-8型聚氯乙烯、硫醇有机锡、磷片石墨、六方氮化铝、氧化铝和丙烯腈-丁二烯-苯乙烯三元共聚物加入混合机中,保持200rpm的转速,混合10min,获得均匀的混合物;
将上述混合物经同向平行双螺杆挤出机进行挤出造粒。加工温度为130-180℃。
上述材料经测,体积电阻为3056Ωm,导热系数为4.3W/mk,同时达到UL-94测试标准定义的离火自熄阻燃等级。
实施例2:
一种离火自熄且可导电导热的阻燃塑料合金,包含以下组分:
Figure GDA0002696380290000041
Figure GDA0002696380290000051
依次将SG-8型聚氯乙烯、硫醇有机锡、磷片石墨、六方氮化铝、氧化铝、丙烯腈-苯乙烯共聚物和丁烯橡胶加入混合机中,保持180rpm的转速,混合15min,获得均匀的混合物;
将上述混合物经同向平行双螺杆挤出机进行挤出造粒。加工温度为130-180℃。
上述材料经测,体积电阻为8187Ωm,导热系数为2.9W/mk,同时达到UL-94测试标准定义的离火自熄阻燃等级。
实施例3:
一种离火自熄且可导电导热的阻燃塑料合金,包含以下组分:
组分名称 质量百分比(%)
丙烯腈-丁二烯-苯乙烯三元共聚物 19
SG-8型聚氯乙烯 44
磷片石墨 22
六方氮化铝 7
硫醇有机锡 3
氧化铝 5
依次将SG-8型聚氯乙烯、硫醇有机锡、磷片石墨、六方氮化铝、氧化铝和丙烯腈-丁二烯-苯乙烯三元共聚物加入混合机中,保持200rpm的转速,混合10min,获得均匀的混合物;
将上述混合物经同向平行双螺杆挤出机进行挤出造粒。加工温度为130-180℃。
上述材料经测,体积电阻为1056Ωm,导热系数为3.7W/mk,同时达到UL-94测试标准定义的离火自熄阻燃等级。
实施例4:
一种离火自熄且可导电导热的阻燃塑料合金,包含以下组分:
组分名称 质量百分比(%)
丙烯腈-丁二烯-苯乙烯三元共聚物 19
SG-8型聚氯乙烯 44
磷片石墨 20
六方氮化铝 9
硫醇有机锡 3
氧化铝 5
依次将SG-8型聚氯乙烯、硫醇有机锡、磷片石墨、六方氮化铝、氧化铝和丙烯腈-丁二烯-苯乙烯三元共聚物加入混合机中,保持200rpm的转速,混合10min,获得均匀的混合物;
将上述混合物经同向平行双螺杆挤出机进行挤出造粒。加工温度为130-180℃。
上述材料经测,体积电阻为7566Ωm,导热系数为4.9W/mk,同时达到UL-94测试标准定义的离火自熄阻燃等级。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。

Claims (10)

1.离火自熄且可导电导热的阻燃塑料合金,其特征在于,包括如下组分:
Figure FDA0002696380280000011
所述阻燃塑料合金的体积电阻率为1000Ωm-10000Ωm;导热系数为3-5W/mK;阻燃等级为离火自熄。
2.根据权利要求1所述的离火自熄且可导电导热的阻燃塑料合金,其特征在于,所述丙烯腈-丁二烯-苯乙烯三元共聚物中丁二烯的含量为22-24wt%。
3.根据权利要求1或2所述的离火自熄且可导电导热的阻燃塑料合金,其特征在于,所述丙烯腈-丁二烯-苯乙烯三元共聚物的熔体质量流动速率在5kg及200℃条件下为0.5-9g/10min。
4.根据权利要求1所述的离火自熄且可导电导热的阻燃塑料合金,其特征在于,所述聚氯乙烯为经悬浮法聚合而成的疏松型聚氯乙烯,聚合度为700-720。
5.根据权利要求1所述的离火自熄且可导电导热的阻燃塑料合金,其特征在于,所述石墨为鳞片型石墨,粒径为100-150μm。
6.根据权利要求1所述的离火自熄且可导电导热的阻燃塑料合金,其特征在于,所述氮化铝为六方氮化铝,粒径为6-8μm。
7.根据权利要求1所述的离火自熄且可导电导热的阻燃塑料合金,其特征在于,所述硫醇有机锡是质量比为20:80的硫醇一甲基锡和硫醇二甲基锡的混合物。
8.离火自熄且可导电导热的阻燃塑料合金的制备方法,其特征在于,采用权利要求1中的组分及配比,包括如下步骤:
(1)将聚氯乙烯置于混合机中慢速搅拌,并缓缓加入硫醇有机锡;
(2)保持低速混合,并依次将石墨、氮化铝、金属氧化物和丙烯腈-丁二烯-苯乙烯三元共聚物加入步骤(1)形成的混合物中,充分混合均匀;
(3)将步骤(2)形成的混合物投入同向平行双螺杆挤出机中进行挤出造粒加工,即获得所述离火自熄且可导电导热的阻燃塑料合金。
9.如权利要求8所述的方法,其特征在于,所述同向平行双螺杆挤出机的长径比为44:1。
10.如权利要求8所述的方法,其特征在于,所述挤出造粒加工的温度为130-180℃。
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Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Contract record no.: X2023980037257

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Assignee: ZHEJIANG FUMINGXING SPORTS PRODUCTS Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037254

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Assignee: Wenling Shuangding Sole Co.,Ltd.

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Contract record no.: X2023980037253

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Assignee: ZHEJIANG BIDI SPORTS GOODS Co.,Ltd.

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Contract record no.: X2023980037252

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Assignee: Wenling Shuolong Shoes Material Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037275

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Assignee: Wenling Xinjun Shoes Material Co.,Ltd.

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Contract record no.: X2023980037271

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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Assignee: Wenling Nanchen Shoes Material Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037270

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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License type: Common License

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Assignee: Taizhou Yimei Shoe Industry Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037251

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

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Assignee: Wenling Bana Shoes Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037293

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

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License type: Common License

Record date: 20230703

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Assignee: Wenling Guanlan Paper Box Factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037291

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230703

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Assignee: Wenling Rundebao Shoes Factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037167

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Qiaohu Shoes Factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037166

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Shi Nian Chaofa Shoes Factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037161

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Jiayi Shoes Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037280

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230703

Application publication date: 20190308

Assignee: Wenling City Saiwang Shoes Factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037339

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230703

Application publication date: 20190308

Assignee: Wenling Meijiasi Shoes Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037162

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Jianqiu Shoes Factory (general partnership)

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037169

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Chaoxuan Shoes Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037153

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Jiaxiu Shoes Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037110

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Taizhou Taste Shoes Industry Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037150

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

Application publication date: 20190308

Assignee: Wenling Yile Shoe Industry Co.,Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037428

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230704

Application publication date: 20190308

Assignee: Wenling Chengbei Liantong shoes factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037142

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230630

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20190308

Assignee: Wenling Xingfang Shoes Factory

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980037649

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230706

EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20190308

Assignee: Taizhou cloud makes intelligent technology Ltd.

Assignor: RESEARCH INSTITUTE OF ZHEJIANG University TAIZHOU

Contract record no.: X2023980039510

Denomination of invention: Flame retardant plastic alloy with self extinguishing and conductive and thermal conductivity after ignition and its preparation method

Granted publication date: 20201127

License type: Common License

Record date: 20230814