CN103360681B - 一种无卤阻燃高光聚丙烯及其制备方法 - Google Patents
一种无卤阻燃高光聚丙烯及其制备方法 Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 62
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- -1 polypropylene Polymers 0.000 title claims abstract description 49
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 44
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 10
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- 230000003647 oxidation Effects 0.000 claims description 9
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- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 5
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及热塑性高分子材料改性技术领域,公开了一种应用于家用电器、电子电器等方面的无卤阻燃高光聚丙烯,由以下材料组成:聚丙烯、成核剂、无卤阻燃剂、超细硫酸钡填充剂、抗氧剂及加工助剂;还公开了该种无卤阻燃高光聚丙烯的制备方法。本发明的目的是提供一种高光泽度及无卤阻燃的改性聚丙烯,能应用于面包机、饮水机及电器外壳等。
Description
技术领域
本发明涉及一种无卤阻燃高光聚丙烯的制备方法,属于热塑性高分子材料改性技术领域。本发明的产品为一种高光泽度及无卤阻燃的改性聚丙烯,能应用于面包机、饮水机及电器外壳等。
背景技术
聚丙烯为无毒、无臭、无味的乳白色高结晶的聚合物,密度只有0.90-0.91g/cm-3,是目前所有塑料中最轻的品种之一。它对水特别稳定,在水中的吸水率仅为0.01%,分子量约8万-15万。成型性好,但因收缩率大(为1%~2.5%),厚壁制品易凹陷,对一些尺寸精度较高零件,还难于达到要求,降低成品收缩率可以在PP树脂里添加玻璃纤维、滑石粉、硫酸钡、云母等,同时可提高刚性、耐热性,但玻纤因长径比大,对制品表面光泽不利,而粒度细的填料对于表面、刚性及耐热均有不同程度的提高;通过添加α晶型成核剂,能使其晶体变小,结晶率更高,提升制品表面光泽度,提高耐热温度及刚性指标,并能缩短制品成型周期,CN102485785A中的一种耐热、耐划痕高光聚丙烯材料,利用超细填料制备高光PP,主要利用填料来提升刚性及耐热。
PP的极限氧指数(LOI)只有18,属于易燃材料,而传统的溴系阻燃剂虽然有环保型,但锑资源价格的上涨已致其成本优势丧失,添加量大,对性能有一定影响,且长时间使用会腐蚀模具等不利因素均使无卤阻燃的必要性进一步提高。本发明所使用的无卤阻燃剂为市面上新推的以磷氮元素进行气相和凝聚相阻燃的高效阻燃剂,完全不含卤素,添加量小,无析出,对光泽度、物性等指标影响甚小,能使PP的氧指数提高到27,灼热丝(GWFI)可燃指数达到850度。
发明内容
本发明的目的在提供一种高光泽度及无卤阻燃的改性聚丙烯,能应用于面包机、饮水机及电器外壳等。
本发明的另一目的是提供一种无卤阻燃高光聚丙烯的制备方法。
为了实现上述第一发明目的,本发明的技术方案是:
一种无卤阻燃高光聚丙烯,由以下材料组成:聚丙烯、成核剂、超细硫酸钡、无卤阻燃剂、抗氧剂、加工助剂。
可选地,所述无卤阻燃高光聚丙烯按重量百分比由下述材料制成:
聚丙烯 70~85%;
超细硫酸钡 15~25%;
无卤阻燃剂 2~3%;
成核剂 0.2~0.5%;
抗氧剂 0.3~0.5%;
加工助剂 0.5~0.8%。
本发明采用高效的气相及凝聚相阻燃的磷氮型阻燃剂,添加量小,基本不影响材料的物性和耐热度,同时添加成核剂细化PP的结晶颗粒,提高综合性能及光泽度;而添加的超细硫酸钡能增加产品密度,提高尺寸稳定性和刚性,使制备出的产品不但能满足常用的小家电外壳所需的阻燃及灼热丝要求,并具有表面光泽好,加工成型优异的特点。
可选地,所述聚丙烯为均聚型聚丙烯,自身的刚性与光泽度比共聚型的好。
可选地,所述超细硫酸钡为沉淀法粒度为10000目的粉体,因沉淀法硫酸钡杂质含量少,粒度分布均匀,1万目的超细粉体对物性影响较小。
可选地,所述所述无卤阻燃剂为含磷氮元素的阻燃剂,因其添加量小,不影响机械性能,且不易析出;
可选地,所述成核剂为芳基羧酸盐类α晶型成核剂。
可选地,所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯。
可选地,所述加工助剂为EBS(乙撑双硬脂酰胺)和聚丙烯蜡。
一种无卤阻燃高光聚丙烯的制备方法,包括以下步骤:
S1.根据以下重量百分比称取各组分:
聚丙烯 70~85%;
超细硫酸钡 15~25%;
无卤阻燃剂 2~3%;
成核剂 0.2~0.5%;
抗氧剂 0.3~0.5%;
加工助剂 0.5~0.8%。
S2.将称取的所有原料混合均匀;
S3.将混合原料加入平行双螺杆挤出机,经熔融挤出,造粒。
可选地,所述步骤S2具体是:在常温下将称取的所有原料搅拌10~20分钟,混合均匀。
优选地,所述步骤S3中熔融阶段的工艺条件为:
所述平行双螺杆挤出机的螺杆直径为35~75毫米,螺杆长径比为36:1;
在双螺杆机控温段中,一区温度为180℃,二区温度为185℃,三区温度为190℃,四区温度为200℃,五区温度为200℃,六区温度为200℃,七区温度为195℃,八区温度为200℃,双螺杆机的机头温度为205℃;
螺杆转速为250~450r/min,转速太小产量不高;转速太大,机器易磨损;故选择250~450r/min的转速较合适;
与现有技术相比,应用本发明的技术方案,有如下有益效果:
本发明无卤阻燃高光聚丙烯通过在配方中加入均聚聚丙烯、无卤阻燃剂、成核剂、超细硫酸钡、抗氧剂、加工助剂组成,通过添加高效的磷氮型无卤阻燃剂提高PP的阻燃性能且不降低其机械性能,同时添加α晶型成核剂与超细硫酸钡,能大大提高制品的光泽度、刚性及耐热度。
具体实施方式
下面将结合具体实施例来详细说明本发明,在此本发明的示意性实施例以及说明用来解释本发明,但并不作为对本发明的限定。
本发明所述的一种无卤阻燃高光聚丙烯的实施例,由以下材料组成:聚丙烯、成核剂、无卤阻燃剂、超细硫酸钡填充剂、抗氧剂及加工助剂,通过添加无卤阻燃剂和成核剂、超细填料,制备出无卤阻燃与光泽度高、机械性能与耐热性能较好的小家电面板专用料。
本发明实施例中:
聚丙烯为均聚型;
超细硫酸钡为沉淀法粒度为10000目的粉体;
无卤阻燃剂为含磷氮元素的阻燃剂;
成核剂为芳基羧酸盐类α晶型成核剂;
抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯;
加工助剂为EBS(乙撑双硬脂酰胺)和聚丙烯蜡。
本发明实施例的无卤阻燃高光聚丙烯均可采用同样的制备方法,包括以下步骤:
S1.根据以下重量百分比称取各组分:
聚丙烯 70~85%;
超细硫酸钡 15~25%;
无卤阻燃剂 2~3%;
成核剂 0.2~0.5%;
抗氧剂 0.3~0.5%;
加工助剂 0.5~0.8%。
S2.将称取的所有原料混合均匀;
S3.将混合原料加入平行双螺杆挤出机,经熔融挤出,造粒。
其中,本发明实施例中平行双螺杆挤出机熔融阶段的工艺条件为:平行双螺杆挤出机的螺杆直径为35~75毫米;在双螺杆机控温段中,一区温度为180℃,二区温度为185℃,三区温度为190℃,四区温度为200℃,五区温度为200℃,六区温度为200℃,七区温度为195℃,八区温度为200℃,双螺杆机的机头温度为205℃;螺杆转速控制在250~450r/min;经双螺杆挤出机熔融共混挤出、水冷、风干、切粒,最后包袋成无卤阻燃高光聚丙烯成品。
实施例1:
(1)称取均聚PP82kg,超细硫酸钡15kg,无卤阻燃剂2kg,成核剂0.2kg,抗氧剂10100.1kg,1680.2kg,润滑剂EBS0.2kg,聚丙烯蜡0.3KG;
(2)将称取的所有原料在高速混合机中混合10min;
(3)将混合均匀的料加入到双螺杆挤出机的料斗中,经双螺杆挤出机熔融共混挤出、水冷、风干、切粒,最后包袋成成品。其中,螺杆转速为250r/min。
将上述的无卤阻燃高光PP注塑成标准试样,测试性能如表1所示。
实施例2:
(1)称取均聚PP70.2kg,超细硫酸钡25kg,无卤阻燃剂3kg,成核剂0.5kg,抗氧剂10100.3kg,1680.2kg,润滑剂EBS0.3kg,聚丙烯蜡0.5KG;
(2)将称取的所有原料在高速混合机中混合20min;
(3)将混合均匀的料加入到双螺杆挤出机的料斗中,经双螺杆挤出机熔融共混挤出、水冷、风干、切粒,最后包袋成成品。其中,螺杆转速为450r/min。
将上述的无卤阻燃高光PP注塑成标准试样,测试性能如表1所示。
实施例3:
(1)称取均聚PP78.7kg,超细硫酸钡18kg,无卤阻燃剂2kg,成核剂0.3kg,抗氧剂10100.2kg,1680.2kg,润滑剂EBS0.3kg,聚丙烯蜡0.3KG;
(2)将称取的所有原料在高速混合机中混合15min;
(3)将混合均匀的料加入到双螺杆挤出机的料斗中,经双螺杆挤出机熔融共混挤出、水冷、风干、切粒,最后包袋成成品。其中,螺杆转速为350r/min。
将上述的无卤阻燃高光PP注塑成标准试样,测试性能如表1所示。
实施例4:
(1)称取均聚PP73.2kg,超细硫酸钡23kg,无卤阻燃剂2.5kg,成核剂0.3kg,抗氧剂10100.1kg,1680.2kg,润滑剂EBS0.3kg,聚丙烯蜡0.4KG;
(2)将称取的所有原料在高速混合机中混合15min;
(3)将混合均匀的料加入到双螺杆挤出机的料斗中,经双螺杆挤出机熔融共混挤出、水冷、风干、切粒,最后包袋成成品。其中,螺杆转速为300r/min。
将上述的无卤阻燃高光PP注塑成标准试样,测试性能如表1所示。
对比例:
(1)称取均聚PP79kg,超细硫酸钡20kg,抗氧剂10100.1kg,1680.2kg,润滑剂EBS0.3kg,聚丙烯蜡0.4KG;
(2)将称取的所有原料在高速混合机中混合10min;
(3)将混合均匀的料加入到双螺杆挤出机的料斗中,经双螺杆挤出机熔融共混挤出、水冷、风干、切粒,最后包袋成成品。其中,螺杆转速为300r/min。
将上述的无卤阻燃高光PP注塑成标准试样,测试性能如表1所示。
表1无卤阻燃高光PP性能表
通过表1的对比,本发明在阻燃性与灼热丝上均优于填充PP,在物性基本相近的情况下,本体系能大幅提高阻燃性,并提高了光泽度。
Claims (6)
1.一种无卤阻燃高光聚丙烯,其特征是,按重量百分比由下述材料制成:
其中,所述超细硫酸钡为沉淀法粒度为10000目的粉体,所述无卤阻燃剂为含磷氮元素的阻燃剂,所述成核剂为芳基羧酸盐类α晶型成核剂,所述加工助剂为EBS(乙撑双硬脂酰胺)和聚丙烯蜡。
2.根据权利要求1所述的一种无卤阻燃高光聚丙烯,其特征是:所述聚丙烯为均聚型聚丙烯。
3.根据权利要求1所述的一种无卤阻燃高光聚丙烯,其特征是:所述抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和亚磷酸三(2,4-二叔丁基苯基)酯。
4.一种无卤阻燃高光聚丙烯的制备方法,其特征是,包括以下步骤:
S1.根据以下重量百分比称取各组分:
S2.将称取的所有原料混合均匀;
S3.将混合原料加入平行双螺杆挤出机,经熔融挤出,造粒;
其中,所述超细硫酸钡为沉淀法粒度为10000目的粉体,所述无卤阻燃剂为含磷氮元素的阻燃剂,所述成核剂为芳基羧酸盐类α晶型成核剂。
5.根据权利要求4所述的无卤阻燃高光聚丙烯的制备方法,其特征是,所述步骤S2具体是:在常温下将称取的所有原料搅拌10~20分钟,混合均匀。
6.根据权利要求4所述的一种无卤阻燃高光聚丙烯的制备方法,其特征是,所述步骤S3中熔融阶段的工艺条件为:
所述平行双螺杆挤出机的螺杆直径为35~75毫米,螺杆长径比为36:1;
在双螺杆机控温段中,一区温度为180℃,二区温度为185℃,三区温度为190℃,四区温度为200℃,五区温度为200℃,六区温度为200℃,七区温度为195℃,八区温度为200℃,双螺杆机的机头温度为205℃;
螺杆转速为250~450r/min。
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