CN103483676A - 无卤阻燃线性低密度聚乙烯材料及其制备方法 - Google Patents
无卤阻燃线性低密度聚乙烯材料及其制备方法 Download PDFInfo
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- 229920000092 linear low density polyethylene Polymers 0.000 title claims abstract description 60
- 239000004707 linear low-density polyethylene Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000003063 flame retardant Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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 title abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 20
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 11
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 11
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 7
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- 229920000573 polyethylene Polymers 0.000 claims description 9
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- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
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- 239000001301 oxygen Substances 0.000 abstract description 7
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Abstract
本发明公开了一种无卤阻燃线性低密度聚乙烯材料及其制备方法,该材料由下述重量份的组分制成:LLDPE树脂100份,增韧相容剂10~30份,润滑分散剂10~20份,无卤复合阻燃剂350~450份;无卤复合阻燃剂由氢氧化镁/氢氧化铝、硼酸锌以及微胶囊红磷按照(10.5~11.5)∶1∶(1.05~1.15)的重量比组成。该材料的制备方法如下:将各组分倒入高速混合机中混合,直至温度升高至90℃~105℃,出料冷却,然后熔融挤出,接着水槽冷却,最后牵引造粒即得。本发明的无卤阻燃线性低密度聚乙烯材料阻燃性能好,极限氧指数在40%以上;同时力学性能优异,拉伸强度在18MPa以上,断裂伸长率在75%以上。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种无卤阻燃线性低密度聚乙烯材料及其制备方法。
背景技术
线性低密度聚乙烯(简称LLDPE)是一种通用塑料,具有来源广、价格低廉、比重轻、无毒、耐腐蚀、成型加工容易等优点,被广泛用于管材、建筑装饰、电线电缆、泡沫材料等制品的生产。LLDPE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,这对LLDPE材料的安全使用带来极大隐患。
中国专利文献CN103232631A公开了一种无卤低烟阻燃电缆护套料及其制备方法,它是由线性低密度聚乙烯100份,无机阻燃剂60~80份,协效阻燃剂6~10份,抑烟添加剂5~12份,硅烷偶联剂2份制成;其中无机阻燃剂为氢氧化铝、氢氧化镁或其混合物;协效阻燃剂为微胶囊红磷、硅烷偶联剂改性聚磷酸铵、聚硅氧烷改性聚磷酸铵或三聚氰胺多磷酸盐;抑烟添加剂为硼酸锌、锡酸锌或者双羟基镁铝复合金属氧化物。该文献的不足在于:(1)虽然有效控制了烟密度,但是阻燃性能不佳,极限氧指数低于40%;(2)协效阻燃剂采用微胶囊红磷时的力学性能不佳,拉伸强度只有12MPa左右,断裂伸长率不到60%。
发明内容
本发明的目的之一在于解决上述问题,提供一种阻燃性能和力学性能均较佳的无卤阻燃线性低密度聚乙烯材料。
本发明的另一目的则是提供上述无卤阻燃线性低密度聚乙烯材料的制备方法。
实现本发明第一种目的的技术方案是:一种无卤阻燃线性低密度聚乙烯材料,由下述重量份的组分制成:LLDPE树脂100份,增韧相容剂10~30份,润滑分散剂10~20份,无卤复合阻燃剂350~450份;所述的无卤复合阻燃剂由氢氧化镁/氢氧化铝、硼酸锌以及微胶囊红磷按照(10.5~11.5)∶1∶(1.05~1.15)的重量比组成。
为了提高无卤阻燃线性低密度聚乙烯材料的成型加工性能,所述的LLDPE树脂的熔体流动速率为2g/10min~8g/10min。
所述的增韧相容剂为马来酸酐接枝EVA,其接枝率为2%~5%。
所述的润滑分散剂为聚乙烯蜡,其相对分子量为2000~4000。
实现本发明第二种目的的技术方案是:上述无卤阻燃线性低密度聚乙烯材料的制备方法,具有以下步骤:①将按照配方称取的LLDPE树脂、增韧相容剂、润滑分散剂以及无卤复合阻燃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90℃~105℃(这样可以进一步提高无卤阻燃线性低密度聚乙烯材料的成型加工性能),出料冷却;②将步骤①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,即得无卤阻燃线性低密度聚乙烯材料。
所述的高速混合机的工作转速为450转/分钟~900转/分钟。
所述的双螺杆挤出机各区的温度为:T1=110℃;T2=150℃;T3=158℃;T4=177℃;T5=185℃;T6=190℃;T7=190℃;T8=195℃;T9=195℃;T模=185℃。
本发明具有的积极效果:(1)本发明的无卤阻燃线性低密度聚乙烯材料采用氢氧化镁/氢氧化铝、硼酸锌以及微胶囊红磷组成无卤复合阻燃体系,并控制无卤复合阻燃体系的用量在线性低密度聚乙烯用量的3.5~4.5倍之间,同时控制氢氧化镁/氢氧化铝、硼酸锌以及微胶囊红磷的重量比在(10.5~11.5)∶1∶(1.05~1.15),这样一方面使得该无卤复合阻燃体系具有最佳的阻燃协同效应,从而大大提高阻燃性能,另一方面采用增韧相容剂有效提高无卤复合阻燃体系与LLDPE树脂的相容性,从而改善无卤阻燃线性低密度聚乙烯材料的力学性能。最终可以得到极限氧指数在40%以上、拉伸强度在18MPa以上、断裂伸长率在75%以上的无卤阻燃线性低密度聚乙烯材料。(2)本发明采用熔体流动速率为2g/10min~8g/10min的LLDPE树脂粉作为原料,这样有利于无卤复合阻燃体系与其均匀混合,从而使的无卤阻燃线性低密度聚乙烯材料具有更好的成型加工性能。同时,在制备过程中将物料混合温度升高至90℃~105℃,这样有利于润滑分散剂聚乙烯蜡熔化均匀覆盖在LLDPE树脂粉和无卤复合阻燃体系表面,进一步提高无卤阻燃线性低密度聚乙烯材料的成型加工性能。
具体实施方式
(实施例1)
本实施例的无卤阻燃线性低密度聚乙烯材料由下述重量份的组分制成:
100kg的LLDPE树脂粉,其熔体流动速率为5g/10min。
15kg的作为增韧相容剂的马来酸酐接枝EVA,其接枝率为3%。
15kg的作为润滑分散剂的聚乙烯蜡,其相对分子量为3000。
393kg的无卤复合阻燃剂,由330kg的氢氧化镁(1250目)、30kg的硼酸锌以及33kg的微胶囊红磷组成。
上述无卤阻燃线性低密度聚乙烯材料的制备方法如下:
①将按照上述配方称取的LLDPE树脂粉、马来酸酐接枝EVA、聚乙烯蜡、氢氧化镁、硼酸锌以及微胶囊红磷依次倒入高速混合机中,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100℃(此时聚乙烯蜡全部融化均匀覆盖在LLDPE树脂粉和无卤复合阻燃剂表面),即可出料冷却。
②将步骤①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线性低密度聚乙烯材料。
双螺杆挤出机各区的温度依次为:T1=110℃;T2=150℃;T3=158℃;T4=177℃;T5=185℃;T6=190℃;T7=190℃;T8=195℃;T9=195℃;T模=185℃。
(实施例2~实施例7)
各实施例与实施例1基本相同,不同之处在于表1。
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | |
LLDPE | 100kg | 100kg | 100kg | 100kg | 100kg | 100kg | 100kg |
马来酸酐接枝EVA | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg |
聚乙烯蜡 | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg |
氢氧化镁 | 330kg | 330kg | 330kg | 315kg | 345kg | 315kg | 345kg |
硼酸锌 | 30kg | 30kg | 30kg | 30kg | 30kg | 30kg | 30kg |
微胶囊红磷 | 33kg | 31.5kg | 34.5kg | 33kg | 33kg | 31.5kg | 34.5kg |
(应用例)
将实施例1~实施例7制得的无卤阻燃线性低密度聚乙烯材料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,测试其力学性能和阻燃性能,测试结果见表2。
表2
测试性能 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 |
缺口抗冲击强度/kJ·m-2 | 15.2 | 15.3 | 15.1 | 15.5 | 14.9 | 15.7 | 14.7 |
拉伸强度/MPa | 18.8 | 19.1 | 18.6 | 19.4 | 18.2 | 19.8 | 17.8 |
断裂伸长率/% | 85 | 87 | 82 | 88 | 80 | 90 | 78 |
最大烟密度 | 58 | 67 | 63 | 68 | 64 | 71 | 60 |
极限氧指数/% | 44.5 | 41.8 | 42.6 | 41.1 | 42.7 | 40.6 | 43.8 |
表2中,缺口抗冲击强度的测试标准为GB/T1043-2008,拉伸强度的测试标准为GB/T1040-2006,断裂伸长率的测试标准为GB/T1040-2006,最大烟密度的测试标准为GB/T8627-2007,极限氧指数的测试标准为GB/T2406-1993。
(对比例)
其中,对比例1为中国专利文献CN103232631A实施例1制得的阻燃材料。
对比例2~对比例8与实施例1基本相同,不同之处在于表3。
表3
对比例2 | 对比例3 | 对比例4 | 对比例5 | 对比例6 | 对比例7 | 对比例8 | |
LLDPE | 100kg | 100kg | 100kg | 100kg | 100kg | 100kg | 100kg |
马来酸酐接枝EVA | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg |
聚乙烯蜡 | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg | 15kg |
氢氧化镁 | 440kg | 220kg | 480kg | 360kg | 300kg | 250kg | 200kg |
硼酸锌 | 40kg | 20kg | 30kg | 30kg | 30kg | 30kg | 30kg |
微胶囊红磷 | 44kg | 22kg | 48kg | 36kg | 30kg | 25kg | 30kg |
(对比应用例)
将对比例1~对比例8的阻燃材料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,测试其力学性能和阻燃性能,测试结果见表4。
表4
测试性能 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | 对比例6 | 对比例7 | 对比例8 |
缺口抗冲击强度/kJ·m-2 | 10.0 | 9.4 | 12.6 | 9.1 | 9.8 | 10.4 | 12.2 | 12.4 |
拉伸强度/MPa | 12.1 | 10.5 | 16.8 | 10.1 | 11.8 | 12.6 | 16.4 | 16.6 |
断裂伸长率/% | 58 | 52 | 67 | 50 | 55 | 58 | 63 | 65 |
最大烟密度 | 55 | 52 | 54 | 60 | 62 | 65 | 61 | 62 |
极限氧指数/% | 38.1 | 42.0 | 36.5 | 41.5 | 40.1 | 39.5 | 36.0 | 35.5 |
由表2和表4可以看出:
(1)本发明的无卤阻燃线性低密度聚乙烯材料相比于中国专利文献CN103232631A的阻燃材料,阻燃性能和力学性能均更佳,而最大烟密度也相差不大。
(2)当无卤复合阻燃体系的用量超过线性低密度聚乙烯的4.5倍时(对比例2、4),不但力学性能大大降低,阻燃性能也不及本发明的无卤阻燃线性低密度聚乙烯材料。
(3)当无卤复合阻燃体系的用量低于线性低密度聚乙烯的3.5倍时(对比例3、7、8),不但阻燃性能大大降低,力学性能也不及本发明的无卤阻燃线性低密度聚乙烯材料。
(4)当无卤复合阻燃体系的用量为线性低密度聚乙烯的4倍左右,但是氢氧化镁/氢氧化铝、硼酸锌以及微胶囊红磷的重量比不在(10.5~11.5)∶1∶(1.05~1.15)的范围时(对比例5、6),阻燃性能和力学性能均有一定的降低。
Claims (10)
1.一种无卤阻燃线性低密度聚乙烯材料,其特征在于由下述重量份的组分制成:
LLDPE树脂100份,增韧相容剂10~30份,润滑分散剂10~20份,无卤复合阻燃剂350~450份;
所述的无卤复合阻燃剂由氢氧化镁/氢氧化铝、硼酸锌以及微胶囊红磷按照(10.5~11.5)∶1∶(1.05~1.15)的重量比组成。
2.根据权利要求1所述的无卤阻燃线性低密度聚乙烯材料,其特征在于:所述的LLDPE树脂的熔体流动速率为2g/10min~8g/10min。
3.根据权利要求1所述的无卤阻燃线性低密度聚乙烯材料,其特征在于:所述的增韧相容剂为马来酸酐接枝EVA,其接枝率为2%~5%。
4.根据权利要求1所述的无卤阻燃线性低密度聚乙烯材料,其特征在于:所述的润滑分散剂为聚乙烯蜡,其相对分子量为2000~4000。
5.权利要求1所述的无卤阻燃线性低密度聚乙烯材料的制备方法,其特征在于具有以下步骤:
①将按照配方称取的LLDPE树脂、增韧相容剂、润滑分散剂以及无卤复合阻燃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90℃~105℃,出料冷却;
②将步骤①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,即得无卤阻燃线性低密度聚乙烯材料。
6.根据权利要求5所述的无卤阻燃线性低密度聚乙烯材料的制备方法,其特征在于:所述的LLDPE树脂的熔体流动速率为2g/10min~8g/10min。
7.根据权利要求5所述的无卤阻燃线性低密度聚乙烯材料的制备方法,其特征在于:所述的增韧相容剂为马来酸酐接枝EVA,其接枝率为2%~5%。
8.根据权利要求5所述的无卤阻燃线性低密度聚乙烯材料的制备方法,其特征在于:所述的润滑分散剂为聚乙烯蜡,其相对分子量为2000~4000。
9.根据权利要求5所述的无卤阻燃线性低密度聚乙烯材料的制备方法,其特征在于:所述的高速混合机的工作转速为450转/分钟~900转/分钟。
10.根据权利要求5至9之一所述的无卤阻燃线性低密度聚乙烯材料的制备方法,其特征在于:所述的双螺杆挤出机各区的温度为:T1=110℃;T2=150℃;T3=158℃;T4=177℃;T5=185℃;T6=190℃;T7=190℃;T8=195℃;T9=195℃;T模=185℃。
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