CN116874941A - 钢塑复合给水管材用耐候聚乙烯材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种钢塑复合给水管材用耐候聚乙烯材料,包括以下重量份数的原料:改性聚乙烯90‑110份,硅烷接枝聚烯烃弹性体DF610 1‑4份,所述改性聚乙烯结构中含有丙烯酸酯结构、硅氧烷结构和哌啶结构,能够赋予其优异的抗老化性能和耐热性;本发明还公开了该耐候聚乙烯材料的制备方法,步骤为:将改性聚乙烯与硅烷接枝聚烯烃弹性体DF610混匀后挤出成片,再采用水浴交联法,即得。本发明提供的聚乙烯材料具有优异的抗老化性能、低温冲击脆化性能、耐环境应力开裂性能和熔体流动速率。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及钢塑复合给水管材用耐候聚乙烯材料及其制备方法。
背景技术
聚乙烯(PE)具有分子量高、支化度小、力学性能优异、电绝缘性能优良、耐低温性和易加工成型性以及化学稳定性优异等优点,已广泛应用于工业、农业、建筑和国防等领域,产品诸如薄膜、管材、电线、电缆、家电、塑料制品、包装材料和汽车配件等。随着石油化工的发展,聚乙烯生产得到迅猛发展,产量约占塑料总产量的四分之一,用量亦居各合成树脂之首。近几年,随着聚乙烯系产品的增多,聚乙烯材料的性能越发引起人们的关注。
聚乙烯系产品的耐候性和耐环境应力开裂性能较差,在户外使用时需添加抗氧剂、紫外线吸收剂、粘接剂等来提高其耐候性能和耐环境应力开裂性能,申请号为CN201910234175.1的专利提供了一种适用于水面接触的耐候抗老化聚乙烯塑料,包括以下组分:抗氧剂1010、抗氧剂1330、抗氧剂168、光稳定剂2020、聚乙烯7042、聚乙烯0220A,该发明将聚乙烯、抗氧化剂、光稳定剂进行复配,通过配料、挤出造粒、注塑成型得到的聚乙烯塑料具有优异的力学性能和耐高温高湿性能,显著延长其在水中的使用寿命;申请号为201610315757.9的专利提供了一种耐环境应力开裂的长链支化高密度聚乙烯材料,包括以下组分:高密度聚乙烯、二官能度单体、二硫代氨基甲酸锌盐、引发剂、抗氧剂,通过熔融反应加工法对高密度聚乙烯进行长链支化改性,得到低凝胶量的长链支化高密度聚乙烯,该聚乙烯材料具有优异的耐环境应力开裂性和力学性能;上述专利中抗氧化剂均采用低分子化合物,聚乙烯为高分子聚合物,两者分子结构相差较远,低分子化合物容易从高分子材料中析出,导致抗氧化剂在初期可以起到明显的效果,但随着时间推移,抗氧化性能迅速下降。
因此,为满足使用需求,迫切需要开发一种耐候性能好、耐环境应力开裂、力学性能好、加工性能优异的聚乙烯材料。
发明内容
针对现有技术的不足,本发明的目的在于提供一种钢塑复合给水管材用耐候聚乙烯材料,该复合耐火材料具有优异的抗老化性能、低温冲击脆化性能、耐环境应力开裂性能和加工性能,本发明还提供了该耐候聚乙烯材料的制备方法。
本发明为实现上述目的所采取的技术方案为:
钢塑复合给水管材用耐候聚乙烯材料,包括以下重量份数的原料:改性聚乙烯90-110份,硅烷接枝聚烯烃弹性体DF610 1-4份;所述改性聚乙烯的制备方法如下:
S1、将聚乙烯、丙烯酸、过氧化二异丙苯混合均匀,在流变仪中进行熔融共混接技,得到接枝产物,将接枝产物分散于二甲苯中,加热至70-80℃,搅拌回流0.5-1.5h,冷却至室温,加入乙醇,继续搅拌30-40min,过滤,取滤渣,经洗涤、干燥、研磨,得到中间体1;
S2、将步骤S1所得中间体1分散于二甲苯中,依次加入环氧丁基三甲氧基硅烷、乙酸铬,升温至90-100℃,搅拌3-6h,冷却至室温,过滤,取滤渣,经洗涤、干燥、研磨,得到中间体2;
S3、将步骤S2所得中间体2分散于二甲苯中,依次加入3-(溴甲基)哌啶、氢氧化钾、苄基三乙基溴化铵,升温至60-80℃,搅拌3-5h,冷却至室温,过滤,取滤渣,经洗涤、干燥、研磨,即得改性聚乙烯;
所述改性聚乙烯的合成路线如下:
;
;
。
本发明以聚乙烯、丙烯酸为起始原料,在过氧化二异丙苯自由基引发剂下,发生自由基接枝反应,得到中间体1;在乙酸铬作用下,中间体1结构中的羧基与环氧丁基三甲氧基硅烷中的环氧烷发生开环反应,得到中间体2;中间体2结构中含有羟基,在氢氧化钾、苄基三乙基溴化铵作用下,进一步与3-(溴甲基)哌啶中的卤素发生O-烷基化反应,得到改性聚乙烯。
为了得到改性聚乙烯,并保证产物一致性,步骤S1中所述聚乙烯、丙烯酸、过氧化二异丙苯的质量比为100:5-15:0.1-0.3,所述接枝温度为150-170℃,时间为15-25min,流变仪转速为55-65r/min;步骤S2中所述中间体1、环氧丁基三甲氧基硅烷与乙酸铬的质量比为100:10-15:0.5-1.5,二甲苯中中间体1的加入量为0.15-0.25g/mL;步骤S3中所述中间体2、3-(溴甲基)哌啶、氢氧化钾与苄基三乙基溴化铵的质量比为100:4-5:3-4:0.15-0.25,二甲苯中中间体2的加入量为0.2-0.3g/mL。
为了促使改性聚乙烯之间、改性聚乙烯与聚烯烃弹性体DF610之间形成化学交联,提高原料结合强度,改善聚乙烯材料的加工性能和力学性能,对聚烯烃弹性体DF610进行硅烷接枝,制备方法为:将聚烯烃弹性体DF610、乙烯基三乙氧基硅烷、过氧化二异丙苯预先混合均匀,在密炼机中进行熔融密炼,密炼温度为150-165℃,时间为5-15min,密炼机转速为40-70r/min;其中,聚烯烃弹性体DF610、乙烯基三乙氧基硅烷与过氧化二异丙苯的质量比为100:4-8:0.2-0.5。
本发明还提供了钢塑复合给水管材用耐候聚乙烯材料的制备方法,包括以下步骤:将改性聚乙烯、硅烷接枝聚烯烃弹性体DF610混合均匀,加入到挤出机中挤出成片,然后浸没于70-90℃的水中反应4-8h,取出干燥,即得耐候聚乙烯材料。
本发明具有如下有益效果:本发明依次通过自由基接枝反应、环氧化合物开环反应和O-烷基化反应得到改性聚乙烯,该改性聚乙烯结构中含有丙烯酸酯结构、硅氧烷结构和哌啶结构,能够赋予其优异的抗老化性能和耐热性;将改性聚乙烯与硅烷接枝聚烯烃弹性体DF610进行复配,再采用水浴交联法制备聚乙烯材料,能够显著改善聚乙烯材料的力学性能和加工性能,避免出现低分子化合物析出、聚乙烯制品过硬等现象。本发明提供的聚乙烯材料具有优异的抗老化性能、低温冲击脆化性能、耐环境应力开裂性能和熔体流动速率。
具体实施方式
下面将结合本申请实施例,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。下述实施例中所用原料均为普通市售产品。
实施例1
一种改性聚乙烯的制备方法,包括以下步骤:
S1、将聚乙烯(牌号LL0220KJ,购自东莞市英翔塑胶原料有限公司)、丙烯酸、过氧化二异丙苯混合均匀,在流变仪中进行熔融共混接技,得到接枝产物,将接枝产物分散于二甲苯中(接枝产物的质量分数为2%),加热至75℃,搅拌回流1h,冷却至室温,加入乙醇,继续搅拌30min,过滤,取滤渣,用乙醇洗涤,于50℃真空干燥24h,研磨,得到中间体1,通过元素分析法测定中间体1的取代度为8.5%;其中聚乙烯、丙烯酸、过氧化二异丙苯的质量比为100:10:0.2,接枝温度为160℃,时间为20min,流变仪转速为60r/min,二甲苯与乙醇的质量比为2:1;
S2、将步骤S1所得中间体1分散于二甲苯中,依次加入环氧丁基三甲氧基硅烷、乙酸铬,升温至100℃,搅拌5h,冷却至室温,过滤,取滤渣,用乙醇洗涤,于50℃真空干燥24h,研磨,得到中间体2;其中,中间体1、环氧丁基三甲氧基硅烷与乙酸铬的质量比为100:13:0.8,二甲苯中中间体1的加入量为0.2g/mL;
S3、将步骤S2所得中间体2分散于二甲苯中,依次加入3-(溴甲基)哌啶、氢氧化钾、苄基三乙基溴化铵,升温至75℃,搅拌4h,冷却至室温,过滤,取滤渣,用乙醇洗涤,于50℃真空干燥24h,研磨,即得改性聚乙烯;其中,中间体2、3-(溴甲基)哌啶、氢氧化钾与苄基三乙基溴化铵的质量比为100:4.5:3.6:0.2,二甲苯中中间体2的加入量为0.25g/mL;
所述改性聚丙烯的合成路线如下:
;
;
。
一种硅烷接枝聚烯烃弹性体DF610的制备方法,包括以下步骤:
将聚烯烃弹性体DF610(日本三井化学)、乙烯基三乙氧基硅烷、过氧化二异丙苯预先混合均匀,在密炼机中进行熔融密炼,密炼温度为155℃,时间为10min,密炼机转速为50r/min,聚烯烃弹性体DF610、乙烯基三乙氧基硅烷与过氧化二异丙苯的质量比为100:5:0.3。
实施例2
钢塑复合给水管材用耐候聚乙烯材料的制备方法,包括以下步骤:
按重量份数称取100份实施例1所制备的改性聚乙烯、2份实施例1所制备的硅烷接枝聚烯烃弹性体DF610,混合均匀后加入到DJ-30型挤出机中混炼挤塑,得到1mm厚的片材,然后将片材浸没于80℃的去离子水中交联反应7h,取出干燥,即得耐候聚乙烯材料;其中挤出机各区温度设定为:一区160℃,二区190℃,三区210℃,机头230℃,挤出机转速为60rpm。
实施例3
钢塑复合给水管材用耐候聚乙烯材料的制备方法,按照实施例2的方法制备,区别在于:改变改性聚乙烯的重量份数为90份,硅烷接枝聚烯烃弹性体DF610的重量份数保持不变。
实施例4
钢塑复合给水管材用耐候聚乙烯材料的制备方法,按照实施例2的方法制备,区别在于:改变改性聚乙烯的重量份数为110份,硅烷接枝聚烯烃弹性体DF610的重量份数保持不变。
对比例1
钢塑复合给水管材用耐候聚乙烯材料的制备方法,按照实施例2的方法制备,区别在于:将改性聚乙烯替换为聚乙烯、乙烯基三乙氧硅烷、抗氧剂1024共混物(聚乙烯、乙烯基三乙氧硅烷、抗氧剂1024的质量比为100:3:0.5)。
对比例2
钢塑复合给水管材用耐候聚乙烯材料的制备方法,按照实施例2的方法制备,区别在于:将改性聚乙烯替换为聚乙烯。
对实施例2-4及对比例1-2所制备的聚乙烯材料进行相关性能测试。拉伸强度和断裂伸长率按照GB/T1040-2006《塑料拉伸性能的测定》进行;热老化测试条件为(135±2)℃×168h;氙灯人工加速老化测试按照GB/T16422.2-2022《塑料 实验室光源暴露试验方法第2部分:氙弧灯》进行,试验温度(65±3)℃,相对湿度(65±5)%,测试时间为1000h;耐环境应力开裂测试按照GB/T1842-2008《塑料 聚乙烯环境应力开裂试验方法》进行,以壬基酚聚氧乙烯醚(TX-10)体积分数为10%的水溶液作为试剂,温度为50℃测样品的ESCR时间F50,测试时间范围0-1300h;低温冲击脆化温度测试按照GB/T5470-2008《塑料冲击法脆化温度的测定》进行,冲击脆化温度为-76℃,失效数≤15/30;熔体流动速率测试按照GB/T3682-2000《热塑性塑料熔体质量流动速率和熔体体积流动速率的测定》;结果如表1所示。实施例2-4所制备的聚乙烯材料的抗老化性能、低温冲击脆化性能、耐环境应力开裂性能均明显优于对比例1-2;通过改性聚乙烯与硅烷接枝聚烯烃弹性体DF610复配,显著提高了聚乙烯材料的熔体流动速率,实施例2-4所制备的聚乙烯材料的熔体流动速率均为0.8-1.0g/10min,熔融状态下熔体粘度更小,流动性和加工性能更好;实施例2-4与对比例1相比,对聚乙烯进行化学表面改性能够使聚乙烯材料的力学性能得到较大提高,耐环境应力开裂性能更优异。
表1耐候聚乙烯材料性能测试结果
本发明通过三步法得到改性聚乙烯,该改性聚乙烯结构中含有丙烯酸酯结构、硅氧烷结构和哌啶结构,能够赋予其优异的抗老化性能和耐热性;将改性聚乙烯与硅烷接枝聚烯烃弹性体DF610进行复配,再采用水浴交联法制备聚乙烯材料,能够显著改善聚乙烯材料的力学性能和加工性能,避免出现低分子化合物析出、聚乙烯制品过硬等现象。本发明提供的聚乙烯材料具有优异的抗老化性能、低温冲击脆化性能、耐环境应力开裂性能和熔体流动速率。
尽管已经示出和描述了本申请的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本申请的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本申请的范围由所附权利要求及其等同物限定。
Claims (10)
1.钢塑复合给水管材用耐候聚乙烯材料,其特征在于,包括以下重量份数的原料:改性聚乙烯90-110份,硅烷接枝聚烯烃弹性体DF610 1-4份;所述改性聚乙烯的制备方法如下:
S1、将聚乙烯、丙烯酸、过氧化二异丙苯混合均匀,在流变仪中进行熔融共混接技,得到接枝产物,将接枝产物分散于二甲苯中,加热至70-80℃,搅拌回流0.5-1.5h,冷却至室温,加入乙醇,继续搅拌30-40min,过滤,取滤渣,经洗涤、干燥、研磨,得到中间体1,中间体1的结构式为:
;
S2、将步骤S1所得中间体1分散于二甲苯中,依次加入环氧丁基三甲氧基硅烷、乙酸铬,升温至90-100℃,搅拌3-6h,冷却至室温,过滤,取滤渣,经洗涤、干燥、研磨,得到中间体2,中间体2的结构式为:
;
S3、将步骤S2所得中间体2分散于二甲苯中,依次加入3-(溴甲基)哌啶、氢氧化钾、苄基三乙基溴化铵,升温至60-80℃,搅拌3-5h,冷却至室温,过滤,取滤渣,经洗涤、干燥、研磨,即得改性聚乙烯,改性聚乙烯的结构式为:
。
2.根据权利要求1所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,步骤S1中所述聚乙烯、丙烯酸、过氧化二异丙苯的质量比为100:5-15:0.1-0.3。
3.根据权利要求1所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,步骤S1中所述接枝温度为150-170℃,时间为15-25min,流变仪转速为55-65r/min。
4.根据权利要求1所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,步骤S2中所述中间体1、环氧丁基三甲氧基硅烷与乙酸铬的质量比为100:10-15:0.5-1.5。
5.根据权利要求4所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,所述二甲苯中中间体1的加入量为0.15-0.25g/mL。
6.根据权利要求1所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,步骤S3中所述中间体2、3-(溴甲基)哌啶、氢氧化钾与苄基三乙基溴化铵的质量比为100:4-5:3-4:0.15-0.25。
7.根据权利要求6所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,所述二甲苯中中间体2的加入量为0.2-0.3g/mL。
8.根据权利要求1所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,所述硅烷接枝聚烯烃弹性体DF610的制备方法为:将聚烯烃弹性体DF610、乙烯基三乙氧基硅烷、过氧化二异丙苯预先混合均匀,在密炼机中进行熔融密炼,密炼温度为150-165℃,时间为5-15min,密炼机转速为40-70r/min。
9.根据权利要求8所述的钢塑复合给水管材用耐候聚乙烯材料,其特征在于,所述聚烯烃弹性体DF610、乙烯基三乙氧基硅烷与过氧化二异丙苯的质量比为100:4-8:0.2-0.5。
10.根据权利要求1-9任一项所述的钢塑复合给水管材用耐候聚乙烯材料的制备方法,其特征在于,包括以下步骤:将改性聚乙烯、硅烷接枝聚烯烃弹性体DF610混合均匀,加入到挤出机中挤出成片,然后浸没于70-90℃的水中反应4-8h,取出干燥,即得。
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