CN114806000A - 适用于辐照交联工艺的聚乙烯色母粒及其制备方法 - Google Patents
适用于辐照交联工艺的聚乙烯色母粒及其制备方法 Download PDFInfo
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- 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 claims abstract description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
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Abstract
本发明公开了适用于辐照交联工艺的聚乙烯色母粒及其制备方法,涉及聚乙烯色母粒领域,通过将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,再投入双螺杆挤出机进行挤出造粒;解决了现有的聚乙烯色母粒在应用于辐射交联时,导致聚合物发生氧化分解,形成不饱和双键以及发生材料变色等现象,严重影响其使用,且色母粒的阻燃性差的问题;通过添加抗氧剂增加聚乙烯色母粒的抗氧化性能,添加氯化石蜡增加色母粒的韧性,再通过添加阻燃剂提高色母粒的阻燃性能,通过交联助剂有效提高辐射交联时的交联程度,降低生产成本。
Description
技术领域
本发明涉及聚乙烯色母粒领域,具体涉及适用于辐照交联工艺的聚乙烯色母粒及其制备方法。
背景技术
色母粒是由树脂和大量颜料或染料配制成高浓度颜色的混合物,色母又名色种,是一种把超常量的颜料或染料均匀载附于树脂之中而制得的聚集体,加工时用少量色母料和未着色树脂掺混,就可达到设计颜料法度的着色树脂或制品,色母料广泛应用在广泛用于聚乙烯、聚丙烯、聚苯乙烯、ABS、尼龙、PC、PMMA、PET等树脂中,生产出了五颜六色的纤维、服装、日用塑料、电线及电缆、家用电器、农用薄膜、汽配件、保健器械等制品。
聚乙烯色母粒是以聚乙烯为载体所制成的粒状色母,颜料的含量较高,将颜料超常量均匀地载附于树脂中,从而大大提高了颜料的分散性能和着色效率,具有操作简单、成本低廉、对环境无污染等优点,现有的聚乙烯色母粒在应用于辐射交联时,高辐照剂量的应用除增加成本外,同时导致聚合物发生氧化分解,形成不饱和双键以及发生材料变色等现象,严重影响其使用,交联程度低,效果不好,且色母粒的阻燃性能差,易于燃烧。
发明内容
为了克服上述的技术问题,本发明的目的在于提供了适用于辐照交联工艺的聚乙烯色母粒及其制备方法:
(1)将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,通过密炼机密炼,再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒,解决了现有的聚乙烯色母粒在应用于辐射交联时,导致聚合物发生氧化分解,形成不饱和双键以及发生材料变色等现象,严重影响其使用,交联程度低,效果不好,且色母粒的阻燃性能差,易于燃烧的问题;
(2)在三口烧瓶中加入4,4′-二氨基二苯甲烷、无水碳酸钠和1,4-二氧六环,将2,4-二氯-6-苯基-1,3,5-三嗪溶解在1,4-二氧六环中,分批次将加入反应瓶中,得到中间体A,在氩气气氛下将中间体A放入圆底烧瓶中,倒入N,N-二甲基甲酰胺中,加入2-苯基顺酐,得到中间体B,将中间体B、乙酸钠和乙酸酐混合,过滤,沉淀物用NaHCO3溶液洗涤,得到该交联助剂,解决了现有的聚乙烯色母粒在应用于辐射交联时,导致聚合物发生氧化分解,形成不饱和双键以及发生材料变色等现象,严重影响其使用,交联程度低,效果不好的问题;
(3)称取三聚氯氰溶于丙酮中,倒入恒压滴液漏斗中,量取2-叔丁基-4-甲基苯酚在丙酮中溶解,加入三口瓶中,加入三乙胺于三口烧瓶中,滴加三聚氯氰的丙酮溶液,得到中间体C,在三口烧瓶中,分别加入季戊四醇、乙腈和三氯氧磷,得到中间体D,加入中间体C和N,N-二甲基甲酰胺,再加入对苯二胺,得到该阻燃剂,解决了现有的聚乙烯色母粒的阻燃性能差,易于燃烧的问题。
本发明的目的可以通过以下技术方案实现:
适用于辐照交联工艺的聚乙烯色母粒,包括以下重量份的组分:
线性低密度聚乙烯30-40份、高密度聚乙烯35-40份、马来酸酐接枝聚乙烯25-30份、氢氧化镁15-25份、重钙10-15份、二氧化钛6-8份、抗氧剂1-3份、钛酸丁酯3-5份、氯化石蜡0.5-1份、交联助剂5-8份、阻燃剂3-5份、颜料15-30份;
该适用于辐照交联工艺的聚乙烯色母粒由以下步骤制备得到:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒;
所述交联助剂由以下步骤制备得到:
S11:氮气氛围下,在装有回流冷凝管的三口烧瓶中,先加入4,4′-二氨基二苯甲烷、无水碳酸钠和1,4-二氧六环,加热回流30-40min,将2,4-二氯-6-苯基-1,3,5-三嗪溶解在1,4-二氧六环中,以每次2-4mL、间隔5-10min分批次将溶液加入反应瓶中,然后在120-130℃下充分回流4-6h,将反应液倒入冰水中,有白色固体析出,抽滤,真空干燥后,得到中间体A,产率为76.32%;
化学反应式为:
S12:在氩气气氛下将中间体A放入圆底烧瓶中,倒入干燥的N,N-二甲基甲酰胺中,搅拌30-40min,然后向烧瓶中加入2-苯基顺酐,混合溶液在室温下继续搅拌24-28h,将上述溶液倒入蒸馏水中,过滤,用蒸馏水反复洗涤3-4次,在80-90℃,2.718mmHg高真空下干燥24-30h,得到中间体B;
化学反应式为:
S13:将中间体B、乙酸钠和乙酸酐混合,体系升温至60-70℃,并在该温度下保持3-5h,然后将溶液在冰水浴中冷却至室温,将冷却后的溶液倒入蒸馏水中,过滤,沉淀物用NaHCO3溶液洗涤1-2次,用蒸馏水洗涤3-4次,用乙醇洗涤1-2次,然后在80-85℃,2.718mmHg高真空下干燥24-28h,得到该交联助剂。
化学反应式为:
作为本发明进一步的方案:步骤S11中所述4,4′-二氨基二苯甲烷、无水碳酸钠与1,4-二氧六环的用量比为7.0162g:0.9379g:20mL,所述2,4-二氯-6-苯基-1,3,5-三嗪与1,4-二氧六环的用量比为1.0000g:14mL,所述4,4′-二氨基二苯甲烷与2,4-二氯-6-苯基-1,3,5-三嗪的用量比为7.0162g:1g。
作为本发明进一步的方案:步骤S12中所述中间体A、N,N-二甲基甲酰胺与2-苯基顺酐的用量比为28.4512g:50mL:68.2405g。
作为本发明进一步的方案:步骤S13中所述中间体B、乙酸钠与乙酸酐的用量比为12.30g:2.72g:20mL,所述NaHCO3溶液的质量分数为5%。
作为本发明进一步的方案:所述阻燃剂由以下步骤制备得到:
S51:称取三聚氯氰溶于丙酮中,溶解后倒入恒压滴液漏斗中,量取2-叔丁基-4-甲基苯酚在丙酮中溶解,加入三口瓶中,加入三乙胺于三口烧瓶中,并严格控制温度在0-5℃,打开恒压滴液漏斗阀门,开始滴加三聚氯氰的丙酮溶液,控制滴加速度为1-2滴/s,滴加完毕后,反应时间为1-2h,旋蒸出丙酮,抽滤,在30-35℃下真空干燥,得到中间体C;
化学反应式为:
S52:在装有磁力搅拌器、回流冷凝管和尾气吸收装置的三口烧瓶中,分别加入季戊四醇、乙腈和三氯氧磷,80-90℃反应12-14h,冷却至室温,抽滤,产物依次用二氯甲烷、无水乙醚洗涤,40-50℃下真空干燥48-50h,得到中间体D,产率72%;
化学反应式为:
S53:在装有磁力搅拌器、回流冷凝管、N2保护装置的三口烧瓶中,加入中间体D、中间体C和N,N-二甲基甲酰胺,再加入对苯二胺,N2保护下,在50-60℃反应5-8h:升温至95-100℃继续反应10-12h,冷却至室温,抽滤,用乙腈、丙酮和水洗涤,在80-90℃下真空干燥48-50h,得到该阻燃剂。
化学反应式为:
作为本发明进一步的方案:步骤S51中所述三聚氯氰与丙酮的用量比为7.4g:50mL,所述2-叔丁基-4-甲基苯酚、丙酮与三乙胺的用量比为9.8544g:20mL:16.7mL,所述三聚氯氰与2-叔丁基-4-甲基苯酚的摩尔比为2:3。
作为本发明进一步的方案:步骤S52中所述季戊四醇、乙腈、三氯氧磷的用量比为17.6g:264mL:28.8mL,步骤S53中所述中间体D、中间体C、N,N-二甲基甲酰胺与对苯二胺的用量比为1g:1.2g:50mL:1.614g。
作为本发明进一步的方案:所述抗氧剂为受阻酚类、受阻胺类、亚磷酸酯类抗氧剂的一种或两种以上按任意比例混合。
适用于辐照交联工艺的聚乙烯色母粒的制备方法,包括以下步骤:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒。
本发明的有益效果:
(1)本发明是通过将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,通过密炼机密炼,再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒,通过添加抗氧剂增加聚乙烯色母粒的抗氧化性能,添加氯化石蜡增加色母粒的韧性,再通过添加阻燃剂提高色母粒的阻燃性能,通过交联助剂有效提高辐射交联时的交联程度,降低生产成本;
(2)在三口烧瓶中加入4,4′-二氨基二苯甲烷、无水碳酸钠和1,4-二氧六环,将2,4-二氯-6-苯基-1,3,5-三嗪溶解在1,4-二氧六环中,分批次将加入反应瓶中,得到中间体A,在氩气气氛下将中间体A放入圆底烧瓶中,倒入N,N-二甲基甲酰胺中,加入2-苯基顺酐,得到中间体B,将中间体B、乙酸钠和乙酸酐混合,过滤,沉淀物用NaHCO3溶液洗涤,得到该交联助剂,该交联助剂是一种可以促进聚合物辐照交联的化合物,且在辐照作用下不易发生自聚,100eV下形成的交联点数目Gx值增加至24倍以上,聚合物进行辐照交联时,产生自由基,引发分子链间的化学反应,形成三维网状结构,减小辐照剂量,使聚合物不需经受高强度的辐射剂量,就可以提高其高温力学性能,该交联助剂在辐照作用下可以优先与分子主链发生交联反应,实现在小剂量下分子内交联度的有效提高,该交联助剂分子结构内含有不饱和官能团双键,在结构上增加苯环占比,也充分提高了自身的抗热性能,避免自身高温挥发和高温自聚的发生,从而有效地提高了交联效率;
(3)称取三聚氯氰溶于丙酮中,倒入恒压滴液漏斗中,量取2-叔丁基-4-甲基苯酚在丙酮中溶解,加入三口瓶中,加入三乙胺于三口烧瓶中,滴加三聚氯氰的丙酮溶液,得到中间体C,在三口烧瓶中,分别加入季戊四醇、乙腈和三氯氧磷,得到中间体D,加入中间体C和N,N-二甲基甲酰胺,再加入对苯二胺,得到该阻燃剂,该阻燃剂中的N与P存在协同阻燃作用,N元素不但可以促进P元素氧化为磷酸,促进碳源的炭化作用,还可以释放惰性气体,使炭层发泡,从而达到膨胀阻燃的作用,三聚氯氰的三嗪结构不但具有成炭作用,其结构中的N元素也具有气源的作用,苯环也具有良好的热稳定性和成炭性能,不但可以显著提高该阻燃剂膨胀炭层的含量,还可以提高该阻燃剂的热稳定性,通过反应合成,将几种阻燃元素和官能团合成到该阻燃剂分子上,从而提高色母粒的阻燃性。
具体实施方式
下面将结合本发明实施例,对本发明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发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1:
本实施例为适用于辐照交联工艺的聚乙烯色母粒,包括以下重量份的组分:
线性低密度聚乙烯30份、高密度聚乙烯40份、马来酸酐接枝聚乙烯25份、氢氧化镁15份、重钙15份、二氧化钛6份、抗氧剂1份、钛酸丁酯3份、氯化石蜡0.5份、交联助剂5份、阻燃剂3份、颜料15份;
该适用于辐照交联工艺的聚乙烯色母粒由以下步骤制备得到:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒;
交联助剂由以下步骤制备得到:
S11:氮气氛围下,在装有回流冷凝管的三口烧瓶中,先加入7.0162g的4,4′-二氨基二苯甲烷、0.9379g的无水碳酸钠和20mL的1,4-二氧六环,加热回流30min,将1.0000g的2,4-二氯-6-苯基-1,3,5-三嗪溶解在14mL的1,4-二氧六环中,以每次2mL、间隔5min分批次将溶液加入反应瓶中,然后在120℃下充分回流4h,将反应液倒入40mL冰水中,有白色固体析出,抽滤,真空干燥后,得到中间体A,产率为76.32%;
S12:在氩气气氛下将28.4512g中间体A放入圆底烧瓶中,倒入50mL干燥的N,N-二甲基甲酰胺中,搅拌30min,然后向烧瓶中加入68.2405g的2-苯基顺酐,混合溶液在室温下继续搅拌24h,将上述溶液倒入500mL蒸馏水中,过滤,用蒸馏水反复洗涤3次,在80℃,2.718mmHg高真空下干燥24h,得到中间体B;
S13:将12.30g的中间体B、2.72g的乙酸钠和20mL乙酸酐混合,体系升温至60℃,并在该温度下保持3h,然后将溶液在冰水浴中冷却至室温,将冷却后的溶液倒入500mL蒸馏水中,过滤,沉淀物用NaHCO3溶液洗涤1次,用蒸馏水洗涤3次,用乙醇洗涤1次,然后在80℃,2.718mmHg高真空下干燥28h,得到该交联助剂;
阻燃剂由以下步骤制备得到:
S51:称取7.4g的三聚氯氰溶于50mL丙酮中,溶解后倒入恒压滴液漏斗中,量取9.8544g的2-叔丁基-4-甲基苯酚在20mL丙酮中溶解,加入三口瓶中,加入16.7mL三乙胺于三口烧瓶中,并严格控制温度在0℃,打开恒压滴液漏斗阀门,开始滴加三聚氯氰的丙酮溶液,控制滴加速度为1滴/s,滴加完毕后,反应时间为1h,旋蒸出丙酮,抽滤,在30℃下真空干燥,得到中间体C;
S52:在装有磁力搅拌器、回流冷凝管和尾气吸收装置的三口烧瓶中,分别加入17.6g季戊四醇、264mL乙腈和28.8mL三氯氧磷,80℃反应12h,冷却至室温,抽滤,产物依次用二氯甲烷、无水乙醚洗涤,40℃下真空干燥48h,得到中间体D,产率72%;
S53:在装有磁力搅拌器、回流冷凝管、N2保护装置的三口烧瓶中,加入1g中间体D、1.2g中间体C和50mL的N,N-二甲基甲酰胺,再加入1.614g对苯二胺,N2保护下,在50℃反应5h:升温至95℃继续反应10h,冷却至室温,抽滤,用乙腈、丙酮和水洗涤,在80℃下真空干燥48h,得到该阻燃剂。
实施例2:
本实施例为适用于辐照交联工艺的聚乙烯色母粒,包括以下重量份的组分:
线性低密度聚乙烯30份、高密度聚乙烯35份、马来酸酐接枝聚乙烯30份、氢氧化镁25份、重钙15份、二氧化钛6份、抗氧剂1份、钛酸丁酯3份、氯化石蜡0.5份、交联助剂5份、阻燃剂5份、颜料15份;
该适用于辐照交联工艺的聚乙烯色母粒由以下步骤制备得到:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒;
交联助剂由以下步骤制备得到:
S11:氮气氛围下,在装有回流冷凝管的三口烧瓶中,先加入7.0162g的4,4′-二氨基二苯甲烷、0.9379g的无水碳酸钠和20mL的1,4-二氧六环,加热回流40min,将1.0000g的2,4-二氯-6-苯基-1,3,5-三嗪溶解在14mL的1,4-二氧六环中,以每次4mL、间隔10min分批次将溶液加入反应瓶中,然后在130℃下充分回流6h,将反应液倒入40mL冰水中,有白色固体析出,抽滤,真空干燥后,得到中间体A,产率为76.32%;
S12:在氩气气氛下将28.4512g中间体A放入圆底烧瓶中,倒入50mL干燥的N,N-二甲基甲酰胺中,搅拌40min,然后向烧瓶中加入68.2405g的2-苯基顺酐,混合溶液在室温下继续搅拌28h,将上述溶液倒入500mL蒸馏水中,过滤,用蒸馏水反复洗涤4次,在90℃,2.718mmHg高真空下干燥30h,得到中间体B;
S13:将12.30g的中间体B、2.72g的乙酸钠和20mL乙酸酐混合,体系升温至70℃,并在该温度下保持5h,然后将溶液在冰水浴中冷却至室温,将冷却后的溶液倒入500mL蒸馏水中,过滤,沉淀物用NaHCO3溶液洗涤2次,用蒸馏水洗涤4次,用乙醇洗涤2次,然后在85℃,2.718mmHg高真空下干燥28h,得到该交联助剂;
阻燃剂由以下步骤制备得到:
S51:称取7.4g的三聚氯氰溶于50mL丙酮中,溶解后倒入恒压滴液漏斗中,量取9.8544g的2-叔丁基-4-甲基苯酚在20mL丙酮中溶解,加入三口瓶中,加入16.7mL三乙胺于三口烧瓶中,并严格控制温度在5℃,打开恒压滴液漏斗阀门,开始滴加三聚氯氰的丙酮溶液,控制滴加速度为2滴/s,滴加完毕后,反应时间为2h,旋蒸出丙酮,抽滤,在35℃下真空干燥,得到中间体C;
S52:在装有磁力搅拌器、回流冷凝管和尾气吸收装置的三口烧瓶中,分别加入17.6g季戊四醇、264mL乙腈和28.8mL三氯氧磷,90℃反应14h,冷却至室温,抽滤,产物依次用二氯甲烷、无水乙醚洗涤,50℃下真空干燥50h,得到中间体D,产率72%;
S53:在装有磁力搅拌器、回流冷凝管、N2保护装置的三口烧瓶中,加入1g中间体D、1.2g中间体C和50mL的N,N-二甲基甲酰胺,再加入1.614g对苯二胺,N2保护下,在60℃反应8h:升温至100℃继续反应12h,冷却至室温,抽滤,用乙腈、丙酮和水洗涤,在90℃下真空干燥50h,得到该阻燃剂。
实施例3:
本实施例为适用于辐照交联工艺的聚乙烯色母粒,包括以下重量份的组分:
线性低密度聚乙烯40份、高密度聚乙烯40份、马来酸酐接枝聚乙烯30份、氢氧化镁25份、重钙15份、二氧化钛8份、抗氧剂3份、钛酸丁酯5份、氯化石蜡1份、交联助剂8份、阻燃剂5份、颜料30份;
该适用于辐照交联工艺的聚乙烯色母粒由以下步骤制备得到:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒;
交联助剂由以下步骤制备得到:
S11:氮气氛围下,在装有回流冷凝管的三口烧瓶中,先加入7.0162g的4,4′-二氨基二苯甲烷、0.9379g的无水碳酸钠和20mL的1,4-二氧六环,加热回流40min,将1.0000g的2,4-二氯-6-苯基-1,3,5-三嗪溶解在14mL的1,4-二氧六环中,以每次4mL、间隔10min分批次将溶液加入反应瓶中,然后在130℃下充分回流6h,将反应液倒入40mL冰水中,有白色固体析出,抽滤,真空干燥后,得到中间体A,产率为76.32%;
S12:在氩气气氛下将28.4512g中间体A放入圆底烧瓶中,倒入50mL干燥的N,N-二甲基甲酰胺中,搅拌40min,然后向烧瓶中加入68.2405g的2-苯基顺酐,混合溶液在室温下继续搅拌28h,将上述溶液倒入500mL蒸馏水中,过滤,用蒸馏水反复洗涤4次,在90℃,2.718mmHg高真空下干燥30h,得到中间体B;
S13:将12.30g的中间体B、2.72g的乙酸钠和20mL乙酸酐混合,体系升温至70℃,并在该温度下保持5h,然后将溶液在冰水浴中冷却至室温,将冷却后的溶液倒入500mL蒸馏水中,过滤,沉淀物用NaHCO3溶液洗涤2次,用蒸馏水洗涤4次,用乙醇洗涤2次,然后在85℃,2.718mmHg高真空下干燥28h,得到该交联助剂;
阻燃剂由以下步骤制备得到:
S51:称取7.4g的三聚氯氰溶于50mL丙酮中,溶解后倒入恒压滴液漏斗中,量取9.8544g的2-叔丁基-4-甲基苯酚在20mL丙酮中溶解,加入三口瓶中,加入16.7mL三乙胺于三口烧瓶中,并严格控制温度在5℃,打开恒压滴液漏斗阀门,开始滴加三聚氯氰的丙酮溶液,控制滴加速度为2滴/s,滴加完毕后,反应时间为2h,旋蒸出丙酮,抽滤,在35℃下真空干燥,得到中间体C;
S52:在装有磁力搅拌器、回流冷凝管和尾气吸收装置的三口烧瓶中,分别加入17.6g季戊四醇、264mL乙腈和28.8mL三氯氧磷,90℃反应14h,冷却至室温,抽滤,产物依次用二氯甲烷、无水乙醚洗涤,50℃下真空干燥50h,得到中间体D,产率72%;
S53:在装有磁力搅拌器、回流冷凝管、N2保护装置的三口烧瓶中,加入1g中间体D、1.2g中间体C和50mL的N,N-二甲基甲酰胺,再加入1.614g对苯二胺,N2保护下,在60℃反应8h:升温至100℃继续反应12h,冷却至室温,抽滤,用乙腈、丙酮和水洗涤,在90℃下真空干燥50h,得到该阻燃剂。
对比例1:
对比例1与实施例1的区别在于不添加阻燃剂。
对比例2:
对比例2使用中国专利CN201010572067.4所公开的实施例5中配料成分制备色母粒。
性能测试
将实施例1-3以及对比例1-2的聚乙烯色母粒与PE-RT树脂以1:50混合,经注塑制得样板进行检测,垂直燃烧等级为新制备成品检测,浸泡5d后垂直燃烧等级为30℃水中浸泡5d后测得,耐热性测试为试样经500℃空气环境保温5天后的状态,拉伸强度和伸长率采用ASTM的D638、氧化诱导期采用ASTM的D3895进行检测;
检测结果如下表所示:
由上表可知,实施例的拉伸强度达到了214-220Kg/cm2,而不添加阻燃剂的对比例1拉伸强度为216Kg/cm2,对比例2的拉伸强度为205Kg/cm2,实施例的伸长率达到了715-720%,而不添加阻燃剂的对比例1伸长率为718%,对比例2的伸长率为711%,实施例新制品的垂直燃烧等级达到了V-0,而不添加阻燃剂的对比例1的新制品易燃,实施例浸泡5d后制品的垂直燃烧等级达到了V-0,而不添加阻燃剂的对比例1浸泡5d后的制品易燃,对比例2的浸泡5d后制品的垂直燃烧等级为V-1,实施例的各项数据均优于对比例,说明本发明所制备的阻燃剂添加到聚乙烯色母粒中,可以使制备得到的聚乙烯色母粒材料具备更加优异的阻燃性能。
在本说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (9)
1.适用于辐照交联工艺的聚乙烯色母粒,其特征在于,包括以下重量份的组分:
线性低密度聚乙烯30-40份、高密度聚乙烯35-40份、马来酸酐接枝聚乙烯25-30份、氢氧化镁15-25份、重钙10-15份、二氧化钛6-8份、抗氧剂1-3份、钛酸丁酯3-5份、氯化石蜡0.5-1份、交联助剂5-8份、阻燃剂3-5份、颜料15-30份;
该适用于辐照交联工艺的聚乙烯色母粒由以下步骤制备得到:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒;
所述交联助剂由以下步骤制备得到:
S11:氮气氛围下,在三口烧瓶中,先加入4,4′-二氨基二苯甲烷、无水碳酸钠和1,4-二氧六环,将2,4-二氯-6-苯基-1,3,5-三嗪溶解在1,4-二氧六环中,分批次将加入反应瓶中,抽滤,真空干燥后,得到中间体A;
S12:在氩气气氛下将中间体A放入圆底烧瓶中,倒入干燥的N,N-二甲基甲酰胺中,然后向烧瓶中加入2-苯基顺酐,得到中间体B;
S13:将中间体B、乙酸钠和乙酸酐混合,过滤,沉淀物用NaHCO3溶液洗涤,再用蒸馏水、乙醇洗涤,高真空下干燥,得到该交联助剂。
2.根据权利要求1所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,步骤S11中所述4,4′-二氨基二苯甲烷、无水碳酸钠与1,4-二氧六环的用量比为7.0162g:0.9379g:20mL,所述2,4-二氯-6-苯基-1,3,5-三嗪与1,4-二氧六环的用量比为1.0000g:14mL,所述4,4′-二氨基二苯甲烷与2,4-二氯-6-苯基-1,3,5-三嗪的用量比为7.0162g:1g。
3.根据权利要求1所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,步骤S12中所述中间体A、N,N-二甲基甲酰胺与2-苯基顺酐蒸馏水的用量比为28.4512g:50mL:68.2405g。
4.根据权利要求1所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,步骤S13中所述中间体B、乙酸钠与乙酸酐的用量比为12.30g:2.72g:20mL,所述NaHCO3溶液的质量分数为5%。
5.根据权利要求1所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,所述阻燃剂由以下步骤制备得到:
S51:称取三聚氯氰溶于丙酮中,倒入恒压滴液漏斗中,量取2-叔丁基-4-甲基苯酚在丙酮中溶解,加入三口瓶中,加入三乙胺于三口烧瓶中,打开恒压滴液漏斗阀门,滴加三聚氯氰的丙酮溶液,得到中间体C;
S52:在三口烧瓶中,分别加入季戊四醇、乙腈和三氯氧磷,得到中间体D;
S53:在三口烧瓶中加入中间体D、中间体C和N,N-二甲基甲酰胺,再加入对苯二胺,抽滤,真空干燥,得到该阻燃剂。
6.根据权利要求5所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,步骤S51中所述三聚氯氰与丙酮的用量比为7.4g:50mL,所述2-叔丁基-4-甲基苯酚、丙酮与三乙胺的用量比为9.8544g:20mL:16.7mL,所述三聚氯氰与2-叔丁基-4-甲基苯酚的摩尔比为2:3。
7.根据权利要求5所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,步骤S52中所述季戊四醇、乙腈、三氯氧磷的用量比为17.6g:264mL:28.8mL,步骤S53中所述中间体D、中间体C、N,N-二甲基甲酰胺与对苯二胺的用量比为1g:1.2g:50mL:1.614g。
8.根据权利要求1所述的适用于辐照交联工艺的聚乙烯色母粒,其特征在于,所述抗氧剂为受阻酚类、受阻胺类、亚磷酸酯类抗氧剂的一种或两种以上按任意比例混合。
9.根据权利要求1-8任一项所述的适用于辐照交联工艺的聚乙烯色母粒的制备方法,其特征在于,包括以下步骤:
S1:按重量份将线性低密度聚乙烯、高密度聚乙烯、马来酸酐接枝聚乙烯、氢氧化镁、重钙、二氧化钛、抗氧剂、钛酸丁酯、氯化石蜡、交联助剂、颜料和阻燃剂均匀混合,得到共混料;
S2:将共混料加入密炼机,进行密炼;
S3:再投入双螺杆挤出机进行挤出造粒,经水冷、风干、筛选磁选、计量、包装,得到该适用于辐照交联工艺的聚乙烯色母粒。
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