CN106566021A - 一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料及其制备方法 - Google Patents
一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料及其制备工艺,其特征在于,以丁二烯(聚合级)、环烷油、环烷酸镍、三异丁基铝、三氟化硼乙醚络合物、辛醛、聚己内酯二元醇、石墨、抗氧剂TNP、紫外线吸收剂UV‑9、甲苯二异氰酸酯、二甲硫基甲苯二胺、多壁碳纳米管、二甲基甲酰胺、十二烷基苯磺酸钠、四氯化硅、双环戊二烯树脂、尼龙、蛭石、十六烷基三甲基溴化铵等为原料。本发明通过预聚体法制备了耐水解聚氨酯弹性体,制备了分散均匀、表面含有胺基官能团的多壁碳纳米管,改善了与尼龙之间的相容性,提高了在尼龙基体中的分散性;得到一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料。
Description
技术领域
本发明涉及高分子材料加工技术,具体涉及一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料,及其制备工艺。
背景技术
聚丁二烯橡胶具有高拉伸强度、高撕裂强度、高耐磨性等众多优异的性能特征。尼龙具有良好的综合性能,包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性,且摩擦系数低,有一定的阻燃性,易于加工。
赵永兵在其硕士论文《充油顺丁橡胶工艺技术的研究与发展》中,配制丁二烯与溶剂油(加氢汽油;填充油:环烷油)的混合物,放入恒温水浴,加热至聚合温度70℃,用针管将配制好的催化剂(环烷酸镍和三异丁基铝混合,陈化;三氟化硼乙醚络合物和辛醛先按一定比例配好,并稀释至500-1000倍)加入其中,搅拌使其充分混匀,待釜内温度稳定后搅拌2h充油完成,再将充油顺丁橡胶胶液经水蒸气凝聚后,用开炼机干燥。但用于高压油管存在耐腐蚀性不足。
本发明以聚己内酯二元醇、甲苯二异氰酸酯和二甲硫基甲苯二胺为原材料,以石墨为填料,通过预聚体法制备了耐水解聚氨酯弹性体,石墨与聚氨酯基体发生了插层聚合且在基体中的分散性良好;制备了分散均匀、表面含有胺基官能团的多壁碳纳米管,改善了与尼龙之间的相容性,提高了在尼龙基体中的分散性;
通过调节催化剂配比合成高门尼粘度基础胶;通过离子交换法对蛭石进行载银和有机化改性,制备稳定性高、成本低的抗菌蛭石;得到一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料。
发明内容
本发明主要解决的技术问题是提供一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料及其制备工艺,依照该工艺制作的汽车吸塑材料具有耐磨、耐油、耐撕裂、回弹力好、耐化学腐蚀等优良性能。
本发明所要解决的技术问题采用以下的技术方案来实现:
丁二烯(聚合级)22-30,环烷油10-19,环烷酸镍3-5,三异丁基铝4-8,三氟化硼乙醚络合物3-7,辛醛2-4,聚己内酯二元醇2-3,石墨1-2,抗氧剂TNP 0.5-1,紫外线吸收剂UV-90.1-0.3,甲苯二异氰酸酯1-3,二甲硫基甲苯二胺1-3,多壁碳纳米管1-2,二甲基甲酰胺1-2,乙二胺1-2,十二烷基苯磺酸钠2-4,四氯化硅1-2,双环戊二烯树脂3-5,尼龙5-7,蛭石1-3,十六烷基三甲基溴化铵2-4,SOCl2、四氢呋喃、乙醇、环己烷、NaCl溶液、AgNO3溶液适量。
一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料的制备方法,其特征在于,按以下步骤进行:
a. 将聚己内酯二元醇和石墨混合搅拌1-2h,升温到100-140℃真空脱水1-2h,降温至40-50℃后,快速搅拌下加入抗氧剂TNP、紫外线吸收剂UV-9、甲苯二异氰酸酯,在70-90℃下反应1-3h,真空脱泡1-2h,再加热至80-90℃,加入二甲硫基甲苯二胺,迅速搅拌均匀,将混合物置于105-115℃,预热、凝胶;
b. 向多壁碳纳米管中以20:1-2加入SOCl2和二甲基甲酰胺,于60-90℃的水浴中恒温加热搅拌2-4h,与乙二胺混合,在恒温130-170℃油浴下搅拌1-2h,用四氢呋喃和乙醇洗涤3-5次,过滤,将滤饼在70-90℃下真空干燥2-5h后,待用;
c. 将十二烷基苯磺酸钠、环烷酸镍、三异丁基铝混合,于50-90℃恒温加热磁力搅拌,反应2-3h后,加入三氟化硼乙醚络合物、辛醛、四氯化硅进行偶联1-2h,用乙醇洗涤3-5次,过滤,将产物先于通风橱中风干,再置于50-80℃的真空干燥箱中,干燥至恒重;
d. 将丁二烯与环烷油混合,加入双环戊二烯树脂的环己烷溶液,放入恒温水浴,加热至聚合温度70-90℃,用针管将c中配制好的催化剂加入其中,搅拌使其充分混匀,温度稳定为60-80℃搅拌2-4h充油完成,再将充油顺丁橡胶胶液经水蒸气凝聚后,在110-140℃滚筒上滚干;
e. 向蛭石中加入NaCl溶液,40-80℃下搅拌反应2-4h,离心分离,得钠化蛭石,将其加入AgNO3溶液中,50-90℃下反应4h后进行离心分离,制得载Ag蛭石,将其与十六烷基三甲基溴化铵混合,60-90℃搅拌条件下进行阳离子交换反应2-4h后,离心分离,制得载银并有机化插层蛭石;
f. 将a、b、d、e中所得物料及其他剩余成分混合均匀,加入双螺杆挤出机
内,于230-260℃、50-120r/min 熔融共混,挤出造粒,即得到一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料。
本发明的反应机理及有益效果如下:
(1)以聚己内酯二元醇、甲苯二异氰酸酯和二甲硫基甲苯二胺为原材料,以石墨为填料,通过预聚体法制备了耐水解聚氨酯弹性体,石墨与聚氨酯基体发生了插层聚合且在基体中的分散性良好,复合材料具有优异的耐磨、耐油、耐撕裂、回弹力好、耐化学腐蚀等特性,从而延长了油管的使用寿命。
(2)对多壁碳纳米管进行胺化处理,在其表面接枝了胺基官能团,制备了分散均匀、表面含有胺基官能团的多壁碳纳米管,改善了与尼龙之间的相容性,提高了在尼龙基体中的分散性。
(3)以十二烷基苯磺酸钠、环烷酸镍、三异丁基铝、三氟化硼乙醚络合物、辛醛、四氯化硅制备新型催化剂,调节催化剂配比合成高门尼粘度基础胶;使高门尼基础胶生产简便易行、控制灵活,门尼粘度高,充油性好,性能稳定。
(4)蛭石具有较高的阳离子交换容量的特点,将其作为载体吸附银离子,并将其有机化处理,通过离子交换法对蛭石进行载银和有机化改性,制备稳定性高、成本低的抗菌蛭石,是具有极强抗菌作用的材料,与尼龙基体界面间有较强的结合。
(5)尼龙具有良好的综合性能,包括力学性能、耐热性、耐磨损性、耐化学药品性和自润滑性,且摩擦系数低,有一定的阻燃性,易于加工;聚丁二烯橡胶具有高拉伸强度、高撕裂强度、高耐磨性等众多优异的性能特征。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
实施例
一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料,由下述重量份(g)的原料制得:
丁二烯(聚合级)26,环烷油16,环烷酸镍5,三异丁基铝4,三氟化硼乙
醚络合物6,辛醛4,聚己内酯二元醇2,石墨1,抗氧剂TNP 0.5,紫外线吸收剂UV-9 0.1,甲苯二异氰酸酯1,二甲硫基甲苯二胺3,多壁碳纳米管2,二甲基甲酰胺1,乙二胺1,十二烷基苯磺酸钠2,四氯化硅1,双环戊二烯树脂3,尼龙5,蛭石1,十六烷基三甲基溴化铵2,SOCl2、四氢呋喃、乙醇、环己烷、NaCl溶液、AgNO3溶液适量。
一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料的制备方法,其特征在于,按以下步骤进行:
a. 将聚己内酯二元醇和石墨混合搅拌1h,升温到100-110℃真空脱水1h,降温至40-50℃后,快速搅拌下加入抗氧剂TNP、紫外线吸收剂UV-9、甲苯二异氰酸酯,在70-80℃下反应1h,真空脱泡1h,再加热至80-90℃,加入二甲硫基甲苯二胺,迅速搅拌均匀,将混合物置于105-115℃,预热、凝胶;
b. 向多壁碳纳米管中以20:1加入SOCl2和二甲基甲酰胺,于60-70℃的水浴中恒温加热搅拌2h,与乙二胺混合,在恒温160-170℃油浴下搅拌1h,用四氢呋喃和乙醇洗涤3次,过滤,将滤饼在80-90℃下真空干燥2h后,待用;
c. 将十二烷基苯磺酸钠、环烷酸镍、三异丁基铝混合,于70-80℃恒温加热磁力搅拌,反应2h后,加入三氟化硼乙醚络合物、辛醛、四氯化硅进行偶联1h,用乙醇洗涤5次,过滤,将产物先于通风橱中风干,再置于70-80℃的真空干燥箱中,干燥至恒重;
d. 将丁二烯与环烷油混合,加入双环戊二烯树脂的环己烷溶液,放入恒温水浴,加热至聚合温度70-80℃,用针管将c中配制好的催化剂加入其中,搅拌使其充分混匀,温度稳定为60-70℃搅拌4h充油完成,再将充油顺丁橡胶胶液经水蒸气凝聚后,在110-120℃滚筒上滚干;
e. 向蛭石中加入NaCl溶液,60-80℃下搅拌反应2h,离心分离,得钠化蛭石,将其加入AgNO3溶液中,50-70℃下反应4h后进行离心分离,制得载Ag蛭石,将其与十六烷基三甲基溴化铵混合,70-90℃搅拌条件下进行阳离子交换反应4h后,离心分离,制得载银并有机化插层蛭石;
f. 将a、b、d、e中所得物料及其他剩余成分混合均匀,加入双螺杆挤出机
内,于240-260℃、90-110r/min 熔融共混,挤出造粒,即得到一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料。
上述实施例制备的一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料的性能检测结果如下所示:
拉伸强度89MPa,断裂生长率181%;
热老化试验(160℃,200h):拉伸强度变化率11.6%,断裂伸长率变化率11.6%;
耐矿物油实验(80℃,200h):拉伸强度变化率12.3%,断裂伸长率变化率12.6%。
Claims (2)
1.一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料,其特征在于,由下述重量份的原料制得:
丁二烯(聚合级)22-30,环烷油10-19,环烷酸镍3-5,三异丁基铝4-8,三
氟化硼乙醚络合物3-7,辛醛2-4,聚己内酯二元醇2-3,石墨1-2,抗氧剂TNP 0.5-1,紫外线吸收剂UV-9 0.1-0.3,甲苯二异氰酸酯1-3,二甲硫基甲苯二胺1-3,多壁碳纳米管1-2,二甲基甲酰胺1-2,乙二胺1-2,十二烷基苯磺酸钠2-4,四氯化硅1-2,双环戊二烯树脂3-5,尼龙5-7,蛭石1-3,十六烷基三甲基溴化铵2-4,SOCl2、四氢呋喃、乙醇、环己烷、NaCl溶液、AgNO3溶液适量。
2.根据权利要求1所述的一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料的制备方法,其特征在于,按以下步骤进行:
a. 将聚己内酯二元醇和石墨混合搅拌1-2h,升温到100-140℃真空脱水1-2h,降温至40-50℃后,快速搅拌下加入抗氧剂TNP、紫外线吸收剂UV-9、甲苯二异氰酸酯,在70-90℃下反应1-3h,真空脱泡1-2h,再加热至80-90℃,加入二甲硫基甲苯二胺,迅速搅拌均匀,将混合物置于105-115℃,预热、凝胶;
b. 向多壁碳纳米管中以20:1-2加入SOCl2和二甲基甲酰胺,于60-90℃的水浴中恒温加热搅拌2-4h,与乙二胺混合,在恒温130-170℃油浴下搅拌1-2h,用四氢呋喃和乙醇洗涤3-5次,过滤,将滤饼在70-90℃下真空干燥2-5h后,待用;
c. 将十二烷基苯磺酸钠、环烷酸镍、三异丁基铝混合,于50-90℃恒温加热磁力搅拌,反应2-3h后,加入三氟化硼乙醚络合物、辛醛、四氯化硅进行偶联1-2h,用乙醇洗涤3-5次,过滤,将产物先于通风橱中风干,再置于50-80℃的真空干燥箱中,干燥至恒重;
d. 将丁二烯与环烷油混合,加入双环戊二烯树脂的环己烷溶液,放入恒温水浴,加热至聚合温度70-90℃,用针管将c中所得催化剂加入其中,搅拌使其充分混匀,温度稳定为60-80℃搅拌2-4h充油完成,再将充油顺丁橡胶胶液经水蒸气凝聚后,在110-140℃滚筒上滚干;
e. 向蛭石中加入NaCl溶液,40-80℃下搅拌反应2-4h,离心分离,得钠化蛭石,将其加入AgNO3溶液中,50-90℃下反应4h后进行离心分离,制得载Ag蛭石,将其与十六烷基三甲基溴化铵混合,60-90℃搅拌条件下进行阳离子交换反应2-4h后,离心分离,制得载银并有机化插层蛭石;
f. 将a、b、d、e中所得物料及其他剩余成分混合均匀,加入双螺杆挤出机
内,于230-260℃、50-120r/min 熔融共混,挤出造粒,即得到一种含抗菌蛭石的用于高压油管的耐油耐腐蚀材料。
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