CN106243608A - 一种铅酸蓄电池高强度塑壳制备方法 - Google Patents
一种铅酸蓄电池高强度塑壳制备方法 Download PDFInfo
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Abstract
本发明公开了一种铅酸蓄电池高强度塑壳制备方法,包括以下步骤:(1)制备表面改性竹纤维;(2)制备改性氢氧化铝;(3)制备改性沸石粉;(4)注塑成型。本发明在对塑壳材料配方进行优化改进的基础上,同时优化了注塑成型工艺参数,采用注塑机直接注塑成型工艺得到壳体,工艺步骤简单,易实施,对设备要求低,生产成本与能耗低,生产效率高,适合工业化生产,制得的塑壳环保,生产成本低,阻燃且机械性能与耐候性优良。
Description
技术领域
本发明涉及铅酸蓄电池制造技术领域,尤其是涉及一种铅酸蓄电池高强度塑壳制备方法。
背景技术
当今国际能源竞争日趋激烈,世界能源格局加快调整,在传统能源清洁高效利用的基础上,发展以再生能源和生物能源为主的清洁能源,推动经济绿色增长,成为必由之路和共同选择。中国政府在保持经济高速发展的同时,也先后出台了一系列绿色能源及新能源合理开发、利用、保护的政策、法规。而蓄电池作为一种新型绿色能源,因其本身安全可靠,性价比高,环境适应能力强等优点,被广泛应用于各行各业。
对于蓄电池而言,作为用来盛放电解液和极群载体的铅蓄电池壳则是重要组成部分。目前的铅酸蓄电池壳体通常以ABS树脂为主要原料经注塑成型而得到,但常用ABS树脂阻燃性能较差,存在一定安全隐患,且耐候性能与机械性能较差,在储存、加工成型过程及使用过程中随时间而发生结构变化,出现力学性能劣化、材料变硬发脆等问题,同时由于ABS树脂的吸湿性和对水分的敏感性较大,很难对其充分干燥,因此极易导致产品表面出现水花银丝纹现象,而目前为保证ABS树脂能充分干燥,通常采用提高干燥温度或者干燥时间的方式,这样或导致能耗高,或导致生产效率大大降低。
发明内容
本发明是为了解决现有技术的铅酸蓄电池塑壳所存在的上述问题,提供了一种工艺步骤简单,易实施,对设备要求低,生产成本与能耗低,生产效率高,适合工业化生产的铅酸蓄电池高强度塑壳制备方法,制得的铅酸蓄电池高强度塑壳环保,阻燃、导热及机械性能优异。
为了实现上述目的,本发明采用以下技术方案:
本发明的一种铅酸蓄电池高强度塑壳制备方法,包括以下步骤:
(1)制备表面改性竹纤维:将竹纤维加入氯磺酸中,加热至80~100℃溶胀1~3h,冷却,过滤,将过滤物用水洗至pH呈中性,真空干燥,再加入浸润剂中进行浸泡30~60min后于95~105℃下烘干,即得表面改性竹纤维。氯磺酸能使竹纤维集束充分溶胀,使其分散,有利于改善其分散性,便于浸润剂充分、均匀浸润;浸润剂可使得烘干后的竹纤维表面能形成一层保护膜,避免材料在注塑成型时损伤,尽量保证竹纤维的保留长度,另外,经浸泡过的竹纤维表面粗糙度也变大,与树脂之间形成较多的化学键,增加与树脂之间的摩擦系数,从而使界面剪切强度增加,提高了韧性。
(2)制备改性氢氧化铝:先将氢氧化铝分散于水中配制成质量百分浓度5~10%的分散液,搅拌加热至70~80℃后,将为氢氧化铝质量10~15%的三聚氰胺加入分散液中加拌均匀,得反应液;再按三聚氰胺与甲醛物质的量比1:2~3,将甲醛溶液滴加至反应液中恒温反应4~8h,将反应物过滤、洗涤、干燥后,得改性氢氧化铝。通过三聚氰胺与甲醛交联可在氢氧化铝表面形成一层薄膜,既能提高氢氧化铝的热稳定性,更能使氢氧化铝与树脂基体间的界面结合强度大大提高,且分散性能也更为优异。
(3)制备改性沸石粉:将沸石粉于300~500℃温度下煅烧30~60min,冷却后浸于质量浓度为5~10%的硝酸溶液中超声处理30~40min,过滤后再将沸石粉置于改性剂中超声处理30~60min,在70~80℃下烘干即得改性沸石粉。
(4)注塑成型:按40~50份ABS树脂,20~30份PVC树脂,5~10份表面改性竹纤维,5~10份改性氢氧化铝,3~5份改性沸石粉,5~10份氯化聚乙烯,1~3份润滑剂的重量份配比称取各组分后,将ABS树脂和PVC树脂置于无水乙醇中浸泡并搅拌5~10min,烘干,将各组分混合均匀后加入注塑机注塑成型,最后经检验合格即得铅酸蓄电池高强度塑壳。本发明对塑壳材料的配方进行优化改进,在ABS树脂中加入定量PVC树脂,通过两者材料协同作用,使得塑壳的耐候性得到大幅度提高,有效解决了壳体易变脆发黄的问题,并同时保持了铅蓄电池壳体的冲击强度和韧性达到国家标准规定;氢氧化铝为一种廉价的阻燃剂,在阻燃材料中广泛应用,但是其需要较大的添加量(通常需要20%以上)才具有阻燃作用,同时其与ABS树脂、PVC树脂兼容性差,且在材料中分散性差,本发明中采用改性氢氧化铝作为阻燃剂,阻燃性能更为优异,热稳定性良好,且分散性好,与材料体系间的界面结合性得到提高,采用改性沸石粉作为阻燃促进剂,改性沸石粉能有选择的吸附、透过粒子,能够有效提高改性氢氧化铝的阻燃效率,采用改性氢氧化铝和改性沸石粉作为阻燃体系,可大大减少改性氢氧化铝的使用量,阻燃效果好;表面改性竹纤维与树脂基体间有较好的相容性,可大大提高树脂基体的力学性能和耐热性。
作为优选,步骤(1)中,所述浸润剂由以下质量百分比的组分组成:40~50%聚四氟乙烯分散乳液,0.1~0.2%季铵盐,0.3~0.5%硬脂酸聚氧乙烯酯,0.1~0.3%硅烷偶联剂KH-550,1~3%纳米氮化硅,余量为水。本发明中的浸润剂是关键点,聚四氟乙烯分散乳液为主成膜剂,硬脂酸聚氧乙烯酯为辅成膜剂,季铵盐为抗静电剂,硅烷偶联剂KH-550为分散、乳化剂,能使纳米氮化硅均匀分散,纳米氮化硅具有优异的散热性能,可提高散热性,并可附着于膜表面可增加竹纤维的比表面积,增加竹纤维与树脂基体的接触面积,提高两者的结合强度,有利于提高塑壳力学性能,最重要的是塑壳受力时纳米氮化硅粒子与基体之间产生微裂纹,可吸收外界能量,同时纳米氮化硅起到应力集中点的作用,使纳米氮化硅周围树脂发生大的塑性变形而吸收冲击能,从而达到增韧的效果。
作为优选,步骤(3)中,所述改性剂由以下质量百分比的组分组成:3~5%聚氧化乙烯,0.1~0.5%硅烷偶联剂KH-550,余量为水。
作为优选,步骤(4)中,所述润滑剂为乙撑双硬脂酰胺、硬脂酸镁、硬脂酸锌及聚乙烯蜡中的一种或多种。
作为优选,步骤(4)中,注塑成型的具体步骤为:注塑→成型→保压→脱模→冷却。
作为优选,注塑料桶温度为190~210℃;成型模具温度为60~70℃;保压压力50~60MPa,保压时间5~7s。
因此,本发明具有如下有益效果:
(1)在ABS树脂中加入定量PVC树脂,通过两者材料协同作用,使得塑壳的耐候性得到大幅度提高,有效解决了壳体易变脆发黄的问题;
(2)采用改性氢氧化铝和改性沸石粉作为阻燃体系,可大大减少改性氢氧化铝的使用量,阻燃效果好;
(3)在对塑壳材料配方进行优化改进的基础上,同时优化了注塑成型工艺参数,采用注塑机直接注塑成型工艺得到壳体,工艺步骤简单,易实施,对设备要求低,生产成本与能耗低,生产效率高,适合工业化生产,制得的塑壳环保,生产成本低,阻燃且机械性能与耐候性优良。
具体实施方式
下面通过具体实施方式对本发明做进一步的描述。
实施例1
(1)制备表面改性竹纤维:将竹纤维加入氯磺酸中,加热至90℃溶胀2h,冷却,过滤,将过滤物用水洗至pH呈中性,真空干燥,再加入浸润剂中进行浸泡40min后于100℃下烘干,即得表面改性竹纤维,其中浸润剂由以下质量百分比的组分组成:45%聚四氟乙烯分散乳液,0.15%季铵盐,0.4%硬脂酸聚氧乙烯酯,0.2%硅烷偶联剂KH-550,2%纳米氮化硅,余量为水;
(2)制备改性氢氧化铝:先将氢氧化铝分散于水中配制成质量百分浓度7%的分散液,搅拌加热至75℃后,将为氢氧化铝质量12%的三聚氰胺加入分散液中加拌均匀,得反应液;再按三聚氰胺与甲醛物质的量比1:2.5,将甲醛溶液滴加至反应液中恒温反应5h,将反应物过滤、洗涤、干燥后,得改性氢氧化铝;
(3)制备改性沸石粉:将沸石粉于400℃温度下煅烧50min,冷却后浸于质量浓度为7%的硝酸溶液中超声处理35min,过滤后再将沸石粉置于改性剂中超声处理40min,在75℃下烘干即得改性沸石粉,其中改性剂由以下质量百分比的组分组成:4%聚氧化乙烯,0.2%硅烷偶联剂KH-550,余量为水。
(4)注塑成型:按42KgABS树脂,25KgPVC树脂,8Kg表面改性竹纤维,6Kg改性氢氧化铝,4Kg改性沸石粉,8Kg氯化聚乙烯,2Kg润滑剂(乙撑双硬脂酰胺与硬脂酸锌按质量比1:1混合)的重量配比称取各组分后,将ABS树脂和PVC树脂置于无水乙醇中浸泡并搅拌8min,烘干,将各组分混合均匀后加入注塑机注塑成型,最后经检验合格即得铅酸蓄电池高强度塑壳,其中注塑成型的具体步骤为:注塑→成型→保压→脱模→冷却,注塑料桶温度为200℃;成型模具温度为65℃;保压压力52MPa,保压时间6s。
实施例2
(1)制备表面改性竹纤维:将竹纤维加入氯磺酸中,加热至100℃溶胀3h,冷却,过滤,将过滤物用水洗至pH呈中性,真空干燥,再加入浸润剂中进行浸泡60min后于105℃下烘干,即得表面改性竹纤维,其中浸润剂由以下质量百分比的组分组成:50%聚四氟乙烯分散乳液,0.2%季铵盐,0.5%硬脂酸聚氧乙烯酯,0.3%硅烷偶联剂KH-550,3%纳米氮化硅,余量为水;
(2)制备改性氢氧化铝:先将氢氧化铝分散于水中配制成质量百分浓度10%的分散液,搅拌加热至80℃后,将为氢氧化铝质量15%的三聚氰胺加入分散液中加拌均匀,得反应液;再按三聚氰胺与甲醛物质的量比1:3,将甲醛溶液滴加至反应液中恒温反应8h,将反应物过滤、洗涤、干燥后,得改性氢氧化铝;
(3)制备改性沸石粉:将沸石粉于500℃温度下煅烧60min,冷却后浸于质量浓度为10%的硝酸溶液中超声处理40min,过滤后再将沸石粉置于改性剂中超声处理60min,在80℃下烘干即得改性沸石粉,其中改性剂由以下质量百分比的组分组成:5%聚氧化乙烯,0.5%硅烷偶联剂KH-550,余量为水。
(4)注塑成型:按50KgABS树脂,30KgPVC树脂,10Kg表面改性竹纤维,10Kg改性氢氧化铝,5Kg改性沸石粉,10Kg氯化聚乙烯,3Kg润滑剂(硬脂酸镁)的重量配比称取各组分后,将ABS树脂和PVC树脂置于无水乙醇中浸泡并搅拌10min,烘干,将各组分混合均匀后加入注塑机注塑成型,最后经检验合格即得铅酸蓄电池高强度塑壳,其中注塑成型的具体步骤为:注塑→成型→保压→脱模→冷却,注塑料桶温度为210℃;成型模具温度为70℃;保压压力60MPa,保压时间7s。
实施例3
(1)制备表面改性竹纤维:将竹纤维加入氯磺酸中,加热至80℃溶胀1h,冷却,过滤,将过滤物用水洗至pH呈中性,真空干燥,再加入浸润剂中进行浸泡30min后于95℃下烘干,即得表面改性竹纤维,其中浸润剂由以下质量百分比的组分组成:40%聚四氟乙烯分散乳液,0.1%季铵盐,0.3%硬脂酸聚氧乙烯酯,0.1%硅烷偶联剂KH-550,1%纳米氮化硅,余量为水;
(2)制备改性氢氧化铝:先将氢氧化铝分散于水中配制成质量百分浓度5%的分散液,搅拌加热至70℃后,将为氢氧化铝质量10%的三聚氰胺加入分散液中加拌均匀,得反应液;再按三聚氰胺与甲醛物质的量比1:2,将甲醛溶液滴加至反应液中恒温反应4h,将反应物过滤、洗涤、干燥后,得改性氢氧化铝;
(3)制备改性沸石粉:将沸石粉于300℃温度下煅烧30min,冷却后浸于质量浓度为5%的硝酸溶液中超声处理30min,过滤后再将沸石粉置于改性剂中超声处理30min,在70℃下烘干即得改性沸石粉,其中改性剂由以下质量百分比的组分组成:3%聚氧化乙烯,0.1%硅烷偶联剂KH-550,余量为水。
(4)注塑成型:按40KgABS树脂,20KgPVC树脂,5Kg表面改性竹纤维,5Kg改性氢氧化铝,3Kg改性沸石粉,5Kg氯化聚乙烯,1Kg润滑剂(乙撑双硬脂酰胺)的重量配比称取各组分后,将ABS树脂和PVC树脂置于无水乙醇中浸泡并搅拌5min,烘干,将各组分混合均匀后加入注塑机注塑成型,最后经检验合格即得铅酸蓄电池高强度塑壳,其中注塑成型的具体步骤为:注塑→成型→保压→脱模→冷却,注塑料桶温度为190℃;成型模具温度为60℃;保压压力50MPa,保压时间5s。
通过本发明制得的铅酸蓄电池高强度塑壳氧指数≥30.5%,阻燃性能超过塑料材料可燃性能标准V-0级阻燃标准,其他各项指标(均按照GB/T 23754-2009执行)为:
质量变化率:0.3%;
耐冲击:低温-30℃以下无裂纹;
耐热性:70±2℃、3小时后变化量:0.2mm;
耐气压:变化量:0.1mm;
耐电压:20000V未被击穿;
还原高锰酸钾:0.4ml/g;
耐高温性能(℃)≤102,一般ABS只能达到75℃左右;
抗张强度(Mpa) ≥600;
弯曲强度(Mpa)≥950 ;
弯曲模数(Mpa)≥3000;
耐热变形温度(℃)≤132;
冲击强度(J/m)≥2900。
各指标远超过GB/T 23754-2009《铅酸蓄电池槽》标准要求,具有优异的阻燃、导热及力学性能。
以上所述的实施例只是本发明的一种较佳的方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (6)
1.一种铅酸蓄电池高强度塑壳制备方法,其特征在于,包括以下步骤:
(1)制备表面改性竹纤维:将竹纤维加入氯磺酸中,加热至80~100℃溶胀1~3h,冷却,过滤,将过滤物用水洗至pH呈中性,真空干燥,再加入浸润剂中进行浸泡30~60min后于95~105℃下烘干,即得表面改性竹纤维;
(2)制备改性氢氧化铝:先将氢氧化铝分散于水中配制成质量百分浓度5~10%的分散液,搅拌加热至70~80℃后,将为氢氧化铝质量10~15%的三聚氰胺加入分散液中加拌均匀,得反应液;再按三聚氰胺与甲醛物质的量比1:2~3,将甲醛溶液滴加至反应液中恒温反应4~8h,将反应物过滤、洗涤、干燥后,得改性氢氧化铝;
(3)制备改性沸石粉:将沸石粉于300~500℃温度下煅烧30~60min,冷却后浸于质量浓度为5~10%的硝酸溶液中超声处理30~40min,过滤后再将沸石粉置于改性剂中超声处理30~60min,在70~80℃下烘干即得改性沸石粉;
(4)注塑成型:按40~50份ABS树脂,20~30份PVC树脂,5~10份表面改性竹纤维,5~10份改性氢氧化铝,3~5份改性沸石粉,5~10份氯化聚乙烯,1~3份润滑剂的重量份配比称取各组分后,将ABS树脂和PVC树脂置于无水乙醇中浸泡并搅拌5~10min,烘干,将各组分混合均匀后加入注塑机注塑成型,最后经检验合格即得铅酸蓄电池高强度塑壳。
2.根据权利要求1所述的一种铅酸蓄电池高强度塑壳制备方法,其特征在于,步骤(1)中,所述浸润剂由以下质量百分比的组分组成:40~50%聚四氟乙烯分散乳液,0.1~0.2%季铵盐,0.3~0.5%硬脂酸聚氧乙烯酯,0.1~0.3%硅烷偶联剂KH-550,1~3%纳米氮化硅,余量为水。
3.根据权利要求1所述的一种铅酸蓄电池高强度塑壳制备方法,其特征在于,步骤(3)中,所述改性剂由以下质量百分比的组分组成:3~5%聚氧化乙烯,0.1~0.5%硅烷偶联剂KH-550,余量为水。
4.根据权利要求1所述的一种铅酸蓄电池高强度塑壳制备方法,其特征在于,步骤(4)中,所述润滑剂为乙撑双硬脂酰胺、硬脂酸镁、硬脂酸锌及聚乙烯蜡中的一种或多种。
5.根据权利要求1所述的一种铅酸蓄电池高强度塑壳制备方法,其特征在于,步骤(4)中,注塑成型的具体步骤为:注塑→成型→保压→脱模→冷却。
6.根据权利要求5所述的一种铅酸蓄电池高强度塑壳制备方法,其特征在于,注塑料桶温度为190~210℃;成型模具温度为60~70℃;保压压力50~60MPa,保压时间5~7s。
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