CN111136895A - 一种涂抹涂料用防溅涂料桶材料的制备方法 - Google Patents
一种涂抹涂料用防溅涂料桶材料的制备方法 Download PDFInfo
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Abstract
本发明涉及塑料复合材料制备技术领域，具体涉及一种涂抹涂料用防溅涂料桶材料的制备方法。本发明涂料桶材料由外塑板和内层无机填充料构成，用EPDM掺杂改性可以有效提高涂料桶材料的韧性和弹性，而且EPDM具有耐油，耐酸碱腐蚀性能较好，相当于给涂抹涂料用防溅涂料桶材料提供了一层防腐保护膜，并且经过环氧大豆油改性后的外塑板对大部分油性涂料的亲和型提高，不易发生飞溅，以高密度聚乙烯粉末为主要原料硫化成型制备外塑板，通过内层无机填充料中添加甲基丙烯酸锌作为耐热抗氧化剂，同时它还能作为助硫化剂促进外塑板中橡胶的交联，提高了涂料桶材料中掺杂成分的相容性，进一步提升防腐性能，具有广阔的应用前景。
Description
技术领域
本发明涉及塑料复合材料制备技术领域，具体涉及一种涂抹涂料用防溅涂料桶材料的制备方法。
背景技术
塑料桶多用于各种液体的储存和运输，对特殊的危险品包装具有良好的特性，它有不易碎、不生锈、质轻等特点，而且耐油、耐强腐蚀性能好优异，多用于需要保温、防潮、耐压、抗腐蚀的危险品包装。
塑料桶的材料多采用聚乙烯、聚丙烯、聚酯等塑料吹塑、注塑、吸塑、滚塑而成，多用于盛装化工、农药、医药、食品、五金电子、机电等行业液体、固体物品。
规格从0.25～220L。
目前塑料桶中涂料桶材料不具备长久的防腐性，涂抹涂料时由于涂料桶与涂料的亲和性不佳，导致涂料飞溅，不仅浪费涂料，还对涂装环境产生污染。
因而，研制一种涂抹涂料用防溅涂料桶材料是涂料桶制备的大势所趋。
发明内容
本发明的目的在于提供一种涂抹涂料用防溅涂料桶材料的制备方法，以解决现有技术中的问题。
为了解决上述技术问题，本发明所采用的技术方案是：
一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于具体制备步骤为：
(1)将丁腈橡胶、ABS树脂母粒、PET树脂母粒、粒径为2～3mm的聚苯胺颗粒置于双辊混炼机中，在前辊温度为55～60℃，后辊温度为50～55℃，辊距为6～8mm的条件下塑炼后，再向双辊混炼机中加入水滑石、白炭黑，混合塑炼，得到导电塑料；
(2)将高密度聚乙烯粉末、导电塑料、环氧大豆油、EPDM原胶、氧化锌、硬脂酸铝混合得到混炼原料，以温度为70～80℃和压力为1.2～1.5MPa的条件热压成型为外塑板；
(3)将纳米氧化铝、硼酸钙、细度为200目的石墨粉加入到粉碎机中粉碎后倒入混砂机中，随后加入甲基丙烯酸锌、二氧化锆、石墨烯，搅拌混合10～20min，再球磨过200目筛得到内层无机填充料；
(4)取200～220mL正硅酸乙酯与300～350mL无水乙醇混合放入烧杯中，向烧杯中加入60～80mL质量分数为10％的盐酸，用磁力搅拌器以400～450r/min的转速，搅拌1～2h，得到二氧化硅溶胶，向二氧化硅溶胶中加入20～30mL质量分数为5％的聚乙烯醇，室温下陈化20～24h，得到二氧化硅溶胶；
(5)将上述内层无机填充料和上述二氧化硅溶胶按质量比为3︰1混合，得到内层填充胶液，将外塑板双层叠放至于涂布脱模剂的热压模具中，向所述热压模具中注入内层填充胶液，置于热压设备中热压处理30～35min，控制热压压力为4～5MPa，热压温度为100～150℃，得到涂抹涂料用防溅涂料桶材料。
步骤(1)所述的导电塑料各组分原料，按重量份数计，包括10～15丁腈橡胶、20～30份ABS树脂母粒、30～35份PET树脂母粒、6～8份粒径为2～3mm的聚苯胺颗粒、10～12份水滑石、4～5份白炭黑。
步骤(2)所述的外塑板各组分原料，按重量份数计，包括50～55份高密度聚乙烯粉末、8～10份导电塑料、10～15份环氧大豆油、10～12份EPDM原胶、5～10份氧化锌、7～8份硬脂酸铝。
步骤(2)所述的高密度聚乙烯粉末分子量为2～5万，结晶度为80～85％，EPDM原胶的乙烯含量为50～55％。
步骤(3)所述的内层无机填充料的各组分原料，按重量份数计，包括30～35份纳米氧化铝、20～25份硼酸钙、10～15份细度为200目的石墨粉、8～10份甲基丙烯酸锌、4～6份二氧化锆、5～8份石墨烯。
步骤(5)所述的脱模剂为硅油、聚乙二醇、低分子量聚乙烯的一种。
本发明的有益效果是：
(1)本发明涂料桶材料由外塑板和内层无机填充料构成，所用EPDM原胶中乙烯含量在50～55％，可以避免形成丙烯嵌段，以保证丙烯、乙烯在EPDM分子中无规则分布，使EPDM具有低温弹性，虽然高密度聚乙烯粉末分子链柔顺性差，EPDM分子的内聚能较低，没有大量的侧基阻碍分子链的运动，分子链可在较宽范围内保持良好的柔顺性和弹性，故用EPDM掺杂改性可以有效提高涂抹涂料用防溅涂料桶材料的韧性和弹性，而且EPDM具有耐油，耐酸碱腐蚀性能较好，相当于给涂抹涂料用防溅涂料桶材料提供了一层防腐保护膜，并且经过环氧大豆油改性后的外塑板对大部分油性涂料的亲和型提高，不易发生飞溅；
(2)本发明以高密度聚乙烯粉末为主要原料硫化成型制备外塑板，通过内层无机填充料中添加甲基丙烯酸锌作为耐热抗氧化剂，同时它还能作为助硫化剂促进外塑板中橡胶的交联，这是由于甲基丙烯酸锌中的二价锌离子首先作为路易斯酸，催化涂抹涂料用防溅涂料桶材料中如EPDM或环氧大豆油等环氧化合物发生开环反应，并伴随生成羟基，开环生成的羟基进一步与不饱和羧酸金属盐上的双键发生亲核加成反应，即氧杂-迈克尔反应，提高了涂料桶材料中掺杂成分的相容性，并使无机内层无机填充料对涂料桶材料中外塑板的粘结力提升，进一步提升防腐性能，具有广阔的应用前景。
具体实施方式
按重量份数计，将10～15丁腈橡胶、20～30份ABS树脂母粒、30～35份PET树脂母粒、6～8份粒径为2～3mm的聚苯胺颗粒置于双辊混炼机中，在前辊温度为55～60℃，后辊温度为50～55℃，辊距为6～8mm的条件下塑炼后，再向双辊混炼机中加入10～12份水滑石、4～5份白炭黑，混合塑炼，得到导电塑料；
按重量份数计，将50～55份高密度聚乙烯粉末、8～10份导电塑料、10～15份环氧大豆油、10～12份EPDM原胶、5～10份氧化锌、7～8份硬脂酸铝混合得到混炼原料，以温度为70～80℃和压力为1.2～1.5MPa的条件热压成型为外塑板，所述的高密度聚乙烯粉末分子量为2～5万，结晶度为80～85％，EPDM原胶的乙烯含量为50～55％；按重量份数计，将30～35份纳米氧化铝、20～25份硼酸钙、10～15份细度为200目的石墨粉加入到粉碎机中粉碎后倒入混砂机中，随后加入8～10份甲基丙烯酸锌、4～6份二氧化锆、5～8份石墨烯，搅拌混合10～20min，再球磨过200目筛得到内层无机填充料；取200～220mL正硅酸乙酯与300～350mL无水乙醇混合放入烧杯中，向烧杯中加入60～80mL质量分数为10％的盐酸，用磁力搅拌器以400～450r/min的转速，搅拌1～2h，得到二氧化硅溶胶，向二氧化硅溶胶中加入20～30mL质量分数为5％的聚乙烯醇，室温下陈化20～24h，得到二氧化硅溶胶；将上述内层无机填充料和上述二氧化硅溶胶按质量比为3︰1混合，得到内层填充胶液，将外塑板双层叠放至于涂布脱模剂的热压模具中，向所述热压模具中注入内层填充胶液，置于热压设备中热压处理30～35min，控制热压压力为4～5MPa，热压温度为100～150℃，得到涂抹涂料用防溅涂料桶材料，所述的脱模剂为硅油、聚乙二醇、低分子量聚乙烯的一种。
实例1
按重量份数计，将10份丁腈橡胶、20份ABS树脂母粒、30份PET树脂母粒、6份粒径为2mm的聚苯胺颗粒置于双辊混炼机中，在前辊温度为55℃，后辊温度为50～55℃，辊距为6mm的条件下塑炼后，再向双辊混炼机中加入10份水滑石、4份白炭黑，混合塑炼，得到导电塑料；按重量份数计，将50份高密度聚乙烯粉末、8份导电塑料、10份环氧大豆油、10份EPDM原胶、5份氧化锌、7份硬脂酸铝混合得到混炼原料，以温度为70℃和压力为1.2MPa的条件热压成型为外塑板，所述的高密度聚乙烯粉末分子量为2万，结晶度为80％，EPDM原胶的乙烯含量为50％；按重量份数计，将30份纳米氧化铝、20份硼酸钙、10份细度为200目的石墨粉加入到粉碎机中粉碎后倒入混砂机中，随后加入8份甲基丙烯酸锌、4份二氧化锆、5份石墨烯，搅拌混合10min，再球磨过200目筛得到内层无机填充料；取200mL正硅酸乙酯与300mL无水乙醇混合放入烧杯中，向烧杯中加入60mL质量分数为10％的盐酸，用磁力搅拌器以400r/min的转速，搅拌1h，得到二氧化硅溶胶，向二氧化硅溶胶中加入20mL质量分数为5％的聚乙烯醇，室温下陈化20h，得到二氧化硅溶胶；将上述内层无机填充料和上述二氧化硅溶胶按质量比为3︰1混合，得到内层填充胶液，将外塑板双层叠放至于涂布脱模剂的热压模具中，向所述热压模具中注入内层填充胶液，置于热压设备中热压处理30min，控制热压压力为4MPa，热压温度为100℃，得到涂抹涂料用防溅涂料桶材料，所述的脱模剂为聚乙二醇。
实例2
按重量份数计，13丁腈橡胶、25份ABS树脂母粒、33份PET树脂母粒、7份粒径为3mm的聚苯胺颗粒置于双辊混炼机中，在前辊温度为58℃，后辊温度为52℃，辊距为7mm的条件下塑炼后，再向双辊混炼机中加入11份水滑石、5份白炭黑，混合塑炼，得到导电塑料；按重量份数计，将53份高密度聚乙烯粉末、9份导电塑料、13份环氧大豆油、11份EPDM原胶、8份氧化锌、8份硬脂酸铝混合得到混炼原料，以温度为75℃和压力为1.3MPa的条件热压成型为外塑板，所述的高密度聚乙烯粉末分子量为4万，结晶度为83％，EPDM原胶的乙烯含量为53％；按重量份数计，将33份纳米氧化铝、23份硼酸钙、13份细度为200目的石墨粉加入到粉碎机中粉碎后倒入混砂机中，随后加入9份甲基丙烯酸锌、5份二氧化锆、7份石墨烯，搅拌混合15min，再球磨过200目筛得到内层无机填充料；取210mL正硅酸乙酯与330mL无水乙醇混合放入烧杯中，向烧杯中加入70mL质量分数为10％的盐酸，用磁力搅拌器以420r/min的转速，搅拌2h，得到二氧化硅溶胶，向二氧化硅溶胶中加入25mL质量分数为5％的聚乙烯醇，室温下陈化22h，得到二氧化硅溶胶；将上述内层无机填充料和上述二氧化硅溶胶按质量比为3︰1混合，得到内层填充胶液，将外塑板双层叠放至于涂布脱模剂的热压模具中，向所述热压模具中注入内层填充胶液，置于热压设备中热压处理33min，控制热压压力为5MPa，热压温度为130℃，得到涂抹涂料用防溅涂料桶材料，所述的脱模剂为低分子量聚乙烯。
实例3
按重量份数计，15份丁腈橡胶、30份ABS树脂母粒、35份PET树脂母粒、8份粒径为3mm的聚苯胺颗粒置于双辊混炼机中，在前辊温度为60℃，后辊温度为55℃，辊距为8mm的条件下塑炼后，再向双辊混炼机中加入12份水滑石、5份白炭黑，混合塑炼，得到导电塑料；按重量份数计，将55份高密度聚乙烯粉末、10份导电塑料、15份环氧大豆油、12份EPDM原胶、10份氧化锌、8份硬脂酸铝混合得到混炼原料，以温度为80℃和压力为1.5MPa的条件热压成型为外塑板，所述的高密度聚乙烯粉末分子量为5万，结晶度为85％，EPDM原胶的乙烯含量为55％；按重量份数计，将35份纳米氧化铝、25份硼酸钙、15份细度为200目的石墨粉加入到粉碎机中粉碎后倒入混砂机中，随后加入10份甲基丙烯酸锌、6份二氧化锆、8份石墨烯，搅拌混合20min，再球磨过200目筛得到内层无机填充料；取220mL正硅酸乙酯与350mL无水乙醇混合放入烧杯中，向烧杯中加入80mL质量分数为10％的盐酸，用磁力搅拌器以450r/min的转速，搅拌2h，得到二氧化硅溶胶，向二氧化硅溶胶中加入30mL质量分数为5％的聚乙烯醇，室温下陈化24h，得到二氧化硅溶胶；将上述内层无机填充料和上述二氧化硅溶胶按质量比为3︰1混合，得到内层填充胶液，将外塑板双层叠放至于涂布脱模剂的热压模具中，向所述热压模具中注入内层填充胶液，置于热压设备中热压处理35min，控制热压压力为5MPa，热压温度为150℃，得到涂抹涂料用防溅涂料桶材料，所述的脱模剂为硅油。
对比例
以苏州市某公司生产的涂料桶材料作为对比例
对本发明制得的防腐涂抹涂料用防溅涂料桶材料和对比例中的涂料桶材料进行检测，检测结果如表1所示︰
1、防腐性
将本发明制备的实例1～3和对比例样品，在温度为85℃，相对湿度为100％的环境下进行湿热试验。
将本发明制备的实例1～3和对比例的涂抹涂料用防溅涂料桶材料进行耐酸、耐碱性能测试，在浓度为20％的浓硫酸中浸泡48h，在浓度为20％的氢氧化钠溶液浸泡48h，并进行记录。
2、热稳定性
将本发明制备的实例1～3和对比例样品制成相同的小桶后装一半涂料，以60r/min的转速进行旋转，一小时后查看涂料的损失率。
表1
由表1数据可知，本发明制得的防腐涂抹涂料用防溅涂料桶材料耐腐蚀性强、防飞溅性能，明显优于对比例样品。因此，具有广阔的使用前景。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内，不应将权利要求中的任何标记视为限制所涉及的权利要求。
Claims (6)
1.一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于具体制备步骤为：
(1)将丁腈橡胶、ABS树脂母粒、PET树脂母粒、粒径为2～3mm的聚苯胺颗粒置于双辊混炼机中，在前辊温度为55～60℃，后辊温度为50～55℃，辊距为6～8mm的条件下塑炼后，再向双辊混炼机中加入水滑石、白炭黑，混合塑炼，得到导电塑料；
(2)将高密度聚乙烯粉末、导电塑料、环氧大豆油、EPDM原胶、氧化锌、硬脂酸铝混合得到混炼原料，以温度为70～80℃和压力为1.2～1.5MPa的条件热压成型为外塑板；
(3)将纳米氧化铝、硼酸钙、细度为200目的石墨粉加入到粉碎机中粉碎后倒入混砂机中，随后加入甲基丙烯酸锌、二氧化锆、石墨烯，搅拌混合10～20min，再球磨过200目筛得到内层无机填充料；
(4)取200～220mL正硅酸乙酯与300～350mL无水乙醇混合放入烧杯中，向烧杯中加入60～80mL质量分数为10％的盐酸，用磁力搅拌器以400～450r/min的转速，搅拌1～2h，得到二氧化硅溶胶，向二氧化硅溶胶中加入20～30mL质量分数为5％的聚乙烯醇，室温下陈化20～24h，得到二氧化硅溶胶；
(5)将上述内层无机填充料和上述二氧化硅溶胶按质量比为3︰1混合，得到内层填充胶液，将外塑板双层叠放至于涂布脱模剂的热压模具中，向所述热压模具中注入内层填充胶液，置于热压设备中热压处理30～35min，控制热压压力为4～5MPa，热压温度为100～150℃，得到涂抹涂料用防溅涂料桶材料。
2.根据权利要求1所述的一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于：步骤(1)所述的导电塑料各组分原料，按重量份数计，包括10～15丁腈橡胶、20～30份ABS树脂母粒、30～35份PET树脂母粒、6～8份粒径为2～3mm的聚苯胺颗粒、10～12份水滑石、4～5份白炭黑。
3.根据权利要求1所述的一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于：步骤(2)所述的外塑板各组分原料，按重量份数计，包括50～55份高密度聚乙烯粉末、8～10份导电塑料、10～15份环氧大豆油、10～12份EPDM原胶、5～10份氧化锌、7～8份硬脂酸铝。
4.根据权利要求1所述的一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于：步骤(2)所述的高密度聚乙烯粉末分子量为2～5万，结晶度为80～85％，EPDM原胶的乙烯含量为50～55％。
5.根据权利要求1所述的一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于：步骤(3)所述的内层无机填充料的各组分原料，按重量份数计，包括30～35份纳米氧化铝、20～25份硼酸钙、10～15份细度为200目的石墨粉、8～10份甲基丙烯酸锌、4～6份二氧化锆、5～8份石墨烯。
6.根据权利要求1所述的一种涂抹涂料用防溅涂料桶材料的制备方法，其特征在于：步骤(5)所述的脱模剂为硅油、聚乙二醇、低分子量聚乙烯的一种。
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