CN109485796B - 一种橡胶制品表面涂覆水溶性固化特氟龙材料及其制备方法 - Google Patents
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Abstract
一种橡胶制品表面涂覆水溶性固化特氟龙材料及其制备方法,涉及一种耐候性涂料及其制备方法,将功能单体丙烯酸羟酯类单体和二异氰酸酯类单体加入到反应器中,之后加入二羟基丁二酸继续反应,之后将溶剂乙酸丁酯加入到溶解槽中,在搅拌状态下慢慢加入引发剂过氧化二苯甲酰,将大分子单体、引发剂的混合溶液吸入到聚合釜,降温至室温。通过单体回收系统将未反应的四氟乙烯类单体回收到回收槽,然后过滤出料。材料分子结构中含有耐候性的四氟乙烯类结构,柔顺性好的氨酯键结构,附着力强的羟基结构以及可以满足水溶性要求的羧酸根结构。本发明实现室温固化,同时也克服了目前橡胶涂覆用水性特氟龙树脂需要高温固化的缺点,因此具有非常广阔的市场前景。
Description
技术领域
本发明涉及一种耐候性涂料及其制备方法,特别是涉及一种橡胶制品表面涂覆水溶性固化特氟龙材料及其制备方法。
背景技术
橡胶制品的耐候性是指橡胶材料因受到阳光照射,温度变化,风吹雨淋等外界条件的影响,而出现的褪色,变色,龟裂,粉化和强度下降等一系列老化的现象。普通橡胶材料的耐候性一般不好,这是由于大多数橡胶制品的分子结构中含有少量双键,在自然环境下(如紫外线),很容易发生老化现象,而采用表面涂覆的方法提高其耐候性是一种很好的方法。聚四氟乙烯类材料由于分子中的氟元素电负性大,碳氟键能强,因此其耐候性优异,但是聚四氟乙烯类制品大多数是模压高温烧结而成的,难以对橡胶材料表面进行涂覆操作,而且由于氟-碳链分子间作用力极低,具有不粘性,这导致该树脂与橡胶材料的结合力不强。
目前,涂覆用特氟龙树脂主要有两类,一类是极性溶剂溶解的,这种可室温固化,但不环保;另一种是水性的,但需要高温固化,只适合于金属的表面处理。因此,为了提高橡胶制品的耐候性,最有前途的是水性可室温固化的特氟龙树脂。
这种水性可室温固化的耐候性特氟龙树脂应具有如下特点,一是要选择耐候性单体,二是树脂的柔韧性要好,三是树脂的附着力要高,四是树脂应有不错的水溶性。
发明内容
本发明的目的在于提供一种橡胶制品表面涂覆水溶性固化特氟龙材料及其制备方法,本发明因为引入了亲水性羧酸基团使得这种含氟树脂具备了在水中的可溶性,克服了这种氟树脂需用有机溶剂溶解的弊端,也克服需烧结成膜的缺点,使其可按普通的涂料成膜方式固化。制得的含氟聚氨酯涂料不仅耐候性优异,而且耐酸碱及耐溶剂性优良,且柔韧性很好,完全可用于橡胶材料的表面涂装。
本发明的目的是通过以下技术方案实现的:
一种橡胶制品表面涂覆水溶性固化特氟龙材料,所述材料分子结构中含有耐候性的四氟乙烯类结构,柔顺性好的氨酯键结构,附着力强的羟基结构以及可以满足水溶性要求的羧酸根结构,分子结构式如下:
其中:-X为-F或-Cl;
-R1为-H或-CH3;
-R2为-CH2- CH2- CH2- CH2- CH2- CH2-;
一种橡胶制品表面涂覆水溶性固化特氟龙材料制备方法,所述方法采用如下工艺:
将功能单体丙烯酸羟酯类单体和二异氰酸酯类单体加入到反应器中,常温反应1h,之后加入二羟基丁二酸继续反应0.5h,反应结束后加入氢氧化钠水溶液进行中和即可得到大分子单体;之后将溶剂乙酸丁酯加入到溶解槽中,启动搅拌混合,在搅拌状态下慢慢加入引发剂过氧化二苯甲酰,搅拌使之溶解;将2L的聚合釜抽真空、氮气置换、再抽真空,用聚合釜内的真空,将大分子单体、引发剂的混合溶液吸入到聚合釜,聚合釜再次抽真空,夹套通冷冻盐水降温,并开启搅拌,待温度降至-10~ -20℃后,开启四氟乙烯类单体阀门,反应压力为0.8-2.8MPa,反应4~8h至聚合釜压力不再降低,降温至室温。停止搅拌,通过单体回收系统将未反应的四氟乙烯类单体回收到回收槽,然后过滤出料。
所述一种橡胶制品表面涂覆水溶性固化特氟龙材料制备方法,所提及的单体丙烯酸羟酯类单体是丙烯酸羟甲(乙)酯,甲基丙烯酸羟甲(乙)酯。
所述一种橡胶制品表面涂覆水溶性固化特氟龙材料制备方法,所提及的二异氰酸酯类单体为己二异氰酸酯。
所述一种橡胶制品表面涂覆水溶性固化特氟龙材料制备方法,所提及的四氟乙烯类单体为一氯三氟乙烯,四氟乙烯。
本发明的优点与效果是:
由于本发明所制得树脂的特殊结构,因为引入了亲水性羧酸基团使得这种含氟树脂具备了在水中的可溶性,克服了这种氟树脂需用有机溶剂溶解的弊端,也克服需烧结成膜的缺点,使其可按普通的涂料成膜方式固化。它可以和封闭型多异氰酸酯或三聚氰胺树脂制成单组分常温处理涂料,也可以和多异氰酸酯制成双组分涂覆材料,达到常温固化的目的,制得的含氟聚氨酯涂料不仅耐候性优异,而且耐酸碱及耐溶剂性优良,且柔韧性很好,完全可用于橡胶材料的表面涂装。
具体实施方式
下面结合实施例对本发明进行详细说明。
本发明通过以下工艺过程实现的:
1)将功能单体丙烯酸羟酯类单体和二异氰酸酯类单体加入到反应器中,常温反应1h;
2)加入二羟基丁二酸继续反应0.5h;
3)反应结束后加入氢氧化钠水溶液进行中和即可得到大分子单体;
4)之后将溶剂乙酸丁酯加入到溶解槽中,启动搅拌混合,在搅拌状态下慢慢加入引发剂过氧化二苯甲酰,搅拌使之溶解;
5)将2L的聚合釜抽真空、氮气置换、再抽真空,用聚合釜内的真空,将大分子单体、引发剂的混合溶液吸入到聚合釜;
6)聚合釜再次抽真空,夹套通冷冻盐水降温,并开启搅拌,待温度降至-10~ -20℃后,开启四氟乙烯类单体阀门,反应压力为0.8-2.8MPa,反应4~8h至聚合釜压力不再降低,降温至室温;
7)停止搅拌,通过单体回收系统将未反应的四氟乙烯类单体回收到回收槽,然后过滤出料。
实例1:
1)将130.14g甲基丙烯酸羟乙酯单体和262.35g的1,6-己二异氰酸酯单体加入到反应器中,常温反应1h;
2)加入150.09g二羟基丁二酸继续反应0.5h;
3)反应结束后加入40g的5%氢氧化钠水溶液进行中和即可得到大分子单体;
4)之后将500g的溶剂乙酸丁酯加入到溶解槽中,启动搅拌混合,在搅拌状态下慢慢加入0.2g引发剂过氧化二苯甲酰,搅拌使之溶解;
5)将2L的聚合釜抽真空、氮气置换、再抽真空,用聚合釜内的真空,将大分子单体、引发剂的混合溶液吸入到聚合釜;
6)聚合釜再次抽真空,夹套通冷冻盐水降温,并开启搅拌,待温度降至-10℃后,开启四氟乙烯单体阀门,反应压力为0.8MPa,反应5.5h至聚合釜压力不再降低,降温至室温;
7)停止搅拌,通过单体回收系统将未反应的四氟乙烯类单体回收到回收槽,然后过滤出料。
实例2:
1)将116.12g甲基丙烯酸羟乙酯单体和262.35g的1,6-己二异氰酸酯单体加入到反应器中,常温反应1h;
2)加入150.09g二羟基丁二酸继续反应0.5h;
3)反应结束后加入40g的5%氢氧化钠水溶液进行中和即可得到大分子单体;
4)之后将500g的溶剂乙酸丁酯加入到溶解槽中,启动搅拌混合,在搅拌状态下慢慢加入0.2g引发剂过氧化二苯甲酰,搅拌使之溶解;
5)将2L的聚合釜抽真空、氮气置换、再抽真空,用聚合釜内的真空,将大分子单体、引发剂的混合溶液吸入到聚合釜;
6)聚合釜再次抽真空,夹套通冷冻盐水降温,并开启搅拌,待温度降至-15℃后,开启四氟乙烯类单体阀门,反应压力为1.5MPa,反应7.5h至聚合釜压力不再降低,降温至室温;
7)停止搅拌,通过单体回收系统将未反应的一氯三氟乙烯类单体回收到回收槽,然后过滤出料。
实例3:
1)将86.09g丙烯酸羟甲酯单体和262.35g的1,6-己二异氰酸酯单体加入到反应器中,常温反应1h;
2)加入150.09g二羟基丁二酸继续反应0.5h;
3)反应结束后加入40g的5%氢氧化钠水溶液进行中和即可得到大分子单体;
4)之后将500g的溶剂乙酸丁酯加入到溶解槽中,启动搅拌混合,在搅拌状态下慢慢加入0.2g引发剂过氧化二苯甲酰,搅拌使之溶解;
5)将2L的聚合釜抽真空、氮气置换、再抽真空,用聚合釜内的真空,将大分子单体、引发剂的混合溶液吸入到聚合釜;
6)聚合釜再次抽真空,夹套通冷冻盐水降温,并开启搅拌,待温度降至-20℃后,开启四氟乙烯单体阀门,反应压力为2.4MPa,反应7.5h至聚合釜压力不再降低,降温至室温;
7)停止搅拌,通过单体回收系统将未反应的四氟乙烯类单体回收到回收槽,然后过滤出料。
Claims (2)
2.根据权利要求1所述的一种橡胶制品表面涂覆水溶性固化特氟龙材料的制备方法,其特征在于,所述方法采用如下工艺:
将功能单体丙烯酸羟酯类单体和二异氰酸酯类单体加入到反应器中,常温反应1h,之后加入二羟基丁二酸继续反应0.5h,反应结束后加入氢氧化钠水溶液进行中和即可得到大分子单体;之后将溶剂乙酸丁酯加入到溶解槽中,启动搅拌混合,在搅拌状态下慢慢加入引发剂过氧化二苯甲酰,搅拌使之溶解;将2L的聚合釜抽真空、氮气置换、再抽真空,用聚合釜内的真空,将大分子单体、引发剂的混合溶液吸入到聚合釜,聚合釜再次抽真空,夹套通冷冻盐水降温,并开启搅拌,待温度降至-10~ -20℃后,开启四氟乙烯类单体阀门,反应压力0.8-2.8MPa,反应4~8h至聚合釜压力不再降低,降温至室温;停止搅拌,通过单体回收系统将未反应的四氟乙烯类单体回收到回收槽,然后过滤出料。
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