CN117304730A - 一种haa粉末涂料用消光剂及其制备方法 - Google Patents
一种haa粉末涂料用消光剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种HAA粉末涂料用消光剂及其制备方法,其为含有活性差异较大的羟基及环氧基等特殊基团的消光聚合物。该消光聚合物主要由甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、5‑降冰片烯‑2‑甲醇、2‑甲基‑3‑丁烯‑2‑醇及二氧化双环戊二烯、羟基聚酯树脂、促进剂等制备得到。该产品由于自身结构含有不同活性的羟基及环氧基,再辅助促进剂及制备工艺中物理分散的作用,产品的消光能力出色,而且储存及消光稳定性好,可以将HAA体系的粉末涂料光泽降低至3‑10%。
Description
技术领域
本发明涉及HAA粉末涂料助剂领域,具体地,涉及一种HAA粉末涂料用消光剂及其制备方法。
背景技术
目前户外体系的粉末涂料主要是TGIC固化体系和HAA固化体系,HAA体系粉末涂料具有无毒、成本低等优点,但是其也存在着消光困难等不足,目前行业多采用干混法制备HAA消光粉末涂料,但是干混消光工艺繁琐,且消光稳定性较差,难以大规模应用,而目前市场上的消光剂主要是采用蜡粉等外加材料,消光稳定性差且消光度难以达到要求。随着HAA粉末涂料的应用增加,客户对于HAA粉末涂料要求能够达到TGIC的消光效果,也就是5-10%,目前市场产品难以稳定做到,而CN201910838549.0也开发了一款HAA消光剂产品,但是其要使用到液体的乳化剂,导致消光剂的储存稳定性较差,而且该消光剂的光泽仅仅能消光至20-30%,无法达到10%以下的消光目标,而CN202011443527.3及202110960545.7均采用羧基化合物与环氧化合物混合的方式来进行制备,其缺陷是羧基与环氧在储存时容易发生固化,尤其是其外加催化剂的存在下,导致储存稳定性较差,另一方面,其方案采用物理混合的方式,难以实现批次物料的均匀性,导致消光稳定性较差,因此,难以实现大规模应用。
针对上述不足,本方案提供了一种HAA粉末涂料用消光剂及其制备方法,其是含有活性差异较大的羟基及环氧基等特殊基团的消光聚合物,该消光聚合物主要是由甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、5-降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇及二氧化双环戊二烯、羟基聚酯树脂、促进剂等原料制备得到。先将甲基丙烯酸缩水甘油酯、甲基丙烯酸丁酯、降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇经过聚合得到含有环氧基及不同羟基结构的聚合物,聚合物的软化点控制在108-115℃,然后再与双环戊二烯、羟基聚酯树脂、促进剂等进行物理粉碎混合得到粉状的消光剂产品。该产品由于自身结构含有不同活性的羟基及环氧基,再辅助促进剂及制备工艺中物理分散的作用,产品的消光能力出色,而且储存及消光稳定性好,可以将HAA体系的粉末涂料光泽降低至3-10%。
发明内容
本发明涉及一种HAA粉末涂料用消光剂及其制备方法,其为含有不同活性的羟基、环氧基等特殊基团的消光聚合物,具体包括如下质量份的原料:
原料中还包括引发剂与促进剂。
优选的,引发剂为过氧化苯甲酰(BPO)或偶氮二异丁腈(AIBN),用量甲基丙烯酸缩水甘油酯的2-5%;
优选的,促进剂为氯化锌或者醋酸锰,用量为原料总质量的0.1-0.2%;
所述二氧化双环戊二烯又叫二环戊二烯环氧化物,CAS号81-21-0,普通市售可得。
所述羟基聚酯树脂的羟值25-35mgKOH/g,例如可购自安徽神剑新材料股份有限公司,型号SJ1108。
所述HAA粉末涂料用消光剂的制备方法,包括以下步骤:
A、将配方量的甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、5-降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇、引发剂先室温混合均匀后,泵送入高位槽中备用;
B、将配方量的溶剂二甲苯加入不锈钢反应釜中,升温至105-125℃并保温,然后开始滴加高位槽中的混合单体及引发剂溶液进行聚合反应,滴加完毕后,继续保温反应;
C、待聚合物的软化点达到108-115℃时,加入配方量的二氧化双环戊二烯及羟基聚酯树脂,升温至130-135℃并保温,充分搅拌使其充分溶解,然后启动真空系统进行减压脱除二甲苯溶剂即得到消光树脂;
D、待挥发份达到1%以内时,停止真空,搅拌均匀后,放料、冷却、粉碎、加入配方量的促进剂物理混合得到HAA消光剂产品。
优选的,步骤B中,所述滴加时间控制在2-2.5h;步骤C中,真空度控制在-0.096至-0.098Mpa;步骤D中,所述消光剂产品的粒度控制在80-120目。
例如,所述的制备方法,包括以下步骤:
A、将配方量的甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇、引发剂先室温混合均匀后,泵送入高位槽中备用;
B、将配方量的溶剂二甲苯加入不锈钢反应釜中,升温至105-125℃并保温,然后开始滴加高位槽中的混合单体及引发剂溶液进行聚合反应,滴加时间控制在2-2.5h,滴加完毕后,继续保温反应;
C、待聚合物的软化点达到108-115℃时,加入配方量的双环戊二烯及羟基聚酯树脂,升温至130-135℃并保温,充分搅拌使其充分溶解,然后启动真空系统进行减压脱除二甲苯溶剂即得到消光树脂;真空度控制在-0.096至-0.098Mpa;
D、待挥发份达到1%以内时,停止真空,搅拌均匀后,放料、冷却、粉碎、加入配方量的促进剂物理混合得到HAA消光剂产品,消光剂产品的粒度控制在80-120目。
所得产品外观为白色粉末,环氧当量为340-400g/mol,羟值为110-140mgKOH/,软化点为110-120℃。
本发明还涉及消光型HAA体系粉末涂料体系,例如其可采用纯聚酯树脂、HAA、上述制得的消光剂、钛白粉、消光硫酸钡、流平剂、消光剂、安息香等得到。按照上述聚酯粉末涂料配方将各物料混匀,用双螺杆挤出机挤出、压片、破碎,然后将片料粉碎过筛(150-180目)制成粉末涂料。粉末涂料采用静电喷枪喷涂在经表面处理后的马口铁基材上,喷涂厚度70-80μm,经180℃/15min固化,即得粉末涂料涂膜。
有益效果:
(1)本发明通过甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、5-降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇共聚的方式获得不同活性的羟基及环氧基,羟基与环氧基在后续固化时由于与羧基聚酯树脂的固化速度差异而实现消光;
(2)本发明特殊选用二氧化双环戊二烯这种高熔点、且刚性较强的双环氧化合物为消光剂提供差异化的环氧,而且搭配高温溶解分散制备工艺,将其均匀分散在聚合物体系中,避免了物理混合法制备的工艺稳定性导致的消光稳定性差的问题,二氧化双环戊二烯的环氧基与甲基丙烯酸缩水甘油酯所引入聚合物的环氧基活性差异大,消光效果明显;而且二氧化双环戊二烯的引入也增强了固化后涂膜的刚性及耐水煮性能;
(3)本发明特殊选用的羟基聚酯树脂采用外加溶解均匀分散的方式引入聚合物体系中,避免了物理混合法制备的工艺稳定性导致的消光稳定性差的问题,而且引入了与聚合物中羟基的差异性,且羟基聚酯树脂是独立的树脂体系,在合适的用量范围引入能够增强消光效果且不会对涂膜产生缺陷;
(4)本发明选用特殊的促进剂品种用于促进在固化温度下对聚酯树脂的交联固化,同时实现与HAA固化剂的固化差异能力。
具体实施方式
下面结合附图和实施例对本发明进一步说明。需要说明的是,在不冲突的情况下,本申请中的实施例及实施例中的技术特征可以相互结合。需要指出的是,除非另有指明,本申请使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。本发明公开使用的“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同,而不排除其他元件或者物件。
本发明所述原料均为市售可得;如所述羟基聚酯树脂的羟值25-35mgKOH/g,可购自安徽神剑新材料股份有限公司,型号SJ1108。
制备例1
一种HAA粉末涂料用消光剂,具体包括如下质量份的原料:
引发剂为过氧化苯甲酰(BPO),用量甲基丙烯酸缩水甘油酯的3%;
促进剂为氯化锌,用量为原料总质量的0.1%;
制备方法包括以下步骤:
A、将配方量的甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、5-降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇、引发剂先室温混合均匀后,泵送入高位槽中备用;
B、将配方量的溶剂二甲苯加入不锈钢反应釜中,升温至120℃并保温,然后开始滴加高位槽中的混合单体及引发剂溶液进行聚合反应,滴加时间控制在2.5h,滴加完毕后,继续保温反应;
C、待聚合物的软化点达到预期时,加入配方量的双环戊二烯及羟基聚酯树脂,升温至132℃并保温,充分搅拌使其充分溶解,然后启动真空系统进行减压脱除二甲苯溶剂即得到消光树脂;真空度控制在-0.096Mpa;
D、待挥发份达到1%以内时,停止真空,搅拌均匀后,放料、冷却、粉碎、加入配方量的促进剂物理混合得到HAA消光剂产品,消光剂产品的粒度控制在80目。
产品外观为白色粉末,环氧当量:352g/mol,羟值122mgKOH/g,软化点:112℃。
制备例2
一种HAA粉末涂料用消光剂,具体包括如下质量份的原料:
引发剂为偶氮二异丁腈(AIBN),用量甲基丙烯酸缩水甘油酯的5%;
促进剂为醋酸锰,用量为原料总质量的0.2%;
制备方法同制备例1。
产品外观为白色粉末,环氧当量:369g/mol,羟值130mgKOH/g,软化点:118℃。
制备例3
一种HAA粉末涂料用消光剂,具体包括如下质量份的原料:
引发剂为过氧化苯甲酰(BPO),用量甲基丙烯酸缩水甘油酯的5%;
促进剂为醋酸锰,用量为原料总质量的0.2%;
制备方法同制备例1。
产品外观为白色粉末,环氧当量:364g/mol,羟值129mgKOH/g,软化点:116℃。
制备例4
一种HAA粉末涂料用消光剂,具体包括如下质量份的原料:
引发剂为过氧化苯甲酰(BPO),用量甲基丙烯酸缩水甘油酯的5%;
促进剂为氯化锌,用量为原料总质量的0.1%;
制备方法同制备例1。
产品外观为白色粉末,环氧当量:386g/mol,羟值128mgKOH/g,软化点:115℃。
应用例1-4(消光剂分别由上述制备例1-4制得):
消光型HAA体系粉末涂料,以重量份计配方如下:
聚酯树脂采用安徽神剑新材料股份有限公司所生产的HAA专用聚酯树脂SJ4B。
涂料涂层制备
按照上述聚酯粉末涂料配方将各物料混匀,用双螺杆挤出机挤出、压片、破碎,然后将片料粉碎过筛(150-180目)制成粉末涂料。粉末涂料采用静电喷枪喷涂在经表面处理后的马口铁基材上,喷涂厚度70-80μm,经180℃/15min固化,即得粉末涂料涂膜。
消光剂自身及制备成的消光型粉末涂料的储存稳定性测试依据GB/T21782.8-2008《粉末涂料第八部分热固性粉末储存稳定性的评定》进行,0级为无变化,1级出现轻微结团;2级出现明显结团。
涂层指标检测依据GB/T 21776-2008《粉末涂料及其涂层的检测标准指南》,附着力等级按照GB/T 9286-1998《色漆和清漆漆膜的画格实验》进行。
表1实施例中产品涂膜后的性能对比
从以上的表1中的数据对比可以看出:本发明产品自身及制备的成品消光型粉末涂料的储存稳定性较优,40℃/120天的储存条件下仍无结团现象,而制成的消光粉末涂料也具有优良的综合性能,如涂膜表观、抗冲击性能、光泽、耐沸水煮性能及附着力。
以上只通过说明的方式描述了本发明的某些示范性实施例,毋庸置疑,对于本领域的普通技术人员,在不偏离本发明的精神和范围的情况下,可以用各种不同的方式对所描述的实施例进行修正。因此,上述附图和描述在本质上是说明性的,不应理解为对本发明权利要求保护范围的限制。
Claims (8)
1.一种HAA粉末涂料用消光剂,其特征在于,包括如下质量份的原料:
原料中还包括引发剂与促进剂。
2.如权利要求1所述一种HAA粉末涂料用消光剂,其进一步特征在于,所述引发剂为过氧化苯甲酰(BPO)或偶氮二异丁腈(AIBN),用量为甲基丙烯酸缩水甘油酯的2-5%。
3.如权利要求1所述一种HAA粉末涂料用消光剂,其进一步特征在于,所述促进剂为氯化锌或者醋酸锰,用量为原料总质量的0.1-0.2%。
4.如权利要求1所述一种HAA粉末涂料用消光剂,其进一步特征在于,所述羟基聚酯树脂的羟值25-35mgKOH/g。
5.一种权利要求1-4所述HAA粉末涂料用消光剂的制备方法,包括以下步骤:
A、将配方量的甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯、丙烯酸丁酯、5-降冰片烯-2-甲醇、2-甲基-3-丁烯-2-醇、引发剂先室温混合均匀后,泵送入高位槽中备用;
B、将配方量的溶剂二甲苯加入不锈钢反应釜中,升温至105-125℃并保温,然后开始滴加高位槽中的混合单体及引发剂溶液进行聚合反应,滴加完毕后,继续保温反应;
C、待聚合物的软化点达到108-115℃时,加入配方量的二氧化双环戊二烯及羟基聚酯树脂,升温至130-135℃并保温,充分搅拌使其充分溶解,然后启动真空系统进行减压脱除二甲苯溶剂即得到消光树脂;
D、待挥发份达到1%以内时,停止真空,搅拌均匀后,放料、冷却、粉碎、加入配方量的促进剂混合得到HAA消光剂产品。
6.如权利要求5所述HAA粉末涂料用消光剂的制备方法,其进一步特征在于,步骤B中,所述滴加时间控制在2-2.5h。
7.如权利要求5所述HAA粉末涂料用消光剂的制备方法,其进一步特征在于,步骤C中,真空度控制在-0.096至-0.098Mpa。
8.如权利要求5所述HAA粉末涂料用消光剂的制备方法,其进一步特征在于,步骤D中,所述消光剂产品的粒度控制在80-120目。
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