CN113121737A - 含有酐基官能团的固体聚丙烯酸酯类树脂及其制备和使用方法 - Google Patents
含有酐基官能团的固体聚丙烯酸酯类树脂及其制备和使用方法 Download PDFInfo
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Abstract
本发明的目的是提供一种含有酐基官能团的固体聚丙烯酸酯类树脂及其制备和使用方法。本发明的树脂以不饱和酐基功能单体、甲基丙烯酸酯类单体、丙烯酸酯类单体、丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯、以及苯乙烯和/或叔碳酸乙烯酯单体为原料,采用自由基溶液聚合方法共聚而成。该树脂与固体环氧树脂或混合型环氧树脂体系、TGIC粉末涂料体系、HAA粉末涂料体系配套使用,提供固化、消光、消除漆膜缺陷等一系列功能。
Description
技术领域
本发明属于粉末涂料材料合成技术领域,特别涉及一种含有酐基官能团的固体聚丙烯酸酯类树脂及其制备和使用方法。
背景技术
羧基型固体聚丙烯酸酯树脂是粉末涂料中重要的功能应用粉末,与羟基型聚酯树脂、环氧及混合环氧型树脂、环氧型丙烯酸树脂等配套使用,提供固化、消光等功能,尤其是固体丙烯酸酯树脂良好的装饰性、抗老化性、高硬度及抗划伤性能,使其成为粉末涂料中一类不可替代的组分,其常规合成方法是采用自由基溶液聚合的方法,将丙烯酸、甲基丙烯酸类羧基型功能单体与硬单体(甲基丙烯酸酯类、(甲基)丙烯酸-异丙片酯类、苯丙烯等)、软单体(丙烯酸酯类)按照一定比例混配,在自由基引发条件下进行溶液混合,最后将溶剂蒸出后得到符合要求的不同酸值和软化点的固体羧基型聚丙烯酸酯类粉末,但是此类树脂由于自身结构性问题存在以下三大缺陷:
1、由于其中含有羧基等高极性官能团,树脂粘度高,尤其是高酸值(AV>100)品种更是如此,给其生产和应用带来了诸多限制;2、由于羧基的反应活性低、及其与羟基官能团反应时生成小分子水,加热固化时受热逸出,影响其固化温度和时间窗口(需要高温烘烤和更长的烘烤时间)及漆膜表观(容易产生针孔、弹坑等漆膜缺陷);3、由于羧基的反应活性及其在聚丙烯酸酯类树脂聚合物中的分布特点影响了其消光、固化效果,不能用于生产极低光泽及死光的粉末涂料品种。
发明内容
本发明的目的是提供一种含有酐基官能团的固体聚丙烯酸酯类树脂及其制备和使用方法。酸酐型固体聚丙烯酸酯树脂的合成方法,未见专利和文献报道。该树脂与固体环氧树脂或混合型环氧树脂体系、TGIC粉末涂料体系、HAA粉末涂料体系配套使用,提供固化、消光、消除漆膜缺陷等一系列功能。
本发明的技术方案之一为,一种含有酐基官能团的聚丙烯酸酯类树脂,以不饱和酐基功能单体、甲基丙烯酸酯类单体、丙烯酸酯类单体、丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯、以及苯乙烯和/或叔碳酸乙烯酯单体为原料,采用自由基溶液聚合方法共聚而成。
进一步的,上述含有酐基官能团的丙烯酸酯类树脂,各种单体的质量百分比如下,总量为100%:
不饱和酐基功能单体:10~40%;
丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯:10~30%;
苯乙烯和/或叔碳酸乙烯酯单体:10~25%;
甲基丙烯酸酯类单体:20~40%;
丙烯酸酯类单体:15~30%;
其中,所述不饱和酐基功能单体为纳迪克酸酐,甲基纳迪克酸酐,四氢苯酐、衣康酸酐和马来酸酐及上述化合物的衍生物中的一种或多种的混合物;
所述甲基丙烯酸酯类单体为甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸正丙酯,甲基丙烯酸异丙酯,甲基丙烯酸正丁酯、甲基丙烯酸异丁酯中的一种或多种的混合物;
所述丙烯酸酯类单体为丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丁酯,丙烯酸异辛酯中的一种或多种的混合物。
进一步的,上述含有酐基官能团的聚丙烯酸酯类树脂,树脂的酸值:20-200mg·KOH/g,玻璃化温度:45-80℃,软化点:50-130℃,粘度为2500-6000mPa·s(190℃)。
进一步的,上述含有酐基官能团的聚丙烯酸酯类树脂,树脂粉末为透明、白色或淡黄色。
本发明的技术方案之二为,上述含有酐基官能团的聚丙烯酸酯类树脂的制备方法,包括如下步骤:
1)将溶剂在氮气保护下,加热到85~120℃;
2)并且,将引发剂和分子量调节剂与不饱和酐基功能单体、丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯、苯乙烯和/或叔碳酸乙烯酯单体、甲基丙烯酸酯类单体和丙烯酸酯类单体按比例混合,得到混合溶液;
3)保持溶剂温度85~120℃,将步骤2)得到的混合溶液滴加到溶剂中,滴加时间控制在4-6小时;滴加结束后,继续保温反应30~45min;
4)向反应溶液中补加适量引发剂-溶剂的溶液,继续保温反应2~4h;
5)反应结束后,升温至150~190℃,蒸去溶剂,降温至120~130℃,在氮气保护下放料,物料冷却至室温,固化后既得;
进一步的,上述制备方法,所述溶剂为甲苯、二甲苯和乙酸丁酯溶剂中的一种或多种;溶剂与单体总质量的液质比0.9~1.5:1mL/g;
进一步的,上述制备方法,所述引发剂为偶氮二异丁腈(AIBN)或过氧化苯甲酰(BPO);
进一步的,上述制备方法,所述分子量调节剂为AMSD;
进一步的,上述制备方法,所述引发剂的总加入量为各种单体总质量的1~2%;其中,步骤4)中引发剂的加入量为各种单体总质量的0.2~0.3%;
进一步的,上述制备方法,所述分子量调节剂加入量为各种单体总重量的0.1~2%;
进一步的,上述制备方法,步骤4)中的引发剂-溶剂中,引发剂的浓度为20~30g/L。
本发明的技术之三为,上述含有酐基官能团的固体聚丙烯酸酯类树脂的使用方法,树脂作为成膜物质、小分子水捕捉剂、固化剂、消光剂或固化消光剂用于粉末涂料系统。
进一步的,上述的使用方法,树脂用于配制极低光泽(<10°)及死光的环氧树脂/羧基型聚酯树脂体系,TGIC/羧基型聚酯体系,环氧型固体聚丙烯酸酯树脂体系,以及HAA粉末涂料体系的粉末涂料。
与现有技术相比,本发明的优势在于:
1、本发明利用不饱和酸酐单体与(甲基)丙烯酸酯类单体,苯乙烯及叔碳酸乙烯酯等单体进行自由基溶液共聚,去除溶剂后得到了固体酸酐型聚丙烯酸酯树脂,该树脂的技术指标范围为:酸值:20-200mgKOH/g,玻璃化温度:45-80℃,软化点:50-130℃,粘度范围为2500-6000mPa·s(190℃)。
2、本发明的产物可广泛应用于粉末涂料体系,起到固化、消光和消除漆膜缺陷的功效。
3、本发明制备的酸酐型固体聚丙烯酸酯树脂很好地解决了羧基型固体聚丙烯酸酯树脂的缺陷:
1)由于酐基官能团较羧基官能团的极性低,在与羧基型相似的分子量分布范围内,酐基聚丙烯酸酯树脂的粘度小得多,极大地方便了生产和应用过程,能够很容易的生产高酸值(AV>100)和高分子量的树脂品种,同时低粘度也极大地方便了用户灵活使用该产品;
2)由于酐基与羧基相比具有较高的反应活性及其与羟基官能团反应时无小分子水分子生成,提供了宽范围的固化温度和时间窗口,提高了漆膜的外观表现(较少产生针孔、弹坑等漆膜缺陷);
3)由于酐基相较于羧基的高反应活性及其在丙烯酸酯树脂聚合分布的相对集中性的特点,极大地提高了其固化、消光效果,可以用来配制极低光泽的粉末涂料品种,消光范围从半光到死光,消光、固化效果稳定,漆膜性能优异。
具体实施方式
分子量调节剂AMSD购自无锡市致远化学品有限公司。
实施例1
一种含有酐基官能团的丙烯酸酯类树脂,制备方法如下:
1)将100mL甲苯在氮气保护下,加热到85℃;
2)将引发剂偶氮二异丁腈1.2g和分子量调节剂1g与四氢苯酐10g、丙烯酸异冰片酯10g、苯乙烯10g、甲基丙烯酸甲酯40g和丙烯酸甲酯30g混合,得到混合溶液;
3)保持溶剂温度85℃,将步骤2)得到的混合溶液滴加到甲苯中,滴加时间为5小时;滴加结束后,继续保温反应30min;
4)向反应溶液中加入溶于10毫升甲苯的偶氮二异丁腈0.3g,继续保温反应4h;
5)反应结束后,升温至150℃,蒸去溶剂,降温至120℃,在氮气保护下放料,物料冷却至室温,粉碎得到白色粉末。
本实施例制得的树脂的技术指标如下:
外观:白色固体粉末,玻璃化温度(Tg):50.2℃(DSC),熔点:70-80℃(熔点仪),粘度:3000mPa·s (190℃),酸值:73.5mgKOH/g(滴定法)。
实施例2
一种含有酐基官能团的丙烯酸酯类树脂,制备方法如下:
1)将100ml甲苯和二甲苯(1:1v/v)混合溶液在氮气保护下,加热到120℃;
2)将引发剂过氧化苯甲酰1.1g和分子量调节剂0.6g与甲基纳迪克酸酐10g、甲基丙烯酸异冰片酯30g、叔碳酸乙烯酯25g、甲基丙烯酸正丁酯20g和丙烯酸正丁酯15g混合,得到混合溶液;
3)保持溶剂温度120℃,将步骤2)得到的混合溶液滴加到溶剂中,滴加时间为4小时;加入结束后,继续保温反应45min;
4)向反应溶液中加入溶于10毫升甲苯的过氧化苯甲酰0.2g溶液,继续保温反应2h;
5)反应结束后,升温至190℃,蒸去溶剂,降温至130℃,在氮气保护下放料,物料冷却至室温固化后粉碎成白色粉末既得。
本实施例制得的树脂的技术指标如下:
外观:白色固体粉末,玻璃化温度(Tg):48℃(DSC),熔点:63-70℃(熔点仪),粘度:3200mPa·s (190℃),酸值:62.5mgKOH/g(滴定法)。
实施例3
一种含有酐基官能团的丙烯酸酯类树脂,制备方法如下:
1)将100ml乙酸丁酯在氮气保护下,加热到110℃;
2)将引发剂偶氮二异丁腈1.7g和分子量调节剂0.8g与纳迪克酸酐10g,甲基纳迪克酸酐10g,丙烯酸异冰片酯15g,甲基丙烯酸异冰片酯15g,苯乙烯10g,叔碳酸乙烯酯5g,甲基丙烯酸乙酯10g,甲基丙烯酸正丁酯10g,丙烯酸乙酯10g,丙烯酸异辛酯5g混合,得到混合溶液;
3)保持溶剂温度103℃,将步骤2)得到的混合溶液滴加到溶剂中,滴加时间6小时;加入结束后,继续保温反应40min;
4)向反应溶液中加入溶于10ml乙酸丁酯的偶氮二异丁腈0.25g,继续保温反应3h;
5)反应结束后,升温至170℃,蒸去溶剂,降温至125℃,在氮气保护下放料,物料冷却至室温既得;
本实施例制得的树脂的技术指标如下:
外观:白色固体粉末,玻璃化温度(Tg):55℃(DSC),熔点:80-87℃(熔点仪),粘度:4500mPa·s (190℃)酸值:131.2mgKOH/g(滴定法)。
实施例4
一种含有酐基官能团的丙烯酸酯类树脂,制备方法如下:
1)将100ml甲苯在氮气保护下,加热到100℃;
2)将引发剂偶氮二异丁腈1g和分子量调节剂0.2g与马来酸酐5g、衣康酸酐15g、丙烯酸异冰酯20g、叔碳酸乙烯酯类单体10g、甲基丙烯酸乙酯10g、甲基丙烯酸丁酯20g、丙烯酸乙酯20g混合,得到混合溶液;
3)保持溶剂温度100℃,将步骤2)得到的混合溶液滴加到上述溶剂中,滴加时间5小时;加入结束后,继续保温反应35min;
4)向反应溶液中加入溶于10ml甲苯的偶氮二异丁腈0.3g,继续保温反应3h;
5)反应结束后,升温至170℃,蒸去溶剂,降温至125℃,在氮气保护下放料,物料冷却至室温,粉碎既得白色固体粉末;
本实施例制得的树脂的技术指标如下:
外观:白色固体粉末,玻璃化温度(Tg):65℃(DSC),熔点:85-90℃(熔点仪),粘度:5200mPa·s (190℃),酸值:200.1mgKOH/g (滴定法)。
实施例5
一种含有酐基官能团的丙烯酸酯类树脂,制备方法如下:
1)将100ml甲苯和二甲苯(1:1v/v)在氮气保护下,加热到100℃;
2)将引发剂偶氮二异丁腈1.8g和分子量调节剂0.1g与衣康酸酐40g、丙烯酸异冰酯10g、叔碳酸乙烯酯类单体10g、甲基丙烯酸乙酯10g、甲基丙烯酸丁酯10g、丙烯酸乙酯20g混合,得到混合溶液;
3)保持溶剂温度100℃,将步骤2)得到的混合溶液滴加到上述溶剂中,滴加时间5小时;加入结束后,继续保温反应35min;
4)向反应溶液中加入溶于10ml甲苯的偶氮二异丁腈0.2g,继续保温反应3h;
5)反应结束后,升温至170℃,蒸去溶剂,降温至125℃,在氮气保护下放料,物料冷却至室温,粉碎既得白色固体粉末。
本实施例制得的树脂的技术指标如下:
外观:白色固体粉末,玻璃化温度(Tg):68℃(DSC),熔点:97-105℃(熔点仪),粘度:5500mPa·s (190℃),酸值:200.2mgKOH/g (滴定法)
应用方法:
本发明所制备的酸酐型固体聚丙烯酸酯树脂,可广泛应用于环氧树脂/羧基型聚酯树脂体系,TGIC/羧基型聚酯体系,环氧型固体聚丙烯酸酯树脂体系,HAA粉末涂料体系,提供固化、消光和小分子水捕捉剂(HAA体系)等诸多功能,固化、消光效果优异,同时提高漆膜的机械和装饰性能,消除漆膜缺陷。
应用例1
作为小分子补水剂用于HAA体系粉末涂料,该体系的各个原料按重量百分比计包括:含有羧基聚酯树脂55-65%、羟烷基酰胺固化剂3-4%、小分子水捕捉剂(使用实施例4的酐基官能团的丙烯酸酯类树脂)0.5-4%、颜料和/或助剂30-38%。
经实验:
300份羧基聚酯树脂SJ5122、10份小分子水捕捉剂、17份羟烷基酰胺固化剂AHA6552、5份流平剂AHA1088P、1份安息香AHA4100、75份硫酸钡、100份钛白粉。
1、针孔为:轻微针孔;
2、膜厚,μm(GB/T 4957)为:60-70。
应用例2
作为粉末涂料消光剂用于消光粉末涂料,该体系的原料按重量百分比计包括:含羧基的聚酯树脂25-55%、固化剂5-30%、消光剂(使用实施例3的酐基官能团的丙烯酸酯类树脂+金属有机化合物)5-7%、助剂和/或颜填料30-38%。
经实验:
170份羧基聚酯树脂SJ6B、118份环氧树脂E-12、30份消光剂:2-硫醇基苯并噻唑锌盐的质量比为12:1)、5份流平剂AHA1088P、2份安息香AHA4100、75份硫酸钡、100份钛白粉。
1、光泽%,60°(GB/T 1743)为:20.4;
2、膜厚,μm(GB/T 4957)为:75-80。
应用例3
作为成膜物质用于聚丙烯酸树脂/TGIC体系消光粉末涂料,原料按重量百分比计,包括:成膜物质(使用实施例2的酐基官能团的丙烯酸酯类树脂)51~61%、固化剂7.5~8.5%、催化剂0~0.6%、助剂和/或颜填料30~40%。
经实验:
278份成膜物质、39份固化剂AHA6810、5份流平剂AHA1088P、3份安息香AHA4100、75份消光钡W44、100份钛白粉。
1、光泽%,60°(GB/T 1743)为:10.8;
2、膜厚,μm(GB/T 4957)为:65-75。
应用例4
作为消光固化剂用于消光粉末涂料,原料按重量百分比计,包括:成膜物质30~40%、消光固化剂(使用实施例1的酐基官能团的丙烯酸酯类树脂) 25~32%、催化剂0.2~0.8%、助剂和/或颜填料30~38%。
经实验:
158份环氧树脂E- 12、158份消光固化剂、1份催化剂、5份流平剂AHA1088P、3份安息香AHA4100、75份消光钡W44、100份钛白粉AHA6312。
1、光泽%,60°(GB/T 1743)为:4.9;
2、膜厚,μm(GB/T 4957)为:70-80。
Claims (10)
1.一种含有酐基官能团的聚丙烯酸酯类树脂,其特征在于,以不饱和酐基功能单体、甲基丙烯酸酯类单体、丙烯酸酯类单体、丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯、以及苯乙烯和/或叔碳酸乙烯酯单体为原料,采用自由基溶液聚合方法共聚而成。
2.根据权利要求1所述的含有酐基官能团的聚丙烯酸酯类树脂,其特征在于,所述不饱和酐基功能单体为纳迪克酸酐,甲基纳迪克酸酐,四氢苯酐、衣康酸酐和马来酸酐及上述化合物的衍生物中的一种或多种的混合物;
所述甲基丙烯酸酯类单体为甲基丙烯酸甲酯,甲基丙烯酸乙酯,甲基丙烯酸正丙酯,甲基丙烯酸异丙酯,甲基丙烯酸正丁酯、甲基丙烯酸异丁酯中的一种或多种的混合物;
所述丙烯酸酯类单体为丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丁酯,丙烯酸异辛酯中的一种或多种的混合物。
3.根据权利要求1所述的含有酐基官能团的聚丙烯酸酯类树脂,其特征在于,各种单体的质量百分比如下,总量为100%:
不饱和酐基功能单体:10~40%;
丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯:10~30%;
苯乙烯和/或叔碳酸乙烯酯单体:10~25%;
甲基丙烯酸酯类单体:20~40%;
丙烯酸酯类单体:15~30%。
4.根据权利要求1所述的含有酐基官能团的聚丙烯酸酯类树脂,其特征在于,树脂的酸值:20-200mg·KOH/g,玻璃化温度:45-80℃,软化点:50-130℃,粘度为2500-6000mPa·s。
5.根据权利要求1所述的含有酐基官能团的聚丙烯酸酯类树脂,其特征在于,树脂粉末为透明、白色或淡黄色。
6.权利要求1-5中任意一项所述的含有酐基官能团的聚丙烯酸酯类树脂的制备方法,其特征在于,包括如下步骤:
1)将溶剂在氮气保护下,加热到85~120℃;
2)并且,将引发剂和分子量调节剂与不饱和酐基功能单体、丙烯酸异冰片酯和/或甲基丙烯酸异冰片酯、苯乙烯和/或叔碳酸乙烯酯单体、甲基丙烯酸酯类单体和丙烯酸酯类单体按比例混合,得到混合溶液;
3)保持溶剂温度85~120℃,将步骤2)得到的混合溶液滴加到溶剂中,滴加时间控制在4-6小时;滴加结束后,继续保温反应30~45min;
4)向反应溶液中补加适量引发剂-溶剂的溶液,继续保温反应2~4h;
5)反应结束后,升温至150~190℃,蒸去溶剂,降温至120~130℃,在氮气保护下放料,物料冷却至室温,固化后既得。
7.根据权利要求6所述的含有酐基官能团的聚丙烯酸酯类树脂的制备方法,其特征在于,所述溶剂为甲苯、二甲苯和乙酸丁酯溶剂中的一种或多种;
所述引发剂为偶氮二异丁腈或过氧化苯甲酰;
所述分子量调节剂为AMSD;
所述引发剂的总加入量为各种单体总质量的1~2%;其中,步骤4)中引发剂的加入量为各种单体总质量的0.2~0.3%;
所述分子量调节剂加入量为各种单体总重量的0.1~2%。
8.根据权利要求6所述的含有酐基官能团的聚丙烯酸酯类树脂的制备方法,其特征在于,步骤4)中的引发剂-溶剂中,引发剂的浓度为20~30g/L。
9.权利要求1~5任意一项所述的含有酐基官能团的聚丙烯酸酯类树脂的使用方法,其特征在于,树脂作为成膜物质、小分子水捕捉剂、固化剂、消光剂或固化消光剂用于粉末涂料系统。
10.根据权利要求9所述的含有酐基官能团的聚丙烯酸酯类树脂的使用方法,其特征在于,树脂用于配制极低光泽及死光的环氧树脂/羧基型聚酯树脂体系,TGIC/羧基型聚酯体系,环氧型固体聚丙烯酸酯树脂体系,以及HAA粉末涂料体系的粉末涂料。
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