CN115353606B - 一种防渗色水性聚氨酯树脂及其制备方法和应用 - Google Patents
一种防渗色水性聚氨酯树脂及其制备方法和应用 Download PDFInfo
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- CN115353606B CN115353606B CN202211120943.9A CN202211120943A CN115353606B CN 115353606 B CN115353606 B CN 115353606B CN 202211120943 A CN202211120943 A CN 202211120943A CN 115353606 B CN115353606 B CN 115353606B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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Abstract
本发明公开了一种防渗色水性聚氨酯树脂及其制备方法和应用,属于水性涂料技术领域。所述防渗色水性聚氨酯树脂由包括以下重量份的原料组成:耐水解多元醇5‑30份,水溶性单体2‑12份,异氰酸酯单体5‑25份,功能单体3‑12份,扩链剂3‑10份,催化剂0.6‑5份,胺4‑7份,本发明的制备方法包括按照一定顺序加入原料反应。本发明的防渗色水性聚氨酯树脂通过耐水解多元醇和功能单体搭配,提高树脂的耐水解和耐溶剂效果,实现树脂稳定性和抗渗色综合性能的提升,可用于制备水性涂料,或应用于涂装工艺中。
Description
技术领域
本发明属于水性涂料技术领域,具体涉及一种防渗色水性聚氨酯树脂及其制备方法和应用。
背景技术
传统的涂装工艺采用的是“三涂两烘”,就是涂一层漆之后先烤干,然后再涂下一层漆,这样可以有效避免涂层渗色,但是在烘烤的过程中会造成VOCs的挥发和能源的消耗。受到环保方面VOCs污染排放法规的影响,涂装工艺也在不断创新发展,新型涂装工艺为了减少能源消耗和有害气体排放,降低成本,保护环境,采用降低烘烤的温度,减少烘烤的时间,缩短涂装的流程,或者在不烘烤的条件下,完成多涂层的配合,但是这种涂装工艺涂层容易出现渗色问题,对涂料的抗渗色性能提出了较高要求。
水性聚氨酯以水为主要介质,不含或仅含有少量有机溶剂,具有VOCs含量低、气味小、绿色环保等特点,已在汽车用水性中涂漆和汽车用水性色漆中广泛使用。然而普通的水性聚氨酯耐水解和耐溶剂效果较差,不能保持树脂的长时间稳定性和抗渗色性能。
发明内容
本发明旨在至少克服现有技术的缺陷之一,提供一种防渗色水性聚氨酯树脂及其制备方法和应用,解决水性涂料抗渗色性差的问题,提高水性聚氨酯树脂的耐水解和耐溶剂效果,提升长时间稳定性。
第一方面,本发明实施例提供一种防渗色水性聚氨酯树脂,通过以下技术方案实现:
一种防渗色水性聚氨酯树脂,由包括以下重量份的原料组成:耐水解多元醇5-30份,水溶性单体2-12份,异氰酸酯5-25份,功能单体3-12份,扩链剂3-10份,催化剂0.6-5份,胺4-7份。
根据本发明实施例的防渗色水性聚氨酯树脂,至少具有如下有益效果:
本发明通过耐水解多元醇和功能单体搭配,树脂内接入功能单体,使树脂具有空间位阻和疏水效应,可以有效阻隔化学键的水解,改善耐化学品性质,提高树脂的耐水解和耐溶剂效果,实现树脂稳定性和抗渗色综合性能的提升。
水溶性单体可以使提高防渗色水性聚氨酯树脂的稳定性,使树脂在水中稳定存在。
根据本发明的一些实施方式,所述防渗色水性聚氨酯树脂的制备原料还包括水。
根据本发明的一些实施方式,所述防渗色水性聚氨酯树脂羟值为5-35mgKOH/g,粘度为30-800mPa·s,分子量为3500-80000,固含量为28%-43%。水性聚氨酯树脂含有羟基基团,能够与氨基树脂进行分子间交联反应,获得较好的交联密度,使涂层获得较佳的耐水性和附着力。
进一步,所述防渗色水性聚氨酯树脂的玻璃化温度10-30℃。
根据本发明的一些实施方式,所述耐水解多元醇的制备原料包括多元酸、多元醇、酸酐、环氧单体、己内酯中的至少两种,且至少包含多元醇。
进一步,所述多元酸选自间苯二甲酸、对苯二甲酸、丁二酸、己二酸、二聚酸、顺丁烯二酸、1,4-环己烷二甲酸。
进一步,所述酸酐选自苯酐、马来酸酐、六氢苯酐。
进一步,所述多元醇选自1,6-己二醇、乙二醇、丙三醇、1,4-环己烷二甲醇、2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯、1,2-丙二醇。
进一步,所述环氧单体选自环氧丙烷和/或环氧乙烷。
根据本发明的一些实施方式,所述异氰酸酯包括多异氰酸酯和/或异氰酸酯预聚体。
进一步,多异氰酸酯选自二异氰酸酯、三异氰酸酯;异氰酸酯预聚体选自异氰酸酯二聚体、异氰酸酯三聚体。
更进一步,所述异氰酸酯包括甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯缩二脲、六亚甲基二异氰酸酯三聚体、异佛尔酮二异氰酸酯三聚体、四甲基苯二亚甲基二异氰酸酯中的至少一种。
根据本发明的一些实施方式,所述水溶性单体包括二羟甲基丁酸、二羟甲基丙酸、1,4-丁二醇-2-磺酸钠、1,2-丙二醇-3-磺酸钠、乙二醇、甲基丙烯酸、丙烯酸、季胺盐中的至少一种。
根据本发明的一些实施方式,所述功能单体包括叔碳酸缩水甘油酯、γ-氨丙基三乙氧基硅烷、3-甲基-1,5-戊二醇、亚油酸、大豆油酸、桐油酸、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的至少一种。
根据本发明的一些实施方式,所述扩链剂包括乙二醇、1,2-丙二醇、1,4-丁二醇、二甘醇、1,6-己二醇、乙二胺、己二胺、一缩二丙二醇、蓖麻油中的至少一种。
根据本发明的一些实施方式,所述胺包括三乙胺、三乙醇胺、N,N`-二甲基乙醇胺、N,N`-二异丙基乙胺、二异丙胺中的至少一种。
根据本发明的一些实施方式,所述催化剂包括有机锡、有机铋。
第二方面,本发明实施例提供上述水性聚氨酯树脂的制备方法,通过以下技术方案实现:
上述水性聚氨酯树脂的制备方法,包括以下步骤:
(1)在保护气氛围下,将所述耐水解多元醇、异氰酸酯混合反应;
(2)加入所述水溶性单体、催化剂反应;
(3)加入所述功能单体反应;
(4)加入所述扩链剂反应;
(5)加入胺进行中和;
(6)将所述中和后的产物分散于水中。
根据本发明实施例的防渗色水性聚氨酯树脂的制备方法,至少具有如下有益效果:
本发明的制备方法操作方法简单,适合工业化生产,以水作为分散剂,降低了VOCs排放,减少对环境的污染。
根据本发明的一些实施方式,所述步骤(1)中,所述反应前还包括:加入第一溶剂与所述水溶性单体、催化剂混合。
根据本发明的一些实施方式,所述步骤(1)中的保护气选自氮气、氦气、氖气、氩气中的一种。
根据本发明的一些实施方式,所述步骤(1)中反应温度为70-100℃。
根据本发明的一些实施方式,所述步骤(1)中反应时间为1-3h。
根据本发明的一些实施方式,所述步骤(2)中反应温度为80-100℃。
根据本发明的一些实施方式,所述步骤(2)中反应时间为1-3h。
根据本发明的一些实施方式,所述步骤(3)中反应时间为2-4h。
根据本发明的一些实施方式,所述步骤(4)中反应时间为1-4h。
根据本发明的一些实施方式,所述步骤(5)之前,还包括:在步骤(4)所得反应物中加入第二溶剂混合。加入第二溶剂可以避免体系的粘度过大。
进一步,所述第一溶剂和第二溶剂溶剂可分别独立选自丁酮、乙二醇丁醚、丙二醇丁醚、丙二醇甲醚、丙二醇甲醚醋酸酯、乙酸丁酯、丙酮、甲基异丁酮、N-甲基吡咯烷酮、二乙二醇丁醚中的至少一种。
根据本发明的一些实施方式,在加入有所述第一溶剂和/或第二溶剂时,所述步骤(6)之后还包括去除溶剂的操作。
进一步,所述去除溶剂的方法为减压抽滤。
第三方面,本发明实施例提供一种水性涂料,其含有上述防渗色水性聚氨酯树脂。
根据本发明的一些实施方式,所述水性涂料包括水性中涂漆、水性色漆。
根据本发明的一些实施方式,所述水性涂料的主体树脂还包括丙烯酸分散体、氨基树脂中的至少一种。
第四方面,本发明实施例提供所述防渗色水性聚氨酯树脂在涂装工艺中的应用。
根据本发明的一些实施方式,所述涂装工艺包括依次涂装中涂层和色涂层,其中,所述中涂层和/或色涂层的制备原料包括所述防渗色水性聚氨酯树脂。
根据本发明的一些实施方式,所述中涂层通过第一晾晒进行干燥。
进一步,所述中涂层的第一晾晒的温度为室温。
进一步,所述中涂层第一晾晒的时间为3-5分钟。
根据本发明的一些实施方式,所述色涂层依次经第二晾晒和烘烤进行干燥。
进一步,所述第二晾晒的温度为室温。
进一步,所述第二晾晒的时间为4-6分钟。
进一步,所述烘烤的温度为70-90℃。
进一步,所述烘烤的时间为4-6分钟。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚,下面将结合具体实施例作进一步地详细描述。此处所描述的实施例仅是本申请一部分实施例,不能理解为对本申请保护范围的限制。
实施例1
防渗色水性聚氨酯树脂的制备:
将15份苯酐、15份对苯二甲酸、10份丙三醇、20份1,4-环己烷二甲醇进行混合,选用钛酸异丙酯作为催化剂,丁酮为溶剂,在150-220℃反应20个小时,制得耐水解多元醇。
在氮气保护下,将20份耐水解多元醇、15份异佛尔酮二异氰酸酯三聚体、3份六亚甲基二异氰酸酯、20份丁酮加入反应器中,85℃反应3h;加入6份二羟甲基丁酸、1份二月桂酸锡,反应2h;加入3份大豆油酸,反应1h;再加入3份1.2-丙二醇进行扩链,搅拌反应1h。加入5份丁酮,待反应完全后,加入6份三乙胺进行中和。在高剪切条件下将树脂加入到115份去离子水中,搅拌1h。通过减压抽滤去除溶剂,制得水性聚氨酯树脂。树脂固含为30%,粘度为550mPa·s,树脂分子量为18000,玻璃化温度为25℃。
实施例2
防渗色水性聚氨酯树脂的制备:
将15份二聚酸、15份对马来酸酐、10份1,6-己二醇、18份乙二醇、5份丙三醇进行混合,选用钛酸异丙酯作为催化剂,丁酮为溶剂,在150-220℃反应20个小时,制得耐水解多元醇。
在氮气保护下,将20份耐水解多元醇、25份六亚甲基二异氰酸酯、20份甲基异丁酮加入反应器中,90℃反应2h;加入6份二羟甲基丙酸、1.5份有机铋,反应1h;加入3份γ-氨丙基三乙氧基硅烷,反应2h;再加入6份1,6-己二醇进行扩链,搅拌反应2h。加入4份丁酮,待反应完全后,加入5份N,N`-二甲基乙醇胺进行中和。在高剪切条件下将树脂加入到105份去离子水,搅拌2h。通过减压抽滤去除溶剂,制得水性聚氨酯树脂。树脂固含为36%,粘度为750mPa·s,树脂分子量为53500,玻璃化温度为18℃。
实施例3
防渗色水性聚氨酯树脂的制备:
将15份顺丁烯二酸、12份1,4-环己烷二甲酸、5份对苯二甲酸、10份丙三醇、3份乙二醇、18份1,4-环己烷二甲醇进行混合,选用钛酸异丙酯作为催化剂,丁酮为溶剂,在150-220℃反应20个小时,制得耐水解多元醇。
在氮气保护下,将20份耐水解多元醇、25份四甲基苯二亚甲基二异氰酸酯、12份N-甲基吡咯烷酮加入反应器中,90℃反应1h;加入5份二羟甲基丙酸,1份有机铋,反应1.5h;加入5份叔碳酸缩水甘油酯E10p,反应2h;再加入3份1,4-丁二醇进行扩链,搅拌反应1h,加入10份N-甲基吡咯烷酮,待反应完全后,加入4份N,N`-二异丙基乙醇胺进行中和。在高剪切条件下将树脂加入到150份去离子水,搅拌1h。通过减压抽滤去除溶剂,制得水性聚氨酯树脂。树脂固含为32%,粘度为120mPa·s,树脂分子量为6800,玻璃化温度为15℃。
实施例4
防渗色水性聚氨酯树脂的制备:
将5份间苯二甲酸、12份苯酐、15份丁二酸、20份1,2-丙二醇、10份环氧丙烷、3份环氧乙烷进行混合,选用钛酸异丙酯作为催化剂,丁酮为溶剂,在150-220℃反应20个小时,制得耐水解多元醇。
在氮气保护下,将25份耐水解多元醇、15份六亚甲基二异氰酸酯,5份四甲基苯二亚甲基二异氰酸酯、15份丙酮加入反应器中,80℃反应4h;加入6份二羟甲基丁酸、1份氯化亚锡,反应1h;加入3份亚油酸,反应1h,再加入3份己二胺进行扩链,搅拌反应1h。加入8份丙酮,待反应完全后,加入6份N,N`-二甲基乙醇胺进行中和反应。在高剪切条件下将树脂加入到150份去离子水,搅拌1h。通过减压抽滤去除溶剂,制得水性聚氨酯树脂。树脂固含为31%,粘度为200mPa·s,树脂分子量为10200,玻璃化温度为10℃。
对比例1
水性聚氨酯树脂的制备:在氮气保护下,将35份聚酯多元醇、10份二环己基甲烷二异氰酸酯、10份六亚甲基二异氰酸酯加入反应器中,90℃反应2h;加入9份二羟甲基丁酸、3份三羟甲基丙烷,反应2h;待反应完成过后降温,加入9份三乙胺进行中和反应0.5h。在高剪切条件下加入去离子水和乙二胺,搅拌2h,制得水性聚氨酯树脂。树脂固含32%,粘度为50mPa·s。
对比例2
水性聚氨酯树脂的制备:在氮气保护下,将30份聚醚二醇、2份1,4-二羟基-2-丁烷磺酸钠、25份环己烷二亚甲基二异氰酸酯、1.2份氯化亚锡加入到反应器中,升温到75℃,反应4h;加入2份三羟甲基丙烷,进一步反应2h,再加入3份己二胺,搅拌反应2h,降温,加入6份N,N`-二异丙基乙胺进行中和反应;在高剪切条件下加入135份去离子水,搅拌3h,即得水性聚氨酯树脂,树脂固含为35.3%,粘度为5500mPa·s。
将实施例1-4和对比例1-2中的树脂在50℃条件下存放1个月,树脂水解会生成羧酸,引起酸值升高,根据检测酸值浓度反映耐水解等级,来判断树脂耐水解性,测试结果见表1:
表1
从表1可以看出,实施例1-4制备的树脂由于采用特定耐水解多元醇和功能单体搭配,提高树脂的耐水解性,使得树脂保存时间更长,耐水解等级均为1级。对比例1和2由于采用普通聚酯和聚醚为原料,制得的树脂稳定性相对较差,易水解,存放时间短,不能长期保存使用。
按照表2配方制备水性中涂漆,其中水性聚氨酯树脂分别选自实施例1-4和对比例1-2制备的防渗色水性聚氨酯树脂。
表2
材料 | 重量(g) |
色浆 | 32 |
湛新6803丙烯酸分散体 | 12 |
水性聚氨酯树脂 | 18 |
湛新305氨基树脂 | 4 |
BYK-052消泡剂 | 0.1 |
BYK-AT204分散剂 | 0.1 |
BYK-349流平剂 | 0.2 |
去离子水 | 8 |
按照表3配方制备水性色漆,其中水性聚氨酯树脂分别选自实施例1-4和对比例1-2制备的防渗色水性聚氨酯树脂。
表3
将使用相应实施例和对比例的水性聚氨酯树脂所制备的水性中涂漆和水性色漆进行涂装,涂装包括中涂层和色涂层两层,中涂层在室温下晾晒4分钟,色涂层先在室温晾晒5分钟,然后在80℃烘烤5分钟,中涂层的涂布厚度为20μm,色涂层的涂布厚度为15μm,涂布的基材为PC塑料板,测试结果见表4:
表4
表4测试结果显示,在固定涂层配方的前提下,实施例1-4树脂具有空间位阻和疏水效应,可以有效阻隔化学键的水解,改善耐化学品性质,抗渗咬能力优于对比例1和2,使得添加实施例1-4制备的涂层在喷涂时没有出现渗咬或发花现象,板面平整,使配套涂层获得好的外观及附着力。对比例1和2抗渗咬性能低于实施例1-4,在使用对比例1和2制备涂层时出现局部渗咬发花现象,最终导致涂层整体外观及附着力不佳。
对使用实施例1-4水性聚氨酯树脂制备的涂料的性能进行测试,测试结果见表5:
表5
表5测试结果显示,涂料的耐水性和耐酸碱性均能达到要求。
Claims (6)
1.一种防渗色水性聚氨酯树脂,其特征在于,其制备原料包括以下重量份的原料:
耐水解多元醇5-30份,水溶性单体2-12份,异氰酸酯5-25份,功能单体3-12份,扩链剂3-10份,催化剂0.6-5份,胺4-7份;
所述耐水解多元醇的制备原料包括多元酸、多元醇、酸酐、环氧单体、己内酯中的至少两种,且至少包含多元醇;所述多元酸选自间苯二甲酸、对苯二甲酸、丁二酸、己二酸、二聚酸、顺丁烯二酸、1,4-环己烷二甲酸;所述酸酐选自苯酐、马来酸酐、六氢苯酐;所述多元醇选自1,6-己二醇、乙二醇、丙三醇、1,4-环己烷二甲醇、2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯、1,2-丙二醇;所述环氧单体选自环氧丙烷和/或环氧乙烷;
所述水溶性单体包括二羟甲基丁酸、二羟甲基丙酸中的至少一种;
所述功能单体包括叔碳酸缩水甘油酯、γ-氨丙基三乙氧基硅烷、3-甲基-1,5-戊二醇、亚油酸、大豆油酸、桐油酸、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷中的至少一种。
2.根据权利要求1所述的防渗色水性聚氨酯树脂,其特征在于,所述异氰酸酯包括多异氰酸酯和/或异氰酸酯预聚体。
3.根据权利要求1所述的防渗色水性聚氨酯树脂,其特征在于,所述扩链剂包括乙二醇、1,2-丙二醇、1,4-丁二醇、二甘醇、1,6-己二醇、乙二胺、己二胺、一缩二丙二醇、蓖麻油中的至少一种。
4.一种制备如权利要求1-3任一项所述防渗色水性聚氨酯树脂的方法,其特征在于,包括以下步骤:
(1)在保护气氛围下,将所述耐水解多元醇、异氰酸酯混合反应;
(2)加入所述水溶性单体、催化剂反应;
(3)加入所述功能单体反应;
(4)加入所述扩链剂反应;
(5)加入胺进行中和;
(6)将所述中和后的产物分散于水中。
5.一种水性涂料,其特征在于,其含有如权利要求1-3中任一项所述的防渗色水性聚氨酯树脂。
6.如权利要求1-3任一项所述防渗色水性聚氨酯树脂,或采用如权利要求4所述的方法制得的防渗色水性聚氨酯树脂在涂装工艺中的应用。
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