CN114316240B - 一种阳离子型可固化组合物 - Google Patents
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
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Abstract
本发明公开一种阳离子型可固化组合物,包含可阳离子聚合的化合物、超强酸和水。该组合物能够解决现有强酸固化难以实施、以及光固化组合物粘度高、易黄变和应用场景受限的问题。
Description
技术领域
本发明属于化学和光电交叉技术领域,具体涉及一种阳离子型可固化组合物。
背景技术
阳离子聚合主要是利用催化剂来促使链的开始,所用引发剂都是亲电试剂,主要有质子酸、路易斯酸等。作为质子酸的一种,超强酸虽然酸性强、解离常数大、活性高、引发速度快,但是生成的抗衡阴离子亲核性弱,难以与增长链活性中心成共价键而使反应终止,单体选择性有限,很大程度上限制了其应用。
近些年,阳离子型光聚合发展很快,其具有不受氧影响、体积收缩小等优点。但是,阳离子自由基不稳定且光聚合条件较为苛刻,微量水、空气、杂质对聚合都影响极大,实验重复性差,在很大程度上限制了其发展;同时,为了提高引发效率,往往需要增大引发剂的吸收波长,使得组合物应用后容易产生黄变,并且组合物的粘度调整很有限,应用领域受到限制。
发明内容
针对现有技术的不足,本发明的目的主要在于提供一种阳离子型可固化组合物,以解决现有强酸固化难以实施、以及光固化组合物粘度高、易黄变和应用场景受限的问题。
为了实现上述目的,提供了一种阳离子型可固化组合物,包含下列组分:
(A)可阳离子聚合的化合物;
(B)超强酸;
(C)水。
作为组分(A),可阳离子聚合的化合物为环醚化合物和乙烯基醚类化合物中的一种或多种,优选环醚化合物。
进一步地,上述环醚化合物为环氧化合物和氧杂环丁烷类化合物中的一种或多种。
作为环氧化合物,可以是脂环族环氧化合物和/或非脂环族环氧化合物。从进一步提高固化速度的方面考虑,可优先考虑使用分子中具有2个或2个以上脂环式环氧基的多官能脂环式环氧化合物,和/或分子中具有1个脂环式环氧基且具有乙烯基等不饱和双键基团的脂环式环氧化合物;优选具有环氧环己基的环氧化合物,如3,4-环氧环己基甲基-3’,4’-环氧环己基羧酸酯、ε-己内酯改性-3,4-环氧环己基甲基-3’,4’-环氧环己基羧酸酯、双((3,4-环氧环己基)甲基)己二酸酯、环氧环己烷、2-(3,4-环氧环己烷)乙基三甲氧基硅烷、3,4-环氧环己基甲基甲基丙烯酸酯、3,4-环氧环己基甲基丙烯酸酯、1,2-环氧-4-乙烯基环己烷、3,4-环氧环己烷羧酸酯、3,4-环氧环己基甲基-3’,4’-环氧环己基甲酸酯和己内酯的聚合产物、4-甲基-1,2-环氧环己烷、2,2-二(3,3’-环氧环己基)丙烷、2-(3,4-环氧环己烷)乙基三甲氧基硅烷等。从组合物储存稳定性的方面考虑,可优先考虑使用非脂环族环氧化合物,如双酚A的二缩水甘油醚、烷氧基化双酚A的二缩水甘油醚或三缩水甘油醚、线型酚醛清漆环氧化物等。
作为氧杂环丁烷类化合物,对其种类没有特别的限制,可以是单官能度的,也可以是双或多官能度的。理论上,阳离子型可固化组合物领域使用过的氧杂环丁烷类化合物均可适用。示例性地,可使用公开号为CN107619399A、CN107621752A、CN109305947A、CN109400551A的中国发明专利申请中记载的那些氧杂环丁烷类化合物,在此将其中记载的相关内容引入本申请。
进一步地,上述环醚化合物优选是一种或多种与水相容的羟基官能化的环醚化合物与不含羟基官能团的环醚化合物的组合,所述羟基官能化的环醚化合物优选是含羟基的氧杂环丁烷类化合物。
优选地,作为含羟基的氧杂环丁烷类化合物,包含或选自具有如下通式I所示结构的化合物中的至少一种:
其中,
R1代表氢或C1-C6的烷基;
R2代表C1-C80的直链或支链的m+n价烷基或链烯基,任选地(optionally),烷基或链烯基中的一个或多个-CH2-可各自独立地被-O-、-COO-、-OCO-、1,4-亚苯基、取代,前提是-O-不直接相连,并且任选地,R2中还可含有至少一个环氧基团;
n代表1-6的整数;
m代表1-6的整数。
作为优选实施方案,上述通式I结构中:
R1代表氢或C1-C4的烷基;
R2代表C1-C60的直链或支链的m+n价烷基或链烯基,任选地,烷基或链烯基中的一个或多个-CH2-可各自独立地被-O-、-COO-、-OCO-、1,4-亚苯基、取代,前提是-O-不直接相连,并且任选地,R2在至少一个末端连接有环氧基团;
n代表1、2、3或4;
m代表1、2、3或4。
示例性地,氧杂环丁烷类化合物可选自具有如下结构的化合物:
在总量为100质量份的阳离子型可固化组合物中,组分(A)可阳离子聚合的化合物的含量为30-95质量份,优选为60-90质量份。
作为组分(B),超强酸优选是以M-、ClO4 -、CN-、HSO4 -、NO3 -、CF3COO-、(BM4)-、(SbM6)-、(AsM6)-、(PM6)-、Al[OC(CF3)3]4 -、HSO3 -、FSO3 -、CF3SO3 -、B(C6M5)4 -或[(Rf)bPF6-b]-为阴离子的酸中的至少一种,其中,M表示卤素(如氟、氯、溴、碘),b表示1-5的整数,Rf可相同也可不同,各自独立地表示≥80%的氢原子被氟原子取代的烷基。
进一步优选地,所述超强酸的阴离子选自BF4 -、ClO4 -、FSO3 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、B(C6H5)4 -、B(C6F5)4 -。示例性地,超强酸可以是六氟磷酸、六氟锑酸、四五氟苯基硼酸、六氟砷酸等。
在总量为100质量份的阳离子型可固化组合物中,组分(B)超强酸的含量为0.1-10质量份,优选为0.5-5质量份。
作为组分(C),水用作稀释剂用于控制粘度和保证组合物一定的稳定性。对水没有特别的限定,优选去离子水。
在总量为100质量份的阳离子型可固化组合物中,组分(C)水的含量为1-99质量份,优选为5-40质量份。
进一步地,根据产品应用需要,本发明的可固化组合物中还可选择性地添加本领域中常用的有机和/或无机添加剂,包括但不限于溶剂、填料、流平剂、分散剂、消泡剂、颜料、染料、表面活性剂、溶剂等,这对本领域技术人员而言是容易理解和确定的常规技术。
进一步的,本发明所述的各个组分可以混合后直接应用,可以储存一定时间后应用,也可以将部分组分先配置成预浸料,应用时进一步混合。
本发明的阳离子型可固化组合物具有较高的增强反应性、较低的粘度和优异的耐黄变性能。配方中各组份形成单相的混合物,流变能力控制性强,能够适用于各种应用场景。
具体实施方式
以下将结合具体实施例对本发明作进一步详细说明,但不应将其理解为对本发明保护范围的限制。
一、可固化组合物基本性能评价
按照表1中所示配方,将各组分混合均匀,得到可固化组合物。各实施例中所述数量均为重量份数。
表1
1、粘度
采用粘度计(DV-1)测试可固化组合物在25℃下的粘度。
2、固化时间
使用15μm线棒将可固化组合物涂布于马口铁基材,形成约10μm厚的涂层。然后将样品置于80℃烘箱,记录涂层指触表干所需要的最少时间。时间越短,代表固化速度越快。
3、硬度
参考GB T 6739-1996,测试固化膜的硬度。
4、附着力
参考GB 1720-1979,测试固化膜的附着力。
评价结果记录在表2中。
表2
评价结果显示:本发明的阳离子型可固化组合物粘度低,流变性强,具有很好的可操作性;涂覆后涂层固化时间短,实施例6、9和10仅为30s,且固化膜的硬度和附着力高,表现出了优异的固化性能。
二、水性强酸固化与阳离子光固化黄变性能对比
按照表3中所示配方,配制实施例11-13和对比例1-3的可固化组合物,然后分别将组合物通过30μm施线棒手动涂布于马口铁基材,干燥后涂层厚度约为20μm。
实施例11-13的样品通过80℃加热1min固化成膜,对比例1-3的样品通过高压汞灯(型号:RW-UVATP201-20)给予2000mj/cm2的紫外辐射固化成膜。采用爱色丽色差仪(型号:Ci7600)测试固化前后的黄变△b值。
表3
备注:阳离子引发剂6990为混合的六氟磷酸三芳基硫鎓盐,产自常州强力电子新材料股份有限公司,可商购获得。
测试结果显示,相比于光固化水性涂料,本发明的阳离子型可固化组合物在耐黄变方面具有明显优势,黄变△b值低了整整一个量级。
三、着色体系固化性对比
按照表4中所示配方,配制实施例14-16和对比例4-6的可固化组合物,然后分别将组合物通过30μm施线棒手动涂布于马口铁基材,干燥后涂层厚度约为20μm。
实施例14-16的样品通过80℃加热1min,对比例4-6的样品通过高压汞灯(型号:RW-UVATP201-20)给予2000mJ/cm2的紫外辐射。通过指触法评估固化成膜性。
表4
备注:颜料蓝60,无锡大洋化工有限责任公司。
测试结果显示,着色体系对光固化成膜性具有很大影响,当着色剂浓度高时(如对比例5和6),组合物涂层将无法固化成膜;应用本发明的可固化组合物则不受影响,均能顺利成膜,相比于光固化水性涂料具有明显的优势。
以上仅为本发明的优选实施例,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化,凡在本发明的精神和原则之内所作的任何修改、替换、改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种阳离子型可固化组合物,包含下列组分:
(A)可阳离子聚合的化合物,所述可阳离子聚合的化合物为环醚化合物;
(B)超强酸,所述超强酸是以M-、ClO4 -、CN-、HSO4 -、NO3 -、CF3COO-、(BM4)-、(SbM6)-、(AsM6)-、(PM6)-、Al[OC(CF3)3]4 -、HSO3 -、FSO3 -、CF3SO3 -、B(C6M5)4 -或[(Rf)bPF6-b]-为阴离子的酸中的至少一种,其中,M表示卤素,b表示1-5的整数,Rf可相同也可不同,各自独立地表示≥80%的氢原子被氟原子取代的烷基;
(C)水;
所述环醚化合物是一种或多种与水相容的羟基官能化的环醚化合物与不含羟基官能团的环醚化合物的组合,所述羟基官能化的环醚化合物是含羟基的氧杂环丁烷类化合物;
作为含羟基的氧杂环丁烷类化合物,包含具有如下通式I所示结构的化合物中的至少一种:
其中,
R1代表氢或C1-C6的烷基;
R2代表C1-C80的直链或支链的m+n价烷基或链烯基,任选地,烷基或链烯基中的一个或多个-CH2-可各自独立地被-O-、-COO-、-OCO-、1,4-亚苯基、取代,前提是-O-不直接相连,并且任选地,R2中还可含有至少一个环氧基团;
n代表1-6的整数;
m代表1-6的整数。
2.根据权利要求1所述的阳离子型可固化组合物,其特征在于,通式I结构中:
R1代表氢或C1-C4的烷基;
R2代表C1-C60的直链或支链的m+n价烷基或链烯基,任选地,烷基或链烯基中的一个或多个-CH2-可各自独立地被-O-、-COO-、-OCO-、1,4-亚苯基、取代,前提是-O-不直接相连,并且任选地,R2在至少一个末端连接有环氧基团;
n代表1、2、3或4;
m代表1、2、3或4。
3.根据权利要求1所述的阳离子型可固化组合物,其特征在于:所述超强酸的阴离子选自BF4 -、ClO4 -、FSO3 -、PF6 -、AsF6 -、SbF6 -、CF3SO3 -、B(C6H5)4 -、B(C6F5)4 -。
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CN103354829A (zh) * | 2010-12-23 | 2013-10-16 | 好利获得股份公司 | 喷墨印刷用双组分反应性油墨 |
CN105143375A (zh) * | 2013-03-15 | 2015-12-09 | 汉高知识产权控股有限责任公司 | 双组分的氰基丙烯酸酯/阳离子固化性粘合剂体系 |
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