CN105152898B - 苯基丁酮衍生物与其作为光引发剂的应用 - Google Patents
苯基丁酮衍生物与其作为光引发剂的应用 Download PDFInfo
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- CN105152898B CN105152898B CN201510355552.9A CN201510355552A CN105152898B CN 105152898 B CN105152898 B CN 105152898B CN 201510355552 A CN201510355552 A CN 201510355552A CN 105152898 B CN105152898 B CN 105152898B
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明提供了新的化合物1‑(4‑甲基苯基)‑2‑乙基‑2‑羟基‑1‑丁酮,及其制备方法和其作为光引发剂的用途。本发明还公开了含有所述化合物作为光引发剂的可光聚合的组合物和其应用,以及提供了涂有所述组合物的涂布基材。
Description
技术领域
本发明涉及辐射光照射固化领域。具体的,本发明提供了1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮和其制备方法,以及1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮作为光引发剂的应用。
背景技术
辐射固化技术是指利用紫外光(UV)和电子束(EB)、红外光、可见光、激光、化学荧光等辐射光照射固化聚合物的新型技术,具有高效、经济、节能、环境友好的特点,属于新型节能环保技术。
在辐射固化技术中,光引发剂是最重要的因素之一。光引发剂又称为光敏剂或光固化剂,是一类能在紫外光区(250~420nm)或可见光区(400~800nm)吸收一定波长的能量,产生自由基、阳离子等,从而引发单体聚合交联固化的化合物。光引发剂可制备成光固化胶黏剂,对固化速率起着决定性作用。光引发剂受紫外光照射后,吸收光的能量,分裂成2个活性自由基,引发光敏树脂和活性稀释剂发生连锁聚合,使胶黏剂交联固化。
现在,光引发剂已经在涂料﹑油墨行业广泛应用。随着人们生活水平的提高,对环境和食品安全问题越来越重视。涂料行业以及包装业,尤其是食品包装行业的彩色印刷,对有害挥发性有机物(VOC),如丙酮、苯、四氯化碳、氯仿等,有明确的限量。过去用于食品领域的光引发剂,由于在使用过程中受光引发作用,会产生如丙酮、苯等VOC,目前已经禁止使用。另外,目前市场上光引发剂由于其性能或价格问题, 不能够满足生产厂家的要求。
R.Klos等人于1991年在Journal of Macromolecular Science,Chemistry,Volume:A28,Issue:9上发表的Photoinitiators with Functional Groups.PartI.Polymer Photoinitiators中公开了一种可用作光引发剂的化合物1-(4-乙烯基苯基)-2-甲基-2-羟基-1-丁酮。该化合物能在特定的光照射下有效地吸收能量,引发单体聚合交联固化。但随着技术发展,其活性工艺的问题使得该化合物已不能满足当代技术领域的要求。
市售的光引发剂2-羟基-2-甲基-1-苯基丙酮和1-(4-叔丁基苯基)-2-甲基-2-羟基-1-丙酮为当前市面上广泛使用的一类光引发助剂。这些化合物在特定光照下光吸收效率高,本身降低了产品的气味,降低了光引发剂在体系中的迁移率,但仍有在光聚合反应过程以及产品存在过程中产生苯和丙酮的缺点。
丙酮是重要的有机合成原料,广泛应用于各个工业领域中,但其同时对人体有较大危害,过量接触会产生中毒反应,长期接触该品出现眩晕、灼烧感、咽炎、支气管炎、乏力、易激动等。皮肤长期反复接触可致皮炎。并且丙酮本身极度易燃,对环境和使用者有潜在危险。
因此,在光聚合技术领域中,仍然需要对环境更为友好,具有更高活性、容易制备且容易处理等优点的光引发剂。
发明内容
本发明提供了一种新的化合物,其为:
1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮。
本发明还提供了上述本发明化合物作为光引发剂的用途。本发明的化合物1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮在光聚合反应中具有良好的性能,能够有效地在例如紫外(UV)光的照射时产生聚合引发基。本发明的聚合物光引发剂可用于制备范围广泛的辐射固化材料,包括压敏热熔粘合剂和涂料组合物,例如装饰和耐磨涂料、清漆、纤维增强复合物、微电子封铸材料、塑料主板、油墨印刷涂料、光纤涂料、模塑料、UV固化结构树脂等。
本发明还提供了一种可光聚合的组合物,其中包含:
(a)作为光引发剂的下式化合物
(b)至少一种烯属不饱和可光聚合的化合物。
在本发明的一个方面,本发明提供的可光聚合的组合物中还可含有其它已知的光引发剂,例如二苯甲酮、二苯甲酮衍生物如2,4-二羟基二苯甲酮、苯乙酮、苯乙酮衍生物,二苯基乙酮、α,α-二甲氧基-α-苯基苯乙酮、α,α-二乙氧基苯乙酮、α-羟烷基苯酮、α-胺烷基苯酮、樟脑醌、苯偶酰缩酮,苯基乙醛酸及其衍生物、二乙酰基、过酸酯等。
在本发明的一个方面,可光聚合组合物的光引发剂一般占组合物重量的0.5-20%,优选为1-10%,更优选为3-6%。如果在组合物中使用光引发剂的混合物,该量所指为所有添加的光引发剂的总和。可根据应用厚度选择浓度。也可使用两种或多种光引发剂的组合以获得配置组合物可能的最佳固化性。优选使用能在加工生产线上引发固化并且达到最终期望的使用强度的最低必需量的光引发剂。这个用量取决于聚合物组合物以及辐射源、接受的辐射量、生产线速度和在基材上的涂层厚度。
在本发明的一个方面,组分(b)中所述烯属不饱和可光聚合的化合物包括本领域各种已知的化合物。通常所述烯属不饱和可光聚合的化合物包括一个或多个烯属双键。所述包括一个或多个烯属双键的可光聚合的化合物单体的例子包括:丙烯酸烷基酯、甲基丙烯酸烷基酯、羟烷基酯、环氧烷基酯、(甲基)丙烯酰胺、N-取代的(甲基)丙烯酰胺、不饱和羧酸酐、不饱和酯、乙烯基醚、异氰脲酸酯、N-乙烯基杂环化合物等。
在本发明的一个方面,所述烯属不饱和可光聚合的化合物为烯属不饱和羧酸与多元醇或聚环氧化物的酯。所述不饱和羧酸的例子为丙烯酸、甲基丙烯酸、不饱和脂肪酸如亚麻酸或油酸。优选的,所述不饱和羧酸为丙烯酸和甲基丙烯酸。所述多元醇可为芳族,脂族或环脂族多元醇。芳族多元醇的例子为对苯二酚、4,4-二羟基联苯、2,2-二(4-羟基苯基)丙烷、以及线型酚醛树脂和酚醛树脂A。
组分(b)中所述烯属不饱和可光聚合的化合物可以是其中的一种,也可以是其中的两种的混合物或是两种以上的混合物。
在本发明的一个方面,所述烯属不饱和可光聚合的化合物为聚氨酯丙烯酸酯、丙烯酸酯化的环氧树脂、丙烯酸烷基酯、丙烯酸烷氧基酯或其混合物,优选为聚氨酯丙烯酸酯、1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯或其混合物。
在本发明的可光聚合的组合物中,组分(b)烯属不饱和可光聚合的化合物一般用量为约8%至约80%,优选约30%至约60%,更优选约40%至约60%。
本发明提供的可光聚合的组合物中还可含有其它添加剂(c)。
在本发明的一个方面,可光聚合组合物中含有的添加剂(c)为反应性胺助引发剂,包括水溶性叔胺类例如脂肪族叔胺。常见的如丁胺、对二甲基氨基苯甲酸乙酯、三乙醇胺、N-甲基-二乙醇胺、N’N’-二甲基乙醇胺等。本发明的可光聚合组合物中的反应性胺助引发剂通常占该组合物重量的约0.5-10%,最优选为约3-8%。
本发明可光聚合组合物中含有的其它添加剂的例子还包括用于防止 过早聚合反应的热阻聚剂,其例子为氢醌及其衍生物、对苯二酚、对苯二酚衍生物、对-甲氧基苯酚、β-萘酚或空间位阻苯酚。另外,可少量加入的光稳定剂如UV吸收剂,例如邻羟基二苯甲酮类、苯并三唑类、水杨酸酯类、三嗪类、取代丙烯腈类、羟基苯基三唑、羟基苯基-二苯甲酮、草酰胺或羟基苯基-s-三嗪类。
本领域已知的其它添加剂还包括增稠剂、润湿分散剂、防浮色剂、消泡流平剂、消光剂等。添加剂的选择取决于应用领域以及该领域所需的性能。上述添加剂是本领域常用的,因此其加入量为相应场合的常规量。
本发明提供了一种可光聚合组合物,其包含:
本发明的可光聚合组合物的感光性包括190-600纳米(UV-可见光区)。合适的射线可以是日光或来自人造光源的光。因此,可以采用许多明显不同种类的光源。灯与要按照本发明曝光的基材之间的距离可根据预期用途以及灯的种类和输出而变化。也可使用在可见光区的激光。
在本发明的一个方面,提供了至少一个表面上涂有上述可光聚合组合物的涂布基材。本发明的可光聚合组合物适用于其上需涂覆保护层的所有种类的基材,例如木材、纺织品、纸、陶瓷、玻璃、塑料,如聚酯、聚对苯二甲酸乙二醇酯、聚烯烃或乙酸纤维素,尤其是形成膜,以及金属,如Al、Cu、Ni、Fe、Zn、Mg或Co和GaAs、Si或SiO2的涂料,或以成像方式进行曝光以生成图像。
在本发明的一个方面,提供了本发明的上述可光聚合组合物的应用,包括用于套印涂料,印刷油墨,如丝网印刷油墨,油墨,胶印或柔性版印刷,喷墨油墨,油墨,单张纸印刷,电子照相油墨,凹版油 墨,清漆,白大衣或彩色颜料的涂层,用于木材或金属,油漆,粉刷/油漆道路,房屋,建筑物,车辆,飞机等;进行照相复制过程,用于图像记录,用于制作进行丝网印刷的掩模,牙科填充化合物,作为蚀刻抗蚀剂或永久抗蚀剂;作为电子电路中的焊接掩膜,作为复合材料凝胶涂层的层状组合物成分,用于涂料或电子元件的密封或作为光纤涂层。所述组合物还适合用于制作光学透镜,如隐形眼镜或菲涅尔透镜,以及在医疗设备或植入物的制造。
本发明还提供了制备前述下式本发明化合物的方法
1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮
,包括以下步骤:
(1)2-乙基丁酰氯与甲苯生成式化合物1c
(2)化合物1c反应生成式化合物2c
(3)化合物2c反应生成化合物3c
具体实施方式
通过下述实施例有助于进一步理解本发明,但不用于限制本发明的内容。
实施例1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮的合成
1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮的合成路径如下式所示:
式1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮的合成途径
(1)在氮气保护下,往夹套反应釜中加入无水三氯化铝74g(0.56mol)和二氯甲烷150mL,搅拌并冷却混合液到0℃,然后将2-乙基丁酰氯75.0g(0.56mol)和甲苯60g的溶液缓慢滴加到反应釜中,保持釜内温度为0℃,2h内加完。混合液滴加完毕,恒温搅拌1h。反应结束, 反应混合液分别用1M的盐酸,饱和碳酸氢钠溶液和水洗涤。减压蒸干溶剂二氯甲烷,得到无色油状物目标产品化合物(1c),产率为89%。
(2)在室温下,往夹套反应釜中加入化合物(1c)95.0g(0.50mol)和二氯甲烷95g,搅拌均匀,然后将溴素96g(0.60mol)和二氯甲烷76g的混合液滴加入反应釜中,1h内加完。混合液滴加完毕,加热反应液到40℃,反应3.5h。反应结束,冷却反应液到0℃,缓慢加入饱和的亚硫酸钠溶液300mL,升温至室温,混合液搅拌30mins,静置分层,收集二氯甲烷相,保留水相在釜中。往水相中加入二氯甲烷150mL萃取水相,合并二氯甲烷溶液,用分别用饱和碳酸氢钠300mL溶液和水300mL洗涤二氯甲烷溶液。最后,减压蒸干二氯甲烷溶液得到棕黄色油状物目标产品化合物(2c),产率为98%。
(3)取溴代物12.0g(0.045mol),和四氢呋喃50.0g加入到250mL的反应瓶中,再加入53.2g 6%氢氧化钠水溶液和催化量的四丁基溴化铵。反应混合物在50℃搅拌4小时。冷却至室温后,进行分相。后加入40ml 2-甲基四氢呋喃萃取水相两次,合并有机相。除去有机溶剂得到粗产物,经过柱层析提纯得到油状目标产物化合物(3c),产率70%。
产物分析结果:1H NMR(400Hz,CDCl3)δ0.81(t,J=7.6Hz,6H),1.94-2.13(m,4H),2.44(s,3H),4.46(br,1H),7.28(d,J=8.0Hz,2H),7.93(d,J=8.0Hz,2H);13C NMR(100Hz,CDCl3)δ7.7,21.6,33.3,82.3,129.2,129.3,131.8,144.1,204.3。
实施例2清漆制剂的制备
根据以下配方配置紫外线固化清漆制剂。
具体配方如下:
根据上述配方,分别以以下五种化合物作为光引发剂:
光引发剂(1):化合物1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮,
光引发剂(2):化合物1-(4-乙烯基苯基)-2-甲基-2-羟基-1-丁酮,
光引发剂(3):1-(4-正丙醇基苯基)-2-甲基-2-羟基-1-丙酮(商购),
光引发剂(4):1-(4-叔丁基苯基)-2-甲基-2-羟基-1-丙酮(巴斯夫185光引发剂),
光引发剂(5):2-羟基-2-甲基-1-苯基丙酮,
作为光引发剂制备得到发明制剂1,对比制剂2,对比制剂3,对比制剂4,对比制剂5。
实施例3固化效果测试
将实施例2中配制所得的清漆制剂用印刷适性仪涂布约15微米厚度于空白纸张上,用一台功率为50W/CM线功率的中压水银弧光灯以100米/分速度进行固化,记录获得良好的表面及彻底固化所需要的灯下通过次数。
结果表明采用本发明的化合物1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮作为光引发剂而制备得到的清漆制剂的固化速度明显优于采用与现有技术的光引发剂1-(4-乙烯基苯基)-2-甲基-2-羟基-1-丁酮和1-(4-正丙醇基苯基)-2-甲基-2-羟基-1-丙酮为光引发剂而制备得到的清漆制剂,固化速度也好于或不次于光引发剂1-(4-叔丁基苯基)-2-甲基-2-羟基-1-丙酮和2-羟基-2-甲基-1-苯基丙酮为光引发剂而制备得到的清漆制剂。
实施例4丙酮释放分析
采用如下所述的顶空-气相色谱法测定固化膜中的丙酮释放量:
1)定量分析工作曲线绘制:
1.在250ml容量瓶中加入丙酮20mg,准确称量(准确至0.lmg),以三醋酸甘油酯定容,定为第1级标准溶液;
2.取第1级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第2级标准溶液;
3.取第2级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第3级标准溶液;
4.取第3级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酷酯定容,定为第4级标准溶液;
5.取第4级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第5级标准溶液;
6.分别取第1-5级标准溶液1000uL进行顶空-气相色谱分析,每级标准溶液重复测定两次,取平均值。根据丙酮的峰面积及其含量(将标液浓度换算为单位面积膜中所含苯的质量数,mg/m2),建立工作曲线,工作曲线原点强制过原点。
2)待测样品制备及测定:
将配制所得的发明制剂1,对比制剂4得到的固化样品膜,将膜从玻璃板上剥离,剪取100cm2,放入顶空瓶中,加入1000uL三醋酸甘油酯,进行顶空-气相色谱分析,根据丙酮的峰面积A及工作曲线斜率K进行释放量的计算,公式:C=A/K。
3)测定结果:
*所述限量指标根据中国烟草专卖局发布的行业标准YC 263-2008《卷烟条与盒包装纸中挥发性有机化合物的限量》
实施例5苯释放分析
采用如下所述的顶空-气相色谱法测定固化膜中的苯释放量:
1)定量分析工作曲线绘制:
1.在250ml容量瓶中加入苯20mg,准确称量(准确至0.lmg),以三醋酸甘油酯定容,定为第1级标准溶液;
2.取第1级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第2级标准溶液;
3.取第2级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第3级标准溶液;
4.取第3级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酷酯定容,定为第4级标准溶液;
5.取第4级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第5级标准溶液;
6.分别取第1-5级标准溶液1000uL进行顶空-气相色谱分析,每级标准溶液重复测定两次,取平均值。根据苯的峰面积及其含量(将标液浓度换算为单位面积膜中所含苯的质量数,mg/m2),建立工作曲线,工作曲线原点强制过原点。
2)待测样品制备及测定:
将配制所得的清漆制剂得到的固化样品膜,将膜从玻璃板上剥离,剪取100cm2,放入顶空瓶中,加入1000uL三醋酸甘油酯,进行顶空-气相色谱分析,根据苯的峰面积A及工作曲线斜率K进行释放量的计算,公式:C=A/K。
3)测定结果:
*所述指标为中国烟草专卖局发布的行业标准YC 263-2008《卷烟条与盒包装纸中挥发性有机化合物的限量》
结果表明采用本发明的化合物1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮作为光引发剂而制备得到的清漆制剂用于固化后,释放有害气体丙酮和/或苯的量远小于以1-(4-叔丁基苯基)-2-甲基-2-羟基-1-丙酮和2-羟基-2-甲基-1-苯基丙酮为光引发剂而制备得到的清漆制剂。采用本发明的化合物作为光引发剂的紫外线固化清漆制剂能满足国家对挥发性有机化合物的限量要求,而现有技术的紫外线固化清漆制剂则释放大量有害气体,不能满足有关限量要求。
本发明出人意料地发现,创新性的化合物1-(4-甲基苯基)-2-乙基-2-羟基-1-丁酮在光聚合反应中具有良好的性能,能够有效地在例如紫外(UV)光的照射时产生聚合引发基。配方试验证明,同等条件下,与现有技术的光引发剂1-(4-乙烯基苯基)-2-甲基-2-羟基-1-丁酮和1-(4-正丙醇基苯基)-2-甲基-2-羟基-1-丙酮等比较,本发明提供的化合物制备的清漆制剂完全固化所需次数少,效率高。而且,配方试验证明,同等条件下,与现有技术的光引发剂1-(4-叔丁基苯基)-2-甲基-2-羟基-1-丙酮及2-羟基-2-甲基-1-苯基丙酮比较,采用本发明的化合物作为光引发 剂的紫外线固化清漆制剂基本不释放有害挥发性有机化合物,能满足国家标准对挥发性有机化合物的限量要求。可见,本发明提供的化合物工作效率高,并且生产成本明显降低,生产工艺简单,后处理简单,满足环境保护要求。
除非另外指出,本发明的实践将使用有机化学、聚合物化学等的常规技术,显然除在上述说明和实施例中所特别描述之外,还可以别的方式实现本发明。其它在本发明范围内的方面与改进将对本发明所属领域的技术人员显而易见。根据本发明的教导,许多改变和变化是可行的,因此其在本发明的范围之内。
Claims (13)
1.一种具有下式的化合物
2.权利要求1的化合物作为光引发剂的用途。
3.一种可光聚合的组合物,包含:
(a)权利要求1的化合物,其作为光引发剂,占该组合物重量的0.5-20%;
(b)至少一种烯属不饱和可光聚合的化合物。
4.根据权利要求3的可光聚合组合物,其中所述权利要求1的化合物占该组合物重量的3-6%。
5.根据权利要求3的可光聚合组合物,其中所述烯属不饱和可光聚合的化合物为烯属不饱和羧酸与多元醇的酯或烯属不饱和羧酸与聚环氧化物的酯。
6.根据权利要求5所述的可光聚合组合物,其中所述烯属不饱和可光聚合的化合物为聚氨酯丙烯酸酯、丙烯酸酯化的环氧树脂、丙烯酸烷基酯、丙烯酸烷氧基酯或其混合物。
7.根据权利要求6所述的可光聚合组合物,其中所述烯属不饱和可光聚合的化合物为聚氨酯丙烯酸酯、1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯或其混合物。
8.根据权利要求3的可光聚合组合物,其还含有反应性胺助引发剂,所述胺助引发剂占该组合物重量的0.5-10%。
9.根据权利要求8的可光聚合组合物,其中所述反应性胺助引发剂为水溶性叔胺类。
10.根据权利要求8的可光聚合组合物,其中所述胺助引发剂占该组合物重量的3-8%。
11.根据权利要求3的可光聚合组合物,其包含:
其中所述百分比为其在组合物中所占重量比。
12.至少一个表面上涂有权利要求3-11中任何一项的组合物的涂布基材。
13.一种制备下式化合物的方法,
包括以下步骤:
(1)2-乙基丁酰氯与甲苯生成式化合物1c
(2)化合物1c反应生成式化合物2c
(3)化合物2c反应生成化合物3c
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