CN110144020B - 一种环糊精基光引发剂、其制备方法及应用 - Google Patents
一种环糊精基光引发剂、其制备方法及应用 Download PDFInfo
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims abstract description 25
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- DRBXETAUXNKALW-UHFFFAOYSA-N Cc1cc(C)c(C(=O)c2ccccc2P(O)(O)=O)c(C)c1 Chemical compound Cc1cc(C)c(C(=O)c2ccccc2P(O)(O)=O)c(C)c1 DRBXETAUXNKALW-UHFFFAOYSA-N 0.000 claims description 6
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- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
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Abstract
本发明公布了一种环糊精基光引发剂及其制备方法与应用,环糊精基增大了引发剂在水溶性体系中的溶解度,大分子的结构也限制了光引发剂在固化过程中的迁移;该光引发剂在各类树脂单体、低聚物、稀释剂中溶解性好,引发速率快,尤其适用于涂料、油墨等的表面固化。
Description
技术领域
本发明涉及一种环糊精基光引发剂、其制备方法及应用。
技术背景
酰基膦氧化物是一种高效的自由基(I)型光引发剂,其有效吸收峰值为350-400nm,经光照后可生成苯甲酰和磷酰基两个自由基,都能引发聚合,因此光固化速度快,适合于厚膜深层固化。同时该类引发剂还具有光漂白作用,涂层不变黄的特性,它在白色或高钛白粉颜料化表面均能完全固化,后聚合效应低,无残留,也可用于透明涂层,对于低气味要求的产品尤其适合。
TPO-L是一种液态酰基膦氧化物,因其引发活性高、在不饱和单体和树脂中分散性好被广泛应用于紫外光固化涂料、油墨体系;但TPO-L也存在一些使用缺陷,其一是分子量太小,在紫外固化过程中产生的裂解碎片容易发生迁移;其二是TPO-L水溶性不够好,限制了其在水性体系的使用;
我们发现了一类环糊精基TPO-L衍生物克服了以上缺点,表现出了高效的引发性能,该类化合物在环糊精基骨架结构上引入了类TPO-L分子结构,一方面增强了其在水中的溶解度以使其适用于水性光固化体系,另一方面,超支化的大分子结构不仅增加了活性官能团的数目而且增大了分子量,能有效的防止固化过程中小分子碎片的迁移。
发明内容
本发明提供了一种环糊精基光引发剂,其分子结构如式[Ⅰ]:
其中:n为0、1、2;
R为H或式[Ⅱ]结构除去-OH后的残基,且至少有1个R为式[Ⅱ]结构除去-OH后的残基。
本发明还提供了该化合物的制备方法,其具体制备步骤为:
(1)在中性条件下,2,4,6-三甲基苯甲酰基苯基膦酸乙酯与碘化钠反应,生成有机磷钠盐,如下式反应:
(2)有机磷钠盐与稀酸酸化生成2,4,6-三甲基苯甲酰基苯基膦酸:
(3)2,4,6-三甲基苯甲酰基苯基膦酸与酰卤化试剂反应得到酰卤化合物:
其中:X为Cl或Br
(4)酰卤化合物与环糊精在缚酸剂催化下反应生成环糊精基光引发剂:
其中R、X意义与上述相同。
根据以上所述制备方法,步骤(2)中所述稀酸指稀盐酸或稀硫酸,步骤(3)中所述酰卤化试剂指二氯亚砜、三氯化磷、三溴化磷、五氯化磷、五溴化磷、草酰氯、光气。步骤(4)中缚酸剂可以是有机碱或无机碱类化合物。
本发明还涉及式[Ⅰ]光引发剂的应用,所述式[Ⅰ]光引发剂用于UV固化配方时,配方包含:
(A)至少一种可以进行光聚合的烯属不饱和化合物和
(B)至少一种权利要求1所述的式[Ⅰ]化合物作为光引发剂。
其除组分(B)外,还可以包含其他紫外引发剂、胺促进剂、增敏剂和/或其他添加剂。
组分(A)中烯属不饱和化合物是包括:
含烯类不饱和基团预聚物;
含烯类不饱和基团的单体。
所述烯类不饱和基团预聚物包括环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚醚丙烯酸树脂、纯丙烯酸酯树脂、乙烯基树脂或它们的任意混合物。
所述烯类不饱和基团单体类别包括丙烯酸烷基酯、甲基丙烯酸羟基酯、带有环状结构或苯环的(甲基)丙烯酸酯、乙烯基活性稀释剂、乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯、其他二醇类二丙烯酸酯、多官能团活性稀释剂、烷氧基化丙烯酸酯、丙烯酸二噁茂酯、烷氧基化双酚A二(甲基)丙烯酸酯、乙烯基醚类活性稀释剂、含甲氧端基的(甲基)丙烯酸酯、含磷的阻燃性丙烯酸酯。
所述应用配方适用于光固化体系,主要适用于紫外光固化体系,尤其适用于紫外光固化油墨及涂料体系。
该应用配方在物体表面涂膜后经紫外光源辐射固化成型,其中所述紫外光源可以是高压汞灯光源,也可以是UV-LED光源;所述紫外光源波长范围可以是200nm-500nm。
本发明光引发剂的突出特点在于:
(1具有的大分子的结构保证了引发剂本身及引发过程中不产生VOC排放。
(2)环糊精的骨架结构促使引发剂在水性光固化体系中的溶解度进一步提高,适用领域大大拓宽。
(3)超支化的分子结构提供了多个活性官能团,进一步的提高了引发剂的引发活性。
附图说明
图1为环糊精基酰基膦光引发剂P6401结构示意图图。
图2为环糊精基酰基膦光引发剂P6401紫外扫描图。
具体实施方式
下列实施例详细说明本发明,但以下例子又不仅限于本发明。
实施例1:
一、环糊精基光引发剂P6401的制备
a、2,4,6-三甲基苯甲酰基苯基膦酸
将644g 2,4,6-三甲基苯甲酰基膦酸乙酯溶于3000ml甲基乙基酮中,285g碘化钠加入溶液中,常温搅拌15min后升温至65℃保温反应24h,过滤,得到2,4,6-三甲基苯甲酰基膦酸钠盐。
把401g 2,4,6-三甲基苯甲酰基膦酸钠盐溶于1500ml水中,分别用500ml石油醚萃取2次,分离后水相中滴加1300ml0.5M硫酸至PH=1,酸化1h后,加入1500ml苯进行萃取,水洗,脱溶后用2000ml乙酸乙酯重结晶,过滤、干燥得到2,4,6-三甲基苯甲酰基膦酸396.5g,收率68%。
b、2,4,6-三甲基苯甲酰基苯基膦酰氯
25g 2,4,6-三甲基苯甲酰基苯基膦酸,70ml甲苯和10.28g吡啶加入500ml三口烧瓶中,搅拌,加热至60℃,缓慢滴加约90ml二氯亚砜,控制滴加速度使反应温度不超过70℃,滴加完毕后60℃保温3h,除去溶剂甲苯及多余的二氯亚砜,得到产物用氯仿溶解待用。
c、环糊精基光引发剂P6401合成
将14gα-环糊精,50ml氯仿及12g吡啶置于500ml三口烧瓶中,升温至50℃,40min滴完b中酰氯氯仿溶液,滴完后保温反应1h;冷却至室温,加入蒸馏水洗涤三次,有机相用无水硫酸钠干燥,过滤后旋蒸,得到27.2g深棕色油状液体,收率71.2%。
二:光引发剂的应用
a、.将水性聚氨酯丙烯酸乳液,30~60份;式[Ⅰ]光引发剂,0.5~5份;颜料,8~15份;助剂,5~10份;去离子水,8~20份混合配成水溶性油墨;其中,水性聚氨酯丙烯酸乳液是由以重量份计的以下组分组成:二异氰酸酯10~20份;聚酯二元醇5~10份;二月桂酸二丁基锡0.05~0.2份;甲基丙烯酸羟丙酯10~20份;丙烯酸羟丙硅酯5~10份;阻聚剂0.05~1份;乳化剂5~10份。
b、上述油墨涂布于玻璃片上,在汞灯辐射下固化,用指压法判断固化膜的表干以表征固化速度。
c、附着力测定:利用画格法测定固化膜附着力。
d、硬度测定:利用铅笔硬度法测试固化膜硬度。
e、气味测定:将样品用线棒涂布器分别涂在PT纸上,涂布面积为1dm2,经紫外线固化机固化后,60℃恒温30min,评价其气味大小。数值越小表示气味越低。
f、黄变测试:按照GB/T1865-2009标准判定。
光引发剂P6601的测试结果如下(选取光引发剂TPO-L做对比项):
光引发剂 | 固化速度 | 附着力 | 硬度 | 气味 | 黄变(△E) |
P6401 | 25s | 5 | HB | 1 | 0.22 |
TPO-L | 60s | 3 | 2B | 3 | 0.24 |
从表中数据可知,本发明光引发剂P6401在性能测试中相比较光引发剂TPO-L,良好的水溶性体现了更快的固化速度,大分子的结构也使得固化后气味更小。
Claims (8)
3.根据权利要求2所述制备方法,步骤(2)中所述稀酸指稀盐酸或稀硫酸,步骤(3)中所述酰卤化试剂指二氯亚砜、三氯化磷、三溴化磷、五氯化磷、五溴化磷、草酰氯、光气中的一种。
4.一种权利要求1所述环糊精基光引发剂的应用,其特征在于:该环糊精基光引发剂用于UV固化配方时,配方包含:
(A)至少一种可以进行光聚合的烯属不饱和化合物和
(B)至少一种权利要求1所述的式[Ⅰ]化合物作为光引发剂。
5.根据权利要求4所述环糊精基光引发剂的应用,其特征在于:UV固化配方还可以包含其他紫外引发剂、胺促进剂、增敏剂和/或其他添加剂。
6.根据权利要求4所述环糊精基光引发剂的应用,其特征在于:UV固化配方组分(A)中烯属不饱和化合物包括:
含烯类不饱和基团预聚物;
含烯类不饱和基团的单体。
7.根据权利要求4所述环糊精基光引发剂的应用,其特征在于:该UV固化配方适用于紫外光固化体系。
8.根据权利要求4所述环糊精基光引发剂的应用,其特征在于:该UV固化配方在物体表面涂膜后经紫外光源辐射固化成型,其中所述紫外光源是高压汞灯光源或UV-LED光源;所述紫外光源波长范围是200nm-500nm。
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