CN112409587A - 制备聚碳酸酯光引发剂的方法及一种涂料 - Google Patents
制备聚碳酸酯光引发剂的方法及一种涂料 Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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Abstract
本发明属于涂料技术领域。针对现有的光固化涂料中使用的小分子引发剂存在的易挥发、毒性、分子迁移率高的上述问题,提供一种制备聚碳酸酯光引发剂的方法及一种涂料。一种制备聚碳酸酯光引发剂的方法,包括以下步骤:将小分子引发剂Irgacure 2959以及碳酸二酯溶于有机溶剂或者离子液体中,随后加入催化剂在30‑120℃条件下,反应0.5‑36h;停止反应,将产物反沉淀在反溶剂中析出,会得到沉淀产物,重复溶解‑反沉淀洗涤3次除去杂质,干燥最后最终产物。本发明通过高分子聚合方法,将小分子化的引发剂制备成高分子光引发剂,其引发剂活性比现有的小分子引发剂引发活性更高,同时在固化涂层中迁移率低,挥发性低,毒性小。
Description
技术领域
本发明属于涂料技术领域,具体涉及一种制备聚碳酸酯光引发剂的方法及一种涂料。
背景技术
UV光聚合体系主要构成部分有:光固化树脂、UV单体、UV引发剂构成,同时根据需要,还会加入助剂、颜填料组分来达到特定性能。最为一门新兴技术,具有高效、经济、节能、环境友好、适应性广等显著特点,目前已经在3C,木器漆、包装等领域具有广泛应用。
其中UV引发剂是产生聚合的关键,紫外线的照射可以激发出活性自由基从而促使分子之间的交联成膜,光引发剂作用原理的不同,可以分为两类:第一类为裂解型光引发剂,目前主流使用的包括,2-羟基-2-甲基-1-苯基-1-丙酮(1173)以及1-羟基环己基苯基甲酮(184),以及深层固化的2,4,6-三甲基苯甲酰基-二苯基氧膦(TPO),苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)等引发剂;第二类为夺氢型光引发剂,主流使用的包括二苯甲酮(BP),邻苯甲酰苯甲酸甲酯(OMBB),4-氯二苯甲酮(CPB),4-苯基二苯甲酮(PBZ)等。虽然第一类引发剂则种类较多,不同结构的引发剂可以赋予净味、耐黄、引发效率快速、深层固化等性质,但是由于都是小分子量,还是存在挥发、毒性、分子迁移率高等缺点,从而限制了其应用范围。
发明内容
针对现有的光固化涂料中使用的小分子引发剂存在的易挥发、毒性、分子迁移率高的上述问题,本发明提供一种制备聚碳酸酯光引发剂的方法及一种涂料,通过高分子聚合方法,将小分子化的引发剂制备成高分子光引发剂,其引发剂活性比现有的小分子引发剂引发活性更高,同时在固化涂层中迁移率低,挥发性低,毒性小。
一种制备聚碳酸酯光引发剂的方法,包括以下步骤:
(1)将小分子引发剂2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮(Irgacure 2959)以及碳酸二酯溶于有机溶剂或者离子液体中,随后加入催化剂,催化剂的摩尔量为碳酸二酯摩尔量的0.01%-10%,在30-120℃条件下,反应0.5-36h;
所述小分子引发剂与所述碳酸二酯的摩尔比为:1:(0.3-8);
所述催化剂选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5-二氮杂双环[4.3.0]壬-5-烯、三乙胺、4-二甲氨基吡啶、吡啶、二月桂酸二丁基锡、1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-亚基、1,3-二叔丁基咪唑-2-亚基、三乙烯二胺中的至少一种;
所述离子液体为咪唑类离子液体、吡啶类离子液体和季铵盐类离子液体中的至少一种;
(2)停止反应,将产物反沉淀在反溶剂中析出,得到目标反沉淀产物,重复溶解-反沉淀洗涤3次,干燥最后最终产物。
所制备的聚碳酸酯光引发剂的结构如下:
其中R为苯环、甲基、乙基或者烯丙基。
进一步的,步骤(1)中,所述碳酸二酯试剂选自以下至少一种:
进一步的,步骤(1)中,所述小分子引发剂与所述碳酸二酯的摩尔比为:1:(1-3)。
进一步的,步骤(1)中,所述有机溶剂为乙酸乙酯、乙酸丁酯、乙腈、DMF、DMSO、甲苯、二甲苯和二氯甲烷中的至少一种。
进一步的,步骤(1)中,所述咪唑类离子液体为以下至少一种:
所述吡啶类离子液体为以下至少一种:
所述季铵盐类离子液体为以下至少一种:
进一步的,步骤(1)中,反应温度范围为60-80℃,反应时间为12-24h。
进一步的,步骤(2)中,所使用的反溶剂为石油醚和/或乙醚。
本发明还提供一种光固化涂料,采用以上制备的聚碳酸酯光引发剂,按照质量百分比计,其组分组成为:
环氧丙烯酸酯20-30%,聚酯丙烯酸酯或者聚氨酯丙烯酸酯25-35%,流平剂0.1-0.5%,消泡剂0.1-0.3%,分散剂0.5-1.5%,粉料15-25%,聚碳酸酯光引发剂2-7%,单体二丙二醇二丙烯酸酯或者二丙二醇二丙烯酸酯15-22%,以上各组分总和为100%。
进一步的,其组分组成为:
环氧丙烯酸酯25%,聚酯丙烯酸酯或者聚氨酯丙烯酸酯30%,流平剂0.3%,消泡剂0.2%,分散剂1%,粉料20%,聚碳酸酯光引发剂5%,单体二丙二醇二丙烯酸酯或者二丙二醇二丙烯酸酯18.5%。
与现有技术相比,本发明具有以下有益效果:
本发明通过碳酸二酯的酯交换法制备的聚碳酸酯光引发剂,其引发剂活性比现有的小分子引发剂引发活性更高,同时在固化涂层中迁移率低,而且挥发性低,耐黄变性好,气味小,储存稳定性好,避免了小分子引发剂可导致的毒性,气味等问题,产品适合于食品包装,3C电子器件,以及木器家具涂装等领域。
附图说明
图1为实施例1聚碳酸酯光引发剂红外谱图。
具体实施方式
下面结合具体实施例及附图对本发明做进一步详细说明。
实施例1
一种通过碳酸二酯的酯交换法制备聚碳酸酯光引发剂的方法,关于引发剂的制备过程如下所述:
(1)将小分子引发剂(Irgacure 2959)1mol,以及碳酸二苯酯试剂2mol溶于乙酸乙酯中,随后加入三乙胺催化剂10mmol,在60℃条件下,反应12h。
(2)停止反应,将产物反沉淀在乙醚中,得到产物,重复溶解-反沉淀洗涤3次,干燥最后最终产物。
最后产物为白色粉末,产率为86.2%,红外谱图如下文图1所示,在3405cm-1为–OH峰,1755cm-1为碳酸酯基团峰,说明成功制备出含碳酸酯结构的大分子光引发剂。
实施例2
一种通过碳酸二酯的酯交换法制备聚碳酸酯光引发剂的方法,关于引发剂的制备过程如下所述:
(1)将小分子引发剂(Irgacure 2959)1mol,以及碳酸二苯酯试剂3mol溶于乙酸乙酯中,随后加入二乙胺催化剂20mmol,在50℃条件下,反应24h。
(2)停止反应,将产物反沉淀在乙醚中,得到产物,重复溶解-反沉淀洗涤3次,干燥最后最终产物。
本实验案例条件不同于实验案例1,最后产物为白色粉末,产率为81.7%,说明在不同条件下也可以制备出含碳酸酯结构的大分子光引发剂。
实施例3
一种通过碳酸二酯的酯交换法制备聚碳酸酯光引发剂的方法,关于引发剂的制备过程如下所述:
(1)将小分子引发剂(Irgacure 2959)1mol,以及碳酸二苯酯试剂3mol溶于BminCl离子液体中,随后加入吡啶催化剂20mmol,在90℃条件下,反应6h。
(2)停止反应,将产物反沉淀在乙醚中,得到产物,重复溶解-反沉淀洗涤3次,干燥最后最终产物。
本实验案例条件不同于实验案例1和2,最后产物为白色粉末,说明在不同条件下也可以制备出含碳酸酯结构的大分子光引发剂。
实施例4
一种光固化涂料,按照质量百分比计,其组分组成为:
环氧丙烯酸酯25%(三木化学SM6105-80),聚酯丙烯酸酯30%(科田化学2202),流平剂0.3%(BYK358N),消泡剂0.2%(Tego920),分散剂1%(BYK2009),粉料20%,实施例1制备的碳酸二苯酯型大分子光引发剂5%,单体二丙二醇二丙烯酸酯(DPGDA)用量18.5%。
此配方制备得到的涂料按照机械喷涂方法喷涂于水曲柳木材表面,经紫外光快速固化,可极大的提高生产效率,其性能检测结果如表1所示。
实施例5
一种光固化涂料,按照质量百分比计,其组分组成为:
环氧丙烯酸酯25%(三木化学SM6105-80),聚氨酯丙烯酸酯30%(科田化学2202),流平剂0.3%(BYK358N),消泡剂0.2%(Tego920),分散剂1%(BYK2009),粉料20%,实施例2制备的碳酸二甲酯型大分子光引发剂5%,单体二丙二醇二丙烯酸酯(DPGDA)用量18.5%。
此配方制备得到的涂料按照机械喷涂方法喷涂于水曲柳木材表面,经紫外光快速固化,可极大的提高生产效率,其性能检测结果如表1所示。
实施例6
一种光固化涂料,按照质量百分比计,其组分组成为:
聚酯丙烯酸酯25%(科田化学2202),聚氨酯丙烯酸酯30%(长兴化学61438),流平剂0.3%(BYK358N),消泡剂0.2%(Tego920),分散剂1%(BYK2009),粉料20%,实施例3制备的碳酸二乙酯型大分子光引发剂5%,单体三丙二醇二丙烯酸酯(TPGDA)用量18.5%。
此配方制备得到的涂料按照机械喷涂方法喷涂于水曲柳木材表面,经紫外光快速固化,可极大的提高生产效率,其性能检测结果如表1所示。
实施例7
一种光固化涂料,按照质量百分比计,其组分组成为:
聚酯丙烯酸酯25%(科田化学2202),聚氨酯丙烯酸酯30%(长兴化学61438),流平剂0.3%(BYK358N),消泡剂0.2%(Tego920),分散剂1%(BYK2009),粉料20%,实施例1制备的碳酸二苯酯型大分子光引发剂3%,碳酸二乙酯型大分子光引发剂2%,单体三丙二醇二丙烯酸酯(TPGDA)用量18.5%。
此配方制备得到的涂料按照真空喷涂方法喷涂于水曲柳木材表面,经紫外光快速固化,可极大的提高生产效率,其性能检测结果如表1所示。
实施例8
一种通过碳酸二酯的酯交换法制备聚碳酸酯光引发剂的方法,按照质量百分比计,涂料组分组成为:
聚酯丙烯酸酯25%(科田化学2202),聚氨酯丙烯酸酯30%(长兴化学61438),流平剂0.3%(BYK358N),消泡剂0.2%(Tego920),分散剂1%(BYK2009),粉料20%,实施例2制备的碳酸二甲酯型大分子光引发剂3%,碳酸二烯丙基型大分子光引发剂2%,单体三丙二醇二丙烯酸酯(TPGDA)用量18.5%。
此配方制备得到的涂料按照机械喷涂方法喷涂于水曲柳木材表面,经紫外光快速固化后流平性和附着力极佳,能够有效保护基材,提高装饰美感。
表1实施例4-8的性能检测结果
为了充分说明本发明的聚碳酸酯光引发剂的性能,特做如下性能对比:
表2对引发剂性能对比测试实验
对上述的表格测试性能指标效果如下表3所示:
表3性能对比测试
性能指标 | 方案1 | 方案2 | 方案3 | 方案4 |
气味 | 净味 | 净味 | 刺激 | 刺激 |
耐黄性 | 高度耐黄 | 耐黄 | 耐黄 | 耐黄 |
引发活性 | 高活性 | 高活性 | 高活性 | 高活性 |
挥发性 | 难挥发 | 易挥发 | 易挥发 | 易挥发 |
相容性 | 易溶解 | 易溶解 | 易溶解 | 易溶解 |
上述实验说明本发明制备的聚碳酸酯型光引发剂和小分子引发剂相比,固化气味较低,同时漆膜高度耐黄,挥发性低,可以有效避免小分子引发剂的缺点,在聚合过程中聚碳酸酯型大分子引发剂综合性能比较优异,具有较大应用价值。
以上所述的实施例仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案作出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (9)
1.一种制备聚碳酸酯光引发剂的方法,其特征在于,包括以下步骤:
(1)将小分子引发剂2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮以及碳酸二酯溶于有机溶剂或者离子液体中,随后加入催化剂,催化剂的摩尔量为碳酸二酯摩尔量的0.01%-10%,在30-120℃条件下,反应0.5-36h;
所述小分子引发剂与所述碳酸二酯的摩尔比为:1:(0.3-8);
所述催化剂选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5-二氮杂双环[4.3.0]壬-5-烯、三乙胺、4-二甲氨基吡啶、吡啶、二月桂酸二丁基锡、1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-亚基、1,3-二叔丁基咪唑-2-亚基、三乙烯二胺中的至少一种;
所述离子液体为咪唑类离子液体、吡啶类离子液体和季铵盐类离子液体中的至少一种;
(2)停止反应,将产物反沉淀在反溶剂中析出,得到目标反沉淀产物,重复溶解-反沉淀洗涤3次,干燥最后最终产物。
3.根据权利要求1所述的方法,其特征在于,步骤(1)中,所述小分子引发剂与所述碳酸二酯的摩尔比为:1:(1-3)。
4.根据权利要求1所述的方法,其特征在于,步骤(1)中,所述有机溶剂为乙酸乙酯、乙酸丁酯、乙腈、DMF、DMSO、甲苯、二甲苯和二氯甲烷中的至少一种。
6.根据权利要求1所述的方法,其特征在于,步骤(1)中,反应温度范围为60-80℃,反应时间为12-24h。
7.根据权利要求1所述的方法,其特征在于,步骤(2)中,所使用的反溶剂为石油醚和/或乙醚。
8.一种光固化涂料,其特征在于,采用权力要求1制备的聚碳酸酯光引发剂,按照质量百分比计,其组分组成为:
环氧丙烯酸酯20-30%,聚酯丙烯酸酯或者聚氨酯丙烯酸酯25-35%,流平剂0.1-0.5%,消泡剂0.1-0.3%,分散剂0.5-1.5%,粉料15-25%,聚碳酸酯光引发剂2-7%,单体二丙二醇二丙烯酸酯或者二丙二醇二丙烯酸酯15-22%,以上各组分总和为100%。
9.根据权力要求8所述的光固化涂料,其特征在于,其组分组成为:
环氧丙烯酸酯25%,聚酯丙烯酸酯或者聚氨酯丙烯酸酯30%,流平剂0.3%,消泡剂0.2%,分散剂1%,粉料20%,聚碳酸酯光引发剂5%,单体二丙二醇二丙烯酸酯或者二丙二醇二丙烯酸酯18.5%。
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