CN105837731A - 大分子光引发剂及其制备方法 - Google Patents
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- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
本发明属于光固化领域,具体涉及一种大分子光引发剂及其制备方法,一种大分子光引发剂,其特征在于,所述的光引发剂的化学结构如(I)示出:
Description
技术领域
本发明属于光固化领域,具体涉及一种大分子光引发剂及其制备方法。
背景技术
自1946年美国某公司首次发表了不饱合聚酯/苯乙烯紫外光UV固化技术专利,光固化技术在光固化涂料、光刻胶、光固化油墨、电子封装材料、粘合剂、光盘复制、纸张上光等工业领域得到广泛应用,光固化技术保持高速发展。紫外光固化涂料在木器上得到长足发展,主要优点包括:第一,干燥速度快。在施工过UV涂料后,只需经过几秒钟的紫外光照射,便可在瞬间成膜。第二,一次性成膜厚。UV涂料可制成100%固含量,提高了生产效率。第三,较低的有机成分挥发(VOC),比传统的溶剂型涂料更环保。但是由于紫外光固化涂料的单体毒性大,最终成膜后仍会有少量单体残留,对施工人员的身体健康不利,对环境也有一定影响,目前最环保的产品首推水性木器漆,该产品以水为稀释剂,无毒无味,全环保,对环境和人体均无害,在近些年得到迅速发展。但是目前的水性木器漆产品以单组份为主,干燥速度、物理性能存在局限性。在这一大环境下,水性木器UV涂料应运而生,兼具备了水性漆的环保和UV漆的干燥快速的特点,不含小分子丙烯酸酯单体,无化学迁移,毒性残留小。
双(2,4,6-三甲基苯甲酰基)-苯基-氧化膦是当前水性UV常用的高效光引发剂,但是,由于其较低的分子量,易在施工后的干膜中产生迁移、挥发,气味长期残留于漆膜中;同时该引发剂亲水性不足,长期储存后容易析出,水性体系的稳定性和相容性影响整体涂膜的干燥效果。同时在长时间的储存过程及成膜后,小分子型光引发剂由于与光固体系相容性差和活动性强而容易发生挥发和迁移,这一方面导致了光聚合引发效率低,另一方面也会导致产品黄变、产生气味和毒性,难以符合环保要求。
发明内容
本发明的目的在于克服现有技术中小分子型光引发剂亲水性不足,容易发生挥发和迁移的问题,提供一种新型的光引发剂。
为实现本发明的目的所采用的技术方案是:
一种光引发剂,所述的光引发剂的化学结构如(I)示出:
其中,m=50-500,n=50-500。R选自氢或者含有2-4个碳原子的烷基或者烷氧基。
制备光引发剂的方法,采用下述步骤:
1)制备4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物,结构式如(II)所示:
2)经步骤1)下述重量份的组分室温混合,
4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物 0.5-0.8份
丙烯酸 10-15份
苯乙烯 4-6份
偶氮二异丁腈 0.1-0.2份
3)经步骤2)得到的混合物加热至60-70℃,反应6小时;
4)步骤3)得到的产物经离心分离,得到白色共聚物,用有机溶剂洗涤,干燥,最后得到目标产物。
所述步骤4)得到的目标产物为不规则的共聚产物。
所述的步骤4)得到的目标产物中光敏单体在共聚合物中的重量含量为4-5.5%,所述的光敏单体为苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物。
其中,步骤4)中的有机溶剂为体积比石油醚:乙酸乙酯=2:1,
与现有技术相比,本发明的有益效果是:
1)首先,与现有的光引发剂相比,本发明所述的光引发剂属于大分子光引发剂,具有抗迁移性的特点,且不容易挥发,更适用于卫生要求较高的光固化领域。
2)其次,本发明所选用的光引发剂为有机膦类大分子光引发剂,该引发剂具有更高的光引发活性,使得光固化速率更快,固化更完善。
3)最后,本发明的光引发剂为亲水性强,长期储存后不容易析出,使成膜后整体的干燥性能提高。
具体实施方式
为了使本技术领域的技术人员更好地理解本发明的技术方案,下面结合实施例对本发明作进一步的详细说明。
实施例1:4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物的制备。
以下今仅给出关于4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物常用的制备方法:
1):起始原料4-乙烯基苯基二氯化膦的制备,如式(III)示出。
4-乙烯基苯基二氯化膦可按文献方法(CA:56:46102)由4-乙基苯基二氯化膦经氯化、高温BaCl2作用下脱HCl方法制得;亦可采用另外的文献报道类似方法(J.Chem.Soc.1935,462;J.Chem.Soc.1944,276.)由苯乙烯与PCl3在无水AlCl3作用下制得。
2):单体4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物的制备如式(IV)示出:
典型操作:在干燥的氮气氛下,向300mL甲苯中加入金属锂屑(6.5g,0.92mol)及结晶萘(1.0g,0.008mol),室温搅拌10min,反应混合物变为深黑色。继续搅拌,滴加4-乙烯基苯基二氯化膦(41.0g,0.20mol)在120mL甲苯中的溶液,滴加过程中控制反应温度在20-25℃,1小时左右滴加完,并继续反应0.5小时。然后在冰水浴冷却及搅拌下,向反应混合物中滴加2,4,6-三甲基苯甲酰氯(73.0g,0.4mol)在200mL甲苯中的溶液,1.5小时滴加完,并在室温下继续反应1小时。然后将反应混合物温热至30-40℃,并在快速搅拌下滴加30%双氧水水溶液(23.0g,0.2mol),并反应0.5小时。停止反应。向反应混合物中加入40mL水,搅拌、过滤并分液,有机相分别用10%NaHCO3溶液和水各洗2次,无水MgSO4干燥。经过滤及减压下脱除溶剂后,得粗产品82.6g。此粗产品经石油醚-乙酸乙酯(体积比为9:1,120-200mL)重新析出,去除溶液相后经真空干燥,得淡黄色固体73.0g(收率82%),产品结构经1HNMR、31PNMR检验,纯度达95%。
3)大分子光引发剂的制备如反应式(V)示出:
下述重量份的组分室温混合,
4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物 0.5份
丙烯酸 10份
苯乙烯 4份
偶氮二异丁腈 0.1份
3)经步骤2)得到的混合物加热至60-70℃,反应6小时;
4)步骤3)得到的产物经离心分离,得到白色共聚物,用有机溶剂洗涤,干燥,最后得到目标产物1#。
所用的有机溶剂为体积比石油醚:乙酸乙酯=2:1。
产品经1H NMR测定(溶剂:DMSO-d6),光敏单体在共聚物中的含量约占重量的5.5%。经测定,此共聚物在pH为7的水溶液介质中溶解度可达12g/L(需加NaOH水溶液调节溶液pH值),显示出较好的水溶性。
实施例2:
实施例2中4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物的制备方法与实施例1相同,区别仅为大分子光引发剂中各组分的重量份为:
4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物 0.8份
丙烯酸乙酯 15份
苯乙烯 6份
偶氮二异丁腈 0.2份
得到目标产物,产品经1H NMR测定(溶剂:DMSO-d6),光敏单体在共聚 物中的含量约占重量的4.9%。经测定,此共聚物在pH为7的水溶液介质中溶解度可达8g/L(需加NaOH水溶液调节溶液pH值),显示出较好的水溶性。
实施例3:
实施例3中4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物的制备方法与实施例1相同,区别仅为大分子光引发剂中各组分的重量份为:
4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物 0.6份
丙烯酸 12份
苯乙烯 5份
偶氮二异丁腈 0.15份
得到目标产物,产品经1HNMR测定(溶剂:DMSO-d6),光敏单体在共聚物中的含量约占重量的4.5%。经测定,此共聚物在pH为7的水溶液介质中溶解度可达10g/L(需加NaOH水溶液调节溶液pH值),显示出较好的水溶性。
实验效果测试,对比四种光引发的引发效率。
在光固化色漆实验性配方中,保持各组分的含量不变,通过改变光引发剂的种类配制成不同的光固化色漆配方,其中,三组对比的实验配方所选用的光引发剂分别为二苯甲酮,汽巴500以及汽巴819DW(BAPO)。
试验方法:
1:固化性比较
本实施例和对照例中的配方组分包含光引发剂,氨基甲酸酯丙烯酸酯分散体(Bayhydrol UV VP LS 2282),去离子水以及表面助剂-流平剂(毕克化学BYK346)、消泡剂(迪高TEGO810)各组分的重量百分含量如表1所示:
表1
成分 | 重量百分比% |
光引发剂 | 3 |
氨基甲酸酯丙烯酸酯分散体 | 70 |
去离子水 | 26 |
表面助剂-流平剂、消泡剂 | 1 |
配制成的清漆1-6#(其中1#为实施例1产物配置而成,2#为实施例2,3#为实施例3,4#为二苯甲酮,5#为汽巴500,6#为汽巴819DW)
用10微米线棒涂布器施工于马口铁板上,用一台功率2KW汞灯以10米/分钟速度进行固化,光能380mj/c㎡。记录获得良好的表面效果及彻底固化所需要的灯下次数,气味最大的为5级,气味最小的为1级。黄度由SC-80C全自动色差仪测定。结果如表2所示。
表2
其中:1为最好,5为最差
2:防水性比较:
在固化后漆膜表面放置浸透水分的湿布,放置6-8小时,本发明3个产品表面均没有水痕,得到很好的防水效果。
3.硬度比较:用摆杆硬度计测试,中华铅笔,1KG力。结果如表3示出。
表3
1# | 2H++ |
2# | 2H |
3# | 2H+ |
4# | HB |
5# | HB |
6# | HB |
试验结果:
这些结果表明,本发明的三种光引发剂化合物的固化速度高于对比引发剂的固化速度。用本发明化合物(APBPO)做光引发剂的清漆固化后的臭味都低于用二苯甲酮、汽巴500、汽巴819DW(BAPO)做引发剂的清漆,所有清漆固化后的黄变也有差异。且长期储存后,用二苯甲酮和汽巴500制成的清漆,全部固化所需的通过次数增加,说明引发剂亲水性不足,造成长期储存后引发剂的析出,水性体系的稳定性和相容性影响整体涂膜的干燥效果。而汽巴819DW(BAPO)做引发剂的清漆,虽然引发效率没有变,但气味也远大于用APBPO制成清漆紫外光固化涂膜的气味。同时本发明测试了三种光引发剂的防水性能,以及硬度比较,从结果可以看出,本发明的光引发剂性能上均优于现有的光引发剂。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (5)
1.一种大分子光引发剂,其特征在于,所述的光引发剂的化学结构如(I)示出:
其中,m=50-500,n=50-500,R选自氢或者含有2-4个碳原子的烷基或者烷氧基。
2.一种制备权利要求1所述的大分子光引发剂的方法,其特征在于,采用下述步骤:
1)制备4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物,结构式如(II)所示:
2)经步骤1)下述重量份的组分室温混合,
4-乙烯基苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物 0.5-0.8份
丙烯酸类单体 10-15份
苯乙烯 4-6份
偶氮二异丁腈 0.1-0.2份
3)经步骤2)得到的混合物加热至60-70℃,反应6小时;
4)步骤3)得到的产物经离心分离,得到白色共聚物,用有机溶剂洗涤,干燥,最后得到目标产物。
其中,所述丙烯酸类单体为丙烯酸、丙烯酸甲酯或者丙烯酸乙酯中的一种。
3.根据权利要求2所述的制备大分子光引发剂的方法,其特征在于,所述步骤4)得到的目标产物为不规则的共聚产物。
4.根据权利要求3所述的制备大分子光引发剂的方法,其特征在于,所述的步骤4)得到的目标产物中光敏单体在共聚合物中的重量含量为4-5.5%,所述的光敏单体为苯基-双(2,4,6-三甲基苯甲酰基)膦氧化物。
5.根据权利要求2所述的制备大分子光引发剂的方法,其特征在于,步骤4)中的有机溶剂为体积比石油醚:乙酸乙酯=2:1。
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