CN106117394B - 一种含有氟碳链的膦酸酯类光引发剂及其制备方法 - Google Patents
一种含有氟碳链的膦酸酯类光引发剂及其制备方法 Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
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Abstract
本发明公开了一种含有氟碳链的膦酸酯类光引发剂,所述光引发剂的化学结构如(I)所示:其中,4≤n≤18;X为亚乙氧基‑OCH2CH2‑或者X为如结构II所示的酯键
Description
技术领域
本发明涉及感光材料和光固化材料领域,更具体地说,本发明是关于一种膦酸酯类光引发剂及其制备方法。
背景技术
光固化是指有机配方材料体系在紫外光辐照下瞬间聚合交联固化的技术,其组成主要包括光固化树脂、光固化活性稀释单体、光引发剂,主要应用于涂料、油墨、胶粘剂领域。然而传统自由基型的光固化技术,尽管固化速度快,但由于自由基聚合普遍存在氧阻聚效应,光固化涂层表面始终存在不容忽视的氧阻聚,导致涂层表面聚合交联不充分,出现表层耐磨性不足,甚至表面发粘、返粘等弊病。
另一方面,传统光固化使用中压汞灯作为辐照光源,电能转换为紫外光能的效率不高,较多电能转换为热能和相对无用的红外、可见光,较大的发热量影响了光固化技术在某些热敏基材上的使用,同时在节能方面还有很大挖掘空间。有鉴于此,能够发射较窄谱带宽度紫外光的UV LED光源可以在光固化领域获得应用,产生更高的节能效益和更小的热效应。然而光固化领域适合主流385-395nm 发射UV LED的光引发剂性能普遍不佳,现有光引发剂对385-395nm发射紫外光的吸收能力较低,感光产生自由基的效率不高,依然导致严重表面氧阻聚,限制UV LED在光固化中的应用。
发明内容
本发明要解决的技术问题是针对现有技术的不足,提供一种具有较低表面张力、能够有效抑制氧阻聚效应的光引发剂。该光引发剂可在涂层配方中富集于涂层表面,提高涂层表层的光引发剂浓度,在长波紫外性质的UV LED光源辐照下,可有效抑制涂层表面的氧阻聚效应,促进整个涂层由表及里的完善固化,获得性能更佳的光固化涂层。
本发明要解决的另一技术问题是提供一种长波吸收、高效率的光引发剂的制备方法。
为了解决第一个技术问题,本发明提供了一种含有氟碳链的膦酸酯类光引发剂,所述光引发剂的化学结构如(I)所示:
其中,4≤n≤18;
X为亚乙氧基-OCH2CH2-或者
X为如结构II所示的酯键
所述光引发剂中,其氧化的磷原子同时连有一个通过X基团连接的氟碳烷基。长链氟碳烷基包括碳原子数为4-18的全氟碳直链烷基。
本发明要解决的另一技术问题是提供一种制备制备含有氟碳链的膦酸酯类光引发剂的方法,通过化合物A与化合物B取代反应或环氧基开环酯化反应制得,
所述化合物A的化学结构如(III)所示:
其中,M表示H或Na或K;
所述化合物B为全氟烷基乙基碘或全氟烷基乙基溴或全氟烷基羧酸缩水甘油酯,当所述化合物B为全氟烷基乙基碘或全氟烷基乙基溴时,所述全氟烷基为碳原子数4-18的直链基团,当所述化合物B为全氟烷基羧酸缩水甘油酯时,所述全氟烷基为碳原子数3-17的直链结构。其中,全氟烷基乙基碘分子式为 CF3(CF2)nCH2CH2I,全氟烷基乙基溴分子式为CF3(CF2)nCH2CH2Br,全氟烷基羧酸缩水甘油酯化学结构式如下所示:
本发明通过在化合物A上,即在芳甲酰基芳基膦酸或其钠、钾盐上引入足够长度的氟碳链,获得氟碳链改性的膦酸酯类光引发剂,具有较低的表面张力,于常规光固化配方中极易上浮,富集于涂层表面。其最大吸收波长375nm,相应摩尔消光系数ε为218L·mol-1·cm-1左右。
具体来说,本发明可通过化合物A与带有碘取代烷基、溴取代烷基、缩水甘油基的官能化氟碳链化合物通过取代反应或环氧基开环酯化反应获得所述光引发剂。
优选的,所述制备方法中,所述化合物A与化合物B的摩尔比为0.95-1.0: 1.0。所述取代反应或环氧基开环酯化反应的反应温度为60-80℃。待反应至基本完全,分离除去无机盐沉淀,蒸馏除去有机溶剂和可能存在的过剩含氟原料,获得目标产物。
所述取代反应或环氧基开环酯化反应优选中等至较高极性的溶剂环境下进行,所述溶剂优选为总数7-9个碳原子的烷基取代苯系溶剂、4-6个碳原子的酮类溶剂或者4-7个碳原子的酯类溶剂。
本发明合成的氟碳链膦酸酯光引发剂在375nm左右具有吸收峰,摩尔消光系数ε为218L·mol-1·cm-1左右,吸收峰红向拖尾覆盖385、395nm,添加于丙烯酸酯单体和/或丙烯酸酯化的树脂体系中,可用365-395nm主发射的UV-LED光源实施有效固化,以其较低表面张力,克服表面氧阻聚。
具体实施方式
实施例1
2,4,6-三甲苯甲酰基苯基膦酸钠0.095mol与0.10mol全氟辛基乙基碘在200 ml甲苯中,快速搅拌,60℃加热反应20小时,取少量沉淀不溶物,用丙酮清洗 ,热风吹干,进行红外光谱测试,确证红外吸收光谱中2900cm-1附近及1658cm-1处代表2,4,6-三甲苯甲酰基苯基膦酸盐的特征吸收峰完全消失,说明反应进行完全。结束反应,过滤,滤液减压蒸馏,除去溶剂,得液态产物72.5克。质谱测试证明含有目标产物对应的分子离子峰734。
实施例2
2,4,6-三甲苯甲酰基苯基膦酸钾0.095mol与0.10mol全氟丁基乙基溴在200 ml乙酸丁酯中,快速搅拌,80℃加热反应10小时,取少量沉淀不溶物,丙酮清洗,热风吹干,进行红外光谱测试,证实苯甲酰基膦酸盐特征结构消失,反应完全。结束反应,过滤,滤液减压蒸馏,除去溶剂,得液态产物52.8克。质谱测试证明含有目标产物对应的分子离子峰534。
实施例3
2,4,6-三甲苯甲酰基苯基膦酸钠0.095mol与0.1mol全氟十八烷基乙基碘在200ml环己酮中,快速搅拌,80℃加热反应16小时,取少量沉淀不溶物,丙酮清洗,热风吹干,进行红外光谱测试,证实苯甲酰基膦酸盐特征结构消失,反应完全。结束反应,过滤,滤液减压蒸馏,除去溶剂,得液态产物122.9克。质谱测试证明含有目标产物对应的分子离子峰1234。
实施例4
2,4,6-三甲苯甲酰基苯基膦酸0.10mol与0.10mol全氟辛酸缩水甘油酯在 200ml甲苯中,加入0.005mol的四丁基溴化铵,搅拌,80℃加热反应8小时,取少量溶液样本,热风挥干溶剂,进行红外光谱测试,红外光谱图中910cm-1附近原本归属为环氧基的特征吸收峰完全消失,说明反应已完全。结束反应,溶液减压蒸馏,除去溶剂,得液态产物75.2克。质谱测试证明含有目标产物对应的分子离子峰758。
实施例5
2,4,6-三甲苯甲酰基苯基膦酸0.10mol与0.10mol全氟丁酸缩水甘油酯在 200ml乙酸丁酯中,加入0.005mol的四丁基溴化铵,搅拌,60℃加热反应9小时,取少量溶液样本,热风挥干溶剂,进行红外光谱测试,红外光谱图中910cm-1附近原本归属为环氧基的特征吸收峰完全消失,说明反应已完全。结束反应,溶液减压蒸馏,除去溶剂,得液态产物55.0克。质谱测试证明含有目标产物对应的分子离子峰558。
实施例6
光固化性能对照实验,光固化树脂和活性稀释剂均为市场获得通用品,TPO 与Darocure 1173(简称D1173)为市场通用型光引发剂。辐照光源包括中压汞灯与UV LED。其中,中压汞灯2000W,辐照面光强180mW/cm2,含有UVA和 UVB紫外线;365nm UV LED、385nmUV LED、395nm UV LED光源辐照面光强分别为86、155、220W/cm2,含有UVA紫外线,但不含UVB紫外线。
取环氧丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三乙二醇三丙烯酸酯、光引发剂混合均匀,四者的重量比分别为55%、26%、15%和4%,滚涂于玻璃板上,以不同规格紫外光源辐照30秒,分别用手指触压、丙酮擦拭后表面光泽度变化等指标检验涂层表面固化情况,条件与结果如表1所示,其中,╳表示有指纹印,〇表示无指纹印,丙酮擦拭采用棉球蘸取,单次单向擦拭方法。
表1
Claims (5)
1.一种含有氟碳链的芳甲酰基膦酸酯类光引发剂,其特征在于,所述光引发剂的化学结构如(I)所示:
其中,4≤n≤18;
X为亚乙氧基-OCH2CH2-或者
X为如结构II所示的酯键
2.一种制备含有氟碳链的膦酸酯类光引发剂的方法,其特征在于,通过化合物A与化合物B取代反应或环氧基开环酯化反应制得,
所述化合物A的化学结构如(III)所示:
其中,M表示H或Na或K;
所述化合物B为全氟烷基乙基碘或全氟烷基乙基溴或全氟烷基羧酸缩水甘油酯,当所述化合物B为全氟烷基乙基碘或全氟烷基乙基溴时,所述全氟烷基为碳原子数4-18的直链基团,当所述化合物B为全氟烷基羧酸缩水甘油酯时,所述全氟烷基为碳原子数3-17的直链结构。
3.根据权利要求2所述制备膦酸酯类光引发剂的方法,其特征在于,所述化合物A与化合物B的摩尔比为0.95-1.0:1.0。
4.根据权利要求2所述制备膦酸酯类光引发剂的方法,其特征在于,所述取代反应或环氧基开环酯化反应的反应温度为60-80℃。
5.根据权利要求2所述制备膦酸酯类光引发剂的方法,其特征在于,所述取代反应或环氧基开环酯化反应在总数7-9个碳原子的烷基取代苯系溶剂、4-6个碳原子的酮类溶剂或者4-7个碳原子的酯类溶剂中进行。
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