CN115557986A - Si-H取代硫杂蒽酮化合物及其制备方法和光聚合体系应用 - Google Patents
Si-H取代硫杂蒽酮化合物及其制备方法和光聚合体系应用 Download PDFInfo
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- CN115557986A CN115557986A CN202110743178.5A CN202110743178A CN115557986A CN 115557986 A CN115557986 A CN 115557986A CN 202110743178 A CN202110743178 A CN 202110743178A CN 115557986 A CN115557986 A CN 115557986A
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- thioxanthone
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- 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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Abstract
本发明涉及有机功能新材料化学品领域,首次披露了一类新奇的含有硅‑氢(Si‑H)取代的硫杂蒽酮类新结构化合物,其制备方法,以及含有该类化合物的辐射固化配方材料体系及其应用。这些含硅硫杂蒽酮物质是重要的含烯不饱和体系光聚合过程的光敏引发剂(Photo‑initiator)关键精细化学品。
Description
技术领域
本发明涉及有机功能新材料化学品领域,首次披露了一类新奇的含有硅-氢(Si-H)取代的硫杂蒽酮类新结构化合物,其制备方法,以及含有该类化合物的辐射固化配方材料体系及其应用。这些含硅硫杂蒽酮物质是重要的含烯不饱和体系光聚合过程的光敏引发剂(Photo-initiator)关键精细化学品。
背景技术
硫杂蒽酮类化合物由于其优异的紫外及可见光宽泛吸收性能,是已知的应用广泛的光引发剂化合物和/或光敏化剂(Sensitizer)化合物,代表性产品是例如已经商业化的品牌为ITX或DETX,其相应的化学结构特征分别是2-位或4-位异丙基取代的硫杂蒽酮,和2-位与4-位同时乙基取代的硫杂蒽酮;
本领域技术人员所熟知的,硫杂蒽酮型化合物的一个缺陷是,恰恰由于其宽泛光吸收性能,其自身呈现(深)黄色并在光固化过程中造成明显的不良黄变现象(Yellowing),这在很多场合,特别是常见的清漆,光油,或白色体系是不可接受的。例如,将ITX或DETX与活性胺复配,形成含烯不饱和体系在光固化下优良的光聚合引发活性,特别是表干(Surface Curing)活性,是业界熟知的技术实践,但是导致的严重黄变并不适用于上述清漆,光油,或白色体系。这是长久以来亟待解决的行业技术难题。
发明内容
本项申请首次实现了通式(I)所示硅-氢(Si-H)取代的硫杂蒽酮化合物的制备,同时发现该类化合物是性能优异的耐黄变(anti-yellowing)光敏化剂和光引发剂化合物,兼具优异的UV或LED光固化表干性能。
定义R0是一个含有1-24个碳原子(标记为C1-C24)的支链或直链或环状的烷烃,或取代或非取代的(杂)芳烃基,或C=C碳-碳不饱和基;定义R是SiHR9R10,其中R9或R10分别独立地取值为R0或OR0或氢。处于硫杂蒽酮环系的R1-R8取代基彼此独立地分别是R,OH,SH,卤素原子,R0,OR0,SR0,NHR0,或N(R0)2;约束条件是,R1-R8取代基中至少一个取值为R。
符合通式(I)定义的化合物的示例性而非限定性结构如下:
通式(I)化合物的高引发活性以及其优异耐黄变性的一个物理化学结构分子机制是其在吸收光后激发态里Si-H键作为氢给体(Hydrogen Donor)能被羰基攫氢,从而自身生成高活性且耐氧性的硅自由基(Silyl Radical),进而引发含烯不饱和体系的光聚合反应。
通式(I)化合物的制备方法披露如下,其涉及硫代水杨酸前体A和Si-H取代芳烃B的酸促进直接环合反应。其中X是氢,氯,或与其相连取代基等价(即为二硫代水杨酸结构)。
我们同时批露一类新型的辐射固化新材料配方体系,其特征是:
(1) 至少含有一种本发明通式(I)披露的光引发剂或其混合物;
(2) 至少含有一种含烯键(C=C)不饱和化合物(单体或树脂)。
优选的,该配方体系中所含有的“至少一种本发明披露的光引发剂或其混合物”的添加量是0.001-50%质量百分比,更优选的是0.01-20%质量百分比;进一步更优选的是0.1-10%质量百分比。
优选的,该配方体系含有其他文献已知的光引发剂物质。
所述“文献已知的光引发剂物质”是下述任意一种光引发剂化合物或任意两种或两种以上光引发剂化合物组成的复配混合物: 包括羟基酮型(Hydroxyketones),胺基酮型(Aminoketones),膦酰型(Acylphosphine Oxides),肟酯型(Oxime Esters),二苯甲酮型(Benzophenones),苯甲酰甲酸酯型(Phenylglyoxylates),硫杂蒽酮型(Thioxanthones),鎓盐型阳离子光引发剂(Sulfoniums或Iodoniums或Photo-Acid Generators,即所谓PAGs),或染料作为实质性光敏化剂(Dye Sensitizers)的光引发剂物质。光引发剂的例子是Darocur 1173,Irgacure 184,APi-180 (深圳有为技术控股集团有限公司),APi-307(深圳有为技术控股集团有限公司),APi-308 (深圳有为技术控股集团有限公司),APi-1206 (深圳有为技术控股集团有限公司产品),APi-1207(深圳有为技术控股集团有限公司),Irgacure 2959,Irgacure MBF,Irgacure 127,Irgacure 651,Esacure KIP-150,Esacure KIP-160,Esacure KIP-1001,Esacure 01,Irgacure 907,Irgacure 500,Irgacure 2200,Irgacure 2022,Irgacure 4500,Irgacure 369,Irgacure 379,Irgacure819,Irgacure TPO,Irgacure TPO-L,BP,甲基或乙基米蚩酮,Esacure TZT,Irgacure 754,Irgacure ITX,Irgacure DETX,Irgacure CPTX,Irgacure OXE-01,Irgacure OXE-02,Irgacure OXE-03,Irgacure OXE-03,Tronly 304(常州强力电子新材料股份有限公司),Tronly 305(常州强力电子新材料股份有限公司),Irgacure 250,ADEKA NCI-831(日本艾迪科株式会社),ADEKA N-1414(日本艾迪科株式会社),Irgacure 290,Irgacure 270,以及香豆素型染料光敏化剂等,上述体系也可以复配相应的助引发剂(Co-initiator),例如活性胺,和/或氢硅烷类活性氢给体型助引发剂。
所述含烯键(C=C)不饱和化合物(单体)是任何含烯键可聚合单体,包括但不限于(甲基)丙烯酸酯,丙烯醛,烯烃,共轭双烯烃,苯乙烯,马来酸酐,富马酸酐,乙酸乙烯酯,乙烯基吡咯烷酮,乙烯基咪唑,(甲基)丙烯酸,(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺,乙烯基卤化物,亚乙烯基卤化物等。所述含烯键(C=C)不饱和化合物(树脂)是任何含烯键预聚物和低聚物,包括但不限于(甲基)丙烯酰官能基的(甲基)丙烯酸共聚物,聚氨酯甲酸酯(甲基)丙烯酸酯,聚酯(甲基)丙烯酸酯,不饱和聚酯,聚醚(甲基)丙烯酸酯,硅氧烷(甲基)丙烯酸酯,环氧树脂(甲基)丙烯酸酯等,以及上述物质的水溶性或水分散性的类似物。
所述功能性添加剂是合适的各类添加剂,为本领域技术人员所知晓的是如下各类添加剂,包括但不限于阻聚剂,活性胺助引发剂,流平剂,消泡剂,抗流挂剂,增稠剂,增粘剂,分散剂,抗静电剂,增溶剂,稀释剂,水或有机溶剂,抗菌剂,阻燃剂,无机或有机填充剂(例如纳米氧化铝,二氧化硅,碳酸钙,硫酸钡等)和/或着色剂(例如颜料或染料等),增强涂料油墨耐候性的紫外线吸收剂或/和光稳定剂,及上述组分的合适的水性分散体或水溶解性产品。
本发明披露的上述新型辐射固化材料配方体系,包括光固化涂料或油墨材料,配合各种不同的施工方式(例如喷涂,滚涂,淋涂,擦涂,浸涂等)和/或施工工序(例如腻子,底涂,上色,中涂,面涂等),在PCB油墨,激光直接成像(LDI)油墨,印刷包装油墨,木器家具,塑胶产品,印刷包装,喷墨打印,电子消费品,机动车辆内外饰,管道型材,工业地坪,建筑幕墙,3D打印增材制作,以及船舶或集装箱体等下游市场均具有极为广阔的应用价值。
特别有价值的示例性而非限定性应用例如,该等涂料或油墨用于制备着色和未着色的油漆和清漆、粉末涂料、PCB油墨、LDI油墨、印刷油墨、印版、胶粘剂、压敏胶粘剂、牙科组合物、凝胶涂料、电子器件用光致抗蚀剂、电锻抗蚀剂、蚀刻抗蚀剂、液态和干膜二者、焊接抗蚀剂、制造用于各种显示器应用的滤色器的抗蚀剂,制备等离子显示面板的制造方法中的结构、电致发光显示器和LCD的抗蚀剂,用于LCD、全息数据储存,用于包封电子组件的组合物,用于制备磁记录材料、微机械部件、波导、光学开关、锻覆掩膜、蚀刻掩膜、彩色打样体系、玻璃纤维电缆涂料、丝网印刷模版,用于借助立体光刻产生三维物体,作为图像记录材料,用于全息记录、微电子电路、脱色材料,用于图像记录材料的脱色材料,用于使用微胶囊的图像记录材料,作为光致抗蚀剂材料用于UV和可见激光直接成像体系,作为光致抗蚀剂材料用于形成印刷电路板的依序构建层中的介电层;特别地,使用上文所述的可光聚合组合物来制备着色和未着色的油漆和清漆、粉末涂料、印刷油墨(例如丝网印刷油墨、用于胶版、柔版或喷墨印刷的油墨)、印版、胶粘剂、密封件、灌封组分、牙科组合物、泡沫、模制复合物、复合 材料组合物、玻璃纤维电缆涂料、丝网印刷模版,用于借助立体光刻产生三维物体,和作为图像记录材料、光致抗蚀剂组合物、脱色材料、用于图像记录材料的脱色材料,用于使用微胶囊的图像记录材料。
在实施例中我们将进一步说明。
具体实施方式
实施例: 2-(dimethylsilyl)-9H-thioxanthen-9-one的合成
在室温和氮气保护下, 将15毫升浓硫酸加入100毫升烧瓶中,随后称取 2克的硫代水杨酸加入其中并溶解,再向其缓慢滴加2毫升二甲基苯硅烷。滴加完毕后,升温至75 ℃反应 15小时,经TLC检测反应完毕,将反应液滴加到冰水浴中淬灭,用乙酸乙酯萃取分液,洗涤,硫酸钠干燥,浓缩,和硅胶柱色谱分离得淡黄色固体产品1.3克。1H NMR (400 MHz,CD2Cl2): δ = 8.62, 8.60, 7.69-7.62 (m), 7.55-7.51 (m), 0.16。13C NMR (100 MHz,CD2Cl2): δ = 179.6, 137.3, 132.3, 129.6, 129.3, 126.3, 126.1, 0.77。
实施例: 光聚合引发活性和耐黄变性评估
含烯键(丙烯酸酯)UV辐射固化材料配方体系样品按下列配方制作(以重量百分比计):深圳有为技术公司改性双酚A环氧丙烯酸酯:23%;胺改性丙烯酸酯:12%(活性胺树脂);氨基丙烯酸酯(Ebecryl 7100):10%;三羟甲基丙烷三丙烯酸酯:22%;丙烯酰吗啉:30%;光引发剂:3%。
光固化性能评估:将上述样品涂覆于卡纸板上形成约20-25微米的涂层,以UV高压汞灯(距离基材约20厘米)为辐照光源,变速传送带试验。以指甲反复压刻刮擦不产生印迹为光聚合固化完成的判据。
结果如下:当光引发剂是3% 的2-异丙基-硫杂蒽酮,光固化完全最大线速度为45米/分钟,黄变指数为3.8;当光引发剂是3% 的实施例化合物,光固化完全最大线速度为43米/分钟,黄变指数仅为1.8。
同等条件下,以功率为16 W/cm2的395纳米LED光为辐照光源,结果如下:当光引发剂是3% 的2-异丙基-硫杂蒽酮,光固化完全最大线速度为36米/分钟,黄变指数为3.9;当光引发剂是3% 的实施例化合物,光固化完全最大线速度为35米/分钟,黄变指数仅为1.5。
上述试验展现了本发明批露化合物优异的光聚合引发活性以及耐黄变性能。
需要强调的是,上述实施例仅仅为示例性而非限定性说明,基于本项申请披露,任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨,本专利的保护范围应以相关的权利书记载条目为准。
Claims (5)
4.一类新型的辐射固化新材料配方体系,其特征是:
(1) 至少含有一种本发明通式(I)披露的光引发剂或其混合物;
(2) 至少含有一种含烯键(C=C)不饱和化合物(单体或树脂)。
5.根据权利要求(1)和(4),所述光引发剂和辐射固化配方体系,即光固化涂料或油墨材料,配合各种不同的施工方式(喷涂,滚涂,淋涂,擦涂,浸涂等)和/或施工工序(腻子,底涂,上色,中涂,面涂等),在PCB油墨,激光直接成像(LDI)油墨,印刷包装油墨,木器家具,塑胶产品,印刷包装,喷墨打印,电子消费品,机动车辆内外饰,管道型材,工业地坪,建筑幕墙,3D打印增材制作,以及船舶或集装箱体等下游市场的应用。
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