新型阳离子光引发剂双茂铁芳烃盐的制备及其应用 Novel Cationic photoinitiators preparation and application of agents double ferrocene aromatic salt

技术领域 Technical Field

本发明涉及一种新型的阳离子光聚合弓I发剂，合成了一系列[二(环戊二烯一铁)芳烃]盐的一类双茂铁芳烃盐，属于有机合成及阳离子光聚合技术领域。 The present invention relates to a novel cationic photopolymerization initiator bow I synthesized a series of [bis (cyclopentadienyl-Fe) arene] a class of two ferrocene aromatic salt salts, organic synthesis and belong to the technical field cationic photopolymerization . 背景技术 Background

紫外光（uv)固化具有固化速度快、节省能源、无环境污染、涂层性能优异、经济效益高等特点。 Ultraviolet (uv) curing with a curing speed, energy saving, pollution-free environment, excellent coating properties, and high economic efficiency. 最早研究的uv固化体系是自由基光固化体系，与其 The earliest studies of uv light curing system is a free radical curing system, with its

相比，阳离子光固化体系具有以下突出特点：①光引发阳离子单体和预聚体种 Compared cationic UV curing system has the following salient features: ① photoinitiator cationic monomers and prepolymers species

类多；②不受氧阻聚；③阳离子光聚合是活性聚合。 Class of; ② without oxygen inhibition; ③ cationic photo polymerization is a living polymerization.

自由基型光引发剂种类众多，且发展已比较成熟，而阳离子型的光引发剂种类较少，常用的为二芳基碘鐵盐和三芳基硫鎿盐，且大多数碘鎿盐和硫鐵盐在300nm以上很少或几乎没有吸收，不能与一些常用的光源相匹配，严重限制了阳离子光聚合的应用。 Radical photoinitiator many species, and development has been more mature, and cationic photoinitiator type less, commonly used for the diaryliodonium iron salts and triarylsulfonium Na salt, and most of the iodine Na salt and sulfur ferric little or no absorption at 300nm or more, can not match some common source, severely limiting the use of cationic photopolymerization.

芳茂铁盐具有光引发活性是在1986年首次被提出的(Meier K and Zweifel H， J Image Sci， 1986,30:174-176)。 Aryl ferrocenium having a light trigger activity in 1986 was first proposed (Meier K and Zweifel H, J Image Sci, 1986,30: 174-176). 由于它们具有良好的热稳定性和在近紫外和可见光区的较强吸收，受到人们的重视。 Due to their good thermal stability and strong absorption in the near ultraviolet and visible region, attention has been paid. 其结构如下： Its structure is as follows:

其中，MXn=BF4、 PF6、 SbF6 、 AsF6、 （C6F5)4B、 C104、 CF3S03、 FS03、 Where, MXn = BF4, PF6, SbF6, AsF6, (C6F5) 4B, C104, CF3S03, FS03,

CH3SO^nC4F9S03。 CH3SO ^ nC4F9S03. 常见芳烃如苯、甲苯、异丙苯、萘、蒽、菲、芘及其衍生物等。 Common aromatic hydrocarbons such as benzene, toluene, cumene, naphthalene, anthracene, phenanthrene, pyrene and derivatives thereof.

芳茂铁盐由于配体结构可以改变，其种类很多，且随着配体芳环结构的改变，其紫外光谱的特征也可随之改变，如稠环取代的芳茂铁盐的紫外特征吸收峰随着环数的增加向长波方向移动。 Since aromatic ferrocenium ligand structure can alter many of its kind, and with the change of the ligand aromatic ring structure, its characteristic UV spectra can also be changed, such as UV fused ring substituted aryl wherein ferrocenium salt absorption Peak increases the number of rings to move to a longer wavelength.

一取代芳茂铁盐在长波紫外和可见光区的吸收增强，因此其光敏活性增强，但是同自由基型光引发剂相比，其光敏活性仍然较低，另外这些芳茂铁盐 Aryl substituted ferrocenium in a long-wave ultraviolet and visible region absorption enhanced, thus enhancing its photosensitivity, but with a radical type photoinitiator compared to the photosensitivity is still low, while the aryl ferrocenium

对400nm以上的吸收较弱，摩尔消光系数小于1000 M—'cm—'，因此不能成为有效的以可见光为光源的光敏剂。 Weak absorption of 400nm or more, the molar extinction coefficient less than 1000 M-'cm- ', and therefore can not be an effective light source of visible light photosensitizer. 本发明中的双茂铁芳烃盐同单取代芳茂铁盐相比, 在300nm以上由d_d跃迁产生的吸收峰其摩尔消光系数提高了近10倍，是一类可应用于长波紫外和可见光源的新型阳离子光引发剂。 The present invention is a double ferrocene aromatic salt with a mono-substituted aryl ferrocenium compared to the absorption peak of its molar extinction coefficient at 300nm or more transition generated by the d_d increased nearly 10-fold, is a class can be applied to long-wave ultraviolet and visible light The novel cationic photoinitiator.

发明内容 DISCLOSURE

本发明的目的是制备出性能高效的以长波紫外为光源的阳离子光固化引发剂。 Object of the present invention is to prepare a highly efficient performance with long-wave ultraviolet light as a light source of a cationic curing initiator.

本发明的目的是通过如下技术方案实现的- The purpose of the present invention is achieved by the following technical solutions -

本发明提出一种名称为[二(环戊二烯一铁)芳烃]盐的化合物，其通式为:<formula>formula see original document page 5</formula> The present invention provides a name for the [diarene (cyclopentadienyl-Fe)] salt compound having the formula: <formula> formula see original document page 5 </ formula>

其中，MXn=BF4、 PF6、 SbF6 、 AsF6、 （C6F5)4B、 C104、 CF3S03、 FS03、 Where, MXn = BF4, PF6, SbF6, AsF6, (C6F5) 4B, C104, CF3S03, FS03,

CH3SOJB C4F9S03等；常见的芳烃为多苯芳烃和稠环芳烃，如联苯及其衍生 CH3SOJB C4F9S03 like; common aromatic aromatics and benzene fused multi-ring aromatic hydrocarbons, such as biphenyl and its derivatives

物、二苯甲垸及其衍生物、二苯醚及其衍生物、咔唑及其衍生物、萘及其衍生 Thereof, benzophenone and derivatives thereof embankment, diphenyl ether and its derivatives, carbazole and derivatives thereof, naphthalene and derivatives

物和蒽及其衍生物；该类化合物在阳离子光聚合中，用作光引发剂。 And anthracene and derivatives thereof; these compounds in cationic photopolymerization, a photoinitiator is used.

当芳烃为二苯醚时，MXn—为PFeT，该化合物为[二(环戊二烯一铁)-二苯醚] 六氟磷酸盐，结构式为： When the aromatic hydrocarbon to ether when, MXn- to PFeT, the compound is [bis (cyclopentadienyl-Fe) - ether] hexafluorophosphate, structural formula is:

<formula>formula see original document page 5</formula>当芳烃为联苯时，MXn—为PFe—，该化合物为[二(环戊二烯一铁)-联苯]六氟 <Formula> formula see original document page 5 </ formula> When the aromatic biphenyl time, MXn- to PFe-, the compound is [bis (cyclopentadienyl-Fe) - biphenyl] hexafluoropropane

磷酸盐，结构式为： Phosphates of the formula:

<formula>formula see original document page 5</formula>当芳烃为咔唑时，MXn—为PFe—，该化合物为[二(环戊二烯一铁)-咔唑]六氟 <Formula> formula see original document page 5 </ formula> When the aromatic carbazolyl, MXn- to PFe-, the compound is [bis (cyclopentadienyl-Fe) - carbazole] hexafluoropropane

磷酸盐，结构式为： Phosphates of the formula:

<formula>formula see original document page 5</formula>当芳烃为萘时，MXn—为PFe—，该化合物为[二(环戊二烯一铁)-萘]六氟磷酸 <Formula> formula see original document page 5 </ formula> When the aromatic hydrocarbon is naphthalene, MXn- to PFe-, the compound is [bis (cyclopentadienyl-Fe) - naphthalene] hexafluorophosphate

盐，结构式为： Salt, of the formula:

当芳烃为二苯甲垸时，MXn—为PF6—，该化合物为[二(环戊二烯一铁)-二苯甲垸]六氟磷酸盐，结构式为： When the aromatic hydrocarbon as benzophenone embankment, MXn- to PF6-, the compound is [bis (cyclopentadienyl-Fe) - benzophenone embankment] hexafluorophosphate, structural formula is:

-Fe-PF6_ -Fe-PF6_

当芳烃为蒽时，MXn—为PF,，该化合物为[二(环戊二烯一铁)-蒽]六氟磷! 盐，结构式为： When the aromatic hydrocarbon anthracene, MXn- as PF ,, the compound [bis (cyclopentadienyl-Fe) - anthracene] hexafluorophosphate salt of the formula!:

化合物[二(环戊二烯一铁)芳烃]盐的制备方法如下： Compound [bis (cyclopentadienyl iron a) arene] The method for preparing a salt as follows:

(1)由二茂铁、多苯芳烃和Lewis酸反应制得[二(环戊二烯一铁)芳烃] (1) consists of ferrocene, benzene, aromatics and multi-Lewis acid reaction of [bis (cyclopentadienyl-Fe) arene]

盐。 Salt. 反应式为： Reaction is:

<table>table see original document page 6</column></row> <table>(I ) <Table> table see original document page 6 </ column> </ row> <table> (I)

反应条件为：将0.05-0.3mol 二茂铁、0.02-0. lmol芳烃、0. 1-0. 6mol 无水A1CL、0. 05-0. 3molAl粉和50-300ml环烷烃倒入三口烧瓶中，搅拌均匀后， 将反应混合液缓慢加热到40-200°C，维持回流5-40h，待反应冷却后即得产物(1)。 The reaction conditions are as follows:..... The 0.05-0.3mol ferrocene, 0.02-0 lmol aromatics, 0 1-0 6mol anhydrous A1CL, 0 05-0 3molAl powder and 50-300ml naphthenic poured three-necked flask , stir, and the reaction mixture was slowly heated to 40-200 ° C, to maintain reflux 5-40h, after cooling of the reaction product was obtained (1).

(2)由产物（I)水解后和NaMXn或KMXn反应制得产物（II) [二（环戊二烯一铁)芳烃]盐，反应式为： (2) the product of (I) after hydrolysis and NaMXn or KMXn prepared by the reaction product of (II) [bis (cyclopentadienyl-Fe) arene] salt, the reaction is:

<table>table see original document page 6</column></row> <table>反应条件为：向产物(I)中缓慢地加入甲醇，再将反应混合物倒入装有冰水的烧杯中，充分搅拌，过滤，分液。 <Table> table see original document page 6 </ column> </ row> <table> Reaction conditions: methanol slowly added to the product of (I), and the reaction mixture was poured into a beaker containing ice water, sufficient stirred, filtered liquid separation. 有机相用少量水萃取，合并水相，然后向其中加入过量的KPF6水溶液，析出的固体即为粗产品。 The organic phase was extracted with a small amount of water, the combined aqueous phase was then added thereto excess aqueous KPF6, the crude product is precipitated solid. 固体干燥后，经提纯即得产物[二(环戊二烯一铁)芳烃]六氟磷酸盐。 The solid was dried, purified to obtain the product [bis (cyclopentadienyl-Fe) arene] hexafluorophosphate.

本发明的有益效果：[二(环戊二烯一铁)芳烃]盐是一种制备简单方便的阳离子光固化引发剂，在300nm以上仍有较强吸收，能与长波紫外光源相匹配， The beneficial effects of the present invention: [bis (cyclopentadienyl-Fe) arene] Salt is a simple preparation of cationic light curing initiator, there is still a strong absorption at 300nm or more, to match the long-wave ultraviolet light source,

可有效地弓i发环氧类化合物和乙烯基醚类化合物的光聚合。 I can effectively bow hair photopolymerizable epoxy compounds and vinyl ether compounds. 具体实施方式 DETAILED DESCRIPTION

实施例l制备[二(环戊二烯一铁)-二苯醚]六氟磷酸盐 Hexafluorophosphate - Preparation Example l [diphenyl ether (cyclopentadienyl-Fe)] implementation

向三口烧瓶中投入O. 15mol二茂铁、7.83ml二苯醚、0. 3mo1无水A1C13、 0.15mol Al粉和200ml环己烷使其搅拌溶解，然后缓慢升温至8(TC，维持回流状态24h。 To a three-necked flask was charged ferrocene O. 15mol, 7.83ml ether, 0. 3mo1 anhydrous A1C13, 0.15mol Al powder and 200ml of cyclohexane with stirring to dissolve it, and then slowly warmed to 8 (TC, maintain reflux 24h.

待反应液冷却，向其中倒入5%甲醇溶液，搅拌水解，过滤，分液，将有机相用水洗，与水相合并后，用环己烷反复洗涤，然后加入过量的KPF6水溶液即有土黄色沉淀析出。 After the reaction mixture was cooled, to which was poured into a 5% methanol solution, stirred for hydrolysis, filtration, liquid separation, and the organic phase was washed with water, and the aqueous phase were combined, washed repeatedly with cyclohexane, followed by addition of an excess of an aqueous solution that is soil KPF6 yellow precipitate. 将固体干燥，经柱层析提纯即得产物[二(环戊二烯一铁)-二苯醚]六氟磷酸盐，产率38.58%。 The solid was dried and purified by column chromatography to give the product [bis (cyclopentadienyl-Fe) - ether] hexafluorophosphate, yield 38.58%.

实施例2制备[二(环戊二烯一铁)-咔唑]六氟磷酸盐 Hexafluorophosphate - Preparation Example 2 [carbazole-bis (cyclopentadienyl iron a)] embodiment

向三口烧瓶中投入0. 135mol 二茂铁、0. 045mol咔唑、0. 27mol无水A1C13、 0. 135mol Al粉和250ml环己垸使其搅拌溶解，然后缓慢升温至84°C ，维持回流状态18h。 To a three-necked flask was charged with 0. 135mol ferrocene, 0. 045mol carbazole, 0. 27mol of anhydrous A1C13, 0. 135mol Al powder and 250ml cyclohexane embankment allowed to stir to dissolve, then slowly warmed to 84 ° C, to maintain reflux state 18h. ' '

待反应液冷却，向其中倒入10%甲醇溶液，搅拌水解，过滤，分液，将有机相用水洗，与水相合并后，用环己垸反复洗涤，然后加入过量的KPFe水溶液即有黄色沉淀析出。 After the reaction mixture was cooled, to which was poured into 10% methanol solution, stirred for hydrolysis, filtration, liquid separation, and the organic phase was washed with water, combined with the aqueous phase, washed repeatedly with cyclohexyl embankment, and then adding an excess of an aqueous solution that is yellow KPFe precipitation. 将固体干燥，经柱层析提纯即得产物[二(环戊二烯一铁)-咔唑]六氟磷酸盐，产率66.7%。 The solid was dried and purified by column chromatography to give the product [bis (cyclopentadienyl-Fe) - carbazole] hexafluorophosphate yield of 66.7%.

实施例3制备[二(环戊二烯一铁)-联苯]六氟磷酸盐 EXAMPLE 3 Preparation of [bis (cyclopentadienyl-Fe) - biphenyl] hexafluorophosphate

向三口烧瓶中投入0. 1125mol 二茂铁、0.0375mol联苯、0. 225mol无水A1C13、 0. 1125mol Al粉和210ml十氢萘使其搅拌溶解，然后缓慢升温至160 °C，维持回流状态24h。 To a three-necked flask was charged with 0. 1125mol ferrocene, 0.0375mol biphenyl, 0. 225mol anhydrous A1C13, 0. 1125mol Al powder and 210ml decahydronaphthalene stirred to dissolve it, and then slowly warmed to 160 ° C, maintaining reflux 24h.

待反应液冷却，向其中倒入12%甲醇溶液，搅拌水解，过滤，分液，将有机相用水洗，与水相合并后，用环己烷反复洗涤，然后加入过量的KPFe水溶液即有淡黄色沉淀析出。 After the reaction mixture was cooled, to which was poured into 12% methanol solution, stirred for hydrolysis, filtration, liquid separation, and the organic phase was washed with water, combined with the aqueous phase repeatedly washed with cyclohexane, and then adding an excess of an aqueous solution that is light KPFe yellow precipitate. 将固体干燥，经柱层析提纯即得产物[二(环戊二烯一铁)-联苯]六氟磷酸盐，产率49.12%。 The solid was dried and purified by column chromatography to give the product [bis (cyclopentadienyl-Fe) - biphenyl] hexafluorophosphate, yield 49.12%.

实施例4制备[二(环戊二烯一铁)-萘]六氟磷酸盐 Hexafluorophosphate - Example 4 Preparation of [naphthalene bis (cyclopentadienyl iron a)] embodiment

向三口烧瓶中投入0. 1125mol 二茂铁、0.0375mol萘、0. 225mol无水A1C13、 0.1125mol Al粉和260ml十氢萘使其搅拌溶解，然后缓慢升温至165 °C,维持回流状态20h。 To a three-necked flask was charged with 0. 1125mol ferrocene, 0.0375mol naphthalene, 0. 225mol anhydrous A1C13, 0.1125mol Al powder and 260ml decahydronaphthalene stirred to dissolve it, and then slowly warmed to 165 ° C, maintaining reflux 20h.

待反应液冷却，向其中倒入20%甲醇溶液，搅拌水解，过滤，分液，将有机相用水洗，与水相合并后，用环己垸反复洗涤，然后加入过量的KPFe水溶液 After the reaction mixture was cooled, to which was poured into a 20% methanol solution, stirred for hydrolysis, filtration, liquid separation, and the organic phase was washed with water, and the aqueous phase were combined, washed repeatedly with cyclohexyl embankment, and then adding an excess of aqueous KPFe

即有淡黄色沉淀析出。 That is a pale yellow precipitate. 将固体干燥，经柱层析提纯即得产物[二(环戊二烯一 The solid was dried and purified by column chromatography to give the product [bis (cyclopentadienyl a

铁)-萘]六氟磷酸盐，产率62.32%。 Iron) - naphthalene] hexafluorophosphate, yield 62.32%.

实施例5将1份制得的光固化引发剂，50份3， 4-环氧基环己基甲酸-3， 4-环氧基环己基甲酯（ERL4221) ， 6份乙腈混合搅拌，制成树脂，将此树脂涂在载玻片上，然后于5. 5W/cm的镝灯下照射，即在片上形成牢固的固化薄膜。 1 5 parts obtained photocurable initiator, 50 parts of 3,4-epoxy cyclohexyl carboxylate -3,4-epoxy cyclohexyl methyl (ERL4221), 6 parts of acetonitrile was stirred embodiment mixed to prepare resin, this resin is coated on a glass slide, and then to 5. 5W / cm dysprosium lamp irradiation, i.e. cured to form a solid film on the sheet.