CN101624408A - Pendant naphthalene group-containing benzene ligand ferrocenium salt cationic photoinitiators and preparation method thereof - Google Patents
Pendant naphthalene group-containing benzene ligand ferrocenium salt cationic photoinitiators and preparation method thereof Download PDFInfo
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- CN101624408A CN101624408A CN200810116285A CN200810116285A CN101624408A CN 101624408 A CN101624408 A CN 101624408A CN 200810116285 A CN200810116285 A CN 200810116285A CN 200810116285 A CN200810116285 A CN 200810116285A CN 101624408 A CN101624408 A CN 101624408A
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Abstract
The invention discloses pendant naphthalene group-containing cyclopentadienyl-iron-benzyl ferrocenium salt compounds used as photoinitiators for cationic photopolymerization, and belongs to the technical fields of organic synthesis and cationic photopolymerization. The preparation method of the compounds comprises two steps: 1, taking ferrocene and chlorobenzene as raw materials, and generating ligand exchange reaction to obtain cyclopentadienyl-iron-chlorobenzene salts under the catalysis of Lewis acid; and 2, generating nucleophilicsubstitutionreaction with corresponding naphthol compounds under alkaline environment, and introducing the pendant naphthalene group onto the benzene ligand. The compounds have good ultraviolet absorptivity and photo initiating activity, can initiate polymerization of epoxy compounds and vinyl ethers compounds, and have wide study potential and application prospect in the field of photocuring application.
Description
Technical field
The present invention relates to the luxuriant iron hexafluorophosphate of benzene part type cation light initiator that contains naphthalene oxygen side group and preparation method thereof, belong to organic synthesis and cationic photopolymerization technical field.
Background technology
Since people such as Crivello had successfully studied the cationic photopolymerization initiating activity of diaryl group iodized salt and triaryl sulfonium salts from the seventies, the research of cationic photopolymerization had obtained very big development with using.Compare with the radical photoinitiator curing system, light-initiated cationic monomer of cation photocuring system tool and performed polymer kind are many, are not subjected to advantages such as oxygen inhibition and living polymerization.Numerous with respect to kind, develop the more sophisticated radical photoinitiator that is used for the radical photopolymerization system, the initiator type that is used for cationic photopolymerization is less, and cation light initiator commonly used is diaryl group iodized salt and triaryl sulfonium salts.The absorption peak of this two compounds in uv-visible absorption spectra is positioned at below the 300nm, almost do not absorb more than 300nm, therefore can not be complementary with some light source such as high voltage mercury lamps commonly used.
20th century the mid-80, the people such as F.Lohse of Ciba company have developed fragrant ferrocenium salt cationic photoinitiators, the light-initiated mechanism of such material is different with the triggering mechanism of diaryl group iodized salt and triaryl sulfonium salts, and the species with initiating activity are to take off the aromatic hydrocarbons part after the fragrant luxuriant molysite photodissociation and the ferrous ion that generates.The luxuriant molysite of virtue has good thermostability, and it is positioned near ultraviolet and visible region by absorption peak that the d-d transition produces, and therefore can be complementary with the long wave ultraviolet light source, as high voltage mercury lamp etc.Discover that the light-initiated activity of the luxuriant molysite of simple benzene part virtue is relatively poor, by introducing the condensed ring part, its ultraviolet charateristic avsorption band is moved to long wavelength's direction, light absorptive increases, thereby improves the light-initiated activity of fragrant luxuriant molysite.
Summary of the invention
The objective of the invention is to prepare a kind of benzene ligand ferrocenium salt novel cation light trigger that contains naphthalene oxygen side group, this initiator has better absorption in the long wavelength zone, and molar extinction coefficient is higher, has higher light-initiated activity in cationic photopolymerization.
The invention discloses the luxuriant molysite compound that a class contains naphthalene oxygen side group, it is characterized in that chemical structure of general formula as shown in the formula:
Sauerstoffatom is positioned at the α or the β position of naphthalene nucleus in the structural formula, and R is alkyl, substituted alkyl, halogen atom, carboxyl of H or C=1-14 etc., MXn
-Be non-nucleophilicity negatively charged ion: SbF
4 -, AsF
6 -, PF
6 -, BF
- 4, CF
3SO
3 -Or CH
3SO
3 -
When Sauerstoffatom is positioned at the α position of naphthalene nucleus, when R is H, MXn
-Be PF
6 -, this compound is the luxuriant iron hexafluorophosphate of the benzene part of alpha-naphthoxy side group, structural formula is:
When Sauerstoffatom is positioned at the β position of naphthalene nucleus, when R is H, MXn
-Be PF
6 -, this compound is the luxuriant iron hexafluorophosphate of benzene part of β-naphthalene oxygen side group, structural formula is:
The luxuriant iron hexafluorophosphate of the benzene part compounds process for production thereof that contains the alpha-naphthoxy side group is as follows:
(1) reacts under the Lewis acid catalysis by ferrocene, chlorobenzene and make cyclopentadiene-iron-chlorobenzene salt (I).Reaction formula is:
Reaction conditions is: add 0.05mol ferrocene, the anhydrous AlCl of 0.15mol in the there-necked flask of 250ml
3, 0.15mol aluminium powder and 10ml chlorobenzene with 50ml cyclohexane give solvent, stir, and reflux 10 hours gets compound (I).
(2) make product (II) cyclopentadiene-iron-chlorobenzene salt by adding NaMXn or KMXn reaction after product (I) hydrolysis, reaction formula is:
Reaction conditions is: will add methyl alcohol lentamente in the product (I), reaction mixture is poured in the beaker that frozen water is housed again, fully stir, filter separatory.Organic phase extracts with less water, merges water, then to wherein adding excessive KPF
6The aqueous solution, the yellow solid of separating out is thick product.Behind the solid drying, promptly get compound (II) through purifying.
(3) make benzene ligand ferrocenium salt that product (III) contain alpha-naphthoxy side group with naphthyl alcohol generation nucleophilic substitution reaction by product (II) under alkaline condition, reaction formula is as follows:
Reaction conditions is: 0.01mol compound (II) and 0.02mol naphthyl alcohol are dissolved in N, and dinethylformamide, reaction is 9-11 hour under the catalysis of 0.02mol salt of wormwood, adds 15% hydrochloric acid and transfers to acidity, and suction filtration adds saturated KPF
6The aqueous solution gets yellow crude product.Drying, column chromatography are purified and are obtained the luxuriant iron hexafluorophosphate of benzene part of product (III) alpha-naphthoxy side group.
The luxuriant iron hexafluorophosphate of the benzene part compounds process for production thereof that contains β-naphthalene oxygen side group is for to make benzene ligand ferrocenium salt that product (IV) contain β-naphthalene oxygen side group with 2-Naphthol generation nucleophilic substitution reaction by product (II) under alkaline condition, reaction formula is as follows:
Reaction conditions is: 0.01mol compound (II) and 0.02mol 2-Naphthol are dissolved in N, and dinethylformamide, reaction is 7-9 hour under the catalysis of 0.02mol salt of wormwood, adds 15% hydrochloric acid and transfers to acidity, and suction filtration adds saturated KPF
6The aqueous solution gets yellow crude product.Drying, column chromatography are purified and are obtained the luxuriant iron hexafluorophosphate of benzene part of product (IV) β-naphthalene oxygen side group.
The benzene ligand ferrocenium salt that usefulness of the present invention is to contain naphthalene oxygen side group is a kind of preparation cation photocuring initiator simply and easily, more than 300nm, still have more by force and absorb, can be complementary with the long wave ultraviolet light source, can cause the photopolymerization of epoxy compounds and vinyl ethers compound effectively.
The uv-absorbing test structure shows that the benzene ligand ferrocenium salt that contains naphthalene oxygen side group of the present invention's preparation has absorption more by force in the near ultraviolet region; Utilize long wavelength ultraviolet light source such as high voltage mercury lamp that the test result of its light-initiated performance is shown, such luxuriant molysite compound has good light-initiated activity.
The present invention utilizes the method for light-initiated performance of the luxuriant molysite compound of online infrared test following (following all represent with weight fraction):
The benzene ligand ferrocenium salt that contains naphthalene oxygen side group and 100 parts of alicyclic epoxide compound ERL4221 of 1-3 part are mixed, take a morsel and press from both sides into the film of fixed thickness with two bromination sylvite sheets, be placed on the sample table, the light source irradiation with 365nm detects with infrared spectra simultaneously.
Description of drawings
Fig. 1 is that concentration is 1 * 10
-4The ultra-violet absorption spectrum of luxuriant iron hexafluorophosphate in methylene dichloride that contains naphthalene oxygen side group of mol/L.
Fig. 2 is the light-initiated curve that detects the luxuriant iron phosphofluoric acid salt pair alicyclic epoxide compound ERL4221 that contains naphthalene oxygen side group of two kinds of 3%w by PHOTO-IR.
Fig. 3 is the luxuriant iron hexafluorophosphate of the benzene part infrared spectrum of alpha-naphthoxy side group.
Fig. 4 is the luxuriant iron hexafluorophosphate of the benzene part infrared spectrum of β-naphthalene oxygen side group.
Embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1 preparation cyclopentadiene-iron-chlorobenzene hexafluorophosphate
N
2Protection adds 0.05mol ferrocene, the anhydrous AlCl of 0.15mol down in the there-necked flask of 250ml
3, 0.15mol aluminium powder and 10ml chlorobenzene with 50ml cyclohexane give solvent, stir, and keep reflux 10 hours.
The question response liquid cooling but, in reaction solution, add 10% methyl alcohol lentamente, reaction mixture is poured in the beaker that frozen water is housed again, fully stir, filter separatory, organic phase is washed with water, after the water merging, use the hexanaphthene repetitive scrubbing, adding the excessive KPF6 aqueous solution then promptly has yellow mercury oxide to separate out.Behind the solid drying, promptly get cyclopentadiene-iron-chlorobenzene hexafluorophosphate, productive rate 40% through the column chromatography purification.
The luxuriant iron hexafluorophosphate of benzene part of embodiment 2 preparation alpha-naphthoxy side groups
N
2Protection down; in the 100ml round-bottomed flask, 0.01mol cyclopentadiene-iron-chlorobenzene hexafluorophosphate and 0.02mol naphthyl alcohol are dissolved in 10mlN; dinethylformamide; reaction is 9 hours under the catalysis of 0.02mol salt of wormwood; after reaction finishes; add 15% hydrochloric acid and transfer to acidity, suction filtration adds saturated KPF
6The aqueous solution gets yellow crude product.Drying, column chromatography are purified and are obtained the luxuriant iron hexafluorophosphate of benzene part of product alpha-naphthoxy side group, productive rate 85%.
The luxuriant iron hexafluorophosphate of benzene part of embodiment 3 preparation β-naphthalene oxygen side groups
N
2Protection is dissolved in 10mlN with 0.01mol cyclopentadiene-iron-chlorobenzene hexafluorophosphate and 0.02mol 2-Naphthol, dinethylformamide down in the 100ml round-bottomed flask; reaction is 7 hours under the catalysis of 0.02mol salt of wormwood; add 15% hydrochloric acid and transfer to acidity, suction filtration adds saturated KPF
6The aqueous solution gets yellow crude product.Drying, column chromatography are purified and are obtained the luxuriant iron hexafluorophosphate of benzene part of product β-naphthalene oxygen side group, productive rate 88%.
Claims (5)
1 one classes contain the luxuriant molysite compound of naphthalene oxygen side group, it is characterized in that chemical structure of general formula as shown in the formula:
Sauerstoffatom is positioned at the α or the β position of naphthalene nucleus in the structural formula, and R is alkyl, substituted alkyl, halogen atom, carboxyl of H or C=1-14 etc., MXn
-Be non-nucleophilicity negatively charged ion: SbF
4 -, AsF
6 -, PF
6 -, BF
- 4, CF
3SO
3 -Or CH
3SO
3 -
2 compounds according to claim 1 are worked as the α position that Sauerstoffatom is positioned at naphthalene nucleus especially, when R is H, and MXn
-Be PF
6 -, this compound is the luxuriant iron hexafluorophosphate of the benzene part of alpha-naphthoxy side group, structural formula is:
3 compounds according to claim 1 are worked as the β position that Sauerstoffatom is positioned at naphthalene nucleus especially, when R is H, and MXn
-Be PF
6 -, this compound is the luxuriant iron hexafluorophosphate of benzene part of β-naphthalene oxygen side group, structural formula is:
4 preparation methods of compound according to claim 1 is characterized in that:
(a) react under the Lewis acid catalysis by ferrocene, chlorobenzene and make cyclopentadiene-iron-chlorobenzene salt.Reaction conditions is: with 1 part of ferrocene, 3 parts of anhydrous AlCl
3,, 3 parts of aluminium powders and 1 part of chlorobenzene be dissolved in 10-20 part hexanaphthene, after stirring, slowly is heated to reflux temperature, keeps reaction 8-10 hour, compound (I), add NaMXn after the hydrolysis or KMXn obtains cyclopentadiene-iron-chlorobenzene salt (II).
(b) be raw material with cyclopentadiene-iron-chlorobenzene salt (II), under alkaline condition, make the benzene ligand ferrocenium salt (III) that contains the alpha-naphthoxy side group with naphthyl alcohol generation nucleophilic substitution reaction.Reaction conditions is: 1 part of cyclopentadiene-iron-chlorobenzene salt (II) and 1.5-2 part naphthyl alcohol are dissolved in 5-10 part N, dinethylformamide, reaction is 9-11 hour under the catalysis of 1.5-2 part alkali, reaction finishes the back and adds the saturated NaMXn or the KMXn aqueous solution, gets the benzene ligand ferrocenium salt (III) of product alpha-naphthoxy side group.
(c) be raw material by cyclopentadiene-iron-chlorobenzene salt (II), under alkaline condition, make the benzene ligand ferrocenium salt (IV) that contains β-naphthalene oxygen side group with 2-Naphthol generation nucleophilic substitution reaction.Reaction conditions is: 1 part of cyclopentadiene-iron-chlorobenzene salt (II) and 1.5-2 part 2-Naphthol are dissolved in 5-10 part N, dinethylformamide, reaction is 7-9 hour under the catalysis of 1.5-2 part alkali, reaction finishes the back and adds the saturated NaMXn or the KMXn aqueous solution, gets the benzene ligand ferrocenium salt (III) of product β-naphthalene oxygen side group.
5 according to claim 1 compound in cationic photopolymerization, be used to cause epoxy compounds and vinyl ethers compound.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675375A (en) * | 2011-03-18 | 2012-09-19 | 北京化工大学 | Cationic ferrocene complexation azoic compound |
| CN103242377A (en) * | 2013-04-22 | 2013-08-14 | 苏州志向纺织科研股份有限公司 | Alpha,omega-biferrocene hydrocarbon and preparation method thereof |
| CN103373751A (en) * | 2012-04-26 | 2013-10-30 | 北京化工大学 | Application of cationic iron arene complex serving as catalyst for photo-degradation of organic dye |
| CN105295092A (en) * | 2014-06-20 | 2016-02-03 | 北京化工大学 | Cyclopentadienyl iron salt flame retardant containing phosphorus and nitrogen elements, and preparation method and application thereof |
| CN115073533A (en) * | 2021-03-16 | 2022-09-20 | 安庆北化大科技园有限公司 | Photoinitiator [ Cp-Fe-arene] + MXn - Synthetic method of ferrocenium salt |
-
2008
- 2008-07-08 CN CN200810116285A patent/CN101624408A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675375A (en) * | 2011-03-18 | 2012-09-19 | 北京化工大学 | Cationic ferrocene complexation azoic compound |
| CN103373751A (en) * | 2012-04-26 | 2013-10-30 | 北京化工大学 | Application of cationic iron arene complex serving as catalyst for photo-degradation of organic dye |
| CN103373751B (en) * | 2012-04-26 | 2015-04-15 | 北京化工大学 | Application of cationic iron arene complex serving as catalyst for photo-degradation of organic dye |
| CN103242377A (en) * | 2013-04-22 | 2013-08-14 | 苏州志向纺织科研股份有限公司 | Alpha,omega-biferrocene hydrocarbon and preparation method thereof |
| CN103242377B (en) * | 2013-04-22 | 2016-02-10 | 苏州志向纺织科研股份有限公司 | A kind of α, ω-di-ferrocene hydrocarbon and preparation method thereof |
| CN105295092A (en) * | 2014-06-20 | 2016-02-03 | 北京化工大学 | Cyclopentadienyl iron salt flame retardant containing phosphorus and nitrogen elements, and preparation method and application thereof |
| CN105295092B (en) * | 2014-06-20 | 2018-06-26 | 北京化工大学 | A kind of phosphorous, nitrogen luxuriant molysite fire retardant and its preparation method and application |
| CN115073533A (en) * | 2021-03-16 | 2022-09-20 | 安庆北化大科技园有限公司 | Photoinitiator [ Cp-Fe-arene] + MXn - Synthetic method of ferrocenium salt |
| CN115073533B (en) * | 2021-03-16 | 2023-07-04 | 安庆北化大科技园有限公司 | Photoinitiator [ Cp-Fe-area ]] + MXn - Synthesis method of arene ferric salt |
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Open date: 20100113 |