CN102675489A - Benzoxazine structure-containing benzophenone photoinitiator and preparation method thereof - Google Patents
Benzoxazine structure-containing benzophenone photoinitiator and preparation method thereof Download PDFInfo
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- CN102675489A CN102675489A CN2012101381567A CN201210138156A CN102675489A CN 102675489 A CN102675489 A CN 102675489A CN 2012101381567 A CN2012101381567 A CN 2012101381567A CN 201210138156 A CN201210138156 A CN 201210138156A CN 102675489 A CN102675489 A CN 102675489A
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Abstract
The invention discloses a benzoxazine structure-containing benzophenone photoinitiator and a preparation method thereof. The preparation method of the novel photoinitiator comprises the step of introducing micromolecule hydrogen abstraction type photoinitiator and coinitiator amine onto the same polymer chain. The preparation method is simple, the raw materials are easy to obtain, the cost is lower, and the main chain of the obtained photoinitiator simultaneously contains a photo-initiation structure and a co-initiation tertiary amine structure, so that the energy transfer between the photo-initiation structure and the co-initiation tertiary amine structure can be preferably carried out, the photo-initiation efficiency can be improved, the introduction of the long-chain alkoxy is well compatible with a plurality of solvents and monomers, and the benzoxazine structure-containing benzophenone photoinitiator disclosed by the invention is low in transport factor, small in toxicity, and good in environmental compatibility; therefore, the invention is wide in application prospect in the aspects of coating material, printing ink, microelectronics, photoresist, dental materials, and the like.
Description
Technical field
The present invention relates to the photosensitive high molecular field, particularly a kind of diphenyl ketone photo initiator and preparation method thereof.
Background technology
UV-curing technology is advantages such as curing speed is fast, energy-conserving and environment-protective owing to having, thereby are widely used and bright development prospect at industrial circles such as photo-cured coating, light-curable ink, photoresist material, electronic package material, tackiness agent, paper glazing, optical media replications.In the ultraviolet light polymerization system, light trigger is most important, and the UVNUL MS-40 photoinitiator is one type of common hydrogen-abstraction free radical photo-initiation, has good light-initiated performance.
In recent years, the hydrogen-abstraction light initiation system of being made up of light trigger and coinitiator amine receives extensive concern.But along with science and technology development, not only require light trigger that good light-initiated performance is arranged, and requirement and photocuring system consistency are good, mobility is low, toxicity is little, and environment compatibility is good, and storage stability is high.Traditional small molecules is because poor with the consistency of curing system, and volatilization and migration easily causes the efficiency of initiation attenuating on the one hand after solidifying, and can produce smell and toxicity on the other hand.Therefore, stable, the low toxicity of exploitation, high-efficiency environment friendly and receive increasing concern with light initiation system that curing system has an excellent compatibility.
Summary of the invention
The objective of the invention is to deficiency, a kind of benzoxazine structure diphenyl ketone photo initiator and preparation method thereof that contains is provided, in the You Yu oxazine ring tertiary amine structure is arranged to prior art; Coinitiator can be provided, because initiator functional group and coinitiator functional group be positioned on the same molecular chain, so the gained light trigger has higher efficiency of initiation; With a lot of solvents and monomer good consistency is arranged, toxicity is low, has wide range of applications; The preparation method is simple simultaneously, realizes easily.
For realizing this purpose, the present invention is synthesized to small molecules light trigger and coinitiator amine on the same macromole through the method for polycondensation, prepares a kind of novel light trigger.
Contain the benzoxazine structure diphenyl ketone photo initiator among the present invention, its structural formula is following:
M=1 wherein～500; X=2.5～33, y=0, z=0 or x+z=6, y=39.
The structure that absorbs photon excitation in the light trigger of the present invention is following:
Provide the structure of Wasserstoffatoms following in the light trigger of the present invention:
Wherein R is the linear structure of being made up of alkoxyl group.
Preparing method's following steps of the diphenyl ketone photo initiator that contains benzoxazine structure among the present invention are carried out:
" part " of the following stated is " molar part ".
Formaldehyde among the present invention such as can use to replace at the Paraformaldehyde 96 of aldehyde radical molar weight.
The used polyether diamine of the present invention is any among polyether diamine D230, polyether diamine D400, polyether diamine D2000, the polyether diamine ED2003.
Organic solvent used in the present invention is alcohols, chloroform, 1,4-dioxane, DMSO 99.8MIN., N, N '-N, N, any in N '-N,N-DIMETHYLACETAMIDE, N-methyl-pyrrolidone, toluene or the YLENE.
The method of removing solvent is known any method, preferably revolves to steam to remove.
The diphenyl ketone photo initiator that contains benzoxazine structure that the present invention obtains; Contain light-initiated structure of hydrogen-abstraction and the tertiary amine structure that causes altogether in its molecule simultaneously; The energy that helps between the two shifts; Can produce the free radical activity kind more, faster, improved efficiency of initiation, and use need not to add coinitiator again; Simultaneously, Environmental compatibility is good, and its long-chain alkoxy base provides and business-like monomeric good consistency, has both improved light-initiated performance, behind photocuring, is difficult for moving to resin surface again, has reduced the toxicity of light trigger.Therefore it has broad application prospects in the photocuring field.
Description of drawings
Fig. 1 is the ir spectra that contains the diphenyl ketone photo initiator of benzoxazine structure.
Fig. 2 is the nucleus magnetic hydrogen spectrum that contains the diphenyl ketone photo initiator of benzoxazine structure.
Fig. 3 is the hot system photo-DSC transformation efficiency-time diagram of light quantity that contains the diphenyl ketone photo initiator of benzoxazine structure.
Embodiment
The entire reaction equation that the invention preparation contains the benzoxazine structure diphenyl ketone photo initiator can be expressed as:
Below in conjunction with embodiment the present invention is elaborated.But should be understood that following examples only are to the illustrating of embodiment of the present invention, but not be that scope of the present invention is limited.
Testing method:
Ir spectra adopts Fourier transformation infrared spectrometer, Spectrum 100 tests.
Nucleus magnetic hydrogen spectrum adopts nuclear magnetic resonance spectrometer (NMR) MERCURYplus 400 tests.
Light-initiated transformation efficiency-time diagram adopts differential scanning calorimeter DSC 6200 (SeikoInstrument Inc.) test.
Only if outside the raw material in following examples specialized, all the other were commercially available.
Embodiment 1
2.142g (0.01mol) 4; The polyether diamine D230 of 4-dihydroxy benaophenonel, 2.3g (0.01mol) Hensel Man is (about x=2.5; Y=0, z=0) and 1.2g (containing the 0.04mol aldehyde radical) Paraformaldehyde 96 be solvent 60 ° of C backflow 40h under nitrogen protection with the chloroform.After reaction finished, product revolved and steams except that after desolvating, and the alkali cleaning washing obtains title product DHBP-D230.
Fig. 1 and Fig. 2 comprise the ir spectra and the nucleus magnetic hydrogen spectrum of title product respectively.
1H-NMR(DMSO)：δ＝4.9-4.0(-CH
2?of?benzoxazine?ring)，4.8-5.0(N-CH
2-O)，3.9-4.1(N-CH
2-ph)，0.9-1.1(-CH
3)，3.2-3.7(-CH
2)，6.5-8(aromatic).
FT-IR(KBr)：1367(C-O-C?oxazine?ring)，1593(C＝O)，1249(oxazinering)
The hot system photo-DSC transformation efficiency-temporal image of the light quantity of the light-initiated 1,6 hexanediol diacrylate of Fig. 3 display-object product, comparison is UVNUL MS-40 (BP) among the figure.
2.142g (0.01mol) 4, the graceful polyether diamine D400 of 4-dihydroxy benaophenonel, 4.0g (0.01mol) Hensel (about x=6.1, y=0, z=0) and 1.2g (containing the 0.04mol aldehyde radical) formaldehyde be solvent 110 ° of C backflow 20h under nitrogen protection with the butanols.After reaction finished, product revolved and steams except that after desolvating, and the alkali cleaning washing obtains title product DHBP-D400.
Fig. 1 and Fig. 2 comprise the ir spectra and the nucleus magnetic hydrogen spectrum of title product respectively.
1H-NMR(DMSO)：δ＝4.9-4.0(-CH
2?of?benzoxazine?ring)，4.8-5.0(N-CH
2-O)，3.9-4.1(N-CH
2-ph)，0.9-1.1(-CH
3)，3.2-3.7(-CH
2)，6.5-8(aromatic).
FT-IR(KBr)：1367(C-O-C?oxazine?ring)，1593(C＝O)，1249(oxazinering)
Fig. 3 has shown the hot system photo-DSC transformation efficiency-temporal image of the light quantity of the light-initiated 1,6 hexanediol diacrylate of title product, and comparison is UVNUL MS-40 (BP) among the figure.
Embodiment 3
2.142g (0.01mol) 4; The polyether diamine D2000 of 4-dihydroxy benaophenonel, 20.0g (0.01mol) Hensel Man is (about x=33; Y=0, z=0) and 1.2g (containing the 0.04mol aldehyde radical) Paraformaldehyde 96 be solvent 140 ° of C backflow 5h under nitrogen protection with the methyl-sulphoxide.After reaction finished, product revolved and steams except that after desolvating, and the alkali cleaning washing obtains title product DHBP-D2000.
Fig. 1 and Fig. 2 comprise the ir spectra and the nucleus magnetic hydrogen spectrum of title product respectively.
1H-NMR(DMSO)：δ＝4.9-4.0(-CH
2?of?benzoxazine?ring)，4.8-5.0(N-CH
2-O)，3.9-4.1(N-CH
2-ph)，0.9-1.1(-CH
3)，3.2-3.7(-CH
2)，6.5-8(aromatic).
FT-IR(KBr)：1367(C-O-C?oxazine?ring)，1593(C＝O)，1249(oxazinering)
Fig. 3 has shown the hot system photo-DSC transformation efficiency-temporal image of the light quantity of the light-initiated 1,6 hexanediol diacrylate of title product, and comparison is UVNUL MS-40 (BP) among the figure.
2.142g (0.01mol) 4; The polyether diamine ED2003 (about x+z=6, about y=39) of 4-dihydroxy benaophenonel, 20.0g (0.01mol) Hensel Man and 1.2g (containing the 0.04mol aldehyde radical) Paraformaldehyde 96 are solvent 120 ° of C backflow 10h under nitrogen protection with YLENE.After reaction finished, product revolved and steams except that after desolvating, and the alkali cleaning washing obtains title product DHBP-ED2003.
Fig. 1 and Fig. 2 comprise the ir spectra and the nucleus magnetic hydrogen spectrum of title product respectively.
1H-NMR(DMSO)：δ＝4.9-4.0(-CH
2?of?benzoxazine?ring)，4.8-5.0(N-CH
2-O)，3.9-4.1(N-CH
2-ph)，0.9-1.1(-CH
3)，3.2-3.7(-CH
2)，6.5-8(aromatic).
FT-IR(KBr)：1367(C-O-C?oxazine?ring)，1593(C＝O)，1249(oxazinering)
Fig. 3 has shown the hot system photo-DSC transformation efficiency-temporal image of the light quantity of the light-initiated 1,6 hexanediol diacrylate of title product, and comparison is UVNUL MS-40 (BP) among the figure.
Claims (5)
1. diphenyl ketone photo initiator that contains benzoxazine structure is characterized in that described structure is shown below:
M=1～500 wherein; X=2.5～33, y=0, z=0 or x+z=6, y=39.
2. preparation method who contains the diphenyl ketone photo initiator of benzoxazine structure; It is characterized in that in molar part 1 part 4,4-dihydroxy benaophenonel, 1 part of polyamides diamines and 4 parts of formaldehyde are dissolved in the organic solvent; 60～140 ℃ of reaction 5～40h under nitrogen protection; After reaction product was removed solvent, the alkali cleaning washing obtained containing the benzoxazine structure diphenyl ketone photo initiator.
3. a kind of preparation method who contains the diphenyl ketone photo initiator of benzoxazine structure according to claim 2 is characterized in that described polyether diamine is polyether diamine D230, polyether diamine D400, polyether diamine D2000 or polyether diamine ED2003.
4. a kind of preparation method who contains the diphenyl ketone photo initiator of benzoxazine structure according to claim 2; It is characterized in that organic solvent is alcohols, chloroform, 1; 4-dioxane, DMSO 99.8MIN., N; N '-N, N, N '-N,N-DIMETHYLACETAMIDE, N-methyl-pyrrolidone, toluene or YLENE.
5. a kind of preparation method who contains the diphenyl ketone photo initiator of benzoxazine structure according to claim 2 is characterized in that revolving the steaming method and removes described organic solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694192A (en) * | 2013-12-26 | 2014-04-02 | 上海交通大学 | Benzoxazine compound with photo-initiation performance, preparation method and application of benzoxazine compound |
| CN110760045A (en) * | 2019-10-08 | 2020-02-07 | 华东理工大学 | Novel benzoxazine resin with ultraviolet absorption function and one-step preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| US5973144A (en) * | 1997-10-03 | 1999-10-26 | Ishida; Hatsuo | High char yield benzoxazines |
| CN102093556A (en) * | 2011-01-19 | 2011-06-15 | 华东理工大学 | Preparation method of low viscosity benzoxazine |
-
2012
- 2012-05-04 CN CN201210138156.7A patent/CN102675489B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| US5973144A (en) * | 1997-10-03 | 1999-10-26 | Ishida; Hatsuo | High char yield benzoxazines |
| CN102093556A (en) * | 2011-01-19 | 2011-06-15 | 华东理工大学 | Preparation method of low viscosity benzoxazine |
Non-Patent Citations (1)
| Title |
|---|
| TAREK AGAG ET AL.: "Low-Viscosity Polyether-Based Main-Chain Benzoxazine Polymers: Precursors for Flexible Thermosetting Polymers", 《MACROMOLECULES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694192A (en) * | 2013-12-26 | 2014-04-02 | 上海交通大学 | Benzoxazine compound with photo-initiation performance, preparation method and application of benzoxazine compound |
| CN103694192B (en) * | 2013-12-26 | 2015-06-17 | 上海交通大学 | Benzoxazine compound with photo-initiation performance, preparation method and application of benzoxazine compound |
| CN110760045A (en) * | 2019-10-08 | 2020-02-07 | 华东理工大学 | Novel benzoxazine resin with ultraviolet absorption function and one-step preparation method thereof |
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