CN103113498A - Polymeric photoinitiator and preparation method thereof - Google Patents
Polymeric photoinitiator and preparation method thereof Download PDFInfo
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- CN103113498A CN103113498A CN2013100393294A CN201310039329A CN103113498A CN 103113498 A CN103113498 A CN 103113498A CN 2013100393294 A CN2013100393294 A CN 2013100393294A CN 201310039329 A CN201310039329 A CN 201310039329A CN 103113498 A CN103113498 A CN 103113498A
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Abstract
The invention relates to a polymeric photoinitiator and a preparation method thereof. The structural formula of the polymeric photoinitiator is shown in the specification. The method comprises the following steps: reacting a hydroxyl-containing benzophenone derivative, paraformaldehyde and diglycolamine which serve as raw materials to synthesize red liquid (BZOH) through a Mannich reaction; and reacting BZOH with acryloyl chloride to generate the polymeric photoinitiator (BZOA). The macromolecule initiator simultaneously contains benzophenone and tertiary amine, and the efficiency of generating reactive species through photosensitive decomposition is improved. Because the initiator contains the benzoxazine structure and unsaturated double bonds, the compatibility with an initiating system is improved, the surface migration of the photoinitiator is reduced, and the photoinitiator can serve as a monomer for synthesizing macromolecules and is widely applied to the fields of ultraviolet light polymerization and the like. R1 and R2 are mutually independent -H, -CH3, -OH or -CH2Cl, wherein at least one substituent group exists at the ortho-position in the hydroxyl-containing benzophenone derivative.
Description
Technical field
The present invention relates to the photosensitive macromolecular material technical field, relate in particular to a kind of benzophenone macromole that contains as light trigger.
Background technology
Photocuring technology is the novel green technology of coming out the sixties in 20th century, is that to utilize light (UV-light or visible light) or electron beam be the energy, and causing the fluent meterial fast transition with chemical reactivity is solid-state process.Along with the development of science and technology and to the pay attention to day by day of environmental protection, the photocuring technology fast development, at present this technology has been widely used in plate making, stereolithography, printing ink, coating, tackiness agent, and the biomedical materials field such as gear division, orthopaedics repair materials, contact lens.
Photocuring technology and traditional thermofixation technology difference are: photocuring reaction essence is polymerization, the crosslinking reaction that has UV-light to cause, any one photocuring system comprises following three components at least: (1) resin (or claiming prepolymer, oligopolymer) gives material basic physical and chemical performance; (2) monomer (or claim reactive thinner), be mainly used in regulating the viscosity in whole formula system, but also influential to the performance of the solidification rate of whole formula system and material; (3) light trigger under the irradiation of UV-light, produces the spike (free radical or positively charged ion) of initiated polymerization.
Difference according to triggering mechanism, light trigger can be divided into free radical photo-initiation and cation light initiator, the mechanism of action of pressing radical initiator generation living radical is different, and free radical photo-initiation can be divided into hydrogen-capture-type light initiator and crack type photoinitiator again.In daily industrial production, be most widely used with free radical photo-initiation.
Since American I nmont company has delivered unsaturated polyester/vinylbenzene ultraviolet (UV) light-curable ink technical patent first in nineteen forty-six, photocuring technology keeps high speed development always.In the technical progress process of photocuring system, the research and development of novel photoinitiator system are all the time in occupation of very important position.In radical photopolymerization, benzophenone derivates is to use to get light trigger the most widely.But the uv-absorbing of traditional diphenyl ketone photo initiator is lower, and initiating activity is relatively poor.Hu Xianming etc. disclose preparation 2,3,4-trihydroxybenzophenone a kind of novel method (publication number: 1690042), take pyrogallol as starting raw material, under protection of inert gas, at catalyzer (ZnCl
2, AlCl
3) existence under, in the binary mixed solvent that aromatic hydrocarbon and water form, with the trichlorotoluene zotrichloride reaction, the aftertreatment through aromatic hydrocarbon solvent can obtain 2,3,4-trihydroxybenzophenone productive rate and reach 80～90%.
Have two kinds of means can obtain hydrogen-abstraction high-molecular optical initiator: the one, adopt respectively macromolecular hydrogen donor and macromolecular tertiary amine; In addition coinitiator and light trigger are incorporated on macromolecular chain simultaneously.because benzophenone is cheap, it is more that this type of high-molecular optical initiator is studied, as Carlini etc. by free-radical polymerized and obtain high-molecular optical initiator (C.Carlini, F.Gurzoni, Optically active polymers containing side-chain benzophenone chromophores[J] .Polymer, 1983 (24), 101), Stephen Davidson etc. obtains benzophenone high-molecular optical initiator (R.Stephen Davidson by polycondensation, A.A.Dias, D.Illsley, A new series of type II (benzophenone) polymeric photoinitiators[J] .Photobio.Photochem.A:Chem., 1995 (89), 75.).
Because the ultraviolet maximum absorption wavelength of benzophenone is short, the hydrogen-abstraction high-molecular optical initiators such as thioxanthone, camphorquinone and anthraquinone draw attention gradually.As people such as Jiang Xuesong, epoxide group is incorporated into thioxanthone, a series of high-molecular optical initiators that contain coinitiator amine have been prepared by the open loop polycondensation, do not need to add in addition tertiary amine initiated polymerization (X.S.Jiang effectively, H.J.Xu, J.Yin, Polymeric Amine Bearing Side-Chain Thioxanthone as a Novel Photoinitiator for Photopolymerization[J] .Polymer, 2004; 45:133.).Wang Hongyu prepares and has studied the diphenyl ketone type macromolecular photoinitiator, and amine is incorporated in molecular structure, result of study proves that the macromolecular efficiency of initiation of this class is than the much bigger (Wang Hongyu of the title complex of benzophenone and amine, the research [D] of efficient polymerizable and high molecular benzophenone photoinitiator, Shanghai Communications University, 2006.).
In curing, the small molecules light trigger is easily volatilization and migration in applicable process, causes reaction efficiency to reduce, affect material property, especially the light-curable ink that prints on food Package forbids to use the small molecules light trigger, in order to avoid see through the doggie bag contaminated food products.Polymerizable type light trigger is the effective way that addresses the above problem.This class initiator is to contain simultaneously the monomer of optical active group and unsaturated group in molecule, under the UV irradiation, causes unsaturated performed polymer polymerization and participates in reaction; Also but self initiated polymerization generates polymer; The polymerizable type monomer copolymerization that contains dissimilar light-initiated group can also obtain the good high-molecular optical initiator of efficiency of initiation.This photoinitiator is residual without small molecules, and is good with resin compatible, and non-volatility and transport property problem have improved the performance such as weathering resistance, glossiness of product.In addition, the light trigger high molecular due to the possibility that has reduced its volatilization, thereby has reduced infiltration to people, animal skin, stimulation and to the pollution of environment.
The present invention is just for the shortcoming of small molecules diphenyl ketone photo initiator and nearest development trend, prepared the diphenyl ketone photo initiator that contains coinitiator amine by molecular designing, by polymerisable unsaturated group is incorporated in benzophenone structural, made polymerisable light trigger.
The preparation method of polymerizable photoinitiator of the present invention has following advantage: the designability of (1) molecular structure is strong.(2) preparation cost is low, and is simple to operate.(3) macromole evocating agent has solved light trigger and system is incompatible or consistency is bad disadvantage.(4) low odor, low VOC discharge.
Summary of the invention
The invention provides a kind of polymerizable photoinitiator and preparation method thereof, the present invention is from Molecular Structure Design, not only aided initiating is incorporated in benzophenone structural by molecular designing, also introduced simultaneously unsaturated double-bond, synthesize polymerizable photoinitiator, see its structure, also can be used as novel benzoxazine monomer and use.And its preparation cost is low, and is simple to operate.
The polymerizable photoinitiator of the present invention's preparation, the chemical structural formula of this light trigger is as follows:
R
1, R
2For-H ,-CH
3,-OH or-CH
2Cl.Wherein, the ortho position of in the benzophenone derivates of hydroxyl-OH has at least one substituting group must not be arranged.
The invention provides a kind of synthetic method of polymerizable photoinitiator, comprise following steps: followingly all represent with functional group's molar fraction
(a) benzophenone derivates of monomer 1-1.5 part hydroxyl, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of organic solvents, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5-10h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.2-1.5 part triethylamine (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, 1.2-1.5 part acrylate chloride is joined in constant pressure funnel, controlling a fast 4-5s/ drips, ice bath, lucifuge, after magnetic agitation 12-24h, filter, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
The reaction formula of polymerizable photoinitiator of the present invention is as follows: (take to hydroxyl benzophenone derivant as example)
The benzophenone derivates of the hydroxyl described in the present invention is selected dihydroxy benaophenonel, 4,4'-Dihydroxybenzophenone, 4-hydroxyl-4 '-methyldiphenyl ketone or 4-hydroxyl-4 '-chloromethyl benzophenone.
Organic solvent described in the present invention is selected dimethylbenzene, Isosorbide-5-Nitrae-dioxane, methyl-sulphoxide or toluene.
Embodiment:
Embodiment 1
(a) 1.2 parts of monomers are dissolved in 30 parts of Isosorbide-5-Nitrae-dioxane dihydroxy benaophenonel, 2 parts of paraformaldehydes, 1 part of diglycolamine, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.2 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.2 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 24h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 2
(a) 1.4 parts of monomers are dissolved in 30 parts of butanone dihydroxy benaophenonel, 2 parts of paraformaldehydes, 1 part of diglycolamine, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 10h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 18h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 3
(a) 1.2 parts of 4,4'-Dihydroxybenzophenones of monomer, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of Isosorbide-5-Nitrae-dioxane, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 12h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 4
(a) 1.2 parts of 4,4'-Dihydroxybenzophenones of monomer, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of methyl-sulphoxides, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 10h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 24h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 5
(a) 1.3 parts of 4,4'-Dihydroxybenzophenones of monomer, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of Isosorbide-5-Nitrae-dioxane, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 8h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 24h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 6
(a) 1.5 parts of 4-hydroxyls-4 ' of monomer-methyldiphenyl ketone, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of methyl-sulphoxides, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 18h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 7
(a) 1.5 parts of 4-hydroxyls-4 ' of monomer-methyldiphenyl ketone, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of Isosorbide-5-Nitrae-dioxane, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 12h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 8
(a) 1.2 parts of 4-hydroxyls-4 ' of monomer-chloromethyl benzophenone, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of Isosorbide-5-Nitrae-dioxane, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.3 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.3 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 24h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 9
(a) 1.5 parts of 4-hydroxyls-4 ' of monomer-chloromethyl benzophenone, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of DMFs, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 24h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Embodiment 10
(a) 1.2 parts of monomers are dissolved in 30 parts of methyl-sulphoxides dihydroxy benaophenonel, 2 parts of paraformaldehydes, 1 part of diglycolamine, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 10h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying.
1 part of BZOH and 1.5 parts of triethylamines (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, and 1.5 parts of acrylate chlorides are joined in constant pressure funnel, control to drip a fast 4-5s/ and drip, ice bath, lucifuge after magnetic agitation 24h, is filtered, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
Claims (4)
1. polymerizable photoinitiator, its chemical structural formula is as follows:
R
1, R
2For-H ,-CH
3,-OH or-CH
2Cl.Wherein, the ortho position of in the benzophenone derivates of hydroxyl-OH has at least one substituting group must not be arranged.
2. require the preparation method of 1 described a kind of polymerizable photoinitiator as patent, it is characterized in that comprising the following steps: followingly all represent with functional group's molfraction
(a) benzophenone derivates of 1-1.5 part hydroxyl, 2 parts of paraformaldehydes, 1 part of diglycolamine are dissolved in 30 parts of organic solvents, mechanical stirring is to dissolving fully.Temperature rise rate with 5 ℃/min slowly is heated to the generation that refluxes, after keeping back flow reaction 5-10h, and the stopped heating cool to room temperature, the underpressure distillation desolventizing adds the chloroform dissolving, washs 5 times respectively deionized water wash 5 times with the 0.1N aqueous sodium hydroxide washes.Then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate distillation desolventizing, obtain orange red oily liquids (BZOH) after vacuum-drying;
1 part of BZOH and 1.2-1.5 part triethylamine (TEA) that (b) will obtain are dissolved in 30 parts of methylene dichloride, 1.2-1.5 part acrylate chloride is joined in constant pressure funnel, controlling a fast 4-5s/ drips, ice bath, lucifuge, after magnetic agitation 12-24h, filter, add saturated sodium bicarbonate solution washing 3 times in filtrate, use again deionized water wash 3 times, then use the anhydrous sodium sulfate drying organic layer, filter, after filtrate decompression distillation desolventizing, obtain orange-yellow oily liquid (BZOA) after vacuum-drying.
3. according to claim 2 preparation method, the benzophenone derivates that it is characterized in that the hydroxyl described in step (a) is selected dihydroxy benaophenonel, 4,4'-Dihydroxybenzophenone, 4-hydroxyl-4 '-methyldiphenyl ketone or 4-hydroxyl-4 '-chloromethyl benzophenone.
4. according to claim 2 preparation method is characterized in that the organic solvent described in step (a) selects butanone, Isosorbide-5-Nitrae-dioxane, methyl-sulphoxide or DMF.
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| CN103497263A (en) * | 2013-09-17 | 2014-01-08 | 常州大学 | Benzophenone-containing macromolecular photoinitiator and preparation method thereof |
| CN104230837A (en) * | 2013-06-24 | 2014-12-24 | 北京化工大学 | Aminopyrene type benzoxazine compound and preparation method thereof |
| CN104761661A (en) * | 2015-03-31 | 2015-07-08 | 北京化工大学 | Polymerizable water-soluble benzophenone type photoinitiator and preparation method thereof |
| CN108794660A (en) * | 2017-04-26 | 2018-11-13 | 常州强力先端电子材料有限公司 | Photoinitiator of bifunctionality structure containing sulfone and its preparation method and application |
| CN109734635A (en) * | 2018-12-28 | 2019-05-10 | 天津久日新材料股份有限公司 | A kind of method and application of the photoinitiator introducing light-cured resin and monomer |
| CN111269336A (en) * | 2020-03-22 | 2020-06-12 | 胥彩虹 | Polymerizable photoinitiator and preparation method thereof |
| CN114276241A (en) * | 2021-11-17 | 2022-04-05 | 南昌航空大学 | Bifunctional polymerizable cinnamoyl modified benzophenone photoinitiator and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104230837A (en) * | 2013-06-24 | 2014-12-24 | 北京化工大学 | Aminopyrene type benzoxazine compound and preparation method thereof |
| CN104230837B (en) * | 2013-06-24 | 2016-04-06 | 北京化工大学 | pyrene amine type benzoxazine compound and preparation method thereof |
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| CN108794660B (en) * | 2017-04-26 | 2020-12-01 | 常州强力先端电子材料有限公司 | Bifunctional photoinitiator containing sulfone structure and preparation method and application thereof |
| CN109734635A (en) * | 2018-12-28 | 2019-05-10 | 天津久日新材料股份有限公司 | A kind of method and application of the photoinitiator introducing light-cured resin and monomer |
| CN111269336A (en) * | 2020-03-22 | 2020-06-12 | 胥彩虹 | Polymerizable photoinitiator and preparation method thereof |
| CN114276241A (en) * | 2021-11-17 | 2022-04-05 | 南昌航空大学 | Bifunctional polymerizable cinnamoyl modified benzophenone photoinitiator and preparation method thereof |
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