CN102241792B - Hydrophilic high-molecular polymer photosensitive initiator and preparation method thereof - Google Patents
Hydrophilic high-molecular polymer photosensitive initiator and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 title claims abstract description 19
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- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
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- 238000003756 stirring Methods 0.000 claims description 31
- -1 4-ethenylphenyl dichloride phosphine Chemical compound 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
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- 239000007787 solid Substances 0.000 claims description 13
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 229940050176 methyl chloride Drugs 0.000 claims description 8
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
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- 230000006837 decompression Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
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- AOIAURCMPYRFGB-UHFFFAOYSA-N Cc1ccc(CC#C)cc1 Chemical compound Cc1ccc(CC#C)cc1 AOIAURCMPYRFGB-UHFFFAOYSA-N 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a hydrophilic high-molecular polymer photosensitive initiator, and a preparation method thereof. A repeating structure unit of the hydrophilic high-molecular polymer photosensitive initiator is represented by a formula in the specification, and in the formula, m is 50 to 1000, n is 50 to 1000, R' is selected from hydrogen or alkyl or hydroxyalkyl containing two-four carbon atoms. The photosensitive initiator is an acrylate-4-vinylphenyl-bis(2,4,6-trimethylbenzene benzoyl)phosphine oxide copolymer. The acrylate-4-vinylphenyl-bis(2,4,6-trimethylbenzene benzoyl)phosphine oxide copolymer prepared in the invention has a good hydrophilism which allows the storage stability to be improved, has a macromolecular structure which allows no chemical migration after film forming to be achieved and residual smell of the film to be reduced, and enables the cost to be reduced.
Description
Technical field
The present invention relates to light trigger, specifically, is a kind of hydrophilic high molecular polymer photoinitiator and preparation method thereof.
Background technology
U.S. company has delivered not saturated polyester/vinylbenzene UV-light UV curing technology patent first from nineteen forty-six; Photocuring technology is used widely at industrial circles such as photo-cured coating, photoresist material, light-curable ink, electronic package material, tackiness agent, optical media replication, paper glazings, and photocuring technology keeps high speed development.Ultraviolet-curing paint obtains tremendous development on woodenware, major advantage comprises: the first, and rate of drying is fast.Behind the UV coating of constructing, only need UV-irradiation through several seconds, just can be in the moment film forming.The second, disposable one-tenth thickness.UV coating can be made into 100% solid content, has improved production efficiency.The 3rd, lower organic composition volatilization (VOC) is than the more environmental protection of traditional solvent based coating.But because monomer toxicity is big, it is residual still to have small amounts of monomer after the final film forming, and healthy unfavorable to the workmen also has certain influence to environment, the first-elected certainly aqueous woodware paint of product of environmental protection.With water is thinner, nonpoisonous and tasteless, and loopful is protected, and is all harmless to environment and human body, developed rapidly in recent years.Present aqueous woodware paint product is main with single-component, and there are limitation in rate of drying, physicals.Under this overall situation, aqueous wooden ware UV coating arises at the historic moment, and the drying that has the environmental protection that has been equipped with water-miscible paint and UV lacquer concurrently is characteristics fast, do not contain the small molecules acrylate monomer, no chemical transport, and toxic residue is little.Two (2,4, the 6-trimethylbenzoyl)-phenyl-phosphine oxides are current water-based UV efficiency light initiators commonly used, and still, because its lower molecular weight is prone to produce migration, volatilization in the dry film after construction, the smell extended residual is in paint film; Wetting ability is not enough, causes separating out of initiator after the standing storage, the drying effect that the stability of water-based system and consistency influence integral body are filmed.For the aqueous photo-curing system; After long storage process and film forming; Volatilization and migration owing to take place with light solid system consistency difference and reactivity in small molecules type light trigger by force and easily; This has caused the photopolymerization efficiency of initiation low on the one hand, also can cause the product xanthochromia on the other hand, produce smell and toxicity, is difficult to compliance with environmental protection requirements.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of efficient, environmental protection, suitable more aqueous wooden ware UV solidified hydrophilic high molecular polymer photoinitiator and preparation method thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is: a kind of hydrophilic high molecular polymer photoinitiator, and the repeated structural unit of hydrophilic high molecular polymer photoinitiator is as follows:
In the formula, m=50-1000, n=50-1000, R ' are selected from hydrogen or contain the alkyl or the hydroxyalkyl of 2-4 carbon atom.
The preparation method of described hydrophilic high molecular polymer photoinitiator may further comprise the steps:
1) preparation of starting raw material 4-ethenylphenyl dichloride phosphine
2) preparation of monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
Under the exsiccant nitrogen atmosphere, in toluene, add metallic lithium bits and crystallization naphthalene, stirring at room; Reaction mixture becomes aterrimus, continues to stir, and drips the toluene solution of 4-ethenylphenyl dichloride phosphine; Control reaction temperature dripped at 20-25 ℃ in 50 minutes～70 minutes in the dropping process, and continued reaction 0.5 hour～1 hour; Under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4 then; The toluene solution of 6-tri-methyl chloride dripped in 1.5 hours～2 hours, and at room temperature continued reaction 1 hour～1.5 hours; Then reaction mixture is warmed to 30-40 ℃, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution under stirring fast, and reacted 0.5 hour～1 hour; In reaction mixture, add entry, stir, filter and separatory, organic phase uses mass percent concentration to be 10%NaHCO respectively
3Solution and water are respectively washed 2～3 times, anhydrous MgSO
4Dry; After removing solvent under filtration and the decompression, get thick product; Thick product is separated out through petroleum ether-ethyl acetate again, removes solution mutually after vacuum-drying gets faint yellow solid;
3) preparation of acrylic ester copolymer 4-ethenylphenyl-two (2,4,6-trimethylbenzene benzoyl-) phosphine oxide
With water, vinylformic acid or propenoate, on go on foot prepared monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxides and Diisopropyl azodicarboxylate at room temperature mixes; The gained mixture is heated to 60-70 ℃ under stirring fast, reacted 5～7 hours, is cooled to room temperature; Through spinning, get white copolymer, wash 2～3 times with the petroleum ether-ethyl acetate mixed solvent; Through vacuum-drying, get white solid.
Said step 1) is that 4-ethylphenyl dichloride phosphine is through chlorination, high temperature BaCl
2Take off the HCl method under the effect and make 4-ethenylphenyl dichloride phosphine.
Said step 1) is by vinylbenzene and PCl
3At anhydrous AlCl
3Make 4-ethenylphenyl dichloride phosphine under the effect.
Said step 2) be: under the exsiccant nitrogen atmosphere, in 300mL toluene, add metallic lithium bits 0.92mol and crystallization naphthalene 0.008mol, stirring at room 10min, reaction mixture becomes aterrimus, continues to stir; 0.20mol is dissolved in the 120mL toluene with 4-ethenylphenyl dichloride phosphine; The toluene solution that drips 4-ethenylphenyl dichloride phosphine is in above-mentioned solution; Control reaction temperature drips about 1 hour at 20-25 ℃ in the dropping process, and continues reaction 0.5 hour; Under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4 then; The toluene solution of 6-tri-methyl chloride, described 2,4; The toluene solution of 6-tri-methyl chloride is 2,4, and 6-tri-methyl chloride 0.4mol is dissolved in the 200mL toluene and makes; 1.5 hour drip, and at room temperature continue reaction 1 hour; Then reaction mixture is warmed to 30-40 ℃, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution 0.2mol under stirring fast, and reacted 0.5 hour; Stopped reaction adds 40mL water in reaction mixture, stir, filter and separatory, and organic phase uses mass percent concentration to be 10%NaHCO respectively
3Solution and water are respectively washed 2 times, anhydrous MgSO
4Drying after removing solvent under filtration and the decompression, gets thick product; Thick product is separated out through weight ratio 9: 1,120-200mL petroleum ether-ethyl acetate again, removes solution mutually after vacuum-drying gets faint yellow solid.
Said step 3) is: water 50mL, vinylformic acid 10-15g, monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide 0.5-0.8g and Diisopropyl azodicarboxylate 0.1-0.2g are at room temperature mixed; The gained mixture is heated to 60-70 ℃ under stirring fast, reacted 2～6 hours, is cooled to room temperature; Through spinning; Get white copolymer, wash 2 times, remove excessive not polymeric acrylate monomer and other impurity in order to 2: 1 petroleum ether-ethyl acetate mixed solvent of weight ratio; Through vacuum-drying, get white solid.
The acrylic ester copolymer 4-ethenylphenyl that the present invention makes-two (2,4,6-trimethylbenzene benzoyl-) phosphine oxide has good hydrophilicity and makes stability in storage improve; Macromolecular structure makes does not have chemical transport after the film forming, and the residual smell of filming reduces; Reduce cost.
Embodiment
Below in conjunction with embodiment the present invention is done further explain:
One. the preparation of polymer monomer
1) preparation of starting raw material 4-ethenylphenyl dichloride phosphine
4-ethenylphenyl dichloride phosphine can be by literature method (CA:56:46102) by 4-ethylphenyl dichloride phosphine through chlorination, high temperature BaCl
2Taking off the HCl method under the effect makes; Also can adopt other bibliographical information similar approach (J.Chem.Soc.1935,462; J.Chem.Soc.1944,276.) by vinylbenzene and PCl
3At anhydrous AlCl
3Make under the effect.
2) preparation of monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
Under the exsiccant nitrogen atmosphere, in 300mL toluene, add the metallic lithium bits (6.5g, 0.92mol) and crystallization naphthalene (1.0g.0.008mol), stirring at room 10min, reaction mixture becomes aterrimus.Continue to stir, (41.0g 0.20mol) is dissolved in the 120mL toluene with 4-ethenylphenyl dichloride phosphine; The toluene solution that drips 4-ethenylphenyl dichloride phosphine is in above-mentioned solution; Control reaction temperature drips about 1 hour at 20-25 ℃ in the dropping process, and continues reaction 0.5 hour.Under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4 then; The toluene solution of 6-tri-methyl chloride, described 2,4; The toluene solution of 6-tri-methyl chloride is 2,4,6-tri-methyl chloride (73.0g; 0.4mol) be dissolved in the 200mL toluene and make, dripped in 1.5 hours, and at room temperature continue reaction 1 hour.Then reaction mixture is warmed to 30-40 ℃, and the dropping mass percent concentration is that (23.0g 0.2mol), and reacted 0.5 hour 30% aqueous hydrogen peroxide solution under stirring fast.Stopped reaction.In reaction mixture, add 40mL water, stir, filter and separatory, organic phase uses mass percent concentration to be 10%NaHCO respectively
3Solution and water are respectively washed 2 times, anhydrous MgSO
4Dry.After reaching decompression after filtration and down removing solvent, must thick product 82.6g.(120-200mL) separate out again, removes solution mutually after vacuum-drying gets faint yellow solid 73.0g (yield 82%), the product structure warp by weight ratio 9: 1 through petroleum ether-ethyl acetate for this thick product
1H,
31P NMR check, purity reaches 95%.
Two. with the preparation of multipolymer-title product acrylic ester copolymer 4-ethenylphenyl-two (2,4,6-trimethylbenzene benzoyl-) phosphine oxide (APBPO) of vinylformic acid (ester)
During R '=H, monomer is a vinylformic acid
With vinylformic acid is example:
With water (50mL), vinylformic acid (10g), on go on foot prepared monomer 4-ethenylphenyl-two (2; 4; The 6-trimethylbenzoyl) phosphine oxide (0.5g) and Diisopropyl azodicarboxylate (0.1g) at room temperature mix, and the gained mixture is heated to 60-70 ℃ under stirring fast, reacted 6 hours.Be cooled to room temperature,, get white copolymer, wash (each 10mL) 2 times,, get white solid 9.7g (yield 92%), the product warp through vacuum-drying with petroleum ether-ethyl acetate (2: 1 weight ratios) mixed solvent through spinning
1H NMR measures (solvent: DMSO-d
6), the content of photosensitive monomer in multipolymer accounts for 4.9% of weight.Through measuring, this multipolymer is that solubleness can reach 12g/L (need add NaOH aqueous solution regulator solution pH value) in an aqueous medium of 7 at pH, demonstrates better water solubility.
With the ethyl propenoate is example:
With water (50mL), ethyl propenoate (13g), on go on foot prepared monomer 4-ethenylphenyl-two (2; 4; The 6-trimethylbenzoyl) phosphine oxide (0.6g) and Diisopropyl azodicarboxylate (0.2g) at room temperature mix, and the gained mixture is heated to 60-70 ℃ under stirring fast, reacted 4 hours.Be cooled to room temperature,, get white copolymer, wash (each 10mL) 2 times,, get white solid 11.2g (yield 81%), the product warp through vacuum-drying with petroleum ether-ethyl acetate (2: 1 weight ratios) mixed solvent through spinning
1H NMR measures (solvent: DMSO-d
6), the content of photosensitive monomer in multipolymer accounts for 4.2% of weight.Through measuring, this multipolymer is solubleness 4g/L (need add NaOH aqueous solution regulator solution pH value) in an aqueous medium of 7 at pH, water-soluble decline.
Can certainly select the vinylformic acid glycol ester for use, or the mixture of several kinds of propenoate.No longer specifically narrate at this.
Three, the application testing of APBPO in waterborne UV coating
1) test objective: contrast four light-initiated efficiency of initiations
UVNUL MS-40, vapour crust 500, vapour crust 819DW, hydrophilic high molecular polymer photoinitiator (APBPO).
2) TP:
Solidified nature relatively
With 1. UVNUL MS-40,2. vapour crust 500,3. vapour crust 819DW, 4. hydrophilic high molecular polymer photoinitiator (APBPO) is a light trigger, is mixed with corresponding ultraviolet light polymerization varnish preparation.
Table 1
The varnish 1-4 that is mixed with constructs on tinplate with 10 micro wires rod spreader, is cured luminous energy 90mj/cm with 10 meters/minute speed with a power 500W mercury lamp
2Record obtains the surface of good effect and thoroughly solidifies number of times under the needed lamp, and what smell was maximum is 5 grades, and what smell was minimum is 1 grade.Huang Du is measured by the full-automatic color difference meter of SC-80C.The result is as shown in table 2
Table 2
| The varnish preparation | All solidify required number of pass times | Oder levels | Huang Du | Store and all solidify required number of pass times after 3 months | Consistency with water |
| Preparation 1 | 5 | 5 | 0.56 | 6 | 5 |
| Preparation 2 | 4 | 3 | 0.55 | 5 | 4 |
| Preparation 3 | 4 | 3 | 0.55 | 4 | 3 |
| Preparation 4 | 2 | 1 | 0.53 | 2 | 1 |
Annotate: 1 is best 5 for the poorest
3) test-results
These results show that the curing speed of compound of the present invention is higher than the curing speed that contrasts initiator.Stink after the varnish of doing light trigger with The compounds of this invention (APBPO) solidifies all is lower than the varnish of making initiator of UVNUL MS-40, vapour crust 500, vapour crust 819DW, and the xanthochromia after all varnish curing is also variant.And after the standing storage; With the varnish that UVNUL MS-40 and vapour crust 500 are processed, all solidifying required number of pass times increases, and explains that the initiator wetting ability is not enough; That causes initiator after the standing storage separates out the stability of water-based system and the whole drying effect of filming of consistency influence.And vapour crust 819DW makees the varnish of initiator, though efficiency of initiation does not become, smell is also much larger than process the smell that the varnish ultraviolet light polymerization is filmed with APBPO.
4) conclusion
The preparation that long chains of modified phosphine oxide photoinitiator of the present invention (APBPO) is processed; Smell, and the consistency of water, curing efficiency, extended storage stability aspect be UVNUL MS-40, vapour crust 500, vapour crust 819DW (two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide) make initiator varnish incomparable.Improve the performance of each side, met environmental protection requirement.
Above-described embodiment only is used to explain technological thought of the present invention and characteristics; Its purpose is to make those skilled in the art can understand content of the present invention and implements according to this; Can not only limit claim of the present invention with present embodiment; Be equal variation or the modification that all disclosed spirit is done, still drop in the claim of the present invention.
Claims (6)
1. a hydrophilic high molecular polymer photoinitiator is characterized in that, the repeated structural unit of hydrophilic high molecular polymer photoinitiator is as follows:
In the formula, m=50-1000, n=50-1000, R ' are selected from hydrogen or contain the alkyl or the hydroxyalkyl of 2-4 carbon atom.
2. the preparation method of hydrophilic high molecular polymer photoinitiator as claimed in claim 1 is characterized in that, may further comprise the steps:
1) preparation of starting raw material 4-ethenylphenyl dichloride phosphine
2) preparation of monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
Under the exsiccant nitrogen atmosphere, in toluene, add metallic lithium bits and crystallization naphthalene, stirring at room; Reaction mixture becomes aterrimus, continues to stir, and drips the toluene solution of 4-ethenylphenyl dichloride phosphine; Control reaction temperature dripped at 20-25 ℃ in 50 minutes～70 minutes in the dropping process, and continued reaction 0.5 hour～1 hour; Under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4 then; The toluene solution of 6-tri-methyl chloride dripped in 1.5 hours～2 hours, and at room temperature continued reaction 1 hour～1.5 hours; Then reaction mixture is warmed to 30-40 ℃, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution under stirring fast, and reacted 0.5 hour～1 hour; In reaction mixture, add entry, stir, filter and separatory, organic phase uses mass percent concentration to be 10%NaHCO respectively
3Solution and water are respectively washed 2～3 times, anhydrous MgSO
4Dry; After removing solvent under filtration and the decompression, get thick product; Thick product is separated out through petroleum ether-ethyl acetate again, removes solution mutually after vacuum-drying gets faint yellow solid;
3) preparation of vinylformic acid or acrylic ester copolymer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxide
With water, vinylformic acid or propenoate, on go on foot prepared monomer 4-ethenylphenyl-two (2,4, the 6-trimethylbenzoyl) phosphine oxides and Diisopropyl azodicarboxylate at room temperature mixes; The gained mixture is heated to 60-70 ℃ under stirring fast, reacted 5～7 hours, is cooled to room temperature; Through spinning, get white copolymer, wash 2～3 times with the petroleum ether-ethyl acetate mixed solvent; Through vacuum-drying, get white solid.
3. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 2 is characterized in that, said step 1) is that 4-ethylphenyl dichloride phosphine is through chlorination, high temperature BaCl
2Take off the HCl method under the effect and make 4-ethenylphenyl dichloride phosphine.
4. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 2 is characterized in that, said step 1) is by vinylbenzene and PCl
3At anhydrous AlCl
3Making 4-ethenylphenyl dichloride phosphine under the effect replaces.
5. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 2; It is characterized in that; Said step 2) is: under the exsiccant nitrogen atmosphere, in 300mL toluene, add metallic lithium bits 0.92mol and crystallization naphthalene 0.008mol, stirring at room l0min; Reaction mixture becomes aterrimus, continues to stir; 0.20mol is dissolved in the 120mL toluene with 4-ethenylphenyl dichloride phosphine, and the toluene solution that drips 4-ethenylphenyl dichloride phosphine is in above-mentioned solution, and control reaction temperature dripped at 20-25 ℃ in 1 hour in the dropping process, and continued reaction 0.5 hour; Under the ice-water bath cooling and stirring, in reaction mixture, drip 2,4 then; The toluene solution of 6-tri-methyl chloride, described 2,4; The toluene solution of 6-tri-methyl chloride is 2,4, and 6-tri-methyl chloride 0.4mol is dissolved in the 200mL toluene and makes; 1.5 hour drip, and at room temperature continue reaction 1 hour; Then reaction mixture is warmed to 30-40 ℃, and the dropping mass percent concentration is 30% aqueous hydrogen peroxide solution 0.2mol under stirring fast, and reacted 0.5 hour; Stopped reaction adds 40mL water in reaction mixture, stir, filter and separatory, and organic phase uses mass percent concentration to be 10%NaHCO respectively
3Solution and water are respectively washed 2 times, anhydrous MgSO
4Drying after removing solvent under filtration and the decompression, gets thick product; Thick product is separated out through weight ratio 9: 1,120-200mL petroleum ether-ethyl acetate again, removes solution mutually after vacuum-drying gets faint yellow solid.
6. the preparation method of hydrophilic high molecular polymer photoinitiator according to claim 5 is characterized in that, said step 3) is: with water 50mL, vinylformic acid 10-15g, monomer 4-ethenylphenyl-two (2; 4,6-trimethylbenzoyl) phosphine oxide 0.5-0.8g and Diisopropyl azodicarboxylate 0.1-0.2g at room temperature mix, and the gained mixture is being heated to 60-70 ℃ under stirring fast; Reacted 5～6 hours, and be cooled to room temperature, through spinning; Get white copolymer, wash 2 times, remove excessive not polymeric acrylic acid and other impurity in order to 2: 1 petroleum ether-ethyl acetate mixed solvent of weight ratio; Through vacuum-drying, get white solid.
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| WO2014051026A1 (en) * | 2012-09-27 | 2014-04-03 | 富士フイルム株式会社 | Ink composition, ink jet recording method, printed material, bisacyl phosphine oxide compound, and monoacyl phosphine oxide compound |
| JP6016768B2 (en) | 2013-02-21 | 2016-10-26 | 富士フイルム株式会社 | Ink composition, ink jet recording method, and polymer initiator |
| CN105837731A (en) * | 2016-03-30 | 2016-08-10 | 天津市裕北涂料有限公司 | Macromolecular photoinitiator and preparation method thereof |
| CN110144020B (en) * | 2019-06-11 | 2021-11-02 | 长沙新宇高分子科技有限公司 | Cyclodextrin-based photoinitiator, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348470A (en) * | 1999-03-16 | 2002-05-08 | 法玛西雅格罗宁根有限公司 | Hydrophilic macromolecular compounds |
| CN100436461C (en) * | 2003-07-31 | 2008-11-26 | 巴斯福股份公司 | A process for the preparation of acylphosphines |
| WO2009068590A1 (en) * | 2007-11-29 | 2009-06-04 | Agfa Graphics Nv | Preparation method of copolymerizable photoinitiators |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1348470A (en) * | 1999-03-16 | 2002-05-08 | 法玛西雅格罗宁根有限公司 | Hydrophilic macromolecular compounds |
| CN100436461C (en) * | 2003-07-31 | 2008-11-26 | 巴斯福股份公司 | A process for the preparation of acylphosphines |
| WO2009068590A1 (en) * | 2007-11-29 | 2009-06-04 | Agfa Graphics Nv | Preparation method of copolymerizable photoinitiators |
Non-Patent Citations (1)
| Title |
|---|
| LUIGI ANGIOLINI et al.POLYMERIC PHOTOINITIATORS BEARING SIDE-CHAIN BENZOYLDIPHENYLPHOSPHINOXIDE MOIETIES FOR UV CURABLE COATINGS..《Journal of Applied Polymer Science》.1994,第51卷 * |
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