CN102746480B - Polymerizable macromolecule photoinitiator and preparation method thereof - Google Patents
Polymerizable macromolecule photoinitiator and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a polymerizable macromolecule photoinitiator and a preparation method thereof. The preparation method comprises: adding 4-hydroxybenzophenone and a formaldehyde solution to a three-necked flask filled with an alkali adopted as a catalyst, carrying out heating stirring to a temperature of 95 DEG C, and carrying out a reaction for 2 hours; heating to a temperature of 150 DEG C, carrying out a reaction, and carrying out a reduced pressure suction filtration reaction for 20 minutes; cooling to a temperature of 105 DEG C after completing the reaction, and collecting the product; pouring the product into water to carry out precipitation, and carrying out suction filtration to obtain a benzophenone-containing macromolecule photoinitiator; dissolving the benzophenone-containing macromolecule photoinitiator in an organic solvent, and simultaneously adding the benzophenone-containing macromolecule photoinitiator and a tertiary amine to the three-necked flask to carry out stirring; dissolving acryloyl chloride in an organic solvent, and slowly adding the organic solvent containing the acryloyl chloride to the mixing solution in a dropwise manner, wherein thereaction temperature is 0-5 DEG C; after completing the addition, stirring for 3 hours at a room temperature, and standing overnight; carrying out suction filtration, washing and drying on the resulting solution; and carrying out rotary evaporation to remove the solvent to obtain the polymerizable macromolecule photoinitiator. The photoinitiator prepared by the preparation method of the present invention has characteristics of large molecular weight, relatively small mobility, self-polymerization, and the like.
Description
Technical field
The invention belongs to the light sensitive molecule Material Field, be specifically related to the preparation method that a kind of polymerizable contains the macromolecular photoinitiator of benzophenone.
Background technology
Photopolymerization (claiming again photocuring) is to shine on photosensitive compound by light (UV-light or visible light), make it that a series of optical physics, photochemical reaction occur, generate biologically active fragment, biologically active fragment causes again liquid-state oligomers (comprising monomer) polymerization, and liquid coating moment is converted into the process of solid-state macromolecular material the most at last.
Light trigger is most important in Photopolymer System, and can it be related to formula system oligopolymer and thinner when rayed and be transformed into rapidly solid-state by liquid state.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, this technology is applied to coating, printing ink, tackiness agent, microelectronics in real life at present, tooth section repairs and the field such as biomaterial.
At present, light trigger mainly is divided into cationic and free radical type two large classes.Cation light initiator mainly contains sulfosalt, salt compounded of iodine.Cationic photoinitiator generally is to utilize the ring-opening polymerization of the protonic acid catalysis epoxy group(ing) that cation light initiator produces under illumination or the cationoid polymerisation of electron rich carbon-carbon double bond (such as vinyl ether).The advantage of cation photocuring system maximum is the problem that does not have oxygen inhibition, and cure shrinkage is less and bonding strength is stronger in addition.Shortcoming is that curing speed is slower than free radical system, and cost of material is more expensive.Radical photoinitiator is accepted luminous energy and is become excited state from ground state under illumination, then further resolve into free radical.Free radical is combined with the carbon-carbon double bond of monomer, and carries out chain-growth on this basis, makes carbon-carbon double bond generation polymerization.The radical UV curing system is most widely used system in the photo-cured coating, and advantage is that curing speed is fast, and cost of material is relatively cheap.But problem, the especially latter such as this system existence is shunk greatly, oxygen inhibition usually are the problems that must overcome in the formulating of recipe.Therefore, be necessary radical photoinitiator is improved, solve its oxygen inhibition and shrink the problems such as large.In addition, in the reality prescription, great majority are small molecules light triggers, the photodestruciton reaction can occur when polymerization produce free small organic molecule, and this point restricts its application on biology, medicine and packaging material for food.So, study a kind of self polymerisable macromolecular photoinitiator and reduce photolytic product the impact of system is had good development prospect.
The benzophenone photoinitiator is the most widely radical photoinitiator that uses, but its uv-absorbing is lower, cause effect relatively poor (R.Liska, Journal of Polymer Science PartA:polymerchemistry, 2002 (40): 1504-1518).The people such as F.Sun have studied (Nucl.Instrum.MethodsPhys.Rss., SectB, 2009 (267): 3590-3593) a kind of dynamic performance of siliceous benzophenone derivates light trigger research.Chinese patent CN1850798A (open day: 2006.10.25) disclose a kind of diphenyl ketone photo initiator and preparation method thereof of sulfur-bearing.Chinese patent CN101220106A (open day: 2008.7.16) disclose a kind of silicon-containing polymeric photoinitiator, its synthetic method and purposes.Chinese patent CN1850784A (open day: 2006.10.25) disclose and contain diphenyl ketone photo initiator of phenoxy group and preparation method thereof.
There is following shortcoming in above these methods: 1, the molecular weight less of initiator, and transport property is larger, easily produces free small molecules during photodissociation; 2, do not contain two keys in the molecule, itself is polymerizable not.
Summary of the invention
The object of the invention is to solve the problems of the prior art, from Molecular Structure Design, the two keys in the acrylate are introduced in the resol molecule, provide a kind of molecular weight relatively large, transport property is little, the preparation method of self polymerisable macromolecular photoinitiator.This structure of initiator general formula is as follows:
In the formula, R
1A kind of in hydrogen atom, methyl, methoxyl group, the halogen.
1, a kind of preparation method of polymerisable macromolecular photoinitiator is characterized in that may further comprise the steps:
(1) 4-dihydroxy benaophenonel and excessive formaldehyde solution are joined in the there-necked flask, after mixing, add alkali as a catalyst, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃ of reactions, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain containing the macromolecular photoinitiator of benzophenone;
The macromolecular photoinitiator that contains benzophenone that (2) will obtain is dissolved in the organic solvent, join in the there-necked flask simultaneously with tertiary amine and to stir, acrylate chloride is dissolved in the organic solvent, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night;
(3) mentioned solution is carried out suction filtration, washing, drying, the rotary evaporation desolventizing namely gets polymerisable macromolecular photoinitiator.
2, method according to claim 1 is characterized in that, macromolecular photoinitiator and the tertiary amine that will contain benzophenone in the step (2) join in the there-necked flask simultaneously, and wherein the mol ratio of 4-dihydroxy benaophenonel and tertiary amine is 1: 1～3.
3, method according to claim 1 is characterized in that, the organic solvent described in the step (2) is a kind of in methylene dichloride, trichloromethane, acetone, the ethanol.
4, method according to claim 1 is characterized in that, the tertiary amine described in the step (2) is a kind of in triethylamine, tripropyl amine, tri-isopropyl amine, the tri-n-butylamine.
5, method according to claim 1 is characterized in that, acrylate chloride is dripped in mixed solution described in the step (2), and wherein the mol ratio of 4-dihydroxy benaophenonel and acrylate chloride is 1: 1～2.
6, method according to claim 1 is characterized in that, acrylate chloride is dripped into mixed solution described in the step (2), and wherein acrylate chloride is a kind of in methacrylic chloride, methoxyl group propylene acyl chlorides, the 2-propenyl chloride acyl chlorides.
7, method according to claim 1 is characterized in that, solution suction filtration, washing after reaction is finished described in the step (3), and wherein washing process is used respectively 1mol/L HCl solution, 1mol/L NaHCO
3Solution, deionized water wash three times.
Compared with prior art, the present invention has the following advantages:
1, the preparation method of a kind of polymerisable macromolecular photoinitiator provided by the invention has avoided too much reactions steps, and operational condition is simple, and is active high, reduced the cost in the actual mechanical process.
2, the polymerisable macromolecular photoinitiator of the present invention's preparation is the 300nm place at wavelength, can absorb UV-light, and trigger monomer carries out polymerization, has improved the initiation performance of light trigger.
3, the polymerisable macromolecular photoinitiator of the present invention's preparation, containing two keys in the molecule can self-polymerization, has increased molecular weight, has reduced the free small organic molecule that the photodestruciton reaction produces, be applied to biomaterial, the potentiality in food, drug packing material field.
Embodiment
Embodiment 1
Synthesizing of the polymerisable macromolecule photoinitiator that hydrogen replaces
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44gNaOH, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 21.2g methylene dichloride, join in the there-necked flask simultaneously with the 10.21g triethylamine and to stir, the 5.48g acrylate chloride is dissolved in the 11g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, desolventizing, and obtaining yellow solid is the polymerisable macromolecule photoinitiator that hydrogen replaces, its structure is shown in structural formula 1.
Structural formula 1
Embodiment 2
Synthesizing of methyl substituted polymerisable macromolecule photoinitiator
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44gNaOH, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 22g methylene dichloride, join in the there-necked flask simultaneously with the 10.21g triethylamine and to stir, the 6.33g methacrylic chloride is dissolved in the 13g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, desolventizing, and obtaining yellow solid is methyl substituted polymerisable macromolecule photoinitiator, its structure is shown in structural formula 2.
Structural formula 2
Embodiment 3
Synthesizing of the polymerisable macromolecule photoinitiator of methoxy substitution
10g4-dihydroxy benaophenonel and 4.6g formaldehyde solution are joined in the there-necked flask, add 0.5g alkali, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 21g methylene dichloride, join in the there-necked flask simultaneously with the 10.3g triethylamine and to stir, 7.3g methoxyl group propylene acyl chlorides is dissolved in the 15g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, and desolventizing obtains the polymerisable macromolecule photoinitiator that yellow solid is methoxy substitution, and its structure is shown in structural formula 3.
Structural formula 3
Embodiment 4
Synthesizing of the polymerisable macromolecule photoinitiator that chlorine replaces
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44g alkali, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 22g methylene dichloride, join in the there-necked flask simultaneously with the 10.21g triethylamine and to stir, 7.57g2-propenyl chloride acyl chlorides is dissolved in the 15g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, desolventizing, and obtaining yellow solid is the polymerisable macromolecule photoinitiator that chlorine replaces, its structure is shown in structural formula 4.
Structural formula 4
Embodiment 5
Synthesizing of the polymerisable macromolecule photoinitiator that hydrogen replaces
11.5g4-dihydroxy benaophenonel and 5.22g formaldehyde solution are joined in the there-necked flask, add 0.5gNaOH, heated and stirred to 98 ℃, reaction 2h; Then be warming up to 145 ℃, carry out decompress filter reaction 20min, be cooled to 104 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 25g methylene dichloride, join in the there-necked flask simultaneously with the 11.74g triethylamine and to stir, the 6.3g acrylate chloride is dissolved in the 12.5g methylene dichloride, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, desolventizing, and obtaining yellow solid is the polymerisable macromolecule photoinitiator that hydrogen replaces, its structure is shown in structural formula 5.
Structural formula 5
Embodiment 6
Synthesizing of the polymerisable macromolecule photoinitiator that hydrogen replaces
11.5g4-dihydroxy benaophenonel and 5.22g formaldehyde solution are joined in the there-necked flask, add 0.5gNaOH, heated and stirred to 98 ℃, reaction 2h; Then be warming up to 145 ℃, carry out decompress filter reaction 20min, be cooled to 104 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 25g acetone, join in the there-necked flask simultaneously with the 11.74g triethylamine and to stir, the 6.3g acrylate chloride is dissolved in the 12.5g acetone, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, desolventizing, and obtaining yellow solid is the polymerisable macromolecule photoinitiator that hydrogen replaces, its structure is shown in structural formula 6.
Structural formula 6
Embodiment 7
Synthesizing of methyl substituted polymerisable macromolecule photoinitiator
10g4-dihydroxy benaophenonel and 4.5g formaldehyde solution are joined in the there-necked flask, add 0.44gNaOH, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain the faint yellow macromolecular photoinitiator that contains benzophenone.The faint yellow macromolecular photoinitiator that contains benzophenone that obtains is dissolved in the 22g trichloromethane, join in the there-necked flask simultaneously with the 10.21g triethylamine and to stir, the 6.33g methacrylic chloride is dissolved in the 13g trichloromethane, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night.Yellow liquid obtained above is used dilute hydrochloric acid solution (1mol/L), NaHCO successively
3(1mol/L) behind solution and the distilled water wash (retaining liquid is upper strata liquid), use anhydrous Na
2SO
4Drying is filtered, desolventizing, and obtaining yellow solid is methyl substituted polymerisable macromolecule photoinitiator, its structure is shown in structural formula 7.
Structural formula 7
Claims (8)
1. polymerisable macromolecular photoinitiator, general structure is as follows:
In the formula, R
1A kind of in hydrogen atom, methyl, methoxyl group, the halogen.
2. the preparation method of a polymerisable macromolecular photoinitiator is characterized in that may further comprise the steps:
(1) 4-dihydroxy benaophenonel and excessive formaldehyde solution are joined in the there-necked flask, after mixing, add alkali as a catalyst, heated and stirred to 95 ℃, reaction 2h; Then be warming up to 150 ℃ of reactions, carry out decompress filter reaction 20min, be cooled to 105 ℃ after reaction finishes and collect product, product is poured into water precipitation, behind suction filtration, obtain containing the macromolecular photoinitiator of benzophenone;
The macromolecular photoinitiator that contains benzophenone that (2) will obtain is dissolved in the organic solvent, join in the there-necked flask simultaneously with tertiary amine and to stir, acrylate chloride is dissolved in the organic solvent, slowly drip mixed solution to there-necked flask in 3 hours, temperature of reaction is 0-5 ℃, after dropwising, stir 3h under the room temperature, standing over night;
(3) mentioned solution is carried out suction filtration, washing, drying, the rotary evaporation desolventizing namely gets polymerisable macromolecular photoinitiator.
3. method according to claim 2 is characterized in that, macromolecular photoinitiator and the tertiary amine that will contain benzophenone in the step (2) join in the there-necked flask simultaneously, and wherein the mol ratio of 4-dihydroxy benaophenonel and tertiary amine is 1:1～3.
4. method according to claim 2 is characterized in that, the organic solvent described in the step (2) is a kind of in methylene dichloride, trichloromethane, acetone, the ethanol.
5. method according to claim 2 is characterized in that, the tertiary amine described in the step (2) is a kind of in triethylamine, tripropyl amine, tri-isopropyl amine, the tri-n-butylamine.
6. method according to claim 2 is characterized in that, acrylate chloride is dripped in mixed solution described in the step (2), and wherein the mol ratio of 4-dihydroxy benaophenonel and acrylate chloride is 1:1～2.
7. method according to claim 2 is characterized in that, acrylate chloride is dripped into mixed solution described in the step (2), and wherein acrylate chloride is substitutable for a kind of in methacrylic chloride, methoxyl group propylene acyl chlorides, the 2-propenyl chloride acyl chlorides.
8. method according to claim 2 is characterized in that, solution suction filtration, washing after reaction is finished described in the step (3), and wherein washing process is used respectively 1mol/L HCl solution, 1mol/L NaHCO
3Solution, deionized water wash three times.
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| CN103122041A (en) * | 2013-01-31 | 2013-05-29 | 北京化工大学常州先进材料研究院 | Novel self-hydrogen-supplying diphenyl ketone macromolecular photoinitiator and preparation method thereof |
| CN103113498A (en) * | 2013-01-31 | 2013-05-22 | 北京化工大学常州先进材料研究院 | Polymeric photoinitiator and preparation method thereof |
| CN105384852B (en) * | 2015-11-23 | 2017-06-23 | 中山大学 | A kind of polymerizable type light trigger based on benzophenone and preparation method thereof |
| CN110922515B (en) * | 2018-09-19 | 2022-05-03 | 北京鼎材科技有限公司 | Macromolecular photoinitiator and application and preparation method thereof |
| CN109988262B (en) * | 2019-04-03 | 2020-07-14 | 北京化工大学 | Polymeric macromolecular photoinitiator and preparation method thereof |
| CN109970727B (en) * | 2019-04-03 | 2021-04-06 | 北京化工大学 | Long-wavelength polymerizable photoinitiator and preparation method thereof |
| CN110003365B (en) * | 2019-04-03 | 2020-06-09 | 北京化工大学 | Macromolecular photoinitiator and preparation method thereof |
| CN109988268B (en) * | 2019-04-03 | 2020-08-04 | 北京化工大学 | Copolymerization macromolecular photoinitiator and preparation method thereof |
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| CN1847275A (en) * | 2006-04-13 | 2006-10-18 | 上海交通大学 | High molecular benzophenone photoinitiator and its prepn process |
| CN101812141A (en) * | 2010-01-08 | 2010-08-25 | 北京化工大学 | Diphenyl ketone photo initiator containing cyclic acctals and preparation method thereof |
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| CN1847275A (en) * | 2006-04-13 | 2006-10-18 | 上海交通大学 | High molecular benzophenone photoinitiator and its prepn process |
| CN101812141A (en) * | 2010-01-08 | 2010-08-25 | 北京化工大学 | Diphenyl ketone photo initiator containing cyclic acctals and preparation method thereof |
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