CN101619110B - Water-soluble photo-polymerization initiator and preparation method thereof - Google Patents
Water-soluble photo-polymerization initiator and preparation method thereof Download PDFInfo
- Publication number
- CN101619110B CN101619110B CN2008101161382A CN200810116138A CN101619110B CN 101619110 B CN101619110 B CN 101619110B CN 2008101161382 A CN2008101161382 A CN 2008101161382A CN 200810116138 A CN200810116138 A CN 200810116138A CN 101619110 B CN101619110 B CN 101619110B
- Authority
- CN
- China
- Prior art keywords
- amino
- hours
- polymerization initiator
- initiator
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 CC*C1C(C)CCC1 Chemical compound CC*C1C(C)CCC1 0.000 description 5
- DVIMGHWEXQZITN-UHFFFAOYSA-N CC(C)C(COCCOc(cc1)ccc1C(C(C)(C)O)=O)NCl Chemical compound CC(C)C(COCCOc(cc1)ccc1C(C(C)(C)O)=O)NCl DVIMGHWEXQZITN-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a water-soluble photo-polymerization initiator and a preparation method thereof, and belongs to the field of photo-polymerization. The prior photo-polymerization initiator has hydrophobic property, and limits the application and popularization of the photo-polymerization technology in protein pharmaceutical conveying systems and tissue engineering fields. The chemical structure of the initiator provided by the invention is represented as general formula I, II or III. After a primary hydroxyl group of Irgacure 2959 is halogenated, the primary hydroxyl group reacts with amino alcohol after amino protection or diamine with protected single amido under an alkali condition, and a product is subjected to acid hydrolysis to obtain the water-soluble photo-polymerization initiator I, II or III. The initiator has good monomer initiated polymerization capacity and biocompatibility, has high water solubility and reaction activity at the same time, and can be applied in the field of biomaterials. In the formula, R1 and R3 are selected from alkyl chains containing n methylene units respectively, wherein n is more than 1 and less than 6; R2 is isopropyl or 2-isobutyl; and R is chloride ions or trifluoroacetic ions.
Description
Technical field
The invention belongs to the photopolymerization field, be specifically related to a kind of water-soluble photo-polymerization initiator and preparation method thereof.
Background technology
Since nineteen sixty-eight, Germany Bayer company successfully developed curable wood coating, light polymerization technique is except being used widely in fields such as coating, printing ink, tackiness agent, microelectronics and the reparations of tooth section, because this polymerization technique has the polymerizing condition gentleness, fixed cell is rapid, advantages such as cell mortality is low, therefore in organizational project, biological fields such as drug conveying are also paid attention to greatly.The photopolymerization system generally comprises three fundamentals: (1) light source, crack initiator is provided, and produce free radical, keep the energy of polyreaction; (2) light trigger, be used to produce can initiated polymerization free radical or ion; (3) monomer is used to produce polymkeric substance.
At present, its chemical structure of initiator that is used for light polymerization technique is abundant, but most light trigger has hydrophobic property, and solubleness is extremely low in the aqueous solution, even the light trigger Irgacure2959 of Ciba company exploitation has amphipathic characteristic, but the dissolving situation in the aqueous solution allows of no optimist.The hydrophobic property of light trigger has had a strong impact on light polymerization technique at the pharmaceutical grade protein delivery system, application in the field of tissue engineering technology and popularization.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, provide a kind of preparation condition gentleness, water-soluble photo-polymerization initiator easy and simple to handle and preparation method thereof.Initiator provided by the present invention has excellent monomer initiated polymerization ability and biocompatibility, and water-soluble strong, initiator structure functional end-group chemically reactive height, can with multiple functional group reactions, have very strong further chemical derivatization ability.
The chemical structure of general formula of water-soluble photo-polymerization initiator provided by the present invention is shown in I, II or III:
In the formula, R
1And R
3Be selected from the straight chained alkyl that contains the individual MU (methylene unit) of n (1＜n＜6) respectively; Wherein, preferred-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-,-CH (CH
3)-CH
2-;
R
2Be selected from
R is selected from chlorion or trifluoroacetic ions.
The preparation method of water-soluble photo-polymerization initiator provided by the present invention may further comprise the steps:
1) 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone and Phosphorates phosphorus Halides or halocarbon 1.0: 1.1 in molar ratio～1.5 are dissolved in methylene dichloride after, in ice bath, stirred 4～5 hours, under room temperature, continue again to stir 8～10 hours, concentrate, column chromatography for separation obtains 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone halides IV;
In the formula, X is chlorine, bromine or iodine;
2) chloroformic solution with tert-Butyl dicarbonate is added drop-wise in the haloform reaction solution that contains amino alcohol and triethylamine or diamines and triethylamine, stirred in the ice bath 3～6 hours, then be warming up to room temperature naturally, continue to stir 8～12 hours, make amino protected hydramine (V or VI) or the protected diamines of mono amino (VII), wherein, the metering mol ratio of reactant tert-Butyl dicarbonate, triethylamine and amino alcohol or diamines is 1: 1: 2～1: 1: 10;
In the formula: R
1And R
3Be selected from the straight chained alkyl that contains the individual MU (methylene unit) of n (1＜n＜6) respectively;
3) with compound IV and V, VI or VII 1: 1 in molar ratio, under alkaline condition, be dissolved in acetonitrile, benzene or the toluene, and under 50～65 ℃ of temperature heated and stirred 5～8 hours, after the reaction cooling, add water and ethyl acetate extraction, organic phase concentrates behind anhydrous sodium sulfate drying, crosses the post separation and makes compound VIII, IX or X, wherein, when being solvent with toluene or benzene, need to add phase transfer reagent tetrabutyl ammonium sulfate, the mol ratio of tetrabutyl ammonium sulfate and compound IV is 1: 2;
In the formula: R
1And R
3Be selected from the straight chained alkyl that contains the individual MU (methylene unit) of n (1＜n＜6) respectively; R
2Choosing
4) compound VIII, IX or X are dissolved in the dioxane solution of hydrogenchloride that concentration is 4M or the trifluoracetic acid (wherein; compound VIII, IX or X and hydrogenchloride or trifluoroacetic mol ratio are 1: 10); stir under the room temperature and took off protecting group in 1～4 hour; after reaction finishes; remove unnecessary acid and low-boiling products through decompression, obtain water-soluble photo-polymerization initiator I, II or III.
Phosphorates phosphorus Halides described in the step 1) is phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or phosphorus tribromide; Described halocarbon is tetracol phenixin or carbon tetrabromide.
Step 2) amino alcohol described in is an amino-1, ammediol, 2-aminopropanol, 3-aminopropanol, 2-amino-1-butanols, 4-amino-1-butanols, 2-amino-3-methyl isophthalic acid-butanols, 2-amino-1-amylalcohol or 5-amino-1-amylalcohol; Described diamines is quadrol, propylene diamine, methyl ethylenediamine, butanediamine or pentamethylene diamine.
Step 2) and 3) described in R
1And R
3Be selected from respectively-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-,-CH (CH
3)-CH
2-.
Alkali described in the step 3) is yellow soda ash, salt of wormwood, potassium hydroxide or sodium hydroxide.
Compared with prior art, the present invention has following beneficial effect:
The inventive method is easy and simple to handle, reaction conditions is gentle, and prepared water-soluble photo-polymerization initiator is compared with Irgacure2959, on the basis that keeps excellent monomer initiated polymerization ability and biocompatibility, has higher water-soluble; And the existence of molecular structure terminal amino functional groups makes this photoinitiator have higher reactive behavior, this for further chemically modified or initiator derivatize provide more may.Initiator provided by the present invention can be applied to technical field of biological material such as organizational project, drug delivering material.
Description of drawings
Fig. 1,2-hydroxy ethyl methacrylate monomer (HEA) are gone up the conversion of carbon-carbon double bond functional group and the graph of a relation of light application time.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
Embodiment 1
1) fills 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone with 250 milliliters, 0.01mol the round-bottomed flask of triphenylphosphine and 150 milliliters of methylene dichloride places ice bath, start agitator, slowly drip the mixing solutions of 0.01mol carbon tetrabromide and 50 milliliters of methylene dichloride, dropwise, keep ice bath, stirred 4 hours, naturally be warming up to room temperature, continue to stir 8 hours, monitor through TLC, termination reaction, after reaction solution concentrated, column chromatography for separation obtained 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol quadrol in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 3 hours, naturally be warming up to room temperature, continue to stir 10 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the quadrol of monoamine base protection;
3) quadrol and the 0.01mol salt of wormwood with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protection of 0.01mol monoamine base is dissolved in 20 milliliters of acetonitriles, stirred 8 hours down in 60 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) be 1 of 4M hydrogenchloride with 0.01mol initiator precursor and 0.1mol concentration, the 4-dioxane solution is mixed, and at room temperature stirs 1 hour, and acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-1.
PI-1
Embodiment 2
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroformic solutions after, it slowly is added drop-wise to 0.1mol propylene diamine in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 8 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the propylene diamine of monoamine base protection;
3) propylene diamine and the 0.01mol salt of wormwood with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protection of 0.01mol monoamine base is dissolved in 20 milliliters of acetonitriles, stirred 6 hours down in 60 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) be 1 of 4M hydrogenchloride with 0.01mol initiator precursor and 0.1mol concentration, the 4-dioxane solution is mixed, and at room temperature stirs 1 hour, and acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-2.
PI-2
Embodiment 3
1) mixing solutions with 0.01mol tetracol phenixin and 40 milliliters of methylene dichloride formation slowly is added drop-wise in the mixing solutions of 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone, 0.01mol triphenylphosphine and 200 milliliters of methylene dichloride in the ice bath, keep ice bath, stirred 5 hours, naturally be warming up to room temperature, continue to stir 10 hours, monitor through TLC, termination reaction, after reaction solution concentrated, column chromatography for separation obtained 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenylpropyl alcohol chloro thing;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 1-methyl-quadrol in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 4 hours, naturally be warming up to room temperature, continue to stir 12 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the 1-methyl-quadrol of monoamine base protection;
3) 1-methyl-quadrol and the 0.01mol salt of wormwood with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protection of 0.01mol monoamine base is dissolved in 20 milliliters of acetonitriles, stirred 6 hours down in 60 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 2 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-3.
PI-3
Embodiment 4
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 1 in the ice bath, 4-butanediamine, 0.1mol in the mixing solutions of triethylamine and 100 milliliters of chloroform formation, keep ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 9 hours, after reaction solution concentrates, through dichloromethane extraction, dry, concentrate, obtain 1 of monoamine base protection, the 4-butanediamine;
3) with 1 of 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protection of 0.01mol monoamine base, 4-butanediamine and 0.01mol salt of wormwood are dissolved in 20 milliliters of acetonitriles, stirred 7 hours down in 55 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 3 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-4.
PI-4
Embodiment 5
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, its liquid slowly is added drop-wise to 0.1mol 1 in the ice bath, 5-pentamethylene diamine, 0.1mol in the mixing solutions of triethylamine and 100 milliliters of chloroform formation, keep ice bath, stir after 6 hours, naturally be warming up to room temperature, continue to stir 12 hours, after reaction solution concentrates, through dichloromethane extraction, dry, concentrate, obtain 1 of monoamine base protection, the 5-pentamethylene diamine;
3) with 1 of 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protection of 0.01mol monoamine base, 5-pentamethylene diamine and 0.01mol salt of wormwood are dissolved in 20 milliliters of acetonitriles, stirred 8 hours down in 60 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 3 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-5.
PI-5
Embodiment 6
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 2-monoethanolamine in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 8 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the protected thanomin of amido;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected ethanol of 0.01mol amido, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, stirred 5 hours in 50 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) be 1 of 4M hydrogenchloride with 0.01mol initiator precursor and 0.1mol concentration, the 4-dioxane solution is mixed, and at room temperature stirs 2 hours, and acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-6.
PI-6
Embodiment 7
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 2-aminopropanol in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 4 hours, naturally be warming up to room temperature, continue to stir 5 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the protected 2-aminopropanol of amido;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected 2-aminopropanol of 0.01mol amido, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 15 milliliters of benzene and 3 ml waters, stirred 8 hours in 55 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) be 1 of 4M hydrogenchloride with 0.01mol initiator precursor and 1mol concentration, the 4-dioxane solution is mixed, and at room temperature stirs 3 hours, and acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-7.
PI-7
Embodiment 8
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, its liquid slowly is added drop-wise to 0.1mol 3-aminopropanol in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 4 hours, naturally be warming up to room temperature, continue to stir 11 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the protected 3-aminopropanol of amido;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected 3-aminopropanol of 0.01mol amido, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, stirred 8 hours in 65 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 4 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-8.
PI-8
Embodiment 9
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 2-ethyl-2-monoethanolamine in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 12 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the protected 2-ethyl of amido-2-monoethanolamine;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected 2-ethyl of 0.01mol amido-2-monoethanolamine, 0.01mol potassium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, stirred 8 hours in 55 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) be 1 of 4M hydrogenchloride with 0.01mol initiator precursor and 1mol concentration, the 4-dioxane solution is mixed, and at room temperature stirs 3 hours, and acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-9.
PI-9
Embodiment 10
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 4-amino butanol in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 6 hours, naturally be warming up to room temperature, continue to stir 5 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the protected 4-amino butanol of amido;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected butylamine base of 0.01mol amido alcohol, 0.01mol potassium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, stirred 6 hours in 65 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 4 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-10.
PI-10
Embodiment 11
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 3-methyl-2-amino butanol in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 4 hours, naturally be warming up to room temperature, continue to stir 6 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the protected 3-methyl of amido-2-amino butanol;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected 4-methyl of 0.01mol amido-2-amino butanol, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, 55 ℃ were stirred 6 hours, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 4 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-11.
PI-11
Embodiment 12
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to the amino amylalcohol of 0.1mol 2-in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 12 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the amino amylalcohol of the protected 2-of amido;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the amino amylalcohol of the protected 2-of 0.01mol amido, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 15 milliliters of toluene and 3 ml waters, 65 ℃ were stirred 7 hours, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 3 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-12.
PI-12
Embodiment 13
1) with embodiment 1 step 1;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to the amino amylalcohol of 0.1mol 5-in the ice bath, in the mixing solutions that 0.1mol triethylamine and 100 milliliters of chloroforms form, keeps ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 9 hours, after reaction solution concentrates, through dichloromethane extraction, drying concentrates, and obtains the amino amylalcohol of the protected 5-of amido;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the amino amylalcohol of the protected 5-of 0.01mol amido, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 15 milliliters of toluene and 3 ml waters, stirred 8 hours in 60 ℃, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying concentrates, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is at room temperature mixed with the 0.1mol trifluoracetic acid, stirred 2 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-13.
PI-13
Embodiment 14
1) gets the acetone soln of 2-hydroxyl-4-(2-the hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative for preparing in 0.01mmol embodiment 1 step 1), and adding 0.012mol sodium iodide, stir after 20 hours under the room temperature, filter, concentrated filtrate obtains 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone iodide;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 2-amino-1 in the ice bath, ammediol, 0.1mol in the mixing solutions of triethylamine and 100 milliliters of chloroform formation, keep ice bath, stir after 5 hours, naturally be warming up to room temperature, continue to stir 7 hours, after reaction solution concentrates, through dichloromethane extraction, dry, concentrate, obtain the protected 2-amino-1 of amido, ammediol;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative and the protected 2-amino-1 of 0.01mol amido, ammediol, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, 60 ℃ were stirred 7 hours, after reaction solution concentrates, and chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is at room temperature mixed with the 0.1mol trifluoracetic acid, stirred 3 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-14.
PI-14
Embodiment 15
1) gets the acetone soln of 2-hydroxyl-4-(2-the hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative for preparing in 0.01mmol embodiment 1 step 1), and adding 0.012mol sodium iodide, stir after 20 hours under the room temperature, filter, concentrated filtrate obtains 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone iodide;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it slowly is added drop-wise to 0.1mol 2-aminomethylene-1 in the ice bath, ammediol, 0.1mol in the mixing solutions of triethylamine and 100 milliliters of chloroform formation, keep ice bath, stir after 4 hours, naturally be warming up to room temperature, continue to stir 8 hours, after reaction solution concentrates, through dichloromethane extraction, dry, concentrate, obtain the protected 2-aminomethylene-1 of amido, ammediol;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected 2-amino-1 of 0.01mol amido, ammediol, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, in 55 ℃ of stirrings 7 hours, after reaction solution concentrates, chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is at room temperature mixed with the 0.1mol trifluoracetic acid, stirred 4 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-15.
PI-15
Embodiment 16
1) gets the acetone soln of 2-hydroxyl-4-(2-the hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative for preparing in 0.01mmol embodiment 1 step 1), and adding 0.012mol sodium iodide, stir after 20 hours under the room temperature, filter, concentrated filtrate obtains 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone iodide;
2) the 0.01mol tert-Butyl dicarbonate is dissolved in 40 milliliters of chloroforms after, it is added drop-wise to 0.1mol 2-amino-2-methyl-1 in the ice bath, ammediol, 0.1mol in the solution of triethylamine and 100 milliliters of chloroform formation, keep ice bath, stir after 4 hours, naturally be warming up to room temperature, continue to stir 8 hours, after reaction solution concentrates, through dichloromethane extraction, dry, concentrate, obtain the protected 2-amino-2-methyl-1 of amido, ammediol;
3) with 0.01mol 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone bromo-derivative, the protected 2-amino-2-methyl-1 of 0.01mol amido, ammediol, 0.01mol sodium hydroxide and 0.005mol tetrabutyl ammonium sulfate are dissolved in the mixing solutions of 10 milliliters of toluene and 3 ml waters, 50 ℃ were stirred 8 hours, after reaction solution concentrates, and chloroform extraction, anhydrous sodium sulfate drying, reconcentration, column chromatography for separation obtains amino protected initiator precursor;
4) the 0.01mol initiator precursor is mixed with the 0.1mol trifluoracetic acid, at room temperature stirred 2 hours, acid and low-boiling by-products are removed in decompression, obtain water-soluble photo-polymerization initiator PI-16.
PI-16
Get the water-soluble photo-polymerization initiator (PI-1 and PI-6) and 2-hydroxyl-4-(2-the hydroxy ethoxy)-2-methyl phenyl ketone of preparation in embodiment 1 and 6, utilize its trigger monomer polymeric ability of online near-infrared analysis: at 5mW/cm
2Light intensity, 320-500nm grating and light trigger volumetric molar concentration are under 5% condition, the ability that causes 2-hydroxy ethyl methacrylate monomer polymerization as shown in Figure 1, water-soluble photo-polymerization initiator provided by the present invention as can be seen from Figure has the same good initiated polymerization ability with 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone.
Claims (9)
1. a water-soluble photo-polymerization initiator is characterized in that, the chemical structure of described initiator is shown in general formula I, II or III:
In the formula, R
1And R
3Be selected from the alkyl chain that contains n MU (methylene unit) respectively, 1＜n＜6; R
2For
R is a chlorion.
2. water-soluble photo-polymerization initiator according to claim 1 is characterized in that, described R
1And R
3Be selected from respectively-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-,-CH
2-CH (CH
3)-.
3. the preparation method of water-soluble photo-polymerization initiator according to claim 1 and 2 is characterized in that, may further comprise the steps:
1) 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone and Phosphorates phosphorus Halides or halocarbon 1.0: 1.1 in molar ratio～1.5 are dissolved in methylene dichloride after, in ice bath, stirred 4～5 hours, under room temperature, continue again to stir 8～10 hours, concentrate, column chromatography for separation obtains 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone halides IV;
In the formula, X is chlorine, bromine or iodine;
2) chloroformic solution with tert-Butyl dicarbonate is added drop-wise in the haloform reaction solution that contains amino alcohol and triethylamine or diamines and triethylamine, stirred in the ice bath 3～6 hours, then be warming up to room temperature naturally, continue to stir 8～12 hours, make the protected diamines V of amino protected hydramine or mono amino, VI or VII, wherein, the metering mol ratio of reactant tert-Butyl dicarbonate, triethylamine and amino alcohol or diamines is 1: 1: 2～1: 1: 10;
In the formula: R
1And R
3Be selected from the alkyl that contains n MU (methylene unit) respectively, 1＜n＜6; R
2Be selected from
3) with compound IV and V, VI or VII with mol ratio 1: 1, under alkaline condition, be dissolved in acetonitrile, benzene or the toluene, and 50～65 ℃ of heated and stirred 5～8 hours, after the reaction solution cooling, add water and ethyl acetate extraction, organic phase concentrates behind anhydrous sodium sulfate drying, crosses the post separation and makes compound VIII, IX or X, wherein, when being solvent with toluene or benzene, need to add phase transfer reagent tetrabutyl ammonium sulfate, the mol ratio of tetrabutyl ammonium sulfate and compound IV is 1: 2;
In the formula: R
1And R
3Be selected from the alkyl that contains n MU (methylene unit) respectively, 1＜n＜6; R
2Be selected from
4) be that the dioxane solution or the trifluoracetic acid of the hydrogenchloride of 4M mixes with compound VIII, IX or X and concentration, wherein, compound VIII, IX or X and hydrogenchloride or trifluoroacetic mol ratio are 1: 10, after stirring 1～4 hour under the room temperature, underpressure distillation obtains water-soluble photo-polymerization initiator I, II or III.
4. method according to claim 3 is characterized in that, the Phosphorates phosphorus Halides described in the step 1) is phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or phosphorus tribromide.
5. method according to claim 3 is characterized in that, the halocarbon described in the step 1) is tetracol phenixin or carbon tetrabromide.
6. method according to claim 3, it is characterized in that, step 2) amino alcohol described in is an amino-1, ammediol, 2-aminopropanol, 3-aminopropanol, 2-amino-1-butanols, 4-amino-1-butanols, 2-amino-3-methyl isophthalic acid-butanols, 2-amino-1-amylalcohol or 5-amino-1-amylalcohol.
7. method according to claim 3 is characterized in that step 2) described in diamines be quadrol, propylene diamine, methyl ethylenediamine, butanediamine or pentamethylene diamine.
8. method according to claim 3 is characterized in that step 2) and 3) described in R
1And R
3Be selected from respectively-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-or-CH
2-CH (CH
3)-.
9. method according to claim 3 is characterized in that, the alkali described in the step 3) is yellow soda ash, salt of wormwood, potassium hydroxide or sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101161382A CN101619110B (en) | 2008-07-04 | 2008-07-04 | Water-soluble photo-polymerization initiator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101161382A CN101619110B (en) | 2008-07-04 | 2008-07-04 | Water-soluble photo-polymerization initiator and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101619110A CN101619110A (en) | 2010-01-06 |
| CN101619110B true CN101619110B (en) | 2011-05-04 |
Family
ID=41512529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101161382A Expired - Fee Related CN101619110B (en) | 2008-07-04 | 2008-07-04 | Water-soluble photo-polymerization initiator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101619110B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724204B (en) * | 2013-11-27 | 2016-05-11 | 北京化工大学 | A kind of water soluble starter and preparation |
| CN112409587B (en) * | 2020-11-23 | 2022-08-09 | 濮阳展辰新材料有限公司 | Method for preparing polycarbonate photoinitiator and coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230568A (en) * | 1998-03-12 | 1999-10-06 | 互应化学工业株式会社 | Photosensitive resin composition and photoresist ink for manufacturing printed wiring boards |
| CN1384138A (en) * | 2001-05-01 | 2002-12-11 | 东京应化工业株式会社 | Photosensitive insulated glue composition and photosensitive film of the glue |
| CN1628132A (en) * | 2001-09-11 | 2005-06-15 | 东亚合成株式会社 | Process for producing water-soluble polymer |
-
2008
- 2008-07-04 CN CN2008101161382A patent/CN101619110B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230568A (en) * | 1998-03-12 | 1999-10-06 | 互应化学工业株式会社 | Photosensitive resin composition and photoresist ink for manufacturing printed wiring boards |
| CN1384138A (en) * | 2001-05-01 | 2002-12-11 | 东京应化工业株式会社 | Photosensitive insulated glue composition and photosensitive film of the glue |
| CN1628132A (en) * | 2001-09-11 | 2005-06-15 | 东亚合成株式会社 | Process for producing water-soluble polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101619110A (en) | 2010-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101397354B (en) | Hydrophobic modified cationic block polyacrylamide and synthesis method and application thereof | |
| CN101312941B (en) | Polynucleotide labelling reagent | |
| EP1664144B1 (en) | Acid-sensitive polyacetals and methods | |
| JPH0247138A (en) | Siloxane copolymer having quaternary ammonium group as its side chain | |
| CN101619110B (en) | Water-soluble photo-polymerization initiator and preparation method thereof | |
| CN103450372B (en) | Synthesis of chain transfer agent with thermal initiation function | |
| WO2010141507A1 (en) | Biomolecule-polymer conjugates and methods of making same | |
| CN105164169A (en) | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation | |
| CN111470994A (en) | Preparation method of p-chlorobenzene glycine | |
| CN103755969A (en) | Chitosan and poly-dimethyl diallyl ammonium chloride compound and preparation method thereof | |
| Merle et al. | Acyclic oligonucleotide analogues | |
| CN109161019A (en) | A kind of preparation method of beta-dicarbonyl compound modified polyaspartic acid | |
| MX2007013689A (en) | Generation of phosphorus oxychloride as by-product from phosphorus pentachloride and dmf and its use for chlorination reaction by converting into vilsmeier-haack reagent. | |
| CN102516536A (en) | Polyethyleneimine (PEI) derivative taking amphipathic chitosan as cross linker and preparation method and application thereof | |
| CN109824891A (en) | A kind of synthetic method of polyaniline | |
| US6384068B1 (en) | Imidazole containing compounds having relatively low hydrogen content and relatively high nitrogen content and polymers and copolymers formed therefrom | |
| ES2453114T3 (en) | Procedure for the preparation of sevelamer | |
| CN103012803A (en) | Polyamidoamine derivative and preparation method and application thereof | |
| CN109575077A (en) | A kind of environment-friendly preparation method thereof of fosfomycin calcium | |
| CN114685778B (en) | Method for synthesizing long-circulating cationic liposome | |
| US5760271A (en) | Production of polyorganophosphazenes | |
| CN102731583A (en) | Preparation method of sucrose benzoate | |
| CN114957364B (en) | Iodine base, preparation method thereof and constructed amphiphilic nucleic acid | |
| CN102277369A (en) | Modified polyhydroxyethyl acrylamide transgenic vector and preparation method and application thereof | |
| CN1358774A (en) | Method for preparing polyacrylic sodium from waste acrylic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110504 Termination date: 20140704 |
|
| EXPY | Termination of patent right or utility model |