CN102174127B - Macromolecular photoinitiator for gradient polymerization and synthesis method and application thereof - Google Patents
Macromolecular photoinitiator for gradient polymerization and synthesis method and application thereof Download PDFInfo
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- CN102174127B CN102174127B CN2011100382638A CN201110038263A CN102174127B CN 102174127 B CN102174127 B CN 102174127B CN 2011100382638 A CN2011100382638 A CN 2011100382638A CN 201110038263 A CN201110038263 A CN 201110038263A CN 102174127 B CN102174127 B CN 102174127B
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Abstract
The invention discloses a macromolecular photoinitiator for gradient polymerization and performance research thereof. The photoinitiator is characterized in that: an organic silicon macromolecular photoinitiator is prepared by reacting organic silicon polymer with a micromolecular photoinitiator. The photoinitiator is applied to the gradient polymerization, polymer with molecular weight in gradient change can be obtained by one-time polymerization, the gradient change of the molecular weight is uniform along the vertical direction, and an obvious component interface does not exist; in addition, the photoinitiator overcomes the defects that the micromolecular photoinitiator is easy to yellow, volatilize and migrate, has high toxicity and low heat resistance, and the like, has a spontaneous floating capability due to the characteristics of low surface energy and surface tension of organic silicon, and effectively prevents oxygen polymerization inhibition.
Description
This application is the division of application number 2009100885362.
Technical field
The present invention relates to macromolecule photoinitiator for gradient polymerization and preparation method thereof, belong to the synthetic field of macromolecular material.
Background technology
Gradient polymer is meant that the key element (composition, structure) that constitutes polymkeric substance is the character of continuous gradient variation, material and a kind of type material that function also changes in gradient along a certain direction by a side direction opposite side.Molecular weight is a fundamental of polymkeric substance, and it all has very big influence to the use properties and the processing characteristics of polymkeric substance.When the molecular weight of polymkeric substance changed, polymer properties such as mechanical property (intensity etc.), optical property (specific refractory power etc.), thermal property (second-order transition temperature etc.), electric property (specific conductivity etc.), processing characteristics (rheological etc.) etc. all can change thereupon.When the molecular weight of polymkeric substance is changed by a side direction opposite side continuous gradient along a certain direction; Can make polymer properties continuous gradient also occur and change, this molecular weight is molecular weight gradient polymer along a certain direction by the polymkeric substance that a side direction opposite side is the continuous gradient variation.
Light trigger is one of photopolymerisable important factor of influence, and its ability absorbing ultraviolet light or visible radiation ability make oligopolymer and thinner become the compound of solid matter rapidly by liquid transformation.Traditional small molecules radical photopolymerization initiator and remain in easily migration and the volatilization of photolysis debris in the system makes the product xanthochromia that wears out, and smell and toxicity occur, has restricted the application of photocuring system at aspects such as food and drug packages.Therefore the macromolecular photoinitiator that has reactive group becomes the important development direction in this field, is connected to optical active group on macromolecular photoinitiator main chain or the side chain, produces living radical behind the absorbing radiation energy and causes photopolymerization system crosslinking curing.And in photopolymerization; When if light trigger is the Gradient distribution of successively decreasing successively from the upper layer to the deep layer in polymerization system, under photoirradiation, graded can take place in the polymerization degree from the top layer of system to deep layer; Promptly solidify the molecular weight distribution gradient of back material, realize gradient polymeric.Simultaneously, the upper layer initiator concentration is maximum, can effectively reduce surperficial oxygen inhibition in the photopolymerization.For reaching this purpose, need carry out the specific molecule design to light trigger.The ability that the characteristic of organosilicon low surface energy and low surface tension is given its spontaneous come-up has exactly satisfied above-mentioned demand, and the light trigger that preparation is applied in the gradient polymeric becomes possibility.
Summary of the invention
The present invention provides a kind of macromolecule photoinitiator for gradient polymerization and preparation method thereof, for realizing that gradient polymeric provides new way and novel method.Realize gradient polymeric through in photoinitiator molecules, introducing the organosilicon segment, effectively solved photocuring surface oxygen inhibition problem simultaneously.The present invention also provides a kind of compsn that comprises this macromolecule photoinitiator for gradient polymerization.
Particularly, the present invention includes:
1. macromolecule photoinitiator for gradient polymerization that general formula is (I)
Wherein, M is the residue that is derived from bitter almond oil camphor class, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound; This small molecules photoinitiator compound has and is selected from hydroxyl; Amino, the group of carboxyl and epoxide group;
R
1And R
2Identical or different, and be independently selected from C
1-C
12Alkyl, N, O, the substituted C of S heteroatoms
1-C
12Alkyl, C
1-C
12Alkoxyl group, or its combination;
R
3And R
4Identical or different, and be independently selected from-R '-,-R '-COO-,-R '-CH (CH
2OH) O-,-R ' CONH-R ", C
1-C
12Haloalkyl, wherein R ' and R " are selected from C independently of one another
1-C
12Alkyl;
n＝3-50。
2. according to the macromolecular photoinitiator of item 1, wherein M is the residue that is derived from the small molecules photoinitiator compound of alkyl acetophenones and benzophenone, and this small molecules photoinitiator compound has and is selected from hydroxyl, the group of amino and carboxyl.
3. according to the macromolecular photoinitiator of item 1, R wherein
1And R
2Identical, and be C
1-C
12Alkyl, preferred C
1-C
2Alkyl.
4. according to the macromolecular photoinitiator of item 1, R wherein
3And R
4Identical, and be-R '-COO-or-R '-CH (CH
2OH) O-, wherein R ' is independently selected from C
1-C
3Alkyl.
5. according to the macromolecular photoinitiator of item 2, wherein this small molecules photoinitiator compound has hydroxyl.
6. method for preparing a macromolecular photoinitiator of 1 is characterized in that making that the mixture that comprises following substance A and B reacts:
Substance A is that general formula is the organosilicon polymer of (II)
Wherein the definition of n such as item 1 are said;
R
1' and R
2' identical or different, and be independently selected from C
1-C
12Alkyl, N, O, the substituted C of S heteroatoms
1-C
12Alkyl, C
1-C
12Alkoxyl group, H, or its combination;
R
3' and R
4' identical or different, and be independently selected from-R ' OH ,-R ' NH ,-R ' COOH and
Wherein R ' is C
1-C
12Alkyl.
Substance B is bitter almond oil camphor class, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound; This small molecules photoinitiator compound has and is selected from hydroxyl; Amino, the group of carboxyl and epoxide group.
7. according to the method for item 6, wherein said reaction is esterification, transesterification reaction, amidate action, epoxy addition reaction, addition reaction of silicon with hydrogen, condensation reaction, Michael reaction or nucleophilic substitution reaction.
8. according to the method for item 6, wherein substance B is the small molecules photoinitiator compound of alkyl acetophenones and benzophenone, and this small molecules photoinitiator compound has and is selected from hydroxyl, the group of amino and carboxyl.
9. according to the method for item 8, wherein this small molecules photoinitiator compound has hydroxyl.
10. according to the method for item 6, wherein said mixture also comprises the solvent and the catalysts that can dissolve said organosilicon polymer.
11. according to the method for item 10, wherein said organosilicon polymer, the mol ratio of said small molecules photoinitiator compound and said catalyzer is 1: (0.5～2): (0.1～3).
12. according to the method for item 6, wherein said organosilicon polymer is selected from hydroxy silicon oil, contains hydroxyl alkyl silicone oil, contains ammonia alkyl silicone oil, contains carboxylic alkyl silicone oil, carboxamido-group silicone oil, epoxy silicon oil and composition thereof.
13. according to the method for item 10, wherein said reaction is an esterification, said catalyzer is selected from sulfuric acid, heteropolyacid catalyst, molecular sieve, oxide catalyst, polymer supported catalyst, ionic-liquid catalyst, macroporous ion exchange resin; Perhaps said reaction is the epoxy addition reaction, and said catalysts is selected from protonic acid, lewis acid; Solid acid, alkali metal cpd, alkaline earth metal cpds; Fe (III) catalyzer alkyl metal catalyst, metal alkoxides catalyzer, bimetallic cyanide complex catalyst; Bimetal oxygen joins alkoxide, the condenses of organotin and SULPHOSUCCINIC ACID ESTER, rare earth compound and enzyme.
14. a radical photoinitiator solidified coating material, it comprises the macromolecular photoinitiator of item 1.
15. the compsn of item 14, wherein said composition comprises the said macromolecular photoinitiator of 1%-5% and light reactive resin or the reactive monomer of 95%-99%, based on the gross weight of said composition.
16. the compsn of item 15; Wherein said photoresponse resin is selected from epoxy (methyl) vinyl resin, urethane (methyl) vinyl resin, polyester (methyl) vinyl resin, polyethers (methyl) vinyl resin, acroleic acid esterification and gathers (methyl) vinyl resin; Described reactive monomer is a simple function group, bifunctional or polyfunctional group (methyl) acrylate monomer.
Embodiment
It is the macromolecule photoinitiator for gradient polymerization of (I) that the present invention provides general formula.
Above-mentioned macromolecule photoinitiator for gradient polymerization is to use with the organosilicon polymer of following formula (II) and small molecules light trigger and reacts acquisition.
Generally speaking, the organosilicon polymer that uses can have the silicone oil of reactive group (for example hydroxyl, amino, carboxyl, hydroxyl alkyl, ammonia alkyl, carboxylic alkyl, carboxamido-group, epoxy group(ing)) as the end.For example, silicone oil can be selected from hydroxy silicon oil, amido silicon oil, silicone oil of carboxyl, contains hydroxyl alkyl silicone oil, contains ammonia alkyl silicone oil, contains the carboxylic alkyl, carboxamido-group silicone oil, epoxy silicon oil and composition thereof.
Generally speaking; The small molecules light trigger that uses is to have hydroxyl; Amino; The light trigger of carboxyl or epoxide group particularly is bitter almond oil camphor class, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound.
It will be understood to those of skill in the art that; The selection of silicone oil and small molecules light trigger will make silicone oil and small molecules light trigger have the reactive group that can react to each other; So that through for example reactions such as esterification, transesterification reaction, amidate action, epoxy addition reaction, addition reaction of silicon with hydrogen, condensation reaction, Michael reaction or nucleophilic substitution reaction; Make silicone oil and small molecules light trigger react, thereby obtain macromolecular photoinitiator of the present invention.
Preferably, this small molecules photoinitiator compound has and is selected from hydroxyl, the group of amino and carboxyl.Preferably, said organosilicon polymer be selected from hydroxy silicon oil, contain hydroxyl alkyl silicone oil, contain ammonia alkyl silicone oil, contain the carboxylic alkyl, carboxamido-group silicone oil, epoxy silicon oil and composition thereof.
More preferably this small molecules light trigger small molecules photoinitiator compound that is alkyl acetophenones and benzophenone, and have and be selected from hydroxyl, the group of amino and carboxyl.
Correspondingly, further preferred, said organosilicon polymer is selected from hydroxy silicon oil, hydroxyl alkyl silicone oil, carboxylic alkyl silicone oil, epoxy silicon oil and composition thereof.
This reaction can be used solvent as required.Solvent to using in the reaction has no restriction, as long as this solvent can dissolve the organosilicon polymer of use.
This reaction for example can be carried out as follows, and organosilicon polymer is dissolved in the appropriate solvent, adds reaction vessel; After transferring to appropriate reaction temperature adding catalyzer; The small molecules light trigger is splashed into reaction system through constant pressure funnel, and the control rate of addition keeps temperature of reaction and reaction times; Reaction finishes the back except that desolvating, and obtains title product silicone macromolecule light trigger.
The present invention also provides the compsn that comprises above-mentioned macromole evocating agent, more specifically radical photoinitiator solidified coating material.Generally speaking, said composition can comprise the said macromolecular photoinitiator of 1%-5% and light reactive resin or the reactive monomer of 95%-99%, based on the gross weight of said composition.
The present invention has no restriction for light reactive resin or reactive monomer, as long as this resin or monomer can be caused by light trigger.Generally speaking, the photoresponse resin can be selected from epoxy (methyl) vinyl resin, urethane (methyl) vinyl resin, polyester (methyl) vinyl resin, polyethers (methyl) vinyl resin, acroleic acid esterification and gathers (methyl) vinyl resin.Reactive monomer can be preferably simple function group, bifunctional or polyfunctional group (methyl) acrylate monomer.
Silicone macromolecule light trigger disclosed by the invention is not only applicable to conventional photocuring system, is a kind of novel photoinitiator that utilizes the light trigger self character to realize gradient polymeric yet.
Effect of the present invention: the organosilicon segment is introduced in (1) in molecular structure; Utilize its lower surface tension, can prepare macromolecular photoinitiator, this light trigger distribution gradient in prescription with come-up characteristic; For realizing that gradient polymeric provides new way and novel method; Simplified gradient polymeric technology, easy and simple to handle, efficient.(2) effectively solved the problem of surperficial oxygen inhibition in the photopolymerization.
Among the present invention, the polymer properties testing method is: (1) vertically is divided into plurality of sections (being generally a section every centimetre) with resulting polymers, and vacuum-drying at room temperature is at least 48 hours then; (2) gel gc (GPC) method is measured the molecular weight of gained stage feeding polymerization thing.
Synthetic embodiment
Embodiment 1
Synthesizing of 184-Tego2342 silicone macromolecule light trigger
With 7g (2.5mmol) molecular formula is that Tegomer2342 (DEGUSSA company), 1.133g (5.5mmol) DCC (dicyclohexyl carbodiimide) of Formula 1 is dissolved in the middle of the 150mL ETHYLE ACETATE; Under the condition of the isolated steam of room temperature, stirred 30 minutes; Drip 1.02g (5mmol) Irgacure 184 (1-hydroxy-cyclohexyl phenyl ketones), finish in room temperature reaction 24 hours.Filter, filtrating is with 5% NaOH solution and deionized water wash 3 times, and solvent distillation obtains the liquid product that molecular formula is Formula 2 under vacuum condition at last.Measuring the number average relative molecular mass through gel chromatography (GPC) is 3001.In the infrared spectrogram, 3300cm
-1Near hydroxyl absorption peak disappears, at 1752cm
-1The charateristic avsorption band that ester group occurred.
From DEGUSSA Company products data, the value of m and n makes the molecular weight of Tegomer2342 be about 2800 among the formula Formula 1.
Embodiment 2
Synthesizing of HBP-Tego2342 silicone macromolecule light trigger
With 7g (2.5mmol) molecular formula is that Tegomer2342 (DEGUSSA company), 1.133g (5.5mmol) DCC (dicyclohexyl carbodiimide) of Formula 1 is dissolved in the middle of the 150mL ETHYLE ACETATE; Under the condition of the isolated steam of room temperature, stirred 30 minutes; Drip 0.99g (5mmol) HBP (4-dihydroxy benaophenonel), finish in room temperature reaction 24 hours.Filter, filtrating is with 5% NaOH solution and deionized water wash 3 times, and solvent distillation obtains the liquid product that molecular formula is Formula 3 under vacuum condition at last.Measuring the number average relative molecular mass through gel chromatography (GPC) is 2993.In the infrared spectrogram, 3145cm
-1Near hydroxyl absorption peak disappears, at 1704cm
-1The charateristic avsorption band that ester group occurred.
Embodiment 3
Synthesizing of 1173-Tego2342 silicone macromolecule light trigger
With 7g (2.5mmol) molecular formula is that Tegomer2342 (DEGUSSA company), 1.133g (5.5mmol) DCC (dicyclohexyl carbodiimide) of Formula 1 is dissolved in the middle of the 150mL ETHYLE ACETATE; Under the condition of the isolated steam of room temperature, stirred 30 minutes; Drip 0.821g (5mmol) 1173 (2-hydroxy-2-methyls-1-phenyl-1-acetone), finish in room temperature reaction 24 hours.Filter, filtrating is with 5% NaOH solution and deionized water wash 3 times, and solvent distillation obtains the liquid product that molecular formula is Formula 4 under vacuum condition at last.Measuring the number average relative molecular mass through gel chromatography (GPC) is 2956.In the infrared spectrogram, 3300cm
-1Near hydroxyl absorption peak disappears, at 1750cm
-1The charateristic avsorption band that ester group occurred.
Embodiment 4
Synthesizing of 1173-TegomerE-Si 2330 silicone macromolecule light triggers
With 7g (2.5mmol) molecular formula is that TegomerE-Si 2330 (DEGUSSA company), the 0.1g triethylamine of Formula 5 is dissolved among the 150mlDMF; 70 ℃ drip 0.821g (5mmol) 1173 (2-hydroxy-2-methyls-1-phenyl-1-acetone) down, finish in 70 ℃ of reactions 10 hours.Reaction finishes, and solvent distillation obtains the liquid product that molecular formula is Formula 6 under vacuum condition.Measuring the number average relative molecular mass through gel chromatography (GPC) is 2580.In the infrared spectrogram, 980cm
-1, 910cm
-1, 771cm
-1Near epoxy group(ing) absorption peak disappears.
From DEGUSSA Company products data, the value of n makes the molecular weight of Tegomer2330 be about 2420 among the formula Formula 5.
The application implementation example
Embodiment 1
, internal diameter adds Hydroxyethyl acrylate 10g in being the flat quartz glass reaction pipe of 18mm, 0.5g184-Tego2342 silicone macromolecule light trigger, and reaction tubes is vertically placed, and its height of liquid layer is 8cm.The logical nitrogen flooding oxygen of this reaction solution seal after 30 minutes and places under the 1kW high voltage mercury lamp, and obtaining behind the irradiation 25min highly is 8cm, the molecular weight polyacrylic ester of variation in gradient vertically.In the reaction process, liquid layer surface light intensity is 50W/m
2, reacting liquid temperature is a room temperature.Vertically divide 8 sections with the gained polyacrylic ester, adopt gel gc (GPC) determining molecular weight, the molecular-weight average that obtains vertically each section polyacrylic ester from top to bottom is respectively 2.5 * 10
6, 2.9 * 10
6, 3.3 * 10
6, 4.0 * 10
6, 4.9 * 10
6, 5.7 * 10
6, 6.9 * 10
6, 7.6 * 10
6
Claims (6)
1. a general formula is used for the application of gradient polymeric for the macromolecular photoinitiator of (I),
Wherein, M is the residue that is derived from bitter almond oil camphor class, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone or camphorphorone micromolecular photoinitiator compound; This small molecules photoinitiator compound has and is selected from hydroxyl; Amino, the group of carboxyl and epoxide group;
R
1And R
2Identical or different, and be independently selected from C
1-C
12Alkyl, N, O, the substituted C of S heteroatoms
1-C
12Alkyl, C
1-C
12Alkoxyl group, or its combination;
R
3And R
4Identical or different, and be independently selected from-R '-,-R '-COO-,-R '-CH (CH
2OH) O-,-R ' CONH-R ", C
1-C
12Haloalkyl, wherein R ' and R " are selected from C independently of one another
1-C
12Alkyl; N=3-50.
2. according to the application of claim 1, wherein M is the residue that is derived from the small molecules photoinitiator compound of alkyl acetophenones and benzophenone, and this small molecules photoinitiator compound has and is selected from hydroxyl, the group of amino and carboxyl.
3. according to the application of claim 1, R wherein
1And R
2Identical, and be C
1-C
12Alkyl.
4. according to the application of claim 3, R wherein
1And R
2Identical, and be C
1-C
2Alkyl.
5. according to the application of claim 1, R wherein
3And R
4Identical, and be-R '-COO-or-R '-CH (CH
2OH) O-, wherein R ' is independently selected from C
1-C
3Alkyl.
6. according to the application of claim 2, wherein this small molecules photoinitiator compound has hydroxyl.
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| CN103073659B (en) * | 2013-01-18 | 2014-11-19 | 北京化工大学 | Water-soluble organic silicon macromolecular photoinitiator and preparation method thereof |
| CN106146852A (en) * | 2016-07-08 | 2016-11-23 | 北京化工大学 | A kind of siliceous macromole cation light initiator and preparation method thereof |
| CN106065076B (en) * | 2016-07-08 | 2020-05-19 | 北京化工大学 | Water-soluble silyl ether block ionic liquid type macromolecular photoinitiator and preparation method thereof |
| CN106008756B (en) * | 2016-07-12 | 2019-02-12 | 北京化工大学 | A kind of polymerizable water-soluble silicon ether block ion liquid type photoinitiator and preparation method thereof |
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| JP2007214543A (en) * | 2006-01-12 | 2007-08-23 | Shin Etsu Chem Co Ltd | Uv-curing silicone composition for light-emitting diode element |
| CN101077897A (en) * | 2007-06-29 | 2007-11-28 | 西北工业大学 | Super-branching silicon-base macromolecule optical initiator and preparation method thereof |
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|---|---|---|---|---|
| JP2007214543A (en) * | 2006-01-12 | 2007-08-23 | Shin Etsu Chem Co Ltd | Uv-curing silicone composition for light-emitting diode element |
| CN101077897A (en) * | 2007-06-29 | 2007-11-28 | 西北工业大学 | Super-branching silicon-base macromolecule optical initiator and preparation method thereof |
| CN101220106A (en) * | 2007-12-21 | 2008-07-16 | 北京化工大学 | Silicon containing macromolecule photo-initiation agent, synthesis and uses thereof |
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