CN100526340C - Silicon containing macromolecule photo-initiation agent, synthesis and uses thereof - Google Patents
Silicon containing macromolecule photo-initiation agent, synthesis and uses thereof Download PDFInfo
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- CN100526340C CN100526340C CNB2007103039357A CN200710303935A CN100526340C CN 100526340 C CN100526340 C CN 100526340C CN B2007103039357 A CNB2007103039357 A CN B2007103039357A CN 200710303935 A CN200710303935 A CN 200710303935A CN 100526340 C CN100526340 C CN 100526340C
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- photoinitiator
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- macromolecular photoinitiator
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Abstract
The invention relates to a Si-containing macromolecular photoinitiator and the synthesizing method and the uses belong to the photographic polymer material field. In a general formula of the photoinitiator being (I), I is the photoinitiator with hydroxyl, i.e. the hydroxyl-containing benzoin class, benzoin ethers, alkyl-acetophenones, alkyla-acetophenones, benzophenone type, thioxcanthone derivatives, coumarone class and camphorquinone compound; R1 is the alkyl of C1-C12, or the alkyl or aryl of C1-C12 substituted by N, O, S heteroatoms; R2 and R3 are alkyls of C1-C12, the alkyls of C1-C12 substituted by N, O, S heteroatoms, or alkoxyls of C1-C12; n is equal to 3 to 50. The synthesizing method obtains the compounds of isocyanate with photoinitiator by the reaction of the hydroxyl-containing micro-molecular photoinitiator with an isocyanate group of the diisocyanate, and allows the reaction of the photoinitiator-containing compounds of isocyanate with the hydroxyl-containing siloxane macromolecular compounds. The synthesizing method is used for initiating the free radical photopolymerization, improving the speed and efficiency of producing active species by photo sensitive decomposition and reducing the micro-molecular residue and biological toxicity of coatings.
Description
Technical field
The invention belongs to field of light-sensitive high molecular materials, particularly relate to the free radical photo-initiation field.
Background technology
Photopolymerization is to utilize light as reaction power, on photosensitive compound, makes it that a series of optical physics take place by light action, photochemical reaction, generate active substance, thus the initiating activity monomer polymerization, and Ye Tai resin is converted into solid-state macromolecular material the most at last.Its polymerization characteristics are to save the energy, environmental friendliness, and economical and efficient, device is compact, the production efficiency height.In addition, photopolymerization compares to traditional polymerization technique outstanding advantage, and for example polymerized at room temperature helps the processing of heat-sensitive substrate material; Polymerization formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height.Therefore photopolymerization is the advanced manufacturing technology of a kind of ＂ of being described as green technology ＂.
Light trigger is an integral part main in the photopolymerization material, and its character directly affects the character of the curing characteristics and the final product of material.Using in the practical formulation now substantially all is simple small molecules light trigger, the photodestruciton reaction can take place in such light trigger when photopolymerization reaction, produce the free small organic molecule, this also is the major cause that photopolymerization material can not fully be used in biology, medicine and food associated materials always.For this reason, Recent study person begin to carry out the exploitation of macromole type or polymerizable light trigger, and this will reduce or eradicate the generation of micromolecular light trigger photolytic product, have a good application prospect.In addition, because radical polymerization has tangible oxygen inhibition effect, make that coating top layer and inside are all solidified fully, the concentration of light trigger will be strengthened, make it on the coatingsurface of oxygen concentration maximum, can realize fully causing effect, this can further strengthen the concentration of light trigger photolytic product, and its harm has also just increased.If, will when guarantee rational laser curing velocity, reduce light trigger and use concentration so can make light trigger hold enrichment at coatingsurface.
Summary of the invention
The object of the invention provides a kind of siliceous macromolecular photoinitiator, its synthetic method and the purposes of a kind of general formula for (I)
(I) in the formula, I is the light trigger that has hydroxyl, promptly has the bitter almond oil camphor class of hydroxyl, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone and camphorquinone compounds; R
1Be C
1-C
12The alkyl of different chain length, N, O, the C that heteroatomss such as S replace
1-C
12The alkyl of different chain length and the aryl that has different substituents; R
2, R
3Be C
1-C
12The alkyl of different chain length, N, O, the C that heteroatomss such as S replace
1-C
12The alkyl of different chain length, C
1-C
12The alkoxyl group of different chain length; N=3-50.
This synthetic method is characterized in that reaction was divided into for two steps, and an isocyanate groups reacts in the small molecules light trigger that the first step will contain hydroxyl and the vulcabond, obtains having the isocyanate compound of light trigger; Second step will have the isocyanate compound and the polysiloxane macromonomer compound reaction that has hydroxyl of light trigger.By top two-step reaction, just can obtain target product.
The purposes of siliceous macromolecular photoinitiator disclosed by the invention is to be used to cause the radical photopolymerization reaction.
Contain the siloxanes macromolecular photoinitiator, can be used as light solidifying coating material, photoetching material, photoimaging material, hologram recording material, the light trigger during photocurings such as optical material, three-dimensional modeling material, tooth section repair composite material.
The resin that can be used for radical photopolymerization can be epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of acroleic acid esterification etc.
When using macromolecular photoinitiator that contains siloxanes of the present invention and monomer and carrying out polymerization, can adopt light sources such as mercuryarc lamp, electrodeless lamp, xenon lamp, metal halide lamp, LED lamp.
The preparation method of siliceous macromolecular photoinitiator
Diisocyanate cpd is dissolved in adds reaction vessel in the solvent, when treating that temperature rises to 60 ℃, after adding the catalyzer dibutyl tin laurate, the photoinitiator compound that waits mole to have hydroxyl is splashed into reaction system by constant pressure funnel, control rate of addition, keep being reflected under 60 ℃ of conditions reacting, react after three hours, measure the isocyanide acid number, treat that it reaches half of duration just after, remove and desolvate, obtain having the light trigger of isocyanate groups.
Hydroxyl polysiloxane macromolecular cpd is added in the reaction vessel, equimolar the first step reaction product is added, reacted 6 hours down at 60-75 ℃.With infrared spectroscopy detect treat that isocyanate groups reacts completely after, just obtain siliceous macromolecular photoinitiator.
The polysiloxane-based macromolecular cpd that has hydroxyl, molecular weight are between 500-3000; The light trigger that has hydroxyl promptly has the bitter almond oil camphor class of hydroxyl, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone and camphorquinone compounds; Vulcabond is aromatic series or aliphatic diisocyanate cpd, i.e. tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate etc.
This two-step reaction all is simple chemical reaction, and its reaction conditions is conventional technology, so need not more to describe in detail, those skilled in the art can both need not performing creative labour and implement the present invention.
Consumption and compound method when siliceous macromolecular photoinitiator is used for radical photoinitiator solidified coating material: (weight percentage)
Light reactive resin 35%-60%
Reactive thinner 35%-60%
Siliceous macromolecular photoinitiator 1%-5%
Auxiliary agent 0.1%-0.5%
In the container of whipping device is housed, add 30%-60% reactive thinner, the siliceous macromolecular photoinitiator of 1%-5% and 1%-5% auxiliary agent, after the stirring and dissolving, the light reactive resin that adds 30%-60% again, under the 20-500C temperature, stirring makes it to mix and promptly obtains radical photoinitiator solidified coating material.
Described light reactive resin is epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of acroleic acid esterification etc.
Described reactive thinner is a simple function group, bifunctional or polyfunctional group (methyl) acrylate monomer.
Described auxiliary agent is a flow agent, defoamer etc.
Effect of the present invention: in molecular structure, introduce siloxane groups, utilize its higher surface tension, can prepare macromole or polymerisable light trigger with surface enrichment effect, compare with the ordinary light initiator, this light trigger also can reach good initiation effect when less volumetric molar concentration.
Embodiment
Synthetic embodiment
Embodiment 1
Synthesizing of 1173-IPDI-Tego 2311 macromolecular photoinitiators
17.76g (0.08mol) IPDI (isophorone diisocyanate), 400ml ethyl acetate are joined in the there-necked flask, start to stir and begin and heat, when treating that temperature rises to 60 ℃, add 0.06g catalyzer dibutyl tin laurate, and begin to drip 13.36g (0.08mol) 1173 (hydroxyl dimethyl acetophenone), after three hours, the isocyanide acid number is measured in sampling, after reaching half of initial value, stopped reaction after Rotary Evaporators is removed, obtains 1173-IPDI with ethyl acetate.
The Tego 2311 (DEGUSSA company) of 50g (0.04mol) is added in the 1000ml there-necked flask, start magnetic agitation, and begin to heat, when treating that temperature rises to 75 ℃, begin to drip the 1173-IPDI15.56g (0.04mol) that the back reaction obtains, react after six hours, after infrared spectra assert that isocyanate groups reacts completely, obtain target product.
Product is by infrared spectra, and UV spectrum is identified.
Embodiment 2
Synthesizing of 184-TDI-Tego 2311 macromolecular photoinitiators
13.92g (0.08mol) TDI (tolylene diisocyanate), 350ml toluene are joined in the there-necked flask; start to stir and begin and heat; when treating that temperature rises to 60 ℃, add 0.06g catalyzer dibutyl tin laurate, and begin to drip 16.32g (0.08mol) 184 (1-benzoyl cyclohexyl-1-alcohol); after three hours; the isocyanide acid number is measured in sampling, reach half of initial value after; solvent after Rotary Evaporators is removed, is obtained 184-TDI.
The Tego 2311 of 50g (0.04mol) is added in the 1000ml there-necked flask, start magnetic agitation, and begin to heat, when treating that temperature rises to 75 ℃, begin to drip the 184-TDI15.12g (0.04mol) that the back reaction obtains, react after six hours, after infrared spectra assert that isocyanate groups reacts completely, obtain target product.
Product is by infrared spectra, and UV spectrum is identified.
Embodiment 3
Synthesizing of benzophenone-HDI-550 macromolecular photoinitiator
13.44g (0.08mol) HDI (hexamethylene diisocyanate), 400ml tetrahydrofuran (THF) are joined in the there-necked flask, start to stir and begin and heat, when treating that temperature rises to 60 ℃, add 0.06g catalyzer dibutyl tin laurate, and begin to drip 15.84g (0.08mol) hydroxy benzophenone, after three hours, the isocyanide acid number is measured in sampling, after reaching half of initial value, stopped reaction after Rotary Evaporators is removed, obtains 184-HDI with solvent.
The polydimethyl silane 550 (ACROS company) of 50g (0.04mol) is added in the 1000ml there-necked flask, start magnetic agitation, and begin to heat, when treating that temperature rises to 60 ℃, begin to drip benzophenone-HDI14.64g (0.04mol) that the back reaction obtains, react after six hours, after infrared spectra assert that isocyanate groups reacts completely, obtain target product.
Product is by infrared spectra, and UV spectrum is identified.
Embodiment 4
Synthesizing of ITX-MDI-550 macromolecular photoinitiator
20.02g (0.08mol) MDI (diphenylmethanediisocyanate), 400ml toluene are joined in the there-necked flask, start to stir and begin and heat, when treating that temperature rises to 60 ℃, add 0.06g catalyzer dibutyl tin laurate, and begin to drip 15.84g (0.08mol) hydroxyl isopropyl thioxanthone (ITX), after three hours, the isocyanide acid number is measured in sampling, after reaching half of initial value, stopped reaction after Rotary Evaporators is removed, obtains ITX-MDI with solvent.
The polydimethyl silane 550 of 50g (0.04mol) is added in the 1000ml there-necked flask, start magnetic agitation, and begin to heat, when treating that temperature rises to 70 ℃, begin to drip the ITX-MDI17.93g (0.04mol) that the back reaction obtains, react after six hours, after infrared spectra assert that isocyanate groups reacts completely, obtain target product.
Product is by infrared spectra, and UV spectrum is identified.
Application Example
Embodiment 1
Under the lucifuge condition, in being housed, the container of agitator adds 15g1,6-hexylene glycol double methacrylate, the 10g Viscoat 295,0.5g184-TDI-Tego2311 macromolecular photoinitiator, 23g bisphenol A epoxy acrylate 6210 (Changxing company) adds 0.25gBYK-306,0.25gBYK-141 again after 40 ℃ of following stirring and dissolving.
The solution for preparing is applied on the substrate, placed under the 500W high voltage mercury lamp illumination 1 minute, the photocuring that obtains pencil hardness and be 2H is filmed, and is identical with the commercial coat effect.
Embodiment 2
Urethane acrylate CN973 (Sartomer company) 17.5g
Hydroxyethyl methylacrylate 6g
Tripropylene glycol double methacrylate 10g
Pentaerythritol triacrylate 14g
ITX-MDI-550 macromolecular photoinitiator 2g
BYK-371 0.25g
BYK-066 0.25g
Press embodiment 1 method preparation and coating, placed under the 500W high voltage mercury lamp illumination 1.5 minutes, the photocuring that obtains pencil hardness and be 1H is filmed, and is identical with the commercial coat effect.
Embodiment 3
Polyester acrylate EB811 (Cytec company) 25g
Neopentyl glycol double methacrylate 12g
Ethoxyquin Viscoat 295 10g
1173-IPDI-Tego2311 macromolecular photoinitiator 2.5g
TEGO-205 0.25g
BYK-088 0.25g
Press embodiment 1 method preparation and coating, placed under the 500W high voltage mercury lamp illumination 2 minutes, the photocuring that obtains pencil hardness and be HB is filmed, and is identical with the commercial coat effect.
Embodiment 4
Amido acrylate 6106 (three wooden companies) 30g
Isobornyl acrylate 5g
Neopentyl glycol double methacrylate 6g
Double pentaerythritol C5 methacrylate 6g
Benzophenone-HDI-550 macromolecular photoinitiator 2.5g
TEGO-205 0.25g
BYK-088 0.25g
Press embodiment 1 method preparation and coating, place under the 500W high voltage mercury lamp 40 seconds of illumination, the photocuring that obtains pencil hardness and be 3H is filmed, and is identical with the commercial coat effect.
Claims (6)
1. a siliceous macromolecular photoinitiator is characterized in that described siliceous macromolecular photoinitiator is that general formula is the compound of I
(I) in the formula, I is the light trigger that has hydroxyl, promptly has the bitter almond oil camphor class of hydroxyl, st-yrax ethers, alkyl acetophenones, alkylamino radical acetophenones, benzophenone, thioxanthones, tonka-bean ketone and camphorquinone compounds; R
1Be C
1-C
12The alkyl of different chain length, N, O, the C that the S heteroatoms replaces
1-C
12The alkyl of different chain length or have the aryl of different substituents; R
2, R
3Be C
1-C
12The alkyl of different chain length, N, O, the C that the S heteroatoms replaces
1-C
12The alkyl of different chain length or C
1-C
12The alkoxyl group of different chain length; N=3-50.
2. the synthetic method of this siliceous macromolecular photoinitiator described in claim 1 is characterized in that:
Reaction is carried out in two steps, diisocyanate cpd is dissolved in adds reaction vessel in the solvent, when treating that temperature rises to 60 ℃, after adding the catalyzer dibutyl tin laurate, the photoinitiator compound that waits mole to have hydroxyl is splashed into reaction system by constant pressure funnel, control rate of addition, keep being reflected under 60 ℃ of conditions reacting, react after 3 hours, remove and desolvate, obtain having the light trigger of isocyanate groups;
Hydroxyl polysiloxane macromolecular cpd is added in the reaction vessel, the light trigger that adds above-mentioned equimolar isocyanate groups, 60-75 ℃ of down reactions 6 hours, with infrared spectroscopy detect treat that isocyanate groups reacts completely after, just obtain siliceous macromolecular photoinitiator.
3. the purposes of the siliceous macromolecular photoinitiator described in claim 1, when it is characterized in that described siliceous macromolecular photoinitiator as the initiator of photocuring system, each component and weight percentage thereof are:
Light reactive resin 35%-60%
Reactive thinner 35%-60%
Siliceous macromolecular photoinitiator 1%-5%
Auxiliary agent 0.1%-0.5%
4. the purposes of the siliceous macromolecular photoinitiator described in claim 3, it is characterized in that light reactive resin be among epoxy (methyl) acrylic resin, urethane (methyl) acrylic resin, polyester (methyl) acrylic resin, polyethers (methyl) acrylic resin, poly-(methyl) acrylic resin of acroleic acid esterification one or more.
5. the purposes of siliceous macromolecular photoinitiator as claimed in claim 3 is characterized in that reactive thinner is a simple function group, bifunctional, among polyfunctional group (methyl) acrylate monomer one or more.
6 the purposes of siliceous macromolecular photoinitiator described in claim 3, it is characterized in that auxiliary agent be flow agent, defoamer one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007103039357A CN100526340C (en) | 2007-12-21 | 2007-12-21 | Silicon containing macromolecule photo-initiation agent, synthesis and uses thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007103039357A CN100526340C (en) | 2007-12-21 | 2007-12-21 | Silicon containing macromolecule photo-initiation agent, synthesis and uses thereof |
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| CN100526340C true CN100526340C (en) | 2009-08-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102174127B (en) * | 2009-07-09 | 2012-07-04 | 北京化工大学 | Macromolecular photoinitiator for gradient polymerization and synthesis method and application thereof |
| CN103333276B (en) * | 2013-06-08 | 2015-07-29 | 新丰博兴聚合材料有限公司 | Longwave absorption light trigger of a kind of silicone-containing group and preparation method thereof |
| CN103342764B (en) * | 2013-06-09 | 2015-08-26 | 中山大学 | A kind of light trigger and preparation method thereof |
| RU2019119411A (en) * | 2016-11-22 | 2020-12-24 | Колопласт А/С | PHOTO INITIATORS |
| CN107325288B (en) * | 2017-06-23 | 2021-02-12 | 武汉长盈鑫科技有限公司 | Organic silicon modified photoinitiator for improving surface curing effect and preparation method thereof |
| CN108929062A (en) * | 2018-07-04 | 2018-12-04 | 穆琳瑛 | A kind of polycarboxylate water-reducer and its preparation process |
| CN114230747B (en) * | 2021-12-20 | 2024-02-02 | 江苏三木化工股份有限公司 | Preparation method of high-solid low-viscosity self-initiated epoxy acrylate oligomer |
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