CN100558764C - Salt compounded of iodine of cationic photoinitiator polystyrene or its multipolymer and preparation method thereof - Google Patents
Salt compounded of iodine of cationic photoinitiator polystyrene or its multipolymer and preparation method thereof Download PDFInfo
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- CN100558764C CN100558764C CNB2007103024421A CN200710302442A CN100558764C CN 100558764 C CN100558764 C CN 100558764C CN B2007103024421 A CNB2007103024421 A CN B2007103024421A CN 200710302442 A CN200710302442 A CN 200710302442A CN 100558764 C CN100558764 C CN 100558764C
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Abstract
Salt compounded of iodine of cationic photoinitiator polystyrene or its multipolymer and preparation method thereof belongs to organic synthesis and cationic curing technical field.The present invention proposes the salt compounded of iodine compound that name is called polystyrene or polystyrene copolymer series; Its preparation method is for making hydroxyl tolysulfonyl oxygen base iodobenzene earlier; And with the reaction of polystyrene or polystyrene copolymer, product continues to make with the hexaflouroantimonate family salts reaction salt compounded of iodine-hexaflouroantimonate family salts of polystyrene or polystyrene copolymer series.This series compound is that a kind of preparation is simple, and is convenient, the cation photocuring initiator that cost is low.The introducing of macro-radical makes that its rate of migration is low, toxicity is little and environment compatibility is good, in non-polar resin, has solvability preferably, the ultraviolet maximum absorption wavelength of this serial salt compounded of iodine can red shift to 270nm, its mobility only is the 0.1%-1.5% of commercially available small molecules salt compounded of iodine IGM445 mobility.It is mixed with Resins, epoxy especially cycloaliphatic epoxy resin, and cohesive strength is comparatively excellent.
Description
Technical field
The present invention relates to the preparation of the initiator in the cationoid polymerisation, synthesized a series of macromole diaryl group iodized salts, have a wide range of applications, belong to organic synthesis and cationic curing technical field in coating, microelectronics, optics and food product pack field.
Background technology
Ultraviolet light polymerization (UV curing) has characteristics such as speed is fast, energy consumption is low, non-environmental-pollution, coating performance excellence.It is the research basis that UV the earliest solidifies with the free radical mechanism, and cationic curing is just to grow up the end of the seventies, compares with radically curing, and the cationic curing system has the following advantages: 1. not by oxygen inhibition; 2. volumetric shrinkage is little during the positively charged ion ring-opening polymerization, and formed coating adhesion is stronger; 3. curing reaction is difficult for stopping, and is applicable to the photocuring of thick film and colored paint.
Diaryl group iodized salt (A) and triaryl sulfonium salts (B) have preferable thermostability, and are easy to synthesize as a kind of cation light initiator commonly used, therefore very fast the and shiploads of merchandiseization of development.
Its maximum shortcoming is to cost an arm and a leg, and the solvability of salt in non-polar resin is not enough, and be poisonous, and light-initiated back produces fragment and migration.
This series macromolecular photoinitiator has following advantage:
1. smell is low, volatility is low;
2. rate of migration is low, toxicity is little, environment compatibility is good, is difficult for moving to the surface, has reduced the toxicity of light trigger;
3. the consistency with resin is good;
Along with science and technology development, also more and more higher to various performances (velocity of initiation is with the consistency of photocuring system, toxicity, the stability in storage) requirement of light trigger.For photocuring system, in long process of preservation, because photocuring system consistency difference and volatilize easily and move, this can reduce the photopolymerization efficiency of initiation on the one hand, can cause product smell and toxicity to occur on the other hand as the light trigger of small molecules type.Therefore research and development polymer light trigger efficient, low toxicity becomes the focus that people pay close attention to.
Summary of the invention
The purpose of this invention is to provide salt compounded of iodine of a kind of cationic photoinitiator polystyrene or its multipolymer and preparation method thereof, it is simple to be used for preparation, convenient, the macromole cation photocuring initiator that cost is low.
The objective of the invention is to be achieved through the following technical solutions:
Technical scheme of the present invention: name is called the compound of the salt compounded of iodine of polystyrene or polystyrene copolymer series, and its general formula is:
R or do not exist or R is that methyl methacrylate or R are that vinylformic acid or R are that methacrylic tert-butyl acrylate or R are maleic anhydride wherein; R
1, R
2For hydrogen or be alkyl or for alkoxyl group; X is: SbF
6, AsF
6, PF
6, BF
4, ClO
4, CF
3SO
3, FSO
3, CH
3SO
3Or C
4F
9SO
3This compound is used as light trigger in cationoid polymerisation, wherein, and polymerization degree n=100-500, m=10-100.
Described compound, wherein R does not exist, and X is SbF
6, R
1, R
2For hydrogen or be alkyl or for alkoxyl group, this compound is poly-(vinylbenzene iodo-hexafluoro antimonate), structural formula is:
Described compound, wherein R is a methyl methacrylate, X is SbF
6, R
1, R
2For hydrogen or be alkyl or for alkoxyl group, this compound is poly-(vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate), structural formula is:
Described compound, wherein R is the methacrylic tert-butyl acrylate, X is SbF
6, R
1, R
2For hydrogen or be alkyl or for alkoxyl group, this compound is poly-(vinylbenzene iodo-hexafluoro antimonate-co-methacrylic tert-butyl acrylate), structural formula is:
Described compound, wherein R is a vinylformic acid, X is SbF
6, R
1, R
2For hydrogen or be alkyl or for alkoxyl group, this compound is poly-(vinylbenzene iodo-hexafluoro antimonate-co-vinylformic acid), structural formula is:
Described compound, wherein R is a maleic anhydride, X is SbF
6, R
1, R
2For hydrogen or be alkyl or for alkoxyl group, this compound is poly-(vinylbenzene iodo-hexafluoro antimonate-alt-maleic anhydride), structural formula is:
The preparation method of described compound:
(1) make Peracetic Acid by acetate and superoxol reaction, reaction formula is:
CH
3COOH+H
2O
2→CH
3COOOH+H
2O (I)
Reaction conditions is: acetate and hydrogen peroxide react with equimolar amount, in the 250mL there-necked flask that has whipping appts and thermometer, add glacial acetic acid earlier, add hydrogen peroxide again, the vitriol oil that adds the two weight sum 1% at last, add material after, at room temperature stir 3h, leave standstill 20h, promptly get Peracetic Acid;
(2) the Peracetic Acid method is carried out the synthetic of hydroxyl tolysulfonyl oxygen base iodobenzene, and reaction formula is:
Reaction conditions is: phenyl-iodide and Peracetic Acid were with 1: 2 molar ratio reaction, in the there-necked flask that has agitator, prolong and thermometer, add phenyl-iodide and Peracetic Acid, temperature of reaction is controlled at 50 ℃, and the reaction times is 1 hour, continues to keep system temperature at 50 ℃, add tosic acid continuation reaction with the phenyl-iodide equimolar amount, reaction 2h, through suction filtration, crystallization, obtain product hydroxyl tolysulfonyl oxygen base iodobenzene, reach 85% in the phenyl-iodide productive rate;
(3) make poly-(vinylbenzene iodo-tolysulfonyl oxygen base salt) by polystyrene and the product reaction of (2) step, reaction formula is:
Reaction conditions is: polystyrene is dissolved in the solvents tetrahydrofurane, adds hydroxyl tolysulfonyl oxygen base iodobenzene and glacial acetic acid again, and at 50 ℃ of condensing reflux reaction 6h, reaction is finished, and rotary evaporation boils off tetrahydrofuran (THF);
(4) by poly-(vinylbenzene iodo-tolysulfonyl oxygen base salt) and sodium hexafluoroantimonate reaction, make product poly-(vinylbenzene iodo-hexafluoro antimonate), reaction formula is:
Reaction conditions is: add ethanol in poly-(the vinylbenzene iodo-tolysulfonyl oxygen base salt) of gained, add sodium hexafluoroantimonate again with hydroxyl tolysulfonyl oxygen base iodobenzene equimolar amount, stir, suction filtration, rotary evaporation boils off ethanol and gets yellow oil, places 12 hours, centrifugal, tetrahydrofuran (THF)/water dissolves and precipitation repeatedly, and vacuum-drying must gather (vinylbenzene iodo-hexafluoro antimonate) to constant weight;
Used sodium hexafluoroantimonate NaSbF
6, use hexafluoroarsenate sodium NaAsF instead
6Or sodium hexafluoro phosphate NaPF
6Replace, the same process products therefrom is respectively poly-(vinylbenzene iodo-hexafluoro arsenate), poly-(vinylbenzene iodo-hexafluorophosphate).
Or used R
1, R
2Use alkyl or alkoxyl group instead, under similar technology, obtain the salt compounded of iodine of alkylation or oxyalkylated polystyrene or its multipolymer.
Or used polystyrene is used polystyrene copolymer instead, under the same process condition, gathered (vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-methacrylic tert-butyl acrylate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-vinylformic acid), poly-(vinylbenzene iodo-hexafluoro antimonate-alt-maleic anhydride).
Beneficial effect of the present invention: the salt compounded of iodine of polystyrene and multipolymer thereof is that a kind of preparation is simple, and is convenient, the cation photocuring initiator that cost is low.The introducing of macro-radical makes that its rate of migration is low, toxicity is little and environment compatibility is good, has solvability preferably in non-polar resin, the ultraviolet maximum absorption wavelength of this serial salt compounded of iodine can red shift to 270nm.In 40 ℃ of fatty simulated solutions, place 24h, 48h, 72h, 96h, 120h after, measure its mobility and only be the 0.1%-1.5% of commercially available small molecules salt compounded of iodine IGM445 mobility.It is mixed with Resins, epoxy especially cycloaliphatic epoxy resin, and cohesive strength is comparatively excellent.
Embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Synthesizing of embodiment 1 hydroxyl tolysulfonyl oxygen base iodobenzene
In the 250mL there-necked flask that has whipping appts and thermometer, add the 0.5mol glacial acetic acid earlier, add the 0.5mol hydrogen peroxide, add the vitriol oil that is equivalent to the two weight 1% at last.After adding material, at room temperature stir 3h, leave standstill 20h, promptly get Peracetic Acid.
Add 0.2mol phenyl-iodide and 0.4mol Peracetic Acid in the there-necked flask that has agitator, prolong and thermometer, temperature of reaction is controlled at 50 ℃, and the reaction times is 1h.Continue to keep system temperature at 50 ℃, the tosic acid that adds 0.2mol continues reaction 2h.Through suction filtration, crystallization obtains product hydroxyl tolysulfonyl oxygen base iodobenzene.Productive rate 85% (in phenyl-iodide).
Embodiment 2 preparations poly-(vinylbenzene iodo-hexafluoro antimonate)
The polystyrene (PS) of polymerization degree n=100-500 is dissolved in the tetrahydrofuran solvent, pours in the 250mL three-necked bottle, add hydroxyl tolysulfonyl oxygen base iodobenzene and glacial acetic acid that embodiment 1 makes again.The reaction mole dosage of polystyrene and hydroxyl tolysulfonyl oxygen base iodobenzene was suitable, is about 0.2mol, 50 ℃ of condensing reflux reactions 6 hours.Reaction is finished, and rotary evaporation boils off tetrahydrofuran (THF).In the faint yellow oily thing of gained, add 50mL ethanol, make it dissolving, add the 0.2mol sodium hexafluoroantimonate again, stir.Suction filtration, rotary evaporation gets yellow oil, places 12 hours, and is centrifugal, and tetrahydrofuran (THF)/water dissolves and precipitation repeatedly, and vacuum-drying must gather (vinylbenzene iodo-hexafluoro antimonate) to constant weight.Productive rate is 66.8%.
Embodiment 3 preparations poly-(vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate)
With 107mL distilled water and 0.0054g polyvinyl alcohol (0.04%, mass ratio descends together); 0.013g Sodium dodecylbenzene sulfonate (0.01%); calcium phosphate 1.3g (1%) adds in people's there-necked flask, and there-necked flask is placed in the water bath, and logical people's nitrogen is protected; open whipping appts; seal remaining opening, regulate stirring velocity, keeping water-bath is 90 ℃; 0.5h is stirred in timing, the activation dispersion agent.During precipitation temperature to 70 ℃, adopt one time feeding mode then, add monomer (methyl methacrylate 15mL, vinylbenzene 4.1mL) and initiator dibenzoyl peroxide 0.63g (0.05%), 70 ℃ of constant temperature, 6h is reacted in nitrogen protection.Reaction back premium on currency temperature to 90 ℃, slaking 2h finishes reaction.Leave standstill hypsokinesis and go out supernatant liquid, use HCl/H
2O (2: 1) washing is washed till neutrality with a large amount of distilled water, filters, and vacuum-drying, screening obtains transparent beaded product.
The 0.01mol multipolymer is dissolved in the solvent 50mL tetrahydrofuran (THF), adds hydroxyl tolysulfonyl oxygen base iodobenzene and Glacial acetic acid again.Under 50 ℃, make hydroxyl tolysulfonyl oxygen base iodobenzene dissolve fully.Reaction is finished, and rotary evaporation boils off tetrahydrofuran (THF).In the faint yellow oily thing of gained, add 50mL ethanol, make it dissolving, add sodium hexafluoroantimonate again, stir, generate the paratoluenesulfonic acid sodium salt white precipitate at once.Suction filtration, rotary evaporation gets yellow oil, places 12 hours, and is centrifugal, and tetrahydrofuran (THF)/water dissolves and precipitation repeatedly, and vacuum-drying gets product poly-(vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate) to constant weight.
Embodiment 4 preparations poly-(vinylbenzene iodo-hexafluoro arsenate-co-vinylformic acid)
PAA's is synthetic: add an amount of initiator ethyl bromide, 2 in the 50mL round-bottomed flask, 2 '-dipyridyl, cuprous bromide and vinylformic acid, after liquid nitrogen freezing-vacuumize-thaw fills nitrogen three times,, be placed in 100 ℃ of constant temperature oil baths and react in the nitrogen atmosphere sealing.Behind the reaction certain hour, open sealing, reaction solution is diluted with tetrahydrofuran (THF), use methanol extraction, behind tetrahydrofuran (THF) dissolving-methanol extraction three times, filtration drying obtains polyacrylic acid.Synthetic the same with purification step, wherein replace alpha-brominated ethyl acetate as macromole evocating agent with above-mentioned synthetic polyacrylic acid, replace vinylformic acid as polymerization single polymerization monomer with vinylbenzene, polymeric reaction temperature is 130 ℃.
To go up the step product and be dissolved in the solvent 50mL tetrahydrofuran (THF), add hydroxyl tolysulfonyl oxygen base iodobenzene and Glacial acetic acid again.50 ℃ of following condensing reflux reactions.Reaction is finished, and rotary evaporation boils off tetrahydrofuran (THF).In the faint yellow oily thing of gained, add 50mL ethanol, make it dissolving, add hexafluoroarsenate sodium again, stir.Suction filtration, rotary evaporation gets yellow oil, places 12 hours, and is centrifugal, and tetrahydrofuran (THF)/water dissolves and precipitation repeatedly, and vacuum-drying must gather (vinylbenzene iodo-hexafluoro arsenate-co-vinylformic acid) to constant weight.
Application Example 1
Under the lucifuge condition, in the Glass Containers of agitator is housed, add 3g cycloaliphatic epoxy resin K-126, add poly-(vinylbenzene iodo-hexafluoro antimonate) high-molecular optical initiator that 0.09g embodiment 2 makes again, 25 ℃ of following stirring and dissolving.The solution for preparing is applied on the substrate, placed under the 250W medium pressure mercury lamp illumination 2 minutes, photocuring is filmed.
The solution for preparing is applied between two sheet glass, behind the UV irradiation, records its shearing resistance with the microcomputer control universal testing machine and be about 8.16MPa, tensile strength is about 9.79MPa.
Application Example 2
Under the lucifuge condition, in the Glass Containers of agitator is housed, add 3g bisphenol A epoxide resin E-44, add poly-(vinylbenzene iodo-hexafluoro antimonate) high-molecular optical initiator that 0.09g embodiment 2 makes again, 25 ℃ of following stirring and dissolving.The solution for preparing is applied on the substrate, placed under the 250W medium pressure mercury lamp illumination 2 minutes, photocuring is filmed.
The solution for preparing is applied between two sheet glass, behind the UV irradiation, records its shearing resistance with the microcomputer control universal testing machine and be about 5.08MPa, tensile strength is about 8.35MPa.
Application Example 3
Under the lucifuge condition, in the Glass Containers of agitator is housed, add 3g bisphenol A epoxide resin E-51, add poly-(vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate) high-molecular optical initiator that 0.09g embodiment 3 makes again, 25 ℃ of following stirring and dissolving.The solution for preparing is applied on the substrate, placed under the 250W medium pressure mercury lamp illumination 2 minutes, photocuring is filmed.
The solution for preparing is applied between two sheet glass, behind the UV irradiation, records its shearing resistance with the microcomputer control universal testing machine and be about 4.88MPa, tensile strength is about 7.14MPa.
Application Example 4
Under the lucifuge condition, in the Glass Containers of agitator is housed, add 3g bisphenol A epoxide resin E-55, add poly-(vinylbenzene iodo-hexafluoro arsenate-co-vinylformic acid) high-molecular optical initiator that 0.09g embodiment 4 makes again, 25 ℃ of following stirring and dissolving.The solution for preparing is applied on the substrate, placed under the 250W medium pressure mercury lamp illumination 2 minutes, photocuring is filmed.
The solution for preparing is applied between two sheet glass, behind the UV irradiation, records its shearing resistance with the microcomputer control universal testing machine and be about 4.78MPa, tensile strength is about 4.62MPa.
Claims (1)
1. the preparation method of the compound of the salt compounded of iodine of polystyrene or polystyrene copolymer series, it is characterized in that: the structural formula of described compound is:
R or do not exist or R is that methyl methacrylate or R are that vinylformic acid or R are that methacrylic tert-butyl acrylate or R are maleic anhydride wherein; R
1, R
2Be hydrogen; X is: SbF
6, AsF
6, or PF
6This compound is used as light trigger in cationoid polymerisation, wherein, and polymerization degree n=100-500, m=10-100;
Described compound is selected from poly-(vinylbenzene iodo-hexafluoro antimonate), poly-(vinylbenzene iodo-hexafluoro arsenate), poly-(vinylbenzene iodo-hexafluorophosphate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-methacrylic tert-butyl acrylate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-vinylformic acid) or poly-(vinylbenzene iodo-hexafluoro antimonate-alt-maleic anhydride);
Preparation method's step is:
(1) make Peracetic Acid by acetate and superoxol reaction, reaction formula is:
CH
3COOH+H
2O
2→CH
3COOOH+H
2O (I)
Reaction conditions is: acetate and hydrogen peroxide react with equimolar amount, in the 250mL there-necked flask that has whipping appts and thermometer, add glacial acetic acid earlier, add hydrogen peroxide again, the vitriol oil that adds the two weight sum 1% at last, add material after, at room temperature stir 3h, leave standstill 20h, promptly get Peracetic Acid;
(2) the Peracetic Acid method is carried out the synthetic of hydroxyl tolysulfonyl oxygen base iodobenzene, and reaction formula is:
Reaction conditions is: phenyl-iodide and Peracetic Acid were with 1: 2 molar ratio reaction, in the there-necked flask that has agitator, prolong and thermometer, add phenyl-iodide and Peracetic Acid, temperature of reaction is controlled at 50 ℃, and the reaction times is 1 hour, continues to keep system temperature at 50 ℃, add tosic acid continuation reaction with the phenyl-iodide equimolar amount, reaction 2h, through suction filtration, crystallization, obtain product hydroxyl tolysulfonyl oxygen base iodobenzene, reach 85% in the phenyl-iodide productive rate;
(3) make poly-(vinylbenzene iodo-tolysulfonyl oxygen base salt) by polystyrene and the product reaction of second step, reaction formula is:
Reaction conditions is: polystyrene is dissolved in the solvents tetrahydrofurane, adds hydroxyl tolysulfonyl oxygen base iodobenzene and glacial acetic acid again, and at 50 ℃ of condensing reflux reaction 6h, reaction finishes, and rotary evaporation boils off tetrahydrofuran (THF);
(4) by poly-(vinylbenzene iodo-tolysulfonyl oxygen base salt) and sodium hexafluoroantimonate reaction, make product poly-(vinylbenzene iodo-hexafluoro antimonate), reaction formula is:
Reaction conditions is: add ethanol in poly-(the vinylbenzene iodo-tolysulfonyl oxygen base salt) of gained, add sodium hexafluoroantimonate again with hydroxyl tolysulfonyl oxygen base iodobenzene equimolar amount, stir, suction filtration, rotary evaporation boils off ethanol and gets yellow oil, places 12 hours, centrifugal, tetrahydrofuran (THF)/water is dissolution precipitation repeatedly, and vacuum-drying must gather (vinylbenzene iodo-hexafluoro antimonate) to constant weight;
Used sodium hexafluoroantimonate NaSbF
6, use hexafluoroarsenate sodium NaAsF instead
6Or sodium hexafluoro phosphate NaPF
6Replace, the same process products therefrom is respectively poly-(vinylbenzene iodo-hexafluoro arsenate), poly-(vinylbenzene iodo-hexafluorophosphate);
Or used polystyrene is used polystyrene copolymer instead, under the same process condition, gathered (vinylbenzene iodo-hexafluoro antimonate-co-methyl methacrylate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-methacrylic tert-butyl acrylate), poly-(vinylbenzene iodo-hexafluoro antimonate-co-vinylformic acid) or poly-(vinylbenzene iodo-hexafluoro antimonate-alt-maleic anhydride).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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|---|---|---|---|
| CNB2007103024421A CN100558764C (en) | 2007-12-26 | 2007-12-26 | Salt compounded of iodine of cationic photoinitiator polystyrene or its multipolymer and preparation method thereof |
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| CN113604965B (en) * | 2021-08-25 | 2022-08-23 | 辽宁洁花环保科技装备有限公司 | Non-woven fabric and preparation method thereof |
| CN117487087B (en) * | 2024-01-03 | 2024-03-22 | 北京中科康仑环境科技研究院有限公司 | Hybrid modified high oil absorption resin and preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
|---|
| 新型大分子阳离子光引发剂的合成及其光敏性能研究. 夏朝荣，刘仁，安丰磊，刘晓亚.第八届中国辐射固化年会论文汇编. 2007 |
| 新型大分子阳离子光引发剂的合成及其光敏性能研究. 夏朝荣，刘仁，安丰磊，刘晓亚.第八届中国辐射固化年会论文汇编. 2007 * |
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