CN102827382A - Preparation method of photoactive microgel based on ultraviolet radiation technique - Google Patents
Preparation method of photoactive microgel based on ultraviolet radiation technique Download PDFInfo
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- CN102827382A CN102827382A CN2012103344492A CN201210334449A CN102827382A CN 102827382 A CN102827382 A CN 102827382A CN 2012103344492 A CN2012103344492 A CN 2012103344492A CN 201210334449 A CN201210334449 A CN 201210334449A CN 102827382 A CN102827382 A CN 102827382A
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Abstract
The invention relates to a preparation method of a photoactive microgel based on ultraviolet radiation technique, belonging to the field of polymer material. The method provided by the invention uses the ultraviolet radiation technique and comprises the steps of adding a photocurable monomer, a photoinitiator, a cosolvent and water to water-borne photocurable resin for photopolymerization after photosensitive micelle of the water-borne photocurable resin is formed in water. The photoactive microgels with different photoactive double bond contents are prepared through controlling the violet radiation energy. The method is simple, easy to implement, high efficient and controllable, and is beneficial to the implement of continuous preparation process.
Description
Technical field
The invention belongs to polymeric material field, especially relate to the uv irradiation method is obtained the photolytic activity microgel by the aqueous photo-curing micella method.
Background technology
Polymer microgel is that a kind of molecular structure has a colloidal-sized (1～1000nm) and the polymer beads of intramolecular crosslinking between branched macromolecule and macroscopical polymer network.Reactive micro-gel then is a kind of intramolecular crosslinking, surface or the inner colloidal particle that has certain reactive group.Owing to its particular structure and rheological property are widely used in aspects such as biological medicine, coating and dyestuff, oil production., it often can give performances such as its excellent tensile strength, resistance to impact shock, water tolerance, thermotolerance, weathering resistance, photostabilization and weather resistance after joining in the polymkeric substance.The main preparation method of reactive micro-gel has methods such as letex polymerization, dispersion polymerization, solution polymerization, and methods such as precipitation polymerization, suspension polymerization, dispersion polymerization have also obtained certain development in recent years.But these methods mostly need add stablizer, can influence the final performance of product, and preparation efficiency are relatively low.
The uv irradiation technology is that a kind of speed is fast, energy consumption is low, the photo-crosslinking of environmental protection technology, can fast the two keys of photolytic activity be carried out crosslinkedly, is a kind of eco-friendly green technology.Use it for the preparation of photolytic activity microgel, can when significantly improving preparation efficiency, be evenly distributed, the microgel particle of median size between 10-500nm.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the photolytic activity microgel; Can make median size photolytic activity microgel particle between 10-500nm by the aqueous photo-curing micella rapidly through the uv irradiation technology, this method is applicable to multiple aqueous photo-curing resin system.
Technical scheme provided by the invention is following: utilize the uv irradiation technology, through the median size and the photolytic activity double bond content of control photolytic activity microgel particles such as control uv irradiation intensity, temperature, irradiation time, light trigger kind and consumption.
A kind of uv irradiation legal system provided by the invention is equipped with the method for photolytic activity microgel, it is characterized in that: at first aqueous photo-curing resin, light trigger and solubility promoter are mixed, and add the photosensitive micellar aqueous solution of formation in the entry; Then the solution that mixes being accepted ultraviolet light irradiation under flow state carries out partial cross-linked; The mass percent of aqueous photo-curing resin, photo-curing monomer, light trigger, solubility promoter and water is among this active microgel preparation method:
Preparation condition:
Light intensity 20Mw/cm
2-300Mw/cm
2
Irradiation time 0.5s-600s
Temperature 1-75 ℃
The aqueous photo-curing resin is one or more in aqueous polyurethane (methyl) propenoic acid ester photocureable resin, water-base epoxy (methyl) propenoic acid ester photocureable resin, water-and acrylate light-cured resin, waterborne polyester light-cured resin and the water alcohol acid light-cured resin among the present invention.Photo-curing monomer is one or more in simple function group (methyl) acrylate monomer, bifunctional (methyl) acrylate monomer and polyfunctional group (methyl) acrylate monomer.Light trigger is st-yrax, benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, phenylbenzene ethyl ketone, α; α-methoxyl group-α-phenyl methyl phenyl ketone, α; In α-phenetole ethyl ketone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, two benzoyl-phenyl phosphine oxide, UVNUL MS-40,2,4 dihydroxyl benzophenone, Michler's keton, sulfo-propoxy-thioxanthone and the isopropyl thioxanthone one or more.Solubility promoter is one or more in ethanol, propyl alcohol, Virahol, propyl carbinol, EGME, butyl glycol ether, propylene glycol monomethyl ether, Ucar 35 butyl ether, glycol methyl ether acetate and the 1-Methoxy-2-propyl acetate.
Description of drawings
The microgel powder of Fig. 1 embodiment 1 and swelling solution photo thereof.
The infrared spectrum of the microgel of Fig. 2 embodiment 1,2,3.
The nuclear magnetic spectrogram of the microgel of Fig. 3 embodiment 1,2,3.
Fig. 4 adds the Electronic Speculum figure that the photocuring of (left figure) back (right figure) is filmed before the microgel powder of embodiment 2.
Embodiment
To further explain of the present invention, but the present invention is not limited thereto below in conjunction with instance.
Embodiment 1
Take by weighing 10g water-and acrylate light-cured resin; Add 0.2g1173 and 1g EGME; Mix back adding 330g deionized water and fully stir formation water-and acrylate photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 80mW/cm
2, irradiation time 15s, making median size is the microgel PANM-L of 35.59nm; Fig. 1 be its powdered samples and in solvent swelling solution; Prove the existence of its internal crosslinking structure thus, Fig. 2 and Fig. 3 are respectively infrared and nuclear magnetic spectrogram, prove the existence of the two keys of its photolytic activity.
Take by weighing 10g water-base epoxy light-cured resin, add 0.2g1173 and 1g ethanol, mix back adding 330g deionized water and fully stir formation water-and acrylate photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 40mW/cm
2, irradiation time 30s, making median size is the microgel PANM-M of 37.96nm, Fig. 2 and Fig. 3 are respectively infrared and nuclear magnetic spectrogram, prove the existence of the two keys of its photolytic activity.Fig. 4 is for adding before the PANM-M microgel powder (left figure) photocuring of (right figure) Electronic Speculum figure that films afterwards, and the photolytic activity microgel effectively is scattered in during photocuring films, and can be used for fields such as photo-cured coating, sizing agent and printing ink.
Embodiment 3
Take by weighing 10g water-and acrylate light-cured resin; Add 0.2g1173 and 1g Ucar 35 butyl ether; Mix back adding 330g deionized water and fully stir formation water-and acrylate photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 300mW/cm
2, irradiation time 0.5s, making median size is the microgel PANM-H of 39.57nm, Fig. 2 and Fig. 3 are respectively infrared and nuclear magnetic spectrogram, prove the existence of the two keys of its photolytic activity.
Take by weighing 48g water alcohol acid light-cured resin; Add 2.0g184 and 10g glycol methyl ether acetate; Mix back adding 340g deionized water and fully stir formation water-and acrylate photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 20mW/cm
2, irradiation time 600s, making median size is the photolytic activity microgel of 36.79nm.
Embodiment 5
Take by weighing 40g aqueous polyurethane light-cured resin; Add 4.0g184,16.0g Viscoat 295 and 20g butyl glycol ether; Mix back adding 320g deionized water and fully stir formation aqueous polyurethane photocuring micella; Under whipped state, adopt ultraviolet source to shine, light intensity is 50mW/cm
2, irradiation time 30s, making median size is the photolytic activity microgel of 76.82nm.
Take by weighing 2g aqueous polyurethane light-cured resin; Add 0.8g1173,60g dipentaerythritol acrylate and 4g butyl glycol ether; Mix back adding 329g deionized water and fully stir formation aqueous polyurethane photocuring micella; Under whipped state, adopt ultraviolet source to shine, light intensity is 30mW/cm
2, irradiation time 100s, making median size is the photolytic activity microgel of 79.33nm.
Embodiment 7
Take by weighing 80g water-base epoxy light-cured resin, add 8.0g184 and 32g propylene glycol monomethyl ether, mix back adding 280g deionized water and fully stir formation water-base epoxy photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 20mW/cm
2, irradiation time 20s, making median size is the photolytic activity microgel of 103.67nm.
Take by weighing 1.5g waterborne polyester light-cured resin, add 0.6g1173 and 1.5g butyl glycol ether, mix back adding 297g deionized water and fully stir formation water-base epoxy photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 50mW/cm
2, irradiation time 70s, making median size is the photolytic activity microgel of 93.21nm.
Embodiment 9
Take by weighing 13g water alcohol acid epoxy light-cured resin; Add 0.3g1173,0.4g184 and 3g propyl carbinol; Mix back adding 330g deionized water and fully stir formation water-base epoxy photocuring micella, under whipped state, adopt ultraviolet source to shine, light intensity is 40mW/cm
2, irradiation time 20s, making median size is the photolytic activity microgel of 96.39nm.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (5)
1. the preparation method based on the photolytic activity microgel of uv irradiation technology is characterized in that: at first aqueous photo-curing resin, light trigger and solubility promoter are mixed, add the photosensitive micellar aqueous solution of formation in the entry; Then the aqueous solution that mixes being accepted ultraviolet light irradiation under flow state carries out partial cross-linked; The mass percent of aqueous photo-curing resin, photo-curing monomer, light trigger, solubility promoter and water is among this active microgel preparation method:
Preparation condition:
Light intensity 20Mw/cm
2-300Mw/cm
2
Irradiation time 0.5s-600s
Temperature 1-75 ℃
2. the preparation method based on the technological photolytic activity microgel of uv irradiation according to claim 1, it is characterized in that: said aqueous photo-curing resin is one or more in aqueous polyurethane (methyl) propenoic acid ester photocureable resin, water-base epoxy (methyl) propenoic acid ester photocureable resin, water-and acrylate light-cured resin, waterborne polyester light-cured resin and the water alcohol acid light-cured resin.
3. the preparation method based on the technological photolytic activity microgel of uv irradiation according to claim 1, it is characterized in that: described photo-curing monomer is one or more in simple function group (methyl) acrylate monomer, bifunctional (methyl) acrylate monomer and polyfunctional group (methyl) acrylate monomer.
4. the preparation method based on the technological photolytic activity microgel of uv irradiation according to claim 1; It is characterized in that: described light trigger is st-yrax, benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, phenylbenzene ethyl ketone, α; Alpha, alpha-dimethyl oxygen base-α-phenyl methyl phenyl ketone, α; In α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, two benzoyl-phenyl phosphine oxide, UVNUL MS-40,2,4 dihydroxyl benzophenone, Michler's keton, sulfo-propoxy-thioxanthone and the isopropyl thioxanthone one or more.
5. the preparation method based on the technological photolytic activity microgel of uv irradiation according to claim 1, it is characterized in that: described solubility promoter is one or more in ethanol, propyl alcohol, Virahol, propyl carbinol, EGME, butyl glycol ether, propylene glycol monomethyl ether, Ucar 35 butyl ether, glycol methyl ether acetate and the 1-Methoxy-2-propyl acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922729A (en) * | 2015-08-31 | 2018-04-17 | 富士胶片株式会社 | Water dispersion and its manufacture method and image forming method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1236507A2 (en) * | 2001-02-28 | 2002-09-04 | Dainippon Ink And Chemicals, Inc. | Water absorbent material comprising polysaccharide derivatives |
| CN1477168A (en) * | 2002-08-20 | 2004-02-25 | 北京英力科技发展有限公司 | Photocurable water coating agent |
| CN1844229A (en) * | 2006-05-16 | 2006-10-11 | 广东工业大学 | UV curable aqueous resin composition |
| CN101613571A (en) * | 2009-08-07 | 2009-12-30 | 长春帝博科技有限公司 | UV-curable water-borne wood coating |
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- 2012-09-12 CN CN2012103344492A patent/CN102827382A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1236507A2 (en) * | 2001-02-28 | 2002-09-04 | Dainippon Ink And Chemicals, Inc. | Water absorbent material comprising polysaccharide derivatives |
| CN1477168A (en) * | 2002-08-20 | 2004-02-25 | 北京英力科技发展有限公司 | Photocurable water coating agent |
| CN1844229A (en) * | 2006-05-16 | 2006-10-11 | 广东工业大学 | UV curable aqueous resin composition |
| CN101613571A (en) * | 2009-08-07 | 2009-12-30 | 长春帝博科技有限公司 | UV-curable water-borne wood coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922729A (en) * | 2015-08-31 | 2018-04-17 | 富士胶片株式会社 | Water dispersion and its manufacture method and image forming method |
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Application publication date: 20121219 |