CN111875738A - Photochromic light-cured resin composition, cured product thereof, preparation method and application - Google Patents
Photochromic light-cured resin composition, cured product thereof, preparation method and application Download PDFInfo
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- CN111875738A CN111875738A CN202010846254.0A CN202010846254A CN111875738A CN 111875738 A CN111875738 A CN 111875738A CN 202010846254 A CN202010846254 A CN 202010846254A CN 111875738 A CN111875738 A CN 111875738A
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- photochromic
- resin
- light
- cured
- azobenzene
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- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 124
- 239000011347 resin Substances 0.000 claims abstract description 124
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 230000004044 response Effects 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000003860 storage Methods 0.000 claims abstract description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000016 photochemical curing Methods 0.000 claims description 89
- 235000012424 soybean oil Nutrition 0.000 claims description 65
- 239000003549 soybean oil Substances 0.000 claims description 65
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 63
- 238000001723 curing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 9
- -1 nitro, methoxy Chemical group 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 238000007306 functionalization reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 description 61
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- 229920006267 polyester film Polymers 0.000 description 24
- 238000002156 mixing Methods 0.000 description 22
- 239000007787 solid Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006025 bioresin Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
- C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F234/00—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring
- C08F234/02—Copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain and having one or more carbon-to-carbon double bonds in a heterocyclic ring in a ring containing oxygen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/12—Photopolymer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
Abstract
Hair brushThe invention discloses a photochromic light-cured resin composition, a cured product, a preparation method and application. The photochromic light-cured resin composition comprises an azobenzene light-cured resin monomer, a light-cured resin and an initiator, wherein the azobenzene light-cured resin monomer has a structure shown as the following formula:
Rmand RnSelected from H, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro, methoxy and the like, m is an integer of 1-4, and n is an integer of 5-8; raAnd RbSelected from the following structures:
the method has the advantages of simple equipment, simple and convenient operation, easy control and high production efficiency, and is suitable for industrial production; the prepared photochromic light-cured resin has high mechanical property and high hardness, and the response speed of photochromic is faster than 20 seconds, so the photochromic light-cured resin has important significance in promoting the development of thermosetting epoxy resin functionalization and the application of the photochromic light-cured resin in the fields of information storage elements and self-development holographic recording materials and the like.
Description
Technical Field
The invention relates to a light-cured resin material, in particular to a photochromic light-cured resin composition, a cured product thereof, a preparation method and application thereof, belonging to the technical field of high polymer materials.
Background
Photochromic materials are materials that change their molecular structure with color change under the stimulation of a light source with specific wavelength and recover under the action of heat or light. In the 60 s of the 20 th century, the first photochromic material was discovered and produced by the corning company in the United states, and the variety, application range and performance of the photochromic material are continuously and abundantly improved after decades of development to the present. At present, photochromic materials are widely applied to various fields such as decoration, protective packaging, intelligent windows, optical devices, information storage elements, self-developing holographic recording photographic materials and the like, and play more and more important roles in social development.
Can be classified as none according to the composition and source of the photochromic materialOrganic and organic. The inorganic photochromic material comprises a transition metal oxide (WO)3、MoO3And TiO3Etc.), metal halides (CaI, HgI, CuCl)2And AgCl2Etc.) and rare earth complexes (linfellin, etc.); organic photochromic materials include spiropyrans, fulgides, diarylethenes and azobenzenes. Among them, azobenzene photochromic materials have the advantages of low cost, high stability and repeatability, etc., and especially have the characteristics of ultrahigh storage density, nondestructive information reading, etc. and are widely concerned by people. The light-cured photochromic resin is less researched, and is generally prepared by blending an azobenzene olefin derivative and a light-cured raw material and initiating double bond crosslinking under the action of an initiator. The photochromic azobenzene material prepared by the method has poor mechanical property and high price, and the application range of the photochromic azobenzene material is greatly limited. Moreover, the materials are difficult to degrade, and cause serious negative effects on the environment. Therefore, the development of the azo color-changing light-cured resin which has high cost performance, particularly excellent mechanical property and is environment-friendly has important significance.
Disclosure of Invention
The invention mainly aims to provide a photochromic light-cured resin composition taking bio-based resin as a main body, a cured product thereof, a preparation method and application thereof, so as to enrich the application range of the bio-based light-cured resin.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
an embodiment of the present invention provides a photochromic photocurable resin composition, which includes: the resin A comprises an azobenzene photocuring monomer and has a structure shown as a formula (1), and the resin B comprises a photocuring resin:
wherein R ismAnd RnAre all independently selected from at least one of H, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro and methoxy, and R ismWherein m is an integer of 1 to 4, RnWherein n is an integer of 5-8; raAnd RbAre each independently selected from any one of the following structures:
In some embodiments, the mass ratio of the resin A to the resin B is 0.5-30: 70-99.5.
In some embodiments, the mass ratio of the initiator to the combination of resin A and resin B is 0.5-5: 100.
In some embodiments, the photocurable resin includes epoxidized soybean acrylate and/or epoxidized soybean acrylate derivatives, but is not limited thereto.
The embodiment of the invention also provides a preparation method of the photo-discoloration light-cured resin condensate, which comprises the following steps: and carrying out curing reaction on the photochromic light-cured resin composition at 25-150 ℃ for 10 min-2 h under the irradiation of ultraviolet light to obtain a photochromic light-cured resin cured product.
The embodiment of the invention also provides a photochromic light-cured resin cured product prepared by the method, wherein the photochromic response speed is less than 20s, and the cycle stability times are more than 100.
Further, the photochromic light-cured resin cured material has photochromic performance, is red under the irradiation of 310-390 nm ultraviolet light rays, and is changed into yellow from red under the irradiation of 400-580 nm visible light rays.
The embodiment of the invention also provides application of the photochromic light-cured resin cured product in the fields of preparing information storage elements or self-developing holographic recording photographic materials and the like.
The embodiment of the invention also provides an information writing and erasing method, which comprises the following steps:
providing a film made of the cured product of the photochromic light-curing resin;
writing information on the film through a photomask in an ultraviolet photoetching mode;
and erasing the information written on the film by irradiating with visible light and/or heat treatment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the photochromic light-cured resin is prepared by mainly blending and curing an azobenzene light-cured monomer and epoxy soybean oil acrylic resin light-cured resin, and the prepared photochromic light-cured resin has high mechanical property and hardness, and the photochromic response speed is faster than 20 seconds;
(2) the method can greatly reduce the price of the photochromic light-cured resin and enrich the application field of the photochromic light-cured resin; meanwhile, the preparation method provided by the invention has the advantages of simple equipment, simple and convenient operation, easy control, high production efficiency, low cost, excellent processing performance, suitability for industrial production and convenience for large-scale preparation and application;
(3) the photochromic light-cured resin prepared by the invention has important significance in promoting the development of the functionalization of the thermosetting light-cured resin, the application of the resin in the fields of information storage elements and self-development holographic recording photographic materials and the like;
(4) the bio-based light-cured resin prepared by the invention is the main part of the composite resin, accounts for more than 70 percent, and has the characteristic of environmental friendliness.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a diagram showing the response times of photochromism and the reflectivity at 550nm wavelength of the photochromic light-curing resin prepared in example 1 of the present invention;
FIG. 2 is a schematic diagram of the mechanism of storing photochromic information of a photochromic light-curing resin D5 thin film prepared in example 5 of the present invention;
FIG. 3 is a photograph of a photochromic light-curable resin D5 film prepared in example 5 of the present invention during 100 successive erase-write cycles.
Detailed Description
In view of the defects in the prior art, the inventors of the present invention have made long-term research and extensive practice to provide a technical solution of the present invention, which is to blend and cure an azobenzene photocurable monomer and a bio-based photocurable resin to obtain a photochromic photocurable resin, wherein the photochromic photocurable resin has both excellent mechanical properties and excellent photochromic properties.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aspect of an embodiment of the present invention provides a photochromic photocurable resin composition, including: the resin A comprises an azobenzene photocuring resin monomer and has a structure shown as a formula (1), and the resin B comprises a photocuring resin:
wherein R ismAnd RnAre all independently selected from at least one of H, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro and methoxy, and R ismWherein m is an integer of 1 to 4, RnWherein n is an integer of 5-8; raAnd RbAre each independently selected from any one of the following structures:
In some embodiments, the combination of resin a and resin B in the photochromic light-curable resin composition comprises the following components, calculated as molar mass ratios: 0.5-30% of resin A and 70-99.5% of resin B. That is, the mass ratio of the resin A to the resin B is 0.5-30: 70-99.5.
In some more specific embodiments, the mass ratio of the initiator to the combination of resin A and resin B is 0.5-5: 100, i.e., the mass of the initiator is 0.5-5 wt% of the total mass of resin A and resin B.
Further, the molar content of the resin A azobenzene photocuring resin monomer in the combination of the resin A and the resin B in the total components is 0.5-30%.
Further, in the combination of the resin A and the resin B, the molar content of the resin A azobenzene photocuring resin monomer in the total components is 0.5-20%.
Further, the mole content of the resin B in the combination of the resin A and the resin B in the total components is 70-99.5%.
Further, the resin B light-cured resin in the combination of the resin A and the resin B accounts for 70-95% of the total components in molar content.
In some embodiments, the resin B photocurable resin includes at least one of epoxidized soybean oil acrylate, epoxidized soybean oil acrylate derivatives, and the like, but is not limited thereto.
Further, the light-cured resin has a structure as shown in formula (2):
wherein R is selected from
Any one of the above.
In some embodiments, the initiator may be any one or a combination of two or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, Iragacure819, Iragacure754, Iragacure 2022, Iragacure2100, Iragacure 784, Darocur BP, Iragacure 907, Iragacure1174, and the like, but is not limited thereto.
Another aspect of the embodiments of the present invention also provides a method for preparing a cured product of a photochromic light-curable resin, including: and carrying out curing reaction on the photochromic light-cured resin composition under the irradiation of ultraviolet light at the temperature of 25-150 ℃ for 10 min-2 h to obtain a photochromic light-cured resin cured product.
Further, the components for synthesizing the cured product of the photochromic light-curing resin comprise:
and (2) component A: the azobenzene photocuring monomer has the following structure (1):
Rmand RnMay be at least one of H, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro, methoxy, etc., and RaAnd RbAt least one of the following. Wherein m is an integer of 1-4, and n is an integer of 5-8;
The azobenzene photocuring resin monomer is synthesized by the following steps: for RmAnd RnThe synthesis of compounds each independently selected from H, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro, methoxy is described in the following references (NATURE | VOL 546|29JUNE 2017, adv. Mater.2019, 31, 1805750, chem. Commun., 2014, 50, 14613- -14615|14613, ACS Nano 2018, 12, 1821. alkano 182, J.Am. chem. Soc.2011, 133, 19684. 19687, Macromolecules 2016, 49, 6368. 6373, NATURE COMMUNICATIONS | (2018) 9: 3234, Angew. chem.2016, 128, 10062. alkano 10066, J.Phys. chem.A, Vol.113, No.24, 2009), examples RmAnd RnAll independently selected from H:
in the first reference (labeling waves in a photoactive polymer film, Nature, 564, 632-636), 4-aminophenol (300mmol, 32g, 1 eq) was suspended in water (82 mL). After HCl (82mL) was added dropwise, the reaction mixture was stirred and cooled to 0 ℃. After stirring for 10min, a solution of sodium nitrite (340mmol, 22.8g, 1.1 eq) in water (70mL) was added dropwise. The solution was stirred at 0 ℃ for 2 hours. Stirring was continued for 3 hours while the mixture was warmed to room temperature. The solution was acidified with 1M HCl and a red solid (structure formula (7)) precipitated as pure product in 85% yield.
The second step is that: the above-obtained red solid (30.00g) and 2-bromoethanol (77.00g) were added to K2CO3(85.16g) and DMF (500 mL). After KI (1.16g) was added as a catalyst, the mixture was refluxed at 80 ℃ for 12 hours. After cooling to room temperature, the reaction mixture was poured into water (800mL) and filtered to give a yellow precipitate. The crude product was neutralized with hydrochloric acid, then filtered and washed with HCl, then filtered and washed three times with 800mL of distilled water. The precipitate was dried under vacuum at 80 ℃ for 24 hours to give a yellow powder as a solid product, i.e., the first diol azobenzene compound (structure formula (3)) (27.52g, 65%).
The third step: a solution of methacryloyl chloride (24.94g) in THF (300mL) was added dropwise to a solution containing the yellow powder from the second step (10g) triethylamine (8.35g) and THF (150mL) under ice-water bath conditions. Thereafter, the reaction mixture was continuously stirred at room temperature for 24 hours. The reaction mixture was poured into cold water (1500mL) to give a yellow precipitate. The yellow precipitate was then washed with water until pH 7. Finally, the precipitate was dried under vacuum at 80 ℃ for 24 hours to give a yellow solid (21.26g, 83%).
And (B) component: is a light-cured resin;
and (3) component C: and (3) an initiator.
Further, the preparation method of the photochromic epoxy resin cured product specifically comprises the following steps: and (2) forming the photochromic light-cured resin by the mixture containing the component A, the component B and the initiator under the irradiation of ultraviolet light.
The invention also provides a photochromic light-cured resin cured product prepared by the method, which has photochromic response speed less than 20s and cycle stability times more than 100.
Further, the photochromic light-cured resin cured product has photochromic performance, is red under the irradiation of 310-399 nm ultraviolet light and is changed into yellow from red under the irradiation of 400-580 nm visible light.
Further, the photochromic light-cured resin has photochromic performance, shows red under 365nm ultraviolet light irradiation, and is changed into yellow under 405nm and/or 550nm light irradiation.
In another aspect, the present invention provides the use of the cured photochromic light-curable resin in the fields of information storage devices, self-developing holographic recording materials, and the like.
Another aspect of the embodiments of the present invention further provides an information writing and erasing method, including:
providing a film made of the cured product of the photochromic light-curing resin;
writing information on the film through a photomask in an ultraviolet photoetching mode;
and erasing the information written on the film by irradiating with visible light and/or heat treatment.
Further, the wavelength of the ultraviolet light is 310-399 nm, but not limited thereto.
Further, the wavelength of the visible light is 400-580 nm, but not limited thereto.
Further, the temperature of the heating treatment is 10-50 ℃, and the time is 1-30 min.
In conclusion, the preparation method provided by the invention has the advantages of simple equipment, simplicity and convenience in operation, easiness in control and high production efficiency, and is suitable for industrial production; the prepared photochromic light-cured resin has high mechanical property and high hardness, and the response speed of photochromic is faster than 20 seconds, so the photochromic light-cured resin has important significance in promoting the development of thermosetting epoxy resin functionalization and the application of the photochromic light-cured resin in the fields of information storage elements and self-development holographic recording materials and the like.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
In the following examples UV-vis absorption spectra were recorded on a Lamda 900 spectrometer (Perkin Elmer) with a UV light source (365nm, 300. mu.W/cm)2) Visible light source (550m, 100. mu.W/cm)2)。
Example 1
Blending an azobenzene photocuring monomer (formula 4), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure819), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 0.5: 99.5, the content of the photoinitiator is 0.5 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, coating a polyester film with the thickness of 20 mu m, and keeping the polyester film at 150 ℃ for 2 hours to obtain the epoxy resin with the pencil hardness of 3H and the photochromic response speed of 10 seconds. Fig. 1 shows a reflectivity diagram of the photochromic light-cured resin prepared in this embodiment with respect to the response times of photochromism at a wavelength of 550 nm.
Wherein R is selected from
Any one of the above.
Example 2
Blending an azobenzene photocuring monomer (formula 5), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Darcurby BP), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 10: 90, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, coating a polyester film on the polyester film, the thickness of the polyester film is 20 mu m, keeping the polyester film at 130 ℃ for 1 hour to obtain the photocuring resin, the pencil hardness is 3H, and the photochromic response speed is 15 seconds.
Example 3
Blending an azobenzene photocuring monomer (formula 6), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure754), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 80 ℃ for 0.5 hour to obtain the photocuring resin, wherein the pencil hardness is 3H, and the photochromic response speed is 16 seconds.
Example 4
Blending an azobenzene photocuring monomer (formula 7), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure2100), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 50 ℃ for 2 hours to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 11 seconds.
Example 5
Blending an azobenzene photocuring monomer (formula 8), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure1174), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 20: 80, the content of the photoinitiator is 5 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the thickness at 25 ℃ for 2 hours to obtain the photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 17 seconds.
Fig. 2 shows a mechanism of storing photochromic information of the photochromic light-curing resin D5 film prepared in this embodiment, and fig. 3 shows a photograph of the photochromic light-curing resin D5 film during 100 consecutive erasing and writing cycles.
Example 6
Blending an azobenzene photocuring monomer (formula 9), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure907), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 30: 70, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in dry film thickness, keeping the dry film at 130 ℃ for 2 hours to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 18 seconds.
Example 7
Blending an azobenzene photocuring monomer (formula 10), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure819), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 2 hours to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 20 seconds.
Example 8
Blending an azobenzene photocuring monomer (formula 11), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure819), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 25 ℃ for 2 hours to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 13 seconds.
Example 9
Blending an azobenzene photocuring monomer (formula 12), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (Irgacure819), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 10: 90, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 2 hours to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 16 seconds.
Example 10
Blending an azobenzene photocuring monomer (formula 13), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (benzoyl peroxide), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 30: 70, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in dry film thickness, keeping the dry film at 130 ℃ for 2 hours to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 11 seconds.
Example 11
Blending an azobenzene photocuring monomer (formula 14), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (lauroyl peroxide), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film with the thickness of 20 mu m, keeping the temperature at 130 ℃ for 2 hours to obtain a photocuring resin, wherein the pencil hardness is 3H, and the photochromic response speed is 10 seconds.
Example 12
Blending an azobenzene photocuring monomer (formula 15), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (cumene hydroperoxide), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to ensure that the solid content is 50 wt%, coating a polyester film with the thickness of 20 mu m, keeping the film at 130 ℃ for 2 hours to obtain a photocuring resin, wherein the pencil hardness is 3H, and the photochromic response speed is 16 seconds.
Example 13
Blending an azobenzene photocuring monomer (formula 16), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (tert-butyl peroxybenzoate), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 19 seconds.
Example 14
Blending an azobenzene photocuring monomer (formula 17), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (cyclohexanone peroxide), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film with the thickness of 20 mu m, keeping the temperature at 130 ℃ for 10min to obtain the photocuring resin, wherein the pencil hardness is 3H, and the photochromic response speed is 19 seconds.
Example 15
Blending an azobenzene photocuring monomer (formula 18), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (methyl ethyl ketone peroxide), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film with the thickness of 20 mu m, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, wherein the pencil hardness is 3H, and the photochromic response speed is 19 seconds.
Example 16
Blending an azobenzene photocuring monomer (formula 19), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (tert-butyl hydroperoxide), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 19 seconds.
Example 17
Blending an azobenzene photocuring monomer (formula 20), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (azodiisoheptanonitrile), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 19 seconds.
Example 18
Blending an azobenzene photocuring monomer (formula 21), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (tert-butyl peroxybenzoate), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 19 seconds.
Example 19
Blending an azobenzene photocuring monomer (formula 22), an epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (dicyclohexyl peroxydicarbonate), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 19 seconds.
Example 20
Blending an azobenzene photocuring monomer (formula 23), epoxy soybean oil modified acrylate (formula 2) and a photoinitiator (tert-butyl peroxypivalate), wherein the weight part ratio of the azobenzene photocuring monomer to the epoxy soybean oil modified acrylate is 1: 99, the content of the photoinitiator is 3 wt% of the total mass of the azobenzene photocuring monomer and the epoxy soybean oil modified acrylate, adding acetone to enable the solid content to be 50 wt%, coating a polyester film to be 20 mu m in thickness, keeping the temperature at 130 ℃ for 10min to obtain a photocuring resin, and the pencil hardness is 3H and the photochromic response speed is 19 seconds.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A photochromic photocurable resin composition characterized by comprising: the resin A comprises an azobenzene photocuring resin monomer and has a structure shown as a formula (1), and the resin B comprises a photocuring resin:
wherein R ismAnd RnAre all independently selected from at least one of H, F, Cl, Br, I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro and methoxy, and R ismWherein m is an integer of 1 to 4, RnWherein n is an integer of 5-8; raAnd RbAre each independently selected from any one of the following structures:
2. The photochromic light-curable resin composition according to claim 1, wherein: the mass ratio of the resin A to the resin B is 0.5-30: 70-99.5; and/or the mass ratio of the initiator to the combination of the resin A and the resin B is 0.5-5: 100.
3. The photochromic light-curable resin composition according to claim 1, wherein: the light-cured resin comprises epoxidized soybean oil acrylate and/or epoxidized soybean oil acrylate derivatives.
4. The photochromic photocurable resin composition according to claim 3, wherein the photocurable resin has a structure represented by formula (2):
wherein R is selected from
Any one of the above.
5. The photochromic light-curable resin composition according to claim 1, wherein: the initiator comprises any one or the combination of more than two of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, Iragacure819, Iragacure754, Iragacure 2022, Iragacure2100, Iragacure 784, Darocur BP, Iragacure 907 and Iragacure 1174.
6. A method for preparing a photochromic light-cured resin condensate is characterized by comprising the following steps: curing the photochromic light-curing resin composition of any one of claims 1 to 5 at 25 to 150 ℃ for 10min to 2h under the irradiation of ultraviolet light to obtain a photochromic light-curing resin cured product.
7. The cured product of the photochromic light-curable resin prepared by the method of claim 6, wherein the photochromic response speed is less than 20s, and the cycle stability times is more than 100.
8. The cured photochromic photocurable resin according to claim 7, wherein: the photochromic light-cured resin cured material has photochromic performance, is red under the irradiation of 310-390 nm ultraviolet light rays, and is changed into yellow from red under the irradiation of 400-580 nm visible light rays.
9. Use of the photochromic light-curable resin cured product according to claim 7 or 8 for the production of information storage elements or self-developing holographic recording materials.
10. An information writing and erasing method is characterized by comprising
Providing a film made of a cured product of the photochromic light-curable resin according to claim 7 or 8;
writing information on the film through a photomask in an ultraviolet photoetching mode;
erasing the information written on the film by adopting a visible light irradiation and/or heating treatment mode;
preferably, the wavelength of the ultraviolet light is 310-390 nm; preferably, the wavelength of the visible light is 400-580 nm; preferably, the temperature of the heating treatment is 10-50 ℃, and the time is 1-30 min.
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| CN117363130A (en) * | 2023-10-17 | 2024-01-09 | 佛山市威仕利通用纳米化工有限公司 | Water-based heat-insulating weather-resistant waterproof coating and preparation method thereof |
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