CN106496401B - A kind of crosslink propylene acid esters lotion and preparation method thereof containing fluorescent dye - Google Patents
A kind of crosslink propylene acid esters lotion and preparation method thereof containing fluorescent dye Download PDFInfo
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- CN106496401B CN106496401B CN201611021951.2A CN201611021951A CN106496401B CN 106496401 B CN106496401 B CN 106496401B CN 201611021951 A CN201611021951 A CN 201611021951A CN 106496401 B CN106496401 B CN 106496401B
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- acid esters
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- 239000006210 lotion Substances 0.000 title claims abstract description 67
- 239000002253 acid Substances 0.000 title claims abstract description 45
- 150000002148 esters Chemical class 0.000 title claims abstract description 44
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 125000005396 acrylic acid ester group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229940114081 cinnamate Drugs 0.000 claims description 10
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 9
- -1 methacryloxypropyl Chemical group 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XWZOKATWICIEMU-UHFFFAOYSA-N (3,5-difluoro-4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC(F)=C(C=O)C(F)=C1 XWZOKATWICIEMU-UHFFFAOYSA-N 0.000 claims description 5
- UTTFXJZCRVZYQF-UHFFFAOYSA-N 3-(diethylamino)-7-oxo-7h-(1)benzopyrano(3',2':3,4)pyrido(1,2-a)benzimidazole-6-carbonitrile Chemical compound C1=CC=C2N(C(=O)C(C#N)=C3C4=CC5=CC=C(C=C5O3)N(CC)CC)C4=NC2=C1 UTTFXJZCRVZYQF-UHFFFAOYSA-N 0.000 claims description 5
- AFYCEAFSNDLKSX-UHFFFAOYSA-N coumarin 460 Chemical compound CC1=CC(=O)OC2=CC(N(CC)CC)=CC=C21 AFYCEAFSNDLKSX-UHFFFAOYSA-N 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- LIIALPBMIOVAHH-UHFFFAOYSA-N herniarin Chemical compound C1=CC(=O)OC2=CC(OC)=CC=C21 LIIALPBMIOVAHH-UHFFFAOYSA-N 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- FGRJGEWVJCCOJJ-UHFFFAOYSA-N 2,2-dimethylaziridine Chemical compound CC1(C)CN1 FGRJGEWVJCCOJJ-UHFFFAOYSA-N 0.000 claims 1
- 235000003392 Curcuma domestica Nutrition 0.000 claims 1
- 244000008991 Curcuma longa Species 0.000 claims 1
- 235000003373 curcuma longa Nutrition 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 235000013976 turmeric Nutrition 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 abstract description 2
- 210000000481 breast Anatomy 0.000 description 10
- 238000002296 dynamic light scattering Methods 0.000 description 9
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 8
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 229940109262 curcumin Drugs 0.000 description 4
- 235000012754 curcumin Nutrition 0.000 description 4
- 239000004148 curcumin Substances 0.000 description 4
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000001506 fluorescence spectroscopy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 2
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 241000522254 Cassia Species 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a kind of crosslink propylene acid esters lotions and preparation method thereof containing fluorescent dye.Fluorescent dye is dissolved in acrylate monomer by the present invention, and photo-crosslinking monomer is added, by emulsifier-free emulsion polymerization, obtain the acrylic acid ester emulsion for containing fluorescent dye, the lotion realizes crosslinking after UV Light again, obtains the lotion with cross-linked structure and fluorescent characteristic.The obtained crosslink propylene acid esters lotion fluorescence intensity for containing fluorescent dye is big, can show very strong fluorescence at low concentrations.The fluorescent emulsion is acrylic acid ester emulsion, and compatibility is good, can be well in common water paint lotion（Such as acrylic emulsion, styrene-acrylic emulsion and aqueous polyurethane emulsion）In it is evenly dispersed, prepare fluorescent paint.The preparation of the lotion uses surfactant-free emulsion polymerization process simultaneously, and process is simple, has a extensive future.
Description
Technical field
The invention belongs to chemical technology fields.More particularly, to a kind of crosslink propylene acid esters breast containing fluorescent dye
Liquid and preparation method thereof.
Background technology
Fluorescent dye not only coloring properties with Conventional dye, but also can launch fluorescence, make the saturation degree of color and bright-coloured
Degree significantly improves, and to people, eye-catching, deep impression, is widely used in advertising, traffic sign, anti-counterfeit package and particular field
Label.
Water base fluorescent dye has many advantages, such as nontoxic, odorlessness, and compared to conventional fluorescent dyestuff, it more meets health environment-friendly
Theory also becomes fluorescent dye development trend.The design feature of fluorescent dye especially organic fluorescent dye makes it in aqueous systems
In be not easy stable dispersion, and due to the demand of environmental protection, gradually without using organic solvent in coating or ink, thus organic fluorescence
Dispersion of the dyestuff in water phase, which is one, to be solved the problems, such as.The quality of dispersion of the fluorescent dye in water phase directly affects institute
The storage stability of fluorescent paint or ink obtained, the appearance of the difficulty or ease of painting operation and film.
Currently, usually using Hydrophilic dispersant to solve scattering problem of the fluorescent dye in water phase.But dispersant
Absorption on pigment particles surface is not often very secured, is easy to desorb from particle surface, so as to cause scattered particle
It reassembles or precipitates, the long-time stability of system are not good enough.To overcome the limitation of traditional dispersant, develops and apply in recent years
Macromolecule dispersing agent.Macromolecule dispersing agent obtains extensively because it acts in water paint the stably dispersing of pigment brilliance
Using, but cause water resistance to decline there are still some defects, such as easy moisture absorption of glued membrane of formation.In addition, macromolecule dispersing agent pair
Dye selection is strong, if water-wet side in macromolecule dispersing agent and hydrophobic side length are improper, will appear bridge formation effect instead
It answers or particle entanglement effect causes to flocculate.
Invention content
The technical problem to be solved by the present invention is to overcome the scattering problem of above-mentioned fluorescent paint in the prior art in water, carry
It is a kind of photo-crosslinking prepared by emulsifier-free emulsion polymerization for a kind of novel crosslink propylene acid esters lotion for containing fluorescent dye
Fluorescence miniemulsion pigment, specifically first by methyl methacrylate, butyl acrylate, photo-crosslinking monomer methylacryoyloxyethyl
Cinnamate and the hydrophobic fluorescence dye to be wrapped up carry out emulsifier-free emulsion polymerization in one pot reaction, then by ultraviolet light cross-linking,
The stability of gained fluorescence acrylic acid ester emulsion is improved, the lotion with cross-linked structure and fluorescent characteristic is obtained.
The object of the present invention is to provide a kind of crosslink propylene acid esters lotions containing fluorescent dye.
Another object of the present invention is to provide the preparation method of the crosslink propylene acid esters lotion for containing fluorescent dye.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method for the crosslink propylene acid esters lotion containing fluorescent dye, is that fluorescent dye is dissolved in acrylate
In monomer, and photo-crosslinking monomer is added, by emulsifier-free emulsion polymerization, obtains the acrylic acid ester emulsion for containing fluorescent dye, the breast
Liquid is again through ultraviolet light（UV）Crosslinking is realized after illumination, obtains the lotion with cross-linked structure and fluorescent characteristic.
Wherein it is preferred to which the fluorescent dye is oil-soluble fluorescent dyestuff.
It is highly preferred that the oil-soluble fluorescent dyestuff is Nile red, curcumin, coumarin 1 53, vat red 41,6,7- first
Oxygroup cumarin, solvent yellow 98 or solvent red 196 etc..
Preferably, the acrylate monomer is methyl methacrylate and/or butyl acrylate.
Preferably, the photo-crosslinking monomer is methylacryoyloxyethyl cinnamate.Its structural formula is as follows：
By emulsifier-free emulsion polymerization refer to adding azo-bis-isobutyrate hydrochloride furthermore it is preferred that described（V-50）It is molten
Polymerisation is stirred after liquid, at 70~80 DEG C 20~30 hours.
It is highly preferred that being to stir polymerisation at 75 DEG C 24 hours.
Preferably, the ultraviolet light is 300~400 nano-ultraviolet lights, and the light application time is 0.7~1.5 hour.
It is highly preferred that the ultraviolet light is 365 nano-ultraviolet lights.
It is highly preferred that the light application time is 0.8~1.2 hour.
It is highly preferred that the light application time is 1 hour.
Preferably, according to mass ratio meter, fluorescent dye accounts for monomer mass（Methyl methacrylate+butyl acrylate+methyl
Acrylyl oxy-ethyl cinnamate）3~12%.
Preferably, according to mass ratio meter, methyl methacrylate：Butyl acrylate：Methylacryoyloxyethyl cinnamic acid
Ester=1.8~2.2：1.8~2.2：0.18~0.22.
It is highly preferred that according to mass ratio meter, methyl methacrylate：Butyl acrylate：Methylacryoyloxyethyl Chinese cassia tree
Acid esters=1：1：0.1.
Preferably, the azo-bis-isobutyrate hydrochloride solution is the aqueous solution of 0.007~0.009g/mL of concentration.
It is highly preferred that the azo-bis-isobutyrate hydrochloride solution is the aqueous solution of concentration 0.0084g/mL.
Preferably, it counts in mass ratio, the dosage of the azo-bis-isobutyrate hydrochloride accounts for the 3.5~4% of monomer mass.
It is highly preferred that count in mass ratio, the dosage of the azo-bis-isobutyrate hydrochloride account for monomer mass 3.7~
3.9%。
Most preferably, in the emulsifier-free emulsion polymerization, methyl methacrylate, butyl acrylate and cross-linking monomer methyl
The quality rate of charge of acrylyl oxy-ethyl cinnamate is 1：1：0.1；Oil-soluble fluorescent dyestuff is previously dissolved in monomer, and dosage is
The 3~12% of monomer mass；Using V-50 as initiator, dosage is the 3.7~3.9% of monomer mass.
In addition specifically, the preparation method of the above-mentioned crosslink propylene acid esters lotion for containing fluorescent dye, includes the following steps：
S1. to equipped with condenser pipe and churned mechanically container（Such as 500 mL three-neck flasks）In, Nile red, methyl-prop is added
E pioic acid methyl ester, butyl acrylate and methylacryoyloxyethyl cinnamate, stirring make Nile red dissolve；
S2. container is added to after azo-bis-isobutyrate hydrochloride being dissolved in pure water（Three-neck flask）In, it is stirred at 70~80 DEG C
It mixes polymerisation 20~30 hours, obtains the acrylic acid ester emulsion for containing fluorescent dye；
S3. lotion obtained by step S2 is crosslinked through nano-ultraviolet light illumination, obtains the packet with cross-linked structure and fluorescent characteristic
Carry the crosslink propylene acid esters lotion of fluorescent dye.
Wherein it is preferred in step S1, according to mass ratio meter, oil-soluble fluorescent dyestuff accounts for monomer mass（Methacrylic acid
Methyl esters+butyl acrylate+methylacryoyloxyethyl cinnamate）3~12%.
It is highly preferred that in step S1, according to mass ratio meter, methyl methacrylate：Butyl acrylate：Methacryloxypropyl
Ethyl-cinnamic acid ester=1：1：0.1.
Preferably, azo-bis-isobutyrate hydrochloride solution described in step S2 is the aqueous solution of concentration 0.0084g/mL.By matter
Amount accounts for the 3.7~3.9% of monomer mass than meter, the dosage of the azo-bis-isobutyrate hydrochloride.
The i.e. described azo-bis-isobutyrate hydrochloride solution is 1.96 g azo-bis-isobutyrate hydrochlorides（V-50）It is dissolved in 233
Obtained by mL pure water.
Preferably, polymerisation described in step S2 is polymerisation to be stirred at 75 DEG C 24 hours.
Preferably, ultraviolet light described in step S3 is 365 nano-ultraviolet light
Preferably, light application time described in step S3 is 1 hour.
In addition, the crosslink propylene acid esters lotion for containing fluorescent dye being prepared by the above method, also the present invention's
Within protection domain.
The invention has the advantages that：
The present invention is by oil-soluble fluorescent dyestuff（Such as Nile red, curcumin, coumarin 1 53, vat red 41,6,7- methoxyl groups
Cumarin, solvent yellow 98 and solvent red 196 etc.）It is dissolved in common acrylate monomer（Such as methyl methacrylate, acrylic acid fourth
Ester）In, and add suitable photo-crosslinking monomer methylacryoyloxyethyl cinnamate and wrapped by emulsifier-free emulsion polymerization
The acrylic acid ester emulsion of fluorescent dye is carried, which realizes crosslinking after UV illumination again, gained fluorescence acrylic acid ester emulsion
Stability is more preferable.The obtained crosslink propylene acid esters lotion fluorescence intensity for containing fluorescent dye is big, can show at low concentrations
Very strong fluorescence is shown, and with common water paint or ink lotion such as acrylic emulsion, styrene-acrylic emulsion and aqueous poly-
Urethane emulsion compatibility is good, can be used as fluorescent dye mill base and prepares fluorescent paint or ink.The preparation of the lotion uses nothing simultaneously
Soap emulsion polymerization technique, process is simple, has a extensive future.
Description of the drawings
Fig. 1 is the fluorescent microscopy images of the fluorescence spectrum of lotion prepared by embodiment 1, fluorescence photo and solid film.
Fig. 2 is the scanning electron microscope of lotion prepared by embodiment 1（SEM）Figure.
Fig. 3 is that fluorescence crosslink propylene acid esters lotion prepared by embodiment 1 is mixed with acrylic emulsion（A）Or with aqueous poly- ammonia
Ester lotion mixes（B）Afterwards, the fluorescent microscopy images of dry glued membrane.
Fig. 4 is the fluorescence spectrum and fluorescence photo of the lotion prepared for embodiment 2.
Specific implementation mode
It is further illustrated the present invention below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are purchased in market.
Embodiment 1
1, preparation method
（1）In equipped with condenser pipe and churned mechanically 500 mL three-neck flasks, 5.84 g Nile reds, 25.0 g are added
Methyl methacrylate, 25.0g butyl acrylates and 2.50g methylacryoyloxyethyl cinnamates, stirring make Nile red
Dissolving；
（2）By 1.96 g azo-bis-isobutyrate hydrochlorides（V-50）It is added in three-neck flask after being dissolved in 233 mL pure water,
Polymerisation is stirred at 75 DEG C 24 hours, obtain the acrylic acid ester emulsion for containing fluorescent dye；
（3）Step（2）Gained lotion is crosslinked 1 hour through 365 nanometers of UV illumination.
2, result
（1）The fluorescence spectrum of the crosslink propylene acid esters lotion for containing Nile red of gained, fluorescence photo and solid film
Fluorescent microscopy images are as shown in Fig. 1, gained contain Nile red crosslink propylene acid esters lotion breast can send out it is bright red
Color fluorescence, maximum emission wavelength are each about 640nm.
Lotion is applied on sheet glass and forms a film after natural air drying, and inverted fluorescence microscope observation result shows that glued membrane is equally sent out
Bright red fluorescence.The crosslink propylene acid esters lotion that prepared by the present invention contain Nile red can be shown very at low concentrations
Strong fluorescence.
（2）The SEM image of lotion is as shown in Fig. 2, and regular appearance is rounded.The grain size that dynamic light scattering DLS is surveyed is big
Small about 360 nm.
（3）The crosslink propylene acid esters lotion for containing Nile red of gained can be well in common water paint lotion
（Such as acrylic emulsion and aqueous polyurethane emulsion）In it is evenly dispersed.
Such as by the fluorescence crosslink propylene acid esters lotion of above-mentioned preparation（Contain the crosslink propylene acid esters lotion of Nile red）It presses
4% amount and acrylic emulsion（40% solid content, commercial product）Or aqueous polyurethane emulsion（50% solid content, commercial product）It is mixed
It closes, emulsion system stable, with red fluorescence can be formed.After lotion drying and forming-film, inverted fluorescence microscope observes result figure 3
It has been shown that, the glued membrane of acrylic emulsion（A）With the glued membrane of aqueous polyurethane emulsion（B）All send out bright red fluorescence.
Embodiment 2
1, fluorescence crosslink propylene acid esters lotion is prepared according to 1 identical preparation method of embodiment, but Nile red is added
Amount is reduced to 3.35g from 5.84g.
2, as shown in Fig. 4（The fluorescence spectrum and fluorescence photo of gained lotion）, gained contains the crosslinking third of Nile red
Olefin(e) acid ester lotion breast can send out bright red fluorescence, and maximum emission wavelength is each about 640nm.Dynamic light scattering DLS is surveyed
Particle size be about 340 nm.
Embodiment 3
1, fluorescence crosslink propylene acid esters lotion is prepared according to 1 identical preparation method of embodiment, but Nile red is added
Amount is reduced to 1.62g from 5.84g.
2, lotion obtained carries out fluorescence spectrometry, as a result almost the same with embodiment 2.What dynamic light scattering DLS was surveyed
Particle size is about 330 nm.
Embodiment 4
1, fluorescence crosslink propylene acid esters lotion is prepared according to 1 identical preparation method of embodiment, with step（2）Middle polymerization is anti-
The temperature and time answered is variable, other are the same as embodiment 1.
2, lotion obtained carries out fluorescence spectrometry, the results show that when the condition of polymerisation is to be stirred at 70~80 DEG C
When mixing polymerisation 20~30 hours, the fluorescence crosslink propylene acid esters that stability is good, red fluorescence intensity is big can be successfully obtained
Lotion.
Embodiment 5
1, fluorescence crosslink propylene acid esters lotion is prepared according to 1 identical preparation method of embodiment, with step（3）In it is ultraviolet
Light and light application time are variable, other are the same as embodiment 1.
2, lotion obtained carries out fluorescence spectrometry, the results show that when ultraviolet light is 300~400 nano-ultraviolet lights, light
According to the time be 0.7~1.5 hour when, can successfully obtain the fluorescence crosslink propylene acid esters that stability is good, red fluorescence intensity is big
Lotion.
Embodiment 6
1, fluorescence crosslink propylene acid esters lotion is prepared by 1 identical preparation method of embodiment, but by fluorescent dye Nile red
It is changed to curcumin, addition is constant（5.84g）.
2, the crosslink propylene acid esters lotion breast obtained for containing curcumin can send out bright yellow-green fluorescence, maximum hair
Ejected wave length is about 540nm.The grain size that dynamic light scattering DLS is surveyed is about 360 nm.
Embodiment 7
1, fluorescence crosslink propylene acid esters lotion is prepared by 1 identical preparation method of embodiment, but by fluorescent dye Nile red
It is changed to coumarin 1 53, addition is constant（5.84g）.
2, the crosslink propylene acid esters lotion breast obtained for containing coumarin 1 53 can send out bright greenish yellow fluorescent, most
Big launch wavelength is about 515 nm.The grain size that dynamic light scattering DLS is surveyed is about 355 nm.
Embodiment 8
1, fluorescence crosslink propylene acid esters lotion is prepared by 1 identical preparation method of embodiment, but by fluorescent dye Nile red
It is changed to vat red 41, addition is constant（5.84g）.
2, the crosslink propylene acid esters lotion breast obtained for containing vat red 41 can send out bright red fluorescence, maximum hair
Ejected wave length is about 600 nm.The grain size that dynamic light scattering DLS is surveyed is about 350 nm.
Embodiment 9
1, fluorescence crosslink propylene acid esters lotion is prepared by 1 identical preparation method of embodiment, but by fluorescent dye Nile red
It is changed to 6, ayapanin, addition is constant（5.84g）.
2, obtained to contain 6, it is glimmering that the crosslink propylene acid esters lotion breast of ayapanin can send out bright bluish violet
Light, maximum emission wavelength are about 420 nm.The grain size that dynamic light scattering DLS is surveyed is about 360 nm.
Embodiment 10
1, fluorescence crosslink propylene acid esters lotion is prepared by 1 identical preparation method of embodiment, but by fluorescent dye Nile red
It is changed to solvent yellow 98, addition is constant（5.84g）.
2, the crosslink propylene acid esters lotion breast obtained for containing solvent yellow 98 can send out bright yellow-green fluorescence, maximum
Launch wavelength is about 550 nm.The grain size that dynamic light scattering DLS is surveyed is about 350 nm.
Embodiment 11
1, fluorescence crosslink propylene acid esters lotion is prepared by 1 identical preparation method of embodiment, but by fluorescent dye Nile red
It is changed to solvent red 196, addition is constant（5.84g）.
2, the crosslink propylene acid esters lotion breast obtained for containing solvent red 196 can send out bright red fluorescence, maximum
Launch wavelength is about 620 nm.The grain size that dynamic light scattering DLS is surveyed is about 365 nm.
Claims (8)
1. a kind of preparation method for the crosslink propylene acid esters lotion containing fluorescent dye, which is characterized in that be that fluorescent dye is molten
In acrylate monomer, and photo-crosslinking monomer is added, by emulsifier-free emulsion polymerization, obtains the acrylate for containing fluorescent dye
Lotion, the lotion realize crosslinking after UV Light again, obtain the lotion with cross-linked structure and fluorescent characteristic；Wherein, institute
It is methyl methacrylate and/or butyl acrylate to state acrylate monomer, and the photo-crosslinking monomer is methacryloxypropyl second
Base cinnamate；According to mass ratio meter, fluorescent dye accounts for the 3~12% of monomer total amount；According to mass ratio meter, methyl methacrylate
Ester：Butyl acrylate：Methylacryoyloxyethyl cinnamate=1.8~2.2：1.8~2.2：0.18~0.22.
2. preparation method according to claim 1, which is characterized in that the fluorescent dye is oil-soluble fluorescent dyestuff.
3. preparation method according to claim 2, which is characterized in that the oil-soluble fluorescent dyestuff is Nile red, turmeric
Element, coumarin 1 53, vat red 41,6, ayapanin, solvent yellow 98 or solvent red 196.
4. preparation method according to claim 1, which is characterized in that described by emulsifier-free emulsion polymerization refers to adding idol
Polymerisation is stirred after two NSC 18620 HCI solution of nitrogen, at 70~80 DEG C 20~30 hours.
5. preparation method according to claim 1, which is characterized in that the ultraviolet light is 300~400 nano-ultraviolet lights,
The light application time is 0.7~1.5 hour.
6. preparation method according to claim 4, which is characterized in that the azo-bis-isobutyrate hydrochloride solution is concentration
The aqueous solution of 0.007~0.009g/mL.
7. preparation method according to claim 1, which is characterized in that include the following steps：
S1. in equipped with condenser pipe and churned mechanically container, oil-soluble fluorescent dyestuff, methyl methacrylate, propylene is added
Acid butyl ester and methylacryoyloxyethyl cinnamate, stirring make oil-soluble fluorescent dyestuff dissolve；
S2. be added in container after azo-bis-isobutyrate hydrochloride being dissolved in pure water, at 70~80 DEG C stir polymerisation 20~
30 hours, obtain the acrylic acid ester emulsion for containing fluorescent dye；
S3. lotion obtained by step S2 is crosslinked through nano-ultraviolet light illumination, obtain with cross-linked structure and fluorescent characteristic contain it is glimmering
The crosslink propylene acid esters lotion of photoinitiator dye.
8. the crosslink propylene acid esters lotion for containing fluorescent dye being prepared according to any the method for claim 1~7.
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| CN102161717A (en) * | 2011-01-31 | 2011-08-24 | 长沙三诺生物传感技术股份有限公司 | Method for preparing colored latex particles |
| CN102174144A (en) * | 2011-01-31 | 2011-09-07 | 长沙三诺生物传感技术股份有限公司 | Fluorescent latex particles and preparation method thereof |
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| CN102161717A (en) * | 2011-01-31 | 2011-08-24 | 长沙三诺生物传感技术股份有限公司 | Method for preparing colored latex particles |
| CN102174144A (en) * | 2011-01-31 | 2011-09-07 | 长沙三诺生物传感技术股份有限公司 | Fluorescent latex particles and preparation method thereof |
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| Title |
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| Preparation and Characterization of Acrylic-Based Electronic Inks by In Situ Emulsifier-Free Emulsion Polymerization for Electrophoretic Displays;Yu, DG et al.;《CHEMISTRY OF MATERIALS》;20040903;第16卷(第23期);第4693-4698页 * |
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