CN117024990A - Application of polyether amine-crown ether compound in azo pigment modification - Google Patents
Application of polyether amine-crown ether compound in azo pigment modification Download PDFInfo
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- CN117024990A CN117024990A CN202311001694.6A CN202311001694A CN117024990A CN 117024990 A CN117024990 A CN 117024990A CN 202311001694 A CN202311001694 A CN 202311001694A CN 117024990 A CN117024990 A CN 117024990A
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- crown ether
- solution
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- polyether amine
- polyetheramine
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- 239000000049 pigment Substances 0.000 title claims abstract description 76
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 43
- 229920000570 polyether Polymers 0.000 title claims abstract description 43
- 238000012986 modification Methods 0.000 title claims abstract description 15
- 230000004048 modification Effects 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000005859 coupling reaction Methods 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000010168 coupling process Methods 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 35
- 230000008878 coupling Effects 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000376 reactant Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 18
- 239000012954 diazonium Substances 0.000 claims description 18
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000004809 thin layer chromatography Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 239000002633 crown compound Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012047 saturated solution Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 25
- 238000003756 stirring Methods 0.000 description 20
- 239000000976 ink Substances 0.000 description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 235000010288 sodium nitrite Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- MBJIKIAWNPEHOR-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene-17-carbaldehyde Chemical compound O1CCOCCOCCOCCOC2=CC(C=O)=CC=C21 MBJIKIAWNPEHOR-UHFFFAOYSA-N 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 4
- VRLPHBSFRWMMPW-UHFFFAOYSA-N 2-amino-4-chloro-5-methylbenzenesulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=C(N)C=C1Cl VRLPHBSFRWMMPW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229940099800 pigment red 48 Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 description 1
- BPEXTIMJLDWDTL-UHFFFAOYSA-N 2`-Methylacetanilide Chemical compound CC(=O)NC1=CC=CC=C1C BPEXTIMJLDWDTL-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920005732 JONCRYL® 678 Polymers 0.000 description 1
- -1 amine crown ether compound Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B68/00—Organic pigments surface-modified by grafting, e.g. by establishing covalent or complex bonds, in order to improve the pigment properties, e.g. dispersibility or rheology
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an application of a polyether amine-crown ether compound in azo pigment modification, which belongs to the technical field of pigment modification, and the structure of the polyether amine-crown ether compound is shown as a formula (I), wherein R is CH 3 Or H, x is 25-35, y is 8-12; the polyether amine-crown ether compound can be used for modifying azo pigments, the particle size of the modified azo pigments is obviously reduced, the particle size distribution is more concentrated, the tinting strength and glossiness in an aqueous system are obviously improved, the viscosity is obviously reduced, the azo pigments are easier to disperse in the aqueous system, and the azo pigments have good storage stability.
Description
Technical Field
The invention relates to the technical field of pigment modification, in particular to application of a polyether amine-crown ether compound in azo pigment modification.
Background
Pigments can be classified into two main types, namely inorganic pigments and organic pigments according to chemical composition, wherein the organic pigments are classified into azo pigments and non-azo pigments according to different color bodies of pigment molecules; among them, azo pigments are insoluble organic compounds containing azo groups in the molecular structure, and have bright color, strong tinting strength, but often poor fastness, but are widely used at present because of their convenient manufacture and low price, and are mainly used for plastics, printing inks, office supplies, and the like. Nowadays, as the printing speed of a printer increases, there is also an increasing demand for the color strength, viscosity and storage stability of printing inks. Printing ink is divided into oily ink, water-based ink and the like, and is prepared by dispersing azo pigments in an oily system or a water-based system; the water-based ink has remarkable environmental protection and safety advantages compared with an oily system because of taking water as a dissolution carrier, is nontoxic and harmless, almost generates no volatile organic gas, and is particularly suitable for packaging and printing products with strict sanitary requirements such as cigarettes, wines, foods, beverages, medicines, children toys and the like.
However, the conventional azo pigments have a high stability when applied to an oily system, but if applied to an aqueous system, the conventional azo pigments have a high viscosity and poor storage stability, and the like, resulting in unstable print quality. At present, in order to enhance the dispersion stability of pigment in a system, a method of adding a dispersing agent is a relatively wide method with good dispersion effect.
In the patent application publication number CN101959976a dispersant is disclosed comprising a triblock copolymer having a first block comprising glycidyl (meth) acrylate reacted with naphthoic acid, a second block comprising alkyl (meth) acrylate and a third block comprising alkyl (meth) acrylate, which dispersant is suitable for nanoparticle dispersions comprising pigment particles having an average primary particle size of less than 100 nm; the invention patent with the publication number of CN107207722B discloses a substituted polyether amine with low melting point, which can be used as a crude oil demulsifier to be applied to inkjet pigment dispersion; in order to improve the dispersion stability of the UV ink-jet ink, li Fusheng and the like utilize high acid value solid acrylic resin Joncryl 678 and polyetheramine Jeffamine M2070 to carry out grafting reaction, so that the hyperbranched dispersing agent for the UV ink-jet ink is prepared, and has good dispersion effect and good thermal stability.
However, the above dispersants are all more suitable for oily systems and have corresponding limitations in applicable conditions. The existing dispersing agent can not meet the requirement of high-quality printing, so that development of the dispersing agent with high cost performance and excellent application performance is needed to modify the pigment surface so as to improve the dispersion stability of the azo pigment in an aqueous system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the application of the polyether amine-crown ether compound in the modification of azo pigments, the particle size of the modified azo pigments is obviously reduced, the particle size distribution is more concentrated, the tinting strength and the glossiness in a water-based system are obviously improved, the viscosity is obviously reduced, the azo pigments are easier to disperse in the water-based system, and the azo pigments have good storage stability.
The technical scheme of the invention is as follows:
an application of polyether amine-crown ether compound in azo pigment modification, wherein the structure of the polyether amine-crown ether compound is shown as a formula (I),
wherein R is CH 3 Or H; x is 25-35, y is 8-12.
Preferably, said R is CH 3 。
Preferably, x is 32 and y is 10.
Preferably, the application of the polyetheramine-crown ether compound in azo pigment modification comprises the following steps: in the synthesis process of azo pigments, dissolving a certain amount of polyether amine-crown ether compound in water, and adding the water into coupling liquid to obtain a coupling component; adding diazonium solution into a coupling component for coupling reaction to obtain a reaction solution; and (3) post-treating the reaction liquid to obtain the modified azo pigment.
Preferably, the addition amount of the polyether amine-crown ether compound is 3-5% of the mass of the azo pigment.
Preferably, the post-treatment method comprises the following steps: heat treatment, filtration, and then drying.
A preparation method of a polyetheramine-crown ether compound comprises the steps of reacting benzo-15-crown ether-5 and hexamethylenetetramine in trifluoroacetic acid to generate 4 '-formyl benzo-15-crown ether-5, and reacting the 4' -formyl benzo-15-crown ether-5 with polyetheramine in ethanol to generate the polyetheramine-crown ether compound.
The preparation method of the polyether amine-crown ether compound specifically comprises the following steps:
(1) Preparation of 4' -formyl benzo-15-crown ether-5:
adding benzo-15-crown ether-5, hexamethylenetetramine and trifluoroacetic acid into a reaction container, fully dissolving, heating to 85-95 ℃, and reacting for 22-26 hours under the protection of argon gas in an acidic environment to obtain a reactant 1; cooling the reactant 1 to 0-3 ℃ in ice bath, adding 0-3 ℃ sodium bicarbonate saturated solution to adjust the pH to 6.5-7.5; extracting with dichloromethane for three times, collecting the lower organic phase into a rotary evaporation bottle, and removing dichloromethane by rotary evaporation to obtain 4' -formyl benzo-15-crown ether-5; the reaction scheme of the step (1) is as follows:
(2) Preparation of polyetheramine-crown compounds:
adding ethanol into a reaction container, and fully dissolving the 4 '-formyl benzo-15-crown ether-5 prepared in the step (1) in the ethanol to obtain a 4' -formyl benzo-15-crown ether-5 solution; transferring the 4' -formyl benzo-15-crown ether-5 solution into a constant pressure funnel, slowly dropwise adding the solution into the polyether amine solution, and fully mixing to obtain a mixed solution; heating the mixed solution to 75-85 ℃ under the protection of argon, and carrying out reflux reaction for 2-2.5 h to obtain a reactant 2; transferring the reactant 2 into a rotary steaming bottle, and removing ethanol by rotary steaming to obtain a polyether amine-crown ether compound; the reaction scheme of the step (2) is as follows:
preferably, the reaction vessel in the step (1) and the step (2) is a three-necked flask.
Preferably, thin layer chromatography is used for detecting the progress of the reaction in the reaction process of the step (1) and the step (2); the detection method of the thin layer chromatography comprises the following steps: taking a small amount of reactant, adding methanol with the volume of 5-7 times of that of the reactant for dilution, and simultaneously diluting raw material benzo-15-crown ether-5 or 4' -formylbenzo-15-crown ether-5 with methanol with the volume of 5-7 times of that of the reactant, wherein a developing agent is ethyl acetate; when the thin layer chromatography detects the compound R f The reaction was completed when the values were as follows: benzo-15-crown-5, R f =0.7; 4' -formyl benzo-15-crown ether-5, R f =0.2; polyetheramine-crown ether compounds, R f ＝0.4。
Preferably, the molar ratio of benzo-15-crown-5, hexamethylenetetramine and trifluoroacetic acid in step (1) is 1:2 to 4:9.3 to 20.
Preferably, the polyetheramine solution in step (2) is prepared by dissolving a certain amount of polyetheramine in ethanol to obtain a polyetheramine solution.
Preferably, in the step (2), the mass ratio of the 4' -formyl benzo-15-crown ether-5, polyether amine and ethanol is 1: 6-7: 18 to 35.
Polyetheramines (PEA) are a class of polymers with a polyether structure as the backbone and an amine group as the terminal active functional group; preferably, the polyetheramine in step (2) is a hydrophilic polyetheramine.
Preferably, the polyetheramine is one of L-207 or M41.
The beneficial effects are that:
the invention provides an application of polyether amine-crown ether compound in azo pigment modification, compared with other modified pigments, the particle size of the azo pigment modified by the polyether amine-crown ether compound is obviously reduced and the particle size distribution is more concentrated, the tinting strength of the modified pigment is improved by 5.68-12.70%, the glossiness is improved by 26.82-43.48%, and the viscosity in an aqueous system is reduced by 12-36%, so that the azo pigment modified by the polyether amine-crown ether compound is easier to disperse in the aqueous system and has good storage stability.
Drawings
Fig. 1 shows pigment red 57 before and after modification: 1, a particle size distribution profile;
fig. 2 shows pigment red 48 before and after modification: 1, a particle size distribution profile;
FIG. 3 is a graph showing particle size distribution of pigment yellow 83 before and after modification;
FIG. 4 is a graph showing particle size distribution of pigment yellow 14 before and after modification.
Detailed Description
The following description is made in connection with specific embodiments:
description of sources of experimental materials:
benzo-15-crown-5: purchased from Shanghai Michlin Biochemical technologies Co., ltd;
polyetheramine L-207: from Henschel, mw (molecular weight) is 2000, trade designation L-207;
polyetheramine M41: available from Corey, mw (molecular weight) of 2000, trade designation M41;
polyetheramine derivative BYK-190: available from Pick chemical, germany under the trade designation DIPERBYK-190;
fatty alcohol polyoxyethylene ether: purchased from Jiangsu sea Ann petrochemical plant, trade name O-15;
fatty amine polyoxyethylene ether: purchased from Jiangsu sea Ann petrochemical plant under the trade designation AC-1820;
chromene AS-IRG: purchased from south-pass acetic acid chemical industry Co., ltd;
4B acid (3-methyl-6-aminobenzenesulfonic acid): purchased from wujiang city, tuncun pigment factory;
2B acid (2-amino-4-chloro-5-methylbenzenesulfonic acid): purchased from wujiang city, tuncun pigment factory;
2, 3-acid (2-hydroxy-3-naphthoic acid): purchased from Jining sunshine chemical Co.
Example 1:
polyetheramine-crown compound modified pigment red 57:1 (P.R.57:1)
(1) Preparation of 4' -formylbenzo-15-crown-5
1.53g of benzo-15-crown ether-5, 1.58g of hexamethylenetetramine and 3.9mL of trifluoroacetic acid are respectively added into a 50mL three-port reaction bottle, the temperature is raised to 90 ℃ after stirring and dissolution, the reaction is carried out for 24 hours under the protection of argon, a reactant 1 is obtained, and the reaction progress condition is detected by using thin layer chromatography in the reaction process; cooling the reactant 1 to 0 ℃ in ice bath after the reaction is finished, and adding a saturated solution of sodium bicarbonate at 0-3 ℃ to adjust the pH to 7.0; extracting with dichloromethane for three times, collecting the lower organic phase into a rotary evaporation bottle, and removing dichloromethane by rotary evaporation to obtain 4' -formyl benzo-15-crown ether-5 with a yield of 1.8g;
(2) Preparation of polyetheramine-crown compounds
Adding 1.0g of the 4 '-formyl benzo-15-crown ether-5 prepared in the step (1) into 25mL of absolute ethyl alcohol under stirring to fully dissolve the 4' -formyl benzo-15-crown ether-5 solution; 7.0g of polyetheramine L-207 is added into 25mL of absolute ethyl alcohol for full dissolution, thus obtaining polyetheramine solution; transferring the 4' -formyl benzo-15-crown ether-5 solution into a constant pressure funnel, slowly dropwise adding the solution into the polyether amine solution, and fully mixing to obtain a mixed solution; heating the mixed solution to 80 ℃ under the protection of argon, and carrying out reflux reaction for 2 hours to obtain a reactant 2, wherein the reaction progress is detected by using thin-layer chromatography in the reaction process; transferring the reactant 2 into a rotary steaming bottle, and removing absolute ethyl alcohol by rotary steaming to obtain polyether amine-crown ether compound with the yield of 7.98g;
(3) Preparation of modified pigments
(1) Preparation of diazonium solution: 150mL of water, 2.4g of sodium hydroxide and 11.22g of 4B acid are respectively added into a 500mL beaker, the mixture is dissolved to be clear at room temperature, then 50mL of aqueous solution prepared by 4.4g of sodium nitrite is added, the beaker is placed into an ice bath, then about 150g of crushed ice is added into the beaker, and the temperature is quickly reduced to below 3 ℃; after cooling, 19.4g of hydrochloric acid is quickly added, water is added to adjust the final volume of the solution in the beaker to 400mL, the temperature is adjusted to be 2 ℃, and stirring is carried out for 30min, thus obtaining diazonium solution;
(2) preparation of coupling liquid: 150mL of water, 6.0g of sodium hydroxide and 15.6g of 2, 3-acid are respectively added into a 2000mL beaker, stirred and dissolved until the mixture is clear, 40mL of rosin solution is added, the temperature is adjusted to 11 ℃, 50mL of aqueous solution prepared from 1.0g of polyetheramine-crown ether compound is added, and the final volume is adjusted to 400mL by adding water, so that coupling liquid is obtained;
the preparation method of the rosin solution comprises the following steps: 1.0g of rosin, 0.3g of sodium hydroxide and 40mL of water, and heating and dissolving until the rosin is clear to obtain a rosin solution;
(3) coupling: adding the diazonium solution in the step (1) into the coupling solution in the step (2) for reaction, controlling the adding time to be within 15min, controlling the reaction temperature to be 11-14 ℃, wherein the reaction end point temperature to be 13-14 ℃ and the reaction end point pH to be 6.5-7.0, and obtaining a coupling reaction solution;
(4) post-treatment: adjusting the pH value of the coupling reaction solution in the step (3) to 12 by using a sodium hydroxide solution with the mass fraction of 30%, wherein the temperature is 14 ℃; after stirring for 15min, the pH is 11.8, and the temperature is 18 ℃; after 30min 60mL of an aqueous solution prepared from 23g of calcium chloride was added, at which point the pH was 10.2; adjusting the pH to 11.8 by using a sodium hydroxide solution with the mass fraction of 30% and the temperature to 19 ℃; stirring for 15min, heating to 75deg.C, adding 10g strontium chloride, heating to 95deg.C, and maintaining for 0.5 hr; cooling to 75 ℃, regulating the pH to 6.0-6.5 by using an aluminum sulfate solution (0.1 g/mL), and stirring for 15min; sequentially carrying out suction filtration, water washing and drying at 85 ℃ to obtain modified pigment red 57:1.
example 2:
polyether amine crown ether compound modified pigment Red 48:1 (P.R.48:1)
(1) Preparation of 4' -formylbenzo-15-crown-5
1.53g of benzo-15-crown ether-5, 3.17g of hexamethylenetetramine and 8.4mL of trifluoroacetic acid are respectively added into a 50mL three-port reaction bottle, an oil bath is stirred and dissolved, the temperature is raised to 90 ℃, the reaction is carried out for 24 hours under the protection of argon, a reactant 1 is obtained, and the reaction progress condition is detected by using thin layer chromatography in the reaction process; cooling the reactant 1 to 0 ℃ in ice bath after the reaction is finished, and adding a saturated solution of sodium bicarbonate at 0-3 ℃ to adjust the pH to 7.0; extracting with dichloromethane three times, collecting the lower organic phase into a rotary evaporation bottle, and removing dichloromethane by rotary evaporation to obtain 4' -formyl benzo-15-crown ether-5 with a yield of 1.8g;
(2) Preparation of polyetheramine-crown compounds
Adding 1.0g of the 4 '-formyl benzo-15-crown ether-5 prepared in the step (1) into 25mL of absolute ethyl alcohol under stirring to fully dissolve the 4' -formyl benzo-15-crown ether-5 solution; adding 6.0g of polyether amine M41 into 25mL of absolute ethyl alcohol for full dissolution to obtain polyether amine solution; transferring the 4' -formyl benzo-15-crown ether-5 solution into a constant pressure funnel, slowly and dropwise adding the solution into the polyether amine solution, and fully mixing to obtain a mixed solution; heating the mixed solution to 80 ℃ under the protection of argon, and carrying out reflux reaction for 2 hours to obtain a reactant 2, wherein the reaction progress is detected by using thin-layer chromatography in the reaction process; transferring the reactant 2 into a rotary steaming bottle, and removing absolute ethyl alcohol by rotary steaming to obtain a polyetheramine-crown ether compound product with the yield of 6.98g;
(3) Preparation of modified pigments
(1) Preparation of diazonium solution: 100mL of water, 2.5g of sodium hydroxide, 12.5g of 2B acid were each added to a 500mL beaker, and the mixture was heated to 95℃to dissolve until clear, at which point the pH was 9.0; cooling to 80 ℃, and adding 16.8g of hydrochloric acid for salting out within 5min after cooling; placing the beaker in an ice bath, and adding crushed ice into the beaker to cool to 0 ℃; after cooling, adding 20mL of an aqueous solution prepared from 4.0g of sodium nitrite, wherein the temperature is 5 ℃; continuously adding a proper amount of sodium nitrite solution to adjust the solution to make the KI test paper bluish, adding water to adjust the final volume of the solution in the beaker to 350mL, and stirring for 60min to obtain diazonium solution;
(2) preparation of coupling liquid: 150mL of water, 5.2g of sodium hydroxide and 10.5g of 2,3 acid are respectively added into a 2000mL beaker, stirred and dissolved until the mixture is clear, cooled to 5 ℃, 50mL of aqueous solution prepared from 1.0g of polyetheramine-crown ether compound is added, and the final volume is adjusted to 350mL by adding water, so as to obtain coupling liquid;
(3) coupling: adding the diazonium solution in the step (1) into the coupling solution in the step (2) for reaction, controlling the adding time to be 15min, controlling the reaction temperature to be 8-12 ℃ and the reaction pH to be 9.2, thus obtaining coupling reaction solution;
(4) post-treatment: adding 30mL of rosin solution (rosin solution is prepared by heating and dissolving 1.5g of rosin, 0.45g of sodium hydroxide and 30mL of water) dissolved to be clear into the coupling reaction solution in the step (3), adjusting the pH to be 10, and stirring for 60min; adjusting pH to 8.5, heating to 90deg.C, dropwise adding 80mL of aqueous solution prepared from 16.0g barium chloride within 20min after heating, and maintaining at 90deg.C for 30min; cooling to 60 ℃, adding aluminum sulfate solution (0.1 g/mL), adjusting pH to 6.0-6.5, and stirring for 15min; and sequentially performing filter pressing, water washing and drying at 85 ℃ to obtain modified pigment red 48:1.
Example 3:
polyetheramine-crown ether compound modified pigment yellow 83 (P.Y.83)
(1) Preparation of 4' -formylbenzo-15-crown-5
1.53g of benzo-15-crown ether-5, 2.84g of hexamethylenetetramine and 6.0mL of trifluoroacetic acid are respectively added into a 50mL three-port reaction bottle, the temperature of an oil bath is raised to 90 ℃ after stirring and dissolution, the reaction is carried out for 24 hours under the protection of argon, a reactant 1 is obtained, and the reaction progress condition is detected by using thin layer chromatography in the reaction process; cooling the reactant 1 to 0 ℃ in ice bath after the reaction is finished, and adding a saturated solution of sodium bicarbonate at 0-3 ℃ to adjust the pH to 7.0; extracting with dichloromethane three times, collecting the lower organic phase into a rotary evaporation bottle, and removing dichloromethane by rotary evaporation to obtain 4' -formyl benzo-15-crown ether-5 with a yield of 1.8g;
(2) Preparation of polyetheramine-crown compounds:
adding 1.0g of the 4 '-formyl benzo-15-crown ether-5 prepared in the step (1) into 25mL of absolute ethyl alcohol under stirring to fully dissolve the 4' -formyl benzo-15-crown ether-5 solution; adding 6.45g of polyether amine M41 into 25mL of absolute ethyl alcohol for full dissolution to obtain polyether amine solution; transferring the 4' -formyl benzo-15-crown ether-5 solution into a constant pressure funnel, slowly dropwise adding the solution into the polyether amine solution, and fully mixing to obtain a mixed solution; heating the mixed solution to 80 ℃ under the protection of argon, and carrying out reflux reaction for 2 hours to obtain a reactant 2, wherein the reaction progress is detected by using thin-layer chromatography in the reaction process; transferring the reactant 2 into a rotary steaming bottle, and removing absolute ethyl alcohol by rotary steaming to obtain polyether amine-crown ether compound with the yield of 7.41g;
(3) Preparation of modified pigments
(1) Preparation of diazonium solution: 100mL of water, 16g of hydrochloric acid and 10g of 3,3' -dichlorobenzidine are respectively added into a 500mL beaker, and the mixture is pulped for 60min; placing the beaker in an ice bath, adding crushed ice into the beaker, cooling to 0 ℃, adding 30mL of aqueous solution prepared from 5.8g of sodium nitrite within 10min after cooling, and stirring for 60min; adding sulfamic acid to remove excessive sodium nitrite, continuously adding a small amount of sulfamic acid to adjust the solution until the KI test paper is bluish, adding water to adjust the final volume of the solution in the beaker to 350mL, and obtaining diazonium solution at the temperature of 0 ℃;
(2) preparation of coupling liquid: 220mL of water, 3.75g of sodium hydroxide and 22.5g of chromene AS-IRG are respectively added into a 500mL beaker, stirred and dissolved until the mixture is clear, crushed ice is added to cool to 0 ℃, 50mL of aqueous solution prepared from 1.0g of polyetheramine-crown ether compound is added, and the final volume is adjusted to 350mL by adding water, so AS to obtain coupling solution;
(3) preparation of acid precipitation liquid: adding 14.55g of acetic acid and 3.6g of sodium hydroxide into a 500mL beaker, stirring for 5min, adjusting the final volume of the solution in the beaker to 200mL, and obtaining acid precipitation liquid when a small amount of floating ice exists at the temperature of 0 ℃;
(4) acid precipitation: adding the coupling solution in the step (2) into the acid precipitation solution in the step (3), controlling the adding time within 30-40 min, controlling the end point temperature within 12 ℃ and the end point pH within 5.6-6.0; stirring for 30min to obtain a coupling component;
(5) coupling: heating the coupling component in the step (4) to 38 ℃, slowly dripping the diazonium solution in the step (1) into the coupling component in the step (4), controlling the adding time within 60-70 min, and controlling the pH value to be 4.5-5.0 by using an adjusting alkali in the coupling process; when the coupling is near the end, the coupling speed is slowed down, the content of diazonium salt in the reaction liquid is measured for a plurality of times, and the excessive diazonium salt is avoided, so that the coupling reaction liquid is obtained;
(6) post-treatment: stirring the coupling reaction liquid in the step (5) for 30min, then heating to 95 ℃, finishing color conversion, and preserving heat for 30min; cooling to 70 ℃, filtering, rinsing until the conductivity is within 100 mu S/cm, and drying at 90 ℃ to obtain the modified pigment yellow 83.
Example 4:
polyetheramine-crown ether compounds modified pigment yellow 14 (P.Y.14)
(1) Preparation of 4' -formylbenzo-15-crown-5
1.53g of benzo-15-crown ether-5, 2.38g of hexamethylenetetramine and 7.0mL of trifluoroacetic acid are respectively added into a 50mL three-port reaction bottle, the temperature of an oil bath is raised to 90 ℃ after stirring and dissolution, the reaction is carried out for 24 hours under the protection of argon, a reactant 1 is obtained, and the reaction progress condition is detected by using thin layer chromatography in the reaction process; cooling the reactant 1 to 0 ℃ in ice bath after the reaction is finished, and adding a saturated solution of sodium bicarbonate at 0-3 ℃ to adjust the pH to 7.0; extracting with dichloromethane three times, collecting the lower organic phase into a rotary evaporation bottle, and removing dichloromethane by rotary evaporation to obtain 4' -formyl benzo-15-crown ether-5 with a yield of 1.8g;
(2) Preparation of polyetheramine-crown compounds
Adding 1.0g of the 4 '-formyl benzo-15-crown ether-5 prepared in the step (1) into 25mL of absolute ethyl alcohol under stirring to fully dissolve the 4' -formyl benzo-15-crown ether-5 solution; adding 6.8g of polyetheramine L-207 into 25mL of absolute ethyl alcohol for full dissolution to obtain a polyetheramine solution; transferring the 4' -formyl benzo-15-crown ether-5 solution into a constant pressure funnel, slowly and dropwise adding the solution into the polyether amine solution, and fully mixing to obtain a mixed solution; heating the mixed solution to 80 ℃ under the protection of argon, and carrying out reflux reaction for 2 hours to obtain a reactant 2, wherein the reaction progress is detected by using thin-layer chromatography in the reaction process; transferring the reactant 2 into a rotary steaming bottle, and removing absolute ethyl alcohol by rotary steaming to obtain a polyetheramine-crown ether compound product with the yield of 7.76g;
(3) Preparation of modified pigments
(1) Preparation of diazonium solution: 100mL of water, 16.6g of hydrochloric acid and 10g of 3,3' -dichlorobenzidine are respectively added into a 500mL beaker, and the mixture is pulped for 30min; placing the beaker in an ice bath, adding crushed ice into the beaker, cooling to 0 ℃, adding 30mL of aqueous solution prepared from 5.8g of sodium nitrite, and stirring for 60min; adding sulfamic acid to remove excessive sodium nitrite, continuously adding a small amount of sulfamic acid to adjust the solution until the KI test paper is bluish, adding water to adjust the final volume of the solution in the beaker to 300mL, and obtaining diazonium solution at the temperature of 0 ℃;
(2) preparation of the coupling component: 200mL of water, 13.4g of sodium hydroxide with mass fraction of 30% and 15.6g of o-methylacetanilide are respectively added into a 2000mL beaker, stirred and dissolved, 50mL of aqueous solution prepared from 1.0g of polyether amine-crown ether compound is added, and the final volume of the solution in the beaker is adjusted to 300mL by adding water, so as to obtain coupling solution; adding 8.0g of acetic acid for acid precipitation, wherein the pH value is 5.6-6.0 after the acid precipitation is finished, and the temperature is 15 ℃ to obtain a coupling component;
(3) coupling: dropping the diazonium liquid in the step (1) into the coupling component in the step (2), controlling the dropping time within 80-90 min, and controlling the pH value to be 4.0-5.0 by alkali liquor during the dropping time; when the coupling is near the end, the coupling speed is slowed down, the content of diazonium salt in the reaction liquid is measured for a plurality of times, and the excessive diazonium salt is avoided, so that the coupling reaction liquid is obtained;
(4) post-treatment: stirring the coupling reaction solution in the step (3) for 30min, regulating the pH value to 9.0, heating to 80 ℃, then adding 30mL of an aqueous solution prepared from 0.3g of aluminum sulfate, regulating the pH value to 6.0, continuously heating to 90 ℃, and preserving heat for 30min; cooling to 65 ℃, carrying out suction filtration, and drying at 80 ℃ to obtain the modified pigment yellow 14.
Comparative example 1:
in contrast to example 1, this comparative example was prepared by adding 1.0g of polyetheramine derivative BYK-190 during the preparation of the coupling solution, and the rest of the procedure was the same as in example 1.
Comparative example 2:
unlike example 2, this comparative example was prepared by adding 1.0g of fatty alcohol-polyoxyethylene ether during the preparation of the coupling liquid, and the remaining steps were the same as in example 2.
Comparative example 3:
in this comparative example, 1.0g of polyetheramine L-207 was added during the preparation of the coupling liquid, except for example 3.
Comparative example 4:
unlike example 4, this comparative example was prepared by adding 1.0g of fatty amine polyoxyethylene ether during the preparation of the coupling liquid, and the remaining steps were the same as in example 4.
The modified pigments prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to product performance tests, respectively, as follows:
(1) Detecting and comparing the particle size of the modified pigment dry powder by using a Markov laser particle sizer, wherein the detection results are shown in figures 1-4 and table 1 respectively; where d (0.1), d (0.5) and d (0.9) are particle diameters corresponding to volume fractions up to 10%, 50% and 90%, respectively, and d (0.5) can be regarded as a volume average particle diameter.
TABLE 1 modified pigment dry powder particle size detection results
As can be seen from Table 1 and FIGS. 1 to 4, the modified pigment dry powders of examples 1 to 4 each have a particle size which is significantly smaller than that of comparative examples 1 to 4, and the particle size distribution is more concentrated, which means that the tinting strength and gloss of the pigment are improved.
(2) Performance test of aqueous ink prepared from modified pigment
Weighing 5.0g of modified pigment, 11.5g of aqueous resin liquid and 50g of zirconia beads, and placing the mixture into a sealed container to shake for 60min to obtain aqueous ink;
(1) hue detection: measuring the hue of the aqueous ink sample by using a color measuring instrument to obtain hue data;
(2) and (3) gloss detection: measuring glossiness of the water-based ink sample by using a glossiness meter to obtain glossiness data;
(3) and (3) coloring power detection: 1.0g of water-based ink is weighed, 19.0g of water-based white ink is added, the mixture is uniformly mixed, a sample is scraped, and a color measuring instrument is used for measuring the tinting strength to obtain tinting strength data;
(4) and (3) viscosity detection: measuring the viscosity of the freshly prepared aqueous ink; the shaken aqueous ink was sealed and left in an oven at 55℃for 5 days, taken out and left at room temperature, and the viscosity was measured again.
The above-measured data of each group were recorded, and the results are shown in table 2.
TABLE 2 Performance test of aqueous ink made from modified pigments
As can be seen from table 2, the pigment modified with the polyetheramine-crown ether compound has significantly improved hue, tinting strength and glossiness (high gloss, high viscosity is characteristic of p.y.83 pigment, thus the numerical value is higher in example 3 and comparative example 3) compared with the pigment modified with other polyetheramine derivative or polyoxyethylene ether surfactant; wherein, the pigment tinting strength is improved by 5.68 to 12.70 percent, and the glossiness is improved by 26.82 to 43.48 percent; and the viscosity of the pigment modified by the polyether amine-crown ether compound in the aqueous ink system is reduced by 12-36%, even after the pigment is placed for 5 days at 55 ℃, the viscosity is obviously lower than the initial viscosity in the comparative example, and the placement stability of the modified pigment in the aqueous system is obviously better than that of the comparative example.
In summary, the invention provides a preparation method of a polyether amine-crown ether compound and application thereof in modified azo pigments, the particle size of the modified azo pigments is obviously reduced, the particle size distribution is more concentrated, the hue, the tinting strength and the glossiness are obviously improved, the viscosity in an aqueous system is obviously reduced, and the modified azo pigments have good storage stability.
Claims (10)
1. An application of polyether amine-crown ether compound in azo pigment modification, wherein the structure of the polyether amine-crown ether compound is shown as a formula (I),
wherein R is CH 3 Or H; x is 25-35, y is 8-12.
2. The use according to claim 1, characterized in thatCharacterized in that R is CH 3 。
3. The use of claim 1, wherein x is 32 and y is 10.
4. The use according to claim 1, wherein the application method comprises the steps of: in the synthesis process of azo pigments, dissolving the polyether amine-crown ether compound in water and then adding the water into coupling liquid to obtain a coupling component; adding diazonium solution into a coupling component for coupling reaction to obtain a reaction solution; post-treating the reaction liquid to obtain modified azo pigment; preferably, the addition amount of the polyether amine-crown ether compound is 3-5% of the mass of the azo pigment.
5. A modified azo pigment, which is obtained by modifying an azo pigment with the polyether amine-crown ether compound according to claim 1.
6. A preparation method of a polyether amine-crown ether compound is characterized by comprising the following steps:
(1) Preparation of 4' -formyl benzo-15-crown ether-5:
adding benzo-15-crown ether-5, hexamethylenetetramine and trifluoroacetic acid into a reaction container, fully dissolving, heating to 85-95 ℃, and reacting for 22-26 hours under the protection of argon gas in an acidic environment to obtain a reactant 1; cooling the reactant 1 to 0-3 ℃ in ice bath, adding 0-3 ℃ sodium bicarbonate saturated solution to adjust the pH to 6.5-7.5; extracting with dichloromethane for three times, collecting the lower organic phase into a rotary evaporation bottle, and removing dichloromethane by rotary evaporation to obtain 4' -formyl benzo-15-crown ether-5; the reaction scheme of the step (1) is as follows:
(2) Preparation of polyetheramine-crown compounds:
adding ethanol into a reaction container, and fully dissolving the 4 '-formyl benzo-15-crown ether-5 prepared in the step (1) in the ethanol to obtain a 4' -formyl benzo-15-crown ether-5 solution; transferring the 4' -formyl benzo-15-crown ether-5 solution into a constant pressure funnel, slowly dropwise adding the solution into the polyether amine solution, and fully mixing to obtain a mixed solution; heating the mixed solution to 75-85 ℃ under the protection of argon, and carrying out reflux reaction for 2-2.5 h to obtain a reactant 2; transferring the reactant 2 into a rotary steaming bottle, and removing ethanol by rotary steaming to obtain a polyether amine-crown ether compound; the reaction scheme of the step (2) is as follows:
7. the preparation method according to claim 6, wherein the reaction progress is detected by thin layer chromatography during the reaction of step (1) and step (2), respectively; the detection method of the thin layer chromatography comprises the following steps: taking a small amount of reactant, adding methanol with the volume of 5-7 times of that of the reactant for dilution, and simultaneously diluting raw material benzo-15-crown ether-5 or 4' -formylbenzo-15-crown ether-5 with methanol with the volume of 5-7 times of that of the reactant, wherein a developing agent is ethyl acetate; when the thin layer chromatography detects the compound R f The reaction was completed when the values were as follows: benzo-15-crown-5, R f =0.7; 4' -formyl benzo-15-crown ether-5, R f =0.2; polyetheramine-crown ether compounds, R f ＝0.4。
8. The method according to claim 6, wherein the molar ratio of benzo-15-crown-5, hexamethylenetetramine and trifluoroacetic acid in step (1) is 1:2 to 4:9.3 to 20.
9. The method of claim 6, wherein the polyetheramine solution in step (2) is prepared by dissolving a quantity of polyetheramine in ethanol to obtain a polyetheramine solution; preferably, the mass ratio of the 4' -formyl benzo-15-crown ether-5, polyether amine and ethanol is 1: 6-7: 18 to 35.
10. The method of claim 6, wherein the polyetheramine in step (2) is a hydrophilic polyetheramine; preferably, the polyetheramine is one of L-207 or M41.
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