CN109776710B - Styrene-maleic anhydride structure-containing graft-modified water-based pigment dispersant and preparation method thereof - Google Patents
Styrene-maleic anhydride structure-containing graft-modified water-based pigment dispersant and preparation method thereof Download PDFInfo
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 40
- 239000000049 pigment Substances 0.000 title claims abstract description 36
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 28
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 22
- 150000003440 styrenes Chemical class 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920001400 block copolymer Polymers 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- MCLXOMWIZZCOCA-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propan-1-amine Chemical compound CO[Si](C)(C)CCCN MCLXOMWIZZCOCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 2
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MHHJQVRGRPHIMR-UHFFFAOYSA-N 1-phenylprop-2-en-1-ol Chemical compound C=CC(O)C1=CC=CC=C1 MHHJQVRGRPHIMR-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a water-based pigment dispersant containing a styrene-maleic anhydride structure and subjected to graft modification and a preparation method thereof.
Description
Technical Field
The invention relates to an aqueous pigment dispersant and a preparation method thereof, in particular to an aqueous pigment dispersant containing a styrene-maleic anhydride structure and modified by grafting and a preparation method thereof, belonging to the technical field of fine chemical engineering.
Background
The water-based color paste formed by stably dispersing the pigment particles in a water-based system is an effective scheme for avoiding pigment dust pollution and improving the using effects of tinting strength, vividness, brightness and the like. The dispersant is a key auxiliary agent for ensuring that pigment particles can be stably dispersed in an aqueous system, and has important influence on the application performances such as tinting strength of aqueous color paste, compatibility with a coloring base material and the like. The dispersant is required to be well anchored and fixed on the surface of pigment particles, and strong steric hindrance and electrostatic repulsion are required to be provided among the pigment particles well dispersed in the aqueous color paste to prevent the pigment particles from agglomerating, so that the dispersant has higher requirements on the aspects of dispersant structure, molecular weight, hydrophilicity, anchor group distribution and the like. The segmented copolymer comprises two or more polymer chain segments with different properties, can combine the excellent characteristics of various polymers, and the segmented copolymer can provide more abundant functions and a micro-phase structure, is increasingly emphasized and has wide application in color paste dispersing agents.
The styrene-maleic anhydride copolymer has excellent performance and low cost, and thus is widely used in various fields such as automobile parts, home appliance housings, building materials, office supplies, medical devices, and the like. However, the existing styrene-maleic anhydride copolymer has less steric hindrance and fewer potential points, which affects the application performance of the styrene-maleic anhydride copolymer as pigment dispersant, viscosity reducer and other products, and in order to obtain the styrene-maleic anhydride copolymer with more excellent performance, the prior art discloses the polymers of styrene, maleic anhydride and various monomers: chinese patent with application number CN201410327081.6 discloses a tetrapolymer dispersant, which is copolymerized by unsaturated polyether, hydroxyethyl methacrylate, styrene, and sodium styrene sulfonate; chinese patent with application number CN201510982711.8 discloses a high molecular block dispersant, which is prepared by polymerizing methacrylic acid, sodium styrene sulfonate and N-isopropyl acrylamide, and then polymerizing with hydroxyethyl methacrylate and allyl alcohol polyoxyethylene ether to obtain the high molecular block dispersant applied to the dispersion of nano titanium dioxide, calcium carbonate and ink pigment particles. The prior art also discloses modifying styrene-maleic anhydride copolymers to increase the compatibility of the styrene-maleic anhydride copolymer with the solvent to enhance the dispersing effect: chinese patent application No. CN201710524237.3 discloses a styrene-maleic anhydride copolymer modified with alkylphenol ethoxylates, which is used as viscosity reducer for high-gum asphaltene thick oil. US6406143 discloses a dispersant for inkjet inks in an inkjet printing process, which dispersant is modified with an amine-containing compound, styrene-maleic anhydride.
However, most styrene-maleic anhydride copolymers are difficult to maintain the steric hindrance between high-concentration pigments due to insufficient anchoring ability and poor steric hindrance, and secondary flocculation is easy to occur, so that color paste stability is poor, and the preparation of the high-performance styrene-maleic anhydride structure pigment dispersant is an important work in the field of fine chemical engineering.
Disclosure of Invention
In order to overcome the defects of insufficient anchoring capability and poor steric hindrance of the conventional styrene-maleic anhydride dispersing agent, the invention provides a water-based pigment dispersing agent containing a styrene-maleic anhydride structure and modified by grafting and a preparation method thereof.
The technical scheme of the invention is as follows:
the invention discloses a preparation method of a styrene-maleic anhydride structure-containing graft-modified water-based pigment dispersant, which comprises the following steps:
s1: preparation of block copolymer solution: preparing a mixed solution of four monomers of styrene, a styrene derivative, maleic anhydride and an acrylic acid derivative and a solvent, placing the mixed solution in a reactor, slowly dropwise adding a mixture consisting of an initiator, a chain transfer agent and the solvent into the reactor under the conditions of inert gas protection and temperature control of 70-100 ℃, wherein the preferable dropwise adding time is 2-4 hours, and continuously reacting for 1-3 hours after the dropwise adding is finished to obtain a block copolymer solution;
s2: preparation of graft-modified Block copolymer: and (4) adding a grafting modifier and a catalyst into the block copolymer solution obtained in the step (S1) to perform a grafting reaction at the reaction temperature of 70-100 ℃ for 2-6 h, removing the solvent after the reaction is finished, and cooling to room temperature to obtain the graft modified block copolymer.
The further technical scheme is as follows:
in the step S1:
the styrene derivative is a compound with a structure of a general formula (I):
wherein R is1Is H or methyl; r2Is an alkyl group having 1 to 10 carbon atoms, and contains 1 and 10 carbon atoms. The styrene derivative is prepared by performing esterification reaction on vinyl benzyl alcohol and alkyl acid containing 1-11 carbon atoms (including 1 and 11 carbon atoms), the esterification reaction is a conventional esterification reaction, and a specific preparation method is not repeated in the application.
The acrylic acid derivative is a compound with a structure of a general formula (II):
wherein R is3Is H or methyl, R4Is alkyl containing 1-10 carbon atoms or alkyl alcohol containing 1-10 carbon atoms, and contains 1 and 10.
The solvent is one of 1, 4-dioxane, cyclohexane, tetrahydrofuran and isopropanol.
The initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and tert-butyl peroxybenzoate.
The chain transfer agent is dodecyl mercaptan or alpha-methyl styrene linear dimer.
In the method of inert gas protection inside the reactor, nitrogen is preferably used as the protective gas, and oxygen in the reactor can be evacuated by continuously introducing nitrogen into the reactor for 15-30min, so that the influence of oxygen on the chemical reaction is avoided.
In the step S1, based on the total mass of the four monomers, styrene accounts for 14% to 27% of the total mass of the four monomers, styrene derivatives accounts for 28% to 55% of the total mass of the four monomers, maleic anhydride accounts for 13% to 25% of the total mass of the four monomers, and acrylic acid derivatives accounts for 17% to 38% of the total mass of the four monomers; the initiator accounts for 5-10% of the total mass of the four monomers, and the chain transfer agent accounts for 3-5% of the total mass of the four monomers.
In the step S2:
the grafting modifier is a compound with a structure of a general formula (III):
wherein R is5、R6And R7Is one of methyl, ethyl, methoxy or ethoxy, and R5、R6And R7Are independent of each other; n is an integer from 1 to 10 inclusive. Preferably, the grafting modifier is one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl dimethylmethoxysilane and 3-aminopropyl diethoxymethylsilane. And the mass of the grafting modifier accounts for 40-80% of that of the maleic anhydride.
The catalyst is one of p-toluenesulfonic acid, aluminum trichloride, triethylamine, 4-dimethylaminopyridine and pyridine, the dosage of the catalyst is the conventional dosage of the catalyst used in the reaction of amino and acid anhydride, the technology is a technical scheme well known by a person skilled in the art, and details are not repeated in the application.
The invention also discloses a styrene-maleic anhydride structure-containing graft-modified water-based pigment dispersant prepared by the preparation method, the dispersant is prepared by carrying out free radical copolymerization on four monomers of styrene, styrene derivatives, maleic anhydride and acrylic acid derivatives to form a block copolymer and then carrying out graft modification on the block copolymer by using a graft modifier, wherein the styrene derivatives, the acrylic acid derivatives and the graft modifier are used as described above.
The invention also discloses an application of the aqueous pigment dispersing agent in aqueous pigment color paste.
The beneficial technical effects of the invention are as follows: the invention carries out free radical copolymerization on four monomers of styrene, styrene derivatives, maleic anhydride and acrylic acid derivatives to form a block copolymer, and then carries out graft modification on the block copolymer by using a graft modifier to prepare the water-based pigment dispersing agent containing the styrene-maleic anhydride structure and having graft modification.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
The chemical structures of styrene derivatives and acrylic acid derivatives used in the following specific examples and comparative examples are as follows:
the styrene derivative is a compound with a structure of a general formula (I):
in the styrene derivative A1, R1Is methyl, R2Is C5H11；
In the styrene derivative A2, R1Is H, R2Is C10H21；
In the styrene derivative A3, R1Is methyl, R2Is CH3。
The acrylic acid derivative is a compound with a structure of a general formula (II):
in the acrylic acid derivative B1, R3Is methyl, R4Is C5H10OH；
In the acrylic acid derivative B2, R3Is H, R4Is CH3；
In the acrylic acid derivative B3, R3Is H, R4Is C10H21。
Detailed description of the preferred embodiment 1
Preparing a mixed solution of 27 parts of styrene, 32 parts of styrene derivative A1, 18 parts of maleic anhydride, 23 parts of acrylic acid derivative B1 and 300 parts of 1, 4-dioxane, placing the mixed solution in a reactor, introducing nitrogen for 25min, controlling the temperature to be 85 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of azobisisobutyronitrile, 4 parts of dodecanethiol and 50 parts of 1, 4-dioxane into the reactor for 3 hours, and continuing to react for 2 hours after dropwise adding is finished; and continuously adding 10.8 parts of 3-aminopropyltrimethoxysilane and 4 parts of p-toluenesulfonic acid, reacting at 85 ℃ for 4 hours, removing 1, 4-dioxane after the reaction is finished, and cooling to room temperature to obtain the styrene-maleic anhydride-containing graft-modified water-based pigment dispersant.
Specific example 2
Preparing a mixed solution of 15 parts of styrene, 40 parts of styrene derivative A2, 25 parts of maleic anhydride, 20 parts of acrylic acid derivative B2 four monomers and 300 parts of cyclohexane, placing the mixed solution in a reactor, introducing nitrogen for 15min, controlling the temperature to be 100 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of benzoyl peroxide, 4 parts of alpha-methyl styrene linear dimer and 50 parts of cyclohexane into the reactor for 2 hours, and continuing to react for 3 hours after dropwise adding is finished; and continuously adding 10.8 parts of 3-aminopropyltriethoxysilane and 4 parts of aluminum trichloride, reacting at 100 ℃ for 2 hours, removing cyclohexane after the reaction is finished, and cooling to room temperature to obtain the styrene-maleic anhydride-containing graft-modified water-based pigment dispersing agent.
Specific example 3
Preparing a mixed solution of 21 parts of styrene, 28 parts of styrene derivative A3, 13 parts of maleic anhydride, 38 parts of acrylic acid derivative B3 and 300 parts of tetrahydrofuran, placing the mixed solution in a reactor, introducing nitrogen for 30min, controlling the temperature at 70 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of dicumyl peroxide, 4 parts of dodecanethiol and 50 parts of tetrahydrofuran into the reactor for 4 hours, and continuing to react for 1 hour after dropwise adding is finished; and continuously adding 10.8 parts of 3-aminopropyl dimethyl methoxysilane and 4 parts of triethylamine, reacting at the temperature of 70 ℃ for 6 hours, removing tetrahydrofuran after the reaction is finished, and cooling to room temperature to obtain the styrene-maleic anhydride-containing graft-modified water-based pigment dispersing agent.
Specific example 4
Preparing a mixed solution of 14 parts of styrene, 55 parts of styrene derivative A1, 14 parts of maleic anhydride, 17 parts of acrylic acid derivative B3 and 300 parts of isopropanol, placing the mixed solution into a reactor, introducing nitrogen for 20min, controlling the temperature to be 90 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of di-tert-butyl peroxide, 4 parts of alpha-methyl styrene linear dimer and 50 parts of isopropanol into the reactor for 3 hours, and continuing to react for 3 hours after dropwise adding is finished; and continuously adding 10.8 parts of 3-aminopropyldiethoxymethylsilane and 4 parts of 4-dimethylaminopyridine, reacting at the temperature of 90 ℃ for 3 hours, removing isopropanol after the reaction is finished, and cooling to room temperature to obtain the styrene-maleic anhydride-containing graft-modified water-based pigment dispersant.
Comparative example 5
Preparing 59 parts of styrene, 41 parts of maleic anhydride and 300 parts of 1, 4-dioxane into a mixed solution, placing the mixed solution into a reactor, introducing nitrogen for 25min, controlling the temperature at 85 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of azobisisobutyronitrile, 4 parts of dodecanethiol and 50 parts of 1, 4-dioxane into the reactor for 3 hours, and continuously reacting for 2 hours after dropwise adding is finished; and continuously adding 24.6 parts of 3-aminopropyltrimethoxysilane and 4 parts of p-toluenesulfonic acid, reacting at 85 ℃ for 4 hours, removing 1, 4-dioxane after the reaction is finished, and cooling to room temperature to obtain the water-based pigment dispersing agent.
Comparative example 6
Preparing a mixed solution from 27 parts of styrene, 32 parts of sodium styrene sulfonate, 18 parts of maleic anhydride, 23 parts of acrylic acid derivative B1 and 300 parts of 1, 4-dioxane, placing the mixed solution into a reactor, introducing nitrogen for 25min, controlling the temperature at 85 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of azodiisobutyronitrile, 4 parts of dodecanethiol and 50 parts of 1, 4-dioxane into the reactor for 3 hours, and continuing to react for 2 hours after the dropwise addition is finished; and continuously adding 10.8 parts of 3-aminopropyltrimethoxysilane and 4 parts of p-toluenesulfonic acid, reacting at 85 ℃ for 4 hours, removing 1, 4-dioxane after the reaction is finished, and cooling to room temperature to obtain the water-based pigment dispersing agent.
Comparative example 7
Preparing a mixed solution of 27 parts of styrene, 32 parts of styrene derivative A1, 18 parts of maleic anhydride, 23 parts of acrylic acid derivative B1 and 300 parts of 1, 4-dioxane, placing the mixed solution in a reactor, introducing nitrogen for 25min, controlling the temperature at 85 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of azobisisobutyronitrile, 4 parts of dodecanethiol and 50 parts of 1, 4-dioxane into the reactor for 3 hours, and continuing to react for 2 hours after dropwise adding is finished; and continuously adding 10.8 parts of gamma-methacryloxypropyltrimethoxysilane and 4 parts of p-toluenesulfonic acid, reacting at 85 ℃ for 4 hours, removing 1, 4-dioxane after the reaction is finished, and cooling to room temperature to obtain the water-based pigment dispersing agent.
Comparative example 8
Preparing a mixed solution of 27 parts of styrene, 32 parts of styrene derivative A1, 18 parts of maleic anhydride, 23 parts of acrylic acid derivative B1 and 300 parts of 1, 4-dioxane, placing the mixed solution in a reactor, introducing nitrogen for 25min, controlling the temperature at 85 ℃, slowly dropwise adding a mixed solution consisting of 8 parts of azobisisobutyronitrile, 4 parts of dodecanethiol and 50 parts of 1, 4-dioxane into the reactor for 3 hours, and continuing to react for 2 hours after dropwise adding is finished; and continuously adding 10.8 parts of ethanolamine and 4 parts of p-toluenesulfonic acid, reacting at 85 ℃ for 4 hours, removing 1, 4-dioxane after the reaction is finished, and cooling to room temperature to obtain the water-based pigment dispersant.
The water-based color paste of the specific application examples 9-12 and the comparative application examples 13-16 is prepared as follows:
35 parts of pigment yellow 74, 5 parts of dispersing agent, 2 parts of propylene glycol and 58 parts of deionized water are mixed, dispersed, ground and filtered to obtain the water-based color paste. The corresponding relation between the dispersant and the application example is shown in table 1.
TABLE 1 corresponding relationship between dispersant and aqueous color paste
And (3) carrying out performance test on the prepared water-based color paste, wherein the test method and the test standard are as follows:
and (3) testing tinting strength: the relative tinting strength of the aqueous color pastes of the specific application examples 9-12 and the comparative application examples 13-16 is tested according to appendix B of the chemical industry standard HG/T3951-2007 aqueous color paste for architectural coatings, and the dispersant prepared in the specific application example 9 is used for the aqueous color paste as the standard color paste.
And (3) stability testing: after the aqueous color pastes of the specific application examples 9-12 and the comparative application examples 13-16 are respectively placed in a sealed manner at 25 ℃ for 30 days and 90 days, the storage stability of the dispersant for the aqueous color pastes is judged by visually observing whether the conditions of serious influence on the stability such as obvious pigment particle precipitation, flocculation and the like occur or not.
Table 2 shows the results of the tests of the aqueous color pastes of the specific application examples 9-12 and the comparative application examples 13-16 according to the method. Wherein in the storage stability test, "√" indicates no visual abnormality, and "X" indicates that the occurrence of sedimentation, flocculation, or the like of the pigment particles is visually apparent.
TABLE 2 Performance test results of aqueous color pastes
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a styrene-maleic anhydride structure-containing graft-modified water-based pigment dispersant is characterized by comprising the following steps:
s1: preparation of block copolymer solution: preparing a mixed solution of four monomers of styrene, a styrene derivative, maleic anhydride and an acrylic acid derivative and a solvent, placing the mixed solution in a reactor, slowly dropwise adding a mixture consisting of an initiator, a chain transfer agent and the solvent into the reactor under the conditions of inert gas protection and temperature control of 70-100 ℃, and continuously reacting for 1-3 hours after dropwise adding is finished to obtain a block copolymer solution; wherein, based on the total mass of four monomers of styrene, styrene derivatives, maleic anhydride and acrylic acid derivatives, the styrene accounts for 14-27% of the total mass of the four monomers, the styrene derivatives account for 28-55% of the total mass of the four monomers, the maleic anhydride accounts for 13-25% of the total mass of the four monomers, and the acrylic acid derivatives account for 17-38% of the total mass of the four monomers; the initiator accounts for 5-10% of the total mass of the four monomers, and the chain transfer agent accounts for 3-5% of the total mass of the four monomers;
s2: preparation of graft-modified Block copolymer: adding a grafting modifier and a catalyst into the block copolymer solution obtained in the step S1 to perform a grafting reaction at the reaction temperature of 70-100 ℃ for 2-6 h, removing the solvent after the reaction is finished, and cooling to room temperature to obtain a graft modified block copolymer; wherein the mass of the grafting modifier accounts for 40-80% of the mass of maleic anhydride;
the styrene derivative is a compound with a structure of a general formula (I):
wherein R1 is H or methyl; r2 is an alkyl group with 1-10 carbon atoms, and contains 1 and 10 carbon atoms;
the acrylic acid derivative is a compound with a structure of a general formula (II):
wherein R3 is H or methyl, R4 is C1-10 alkyl or C1-10 alkyl alcohol, 1 and 10;
the grafting modifier is a compound with a structure of a general formula (III):
wherein R5, R6 and R7 are one of methyl, ethyl, methoxy or ethoxy, and R5, R6 and R7 are independent; n is an integer from 1 to 10 inclusive.
2. The method of claim 1, wherein: the initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide and tert-butyl peroxybenzoate.
3. The method of claim 1, wherein: the chain transfer agent is dodecyl mercaptan or alpha-methyl styrene linear dimer.
4. The method of claim 1, wherein: in step S1, the solvent is one of 1, 4-dioxane, cyclohexane, tetrahydrofuran, and isopropanol.
5. The method of claim 1, wherein: in step S2, the grafting modifier is one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylmethoxysilane and 3-aminopropyldiethoxymethylsilane.
6. The method of claim 1, wherein: in the step S2, the catalyst is one of p-toluenesulfonic acid, aluminum trichloride, triethylamine, 4-dimethylaminopyridine and pyridine.
7. An aqueous pigment dispersant containing a styrene-maleic anhydride structure and graft-modified, which is prepared by the process as claimed in any one of claims 1 to 6.
8. Use of the aqueous pigment dispersant according to claim 7 in aqueous pigment pastes.
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| CN111393569B (en) * | 2020-04-07 | 2021-11-05 | 嘉兴华雯化工股份有限公司 | Styrene maleic amide acid copolymer and preparation method thereof |
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| CN113248722B (en) * | 2021-02-07 | 2022-06-21 | 中海油常州涂料化工研究院有限公司 | Styrene-maleic anhydride modified copolymer dispersant and preparation method thereof |
| CN114015245A (en) * | 2021-10-20 | 2022-02-08 | 鄂尔多斯市路泰公路工程有限责任公司 | Stable rubber powder polymer composite modified asphalt and mixture |
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