CN113248722B - Styrene-maleic anhydride modified copolymer dispersant and preparation method thereof - Google Patents
Styrene-maleic anhydride modified copolymer dispersant and preparation method thereof Download PDFInfo
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- CN113248722B CN113248722B CN202110168082.0A CN202110168082A CN113248722B CN 113248722 B CN113248722 B CN 113248722B CN 202110168082 A CN202110168082 A CN 202110168082A CN 113248722 B CN113248722 B CN 113248722B
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- maleic anhydride
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- anhydride modified
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- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229920000147 Styrene maleic anhydride Polymers 0.000 title claims abstract description 52
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 46
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 9
- 150000002576 ketones Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 7
- -1 aliphatic aldehyde Chemical class 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 3
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003827 glycol group Chemical group 0.000 claims 2
- 239000000049 pigment Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004873 anchoring Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- CCHAJZURXPPHJU-UHFFFAOYSA-N 2-naphthalen-1-ylacetaldehyde Chemical compound C1=CC=C2C(CC=O)=CC=CC2=C1 CCHAJZURXPPHJU-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920013747 hydroxypolyethylene Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a novel styrene-maleic anhydride modified copolymer dispersant and a preparation method thereof. The styrene-maleic anhydride modified copolymer dispersant has one of the following structures:
or
In the formula: x is 5-800, y is 5-800, z is 5-750, and z is less than or equal to y; r is2Comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms; r is3Comprises the following steps: an aryl group of 6 to 18 carbon atoms or an aryl group containing a nitrogen atom; r4Comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment; r5Comprises the following steps: polyethylene glycol segments or polypropylene glycol segments.
Description
Technical Field
The invention belongs to the technical field of coating additives, and particularly relates to a styrene-maleic anhydride modified copolymer dispersant and a preparation method thereof.
Background
The pigment is widely applied to the field of coatings, is an important component in a coating system, can play a role in coloring, covering and providing chromaticity, and can also improve the ultraviolet resistance of a coating. Most pigments are not soluble in water and organic solvents, but are dispersed in the medium in the form of aggregates. There are many types of pigments, including organic pigments and inorganic pigments. Organic pigments include phthalocyanine blue, phthalocyanine green, scarlet, organic yellow, quinacridone, and the like. The inorganic pigment includes carbon black, iron yellow, iron red, titanium white, lead chrome yellow, etc.
When the pigment is poorly dispersed in the coating system, problems such as floating/floating, color loss, precipitation, etc. may occur in the coating system, and thus the dispersion process is very important during the use of the pigment. In order to uniformly disperse and stabilize pigment particles, prevent the pigment particles from settling, and reduce energy consumption, a certain amount of dispersant needs to be added in the industrial production process. The dispersing agent has the functions of shortening the grinding time, preventing floating color and floating, improving the stability of a system, improving the content of pigment and reducing the viscosity, so the development of the dispersing agent is a hot spot problem.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a styrene-maleic anhydride modified copolymer dispersant having an acylhydrazone bond anchoring group. The styrene-maleic anhydride modified copolymer dispersant is suitable for dispersing various organic and inorganic pigment water-based systems.
The second purpose of the invention is to provide a preparation method of the styrene-maleic anhydride modified copolymer dispersant.
The technical scheme for realizing the purpose of the invention is as follows: the styrene-maleic anhydride modified copolymer dispersant is prepared by performing partial esterification reaction on a styrene-maleic anhydride copolymer (SMA) and a certain amount of small molecular alcohol (such as methanol, ethanol, isopropanol or butanol) to generate an ester bond, then reacting the ester bond with hydrazine hydrate to generate hydrazide, reacting the hydrazide with aldehyde (or ketone) to generate an acylhydrazone bond, and finally introducing a dissolving chain segment into a modified SMA molecule.
The molecular structural formula of the styrene-maleic anhydride modified copolymer dispersant is one of the following structural formulas:
or
In the formula:
x is 5-800, y is 5-800, z is 5-750, and z is less than or equal to y;
R2comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms;
R3comprises the following steps: an aryl group of 6 to 18 carbon atoms or an aryl group containing a nitrogen atom;
R4comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
R5comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
in order to achieve the purpose, the invention adopts the following reaction mechanism:
or
In the formula:
x is 5-800, y is 5-800, z is 5-750, and z is less than or equal to y;
R2comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms;
R3comprises the following steps: aryl of 6 to 18 carbon atoms or containing nitrogenAn aryl group of atoms;
R4comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
R5comprises the following steps: polyethylene glycol segments or polypropylene glycol segments.
According to the mechanism, the invention adopts the following technical scheme:
a method for preparing the styrene-maleic anhydride modified copolymer dispersant comprises the following specific synthetic steps:
(1) dissolving styrene-maleic anhydride copolymer (SMA) and small molecular alcohol (methanol, ethanol, isopropanol or butanol, etc.) in DMF, and performing esterification reaction at 80 deg.C for 2-4 h;
(2) dropwise adding a mixed solution of hydrazine hydrate and DMF into a reaction bottle, and reacting at the constant temperature of 80 ℃ for 3-5 h;
(3) removing unreacted hydrazine hydrate and micromolecular alcohol generated in the reaction under reduced pressure, dropwise adding a mixed solution of aldehyde or ketone and DMF (dimethyl formamide) into a reaction bottle, dropwise adding 2 drops of glacial acetic acid, and reacting for 3-5h at constant temperature of 80 ℃;
(4) adding polyether alcohol or polyether amine into a reaction bottle, and carrying out esterification reaction for 3h at constant temperature of 140 ℃;
(5) the solvent is removed under reduced pressure and the desired solvent (water or organic) is added to make a dispersion of suitable concentration.
In one embodiment, the styrene-maleic anhydride copolymer is prepared in a molar ratio of styrene to maleic anhydride of 1:1, 2:1, or 3: 1.
In one embodiment, the styrene-maleic anhydride copolymer has a number average molecular weight of 1000-00000 g/mol, a molecular weight distribution coefficient of 1.1-3.0, and an acid value of 100-500mg KOH/g.
In one embodiment, the small molecule alcohol is one or more of methanol, ethanol, isopropanol, n-butanol and n-pentanol.
In one embodiment, the aldehyde or ketone is an aliphatic aldehyde or an aliphatic ketone or an aromatic aldehyde.
In one embodiment, the dissolving segment is one or more of a hydroxyl polyethylene glycol or hydroxyl polypropylene glycol segment, an amino polyethylene glycol or amino polypropylene glycol segment, and the number average molecular weight of the dissolving segment is 500-2000 g/mol.
The novel anchoring group-containing styrene-maleic anhydride modified copolymer dispersant synthesized by the invention is an acylhydrazone bond (-C (O) -NH-N ═ C-). The acylhydrazone bond and metal ions (such as copper ions, iron ions, zinc ions and the like) have strong coordination capacity, and a plurality of pigments (such as phthalocyanine green, phthalocyanine blue, iron yellow and the like) contain copper ions, iron ions and the like, so that the coordination capacity of the dispersant and pigment particles can be improved by introducing a certain amount of acylhydrazone bond into the side chain of styrene-maleic anhydride (SMA) molecules, the acylhydrazone bond can be better anchored on the surface of the pigment, and the dispersion capacity and stability of the dispersant are improved.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
The raw materials used in the examples are, unless otherwise indicated, commercially available industrial products and are commercially available.
The styrene-maleic anhydride modified copolymer dispersant is prepared by performing partial esterification reaction on a styrene-maleic anhydride copolymer (SMA) and a certain amount of small molecular alcohol (such as methanol, ethanol, isopropanol or butanol) to generate an ester bond, then reacting the ester bond with hydrazine hydrate to generate hydrazide, reacting the hydrazide with aldehyde (or ketone) to generate an acylhydrazone bond, and finally introducing a dissolving chain segment into a modified SMA molecule.
The molecular structural formula of the styrene-maleic anhydride modified copolymer dispersant is one of the following structural formulas:
or alternatively
In the formula:
x is 5-800, y is 5-800, z is 5-750, and z is less than or equal to y;
R2comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms;
R3comprises the following steps: an aryl group of 6 to 18 carbon atoms or an aryl group containing a nitrogen atom;
R4comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
R5comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
in order to achieve the purpose, the invention adopts the following reaction mechanism:
or
In the formula:
x is 5-800, y is 5-800, z is 5-750, and z is less than or equal to y;
R2comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms;
R3comprises the following steps: an aryl group of 6 to 18 carbon atoms or an aryl group containing a nitrogen atom;
R4comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
R5comprises the following steps: polyethylene glycol segments or polypropylene glycol segments.
According to the mechanism, the invention adopts the following technical scheme:
a method for preparing the styrene-maleic anhydride modified copolymer dispersant comprises the following specific synthetic steps:
(1) dissolving styrene-maleic anhydride copolymer (SMA) and small molecular alcohol (methanol, ethanol, isopropanol or butanol, etc.) in DMF, and performing esterification reaction at 80 deg.C for 2-4 h;
(2) dropwise adding a mixed solution of hydrazine hydrate and DMF into a reaction bottle, and reacting for 3-5h at the constant temperature of 80 ℃;
(3) decompressing to remove unreacted hydrazine hydrate and micromolecular alcohol generated in the reaction, dripping mixed solution of aldehyde or ketone and DMF into a reaction bottle, dripping 2 drops of glacial acetic acid, and reacting for 3-5h at the constant temperature of 80 ℃;
(4) adding polyether alcohol or polyether amine into a reaction bottle, and carrying out esterification reaction for 3h at constant temperature of 140 ℃;
(5) the solvent is removed under reduced pressure and the desired solvent (water or organic) is added to make a dispersion of suitable concentration.
In one embodiment, the styrene-maleic anhydride copolymer is prepared in a molar ratio of styrene to maleic anhydride of 1:1, 2:1, or 3: 1.
In one embodiment, the styrene-maleic anhydride copolymer has a number average molecular weight of 1000-00000 g/mol, a molecular weight distribution coefficient of 1.1-3.0, and an acid value of 100-500mg KOH/g.
In one embodiment, the small molecule alcohol is one or more of methanol, ethanol, isopropanol, n-butanol and n-pentanol.
In one embodiment, the aldehyde or ketone is an aliphatic aldehyde or an aliphatic ketone or an aromatic aldehyde.
In one embodiment, the dissolving segment is one or more of a hydroxy polyethylene glycol or hydroxy polypropylene glycol segment, an amino polyethylene glycol or amino polypropylene glycol segment, and the number average molecular weight of the dissolving segment is 500-2000 g/mol.
The styrene-maleic anhydride modified copolymer dispersant provided by the invention has an anchoring group and a solvation chain segment, and the anchoring group can form a plurality of anchoring sites with pigment particles, so that the styrene-maleic anhydride modified copolymer dispersant is not easy to desorb and has stronger anchoring capability. The solvating segment can promote the dissolving of the dispersant in the medium and form an adsorption layer with a certain thickness to prevent the pigment from flocculating or precipitating.
Example 1
Preparation of styrene-maleic anhydride modified copolymer dispersant K1: (1) adding 120g of DMF (dimethyl formamide) into a 1L reaction bottle, heating to 80 ℃, slowly adding 80g of SMA1000P, uniformly stirring, slowly dropwise adding 2.6g of methanol, and reacting for 2 hours at 80 ℃; (2) at 80 ℃, dropwise adding a mixed solution of 12.2g of 85% hydrazine hydrate and 10g of DMF (dimethyl formamide) into a reaction bottle, and reacting at 80 ℃ for 3 hours at constant temperature; (3) removing unreacted hydrazine hydrate and methanol generated in the reaction under reduced pressure at 120 ℃, cooling to 80 ℃, slowly dripping mixed solution of 8.5g of benzaldehyde, 30g of DMF and 2 drops of glacial acetic acid into a reaction bottle, and reacting for 3 hours at constant temperature at 80 ℃; (4) adding 384g of MPEG1200 into the reaction bottle, and carrying out esterification reaction for 3h at the constant temperature of 140 ℃; (5) the solvent was removed under reduced pressure and g of distilled water was added.
Example 2
Preparation of styrene-maleic anhydride modified copolymer dispersant K2: (1) adding 120g of DMF (dimethyl formamide) into a 1L reaction bottle, heating to 80 ℃, slowly adding 80g of SMA1000P, uniformly stirring, slowly dropwise adding 3.7g of ethanol, and reacting for 2 hours at 80 ℃; (2) at 80 ℃, dropwise adding a mixed solution of 12.2g of 85% hydrazine hydrate and 10g of DMF (dimethyl formamide) into a reaction bottle, and reacting at 80 ℃ for 3 hours at constant temperature; (3) decompressing at 120 ℃ to remove unreacted hydrazine hydrate and methanol generated in the reaction, cooling to 80 ℃, slowly dripping mixed solution of 9.6g of acetophenone, 30g of DMF and 2 drops of glacial acetic acid into a reaction bottle, and reacting at the constant temperature of 80 ℃ for 3 hours; (4) adding 384g of MPEG1200 into the reaction bottle, and carrying out esterification reaction for 3h at the constant temperature of 140 ℃; (5) the solvent was removed under reduced pressure and g of distilled water was added.
Example 3
Preparation of styrene-maleic anhydride modified copolymer dispersant K3: (1) adding 120g of DMF (dimethyl formamide) into a 1L reaction bottle, heating to 80 ℃, slowly adding 80g of SMA1000P, uniformly stirring, slowly dropwise adding 4.8g of isopropanol, and reacting for 2 hours at 80 ℃; (2) at 80 ℃, dropwise adding a mixed solution of 12.2g of 85% hydrazine hydrate and 10g of DMF (dimethyl formamide) into a reaction bottle, and reacting at 80 ℃ for 3 hours at constant temperature; (3) decompressing at 120 ℃ to remove unreacted hydrazine hydrate and methanol generated in the reaction, cooling to 80 ℃, slowly dripping mixed liquid of 13.6 g of beta-naphthylethanone, 30g of DMF and 2 drops of glacial acetic acid into a reaction bottle, and reacting at 80 ℃ for 3 hours at constant temperature; (4) adding 384g of MPEG1200 into the reaction bottle, and carrying out esterification reaction for 3h at the constant temperature of 140 ℃; (5) the solvent was removed under reduced pressure and g of distilled water was added.
Example 4
Preparation of styrene-maleic anhydride modified copolymer dispersant K4: (1) adding 120g of DMF (dimethyl formamide) into a 1L reaction bottle, heating to 80 ℃, slowly adding 80g of SMA1000P, uniformly stirring, slowly dropwise adding 5.9g of butanol, and reacting for 2 hours at 80 ℃; (2) at 80 ℃, dropwise adding a mixed solution of 12.2g of 85% hydrazine hydrate and 10g of DMF (dimethyl formamide) into a reaction bottle, and reacting at 80 ℃ for 3 hours at constant temperature; (3) decompressing at 120 ℃ to remove unreacted hydrazine hydrate and methanol generated in the reaction, cooling to 80 ℃, slowly dripping mixed solution of 8.6g of 4-pyridylaldehyde, 30g of DMF and 2 drops of glacial acetic acid into a reaction bottle, and reacting at 80 ℃ for 3 hours at constant temperature; (4) adding 384g of MPEG1200 into the reaction bottle, and carrying out esterification reaction for 3h at the constant temperature of 140 ℃; (5) the solvent was removed under reduced pressure and g of distilled water was added.
The styrene-maleic anhydride modified copolymer dispersant for the pigment water-based system is a high-molecular dispersant synthesized by graft modification of the side chain of a styrene-maleic anhydride copolymer. The dispersing agent is synthesized by partially esterifying a styrene-maleic anhydride copolymer with micromolecular alcohol, then reacting ester bonds with hydrazine hydrate to obtain hydrazide compounds, reacting aldehyde or ketone with hydrazide to obtain acylhydrazone bonds, and finally introducing dissolving segments into modified styrene-maleic anhydride copolymer molecules. The macromolecular dispersant of the invention contains acylhydrazone bonds which have strong coordination capacity with metal ions (such as copper ions, iron ions, zinc ions and the like), so that the macromolecular dispersant can form stronger anchoring effect with copper ions, iron ions and zinc ions in a plurality of pigments (such as phthalocyanine green, phthalocyanine blue, iron yellow, iron red, zinc oxide and the like), thereby better anchoring the dispersant on the surface of the pigment, improving the dispersing capacity and stability of the dispersant, and the preparation method is simple and easy to operate.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (8)
1. A styrene-maleic anhydride modified copolymer dispersant, wherein said styrene-maleic anhydride modified copolymer dispersant has one of the following structures:
or
In the formula:
x is 5-800, y is 5-800, z is 5-750, and z is less than or equal to y;
R2comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms;
R3comprises the following steps: an aryl group of 6 to 18 carbon atoms or an aryl group containing a nitrogen atom;
R4comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
R5comprises the following steps: polyethylene glycol segments or polypropylene glycol segments.
2. The preparation method of the styrene-maleic anhydride modified copolymer dispersant is characterized by comprising the following steps:
(1) dissolving styrene-maleic anhydride copolymer and micromolecular alcohol in DMF, and performing esterification reaction at constant temperature of 80 ℃ for 2-4 h;
(2) dropwise adding a mixed solution of hydrazine hydrate and DMF into a reaction bottle, and reacting at the constant temperature of 80 ℃ for 3-5 h;
(3) decompressing to remove unreacted hydrazine hydrate and micromolecular alcohol generated in the reaction, dripping mixed solution of aldehyde or ketone and DMF into a reaction bottle, dripping 2 drops of glacial acetic acid, and reacting for 3-5h at the constant temperature of 80 ℃;
(4) adding polyether alcohol or polyether amine into a reaction bottle, and carrying out esterification reaction for 3h at constant temperature of 140 ℃;
(5) the solvent is removed under reduced pressure, and the desired solvent is added to make a dispersant of suitable concentration.
3. The method for preparing a styrene-maleic anhydride modified copolymer dispersant according to claim 2, wherein: in the preparation process of the styrene-maleic anhydride copolymer, the molar ratio of styrene to maleic anhydride is 1:1, 2:1 or 3: 1.
4. The method for preparing a styrene-maleic anhydride modified copolymer dispersant according to claim 2, wherein: the styrene-maleic anhydride copolymer has a number average molecular weight of 1000-100000 g/mol, a molecular weight distribution coefficient of 1.1-3.0 and an acid value of 100-500mg KOH/g.
5. The method of preparing a styrene-maleic anhydride modified copolymer dispersant according to claim 2, wherein: the small molecular alcohol is one or more of methanol, ethanol, isopropanol, n-butanol and n-pentanol.
6. The method for preparing a styrene-maleic anhydride modified copolymer dispersant according to claim 2, wherein: the aldehyde or ketone is aliphatic aldehyde, aliphatic ketone or aromatic aldehyde.
7. The method for preparing a styrene-maleic anhydride modified copolymer dispersant according to claim 2, wherein: the styrene-maleic anhydride modified copolymer dispersant contains a dissolving chain segment, the dissolving chain segment is one or more of a hydroxyl polyethylene glycol or hydroxyl polypropylene glycol chain segment, an amino polyethylene glycol or amino polypropylene glycol chain segment, and the number average molecular weight of the dissolving chain segment is 500-2000 g/mol.
8. The method for preparing a styrene-maleic anhydride modified copolymer dispersant according to claim 2, wherein: the reaction mechanism of the styrene-maleic anhydride modified copolymer dispersant is as follows:
or alternatively
In the formula:
x-5-800, y-5-800, z-5-750, and z ≦ y;
R2comprises the following steps: H. an alkyl group of 1 to 3 carbon atoms or an aryl group of 6 to 18 carbon atoms;
R3comprises the following steps: an aryl group of 6 to 18 carbon atoms or an aryl group containing a nitrogen atom;
R4comprises the following steps: a polyethylene glycol segment or a polypropylene glycol segment;
R5comprises the following steps: polyethylene glycol segments or polypropylene glycol segments.
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| CN106317285A (en) * | 2016-08-17 | 2017-01-11 | 苏州世名科技股份有限公司 | Waterborne pigment dispersant |
| CN109776710A (en) * | 2018-12-27 | 2019-05-21 | 苏州世名科技股份有限公司 | Structure containing phenylethylene-maleic anhydride and the waterborne pigment dispersant and preparation method thereof of graft modification |
| CN110607090A (en) * | 2019-09-26 | 2019-12-24 | 广东中联邦精细化工有限公司 | High-molecular dispersing agent for water-based paint and preparation method thereof |
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| DE102006062439A1 (en) * | 2006-12-27 | 2008-07-03 | Byk-Chemie Gmbh | Comb (block) copolymers |
| JP6555688B2 (en) * | 2013-11-19 | 2019-08-07 | 一般財団法人バイオダイナミックス研究所 | Derivatives of styrene-maleic acid copolymer |
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| CN106317285A (en) * | 2016-08-17 | 2017-01-11 | 苏州世名科技股份有限公司 | Waterborne pigment dispersant |
| CN109776710A (en) * | 2018-12-27 | 2019-05-21 | 苏州世名科技股份有限公司 | Structure containing phenylethylene-maleic anhydride and the waterborne pigment dispersant and preparation method thereof of graft modification |
| CN110607090A (en) * | 2019-09-26 | 2019-12-24 | 广东中联邦精细化工有限公司 | High-molecular dispersing agent for water-based paint and preparation method thereof |
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