CN113831520A - Polyamine grafted polyether-polyester segmented copolymer dispersant, and preparation method and application thereof - Google Patents
Polyamine grafted polyether-polyester segmented copolymer dispersant, and preparation method and application thereof Download PDFInfo
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- CN113831520A CN113831520A CN202111339824.8A CN202111339824A CN113831520A CN 113831520 A CN113831520 A CN 113831520A CN 202111339824 A CN202111339824 A CN 202111339824A CN 113831520 A CN113831520 A CN 113831520A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 94
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 76
- 229920000768 polyamine Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920001577 copolymer Polymers 0.000 title abstract description 14
- 229920001400 block copolymer Polymers 0.000 claims abstract description 62
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 239000008096 xylene Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001261 hydroxy acids Chemical class 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyclic anhydride Chemical class 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 5
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012454 non-polar solvent Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 4
- 229960003656 ricinoleic acid Drugs 0.000 claims description 4
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000007112 amidation reaction Methods 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000004873 anchoring Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 19
- 239000000049 pigment Substances 0.000 abstract description 17
- 238000007614 solvation Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention belongs to the technical field of dispersants for ceramic pigments, and particularly relates to a polyamine grafted polyether-polyester segmented copolymer dispersant, and a preparation method and application thereof; the polyamine-grafted polyether-polyester block copolymer dispersant is obtained by connecting polyether-polyester block copolymer branched chains on N atoms of polyamine molecules through amide bonds, and the molecular structure of the polyamine-grafted polyether-polyester block copolymer dispersant is as follows:
wherein: r1Is C2-C6 alkyl or aryl; r2Is a straight chain or branched chain alkyl of C1-C17;R3is a straight chain or branched chain alkyl of C2-C4; r4Is a straight chain or branched chain alkyl of C1-C22; m is 3-15; n is 3 to 10. The dispersant simultaneously contains a plurality of amino anchoring groups and a plurality of polyester/polyether solvation chains, has better anchoring effect and dispersing effect, has good controllability of the properties of the solvation chains, and can be further used for solvent systems with different properties.
Description
Technical Field
The invention relates to the technical field of dispersants for ceramic pigments, and particularly relates to a polyamine-grafted polyether-polyester segmented copolymer dispersant, and a preparation method and application thereof.
Background
Dispersant molecules generally comprise two basic units: one basic unit is an anchoring group, which forms a strong adsorption with the surface of the dispersed particle to anchor the dispersant molecule to the surface of the dispersed particle, and this anchoring effect is reversible, and in order to make the dispersant firmly anchored and not easily desorbed, a certain number of anchoring groups are usually introduced into the dispersant molecule. The other basic unit is a solvation chain, which must have good compatibility with the solvent to be well spread in the solvent, so that a protective layer with a certain thickness is formed on the surface of the dispersed particles to play an effective steric hindrance role and prevent the particles from agglomerating, and therefore, the properties of the solvation chain need to be matched with the properties of the used solvent; in order to adapt to solvents with different properties, the solvation chain composition of the dispersant is required to have certain adjustability, for example, hydrophilic and lipophilic components are simultaneously introduced into the solvation chain, and the properties of the solvation chain are controlled by adjusting the ratio of the hydrophilic component to the lipophilic component to adapt to solvent systems with different properties.
In the dispersant molecule, a polyether chain segment is a common hydrophilic component, a polyester chain segment is a common oleophilic component, and patent documents WO 99/55762 and WO 2008/116932 disclose a polyether-polyester block copolymer phosphate dispersant, wherein the polyether-polyester block copolymer phosphate dispersant is obtained by reacting alkyl-terminated polyether with hydroxy acid to obtain a polyether-polyester block copolymer with a hydroxyl at the terminal, and then performing esterification reaction with phosphoric acid or polyphosphoric acid, wherein an anchoring group of the polyether-polyester block copolymer phosphate dispersant is phosphate; patent documents US 2013/0271525, US 2013/0342593, WO 2014/146992 and WO 2017/140538 disclose dispersants for polyethyleneimine grafted polyesters, which are obtained by esterification of a hydroxy acid to obtain a polyester having a carboxyl group at the end, followed by amidation of the polyester with polyethyleneimine, wherein the anchoring group is an amino group contained in polyethyleneimine and the solvating chain is a polyester. Wherein, the solvation chain property of the polyether-polyester phosphate ester can be adjusted by the relative content of the polyether and the polyester, but the anchoring group is single phosphate radical, and the anchoring effect is not as good as that of the polyethyleneimine grafted polyester containing a plurality of anchoring groups; the solvation chain of the existing polyethyleneimine grafted polyester dispersant is a single polyester component, so that the adjustability is very limited, and the applicable solvent system is very limited. It can be seen that the molecular structure and the dispersing properties of the existing dispersants, especially dispersants for ceramic colorants, have yet to be improved.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects of the prior art and provide a polyamine grafted polyether-polyester block copolymer dispersant which simultaneously contains a plurality of amino anchoring groups and a plurality of polyester/polyether solvation chains, has better anchoring effect and dispersing effect, has good controllability of the properties of the solvation chains and can be further used for solvent systems with different properties.
The second purpose of the invention is to provide a preparation method of the polyamine grafted polyether-polyester segmented copolymer dispersant, which does not need to be provided with a pressurized kettle and has simpler and safer reaction equipment and process.
The invention also aims to provide application of the polyamine grafted polyether-polyester block copolymer dispersant in a ceramic pigment dispersion system.
Based on the above, the invention discloses a polyamine-grafted polyether-polyester block copolymer dispersant,
the molecular structure of the polyamine grafted polyether-polyester segmented copolymer dispersant is as follows:
wherein: r1Is C2-C6 alkyl or aryl; r2Is a straight chain or branched chain alkyl of C1-C17; r3Is a straight chain or branched chain alkyl of C2-C4; r4Is a straight chain or branched chain alkyl of C1-C22; m is 3-15; n is 3 to 10.
Preferably, the polyamine grafted polyether-polyester block copolymer dispersant is obtained by linking polyether-polyester block copolymer branches to N atoms of a polyamine molecule through amide bonds.
Further preferably, the polyamine is a compound containing a plurality of amino groups; the polyamine is at least one of diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and polyethyleneimine.
More preferably, the polyamine is tetraethylenepentamine or polyethyleneimine, molecular chains of the two polyamines not only have a plurality of amino groups capable of carrying out grafting reaction with the polyether-polyester block copolymer, but also the reaction system is stable, and the performance stability of the obtained polyamine-grafted polyether-polyester block copolymer dispersant is good.
The invention also discloses a preparation method of the polyamine grafted polyether-polyester segmented copolymer dispersant, which comprises the following steps:
step S1, carrying out polyesterification reaction under the heating condition by using monoalkyl polyether and hydroxy acid as reactants, tetrabutyl titanate as a catalyst and xylene as a solvent, and cooling to obtain a polyether-polyester block copolymer with a hydroxyl at the tail end; the reaction principle of step S1 is shown by the following formula (1):
step S2, adding cyclic anhydride into the polyether-polyester block copolymer with hydroxyl at the tail end of the step S1, and converting the hydroxyl at the tail end of the polyether-polyester block copolymer into carboxyl through heating reaction to obtain the polyether-polyester block copolymer with carboxyl at the tail end; the reaction principle of step S2 is shown by the following formula (2):
and S3, adding polyamine into the polyether-polyester block copolymer with the carboxyl at the tail end of the step S2, and carrying out amidation reaction on the carboxyl at the tail end of the polyether-polyester block copolymer and the amino of the polyamine under the conditions of vacuumizing and heating to connect the polyether-polyester block copolymer to a polyamine molecule, thereby obtaining the polyamine grafted polyether-polyester block copolymer dispersant. The reaction principle of step S3 is shown by the following formula (3):
preferably, in the step S1, after adding monoalkyl polyether, hydroxy acid, tetrabutyl titanate and xylene, heating to 175-190 ℃ (preferably 180 ℃), refluxing for water diversion, reducing the acid value of the reaction system to 0, distilling under reduced pressure to remove xylene, and then cooling to 80-90 ℃ to obtain the polyether-polyester block copolymer with hydroxyl at the terminal.
Preferably, in the step S2, cyclic anhydride is added to the polyether-polyester block copolymer with a hydroxyl group at the end of the step S1 in batches, and after the mixture reacts at 80-90 ℃ for 1-3 hours (preferably 2 hours), the temperature is increased to 110-120 ℃ for 0.6-2 hours (preferably 1 hour), and then the temperature is reduced to <70 ℃ to obtain the polyether-polyester block copolymer with a carboxyl group at the end.
Preferably, in the step S3, polyamine is added to the polyether-polyester block copolymer having a carboxyl group at the terminal of the step S2 in batches, the addition amount of each batch of polyamine is controlled so that the temperature of the reaction system does not exceed 80 ℃, and then the mixture is stirred at 70 to 80 ℃ for 20 to 50 minutes (preferably 0.5 hour), and then the mixture is vacuumized and heated to 115 to 130 ℃ for reaction for 2 to 3 hours (preferably 120 ℃ for reaction for 2 hours), so as to obtain the polyamine grafted polyether-polyester block copolymer dispersant.
Preferably, in step S1, the monoalkyl polyether is at least one of polyether monomethyl ether and fatty alcohol polyether.
Further preferably, the monoalkyl polyether is polyethylene glycol monomethyl ether, isomeric tridecanol polyoxyethylene ether or isomeric tridecanol polyoxyethylene ether.
Preferably, the hydroxy acid is at least one of glycolic acid, lactide, caprolactone, 12-hydroxystearic acid and ricinoleic acid.
Further preferably, the hydroxy acid is 12-hydroxystearic acid or ricinoleic acid.
Preferably, in the step S2, the cyclic anhydride is succinic anhydride or phthalic anhydride.
Preferably, in the steps S1 to S3, the addition amount of each raw material is: 29-43 g of monoalkyl polyether, 120-150 g of hydroxy acid, 0.48-0.54 g of tetrabutyl titanate, 20-25 g of xylene, 9-13.5 g of cyclic anhydride and 5.5-13.6 g of polyamine.
In the preparation method of the polyamine grafted polyether-polyester block copolymer dispersant, the branched chain of the polyether-polyester block copolymer is connected with the N atom in the polyamine molecule through an amido bond (-CO-NH-), so that the synthetic reaction of the steps S1-S3 does not involve the use of epoxy compounds, a pressurized kettle is not needed, and the reaction equipment and the process are simpler and safer.
The invention also discloses application of the polyamine-grafted polyether-polyester block copolymer dispersant, namely the polyamine-grafted polyether-polyester block copolymer dispersant is applied to a ceramic pigment dispersion system added with a non-polar solvent or a medium polar solvent.
Preferably, the ceramic pigment is praseodymium yellow pigment, red brown pigment or cobalt blue pigment.
Compared with the prior art, the invention at least comprises the following beneficial effects:
each polyamine grafted polyether-polyester block copolymer dispersant of the present invention contains a plurality of amino anchoring groups (including primary amino groups, secondary amino groups, tertiary amino groups, and amide groups) and a plurality of polyester/polyether solvating chains; on one hand, compared with a single anchoring group, the dispersing agent with a plurality of amino anchoring groups can better form a strong adsorption effect with the surface of dispersed particles (especially ceramic pigment), and the anchoring effect on the dispersed particles is obviously improved; on the other hand, the dispersing agent with a plurality of polyester/polyether solvation chains has better dispersing effect in a dispersing system, and each polyester/polyether solvation chain of the dispersing agent can realize the regulation and control of the property of the solvation chain by regulating the relative content of polyether and polyester, so that the dispersing agent with a plurality of polyester/polyether solvation chains has better controllability of the property of the solvation chain, and further the dispersing agent can be applied to ceramic pigment dispersing systems with different properties from non-polar solvents to medium-polar solvents.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.
Example 1
The preparation method of the polyamine-grafted polyether-polyester block copolymer dispersant of the embodiment comprises the following steps:
adding 43g of isomeric tridecanol polyoxyethylene ether (emulsifier 1306), 120g of 12-hydroxystearic acid, 0.48g of tetrabutyl titanate and 20g of xylene into a reaction bottle, heating to 180 ℃ for reaction, removing water generated by the reaction through a water separator, reducing the acid value of a reactant to 0, distilling under reduced pressure to remove the xylene, and cooling to 86 ℃; adding 9g succinic anhydride in batches, reacting at 85 ℃ for 2 hours after the addition is finished, then heating to 118 ℃ for reacting for 1 hour, and then cooling to less than 70 ℃; adding 6.5g of polyethyleneimine (PEI20000) in batches, controlling the addition amount of each batch to ensure that the reaction temperature does not exceed 80 ℃, stirring at 73 ℃ for 0.5 hour after the addition is finished, vacuumizing and heating to 120 ℃ for reaction for 2 hours to obtain the polyamine grafted polyether-polyester block copolymer dispersant of the embodiment, which is marked as dispersant 1.
Example 2
The preparation method of the polyamine-grafted polyether-polyester block copolymer dispersant of the embodiment comprises the following steps:
adding 29g of isomeric dodecyl alcohol polyoxyethylene ether (emulsifier 1003), 150g of 12-hydroxystearic acid, 0.51g of tetrabutyl titanate and 20g of xylene into a reaction bottle, heating to 175 ℃ for reaction, removing water generated by the reaction through a water separator, reducing the acid value of a reactant to 0, distilling under reduced pressure to remove the xylene, and cooling to 80 ℃; adding 13.5g of phthalic anhydride in batches, reacting at 80 ℃ for 3 hours after the addition is finished, heating to 120 ℃ for reacting for 0.6 hour, and then cooling to less than 70 ℃; adding 5.5g of tetraethylenepentamine in batches, controlling the adding amount of each batch to ensure that the reaction temperature does not exceed 80 ℃, stirring for 50 minutes at 70 ℃ after the adding is finished, vacuumizing and heating to 115 ℃ to react for 3 hours to obtain the polyamine grafted polyether-polyester segmented copolymer dispersant of the embodiment, which is marked as dispersant 2.
Example 3
The preparation method of the polyamine-grafted polyether-polyester block copolymer dispersant of the embodiment comprises the following steps:
adding 40g of polyethylene glycol (400) monomethyl ether (MPEG400), 150g of ricinoleic acid, 0.54g of tetrabutyl titanate and 25g of xylene into a reaction bottle, heating to 190 ℃ for reaction, removing water generated by the reaction through a water separator, reducing the acid value of a reactant to 0, distilling under reduced pressure to remove the xylene, and cooling to 90 ℃; adding 9g succinic anhydride in batches, reacting at 90 ℃ for 1 hour after adding, then heating to 110 ℃ for reacting for 2 hours, and cooling to less than 70 ℃; adding 13.6g of polyethyleneimine (PEI20000) in batches, controlling the adding amount of each batch to ensure that the reaction temperature does not exceed 80 ℃, stirring for 20 minutes at 80 ℃ after the adding is finished, vacuumizing and heating to 130 ℃ to react for 2 hours to obtain the polyamine grafted polyether-polyester segmented copolymer dispersant of the embodiment, which is marked as dispersant 3.
Application of dispersing agent 1-3 in ceramic pigment and dispersion effect test thereof
The dispersion effect of the obtained dispersants 1-3 on ceramic pigments in a nonpolar to medium-polar solvent system was tested, respectively, as represented by praseodymium yellow, red brown, cobalt blue. The ceramic pigment, a solvent and a dispersant are prepared into a grinding material with the solid content of the pigment of 45 percent and the dosage of the dispersant of 4 percent, the grinding material is ground by a rod tip type sand mill to the required color development granularity of each pigment, and the dispersing effect is evaluated by comparing the granularity, the viscosity and the precipitation rate. The results of the dispersion property test of the dispersants 1 to 3 are shown in Table 1.
TABLE 1 dispersing Effect of dispersants 1 to 3 on ceramic colorants
As shown in Table 1, the polyamine grafted polyether-polyester segmented copolymer dispersant prepared by the invention can adapt to ceramic pigment dispersion systems with different properties from non-polar solvents (white oil) to medium-polar solvents (propylene glycol monomethyl ether acetate); moreover, the particle size of the color paste meets the requirement of color development, the pigment content in the color paste is high, the viscosity of the color paste is low, and the precipitation rate is low, so that the polyamine grafted polyether-polyester segmented copolymer dispersant has excellent anchoring effect and dispersing effect on the three ceramic pigments. Wherein, the polyamine grafted polyether-polyester segmented copolymer dispersant has the best anti-precipitation effect on cobalt blue pigments.
In conclusion, the solvent chain property of the polyamine grafted polyether-polyester segmented copolymer dispersing agent prepared by the invention can be well regulated and controlled, and the dispersing agent can be suitable for ceramic pigment dispersing systems with different properties from a nonpolar solvent (white oil) to a medium polar solvent (propylene glycol monomethyl ether acetate); the polyamine grafted polyether-polyester segmented copolymer dispersing agent contains a plurality of amino anchoring groups and a plurality of polyester/polyether solvation chains, can play excellent anchoring effects and dispersing effects on three ceramic pigment dispersing systems of praseodymium yellow, red brown and cobalt blue, and particularly has good anti-precipitation effects.
While preferred embodiments of the present invention have been described, additional variations and modifications of these embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the embodiments of the invention.
The technical solutions provided by the present invention are described in detail above, and the principle and the implementation of the present invention are explained in this document by applying specific examples, and the descriptions of the above examples are only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. A polyamine grafted polyether-polyester block copolymer dispersant, wherein the molecular structure of the polyamine grafted polyether-polyester block copolymer dispersant is:
wherein: r1Is C2-C6 alkyl or aryl; r2Is a straight chain or branched chain alkyl of C1-C17; r3Is a straight chain or branched chain alkyl of C2-C4; r4Is a straight chain or branched chain alkyl of C1-C22; m is 3-15; n is 3 to 10.
2. The polyamine-grafted polyether-polyester block copolymer dispersant according to claim 1, wherein said polyamine-grafted polyether-polyester block copolymer dispersant is obtained by linking polyether-polyester block copolymer branches to N atoms of a polyamine molecule through amide bonds.
3. The dispersant of claim 2, wherein the polyamine-grafted polyether-polyester block copolymer is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or polyethyleneimine.
4. The polyamine grafted polyether-polyester block copolymer dispersant according to claim 3, wherein said polyamine is tetraethylenepentamine or polyethyleneimine.
5. The method for preparing a polyamine grafted polyether-polyester block copolymer dispersant according to any one of claims 1 to 4, characterized by comprising the following preparation steps:
step S1, carrying out polyesterification reaction under the heating condition by using monoalkyl polyether and hydroxy acid as reactants, tetrabutyl titanate as a catalyst and xylene as a solvent, and cooling to obtain a polyether-polyester block copolymer with a hydroxyl at the tail end;
step S2, adding cyclic anhydride into the polyether-polyester block copolymer with hydroxyl at the tail end of the step S1, and converting the hydroxyl at the tail end of the polyether-polyester block copolymer into carboxyl through heating reaction to obtain the polyether-polyester block copolymer with carboxyl at the tail end;
and S3, adding polyamine into the polyether-polyester block copolymer with the carboxyl at the tail end of the step S2, and carrying out amidation reaction on the carboxyl at the tail end of the polyether-polyester block copolymer and the amino of the polyamine under the conditions of vacuumizing and heating to connect the polyether-polyester block copolymer to a polyamine molecule, thereby obtaining the polyamine grafted polyether-polyester block copolymer dispersant.
6. The preparation method of the polyamine-grafted polyether-polyester block copolymer dispersant according to claim 5, wherein in the step S1, after the monoalkyl polyether, the hydroxy acid, the tetrabutyl titanate and the xylene are added, the mixture is heated to 175-190 ℃, refluxed and water-separated, after the acid value of the reaction system is reduced to 0, reduced pressure distillation is carried out to remove the xylene, and then the temperature is reduced to 80-90 ℃ to obtain the polyether-polyester block copolymer with the hydroxyl at the terminal.
7. The method for preparing the polyamine-grafted polyether-polyester block copolymer dispersant according to claim 5, wherein in the step S2, cyclic anhydride is added in batches to the polyether-polyester block copolymer with hydroxyl at the terminal of the step S1, the mixture is reacted at 80-90 ℃ for 1-3 hours, then the temperature is increased to 110-120 ℃ for 0.6-2 hours, and then the temperature is decreased to <70 ℃ to obtain the polyether-polyester block copolymer with carboxyl at the terminal.
8. The method for preparing the polyamine-grafted polyether-polyester block copolymer dispersant according to claim 5, wherein in the step S3, the polyamine is added to the polyether-polyester block copolymer with the carboxyl group at the terminal of the step S2 in batches, the addition amount of the polyamine in each batch is controlled so that the temperature of the reaction system does not exceed 80 ℃, and then the mixture is stirred for 20-50 minutes at 70-80 ℃, and then is vacuumized and heated to 115-130 ℃ for reaction for 2-3 hours, so that the polyamine-grafted polyether-polyester block copolymer dispersant is obtained.
9. The method for preparing a polyamine grafted polyether-polyester block copolymer dispersant according to claim 5,
in the step S1, the monoalkyl polyether is polyethylene glycol monomethyl ether, isomeric tridecanol polyoxyethylene ether or isomeric tridecanol polyoxyethylene ether; the hydroxy acid is 12-hydroxystearic acid or ricinoleic acid;
in the step S2, the cyclic acid anhydride is succinic anhydride or phthalic anhydride.
10. Use of a polyamine-grafted polyether-polyester block copolymer dispersant according to any one of claims 1 to 4 in a ceramic colorant dispersion system to which a non-polar solvent or a moderately polar solvent is added.
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| CN101069827A (en) * | 2007-03-23 | 2007-11-14 | 上海点阵材料科技有限公司 | Block dispersant and preparing method |
| CN111247192A (en) * | 2017-09-19 | 2020-06-05 | 路博润先进材料公司 | Polyamine polyester dispersants prepared via anhydride intermediates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101069827A (en) * | 2007-03-23 | 2007-11-14 | 上海点阵材料科技有限公司 | Block dispersant and preparing method |
| CN111247192A (en) * | 2017-09-19 | 2020-06-05 | 路博润先进材料公司 | Polyamine polyester dispersants prepared via anhydride intermediates |
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