CN116375991A - Hyper-dispersant and application thereof in photo-curing coating - Google Patents
Hyper-dispersant and application thereof in photo-curing coating Download PDFInfo
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- CN116375991A CN116375991A CN202310403453.8A CN202310403453A CN116375991A CN 116375991 A CN116375991 A CN 116375991A CN 202310403453 A CN202310403453 A CN 202310403453A CN 116375991 A CN116375991 A CN 116375991A
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- hyperdispersant
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- diglycidyl ether
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 title claims abstract description 28
- 238000000016 photochemical curing Methods 0.000 title abstract description 6
- -1 diglycidyl ether compound Chemical class 0.000 claims abstract description 36
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 9
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- OOFAEFCMEHZNGP-UHFFFAOYSA-N 1-n',1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(N)N(C)C OOFAEFCMEHZNGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002734 clay mineral Substances 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000007614 solvation Methods 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 4
- 101100217475 Arabidopsis thaliana ACA1 gene Proteins 0.000 description 27
- 101100533932 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SPA2 gene Proteins 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 230000001376 precipitating effect Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 229920001610 polycaprolactone Polymers 0.000 description 7
- 239000004632 polycaprolactone Substances 0.000 description 7
- 238000004873 anchoring Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000013530 defoamer Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Images
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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen 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
- C08G63/66—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
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a hyper-dispersant, which comprises the following steps: (1) The diglycidyl ether compound and the amine compound are used as reaction monomers, and the linear polyether amine is prepared through ring-opening polymerization; (2) Under the action of a catalyst, the linear polyether amine and the cyclic lactone undergo a ring-opening reaction, and then are purified to prepare the hyper-dispersant. The hyper-dispersant disclosed by the invention takes the linear polyether amine as a main chain, and the polyester chain segment as a solvation chain segment, so that the inorganic filler in the photo-curing coating can be effectively dispersed.
Description
Technical Field
The invention relates to the technical field of dispersing agents, in particular to a hyper-dispersing agent and application thereof in photo-curing coating.
Background
Hyperdispersant can generally avoid flocculation of inorganic filler particles in the coating due to surface interaction, thereby reducing the viscosity of the coating and improving the leveling property of the coating. The structure of the hyperdispersant is mainly divided into two parts, wherein the first part is a group capable of forming a physical and chemical action with solid particles, and is called an anchoring group. The second part is a solvating segment capable of forming good compatibility with the coating medium, forming a steric hindrance. Common anchoring groups are polyamines, polyethers, carboxylic acid groups, sulfonic acid groups and salts thereof, and the like, which form firm adsorption with the surface of solid particles by means of ionic bonds, hydrogen bonds or van der Waals forces. Solvated segments can generally be divided into low polarity polyolefin segments, high polarity polyether segments, and medium polarity polyester segments and polyacrylate segments.
Chinese application CN202210433720.1 synthesizes terpolymer by free radical polymerization of acrylamide, acrylic acid and butyl acrylate, adsorbs silica by using amide group as anchor group, and the negative charge carried by acrylic acid provides electrostatic repulsion to disperse silica. However, it uses radical polymerization and requires high reaction conditions. Meanwhile, the anchoring groups of the synthesized random copolymer are unevenly distributed, and the static acting force in an oily system is weak, so that the dispersion stability of the filler is not facilitated.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a hyper-dispersant and application thereof in photo-curing paint. The hyper-dispersant disclosed by the invention takes the linear polyether amine as a main chain, and the polyester chain segment as a solvation chain segment, so that the inorganic filler in the photo-curing coating can be effectively dispersed.
The technical scheme of the invention is as follows:
the first object of the present invention is to provide a hyperdispersant, the preparation method of which comprises the following steps:
(1) The diglycidyl ether compound and the amine compound are used as reaction monomers, and the linear polyether amine is prepared through ring-opening polymerization;
(2) Under the action of a catalyst, the linear polyether amine and the cyclic lactone undergo a ring-opening reaction, and then are purified to prepare the hyper-dispersant.
In one embodiment of the present invention, in the step (1), the diglycidyl ether compound is one of glycidyl ether, 1, 4-butanediol diglycidyl ether, and 1, 6-hexanediol diglycidyl ether.
In one embodiment of the present invention, in the step (1), the amine compound is one of N, N-dimethylethylenediamine and N, N-dimethylpropanediamine.
In one embodiment of the present invention, in step (1), the specific preparation method of the linear polyetheramine is: after diglycidyl ether compound, amine compound and ethanol are mixed, the mixture is reacted for 24 to 48 hours at normal temperature, then the temperature is raised to 30 to 60 ℃ for reaction for 24 to 48 hours, and then the mixture is purified to obtain linear polyether amine. The purification method comprises the following steps: after spin-concentrating, the dissolution-precipitation operation is performed, and the precipitate is dried in vacuum.
In one embodiment of the invention, the molar ratio of the diglycidyl ether compound to the amine compound is 1:1-1.5; the mass volume concentration of the total mass of the diglycidyl ether compound and the amine compound and the ethanol is 0.1-1.0 g/mL.
In one embodiment of the present invention, in the step (1), the structure of the linear polyetheramine is represented by the general formula (1):
in the general formula (1), R 1 Represented by oxygen,
One of the following;
R 2 expressed as one of ethylene and n-propylene.
In one embodiment of the present invention, in the step (2), the catalyst is one of stannous octoate, dibutyl tin dilaurate and dibutyl tin diacetate.
In one embodiment of the present invention, in step (2), the cyclic lactone is one of γ -valerolactone and ε -caprolactone.
In one embodiment of the present invention, in step (2), the mass ratio of the linear polyetheramine to the cyclic lactone is 1:3-60; the dosage of the catalyst is 0.3-3% of the total mass of the linear polyether amine and the cyclic lactone.
In one embodiment of the present invention, in step (2), the conditions of the ring-opening reaction are: reacting for 2-24 h at 120-160 ℃.
In one embodiment of the invention, in step (2), the purification method is: after spin-concentrating, the dissolution-precipitation operation is performed, and the precipitate is dried in vacuum.
In one embodiment of the present invention, in the step (2), the structure of the hyperdispersant is as shown in the general formula (2):
in the general formula (2), R 1 Represented by oxygen,
One of the following;
R 2 one of ethylene and n-propylene; n represents an integer of 5 to 60;
R 3 represented as
One of them.
A second object of the present invention is to provide the use of a hyperdispersant, characterized by the dispersion of an inorganic filler for use in a photocurable coating; the inorganic filler is one or more of silicon dioxide, diatomite, quartz, silica gel, clay mineral, talcum powder, kaolin, mica, aluminum oxide, calcium carbonate, titanium dioxide, zinc oxide and carbon black.
The beneficial technical effects of the invention are as follows:
the hyperdispersant is synthesized into the linear polyether amine through the click chemistry reaction of the epoxy and the amine, the reaction condition is mild, the polymerization is easy to carry out, and the product is stable; the anchor groups on the main chain of the linear polyether amine are uniformly distributed, and the softer polyether chain segments are used for connecting the anchor groups, so that the adsorption of the anchor groups to the inorganic filler is facilitated. The comb polymer has the structural characteristics that the hyper-dispersant provides a plurality of solvation chain segments, and meanwhile, the solvation chain segments and the anchoring sites are more uniformly arranged, so that the steric hindrance effect of the solvation chain segments is improved, and the dispersion effect of inorganic fillers is improved.
The polyether amine in the hyper-dispersant is an anchoring main chain, and the polyester is a solvating chain segment, so that the hyper-dispersant has better solubility with most of coatings in the market, and the steric hindrance effect of the solvating chain is improved. The comb-shaped polymer hyperdispersant prepared by the invention is applied to inorganic filler dispersion in the coating, can effectively reduce the viscosity of the coating, improves the leveling property of the coating, and is beneficial to production and application.
Drawings
FIG. 1 is a chart showing the infrared absorption spectrum of the linear polyetheramine PEA1 prepared in example 1, 0.8, and the hyperdispersant prepared in examples 1-3;
FIG. 2 is a nuclear magnetic resonance spectrum of the hyperdispersant prepared in examples 1-3.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
The preparation method of the hyper-dispersant comprises the following steps:
(1) 1.763g (20 mmol) of N, N-dimethylethylenediamine was dissolved in 15mL of ethanol solution in a reactor, 3.232g (16 mmol) of 1, 4-butanediol diglycidyl ether was added under nitrogen protection, and the temperature was raised to 40℃for reaction for 24 hours. After the reaction is finished, the mixture is concentrated by rotary evaporation and then precipitated by normal hexane, and dried for 24 hours by a vacuum oven to obtain light yellow viscous liquid PEA1:0.8, namely linear polyether amine, with the yield of 84.8 percent.
(2) Adding 0.313g of PEA1:0.8 and 2.85g of epsilon-caprolactone prepared in the step (1) into a reactor, heating to 130 ℃ under nitrogen atmosphere, adding 0.03g of stannous octoate, reacting at constant temperature for 6 hours, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24 hours by using a vacuum oven to obtain yellow waxy solid PEA1:0.8-PCL10, namely the hyper-dispersant, wherein the yield is 68.7%.
Example 2
The preparation method of the hyper-dispersant comprises the following steps:
(1) Step (1) is the same as in example;
(2) Adding 0.313g of PEA1:0.8 and 5.7g of epsilon-caprolactone prepared in the step (1) into a reactor, heating to 130 ℃ under nitrogen atmosphere, adding 0.06g of stannous octoate, reacting at constant temperature for 6 hours, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24 hours by using a vacuum oven to obtain yellow waxy solid PEA1:0.8-PCL20, namely the hyper-dispersant, wherein the yield is 66.3%.
Example 3
The preparation method of the hyper-dispersant comprises the following steps:
(1) Step (1) is the same as in example;
(2) Adding 0.313g of PEA1:0.8 and 8.55g of epsilon-caprolactone prepared in the step (1) into a reactor, heating to 130 ℃ under nitrogen atmosphere, adding 0.09g of stannous octoate, reacting at constant temperature for 6 hours, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24 hours by using a vacuum oven to obtain yellow waxy solid PEA1:0.8-PCL30, namely the hyper-dispersant, wherein the yield is 69.1%.
FIG. 1 is a chart showing the infrared absorption spectrum of the linear polyetheramine PEA1 prepared in example 1, 0.8 and the hyperdispersant prepared in examples 1 to 3. 3300cm -1 The linear polyether amine PEA1:0.8 is provided with a stretching vibration peak of an-OH bond, and with the linear polyether amine PEA1:0.8, ring-opening polymerization of epsilon-caprolactone is initiated, and the distance is 1728cm -1 The stretching vibration peak of C=O on the polycaprolactone side chain appears, which indicates the successful access of the polycaprolactone side chain, and the stretching vibration peak of the-OH bond is weakened due to the access of the polycaprolactone, which indicates the successful synthesis of the comb-shaped hyper-dispersant accessed into the polycaprolactone solvation chain.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the hyperdispersant prepared in examples 1-3. The polymerization degree of polycaprolactone of PEA1:0.8-PCL10, PEA1:0.8-PCL20 and PEA1:0.8-PCL30 is respectively 10.65, 19.18 and 21.64, which are calculated by peak areas and correspond to protons on one methylene group in the polycaprolactone chain at delta=1.29 and correspond to protons beside the terminal hydroxyl group of the polycaprolactone chain at delta=3.64.
Example 4
The preparation method of the hyper-dispersant comprises the following steps:
(1) 1.763g (20 mmol) of N, N-dimethylethylenediamine was dissolved in 15mL of ethanol solution in a reactor, 3.636g (18 mmol) of 1, 4-butanediol diglycidyl ether was added under nitrogen protection, and the temperature was raised to 40℃for reaction for 24 hours. After the reaction is finished, the mixture is concentrated by rotary evaporation and then precipitated by normal hexane, and dried for 24 hours by a vacuum oven to obtain light yellow viscous liquid PEA1:0.9, namely linear polyether amine, with the yield of 85.9 percent.
(2) Adding 0.338g of PEA1:0.9 and 5.7g of epsilon-caprolactone prepared in the step (1) into a reactor, heating to 130 ℃ under nitrogen atmosphere, adding 0.06g of stannous octoate, reacting at constant temperature for 6 hours, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24 hours by using a vacuum oven to obtain yellow waxy solid PEA1:0.9-PCL20, namely the hyper-dispersant, wherein the yield is 68.4%.
Example 5
The preparation method of the hyper-dispersant comprises the following steps:
(1) 1.763g (20 mmol) of N, N-dimethylethylenediamine was dissolved in 15mL of ethanol solution in a reactor, 2.828g (14 mmol) of 1, 4-butanediol diglycidyl ether was added under nitrogen protection, and the temperature was raised to 40℃to react for 24 hours. After the reaction is finished, the mixture is concentrated by rotary evaporation and then precipitated by normal hexane, and dried for 24 hours by a vacuum oven to obtain light yellow viscous liquid PEA1:0.7, namely linear polyether amine, with the yield of 83.5 percent.
(2) Adding 0.288g of PEA1:0.7 and 5.7g of epsilon-caprolactone prepared in the step (1) into a reactor, heating to 130 ℃ under nitrogen atmosphere, adding 0.06g of stannous octoate, reacting at constant temperature for 6 hours, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24 hours by using a vacuum oven to obtain yellow waxy solid PEA1:0.7-PCL20, namely the hyper-dispersant, wherein the yield is 70.3%.
Example 6
The preparation method of the hyper-dispersant comprises the following steps:
(1) 1.763g (20 mmol) of N, N-dimethylethylenediamine was dissolved in 15mL of ethanol solution in a reactor, 3.68g (16 mmol) of 1, 6-hexanediol diglycidyl ether was added under nitrogen protection, and the temperature was raised to 40℃to react for 24 hours. After the reaction is finished, the mixture is concentrated by rotary evaporation and then precipitated by normal hexane, and dried for 24 hours by a vacuum oven to obtain light yellow viscous liquid PEA'1:0.8, namely linear polyetheramine, and the yield is 84.3 percent.
(2) Adding 0.34g of PEA '1:0.8 and 5.7g of epsilon-caprolactone prepared in the step (1) into a reactor, heating to 130 ℃ under nitrogen atmosphere, adding 0.06g of stannous octoate, reacting at constant temperature for 6 hours, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24 hours by using a vacuum oven to obtain yellow waxy solid PEA'1:0.8-PCL20, namely the hyper-dispersant, wherein the yield is 67.7%.
Example 7
The preparation method of the hyper-dispersant comprises the following steps:
(1) Step (1) is the same as in example;
(2) Adding 0.313g of PEA1:0.8 and 5g of gamma-valerolactone prepared in the step (1) into a reactor, heating to 130 ℃ under the nitrogen atmosphere, adding 0.06g of stannous octoate, reacting at constant temperature for 6h, cooling at room temperature after the reaction is finished, adding chloroform for dissolving, precipitating with anhydrous diethyl ether, repeatedly dissolving and precipitating for 3 times, and drying for 24h by using a vacuum oven to obtain yellow waxy solid PEA1:0.8-PVL20, namely the hyper-dispersant, wherein the yield is 65.7%.
Application example 1
A preparation method of the light-cured coating containing the hyperdispersant comprises the following steps: 0.5 part of PEA1 obtained in example 2, 0.8-PCL20,0.5 part of defoamer BYK-530,0.5 part of flatting agent BYK-306, 32 parts of polyurethane acrylic ester and 54 parts of reactive diluent are stirred at normal temperature to be homogeneous, then 4 parts of photoinitiator 1173 and 10 parts of silicon dioxide extinction powder OK500 are added, and stirring is continued for 10 minutes at a rotating speed of 1500r/min in a dark place, so that the dispersed photocureable coating is obtained.
Application example 2
A preparation method of the light-cured coating containing the hyperdispersant comprises the following steps: 0.5 part of PEA1 obtained in example 5, 0.7-PCL20,0.5 part of defoamer BYK-530,0.5 part of flatting agent BYK-306, 32 parts of polyurethane acrylic ester and 54 parts of reactive diluent are stirred at normal temperature to be homogeneous, then 4 parts of photoinitiator 1173 and 10 parts of silicon dioxide extinction powder OK500 are added, and stirring is continued for 10 minutes at a rotating speed of 1500r/min in a dark place, so that the dispersed photocureable coating is obtained.
Application example 3
A preparation method of the light-cured coating containing the hyperdispersant comprises the following steps: 0.5 part of PEA1 obtained in example 2, 0.8-PCL20,0.5 part of defoamer BYK-530,0.5 part of flatting agent BYK-306, 32 parts of polyurethane acrylic ester and 54 parts of reactive diluent are stirred at normal temperature to be homogeneous, then 4 parts of photoinitiator 1173 and 10 parts of mica filler are added, and stirring is continued for 10 minutes at a rotating speed of 1500r/min in a dark place, so that the dispersed photocureable coating is obtained.
Application example 4
A preparation method of the light-cured coating containing the hyperdispersant comprises the following steps: 0.5 part of PEA1 obtained in example 2, 0.8-PCL20,0.5 part of defoamer BYK-530,0.5 part of flatting agent BYK-306, 32 parts of polyurethane acrylic ester and 54 parts of reactive diluent are stirred at normal temperature to be homogeneous, then 4 parts of photoinitiator 1173 and 10 parts of titanium dioxide filler are added, and stirring is continued for 10 minutes at a rotating speed of 1500r/min in a dark place, so that the dispersed photocureable coating is obtained.
Application example 5
A preparation method of the light-cured coating containing the hyperdispersant comprises the following steps: 0.5 part of PEA1 obtained in example 2, 0.8-PCL20,0.5 part of defoamer BYK-530,0.5 part of flatting agent BYK-306, 32 parts of polyurethane acrylic ester and 54 parts of reactive diluent are stirred at normal temperature to be homogeneous, then 4 parts of photoinitiator 1173 and 10 parts of calcium carbonate filler are added, and stirring is continued for 10 minutes at a rotating speed of 1500r/min in a dark place, so that the dispersed photocureable coating is obtained.
Comparative example 1 was used
The difference from application example 1 is that the hyperdispersant was not added to application comparative example 1.
Comparative example 2 was used
The difference from application example 1 is that the commercial hyperdispersant BYK2159 was added in comparative example 2.
Test example:
(1) Paint viscosity test
The coatings of application examples 1 to 2 and application comparative example 1 and application comparative example 2 were tested for viscosity change at different shear rates using a rotary rheometer, and the results are shown in table 1.
TABLE 1
Because the paint with poor filler dispersion is easy to generate flocculation phenomenon, the paint has larger viscosity under low shear rate, and the flocculation is broken and the viscosity is gradually reduced along with the increase of the shear rate, so that the obvious shear thinning phenomenon is presented. Thus, as can be seen from Table 1, the viscosity of the coating added with the hyperdispersant of the present invention is significantly reduced at low shear rate, and the coatings of application example 1 and application example 2 exhibit Newtonian fluid characteristics, and exhibit good dispersion properties.
Application examples 3-5 after the comb-shaped hyperdispersant of the invention is added, no obvious shear thinning phenomenon exists, newtonian fluid characteristics are presented, and good dispersion performance of the hyperdispersant is presented.
(2) Paint fineness test
The fineness of the coating was measured according to GB/T1729-2019, and the results are shown in Table 2.
TABLE 2
| Test case | Fineness (um) |
| Comparative example 1 was used | 27 |
| Application example 1 | 23 |
| Application example 2 | 24 |
As can be seen from the table, the filler fineness of the coating added with the hyper-dispersant provided by the invention is obviously reduced compared with that of the coating without the dispersant, which indicates that the dispersant has a better dispersing effect on the filler.
Claims (10)
1. The preparation method of the hyper-dispersant is characterized by comprising the following steps:
(1) The diglycidyl ether compound and the amine compound are used as reaction monomers, and the linear polyether amine is prepared through ring-opening polymerization;
(2) Under the action of a catalyst, the linear polyether amine and the cyclic lactone undergo a ring-opening reaction, and then are purified to prepare the hyper-dispersant.
2. The hyperdispersant of claim 1, wherein in step (1), the diglycidyl ether compound is one of glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether.
3. The hyperdispersant of claim 1, wherein in step (1), the amine compound is one of N, N-dimethylethylenediamine and N, N-dimethylpropanediamine.
4. The hyperdispersant of claim 1, wherein in step (1), the linear polyetheramine is prepared by the following steps: after diglycidyl ether compound, amine compound and ethanol are mixed, the mixture is reacted for 24 to 48 hours at normal temperature, then the temperature is raised to 30 to 60 ℃ for reaction for 24 to 48 hours, and then the mixture is purified to obtain linear polyether amine.
5. The hyperdispersant of claim 4, wherein the molar ratio of diglycidyl ether compound to amine compound is 1:1-1.5; the mass volume concentration of the total mass of the diglycidyl ether compound and the amine compound and the ethanol is 0.1-1.0 g/mL.
6. The hyperdispersant of claim 1, wherein in step (2), the catalyst is one of stannous octoate, dibutyl tin dilaurate, dibutyl tin diacetate.
7. The hyperdispersant of claim 1, wherein in step (2), the cyclic lactone is one of γ -valerolactone, ε -caprolactone.
8. The hyperdispersant of claim 1, wherein in step (2), the mass ratio of linear polyetheramine to cyclic lactone is from 1:3 to 60; the dosage of the catalyst is 0.3-3% of the total mass of the linear polyether amine and the cyclic lactone.
9. The hyperdispersant of claim 1, wherein in step (2), the ring-opening reaction conditions are: reacting for 2-24 h at 120-160 ℃.
10. Use of the hyperdispersant of claim 1, wherein the dispersion of the inorganic filler is used in a photocurable coating; the inorganic filler is one or more of silicon dioxide, diatomite, quartz, silica gel, clay mineral, talcum powder, kaolin, mica, aluminum oxide, calcium carbonate, titanium dioxide, zinc oxide and carbon black.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117362605A (en) * | 2023-11-08 | 2024-01-09 | 武汉中科先进材料科技有限公司 | Bio-based polycaprolactone polyol and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117362605A (en) * | 2023-11-08 | 2024-01-09 | 武汉中科先进材料科技有限公司 | Bio-based polycaprolactone polyol and preparation method thereof |
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