CN112552497B - High-hydroxyl-value polyester resin for extinction type powder coating and preparation method and application thereof - Google Patents
High-hydroxyl-value polyester resin for extinction type powder coating and preparation method and application thereof Download PDFInfo
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- 239000004645 polyester resin Substances 0.000 title claims abstract description 90
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 90
- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 239000000843 powder Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000008033 biological extinction Effects 0.000 title claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 94
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 20
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims abstract description 11
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 11
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000600 sorbitol Substances 0.000 claims abstract description 11
- YNOWBNNLZSSIHM-UHFFFAOYSA-N tris(oxiran-2-ylmethyl) benzene-1,2,4-tricarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 YNOWBNNLZSSIHM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 10
- 239000001361 adipic acid Substances 0.000 claims abstract description 10
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000000376 reactant Substances 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000007142 ring opening reaction Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000004814 polyurethane Substances 0.000 claims description 8
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 6
- -1 tetrakis [ methyl- β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002966 varnish Substances 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (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 belongs to the technical field of powder coating curing agents, and particularly relates to a high-hydroxyl-value polyester resin for a delustering powder coating, and further discloses a preparation method and application thereof. The high hydroxyl value polyester resin for the extinction type powder coating is obtained by polymerizing isophthalic acid, biphenyldicarboxylic acid, adipic acid, neopentyl glycol, sorbitol, 1,4-cyclohexanedimethanol, triglycidyl trimellitate and 12-hydroxystearic acid serving as raw materials. The polyester resin of the invention increases the variety and the difference of active hydroxyl, realizes the reduction of the hydroxyl value of the polyester resin without influencing the extinction effect, thereby overcoming the defects of high hygroscopicity and high cost brought by the polyester resin product with ultrahigh hydroxyl value and having higher application value.
Description
Technical Field
The invention belongs to the technical field of powder coating curing agents, and particularly relates to a high-hydroxyl-value polyester resin for a delustering powder coating, and further discloses a preparation method and application thereof.
Background
The powder coating is 100% solid powder without organic solvent, which is different from oil-based coating and water-based coating, and the powder coating is a novel environment-friendly coating which does not use solvent or water as a dispersion medium but uses air as a dispersion medium, is uniformly coated on the surface of a workpiece and forms a coating film with special purpose after being heated. The powder coating has the advantages of no solvent, no VOC, recoverability, environmental protection, energy conservation, high construction efficiency, high mechanical strength of a coating film, wide application range and the like, and gradually replaces organic solvent type coatings with the advantages of economy, environmental protection, high efficiency, excellent performance and the like, becomes an important development direction in the coating industry, keeps a faster growth rate all the time, and is particularly widely applied in the field of metal surface coating. The polyester powder coating is widely applied to the coating field due to the characteristics of excellent durability, decoration, processing formability and the like.
The polyurethane powder coating is prepared by curing hydroxyl polyester serving as a main raw material and a curing agent containing-NCO groups. Currently, the most commonly used curing agent for polyurethane powder coatings is the B1530 curing system of Degussa (Degussa), which has excellent hardness, leveling property and scratch resistance, but the matting difficulty of the powder coating system is large, and it is difficult to obtain a coating film with low gloss, such as 10-20%, and the application of polyurethane powder coatings is limited.
At present, the most effective method for solving the extinction problem of the compound of the system is to adopt the polyester resin with the ultrahigh hydroxyl value (the hydroxyl value is 280-300 mgKOH/g) and the polyester resin with the ultralow hydroxyl value (the hydroxyl value is 30-50 mgKOH/g) to realize the extinction through a mixing one-step extrusion method, namely, the extinction is realized by utilizing the curing activity difference between the hydroxyl group of the polyester resin with the ultrahigh hydroxyl value (such as the hydroxyl value is 280-300mgKOH/g in Chinese patent CN 103467714A) and the hydroxyl group of the polyester resin with the ultralow hydroxyl value and a curing agent B1530.
However, because the process method needs to use the polyester resin with an ultrahigh hydroxyl value (the hydroxyl value is 280-300 mgKOH/g), the moisture absorption capacity of the polyester resin is too strong due to the overhigh hydroxyl content, and the prepared finished powder coating is easy to agglomerate when stored, thereby influencing the downstream application; moreover, when the ultrahigh hydroxyl value polyester resin is fully cured, a large amount of B1530 curing agent is required, and the B1530 curing agent is almost imported products at present and has extremely high price, so that the cost and the downstream application potential of the matt powder coating are directly influenced. Therefore, how to effectively reduce the hydroxyl value of the polyester resin used to overcome the above defects while ensuring the extinction capability of the powder coating product is always a problem to be solved in the industry, and has a positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high hydroxyl value polyester resin for a delustering powder coating, which can effectively reduce the hydroxyl value of a product to improve the product performance on the basis of meeting the performance requirement of the delustering powder coating;
the second technical problem to be solved by the invention is to improve the preparation method and application of the high hydroxyl value polyester resin for the delustering powder coating.
In order to solve the technical problems, the preparation raw materials of the high hydroxyl value polyester resin for the extinction type powder coating comprise the following components in parts by mole:
specifically, the high hydroxyl value polyester resin for the delustering powder coating further comprises a polymerization catalyst, wherein the polymerization catalyst comprises monobutyl tin oxide;
the amount of the polymerization catalyst is 0.08-0.2mol% of the total molar amount of the raw materials for preparation.
Specifically, the high hydroxyl value polyester resin for the delustering powder coating further comprises an antioxidant, wherein the antioxidant comprises tetra [ methyl-beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester;
the dosage of the antioxidant is 0.2-0.5mol% of the total molar weight of the raw materials.
The invention also discloses a method for preparing the high hydroxyl value polyester resin for the delustering powder coating, which comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting for later use; adding the isophthalic acid, the biphenyldicarboxylic acid, the adipic acid and the catalyst into the mixed material according to the formula ratio, carrying out heat preservation reaction at 200-210 ℃ under a protective atmosphere, and stopping the reaction when the acid value of the system is reduced to 120-150 mgKOH/g;
(2) Continuously adding 1,4-cyclohexanedimethanol in a formula amount, uniformly mixing, carrying out polymerization reaction at 220-230 ℃, adding the antioxidant in a formula amount when the acid value of a system is reduced to 70-80mgKOH/g, starting a vacuum system for vacuum polycondensation reaction, stopping the reaction when the acid value of a reactant is 20-30mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 140-150 ℃, adding the triglycidyl trimellitate in a formula amount to continue to carry out end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of a reactant is less than 5mgKOH/g, and continuing to carry out epoxy ring-opening grafting reaction at 140-150 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 140-150 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 150-180 mgKOH/g;
(4) Collecting reactants, removing water in the system, discharging at high temperature while the reactants are hot, cooling, crushing and granulating to obtain the catalyst.
Specifically, in the step (1), in the heat preservation reaction step, the whole system is controlled to gradually increase the temperature at 8-10 ℃/h to 200-210 ℃ for reaction.
Specifically, in the step (2), in the polymerization reaction step, the whole system is controlled to gradually increase the temperature at 6-8 ℃/h to 220-230 ℃ for reaction.
Specifically, in the step (2), the vacuum degree in the vacuum polycondensation step is-0.097 to-0.099 Mpa.
The invention also discloses application of the high hydroxyl value polyester resin for the delustering powder coating to preparation of a B1530 curing system polyurethane powder coating.
The invention also discloses a B1530 curing system polyurethane powder coating, namely the polyester resin for preparing the powder coating comprises the high hydroxyl value polyester resin and the low hydroxyl value polyester resin.
Specifically, the hydroxyl value of the low-hydroxyl-value polyester resin is 30-50mgKOH/g.
The high hydroxyl value polyester resin for the delustering powder coating is obtained by polymerizing isophthalic acid, diphenic acid, adipic acid, neopentyl glycol, sorbitol, 1,4-cyclohexanedimethanol, triglycidyl trimellitate and 12-hydroxystearic acid serving as raw materials, wherein the hydroxyl value of a polyester resin product is controlled to be 150-180mgKOH/g, the epoxy equivalent is more than 3000g/mol, and the acid value is lower than 5mgKOH/g. Aiming at the extinction problem of B1530 system powder coating, the high hydroxyl value polyester resin for the extinction type powder coating is designed and synthesized from the aspect of introducing different hydroxyl structures, such as vicinal diol hydroxyl left by sorbitol, cyclic branched hydroxyl brought by 1,4-cyclohexanedimethanol, vicinal hydroxyl containing long branched hydroxyl brought by 12-hydroxystearic acid and vicinal hydroxyl brought by triglycidyl trimellitate and opened by glycidyl ester poaching, so that the polyester product contains active hydroxyl with large activity difference. Therefore, although the hydroxyl value range of the polyester resin product is reduced, the hydroxyl group structure of the polyester resin product is different, the curing activity of the polyester resin product is greatly different from that of the B1530 curing agent, the hydroxyl activity difference is further increased after the polyester resin product is mixed with the ultra-low hydroxyl value polyester resin (the hydroxyl value is 30-50 mgKOH/g), in addition, the compatibility of two polyester resin systems is poor, the activity and the dispersibility of the polyester resin functional groups are not uniform, the compatibility is strong, the gloss of the coating film after the polyester resin product is cured with the isocyanate curing agent B1530 is low, a low-gloss coating film with the gloss of 10-20% is easily obtained, and other properties of the coating film can completely meet various requirements of powder coatings. The polyester resin of the invention increases the variety and the difference of active hydroxyl, realizes the reduction of the hydroxyl value of the polyester resin without influencing the extinction effect, thereby overcoming the defects of high hygroscopicity and high cost brought by the polyester resin product with ultrahigh hydroxyl value and having higher application value.
Detailed Description
Example 1
The high hydroxyl value polyester resin for the extinction type powder coating comprises the following components in parts by mole:
monobutyltin oxide in an amount of 0.08mol% based on the total molar amount of the starting materials;
antioxidant 1010 in an amount of 0.1mol% based on the total molar amount of the raw materials for preparation.
The preparation method of the high hydroxyl value polyester resin for the delustering powder coating comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting at 130 ℃ for later use; then adding the m-phthalic acid, the diphenic acid, the adipic acid and the catalyst in a formula amount into the mixed material, gradually heating to react to 210 ℃ at 8 ℃/h under a protective atmosphere to carry out heat preservation reaction, and stopping the reaction when the acid value of a system is reduced to 122 mgKOH/g;
(2) Continuously adding the 1,4-cyclohexanedimethanol with the formula amount, uniformly mixing, gradually heating to 225 ℃ at 6 ℃/h for polymerization, adding the antioxidant with the formula amount when the acid value of the system is reduced to 71mgKOH/g, starting a vacuum system, controlling the vacuum degree to be-0.098 Mpa for vacuum polycondensation, stopping the reaction when the acid value of the reactant is 25mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 145 ℃, adding the triglycidyl trimellitate in a formula amount to continue to carry out end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of a reactant is less than 5mgKOH/g, and continuing to carry out epoxy ring-opening grafting reaction at 145 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the distilled water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 145 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 155 mgKOH/g;
(4) And then, fully removing water in the system under the condition of decompression (vacuum degree of-0.097 Mpa) at 145 ℃, discharging at high temperature when the water content is lower than 0.5%, cooling the polyester resin by using a steel belt with condensed water, crushing and granulating to obtain the polyester resin.
Through detection, the polyester resin prepared in the embodiment is colorless transparent particles, the hydroxyl value of the product is 153mgKOH/g, and the softening point is 101 ℃.
Example 2
The high hydroxyl value polyester resin for the extinction type powder coating comprises the following components in parts by mole:
monobutyltin oxide in an amount of 0.2mol% based on the total molar amount of the starting materials;
antioxidant 1010 in an amount of 0.2mol% based on the total molar amount of the raw materials for preparation.
The preparation method of the high hydroxyl value polyester resin for the delustering powder coating comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting at the temperature of below 130 ℃ for later use; adding the isophthalic acid, the biphenyldicarboxylic acid, the adipic acid and the catalyst into the mixed material according to the formula ratio, gradually heating to react to 205 ℃ at a speed of 10 ℃/h under a protective atmosphere to perform a heat preservation reaction, and stopping the reaction when the acid value of the system is reduced to 130 mgKOH/g;
(2) Continuously adding the 1,4-cyclohexanedimethanol with the formula amount, uniformly mixing, gradually heating to 220 ℃ at 8 ℃/h for polymerization reaction, adding the antioxidant with the formula amount when the acid value of the system is reduced to 76mgKOH/g, starting a vacuum system, controlling the vacuum degree to be-0.098 Mpa for vacuum polycondensation reaction, stopping the reaction when the acid value of a reactant is 29mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 140 ℃, adding the triglycidyl trimellitate in a formula amount to continue to perform end capping reaction for 1-3h, adding the 12-hydroxystearic acid in the formula amount when the acid value of the reactant is less than 5mgKOH/g, and continuing to perform epoxy ring-opening grafting reaction at 140 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the distilled water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 140 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 170 mgKOH/g;
(4) Collecting reactant, fully removing water in the system under the condition of decompression (vacuum degree of-0.098 Mpa) at 140 ℃, discharging at high temperature when the water content is lower than 0.5%, cooling the polyester resin by a steel belt with condensed water, crushing and granulating to obtain the polyester resin.
Through detection, the polyester resin prepared in the embodiment is colorless transparent particles, the hydroxyl value of the product is 170mgKOH/g, and the softening point is 110 ℃.
Example 3
The high hydroxyl value polyester resin for the extinction type powder coating comprises the following components in parts by mole:
monobutyl tin oxide, the amount of which is 0.15mol% of the total molar amount of the preparation raw materials;
antioxidant 1010 in an amount of 0.15mol% based on the total molar amount of the raw materials for preparation.
The preparation method of the high hydroxyl value polyester resin for the delustering powder coating comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting at the temperature of below 130 ℃ for later use; adding the isophthalic acid, the diphenic acid, the adipic acid and the catalyst into the mixed material according to the formula ratio, gradually heating to 200 ℃ at a speed of 9 ℃/h under a protective atmosphere for carrying out heat preservation reaction, and stopping the reaction when the acid value of the system is reduced to 148 mgKOH/g;
(2) Continuously adding the 1,4-cyclohexanedimethanol with the formula amount, uniformly mixing, gradually heating to 230 ℃ at the speed of 7 ℃/h for polymerization reaction, adding the antioxidant with the formula amount when the acid value of the system is reduced to 80mgKOH/g, starting a vacuum system, controlling the vacuum degree to be-0.099 Mpa for vacuum polycondensation reaction, stopping the reaction when the acid value of a reactant is 22mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 150 ℃, adding the triglycidyl trimellitate in a formula amount to continue to carry out end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of a reactant is less than 5mgKOH/g, and continuing to carry out epoxy ring-opening grafting reaction at 150 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the distilled water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 150 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 178 mgKOH/g;
(4) Collecting reactant, removing water in the system under reduced pressure (vacuum degree-0.099 Mpa) at 150 deg.C, discharging at high temperature when water content is less than 0.5%, cooling polyester resin with steel belt with condensed water, crushing, and granulating.
Through detection, the polyester resin product prepared by the embodiment is colorless transparent particles, the hydroxyl value is 178mgKOH/g, and the softening point is 115 ℃.
Example 4
The high hydroxyl value polyester resin for the extinction type powder coating comprises the following components in parts by mole:
monobutyltin oxide in an amount of 0.12mol% based on the total molar amount of the starting materials;
antioxidant 1010 in an amount of 0.2mol% based on the total molar amount of the raw materials for preparation.
The preparation method of the high hydroxyl value polyester resin for the delustering powder coating comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting at the temperature of below 130 ℃ for later use; adding the isophthalic acid, the diphenic acid, the adipic acid and the catalyst into the mixed material according to the formula ratio, gradually heating to 204 ℃ at a speed of 9 ℃/h under a protective atmosphere for carrying out heat preservation reaction, and stopping the reaction when the acid value of the system is reduced to 135 mgKOH/g;
(2) Continuously adding the 1,4-cyclohexanedimethanol with the formula amount, uniformly mixing, gradually heating to 230 ℃ at the speed of 7 ℃/h for polymerization, adding the antioxidant with the formula amount when the acid value of the system is reduced to 74mgKOH/g, starting a vacuum system, controlling the vacuum degree to be-0.098 Mpa for vacuum polycondensation, stopping the reaction when the acid value of the reactant is 27mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 142 ℃, adding the triglycidyl trimellitate in a formula amount to continue to carry out end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of a reactant is less than 5mgKOH/g, and continuing to carry out epoxy ring-opening grafting reaction at 142 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the distilled water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 142 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 161 mgKOH/g;
(4) Collecting reactant, fully removing water in the system under the condition of decompression (vacuum degree of-0.099 Mpa) at 142 ℃, discharging at high temperature when the water content is lower than 0.5%, cooling polyester resin by a steel belt with condensed water, crushing and granulating to obtain the polyester resin.
Through detection, the polyester resin product prepared in the embodiment is colorless transparent particles, the hydroxyl value is 161mgKOH/g, and the softening point is 114 ℃.
Example 5
The high hydroxyl value polyester resin for the extinction type powder coating comprises the following components in parts by mole:
monobutyltin oxide in an amount of 0.18mol% based on the total molar amount of the starting materials;
antioxidant 1010 in an amount of 0.3mol% based on the total molar amount of the raw materials for preparation.
The preparation method of the high hydroxyl value polyester resin for the delustering powder coating comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting at the temperature of below 130 ℃ for later use; adding the isophthalic acid, the diphenic acid, the adipic acid and the catalyst into the mixed material according to the formula ratio, gradually heating to react to 208 ℃ at a speed of 10 ℃/h under a protective atmosphere to perform heat preservation reaction, and stopping the reaction when the acid value of the system is reduced to 126 mgKOH/g;
(2) Continuously adding 1,4-cyclohexanedimethanol in a formula amount, uniformly mixing, gradually heating to 223 ℃ at 8 ℃/h for polymerization reaction, adding the antioxidant in the formula amount when the acid value of the system is reduced to 78mgKOH/g, then starting a vacuum system, controlling the vacuum degree to be-0.097 Mpa for vacuum polycondensation reaction, stopping the reaction when the acid value of a reactant is 25mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 146 ℃, adding the triglycidyl trimellitate in a formula amount to continue to perform end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of the reactant is less than 5mgKOH/g, and continuing to perform epoxy ring-opening grafting reaction at 146 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the distilled water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 146 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 164 mgKOH/g;
(4) Collecting reactant, removing water in the system under the condition of decompression (vacuum degree of-0.097 Mpa) at 146 ℃, discharging at high temperature when the water content is lower than 0.5%, cooling polyester resin with steel belt with condensed water, crushing and granulating to obtain the product.
Through detection, the polyester resin product prepared by the embodiment is colorless transparent particles, the hydroxyl value is 164mgKOH/g, and the softening point is 108 ℃.
Comparative example 1
The polyester resin of the comparative example is the polyester resin obtained according to example 1 in Chinese patent CN103467714A, and the hydroxyl value of the product is 295mgKOH/g.
Comparative example 2
The polyester resin of this comparative example is the polyester resin obtained in accordance with example 1 of the Chinese patent CN103467714A, and the hydroxyl value of the product is 295mgKOH/g, but the amount of the B1530 curing agent is increased from 130g to 200g in the following experimental powder coating formulation.
Examples of the experiments
The polyester resins prepared in examples 1 to 5 above, respectively, were formulated according to the existing powder coating formulations, generally as follows in parts by weight:
the ultra-low hydroxyl value polyester resin is a product of Anhui Shenjian new material GmbH, model SJ1140, and the hydroxyl value of the product is 42mgKOH/g; b1530 the curing agent adopts the product of Yingchuangdegusan.
And the polyester resin obtained in example 1 of China patent CN103467714A (hydroxyl value of the product is 295 mgKOH/g) is used as a comparative example, as described in the above comparative examples 1-2, the amount of B1530 in comparative example 1 is 130g, and the amount of B1530 in comparative example 2 is 200g.
Preparing a coating layer: mixing the materials according to the formula of the powder coating, extruding, tabletting and crushing by using a double-screw extruder, and then crushing and sieving the tablets to prepare the powder coating. The powder coating is sprayed on the galvanized iron substrate after surface treatment by an electrostatic spray gun, the film thickness is 50-60 mu m, and the powder coating is cured at 200 ℃/15min, thus obtaining the coating.
The detection basis of the coating indexes is as follows: GB/T21776-2008 'Standard guide for testing powder coating and coating thereof', the test standard of adhesion is carried out according to GB/T9286-1998 'test of drawing grid of colored paint and varnish paint film', and moisture absorption performance according to GB/T20312-2012 'method for measuring moisture absorption performance of moisture and heat performance of building materials and products', 30g of sample is taken (the moisture content of the sample before testing is lower than 0.5%, the appearance is loose powder and no agglomeration phenomenon) and is uniformly paved on a glass dish to be tested, wherein the temperature of a constant temperature and humidity box is 30 ℃, the humidity is 45%, and the time is 7 days.
The results of the film properties test are shown in table 1 below.
TABLE 1 product film coating Performance and moisture absorption Performance results of the finished powder coating
Therefore, the powder coating product prepared by mixing the high-hydroxyl polyester resin and the commercially available low-hydroxyl polyester resin has better overall performance, a smooth coating film and lower gloss which is 10-20%, and the B1530 curing agent in the formula has less usage amount, so that the whole powder coating formula has lower cost; meanwhile, the hydroxyl group of the polyester resin with the ultrahigh hydroxyl value is reduced, so that the performance is relatively excellent in a moisture absorption test for 7 days, and no agglomeration phenomenon exists.
The scheme of the comparative example 1 adopts the traditional polyester resin with the ultrahigh hydroxyl value, and because of excessive hydroxyl, in the powder coating formula of the experimental example, because the B1530 curing agent is insufficient, the curing is incomplete, the appearance and the impact resistance of a coating film are poor, the gloss cannot be effectively reduced to be below 30 percent, the phenomenon of severe light loss occurs after water boiling, and the phenomenon of slight agglomeration occurs because of high moisture absorption rate in a moisture absorption test for 7 days.
Compared with the scheme of the comparative example 1, the scheme of the comparative example 2 adopts the traditional polyester resin with the ultrahigh hydroxyl value, increases the dosage of the curing agent B1530, can be completely cured, meets the requirements on the appearance and the impact resistance of a coating film, achieves the gloss of 22 percent, and has no obvious change in water boiling; however, slight caking occurred in the 7-day hygroscopicity test because the hygroscopicity was still high. Therefore, the performance of the product has great influence on the storage period, and is not beneficial to daily transportation and storage.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The high hydroxyl value polyester resin for the extinction type powder coating is characterized by comprising the following components in parts by mole:
the high hydroxyl value polyester resin for the extinction type powder coating also comprises a polymerization catalyst and an antioxidant;
the preparation method of the high hydroxyl value polyester resin for the delustering powder coating comprises the following steps:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting for later use; adding the isophthalic acid, the biphenyldicarboxylic acid, the adipic acid and the catalyst into the mixed material according to the formula ratio, carrying out heat preservation reaction at 200-210 ℃ under a protective atmosphere, and stopping the reaction when the acid value of the system is reduced to 120-150 mgKOH/g;
(2) Continuously adding 1,4-cyclohexanedimethanol in a formula amount, uniformly mixing, carrying out polymerization reaction at 220-230 ℃, adding the antioxidant in a formula amount when the acid value of a system is reduced to 70-80mgKOH/g, starting a vacuum system for vacuum polycondensation reaction, stopping the reaction when the acid value of a reactant is 20-30mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 140-150 ℃, adding the triglycidyl trimellitate in a formula amount to continue to carry out end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of a reactant is less than 5mgKOH/g, and continuing to carry out epoxy ring-opening grafting reaction at 140-150 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 140-150 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 150-180 mgKOH/g;
(4) Collecting reactants, removing water in the system, discharging at high temperature while the reactants are hot, cooling, crushing and granulating to obtain the catalyst.
2. A high hydroxyl number polyester resin for flatting powders according to claim 1 wherein the polymerization catalyst comprises monobutyl tin oxide;
the amount of the polymerization catalyst is 0.08-0.2mol% of the total molar amount of the raw materials for preparation.
3. A high hydroxyl number polyester resin for a matted powder coating according to claim 1 or 2, wherein said antioxidant comprises tetrakis [ methyl- β - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, antioxidant 1010;
the dosage of the antioxidant is 0.1-0.2mol% of the total molar weight of the raw materials.
4. A process for preparing a high hydroxyl number polyester resin for flatting powder coatings according to any one of claims 1 to 3, comprising the steps of:
(1) Uniformly mixing the neopentyl glycol and the sorbitol according to the formula amount, and heating and melting for later use; adding the isophthalic acid, the diphenic acid, the adipic acid and the catalyst in a formula amount into the mixed material, carrying out heat preservation reaction at 200-210 ℃ under a protective atmosphere, and stopping the reaction when the acid value of a system is reduced to 120-150 mgKOH/g;
(2) Continuously adding 1,4-cyclohexanedimethanol in a formula amount, uniformly mixing, carrying out polymerization reaction at 220-230 ℃, adding the antioxidant in a formula amount when the acid value of a system is reduced to 70-80mgKOH/g, starting a vacuum system for vacuum polycondensation reaction, stopping the reaction when the acid value of a reactant is 20-30mgKOH/g, and closing the vacuum system;
(3) Cooling the system to 140-150 ℃, adding the triglycidyl trimellitate in a formula amount to continue to carry out end capping reaction, adding the 12-hydroxystearic acid in the formula amount when the acid value of a reactant is less than 5mgKOH/g, and continuing to carry out epoxy ring-opening grafting reaction at 140-150 ℃; when the acid value of the system reactant is less than 3mgKOH/g, adding the water with the formula amount, and continuing to perform an epoxy ring-opening reaction at 140-150 ℃; stopping the reaction when the epoxy equivalent of the reactant is more than 3000g/mol and the hydroxyl value is 150-180 mgKOH/g;
(4) Collecting reactants, removing water in the system, discharging at high temperature while the reactants are hot, cooling, crushing and granulating to obtain the catalyst.
5. A preparation method of high hydroxyl value polyester resin for a delustring type powder coating according to claim 4, wherein in the step (1), in the heat preservation reaction step, the whole system is controlled to gradually raise the temperature at 8-10 ℃/h to 200-210 ℃ for reaction.
6. A process for preparing a high hydroxyl value polyester resin for a flatting powder coating according to claim 4 or 5, wherein in the step (2), the polymerization step is carried out while controlling the whole system to gradually increase the temperature at 6-8 ℃/h to 220-230 ℃.
7. A process for producing a high hydroxyl value polyester resin for a matting powder coating according to claim 6, wherein in the step (2), the degree of vacuum in the vacuum polycondensation step is from-0.097 to-0.099 MPa.
8. Use of a high hydroxyl number polyester resin for flatting powder coatings according to any of claims 1 to 3 for the preparation of B1530 curing system polyurethane powder coatings.
9. A B1530 cure system polyurethane powder coating wherein the polyester resin from which the powder coating is made comprises the high hydroxyl polyester resin of any of claims 1-3, and a low hydroxyl polyester resin.
10. The B1530 curing system polyurethane powder coating of claim 9, wherein the low hydroxyl polyester resin has a hydroxyl value of 30 to 50mgKOH/g.
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Denomination of invention: A high hydroxyl value polyester resin for dull powder coatings and its preparation method and application Effective date of registration: 20231023 Granted publication date: 20230331 Pledgee: China Postal Savings Bank Limited by Share Ltd. Shexian branch Pledgor: HUANGSHAN ZHENGJIE NEW MATERIALS Co.,Ltd. Registration number: Y2023980062268 |