CN113549205B - Low-cost high-temperature-resistant polyester resin for powder coating and preparation method thereof - Google Patents
Low-cost high-temperature-resistant polyester resin for powder coating and preparation method thereof Download PDFInfo
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- CN113549205B CN113549205B CN202110828226.0A CN202110828226A CN113549205B CN 113549205 B CN113549205 B CN 113549205B CN 202110828226 A CN202110828226 A CN 202110828226A CN 113549205 B CN113549205 B CN 113549205B
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 62
- 239000004645 polyester resin Substances 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 9
- 239000001361 adipic acid Substances 0.000 claims abstract description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 68
- 239000011541 reaction mixture Substances 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000004321 preservation Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 14
- 238000005070 sampling Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 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 group 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
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 abstract description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 229920005749 polyurethane resin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- 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
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
-
- 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
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
Provides a low-cost high-temperature-resistant polyester resin for powder coating and a preparation method thereof. When the polyester resin is prepared, cyanuric acid, 1, 4-cyclohexanedicarboxylic acid and epichlorohydrin are used for a prepolymerization reaction under the action of a catalyst, adipic acid is added for a chain extension reaction to obtain a chain segment intermediate with moderate functionality, neopentyl glycol and terephthalic acid are added for a high-temperature chain extension reaction, and isophthalic acid is used for end capping to obtain a low-cost and high-temperature resistant polyester resin product for the powder coating. The polyester molecular chain segment of the polyester resin contains flame-retardant elements of nitrogen and chlorine atoms; after the modified polyurethane resin and curing agent triglycidyl isocyanurate (TGIC) are cured, the coating film has excellent adhesive force and oil resistance, excellent high-temperature yellowing resistance, certain flame retardant property and low cost, and has wide market application prospect.
Description
Technical Field
The invention belongs to the field of powder coatings, and particularly relates to a low-cost high-temperature-resistant polyester resin for a powder coating and a preparation method thereof.
Background
More and more powder coatings are used in the field of common high temperature resistance, such as laboratory ovens, automobile engine protection plates, medium density fiberboard cabinet table top coating films and the like, all need to use powder coating products with requirements on high temperature resistance, generally can resist the highest temperature of 230 ℃, and do not need to resist the high temperature to 300 ℃.
At present, the high-temperature-resistant powder coating has high cost mainly because the used polyester generally contains fluorine raw materials with high cost, or organic silicon resin modification and the like, the cost is high, or the preparation process is too complex, elements containing fluorine, silicon and the like in the product are easily incompatible with other components in the powder coating, so that the coating film has defects, the market popularization and application are seriously influenced, and particularly, the ultrahigh cost is not suitable for being used in the common high-temperature-resistant field.
Along with the improvement of common high temperature resistance such as the requirement of the conventional oven industry on the high temperature resistance of common powder coatings, the common powder coatings are basically not provided with flame retardant property, and if the powder coatings are used for coating films on furniture such as Medium Density Fiberboard (MDF) and other materials, the powder coatings have potential risk of fire hazard and have certain potential safety hazards.
Therefore, a new high temperature resistant polyester resin for powder coating and a preparation method thereof are needed to solve the above technical problems.
Disclosure of Invention
The invention provides a low-cost high-temperature-resistant polyester resin for powder coating, which comprises the following raw materials in parts by mole:
the polyester resin further contains 0.05 to 0.12% of a catalyst and 0.05 to 0.1% of an antioxidant, relative to the total molar amount of the above raw materials.
Wherein the catalyst is tetrabutyl titanate; the antioxidant is antioxidant 1010.
Wherein the obtained polyester resin is colorless transparent particles, has an acid value of 24-28mgKOH/g and a softening point of 110-121 ℃.
The invention also provides a preparation method of the low-cost high-temperature-resistant polyester resin for the powder coating, which comprises the following steps:
(1) Adding cyanuric acid, 1, 4-cyclohexanedicarboxylic acid, epichlorohydrin and a catalyst into a reaction kettle according to the formula ratio, and heating to 90-100 ℃ for heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epichlorohydrin;
(3) After no obvious epichlorohydrin is evaporated out (less than 1 drop in 30 s), adding adipic acid with the formula amount, heating to 170-175 ℃, and preserving heat to carry out block polymerization;
(4) Sampling and detecting the acid value of the reaction mixture, adding neopentyl glycol according to the formula amount when the acid value of the reaction mixture is less than 35mgKOH/g, heating to 200-210 ℃ under the protection of nitrogen (preferably 205 ℃) and carrying out heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, adding terephthalic acid with the formula amount, and continuously heating to 235-240 ℃ under the protection of nitrogen to carry out heat preservation reaction;
(6) Adding antioxidant in a formula amount when no obvious small molecule (such as water and the like) distillate is distilled out (less than 1 drop in 30 s) and the acid value of a reactant mixture is less than 18mgKOH/g, and performing vacuum polycondensation;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction on the polyester resin at 235-240 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 22-26mgKOH/g, discharging, cooling, crushing and granulating to obtain the polyester resin.
Wherein, in the step (2), the vacuum degree is between-0.097 and-0.099 Mpa.
Wherein in the step (3), the temperature is gradually increased to 170-175 ℃ at the temperature-increasing rate of 15-18 ℃/h
Wherein, in the step (4), the temperature is gradually increased to 200-210 ℃ (preferably 205 ℃) at the temperature increasing rate of 10-12 ℃/h.
Wherein in the step (5), the temperature is gradually increased to 235-240 ℃ at a heating rate of 10-12 ℃/h.
Wherein, in the step (6), the vacuum degree is maintained at-0.097 to-0.99 MPa when the vacuum polycondensation reaction is performed.
In the step (7), the discharging is discharging at a high temperature while the discharging is hot, and the cooling is cooling by using a steel strip with condensed water.
The invention also provides a high-temperature-resistant powder coating which contains the polyester resin.
The invention has the following beneficial technical effects:
the invention adopts cyanuric acid, 1, 4-cyclohexanedicarboxylic acid and epichlorohydrin to carry out prepolymerization reaction under the action of a catalyst, then adds adipic acid to carry out chain extension reaction to obtain a chain segment intermediate with moderate functionality, then adds neopentyl glycol and terephthalic acid to carry out high-temperature chain extension reaction, and finally adopts a capping agent isophthalic acid to cap, thus obtaining the low-cost polyester resin product for the high-temperature-resistant powder coating.
The polyester molecular chain segment contains flame retardant elements of nitrogen and chlorine atoms, and after the polyester molecular chain segment and curing agent triglycidyl isocyanurate (TGIC) are cured, the adhesion force of a coating film can reach 0 level, the oil resistance is excellent (the surface of the coating film is unchanged after 96 hours of soybean oil immersion), the high-temperature yellowing resistance is excellent (the surface of the coating film is almost unchanged at 250 ℃/24 hours), the flame retardant property is certain (the oxygen index of the coating film can reach more than 28.6 percent and belongs to a flame-retardant grade), the cost is low (special expensive fluorine silicon raw materials are not used, the preparation process is simple), in addition, the acid value of the common TGIC polyester resin is low, the TGIC dosage in a powder coating formula is low, the cost and the sensitization of the powder coating are further reduced, and therefore, the polyester molecular chain segment has a wide market application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The examples do not indicate specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
Example 1
The embodiment provides a polyester resin for a high-temperature-resistant powder coating, and a preparation method of the polyester resin comprises the following steps:
(1) Adding 19 mole parts of cyanuric acid, 11 mole parts of 1, 4-cyclohexanedicarboxylic acid, 135 mole parts of epichlorohydrin and a catalyst tetrabutyl titanate of which the total molar weight is 0.09 percent relative to the total molar weight of the raw materials into a reaction kettle, and heating to 92 ℃ for heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epichlorohydrin under the vacuum degree of-0.097 Mpa;
(3) After no obvious epichlorohydrin is evaporated (less than 1 drop in 30 s), adding 12 mol parts of adipic acid, gradually heating to 173 ℃ at a heating rate of 16 ℃/h, and carrying out block polymerization reaction by keeping the temperature;
(4) Sampling and detecting the acid value of the reaction mixture, adding 14 molar parts of neopentyl glycol when the acid value of the reaction mixture is less than 35mgKOH/g, and gradually heating to 205 ℃ at a heating rate of 11 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, 19 mol parts of terephthalic acid is added, and the temperature is continuously increased to 238 ℃ at the temperature increasing rate of 10 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(6) When no obvious small molecular distillate such as moisture is distilled off (less than 1 drop in 30 s) and the acid value of a reactant mixture is less than 18mgKOH/g, adding 0.08 percent of antioxidant 1010 relative to the total molar weight of raw materials, and carrying out vacuum polycondensation reaction under the vacuum degree of-0.097 Mpa;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding 8 molar parts of isophthalic acid, and continuing to perform end capping reaction on the polyester resin at the temperature of 238 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 24mgKOH/g, discharging at high temperature, cooling by using a steel belt with condensed water, and crushing and granulating to obtain the polyester resin.
The polyester resin obtained was colorless transparent particles in appearance, had an acid value of 25mgKOH/g and a softening point of 116 ℃.
Example 2
The embodiment provides a polyester resin for high-temperature-resistant powder coating, and the preparation method comprises the following steps:
(1) Adding 24 mole parts of cyanuric acid, 7 mole parts of 1, 4-cyclohexanedicarboxylic acid, 123 mole parts of epichlorohydrin and a catalyst tetrabutyl titanate which is 0.11 percent relative to the total molar weight of the raw materials into a reaction kettle, and heating to 98 ℃ for heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epichlorohydrin under the vacuum degree of-0.099 Mpa;
(3) After no obvious epichlorohydrin is evaporated (less than 1 drop in 30 s), adding 19 mol parts of adipic acid, gradually heating to 174 ℃ at a heating rate of 17 ℃/h, and carrying out block polymerization reaction by keeping the temperature;
(4) Sampling and detecting the acid value of the reaction mixture, adding 13 molar parts of neopentyl glycol when the acid value of the reaction mixture is less than 35mgKOH/g, and gradually heating to 207 ℃ at a heating rate of 10 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, 22 mol parts of terephthalic acid is added, and the temperature is continuously increased to 236 ℃ at the temperature increasing rate of 10 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(6) When no obvious small molecular distillate such as moisture is distilled off (less than 1 drop in 30 s) and the acid value of a reactant mixture is less than 18mgKOH/g, adding 0.06 percent of antioxidant 1010 relative to the total molar weight of raw materials, and carrying out vacuum polycondensation reaction under the vacuum degree of-0.099 Mpa;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding 8 mol parts of isophthalic acid, and continuing to perform end capping reaction on the polyester resin at 236 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 23mgKOH/g, discharging at high temperature, cooling by using a steel belt with condensed water, and crushing and granulating to obtain the polyester resin.
The polyester resin obtained was colorless transparent particles in appearance, and had an acid value of 26mgKOH/g and a softening point of 120 ℃.
Example 3
The embodiment provides a polyester resin for high-temperature-resistant powder coating, and the preparation method comprises the following steps:
(1) Adding 21 mole parts of cyanuric acid, 10 mole parts of 1, 4-cyclohexanedicarboxylic acid, 125 mole parts of epichlorohydrin and a catalyst tetrabutyl titanate with the total molar weight of 0.06 percent relative to the raw materials into a reaction kettle, heating to 95 ℃ and carrying out heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epichlorohydrin under the vacuum degree of-0.097 Mpa;
(3) After no obvious epichlorohydrin is evaporated (less than 1 drop in 30 s), adding 19 mol parts of adipic acid, gradually heating to 175 ℃ at a heating rate of 15 ℃/h, and carrying out block polymerization reaction by keeping the temperature;
(4) Sampling and detecting the acid value of the reaction mixture, adding 12 molar parts of neopentyl glycol when the acid value of the reaction mixture is less than 35mgKOH/g, and gradually heating to 210 ℃ at a heating rate of 12 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, adding 25 mol parts of terephthalic acid, and continuously heating to 235 ℃ at the heating rate of 12 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(6) Adding antioxidant 1010 accounting for 0.1 percent of the total molar weight of the raw materials when no obvious small molecular distillate such as moisture is distilled out (less than 1 drop in 30 s) and the acid value of a reactant mixture is less than 18mgKOH/g, and carrying out vacuum polycondensation reaction under the vacuum degree of-0.097 Mpa;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding 14 molar parts of isophthalic acid, and continuing to perform end capping reaction on the polyester resin at 235 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 26mgKOH/g, discharging at high temperature, cooling by using a steel belt with condensed water, and crushing and granulating to obtain the polyester resin.
The polyester resin obtained was colorless transparent particles in appearance, and had an acid value of 28mgKOH/g and a softening point of 114 ℃.
Example 4
The embodiment provides a polyester resin for high-temperature-resistant powder coating, and the preparation method comprises the following steps:
(1) Adding 18 mole parts of cyanuric acid, 12 mole parts of 1, 4-cyclohexanedicarboxylic acid, 150 mole parts of epichlorohydrin and a catalyst tetrabutyl titanate which is 0.05 percent relative to the total molar weight of the raw materials into a reaction kettle, and heating to 100 ℃ for heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epichlorohydrin under the vacuum degree of-0.099 Mpa;
(3) After no obvious epichlorohydrin is evaporated (less than 1 drop in 30 s), adding 10 mol parts of adipic acid, gradually heating to 170 ℃ at a heating rate of 15 ℃/h, and carrying out block polymerization reaction by keeping the temperature;
(4) Sampling and detecting the acid value of the reaction mixture, adding 17 molar parts of neopentyl glycol when the acid value of the reaction mixture is less than 35mgKOH/g, and gradually heating to 205 ℃ at a heating rate of 12 ℃/h under the protection of nitrogen to perform heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, adding 15 mol parts of terephthalic acid, and continuously heating to 240 ℃ at the heating rate of 12 ℃/h under the protection of nitrogen to carry out heat preservation reaction;
(6) Adding antioxidant 1010 accounting for 0.05 percent of the total molar weight of the raw materials when no obvious small molecular distillate such as moisture is distilled out (less than 1 drop in 30 s) and the acid value of a reactant mixture is less than 18mgKOH/g, and carrying out vacuum polycondensation reaction under the vacuum degree of-0.99 Mpa;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding 13 mol parts of isophthalic acid, and continuing to perform end-capping reaction on the polyester resin at the temperature of 240 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 22mgKOH/g, discharging at a high temperature, cooling by using a steel belt with condensed water, and crushing and granulating to obtain the polyester resin.
The polyester resin obtained was colorless transparent particles in appearance, and had an acid value of 24mgKOH/g and a softening point of 115 ℃.
Comparative example 1
The preparation method adopts common TGIC system polyester resin sold in markets, and the polyester resin is purchased from Zhejiang Guanghua New materials GmbH, model number GH2200, and acid value 33mgKOH/g.
Comparative example 2
Compared with the comparative example 1, the dosage of the polyester resin in the comparative example 2 in the powder coating formula is reduced to 560g, the mass part of the TGIC curing agent is increased to 40 parts, and the mass parts of other components are not changed.
Powder coating examples A1-A4 and comparative examples B1-B2 were prepared using the polyester resins of examples 1-4 and comparative examples 1-2, respectively, and performance tests were conducted.
Preparation of powder coating: the materials were mixed according to the powder coating formulation shown in table 1 below, extruded, tabletted, and crushed separately with a twin screw extruder, and then the flakes were crushed and sieved to produce the powder coating.
TABLE 1 powder coating formulations of examples A1-A4 and comparative examples B1-B2
Preparing a coating: the prepared powder coating examples A1-A4 and comparative examples B1-B2 are sprayed on the galvanized iron plate substrate after surface treatment by using an electrostatic spray gun, and are cured at 180 ℃/15min to obtain coating examples C1-C4 and comparative examples D1-D2.
And (4) performance testing:
the detection basis of the coating indexes is as follows: GB/T21776-2008 Standard guidelines for testing powder coatings and coatings therefor;
the high temperature resistance is carried out according to GB/T1735-2009 determination of heat resistance of colored paint and varnish; the flame retardant performance (oxygen index) is determined according to GB 8624-2012 'grading of combustion performance of building materials and products', and the cured coating is scraped for flame retardant performance test.
Polyester resins prepared by the above examples and comparative examples powder coatings were prepared according to the powder coating formulation provided by the present invention and the results of testing the coating properties are shown in table 2 below.
TABLE 2 results of performance test of coatings prepared from the polyester resins of examples and comparative examples
As can be seen from the table 2, the product of the invention has relatively good film appearance, impact resistance and gloss, obvious high temperature resistance and flame retardant property, and superior adhesive force and oil resistance due to higher functionality.
The product of the invention does not use expensive fluorine-silicon raw materials, and the preparation process is simple, so the cost of the polyester resin product of the invention is low, and on the basis of matching the functionality and the acid value, the polyester resin product with low acid value (the acid value is 22-26 mgKOH/g) is obtained, on the premise of ensuring the curing effect of a coating, the consumption of curing agent TGIC is reduced, and the cost of the powder coating is further reduced.
The product of the invention has the advantages of excellent flame retardance and oil resistance and low cost under the condition of realizing the conventional common high temperature resistance requirement.
Comparative example 1 because of the use of common polyester resin, acid value is higher, adopting low mass proportion TGIC curing agent can't be fully cured, recoil cracking, the product has poor high temperature resistance yellowing performance, the oxygen index is only 23.1%, the flame retardant ability is also weaker, the adhesive force is poor, because of the low functionality, the coating layer appears obvious bubble phenomenon after long-time immersion in oil.
Compared with the comparative example 1, the comparative example 2 is still common polyester resin, the acid value is higher, the comparative example 2 only adjusts the formula of the powder coating, the using amount of the polyester resin is reduced, the using amount of a curing agent TGIC is increased, full curing can be realized, positive and negative impact can be passed, but the high-temperature yellowing resistance of the product is still poorer, the oxygen index is only 23.6%, the flame retardant capability is still weaker, the coating is whitened after being soaked in oil for a long time, and the oil resistance is general.
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. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The polyester resin for the high-temperature-resistant powder coating comprises the following raw materials in parts by mole:
the polyester resin also contains 0.05-0.12% of catalyst and 0.05-0.1% of antioxidant relative to the total molar weight of the raw materials;
the preparation method of the polyester resin comprises the following steps:
(1) Adding cyanuric acid, 1, 4-cyclohexanedicarboxylic acid, epichlorohydrin and a catalyst into a reaction kettle according to the formula ratio, and heating to 90-100 ℃ for heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epoxy chloropropane;
(3) After no obvious epichlorohydrin is evaporated, adding adipic acid with the formula amount, heating to 170-175 ℃, and carrying out block polymerization reaction by keeping the temperature;
(4) Sampling and detecting the acid value of the reaction mixture, adding neopentyl glycol in a formula amount when the acid value of the reaction mixture is less than 35mgKOH/g, heating to 200-210 ℃ under the protection of nitrogen, and carrying out heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, adding terephthalic acid with the formula amount, and continuously heating to 235-240 ℃ under the protection of nitrogen to carry out heat preservation reaction;
(6) Adding antioxidant with formula amount when no obvious micromolecule distillate is distilled off and the acid value of the reactant mixture is less than 18mgKOH/g, and carrying out vacuum polycondensation;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction on the polyester resin at 235-240 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 22-26mgKOH/g, discharging, cooling, crushing and granulating to obtain the polyester resin.
2. The polyester resin for high temperature resistant powder coating according to claim 1, wherein the catalyst is tetrabutyl titanate; the antioxidant is antioxidant 1010.
3. The polyester resin for high temperature resistant powder coating according to claim 1, wherein the obtained polyester resin has a softening point of 110 to 121 ℃.
4. A process for preparing the polyester resin for high temperature resistant powder coating according to any one of claims 1 to 3, comprising:
(1) Adding cyanuric acid, 1, 4-cyclohexanedicarboxylic acid, epichlorohydrin and a catalyst into a reaction kettle according to the formula ratio, and heating to 90-100 ℃ for heat preservation reaction;
(2) Sampling and detecting the acid value of the reaction mixture, starting a vacuum system when the acid value of the reaction mixture is less than 5mgKOH/g, and decompressing and removing excessive unreacted epoxy chloropropane;
(3) After no obvious epichlorohydrin is evaporated, adding adipic acid with the formula amount, heating to 170-175 ℃, and carrying out block polymerization reaction by keeping the temperature;
(4) Sampling and detecting the acid value of the reaction mixture, adding neopentyl glycol in a formula amount when the acid value of the reaction mixture is less than 35mgKOH/g, heating to 200-210 ℃ under the protection of nitrogen, and carrying out heat preservation reaction;
(5) When the acid value of the reaction mixture is less than 10mgKOH/g, adding terephthalic acid with the formula amount, and continuously heating to 235-240 ℃ under the protection of nitrogen to carry out heat preservation reaction;
(6) Adding antioxidant with formula amount when no obvious micromolecule distillate is distilled off and the acid value of the reactant mixture is less than 18mgKOH/g, and carrying out vacuum polycondensation;
(7) Stopping vacuumizing when the acid value of the reaction mixture is reduced to 15mgKOH/g, then adding the isophthalic acid with the formula amount, and continuing to perform end capping reaction on the polyester resin at 235-240 ℃;
(8) And stopping the reaction when the acid value of the reactant reaches 22-26mgKOH/g, discharging, cooling, crushing and granulating to obtain the polyester resin.
5. The method of preparing polyester resin for high temperature resistant powder coating according to claim 4, wherein the degree of vacuum in the step (2) or (6) is-0.097 to-0.099 MPa.
6. The method for preparing polyester resin for high temperature resistant powder coating as claimed in claim 4, wherein the temperature is gradually increased to 170-175 ℃ at a temperature increasing rate of 15-18 ℃/h in the step (3).
7. The method for preparing polyester resin for high temperature resistant powder coating according to claim 4, wherein the temperature is gradually increased to 200-210 ℃ at a temperature increase rate of 10-12 ℃/h in the step (4).
8. The method for preparing polyester resin for high temperature resistant powder coating as claimed in claim 4, wherein the temperature is gradually increased to 235-240 ℃ at a temperature increasing rate of 10-12 ℃/h in the step (5).
9. The method for preparing polyester resin for high temperature resistant powder coating according to claim 4, wherein in the step (8), the discharging is a hot high temperature discharging, and the cooling is cooling with a steel belt with condensed water.
10. A high-temperature-resistant powder coating comprising the polyester resin according to any one of claims 1 to 3.
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| CN115340668B (en) * | 2022-09-23 | 2024-03-26 | 黄山嘉恒科技有限公司 | Wear-resistant and high-temperature-resistant polyester resin for powder coating and preparation method thereof |
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