CN114133538A - Special polyester resin for anti-sticking hanger powder coating and preparation method thereof - Google Patents
Special polyester resin for anti-sticking hanger powder coating and preparation method thereof Download PDFInfo
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- CN114133538A CN114133538A CN202111522361.9A CN202111522361A CN114133538A CN 114133538 A CN114133538 A CN 114133538A CN 202111522361 A CN202111522361 A CN 202111522361A CN 114133538 A CN114133538 A CN 114133538A
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- polyester resin
- hanger
- powder coating
- sticking
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- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000000843 powder Substances 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 50
- 239000004645 polyester resin Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 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 description 4
- 229920000728 polyester Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic 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
- 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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D5/033—Powdery paints characterised by the additives
-
- 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
Abstract
The invention discloses a polyester resin special for an anti-sticking hanger powder coating and a preparation method thereof, wherein the polyester resin comprises the following raw materials in percentage by weight: polyol: 25% -45%; polybasic acid: 45% -60%; catalyst: 0.06% -0.12%; end-capping agent: 6 to 12 percent; antioxidant: 0.50% -0.75%; curing accelerator: 0.05% -0.15%; the powder coating added with the polyester resin has high glass transition temperature and short curing time during curing, the gelling time of the formed paint film is short, the surface flatness of the formed paint film is good, the workpiece and the hanger can be easily separated after the prepared powder coating is cured into a thick film, and the problem that the hanger and the workpiece are difficult to separate or the workpiece is damaged during separation is solved.
Description
Technical Field
The invention belongs to the technical field of polyester resin, and particularly relates to special polyester resin for an anti-sticking hanger powder coating and a preparation method thereof.
Background
Powder coating is a new type of solvent-free coating consisting of polyester resin, curing agent, pigment and filler, and is gaining increasing acceptance for its excellent properties, organic solvent-free, etc. In recent years, the cost of polyester-epoxy type (mixed type) powder coatings is increasing due to the rising price of epoxy resins, and various large powder coating enterprises adopt polyester-TGIC type (pure polyester type) powder coatings for replacing, so that the requirements of mixed type powder coatings on decoration and other properties can be met.
However, the use of the pure polyester type powder coating has a low crosslinking density and a low glass transition temperature of the coating film, and the powder coating remaining in the place where the hanger contacts the workpiece is insufficiently cured. The number of times of repeated use of the hanger is increased, the more the residual powder is accumulated, the heat transfer effect is further reduced, and the residual powder between the hanger and the workpiece forms certain adhesion performance, so that the hanger is adhered to the workpiece. This defect not only causes damage to the workpiece, but also affects production efficiency.
Disclosure of Invention
In order to solve the technical problem of hanging tool adhesion, the invention provides a special polyester resin for an anti-adhesion hanging tool powder coating, which has higher glass transition temperature and shorter curing time.
The invention also provides a preparation method of the polyester resin special for the anti-sticking hanger powder coating, and the polyester resin special for the anti-sticking hanger powder coating with the acid value of 33-39mgKOH/g, the glass transition temperature of more than or equal to 69 ℃, and the rotational viscosity of 6000-8500mPa.S (200 ℃) can be prepared by controlling the raw material dosage and the process parameters.
The invention also provides the application of the special polyester resin for the anti-sticking hanger powder coating in the powder coating, the gelling time of the powder coating added with the polyester resin is short, the surface flatness of a formed paint film is good, and the anti-sticking hanger effect of the powder coating is excellent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the special polyester resin for the anti-sticking hanger powder coating comprises the following raw materials in percentage by weight:
polyol: 25% -45%;
polybasic acid: 45% -60%;
catalyst: 0.06% -0.12%;
end-capping agent: 6 to 12 percent;
antioxidant: 0.50% -0.75%;
curing accelerator: 0.05 to 0.15 percent.
The acid value of the polyester resin special for the anti-sticking hanger powder coating is 33-39mgKOH/g, the glass transition temperature is more than or equal to 69 ℃, and the rotational viscosity at 200 ℃ is 6000-8500 mPa.S.
The polyalcohol is one or more of neopentyl glycol, ethylene glycol, 2-methyl-1, 3-propylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 2-butyl-2-ethyl-1, 3-propylene glycol, diethylene glycol and trimethylolpropane.
The polybasic acid is any one or more of terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and isophthalic acid.
The catalyst is one or two of monobutyl tin oxide and stannous oxalate.
The end-capping reagent is one or two of isophthalic acid and adipic acid.
The antioxidant is one or two of hindered phenol antioxidant and phosphite antioxidant.
The curing accelerator is one or two of ethyl triphenyl phosphonium bromide and triphenyl phosphine.
The invention provides a preparation method of the polyester resin special for the anti-sticking hanger powder coating, which comprises the following steps:
(1) sequentially adding the polyol, the polyacid and the catalyst with the formula ratio into a reaction kettle with a stirrer, heating to 170 ℃ under the protection of inert gas, then heating to 240 ℃ and 250 ℃ at a heating rate of 1.5-2.5 ℃/15min, and stirring for reaction until the materials are clarified; the acid value of the reaction system at the stage is 8-16 mgKOH/g;
(2) cooling to 225-; the acid value of the reaction system at the stage is 43-49 mgKOH/g;
(3) carrying out negative pressure polycondensation reaction for 3-4h at the temperature of 220-;
(4) releasing the negative pressure, cooling to below 220 ℃, adding an antioxidant and a curing accelerator in a formula amount, continuously stirring for 30-45min, discharging and cooling, wherein the acid value of the polyester resin special for the anti-sticking hanger powder coating prepared finally is 33-39mgKOH/g, the vitrification temperature is not less than 69 ℃, and the rotational viscosity is 6000-plus 7500mPa.S/200 ℃.
In the step (1), the rotating speed of the stirring is 60-85 r/min.
The invention also provides application of the polyester resin special for the anti-sticking hanger powder coating in the powder coating, and the anti-sticking hanger powder coating with excellent performance can be obtained by curing the TGIC without adding other resin matrixes in the powder coating using the polyester resin.
The acid value of the polyester resin special for the anti-sticking hanger powder coating prepared by controlling the composition and the proportion of the raw materials and the preparation process is 33-39mgKOH/g, the glass transition temperature is more than or equal to 69 ℃, the rotational viscosity is 6000-plus-8500 mPa.S/200 ℃, after the polyester resin with the properties is applied to the powder coating, the polyester resin has the same glass transition temperature and gel time as the mixed powder coating, the surface smoothness of the obtained paint film is good, and the anti-sticking hanger effect is excellent.
Compared with the prior art, the invention has the following beneficial effects:
the invention solves the problem that the hanger is easy to stick when pure polyester powder coating is used for replacing epoxy-polyester powder coating, and the polyester resin provided by the invention is cured by triglycidyl isocyanurate (TGIC), so that the curing time is short; the polyester resin provided by the invention has higher glass transition temperature and shorter gelling time, and can obtain a smoother coating film after being applied to the powder coating.
Detailed Description
The present invention will be described in detail with reference to examples.
Comparative example 1
A preparation method of polyester resin comprises the following steps:
(1) adding the polyol with the formula amount into a reaction kettle, starting stirring, stirring for 20 revolutions per minute, adding the polybasic acid and the monobutyl tin oxide, flushing nitrogen for protection, quickly heating to 170 ℃, adjusting the stirring speed to 80 revolutions per minute, then heating to 245 ℃ at the heating speed of 2 ℃/min, carrying out heat preservation reaction until the material is clear and transparent, and measuring the acid value of the material to be within the range of 8-10 mgKOH/g;
(2) cooling to 230 ℃, adding a blocking agent, raising the temperature to 240 ℃, keeping the temperature for 2.5h, and measuring the acid value within the range of 43-49 mgKOH/g;
(3) keeping the temperature at 240 ℃, vacuumizing to-0.095-0.099 MPa, and performing polycondensation for 2h, wherein the acid value is measured to be within the range of 33-38mgKOH/g, and the rotational viscosity at 200 ℃ is measured to be within the range of 6000-7500 mPa.s;
(4) relieving negative pressure, cooling to below 220 deg.C, adding antioxidant and curing promoter, stirring for 30min, discharging, and cooling.
The composition of the raw materials in the above preparation steps is shown in Table 1, and the properties of the polyester resin obtained by the preparation are shown in Table 2.
Comparative example 2
A preparation method of polyester resin comprises the following steps:
(1) adding the polyol with the formula amount into a reaction kettle, starting stirring, stirring for 20 revolutions per minute, adding the polybasic acid and the monobutyl tin oxide, flushing nitrogen for protection, quickly heating to 170 ℃, adjusting the stirring speed to 80 revolutions per minute, then heating to 245 ℃ at the heating speed of 2 ℃/min, carrying out heat preservation reaction until the material is clear and transparent, and measuring the acid value of the material to be within the range of 15-17 mgKOH/g;
(2) cooling to 230 ℃, adding a blocking agent, raising the temperature to 240 ℃, keeping the temperature for 2h, and measuring the acid value within the range of 43-49 mgKOH/g;
(3) keeping the temperature at 240 ℃, vacuumizing to-0.095-0.099 MPa, and performing polycondensation for 2h, wherein the acid value is measured to be within the range of 33-38mgKOH/g, and the rotational viscosity at 200 ℃ is measured to be within the range of 5500-6500 mPa.s;
(4) relieving negative pressure, cooling to below 220 deg.C, adding antioxidant and curing promoter, stirring for 30min, discharging, and cooling.
The composition of the raw materials in the above preparation steps is shown in Table 1, and the properties of the polyester resin obtained by the preparation are shown in Table 2.
Comparative example 3
A preparation method of polyester resin comprises the following steps:
(1) adding the polyol with the formula amount into a reaction kettle, starting stirring, rotating for 20 r/min, adding the polyacid and the monobutyl tin oxide, flushing nitrogen for protection, quickly heating to 170 ℃, adjusting the stirring speed to 80 r/min, then heating to 245 ℃ at the heating speed of 2 ℃/min, carrying out heat preservation reaction until the material is clear and transparent, and measuring the acid value to be in the range of 18-21 mgKOH/g;
(2) cooling to 230 ℃, adding a blocking agent, raising the temperature to 240 ℃, keeping the temperature for 3h, and measuring the acid value within the range of 43-49 mgKOH/g;
(3 keeping the temperature at 240 ℃, vacuumizing to-0.095 to-0.099 MPa, performing polycondensation for 3h, and measuring the acid value to be within the range of 32-38mgKOH/g and the rotational viscosity at 200 ℃ to be within the range of 6000-7500 mPa.s;
(4) relieving negative pressure, cooling to below 220 deg.C, adding antioxidant and curing promoter, stirring for 30min, discharging, and cooling.
The composition of the raw materials in the above preparation steps is shown in Table 1, and the properties of the polyester resin obtained by the preparation are shown in Table 2.
Example 1
A preparation method of polyester resin special for anti-sticking hanger powder coating comprises the following steps:
(1) adding the polyol with the formula amount into a reaction kettle, starting stirring, stirring for 20 revolutions per minute, adding the polybasic acid and the monobutyl tin oxide, flushing nitrogen for protection, quickly heating to 170 ℃, adjusting the stirring speed to 80 revolutions per minute, then heating to 245 ℃ at the heating speed of 2 ℃/min, carrying out heat preservation reaction until the material is clear and transparent, and measuring the acid value of the material to be within the range of 8-10 mgKOH/g;
(2) cooling to 230 ℃, adding a blocking agent, raising the temperature to 240 ℃, keeping the temperature for 2.5h, and measuring the acid value within the range of 43-49 mgKOH/g;
(3) cooling to 230 ℃, vacuumizing to-0.095 to-0.099 MPa, performing polycondensation reaction for 3h, and measuring that the acid value is within the range of 33-38mgKOH/g and the rotational viscosity at 200 ℃ is within the range of 6000-7000 mPa.s;
(4) relieving negative pressure, cooling to below 220 deg.C, adding antioxidant and curing promoter, stirring for 30min, discharging, and cooling.
The composition of the raw materials in the above preparation steps is shown in Table 1, and the properties of the polyester resin obtained by the preparation are shown in Table 2.
Example 2
A preparation method of polyester resin special for anti-sticking hanger powder coating comprises the following steps:
(1) adding the polyol with the formula amount into a reaction kettle, starting stirring, stirring for 20 revolutions per minute, adding the polybasic acid and the monobutyl tin oxide, flushing nitrogen for protection, quickly heating to 170 ℃, adjusting the stirring speed to 80 revolutions per minute, then heating to 245 ℃ at the heating speed of 2 ℃/min, carrying out heat preservation reaction until the material is clear and transparent, and measuring the acid value of the material to be within the range of 8-10 mgKOH/g;
(2) cooling to 230 ℃, adding a blocking agent, raising the temperature to 240 ℃, keeping the temperature for 2.5h, and measuring the acid value within the range of 43-49 mgKOH/g;
(3) cooling to 220 ℃, vacuumizing to-0.095 to-0.099 MPa, performing polycondensation reaction for 4h, and measuring that the acid value is in the range of 33-38mgKOH/g and the rotational viscosity at 200 ℃ is in the range of 7000-8500 mPa.s;
(4) relieving negative pressure, cooling to below 220 deg.C, adding antioxidant and curing promoter, stirring for 30min, discharging, and cooling.
The composition of the raw materials in the above preparation steps is shown in Table 1, and the properties of the polyester resin obtained by the preparation are shown in Table 2.
TABLE 1
The acid value, glass transition temperature and rotational viscosity of the polyester resins obtained in the above examples are shown in Table 2.
TABLE 2
The polyester resin prepared in each embodiment is applied to powder coating, and the application process comprises the steps of uniformly mixing the polyester resin, a curing agent, a flatting agent, a brightener, titanium dioxide, a filler and the like in proportion, extruding the mixture through a double-screw extruder, tabletting, cooling, crushing, grinding, electrostatic spraying, baking at 10min/200 ℃, and checking whether the surface of the mixture can be easily separated from a hanger. The formulation of each powder coating is shown in table 3.
TABLE 3
Component (g) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Example 1 | Example 2 |
Resin a | 560 | -- | -- | -- | -- |
Resin b | -- | 560 | -- | -- | -- |
Resin c | -- | -- | 560 | -- | -- |
Resin d | -- | -- | -- | 560 | -- |
Resin e | -- | -- | -- | -- | 560 |
TGIC | 40 | 40 | 40 | 40 | 40 |
Barium sulfate | 180 | 180 | 180 | 180 | 180 |
Titanium white powder | 200 | 200 | 200 | 200 | 200 |
Benzoinum | 4 | 4 | 4 | 4 | 4 |
Leveling agent | 10 | 10 | 10 | 10 | 10 |
Brightener | 10 | 10 | 10 | 10 | 10 |
The properties of each powder coating and the coating film formed therefrom are shown in table 4.
TABLE 4
In tables 2 and 4, the test methods for the respective properties are as follows:
acid value: the determination was carried out according to the method of Standard GB/T6743-2008 "determination of partial acid value and total acid value of a base for polyester resin color paints and varnishes for plastics".
Melt viscosity: the viscosity is determined according to the standard GB/T9751.1-2008 "color paints and varnishes part 1 with a rotary viscometer: the measurement was carried out by the method of Cone plate viscometer "operating at a high shear rate.
Glass transition temperature: according to standard GB/T19466.2-2004, section 2 of Differential Scanning Calorimetry (DSC) of plastics: measurement of glass transition temperature "was carried out by the method described in (1).
Gel time: measured according to the method of Standard GB/T1699-1997 determination of the gelation time of thermosetting powder coatings at a given temperature.
Gloss: the determination is carried out according to the method of Standard GB/T9754-2007 determination of 20 °, 60 ° and 85 ° specular gloss of paint films of pigmented paints and varnishes which do not contain metallic pigments.
Impact properties: the determination is carried out according to the method of the standard GB/T1732-1993 "determination of the impact resistance of paint films".
And (3) solvent resistance test: detection was carried out according to the standard GB/T23989-.
Hardness: according to standard ISO 15184: 1998 determination of the hardness of the paint film by the colored paint and varnish-pencil method.
Surface flatness: visual inspection.
Anti-sticking hanger effect: visual inspection.
As can be seen from tables 2, 4 and 5, the powder coatings prepared under the same conditions by using the resin d and the resin e prepared in examples 1 and 2 have the same glass transition temperature and gel time as the original mixed powder coating, have good surface flatness and excellent anti-sticking effect, and the resin d has shorter production time and lower energy consumption than the resin e in combination with the actual production process control. The resins a, b and e prepared in the comparative examples 1-3 can not simultaneously meet the requirements of acid value of 33-39mgKOH/g, glass transition temperature of more than or equal to 69 ℃, and rotational viscosity of 6000-8500mPa.S at 200 ℃, so that the coating film has excessively long gel time and improper glass transition temperature when applied to powder coating, and the anti-sticking effect is not ideal.
The formulation and properties of the original mixed powder coating are shown in table 5:
TABLE 5
The above detailed description of an anti-stick hanger powder coating specialized polyester resin and the method of preparation and application thereof with reference to the examples is illustrative and not restrictive, and several examples can be cited within the limits thereof, and thus variations and modifications thereof without departing from the general concept of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The special polyester resin for the anti-sticking hanger powder coating is characterized by comprising the following raw materials in percentage by weight:
polyol: 25% -45%;
polybasic acid: 45% -60%;
catalyst: 0.06% -0.12%;
end-capping agent: 6 to 12 percent;
antioxidant: 0.50% -0.75%;
curing accelerator: 0.05 to 0.15 percent.
2. The polyester resin special for the anti-sticking hanger powder coating as claimed in claim 1, wherein the acid value of the polyester resin special for the anti-sticking hanger powder coating is 33-39mgKOH/g, the glass transition temperature is not less than 69 ℃, and the rotational viscosity at 200 ℃ is 6000-8500 mPa.S.
3. The polyester resin special for the anti-sticking hanger powder coating as claimed in claim 1, wherein the polyhydric alcohol is any one or more of neopentyl glycol, ethylene glycol, 2-methyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 2-butyl-2-ethyl-1, 3-propanediol, diethylene glycol, and trimethylolpropane.
4. The polyester resin special for the anti-sticking hanger powder coating as claimed in claim 1, wherein the polybasic acid is any one or more of terephthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid and isophthalic acid.
5. The special polyester resin for the anti-sticking hanger powder coating as claimed in claim 1, wherein the catalyst is one or two of monobutyl tin oxide and stannous oxalate.
6. The polyester resin special for the anti-sticking hanger powder coating as claimed in claim 1, wherein the end-capping agent is either or both of isophthalic acid and adipic acid.
7. The polyester resin special for the anti-sticking hanger powder coating as claimed in claim 1, wherein the antioxidant is one or two of hindered phenol antioxidant and phosphite antioxidant.
8. The polyester resin special for the anti-sticking hanger powder coating as claimed in claim 1, wherein the curing accelerator is one or two of ethyl triphenyl phosphonium bromide and triphenyl phosphine.
9. The preparation method of the polyester resin special for the anti-sticking hanger powder coating as claimed in any one of claims 1 to 8, wherein the preparation method comprises the following steps:
(1) sequentially adding the polyol, the polybasic acid and the catalyst in the formula ratio into a reaction kettle with stirring, heating to 170 ℃ under the protection of inert gas, then heating to 240 ℃ and 250 ℃ at the heating rate of 1.5-2.5 ℃/min, and stirring for reaction until the materials are clarified;
(2) cooling to 225-;
(3) carrying out negative pressure polycondensation reaction for 3-4h at the temperature of 220-;
(4) releasing the negative pressure, cooling to below 220 ℃, adding the antioxidant and the curing accelerator in the formula amount, continuously stirring for 30-45min, discharging and cooling.
10. Use of the polyester resin for anti-stick hangers powder coatings according to any of claims 1 to 8 in powder coatings.
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