CN110591519A - Mixed extinction powder coating without TMA and preparation method thereof - Google Patents
Mixed extinction powder coating without TMA and preparation method thereof Download PDFInfo
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- CN110591519A CN110591519A CN201910840832.7A CN201910840832A CN110591519A CN 110591519 A CN110591519 A CN 110591519A CN 201910840832 A CN201910840832 A CN 201910840832A CN 110591519 A CN110591519 A CN 110591519A
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 48
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000008033 biological extinction Effects 0.000 title abstract description 28
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001225 polyester resin Polymers 0.000 claims abstract description 31
- 239000004645 polyester resin Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 238000009736 wetting Methods 0.000 claims abstract description 8
- 244000028419 Styrax benzoin Species 0.000 claims abstract description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims abstract description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims abstract description 5
- 229960002130 benzoin Drugs 0.000 claims abstract description 5
- 235000019382 gum benzoic Nutrition 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 238000005070 sampling Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000006224 matting agent Substances 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical group O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003623 enhancer Substances 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
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000000241 respiratory effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000004199 lung function Effects 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08G63/12—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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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 aims to provide a mixed extinction powder coating without TMA and a preparation method thereof, wherein the coating raw materials comprise TMA-free polyester resin, epoxy resin, titanium dioxide, inorganic filler, flatting agent, benzoin, wetting accelerant and flatting agent, the raw materials are mixed according to the mass portion ratio, and the powder coating without trimellitic anhydride is prepared by extrusion, crushing and sieving, and the raw materials used in the preparation process do not contain TMA, are environment-friendly and pollution-free, have good mechanical property of the coating, excellent levelling property, fine and smooth surface and good extinction effect, and the cured coating has fine and smooth surface, low extinction gloss and good adhesive force, impact and bending property.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a mixed extinction powder coating without TMA (mechanical transmission model) and a preparation method thereof.
Background
The extinction powder coating has various types, the polyester/epoxy extinction powder coating has good extinction effect, and the polyester resin in the extinction coating is mostly synthesized by trimellitic anhydride (TMA). TMA has high reaction activity, part of TMA participates in alkyd polycondensation reaction in the synthesis of polyester resin, and part of TMA exists in the polyester resin in a free form, and after the TMA is prepared into powder coating, the difference of the reaction activity is utilized, so that a good extinction effect can be achieved. For the polyester without TMA, the extinction ability is generally insufficient, the leveling property and the mechanical property of the powder coating are poor, and the board surface is not fine and smooth enough.
Although TMA has good extinction ability, it is a substance harmful to the human body. The eu official gazette issues a command to identify TMA as an SVHC substance. Trimellitic anhydride is identified as a highly interesting substance due to its respiratory sensitizing properties according to REACH regulation, clause 57 (f). The data show that trimellitic anhydride causes severe and permanent impairment of lung function if exposure times are extended and no intervention is taken. Also, trimellitic anhydride should be included in the list of candidates under RAECH regulation, article 59 (1), for reasons to be explained: respiratory sensitization profile (clause 57 (f)) -human health. Therefore, how to prepare the mixed powder coating with good extinction performance on the premise of not using TMA is a difficult problem to be solved urgently.
Patents CN107936236A and CN105254863B respectively report a polyester resin for a mixed matting powder coating, trimellitic anhydride is used as a raw material for preparing the polyester resin, and free TMA exists in the prepared powder coating, which is not good for human health. The polyester resin used in the epoxy polyester powder coating reported in patent CN108727530A did not indicate the presence or absence of TMA. Patent CN101787239B reports an environment-friendly matt powder coating, specifically relating to incompatible matting of polyester resins and acrylic acid, unlike the powder coating system of this patent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a mixed extinction powder coating without TMA and a preparation method thereof, wherein the coating raw materials comprise TMA-free polyester resin, epoxy resin, titanium dioxide, inorganic filler, a leveling agent, benzoin, a wetting accelerant and an extinction agent, the raw materials are mixed according to the mass part ratio, and the powder coating without trimellitic anhydride is prepared by extrusion, crushing and sieving, and the raw materials used in the preparation process do not contain TMA, are environment-friendly and pollution-free, have good mechanical property of the coating, excellent leveling property, fine and smooth surface and good extinction effect, and the cured coating has fine and smooth surface, low extinction gloss, good adhesive force, impact and bending property, and solves the problems in the background technology.
The invention aims to provide a mixed extinction powder coating without TMA, which is characterized in that: the composite material comprises the following raw material components in parts by mass: 390 parts of TMA-free type polyester resin, 260 parts of epoxy resin 213, 300 parts of titanium dioxide, 80-140 parts of inorganic filler, 8-12 parts of flatting agent, 3-7 parts of benzoin, 3-7 parts of wetting accelerator and 30-50 parts of matting agent.
The further improvement lies in that: the TMA-free type polyester resin is a carboxyl-terminated saturated polyester resin, and the polyester resin does not contain trimellitic anhydride.
The further improvement lies in that: the preparation method of the TMA-free type polyester resin comprises the following steps: putting 1120 parts by mass of neopentyl glycol, 390 parts by mass of liquid alcohol and 30 parts by mass of trimethylolpropane into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding 2590 parts by mass of terephthalic acid and 4 parts by mass of esterification catalyst, heating to 247 ℃ for maintaining reaction until a reactant is clear, sampling, measuring an acid value, cooling to 220 ℃, adding 260 parts by mass of a capping agent, maintaining the reactant clear, sampling, measuring the acid value, vacuumizing for 3 hours, finally adding 12 parts by mass of a curing accelerator and 35 parts by mass of an antioxidant, and maintaining for 20 minutes to obtain a sample which is a carboxyl-terminated saturated polyester resin.
The further improvement lies in that: the liquid alcohol is one or more of ethylene glycol, diethylene glycol and 2-methyl-1, 3-propylene glycol; the esterification catalyst is stannous oxalate; the end capping agent is one or more of isophthalic acid, adipic acid, succinic acid, cyclohexanedicarboxylic acid and fumaric acid; the curing accelerator is one or more of tetraethyl ammonium bromide, ethyl triphenyl phosphonium bromide and benzyl triethyl ammonium chloride; the antioxidant is 168 or 1010.
The further improvement lies in that: the epoxy resin is epoxy resin E-12 produced by a two-step method; the inorganic filler is delustered barium; the leveling agent is GLP 588; the wetting enhancer is 701B; the matting agent is one of T300, Elatan K7225 and Elatan K7227.
The further improvement lies in that: the mass ratio of the TMA-free type polyester resin to the epoxy resin is 60: 40.
the preparation method of the extinction powder coating without TMA mixed type comprises the following steps: firstly, proportioning raw materials according to the parts by weight, and fully premixing the weighed raw materials in a mixing tank; secondly, extruding the mixture by a double-screw extruder, wherein the parameters are set to be 85-100 ℃ in the region I, 110-125 ℃ in the region II, 100-115 ℃ in the region III, 35Hz in feeding speed frequency and 40Hz in screw speed frequency; and thirdly, crushing the extruded sheet material, grinding, sieving by a 200-mesh sieve, and finally packaging to obtain the finished product.
The invention has the beneficial effects that: the coating raw materials of the invention are TMA-free type polyester resin, epoxy resin, titanium dioxide, inorganic filler, flatting agent, benzoin, wetting accelerant and flatting agent, the raw materials are mixed according to the mass portion proportion, and the powder coating without trimellitic anhydride is prepared by extrusion, crushing and sieving, and the raw materials used in the preparation process do not contain TMA, are environment-friendly and pollution-free, and have good mechanical property, excellent flatting property, fine and smooth surface and good flatting effect, and the cured coating has fine and smooth surface, low flatting gloss and good adhesive force, impact and bending property.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example 1
The raw material components and the parts by mass of the mixed extinction powder coating without TMA are shown in Table 1.
The TMA-free type polyester resin was prepared as follows:
putting 1120 parts by mass of neopentyl glycol, 390 parts by mass of liquid alcohol and 30 parts by mass of trimethylolpropane into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding 2590 parts by mass of terephthalic acid and 4 parts by mass of esterification catalyst, heating to 247 ℃ for maintaining the reaction until the reactant is clear, sampling, cooling to 220 ℃ after testing the acid value, adding 260 parts by mass of a capping agent, maintaining the reactant clear, sampling, vacuumizing for 3 hours after testing the acid value, finally adding 12 parts by mass of a curing accelerator and 35 parts by mass of an antioxidant, maintaining the acid value of the obtained sample for 20 minutes to be 49.6mgKOH/g and the viscosity to be 2050 mPa.
The matt powder coating of the TMA-free hybrid type was prepared as follows:
the components in the mass parts in the table 1 are fully premixed in a mixing tank, and then extruded by a double-screw extruder, wherein the extrusion parameters are 95 ℃ in a region I, 115 ℃ in a region II, 100 ℃ in a region III, 35Hz in feeding speed frequency and 40Hz in screw speed frequency, and then the tablets are crushed, ground and sieved by a 200-mesh screen to prepare the finished product.
Example 2
The raw material components and the parts by mass of the mixed extinction powder coating without TMA are shown in Table 1.
The TMA-free type polyester resin was prepared as follows:
putting 1120 parts by mass of neopentyl glycol, 390 parts by mass of liquid alcohol and 30 parts by mass of trimethylolpropane into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding 2590 parts by mass of terephthalic acid and 4 parts by mass of esterification catalyst, heating to 247 ℃ for maintaining the reaction until the reactant is clear, sampling, cooling to 220 ℃ after testing the acid value, adding 260 parts by mass of a capping agent, maintaining the reactant clear, sampling, vacuumizing for 3 hours after testing the acid value, finally adding 12 parts by mass of a curing accelerator and 35 parts by mass of an antioxidant, maintaining the acid value of the obtained sample for 20 minutes to be 49.6mgKOH/g and the viscosity to be 2050 mPa.
The matt powder coating of the TMA-free hybrid type was prepared as follows:
the components in the mass parts in the table 1 are fully premixed in a mixing tank, and then extruded by a double-screw extruder, wherein the extrusion parameters are 85 ℃ in a region I, 110 ℃ in a region II, 100 ℃ in a region III, 35Hz in feeding speed frequency and 40Hz in screw speed frequency, and then the tablets are crushed, ground and sieved by a 200-mesh screen to prepare the finished product.
Example 3
The raw material components and the parts by mass of the mixed extinction powder coating without TMA are shown in Table 1.
The TMA-free type polyester resin was prepared as follows:
putting 1120 parts by mass of neopentyl glycol, 390 parts by mass of liquid alcohol and 30 parts by mass of trimethylolpropane into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding 2590 parts by mass of terephthalic acid and 4 parts by mass of esterification catalyst, heating to 247 ℃ for maintaining the reaction until the reactant is clear, sampling, cooling to 220 ℃ after testing the acid value, adding 260 parts by mass of a capping agent, maintaining the reactant clear, sampling, vacuumizing for 3 hours after testing the acid value, finally adding 12 parts by mass of a curing accelerator and 35 parts by mass of an antioxidant, maintaining the acid value of the obtained sample for 20 minutes to be 49.6mgKOH/g and the viscosity to be 2050 mPa.
The matt powder coating of the TMA-free hybrid type was prepared as follows:
the components in the mass parts in the table 1 are fully premixed in a mixing tank, and then extruded by a double-screw extruder, wherein the extrusion parameters are that the temperature in a region I is 100 ℃, the temperature in a region II is 125 ℃, the temperature in a region III is 115 ℃, the feeding rotating speed frequency is 35Hz, and the screw rotating speed frequency is 40Hz, and then the sheet materials are crushed, ground and sieved by a 200-mesh screen to prepare the finished product.
Example 4
The raw material components and the parts by mass of the mixed extinction powder coating without TMA are shown in Table 1.
The TMA-free type polyester resin was prepared as follows:
putting 1120 parts by mass of neopentyl glycol, 390 parts by mass of liquid alcohol and 30 parts by mass of trimethylolpropane into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding 2590 parts by mass of terephthalic acid and 4 parts by mass of esterification catalyst, heating to 247 ℃ for maintaining the reaction until the reactant is clear, sampling, cooling to 220 ℃ after testing the acid value, adding 260 parts by mass of a capping agent, maintaining the reactant clear, sampling, vacuumizing for 3 hours after testing the acid value, finally adding 12 parts by mass of a curing accelerator and 35 parts by mass of an antioxidant, maintaining the acid value of the obtained sample for 20 minutes to be 49.6mgKOH/g and the viscosity to be 2050 mPa.
The matt powder coating of the TMA-free hybrid type was prepared as follows:
the components in the mass parts in the table 1 are fully premixed in a mixing tank, and then extruded by a double-screw extruder, wherein the extrusion parameters are 95 ℃ in a region I, 120 ℃ in a region II, 110 ℃ in a region III, 35Hz in feeding speed frequency and 40Hz in screw speed frequency, and then the tablets are crushed, ground and sieved by a 200-mesh screen to prepare the finished product.
Table 1 examples 1-4 raw material amounts/parts by mass
| Examples | 1 | 2 | 3 | 4 |
| TMA-free polyester resin | 333 | 360 | 345 | 321 |
| Epoxy resin | 222 | 240 | 230 | 214 |
| Titanium white powder | 270 | 260 | 240 | 290 |
| Inorganic filler | 109 | 89 | 134 | 103 |
| Leveling agent | 9 | 10 | 8 | 12 |
| Benzoinum | 5 | 7 | 3 | 4 |
| Wetting accelerator | 7 | 4 | 5 | 6 |
| Matting agent | 45 | 30 | 35 | 50 |
The powder coating obtained in the embodiment 1-4 is electrostatically sprayed on the surface of a sample plate, after being cured, the relevant performances such as impact, bending and adhesive force are tested according to the national standard, and the gloss, leveling and fineness of the coating are tested.
TABLE 2 powder coatings correlation Performance test
| Examples | 1 | 2 | 3 | 4 |
| Film thickness μm | 60-80 | 60-80 | 60-80 | 60-80 |
| 60 ℃ gloss (%) | 9.8 | 26.6 | 19.7 | 7.3 |
| Levelling | Is smoother | Leveling | Leveling | Orange peel |
| Impact of | Without cracks | Without cracks | Without cracks | Without cracks |
| Bending | Without cracks | Without cracks | Without cracks | Without cracks |
| Adhesion force | Level 0 | Level 0 | Level 0 | Level 0 |
| Surface state | Fineness of fineness | Fineness of fineness | Fineness of fineness | Fineness of fineness |
From the results, the indoor extinction powder coating prepared by matching TMA-free polyester resin, epoxy resin and an extinction agent avoids the existence of trimellitic anhydride on the raw material of the polyester resin, is environment-friendly and pollution-free, has good performances of coating impact, bending, adhesion and the like, is clear in plate surface and good in extinction performance, can be used for preparing coatings with different gloss of 5-30%, can be used for replacing part of indoor extinction powder coatings, and solves the problem of free TMA in the powder coating.
Claims (7)
1. A mixed matte powder coating without TMA, characterized in that: the composite material comprises the following raw material components in parts by mass: 390 parts of TMA-free type polyester resin, 260 parts of epoxy resin 213, 300 parts of titanium dioxide, 80-140 parts of inorganic filler, 8-12 parts of flatting agent, 3-7 parts of benzoin, 3-7 parts of wetting accelerator and 30-50 parts of matting agent.
2. The hybrid matte powder coating without TMA of claim 1, wherein: the TMA-free type polyester resin is a carboxyl-terminated saturated polyester resin, and the polyester resin does not contain trimellitic anhydride.
3. The hybrid matte powder coating without TMA of claim 2, wherein: the preparation method of the TMA-free type polyester resin comprises the following steps: putting 1120 parts by mass of neopentyl glycol, 390 parts by mass of liquid alcohol and 30 parts by mass of trimethylolpropane into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding 2590 parts by mass of terephthalic acid and 4 parts by mass of esterification catalyst, heating to 247 ℃ for maintaining reaction until a reactant is clear, sampling, measuring an acid value, cooling to 220 ℃, adding 260 parts by mass of a capping agent, maintaining the reactant clear, sampling, measuring the acid value, vacuumizing for 3 hours, finally adding 12 parts by mass of a curing accelerator and 35 parts by mass of an antioxidant, and maintaining for 20 minutes to obtain a sample which is a carboxyl-terminated saturated polyester resin.
4. The hybrid matte powder coating without TMA of claim 3, wherein: the liquid alcohol is one or more of ethylene glycol, diethylene glycol and 2-methyl-1, 3-propylene glycol; the esterification catalyst is stannous oxalate; the end capping agent is one or more of isophthalic acid, adipic acid, succinic acid, cyclohexanedicarboxylic acid and fumaric acid; the curing accelerator is one or more of tetraethyl ammonium bromide, ethyl triphenyl phosphonium bromide and benzyl triethyl ammonium chloride; the antioxidant is 168 or 1010.
5. The hybrid matte powder coating without TMA of claim 1, wherein: the epoxy resin is epoxy resin E-12 produced by a two-step method; the inorganic filler is delustered barium; the leveling agent is GLP 588; the wetting enhancer is 701B; the matting agent is one of T300, Elatan K7225 and Elatan K7227.
6. The hybrid matte powder coating without TMA of claim 1, wherein: the mass ratio of the TMA-free type polyester resin to the epoxy resin is 60: 40.
7. a method of producing a matted powder paint of the TMA-free hybrid type according to claims 1 to 6, wherein: the method comprises the following steps: firstly, proportioning raw materials according to the parts by weight, and fully premixing the weighed raw materials in a mixing tank; secondly, extruding the mixture by a double-screw extruder, wherein the parameters are set to be 85-100 ℃ in the region I, 110-125 ℃ in the region II, 100-115 ℃ in the region III, 35Hz in feeding speed frequency and 40Hz in screw speed frequency; and thirdly, crushing the extruded sheet material, grinding, sieving by a 200-mesh sieve, and finally packaging to obtain the finished product.
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Application publication date: 20191220 |