CN113248694A - Super-weather-resistant flexible polyester resin and preparation method thereof - Google Patents
Super-weather-resistant flexible polyester resin and preparation method thereof Download PDFInfo
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- CN113248694A CN113248694A CN202110440556.2A CN202110440556A CN113248694A CN 113248694 A CN113248694 A CN 113248694A CN 202110440556 A CN202110440556 A CN 202110440556A CN 113248694 A CN113248694 A CN 113248694A
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- polyester resin
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- flexible polyester
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 65
- 239000004645 polyester resin Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 76
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims abstract description 46
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 claims abstract description 35
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 25
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 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 6
- 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 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007590 electrostatic spraying Methods 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims 4
- 244000028419 Styrax benzoin Species 0.000 claims 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims 2
- 229960002130 benzoin Drugs 0.000 claims 2
- 235000019382 gum benzoic Nutrition 0.000 claims 2
- 239000004408 titanium dioxide Substances 0.000 claims 2
- 239000002518 antifoaming agent Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 8
- 238000005886 esterification reaction Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 13
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 150000007519 polyprotic acids Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- WUOWZVFFBAMVAU-IWGRKNQJSA-N 2,3-bis[[(e)-3-(4-methoxyphenyl)prop-2-enoyl]oxy]propyl 2-ethylhexanoate Chemical compound C=1C=C(OC)C=CC=1/C=C/C(=O)OC(COC(=O)C(CC)CCCC)COC(=O)\C=C\C1=CC=C(OC)C=C1 WUOWZVFFBAMVAU-IWGRKNQJSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DRDZUOCYOWQUCR-UHFFFAOYSA-N 5-ethylheptane-2,3-diol Chemical compound CCC(CC)CC(O)C(C)O DRDZUOCYOWQUCR-UHFFFAOYSA-N 0.000 description 1
- KCFOLUKWAIAKFB-UHFFFAOYSA-N CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br Chemical compound CCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Br KCFOLUKWAIAKFB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- -1 acid rain Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides an ultra-weather-resistant flexible polyester resin which is prepared from the following raw materials in percentage by weight: 1.0-8.0% of neopentyl glycol, 5-15% of ethyl butyl propylene glycol, 20.0-35.0% of trimethyl pentanediol, 0-5% of trimethylolpropane, 45.0-55.0% of isophthalic acid, 2.0-12.0% of sebacic acid, 0.02-0.15% of monobutyl tin oxide and 0-1% of curing accelerator. In the invention, the ethyl butyl propylene glycol is selected, and based on the long-chain side group butyl and ethyl on the molecular structure of the ethyl butyl propylene glycol, the steric hindrance density of a resin chain is improved, and the weather resistance of the resin is mainly improved; trimethyl pentanediol and sebacic acid have longer main chains, and the flexibility of resin chains is improved, so that the overall flexibility is improved; trimethylolpropane, due to its high functionality, increases the crosslink density of the paint film, thereby increasing the chemical resistance and weatherability of the resin. The invention controls the feeding sequence and the setting of reaction parameters, so that the esterification reaction has the advantages of high speed, few byproducts, concentrated molecular weight distribution and excellent performance.
Description
Technical Field
The invention belongs to the field of chemical polyester resin, and particularly relates to super-weather-resistant flexible polyester resin and a preparation method thereof.
Background
The thermosetting powder coating has the characteristics of no VOC emission, environmental protection, energy conservation, high construction efficiency, wide application range and the like. Thermosetting powder coatings are widely used for spraying metal substrates due to excellent protection, corrosion resistance and decoration, and the application occasions are more and more extensive. And the powder coating is in outdoor environment, receive the effect of ultraviolet irradiation and water, acid rain, oxygen etc. the coating can constantly age and degrade for life greatly reduced, in addition, because receive external factors such as collision etc. influence, the coating also can produce mechanical damage such as crackle, influences its life. Therefore, the improvement of the weather resistance and the mechanical property of the powder coating is of great significance to energy conservation, emission reduction and the improvement of the service life of the material. The optimization of weather resistance and mechanical properties is also the key to technical improvement as polyester resin is an important component of powder coating.
Under the existing technical conditions, the problem of simply solving the weather resistance or mechanical property of the powder coating is not solved, however, the weather resistance and mechanical property of the powder coating are both considered, so far, the difficulty is still high, the method is mainly limited by a synthetic polyester resin monomer, and a monomer which has good flexibility, good weather resistance and proper cost is not available. Therefore, the solution of the weather resistance and mechanical properties of the powder coating is one of the important directions for the improvement of the polyester resin. Therefore, the research on the super weather-resistant flexible polyester resin adopts TGIC (triglycidyl isocyanurate) to cure to obtain the outdoor powder coating with excellent weather resistance and mechanical properties, and has great market popularization significance for the outdoor polyester resin powder coating.
CN108070077A discloses a high weather-resistant saturated polyester resin, which comprises the following main components in percentage by weight: neopentyl glycol: 15 to 30 percent; 2-ethyl-butyl propylene glycol: 5 to 20 percent; trimethylolpropane: 0.5-10%; isophthalic acid: 15 to 35 percent; adipic acid: 5 to 10 percent; 1, 4-cyclohexanedicarboxylic acid: 5 to 15 percent; butyl tin oxide: 0.01 to 0.2 percent; xylene: 1 to 10 percent; aromatic hydrocarbon solvent 150 #: 15 to 40 percent; ethylene glycol butyl ether: 5 to 20 percent. Although the technical scheme of the polyester resin improves the weather resistance of the polyester resin to a certain extent, the mechanical property and the strength are not enough.
CN103131308B discloses a high-low acid value bi-component carboxyl-terminated polyester resin composition for an ultra-weather-resistant dry-mixed extinction powder coating, which comprises the following components: (1) the high-acid-value carboxyl-terminated polyester resin for the super-weather-resistant powder coating has an acid value of 45-55 mgKOH/g, a hydroxyl value of less than 10mgKOH/g, a glass transition temperature of 60-75 ℃, a melt viscosity of 2000-8500 mPa & s and a number average molecular weight of 2000-8000, and is prepared by condensation polymerization of the following raw materials in percentage by weight: polyol: 25-50%, aromatic polybasic acid: 40-60%, fatty polybasic acid: 0% to 10%, branching agent: 0-3%, acidolysis agent: 7 to 20 percent of esterification catalyst and 0.01 to 0.15 percent of esterification catalyst; (2) the low-acid-value carboxyl-terminated polyester resin for the super-weather-resistant powder coating has an acid value of 17-25 mgKOH/g, a hydroxyl value of less than 10mgKOH/g, a glass transition temperature of 60-70 ℃, a melt viscosity of 2000-8500 mPa & s, a number average molecular weight of 2000-8000, and is prepared by condensation polymerization of the following raw materials in percentage by weight: polyol: 30-45%, aromatic polybasic acid: 45% -65%, fatty polybasic acid: 0% to 10%, branching agent: 0% -2%, acidolysis agent: 4 to 15 percent of the catalyst and 0.01 to 0.15 percent of the esterification catalyst. The technical scheme adopts the combination of the two-component carboxyl-terminated polyester resin with high and low acid values, provides high weather resistance, but has low mechanical property and strength and complex preparation process.
Disclosure of Invention
The invention aims to provide an ultra-weather-resistant flexible polyester resin which is low in production cost and has excellent weather resistance and mechanical properties, and TGIC curing (triglycidyl isocyanurate) is adopted to obtain a powder coating with excellent weather resistance and mechanical properties for outdoor occasions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the super weather-resistant flexible polyester resin is prepared from the following raw materials in percentage by weight: 1.0-8.0% of neopentyl glycol, 5-15% of ethyl butyl propylene glycol, 20.0-35.0% of trimethyl pentanediol, 0-5% of trimethylolpropane, 45.0-55.0% of isophthalic acid, 2.0-12.0% of sebacic acid, 0.02-0.15% of monobutyl tin oxide and 0-1% of a curing accelerator;
the preparation method of the super weather-resistant flexible polyester resin comprises the following steps:
s1, adding neopentyl glycol, ethyl butyl propylene glycol, trimethyl pentanediol, trimethylolpropane, part of isophthalic acid and monobutyl tin oxide into a reaction kettle in proportion, introducing nitrogen with the purity of 99.9%, heating to 180 +/-10 ℃, generating esterified water, distilling off, and obtaining colorless transparent liquid as a distillate; then gradually heating to 240 +/-5 ℃, and preserving the temperature until the solution in the reaction kettle becomes clear, the acid value reaches 8-26mgKOH/g and the viscosity is 800-;
s2, adding the rest isophthalic acid and sebacic acid in proportion at the temperature of 230 +/-5 ℃, heating to 240 +/-5 ℃ and reacting for 1-3 hours until the acid value of the solution in the reaction kettle is 40-45mgKOH/g and the viscosity is 700-1600mPa & s;
s3, at the temperature of 225 +/-5 ℃, vacuumizing until the acid value of the solution in the reaction kettle is 30-36mgKOH/g and the viscosity is 4000-6000mPa & s;
s4, cooling to 210 +/-5 ℃, adding a curing accelerator in proportion, stirring, and discharging to obtain the super weather-resistant flexible polyester resin.
In the invention, the ethyl butyl propylene glycol is selected, and based on the long-chain side group butyl and ethyl on the molecular structure of the ethyl butyl propylene glycol, the steric hindrance density of a resin chain is improved, and the weather resistance of the resin is mainly improved; trimethyl pentanediol and sebacic acid have longer main chains, and the flexibility of resin chains is improved, so that the overall flexibility is improved; trimethylolpropane, due to its high functionality, increases the crosslink density of the paint film, thereby increasing the chemical resistance and weatherability of the resin. Isophthalic acid has improved hardness and toughness due to the presence of phenyl groups, and the use of a large amount of isophthalic acid can improve the weatherability of the resin. In addition, the invention controls the feeding sequence and the setting of reaction parameters, so that the esterification reaction has the advantages of high speed, few byproducts, concentrated molecular weight distribution and excellent performance.
In the invention, preferably, the super weather-resistant flexible polyester resin is prepared from the following raw materials in percentage by weight: 1.0-8.0% of neopentyl glycol, 5-15% of ethyl butyl propylene glycol, 20.0-35.0% of trimethyl pentanediol, 0-5% of trimethylolpropane, 45.0-55.0% of isophthalic acid, 2.0-12.0% of sebacic acid, 0.02-0.15% of monobutyl tin oxide and 0-1% of curing accelerator. Further preferably, the super weather-resistant flexible polyester resin is prepared from the following raw materials in percentage by weight: 3.0-8.0% of neopentyl glycol, 5-15% of ethylbutyl propylene glycol, 20.0-35.0% of trimethyl pentanediol, 2-5% of trimethylolpropane, 45.0-55.0% of isophthalic acid, 6.0-12.0% of sebacic acid, 0.06-0.15% of monobutyl tin oxide and 0-1% of curing accelerator.
In the present invention, preferably, the curing accelerator is one of triphenylphosphine, ethyltriphenylphosphine bromide, tetraethylammonium bromide and tetrabutylammonium bromide.
In the present invention, it is preferable that the amount of the isophthalic acid added in S1 is 80% or more of the total amount of isophthalic acid used.
In the present invention, preferably, the super weather-resistant flexible polyester resin further contains 0 to 2% of an antioxidant, which is a phenolic antioxidant.
In the invention, the method for measuring the solution viscosity specifically comprises the following steps: rotational viscometer method.
The glass transition temperature of the polyester resin prepared by the invention is 60-70 ℃, the number average molecular weight is 3000-8000, and the acid value of the polyester resin is 30-36 mgKOH/g.
The invention also provides an outdoor thermosetting powder coating which is prepared from the following raw materials in parts by weight:
500-600 parts of polyester resin prepared by the invention
Preferably, the thermosetting powder coating is prepared from the following raw materials in parts by weight:
550 parts of polyester resin prepared by the invention
The preparation method of the outdoor thermosetting powder coating comprises the following steps: premixing all the raw materials, extruding by a double-screw extruder, tabletting, crushing, then crushing the sheet materials, sieving by a 200-mesh sieve, spraying on an iron plate by an electrostatic spraying method, and curing at 200 ℃ for 10 min.
Compared with the prior art, the invention has the beneficial effects that:
1. in the invention, the ethyl butyl propylene glycol is selected, and based on the long-chain side group butyl and ethyl on the molecular structure of the ethyl butyl propylene glycol, the steric hindrance density of a resin chain is improved, and the weather resistance of the resin is mainly improved; trimethyl pentanediol and sebacic acid have longer main chains, and the flexibility of resin chains is improved, so that the overall flexibility is improved; trimethylolpropane, due to its high functionality, increases the crosslink density of the paint film, thereby increasing the chemical resistance and weatherability of the resin. Isophthalic acid has improved hardness and toughness due to the presence of phenyl groups, and the use of a large amount of isophthalic acid can improve the weatherability of the resin.
2. The invention controls the feeding sequence and the setting of reaction parameters, so that the esterification reaction has the advantages of high speed, few byproducts, concentrated molecular weight distribution and excellent performance. The polyester resin has low production cost and excellent weather resistance and mechanical property, and can be used for obtaining powder coating with excellent weather resistance and mechanical property for outdoor occasions by adopting TGIC curing (triglycidyl isocyanurate).
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, but the scope of the present invention is not limited to the embodiments.
The starting materials used in the following examples are all commercially available unless otherwise specified.
Example 1:
an ultra-weather-resistant flexible polyester resin,
the formula is as follows:
4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of Trimethylpentanediol (TMPD), 52.8Kg of isophthalic acid, 0.12Kg of monobutyltin oxide, 2.18Kg of sebacic acid (DDDA), 0.1Kg of curing accelerator (ethyltriphenylphosphonium bromide).
The preparation method comprises the following steps: 8
1) Adding 4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of Trimethylpentanediol (TMPD), 49.41Kg of isophthalic acid and 0.12Kg of monobutyltin oxide into a reaction kettle provided with a heating device, a stirrer and a condensing tower according to a proportion, introducing nitrogen with the purity of 99.9 percent, heating to 180 ℃, starting to generate and distill esterified water, gradually heating the distillate to 235 ℃, and preserving the temperature until the melt becomes clear, wherein the product is qualified when the acid value reaches 19.0mgKOH/g and the viscosity is 1100 mPas;
2) adding 3.39Kg of isophthalic acid and 2.18Kg of sebacic acid (DDDA) at 230 ℃ according to a proportion, gradually heating to 240 ℃ and reacting for 2 hours until the acid value is 44.5mgKOH/g and the viscosity is 1400 mPas;
3) vacuumizing at 225 ℃ until the acid value is 32.5mgKOH/g and the viscosity is 4800mPa & s;
4) cooling to 205 ℃, adding 0.1Kg of curing accelerator according to the proportion, stirring and discharging to obtain the super weather-resistant flexible polyester resin.
Example 2:
an ultra-weather-resistant flexible polyester resin,
the formula is as follows:
8.0Kg of neopentyl glycol, 5.0Kg of ethylbutylpropanediol (BEPD), 2.0Kg of trimethylolpropane, 28.8Kg of Trimethylpentanediol (TMPD), 54.0Kg of isophthalic acid, 0.1Kg of monobutyltin oxide, 2.0Kg of sebacic acid (DDDA), 0.1Kg of curing accelerator (triphenylphosphine).
The preparation method comprises the following steps:
1) adding 8.0Kg of neopentyl glycol, 5.0Kg of ethylbutylpropanediol (BEPD), 2.0Kg of trimethylolpropane, 28.8Kg of Trimethylpentanediol (TMPD), 53.5Kg of isophthalic acid and 0.1Kg of monobutyltin oxide into a reaction kettle provided with a heating device, a stirrer and a condensing tower according to a proportion, introducing nitrogen with the purity of 99.9 percent, heating to 180 ℃, starting to generate and distill esterified water, wherein the distillate is colorless transparent liquid, gradually heating to 240 ℃, and preserving heat until the melt becomes clear, and the product is qualified when the acid value reaches 26.0mgKOH/g and the viscosity is 1000 mPas;
2) 0.5Kg of isophthalic acid and 2.0Kg of sebacic acid (DDDA) are added according to a proportion at 225 ℃ and are gradually heated to 240 ℃ for reaction for 2 hours until the mixture is qualified when the acid value is 44.5mgKOH/g and the viscosity is 1150 mPas;
3) vacuumizing at 230 ℃ until the acid value is 35.3mgKOH/g and the viscosity is 6000mPa & s, and then obtaining the product;
4) cooling to 215 ℃, adding 0.1Kg of curing accelerator according to the proportion, stirring and discharging to obtain the super weather-resistant flexible polyester resin.
Example 3:
an ultra-weather-resistant flexible polyester resin,
the formula is as follows:
2.0Kg of neopentyl glycol, 15.0Kg of ethylbutylpropanediol (BEPD), 1.2Kg of trimethylolpropane, 27.0Kg of Trimethylpentanediol (TMPD), 49.6Kg of isophthalic acid, 0.1Kg of monobutyltin oxide, 5.0Kg of sebacic acid (DDDA), 0.1Kg of curing accelerator (tetraethylammonium bromide).
The preparation method comprises the following steps:
1) adding 2.0Kg of neopentyl glycol, 15.0Kg of ethylbutylpropanediol (BEPD), 1.2Kg of trimethylolpropane, 27.0Kg of Trimethylpentanediol (TMPD), 46.0Kg of isophthalic acid and 0.1Kg of monobutyltin oxide into a reaction kettle provided with a heating device, a stirrer and a condensing tower in proportion, introducing nitrogen with the purity of 99.9 percent, heating to 180 ℃, starting to generate and distill esterified water, gradually heating the distillate to 245 ℃, and preserving the temperature until the melt becomes clear, wherein the product is qualified when the acid value reaches 13.0mgKOH/g and the viscosity is 900 mPas;
2) adding 3.6Kg of isophthalic acid and 5.0Kg of sebacic acid (DDDA) in proportion at 230 ℃ to gradually raise the temperature to 240 ℃ for reaction for 2 hours until the acid value is 40mgKOH/g and the viscosity is 900mPa · s;
3) vacuumizing at 200 ℃ until the acid value is 30.5mgKOH/g and the viscosity is 4100 mPas, and then obtaining the product;
4) cooling to 205 ℃, adding 0.1Kg of curing accelerator according to the proportion, stirring and discharging to obtain the super weather-resistant flexible polyester resin.
Example 4:
an ultra-weather-resistant flexible polyester resin,
the formula is as follows:
2.4Kg of neopentyl glycol, 7.0Kg of ethylbutylpropanediol (BEPD), 1.9Kg of trimethylolpropane, 35.0Kg of Trimethylpentanediol (TMPD), 50.5Kg of isophthalic acid, 0.1Kg of monobutyltin oxide, 3.0Kg of sebacic acid (DDDA), 0.1Kg of curing accelerator (tetrabutylammonium bromide).
The preparation method comprises the following steps:
1) adding 2.4Kg of neopentyl glycol, 7.0Kg of ethylbutylpropanediol (BEPD), 1.9Kg of trimethylolpropane, 35.0Kg of Trimethylpentanediol (TMPD), 47.5Kg of isophthalic acid and 0.1Kg of monobutyltin oxide into a reaction kettle provided with a heating device, a stirrer and a condensing tower in proportion, introducing nitrogen with the purity of 99.9 percent, heating to 180 ℃, starting to generate and distill esterified water, wherein the distillate is colorless transparent liquid, gradually heating to 240 ℃, and preserving heat until the melt becomes clear, and the product is qualified when the acid value reaches 10.5mgKOH/g and the viscosity is 1200mPa & s;
2) adding 3.0Kg of isophthalic acid and 3.0Kg of sebacic acid (DDDA) at 230 ℃ according to a proportion, gradually heating to 240 ℃ for reaction for 2 hours until the acid value is 42.5mgKOH/g and the viscosity is 1150 mPas;
3) vacuumizing at 230 ℃ until the acid value is 31.0mgKOH/g and the viscosity is 5900mPa & s;
4) cooling to 215 ℃, adding 0.1Kg of curing accelerator according to the proportion, stirring and discharging to obtain the super weather-resistant flexible polyester resin.
Comparative example 1:
comparative example 1 the parameter settings of the preparation process were different compared to example 1.
An ultra-weather-resistant flexible polyester resin,
the formula is as follows:
4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of Trimethylpentanediol (TMPD), 52.8Kg of isophthalic acid, 0.12Kg of monobutyltin oxide, 2.18Kg of sebacic acid (DDDA), 0.1Kg of curing accelerator (ethyltriphenylphosphonium bromide).
The preparation method comprises the following steps:
1) adding 4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of Trimethylpentanediol (TMPD), 49.41Kg of isophthalic acid and 0.12Kg of monobutyltin oxide into a reaction kettle provided with a heating device, a stirrer and a condensing tower according to a proportion, introducing nitrogen with the purity of 99.9 percent, heating to 180 ℃, starting to generate and distill esterified water, gradually heating the distillate to 245 ℃, and preserving the temperature until the melt becomes clear, and the product is qualified when the acid value reaches 18.6mgKOH/g and the viscosity is 1100 mPas;
2) adding 3.39Kg of isophthalic acid and 2.18Kg of sebacic acid (DDDA) according to a proportion at 220 ℃ to gradually raise the temperature to 240 ℃ for reaction for 2 hours until the acid value is 44.5mgKOH/g and the viscosity is 1200mPa & s;
3) vacuumizing at 220 ℃ until the acid value is 35.0mgKOH/g and the viscosity is 3300mPa & s, and then the product is qualified;
4) cooling to 205 ℃, adding 0.1Kg of curing accelerator according to the proportion, stirring and discharging to obtain the super weather-resistant flexible polyester resin.
Comparative example 2:
comparative example 2 the parameter settings of the preparation process were different compared to example 1.
An ultra-weather-resistant flexible polyester resin,
the formula is as follows:
4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of Trimethylpentanediol (TMPD), 52.8Kg of isophthalic acid, 0.12Kg of monobutyltin oxide, 2.18Kg of sebacic acid (DDDA), 0.1Kg of curing accelerator (ethyltriphenylphosphonium bromide).
The preparation method comprises the following steps:
1) adding 4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of Trimethylpentanediol (TMPD), 49.41Kg of isophthalic acid and 0.12Kg of monobutyltin oxide into a reaction kettle provided with a heating device, a stirrer and a condensing tower according to a proportion, introducing nitrogen with the purity of 99.9 percent, heating to 180 ℃, starting to generate and distill esterified water, gradually heating the distillate to 245 ℃, and preserving the temperature until the melt becomes clear, and the product is qualified when the acid value reaches 18.0mgKOH/g and the viscosity is 1000 mPas;
2) adding 3.39Kg of isophthalic acid and 2.18Kg of sebacic acid (DDDA) according to a proportion at 235 ℃ to gradually raise the temperature to 240 ℃ for reaction for 2 hours until the acid value is 44.5mgKOH/g and the viscosity is 1300mPa & s;
3) vacuumizing at 240 ℃ until the acid value is 31.5mgKOH/g and the viscosity is 8900mPa & s;
4) cooling to 205 ℃, adding 0.1Kg of curing accelerator according to the proportion, stirring and discharging to obtain the super weather-resistant flexible polyester resin.
Comparative example 3:
comparative example 3 compared with example 1, the formulation of the polyester resin was different and the procedure of the preparation method was completely the same.
The formulation of the super weather-resistant flexible polyester resin of this comparative example is as follows:
4.84Kg of neopentyl glycol, 12.11Kg of ethylbutylpropanediol (BEPD), 1.21Kg of trimethylolpropane, 26.64Kg of butanediol, 52.8Kg of isophthalic acid, 0.12Kg of monobutyltin oxide, 2.18Kg of adipic acid, 0.1Kg of cure accelerator (ethyltriphenylphosphonium bromide).
Performance testing
Powder coatings 1 to 7 were powder coatings prepared from the polyester resins obtained in examples 1 to 4 according to the present invention and comparative examples 1 to 3, and the formulations of the powder coatings are shown in Table 1 (in parts by weight). All the raw materials are premixed according to the following table 1, extruded, tabletted and crushed by a double-screw extruder, then the sheet materials are crushed and sieved by a 200-mesh sieve, and then sprayed on an iron plate by an electrostatic spraying method, and various performance tests are carried out after curing at 200 ℃ for 10 min. Simultaneously purchasing super-weather-resistant polyester resin with excellent performance on the market
4488-0) as control, forming powder coating by the same formulation and process, spraying on iron plate by electrostatic spraying, curing at 200 deg.C for 10min, and testing properties.
The test conditions are carried out according to GB/T1732 & 1993 determination method of impact resistance of paint film, national standard GB/T6742 & 2007-T test of bending of colored paint and varnish (cylindrical shaft), national standard GB/T9286 & 1998 test of marking a lattice of colored paint and varnish paint film, GB/T6739 & 2006 method of pencil lead determination of paint film, wherein the hardness is the scratch hardness of the test of Chinese pencil. And (3) weather resistance test: after coating a sample having a coating film thickness of 80 to 100 μm after spraying and placing the sample in an artificial aging tester for 800 hours, the weather resistance was evaluated as follows: the light retention rate of the product is more than 50 percent, and the product is qualified. And (3) testing conditions are as follows: light source, UVB-310 nm; drying at 60 deg.c for 8 hr; condensing for 4 hours at 50 ℃; irradiation of 0.76W/m2。
Table 1 powder coating formulations table
Table 2 table of performance test results
As can be seen from Table 2, the super-weather-resistant flexible polyester resin prepared by the invention is prepared into powder coating and cured to form a coating through the selection of the formula raw materials and the parameter control in the preparation process, the impact resistance strength of the super-weather-resistant flexible polyester resin is obviously superior to that of the common super-weather-resistant polyester resin, and the weather resistance of the super-weather-resistant flexible polyester resin is basically consistent with that of the super-weather-resistant polyester resin, so that the super-weather-resistant flexible polyester resin is very suitable for being used as an outdoor decorative coating.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The super weather-resistant flexible polyester resin is characterized by being prepared from the following raw materials in percentage by weight: 1.0-8.0% of neopentyl glycol, 5-15% of ethyl butyl propylene glycol, 20.0-35.0% of trimethyl pentanediol, 0-5% of trimethylolpropane, 45.0-55.0% of isophthalic acid, 2.0-12.0% of sebacic acid, 0.02-0.15% of monobutyl tin oxide and 0-1% of a curing accelerator;
the preparation method of the super weather-resistant flexible polyester resin comprises the following steps:
s1, adding neopentyl glycol, ethyl butyl propylene glycol, trimethyl pentanediol, trimethylolpropane, part of isophthalic acid and monobutyl tin oxide into a reaction kettle in proportion, introducing nitrogen with the purity of 99.9%, heating to 180 +/-10 ℃, generating esterified water, distilling off, and obtaining colorless transparent liquid as a distillate; then gradually heating to 240 +/-5 ℃, and preserving the temperature until the solution in the reaction kettle becomes clear, the acid value reaches 8-26mgKOH/g and the viscosity is 800-;
s2, adding the rest isophthalic acid and sebacic acid in proportion at the temperature of 230 +/-5 ℃, heating to 240 +/-5 ℃ and reacting for 1-3 hours until the acid value of the solution in the reaction kettle is 40-45mgKOH/g and the viscosity is 700-1600mPa & s;
s3, at the temperature of 225 +/-5 ℃, vacuumizing until the acid value of the solution in the reaction kettle is 30-36mgKOH/g and the viscosity is 4000-6000mPa & s;
s4, cooling to 210 +/-5 ℃, adding a curing accelerator in proportion, stirring, and discharging to obtain the super weather-resistant flexible polyester resin.
2. The super weather-resistant flexible polyester resin as claimed in claim 1, which is prepared from the following raw materials in percentage by weight: 1.0-8.0% of neopentyl glycol, 5-15% of ethyl butyl propylene glycol, 20.0-35.0% of trimethyl pentanediol, 0-5% of trimethylolpropane, 45.0-55.0% of isophthalic acid, 2.0-12.0% of sebacic acid, 0.02-0.15% of monobutyl tin oxide and 0-1% of curing accelerator.
3. The super weather-resistant flexible polyester resin as claimed in claim 2, wherein the curing accelerator is one of triphenylphosphine, ethyltriphenylphosphonium bromide, tetraethylammonium bromide and tetrabutylammonium bromide.
4. The super weather-resistant flexible polyester resin as claimed in claim 1, wherein the amount of the isophthalic acid added as a part in S1 is 80% or more of the total amount of isophthalic acid.
5. The super weather-resistant flexible polyester resin as claimed in claim 1, wherein the viscosity of the resin is measured by a rotational viscometer method.
6. The super weather resistant flexible polyester resin as claimed in claim 1, wherein the super weather resistant flexible polyester resin further comprises 0-2% of an antioxidant, and the antioxidant is a phenolic antioxidant.
7. The super weather-resistant flexible polyester resin as claimed in claim 1, wherein the glass transition temperature of the polyester resin is 60-70 ℃, the number average molecular weight is 3000-8000, and the acid value of the polyester resin is 30-36 mgKOH/g.
8. The outdoor thermosetting powder coating is characterized by being prepared from the following raw materials in parts by weight:
500 to 600 parts of the polyester resin according to claim 1
37-45 parts of TGIC
7-12 parts of flatting agent
7-12 parts of a brightener
1-5 parts of benzoin
180-220 parts of titanium dioxide
160-200 parts of barium sulfate.
9. The thermosetting powder coating for outdoor use according to claim 8, which is prepared from the following raw materials in parts by weight:
550 parts of the polyester resin as claimed in claim 1
TGIC 42 parts
15 portions of flatting agent
9 portions of defoaming agent
Benzoin 9 parts
Titanium dioxide 200 parts
185 parts of barium sulfate.
10. The method of claim 9, wherein all the raw materials are premixed, extruded through a twin screw extruder, tabletted, and crushed, and then the flakes are crushed and sieved through a 200 mesh sieve, and then sprayed on an iron plate by electrostatic spraying, and cured at 200 ℃ for 10 min.
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