CN113388093B - Hydrolysis-resistant polyester resin for water-based coil finish paint and preparation method thereof - Google Patents
Hydrolysis-resistant polyester resin for water-based coil finish paint and preparation method thereof Download PDFInfo
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- CN113388093B CN113388093B CN202110764881.4A CN202110764881A CN113388093B CN 113388093 B CN113388093 B CN 113388093B CN 202110764881 A CN202110764881 A CN 202110764881A CN 113388093 B CN113388093 B CN 113388093B
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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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- 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
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Abstract
The invention belongs to the technical field of polyester resin preparation, and particularly relates to hydrolysis-resistant polyester resin for water-based coil finish paint and a preparation method thereof, wherein the molecular weight of the polyester resin is 1000-20000, the acid value is 20-100mgKOH/g, the hydroxyl value is 50-300mgKOH/g, the solid content is 40-80%, the neutralization degree is 50-100%, and the preparation method comprises the following steps: selecting polyhydric alcohol with excellent hydrolysis resistance, polybasic acid monomer and hydrolysis-resistant monomer, carrying out polycondensation reaction under the condition of a catalyst to obtain a high molecular polymer with medium and low molecular weight, then reacting the substance with a water-based monomer, finally completing neutralization, and adding water to obtain a water-based polyester resin product. The polyester resin provided by the invention is stable in storage, good in weather resistance and high in curing efficiency.
Description
Technical Field
The invention belongs to the technical field of polyester resin preparation, and particularly relates to hydrolysis-resistant polyester resin for a water-based coil finish paint and a preparation method thereof.
Background
At present, the precoated coil coating mainly adopts a solvent type as a main material, and resin as a film forming material is an oily material. The solvent-based coil coating contains a large amount of xylene, S150 and other aromatic solvents, and the solvents are required to be used for dilution in the using process. The organic solvents are volatile and seriously pollute the environment; the material is flammable and explosive, and has safety risks in the transportation and use processes; the gas is toxic, a large amount of toxic gas volatilizes in the using process, inhalation injury can be caused to workers, and in addition, the working environment of a workshop is poor, so that the bodies of the workers are seriously injured.
At present, the national environment protection situation is getting stricter, the voc content of the oil paint is high, and the use of the paint causes huge pollution and damage to the environment. The water-based paint mainly takes water as a solvent, has low voc content, is safe and environment-friendly, reduces the use of organic solvents to a great extent, and has obvious economic and environment-friendly benefits. The resin is a key component of the coating, and the structure and the performance of the resin determine the quality of the coating product; the coil coating mainly takes polyester resin as a film forming substance, has excellent T-bend, hardness and weather resistance, and the water-based polyester resin mainly has the problems of unstable storage, poor weather resistance, low curing efficiency and the like.
Disclosure of Invention
Aiming at the technical problems at present, the invention provides hydrolysis-resistant polyester resin for water-based coil finish paint and a preparation method thereof, the hydrolysis-resistant polyester resin for the water-based coil finish paint is synthesized, and the problems of unstable storage, poor weather resistance, low curing efficiency and the like of the water-based polyester resin are solved.
The hydrolysis-resistant polyester resin for the water-based coil finishing paint has the molecular weight of 1000-20000, the acid value of 20-100mgKOH/g, the hydroxyl value of 50-300mgKOH/g, the solid content of 40-80 percent and the neutralization degree of 50-100 percent.
Preferably, the raw materials for preparing the polyester resin comprise the following components in parts by mass: 10-50 wt% of polyhydric alcohol, 10-50 wt% of polybasic acid, 1-15 wt% of hydrolysis-resistant monomer, 0.01-1 wt% of catalyst, 1-5 wt% of neutralizing agent, 10-30 wt% of hydrophilic solvent, 1-5 wt% of water-based monomer and the balance of deionized water;
the specific synthesis method of the hydrolysis-resistant monomer comprises the following steps: mixing the dibasic acid with the epoxy substance and the like, heating to 130-140 ℃, and reacting for 5-6h to obtain the hydrolysis-resistant monomer.
Further preferably, the specific synthesis method of the hydrolysis-resistant monomer comprises the following steps: mixing the dibasic acid with the epoxy substances and the like, heating to 130 ℃, and reacting for 5 hours to obtain the hydrolysis-resistant monomer.
More preferably, the dibasic acid is one of isophthalic acid, phthalic acid, terephthalic acid, succinic acid and glutaric acid, and the epoxy substance is one of ethylene oxide, propylene oxide, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, diethylene glycol glycidyl ether, dipropylene glycol glycidyl ether and epoxy resin.
Preferably, the catalyst is one of antimony-based and organic tin-based catalysts, and the dosage of the catalyst is 0.01 to 1wt percent of the total mass of the polymer;
preferably, the polyalcohol is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol in any proportion. Further preferably, the polyol is selected from: 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2-methyl-1, 3-propylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 1-methyl-1, 8-octanediol, 3-methyl-1, 6-hexanediol, 4-methyl-1, 7-heptanediol, glycerol, pentaerythritol, trimethylolpropane and hydroxymethylethane; the polybasic acid is one or more of dibasic acid, tribasic acid and anhydride in any proportion. Further preferably, the polyacid is selected from: isophthalic acid, phthalic acid, terephthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, maleic acid, tetrahydrophthalic acid, hexahydroisophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and maleic anhydride, or a plurality of the isophthalic acid, the phthalic acid, the pimelic acid, the suberic acid, the maleic acid, the tetrahydrophthalic acid, the hexahydrophthalic acid and the maleic anhydride in any proportion.
Preferably, the water-based monomer is one or more of phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and maleic anhydride in any proportion.
Preferably, the hydrophilic solvent is one or more selected from the group consisting of ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether acetate, ethanol, n-butanol, isopropanol, and butanol.
Preferably, the neutralizing agent is selected from one of ammonia, N, N-dimethylethanolamine, diethanolamine, triethanolamine, triethylamine, 1-methyldiethanolamine;
the invention selects polyol, polybasic acid monomer and hydrolysis-resistant monomer with excellent hydrolysis resistance to obtain high molecular polymer with medium and low molecular weight through polycondensation reaction under the condition of catalyst, then the material reacts with water-based monomer, and finally neutralization is completed, and water is added to obtain water-based polyester resin product.
A preparation method of hydrolysis-resistant polyester resin for water-based coil finish paint comprises the following preparation steps in sequence:
1) putting polyalcohol, polybasic acid and hydrolysis-resistant monomer into a reactor, slowly heating to 120 ℃, putting a catalyst into the reactor, slowly heating to 150 ℃, and keeping the temperature for 1-1.5 h;
2) continuously heating up to 10 ℃ per hour till 220 ℃, and carrying out heat preservation reaction;
3) observing the water yield of the reaction, starting to measure the acid value when the water yield is 88-93 percent, and cooling to 150-160 ℃ after the acid value is less than 5 mgKOH/g;
4) adding a water-based monomer, reacting for 0.5-1h, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
5) adding a hydrophilic solvent, a neutralizing agent and deionized water at 60 ℃, and fully and uniformly stirring to obtain the polyester resin.
The preparation method is simple, short in time consumption and safe in process; after the hydrolysis-resistant monomer is introduced into the synthesized polyester tree, the polyester tree is stored in a thermostat at 50 ℃ for 6 months without abnormality, the molecular weight distribution is uniform, a paint film obtained by matching amino resin has T-bend of 0T, the light loss rate of 340 ultraviolet aging is within 10 percent after 1500h, the 90cm shock resistance is excellent, the paint film is high in fullness, and the light and color retention are good.
The polyester resin prepared by the invention has active crosslinking sites such as hydroxyl, carboxyl and the like, and can be subjected to curing reaction with amino resin at high temperature (plate temperature 180-240 ℃), so that the polyester resin can be used for preparing coil polyester finish paint with low VOC content and various metal coils, and the baking temperature can be obviously reduced by matching with a catalyst (the existing catalyst), and the film forming effect is excellent.
The hydrolysis-resistant monomer is introduced, is segmented on a polyester molecular main chain, has a large hydrophobic group, is in an umbrella cap state, protects ester bonds from hydrolysis, successfully improves the hydrolysis stability of the water-based polyester, can meet the performance requirement of the water-based paint for the coil, and is used as the polyester resin for the water-based coil finish paint, so that the use amount of a solvent in the paint is effectively reduced, the VOC emission is reduced, and the water-based coil finish paint is safe and environment-friendly; the polyester resin provided by the invention is stable in storage, good in weather resistance and high in curing efficiency.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the present invention is limited to the examples. The techniques realized based on the above contents of the present invention all belong to the scope of the present invention, and the following embodiments are all completed by using the conventional prior art except for the specific description.
Example 1
A preparation method of hydrolysis-resistant polyester resin for water-based coil finish paint comprises the following steps:
synthesis of hydrolysis-resistant monomer (V-1): mixing isophthalic acid, glycol glycidyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain hydrolysis-resistant monomer V-1, and filtering for later use;
adding 110g of neopentyl glycol, 43g of V-1 monomer, 35g of trimethylolpropane, 60g of adipic acid, 200g of isophthalic acid and 25g of 1, 4-cyclohexanedicarboxylic acid into a four-neck flask provided with a thermometer, a stirring device and a condensation water separation device, heating slowly to melt all solid materials, and stirring; adding 0.3g of tin oxide serving as a catalyst under the condition of melting a material at the temperature of 120 ℃, adjusting the temperature of the material to 150 ℃ within 2 hours, carrying out heat preservation reaction for 1 hour, controlling the heating rate to be 10 ℃/hour, gradually heating to 220 ℃, carrying out heat preservation reaction at the temperature, continuously observing the water yield in the reaction process, starting to measure the acid value when the water yield reaches 90 percent of the theoretical water yield, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 160 ℃, adding 30g of trimellitic anhydride, carrying out reaction for 0.5 hour, and cooling to 60 ℃ after the measured acid value is less than 50 mgKOH/g;
dilution stage
Cooling to 60 ℃ in a reaction, adding 25g of neutralizer, namely 25g of N, N-dimethylethanolamine, stirring for reacting for 0.5 hour, then adding 200g of hydrophilic solvent, namely ethylene glycol monobutyl ether, adding 227.7g of deionized water, and adjusting to the solid content of a product of 50 wt%, thereby obtaining hydrolysis-resistant polyester resin for the water-based coil coating finish paint, wherein the molecular weight is 5400, the acid value is 45mgKOH/g, and the viscosity is 1500 mPa.s;
after the hydrolysis-resistant monomer V-1 is introduced into the polyester resin, the polyester resin is stored in a 50 ℃ thermostat for 6 months without abnormity, and the resin without the hydrolysis-resistant monomer is stored in the 50 ℃ thermostat for 10-15 days to cause the phenomena of turbidity and delamination.
Example 2
A preparation method of hydrolysis-resistant polyester resin for water-based coil finish paint comprises the following steps:
and (3) synthesis of hydrolysis-resistant monomer V-1: mixing terephthalic acid with ethylene glycol glycidyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain hydrolysis-resistant monomer V-1, and filtering for later use;
99g of neopentyl glycol, 48g of V-1 monomer, 16g of trimethylolpropane, 35g of 2-methyl glycol, 75g of adipic acid, 140g of terephthalic acid and 25g of 1, 4-cyclohexanedicarboxylic acid are added into a four-neck flask provided with a thermometer, a stirring device and a condensation and water separation device, the temperature is slowly increased by heating to melt all solid materials, and stirring is started. Adding 0.5g of catalyst monobutyl tin oxide under the condition of melting the material at 120 ℃, adjusting the temperature of the material to 150 ℃ within 2 hours, carrying out heat preservation reaction for 1 hour, controlling the temperature rise rate to be 10 ℃/hour, gradually raising the temperature to 220 ℃, and carrying out heat preservation reaction at the temperature. Continuously observing the water yield in the reaction process, starting to measure the acid value when the water yield reaches 88% of the theoretical water yield, cooling the material to 160 ℃ when the theoretical acid value is less than 5mgKOH/g, adding 30g of trimellitic anhydride, reacting for 0.5h, and cooling to 60 ℃ after the acid value is measured to be less than 50 mgKOH/g;
dilution stage
Cooling the reaction to 60 ℃, adding 25g of neutralizer N, N dimethyl ethanolamine, stirring for reaction for 0.5 hour, adding 150g of hydrophilic solvent ethylene glycol monobutyl ether, adding deionized water to adjust the solid content of the product to 50 wt%, and obtaining hydrolysis-resistant polyester resin for the water-based coil coating finish with the molecular weight of 3200, the acid value of 40mgKOH/g and the viscosity of 2300 mPa.s;
after the hydrolysis-resistant monomer V-1 is introduced into the polyester resin, the polyester resin is stored in a 50 ℃ thermostat for 6 months without abnormity, and the resin without the hydrolysis-resistant monomer is stored in the 50 ℃ thermostat for 10-15 days to cause the phenomena of turbidity and delamination.
Example 3
A preparation method of hydrolysis-resistant polyester resin for water-based coil finish paint comprises the following steps:
and (3) synthesis of hydrolysis-resistant monomer V-1: mixing phthalic acid with ethylene glycol glycidyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain hydrolysis-resistant monomer V-1, and filtering for later use;
98g of glycerol, 45g of V-1 monomer, 10g of trimethylolpropane, 40g of 1, 3-butanediol, 75g of adipic acid, 150g of phthalic anhydride and 23g of 1, 2-cyclohexanedicarboxylic acid are added into a four-neck flask provided with a thermometer, a stirring device and a condensation and water separation device, the temperature is slowly increased by heating, the solid materials are completely melted, and stirring is started. Adding 0.5g of esterification catalyst 4100 under the condition of melting a material at 120 ℃, adjusting the temperature of the material to 160 ℃ within 2h, carrying out heat preservation reaction for 1h, controlling the heating rate to be 10 ℃/h, gradually heating to 220 ℃, carrying out heat preservation reaction at the temperature, continuously observing the water yield in the reaction process, starting to measure the acid value when the water yield reaches 93 percent of theoretical water yield, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 155 ℃, adding 30g of trimellitic anhydride, carrying out reaction for 0.5h, and cooling to 60 ℃ after the measured acid value is less than 50 mgKOH/g;
dilution stage
And cooling the reaction to 60 ℃, adding 25g of triethylamine serving as a neutralizing agent, stirring the mixture for reaction for 0.5 hour, adding 180g of propylene glycol monomethyl ether serving as a hydrophilic solvent, and adding deionized water to adjust the solid content of the product to 50 wt% so as to obtain the hydrolysis-resistant polyester resin for the water-based coil coating finish with the molecular weight of 4400, the acid value of 50mgKOH/g and the viscosity of 4500 mPa.s.
After the hydrolysis-resistant monomer V-1 is introduced into the polyester resin, the polyester resin is stored in a 50 ℃ thermostat for 6 months without abnormity, and the resin without the hydrolysis-resistant monomer is stored in the 50 ℃ thermostat for 10-15 days to cause the phenomena of turbidity and delamination.
Example 4
A preparation method of hydrolysis-resistant polyester resin for water-based coil finish paint comprises the following steps:
and (3) synthesis of hydrolysis-resistant monomer V-1: mixing phthalic anhydride with ethylene glycol glycidyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain an anti-hydrolysis monomer V-1, and filtering for later use;
85g of neopentyl glycol, 55g of V-1 monomer, 15g of trimethylolpropane, 53g of hexanediol, 70g of adipic acid, 150g of isophthalic anhydride and 23g of 1, 2-cyclohexanedicarboxylic acid are placed in a four-neck flask equipped with a thermometer, a stirring device and a condensation and water separation device, heated slowly to melt the entire solid material, and stirred. Adding 0.4g of esterification catalyst 4100 under the condition of melting the material at 120 ℃, adjusting the temperature of the material to 160 ℃ within 2 hours, carrying out heat preservation reaction for 1 hour, controlling the heating rate to be 10 ℃/hour, gradually heating to 220 ℃, carrying out heat preservation reaction at the temperature, continuously observing the water yield in the reaction process, starting to measure the acid value when the water yield reaches 90 percent of the theoretical water yield, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 155 ℃, adding 30g of trimellitic anhydride, carrying out reaction for 0.5 hour, and cooling to 60 ℃ after the measured acid value is less than 50 mgKOH/g;
dilution stage
And cooling the reaction to 60 ℃, adding 25g of triethylamine serving as a neutralizing agent, stirring the mixture for reaction for 0.5 hour, adding 200g of hydrophilic propylene glycol monomethyl ether, and adding deionized water to adjust the solid content of the product to 50 wt% so as to obtain the hydrolysis-resistant polyester resin for the water-based coil coating finish paint, wherein the molecular weight of the hydrolysis-resistant polyester resin is 6500, the acid value of the hydrolysis-resistant polyester resin is 60mgKOH/g, and the viscosity of the hydrolysis-resistant polyester resin is 5200 mPa.s.
After the hydrolysis-resistant monomer V-1 is introduced into the polyester resin, the polyester resin is stored in a 50 ℃ thermostat for 6 months without abnormity, and the resin without the hydrolysis-resistant monomer is stored in the 50 ℃ thermostat for 10-15 days to cause the phenomena of turbidity and delamination.
Example 5
A preparation method of hydrolysis-resistant polyester resin for water-based coil finish paint comprises the following steps:
and (3) synthesis of hydrolysis-resistant monomer V-1: mixing phthalic anhydride and diethylene glycol glycidyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain an anti-hydrolysis monomer V-1, and filtering for later use.
85g of methyl propylene glycol, 45g of V-1 monomer, 20g of trimethylolpropane, 45g of hexanediol, 75g of adipic acid, 140g of phthalic anhydride and 22g of suberic acid are added into a four-neck flask provided with a thermometer, a stirring device and a condensation water separation device, the temperature is slowly increased by heating, the solid materials are completely melted, and stirring is started. Adding 0.3g of esterification catalyst 4100 under the condition of melting the material at the temperature of 80 ℃, adjusting the temperature of the material to 150 ℃ within 2 hours, carrying out heat preservation reaction for 1 hour, controlling the temperature rise rate at 10 ℃/h, gradually raising the temperature to 220 ℃, and carrying out heat preservation reaction at the temperature. Continuously observing the water yield in the reaction process, starting to measure the acid value when the water yield reaches the theoretical water yield, cooling the material to 160 ℃ when the theoretical acid value is less than 5mgKOH/g, adding 30g of trimellitic anhydride, reacting for 0.5h, and cooling to 60 ℃ after the acid value is measured to be less than 50 mgKOH/g;
dilution stage
And cooling the reaction to 60 ℃, adding 26g of neutralizing agent diethanolamine, stirring and reacting for 0.5 hour, then adding 200g of hydrophilic propylene glycol methyl ether, and adding deionized water to adjust the solid content of the product to 50 wt%, thereby obtaining the hydrolysis-resistant polyester resin for the water-based coil coating finish with the molecular weight of 1200, the acid value of 35mgKOH/g and the viscosity of 2600 mPa.s.
After the hydrolysis-resistant monomer V-1 is introduced into the polyester resin, the polyester resin is stored in a 50 ℃ thermostat for 6 months without abnormity, and the resin without the hydrolysis-resistant monomer is stored in the 50 ℃ thermostat for 10-15 days to cause the phenomena of turbidity and delamination.
Test of
Selecting the product in the example 1, and preparing the water-based coil coating finish paint according to the following formula, wherein the performance evaluation result is as follows:
TABLE 1 Water-based coil coating topcoat formulation
| Name of raw materials | Proportioning,% |
| Hydrolysis resistant polyester resins | 52.5 |
| Ethylene glycol monobutyl ether | 5 |
| NN dimethylethanolamine | 0.8 |
| Defoaming agent 810 | 0.2 |
| Leveling agent 450 | 0.1 |
| Substrate wetting agent 4100 | 0.1 |
| Titanium white powder | 15 |
| Phthalocyanine blue | 5 |
| Precipitated barium sulfate | 10 |
| Deionized water | 11.3 |
| In total | 100 |
TABLE 2 detection results of the performance of the water-based coil coating finish
| Item | Index requirement | The result of the detection |
| State in the container | Uniformly stirred without hard lumps | Uniformly stirred without hard lumps |
| Hardness of pencil | ≥H | 2H |
| Reverse impact/(kg. cm) | ≥90 | 90 |
| Solvent resistance (MEK) wipe/wipe | ≥100 | 200 |
| T bend/T | ≤3 | 0 |
| Cross-cut adhesion/grade | 0 | 0 |
| Neutral salt fog resistance | 720h | 720h |
| Resistance to artificial aging | 800h | 1000h |
Note: reference standard HG/T3830-plus 2006 coil coating
By evaluating the performance of the colored paint, the performance of the water-based resin reaches the application standard of the oleoresin and is excellent.
Claims (4)
1. An anti-hydrolysis polyester resin for water-based coil finish paint is characterized in that the molecular weight of the polyester resin is 1200-20000, the acid value is 20-100mgKOH/g, the hydroxyl value is 50-300mgKOH/g, the solid content is 50-80%, and the neutralization degree is 50-100%;
carrying out polycondensation reaction on polyol, polybasic acid and hydrolysis-resistant monomer under the condition of a catalyst to obtain a high molecular polymer with medium and low molecular weight, then reacting the polymer with a water-based monomer, finally completing neutralization, and adding water to obtain a water-based polyester resin;
wherein the addition amount of the hydrolysis-resistant monomer is 1-15 wt%;
the specific synthesis method of the hydrolysis-resistant monomer comprises the following steps: mixing the dibasic acid with the epoxy substances and the like, heating to 130-140 ℃, and reacting for 5-6h to obtain an anti-hydrolysis monomer;
the dibasic acid is one of isophthalic acid, phthalic acid, terephthalic acid, succinic acid and glutaric acid, and the epoxy substance is one of ethylene oxide, propylene oxide, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, diethylene glycol glycidyl ether, dipropylene glycol glycidyl ether and epoxy resin;
the preparation raw materials of the polyester resin comprise the following components in parts by weight: 10-50 wt% of polyhydric alcohol, 10-50 wt% of polybasic acid, 1-15 wt% of hydrolysis-resistant monomer, 0.01-1 wt% of catalyst, 1-5 wt% of neutralizing agent, 10-30 wt% of hydrophilic solvent, 1-5 wt% of water-based monomer and the balance of deionized water; the polyalcohol is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol in any proportion; the polybasic acid is one or a mixture of more of dibasic acid, tribasic acid and anhydride in any proportion; the waterborne monomer is one or a mixture of more of phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and maleic anhydride in any proportion; the hydrophilic solvent is one or a mixture of more of ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether acetate, ethanol, n-butanol, isopropanol and butanol in any proportion; the neutralizing agent is selected from one of ammonia water, N, N dimethylethanolamine, diethanolamine, triethanolamine, triethylamine and 1-methyldiethanolamine.
2. The hydrolysis-resistant polyester resin for the water-based coil top coating as claimed in claim 1, wherein the hydrolysis-resistant monomer is synthesized by mixing dibasic acid with epoxy, heating to 130 ℃, and reacting for 5 h.
3. The hydrolysis-resistant polyester resin for the water-based coil top coating material according to claim 1, wherein the catalyst is one of antimony-based and organic tin-based catalysts.
4. The preparation method of the hydrolysis-resistant polyester resin for the water-based coil top-coat paint, which is characterized by comprising the following preparation steps in sequence:
1) putting polyalcohol, polybasic acid and hydrolysis-resistant monomer into a reactor, slowly heating to 120 ℃, putting a catalyst into the reactor, slowly heating to 150 ℃, and keeping the temperature for 1-1.5 h;
2) continuously heating up to 10 ℃ per hour till 220 ℃, and carrying out heat preservation reaction;
3) observing the reaction water yield, starting to measure the acid value at 88-93% of the water yield, and cooling to 150-;
4) then adding waterborne monomer, reacting for 0.5-1h, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
5) adding a hydrophilic solvent, a neutralizing agent and deionized water at 60 ℃, and fully and uniformly stirring to obtain the polyester resin.
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| CN103897646B (en) * | 2012-12-28 | 2016-01-06 | 上海轻工业研究所有限公司 | Resistant to hydrolysis polyester hot-melt adhesive and preparation method thereof |
| CN103555120B (en) * | 2013-10-08 | 2016-06-01 | 雅图高新材料有限公司 | A kind of polyacrylate grafting modified poly ester water-borne coatings and its preparation method |
| CN104629022A (en) * | 2014-12-31 | 2015-05-20 | 海聚高分子材料科技（广州）有限公司 | Hydrolysis resistant polyester polyol, hydrolysis resistant and weather resistant aqueous polyurethane dispersion and use thereof |
| JP6971155B2 (en) * | 2016-02-19 | 2021-11-24 | 昭和電工株式会社 | Organic acid-resistant water-based resin composition, its manufacturing method, and surface treatment method |
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