CN112424286A - Polyester resin composition and preparation method and application thereof - Google Patents
Polyester resin composition and preparation method and application thereof Download PDFInfo
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- CN112424286A CN112424286A CN201980044781.5A CN201980044781A CN112424286A CN 112424286 A CN112424286 A CN 112424286A CN 201980044781 A CN201980044781 A CN 201980044781A CN 112424286 A CN112424286 A CN 112424286A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
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- 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
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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
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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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a polyester resin composition, which comprises an amorphous saturated polyester resin and a semi-crystalline saturated polyester resin, wherein the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin are prepared by the following raw materials in a reaction manner: dihydric alcohol, polyalcohol, aromatic dibasic acid, fatty dibasic acid, acidolysis agent, catalyst and accelerator. The acid value of the amorphous saturated polyester resin is 30-50 mgKOH/g, the hydroxyl value is less than or equal to 10mgKOH/g, the melt viscosity at 200 ℃ is 2000-6000 mPa & s, and the glass transition temperature is 50-63 ℃; the semi-crystalline saturated polyester resin has an acid value of 5 to 50mgKOH/g, a hydroxyl value of 5 to 50mgKOH/g, and a melt viscosity of 10 to 4000mPa · s at 200 ℃; the mass ratio of the amorphous saturated polyester resin to the semi-crystalline saturated polyester resin in the polyester resin composition is 99: 1-80: 20. The polyester resin composition can meet the curing requirements of various curing agents, can be used for preparing weather-resistant powder coating under the curing condition of 140-170 ℃, and has a coating with good mechanical property, leveling property and excellent weather resistance.
Description
Technical Field
The invention belongs to the field of resin formulas, and particularly relates to a polyester resin composition, and a preparation method and application thereof.
Background
The powder coating has been rapidly developed in recent years due to the characteristics of '4E' (high efficiency, resource saving, high performance, economy), and the related application fields include automobiles, household appliances, building materials, engineering machinery, electronics 3C and the like. The rapid development of powder coatings and the expansion of the application field promote the technical progress of the industry and also put higher performance requirements on the coatings. Weather resistance is one of the important indexes for powder coating, and is a key factor for determining the service life of powder coating and substrate. With the application of the powder coating in the fields of high-grade outdoor building materials, curtain walls, photovoltaic modules and the like, the demand of the super-weather-resistant powder coating shows a rapid development trend. The polyester resin is used as an important raw material of the powder coating to determine the performance of the powder coating, and the existing super-weather-resistant powder coating solves the weather resistance problem of the conventional powder coating, but has the defect of mechanical performance. On the other hand, although the powder coating has excellent performance, the powder coating has higher curing temperature compared with a liquid coating, the curing temperature used by the traditional powder coating is higher (180-210 ℃), and the curing time is long (5-30 min), so that the powder coating can only be used for heat-resistant base materials such as metal and the like, and is relatively energy-consuming and time-consuming. However, with the development of the powder coating market, wood products (such as MDF and the like), plastic products, metal plastic composites and the like are increasingly coated with the powder coating. Since these products are heat sensitive, the curing temperature of the powder coating must be reduced to allow the application of these products. Taken together, the curing of powder-type powder coatings under low temperature conditions (140-. Therefore, from the viewpoint of energy conservation and high performance, the powder coating with the low-temperature curing and super-weather-proof characteristics solves the problem of service life of the powder coating and also solves the problem of high energy consumption of the powder coating.
However, the curing temperature often has an important influence on the performance of the powder coating, and the obtained powder coating can bring various problems, such as orange peel and shrinkage cavity caused by the defect of flatness of the coating; reduced mechanical properties, weather resistance defects, and the like. Meanwhile, the conventional super-weather-resistant powder coating also has the defect of mechanical property, and the performance of the conventional super-weather-resistant powder coating cannot meet the requirement even if the curing temperature is reduced, so that the low-temperature curing process, the coating leveling property of the product, the mechanical property of the super-weather-resistant powder coating and the like need to be considered at the same time.
At present, some patents have been studied on polyester resin for super-weather-resistant powder coating, for example, chinese patent CN1042924343A discloses a preparation method of super-weather-resistant low-temperature curing type polyester resin, which mainly solves the problem of coating performance defect under super-weather-resistant low-temperature curing from the perspective of polyester resin structure design, but the leveling problem of low-temperature cured coating cannot be solved. Chinese patent CN102408550A discloses carboxyl-terminated polyester resin for super weather-resistant powder coating and a preparation method thereof, but the curing temperature of the patent is 200 ℃, and the patent is not suitable for low-temperature curing. Chinese patent CN104530408A discloses a polyester resin for super weather-resistant powder coating, a powder coating using the same and a preparation method thereof, wherein the weather resistance of the powder coating is improved by using a fluorine-containing monomer to synthesize the polyester resin, but the curing temperature is high. Chinese patent CN107189045A discloses a low-temperature super-weather-resistant bending-resistant saturated polyester resin for a propylene oxide isocyanate (TGIG) system powder coating and a preparation method thereof, and the patent overcomes the defects of coating performance under low-temperature curing of the powder coating, but the defects of non super-weather-resistant type and weather resistance.
Therefore, the problems of poor leveling property, poor mechanical property, poor weather resistance and the like existing in the polyester resin composition cured at low temperature in the prior art are needed to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polyester resin composition, which comprises amorphous saturated polyester resin and semi-crystalline saturated polyester resin, and a powder coating prepared from the composition has excellent leveling property, mechanical property and weather resistance under the low-temperature curing condition of 140-170 ℃.
The amorphous and semi-crystalline states in the present invention are the polymeric aggregate structures. The chain segment structure of the amorphous polymer is randomly arranged, which is beneficial to the preparation of the powder coating. The chain segments of the semi-crystalline polymer are regularly arranged, which is beneficial to improving the leveling property and the mechanical property of the coating.
The semi-crystalline polyester resin mainly comprises straight-chain non-branched aliphatic monomers, the chain segment structure is uniformly distributed, the semi-crystalline polyester resin has better flexibility, and the prepared coating can better absorb energy of mechanical property and improve the mechanical property of the coating.
The polyester resin in the invention is selected from aromatic dibasic acid such as terephthalic acid and isophthalic acid. The structure of the isophthalic acid is asymmetric and is not beneficial to the mechanical property of a powder coating, but compared with terephthalic acid, the prepared resin has the characteristic of outstanding weather resistance when being applied to the powder coating.
Therefore, through the combined application of the amorphous polyester resin and the semi-crystalline polyester resin, the amorphous saturated polyester resin component provides good weather resistance of the coating and high activity under low-temperature curing; the semi-crystalline saturated polyester resin component solves the defects of flatness and mechanical property of the coating under low-temperature curing, and the semi-crystalline saturated polyester resin component and the coating perform synergistic action in the powder coating to solve the performance defects of the current super-weather-resistant powder coating.
The term "amorphous" means that the physical form of the component is glassy and has an index of glass transition temperature.
The term "semi-crystalline polyester resin" means that both crystalline and amorphous domains exist in the physical form of the component, and that the component has no glassy state in its physical state and no glass transition temperature index.
The term "saturated polyester resin" means that the raw materials for the synthetic polyester resin do not contain unsaturated bonds other than benzene rings and carboxylic acid groups.
The term "low temperature cure" refers to the curing behavior of a powder coating at 140-170 ℃.
The invention aims to provide a polyester resin composition, which is realized by the following technical means:
a polyester resin composition is a mixture comprising an amorphous saturated polyester resin and a semi-crystalline saturated polyester resin.
The amorphous saturated polyester resin is prepared by reacting the following raw materials in percentage by mass:
the semi-crystalline saturated polyester resin is prepared by the following raw materials in percentage by mass:
wherein the mass ratio of the amorphous saturated polyester resin to the semi-crystalline saturated polyester resin is 99: 1-80: 20.
The amorphous state and the semi-crystalline state of the polyester resin are mainly embodied in the aggregation state of a chain segment structure, the chain segment of the amorphous polyester resin is in a random state, and a formula comprises a monomer with a side group structure; the semi-crystalline chain segments are regularly arranged, and the formula mainly comprises straight-chain non-branched aliphatic monomers.
Further, the dihydric alcohol in the amorphous saturated polyester resin is selected from the following components:
wherein the mass percentages of the 2-butyl-2-ethyl-1, 3-propanediol, the hydroxypivalyl hydroxypivalate and the trimethylpentanediol are not 0 at the same time.
The diol monomer structure contains a side group or is an alicyclic monomer, and part of the monomer does not contain beta-hydrogen which is easy to oxidize, so that the weather resistance of the coating is improved; meanwhile, the side group of the chain segment structure protects ester bond through steric hindrance, so that the weather resistance of the coating is prevented from being reduced due to hydrolysis.
Further, the dihydric alcohol of the semi-crystalline saturated polyester resin is one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol or 1, 10-decanediol, wherein the mass percentage of the dihydric alcohol with even number of carbon atoms in the dihydric alcohol is not less than 50%.
Monomers with an even number of carbon atoms favour the formation of crystals.
Further, the polyhydric alcohol of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is one or more selected from trimethylolpropane, trimethylolethane or pentaerythritol.
Further, the aromatic dibasic acid of the amorphous saturated polyester resin is selected from one or two of terephthalic acid or isophthalic acid, and the mass ratio of the isophthalic acid in the aromatic dibasic acid is not less than 50%.
Further, the aromatic dibasic acid of the semi-crystalline saturated polyester resin is selected from terephthalic acid.
The isophthalic acid is beneficial to improving the weather resistance of the coating.
Further, the aliphatic dibasic acid of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from one or more of adipic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid or dodecanedioic acid.
Further, the acidolysis agent of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from one or more of isophthalic acid, adipic acid or 1, 4-cyclohexanedicarboxylic acid.
Further, the semi-crystalline saturated polyester resin acidolysis agent is selected from one or more of adipic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, dodecanedioic acid or 1, 4-cyclohexanedicarboxylic acid.
Further, the catalyst of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from monobutyl tin oxide, monobutyl triisooctanoic acid tin, tetrabutyl titanate or tetraisopropyl titanate.
Further, the accelerator of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from one or more of triphenyl ethyl phosphine bromide, triphenyl phosphine, triphenyl methyl phosphine bromide, tetraethyl ammonium bromide or tetrabutyl ammonium bromide.
Further, the acid value of the amorphous saturated polyester resin is 30-50 mgKOH/g, the hydroxyl value is less than or equal to 10mgKOH/g, the melt viscosity at 200 ℃ is 2000-6000 mPa.s, and the glass transition temperature is 50-63 ℃.
Further, the semi-crystalline saturated polyester resin has an acid value of 5 to 50mgKOH/g, a hydroxyl value of 5 to 50mgKOH/g, and a melt viscosity of 10 to 4000mPa · s at 200 ℃.
Another object of the present invention is to provide a process for preparing the above polyester resin composition, including processes for preparing amorphous saturated polyester resins and semicrystalline saturated polyester resins. The method comprises the following steps: amorphous saturated polyester resin and semi-crystalline saturated polyester resin were prepared separately and then blended in the proportions disclosed in the present invention to obtain a polyester resin composition.
The preparation method of the amorphous saturated polyester resin comprises the following steps:
(1) adding a first part of dihydric alcohol, polyhydric alcohol and a catalyst into a reaction container according to a ratio, adding aromatic dibasic acid and fatty dibasic acid under the protection of inert gas, heating to 230-;
(2) continuously adding a second part of dihydric alcohol to react until the materials are clear and transparent, wherein the second part of dihydric alcohol is selected from one or more of 2-butyl-2-ethyl-1, 3-propanediol, hydroxypivalyl hydroxypivalate or trimethylpentanediol;
(3) adding an acidolysis agent to react for 1-4h until the material is clear and transparent;
(4) carrying out reaction under a vacuum condition until the measured acid value of the material is 30-50 mgKOH/g, the hydroxyl value is less than or equal to 10mgKOH/g, and the melt viscosity at 200 ℃ is 2000-6000 mPa & s, which indicates that the reaction is completely carried out; then adding an accelerant, stirring and dispersing uniformly, and discharging to obtain the amorphous saturated polyester resin.
The dihydric alcohol addition of the amorphous saturated polyester resin adopts a step-by-step addition process. Compared with a one-step adding process, the operation is favorable for improving the regularity of the chain segment structure, thereby being favorable for improving the flexibility and the mechanical property of the coating.
The preparation method of the semi-crystalline saturated polyester resin comprises the following steps:
(1) adding dihydric alcohol, polyhydric alcohol and a catalyst into a reaction vessel according to the proportion, adding aromatic dibasic acid and fatty dibasic acid under the protection of inert gas, heating to 200-250 ℃ for esterification reaction until the materials are clear and transparent;
(2) adding an acidolysis agent to react for 1-4h until the material is clear and transparent;
(3) and (2) carrying out reaction under a vacuum condition until the acid value of the material is 5-50 mgKOH/g, the hydroxyl value is 5-50 mgKOH/g, the melt viscosity at 200 ℃ is 10-4000 mPa & s, adding an accelerator, stirring and dispersing uniformly, and discharging to obtain the semi-crystalline saturated polyester resin.
Further, the inert gas includes nitrogen, helium, neon, argon, krypton, xenon, radon, and preferably nitrogen.
Another object of the present invention is to provide a use of the polyester resin composition in powder coating, comprising the above polyester resin composition.
The composition can be used for preparing powder coating, therefore, the invention also provides a preparation method of the powder coating, which comprises the following steps:
(1) mixing the polyester resin composition, the curing agent, the pigment, the filler and the auxiliary agent according to the proportion; wherein the curing agent is selected from triglycidyl isocyanurate (TGIC) and/or beta-hydroxyalkylamide and/or polyisocyanate;
(2) melting and extruding the mixture through an extruder, cooling, crushing and sieving to prepare powder coating;
(3) the prepared powder coating is coated on the surface of a workpiece in an electrostatic spraying mode, and the curing temperature is 140-170 ℃/6-20 min.
In addition, the above powder coating can be used for coating on the surface of a workpiece to form a protective coating.
The invention has the following beneficial effects:
the polyester resin composition disclosed by the invention is applied to powder coating, can realize that the powder coating still has excellent leveling property, mechanical property and weather resistance after being cured at the low temperature of 140-170 ℃, and overcomes the defects of flatness of a coating after the powder coating is coated, such as orange peel, shrinkage cavity, reduced mechanical property, poor weather resistance and the like, which are easy to occur in the prior art.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the present disclosure, and such equivalents may fall within the scope of the present invention as defined by the appended claims.
Example 1
A series of experiments were designed by first formulating a series of examples of amorphous saturated polyester resins and comparative examples, wherein examples a-e are versions of the invention and comparative examples are f and g. The compositions and properties of the examples of the amorphous saturated polyester resin of the present invention and the comparative examples are shown in Table 1.
Table 1: amorphous saturated polyester resin composition and performance data
The preparation method of the above examples a, c and d comprises the following specific steps:
(1) adding neopentyl glycol, 1, 4-cyclohexanedimethanol, polyol and a catalyst in mass percent according to table 1 into a reaction vessel, gradually heating to 160 ℃ under the protection of nitrogen until the materials are melted, then adding aromatic dibasic acid and fatty dibasic acid in mass percent according to table 1, gradually heating to 230 ℃ for esterification reaction until the materials are clear and transparent;
(2) continuously adding the rest diol in the mass percentage shown in the table 1 into the material in the step (1), and continuously reacting until the material is clear and transparent;
(3) adding acidolysis agent in the mass percentage shown in the table 1 into the material in the step (2), and reacting for 3 hours under the protection of nitrogen at constant temperature until the material is clear and transparent;
(4) and (3) carrying out polycondensation reaction on the material in the step (3) under a vacuum condition, adding an accelerant in the mass percentage shown in the table 1 after reacting for 3 hours, uniformly stirring and dispersing, and then discharging to obtain the amorphous saturated polyester resin.
The preparation method of the above examples b and e comprises the following specific steps:
reference is made to the preparation of example a, with the difference that the esterification temperature in step (1) and the reaction temperatures in steps (2), (3) and (4) of examples b and e are 250 ℃.
The preparation method of the comparative example f comprises the following specific steps:
(1) adding the dihydric alcohol, the polyhydric alcohol, the aromatic dibasic acid, the fatty dibasic acid and the catalyst in the mass percentage shown in the table 1 into a reaction container, and gradually heating to 240 ℃ for esterification reaction until the materials are clear and transparent;
(2) adding acidolysis agent in the mass percentage shown in the table 1 into the material in the step (1), and reacting for 2 hours at the constant temperature of 240 ℃ until the material is clear and transparent;
(3) and (3) after vacuumizing and polycondensation reaction for 2 hours, adding the accelerant with the mass percentage shown in the table 1, uniformly stirring and dispersing, and then discharging to obtain the polyester resin of the comparative example f.
The preparation method of the comparative example g comprises the following specific steps:
(1) adding the dihydric alcohol, the polyalcohol, the aromatic dibasic acid, the fatty dibasic acid, the acidolysis agent and the catalyst in the mass percentage shown in the table 1 into a reaction vessel, gradually heating to 240 ℃ for esterification reaction until the materials are clear and transparent;
(2) and (3) after vacuumizing and polycondensation reaction for 3 hours, adding the accelerator with the mass percentage shown in the table 1, uniformly stirring and dispersing, and then discharging to obtain the polyester resin of the comparative example g.
Example 2
A series of experiments were designed to formulate a series of examples and comparative examples of semi-crystalline saturated polyester resins, where examples I-V are examples provided herein and comparative examples I and II are comparative examples.
Table 2 shows examples and comparative examples of semicrystalline saturated polyester resins according to the invention, examples I to V being embodiments according to the invention and comparative examples I and II being comparative examples. The compositions and properties of the examples of semicrystalline saturated polyester resins of the invention and the comparative examples are shown in Table 2
Table 2: semi-crystalline saturated polyester resin composition and performance data
The preparation method of the above examples I, II and IV comprises the following steps:
(1) adding dihydric alcohol, polyhydric alcohol and a catalyst in mass percent according to table 2 into a reaction vessel, gradually heating to 160 ℃ under the protection of nitrogen until the materials are melted, then adding fatty dibasic acid in mass percent according to table 2, and gradually heating to 200 ℃ for esterification reaction until the materials are clear and transparent;
(2) adding acidolysis agent in the mass percentage shown in the table 2 into the material in the step (1), and reacting under the protection of nitrogen until the material is clear and transparent;
(3) and (3) carrying out polycondensation reaction on the material in the step (2) for 2 hours under a vacuum condition, adding the accelerator in the mass percentage shown in the table 2, uniformly stirring and dispersing, and then discharging to obtain the semi-crystalline saturated polyester resin.
The preparation method of the embodiment III comprises the following specific steps:
reference is made to the preparation of example I, with the difference that the esterification temperature in step (1) and the reaction temperature in steps (2) and (3) of example III are 250 ℃.
The preparation method of the above example V comprises the following specific steps:
(1) adding dihydric alcohol, polyhydric alcohol and a catalyst in mass percent according to table 2 into a reaction vessel, gradually heating to 160 ℃ under the protection of nitrogen until the materials are melted, then adding fatty dibasic acid in mass percent according to table 2, and gradually heating to 220 ℃ for esterification reaction until the materials are clear and transparent;
(2) and (2) carrying out vacuum polycondensation reaction on the material in the step (1) for 2 hours until the acid value of the material is 5mgKOH/g, the hydroxyl value is 50mgKOH/g, and the melt viscosity at 200 ℃ is 800mPa & s, thus obtaining the semi-crystalline saturated polyester resin.
The preparation method of the comparative example I comprises the following specific steps:
(1) adding dihydric alcohol, polyhydric alcohol and a catalyst in mass percent according to table 2 into a reaction vessel, gradually heating to 160 ℃ under the protection of nitrogen until the materials are melted, then adding terephthalic acid in mass percent according to table 2, and gradually heating to 240 ℃ for esterification reaction until the materials are clear and transparent;
(2) adding acidolysis agent in the mass percentage shown in the table 2 into the material in the step (1), and reacting for 2 hours at the constant temperature of 240 ℃ under the protection of nitrogen until the material is clear and transparent;
(3) and (3) carrying out vacuum polycondensation reaction on the material in the step (2) for 2h until the acid value of the material is 32mgKOH/g, the hydroxyl value is 8mgKOH/g, the melt viscosity at 200 ℃ is 3500mPa & s, cooling to 210 ℃, adding an accelerator, stirring, uniformly dispersing, and discharging to obtain the polyester resin in the comparative example I.
The preparation method of the comparative example II comprises the following specific steps:
(1) adding the dihydric alcohol, the polyhydric alcohol and the catalyst in the mass percentage shown in the table 2 into a reaction vessel, and gradually heating to 240 ℃ for esterification reaction until the materials are clear and transparent;
(2) and (2) carrying out vacuum polycondensation reaction on the material in the step (1) for 2 hours until the acid value of the material is 37mgKOH/g, the hydroxyl value is 4mgKOH/g, and the melt viscosity at 200 ℃ is 1500mPa & s, adding the accelerator in the mass percentage shown in the table 2, uniformly stirring and dispersing, and then discharging to obtain the polyester resin in the comparative example II.
Example 3
Amorphous saturated polyester resins and semi-crystalline saturated polyester resins synthesized in tables 1 and 2 were selected and physically mixed according to the formulation of table 3 to form polyester resin compositions, and the specific components and formulation selected are shown in table 3, and the unit is g.
Table 3: polyester resin composition Components
The compositions of Table 3 were then selected, weighed according to the formulation of Table 4, premixed, extruded through an extruder (zone I temperature 100 ℃ C. and zone II temperature 105 ℃ C. of the extruder), tabletted, crushed and sieved to obtain powder coatings. The powder coating formulations obtained are shown in Table 4.
TABLE 4 ingredients of powder coating formulations
Note: the NCO content of the polyisocyanate was 15%.
Example 5
The powder coating prepared in table 4 was applied to the surface of a workpiece by electrostatic spraying, the curing temperature was selected at 140 ℃/20min, and the coating was cured and then tested for performance, the specific test method being shown in table 5.
TABLE 5 relevant test items and reference standards
| Test items | Basis of evaluation |
| Thickness of paint film | ISO2360 |
| Degree of gloss | ISO2813 |
| Leveling property | ACT Test Panel LLC orange peel plate Standard |
| Impact strength | GB/T 1732-1993 |
| T-bend | ISO 1519 |
| Weather resistance | GB/T 1865-2009 |
Specific properties of the cured coatings are shown in table 6.
TABLE 6 comparison of coating Properties
According to the results of the coating property comparison shown in Table 6, the coatings of the powder coatings 1 to 6 according to the invention have good leveling, impact properties and weathering resistance of the coating appearance. Comparative powder coating 1 and comparative powder coating 2 had the disadvantages of leveling, mechanical properties and weathering resistance. The reason for the significant difference in performance between powder coatings 1-6 and comparative powder coatings 1-2 is explained by taking powder coating 1 and comparative powder coating 1 as examples. Powder coating 1 used the polyester resin composition A of example 3, which consisted of the amorphous saturated polyester resin of example a and the semi-crystalline saturated polyester resin of example I. The dihydric alcohol in the embodiment a adopts the combination of neopentyl glycol, 1, 4-cyclohexanedimethanol and trimethyl pentanediol, so that the weather resistance of the coating is ensured, and meanwhile, the dihydric alcohol adopts a step-by-step adding process, so that the regularity of a chain segment structure is improved, and the improvement of the flexibility and the mechanical property of the coating is facilitated. The aromatic dibasic acid is isophthalic acid, so that the weather resistance of the coating is ensured, and meanwhile, the aliphatic dibasic acid uses straight-chain non-branched aliphatic adipic acid, so that the flexibility of a polyester chain segment structure is further improved, and the weather resistance and the mechanical property of the coating are improved. The semi-crystalline saturated polyester resin of powder coating 1 used the ethylene glycol and adipic acid of example I with aliphatic segments, which have a high degree of regularity and improved coating flexibility. Therefore, the performance of the coating layer of the powder coating 1 is excellent in all of impact resistance, leveling property and weather resistance.
Comparative powder coating 1 employed polyester resin composition G, which consisted of the amorphous saturated polyester resin of comparative example f and the semicrystalline saturated polyester resin of comparative example I. Since the amorphous saturated polyester resin diol of comparative example f uses only neopentyl glycol, does not use 1, 4-cyclohexanedimethanol, and does not contain 2-butyl-2-ethyl-1, 3-propanediol, hydroxypivalyl hydroxypivalate, and trimethylpentanediol, the structure of the polyester resin is relatively simple, so that the flexibility of the coating layer is poor at low-temperature curing. Meanwhile, the aromatic dibasic acid does not contain isophthalic acid, so that the weather resistance of the coating is poor, and the acidolysis agent does not contain aliphatic dibasic acid, so that the impact property and the leveling property of the coating under low-temperature curing are reduced. In addition, the semi-crystalline saturated polyester resin of comparative example I uses a large amount of terephthalic acid, does not use fatty dibasic acid, and has a strong segment structure rigidity, which is not beneficial to improving the mechanical property and the coating leveling property. Thus, the properties of the coating layer of comparative powder coating 1 in combination exhibit the disadvantages of poor impact properties, poor leveling and poor weather resistance.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A polyester resin composition, characterized in that it is a mixture comprising an amorphous saturated polyester resin and a semi-crystalline saturated polyester resin,
the amorphous saturated polyester resin is prepared by reacting the following raw materials in percentage by mass:
the semi-crystalline saturated polyester resin is prepared by reacting the following raw materials in parts by weight:
wherein the mass ratio of the amorphous saturated polyester resin to the semi-crystalline saturated polyester resin is 99: 1-80: 20.
2. The polyester resin composition according to claim 1, wherein the diol in the amorphous saturated polyester resin comprises the following components:
wherein the mass percentages of the 2-butyl-2-ethyl-1, 3-propanediol, the hydroxypivalic acid hydroxypivalyl ester and the trimethylpentanediol are not 0 at the same time;
the dihydric alcohol of the semi-crystalline saturated polyester resin is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol or 1, 10-decanediol, wherein the mass percentage of the dihydric alcohol with even number of carbon atoms in the dihydric alcohol is not less than 50%.
3. The polyester resin composition according to claim 1, wherein the polyol of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is one or more selected from trimethylolpropane, trimethylolethane, and pentaerythritol.
4. The polyester resin composition according to claim 1, wherein the aromatic dibasic acid of the amorphous saturated polyester resin is selected from one or two of terephthalic acid and isophthalic acid, and the mass percentage of isophthalic acid in the aromatic dibasic acid is not less than 50%;
the aromatic dibasic acid of the semi-crystalline saturated polyester resin is selected from terephthalic acid.
5. The polyester resin composition according to claim 1, wherein the aliphatic dibasic acid of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is one or more selected from adipic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, and dodecanedioic acid.
6. The polyester resin composition according to claim 1, wherein the amorphous saturated polyester resin acidolysis agent is one or more selected from isophthalic acid, adipic acid, and 1, 4-cyclohexanedicarboxylic acid; the semi-crystalline saturated polyester resin acidolysis agent is one or more selected from adipic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, dodecanedioic acid or 1, 4-cyclohexanedicarboxylic acid.
7. The polyester resin composition according to claim 1, wherein the catalyst for the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from the group consisting of monobutyl oxidizer, monobutyl triisooctanoic acid tin, tetrabutyl titanate and tetraisopropyl titanate; the accelerator of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from one or more of triphenyl ethyl phosphine bromide, triphenyl phosphine, triphenyl methyl phosphine bromide, tetraethyl ammonium bromide or tetrabutyl ammonium bromide.
8. The polyester resin composition according to claim 1, wherein the amorphous saturated polyester resin has an acid value of 30 to 50mgKOH/g, a hydroxyl value of 10mgKOH/g or less, a melt viscosity of 2000 to 6000 mPa-s at 200 ℃ and a glass transition temperature of 50 to 63 ℃;
the semi-crystalline saturated polyester resin has an acid value of 5 to 50mgKOH/g, a hydroxyl value of 5 to 50mgKOH/g, and a melt viscosity of 10 to 4000mPa · s at 200 ℃.
9. A process for producing the polyester resin composition according to any one of claims 1 to 8, which comprises a process for producing an amorphous saturated polyester resin and a process for producing a semicrystalline saturated polyester resin,
the preparation method of the amorphous saturated polyester resin comprises the following steps:
(1) adding a first part of dihydric alcohol, polyhydric alcohol and a catalyst into a reaction container according to a ratio, adding aromatic dibasic acid and fatty dibasic acid under the protection of inert gas, heating to 230-;
(2) continuously adding a second part of dihydric alcohol to react until the materials are clear and transparent, wherein the second part of dihydric alcohol is selected from one or more of 2-butyl-2-ethyl-1, 3-propanediol, hydroxypivalyl hydroxypivalate or trimethylpentanediol;
(3) adding an acidolysis agent to react for 1-4h until the material is clear and transparent;
(4) carrying out reaction under a vacuum condition until the measured acid value of the material is 30-50 mgKOH/g, the hydroxyl value is less than or equal to 10mgKOH/g, and the melt viscosity at 200 ℃ is 2000-6000 mPa & s, then adding an accelerant, stirring and dispersing uniformly, and discharging to obtain amorphous saturated polyester resin;
the preparation method of the semi-crystalline saturated polyester resin comprises the following steps:
(1) adding dihydric alcohol, polyhydric alcohol and a catalyst into a reaction vessel according to the proportion, adding aromatic dibasic acid and fatty dibasic acid under the protection of inert gas, heating to 200-250 ℃ for esterification reaction until the materials are clear and transparent;
(2) adding an acidolysis agent to react for 1-4h until the material is clear and transparent;
(3) and (2) carrying out reaction under a vacuum condition until the acid value of the material is 5-50 mgKOH/g, the hydroxyl value is 5-50 mgKOH/g, the melt viscosity at 200 ℃ is 10-4000 mPa & s, adding an accelerator, stirring and dispersing uniformly, and discharging to obtain the semi-crystalline saturated polyester resin.
10. Use of the polyester resin composition according to any one of claims 1 to 8 in powder coatings.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113248694A (en) * | 2021-04-23 | 2021-08-13 | 广东伊诗德新材料科技有限公司 | Super-weather-resistant flexible polyester resin and preparation method thereof |
| CN114106304A (en) * | 2021-12-23 | 2022-03-01 | 安徽神剑新材料股份有限公司 | Low-temperature curing weather-resistant polyester resin, low-temperature curing weather-resistant powder coating and preparation method |
| CN114231135A (en) * | 2021-12-23 | 2022-03-25 | 安徽神剑新材料股份有限公司 | Outdoor mirror powder coating, preparation method thereof and coating formed by same |
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