WO2021097757A1 - 一种聚酯树脂组合物及其制备方法和应用 - Google Patents

一种聚酯树脂组合物及其制备方法和应用 Download PDF

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Publication number
WO2021097757A1
WO2021097757A1 PCT/CN2019/119963 CN2019119963W WO2021097757A1 WO 2021097757 A1 WO2021097757 A1 WO 2021097757A1 CN 2019119963 W CN2019119963 W CN 2019119963W WO 2021097757 A1 WO2021097757 A1 WO 2021097757A1
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Prior art keywords
polyester resin
acid
saturated polyester
semi
amorphous
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PCT/CN2019/119963
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English (en)
French (fr)
Inventor
谢静
李勇
刘亮
顾宇昕
张捷
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擎天材料科技有限公司
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Priority to PCT/CN2019/119963 priority Critical patent/WO2021097757A1/zh
Priority to CN201980044781.5A priority patent/CN112424286B/zh
Publication of WO2021097757A1 publication Critical patent/WO2021097757A1/zh

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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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the field of resin formulations, and specifically relates to a polyester resin composition and a preparation method and application thereof.
  • Powder coatings have developed rapidly in recent years due to their "4E” (efficient, resource-saving, high-performance, and economical) characteristics.
  • the application fields involved include automobiles, home appliances, building materials, engineering machinery, electronic 3C, etc.
  • the rapid development of powder coatings and the expansion of application fields have promoted the technological progress of the industry, and also put forward higher performance requirements for coatings.
  • Weather resistance is one of the important indicators for measuring powder coatings, and it is a key factor in determining the life of powder coatings and substrates. With the application of powder coatings in high-end outdoor building materials, curtain walls, photovoltaic modules and other fields, the demand for super weather-resistant powder coatings is showing a rapid development trend.
  • Polyester resin as an important raw material for powder coatings, determines the performance of powder coatings.
  • the curing temperature often has an important influence on the performance of powder coatings. If the curing temperature is lowered to a lower temperature, the resulting powder coatings will cause various problems, such as defects in the flatness of the coating, orange peel and shrinkage. ; Decrease in mechanical properties, defects in weather resistance, etc. At the same time, conventional super weather resistant powder coatings themselves also have defects in mechanical properties. Lowering the curing temperature will cause their performance to fail to meet the requirements. Therefore, low temperature curing super weather resistant powder coatings need to take into account the low temperature curing process, as well as the product's coating leveling and super The mechanical properties of weather-resistant powder coatings and other issues.
  • Cid patent CN1042924343A discloses a preparation method of super weather resistant low temperature curing polyester resin. This patent mainly solves the problem of super weather resistance from the perspective of polyester resin structure design. The problem of coating performance defects under weathering and low-temperature curing, but the leveling problem of low-temperature curing coatings cannot be solved.
  • Chinese patent CN102408550A discloses a carboxy-terminated polyester resin for super weather-resistant powder coatings and a preparation method thereof, but the curing temperature of this patent is 200°C, which is not suitable for low-temperature curing.
  • Chinese patent CN104530408A discloses polyester resins for super weather resistant powder coatings, powder coatings using the resins, and preparation methods. The patent uses fluorine-containing monomers to synthesize polyester resins to improve the weather resistance of powder coatings, but there is curing Defects with high temperature.
  • Chinese patent CN107189045A discloses a low-temperature, super-weather-resistant and bending-resistant saturated polyester resin for powder coatings of glycidyl isocyanate (TGIG) system and its preparation method. This patent solves the problem of coating under low-temperature curing of powder coatings. Performance defect, but non-super weather resistance type, there is a defect in weather resistance.
  • TGIG glycidyl isocyanate
  • the present invention aims to overcome the shortcomings and deficiencies of the prior art, and provides a polyester resin composition, which includes an amorphous saturated polyester resin and a semi-crystalline saturated polyester resin.
  • the combination is cured at a low temperature of 140-170°C.
  • the powder coating prepared by the compound has excellent leveling, mechanical properties and weather resistance.
  • the amorphous state and semi-crystalline state in the present invention are aggregated structures of polymers.
  • the amorphous polymer has a random arrangement of chain segments, which is beneficial to the preparation of powder coatings.
  • the semi-crystalline polymer has a regular arrangement of chain segments, which is conducive to the improvement of the leveling and mechanical properties of the coating.
  • the semi-crystalline polyester resin in the present invention is mainly composed of straight-chain unbranched aliphatic monomers, the chain segment structure is uniformly distributed, and it has good flexibility.
  • the prepared coating can better absorb the energy of mechanical properties. Improve the mechanical properties of the coating, but because the monomer for preparing the semi-crystalline polyester resin has more ⁇ -hydrogen, it is easy to form free radicals under the action of ultraviolet rays, resulting in a decrease in the weather resistance of the coating.
  • the polyester resin is selected from aromatic dibasic acids such as terephthalic acid and isophthalic acid.
  • aromatic dibasic acids such as terephthalic acid and isophthalic acid.
  • the structure of isophthalic acid is asymmetric, which is not conducive to the mechanical properties of powder coatings.
  • the resin prepared by it used in powder coatings has outstanding weather resistance compared to terephthalic acid.
  • the amorphous saturated polyester resin component provides the coating with good weather resistance and high activity characteristics under low-temperature curing; while the semi-crystalline saturated polyester resin
  • the components solve the defects of leveling and mechanical properties of the coating under low-temperature curing, and the two work together in the powder coating to solve the performance defects of the current super weather-resistant powder coating.
  • amorphous means that the physical form of the component is glassy and has a glass transition temperature index.
  • semi-crystalline polyester resin means that there are both crystalline and amorphous regions in the physical form of the component, and the physical state of the component does not exist in a glass state, and there is no glass transition temperature index.
  • saturated polyester resin means that the raw material for synthetic polyester resin does not contain unsaturated bonds other than benzene ring and carboxylic acid group.
  • low temperature curing refers to the curing behavior of powder coatings at 140-170°C.
  • An object of the present invention is to provide a polyester resin composition, which can be achieved 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 raw materials with the following mass percentages:
  • the semi-crystalline saturated polyester resin is prepared by reacting raw materials with the following mass percentages:
  • the mass ratio of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is 99:1 to 80:20.
  • the amorphous state and semi-crystalline state of the polyester resin are mainly the manifestation of the aggregation state of the chain segment structure.
  • the chain segments of the polyester resin in the amorphous state present a random shape, and the formula composition contains a monomer with a side group structure;
  • the semi-crystalline chain segments present a regular arrangement, and the formulation composition is mainly composed of linear unbranched aliphatic monomers.
  • diol in the amorphous saturated polyester resin is selected from the following components:
  • the mass percentages of 2-butyl-2-ethyl-1,3-propanediol, hydroxyneopentyl hydroxypivalate, and trimethylpentanediol are not 0 at the same time.
  • the diol monomer structure contains side groups or is an alicyclic monomer, and some monomers do not contain easily oxidized ⁇ -hydrogen to improve the weather resistance of the coating; at the same time, the chain segment structure has side groups The group protects the ester bond through steric hindrance, which can avoid the degradation of the weather resistance of the coating due to hydrolysis.
  • the diol of the semi-crystalline saturated polyester resin is selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane
  • the mass percentage of the glycol in the glycol is not less than 50%.
  • Monomers with an even number of carbon atoms are conducive to the formation of crystals.
  • the polyol of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from one or more of trimethylolpropane, trimethylolethane or pentaerythritol.
  • 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 ratio of isophthalic acid in the aromatic dibasic acid is different. Less than 50%.
  • aromatic dibasic acid of the semi-crystalline saturated polyester resin is selected from terephthalic acid.
  • Isophthalic acid is beneficial to the improvement of the weather resistance of the coating.
  • the fatty dibasic acid of the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from adipic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid or dodecanedioic acid One or more of.
  • the acid disintegrant 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.
  • the semi-crystalline saturated polyester resin acid disintegrant is selected from adipic acid, succinic acid, glutaric acid, azelaic acid, sebacic acid, dodecanedioic acid or 1,4-cyclohexanedicarboxylic acid One or more of.
  • the catalyst for the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from monobutyl tin oxide, monobutyl tin triisooctoate, tetrabutyl titanate or tetraisopropyl titanate.
  • the accelerator for the amorphous saturated polyester resin and the semi-crystalline saturated polyester resin is selected from the group consisting of triphenylethyl phosphine bromide, triphenyl phosphine, triphenyl methyl phosphine bromide, and tetraethyl bromide.
  • the amorphous saturated polyester resin has an acid value of 30-50 mgKOH/g, a hydroxyl value ⁇ 10 mgKOH/g, a melt viscosity of 2000-6000 mPa ⁇ s at 200°C, and a glass transition temperature of 50-63°C.
  • the acid value of the semi-crystalline saturated polyester resin is 5-50 mgKOH/g
  • the hydroxyl value is 5-50 mgKOH/g
  • the melt viscosity at 200°C is 10-4000 mPa ⁇ s.
  • Another object of the present invention is to provide a method for preparing the above polyester resin composition, including a method for preparing an amorphous saturated polyester resin and a semi-crystalline saturated polyester resin.
  • the steps include: separately preparing an amorphous saturated polyester resin and a semi-crystalline saturated polyester resin, and then blending the two in the ratio disclosed in the present invention to obtain a polyester resin composition.
  • the preparation method of the amorphous saturated polyester resin includes the following steps:
  • the first part of diol is selected from neopentyl glycol and 1,4-cyclohexanedimethanol;
  • the second part of the diol is selected from 2-butyl-2-ethyl-1,3-propanediol, hydroxypivalic acid hydroxypivalate One or more of ester or trimethylpentanediol;
  • the reaction is carried out under vacuum conditions until the measured acid value of the material is 30-50mgKOH/g, the hydroxyl value is ⁇ 10mgKOH/g, and the melt viscosity at 200°C is 2000-6000mPa ⁇ s, indicating that the reaction is complete; then add the accelerator After stirring and dispersing uniformly, the material is discharged to obtain an amorphous saturated polyester resin.
  • the diol addition of the above-mentioned amorphous saturated polyester resin adopts a stepwise addition process. Compared with the one-step addition process, this operation is conducive to improving the regularity of the chain segment structure, thereby helping to improve the flexibility and mechanical properties of the coating.
  • the preparation method of semi-crystalline saturated polyester resin includes the following steps:
  • the inert gas includes nitrogen, helium, neon, argon, krypton, xenon, and radon, preferably nitrogen.
  • Another object of the present invention is to provide an application of the polyester resin composition including the above-mentioned polyester resin composition in powder coatings.
  • the composition can be used to prepare powder coatings. Therefore, the present invention also provides a method for preparing the powder coatings, which includes the following steps:
  • the above powder coatings can be applied to the surface of the workpiece to form a protective coating.
  • the polyester resin composition disclosed in the present invention is applied to powder coatings, which can realize that after curing at a low temperature of 140-170°C, the powder coatings still have excellent leveling properties, mechanical properties and weather resistance, and overcome the prior art In the case of powder coatings, the coatings after coating have flatness defects, such as orange peel, shrinkage cavities, decreased mechanical properties, and poor weather resistance.
  • Table 1 Composition and performance data of amorphous saturated polyester resin
  • the difference is that the esterification reaction temperature in step (1) and the reaction temperature in steps (2), (3) and (4) of Examples b and e are 250°C.
  • Table 2 shows the examples and comparative examples of the semi-crystalline saturated polyester resin in the present invention.
  • Examples I to V are the embodiments provided by the present invention, and the comparative examples I and II are comparative schemes.
  • the components and properties of the examples and comparative examples of the semi-crystalline saturated polyester resin of the present invention are shown in Table 2
  • Example III Refer to the preparation method of Example I, except that the temperature of the esterification reaction in step (1) and the reaction temperature of steps (2) and (3) in Example III are 250°C.
  • NCO content of polyisocyanate is 15%.
  • the powder coating prepared in Table 4 was applied to the surface of the workpiece by electrostatic spraying.
  • the curing temperature was selected at 140°C/20min. After the coating was cured, the performance test was performed.
  • the specific test method is shown in Table 5.
  • the coatings of the powder coatings 1-6 of the present invention have good coating appearance leveling, impact performance and weather resistance.
  • Comparative powder coating 1 and comparative powder coating 2 have defects in leveling, mechanical properties and weather resistance.
  • the reasons for the significant differences in the performance of Powder Coating 1-6 and Comparative Powder Coating 1-2 are explained by taking Powder Coating 1 and Comparative Powder Coating 1 as an example.
  • the powder coating 1 uses the polyester resin composition A in Example 3, and the polyester resin composition A is composed of the amorphous saturated polyester resin of Example a and the semi-crystalline saturated polyester resin of Example I.
  • the diol of Example a uses a combination of neopentyl glycol, 1,4-cyclohexanedimethanol and trimethylpentanediol, the weather resistance of the coating is ensured, and the diol is added step by step
  • the technology improves the regularity of the chain segment structure, which is conducive to improving the flexibility and mechanical properties of the coating.
  • the aromatic dibasic acid is isophthalic acid, which ensures the weather resistance of the coating.
  • the aliphatic dibasic acid uses straight-chain unbranched aliphatic adipic acid to further improve the flexibility of the polyester segment structure. The weather resistance and mechanical properties of the coating are improved.
  • the semi-crystalline saturated polyester resin of the powder coating 1 uses the ethylene glycol and adipic acid with aliphatic segments in Example I.
  • the segments have high regularity and improve the flexibility of the coating. Therefore, on the whole, the performance of the coating of the powder coating 1 exhibits excellent characteristics of impact performance, leveling properties, and weather resistance.
  • Comparative powder coating 1 uses polyester resin composition G, which is composed of the amorphous saturated polyester resin of Comparative Example f and the semi-crystalline saturated polyester resin of Comparative Example I. Since the amorphous saturated polyester resin diol of Comparative Example f only uses neopentyl glycol, does not use 1,4-cyclohexanedimethanol, and does not contain 2-butyl-2-ethyl-1, 3-Propanediol, hydroxyneopentyl hydroxypivalate and trimethylpentanediol result in a relatively single structure of the polyester resin, resulting in poor flexibility of the coating under low-temperature curing.
  • the aromatic dibasic acid does not contain isophthalic acid, which makes the coating poor weather resistance, and the absence of aliphatic dibasic acid in the acidolytic agent also reduces the impact and leveling properties of the coating under low-temperature curing.
  • the semi-crystalline saturated polyester resin of Comparative Example I uses a large amount of terephthalic acid instead of aliphatic dibasic acid.
  • the segment structure of the polyester resin is relatively rigid, which is not conducive to mechanical properties and coating leveling. improve. Therefore, in a comprehensive view, the performance of the coating of the comparative powder coating 1 shows the defects of poor impact performance, poor leveling and poor weather resistance.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明公开了一种聚酯树脂组合物，包括无定型饱和聚酯树脂和半结晶饱和聚酯树脂，二者均由如下原料反应制得：二元醇、多元醇、芳香二元酸、脂肪二元酸、酸解剂、催化剂和促进剂。无定型饱和聚酯树脂的酸值为30～50mgKOH/g，羟值≤10mgKOH/g，200℃熔融粘度为2000～6000mPa·s，玻璃化转变温度为50～63℃；半结晶饱和聚酯树脂的酸值为5～50mgKOH/g，羟值为5～50mgKOH/g，200℃熔融粘度为10～4000mPa·s；该聚酯树脂组合物中无定型饱和聚酯树脂和半结晶饱和聚酯树脂的质量比为99:1～80:20。该聚酯树脂组合物可以满足多种类型的固化剂进行固化，可以用于制备140～170℃固化条件下的耐候型粉末涂料，涂层具有良好的机械性能、流平性能以及优异的耐候性。

Description

一种聚酯树脂组合物及其制备方法和应用 技术领域
本发明属于树脂配方领域，具体涉及一种聚酯树脂组合物及其制备方法和应用。
背景技术
粉末涂料因其“4E”(高效、省资源、高性能、经济)的特性，近几年得到了快速发展，涉及的应用领域包括汽车、家电、建筑材料、工程机械、电子3C等。粉末涂料的快速发展与应用领域的扩大促进了行业的技术进步，也对涂料提出了较高的性能要求。耐候性是衡量粉末涂料的重要指标之一，是决定粉末涂料涂层及基材寿命的关键因素。随着粉末涂料在高档户外建材、幕墙、光伏组件等领域的应用，超耐候粉末涂料的需求呈现快速发展趋势。聚酯树脂作为粉末涂料的重要原材料，决定了粉末涂料的性能，目前超耐候粉末涂料虽然解决了常规粉末涂料的耐候性问题，但是存在机械性能的缺陷。另一方面，粉末涂料虽然具有优异的性能，但是相比液体涂料具有较高的固化温度，传统粉末涂料所用的固化温度较高(180℃～210℃)，固化时间长(5～30min)，这限制其只能用于金属等耐热基材，并且相对耗能、耗时。然而，随着粉末涂料市场应用的发展，木质产品(如MDF等)、塑料制品、金属塑料复合件等越来越多的采用粉末涂料进行涂装。由于这些制品均属于热敏性材质，要求粉末涂料的固化温度必须降低才能应用这些产品。综合来看，在低温条件(140-170℃)下固化粉末型粉末涂料已成为行业的趋势之一。因此，从节能与高性能的角度出发，具有低温固化超耐候特性的粉末涂料既解决了粉末涂料的使用寿命问题，又解决了粉末涂料高能耗问题。
但是固化温度对于粉末涂料的性能往往具有重要影响，将固化温度降至更低温度，所得粉末涂料会带来各种各样的问题，如涂层出现平整度上的缺陷产生橘皮、缩孔；机械性能下降、耐候性缺陷等。同时，常规超耐候粉末涂料本身也具有机械性能的缺陷，降低固化温度更会导致其性能无法满足要求，因此低温固化超耐候粉末涂料需要兼顾低温固化工艺，以及产品的涂层流平性和超耐候粉末涂料的机械性能等问题。
目前有一些专利进行了超耐候粉末涂料用聚酯树脂的研究，例如中国专利CN1042924343A公开了一种超耐候低温固化型聚酯树脂的制备方法，该专利主要从聚酯树脂结构设计的角度解决超耐候低温固化下的涂层性能缺陷问题，但是低温固化涂层的流平性问题无法解决。中国专利CN102408550A公开了一种超耐候粉末涂料用端羧基聚酯树脂及其制备方法，但是该专利的固化温度为200℃，不适宜应用于低温固化。中国专利CN104530408A 公开了超耐候粉末涂料用聚酯树脂、使用该树脂的粉末涂料及制备方法，该专利通过使用含氟单体进行聚酯树脂的合成，提高了粉末涂料的耐候性，但是存在固化温度高的缺陷。中国专利CN107189045A公开了一种异氰酸环氧丙醇酯(TGIG)体系粉末涂料用低温超耐候抗折弯的饱和聚酯树脂及其制备方法，该专利解决了粉末涂料低温固化下的涂层性能缺陷，但是非超耐候型，存在耐候性的缺陷。
因此，亟需解决现有技术中聚酯树脂组合物低温固化下存在的流平性缺陷、机械性能差及耐候性差等问题。
发明内容
本发明旨在克服现有技术的缺点与不足，提供一种聚酯树脂组合物，包括无定型饱和聚酯树脂和半结晶饱和聚酯树脂，在140-170℃低温固化条件下，通过该组合物制备的粉末涂料涂层具有优异的流平性、机械性能以及耐候性。
本发明中的无定型态与半结晶态是聚合物的聚集态结构。无定型态的聚合物，链段结构呈现无规排列，有利于粉末涂料的制备。半结晶态的聚合物，链段呈现规整排列，有利于涂层流平性及机械性能的提高。
本发明中的半结晶聚酯树脂主要由直链非支化脂肪族的单体组成，链段结构均匀分布，具有较好的柔韧性，制备的涂层可以较好的吸收机械性能的能量，提高涂层的机械性能，但由于制备半结晶聚酯树脂的单体具有较多的β-氢，在紫外线的作用下容易形成自由基导致涂层耐候性下降。
本发明中聚酯树脂选自芳香二元酸为对苯二甲酸和间苯二甲酸。间苯二甲酸的结构为非对称性，不利于粉末涂料涂层的机械性能，但是其制备的树脂应用于粉末涂料相比对苯二甲酸，具有耐候性突出的特点。
因此本发明通过无定型聚酯树脂和半结晶聚酯树脂的结合应用，无定型饱和聚酯树脂组分提供涂层良好的耐候特性以及低温固化下高活性的特性；而半结晶饱和聚酯树脂组分解决涂层低温固化下流平性以及机械性能的缺陷，二者在粉末涂层中进行协同作用解决目前超耐候粉末涂料涂层存在的性能缺陷。
术语“无定型”是指组分的物理形态为玻璃态，具有玻璃化转变温度指标。
术语“半结晶聚酯树脂”是指组分的物理形态中同时存在晶区和非晶区结构，且组分物理状态不存在玻璃态，无玻璃化转变温度指标。
术语“饱和聚酯树脂”是指合成聚酯树脂的原料中不含除苯环和羧酸基团以外的不饱和键。
术语“低温固化”是指在140-170℃条件下进行粉末涂料的固化行为。
本发明一个目的在于提供一种聚酯树脂组合物，通过以下技术手段得以实现：
一种聚酯树脂组合物，是包括无定型饱和聚酯树脂和半结晶饱和聚酯树脂的混合物。
其中，所述无定型饱和聚酯树脂由质量百分比如下的原料反应制得：
Figure PCTCN2019119963-appb-000001
所述半结晶饱和聚酯树脂由质量百分比如下的原料反应制得：
Figure PCTCN2019119963-appb-000002
其中，所述的无定型饱和聚酯树脂和半结晶饱和聚酯树脂的质量比为99:1～80:20。
所述的聚酯树脂的无定型状态与半结晶状态主要是链段结构聚集态的体现，无定型态聚酯树脂的链段呈现无规状，配方组成含具有侧基结构的单体；半结晶态的链段呈现规整排列，配方组成主要由直链非支化的脂肪族单体组成。
进一步地，所述无定型饱和聚酯树脂中的二元醇，选自以下成分：
Figure PCTCN2019119963-appb-000003
其中，2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯、三甲基戊二醇的质量百分比不同时为0。
所述的二元醇单体结构含侧基基团或者为脂环族单体，部分单体不含有易被氧化的β-氢提高了涂层耐候性；同时链段结构具有的侧基基团通过位阻作用保护酯键，可避免水解作用导致涂层耐候性下降。
进一步地，所述的半结晶饱和聚酯树脂的二元醇，选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇或1,10-癸二醇中的一种或多种，其中碳原子数为偶数的二元醇质量百分数在二元醇中的质量比不低于50％。
碳原子为偶数的单体有利于结晶的形成。
进一步地，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的多元醇，选自三羟甲基丙烷、三羟甲基乙烷或者季戊四醇中的一种或多种。
进一步地，所述无定型饱和聚酯树脂的芳香二元酸，选自对苯二甲酸或间苯二甲酸的一种或两种，且间苯二甲酸在芳香二元酸中的质量比不低于50％。
进一步地，所述的半结晶饱和聚酯树脂的芳香二元酸，选自对苯二甲酸。
间苯二甲酸有利于涂层耐候性的提升。
进一步地，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的脂肪二元酸选自己二酸、丁二酸、戊二酸、壬二酸、癸二酸或十二烷二酸中的一种或多种。
进一步地，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的酸解剂选自间苯二甲酸、己二酸或1,4-环己烷二甲酸的一种或多种。
进一步地，所述半结晶饱和聚酯树脂酸解剂选自己二酸、丁二酸、戊二酸、壬二酸、癸二酸、十二烷二酸或1,4-环己烷二甲酸中的一种或多种。
进一步地，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的催化剂选自单丁基氧化锡、单丁基三异辛酸锡、钛酸四丁酯或钛酸四异丙酯。
进一步地，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的促进剂选自三苯基乙基溴化膦、三苯基膦、三苯基甲基溴化膦、四乙基溴化铵或四丁基溴化铵的一种或多种。
进一步地，所述无定型饱和聚酯树脂的酸值为30～50mgKOH/g，羟值≤10mgKOH/g，200℃熔融粘度为2000～6000mPa·s，玻璃化转变温度为50～63℃。
进一步地，所述半结晶饱和聚酯树脂的酸值为5～50mgKOH/g，羟值为5～50mgKOH/g，200℃熔融粘度为10～4000mPa·s。
本发明的另一个目的在于提供上述聚酯树脂组合物的制备方法，包括无定型饱和聚酯树脂和半结晶饱和聚酯树脂的制备方法。其步骤包括：分别制备无定型饱和聚酯树脂和半结晶 饱和聚酯树脂，然后将二者以本发明所公布的比例共混，从而得到聚酯树脂组合物。
其中无定型饱和聚酯树脂的制备方法，包括以下步骤：
(1)根据配比在反应容器中加入第一部分二元醇、多元醇及催化剂，在惰性气体保护下加入芳香二元酸、脂肪二元酸，升温至230-250℃进行酯化反应至物料澄清透明，其中第一部分二元醇选自新戊二醇和1,4-环己烷二甲醇；
(2)继续加入第二部分二元醇进行反应至物料澄清透明，其中第二部分二元醇选自2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯或三甲基戊二醇的一种或多种；
(3)加入酸解剂进行反应1-4h至物料澄清透明；
(4)真空条件下进行反应，至测得的物料酸值为30～50mgKOH/g，羟值≤10mgKOH/g，200℃熔融粘度为2000～6000mPa·s，表明反应进行完全；然后加入促进剂搅拌分散均匀后出料，得到无定型饱和聚酯树脂。
上述无定型饱和聚酯树脂的二元醇添加采用了分步添加的工艺。这一操作相比于一步添加的工艺，有利于提高链段结构的规整性，从而有利于提升涂层柔韧性和机械性能。
其中半结晶饱和聚酯树脂的制备方法，包括以下步骤：
(1)根据配比在反应容器中加入二元醇、多元醇及催化剂，在惰性气体保护下加入芳香二元酸、脂肪二元酸，升温至200-250℃进行酯化反应至物料澄清透明；
(2)加入酸解剂进行反应1-4h，直至物料澄清透明；
(3)真空条件下进行反应，至物料酸值为5～50mgKOH/g，羟值为5～50mgKOH/g，200℃熔融粘度为10～4000mPa·s，加入促进剂搅拌分散均匀后出料，得到半结晶饱和聚酯树脂。
进一步地，所述惰性气体包括氮气、氦气、氖气、氩气、氪气、氙气、氡气，优选采用氮气。
本发明的另一个目的在于提供一种包括上述聚酯树脂组合物聚酯树脂组合物在粉末涂料中的应用。
该组合物可以用于制备粉末涂料，因此，本发明还提供了该粉末涂料的制备方法，包括以下步骤：
(1)根据配比将聚酯树脂组合物、固化剂、颜料、填料、助剂进行混合；其中固化剂选自异氰尿酸三缩水甘油酯(TGIC)和/或β-羟烷基酰胺和/或多异氰酸酯；
(2)将混合物通过挤出机熔融挤出、冷却破碎、粉碎过筛制成粉末涂料；
(3)将制备的粉末涂料通过静电喷涂的方式涂敷于工件表面，固化温度为140℃～170℃/6～20min。
另外，以上粉末涂料可用于涂覆于工件表面以形成保护涂层。
本发明具有以下有益效果：
本发明公布的聚酯树脂组合物应用在粉末涂料中，可以实现在140-170℃低温条件下固化后，粉末涂料依然具有优异的流平性、机械性能与耐候性，并且克服了现有技术中易出现的粉末涂料涂覆后的涂层出现平整度上的缺陷，如橘皮、缩孔、机械性能下降、耐候性较差等。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明公开的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
设计一系列实验，首先配制了一系列无定型饱和聚酯树脂的实施例与对比例，其中实施例a-e为本发明的方案，对比例为f和g。所述本发明中无定型饱和聚酯树脂的实施例与对比例的组分和性能，如表1所示。
表1：无定型饱和聚酯树脂成分及性能数据
Figure PCTCN2019119963-appb-000004
Figure PCTCN2019119963-appb-000005
以上实施例a、c、d的制备方法具体步骤为：
(1)在反应容器中加入按表1中所述质量百分数的新戊二醇、1,4-环己烷二甲醇、多元醇及催化剂，在氮气保护下逐渐升温至160℃至物料融化，然后加入按表1中所述质量百分数的芳香二元酸与脂肪二元酸，逐渐升温至230℃进行酯化反应，至物料澄清透明；
(2)向(1)的物料中继续加入按表1中所述质量百分数的余下二醇，继续反应至物料澄清透明；
(3)向(2)的物料中加入按表1中所述质量百分数的酸解剂，在氮气保护下恒温下进行反应3h，至物料澄清透明；
(4)真空条件下，对(3)的物料进行缩聚反应，反应3h后加入按表1中所述质量百分数的促进剂搅拌分散均匀后出料，得到无定型饱和聚酯树脂。
以上实施例b、e的制备方法具体步骤为：
参照实施例a的制备方法，其中不同之处在于，实施例b、e的第(1)步中酯化反应温度以及(2)、(3)、(4)步的反应温度为250℃。
以上对比例f的制备方法具体步骤为：
(1)在反应容器中加入按表1中所述质量百分数的二元醇、多元醇、芳香二元酸、脂肪二元酸及催化剂，逐渐升温至240℃进行酯化反应，至物料澄清透明；
(2)向(1)的物料中加入按表1中所述质量百分数的酸解剂，在240℃恒温下进行反应2h至物料澄清透明；
(3)抽真空缩聚反应2h后加入按表1中所述质量百分数的促进剂搅拌分散均匀后出料，得到对比例f聚酯树脂。
以上对比例g的制备方法具体步骤为：
(1)在反应容器中加入按表1中所述质量百分数的二元醇、多元醇、芳香二元酸、脂肪二元酸、酸解剂及催化剂，逐渐升温至240℃进行酯化反应，至物料澄清透明；
(2)抽真空缩聚反应3h后加入按表1中所述质量百分数的促进剂搅拌分散均匀后出料，得到对比例g聚酯树脂。
实施例2
设计一系列实验，配制了一系列半结晶饱和聚酯树脂的实施例与对比例，其中实施例Ⅰ～Ⅴ为本发明提供的实施方案，对比例Ⅰ和Ⅱ为对比方案。
表2为本发明中半结晶饱和聚酯树脂的实施例与对比例，其中实施例Ⅰ～Ⅴ为本发明提供的实施方案，对比例Ⅰ和Ⅱ为对比方案。所述本发明中半结晶饱和聚酯树脂的实施例与对比例的组分和性能，如表2所示
表2：半结晶饱和聚酯树脂成分及性能数据
Figure PCTCN2019119963-appb-000006
Figure PCTCN2019119963-appb-000007
以上实施例Ⅰ、Ⅱ、Ⅳ的制备方法具体步骤为：
(1)在反应容器中加入按表2中所述质量百分数的二元醇、多元醇及催化剂，在氮气保护下逐渐升温至160℃至物料融化，然后加入按表2中所述质量百分数的脂肪二元酸，逐渐升温至200℃进行酯化反应，至物料澄清透明；
(2)向(1)的物料中加入按表2中所述质量百分数的酸解剂，在氮气保护下进行反应至物料澄清透明；
(3)真空条件下，对(2)的物料进行缩聚反应2h，后加入按表2中所述质量百分数的促进剂搅拌分散均匀后出料，得到半结晶饱和聚酯树脂。
以上实施例Ⅲ的制备方法具体步骤为：
参照实施例Ⅰ的制备方法，其中不同之处在于，实施例Ⅲ的第(1)步中酯化反应的温度以及(2)、(3)步的反应温度为250℃。
以上实施例Ⅴ的制备方法具体步骤为：
(1)在反应容器中加入按表2中所述质量百分数的二元醇、多元醇及催化剂，在氮气保护下逐渐升温至160℃至物料融化，然后加入按表2中所述质量百分数的脂肪二元酸，逐渐升温至220℃进行酯化反应，至物料澄清透明；
(2)对(1)的物料进行抽真空缩聚反应2h，至物料酸值为5mgKOH/g，羟值为50mgKOH/g，200℃熔融粘度为800mPa·s，得到半结晶饱和聚酯树脂。
以上对比例Ⅰ的制备方法具体步骤为：
(1)在反应容器中加入按表2中所述质量百分数的二元醇、多元醇及催化剂，在氮气保护下逐渐升温至160℃至物料融化，然后加入按表2中所述质量百分数的对苯二甲酸，逐渐升温至240℃进行酯化反应，至物料澄清透明；
(2)向(1)的物料中加入按表2中所述质量百分数的酸解剂，在氮气保护下240℃恒温下进行反应2h至物料澄清透明；
(3)对(2)的物料进行抽真空缩聚反应2h，至物料酸值为32mgKOH/g，羟值为8mgKOH/g，200℃熔融粘度为3500mPa·s，降温至210℃加入促进剂搅拌分散均匀后出料，得到对比例Ⅰ聚酯树脂。
以上对比例Ⅱ的制备方法具体步骤为：
(1)在反应容器中加入按表2中所述质量百分数的二元醇、多元醇及催化剂，逐渐升温至240℃进行酯化反应，至物料澄清透明；
(2)对(1)的物料进行抽真空缩聚反应2h，至物料酸值为37mgKOH/g，羟值为4mgKOH/g，200℃熔融粘度为1500mPa·s，加入按表2中所述质量百分数的促进剂搅拌分散 均匀后出料，得到对比例Ⅱ聚酯树脂。
实施例3
选取表1和表2中合成的无定型饱和聚酯树脂和半结晶饱和聚酯树脂根据表3的配比进行常规物理混合形成聚酯树脂组合物，所选择的具体成分和配比如表3所示，单位为g。
表3：聚酯树脂组合物成分
Figure PCTCN2019119963-appb-000008
然后选择表3的组合物，按照表4配方进行称料，预混，然后通过挤出机(挤出机Ⅰ区温度100℃、Ⅱ区温度温度105℃)进行挤出、压片、粉碎、过筛得到粉末涂料。所得粉末涂料配方成分如表4所示。
表4 粉末涂料配方的成分
Figure PCTCN2019119963-appb-000009
Figure PCTCN2019119963-appb-000010
注：多异氰酸酯的NCO含量为15％。
实施例5
将表4中制备的粉末涂料通过静电喷涂的方式涂敷于工件表面，固化温度选择140℃/20min，涂层固化后进行性能测试，具体测试方法如表5所示。
表5 相关测试项目及参考标准
测试项目 评测依据
漆膜厚度 ISO2360
光泽度 ISO2813
流平性 ACT Test Panels LLC桔皮板标准
抗冲击强度 GB/T 1732-1993
T弯 ISO 1519
耐候性 GB/T 1865-2009
固化后涂层的具体性能如表6所示。
表6 涂层性能对比
Figure PCTCN2019119963-appb-000011
Figure PCTCN2019119963-appb-000012
根据表6所示的涂层性能对比结果，本发明粉末涂料1-6的涂层具有良好的涂层外观流平性、冲击性能以及耐候性。对比粉末涂料1与对比粉末涂料2存在流平性、机械性能以及耐候性的缺陷。粉末涂料1-6和对比粉末涂料1-2性能上存在显著差异的原因，以粉末涂料1与对比粉末涂料1为例进行解释。粉末涂料1采用了实施例3中的聚酯树脂组合物A，所述聚酯树脂组合物A是由实施例a的无定型饱和聚酯树脂及实施例Ⅰ的半结晶饱和聚酯树脂组成。由于实施例a的二元醇采用了新戊二醇、1,4-环己烷二甲醇以及三甲基戊二醇的组合，保证了涂层的耐候性，同时二元醇采用分步添加的工艺，提高了链段结构的规整度，有利于提升涂层柔韧性和机械性能。芳香二元酸为间苯二甲酸，保证了涂层的耐候性，同时脂肪二元酸使用了直链非支化脂肪族的己二酸，进一步提高了聚酯链段结构的柔韧性，提升了涂层的耐候性与机械性能。粉末涂料1的半结晶饱和聚酯树脂使用了实施例Ⅰ具有脂肪族链段的乙二醇及己二酸，链段具有高度规整性，提高了涂层的柔韧性。因此，综合来看，粉末涂料1的涂层的性能呈现冲击性能、流平性以及耐候性均优异的特性。
对比粉末涂料1采用了聚酯树脂组合物G，是由对比例f的无定型饱和聚酯树脂及对比例Ⅰ的半结晶饱和聚酯树脂组成。由于对比例f的无定型饱和聚酯树脂二元醇仅仅使用了新戊二醇，没有使用1,4-环己烷二甲醇，同时也不含有2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯和三甲基戊二醇，导致聚酯树脂的结构比较单一，使得涂层低温固化下的柔韧性较差。同时芳香二元酸中不含有间苯二甲酸，使得涂层耐候性差，酸解剂中不含有脂肪族二元酸也降低了涂层低温固化下的冲击性能与流平性。另外，对比例Ⅰ的半结晶饱和聚酯树脂使用了大量了对苯二甲酸，没有使用脂肪二元酸，聚酯树脂的链段结构刚性较强，不利于机械性能与涂层流平性的提高。因此，综合来看对比粉末涂料1的涂层的性能呈现冲击性能差、流平性差以及耐候性差的缺陷。
尽管结合优选实施方案具体展示和介绍了本发明，但所属领域的技术人员应该明白，在不脱离所述权利要求书所限定的本发明的精神和范围内，在形式上和细节上可以对本发明做出各种变化，均为本发明的保护范围。

Claims (10)

  1. 一种聚酯树脂组合物，其特征在于，所述聚酯树脂组合物是包括无定型饱和聚酯树脂和半结晶饱和聚酯树脂的混合物，
    其中，所述无定型饱和聚酯树脂由质量百分比如下的原料反应制得：
    Figure PCTCN2019119963-appb-100001
    所述半结晶饱和聚酯树脂由质量份数如下的原料反应制得：
    Figure PCTCN2019119963-appb-100002
    其中，所述的无定型饱和聚酯树脂和半结晶饱和聚酯树脂的质量比为99:1～80:20。
  2. 根据权利要求1所述聚酯树脂组合物，其特征在于，所述无定型饱和聚酯树脂中的二元醇包括以下成分：
    Figure PCTCN2019119963-appb-100003
    其中，2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯、三甲基戊二醇的质量百分比不同时为0；
    所述的半结晶饱和聚酯树脂的二元醇，选自乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇或1,10-癸二醇中的一种或多种，其中碳原子数为偶数的二元醇在二元醇中的质量百分比不低于50％。
  3. 根据权利要求1所述聚酯树脂组合物，其特征在于，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的多元醇，选自三羟甲基丙烷、三羟甲基乙烷或者季戊四醇中的一种或多种。
  4. 根据权利要求1所述聚酯树脂组合物，其特征在于，所述无定型饱和聚酯树脂的芳香二元酸，选自对苯二甲酸或间苯二甲酸的一种或两种，且间苯二甲酸在芳香二元酸中的质量百分比不低于50％；
    所述的半结晶饱和聚酯树脂的芳香二元酸，选自对苯二甲酸。
  5. 根据权利要求1所述聚酯树脂组合物，其特征在于，所述无定型饱和聚酯树脂和半结晶饱和聚酯树脂的脂肪二元酸，选自己二酸、丁二酸、戊二酸、壬二酸、癸二酸或十二烷二酸中的一种或多种。
  6. 根据权利要求1所述聚酯树脂组合物，其特征在于，所述无定型饱和聚酯树脂酸解剂，选自间苯二甲酸、己二酸或1,4-环己烷二甲酸的一种或多种；所述半结晶饱和聚酯树脂酸解剂，选自己二酸、丁二酸、戊二酸、壬二酸、癸二酸、十二烷二酸或1,4-环己烷二甲酸中的一种或多种。
  7. 根据权利要求1所述的聚酯树脂组合物，其特征在于，所述的无定型饱和聚酯树脂和半结晶饱和聚酯树脂的催化剂，选自单丁基氧化剂、单丁基三异辛酸锡、钛酸四丁酯或钛酸四异丙酯；所述的无定型饱和聚酯树脂和半结晶饱和聚酯树脂的促进剂，选自三苯基乙基溴化膦、三苯基膦、三苯基甲基溴化膦、四乙基溴化铵或四丁基溴化铵中的一种或多种。
  8. 根据权利要求1所述聚酯树脂组合物，其特征在于，所述无定型饱和聚酯树脂的酸值为30～50mgKOH/g，羟值≤10mgKOH/g，200℃熔融粘度为2000～6000mPa·s，玻璃化转变温度为50～63℃；
    所述半结晶饱和聚酯树脂的酸值为5～50mgKOH/g，羟值为5～50mgKOH/g，200℃熔融粘度为10～4000mPa·s。
  9. 权利要求1-8任一项所述聚酯树脂组合物的制备方法，其特征在于，包括无定型饱和聚酯树脂和半结晶饱和聚酯树脂的制备方法，
    其中无定型饱和聚酯树脂的制备方法，包括以下步骤：
    (1)根据配比在反应容器中加入第一部分二元醇、多元醇及催化剂，在惰性气体保护下加入芳香二元酸、脂肪二元酸，升温至230-250℃进行酯化反应至物料澄清透明，其中第一部分二元醇为新戊二醇和1,4-环己烷二甲醇；
    (2)继续加入第二部分二元醇进行反应至物料澄清透明，其中第二部分二元醇选自2-丁基-2-乙基-1,3-丙二醇、羟基新戊酸羟基新戊酯或三甲基戊二醇的一种或多种；
    (3)加入酸解剂进行反应1-4h至物料澄清透明；
    (4)真空条件下进行反应，至测得的物料酸值为30～50mgKOH/g，羟值≤10mgKOH/g，200℃熔融粘度为2000～6000mPa·s，然后加入促进剂搅拌分散均匀后出料，得到无定型饱和聚酯树脂；
    其中半结晶饱和聚酯树脂的制备方法，包括以下步骤：
    (1)根据配比在反应容器中加入二元醇、多元醇及催化剂，在惰性气体保护下加入芳香二元酸、脂肪二元酸，升温至200-250℃进行酯化反应至物料澄清透明；
    (2)加入酸解剂进行反应1-4h至物料澄清透明；
    (3)真空条件下进行反应，至物料酸值为5～50mgKOH/g，羟值为5～50mgKOH/g，200℃熔融粘度为10～4000mPa·s，加入促进剂搅拌分散均匀后出料，得到半结晶饱和聚酯树脂。
  10. 权利要求1-8任一项所述聚酯树脂组合物在粉末涂料中的应用。
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CN113845644B (zh) * 2021-11-02 2023-08-15 黄山新佳精细材料有限公司 一种粉末涂料用低氯支化型环氧树脂及其制备方法与应用
CN114891191A (zh) * 2022-06-27 2022-08-12 常州市日新树脂有限公司 一种玻璃钢制品用不饱和聚酯树脂的制备方法
CN114957638A (zh) * 2022-06-27 2022-08-30 常州市日新树脂有限公司 一种耐候性船用树脂生产工艺
CN116925560B (zh) * 2023-07-15 2024-02-09 广东安拓普聚合物科技股份有限公司 一种建筑装饰板材及其制备方法
CN118222213A (zh) * 2024-04-12 2024-06-21 佛山市鼎圣聚合物技术有限公司 一种粘结强度高的反应型热熔胶膜及其制备方法和应用

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