WO2023065131A1 - Saturated polyester copolymer, and preparation method therefor and use thereof - Google Patents

Saturated polyester copolymer, and preparation method therefor and use thereof Download PDF

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Publication number
WO2023065131A1
WO2023065131A1 PCT/CN2021/124807 CN2021124807W WO2023065131A1 WO 2023065131 A1 WO2023065131 A1 WO 2023065131A1 CN 2021124807 W CN2021124807 W CN 2021124807W WO 2023065131 A1 WO2023065131 A1 WO 2023065131A1
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Prior art keywords
saturated polyester
polyester copolymer
compound
acid
anhydride
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PCT/CN2021/124807
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French (fr)
Chinese (zh)
Inventor
陆均杰
李勇
马志平
刘亮
顾宇昕
张捷
梁志健
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擎天材料科技有限公司
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Application filed by 擎天材料科技有限公司 filed Critical 擎天材料科技有限公司
Priority to KR1020247008983A priority Critical patent/KR20240046253A/en
Priority to PCT/CN2021/124807 priority patent/WO2023065131A1/en
Priority to CN202180005528.6A priority patent/CN114466880B/en
Publication of WO2023065131A1 publication Critical patent/WO2023065131A1/en

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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
    • 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
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters

Definitions

  • the invention belongs to the technical field of organic synthesis, and in particular relates to a saturated polyester copolymer and its preparation method and application.
  • plastic substrates include reinforced acrylic sheet (PMMA), polycarbonate (PC), polyacetal (POM), ABS and other engineering plastics, as well as polyester (PET), polyethylene (HDPE/LDPE/LLDPE) , biaxially oriented polypropylene (BOPP), ethylene copolymer (EVA/EVOH/EMM) and polyimide and other polymer substrates can be widely used in electronic products, intelligent manufacturing equipment, packaging materials such as food and drug flexible packaging and flexible Electronic circuit boards and other fields.
  • the above-mentioned plastic substrate often needs to be coated with liquid ink, and the liquid ink is applied on the substrate by printing or roller coating, and the ink forms a dry film on the substrate after the solvent evaporates.
  • Inks for plastic substrates require ideal film-forming properties and excellent adhesion properties, so that the ink coating on plastic substrates will not separate from the substrate under mechanical stress or under the action of a solvent.
  • Polyester resin has performance characteristics such as appearance fullness, adhesion, compatibility and reactivity, and can be used as the main resin of ink.
  • polyester resins used in inks for plastic substrates usually need to work together with other adhesives to obtain the target performance. It is difficult to meet the requirements of adhesion strength and water boiling resistance when used as a single adhesive.
  • the polyester resin used is hyperbranched polyester, which is a polymer with a high-functionality branched structure and a large number of branched terminal nodes. It is not conducive to achieving a balance between flexibility and adhesion, and affects the overall substrate adhesion performance and boiling/boiling resistance of the resin.
  • a saturated polyester copolymer is provided.
  • a preparation method of the above-mentioned saturated polyester copolymer is provided.
  • the technical solution adopted in the present invention is:
  • a kind of saturated polyester copolymer is characterized in that: comprise following raw material:
  • the compound b is formula 2 and/or formula 3:
  • R1 is a hydroxyl group or an amino group, and at least part of it is a hydroxyl group or contains at least a hydroxyl group;
  • R 2 is an alkyl group with 1 to 20 carbon atoms
  • R 3 is a methyl group, an ethyl group or a hydrogen atom
  • n 1 is an integer >1;
  • n 2 is an integer >2;
  • n 3 is 0 or 1;
  • P 1 and P 2 are independently carboxyl, hydroxyl, methyl or hydrogen, and at least one of P 1 and P 2 is carboxyl or hydroxyl;
  • X is an oxygen atom
  • R 4 is a methine group
  • R 5 is a methyl group or an ethyl group
  • n 4 is an integer ⁇ 0.
  • R 1 of the general formula may preferably be a hydroxyl group
  • R 2 may preferably be an alkyl group with 1 to 10 carbon atoms
  • R 3 may preferably be a methyl group or a hydrogen atom.
  • n 1 of the general formula may preferably be an integer ⁇ 4, n 2 may preferably be an integer ⁇ 6, and n 3 is preferably 1.
  • P 1 and P 2 in the general formula of compound b above may preferably be carboxyl or hydroxyl; R 5 is preferably methyl.
  • P 1 and P 2 of the general formula preferably at least one of them is a carboxyl group; n 4 can be preferably 0 or 1.
  • the number average molecular weight of the above-mentioned saturated polyester copolymer is 1-35 KDa.
  • the number average molecular weight of the above-mentioned saturated polyester copolymer is 3-30KDa; more preferably, the number-average molecular weight of the above-mentioned saturated polyester copolymer is 3-28KDa; more preferably, the saturated polyester copolymer
  • the number average molecular weight of the compound is 3-25KDa.
  • Too low number-average molecular weight of polyester copolymer is not conducive to ink adhesion, and too high number-average molecular weight of polyester copolymer will also lead to a decrease in the solubility of the ink main resin and a continuous increase in the difficulty of synthesis.
  • the molar content of hydroxyl groups is higher than that of amino groups.
  • the ratio of the molar content of hydroxyl groups to the molar content of amino groups in the above compound a is 55/45 to 99.99/0.01; more preferably, the ratio of the molar content of hydroxyl groups to the molar content of amino groups in the above compound a is 60/40 to 99.99/0.01 More preferably, the ratio of the molar content of hydroxyl groups to the molar content of amino groups in compound a is 70/30 to 99.99/0.01.
  • the glass transition temperature of the saturated polyester copolymer is -20°C to 70°C.
  • the above-mentioned saturated polyester copolymer has a glass transition temperature of -20°C to 70°C; more preferably, the above-mentioned saturated polyester copolymer has a glass transition temperature of -10°C to 70°C; more preferably, the above-mentioned The glass transition temperature of the saturated polyester copolymer is -5°C to 70°C.
  • the above-mentioned compound a may be selected from 1,1'-bis(4-hydroxy-3-methylphenyl)-cyclohexane (DMBPC) or 1,1'-bis(4 '-aminophenyl)-cyclohexane (BAPC); preferably at least 1,1'-bis(4-hydroxy-3-methylphenyl)-cyclohexane (DMBPC).
  • DMBPC 1,1'-bis(4-hydroxy-3-methylphenyl)-cyclohexane
  • BAPC 1,1'-bis(4 '-aminophenyl)-cyclohexane
  • the above-mentioned compound a has both an alicyclic group and a phenylcyclic group. Based on this, compared to using monomers containing only alicyclic groups and monomers containing only phenylcyclic groups in the synthesis process, the above-mentioned use of monomers containing only aliphatic ring groups and Ring-based monomers and monomers containing only benzene ring groups will lead to inhomogeneity of polyester segment groups.
  • the present invention introduces components having both alicyclic and phenylcyclic groups into the polyester copolymer, which can realize the orderly distribution of space groups in the chain segment, enhance the coupling effect of steric hindrance groups, and improve the efficiency of space groups.
  • the combined anchoring effect on the base material has a significant effect on improving the adhesion of the plastic base material.
  • the molar ratio of the amount of the above-mentioned compound b to the amount of polybasic acid and/or polybasic acid anhydride in the raw material is 0.01/1-8/2; Or the molar ratio of polybasic acid anhydride consumption is 0.01/1-7/3; More preferably, the molar ratio of its consumption and polybasic acid and/or polybasic acid anhydride consumption in raw material is 0.01/1-6/4; Especially preferably, its The molar ratio of the amount to the amount of polybasic acid and/or polybasic acid anhydride in the raw material is 0.01/1-5/5.
  • the molar ratio between the components is arbitrary; preferably, when compound b contains two
  • the molar ratio between the two components is in the range of 99.9/0.1-0.1/99.9; more preferably, when compound b is a mixed component containing two general structures, the composition
  • the molar ratio between the parts is in the range of 99/1-1/99; especially preferably, when the compound b is a mixed component containing two general structures, the molar ratio between the components is in the range of 90/10-10/90 range.
  • the molar ratio between the components is arbitrary.
  • the above compound b can be selected from at least one of bisphenol A diether dianhydride (BisDA) and 4,4'-oxydiphthalic anhydride (ODPA).
  • BisDA bisphenol A diether dianhydride
  • ODPA 4,4'-oxydiphthalic anhydride
  • the above-mentioned compound b is a polyphenyl ring aromatic compound, and the aromatic polyphenyl ring component is used as the main branched component of the resin, which can produce a polyphenyl ring effect to form a highly branched structure, and can effectively improve the ink quality. Adhesion strength on plastic substrates.
  • the above polyols include ethylene glycol, 1,2-propanediol, butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol , 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentane At least one of diols; preferably, the above polyols include 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2-butyl-2-ethyl-1 , at least one of 3-propanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentane
  • three- and four-valent polyols can also be used, including at least one of diglycerin, 1,2,4-butanetriol, and trimethylolethane; the total amount used should not exceed all 30% of the total moles of polyols; preferably, no more than 25% of the total moles of all polyols; more preferably, no more than 20% of the total moles of all polyols; more preferably, no more than 20% of the total moles of all polyols 15% of the total amount.
  • the above-mentioned polybasic acid comprises at least one of succinic acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, cyclobutyldicarboxylic acid and phthalic acid .
  • the above-mentioned compound a its phenolic hydroxyl group is conjugated with the benzene ring, has relatively weak nucleophilicity, and needs to react with an acid anhydride with stronger electrophilicity, so through the synthesis method described in the present invention, The reactivity of compound a in the reaction system can be improved to obtain the expected degree of reaction.
  • the polybasic anhydride includes at least one of succinic anhydride, adipic anhydride, suberic anhydride, sebacic anhydride, phthalic anhydride and trimellitic anhydride.
  • the molar ratio of the amount of the compound a to the amount of the polyol is 0.01/1-9/1.
  • it is 0.01/1-8/2; preferably, it is 0.01/1-7/3; preferably, it is 0.01/1-6/4.
  • the molar ratio of the amount of the compound b to the amount of the polybasic acid and/or polybasic anhydride is 0.01/1-8/2.
  • the total molar ratio of compound a and polyhydric alcohol, and the total molar ratio of compound b and polybasic acid and/or polybasic anhydride is 0.9/1-3/1.
  • the general formula of the above-mentioned saturated polyester copolymer is:
  • R 1 is hydroxyl or amino
  • R 2 is an alkyl group with 1 to 20 carbon atoms
  • R 3 is a methyl group, an ethyl group or a hydrogen atom
  • R 4 is methine
  • R 5 is methyl or ethyl
  • X is an oxygen atom
  • n 1 to n 4 and m are integers.
  • the technical solution adopted in the present invention is:
  • the preparation method of above-mentioned saturated polyester copolymer comprises the following steps:
  • the remaining catalyst is added, and the saturated polyester copolymer is obtained through reaction; the reaction temperature is 240-260° C., and the reaction is carried out under vacuum, and the reaction includes vacuum polycondensation.
  • the vacuum degree of vacuum polycondensation is ⁇ 600Pa.
  • the limitation of the acid value of the system is related to the degree of reaction, and it is more conducive to the improvement of the overall performance of the product within the range of the acid value defined above.
  • the catalyst includes at least one of tin-based catalysts, antimony-based catalysts, titanium-based catalysts and germanium-based catalysts.
  • the above-mentioned catalysts include at least one of tin-based catalysts, antimony-based catalysts, and titanium-based catalysts.
  • the above-mentioned saturated polyester copolymer can be used as the main binder of the ink for plastic substrates, and can form a coating in the form of a single component, and can also undergo a crosslinking reaction with an isocyanate compound to obtain a cured coating.
  • the above-mentioned isocyanate compound may be selected from diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, cyclohexane At least one of hexane diisocyanate, dicyclohexylmethane diisocyanate, and the corresponding blocked isocyanate compound.
  • Another aspect of the present invention also relates to the application of the above-mentioned saturated polyester copolymer in ink.
  • the present invention introduces components having both aliphatic and benzene ring groups in the polyester copolymer, which can realize the orderly distribution of space groups in the chain segment, improve the joint anchoring effect of space groups on the substrate, and Significant improvement in the adhesion of plastic substrates;
  • the present invention introduces compound b in the polyester copolymer, which is a polyphenyl ring aromatic compound, and the component of the aromatic polyphenyl ring is used as the main branched component of the resin, which can produce the polyphenyl ring effect, and at the same time It can also effectively improve the adhesion strength of the ink on the plastic substrate;
  • the present invention changes the application mode in which the existing printing ink realizes the performance requirements of the ink layer in the form of sharing multiple types of binder resins.
  • the saturated polyester copolymer described in the present invention as the main film-forming substance, can be used as In the form of a single adhesive or in combination with an isocyanate curing agent, the ink coating for plastic substrates prepared in this way breaks through the technical bottleneck that the ink layer is difficult to adhere to and easy to fall off on plastic substrates, and significantly improves the adhesion of coatings on plastic substrates Performance, and further improve the comprehensive performance of plastic substrate coatings in solvent resistance, water boiling or cooking resistance, and friction resistance.
  • What the tin catalyst used in the embodiment is stannous oxalate.
  • antimony catalyst used in the embodiment is ethylene glycol antimony.
  • Butyl titanate is used as the titanium catalyst in the examples.
  • the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) -cyclohexane, 2-methyl-1,3-propanediol, succinic anhydride, terephthalic acid and isophthalic acid, and tin catalysts are added to the reactor according to the corresponding dosage shown in Table 1, and the protective Under the atmosphere of nitrogen, gradually raise the temperature and keep it at ⁇ 240°C for ⁇ 6 hours until the acid value of the system is reduced to below 20mgKOH/g.
  • the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) -cyclohexane, neopentyl glycol, 2-ethyl-2-butyl-propylene glycol, phthalic anhydride and isophthalic acid and antimony catalysts, add in the reactor according to the corresponding dosage shown in table 1, Under a protective atmosphere of nitrogen, the temperature is gradually raised and kept at ⁇ 250°C for ⁇ 5 hours until the acid value of the system is reduced to below 25mgKOH/g.
  • the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) - cyclohexane, 1,1'-bis(4'-aminophenyl)-cyclohexane (BAPC), ethylene glycol, 2-methyl-2,4-pentanediol, phthalic anhydride, Terephthalic acid, isophthalic acid, and tin catalysts were added to the reactor according to the corresponding dosage shown in Table 1, and the temperature was gradually raised under a protective atmosphere of nitrogen and kept at ⁇ 240°C for ⁇ 7 hours until the system acid The value drops below 18mgKOH/g.
  • BAPC 1,1'-bis(4-hydroxy-3-methylphenyl) - cyclohexane
  • BAPC 1,1'-bis(4'-aminophenyl)-cyclohexane
  • ethylene glycol 2-methyl-2,4-pentanediol
  • phthalic anhydride Terephthalic acid
  • the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) -cyclohexane, 2-ethyl-2-butyl-propylene glycol, neopentyl glycol, succinic anhydride, terephthalic acid and isophthalic acid and titanium catalyst, according to the corresponding amount shown in table 1, add reaction In the container, under a protective atmosphere of nitrogen, the temperature was gradually raised and kept at ⁇ 250°C for ⁇ 7 hours until the acid value of the system was reduced to below 18mgKOH/g.
  • the raw materials required for the first step reaction include neopentyl glycol, 2-ethyl-2-butyl-propylene glycol, ortho Phthalic anhydride, isophthalic acid, and antimony catalysts were added to the reactor according to the corresponding dosages shown in Table 1, and the temperature was gradually raised under a protective atmosphere of nitrogen and kept at ⁇ 250°C for ⁇ 4 hours until the system acid The value drops below 25mgKOH/g.
  • the saturated polyester copolymer prepared in Examples 1-4 and Comparative Examples 1-2 was used as the main resin, and the corresponding ink was prepared according to the formula shown in Table 3.
  • Duranate TKA-90SB is an HDI (hexamethylene diisocyanate trimer) curing agent from Asahi Kasei, which belongs to the isocyanate type curing agent.
  • HDI hexamethylene diisocyanate trimer
  • the two-component screen printing ink that the saturated polyester copolymer of embodiment 1 ⁇ 4 and comparative example 1 ⁇ 2 is the main binder prepares, is coated on the ABS plate plastic base material with the mode of screen printing respectively, through heat treatment ( 80°C*1h) to form an ink cured coating, and test the performance of the ink coating.
  • the test results are shown in Table 5:
  • the ink prepared with the saturated polyester copolymer prepared by the present invention whether it is a single-component ink or a two-component ink, has better effects on adhesion, alcohol wiping resistance and friction resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Disclosed in the present invention are a saturated polyester copolymer, and a preparation method therefor and the use thereof. The saturated polyester copolymer is prepared from the following raw materials: a compound a, a compound b, a polyhydric alcohol, a polybasic acid and/or a polybasic acid anhydride. In the present invention, the application mode of existing printing ink using multiple types of adhesive resins together to meet the performance requirement of an ink layer is changed. The saturated polyester copolymer of the present invention serves as a main film-forming substance and can be used in the form of a single adhesive or combined with an isocyanate curing agent, and an ink coating prepared therefrom and used for a plastic substrate breaks through the technical bottleneck of an ink layer being difficult to adhere to a plastic substrate and easy to fall off; and the saturated polyester copolymer significantly improves the adhesion performance of the coating on the plastic substrate, and further improves the comprehensive properties such as solvent resistance, boiling resistance or steaming resistance and friction resistance of the coating on the plastic substrate.

Description

一种饱和聚酯共聚物及其制备方法和应用A kind of saturated polyester copolymer and its preparation method and application 技术领域technical field
本发明属于有机合成技术领域，具体涉及一种饱和聚酯共聚物及其制备方法和应用。The invention belongs to the technical field of organic synthesis, and in particular relates to a saturated polyester copolymer and its preparation method and application.
背景技术Background technique
已知的塑料基材包括强化亚克力板(PMMA)、聚碳酸酯(PC)、聚缩醛(POM)、ABS等工程塑料，也包括聚酯(PET)、聚乙烯(HDPE/LDPE/LLDPE)、双向拉伸聚丙烯(BOPP)、乙烯共聚物(EVA/EVOH/EMM)以及聚酰亚胺等聚合物基材，可广泛适用于电子产品、智能制造设备、包装材料例如食品药品软包装以及柔性电子线路板等领域。上述塑料基材上往往需要涂覆液体油墨，该液体油墨以印刷或辊涂的方式涂覆于基材上，油墨在溶剂蒸发后于基材上形成干膜。塑料基材用油墨要求具备理想的成膜特性以及优良的附着性能，以使塑料基材的油墨涂层，在机械应力下或与溶剂共同作用下，不与基材分离。Known plastic substrates include reinforced acrylic sheet (PMMA), polycarbonate (PC), polyacetal (POM), ABS and other engineering plastics, as well as polyester (PET), polyethylene (HDPE/LDPE/LLDPE) , biaxially oriented polypropylene (BOPP), ethylene copolymer (EVA/EVOH/EMM) and polyimide and other polymer substrates can be widely used in electronic products, intelligent manufacturing equipment, packaging materials such as food and drug flexible packaging and flexible Electronic circuit boards and other fields. The above-mentioned plastic substrate often needs to be coated with liquid ink, and the liquid ink is applied on the substrate by printing or roller coating, and the ink forms a dry film on the substrate after the solvent evaporates. Inks for plastic substrates require ideal film-forming properties and excellent adhesion properties, so that the ink coating on plastic substrates will not separate from the substrate under mechanical stress or under the action of a solvent.
聚酯树脂具备外观丰满度，附着性，相容性以及反应活性等性能特点，可作为油墨的主体树脂。目前塑料基材用油墨涉及的聚酯树脂，通常需要与其他粘合剂共同作用以获得目标性能，作为单一粘合剂使用难以满足附着强度与耐水煮性等要求。Polyester resin has performance characteristics such as appearance fullness, adhesion, compatibility and reactivity, and can be used as the main resin of ink. At present, polyester resins used in inks for plastic substrates usually need to work together with other adhesives to obtain the target performance. It is difficult to meet the requirements of adhesion strength and water boiling resistance when used as a single adhesive.
而对于使用多组分粘合剂的油墨来说，其使用的聚酯树脂为超支化聚酯，超支化聚酯是具备高官能度的支化结构与大量支化端基节点的聚合物，不利于实现柔韧性与附着力的平衡，影响树脂整体的基材附着性能以及耐水煮/蒸煮性能。For inks using multi-component adhesives, the polyester resin used is hyperbranched polyester, which is a polymer with a high-functionality branched structure and a large number of branched terminal nodes. It is not conducive to achieving a balance between flexibility and adhesion, and affects the overall substrate adhesion performance and boiling/boiling resistance of the resin.
发明内容Contents of the invention
本发明所要解决的第一个技术问题是：The first technical problem to be solved by the present invention is:
提供一种饱和聚酯共聚物。A saturated polyester copolymer is provided.
本发明所要解决的第二个技术问题是：The second technical problem to be solved by the present invention is:
提供一种上述饱和聚酯共聚物的制备方法。A preparation method of the above-mentioned saturated polyester copolymer is provided.
本发明所要解决的第三个技术问题是：The third technical problem to be solved by the present invention is:
上述饱和聚酯共聚物的应用。Use of the above-mentioned saturated polyester copolymers.
为了解决上述第一个技术问题，本发明采用的技术方案为：In order to solve the above-mentioned first technical problem, the technical solution adopted in the present invention is:
一种饱和聚酯共聚物，其特征在于：包括以下原料：A kind of saturated polyester copolymer is characterized in that: comprise following raw material:
化合物a、化合物b、多元醇、多元酸和或/多元酸酐；Compound a, compound b, polyhydric alcohol, polybasic acid and/or polybasic acid anhydride;
所述化合物a的通式为：The general formula of the compound a is:
Figure PCTCN2021124807-appb-000001
Figure PCTCN2021124807-appb-000001
所述化合物b为式2和/或式3：The compound b is formula 2 and/or formula 3:
Figure PCTCN2021124807-appb-000002
Figure PCTCN2021124807-appb-000002
式中，R 1为羟基或氨基，且至少有一部分为羟基或者至少含有羟基； In the formula, R1 is a hydroxyl group or an amino group, and at least part of it is a hydroxyl group or contains at least a hydroxyl group;
R 2为碳原子数1～20的烷基； R 2 is an alkyl group with 1 to 20 carbon atoms;
R 3为甲基，乙基或者氢原子； R 3 is a methyl group, an ethyl group or a hydrogen atom;
n 1为>1的整数； n 1 is an integer >1;
n 2为>2的整数； n 2 is an integer >2;
n 3为0或者1； n 3 is 0 or 1;
式中，P 1、P 2独立为羧基、羟基、甲基或氢，且P 1、P 2中至少有一个为羧基或羟基； In the formula, P 1 and P 2 are independently carboxyl, hydroxyl, methyl or hydrogen, and at least one of P 1 and P 2 is carboxyl or hydroxyl;
式中，X为氧原子；R 4为次甲基；R 5为甲基或者乙基；n 4为≥0的整数。 In the formula, X is an oxygen atom; R 4 is a methine group; R 5 is a methyl group or an ethyl group; n 4 is an integer ≥ 0.
上述(式2)中，化合物b两端的P 1一致、化合物b两端的P 2一致，以限定单体类别。 In the above (Formula 2), the P 1 at both ends of the compound b is the same, and the P 2 at both ends of the compound b is the same, so as to define the monomer category.
根据本发明的一种实施方式，上述化合物a，其通式的R 1可优选为羟基，R 2可优选为碳原子数1～10的烷基，R 3优选为甲基或者氢原子。 According to one embodiment of the present invention, in the above-mentioned compound a, R 1 of the general formula may preferably be a hydroxyl group, R 2 may preferably be an alkyl group with 1 to 10 carbon atoms, and R 3 may preferably be a methyl group or a hydrogen atom.
根据本发明的一种实施方式，上述化合物a，其通式的n 1可优选为≤4的整数，n 2可优选为≤6的整数，n 3优选为1。 According to one embodiment of the present invention, in the above-mentioned compound a, n 1 of the general formula may preferably be an integer ≤4, n 2 may preferably be an integer ≤6, and n 3 is preferably 1.
根据本发明的一种实施方式，上述化合物b，其通式的P 1与P 2，可优选为羧基或羟基；R 5优选为甲基。 According to one embodiment of the present invention, P 1 and P 2 in the general formula of compound b above may preferably be carboxyl or hydroxyl; R 5 is preferably methyl.
根据本发明的一种实施方式，上述化合物b，其通式的P 1与P 2，优选的至少有一个为羧基；n 4可优选为0或者1。 According to one embodiment of the present invention, in the above-mentioned compound b, P 1 and P 2 of the general formula, preferably at least one of them is a carboxyl group; n 4 can be preferably 0 or 1.
根据本发明的一种实施方式，上述饱和聚酯共聚物的数均分子量为1～35KDa。优选的，上述的饱和聚酯共聚物的数均分子量为3～30KDa；更优选的，上述的饱和聚酯共聚物的数均分子量为3～28KDa；更优选的，所述的饱和聚酯共聚物的数均分子量为3～25KDa。According to one embodiment of the present invention, the number average molecular weight of the above-mentioned saturated polyester copolymer is 1-35 KDa. Preferably, the number average molecular weight of the above-mentioned saturated polyester copolymer is 3-30KDa; more preferably, the number-average molecular weight of the above-mentioned saturated polyester copolymer is 3-28KDa; more preferably, the saturated polyester copolymer The number average molecular weight of the compound is 3-25KDa.
过低的聚酯共聚物数均分子量，不利于油墨附着力，过高的聚酯共聚物数均分子量也会导致油墨主体树脂的溶解性有所下降，以及合成难度的持续提高。Too low number-average molecular weight of polyester copolymer is not conducive to ink adhesion, and too high number-average molecular weight of polyester copolymer will also lead to a decrease in the solubility of the ink main resin and a continuous increase in the difficulty of synthesis.
根据本发明的一种实施方式，上述化合物a中，羟基的摩尔含量高于氨基的摩尔含量。According to one embodiment of the present invention, in the above compound a, the molar content of hydroxyl groups is higher than that of amino groups.
优选的，上述化合物a中羟基摩尔含量与氨基摩尔含量的比例为55/45～99.99/0.01；更优选的，上述化合物a中羟基摩尔含量与氨基摩尔含量的比例为60/40～99.99/0.01；更优选的，上述化合物a中羟基摩尔含量与氨基摩尔含量的比例为70/30～99.99/0.01。Preferably, the ratio of the molar content of hydroxyl groups to the molar content of amino groups in the above compound a is 55/45 to 99.99/0.01; more preferably, the ratio of the molar content of hydroxyl groups to the molar content of amino groups in the above compound a is 60/40 to 99.99/0.01 More preferably, the ratio of the molar content of hydroxyl groups to the molar content of amino groups in compound a is 70/30 to 99.99/0.01.
根据本发明的一种实施方式，上述饱和聚酯共聚物的玻璃化温度为-20℃～70℃。优选的，上述的饱和聚酯共聚物的玻璃化温度为-20℃～70℃；更优选的，上述的饱和聚酯共聚物的玻璃化温度为-10℃～70℃；更优选的，上述的饱和聚酯共聚物的玻璃化温度为-5℃～70℃。According to one embodiment of the present invention, the glass transition temperature of the saturated polyester copolymer is -20°C to 70°C. Preferably, the above-mentioned saturated polyester copolymer has a glass transition temperature of -20°C to 70°C; more preferably, the above-mentioned saturated polyester copolymer has a glass transition temperature of -10°C to 70°C; more preferably, the above-mentioned The glass transition temperature of the saturated polyester copolymer is -5°C to 70°C.
根据本发明的一种实施方式，上述化合物a，可选自1,1’-双(4-羟基-3-甲基苯基)-环己烷(DMBPC)或者1,1’-双(4'-氨基苯基)-环己烷(BAPC)；优选的至少含有1,1’-双(4-羟基-3-甲基苯基)-环己烷(DMBPC)。According to one embodiment of the present invention, the above-mentioned compound a may be selected from 1,1'-bis(4-hydroxy-3-methylphenyl)-cyclohexane (DMBPC) or 1,1'-bis(4 '-aminophenyl)-cyclohexane (BAPC); preferably at least 1,1'-bis(4-hydroxy-3-methylphenyl)-cyclohexane (DMBPC).
上述化合物a同时具备脂环基与苯环基，基于此，相对于在合成过程中分别使用仅含脂环基的单体与仅含苯环基的单体而言，上述分别使用仅含脂环基的单体与仅含苯环基的单体会导致聚酯链段基团的不均匀性。而本发明在聚酯共聚物中引入兼具脂环基与苯环基的组分，可实现链段中空间基团的有序分布，增强空间位阻基团的耦合效应，提升空间基团对基材的联合锚固作用，对塑料基材附着力改善作用显著。The above-mentioned compound a has both an alicyclic group and a phenylcyclic group. Based on this, compared to using monomers containing only alicyclic groups and monomers containing only phenylcyclic groups in the synthesis process, the above-mentioned use of monomers containing only aliphatic ring groups and Ring-based monomers and monomers containing only benzene ring groups will lead to inhomogeneity of polyester segment groups. However, the present invention introduces components having both alicyclic and phenylcyclic groups into the polyester copolymer, which can realize the orderly distribution of space groups in the chain segment, enhance the coupling effect of steric hindrance groups, and improve the efficiency of space groups. The combined anchoring effect on the base material has a significant effect on improving the adhesion of the plastic base material.
根据本发明的一种实施方式，上述化合物b，其用量与原材料中多元酸和/或多元酸酐用量的摩尔比例为0.01/1—8/2；优选地，其用量与原材料中多元酸和/或多元酸酐用量的摩尔比例为0.01/1—7/3；更优选地，其用量与原材料中多元酸和/或多元酸酐用量的摩尔比例为0.01/1—6/4；特别优选地，其用量与原材料中多元酸和/或多元酸酐用量的摩尔比例为0.01/1—5/5。According to one embodiment of the present invention, the molar ratio of the amount of the above-mentioned compound b to the amount of polybasic acid and/or polybasic acid anhydride in the raw material is 0.01/1-8/2; Or the molar ratio of polybasic acid anhydride consumption is 0.01/1-7/3; More preferably, the molar ratio of its consumption and polybasic acid and/or polybasic acid anhydride consumption in raw material is 0.01/1-6/4; Especially preferably, its The molar ratio of the amount to the amount of polybasic acid and/or polybasic acid anhydride in the raw material is 0.01/1-5/5.
根据本发明的一种实施方式，上述化合物b，其为同时含有2种或者以上通式结构的混合组分时，组分间的摩尔比例是任意的；优选地，当化合物b为含有2种通式结构的混合组分时，这两种组分间的摩尔比处于99.9/0.1—0.1/99.9的范围；更优选地，当化合物b为含有2种通式结构的混合组分时，组分间的摩尔比处于99/1—1/99的范围；特别优选地，当化合物b为含有2种通式结构的混合组分时，组分间的摩尔比处于90/10—10/90的范围。According to one embodiment of the present invention, when the above-mentioned compound b is a mixed component containing two or more general structures at the same time, the molar ratio between the components is arbitrary; preferably, when compound b contains two When mixing components of the general structure, the molar ratio between the two components is in the range of 99.9/0.1-0.1/99.9; more preferably, when compound b is a mixed component containing two general structures, the composition The molar ratio between the parts is in the range of 99/1-1/99; especially preferably, when the compound b is a mixed component containing two general structures, the molar ratio between the components is in the range of 90/10-10/90 range.
根据本发明的一种实施方式，上述化合物b为同时含有2种或者以上通式结构的混合组分时，组分间的摩尔比例是任意的。According to one embodiment of the present invention, when the above-mentioned compound b is a mixed component containing two or more general structures, the molar ratio between the components is arbitrary.
根据本发明的一种实施方式，上述化合物b，可选自双酚A型二醚二酐(BisDA)和4,4’-氧双邻苯二甲酸酐(ODPA)中的至少一种。According to one embodiment of the present invention, the above compound b can be selected from at least one of bisphenol A diether dianhydride (BisDA) and 4,4'-oxydiphthalic anhydride (ODPA).
上述化合物b为多苯环芳香族化合物，将该芳香族多苯环的组分作为树脂的主要支化组分，能够产生的多苯环效应以形成高度支化结构，同时还能有效提高油墨在塑料基材的附着强度。The above-mentioned compound b is a polyphenyl ring aromatic compound, and the aromatic polyphenyl ring component is used as the main branched component of the resin, which can produce a polyphenyl ring effect to form a highly branched structure, and can effectively improve the ink quality. Adhesion strength on plastic substrates.
根据本发明的一种实施方式，上述多元醇包括乙二醇、1,2-丙二醇、丁二醇、2-甲基-1,3-丙二醇、新戊二醇、1,6-己二醇、2-丁基-2-乙基-1,3-丙二醇、1,4-环己烷二甲醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇中的至少一种；优选的，上述 多元醇包括2-甲基-1,3-丙二醇、新戊二醇、1,6-己二醇、2-丁基-2-乙基-1,3-丙二醇、1,4-环己烷二甲醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇中的至少一种；更优选的，包括新戊二醇、1,6-己二醇、1,4-环己烷二甲醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇、1,2,4-丁三醇，三羟甲基乙烷的至少；更优选的，包括新戊二醇、1,4-环己烷二甲醇、2-甲基-2,4-戊二醇中的至少一种。According to one embodiment of the present invention, the above polyols include ethylene glycol, 1,2-propanediol, butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol , 2-butyl-2-ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentane At least one of diols; preferably, the above polyols include 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2-butyl-2-ethyl-1 , at least one of 3-propanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol; more preferably, Including neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2,4-Butanetriol, at least of trimethylolethane; more preferred, including neopentyl glycol, 1,4-cyclohexanedimethanol, 2-methyl-2,4-pentanediol at least one of alcohols.
上述多元醇中，也可选用三元及四元的多元醇，包括二甘油，1,2,4-丁三醇，三羟甲基乙烷中的至少一种；其总用量，不超过所有多元醇摩尔总量的30％；优选的，不超过所有多元醇摩尔总量的25％；更优选的，不超过所有多元醇摩尔总量的20％；更优选的，不超过所有多元醇摩尔总量的15％。Among the above-mentioned polyols, three- and four-valent polyols can also be used, including at least one of diglycerin, 1,2,4-butanetriol, and trimethylolethane; the total amount used should not exceed all 30% of the total moles of polyols; preferably, no more than 25% of the total moles of all polyols; more preferably, no more than 20% of the total moles of all polyols; more preferably, no more than 20% of the total moles of all polyols 15% of the total amount.
根据本发明的一种实施方式，上述多元酸包括丁二酸、己二酸、辛二酸、癸二酸、环己烷二甲酸、环丁基二甲酸和邻苯二甲酸中的至少一种。According to one embodiment of the present invention, the above-mentioned polybasic acid comprises at least one of succinic acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, cyclobutyldicarboxylic acid and phthalic acid .
根据本发明的一种实施方式，上述化合物a，其酚羟基与苯环形成共轭，亲核性相对较弱，需要和亲电性更强的酸酐反应，于是通过本发明所述的合成方法，能够提升化合物a在反应体系中的反应活性，以获得预期的反应程度。According to one embodiment of the present invention, the above-mentioned compound a, its phenolic hydroxyl group is conjugated with the benzene ring, has relatively weak nucleophilicity, and needs to react with an acid anhydride with stronger electrophilicity, so through the synthesis method described in the present invention, The reactivity of compound a in the reaction system can be improved to obtain the expected degree of reaction.
根据本发明的一种实施方式，上述多元酸酐包括丁二酸酐、己二酸酐、辛二酸酐、癸二酸酐、邻苯二甲酸酐和偏苯三酸酐中的至少一种。According to an embodiment of the present invention, the polybasic anhydride includes at least one of succinic anhydride, adipic anhydride, suberic anhydride, sebacic anhydride, phthalic anhydride and trimellitic anhydride.
根据本发明的一种实施方式，所述化合物a的用量，与所述多元醇用量的摩尔比例为0.01/1-9/1。优选的，为0.01/1—8/2；优选的，为0.01/1—7/3；优选的，为0.01/1—6/4。According to one embodiment of the present invention, the molar ratio of the amount of the compound a to the amount of the polyol is 0.01/1-9/1. Preferably, it is 0.01/1-8/2; preferably, it is 0.01/1-7/3; preferably, it is 0.01/1-6/4.
根据本发明的一种实施方式，所述化合物b的用量，与所述多元酸和/或多元酸酐用量的摩尔比例为0.01/1-8/2。According to one embodiment of the present invention, the molar ratio of the amount of the compound b to the amount of the polybasic acid and/or polybasic anhydride is 0.01/1-8/2.
根据本发明的一种实施方式，化合物a与多元醇的摩尔总量，和化合物b与多元酸和/或多元酸酐的摩尔总量比例为0.9/1—3/1。According to one embodiment of the present invention, the total molar ratio of compound a and polyhydric alcohol, and the total molar ratio of compound b and polybasic acid and/or polybasic anhydride is 0.9/1-3/1.
根据本发明的一种实施方式，上述饱和聚酯共聚物，通式为：According to one embodiment of the present invention, the general formula of the above-mentioned saturated polyester copolymer is:
Figure PCTCN2021124807-appb-000003
Figure PCTCN2021124807-appb-000003
式中：In the formula:
R 1为羟基或氨基； R 1 is hydroxyl or amino;
R 2为碳原子数1～20的烷基； R 2 is an alkyl group with 1 to 20 carbon atoms;
R 3为甲基、乙基或者氢原子； R 3 is a methyl group, an ethyl group or a hydrogen atom;
R 4为次甲基； R 4 is methine;
R 5为甲基或者乙基； R 5 is methyl or ethyl;
X为氧原子；X is an oxygen atom;
n 1～n 4与m为整数。 n 1 to n 4 and m are integers.
为了解决上述第二个技术问题，本发明采用的技术方案为：In order to solve the above-mentioned second technical problem, the technical solution adopted in the present invention is:
混合化合物a、部分多元醇、部分多元酸和或/部分多元酸酐，加热反应至体系酸值小于25mgKOH/g；Mix compound a, part of polyhydric alcohol, part of polybasic acid and/or part of polybasic acid anhydride, heat and react until the acid value of the system is less than 25 mgKOH/g;
加入化合物b，余量多元醇、余量多元酸和或/余量多元酸酐，反应至体系酸值小于30mgKOH/g，得到所述饱和聚酯共聚物。Add compound b, the remaining amount of polyhydric alcohol, the remaining amount of polybasic acid and/or/the remaining amount of polybasic acid anhydride, and react until the acid value of the system is less than 30 mgKOH/g to obtain the saturated polyester copolymer.
根据本发明的一种实施方式，上述饱和聚酯共聚物的制备方法，包括以下步骤：According to one embodiment of the present invention, the preparation method of above-mentioned saturated polyester copolymer comprises the following steps:
混合化合物a、部分多元醇、部分多元酸和或/部分多元酸酐和部分催化剂，加热反应至体系酸值小于25mgKOH/g；加热反应温度为220～260℃；Mixing compound a, part of polyol, part of polybasic acid and/or part of polybasic acid anhydride and part of catalyst, heating and reacting until the acid value of the system is less than 25mgKOH/g; the heating reaction temperature is 220-260°C;
保持温度，加入化合物b，余下多元醇、余下多元酸和或/余下多元酸酐，反应至体系酸值小于30mgKOH/g；Maintaining the temperature, adding compound b, the remaining polyhydric alcohol, the remaining polybasic acid and/or the remaining polybasic acid anhydride, and reacting until the acid value of the system is less than 30 mgKOH/g;
加入余下催化剂，经反应得到所述饱和聚酯共聚物；反应温度为240～260℃，反应在抽真空下进行，反应包括真空缩聚。真空缩聚的真空度为≤600Pa。The remaining catalyst is added, and the saturated polyester copolymer is obtained through reaction; the reaction temperature is 240-260° C., and the reaction is carried out under vacuum, and the reaction includes vacuum polycondensation. The vacuum degree of vacuum polycondensation is ≤600Pa.
上述方法中，体系酸值的限定与反应程度相关，在上述限定的酸值范围内更利于产物综合性能的改善。In the above method, the limitation of the acid value of the system is related to the degree of reaction, and it is more conducive to the improvement of the overall performance of the product within the range of the acid value defined above.
根据本发明的一种实施方式，上述催化剂包括锡类催化剂、锑类催化剂、钛系催化剂和锗类催化剂中的至少一种。优选的，上述的催化剂包括锡类催化剂，锑类催化剂，钛系催化剂中的至少一种。According to an embodiment of the present invention, the catalyst includes at least one of tin-based catalysts, antimony-based catalysts, titanium-based catalysts and germanium-based catalysts. Preferably, the above-mentioned catalysts include at least one of tin-based catalysts, antimony-based catalysts, and titanium-based catalysts.
上述饱和聚酯共聚物，可作为塑料基材用油墨的主体粘合剂，能够以单组份的形式形成涂层，也可与异氰酸酯化合物进行交联反应获得固化涂层，具备塑料基材上理想的附着强度，耐溶剂性以及耐水煮或者蒸煮性等综合性能。The above-mentioned saturated polyester copolymer can be used as the main binder of the ink for plastic substrates, and can form a coating in the form of a single component, and can also undergo a crosslinking reaction with an isocyanate compound to obtain a cured coating. Ideal adhesion strength, solvent resistance and resistance to boiling or steaming and other comprehensive properties.
根据本发明的一种实施方式，上述异氰酸酯化合物可选自二苯基甲烷二异氰酸酯，异佛尔酮二异氰酸酯，六亚甲基二异氰酸酯，二(异氰酸根合甲基)环己烷，环己烷二异氰酸酯，二环己基甲烷二异氰酸酯中的至少一种，以及对应的封闭型异氰酸酯化合物。According to one embodiment of the present invention, the above-mentioned isocyanate compound may be selected from diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, cyclohexane At least one of hexane diisocyanate, dicyclohexylmethane diisocyanate, and the corresponding blocked isocyanate compound.
本发明的另一个方面，还涉及上述一种饱和聚酯共聚物在油墨中的应用。Another aspect of the present invention also relates to the application of the above-mentioned saturated polyester copolymer in ink.
上述技术方案中的一个技术方案至少具有如下优点或有益效果之一：One of the above technical solutions has at least one of the following advantages or beneficial effects:
1.本发明在聚酯共聚物中引入兼具脂环基与苯环基的组分，可实现链段中空间基团的有序分布，提升空间基团对基材的联合锚固作用，对塑料基材附着力改善作用显著；1. The present invention introduces components having both aliphatic and benzene ring groups in the polyester copolymer, which can realize the orderly distribution of space groups in the chain segment, improve the joint anchoring effect of space groups on the substrate, and Significant improvement in the adhesion of plastic substrates;
2.本发明在聚酯共聚物中引入化合物b，其为多苯环芳香族化合物，将该芳香族多苯环的组分作为树脂的主要支化组分，能够产生多苯环效应，同时还能有效提高油墨在塑料基材的附着强度；2. The present invention introduces compound b in the polyester copolymer, which is a polyphenyl ring aromatic compound, and the component of the aromatic polyphenyl ring is used as the main branched component of the resin, which can produce the polyphenyl ring effect, and at the same time It can also effectively improve the adhesion strength of the ink on the plastic substrate;
3.本发明改变了现有印刷油墨以共用多种类别的粘合剂树脂的形式实现油墨层性能要求的应用方式，本发明所述的饱和聚酯共聚物，作为主体成膜物质，能够以单一粘合剂形式或者与异氰酸酯固化剂结合，由此制备的塑料基材用油墨涂层，突破了油墨层塑料基材难附着易脱落的技术瓶颈，显著改善涂层在塑料基材上的附着性能，并进一步提升塑料基材涂层在耐溶剂，耐水煮或蒸煮，以及耐摩擦等综合性能。3. The present invention changes the application mode in which the existing printing ink realizes the performance requirements of the ink layer in the form of sharing multiple types of binder resins. The saturated polyester copolymer described in the present invention, as the main film-forming substance, can be used as In the form of a single adhesive or in combination with an isocyanate curing agent, the ink coating for plastic substrates prepared in this way breaks through the technical bottleneck that the ink layer is difficult to adhere to and easy to fall off on plastic substrates, and significantly improves the adhesion of coatings on plastic substrates Performance, and further improve the comprehensive performance of plastic substrate coatings in solvent resistance, water boiling or cooking resistance, and friction resistance.
具体实施方式Detailed ways
为详细说明本发明的技术内容、所实现目的及效果，以下结合实施方式予以说明。In order to describe the technical content, achieved objectives and effects of the present invention in detail, the following descriptions will be made in conjunction with the embodiments.
实施例中锡类催化剂采用的是草酸亚锡。What the tin catalyst used in the embodiment is stannous oxalate.
实施例中锑类催化剂采用的是乙二醇锑。What the antimony catalyst used in the embodiment is ethylene glycol antimony.
实施例中钛类催化剂采用的是钛酸丁酯。Butyl titanate is used as the titanium catalyst in the examples.
实施例1-4和对比例1-2的具体原料用量，详见表1。The concrete raw material consumption of embodiment 1-4 and comparative example 1-2, see table 1 for details.
表1实施例1-4及对比例1-2的各步骤的原料及其用量The raw material of each step of table 1 embodiment 1-4 and comparative example 1-2 and consumption thereof
Figure PCTCN2021124807-appb-000004
Figure PCTCN2021124807-appb-000004
Figure PCTCN2021124807-appb-000005
Figure PCTCN2021124807-appb-000005
实施例1Example 1
在装有搅拌器，探温计，回流冷凝器以及通入氮气的反应釜中，将第一步反应所需的原料包括1,1’-双(4-羟基-3-甲基苯基)-环己烷，2-甲基-1,3-丙二醇，丁二酸酐，对苯二甲酸以及间苯二甲酸以及锡类催化剂，按照表1所示的对应用量加入反应器中，通入保护气氛氮气下，逐步升温并在～240℃下保温～6小时，至体系酸值降低至20mgKOH/g以下。In a reaction kettle equipped with a stirrer, a temperature probe, a reflux condenser and nitrogen gas, the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) -cyclohexane, 2-methyl-1,3-propanediol, succinic anhydride, terephthalic acid and isophthalic acid, and tin catalysts are added to the reactor according to the corresponding dosage shown in Table 1, and the protective Under the atmosphere of nitrogen, gradually raise the temperature and keep it at ~240°C for ~6 hours until the acid value of the system is reduced to below 20mgKOH/g.
保持之前的反应条件，加入第二步反应所需的原料包括双酚A型二醚二酐，一缩二乙二醇以及间苯二甲酸按表1所示的对应用量，进行反应至体系酸值降低至30mgKOH/g以下；Keep the previous reaction conditions, add the raw materials required for the second step reaction including bisphenol A diether dianhydride, diethylene glycol and isophthalic acid according to the corresponding dosage shown in Table 1, and react to the system acid The value is reduced to below 30mgKOH/g;
将表1所示用量的0.3g的锡类催化剂加入体系，在～240℃℃进行真空缩聚 (真空度≤600Pa)至目标粘度0.53dl/g，获得饱和聚酯共聚物CP1。Add 0.3g of tin-based catalyst in the amount shown in Table 1 to the system, and carry out vacuum polycondensation (vacuum degree ≤ 600Pa) at ~240°C to target viscosity of 0.53dl/g to obtain saturated polyester copolymer CP1.
实施例2Example 2
在装有搅拌器，探温计，回流冷凝器以及通入氮气的反应釜中，将第一步反应所需的原料包括1,1’-双(4-羟基-3-甲基苯基)-环己烷，新戊二醇，2-乙基-2-丁基-丙二醇，邻苯二甲酸酐以及间苯二甲酸以及锑类催化剂，按照表1所示的对应用量加入反应器中，通入保护气氛氮气下，逐步升温并在～250℃下保温～5小时，至体系酸值降低至25mgKOH/g以下。In a reaction kettle equipped with a stirrer, a temperature probe, a reflux condenser and nitrogen gas, the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) -cyclohexane, neopentyl glycol, 2-ethyl-2-butyl-propylene glycol, phthalic anhydride and isophthalic acid and antimony catalysts, add in the reactor according to the corresponding dosage shown in table 1, Under a protective atmosphere of nitrogen, the temperature is gradually raised and kept at ~250°C for ~5 hours until the acid value of the system is reduced to below 25mgKOH/g.
保持之前的反应条件，加入第二步反应所需的原料包括4,4’-氧双邻苯二甲酸酐，2-甲基-1,3-丙二醇以及己二酸按表1所示的对应用量，进行反应至体系酸值降低至26mgKOH/g以下；Keeping the previous reaction conditions, add the raw materials required for the second step reaction including 4,4'-oxydiphthalic anhydride, 2-methyl-1,3-propanediol and adipic acid according to the correspondence shown in Table 1 Dosage, carry out the reaction until the acid value of the system is reduced to below 26mgKOH/g;
将表1所示用量的锑类催化剂加入体系，在240～260℃进行真空缩聚(真空度≤500Pa)至目标粘度0.53dl/g，获得饱和聚酯共聚物CP2。Add the antimony catalyst in the amount shown in Table 1 into the system, and carry out vacuum polycondensation (vacuum degree ≤ 500Pa) at 240-260°C to the target viscosity of 0.53dl/g to obtain saturated polyester copolymer CP2.
实施例3Example 3
在装有搅拌器，探温计，回流冷凝器以及通入氮气的反应釜中，将第一步反应所需的原料包括1,1’-双(4-羟基-3-甲基苯基)-环己烷，1,1’-双(4'-氨基苯基)-环己烷(BAPC)，乙二醇，2-甲基-2,4-戊二醇，邻苯二甲酸酐，对苯二甲酸以及间苯二甲酸以及锡类催化剂，按照表1所示的对应用量加入反应器中，通入保护气氛氮气下，逐步升温并在～240℃下保温～7小时，至体系酸值降低至18mgKOH/g以下。In a reaction kettle equipped with a stirrer, a temperature probe, a reflux condenser and nitrogen gas, the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) - cyclohexane, 1,1'-bis(4'-aminophenyl)-cyclohexane (BAPC), ethylene glycol, 2-methyl-2,4-pentanediol, phthalic anhydride, Terephthalic acid, isophthalic acid, and tin catalysts were added to the reactor according to the corresponding dosage shown in Table 1, and the temperature was gradually raised under a protective atmosphere of nitrogen and kept at ~240°C for ~7 hours until the system acid The value drops below 18mgKOH/g.
保持之前的反应条件，加入第二步反应所需的原料包括4,4’-氧双邻苯二甲酸酐，双酚A型二醚二酐，2-甲基-1,3-丙二醇以及己二酸按表1所示的对应用量，进行反应至体系酸值降低至25mgKOH/g以下；Keeping the previous reaction conditions, add the raw materials required for the second step reaction including 4,4'-oxydiphthalic anhydride, bisphenol A diether dianhydride, 2-methyl-1,3-propanediol and hexane Diacid is reacted to system acid value and reduces to below 25mgKOH/g by the corresponding dosage shown in table 1;
将表1所示用量的锡类催化剂加入体系，在～260℃进行真空缩聚(真空度≤500Pa)至目标粘度0.52dl/g，获得饱和聚酯共聚物CP3。Add the tin catalyst in the amount shown in Table 1 to the system, and carry out vacuum polycondensation (vacuum degree ≤ 500Pa) at ~260°C to the target viscosity of 0.52dl/g to obtain saturated polyester copolymer CP3.
实施例4Example 4
在装有搅拌器，探温计，回流冷凝器以及通入氮气的反应釜中，将第一步反应所需的原料包括1,1’-双(4-羟基-3-甲基苯基)-环己烷，2-乙基-2-丁基-丙二 醇，新戊二醇，丁二酸酐，对苯二甲酸以及间苯二甲酸以及钛类催化剂，按照表1所示的对应用量加入反应器中，通入保护气氛氮气下，逐步升温并在～250℃下保温～7小时，至体系酸值降低至18mgKOH/g以下。In a reaction kettle equipped with a stirrer, a temperature probe, a reflux condenser and nitrogen gas, the raw materials required for the first step reaction include 1,1'-bis(4-hydroxy-3-methylphenyl) -cyclohexane, 2-ethyl-2-butyl-propylene glycol, neopentyl glycol, succinic anhydride, terephthalic acid and isophthalic acid and titanium catalyst, according to the corresponding amount shown in table 1, add reaction In the container, under a protective atmosphere of nitrogen, the temperature was gradually raised and kept at ~250°C for ~7 hours until the acid value of the system was reduced to below 18mgKOH/g.
保持之前的反应条件，加入第二步反应所需的原料包括双酚A型二醚二酐，2-甲基-2,4-戊二醇以及己二酸按表1所示的对应用量，进行反应至体系酸值降低至15mgKOH/g以下；Keep the previous reaction conditions, add the raw materials required for the second step reaction including bisphenol A type diether dianhydride, 2-methyl-2,4-pentanediol and adipic acid according to the corresponding dosage shown in Table 1, Carry out the reaction until the acid value of the system is reduced to below 15mgKOH/g;
将表1所示用量的钛类催化剂加入体系，在～240℃进行真空缩聚(真空度≤400Pa)至目标粘度0.58dl/g，获得饱和聚酯共聚物CP4。Add the titanium catalyst in the amount shown in Table 1 into the system, and carry out vacuum polycondensation (vacuum degree ≤ 400Pa) at ~240°C to the target viscosity of 0.58dl/g to obtain saturated polyester copolymer CP4.
对比例1Comparative example 1
在装有搅拌器，探温计，回流冷凝器以及通入氮气的反应釜中，按照表1所示加入原料及其对应的用量，在保护气氛下逐步升温，在～250℃下保温6小时，至体系酸值降低至25mgKOH/g以下，进行真空缩聚(真空度≤700Pa)至目标粘度0.53dl/g，获得饱和聚酯共聚物CP5。In a reaction kettle equipped with a stirrer, a temperature probe, a reflux condenser and nitrogen gas, add the raw materials and their corresponding dosages as shown in Table 1, gradually raise the temperature under a protective atmosphere, and keep the temperature at ~250°C for 6 hours , until the acid value of the system is reduced to below 25mgKOH/g, carry out vacuum polycondensation (vacuum degree≤700Pa) to the target viscosity of 0.53dl/g, and obtain saturated polyester copolymer CP5.
对比例2Comparative example 2
在装有搅拌器，探温计，回流冷凝器以及通入氮气的反应釜中，将第一步反应所需的原料包括新戊二醇，2-乙基-2-丁基-丙二醇，邻苯二甲酸酐以及间苯二甲酸以及锑类催化剂，按照表1所示的对应用量加入反应器中，通入保护气氛氮气下，逐步升温并在～250℃下保温～4小时，至体系酸值降低至25mgKOH/g以下。In a reactor equipped with a stirrer, a temperature probe, a reflux condenser and nitrogen gas, the raw materials required for the first step reaction include neopentyl glycol, 2-ethyl-2-butyl-propylene glycol, ortho Phthalic anhydride, isophthalic acid, and antimony catalysts were added to the reactor according to the corresponding dosages shown in Table 1, and the temperature was gradually raised under a protective atmosphere of nitrogen and kept at ~250°C for ~4 hours until the system acid The value drops below 25mgKOH/g.
保持之前的反应条件，加入第二步反应所需的原料包括2-甲基-1,3-丙二醇以及己二酸按表1所示的对应用量，进行反应至体系酸值降低至22mgKOH/g以下；Keep the previous reaction conditions, add the raw materials required for the second step reaction including 2-methyl-1,3-propanediol and adipic acid according to the corresponding dosage shown in Table 1, and carry out the reaction until the acid value of the system is reduced to 22mgKOH/g the following;
将表1所示用量的锑类催化剂加入体系，在～250℃进行真空缩聚(真空度≤500Pa)至目标粘度0.52dl/g，获得饱和聚酯共聚物CP6。Add the antimony catalyst in the amount shown in Table 1 into the system, and carry out vacuum polycondensation (vacuum degree ≤ 500Pa) at ~250°C to the target viscosity of 0.52dl/g to obtain saturated polyester copolymer CP6.
上述CP1-CP6的性能指标如表2。The performance indexes of the above-mentioned CP1-CP6 are shown in Table 2.
表2实施例1～4，对比例1～2制备的饱和聚酯共聚物的指标Table 2 embodiment 1～4, the index of the saturated polyester copolymer prepared by comparative example 1～2
Figure PCTCN2021124807-appb-000006
Figure PCTCN2021124807-appb-000006
Figure PCTCN2021124807-appb-000007
Figure PCTCN2021124807-appb-000007
性能测试：Performance Testing:
将实施例1～4与对比例1～2制备的饱和聚酯共聚物，作为主体树脂，按照表3所示的配方制备对应的油墨。The saturated polyester copolymer prepared in Examples 1-4 and Comparative Examples 1-2 was used as the main resin, and the corresponding ink was prepared according to the formula shown in Table 3.
将实施例1～4与对比例1～2制备的饱和聚酯共聚物，在不添加固化剂的情况下，按照表4所示的配方制备对应的油墨。The saturated polyester copolymers prepared in Examples 1-4 and Comparative Examples 1-2 were used to prepare corresponding inks according to the formula shown in Table 4 without adding a curing agent.
表3.双组分丝印油墨的配方Table 3. Formulation of two-component screen printing ink
组分components 功能Function 用量/克Dosage/gram
饱和聚酯共聚物Saturated Polyester Copolymer 主体树脂Main resin 2929
Duranate TKA-90SBDuranate TKA-90SB HDI型固化剂HDI curing agent 33
丙二醇甲醚醋酸酯Propylene glycol methyl ether acetate 溶剂solvent 24twenty four
醋酸丁酯Butyl acetate 溶剂solvent 1010
异佛尔酮Isophorone 稀释剂Thinner 77
异丙醇Isopropanol 溶剂solvent 77
炭黑carbon black 颜料pigment 99
TEGO Dispers 685TEGO Dispers 685 分散剂Dispersant 1010
TOYOBO 15LPTOYOBO 15LP 附着力促进剂adhesion promoter 11
表4.单组分丝印油墨的配方Table 4. Formulation of one-component screen printing ink
组分components 功能Function 用量/克Dosage/gram
饱和聚酯共聚物Saturated Polyester Copolymer 主体树脂Main resin 2929
丙二醇甲醚醋酸酯Propylene glycol methyl ether acetate 溶剂solvent 23.523.5
醋酸丁酯Butyl acetate 溶剂solvent 1010
异佛尔酮Isophorone 稀释剂Thinner 88
异丙醇Isopropanol 溶剂solvent 88
炭黑carbon black 颜料pigment 99
蜡粉wax powder 填料filler 0.50.5
TEGO Dispers 685TEGO Dispers 685 分散剂Dispersant 1010
TOYOBO 15LPTOYOBO 15LP 附着力促进剂adhesion promoter 22
上述Duranate TKA-90SB是旭化成的一款HDI(六亚甲基二异氰酸酯三聚体)固化剂，属于异氰酸酯型固化剂。The above-mentioned Duranate TKA-90SB is an HDI (hexamethylene diisocyanate trimer) curing agent from Asahi Kasei, which belongs to the isocyanate type curing agent.
实施例1～4与对比例1～2的饱和聚酯共聚物为主体粘合剂制备的双组份丝印油墨，分别以丝网印刷的方式涂覆于ABS平板塑料基材上，经热处理(80℃*1h)形成油墨固化涂层，对油墨涂层的性能进行测试，测试结果如表5所示：The two-component screen printing ink that the saturated polyester copolymer of embodiment 1～4 and comparative example 1～2 is the main binder prepares, is coated on the ABS plate plastic base material with the mode of screen printing respectively, through heat treatment ( 80°C*1h) to form an ink cured coating, and test the performance of the ink coating. The test results are shown in Table 5:
表5实施例与对比例的丝印油墨的性能The performance of the screen printing ink of table 5 embodiment and comparative example
Figure PCTCN2021124807-appb-000008
Figure PCTCN2021124807-appb-000008
以实施例1～4与对比例1～2的饱和聚酯共聚物制备的单组份丝印油墨，分别以丝网印刷的方式涂覆于ABS平板塑料基材上，经热处理(80℃*1h)形成油墨固化涂层，对油墨涂层的性能进行测试，测试结果如表6所示：The single-component screen printing inks prepared from the saturated polyester copolymers of Examples 1-4 and Comparative Examples 1-2 were coated on ABS flat plastic substrates by screen printing respectively, and heat-treated (80°C*1h ) form ink cured coating, the performance of ink coating is tested, test result is as shown in table 6:
表6实施例与对比例的丝印油墨的性能The performance of the screen printing ink of table 6 embodiment and comparative example
Figure PCTCN2021124807-appb-000009
Figure PCTCN2021124807-appb-000009
Figure PCTCN2021124807-appb-000010
Figure PCTCN2021124807-appb-000010
显然，以本发明制备的饱和聚酯共聚物用来制备的油墨，无论是单组分油墨还是双组分油墨，在附着力、耐酒精擦拭性和耐摩擦性上效果都较好。Obviously, the ink prepared with the saturated polyester copolymer prepared by the present invention, whether it is a single-component ink or a two-component ink, has better effects on adhesion, alcohol wiping resistance and friction resistance.
以上仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等同变换，或直接或间接运用在相关的技术领域，均同理包括在本发明的专利保护范围内。The above are only examples of the present invention, and are not intended to limit the patent scope of the present invention. All equivalent transformations made using the content of the description of the present invention, or directly or indirectly used in related technical fields, are equally included in the patent protection of the present invention. within range.

Claims (10)

  1. 一种饱和聚酯共聚物，其特征在于：其制备原料包括：A kind of saturated polyester copolymer is characterized in that: its preparation raw material comprises:
    化合物a、化合物b、多元醇、多元酸和/或多元酸酐；Compound a, compound b, polyhydric alcohol, polybasic acid and/or polybasic acid anhydride;
    所述化合物a的通式为：The general formula of the compound a is:
    Figure PCTCN2021124807-appb-100001
    Figure PCTCN2021124807-appb-100001
    所述化合物b为式2和/或式3：The compound b is formula 2 and/or formula 3:
    Figure PCTCN2021124807-appb-100002
    Figure PCTCN2021124807-appb-100002
    式中，R 1为羟基或氨基，且至少有一部分为羟基或者至少含有羟基； In the formula, R1 is a hydroxyl group or an amino group, and at least part of it is a hydroxyl group or contains at least a hydroxyl group;
    R 2为碳原子数1～20的烷基； R 2 is an alkyl group with 1 to 20 carbon atoms;
    R 3为甲基，乙基或者氢原子； R 3 is a methyl group, an ethyl group or a hydrogen atom;
    n 1为>1的整数； n 1 is an integer >1;
    n 2为>2的整数； n 2 is an integer >2;
    n 3为0或者1； n 3 is 0 or 1;
    式中，P 1、P 2独立为羧基、羟基、甲基或氢，且P 1、P 2中至少有一个为羧基或羟基； In the formula, P 1 and P 2 are independently carboxyl, hydroxyl, methyl or hydrogen, and at least one of P 1 and P 2 is carboxyl or hydroxyl;
    式中，X为氧原子；R 4为次甲基；R 5为甲基或者乙基；n 4为≥0的整数。 In the formula, X is an oxygen atom; R 4 is a methine group; R 5 is a methyl group or an ethyl group; n 4 is an integer ≥ 0.
  2. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述多元醇包括乙二醇、1,2-丙二醇、丁二醇、2-甲基-1,3-丙二醇、新戊二醇、1,6-己二醇、2-丁基-2-乙基-1,3-丙二醇、1,4-环己烷二甲醇、3-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇中的至少一种。The polyols include ethylene glycol, 1,2-propanediol, butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2-butyl-2- At least one of ethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, and 2-methyl-2,4-pentanediol.
  3. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述多元酸包括丁二酸、己二酸、辛二酸、癸二酸、环己烷二甲酸、环丁基二甲酸、邻苯二甲酸中的至少一种。The polybasic acid includes at least one of succinic acid, adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, cyclobutyldicarboxylic acid and phthalic acid.
  4. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述多元酸酐包括丁二酸酐、己二酸酐、辛二酸酐、癸二酸酐和邻苯二甲酸酐、偏苯三酸酐中的至少一种。The polybasic acid anhydride includes at least one of succinic anhydride, adipic anhydride, suberic anhydride, sebacic anhydride, phthalic anhydride and trimellitic anhydride.
  5. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述化合物a的用量，与所述多元醇用量的摩尔比例为0.01/1-9/1；The molar ratio of the amount of the compound a to the amount of the polyol is 0.01/1-9/1;
    所述化合物b的用量，与所述多元酸和/或多元酸酐用量的摩尔比例为0.01/1-8/2。The molar ratio of the amount of the compound b to the amount of the polybasic acid and/or polybasic anhydride is 0.01/1-8/2.
  6. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述化合物a与多元醇的摩尔总量，和化合物b与多元酸和/或多元酸酐的摩尔总量比例为0.9/1—3/1。The ratio of the total molar amount of compound a and polyhydric alcohol to that of compound b and polybasic acid and/or polybasic anhydride is 0.9/1-3/1.
  7. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述饱和聚酯共聚物的数均分子量为1～35KDa。The number average molecular weight of the saturated polyester copolymer is 1-35KDa.
  8. 根据权利要求1所述的一种饱和聚酯共聚物，其特征在于：A kind of saturated polyester copolymer according to claim 1, is characterized in that:
    所述化合物a中，羟基的摩尔含量高于氨基的摩尔含量。In the compound a, the molar content of hydroxyl groups is higher than that of amino groups.
  9. 一种制备如权利要求1至8任一项所述的饱和聚酯共聚物的制备方法，其特征在于：包括以下步骤：A preparation method for preparing the saturated polyester copolymer as claimed in any one of claims 1 to 8, characterized in that: comprising the following steps:
    混合化合物a、部分多元醇、部分多元酸和或/部分多元酸酐，加热反应至体系酸值小于25mgKOH/g；Mix compound a, part of polyhydric alcohol, part of polybasic acid and/or part of polybasic acid anhydride, heat and react until the acid value of the system is less than 25 mgKOH/g;
    加入化合物b，余量多元醇、余量多元酸和或/余量多元酸酐，反应至体系酸值小于30mgKOH/g，得到所述饱和聚酯共聚物。Add compound b, the remaining amount of polyhydric alcohol, the remaining amount of polybasic acid and/or/the remaining amount of polybasic acid anhydride, and react until the acid value of the system is less than 30 mgKOH/g to obtain the saturated polyester copolymer.
  10. 如权利要求1至8任一项所述的一种饱和聚酯共聚物在油墨中的应用。The application of a kind of saturated polyester copolymer as described in any one of claims 1 to 8 in printing ink.
PCT/CN2021/124807 2021-10-20 2021-10-20 Saturated polyester copolymer, and preparation method therefor and use thereof WO2023065131A1 (en)

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JP2010006905A (en) * 2008-06-25 2010-01-14 Toyobo Co Ltd Polyester resin, photocurable-heat curable resin composition, photocurable-heat curable layer, ink, adhesive and printed circuit board
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