WO2023284021A1 - Photocurable resin based on epoxidized vegetable oil and gallic acid, preparation method therefor and application thereof - Google Patents

Photocurable resin based on epoxidized vegetable oil and gallic acid, preparation method therefor and application thereof Download PDF

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WO2023284021A1
WO2023284021A1 PCT/CN2021/109628 CN2021109628W WO2023284021A1 WO 2023284021 A1 WO2023284021 A1 WO 2023284021A1 CN 2021109628 W CN2021109628 W CN 2021109628W WO 2023284021 A1 WO2023284021 A1 WO 2023284021A1
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epoxy
gallic acid
photocurable resin
oil
vegetable oil
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PCT/CN2021/109628
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French (fr)
Chinese (zh)
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刘承果
周永红
朱国强
尚倩倩
胡云
胡立红
张金帅
刘美婷
黄佳
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中国林业科学研究院林产化学工业研究所
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Publication of WO2023284021A1 publication Critical patent/WO2023284021A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the invention belongs to the field of bio-based polymer materials, and in particular relates to a photocurable resin based on epoxy vegetable oil and gallic acid, a preparation method and application thereof.
  • Light-curable 3D printing materials, coating materials, and inks require light-curable resins to have a high curing rate and excellent mechanical and thermodynamic properties. Therefore, it is required that the photocurable resin has a high double bond content, a high rigid structure in the resin molecule, and a low viscosity at the same time.
  • the present invention utilizes the special rigid structure of gallic acid to obtain methacrylated gallic acid after modification with methacrylic acid, and further modifies epoxy vegetable oil to obtain a bio-based epoxy acrylate prepolymer.
  • the performance of the synthesized vegetable oil/gallic acid-based photocurable resin has reached the performance of commercial 3D printing thermosetting resin and coating photocurable resin.
  • the synthesized vegetable oil and gallic acid-based photocurable resin has low toxicity, low viscosity, high photocuring rate, and low volatility, which can replace traditional petroleum-based ink resins.
  • the present invention develops a method of light-curing resin based on vegetable oil and gallic acid, which can reduce the use of petroleum-based resin, reduce carbon emissions, and is very beneficial to the development of low-carbon economy.
  • the present invention overcomes the defects of poor mechanical and thermal properties, slow curing speed, and high viscosity of current vegetable oil-based photocurable resin materials, and provides a ring-based resin with excellent mechanical and thermal properties, fast curing speed, and low viscosity.
  • the preparation method of the photocurable resin of oxygenated vegetable oil and gallic acid can be applied to products such as 3D printing materials, coatings and inks.
  • a light-curable resin based on epoxy vegetable oil and gallic acid first reacting gallic acid and acrylic anhydride compounds to obtain a mixed intermediate of gallic acid triacrylate/acrylic compound; then using epoxy vegetable oil to mix with the obtained The intermediate undergoes an epoxy ring-opening reaction to obtain a bio-based epoxy acrylate prepolymer; finally, dilute monomers, photoinitiators, and uniform dispersion are added to obtain a bio-based photocurable resin.
  • epoxy vegetable oil is epoxy soybean oil, epoxy rapeseed oil, epoxy sunflower oil, epoxy cottonseed oil, epoxy palm oil, epoxy rubber seed oil, epoxy linseed oil, epoxy tung oil, Epoxidized photobark fruit oil, epoxidized castor oil, epoxidized methyl oleate, epoxidized methyl linoleate, epoxidized methyl linoleate, epoxidized methyl oleate, and epoxidized fatty acids at least one of glycidyl esters.
  • the acrylic anhydride compound is at least one of acrylic anhydride and methacrylic anhydride.
  • the preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid the preparation steps are:
  • the polymerization inhibitor described in step (1) and (2) is at least one in hydroquinone, p-benzoquinone, p-methoxyphenol, 2,6-di-tert-butyl p-cresol, and the consumption is 0.1-5% of the total weight.
  • the catalyst is at least one of p-N,N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate, and 4-dimethylaminopyridine, and the amount used is the total amount of raw materials 0.1% to 5% by weight.
  • the molar ratio of gallic acid and methacrylic anhydride in step (1) is 1:2-5, and the molar ratio of epoxy group and carboxyl group in step (2) is 0.5-1.5:1.
  • the diluting monomer described in step (3) is methyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl acetate, isobornyl acrylate, formazan At least one of isobornyl acrylate, tetrahydrofuryl methyl acrylate, tetrahydrofuryl methyl methacrylate, pentaerythritol tetraacrylate and cyclohexyl acrylate, and the amount of diluting monomer is 0 of the amount of bio-based epoxy acrylate prepolymer ⁇ 70%.
  • the photoinitiator described in step (3) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenoxyphosphine, 2-hydroxyl-2-methyl-1- Phenyl-1-propanone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholine benzylphenyl) butanone, 2,4,6-trimethylbenzyl Acyl phosphate ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-isopropylthioxanthone, 4-chlorobenzophenone At least one, the amount of photoinitiator is 0.1%-5% of the total weight of the obtained photocurable resin.
  • bio-based photocurable resin in the preparation of photocurable 3D printing materials, coatings and ink products.
  • the bio-based photocurable resin synthesized by the present invention has high bio-based content, high double bond content, low viscosity, fast curing speed, and excellent mechanical and thermodynamic properties of UV curable materials, which can be applied to 3D printing materials, products such as coatings and inks.
  • the synthesis method used in the present invention is a two-step one-pot synthesis method without any solvent.
  • the method is easy to operate, simple in process, and suitable for large-scale industrial production.
  • Figure 1 is a synthetic process route diagram of bio-based epoxy acrylate prepolymer.
  • Fig. 2 is the infrared spectrum of the gallic acid triacrylate/acrylic compound mixed intermediate.
  • Fig. 3 is the infrared spectrogram of epoxidized soybean oil/gallic acid methacrylate prepolymer.
  • a light-curable resin based on epoxy vegetable oil and gallic acid and its preparation method and application characterized in that the preparation steps are: (1) adding gallic acid and acrylic anhydride compounds in a reactor, gallic acid and acrylic anhydride compounds The molar ratio is 1:(2 ⁇ 5), the amount of polymerization inhibitor is 0.1 ⁇ 5% of the total weight of raw materials, after stirring evenly, it is heated to 50 ⁇ 150°C for 1 ⁇ 8h to obtain gallic acid triacrylate compound and acrylic acid The mixed intermediate of compound; (2) epoxy vegetable oil is joined in the reactor of last step, carry out epoxy ring-opening reaction with gained mixed intermediate, wherein the mol ratio of epoxy group and carboxyl group is (0.5 ⁇ 1.5) : 1, the amount of catalyst is 0.1% to 5% of the total weight of raw materials, the amount of polymerization inhibitor is 0.1% to 5% of the total weight of raw materials, 50 to 150 ° C for 1 to 6 hours to obtain a new type of bio-based epoxy acrylate prepolymerization (3) Dilute monomers and photoiniti
  • the epoxy vegetable oil described in step (1) is epoxy soybean oil, epoxy rapeseed oil, epoxy sunflower oil, epoxy cottonseed oil, epoxy palm oil, epoxy rubber seed oil, epoxy Linseed Oil, Epoxidized Tung Oil, Epoxidized Photobark Fruit Oil, Epoxidized Castor Oil, Epoxidized Methyl Oleate, Epoxidized Methyl Linoleate, Epoxidized Methyl Linoleate, Epoxidized Tung Oil at least one of methyl esters of fatty acids and glycidyl epoxidized fatty acids.
  • the polymerization inhibitor described in step (1) and step (2) is at least one of hydroquinone, p-benzoquinone, p-methoxyphenol, 2,6-di-tert-butyl p-cresol , the dosage ratio is preferably 0.5%.
  • the catalyst described in step (2) is at least one of p-N,N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate, and 4-dimethylaminopyridine species, the catalyst consumption ratio is preferably 1%.
  • the molar ratio of gallic acid and methacrylic anhydride in step (1) is 1:(2-5).
  • the molar ratio of epoxy group to carboxyl group in step (2) is (0.5-1.5):1.
  • the diluting monomer described in step (3) is methyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl acetate, isobornyl acrylate At least one of ester, isobornyl methacrylate, tetrahydrofuryl methyl acrylate, tetrahydrofuryl methyl methacrylate, pentaerythritol tetraacrylate and cyclohexyl acrylate, the amount of diluted monomer is bio-based epoxy acrylate prepolymer 0-70% of the dosage.
  • the photoinitiator described in step (3) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenoxyphos, 2-hydroxyl-2-methyl -1-phenyl-1-propanone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholine benzylphenyl) butanone, 2,4,6-trimethyl ethyl benzoyl phosphate, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-isopropylthioxanthone, 4-chlorobenzhydryl At least one of the ketones, the amount of the photoinitiator is 0.1% to 5% of the total weight of the obtained photocurable resin.
  • the tensile strength of the UV photocurable material based on epoxy vegetable oil and gallic acid photocurable resin described in step (4) is 20-80 MPa.
  • the glass transition temperature of the UV photocurable material based on epoxy vegetable oil and gallic acid photocurable resin described in step (4) is 110-170°C.
  • the viscosity of the photocurable resin based on epoxy vegetable oil and gallic acid described in step (4) is 50-4000 mPas.
  • the bio-based epoxy acrylate resin prepared by the above method.
  • bio-based epoxy acrylate resin in light-curing 3D printing, wood, metal surface coating and ink products.
  • Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy cottonseed oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy tung oil is added in the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1,
  • the dosage of the catalyst triphenylphosphine is 1% of the total weight of the raw materials, the dosage of the polymerization inhibitor hydroquinone is 0.5% of the total weight of the raw materials, and the reaction is carried out at 90° C. for 4 hours to obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy rubber seed oil is added in the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step, and the epoxy ring-opening reaction is carried out, wherein the mol ratio of epoxy group and carboxyl group is 1.3: 1.
  • the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of polymerization inhibitor hydroquinone is 0.5% of the total weight of raw materials, react at 90°C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Glass transition temperature use Q800 solid analyzer (US TA company) to measure its dynamic thermomechanical properties.
  • Viscosity DVS+ rotational viscometer is used to measure the viscosity of the resin (Boler, USA). The volume shrinkage was measured by a ZMD-2 electronic density pycnometer (Shanghai Fangrui Instrument Co., Ltd.).
  • Table 1 The main performance indicators of the light-cured 3D printing resin samples of Examples 1-4
  • Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy rapeseed oil is added in the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3: 1.
  • the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of polymerization inhibitor hydroquinone is 0.5% of the total weight of raw materials, react at 90°C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy linseed oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Coating film performance test the adhesion of the coating film according to the method of GB/T 9286-1998, grade 1 is the best, grade 7 is the worst; test the flexibility of the coating film according to the method of GB/T 1731-93, the minimum diameter of the shaft rod 2mm, the smaller the shaft diameter, the better the toughness; measure the hardness of the paint film according to GB/T 6739-2006, 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B, 6B, of which 6H is the hardest and 6B is the softest.
  • Viscosity DVS+ rotational viscometer is used to measure the resin viscosity (Boler, USA).
  • Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
  • Coating film performance test the adhesion of the coating film according to the method of GB/T 9286-1998, grade 1 is the best, grade 7 is the worst; test the flexibility of the coating film according to the method of GB/T 1731-93, the minimum diameter of the shaft rod 2mm, the smaller the shaft diameter, the better the toughness; measure the hardness of the paint film according to GB/T 6739-2006, 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B, 6B, of which 6H is the hardest and 6B is the softest.
  • Viscosity DVS+ rotational viscometer is used to measure the viscosity of the resin (Boler, USA).
  • the epoxy vegetable oil and gallic acid-based photocurable resin prepared by the present invention have high bio-based content, excellent mechanical and thermal properties of UV curable materials, and moderate resin transmission depth coefficient, which can be used for photocurable 3D Printing, wood, metal surface coating and ink products.

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Abstract

Disclosed are a photocurable resin based on epoxidized vegetable oil and gallic acid, and a preparation method therefor and an application thereof. First, gallic acid and an acrylic anhydride compound are reacted to obtain a gallic acid triacrylate/acrylic compound mixed intermediate; an epoxy ring-opening reaction is then carried out using epoxidized vegetable oil and the obtained mixed intermediate to obtain a novel bio-based epoxy acrylate prepolymer; finally, a diluent monomer, a photoinitiator, a polymerization inhibitor, etc. are added and dispersed uniformly to obtain a bio-based photocurable resin. The obtained resin has advantages including low viscosity and high curing speed, and has excellent mechanical and thermodynamic properties after curing. Therefore, it can be used as a base resin for applications such as photocurable 3D printing materials, coatings, and inks. The present method is simple and environmentally friendly, and most of the raw materials come from renewable resources, so that the method has great significance for promoting sustainable development of photocurable materials.

Description

[根据细则37.2由ISA制定的发明名称]　基于环氧植物油和没食子酸的光固化树脂及其制备方法与应用[Title of the invention established by ISA under Rule 37.2] Light-curing resin based on epoxy vegetable oil and gallic acid and its preparation and application 技术领域technical field
本发明属于生物基高分子材料领域，具体涉及一种基于环氧植物油和没食子酸的光固化树脂及其制备方法与应用。The invention belongs to the field of bio-based polymer materials, and in particular relates to a photocurable resin based on epoxy vegetable oil and gallic acid, a preparation method and application thereof.
背景技术Background technique
光固化技术由于具有高效、节能、适应性广、经济、环保等5E特点，已经在涂料、油墨、胶粘剂、牙科材料、3D打印等领域得到了广泛的应用，形成了新的高附加值产业。随着“碳中和”时代的到来，传统的石油基光固化树脂应用将受到极大的限制，开发生物基光固化树脂具有重要的经济价值和环保价值。生物质资源丰富、可再生、生物相容性好、易降解，更重要的是从源头上减少了石化资源的使用。作为可再生的天然资源，植物油来源丰富，产量大。据统计，2019年全球植物油产量已达到20391万吨。因此，设计合成植物油基光固化树脂受到人们的青睐。目前，环氧大豆油丙烯酸酯(Acrylated Epoxidized Soybean Oil，简称AESO)已经工业化生产和应用。但是，其力学性能和热力学性能较差，难以取代传统的石油基光固化树脂。因此，急需设计合成高性能的植物油基光固化树脂，满足不同领域对性能的要求，扩大植物油基光固化树脂的应用范围，创造更大的经济价值和环境效益。Due to the 5E characteristics of high efficiency, energy saving, wide adaptability, economy, and environmental protection, light curing technology has been widely used in coatings, inks, adhesives, dental materials, 3D printing and other fields, forming a new high value-added industry. With the advent of the era of "carbon neutrality", the application of traditional petroleum-based photocurable resins will be greatly restricted, and the development of bio-based photocurable resins has important economic and environmental values. Biomass resources are abundant, renewable, biocompatible, easy to degrade, and more importantly, reduce the use of petrochemical resources from the source. As a renewable natural resource, vegetable oil has abundant sources and large yields. According to statistics, the global vegetable oil production in 2019 has reached 203.91 million tons. Therefore, designing and synthesizing vegetable oil-based photocurable resins is favored by people. At present, Acrylated Epoxidized Soybean Oil (AESO) has been industrially produced and applied. However, its mechanical properties and thermodynamic properties are poor, and it is difficult to replace traditional petroleum-based photocurable resins. Therefore, it is urgent to design and synthesize high-performance vegetable oil-based photocurable resins to meet the performance requirements of different fields, expand the application range of vegetable oil-based photocurable resins, and create greater economic value and environmental benefits.
光固化3D打印材料，涂层材料，油墨要求光固化树脂具有高的固化速率，优良的力学和热力学性能。因此，需要光固化树脂具有高的双键含量，树脂分子中含有高的刚性结构，同时具有较低的粘度。于此，本发明利用没食子酸的特殊刚性结构，通过甲基丙烯酸改性后得到甲基丙烯酸化没食子酸，进一步改性环氧植物油，得到生物基环氧丙烯酸酯预聚体。所合成的植物油/没食子酸基光固化树脂性能达到了商业3D打印热固性树脂，涂层光固化树脂的性能。同时，所合成的植物油和没食子酸基光固化树脂毒性小、粘度较低、光固化速率高、挥发性低，可替代传统的石油基油墨树脂。总之，本发明开发了一种基于植物油和没食子酸的光固化树脂的方法，可减少石油基树脂的使用，降低碳排放，十分有利于发展低碳经济。Light-curable 3D printing materials, coating materials, and inks require light-curable resins to have a high curing rate and excellent mechanical and thermodynamic properties. Therefore, it is required that the photocurable resin has a high double bond content, a high rigid structure in the resin molecule, and a low viscosity at the same time. Herein, the present invention utilizes the special rigid structure of gallic acid to obtain methacrylated gallic acid after modification with methacrylic acid, and further modifies epoxy vegetable oil to obtain a bio-based epoxy acrylate prepolymer. The performance of the synthesized vegetable oil/gallic acid-based photocurable resin has reached the performance of commercial 3D printing thermosetting resin and coating photocurable resin. At the same time, the synthesized vegetable oil and gallic acid-based photocurable resin has low toxicity, low viscosity, high photocuring rate, and low volatility, which can replace traditional petroleum-based ink resins. In conclusion, the present invention develops a method of light-curing resin based on vegetable oil and gallic acid, which can reduce the use of petroleum-based resin, reduce carbon emissions, and is very beneficial to the development of low-carbon economy.
发明内容Contents of the invention
解决的技术问题：本发明克服目前植物油基光固化树脂材料力学与热学性能差、固化速 度较慢、粘度较高等缺陷，提供一种力学与热学性能优异、固化速度快、粘度较低的基于环氧植物油和没食子酸的光固化树脂的制备方法，可应用于3D打印材料、涂料和油墨等产品中。The technical problem to be solved: the present invention overcomes the defects of poor mechanical and thermal properties, slow curing speed, and high viscosity of current vegetable oil-based photocurable resin materials, and provides a ring-based resin with excellent mechanical and thermal properties, fast curing speed, and low viscosity. The preparation method of the photocurable resin of oxygenated vegetable oil and gallic acid can be applied to products such as 3D printing materials, coatings and inks.
技术方案：一种基于环氧植物油和没食子酸的光固化树脂，首先利用没食子酸和丙烯酸酐类化合物反应，得到没食子酸三丙烯酸酯/丙烯酸类化合物混合中间体；接着利用环氧植物油与所得混合中间体进行环氧开环反应，得到生物基环氧丙烯酸酯预聚体；最后再加入稀释单体、光引发剂、分散均匀，得到生物基光固化树脂。Technical solution: A light-curable resin based on epoxy vegetable oil and gallic acid, first reacting gallic acid and acrylic anhydride compounds to obtain a mixed intermediate of gallic acid triacrylate/acrylic compound; then using epoxy vegetable oil to mix with the obtained The intermediate undergoes an epoxy ring-opening reaction to obtain a bio-based epoxy acrylate prepolymer; finally, dilute monomers, photoinitiators, and uniform dispersion are added to obtain a bio-based photocurable resin.
所述的环氧植物油为环氧大豆油、环氧菜籽油、环氧葵花籽油、环氧棉籽油、环氧棕榈油、环氧橡胶籽油、环氧亚麻油、环氧化桐油、环氧光皮树果油、环氧化蓖麻油、环氧油酸甲酯、环氧亚麻油酸甲酯、环氧化亚麻油酸甲酯、环氧化桐油酸甲酯和环氧化脂肪酸缩水甘油酯中的至少一种。Described epoxy vegetable oil is epoxy soybean oil, epoxy rapeseed oil, epoxy sunflower oil, epoxy cottonseed oil, epoxy palm oil, epoxy rubber seed oil, epoxy linseed oil, epoxy tung oil, Epoxidized photobark fruit oil, epoxidized castor oil, epoxidized methyl oleate, epoxidized methyl linoleate, epoxidized methyl linoleate, epoxidized methyl oleate, and epoxidized fatty acids at least one of glycidyl esters.
所述的丙烯酸酐类化合物为丙烯酸酐、甲基丙烯酸酐中的至少一种。The acrylic anhydride compound is at least one of acrylic anhydride and methacrylic anhydride.
所述基于环氧植物油和没食子酸的光固化树脂的制备方法，制备步骤为：The preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid, the preparation steps are:
(1)在反应器中加入没食子酸和丙烯酸酐类化合物和阻聚剂，搅拌均匀后加热至50～150℃反应1～8h，得到没食子酸三丙烯酸酯类化合物与丙烯酸类化合物的混合中间体；(1) Add gallic acid, acrylic anhydride compound and polymerization inhibitor into the reactor, stir evenly and heat to 50-150°C for 1-8 hours to obtain a mixed intermediate of gallic acid triacrylate compound and acrylic compound ;
(2)将环氧植物油、催化剂和阻聚剂加入到上一步的反应器中，与所得混合中间体进行环氧开环反应，50～150℃反应1～6h，得到生物基环氧丙烯酸酯预聚体；(2) Add epoxy vegetable oil, catalyst and polymerization inhibitor to the reactor in the previous step, and carry out epoxy ring-opening reaction with the obtained mixed intermediate, and react at 50-150 °C for 1-6 hours to obtain bio-based epoxy acrylate Prepolymer;
(3)将稀释单体、光引发剂加入到生物基环氧丙烯酸酯预聚体中，搅拌均匀，去除气泡，得到生物基光固化树脂。(3) adding the diluted monomer and the photoinitiator into the bio-based epoxy acrylate prepolymer, stirring evenly, and removing air bubbles to obtain the bio-based photocurable resin.
步骤(1)和(2)中所述阻聚剂为对苯二酚、对苯醌、对甲氧基苯酚、2,6-二叔丁基对甲基苯酚中至少一种，用量为原料总重量的0.1～5％。The polymerization inhibitor described in step (1) and (2) is at least one in hydroquinone, p-benzoquinone, p-methoxyphenol, 2,6-di-tert-butyl p-cresol, and the consumption is 0.1-5% of the total weight.
步骤(2)催化剂为对N,N-二甲基苄胺、三苯基膦、1-甲基咪唑、钛酸四丁酯、4-二甲氨基吡啶中的至少一种，用量为原料总重量的0.1％～5％。Step (2) The catalyst is at least one of p-N,N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate, and 4-dimethylaminopyridine, and the amount used is the total amount of raw materials 0.1% to 5% by weight.
步骤(1)中所述没食子酸和甲基丙烯酸酐摩尔比为1:2～5，步骤(2)中所述环氧基和羧基摩尔比为0.5～1.5:1。The molar ratio of gallic acid and methacrylic anhydride in step (1) is 1:2-5, and the molar ratio of epoxy group and carboxyl group in step (2) is 0.5-1.5:1.
步骤(3)中所述的稀释单体为丙烯酸甲酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、醋酸乙烯酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸四氢呋喃甲酯、甲基丙烯酸四氢呋喃甲酯、季戊四醇四丙烯酸酯和丙烯酸环己酯中的至少一种，稀释单体用量为生物基环氧丙烯酸酯预聚体用量的0～70％。The diluting monomer described in step (3) is methyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl acetate, isobornyl acrylate, formazan At least one of isobornyl acrylate, tetrahydrofuryl methyl acrylate, tetrahydrofuryl methyl methacrylate, pentaerythritol tetraacrylate and cyclohexyl acrylate, and the amount of diluting monomer is 0 of the amount of bio-based epoxy acrylate prepolymer ~70%.
步骤(3)中所述的光引发剂为1-羟基环已基苯基酮、2,4,6-三甲基苯甲酰二苯氧磷、2- 羟基-2-甲基-1-苯基-1-丙酮、安息香双甲醚、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2，4，6-三甲基苯甲酰基磷酸乙酯、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-异丙基硫杂蒽酮、4-氯二苯甲酮中的至少一种，光引发剂用量为所得光固化树脂总重量的0.1％～5％。The photoinitiator described in step (3) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenoxyphosphine, 2-hydroxyl-2-methyl-1- Phenyl-1-propanone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholine benzylphenyl) butanone, 2,4,6-trimethylbenzyl Acyl phosphate ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-isopropylthioxanthone, 4-chlorobenzophenone At least one, the amount of photoinitiator is 0.1%-5% of the total weight of the obtained photocurable resin.
所述的生物基光固化树脂在制备光固化3D打印材料、涂料和油墨产品中的应用。The application of the bio-based photocurable resin in the preparation of photocurable 3D printing materials, coatings and ink products.
有益效果：Beneficial effect:
(1)本发明所合成的生物基光固化树脂，生物基含量高，双键含量高，粘度较低，固化速度快，并且，UV固化材料力学、热力学性能优良，可应用于3D打印材料、涂料和油墨等产品中。(1) The bio-based photocurable resin synthesized by the present invention has high bio-based content, high double bond content, low viscosity, fast curing speed, and excellent mechanical and thermodynamic properties of UV curable materials, which can be applied to 3D printing materials, products such as coatings and inks.
(2)本发明所使用的合成方法为两步一锅合成法，无需任何溶剂，该方法操作容易，工艺简单，适用于大规模工业化生产。(2) The synthesis method used in the present invention is a two-step one-pot synthesis method without any solvent. The method is easy to operate, simple in process, and suitable for large-scale industrial production.
附图说明Description of drawings
图1为生物基环氧丙烯酸酯预聚体的合成工艺路线图。Figure 1 is a synthetic process route diagram of bio-based epoxy acrylate prepolymer.
图2为没食子酸三丙烯酸酯/丙烯酸类化合物混合中间体的红外谱图。Fig. 2 is the infrared spectrum of the gallic acid triacrylate/acrylic compound mixed intermediate.
图3为环氧大豆油/没食子酸甲基丙烯酸酯预聚体的红外谱图。Fig. 3 is the infrared spectrogram of epoxidized soybean oil/gallic acid methacrylate prepolymer.
具体实施方式detailed description
本发明下面的实施例仅作为本发明内容的进一步说明，不能作为本发明的限定内容或范围。下面结合实施例对本发明作进一步详述。The following examples of the present invention are only used as a further description of the content of the present invention, and cannot be regarded as the content or scope of the present invention. Below in conjunction with embodiment the present invention is described in further detail.
一种基于环氧植物油和没食子酸的光固化树脂及其制备方法与应用，其特征在于制备步骤为：(1)在反应器中加入没食子酸和丙烯酸酐类化合物，没食子酸与丙烯酸酐类化合物的摩尔比为1:(2～5)，阻聚剂用量为原料总重量的0.1～5％，搅拌均匀后加热至50～150℃反应1～8h，得到没食子酸三丙烯酸酯类化合物与丙烯酸类化合物的混合中间体；(2)将环氧植物油加入到上一步的反应器中，与所得混合中间体进行环氧开环反应，其中环氧基和羧基的摩尔比为(0.5～1.5):1，催化剂用量为原料总重量的0.1％～5％，阻聚剂用量为原料总重量的0.1～5％，50～150℃反应1～6h，得到新型的生物基环氧丙烯酸酯预聚体；(3)将稀释单体、光引发剂加入到生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的0～70％，光引发剂用量为所得树脂总重量的0.1～5％，搅拌均匀，去除气泡，得到生物基光固化树脂；(4)将所得到的光固化树脂应用于光固化3D打印、木器、金属表面涂层和油墨产品中，并测试树脂 的透射深度系数、粘度，UV固化材料力学和热力学性能、涂层硬度等性能。A light-curable resin based on epoxy vegetable oil and gallic acid and its preparation method and application, characterized in that the preparation steps are: (1) adding gallic acid and acrylic anhydride compounds in a reactor, gallic acid and acrylic anhydride compounds The molar ratio is 1:(2~5), the amount of polymerization inhibitor is 0.1~5% of the total weight of raw materials, after stirring evenly, it is heated to 50~150°C for 1~8h to obtain gallic acid triacrylate compound and acrylic acid The mixed intermediate of compound; (2) epoxy vegetable oil is joined in the reactor of last step, carry out epoxy ring-opening reaction with gained mixed intermediate, wherein the mol ratio of epoxy group and carboxyl group is (0.5～1.5) : 1, the amount of catalyst is 0.1% to 5% of the total weight of raw materials, the amount of polymerization inhibitor is 0.1% to 5% of the total weight of raw materials, 50 to 150 ° C for 1 to 6 hours to obtain a new type of bio-based epoxy acrylate prepolymerization (3) Dilute monomers and photoinitiators are added to the bio-based epoxy acrylate prepolymer, the amount of dilute monomers is 0 to 70% of the quality of the prepolymer obtained, and the amount of photoinitiators is the total amount of the obtained resin 0.1 to 5% of the weight, stir evenly, remove air bubbles, and obtain bio-based photocurable resin; (4) apply the obtained photocurable resin to photocurable 3D printing, wood, metal surface coating and ink products, and test Resin transmission depth coefficient, viscosity, UV curing material mechanical and thermodynamic properties, coating hardness and other properties.
优选的，步骤(1)中所述的环氧植物油为环氧大豆油、环氧菜籽油、环氧葵花籽油、环氧棉籽油、环氧棕榈油、环氧橡胶籽油、环氧亚麻油、环氧化桐油、环氧光皮树果油、环氧化蓖麻油、环氧油酸甲酯、环氧亚麻油酸甲酯、环氧化亚麻油酸甲酯、环氧化桐油酸甲酯和环氧化脂肪酸缩水甘油酯中的至少一种。Preferably, the epoxy vegetable oil described in step (1) is epoxy soybean oil, epoxy rapeseed oil, epoxy sunflower oil, epoxy cottonseed oil, epoxy palm oil, epoxy rubber seed oil, epoxy Linseed Oil, Epoxidized Tung Oil, Epoxidized Photobark Fruit Oil, Epoxidized Castor Oil, Epoxidized Methyl Oleate, Epoxidized Methyl Linoleate, Epoxidized Methyl Linoleate, Epoxidized Tung Oil at least one of methyl esters of fatty acids and glycidyl epoxidized fatty acids.
优选的，步骤(1)和步骤(2)中所述阻聚剂为对苯二酚、对苯醌、对甲氧基苯酚、2,6-二叔丁基对甲基苯酚中至少一种，用量比例优选0.5％。Preferably, the polymerization inhibitor described in step (1) and step (2) is at least one of hydroquinone, p-benzoquinone, p-methoxyphenol, 2,6-di-tert-butyl p-cresol , the dosage ratio is preferably 0.5%.
优选的，步骤(2)中所述催化剂为对N,N-二甲基苄胺、三苯基膦、1-甲基咪唑、钛酸四丁酯、4-二甲氨基吡啶中的至少一种，催化剂用量用量比例优选1％。Preferably, the catalyst described in step (2) is at least one of p-N,N-dimethylbenzylamine, triphenylphosphine, 1-methylimidazole, tetrabutyl titanate, and 4-dimethylaminopyridine species, the catalyst consumption ratio is preferably 1%.
优选的，步骤(1)中所述没食子酸和甲基丙烯酸酐摩尔比为1:(2～5)。Preferably, the molar ratio of gallic acid and methacrylic anhydride in step (1) is 1:(2-5).
优选的，步骤(2)中所述环氧基和羧基摩尔比为(0.5～1.5):1。Preferably, the molar ratio of epoxy group to carboxyl group in step (2) is (0.5-1.5):1.
优选的，步骤(3)中所述的稀释单体为丙烯酸甲酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、醋酸乙烯酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸四氢呋喃甲酯、甲基丙烯酸四氢呋喃甲酯、季戊四醇四丙烯酸酯和丙烯酸环己酯中的至少一种，稀释单体用量为生物基环氧丙烯酸酯预聚体用量的0～70％。Preferably, the diluting monomer described in step (3) is methyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl acetate, isobornyl acrylate At least one of ester, isobornyl methacrylate, tetrahydrofuryl methyl acrylate, tetrahydrofuryl methyl methacrylate, pentaerythritol tetraacrylate and cyclohexyl acrylate, the amount of diluted monomer is bio-based epoxy acrylate prepolymer 0-70% of the dosage.
优选的，步骤(3)中所述的光引发剂为1-羟基环已基苯基酮、2,4,6-三甲基苯甲酰二苯氧磷、2-羟基-2-甲基-1-苯基-1-丙酮、安息香双甲醚、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2，4，6-三甲基苯甲酰基磷酸乙酯、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-异丙基硫杂蒽酮、4-氯二苯甲酮中的至少一种，光引发剂用量为所得光固化树脂总重量的0.1％～5％。Preferably, the photoinitiator described in step (3) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenoxyphos, 2-hydroxyl-2-methyl -1-phenyl-1-propanone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholine benzylphenyl) butanone, 2,4,6-trimethyl ethyl benzoyl phosphate, 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 2-isopropylthioxanthone, 4-chlorobenzhydryl At least one of the ketones, the amount of the photoinitiator is 0.1% to 5% of the total weight of the obtained photocurable resin.
优选的，步骤(4)中所述的基于环氧植物油和没食子酸光固化树脂的UV光固化材料的拉伸强度为20-80MPa。Preferably, the tensile strength of the UV photocurable material based on epoxy vegetable oil and gallic acid photocurable resin described in step (4) is 20-80 MPa.
优选的，步骤(4)中所述的基于环氧植物油和没食子酸光固化树脂的UV光固化材料的玻璃化转变温度为110-170℃。Preferably, the glass transition temperature of the UV photocurable material based on epoxy vegetable oil and gallic acid photocurable resin described in step (4) is 110-170°C.
优选的，步骤(4)中所述的基于环氧植物油和没食子酸光固化树脂的粘度为50-4000mPas。Preferably, the viscosity of the photocurable resin based on epoxy vegetable oil and gallic acid described in step (4) is 50-4000 mPas.
上述方法制备得到的生物基类环氧丙烯酸酯树脂。The bio-based epoxy acrylate resin prepared by the above method.
上述生物基类环氧丙烯酸酯树脂在光固化3D打印，木器、金属表面涂层和油墨产品中的应用。The application of the above-mentioned bio-based epoxy acrylate resin in light-curing 3D printing, wood, metal surface coating and ink products.
实施例1Example 1
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0， 阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧大豆油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧大豆油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The amount of diluted monomer is 50% of the mass of the obtained prepolymer, and the amount of photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy soybean oil and gallic acid.
实施例2Example 2
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧棉籽油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy cottonseed oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧棉籽油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The amount of diluted monomer is 50% of the mass of the obtained prepolymer, and the amount of photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy cottonseed oil and gallic acid.
实施例3Example 3
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧桐油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量 的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy tung oil is added in the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1, The dosage of the catalyst triphenylphosphine is 1% of the total weight of the raw materials, the dosage of the polymerization inhibitor hydroquinone is 0.5% of the total weight of the raw materials, and the reaction is carried out at 90° C. for 4 hours to obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧桐油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The amount of diluted monomer is 50% of the obtained prepolymer mass, and the amount of photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy tung oil and gallic acid.
实施例4Example 4
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧橡胶仔油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy rubber seed oil is added in the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step, and the epoxy ring-opening reaction is carried out, wherein the mol ratio of epoxy group and carboxyl group is 1.3: 1. The amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of polymerization inhibitor hydroquinone is 0.5% of the total weight of raw materials, react at 90°C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧橡胶仔油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The amount of diluted monomer is 50% of the mass of the obtained prepolymer, and the amount of photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy rubber seed oil and gallic acid.
实施例5-8Example 5-8
分别称取50g实施例1～4树脂，加入0.05g阻光剂2.5-双-(5-叔丁基-2-苯并恶唑基)噻吩搅拌均匀，并脱气处理，倒入Form3 SLA光固化3D打印机(美国Formlabs公司)树脂槽中，进行光固化打印。拉伸性能：按照ASTM D638-2008利用SANS7 CMT-4304型万能试验机(深圳新三思仪器有限公司)测定3D打印模型的力学性能，标距为50mm，拉伸速率为5.0mm/min。模型尺寸为80×10×1mm 3。玻璃化转变温度：采用Q800固体分析仪(美国TA公司)测定其动态热机械性能。粘度：采用DVS+旋转粘度计测量树脂粘度(美国博勒公司)。体积收缩率通过ZMD-2电子密度比重仪(上海方瑞仪器有限公司)。 Weigh 50g of the resins from Examples 1 to 4, add 0.05g of light blocking agent 2.5-bis-(5-tert-butyl-2-benzoxazolyl)thiophene, stir evenly, degas, pour into Form3 SLA light Curing 3D printer (U.S. Formlabs company) resin tank, carry out photocuring printing. Tensile properties: According to ASTM D638-2008, the mechanical properties of the 3D printing model were measured using a SANS7 CMT-4304 universal testing machine (Shenzhen Xinsansi Instrument Co., Ltd.), with a gauge length of 50mm and a tensile rate of 5.0mm/min. The model size is 80×10×1 mm 3 . Glass transition temperature: use Q800 solid analyzer (US TA company) to measure its dynamic thermomechanical properties. Viscosity: DVS+ rotational viscometer is used to measure the viscosity of the resin (Boler, USA). The volume shrinkage was measured by a ZMD-2 electronic density pycnometer (Shanghai Fangrui Instrument Co., Ltd.).
表1实施例1～4光固化3D打印树脂样品的主要性能指标Table 1 The main performance indicators of the light-cured 3D printing resin samples of Examples 1-4
Figure PCTCN2021109628-appb-000001
Figure PCTCN2021109628-appb-000001
实施例9Example 9
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧大豆油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量30％，光引发剂用量为所得光固化树脂总重量的1％。搅拌均匀，去除气泡，得到基于环氧大豆油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The dosage of the diluting monomer is 30% of the weight of the obtained prepolymer, and the dosage of the photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly, remove air bubbles, and obtain a photocurable resin based on epoxy soybean oil and gallic acid.
实施例10Example 10
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧菜籽油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy rapeseed oil is added in the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3: 1. The amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of polymerization inhibitor hydroquinone is 0.5% of the total weight of raw materials, react at 90°C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量30％，光引发剂用量为所得光固化树脂总重量的1％。搅拌均匀，去除气泡，得到基于环氧菜籽油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The dosage of the diluting monomer is 30% of the weight of the obtained prepolymer, and the dosage of the photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly, remove air bubbles, and obtain a photocurable resin based on epoxy rapeseed oil and gallic acid.
实施例11Example 11
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧棕榈油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Add epoxy palm oil to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step, and carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量30％，光引发剂用量为所得光固化树脂总重量的1％。搅拌均匀，去除气泡，得到基于环氧棕榈油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The dosage of the diluting monomer is 30% of the weight of the obtained prepolymer, and the dosage of the photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly, remove air bubbles, and obtain a photocurable resin based on epoxy palm oil and gallic acid.
实施例12Example 12
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧亚麻油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy linseed oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the mol ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量30％，光引发剂用量为所得光固化树脂总重量的1％。搅拌均匀，去除气泡，得到基于环氧亚麻油和没食子酸的光固化树脂。(3) Diluted monomer hydroxyethyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos were added to the bio-based epoxy acrylate prepolymer synthesized in step 2, The dosage of the diluting monomer is 30% of the weight of the obtained prepolymer, and the dosage of the photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly, remove air bubbles, and obtain a photocurable resin based on epoxy linseed oil and gallic acid.
实施例13-16Examples 13-16
别称取20g实施例9～12树脂，加入0.3g碳黑和0.2g聚硅氧烷树脂，搅拌均匀，并脱气处理，得到光固化油墨，最后倒入自制聚四氟乙烯模具中或在马口铁片进行涂膜，经UV固化成膜。涂膜性能：按照GB/T 9286-1998的方法测试涂膜的附着力，1级最好，7级最差；按照GB/T 1731-93的方法测试涂膜的柔韧性，轴棒最小直径为2mm，轴棒直径越小，韧性越好；按照GB/T 6739-2006测定漆膜的硬度，6H，5H，4H，3H，2H，H，HB，B，2B，3B，4B，5B，6B，其中6H最硬，6B最软。粘度：采用DVS+旋转粘度计测量树脂粘度(美国博勒公司)。Weigh 20g of the resins of Examples 9-12, add 0.3g of carbon black and 0.2g of polysiloxane resin, stir evenly, and degas to obtain photocurable ink, and finally pour it into a self-made polytetrafluoroethylene mold or in The tinplate sheet is coated and cured by UV to form a film. Coating film performance: test the adhesion of the coating film according to the method of GB/T 9286-1998, grade 1 is the best, grade 7 is the worst; test the flexibility of the coating film according to the method of GB/T 1731-93, the minimum diameter of the shaft rod 2mm, the smaller the shaft diameter, the better the toughness; measure the hardness of the paint film according to GB/T 6739-2006, 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B, 6B, of which 6H is the hardest and 6B is the softest. Viscosity: DVS+ rotational viscometer is used to measure the resin viscosity (Boler, USA).
表2实施例6～9油墨样品的主要性能指标The main performance index of table 2 embodiment 6～9 printing ink samples
Figure PCTCN2021109628-appb-000002
Figure PCTCN2021109628-appb-000002
实施例17Example 17
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧大豆油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸四氢呋喃甲酯和光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧大豆油和没食子酸的光固化树脂。(3) Add dilute monomer tetrahydrofuryl methyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos into the bio-based epoxy acrylate prepolymer synthesized in step 2, dilute The amount of monomer used is 50% of the weight of the obtained prepolymer, and the amount of photoinitiator used is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy soybean oil and gallic acid.
实施例18Example 18
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧大豆油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体甲基丙烯酸异冰片酯和光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧大豆油和没食子酸的光固化树脂。(3) Add dilute monomer isobornyl methacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphosphine into the bio-based epoxy acrylate prepolymer synthesized in step 2, dilute The amount of monomer used is 50% of the weight of the obtained prepolymer, and the amount of photoinitiator used is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy soybean oil and gallic acid.
实施例19Example 19
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧大豆油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体季戊四醇四丙烯酸酯和光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧大豆油和没食子酸的光固化树脂。(3) Add diluting monomer pentaerythritol tetraacrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos into the bio-based epoxy acrylate prepolymer synthesized in step 2, diluting monomer The dosage is 50% of the mass of the obtained prepolymer, and the dosage of the photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxy soybean oil and gallic acid.
实施例20Example 20
(1)在反应器中加入没食子酸和甲基丙烯酸酐，没食子酸与甲基丙烯酸酐的摩尔比为1:3.0，阻聚剂对苯二酚用量为原料总重量的0.5％，搅拌均匀后加热至60℃反应4h，得到没食子酸 三甲基丙烯酸酯/甲基丙烯酸混合中间体；(1) Add gallic acid and methacrylic anhydride in the reactor, the molar ratio of gallic acid and methacrylic anhydride is 1:3.0, the amount of inhibitor hydroquinone is 0.5% of the total weight of raw materials, after stirring Heating to 60°C for 4 hours to obtain a gallic acid trimethacrylate/methacrylic acid mixed intermediate;
(2)将环氧大豆油加入到上一步得到的没食子酸三甲基丙烯酸酯/甲基丙烯酸混合中间体中，进行环氧开环反应，其中环氧基和羧基的摩尔比为1.3:1，催化剂三苯基膦用量为原料总重量的1％,阻聚剂对苯二酚用量为原料总重量的0.5％，90℃反应4h，得到生物基环氧丙烯酸酯预聚体；(2) Epoxy soybean oil is added to the gallic acid trimethacrylate/methacrylic acid mixed intermediate obtained in the previous step to carry out epoxy ring-opening reaction, wherein the molar ratio of epoxy group and carboxyl group is 1.3:1 , the amount of catalyst triphenylphosphine is 1% of the total weight of raw materials, the amount of hydroquinone as a polymerization inhibitor is 0.5% of the total weight of raw materials, react at 90 ° C for 4 hours, and obtain a bio-based epoxy acrylate prepolymer;
(3)将稀释单体丙烯酸羟乙酯、光引发剂2,4,6-三甲基苯甲酰二苯氧磷加入到步骤2合成的生物基环氧丙烯酸酯预聚体中，稀释单体用量为所得预聚体质量的50％，光引发剂用量为所得光固化树脂总重量的1％，搅拌均匀，去除气泡，得到基于环氧大豆油和没食子酸的光固化树脂。(3) Add dilute monomer hydroxyethyl acrylate and photoinitiator 2,4,6-trimethylbenzoyl diphenoxyphos to the bio-based epoxy acrylate prepolymer synthesized in step 2, dilute The dosage of the polymer is 50% of the weight of the obtained prepolymer, and the dosage of the photoinitiator is 1% of the total weight of the obtained photocurable resin. Stir evenly and remove air bubbles to obtain a photocurable resin based on epoxidized soybean oil and gallic acid.
实施例21-24Examples 21-24
分别称取20g实施例7～20树脂，加入0.4g无机填料助剂纳米二氧化硅，搅拌均匀，并脱气处理，最后倒入自制聚四氟乙烯模具中或在马口铁片进行涂膜，经UV固化成膜。拉伸性能：按照ASTM D638-2008利用SANS7 CMT-4304型万能试验机(深圳新三思仪器有限公司)测定光固化模型的力学性能，标距为50mm，拉伸速率为5.0mm/min。模型尺寸为80×10×1mm 3。玻璃化转变温度：采用Q800固体分析仪(美国TA公司)测定其动态热机械性能。涂膜性能：按照GB/T 9286-1998的方法测试涂膜的附着力，1级最好，7级最差；按照GB/T 1731-93的方法测试涂膜的柔韧性，轴棒最小直径为2mm，轴棒直径越小，韧性越好；按照GB/T 6739-2006测定漆膜的硬度，6H，5H，4H，3H，2H，H，HB，B，2B，3B，4B，5B，6B，其中6H最硬，6B最软。粘度：采用DVS+旋转粘度计测量树脂粘度(美国博勒公司)。 Weigh 20g of the resins of Examples 7-20 respectively, add 0.4g of nano-silica as an inorganic filler additive, stir evenly, and degas, and finally pour into a self-made polytetrafluoroethylene mold or apply a film on a tinplate sheet, UV curing film. Tensile properties: According to ASTM D638-2008, the mechanical properties of the light-cured model were measured using a SANS7 CMT-4304 universal testing machine (Shenzhen Xinsansi Instrument Co., Ltd.), with a gauge length of 50 mm and a tensile rate of 5.0 mm/min. The model size is 80×10×1 mm 3 . Glass transition temperature: use Q800 solid analyzer (US TA company) to measure its dynamic thermomechanical properties. Coating film performance: test the adhesion of the coating film according to the method of GB/T 9286-1998, grade 1 is the best, grade 7 is the worst; test the flexibility of the coating film according to the method of GB/T 1731-93, the minimum diameter of the shaft rod 2mm, the smaller the shaft diameter, the better the toughness; measure the hardness of the paint film according to GB/T 6739-2006, 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B, 6B, of which 6H is the hardest and 6B is the softest. Viscosity: DVS+ rotational viscometer is used to measure the viscosity of the resin (Boler, USA).
表1实施例1～12树脂样品的主要涂膜性能指标The main coating performance index of the resin sample of table 1 embodiment 1～12
Figure PCTCN2021109628-appb-000003
Figure PCTCN2021109628-appb-000003
由表中数据可看到，本发明所制备的环氧植物油和没食子酸基光固化树脂的生物基含量高，UV固化材料力学、热学学性能优良，树脂透射深度系数适中，可用于光固化3D打印、木器、金属表面涂层和油墨产品中。It can be seen from the data in the table that the epoxy vegetable oil and gallic acid-based photocurable resin prepared by the present invention have high bio-based content, excellent mechanical and thermal properties of UV curable materials, and moderate resin transmission depth coefficient, which can be used for photocurable 3D Printing, wood, metal surface coating and ink products.
上述实例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本法明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。The above examples are only to illustrate the technical conception and characteristics of the present invention, and its purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (10)

  1. 一种基于环氧植物油和没食子酸的光固化树脂，其特征在于，首先利用没食子酸和丙烯酸酐类化合物反应，得到没食子酸三丙烯酸酯/丙烯酸类化合物混合中间体；接着利用环氧植物油与所得混合中间体进行环氧开环反应，得到生物基环氧丙烯酸酯预聚体；最后再加入稀释单体、光引发剂、阻聚剂，分散均匀，得到生物基光固化树脂。A kind of photocurable resin based on epoxy vegetable oil and gallic acid is characterized in that, first utilize gallic acid and acrylic anhydride compound to react, obtain gallic acid triacrylate/acrylic compound mixed intermediate; Then utilize epoxy vegetable oil and gained Mix the intermediates for epoxy ring-opening reaction to obtain a bio-based epoxy acrylate prepolymer; finally add diluting monomers, photoinitiators, and polymerization inhibitors to disperse evenly to obtain bio-based photocurable resins.
  2. 根据权利要求1所述一种基于环氧植物油和没食子酸的光固化树脂，其特征在于，所述的环氧植物油为环氧大豆油、环氧菜籽油、环氧葵花籽油、环氧棉籽油、环氧棕榈油、环氧橡胶籽油、环氧亚麻油、环氧化桐油、环氧光皮树果油、环氧化蓖麻油、环氧油酸甲酯、环氧亚麻油酸甲酯、环氧化亚麻油酸甲酯、环氧化桐油酸甲酯和环氧化脂肪酸缩水甘油酯中的至少一种。A kind of photocurable resin based on epoxy vegetable oil and gallic acid according to claim 1, it is characterized in that, described epoxy vegetable oil is epoxy soybean oil, epoxy rapeseed oil, epoxy sunflower oil, epoxy Cottonseed oil, epoxy palm oil, epoxy rubber seed oil, epoxy linseed oil, epoxy tung oil, epoxy barkberry oil, epoxy castor oil, epoxy methyl oleate, epoxy linolenic acid at least one of methyl ester, epoxidized methyl linoleate, epoxidized methyl oleate and epoxidized fatty acid glycidyl ester.
  3. 根据权利要求1所述一种基于环氧植物油和没食子酸的光固化树脂，其特征在于，所述的丙烯酸酐类化合物为丙烯酸酐、甲基丙烯酸酐中的至少一种。A kind of photocurable resin based on epoxy vegetable oil and gallic acid according to claim 1, it is characterized in that, described acrylic anhydride compound is at least one in acrylic anhydride, methacrylic anhydride.
  4. 权利要求1～3任一所述基于环氧植物油和没食子酸的光固化树脂的制备方法，其特征在于，制备步骤为：The preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid described in any one of claims 1 to 3, characterized in that the preparation steps are:
    (1)在反应器中加入没食子酸和丙烯酸酐类化合物和阻聚剂，搅拌均匀后加热至50～150℃反应1～8h，得到没食子酸三丙烯酸酯类化合物与丙烯酸类化合物的混合中间体；(1) Add gallic acid, acrylic anhydride compound and polymerization inhibitor into the reactor, stir evenly and heat to 50-150°C for 1-8 hours to obtain a mixed intermediate of gallic acid triacrylate compound and acrylic compound ;
    (2)将环氧植物油、催化剂和阻聚加入到上一步的反应器中，与所得混合中间体进行环氧开环反应，50～150℃反应1～6h，得到生物基环氧丙烯酸酯预聚体；(2) Add epoxy vegetable oil, catalyst and polymerization inhibitor to the reactor in the previous step, and carry out epoxy ring-opening reaction with the obtained mixed intermediate, and react at 50-150 °C for 1-6 hours to obtain bio-based epoxy acrylate pre- Polymer;
    (3)将稀释单体、光引发剂加入到生物基环氧丙烯酸酯预聚体中，搅拌均匀，去除气泡，得到生物基光固化树脂。(3) adding the diluted monomer and the photoinitiator into the bio-based epoxy acrylate prepolymer, stirring evenly, and removing air bubbles to obtain the bio-based photocurable resin.
  5. 根据权利要求4所述基于环氧植物油和没食子酸的光固化树脂的制备方法，其特征在于，步骤(1)和(2)中所述阻聚剂为对苯二酚、对苯醌、对甲氧基苯酚、2,6-二叔丁基对甲基苯酚中至少一种，用量为原料总重量的0.1～5％。According to the preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid according to claim 4, it is characterized in that, the polymerization inhibitor described in step (1) and (2) is hydroquinone, p-benzoquinone, p-benzoquinone At least one of methoxyphenol and 2,6-di-tert-butyl-p-methylphenol is used in an amount of 0.1-5% of the total weight of raw materials.
  6. 根据权利要求4所述基于环氧植物油和没食子酸的光固化树脂的制备方法，其特征在于，步骤(2)催化剂为对N,N-二甲基苄胺、三苯基膦、1-甲基咪唑、钛酸四丁酯、4-二甲氨基吡啶中的至少一种，用量为原料总重量的0.1％～5％。According to the preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid described in claim 4, it is characterized in that step (2) catalyst is p-N,N-dimethylbenzylamine, triphenylphosphine, 1-methyl At least one of imidazole, tetrabutyl titanate, and 4-dimethylaminopyridine is used in an amount of 0.1% to 5% of the total weight of the raw materials.
  7. 根据权利要求4所述基于环氧植物油和没食子酸的光固化树脂的制备方法，其特征在于，步骤(1)中所述没食子酸和甲基丙烯酸酐摩尔比为1:2～5，步骤(2)中所述环氧基和羧基摩尔比为0.5～1.5:1。According to the preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid described in claim 4, it is characterized in that, gallic acid and methacrylic anhydride mol ratio described in step (1) are 1:2～5, step ( 2) The molar ratio of epoxy group to carboxyl group is 0.5-1.5:1.
  8. 根据权利要求4所述基于环氧植物油和没食子酸的光固化树脂的制备方法，其特征在于， 步骤(3)中所述的稀释单体为丙烯酸甲酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、醋酸乙烯酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、丙烯酸四氢呋喃甲酯、甲基丙烯酸四氢呋喃甲酯、季戊四醇四丙烯酸酯和丙烯酸环己酯中的至少一种，稀释单体用量为生物基环氧丙烯酸酯预聚体用量的0～70％。According to the preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid described in claim 4, it is characterized in that, the dilution monomer described in step (3) is methyl acrylate, hydroxypropyl acrylate, methacrylate hydroxy Propyl ester, Hydroxyethyl acrylate, Hydroxyethyl methacrylate, Vinyl acetate, Isobornyl acrylate, Isobornyl methacrylate, Tetrahydrofuryl methyl acrylate, Tetrahydrofuryl methyl methacrylate, Pentaerythritol tetraacrylate and Cycloacrylate For at least one of the hexyl esters, the amount of the diluting monomer is 0-70% of the amount of the bio-based epoxy acrylate prepolymer.
  9. 根据权利要求4所述基于环氧植物油和没食子酸的光固化树脂的制备方法，其特征在于，步骤(3)中所述的光引发剂为1-羟基环已基苯基酮、2,4,6-三甲基苯甲酰二苯氧磷、2-羟基-2-甲基-1-苯基-1-丙酮、安息香双甲醚、2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2，4，6-三甲基苯甲酰基磷酸乙酯、2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮、2-异丙基硫杂蒽酮、4-氯二苯甲酮中的至少一种，光引发剂用量为所得光固化树脂总重量的0.1％～5％。According to the preparation method of the photocurable resin based on epoxy vegetable oil and gallic acid described in claim 4, it is characterized in that, the photoinitiator described in step (3) is 1-hydroxy cyclohexyl phenyl ketone, 2,4 ,6-trimethylbenzoyldiphenoxyphos, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine- 1-(4-morpholine benzylphenyl) butanone, 2,4,6-trimethylbenzoyl phosphate ethyl ester, 2-methyl-1-(4-methylthiophenyl)-2-morpholine At least one of phenoline-1-acetone, 2-isopropylthioxanthone, and 4-chlorobenzophenone, the amount of the photoinitiator is 0.1% to 5% of the total weight of the obtained photocurable resin.
  10. 权利要求1～3任一所述的生物基光固化树脂在制备光固化3D打印材料、涂料和油墨产品中的应用。The application of the bio-based photocurable resin according to any one of claims 1 to 3 in the preparation of photocurable 3D printing materials, coatings and ink products.
PCT/CN2021/109628 2021-07-13 2021-07-30 Photocurable resin based on epoxidized vegetable oil and gallic acid, preparation method therefor and application thereof WO2023284021A1 (en)

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