CN113201116B - Vinyl ester resin and preparation method thereof, vinyl ester resin modified castor oil-based polyurethane resin and preparation method and application thereof - Google Patents

Vinyl ester resin and preparation method thereof, vinyl ester resin modified castor oil-based polyurethane resin and preparation method and application thereof Download PDF

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CN113201116B
CN113201116B CN202110485931.5A CN202110485931A CN113201116B CN 113201116 B CN113201116 B CN 113201116B CN 202110485931 A CN202110485931 A CN 202110485931A CN 113201116 B CN113201116 B CN 113201116B
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vinyl ester
castor oil
resin
ester resin
diisocyanate
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CN113201116A (en
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杨卓鸿
杨绍恒
方亨
李贵东
吴海华
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Guangdong Meiheng New Material Technology Co ltd
South China Agricultural University
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South China Agricultural University
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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    • 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
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    • 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
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    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a vinyl ester resin and a preparation method thereof, a photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin and a preparation method and application thereof. The invention carries on chain extension to epoxide resin, dicarboxylic acid or dicarboxylic anhydride, then reacts with unsaturated monobasic acid for a certain time, then adds in diluent to dilute and gets vinyl ester resin; reacting diisocyanate and castor oil for a certain time, and adding hydroxyalkyl acrylate for end capping to obtain castor oil-based polyurethane acrylate resin; and mixing the obtained vinyl ester resin with the castor oil-based polyurethane acrylate resin to obtain the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin. The invention can effectively improve the glass-transition temperature and tensile strength performance of the photocuring film, the mechanical property and the glass-transition temperature of the photocuring film can be regularly adjusted, the storage stability is good, and the crosslinking density is high.

Description

Vinyl ester resin and preparation method thereof, vinyl ester resin modified castor oil-based polyurethane resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a vinyl ester resin and a preparation method thereof, a photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin and a preparation method and application thereof.
Background
The surface coating technology is ubiquitous in our lives, and the industry is always hoped to develop a film forming method with low pollution, rapid curing and high energy utilization rate. The ultraviolet curing technology is a coating technology appearing at the beginning of the 20 th century, and generally, a prepared liquefied film prepolymer is placed under ultraviolet light with a certain wavelength for irradiation, so that an active prepolymer and a photoinitiator in the liquefied film prepolymer react, substances in the coating are crosslinked, and finally, the effect of quickly curing and forming a film is achieved.
In the prior art, patent application with publication number CN 111925504 a discloses a castor oil-based polyurethane acrylic resin and a preparation method thereof, wherein a quantitative reactive diluent, isocyanate and castor oil are reacted for a certain time to obtain an isocyanate semi-terminated intermediate, and then hydroxyl acrylate and an antioxidant are added to continue the reaction for a period of time to obtain the castor oil-based polyurethane acrylic resin with high bio-group content. The double bond is positioned at the terminal position of a molecular chain from the structural view, the curing activity is high, and in addition, the double bond has a longer bio-based carbon chain, so the breaking elongation is higher, but the mechanical property, such as tensile strength, of a film obtained by resin photocuring is poorer, and the application range of the film is limited.
Disclosure of Invention
According to a first aspect of the present invention, there is provided a vinyl ester resin having the formula:
Figure BDA0003050230630000011
wherein R is
Figure BDA0003050230630000012
R1Is composed of
Figure BDA0003050230630000021
R2Is composed of
Figure BDA0003050230630000022
Figure BDA0003050230630000023
According to a second aspect of the present invention, there is provided a process for preparing the above vinyl ester resin, which comprises reacting an epoxy resin with a dicarboxylic acid or dicarboxylic acid anhydride under the action of a catalyst and a polymerization inhibitor to obtain a chain-extended epoxy resin, and blocking the chain-extended epoxy resin with an unsaturated monobasic acid to obtain the vinyl ester resin. The reaction scheme of the vinyl ester resins of the present invention is shown in figure 1.
In some embodiments, the method of making is: reacting epoxy resin with dicarboxylic acid or dicarboxylic anhydride at 85-95 ℃ for 0.5-1.5 hours under the action of a catalyst and a polymerization inhibitor, adding unsaturated monoacid, heating to 105-115 ℃, preserving heat for 2-3 hours until the acid value is less than 30mgKOH/g, cooling to below 80 ℃, adding styrene for dilution, and stirring and mixing uniformly to obtain the vinyl ester resin.
In some embodiments, the epoxy resin is any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol a type epoxy resin; the catalyst is one or a mixture of more than one of benzyltriethylammonium chloride, triethylamine and triphenylphosphine in any proportion; the polymerization inhibitor is one or a mixture of more than one of hydroquinone, p-tert-butyl catechol and catechol in any proportion; the dicarboxylic acid is fumaric acid or maleic acid; the dicarboxylic anhydride is maleic anhydride or phthalic anhydride; the unsaturated monobasic acid is one or a mixture of more than one of acrylic acid, methacrylic acid, crotonic acid and phenylacrylic acid in any proportion.
In some embodiments, the molar ratio of epoxy resin, dicarboxylic acid or dicarboxylic anhydride, unsaturated monoacid is 1: 0.2-0.6: 0.8 to 1.6, preferably 1: 0.3-0.35: 1.3-1.4; the dosage of the catalyst is 0.4-2.0 wt%, preferably 0.4-1.0 wt% of the total mass of the epoxy resin, the dicarboxylic acid or dicarboxylic anhydride and the unsaturated monoacid; the amount of the polymerization inhibitor is 0.015 to 0.05 wt%, preferably 0.015 to 0.025 wt%, based on the total mass of the epoxy resin, the dicarboxylic acid or dicarboxylic anhydride and the unsaturated monobasic acid.
According to a third aspect of the present invention, there is provided a photocurable vinyl ester resin modified castor oil based polyurethane acrylate resin, which is prepared from the following raw materials in parts by weight: 50-90 parts of the vinyl ester resin, 10-50 parts of castor oil-based polyurethane acrylate and 0.6-7 parts of a photoinitiator.
In some embodiments, the photoinitiator is photoinitiator 1173, i.e., 2-hydroxy-2-methyl-1-phenyl-1-propanone. The photoinitiator is used in an amount of 1-5 wt%, preferably 3-5 wt%, based on the total mass of the vinyl ester resin and the castor oil-based urethane acrylate.
In some embodiments, the castor oil-based polyurethane acrylate is prepared by the following method:
reacting diisocyanate with hydroxyalkyl acrylate at 40-50 ℃ under the action of a catalyst and a polymerization inhibitor until the NCO value reaches half of the initial NCO value, then adding castor oil, heating to 70-80 ℃ for reaction until the NCO value is 0, and then adding a reactive diluent for dilution until the mixture is uniformly mixed to obtain the product.
In some embodiments, the diisocyanate is one or a mixture of more than one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, hydrogenated phenyl methane diisocyanate, 4-dicyclohexyl methane diisocyanate, p-tetramethylxylylene diisocyanate, ditolyl diisocyanate, and trimethyl hexamethylene diisocyanate in any proportion; the catalyst is dibutyltin dilaurate; the polymerization inhibitor is one or a mixture of more than one of hydroquinone, p-tert-butyl catechol and catechol in any proportion; the hydroxyalkyl acrylate is one or a mixture of more than one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate in any proportion; the reactive diluent is one or a mixture of more than one of tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diisocyanate 200, polyethylene glycol diisocyanate 400 and polyethylene glycol diisocyanate 600 in any proportion.
In some embodiments, the molar ratio of diisocyanate, hydroxyalkyl acrylate, castor oil is 1: 0.8-1.1: 0.3-0.4; the amount of the catalyst is 0.01-0.10 wt%, preferably 0.01-0.03 wt% of the total mass of the diisocyanate, the hydroxyalkyl acrylate, the castor oil and the reactive diluent; the polymerization inhibitor is used in an amount of 0.05 to 0.30 wt%, preferably 0.05 to 0.15 wt%, based on the total mass of the diisocyanate, hydroxyalkyl acrylate, castor oil and reactive diluent.
The preparation method of the castor oil-based polyurethane acrylate resin can also refer to the method disclosed in the Chinese patent application CN 111925504A.
According to a fourth aspect of the present invention, there is provided a preparation method of the above-mentioned photocurable vinyl ester resin modified castor oil-based urethane acrylate resin, wherein the vinyl ester resin, castor oil-based urethane acrylate and photoinitiator are stirred and mixed uniformly to obtain the product.
According to a fifth aspect of the present invention, there is provided a use of the above-mentioned photocurable vinyl ester resin modified castor oil-based polyurethane acrylate resin in a UV curable coating, a UV curable ink, a UV curable adhesive, or 3D printing.
The vinyl ester resin is obtained by chain extension of epoxy resin and dicarboxylic acid or dicarboxylic anhydride and end capping with unsaturated monoacid. Because the dicarboxylic acid or dicarboxylic anhydride contains double bonds, the dicarboxylic acid or dicarboxylic anhydride can also participate in subsequent free radical photocuring, and the mechanical property of the bio-based polyurethane acrylate resin can be further improved.
The invention obtains the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin by adjusting the mixing proportion of the vinyl ester resin and the castor oil-based polyurethane acrylate resin, combines the vinyl ester resin and the bio-based polyurethane acrylate resin through photocuring free radicals, regularly regulates and controls the mechanical property of a castor oil-based polyurethane acrylate resin photocuring film, effectively improves the problems of low tensile strength and low hardness of the bio-based polyurethane acrylate curing film, has uniform appearance and no delamination of the resin, and is particularly suitable for preparing UV curing coatings, UV curing ink, UV curing adhesives or 3D printing.
Drawings
FIG. 1 is a reaction scheme of a vinyl ester resin of the present invention.
FIG. 2 is a reaction scheme of the vinyl ester resin of example 1 of the present invention.
Fig. 3 is a fourier transform infrared spectrum of an epoxy resin, a vinyl ester resin of example 1 of the present invention.
Fig. 4 is a fourier transform infrared spectrum of castor oil, castor oil-based urethane acrylate resin of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available.
Example 1
The preparation method of the photocurable vinyl ester resin modified castor oil-based polyurethane acrylate resin of the embodiment includes the following steps:
(1) putting 227.2g of bisphenol A epoxy resin E-44 (with the molecular weight of 454), 19.72g of fumaric acid, 0.064g of hydroquinone serving as a polymerization inhibitor and 1.48g of benzyltriethylammonium chloride serving as a catalyst into a 1000mL three-neck flask, heating to 90 ℃, carrying out heat preservation reaction for 1 hour, then starting to dropwise add 49.92g of acrylic acid, finishing dropwise adding within 1 hour, heating to 110 ℃, carrying out heat preservation reaction for 2-3 hours after completing dropwise adding until the acid value is less than 30mg KOH/g, then cooling to below 80 ℃, adding 127.28g of styrene for dilution until the mixture is uniformly mixed to obtain the vinyl ester resin.
(2) Under the protection of nitrogen, 99.1g of Toluene Diisocyanate (TDI), 65.9g of hydroxyethyl acrylate (HEA), 0.3616g of hydroquinone serving as a polymerization inhibitor and 0.072g of dibutyltin dilaurate serving as a catalyst are put into another 1000mL three-neck flask, heated to 45 ℃, and subjected to heat preservation reaction until the NCO value reaches half of the initial NCO value to obtain an isocyanate half-blocked intermediate, then 196.64g of castor oil is put into the flask, heated to 75 ℃, subjected to heat preservation reaction until the NCO value reaches 0, and 40.23g of tripropylene glycol diacrylate is added until the mixture is uniformly mixed to obtain the castor oil-based polyurethane acrylate resin.
(3) And uniformly stirring and mixing 90g of vinyl ester resin, 10g of castor oil-based polyurethane acrylate resin and 5g of photoinitiator 1173 to obtain the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin.
The reaction scheme of the vinyl ester resin of this example is shown in figure 2.
The fourier transform infrared spectra of the epoxy resin and the vinyl ester resin of this example are shown in fig. 3, in which the raw material is epoxy resin (denoted as ER) and the product is vinyl ester resin (denoted as VER).
As can be seen in FIG. 3, it is seen in ER that 915cm-1The characteristic peak appeared nearby is the epoxy vibration peak, 1607cm-1Is the stretching vibration of C ═ C on a benzene ring, 830cm-1Is the opposite substitution vibration absorption peak on the benzene ring. 915cm are seen in the VER after the ER has undergone a series of ring-opening blocking reactions-1The characteristic peak of epoxy group disappears, which indicates that the epoxy group reacts with carboxylic acid to complete ring opening, 1724cm-11634cm for stretching and contracting vibration of C ═ O on ester bond-1The newly appearing peak is the stretching vibration of C ═ C on the capped unsaturated monoacid. The FT-IR results therefore show that the product is a vinyl ester resin.
The fourier transform infrared spectrum of the castor oil-based polyurethane acrylate resin of this example is shown in fig. 4, in which the raw material is castor oil (denoted as CO), the isocyanate half-blocked intermediate (denoted as CO-TDI), and the product is a castor oil-based polyurethane acrylate resin (denoted as COPUA).
As can be seen from FIG. 4, 3435.2cm is seen in the CO infrared image-1The characteristic peak appears as-OH stretching vibration peak which is respectively-CH3and-CH2The stretching vibration peak of (1). 2269.2cm in CO-TDI-1The absorption peak was assigned to the characteristic peak of-NCO group in TDI. After reaction of castor oil and TDI, 3435.2cm-1The hydroxyl peak disappeared. After reaction of CO-TDI and HEA, 22659.2cm-1Disappearance of NCO absorption peak, indicating reaction of HEA and CO-TDI, 3338.8cm in COPIA-1And 1731.3cm-1The peaks are characteristic peaks of carbamate N-H and C ═ O respectively, 1537.2cm-1The characteristic peak at (A) is due to the amide vibration of the-NHCOO-group in COPOA. Therefore, the FT-IR result shows that the product is the castor oil-based polyurethane acrylic resin.
Example 2
The preparation method of the photocurable vinyl ester resin modified castor oil-based polyurethane acrylate resin of the embodiment includes the following steps:
(1) putting 227.2g of bisphenol A epoxy resin E-44 (with the molecular weight of 454), 19.72g of fumaric acid, 0.064g of hydroquinone serving as a polymerization inhibitor and 1.48g of benzyltriethylammonium chloride serving as a catalyst into a 1000mL three-neck flask, heating to 90 ℃, carrying out heat preservation reaction for 1 hour, then starting to dropwise add 49.92g of acrylic acid, finishing dropwise adding within 1 hour, heating to 110 ℃, carrying out heat preservation reaction for 2-3 hours after completing dropwise adding until the acid value is less than 30mg KOH/g, then cooling to below 80 ℃, adding 127.28g of styrene for dilution until uniform mixing is carried out, thus obtaining the vinyl ester resin.
(2) Under the protection of nitrogen, 99.1g of toluene diisocyanate, 65.9g of hydroxyethyl acrylate, 0.3616g of hydroquinone serving as a polymerization inhibitor and 0.072g of dibutyltin dilaurate serving as a catalyst are put into another 1000mL three-neck flask, the temperature is increased to 45 ℃, the temperature is kept and the reaction is carried out until the NCO value reaches half of the initial NCO value, 196.64g of castor oil is then put into the flask, the temperature is increased to 75 ℃, the reaction is carried out under the temperature keeping until the NCO value is 0, and 40.23g of tripropylene glycol diacrylate is added until the mixture is uniformly mixed, so that the castor oil-based polyurethane acrylate resin is obtained.
(3) And stirring and mixing 80g of vinyl ester resin, 20g of castor oil-based polyurethane acrylate resin and 5g of photoinitiator 1173 uniformly to obtain the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin.
Example 3
The preparation method of the photocurable vinyl ester resin modified castor oil-based polyurethane acrylate resin of the embodiment includes the following steps:
(1) putting 227.2g of bisphenol A epoxy resin E-44 (with the molecular weight of 454), 19.72g of fumaric acid, 0.064g of hydroquinone serving as a polymerization inhibitor and 1.48g of benzyltriethylammonium chloride serving as a catalyst into a 1000mL three-neck flask, heating to 90 ℃, carrying out heat preservation reaction for 1 hour, then starting to dropwise add 49.92g of acrylic acid, finishing dropwise adding within 1 hour, heating to 110 ℃, carrying out heat preservation reaction for 2-3 hours after completing dropwise adding until the acid value is less than 30mg KOH/g, then cooling to below 80 ℃, adding 127.28g of styrene for dilution until the mixture is uniformly mixed to obtain the vinyl ester resin.
(2) Under the protection of nitrogen, 99.1g of toluene diisocyanate, 65.9g of hydroxyethyl acrylate, 0.3616g of hydroquinone serving as a polymerization inhibitor and 0.072g of dibutyltin dilaurate serving as a catalyst are put into another 1000mL three-neck flask, heated to 45 ℃, kept for reacting until the NCO value reaches half of the initial NCO value, then 196.64g of castor oil is put into the flask, heated to 75 ℃, kept for reacting until the NCO value is 0, and 40.23g of tripropylene glycol diacrylate is added until the mixture is uniformly mixed, so that the castor oil-based polyurethane acrylate resin is obtained.
(3) And (3) stirring and uniformly mixing 70g of vinyl ester resin, 30g of castor oil-based polyurethane acrylate resin and 5g of photoinitiator 1173 to obtain the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin.
Example 4
The preparation method of the photocurable vinyl ester resin modified castor oil-based polyurethane acrylate resin of the embodiment includes the following steps:
(1) putting 227.2g of bisphenol A epoxy resin E-44 (with the molecular weight of 454), 19.72g of fumaric acid, 0.064g of hydroquinone serving as a polymerization inhibitor and 1.48g of benzyltriethylammonium chloride serving as a catalyst into a 1000mL three-neck flask, heating to 90 ℃, carrying out heat preservation reaction for 1 hour, then starting to dropwise add 49.92g of acrylic acid, finishing dropwise adding within 1 hour, heating to 110 ℃, carrying out heat preservation reaction for 2-3 hours after completing dropwise adding until the acid value is less than 30mg KOH/g, then cooling to below 80 ℃, adding 127.28g of styrene for dilution until the mixture is uniformly mixed to obtain the vinyl ester resin.
(2) Under the protection of nitrogen, 99.1g of toluene diisocyanate, 65.9g of hydroxyethyl acrylate, 0.3616g of hydroquinone serving as a polymerization inhibitor and 0.072g of dibutyltin dilaurate serving as a catalyst are put into another 1000mL three-neck flask, the temperature is increased to 45 ℃, the temperature is kept and the reaction is carried out until the NCO value reaches half of the initial NCO value, 196.64g of castor oil is then put into the flask, the temperature is increased to 75 ℃, the reaction is carried out under the temperature keeping until the NCO value is 0, and 40.23g of tripropylene glycol diacrylate is added until the mixture is uniformly mixed, so that the castor oil-based polyurethane acrylate resin is obtained.
(3) And uniformly stirring and mixing 60g of vinyl ester resin, 40g of castor oil-based polyurethane acrylate resin and 5g of photoinitiator 1173 to obtain the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin.
Example 5
The preparation method of the photocurable vinyl ester resin modified castor oil-based polyurethane acrylate resin of the embodiment includes the following steps:
(1) putting 227.2g of bisphenol A epoxy resin E-44 (with the molecular weight of 454), 19.72g of fumaric acid, 0.064g of hydroquinone serving as a polymerization inhibitor and 1.48g of benzyltriethylammonium chloride serving as a catalyst into a 1000mL three-neck flask, heating to 90 ℃, carrying out heat preservation reaction for 1 hour, then starting to dropwise add 49.92g of acrylic acid, finishing dropwise adding within 1 hour, heating to 110 ℃, carrying out heat preservation reaction for 2-3 hours after completing dropwise adding until the acid value is less than 30mg KOH/g, then cooling to below 80 ℃, adding 127.28g of styrene for dilution until the mixture is uniformly mixed to obtain the vinyl ester resin.
(2) Under the protection of nitrogen, 99.1g of toluene diisocyanate, 65.9g of hydroxyethyl acrylate, 0.3616g of hydroquinone serving as a polymerization inhibitor and 0.072g of dibutyltin dilaurate serving as a catalyst are put into another 1000mL three-neck flask, the temperature is increased to 45 ℃, the temperature is kept and the reaction is carried out until the NCO value reaches half of the initial NCO value, 196.64g of castor oil is then put into the flask, the temperature is increased to 75 ℃, the reaction is carried out under the temperature keeping until the NCO value is 0, and 40.23g of tripropylene glycol diacrylate is added until the mixture is uniformly mixed, so that the castor oil-based polyurethane acrylate resin is obtained.
(3) And uniformly stirring and mixing 50g of vinyl ester resin, 50g of castor oil-based polyurethane acrylate resin and 5g of photoinitiator 1173 to obtain the photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin.
In order to test the performance of the photo-cured vinyl ester resin modified castor oil-based polyurethane acrylate resin of the present invention, the photo-cured vinyl ester resin modified castor oil-based polyurethane acrylate resin obtained in examples 1 to 5 was coated, and then the obtained photo-cured film was subjected to a mechanical property test, a dynamic thermal mechanical property test, and a gel fraction test.
1. Preparation and curing of coating films
Selecting a 10cm × 10cm glass plate, placing the 750um surface of a wet film preparation device on the cleaned and dried glass plate, dripping the light-cured resin of example 1 at the bottom of the wet film preparation device by using a rubber head dropper, slowly and uniformly pulling out a film, placing the liquid film under a UV-LED light source for irradiation, wherein the wavelength of the UV-LED light source is 365nm, and the energy intensity is 3600mJ · cm-2Until the cured film was completely cured as evidenced by finger touch.
The photocurable resins obtained in examples 2 to 5 were coated and cured in the same manner as described above.
2. The photocured films prepared in examples 1 to 5 were subjected to mechanical property test, dynamic thermo-mechanical property test, and gel fraction test.
(1) And (3) testing mechanical properties: the tensile test was carried out using an AGS-X1 kN universal tester available from Shimadzu corporation, and a rectangular film sample having a gauge of 40mm × 10mm (length × width) and a crosshead speed of 10 mm. multidot.min-1. Young's modulus is the ratio of tensile strength to elongation at break.
For accuracy, three measurements were made for each sample and averaged.
(2) Dynamic thermomechanical property test: the stretching mode was selected using a Netzsch DMA242E dynamic thermodynamics instrument, and the oscillation frequency was set at 3.333 Hz. The samples were tested by cooling to-80 ℃ with liquid nitrogen and holding at-50 ℃ for 3 minutes, followed by 5 ℃ min-1Is heated to 180 ℃. The specification of the sample is 20mm × 6mm × 0.5mm (length × width × thickness). The glass transition temperature (Tg) of the uv-cured film corresponds to the temperature of the peak on the tan δ/temperature curve.
For accuracy, three measurements were made for each sample and averaged.
(3) And (3) testing the gel rate: weighing a proper amount of the photocuring film sample at room temperature, immersing the photocuring film sample in a sealed glass bottle filled with acetone for 24 hours, taking out the photocuring film sample, drying the photocuring film sample in a vacuum drying oven at 60 ℃ to constant weight, and recording the mass W of the photocuring film before immersion0And mass W of the photo-cured film after drying1The gel fraction was calculated according to the following formula:
gel fraction (%): W1/W0×100％。
For accuracy, three measurements were made for each sample and averaged.
The results of the mechanical property test, the dynamic thermo-mechanical property test and the gel fraction test of the photo-cured films prepared from the vinyl ester resin-modified castor oil-based urethane acrylate resins of examples 1 to 5 are shown in table 1.
TABLE 1 test results of mechanical properties, dynamic thermo-mechanical properties and gel fraction of photocured films
Figure BDA0003050230630000081
As can be seen from Table 1, the Vinyl Ester Resin (VER) with different contents is added into the castor oil-based polyurethane acrylate resin (COPIA), the viscosity is moderate, the mechanical property is greatly improved, the tensile strength is more than 20MPa, the glass transition temperature and the tensile strength of a photocuring film can be effectively improved, and the mechanical property of a product can be linearly adjusted by mixing the VER and the COPIA in different proportions. The light-cured film had a gel fraction of 91.8% or more and a good gel fraction, indicating that the cross-linking density of the light-cured film was good. The resin provided by the invention is uniform in appearance, free of layering and high in stability, and is particularly suitable for application in preparation of UV curing coatings, UV curing printing ink, UV curing adhesives or 3D printing.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (8)

1. The photocuring vinyl ester resin modified castor oil-based polyurethane acrylate resin is characterized by being prepared from the following raw materials in parts by weight: 50-90 parts of vinyl ester resin, 10-50 parts of castor oil-based polyurethane acrylate and 0.6-7 parts of photoinitiator, wherein the structural formula of the vinyl ester resin is as follows:
Figure 955985DEST_PATH_IMAGE001
，
wherein R is
Figure 440100DEST_PATH_IMAGE002
，R1Is composed of
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Or
Figure 843716DEST_PATH_IMAGE004
，R2Is composed of
Figure 43753DEST_PATH_IMAGE005
Or
Figure 771538DEST_PATH_IMAGE006
Or
Figure 978397DEST_PATH_IMAGE007
Or
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；
The castor oil-based polyurethane acrylate is prepared by the following method: reacting diisocyanate with hydroxyalkyl acrylate at 40-50 ℃ under the action of a catalyst and a polymerization inhibitor until the NCO value reaches half of the initial NCO value, then adding castor oil, heating to 70-80 ℃ for reaction until the NCO value is 0, and then adding an active diluent for dilution until the mixture is uniformly mixed to obtain the product.
2. The photocurable vinyl ester resin-modified castor oil-based urethane acrylate resin according to claim 1, wherein the vinyl ester resin is prepared by the following steps: firstly, epoxy resin reacts with dicarboxylic acid or dicarboxylic anhydride under the action of a catalyst and a polymerization inhibitor to prepare chain-extended epoxy resin, and then, unsaturated monoacid is used for blocking to obtain vinyl ester resin.
3. The photocurable vinyl ester resin-modified castor oil-based urethane acrylate resin according to claim 2, wherein the vinyl ester resin is prepared by the following steps: reacting epoxy resin with dicarboxylic acid or dicarboxylic anhydride at 85-95 ℃ for 0.5-1.5 hours under the action of a catalyst and a polymerization inhibitor, adding unsaturated monoacid, heating to 105-115 ℃, preserving heat for 2-3 hours until the acid value is less than 30mgKOH/g, cooling to below 80 ℃, adding styrene for dilution, and stirring and mixing uniformly to obtain the vinyl ester resin.
4. The photocurable vinyl ester resin-modified castor oil-based urethane acrylate resin according to claim 3 wherein the epoxy resin is a bisphenol A type epoxy resin; the catalyst is one or a mixture of more than one of benzyltriethylammonium chloride, triethylamine and triphenylphosphine in any proportion; the polymerization inhibitor is one or a mixture of more than one of hydroquinone, p-tert-butyl catechol and catechol in any proportion; the dicarboxylic acid is fumaric acid or maleic acid; the dicarboxylic anhydride is maleic anhydride; the unsaturated monoacid is one or a mixture of more than one of acrylic acid, methacrylic acid, crotonic acid and phenylacrylic acid in any proportion.
5. A photocurable vinyl ester resin modified castor oil based urethane acrylate resin as claimed in claim 3 wherein the molar ratio of epoxy resin, dicarboxylic acid or dicarboxylic acid anhydride, unsaturated monoacid is 1: 0.2-0.6: 0.8-1.6; the dosage of the catalyst is 0.4 to 2.0 weight percent of the total mass of the epoxy resin, the dicarboxylic acid or dicarboxylic anhydride and the unsaturated monoacid; the amount of the polymerization inhibitor is 0.015-0.05 wt% of the total mass of the epoxy resin, the dicarboxylic acid or dicarboxylic anhydride and the unsaturated monoacid.
6. The photocurable vinyl ester resin-modified castor oil-based polyurethane acrylate resin according to claim 1, wherein the diisocyanate is one or a mixture of more than one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, hydrogenated phenyl methane diisocyanate, 4-dicyclohexylmethane diisocyanate, p-tetramethylxylylene diisocyanate, ditolyl diisocyanate, and trimethylhexamethylene diisocyanate in any ratio; the catalyst is dibutyltin dilaurate; the polymerization inhibitor is one or a mixture of more than one of hydroquinone, p-tert-butyl catechol and catechol in any proportion; the hydroxyalkyl acrylate is one or a mixture of more than one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate in any proportion; the reactive diluent is one or a mixture of more than one of tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diisocyanate 200, polyethylene glycol diisocyanate 400 and polyethylene glycol diisocyanate 600 in any proportion.
7. The method for preparing a photocurable vinyl ester resin-modified castor oil-based urethane acrylate resin according to any one of claims 1 to 6, wherein the photocurable vinyl ester resin-modified castor oil-based urethane acrylate resin is obtained by uniformly stirring and mixing the vinyl ester resin, the castor oil-based urethane acrylate and the photoinitiator.
8. Use of a photocurable vinyl ester resin modified castor oil based polyurethane acrylate resin according to any one of claims 1-6 in a UV curable coating, a UV curable ink, a UV curable adhesive or 3D printing.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157077A (en) * 1990-04-27 1992-10-20 The B. F. Goodrich Company Epoxy resin systems modified with statistical monofunctional reactive polymers
CN102079810A (en) * 2010-12-15 2011-06-01 北京航空航天大学 Synthesis and application of light-cured polyurethane-acrylic acid-epoxy resin adhesive
CN105367754A (en) * 2015-07-16 2016-03-02 漳州亚邦化学有限公司 M-benzene type epoxy vinyl ester glass fiber reinforced plastic resin and synthetic method thereof
CN106866929A (en) * 2017-02-24 2017-06-20 中国林业科学研究院林产化学工业研究所 A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application
CN108164679A (en) * 2016-12-07 2018-06-15 西宁晶海科教化玻仪器有限公司 A kind of corrosion-resistant epoxy vinyl ester resin of high molecular weight and its production method
CN110054757A (en) * 2019-04-26 2019-07-26 永悦科技股份有限公司 A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157077A (en) * 1990-04-27 1992-10-20 The B. F. Goodrich Company Epoxy resin systems modified with statistical monofunctional reactive polymers
CN102079810A (en) * 2010-12-15 2011-06-01 北京航空航天大学 Synthesis and application of light-cured polyurethane-acrylic acid-epoxy resin adhesive
CN105367754A (en) * 2015-07-16 2016-03-02 漳州亚邦化学有限公司 M-benzene type epoxy vinyl ester glass fiber reinforced plastic resin and synthetic method thereof
CN108164679A (en) * 2016-12-07 2018-06-15 西宁晶海科教化玻仪器有限公司 A kind of corrosion-resistant epoxy vinyl ester resin of high molecular weight and its production method
CN106866929A (en) * 2017-02-24 2017-06-20 中国林业科学研究院林产化学工业研究所 A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application
CN110054757A (en) * 2019-04-26 2019-07-26 永悦科技股份有限公司 A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin

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