CN109097198B - Tri-functional castor oil based UV curing prepolymer and preparation method and application thereof - Google Patents

Tri-functional castor oil based UV curing prepolymer and preparation method and application thereof Download PDF

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CN109097198B
CN109097198B CN201810742664.3A CN201810742664A CN109097198B CN 109097198 B CN109097198 B CN 109097198B CN 201810742664 A CN201810742664 A CN 201810742664A CN 109097198 B CN109097198 B CN 109097198B
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castor oil
curing
prepolymer
heating
parts
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CN109097198A (en
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袁腾
梁斌
杨卓鸿
满丽敏
苏宇沛
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South China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of 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
    • 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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • 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
    • C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof

Abstract

The invention belongs to the technical field of UV curing materials, and discloses a trifunctional castor oil based UV curing prepolymer, and a preparation method and application thereof. The preparation method comprises the following steps: (1) heating castor oil and sulfhydryl fatty acid to catalyze esterification reaction to obtain castor oil triacid; (2) preheating castor oil triacid, adding a catalyst N, N-dimethylethanolamine, hydroquinone and acrylate, and heating for reaction to obtain the trifunctional castor oil based UV curing prepolymer. The trifunctional castor oil-based UV curing prepolymer prepared by the invention contains (methyl) acryloyloxy, so that the trifunctional castor oil-based UV curing prepolymer has high UV curing activity, can be quickly cured into a film within 10-60 s, has excellent comprehensive performance, can meet the application requirement of a UV curing material, can be applied to the field of UV curing materials, has the castor oil content of more than 54% in the UV curing prepolymer, and greatly reduces the consumption of traditional petrochemical raw materials.

Description

Tri-functional castor oil based UV curing prepolymer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of UV curing materials, and particularly relates to a trifunctional castor oil based UV curing prepolymer, and a preparation method and application thereof.
Background
The newly revised air pollution prevention and control law of the people's republic of China has been applied in 2016 (1/1), the fact that the paint with low volatile organic matter content needs to be used is determined in the form of national regulations for the first time, and the new environmental protection law provides a severe test for the VOC emission of the paint industry. At present, five departments such as the environmental protection hall of Guangdong province jointly issue a Volatile Organic Compounds (VOCs) treatment and emission reduction working scheme (2018 and 2020). For the furniture manufacturing industry, the working scheme clearly provides that the water-based ultraviolet curing coating with low VOC content is vigorously popularized and used aiming at the wood furniture manufacturing, and the substitution proportion reaches more than 60 percent by 2020. The Shenzhen city in 2018 comprehensively completes the production process transformation of the low-volatility paint in furniture enterprises. The UV curing coating mainly comprises an active diluent, a prepolymer, a photoinitiator, an auxiliary agent and the like, and is rapidly developed due to the advantages of high curing speed, low curing temperature, low pollution, energy conservation and the like. However, the raw materials of the traditional UV curing coating are mainly from petrochemical resources, wherein the prepolymers are mainly prepolymers containing unsaturated acrylate double bonds, such as UV curing polyurethane acrylate, UV curing polyurethane epoxy resin, UV curing polyester acrylic resin, UV curing polyether acrylic resin and the like, and the raw materials for preparing the prepolymers, such as diisocyanate, acrylic hydroxyl ester, dihydric alcohol and the like, come from the traditional petrochemical route; the active diluent is mainly substance containing UV curing active double bond such as acrylic acid hydroxy ester. Therefore, the problems of large consumption of petrochemical resources and high pollution exist.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a preparation method of a trifunctional castor oil based UV curing prepolymer.
According to the invention, the trifunctional castor oil-based UV curing prepolymer is synthesized by taking castor oil as a raw material, the content of castor oil in the prepared prepolymer is more than 54%, the use amount of petrochemical resource raw materials in the UV curing prepolymer is greatly reduced, the pollution is low, and the environment is protected.
Another object of the present invention is to provide a trifunctional castor oil-based UV curable prepolymer prepared by the above method. The prepolymer disclosed by the invention has the advantages of high vegetable oil content, high curing activity, high drying speed, excellent performance of a cured film and the like.
The invention further aims to provide application of the trifunctional castor oil-based UV curing prepolymer in the field of UV curing materials.
The purpose of the invention is realized by the following scheme:
a preparation method of a trifunctional castor oil based UV curing prepolymer comprises the following steps:
(1) heating castor oil and sulfhydryl fatty acid to catalyze esterification reaction to obtain castor oil triacid;
(2) preheating castor oil triacid, adding a catalyst N, N-dimethylethanolamine, hydroquinone and acrylate, and heating for reaction to obtain the trifunctional castor oil based UV curing prepolymer.
The weight ratio of each component is as follows:
step (1), 20-30 parts of castor oil; 11-18 parts of mercapto fatty acid;
20-30 parts of castor oil triacid; 0.14-0.22 part of hydroquinone; 7-10.6 parts of acrylate.
The dosage of the catalyst N, N-dimethylethanolamine is catalytic amount, and preferably 0.2-0.32 part by mass.
In the preparation method of the invention, the mercapto fatty acid can be at least one of thioglycolic acid, mercaptopropionic acid, 2-mercaptobutyric acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid and the like.
The acrylate may be at least one of glycidyl acrylate and glycidyl methacrylate.
In the step (1), the heating is preferably carried out to 70-80 ℃.
In the step (1), the reaction time is preferably 20-24 h.
In step (1), the reaction is preferably carried out in an organic solvent environment, such as chloroform and the like.
In the step (1), the catalyst for catalyzing esterification is a conventional esterification catalyst, such as azobisisobutyronitrile and the like, and the amount of the catalyst is a catalytic amount, preferably 2.1-3.2 parts by mass.
In the step (1), purification treatment can be performed after the reaction to obtain purified castor oil triacid, and the purified castor oil triacid is used for the next reaction. The purification treatment preferably comprises the following steps: and (3) mixing and dissolving the reaction solution after the reaction by using a large amount of diethyl ether and acetone (wherein the volume ratio of the diethyl ether to the acetone is more than 1:1), repeatedly washing by using saturated saline solution, and finally performing rotary distillation to obtain viscous liquid castor oil triacid.
In the step (2), the heating reaction is preferably carried out by heating to 85-95 ℃ and stirring for 2-3 h.
In the step (2), the preheating is preferably carried out to 50-60 ℃. After the N, N-dimethylethanolamine is added, the mixture is preferably continuously heated to 75-80 ℃, and then hydroquinone and acrylic ester are added.
In the step (2), purification treatment may be performed after the heating reaction is completed. The purification treatment comprises the following steps: and dissolving the reaction solution after the reaction is hot by using a solvent, repeatedly washing the reaction solution by using saturated salt solution, and finally carrying out rotary distillation to obtain a viscous liquid castor oil based trifunctional UV curing prepolymer, wherein the solvent is preferably dichloromethane.
The derivatives developed by the vegetable oil are widely applied to the production of high polymer materials, are mainly applied to materials such as coatings, printing ink, polyurethane and the like and fine chemical products at present, well replace petrochemical products, and have important economic and scientific values for research. According to the invention, castor oil and glycidyl (meth) acrylate are subjected to a grafting reaction to synthesize a trifunctional UV-cured castor oil-based prepolymer, vegetable oil is introduced into a UV-cured material system to partially replace raw materials of a fossil resource route, and the resource crisis is alleviated.
The trifunctional castor oil-based UV curing prepolymer prepared by the invention contains (methyl) acryloyloxy, so that the trifunctional castor oil-based UV curing prepolymer has high UV curing activity, can be quickly cured into a film within 10-60 s, and the cured film has excellent comprehensive performance and can meet the application requirements of UV curing materials.
The invention also provides application of the trifunctional castor oil-based UV curing prepolymer in the field of UV curing materials, in particular application in the fields of UV curing materials such as UV curing coatings, printing ink, adhesives and 3D printing.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, inedible natural renewable resource vegetable oil is introduced into a light curing material system to synthesize a castor oil-based trifunctional UV curing prepolymer, so that the content of castor oil in the UV curing prepolymer is more than 54%, thereby greatly reducing the use amount of traditional petrochemical raw materials in the UV curing prepolymer and reducing half; on one hand, the method opens up a new application field for natural materials, improves the use value of the natural materials, has excellent popularization significance for the development of forestry economy, and on the other hand, greatly relieves the pressure of petrochemical industry.
(2) The castor oil content of the prepolymer of the invention is more than 54 percent, the natural plant resource has excellent biodegradability, and on the other hand, the castor oil-based trifunctional UV-curing prepolymer contains 9 aliphatic ester bonds in each molecule, and the aliphatic ester bonds are more than carbamate and more than aliphatic ether bonds more than methylene according to the biodegradability of the polymer, so the prepolymer of the invention has excellent biodegradability.
Drawings
FIG. 1 is a schematic diagram of the chemical reaction of the preparation method of the present invention.
FIG. 2 is an infrared spectrum of the product prepared in example 1, wherein (a) is the starting material castor oil, (b) is castor oil triacid, and (c) is castor oil based trifunctional UV curable prepolymer.
FIG. 3 is a NMR spectrum of castor oil based trifunctional UV curable prepolymer prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available. For process parameters not specifically noted, reference may be made to conventional techniques.
The castor oil-based trifunctional UV-curing prepolymer prepared by taking thioglycolic acid as a raw material and the synthetic reaction formula thereof are shown in figure 1, and the castor oil-based trifunctional UV-curing prepolymer prepared by taking other thioglycolic acid and the synthetic reaction formula thereof are similar.
Example 1
According to the mass volume parts, g/mL, 30 parts of castor oil, 3.2 parts of azodiisobutyronitrile, 18 parts of thioglycollic acid and 50 parts of trichloromethane are sequentially added into a three-neck flask with a stirring device and a condensing device, uniformly stirred and heated to 80 ℃ for reaction for 24 hours. And purifying the A to obtain viscous liquid castor oil triacid. Adding 30 parts of castor oil triacid into a reaction bottle, heating to 60 ℃, adding 0.32 part of N, N-dimethylethanolamine, continuously heating to 80 ℃, adding 0.22 part of hydroquinone and 10.6 parts of glycidyl methacrylate, heating to 95 ℃, stirring for reaction for 3 hours, and purifying to obtain the castor oil based trifunctional UV curing prepolymer.
Purification treatment a preferably comprises the following steps: and (3) mixing and dissolving the reaction solution after the reaction by using a large amount of diethyl ether and acetone (wherein the volume ratio of the diethyl ether to the acetone is more than 1:1), repeatedly washing by using saturated saline solution, and finally performing rotary distillation to obtain viscous liquid castor oil triacid.
The purification treatment B preferably comprises the following steps: and dissolving the reaction solution after the reaction is hot by using a solvent, repeatedly washing the reaction solution by using saturated salt solution, and finally carrying out rotary distillation to obtain a viscous liquid castor oil based trifunctional UV curing prepolymer, wherein the solvent is preferably dichloromethane.
The samples were tested by a Fourier Infrared spectrometer model AVATAR 360FT-IR from Nicolet, USA, and the results are shown in FIG. 2, the IR spectrum of the raw materials Castor Oil (CO), castor oil triacid (MCO) and castor oil based trifunctional UV-curable prepolymer (MCOG). From the FTIR spectrum, it can be seen that CO, MCO and MCOG all have a peak value of 2928cm-1、2855cm-1、1738cm-1Characteristic peaks of-CH respectively2Asymmetric stretching vibration and symmetric stretching vibration of-and a characteristic peak of C ═ O bond on ester group. Compared with CO, the carbon dioxide is 2450-3450 cm in MCO-1The absorption peak of hydrogen bond association on the hydroxyl in the carboxyl appears, the absorption peak of the hydroxyl is widened by the hydrogen bond association, and the absorption peak is overlapped with the absorption peaks of methyl and methylene, so that a wide absorption band is formed, and the absorption band is 1714cm-1The characteristic absorption of the C ═ O bond at the carboxyl group was clearly found, and 1655cm-1The absorption peak of C ═ C double bond on castor oil chain disappears, which shows that the carbon-carbon double bond on thioglycolic acid and castor oil has addition reaction; compared with MCO, the MCOG is 3438cm-1OfThe absorption peak becomes narrower than that of the CO at the position, which indicates that the carboxyl in the MCOG reacts with the epoxy group on the glycidyl methacrylate basically and completely, and a new hydroxyl value is generated, which is 1738cm in the MCOG-1The absorption peak appeared in (A) is that epoxy group of glycidyl methacrylate forms new ester group with carboxyl group to strengthen the absorption peak, and 1638cm-1The absorption peak is the absorption peak of C ═ C double bond on the glycidyl methacrylate, and 809cm is simultaneously observed-1The absorption peak appearing there is also the absorption peak for the C — H bond above the C ═ C double bond on glycidyl methacrylate. The successful synthesis of castor oil based trifunctional UV curable prepolymer (MCOG) was demonstrated by the above infrared spectrograms.
The samples were tested on a Bruker AV 600 NMR spectrometer from Bruker Biospin AG, Switzerland and the results are shown in FIG. 3. As shown in fig. 3, a hydrogen peak of C ═ C double bond bis appears at 5.6 to 6.3 ppm; 4.1 to 4.5ppm of-CH of GMA2A middle hydrogen peak, a hydrogen peak appearing at 3.5 to 3.7ppm is-CH connected with a hydroxyl after an epoxy group is opened2-hydrogen peak; between 2.0 and 2.5ppm of mercapto-linked-CH2Hydrogen peak of-and-CH on GMA3And the appearance of these peaks indicates that the experiment successfully synthesized MCOG.
Example 2
According to the mass volume parts, g/mL, 20 parts of castor oil, 2.1 parts of azodiisobutyronitrile, 11 parts of thioglycollic acid and 30 parts of trichloromethane are sequentially added into a three-neck flask with a stirring device and a condensing device, uniformly stirred and heated to 70 ℃ for reaction for 20 hours. Purifying to obtain viscous liquid castor oil triacid. Adding 20 parts of castor oil triacid into a reaction bottle, heating to 50 ℃, adding 0.20 part of N, N-dimethylethanolamine, continuously heating to 75 ℃, adding 0.14 part of hydroquinone and 7.0 parts of glycidyl acrylate, heating to 85 ℃, stirring for reaction for 2 hours, and purifying to obtain the castor oil based trifunctional UV curing prepolymer. The samples were tested on an AVATAR 360FT-IR Fourier Infrared spectrometer from Nicolet, USA, and a Bruker AV 600 NMR spectrometer from Bruker Biospin AG, Switzerland, and the characteristic peaks of the spectra were similar to those in FIGS. 2 and 3.
Example 3
According to the mass volume parts, g/mL, 25 parts of castor oil, 3 parts of azodiisobutyronitrile, 16 parts of mercaptopropionic acid and 40 parts of trichloromethane are sequentially added into a three-neck flask with a stirring device and a condensing device, uniformly stirred and heated to 75 ℃ for reaction for 22 hours. Purifying to obtain viscous liquid castor oil triacid. Adding 25 parts of castor oil triacid into a reaction bottle, heating to 55 ℃, adding 0.26 part of N, N-dimethylethanolamine, continuously heating to 77 ℃, adding 0.18 part of hydroquinone and 9.6 parts of glycidyl methacrylate, heating to 90 ℃, stirring for reacting for 2.5h, and purifying to obtain the castor oil based trifunctional UV curing prepolymer. The samples were tested on an AVATAR 360FT-IR Fourier Infrared spectrometer from Nicolet, USA, and a Bruker AV 600 NMR spectrometer from Bruker Biospin AG, Switzerland, and the characteristic peaks of the spectra were similar to those in FIGS. 2 and 3.
Example 4
According to the mass volume parts, g/mL, 25 parts of castor oil, 2.7 parts of azodiisobutyronitrile, 15 parts of 2-mercaptobutyric acid and 40 parts of trichloromethane are sequentially added into a three-neck flask with a stirring device and a condensing device, uniformly stirred and heated to 75 ℃ for reaction for 20 hours. Purifying to obtain viscous liquid castor oil triacid. Adding 25 parts of castor oil triacid into a reaction bottle, heating to 60 ℃, adding 0.32 part of N, N-dimethylethanolamine, continuously heating to 80 ℃, adding 0.22 part of hydroquinone and 7.0 parts of glycidyl acrylate, heating to 85 ℃, stirring for reaction for 2 hours, and purifying to obtain the castor oil based trifunctional UV curing prepolymer. The samples were tested on an AVATAR 360FT-IR Fourier Infrared spectrometer from Nicolet, USA, and a Bruker AV 600 NMR spectrometer from Bruker Biospin AG, Switzerland, and the characteristic peaks of the spectra were similar to those in FIGS. 2 and 3.
Example 5
According to the mass volume parts, g/mL, 30 parts of castor oil, 2.1 parts of azodiisobutyronitrile, 11 parts of 3-mercaptobutyric acid and 30 parts of trichloromethane are sequentially added into a three-neck flask with a stirring device and a condensing device, uniformly stirred and heated to 80 ℃ for reaction for 24 hours. Purifying to obtain viscous liquid castor oil triacid. Adding 30 parts of castor oil triacid into a reaction bottle, heating to 55 ℃, adding 0.32 part of N, N-dimethylethanolamine, continuously heating to 80 ℃, adding 0.22 part of hydroquinone and 10.6 parts of glycidyl methacrylate, heating to 90 ℃, stirring for reaction for 3 hours, and purifying to obtain the castor oil based trifunctional UV curing prepolymer. The samples were tested on an AVATAR 360FT-IR Fourier Infrared spectrometer from Nicolet, USA, and a Bruker AV 600 NMR spectrometer from Bruker Biospin AG, Switzerland, and the characteristic peaks of the spectra were similar to those in FIGS. 2 and 3.
Example 6
According to the mass volume parts, g/mL, 30 parts of castor oil, 3.2 parts of azodiisobutyronitrile, 15 parts of 4-mercaptobutyric acid and 40 parts of trichloromethane are sequentially added into a three-neck flask with a stirring device and a condensing device, uniformly stirred and heated to 75 ℃ for reaction for 22 hours. Purifying to obtain viscous liquid castor oil triacid. Adding 25 parts of castor oil triacid into a reaction bottle, heating to 60 ℃, adding 0.32 part of N, N-dimethylethanolamine, continuously heating to 80 ℃, adding 0.22 part of hydroquinone and 10.6 parts of glycidyl acrylate, heating to 90 ℃, stirring for reaction for 3 hours, and purifying to obtain the castor oil based trifunctional UV curing prepolymer. The samples were tested on an AVATAR 360FT-IR Fourier Infrared spectrometer from Nicolet, USA, and a Bruker AV 600 NMR spectrometer from Bruker Biospin AG, Switzerland, and the characteristic peaks of the spectra were similar to those in FIGS. 2 and 3.
Castor oil based trifunctional UV-curing prepolymer and cured film property test examples thereof
The castor oil based trifunctional UV curing prepolymer prepared in each embodiment is mixed with a reactive diluent according to the mass ratio of 7:3, a photoinitiator 1173 is added, then the mixture is uniformly coated on the surface of a polytetrafluoroethylene plate, and the polytetrafluoroethylene plate is subjected to UV curing for 15-30 s under a 2500W ultraviolet lamp with the ultraviolet wavelength of 245-405 nm, so that the relevant performance of a curing film is tested. Surface drying time test according to GB1728-79, a piece of filter paper is pressed on a cured film by a 200g dry weight, the weight is removed after a certain time, the cured film is turned over, and the filter paper can fall freely, namely the cured film is considered to be surface dried. Pencil hardness test method reference is made to Standard ASTM D3363-2005 "Standard test method for measuring coating hardness by Pencil test method". And (3) thermal stability analysis (heat loss Tmax analysis), namely, testing and representing the resin by adopting a model DTG-60 thermogravimetric analyzer of Shimadzu corporation in Japan, wherein the heating rate is as follows: 20 ℃/min; atmosphere: nitrogen gas; crucible material: an aluminum crucible. The thermal degradation temperature at which the mass loss of each example reached 5% was recorded. The storage modulus test is carried out by dynamic thermomechanical analysis (DMA) in a film tension mode of 1Hz in Netzsch DMA 242C dynamic mechanical analysis, the sizes of all samples are 20mm multiplied by 6mm multiplied by 0.5mm, the heating rate is 3 ℃/min and the temperature is minus 80 to 150 ℃. The glass transition temperature (Tg) of the film results from the peak of the tan curve of the DMA test curve. The biodegradability test adopts a sealed compost biodegradation test, the decomposition degree of a film of a cured film is determined by the mineralization rate, and the higher the mineralization rate is, the better the biodegradability is.
Table 1 results of comprehensive performance test of products of each example
Figure BDA0001723574760000081
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (6)

1. A trifunctional castor oil based UV curing prepolymer is characterized by being prepared by the following steps:
(1) heating and catalyzing castor oil and sulfhydryl fatty acid to perform addition reaction to obtain castor oil triacid;
(2) preheating castor oil triacid, adding a catalyst N, N-dimethylethanolamine, hydroquinone and acrylate, and heating for reaction to obtain a trifunctional castor oil based UV curing prepolymer;
the mercapto fatty acid is at least one of thioglycolic acid, mercaptopropionic acid, 2-mercaptobutyric acid, 3-mercaptobutyric acid and 4-mercaptobutyric acid;
the weight ratio of each component is as follows:
step (1), 20-30 parts of castor oil; 11-18 parts of mercapto fatty acid;
20-30 parts of castor oil triacid; 0.14-0.22 part of hydroquinone; 7-10.6 parts of acrylate;
the acrylate is at least one of glycidyl acrylate and glycidyl methacrylate.
2. The tri-functional castor oil based UV curable prepolymer of claim 1, wherein: in the step (1), heating is carried out to 70-80 ℃; the reaction time is 20-24 h.
3. The tri-functional castor oil based UV curable prepolymer of claim 1, wherein: in the step (2), the heating reaction is heating to 85-95 ℃, and stirring for 2-3 hours.
4. The tri-functional castor oil based UV curable prepolymer of claim 1, wherein: in the step (2), the preheating is carried out by heating to 50-60 ℃.
5. The tri-functional castor oil based UV curable prepolymer of claim 1, wherein: and (2) after adding the N, N-dimethylethanolamine, continuously heating to 75-80 ℃, and then adding hydroquinone and acrylate.
6. Use of the trifunctional castor oil-based UV-curable prepolymer according to claim 1 in the field of UV-curable materials.
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