CN111909075A - Rigid acrylate UV (ultraviolet) photocuring modified tung oil resin with high double bond content and preparation method and application thereof - Google Patents

Rigid acrylate UV (ultraviolet) photocuring modified tung oil resin with high double bond content and preparation method and application thereof Download PDF

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CN111909075A
CN111909075A CN202010817120.6A CN202010817120A CN111909075A CN 111909075 A CN111909075 A CN 111909075A CN 202010817120 A CN202010817120 A CN 202010817120A CN 111909075 A CN111909075 A CN 111909075A
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tung oil
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黄玉科
李娟�
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Guangzhou Xierde New Material Technology Co ltd
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    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
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Abstract

The invention belongs to the technical field of high-molecular coatings, printing ink and adhesives, and discloses a rigid acrylate UV (ultraviolet) photocuring modified tung oil resin with high double bond content, and a preparation method and application thereof. The structure of the rigid acrylate UV photocuring modified tung oil resin with high double bond content contains a ring-shaped tetra/hexahydrophthalimide group with higher rigidity and more (methyl) acrylate structures. Upon exposure to UV radiation, the multiple acrylate double bonds polymerize to form a crosslinked network; meanwhile, a plurality of hydroxyl groups generated after the epoxy group of the glycidyl (meth) acrylate is consumed and a tetra/hexahydro o-phenylmaleimide structure with larger polarity enhance intermolecular force between the cured film and the surface of the substrate. The resin provided by the invention is simple in preparation method, the product structural characteristics are beneficial to improving the hardness of the UV curing film and the adhesive force between the curing film and the base material, and the resin can be applied to the fields of high-molecular coatings, printing ink, adhesives and the like.

Description

Rigid acrylate UV (ultraviolet) photocuring modified tung oil resin with high double bond content and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high-molecular coatings, printing ink and adhesives, and particularly relates to a high-double-bond-content rigid acrylate UV (ultraviolet) photocuring modified tung oil resin as well as a preparation method and application thereof.
Background
Compared with a thermal curing technology, UV light curing is a more environment-friendly resin curing technology, and has the advantages of high curing speed, high production efficiency and low operation temperature. Therefore, the UV light curing technology is widely used in the fields of coatings, adhesives, inks, packaging materials, 3D printing, and the like. At present, most of resins for UV light curing are derived from petrochemical raw materials, but the production cost of the petrochemical raw materials is high, and the production conditions have great harm to the environment.
Natural vegetable oil is a renewable energy source with low production cost, and modifying natural vegetable oil is an important way to obtain low-cost UV light-cured resin, which is a feasible solution to alleviate the current energy shortage and reduce environmental pollution. Tung oil is a common vegetable oil, and modified resins based on tung oil have been used in the industrial fields of coatings, inks, adhesives and the like.
In addition, acrylic resins are the basic materials of the chemical industry and also the main components of curable resins, which largely determine the application properties of the cured film, and thus the modification of tung oil with acrylic resins is the most common way. Although the advantages of acrylate modified tung oil resins are many, there are also disadvantages. For example, acrylate-modified tung oil resins generally have longer fatty chains and lower densities of double bonds and rigid groups, which results in weaker intramolecular and intermolecular interactions, and lower hardness and adhesion to substrates of the cured films. If a ring structure is introduced into the structure, the rigidity of the structure can be effectively improved; but the condition for introducing a cyclic structure is harsh, the existing reaction method generally needs to consume a large amount of organic solvent, the reaction temperature is higher (more than 120 ℃), the degradation and oxidation of a resin molecular chain are aggravated under the high-temperature reaction condition, and a large amount of energy is also consumed; at the same time, the introduction of a rigid structure can have an effect on the adhesion. Therefore, how to provide the novel acrylic acid UV photocuring modified tung oil resin which has higher hardness and excellent substrate adhesion and is simple and feasible in preparation method has positive significance for expanding the application of the vegetable oil resin in the industrial fields of coatings, adhesives, packaging materials, printing ink, 3D printing and the like.
Disclosure of Invention
In order to overcome the structural defects and shortcomings of the acrylate modified tung oil resin in the prior art, the invention mainly aims to provide the rigid acrylate UV photocuring modified tung oil resin with high double bond content. The UV light-cured modified tung oil resin cured film has obviously improved hardness and excellent substrate adhesion.
The invention also aims to provide a preparation method of the UV light-cured modified tung oil resin.
The invention further aims to provide application of the UV photocuring modified tung oil resin.
The purpose of the invention is realized by the following scheme:
a rigid acrylate UV photocuring modified tung oil resin with high double bond content has the following structural formula:
Figure BDA0002633125790000021
wherein the content of the first and second substances,
Figure BDA0002633125790000031
or- (CH)2)n-，n＝1-5；
R2is-H or-CH3；
Figure BDA0002633125790000032
As shown in the formula, the structure of the rigid acrylate UV photocuring modified tung oil resin with high double bond content contains a ring-shaped tetra/hexahydrophthalimide group with higher rigidity and more (methyl) acrylate structures. Wherein the radical R1May be a phenyl group or a methylene repeat unit of C1-5, group R2Is hydrogen or methyl; radical R3Is characterized by containing 1-2 (methyl) acrylate double bonds and hydroxyl groups.
Based on the structural characteristics, the resin is coated on the surface of a substrate, and can be cured into a film on the surface of the substrate by initiating the photocrosslinking polymerization reaction of the resin by a proper UV photoinitiator under the irradiation of ultraviolet-visible light, and the obtained cured film has remarkably improved hardness and substrate adhesion.
The invention also provides a preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content, which comprises the following steps:
(1) according to Diels-Alder reaction, modifying tung oil resin by using N-maleimide carboxylic acid to obtain modified tung oil resin (resin A) containing tetrahydrophthalic maleimide group;
(2) according to the Thiol-ene click reaction, modifying the modified tung oil resin obtained in the step (1) by using a mercapto-containing mono-or dicarboxylic acid/alcohol to prepare a modified tung oil resin (resin B) containing a tetra/hexahydro o-maleimide group;
(3) and then the UV light-cured modified tung oil resin is synthesized by ring-opening reaction with epoxy acrylate.
The reaction process of the step (1) is shown as the following formula (II):
Figure BDA0002633125790000041
radical R1The structure of (A) can be seen in formula (I), and can be a phenyl group or a methylene repeating unit of C1-5.
The step (1) is specifically that the tung oil and the N-maleimide carboxylic acid are subjected to Diels-Alder cycloaddition reaction. The obtained product contains a tetrahydrophthalimide structure.
The N-maleimidocarboxylic acid may be at least one of 3-maleimidobenzoic acid, 4-maleimidobenzoic acid, 2-maleimidoacetic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 5-maleimidovaleric acid, 6-maleimidocaproic acid, etc.
The molar ratio of tung oil to N-maleimidocarboxylic acid used is preferably from 1:1 to 1: 3.
The reaction time is preferably 1-8 h; the temperature of the reaction is preferably 60 to 120 ℃.
Polymerization inhibitor is used in the reaction; the polymerization inhibitor may be at least one of 4-Methoxyphenol (MEHQ), Hydroquinone (HQ), and tert-butylhydroquinone (TBHQ). The molar ratio of the tung oil to the polymerization inhibitor is 1:0.01-1: 0.05.
Further, the reaction may be carried out under catalysis of a catalyst; the catalyst can be at least one of zinc chloride, aluminum chloride, stannous octoate, dibutyltin dilaurate and the like. When a catalyst is used, the molar ratio of tung oil to catalyst used is from 1:0.1 to 1: 0.01. The product does not need to be purified.
The reaction process of the step (2) is shown as the following formula (III):
Figure BDA0002633125790000051
step (2) is specifically carried out by using R4Carrying out Thiol-ene free radical addition reaction on the-SH and the modified tung oil resin (resin A) prepared in the step (1) under the action of an initiator.
R4-SH is a mercapto-containing mono-or dicarboxylic acid/alcohol; specifically, R4the-SH may be at least one of 2-mercaptoethanol, 2-mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptosuccinic acid, 1-thioglycerol, and the like.
Resins A and R used4The molar ratio of-SH is preferably from 1:3 to 1: 6.
The molar ratio of resin A used to initiator is preferably from 1:0.01 to 1: 0.05.
The Thiol-ene reaction can be initiated by photoinitiators under UV radiation or by thermal initiators under heating.
When a photoinitiator is used for initiation, the reaction time is preferably from 0.5 to 4 h. The temperature of the reaction is preferably 10 to 30 ℃.
When a thermal initiator is used for initiation, the reaction time is preferably from 0.5 to 8 h. The temperature of the reaction is preferably 60 to 80 ℃.
The photoinitiator can be at least one of DAROCUR1173, IRGACURE184, IRGACURE651, IRGACURE2959, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L) and the like.
The light source of the UV radiation can be a medium-pressure mercury lamp, a low-mercury lamp, a UV-LED lamp and the like; the wavelength range is preferably the middle-long wave band (290-420nm) of the ultraviolet-visible light region; the light intensity is preferably 5-100mW/cm2. The product does not need to be purified.
The thermal initiator may be at least one of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), and the like. The product does not need to be purified.
Specifically, in the step (3), a ring-opening reaction is performed between the epoxy acrylate and the carboxyl/hydroxyl group contained in the resin B prepared in the step (2).
The epoxy acrylate may be at least one of Glycidyl Acrylate (GA) and Glycidyl Methacrylate (GMA), etc.
The molar ratio of resin B and epoxy acrylate used is preferably from 1:5 to 1: 15.
The reaction time is preferably 2 to 8 hours. The temperature of the reaction is preferably 80 to 120 ℃.
The reaction is preferably carried out under catalysis of a catalyst; the catalyst may be at least one of triphenyl phosphine (TPP), Triethylamine (TEA), N-methylmorpholine, N-Dimethylbenzylamine (DMBA), and the like. The molar ratio of resin B used to catalyst is preferably from 1:0.1 to 1: 0.6.
Polymerization inhibitor is used in the reaction; the polymerization inhibitor may be at least one of 4-Methoxyphenol (MEHQ), Hydroquinone (HQ), and tert-butylhydroquinone (TBHQ). The molar ratio of the resin B used to the polymerization inhibitor is preferably from 1:0.01 to 1: 0.05. The product does not need to be purified.
The reaction process of the step (3) is shown as the following formula (IV):
Figure BDA0002633125790000071
the synthetic process of the resin is simple, and the preparation efficiency is high; the structure of the prepared rigid acrylate UV photocuring modified tung oil resin with high double bond content contains a ring-shaped tetra/hexahydrophthalimide group with higher rigidity and more (methyl) acrylate structures; upon exposure to UV radiation, the multiple acrylate double bonds polymerize to form a crosslinked network; meanwhile, a plurality of hydroxyl groups generated after the epoxy group of the glycidyl (meth) acrylate is consumed and a tetra/hexahydro o-phenylmaleimide structure with larger polarity enhance intermolecular force between the cured film and the surface of the substrate. The structural characteristics of the resin are beneficial to improving the hardness of the UV curing film and the adhesive force between the curing film and the base material, and the resin can be applied to the fields of high molecular coatings, printing ink and adhesives. For example, the composition can be applied to the surface of a substrate such as plastic, metal or ceramic, and polymerization is initiated by a photoinitiator under UV irradiation, thereby finally forming a cured film on the surface of the substrate.
The specific operation is as follows: the acrylate UV photocuring modified tung oil resin and the photoinitiator are uniformly mixed, the surface of the base material is coated with a film, the crosslinking polymerization reaction is initiated under the UV irradiation, and the film is formed on the surface of the base material by curing.
The photoinitiator can be at least one of 2-isopropyl thioxanthone, benzophenone, DAROCUR1173, IRGACURE184, IRGACURE651, IRGACURE2959, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate (TPO-L).
The content of the photoinitiator in the system is 0.05-5 wt%.
The thickness of the coating film is preferably 10 to 1000. mu.m.
The light source of the UV radiation can be a medium-pressure mercury lamp, a low-mercury lamp, a UV-LED lamp and the like; the wavelength range is preferably the middle-long wave band (290-420nm) of the ultraviolet-visible light region; the light intensity is preferably 5-100mW/cm2(ii) a The irradiation time is preferably 10 to 600 s.
The substrate can be plastic, metal, ceramic and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the acrylic ester UV photocuring modified tung oil resin has simple synthesis process and high preparation efficiency;
(2) the acrylate UV photocuring modified tung oil resin contains a large-rigidity annular tetra/hexahydrophthalimide structure, more acrylate double bonds and a plurality of groups with strong polarity, and is beneficial to improving the hardness of a curing film and the adhesive force between the curing film and a base material;
(3) the acrylate UV photocuring modified tung oil resin has wide application in the fields of high polymer coatings, adhesives and printing ink.
Drawings
FIG. 1 shows the final product of example 11H NMR chart.
FIG. 2 is a chart of the infrared spectra of the resin of example 4 before and after UV light cure.
FIG. 3 is a UV light cure kinetics curve for the resin of example 5.
FIG. 4 is a graph of the thermal weight loss of a UV-cured film of the resin of example 6.
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 starting materials referred to in the following examples are commercially available. The dosage of each material is g and mL in parts by mass.
Example 1:
(1) synthesis of modified tung oil resin containing tetrahydrophthalic maleimide structure
Tung oil (17.5 parts by mass), 2-maleimidoacetic acid (9.3 parts by mass), MEHQ (0.025 parts by mass) and stannous octoate (0.14 parts by mass) were mixed, heated to 100 ℃, and reacted for 4.0 hours with mechanical stirring. After the reaction is finished, cooling to obtain the 2-maleimide glycine modified tung oil resin with the yield of 100 percent.
(2) Synthesis of tung oil-based resin containing tetrahydrophthalimide structure modified by 1-thioglycerol
Mixing the obtained 2-maleimidoacetic acid modified tung oil resin (13.4 parts by mass), 1-thioglycerol (6.5 parts by mass) and DAROCUR1173(0.42 part by mass), stirring well, and adding 20mW/cm at room temperature2UV-LED lamp (lambda)max365nm) for 1.0 h. After the reaction is finished, the 1-thioglycerol modified tung oil-based resin is obtained, and the yield is 100%.
(3) Synthesis of (methyl) acrylate glycidyl ester modified tung oil resin
The thus-obtained 1-thioglycerol-modified tung oil-based resin (19.9 parts by mass), glycidyl methacrylate (21.3 parts by mass), triphenylphosphine (0.88 part by mass) and 4-methoxyphenol (0.10 part by mass) were mixed, heated to 100 ℃, and then reacted for 6.0 hours with mechanical stirring. And (3) after the reaction is finished, cooling to obtain the final acrylate photocuring UV modified tung oil resin with the yield of 100%.
Of glycidyl methacrylate and products1The H NMR spectrum map is shown in figure 1. As can be seen from the figure, the epoxy signals of glycidyl methacrylate before the reaction were at 2.67ppm, 2.86ppm, 3.25ppm, 4.00ppm and 4.60ppm, and these signals were almost completely disappeared in the product after the reaction, indicating that the methacrylate-modified tung oil-based resin was formed.
Example 2:
(1) synthesis of modified tung oil resin containing tetrahydrophthalic maleimide structure
Tung oil (17.5 parts by mass), 4-maleimidobenzoic acid (13.0 parts by mass), MEHQ (0.025 parts by mass) and stannous octoate (0.14 parts by mass) were mixed, heated to 100 ℃, and reacted for 4.0 hours with mechanical stirring. After the reaction is finished, cooling to obtain the 4-maleimide benzoic acid modified tung oil resin with the yield of 100 percent.
(2) Synthesis of 2-mercaptoacetic acid modified tung oil-based resin containing tetrahydrophthalimide structure
Mixing the obtained 4-maleimidobenzoic acid modified tung oil resin (15.2 parts by mass), 2-mercaptoacetic acid (5.5 parts by mass) and DAROCUR1173(0.42 part by mass), stirring well, and adding 30mW/cm at room temperature2UV-LED lamp (lambda)max365nm) for 1.0 h. After the reaction is finished, the 2-mercaptoacetic acid modified tung oil-based resin is obtained, and the yield is 100%.
(3) Synthesis of (methyl) acrylate glycidyl ester modified tung oil resin
The thus-obtained 2-mercaptoacetic acid-modified tung oil-based resin (20.8 parts by mass), glycidyl acrylate (11.5 parts by mass), triphenylphosphine (0.88 part by mass) and 4-methoxyphenol (0.10 part by mass) were mixed, heated to 100 ℃ and then reacted for 6.0 hours with mechanical stirring. And (3) after the reaction is finished, cooling to obtain the final acrylate photocuring UV modified tung oil resin with the yield of 100%.
Example 3:
(1) synthesis of modified tung oil resin containing tetrahydrophthalic maleimide structure
Tung oil (17.5 parts by mass), 6-maleimidocaproic acid (12.7 parts by mass), MEHQ (0.025 parts by mass) and stannous octoate (0.14 parts by mass) were mixed, heated to 100 ℃, and reacted for 4.0 hours with mechanical stirring. After the reaction is finished, cooling to obtain the 6-maleimidocaproic acid modified tung oil resin with the yield of 100 percent.
(2) Synthesis of 2-mercaptoethanol modified tung oil-based resin containing tetrahydrophthalimide structure
Mixing the obtained 6-maleimidocaproic acid modified tung oil resin (15.1 parts by mass), 2-mercaptoethanol (4.7 parts by mass) and DAROCUR1173(0.42 part by mass), stirring well, and adding 30mW/cm at room temperature2UV-LED lamp (lambda)max365nm) for 1.0 h. After the reaction is finished, the 2-mercaptoethanol modified tung oil-based resin is obtained, and the yield is 100%.
(3) Synthesis of (methyl) acrylate glycidyl ester modified tung oil resin
The thus-obtained 2-mercaptoethanol-modified tung oil-based resin (19.8 parts by mass), glycidyl methacrylate (12.8 parts by mass), triphenylphosphine (0.88 part by mass) and 4-methoxyphenol (0.10 part by mass) were mixed, heated to 100 ℃ and then reacted for 6.0 hours with mechanical stirring. And (3) after the reaction is finished, cooling to obtain the final acrylate photocuring UV modified tung oil resin with the yield of 100%.
Example 4: UV irradiation curing of acrylate modified tung oil resin on surface of plastic substrate
The modified resin of example 1 (4.9 parts by mass) and the photoinitiator TPO (0.1 part by mass) were uniformly mixed at room temperature and roll-coated on the surface of a PC/ABS composite board to a thickness of 250. mu.m. The light intensity is 50mW/cm2UV-LED lamp (lambda)max365nm) for 180 s. The IR spectrum of the mixed resin before and after curing is shown in FIG. 2. As can be seen from the figure, the infrared absorption peak of the carbon-carbon double bond of the acrylate before UV curing is located at 810cm-1And 1635cm-1After curing, the two signals disappear, indicating that the carbon-carbon double bond of the acrylate has cross-linked polymerization reaction under UV irradiation.
Example 5: UV curing kinetics of acrylate UV photocuring modified tung oil resin
The modified resin of example 1 (4.9 parts by mass) and photoinitiator TPO (0.1 part by mass) were uniformly mixed at room temperature, applied to the surface of a KBr chip to a thickness of 100. mu.m, and then irradiated with light having a luminous intensity of 50mW/cm2UV-LED lamp (lambda)max365 nm). Recording the carbon-carbon double bond (C ═ C) of the acrylate by using a Thermo Fisher7600 real-time infrared spectrometer at 1635cm while irradiating-1The change of the characteristic absorption peak area with irradiation time, and finally the conversion rate (C) of the double bond is calculated according to the following formula (1):
Figure BDA0002633125790000111
wherein A is0And AtAt 1635cm, initially and at time t (unit s), respectively, for a carbon-carbon (C ═ C) double bond-1The area of the characteristic absorption peak at (a). The conversion of the double bond obtained is shown in FIG. 3 as a function of the irradiation time. As can be seen from the figure, the conversion of the acrylate carbon-carbon double bonds rises rapidly within 180s, followed by approximately 70%, indicating that the carbon-carbon double bonds undergo cross-linking polymerization under UV irradiation.
Example 6: thermal stability of acrylate UV (ultraviolet) photocuring modified tung oil resin curing film
At room temperature willThe modified resin (4.9 parts by mass) of example 1 and the photoinitiator TPO (0.1 part by mass) were mixed uniformly and applied to the surface of a glass slide to a thickness of 250. mu.m. Placing at a light intensity of 50mW/cm2UV-LED lamp (lambda)max365nm), the cured film was scraped off with an art knife, and 5.0mg was accurately weighed. Finally, the thermogravimetric analyzer of the TGA-50 type (SHIMADZU) was used to determine the thermogravimetric curve of the cured film in the air atmosphere at a heating rate of 10 ℃/min. The thermogravimetric curve of the cured film is shown in FIG. 4. As can be seen from the graph, the thermal decomposition percentage of the cured film at 300 ℃ is less than 5%, indicating that the UV cured film has excellent thermal stability in air.
Example 7: evaluation of adhesion and hardness of cured film on surface of Plastic or Metal substrate
Modified tung oil resins with different contents of tetra/hexahydrophthalimide and C ═ C double bonds were obtained by changing the charge ratio of tung oil, N-maleimidoacetic acid and 1-thioglycerol according to the procedure of example 1.
Adhesion testing: firstly, the prepared acrylate UV photocuring modified tung oil resin and a photoinitiator TPO are uniformly mixed, and the mass percentage of TPO in all samples is maintained at 2%. Uniformly roll-coating the above mixture on the surface of 3M600 adhesive tape with a thickness of 250 μ M, and applying a light intensity of 50mW/cm2UV-LED lamp (lambda)max365nm) was irradiated for 180s to cure the resin. Finally, the magnitude of adhesion between the cured film and the surface of the 3M600 tape was determined according to the specifications of ASTM D3359-90. When in test, the three groups of samples respectively contain 10.6 percent, 13.3 percent and 17.2 percent of tetrahydrophthalimide by mass.
And (3) testing pencil hardness of the cured film: firstly, the prepared acrylate UV photocuring modified tung oil resin and a photoinitiator TPO are uniformly mixed, and the mass percentage of TPO in all samples is maintained at 2%. Secondly, according to the prescribed program of GB/T1727, the mixture is coated on the surface of a tin plate, and then the light intensity is 50mW/cm2UV-LED lamp (lambda)max365nm) was irradiated for 180s to cure the resin. Finally, the pencil hardness of the UV-cured film was determined as specified in GB/T6739-. Quality of acrylate double bond in three groups of samples during testingThe percentage amounts are respectively 9.2%, 8.5% and 7.1%.
The measured adhesion and hardness of the UV cured film of each resin sample are shown in tables 1 and 2.
TABLE 1 adhesion of UV-cured films/substrates
Tetra/hexahydrophthalimide content Adhesion force
10.6％ 3B
13.3％ 4B
17.2％ 4B
TABLE 2 hardness of UV-cured films
Acrylate content of C ═ C double bonds Hardness of pencil
9.2％ 2H
8.5％ 1H
7.1％ HB
The results show that the adhesion of the UV cured film increases with the tetra/hexahydrophthalimide content and the hardness of the cured film increases with the double bond content. The preparation method of the high double bond content rigid acrylate UV photocuring modified tung oil resin is simple and easy to implement, and the cured film obtained by curing has high hardness and excellent substrate adhesion, and has positive significance for expanding the application of the vegetable oil resin in the industrial fields of coatings, adhesives, packaging materials, printing ink, 3D printing and the like.
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 (10)

1. A rigid acrylate UV photocuring modified tung oil resin with high double bond content is characterized in that the structural formula is as follows:
Figure FDA0002633125780000011
wherein the content of the first and second substances,
Figure FDA0002633125780000012
or- (CH)2)n-，n＝1-5；
R2is-H or-CH3；
Figure FDA0002633125780000013
Figure FDA0002633125780000021
2. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content as claimed in claim 1, which is characterized by comprising the following steps: (1) according to Diels-Alder reaction, modifying tung oil resin by using N-maleimide carboxylic acid to obtain modified tung oil resin containing tetrahydrophthalic maleimide group; (2) according to the Thiol-ene click reaction, modifying the modified tung oil resin obtained in the step (1) by using a mercapto-containing mono-or dicarboxylic acid/alcohol to prepare a modified tung oil resin containing a tetra/hexahydro o-maleimide group; (3) and then the UV light-cured modified tung oil resin is synthesized by ring-opening reaction with epoxy acrylate.
3. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content according to claim 2, which is characterized by comprising the following steps: in the step (1), the N-maleimide carboxylic acid comprises at least one of 3-maleimide benzoic acid, 4-maleimide benzoic acid, 2-maleimide acetic acid, 3-maleimide propionic acid, 4-maleimide butyric acid, 5-maleimide valeric acid and 6-maleimide caproic acid; the molar ratio of the tung oil to the N-maleimide carboxylic acid is 1:1-1: 3; the reaction time is 1-8 h; the temperature of the reaction is 60-120 ℃.
4. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content according to claim 2, which is characterized by comprising the following steps: in the step (2), the mercapto-containing mono-or dicarboxylic acid/alcohol comprises at least one of 2-mercaptoethanol, 2-mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptosuccinic acid and 1-thioglycerol; the molar ratio of the modified tung oil resin obtained in the step (1) to the mercapto-containing mono-or dicarboxylic acid/alcohol is 1:3-1: 6.
5. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content according to claim 2, which is characterized by comprising the following steps: in step (2), the Thiol-ene reaction is initiated by a photoinitiator under UV radiation or by a thermal initiator under heating.
6. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content according to claim 5, which is characterized by comprising the following steps:
when a photoinitiator is used for initiation, the reaction time is 0.5-4 h; the reaction temperature is 10-30 ℃;
when a thermal initiator is used for initiation, the reaction time is 0.5-8 h; the temperature of the reaction is 60-80 ℃.
7. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content according to claim 5, which is characterized by comprising the following steps:
the photoinitiator comprises at least one of DAROCUR1173, IRGACURE184, IRGACURE651, IRGACURE2959, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate;
the light source of the UV radiation is a medium-pressure mercury lamp, a low-mercury lamp or a UV-LED lamp; the wavelength range is the medium-long wave band of the ultraviolet-visible light region; the light intensity is 5-100mW/cm2；
The thermal initiator comprises at least one of azobisisobutyronitrile and azobisisoheptonitrile.
8. The preparation method of the rigid acrylate UV photocuring modified tung oil resin with high double bond content according to claim 2, which is characterized by comprising the following steps: in the step (3), the epoxy acrylate comprises at least one of glycidyl acrylate and glycidyl methacrylate; the mole ratio of the modified tung oil resin containing the tetra/hexahydro o-maleimide group to the epoxy acrylate is 1:5-1: 15; the reaction time is 2-8 h; the temperature of the reaction is 80-120 ℃.
9. The use of the rigid acrylate UV light-cured modified tung oil resin with high double bond content of claim 1 in the fields of high molecular coatings, inks and adhesives.
10. The use according to claim 9, characterized by the following specific operations: the rigid acrylate UV photocuring modified tung oil resin with high double bond content as claimed in claim 1 and a photoinitiator are uniformly mixed, the surface of a base material is coated with a film, a crosslinking polymerization reaction is initiated under UV irradiation, and the film is cured on the surface of the base material to form a film.
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TW201134840A (en) * 2009-11-30 2011-10-16 Tamura Seisakusho Kk Curable composition, cured material therefrom, and use thereof
CN102225922A (en) * 2011-04-14 2011-10-26 中山大学 Preparation method of urethane modified tung oil vinylite
CN103614059A (en) * 2013-11-20 2014-03-05 合肥工业大学 Preparation method of aqueous tung oil/acrylic resin insulating paint

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TW201134840A (en) * 2009-11-30 2011-10-16 Tamura Seisakusho Kk Curable composition, cured material therefrom, and use thereof
CN102225922A (en) * 2011-04-14 2011-10-26 中山大学 Preparation method of urethane modified tung oil vinylite
CN103614059A (en) * 2013-11-20 2014-03-05 合肥工业大学 Preparation method of aqueous tung oil/acrylic resin insulating paint

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