Vegetable oil-based epoxy resin material, and preparation method and application thereof

Abstract

The present application relates to the technical fields of epoxy resin synthesis, and particularly relates to a vegetable oil-based epoxy resin material, a preparation method and application thereof; the present application takes glycerol and fatty acid obtained by hydrolysis and separation of vegetable oil as raw materials; the fatty acid is subjected to esterification reaction with a cycloalkene alkanol compound, and the obtained product is subjected to epoxidation reaction to obtain an epoxy cycloalkyl fatty acid ester first monomer; the glycerol is subjected to esterification reaction with a cycloalkene alkanol compound, and the obtained product is subjected to epoxidation reaction to obtain a tricycloepoxy cycloalkyl glycerol ester second monomer; the first monomer and the second monomer are uniformly mixed and solidified to obtain the vegetable oil-based epoxy resin material; the material has high strength, strong weather resistance, and can be used as an adhesive, a plasticizer, a toughening agent and the like, and has wide application advantages.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin synthesis technology, specifically to plant oil-based epoxy resin materials, their preparation methods, and applications. Background Technology

[0002] As an indispensable functional material in modern industry, the green transformation of adhesives has become an inevitable trend in industry development. Traditional petroleum-based adhesives have long dominated the market due to their excellent bonding strength, weather resistance, and processing performance. However, their production relies on non-renewable fossil resources, and their use may release volatile organic compounds (VOCs), posing a potential threat to the environment. Against this backdrop, the development of bio-based adhesives using renewable biomass as raw materials is of great significance.

[0003] The overall performance of currently available bio-based adhesives still falls short of application requirements. Most products suffer from slow curing speeds, low cohesive strength, and poor water and temperature resistance, showing a significant performance gap compared to traditional petroleum-based adhesives. For example, while some starch-based and protein-based adhesives are inexpensive, they are only suitable for applications with low performance requirements, such as packaging and wood splicing. Some adhesives prepared with chitosan and cellulose derivatives, while exhibiting excellent biocompatibility, suffer from low bond strength due to their rigid molecular structure and insufficient cross-linking density, falling far below the typical levels of petroleum-based epoxy adhesives. There are also adhesives made from lignin and plant polyphenols, which are chemically modified, such as through epoxidation and graft copolymerization, to transform them into reactive epoxy prepolymers. However, these adhesives still have significant shortcomings: on the one hand, lignin has a complex molecular structure and contains a large number of inactive components, resulting in low epoxy values, uneven cross-linking networks after curing, and stress concentration that easily leads to cracking; on the other hand, although plant polyphenols (such as tannic acid and gallic acid) have high reactivity, they are rigid and have poor flexibility, which increases the brittleness of the adhesive layer after curing; in addition, due to the batch stability of natural raw materials, their weather resistance (such as resistance to ultraviolet aging and resistance to damp heat cycling) is also significantly lower than that of petroleum-based products.

[0004] Therefore, the technical problem to be solved by this invention is how to overcome the performance bottleneck of bio-based adhesives and develop new materials that have high strength, high weather resistance and performance comparable to petroleum-based products. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides plant oil-based epoxy resin materials, their preparation methods, and applications. This invention utilizes the triglyceride structure of natural plant oils, hydrolyzing it to extract glycerol and fatty acids. Then, an alicyclic structure is introduced under acidic conditions, followed by epoxidation. The resulting epoxy resin system, after curing, exhibits high strength and strong weather resistance, and has broad application prospects.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] The first aspect of this invention provides a plant oil-based epoxy resin material, comprising a first monomer and a second monomer crosslinked and cured;

[0008] The first monomer has the chemical structure of Formula I as follows; the second monomer has the chemical structure of Formula II as follows;

[0009] ; ;

[0010] R' is selected from a straight-chain alkyl group having at least 8 carbon atoms or an isomerized alkyl group thereof, or a straight-chain alkyl group having at least 12 carbon atoms containing an epoxy group or an isomerized alkyl group thereof, wherein the number of the epoxy groups is at least 1.

[0011] More preferably, the first monomer is selected from the following chemical structures:

[0012] ,

[0013] ,

[0014] ,

[0015] ,

[0016] .

[0017] Furthermore, the mass percentage ratio of the second monomer to the first monomer is 100%:0%~0.1%:99.9%.

[0018] Furthermore, the mass percentage ratio of the second monomer to the first monomer is 100%:0%~10%:90%.

[0019] Preferably, the mass percentage ratio of the second monomer to the first monomer is 100%:0%~50%:50%.

[0020] Furthermore, a cationic curing agent of onium salt is used for the crosslinking curing; for example, onium hexafluoroantimonate salt (cationic such as thioonium, iodonium, etc.), and heat curing or ultraviolet curing is selected according to the type of curing agent; the amount of the curing agent is 0.1% to 1% of the total mass of the first monomer and the second monomer.

[0021] Furthermore, the method for obtaining the first monomer is as follows: using fatty acids obtained by hydrolysis and separation of vegetable oil as raw materials, a first esterification reaction is carried out with cycloalkenol compounds under the action of organic sulfonic acid, and the product obtained by the reaction is subjected to an epoxidation reaction to convert its double bonds into epoxy groups, thereby obtaining the first monomer.

[0022] Furthermore, the cycloenol compounds are selected from one or more of the following: cyclopentenyl alcohol (e.g., CAS No. 25125-21-7), trimethylcyclopentenyl alcohol (e.g., CAS No. 1901-38-8), cyclohexenyl alcohol (e.g., CAS No. 3309-97-5, 1679-51-2), methylcyclohexenyl alcohol (e.g., CAS No. 5259-31-4, 50552-10-8), dimethylcyclohexenyl alcohol (e.g., CAS No. 67634-16-6), trimethylcyclohexenyl alcohol (e.g., CAS No. 68527-77-5, 470-99-5), cyclohexene diethanol (e.g., CAS No. 2160-94-3, 13287-81-5), and cyclohexene butanol (e.g., CAS No. 15760-18-6).

[0023] The organic sulfonic acid is selected from p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and pyridine-p-toluenesulfonic acid;

[0024] The solvent used in the first esterification reaction is a benzene-based solvent;

[0025] The temperature of the first esterification reaction is 5°C to 15°C above the boiling point of the benzene solvent, and the reaction time is 5-12 hours.

[0026] The molar ratio of the fatty acid to the cycloalkenol compound is 1:1-1.05; the amount of the organic sulfonic acid is 1.1%-1.5% of the sum of the molar amounts of the fatty acid and the cycloalkenol compound; the ratio of the sum of the molar amounts of the fatty acid and the cycloalkenol compound to the volume of the benzene solvent is 1.5-5 mol / L.

[0027] Furthermore, the second monomer is obtained by: using glycerol obtained from the hydrolysis and separation of vegetable oil as raw material, reacting it with cycloalkenonic acid compounds in the presence of organic sulfonic acid to carry out a second esterification reaction, and then subjecting the product obtained from the reaction to an epoxidation reaction to convert its double bonds into epoxy groups, thereby obtaining the second monomer.

[0028] Furthermore, the fatty acid is selected from any one of octanoic acid, stearic acid, linolenic acid, linoleic acid, and oleic acid; the cycloenanoic acid compound is selected from one or more of cyclopentenic acid (e.g., CAS No. 7686-77-3), cyclohexenic acid (e.g., CAS No. 636-82-8, 4771-80-6), methylcyclohexenic acid (e.g., CAS No. 4342-60-3), cyclohexenedicarboxylic acid (e.g., CAS No. 15573-40-7), cyclohexeneacetic acid (CAS No. 18294-87-6), and cyclohexenebutyric acid (CAS No. 6627-68-5).

[0029] The organic sulfonic acid is selected from p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and pyridine-p-toluenesulfonic acid;

[0030] The solvent used in the second esterification reaction is a benzene-based solvent;

[0031] The temperature of the second esterification reaction is 5°C to 15°C above the boiling point of the benzene solvent, and the reaction time is 12-36 hours.

[0032] The molar ratio of glycerol to the cycloalkenyl acid compound is 1:3-4; the amount of organic sulfonic acid used is 1%-1.3% of the sum of the molar amounts of glycerol and the cycloalkenyl acid compound; the ratio of the sum of the molar amounts of glycerol and the cycloalkenyl acid compound to the volume of the benzene solvent used is 2.8-4 mol / L.

[0033] Furthermore, after the first esterification reaction is completed and after the second esterification reaction is completed, multiple alkaline washes and / or water washes are performed respectively, and then the organic phase is desolventized before the subsequent epoxidation reaction is carried out.

[0034] The epoxidation reaction is carried out by reacting the product obtained from the first esterification reaction and the product obtained from the second esterification reaction with peracetic acid at a temperature below 15°C for 4-6 hours under the action of basic carbonate. The solvent used in the reaction is a halogenated hydrocarbon organic solvent, such as dichloromethane, dichloroethane, dichloropropane, trichloroethane, etc.

[0035] The molar ratio of the product obtained from the first esterification reaction to the peracetic acid is 1:2.8-3.8;

[0036] The molar ratio of the product obtained from the second esterification reaction to the peracetic acid is 1:4-8.5;

[0037] The amount of basic carbonate used is 10%-20% of the total molar amount of the product obtained from the esterification reaction and the peracetic acid.

[0038] A second aspect of this invention provides a method for preparing a plant oil-based epoxy resin material, comprising the following steps:

[0039] Using glycerol and fatty acids obtained by hydrolysis and separation of vegetable oil as raw materials;

[0040] S1. The fatty acid and cycloenol compound are subjected to a first esterification reaction in the presence of organic sulfonic acid, and the product obtained is subjected to an epoxidation reaction to obtain the first monomer of epoxy cycloalkyl fatty acid ester.

[0041] S2. The glycerol is reacted with a cycloalkenyl acid compound in the presence of an organic sulfonic acid to undergo a second esterification reaction, and the product obtained is subjected to an epoxidation reaction to obtain a second monomer of triepoxycycloalkyl glycerate.

[0042] S3. After mixing the first monomer and the second monomer evenly, add a curing agent and cure to obtain a plant oil-based epoxy resin material.

[0043] The reaction process for obtaining the first and second monomers is as follows:

[0044]

[0045] In the vegetable oil, R1, R2, and R3 are selected from straight-chain saturated alkyl groups with at least 8 carbon atoms or their isomerized alkyl groups, or straight-chain unsaturated alkyl groups with at least 12 carbon atoms or their isomerized alkyl groups. R1, R2, and R3 are completely identical, partially identical, or completely different. R is selected from one of R1, R2, and R3, that is, R is selected from straight-chain saturated alkyl groups with at least 8 carbon atoms or their isomerized alkyl groups, or straight-chain unsaturated alkyl groups with at least 12 carbon atoms or their isomerized alkyl groups. Preferably, the fatty acid containing R is selected from one of caprylic acid, stearic acid, linolenic acid, linoleic acid, and oleic acid.

[0046] A third aspect of the present invention provides applications of plant oil-based epoxy resin materials, including the applications of the plant oil-based epoxy resin materials described above in the fields of coatings, electronic packaging, adhesives, plasticizers, and toughening agents.

[0047] Beneficial technical effects: The plant oil-based epoxy resin material of the present invention includes two monomers. Utilizing the triglyceride structure of natural plant oil, glycerol and fatty acids are hydrolyzed to obtain them. Using these as raw materials, an alicyclic structure is introduced under an acidic environment and subsequent epoxidation is carried out to obtain two epoxy monomers. After mixing the two monomers in the presence of a curing agent, the plant oil-based epoxy resin material of the present invention can be obtained.

[0048] The plant oil-based epoxy resin material of this invention contains alicyclic structures and polyepoxy groups in its resin molecules, enabling rapid curing. After curing, the entire resin system has a hyperbranched resin structure, which allows the resin to have intermolecular pores, achieving simultaneous improvement in strength, toughness, and weather resistance, and can replace petroleum-based resin materials. Attached Figure Description

[0049] Figure 1 The raw material OA, the esterification reaction product, and the epoxidation reaction product OBOE in Example 1 1 H NMR spectrum;

[0050] Figure 2 This refers to the preparation of the epoxidation product Tri-OBC using glycerol as a raw material in Example 2. 1 H NMR spectrum;

[0051] Figure 3 The results show the adhesion strength test results of the T8O2 adhesive prepared in Example 6 when it overlaps different substrates;

[0052] Figure 4 The results show the weather resistance test results of the T8O2 adhesive used in Example 6 for bonding iron sheets. Detailed Implementation

[0053] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments and accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0054] Unless otherwise specifically stated, the numerical values ​​set forth in these embodiments do not limit the scope of the invention. Techniques and methods known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques and methods should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that values ​​expressed, for example, as "within the range of ab" or "between the range of ab," do not include the endpoint values ​​a and b; values ​​expressed as "for ab," "is ab," or "ab" include the endpoint values ​​a and b.

[0055] Furthermore, it should be noted that the use of terms such as "first" and "second" to define the individual components is merely for the convenience of referring to each component. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0056] Experimental methods not specified in the following examples are generally performed according to national standards; if there is no corresponding national standard, they are performed according to general standard requirements or general methods.

[0057] The process of hydrolyzing vegetable oil to obtain glycerol and fatty acids can be carried out using existing technologies, such as enzymatic hydrolysis (e.g., CN CN104245949A) or industrial high-pressure hydrolysis (e.g., King JW, Holliday RL, ListG R. Hydrolysis of soybean oil in a subcritical water flow reactor[J]. GreenChemistry, 1999, 1(6): 261-264.).

[0058] Example 1

[0059] This case study describes the steps involved in preparing the first monomer using oleic acid as a raw material:

[0060] 113 g (0.4 mol, abbreviated as OA) of oleic acid and 45.8 g (0.408 mol) of 3-cyclohexenemethanol were added to a 1 L reaction flask, along with 300 g of toluene as solvent. 1.90 g (0.01 mol) of p-toluenesulfonic acid monohydrate was added with stirring, and the first esterification reaction was carried out at 120 °C for 8 h. After cooling to room temperature, the organic phase was washed with alkali and then with water. The solvent was removed by vacuum distillation of the organic phase to obtain 132.1 g of cyclohexyl-3-en-1-ylmethyl(E)-octadecyl-9-enoate (CHMOE), with a yield of 87.7%.

[0061] 101.7 g (0.27 mol) of cyclohexyl-3-en-1-ylmethyl(E)-octadecyl-9-enoate obtained in the previous step was added to a 1 L reaction flask, along with 300 g of dichloroethane and 18.46 g (0.174 mol) of sodium carbonate. The mixture was stirred at a low temperature below 15 °C, and peracetic acid solution (23 wt%, 267.8 g, containing 0.81 mol of peracetic acid) was added dropwise. After epoxidation for 5 h, the mixture was allowed to stand and separated. The organic phase was washed with water and then with alkali. The organic phase was desolvated under reduced pressure to obtain the product, which is the first monomer: 83.2 g of (7-oxabicyclo[4.1.0]hept-methyl 8-(3-octoxy-2-oxacyclopropyl)octanoate (denoted as OBOE), with a yield of 75.4% (epoxy equivalent EEW = 205.82 g / mol).

[0062] Proton NMR spectra were performed on OA, CHMOE, and OBOE, and the results were analyzed. 1 H NMR (400 MHz, CDCl3-d) such as Figure 1 As shown, by Figure 1 As can be seen, the epoxidation reaction converts the unsaturated double bonds in CHMOE into epoxy groups. The OBOE molecular structure is as follows:

[0063] .

[0064] Example 2

[0065] This case study describes the steps involved in preparing the second monomer using glycerol as a raw material:

[0066] 55.26 g (0.6 mol) of glycerol and 287.63 g (2.28 mol) of 3-cyclohexenecarboxylic acid were added to a 2 L reaction flask. 800 g of toluene was added as solvent, and 5.71 g (0.03 mol) of p-toluenesulfonic acid monohydrate was added with stirring. The second esterification reaction was carried out at 120 °C for 24 h. After cooling to room temperature, the organic phase was washed with alkali and then with water. The organic phase was desolvated under reduced pressure to obtain 224.7 g of liquid 1,2,3-propanetriol tris(3-cyclohexene-1-carboxylic acid ester), with a yield of 89.91%.

[0067] 100 g (0.24 mol) of 1,2,3-propanetriol tris(3-cyclohexene-1-carboxylate) was added to a 1 L reaction flask, along with 300 g of dichloroethane and 18.46 g (0.174 mol) of sodium carbonate. The mixture was stirred at a low temperature below 15 °C, and a peracetic acid solution (23 wt%, 357.1 g, containing 1.08 mol of peracetic acid) was added dropwise. After epoxidation for 5 h, the mixture was allowed to stand and separated. The organic phase was washed with water and then with alkali. The organic phase was desolvated under reduced pressure to obtain a pale yellow liquid product, which was the second monomer: 79.5 g of 1,2,3-propanetriol tris[7-oxabicyclo[4.1.0]heptane-3-carboxylate] (denoted as Tri-OBC), with a yield of 71.3% (epoxy equivalent EEW = 163.45 g / mol).

[0068] The Tri-OBC in this case was subjected to proton NMR spectroscopy. 1 H NMR (400 MHz, CDCl3-d) such as Figure 2 As shown.

[0069] Example 3

[0070] This case study describes the steps involved in preparing the first monomer using linoleic acid as a raw material:

[0071] 112.18 g (0.4 mol) of linoleic acid and 45.8 g (0.408 mol) of 3-cyclohexene-methanol were added to a 1 L reaction flask, along with 300 g of toluene as solvent. 1.90 g (0.01 mol) of p-toluenesulfonic acid monohydrate was added with stirring, and the first esterification reaction was carried out at 120 °C for 8 h. After cooling to room temperature, the organic phase was washed with alkali and then with water. The organic phase was then dissolved by vacuum distillation to obtain 126.8 g of cyclohexyl-3-en-1-ylmethyl(9E,12E)-octadec-9,12-dienoate, with a yield of 84.6%.

[0072] 101.1 g (0.27 mol) of cyclohexyl-3-en-1-ylmethyl(9E,12E)-octadec-9,12-dienoate was added to a 2 L reaction flask, along with 300 g of dichloroethane and 18.46 g (0.174 mol) of sodium carbonate. The mixture was stirred at a low temperature below 15 °C, and a peracetic acid solution (23 wt%, 403.4 g, containing 1.22 mol of peracetic acid) was added dropwise. After reacting for 5 h, the mixture was allowed to stand and separated. The organic phase was washed with water and then with alkali. The organic phase was desolvated under reduced pressure to obtain a pale yellow liquid product, which was the first monomer: 89.6 g of 7-(7-oxabicyclo[4.1.0]hept-methyl-8-(3-((3-pentoxyethylene-2-methyl)ethylene-2-yl)octanoate, with a yield of 81.38% (epoxy equivalent EEW = 167.08 g / mol).

[0073] The first monomer in this case was analyzed by proton NMR spectroscopy. 1 ¹H NMR (400 MHz, CDCl₃-d): δ 3.92 – 3.69 (m, 2H), 3.20 – 2.96 (m, 3H), 2.96 – 2.74 (m, 2H), 2.22 (t, J = 7.5 Hz, 2H), 2.16 – 2.04 (m, 1H), 1.96 (m, 1H), 1.80 (m, 1H), 1.74 – 1.61 (m, 2H), 1.55 (m, 3H), 1.49 – 1.34 (m, 8H), 1.35 – 1.08 (m, 14H), 0.83 (m, 3H); The structure of the first monomer in this case is as follows:

[0074] .

[0075] Example 4

[0076] This case study describes the steps involved in preparing the first monomer using linolenic acid as a raw material:

[0077] 111.38 g (0.4 mol) of linolenic acid and 45.8 g (0.408 mol) of 3-cyclohexene-methanol were added to a 1 L reaction flask, along with 300 g of toluene as solvent. 1.90 g (0.01 mol) of p-toluenesulfonic acid monohydrate was added with stirring, and the first esterification reaction was carried out at 120 °C for 8 h. After cooling to room temperature, the organic phase was washed with alkali and then with water. The organic phase was then dissolved by vacuum distillation to obtain 119.5 g of cyclohexyl-3-en-1-methyl(9E,12E,15E)-octadec-9,12,15-trienoic acid ester, with a yield of 80.2%.

[0078] 100.6 g (0.27 mol) of cyclohexyl-3-en-1-methyl(9E,12E,15E)-octadec-9,12,15-trienoic acid ester was added to a 2 L reaction flask, along with 300 g of dichloroethane and 18.46 g (0.174 mol) of sodium carbonate. The mixture was stirred at a low temperature below 15°C, and a peracetic acid solution (23 wt%, 535.6 g, containing 1.62 mg of peracetic acid) was added dropwise. After epoxidation for 5 hours, the mixture was allowed to stand and separated. The organic phase was first washed with water and then with alkali. The organic phase was desolventized under reduced pressure to obtain a pale yellow liquid product, which is the first monomer: 94.2 g of 7-oxabicyclo[4.1.0]heptane-3-ylmethyl 8-(3-(3-(3-ethylethylene oxide-2-ethylene oxide-2-ylmethyl)ethylene oxide-2-yl)octanoate, with a yield of 79.9% (epoxy equivalent EEW = 131.85 g / mol).

[0079] The first monomer in this case was analyzed by proton NMR spectroscopy. 1 ¹H NMR (400 MHz, CDCl₃-d): δ 3.93 – 3.74 (m, 2H), 3.18 – 2.96 (m, 5H), 2.95 – 2.77 (m, 2H), 2.22 (t, J = 7.5 Hz, 2H), 2.10 (m, 1H), 2.03 – 1.90 (m, 1H), 1.85 – 1.61 (m, 5H), 1.60 – 1.35 (m, 10H), 1.35 – 1.16 (m, 8H), 1.06 – 0.88 (m, 3H), 0.88 – 0.75 (m, 1H); The structure of the first monomer molecule in this case is as follows:

[0080] .

[0081] Example 5

[0082] This case study describes the steps involved in preparing the first monomer using stearic acid as a raw material.

[0083] 113.8 g (0.4 mol) of stearic acid and 45.8 g (0.408 mol) of 3-cyclohexene-methanol were added to a 1 L reaction flask, along with 300 g of toluene as solvent. 1.90 g (0.01 mol) of p-toluenesulfonic acid monohydrate was added with stirring, and the first esterification reaction was carried out at 120 °C for 8 h. After cooling to room temperature, the organic phase was washed with alkali and then with water. The organic phase was then dissolved by vacuum distillation to obtain 126.3 g of a yellow solid, cyclohexyl-3-en-1-ylmethylstearate, with a yield of 83.4%.

[0084] 102.2 g (0.27 mol) of cyclohexyl-3-en-1-ylmethylstearate was added to a 1 L reaction flask, along with 300 g of dichloroethane and 18.46 g (0.174 mol) of sodium carbonate. The mixture was stirred at a low temperature below 15 °C, and a peracetic acid solution (23 wt%, 133.9 g, containing 0.41 mol of peracetic acid) was added dropwise. After epoxidation for 5 h, the mixture was allowed to stand and separated. The organic phase was washed with water and then with alkali. The organic phase was desolvated under reduced pressure to obtain a colorless liquid product, which was the first monomer: 83.2 g of 7-oxabicyclo[4.1.0]heptane-3-ylmethylstearate, with a yield of 75.4% (epoxy equivalent EEW = 404.6 g / mol).

[0085] The first monomer in this case was analyzed by proton NMR spectroscopy. 1 ¹H NMR (400 MHz, CDCl₃-d): δ 3.90 – 3.73 (m, 2H), 3.16 – 3.02 (m, 2H), 2.22 (t, J = 7.5 Hz, 2H), 2.10 (m, 1H), 2.04 – 1.90 (m, 1H), 1.87 – 1.75 (m, 1H), 1.70 – 1.38 (m, 5H), 1.19 (s, 29H), 0.81 (t, J = 6.8 Hz, 3H); The structure of the first monomer in this case is as follows:

[0086] .

[0087] Example 6

[0088] This case study demonstrates the preparation of plant oil-based epoxy resin materials.

[0089] The first monomer (7-oxabicyclo[4.1.0]heptane-methyl 8-(3-octoxy-2-oxacyclopropyl)octanoate OBOE) obtained in Example 1 and the second monomer (1,2,3-propanetriol tri[7-oxabicyclo[4.1.0]heptane-3-carboxylic acid ester] Tri-OBC) obtained in Example 2 were stirred evenly according to the mass percentage ratio in Table 1 below. The curing agent, onium hexafluoroantimonate salt (brand name S302), was added. The amount of curing agent added was 0.5% of the total mass of the first monomer and the second monomer.

[0090] The material obtained after curing the first monomer of Example 1 and the second monomer of Example 2 (curing conditions: 85℃ / 1h, 130℃ / 1h, 150℃ / 1h) is denoted as T. a O b The resin (subscripts a and b indicate their ratio), its curing process, and its structure are shown below:

[0091]

[0092] It is evident that the resin of this invention possesses a branched structure. Regarding the cured T... a O b The resin underwent mechanical property testing, and the results are shown in Table 1 below.

[0093] Table 1 T a O b Resin mechanical properties

[0094]

[0095] As shown in Table 1, the mechanical properties of plant oil-based epoxy resin materials are closely related to the amount of the second monomer. When the amount of the second monomer Tri-OBC in the resin is 60wt%-90wt%, the tensile strength of the resin is above 80MPa and the tensile modulus is above 750MPa.

[0096] Example 7

[0097] This case study tested the adhesive strength of the T8O2 resin prepared in Example 6 bonded to different substrates, including copper, steel, aluminum, glass, and wood. The adhesive strength was tested according to GB / T 7124 standard. Specific results of the adhesive strength are shown below. Figure 3 .Depend on Figure 3 It can be seen that the plant oil-based epoxy resin material of the present invention has good adhesion to various matrix materials, and the adhesion strength is at least 4 MPa.

[0098] Example 8

[0099] This case study uses the T8O2 resin prepared in Example 6 to bond iron sheets for weather resistance testing. The bonding strength was measured at different time points during the test, and the weather resistance test was conducted according to ISO 4892-3 standard. A commercially available bisphenol A type epoxy resin (DGEBA-E51 and D230 two-component adhesive) was used as a comparison. Specific results are shown in [link to results]. Figure 4 .Depend on Figure 4 It can be seen that the plant oil-based epoxy resin material of the present invention still has an adhesive strength of more than 6 MPa after aging for 672 hours, and the adhesive strength can retain more than 70% after aging for 672 hours.

[0100] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A vegetable oil based epoxy resin material, characterized by, It is composed of a first monomer and a second monomer cross-linked and cured; The first monomer has the chemical structure of Formula I as follows; the second monomer has the chemical structure of Formula II as follows; ； ； R' is selected from a straight-chain alkyl group having at least 8 carbon atoms or an isomerized alkyl group thereof, or a straight-chain alkyl group having at least 12 carbon atoms containing an epoxy group or an isomerized alkyl group thereof, wherein the number of the epoxy groups is at least 1.

2. The vegetable oil-based epoxy resin material according to claim 1, characterized by The mass percentage ratio of the second monomer to the first monomer is 100%:0%~10%:90%.

3. The vegetable oil-based epoxy resin material according to claim 2, characterized by The mass percentage ratio of the second monomer to the first monomer is 100%:0% to 50%:50%.

4. The vegetable oil-based epoxy resin material according to any one of claims 1 to 3, characterized by, The cross-linking and curing are carried out using an onium salt cationic curing agent; the amount of curing agent used is 0.1% to 1% of the total mass of the first monomer and the second monomer.

5. The vegetable oil-based epoxy resin material according to any one of claims 1 to 3, characterized by, The method for obtaining the first monomer is as follows: fatty acids obtained by hydrolysis and separation of vegetable oil are used as raw materials, and cycloalkenol compounds are subjected to a first esterification reaction under the action of organic sulfonic acid. The product obtained from the reaction is subjected to an epoxidation reaction to convert its double bond into an epoxy group, thereby obtaining the first monomer. The second monomer is obtained by: using glycerol obtained by hydrolysis of vegetable oil as raw material, reacting it with cycloalkenonic acid compounds in the presence of organic sulfonic acid to carry out a second esterification reaction, and then subjecting the product to an epoxidation reaction to convert its double bonds into epoxy groups, thereby obtaining the second monomer.

6. The vegetable oil-based epoxy resin material according to claim 5, characterized by The fatty acid is selected from any one of caprylic acid, stearic acid, linolenic acid, linoleic acid, and oleic acid; The cycloenol compounds are selected from one or more of cyclopentenyl alcohol, trimethylcyclopentenyl alcohol, cyclohexenyl alcohol, methylcyclohexenyl alcohol, dimethylcyclohexenyl alcohol, trimethylcyclohexenyl alcohol, cyclohexenediethanol, and cyclohexenebutanol; The organic sulfonic acid is selected from p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and pyridine-p-toluenesulfonic acid; The solvent used in the first esterification reaction is a benzene-based solvent; The temperature of the first esterification reaction is 5°C to 15°C above the boiling point of the benzene solvent, and the reaction time is 5-12 hours. The molar ratio of the fatty acid to the cycloalkenol compound is 1:1-1.05; the amount of the organic sulfonic acid is 1.1%-1.5% of the sum of the molar amounts of the fatty acid and the cycloalkenol compound; the ratio of the sum of the molar amounts of the fatty acid and the cycloalkenol compound to the volume of the benzene solvent is 1.5-5 mol / L.

7. The vegetable oil-based epoxy resin material according to claim 5, characterized by The cycloenanoic acid compounds are selected from one or more of cyclopentenic acid, cyclohexenic acid, methylcyclohexenic acid, cyclohexenedicarboxylic acid, cyclohexeneacetic acid, and cyclohexenebutyric acid. The organic sulfonic acid is selected from p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and pyridine-p-toluenesulfonic acid; The solvent used in the second esterification reaction is a benzene-based solvent; The temperature of the second esterification reaction is 5°C to 15°C above the boiling point of the benzene solvent, and the reaction time is 12-36 hours. The molar ratio of glycerol to the cycloalkenyl acid compound is 1:3-4; the amount of organic sulfonic acid used is 1%-1.3% of the sum of the molar amounts of glycerol and the cycloalkenyl acid compound; the ratio of the sum of the molar amounts of glycerol and the cycloalkenyl acid compound to the volume of the benzene solvent used is 2.8-4 mol / L.

8. The vegetable oil-based epoxy resin material according to claim 5, characterized by After the first esterification reaction is completed and after the second esterification reaction is completed, multiple alkaline washes and / or water washes are performed respectively, and then the organic phase is desolventized before the subsequent epoxidation reaction is carried out. The epoxidation reaction is carried out by reacting the product obtained from the first esterification reaction and the product obtained from the second esterification reaction with peracetic acid at a temperature of less than 15°C for 4-6 hours under the action of basic carbonate. The solvent used in the reaction is a halogenated hydrocarbon organic solvent. The molar ratio of the product obtained from the first esterification reaction to the peracetic acid is 1:2.8-3.8; The molar ratio of the product obtained from the second esterification reaction to the peracetic acid is 1:4-8.5; The amount of basic carbonate used is 10%-20% of the total molar amount of the product obtained from the esterification reaction and the peracetic acid.

9. A process for the preparation of a vegetable oil based epoxy resin material, characterized in that, The preparation of the vegetable oil-based epoxy resin material according to any one of claims 1-8 comprises the following steps: Using glycerol and fatty acids obtained by hydrolysis and separation of vegetable oil as raw materials; S1. The fatty acid and cycloenol compound are subjected to a first esterification reaction in the presence of organic sulfonic acid, and the product obtained is subjected to an epoxidation reaction to obtain the first monomer of epoxy cycloalkyl fatty acid ester. S2. The glycerol is reacted with a cycloalkenyl acid compound in the presence of an organic sulfonic acid to undergo a second esterification reaction, and the product obtained is subjected to an epoxidation reaction to obtain a second monomer of triepoxycycloalkyl glycerate. S3. After mixing the first monomer and the second monomer evenly, add a curing agent and cure to obtain a plant oil-based epoxy resin material.

10. Use of a vegetable oil based epoxy resin material, characterized in that, This includes the application of plant oil-based epoxy resin materials as described in any one of claims 1-8 in the fields of coatings, electronic packaging, adhesives, plasticizers, and toughening agents.

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