CN119080810A - Bisphenol curing agent containing spirocyclic biboric acid ester group, vegetable oil-based epoxy resin and preparation method and application thereof - Google Patents
Bisphenol curing agent containing spirocyclic biboric acid ester group, vegetable oil-based epoxy resin and preparation method and application thereof Download PDFInfo
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- CN119080810A CN119080810A CN202411170930.1A CN202411170930A CN119080810A CN 119080810 A CN119080810 A CN 119080810A CN 202411170930 A CN202411170930 A CN 202411170930A CN 119080810 A CN119080810 A CN 119080810A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract
本发明提供了一种含螺环双硼酸酯基团的双酚固化剂、植物油基环氧树脂及其制备方法与应用，属于精细化工技术领域。本发明基于交联网络结构设计的方法，通过将4‑羟基苯硼酸与季戊四醇脱水缩合，一步制备出螺环硼酸酯基二元苯酚，用于改善环氧胶黏剂结构性能。在本发明中，螺环硼酸酯基二元苯酚与双酚F都含双苯环结构，有利于提升环氧胶黏剂分子结构刚性，贡献结构内聚强度，同时，B‑O键具有高键结合能和缔合性可逆交联特性，可提高植物油基环氧树脂的胶接强度和再加工性能，能显著改善环氧胶黏剂的结构，制备的植物油基环氧树脂不仅具有更好的胶接强度，并且还具有良好的降解性能和再加工性能。The present invention provides a bisphenol curing agent containing a spiro-biboric acid ester group, a vegetable oil-based epoxy resin and a preparation method and application thereof, and belongs to the field of fine chemical technology. The present invention is based on a method designed for a cross-linked network structure, and a spiro-boric acid ester-based diphenol is prepared in one step by dehydrating and condensing 4-hydroxyphenylboric acid and pentaerythritol, which is used to improve the structural performance of epoxy adhesives. In the present invention, both the spiro-boric acid ester-based diphenol and bisphenol F contain a double benzene ring structure, which is beneficial to improving the rigidity of the molecular structure of the epoxy adhesive and contributing to the structural cohesive strength. At the same time, the B-O bond has high bond binding energy and associative reversible cross-linking characteristics, which can improve the bonding strength and reprocessing performance of the vegetable oil-based epoxy resin, and can significantly improve the structure of the epoxy adhesive. The prepared vegetable oil-based epoxy resin not only has better bonding strength, but also has good degradation performance and reprocessing performance.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a bisphenol curing agent containing spiro bisborate groups, a vegetable oil-based epoxy resin, a preparation method and application thereof.
Background
The epoxy adhesive is one of the most widely applied adhesive materials at present, and is applied to various fields such as aerospace, automobile manufacturing, wind power generation fan blades, structural high-performance resin and the like due to the advantages of excellent performance, adjustable structure, simplicity in preparation and the like. According to different requirements of application scenes, the current research on the epoxy adhesive mainly improves the application performance of the adhesive through a modified curing crosslinked network, and mainly comprises the steps of reinforcing, toughening and modifying the epoxy adhesive, preparing the high-strength epoxy adhesive, preparing the low-temperature/quick-curing high-strength epoxy adhesive, preparing the high-temperature-resistant epoxy adhesive, preparing the water-resistant epoxy adhesive and the like. According to the demands of various fields on materials, light and high-strength standards are increasingly attracting attention, so that the adhesive is required to have excellent bonding strength to endow the materials with structural requirements.
At present, the performance modification of the epoxy adhesive is mainly focused on the following aspects of (1) cross-linking network modification, namely, the structural performance of the epoxy adhesive is improved by designing an epoxy monomer or curing agent structure, such as introducing a hyperbranched structure and the like, the adhesive bonding performance is improved, (2) blending modification, the epoxy adhesive is blended with other adhesives with specific excellent performance, the defect of the epoxy adhesive is improved, the adhesive bonding performance of the epoxy adhesive is improved, and (3) nano hybridization modification is carried out, the structural performance of the epoxy adhesive is improved by taking nano fillers as reinforcing elements, and the adhesive bonding performance is improved.
Patent CN202211122212.8 'a high-strength single-component epoxy adhesive composition and a preparation method thereof', the high-strength epoxy adhesive is obtained by designing a toughening agent and then compounding a curing agent, a diluent, a filler and the like to synergistically modify an epoxy resin crosslinking system. However, most of the methods disclosed at present have complex processes and additives, which are not beneficial to industrial application, and the epoxy resin is mainly petroleum-based product, which does not meet the current requirement of double carbon (or as in CN 201310675056.2' a high-strength adhesive, a preparation method and application thereof). Meanwhile, in the adhesive prepared by using the bio-based environment-friendly materials such as the epoxidized vegetable oil and the like, the adhesive bonding strength is more different than that of the petroleum-based epoxy adhesive (such as CN202410260521.4, a plasma modified chitosan cured epoxidized soybean oil wood adhesive, and a preparation method and application thereof). In addition, with the improvement of the application amount of the epoxy adhesive, after the product completes the service period, the colloid cannot be degraded and removed due to high adhesive strength, and is difficult to reprocess and apply, so that the recycling application of the material cannot be realized.
Moreover, high adhesive strength is contradictory with degradable and reworkable properties, and the integration of the properties cannot be achieved by structural design modification in the prior art. At present, there is a technology for reprocessing an epoxy adhesive by constructing an epoxy hot melt adhesive, for example, in CN112877014B, "an epoxy resin hot melt adhesive and a preparation method thereof", which uses ureido pyrimidinone as a functional structure to achieve repeated bonding. However, there has been no report on the unified integration study of high adhesive strength, reworkability and degradability of bio-based epoxy adhesives. Therefore, how to achieve the high adhesive strength, rapid degradation and repeated adhesive bonding performance of the adhesive is an important point in the development of the current adhesive industry and is also a difficult point.
Disclosure of Invention
The invention aims to provide a bisphenol curing agent containing spiro bisborate groups, a vegetable oil-based epoxy resin, and a preparation method and application thereof, and aims to prepare a bio-based epoxy resin adhesive which has high adhesive strength, can be rapidly degraded and has repeated adhesive bonding (reprocessing) performance against the background that the current high-strength epoxy crosslinking network and degradation performance and reprocessing performance cannot be balanced.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a bisphenol curing agent containing spiro-bisborate groups, which is prepared from 4-hydroxyphenylboric acid and pentaerythritol according to a molar ratio of 2-2.2:1, wherein the structure of the bisphenol curing agent containing spiro-bisborate groups is shown as a formula (I):
the invention also provides a preparation method of the bisphenol curing agent containing the spiro-bisborate group, which comprises the following steps:
mixing 4-hydroxyphenylboric acid, pentaerythritol and absolute ethyl alcohol, then heating for reaction, and performing rotary evaporation to obtain the bisphenol curing agent containing spiro bisborate groups.
Preferably, the molar volume ratio of the pentaerythritol to the absolute ethyl alcohol is 1mol:0.5-1L, the temperature of the heating reaction is 50-70 ℃, and the heating reaction time is 12-24h.
The invention also provides a method for preparing the vegetable oil-based epoxy resin by using the bisphenol curing agent containing the spiro bisborate group, which comprises the following steps:
uniformly stirring and mixing epoxidized soybean oil, bisphenol curing agent containing spiro bisborate groups, curing agent, catalyst and absolute ethyl alcohol, heating and reacting under the condition of negative pressure, defoaming, and thermally drying to obtain the vegetable oil-based epoxy resin.
Preferably, the curing agent comprises one of bisphenol F, bisphenol A and bisphenol S, and the catalyst comprises one of imidazole, acrylic anhydride, aniline, benzyl dimethylamine and phenol.
Preferably, the mole volume ratio of the epoxy soybean oil to the bisphenol curing agent containing the spiro-bisborate groups, the curing agent to the absolute ethyl alcohol is that the epoxy soybean oil to the bisphenol curing agent containing the spiro-bisborate groups, the curing agent to the absolute ethyl alcohol=1 mol:0-2mol:1-1.5L, and the dosage of the catalyst is 0-20% of the weight of the epoxy soybean oil.
Preferably, the pressure of the heating reaction under the negative pressure condition is 0.1-0.5 MPa, the heating reaction temperature is 70-100 ℃, and the heating reaction time is 30-60min.
Preferably, the temperature of the hot baking is 120-160 ℃ and the time is 6 hours.
The invention also provides the vegetable oil-based epoxy resin prepared by the method for preparing the vegetable oil-based epoxy resin.
The invention also provides application of the vegetable oil-based epoxy resin as an adhesive.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention synthesizes a novel spiro borate structure which can be used as a curing agent based on a method of cross-linked network structure design and is used for improving the structural performance of an epoxy adhesive. The spiro borate dihydric phenol is prepared by dehydrating and condensing 4-hydroxyphenylboric acid and pentaerythritol, and the compound is a main functional element for structural modification.
(2) According to the invention, the epoxy soybean oil is modified by compounding the spiro-borate dihydric phenol and the bisphenol F, and the spiro-borate dihydric phenol and the bisphenol F curing agent are beneficial to the remarkable improvement of the adhesive bonding strength. Firstly, the two materials contain a double benzene ring structure, which is beneficial to improving the molecular structure rigidity of the epoxy adhesive and contributing to the cohesive strength of the structure. And secondly, the spiro borate group in the spiro borate dihydric phenol is of a double six-membered ring structure, has a structural strength gain effect similar to that of a benzene ring, and further improves cohesive strength. Meanwhile, boron atoms with electron deficiency in spiro borate dihydric phenol tend to combine with donor groups rich in various substrate surfaces and nucleophilic reagents, so that the interface cementing activity is improved, and the interface cementing performance is contributed. Synchronous optimization of cohesive strength and interfacial adhesion performance synergistically shares excellent adhesion strength.
On the basis of the effect of improving the adhesive bonding strength of the adhesive, the B-O bond also has associative reversible crosslinking characteristic, the three-dimensional crosslinked network is endowed with reprocessing performance, the adhesive has repeated bonding performance, and the B-O bond has high bonding energy (809 kJ/mol) so as to avoid the defect that other dynamic bonding groups reduce the structural strength. The dynamic reversible crosslinking characteristic of the B-O can lead the B-O to be structurally degraded under the conditions of acid and the like, thus realizing the degradation and removal of the colloid material.
(3) The invention realizes the remarkable improvement of the structure of the epoxy adhesive based on the spiro borate group, and the prepared vegetable oil-based epoxy resin not only has better adhesive strength, but also has good degradation performance and reworkability.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention prepares the vegetable oil-based epoxy resin with good adhesive strength and simultaneously has degradation performance and reprocessing performance, and the vegetable oil-based epoxy resin is mainly prepared in two steps, and the specific method is as follows:
(1) Preparation of bisphenol curing agent containing spiro bisborate group:
mixing 4-hydroxyphenylboric acid, pentaerythritol and absolute ethyl alcohol, then heating for reaction, and performing rotary evaporation to obtain a bisphenol curing agent containing spiro bisborate groups;
(2) A method of vegetable oil-based epoxy resins comprising the steps of:
uniformly stirring and mixing epoxidized soybean oil, bisphenol curing agent containing spiro bisborate groups, curing agent, catalyst and absolute ethyl alcohol, heating and reacting under the condition of negative pressure, defoaming, and thermally drying to obtain the vegetable oil-based epoxy resin.
The bisphenol F used in the following examples has the structure shown below:
Example 1
The embodiment 1 of the invention provides a preparation method of a bisphenol curing agent containing spiro bisborate groups, which comprises the following steps:
2mol of 4-hydroxyphenylboric acid, 1mol of pentaerythritol and 1L of absolute ethyl alcohol are mixed and reacted for 24 hours at 50 ℃, and then the bisphenol curing agent containing spiro bisborate groups is obtained by rotary evaporation.
Example 2
The embodiment 2 of the invention provides a method for preparing vegetable oil-based epoxy resin by using bisphenol curing agent containing spiro bisborate groups, which comprises the following steps:
1mol of epoxidized soybean oil (calculated according to the content of 4 epoxy groups in 1 structure), 0.8mol of bisphenol curing agent containing spiro bisborate groups, 1.2mol of bisphenol F, 20 weight percent of imidazole of the epoxidized soybean oil and 1.5L of absolute ethyl alcohol are stirred and mixed uniformly, reacted for 60 minutes at 100 ℃ under the condition of negative pressure of 0.1MPa, defoamed and baked for 6 hours at 120 ℃ to obtain the vegetable oil-based epoxy resin.
Example 3
Example 3 of the present invention provides a method for preparing a vegetable oil-based epoxy resin using a bisphenol curing agent having a spiro-bisborate group, which is different from example 2 in that the bisphenol curing agent having a spiro-bisborate group in example 3 is used in an amount of 2mol and bisphenol F is used in an amount of 0mol.
Example 4
Example 4 of the present invention provides a method for preparing a vegetable oil-based epoxy resin using a bisphenol curing agent having a spiro-bisborate group, which is different from example 2 in that the bisphenol curing agent having a spiro-bisborate group in example 4 is used in an amount of 0.4mol and bisphenol F is used in an amount of 1.6mol.
Example 5
Example 5 of the present invention provides a method for preparing a vegetable oil-based epoxy resin using a bisphenol curing agent having a spiro-bisborate group, which is different from example 2 in that the bisphenol curing agent having a spiro-bisborate group in example 5 is used in an amount of 1.2mol and bisphenol F is used in an amount of 1.4mol.
Example 6
Example 6 of the present invention provides a method for preparing a vegetable oil-based epoxy resin using a bisphenol curing agent having a spiro-bisborate group, which is different from example 2 in that the bisphenol curing agent having a spiro-bisborate group in example 6 is used in an amount of 1.6mol and bisphenol F is used in an amount of 2mol.
Comparative example 1
Comparative example 1 of the present invention provides a method for preparing a vegetable oil-based epoxy resin, which is different from example 2 in that the bisphenol curing agent having a spiro bisborate group in comparative example 1 is used in an amount of 0mol and bisphenol F is used in an amount of 2mol.
Test example 1
According to the invention, the adhesive strength performance of the vegetable oil-based epoxy resins prepared in examples 2-6 and comparative example 1 is detected in test example 1, the prepared vegetable oil-based epoxy resins are coated on the surface of a substrate, another substrate is coated on the surface, and after clamping, the adhesive is cured for 2 hours at 120 ℃ and 140 ℃ to test the shear adhesive strength of the cured adhesive, and the specific results are shown in Table 1.
TABLE 1 adhesive strength Properties of different vegetable oil based epoxy resins
| Grouping | Adhesive strength |
| Example 2 | 16.24±0.81MPa |
| Example 3 | 10.57±1.68MPa |
| Example 4 | 12.96±0.90MPa |
| Example 5 | 14.03±0.15MPa |
| Example 6 | 12.84±1.47MPa |
| Comparative example 1 | 8.33±0.64MPa |
As shown in Table 1, when bisphenol curing agent containing spiro bisborate group is added, the adhesive strength of the vegetable oil-based epoxy resin prepared by the invention is obviously improved.
Test example 2
The repeated cementing performance of the vegetable oil-based epoxy resins prepared in examples 2-6 and comparative example 1 is detected in test example 2, the fractured cementing test pieces of test example 1 subjected to tensile strength test are stacked according to the in-situ position, fracture re-cementing is completed by hot pressing for 1h at 140 ℃ under 3MPa by using a hot press, and the strength test is carried out according to the method of test example 1, and the results are shown in Table 2.
As shown in Table 2, when bisphenol curing agent containing spiro bisborate group is added, the vegetable oil-based epoxy resin prepared by the invention can be used as an adhesive for repeated gluing, and the reworkability is obviously improved.
Test example 3
The repeated cementing performance of the vegetable oil-based epoxy resins prepared in examples 2-6 and comparative example 1 is detected in test example 3, and the specific method is as follows:
2 volumes of water are added into 8 volumes of tetrahydrofuran solvent, HCl is added respectively to make the final concentration of the solution be 0.1, 0.5 and 1.0M, vegetable oil-based epoxy resins prepared in examples 2-6 and comparative example 1 are added under the conditions of 20 and 50 ℃, and the time for complete degradation of the epoxy resins is recorded, and the results are shown in Table 3.
TABLE 3 degradation Properties of vegetable oil epoxy adhesives
| Grouping | 0.1MHCl,20°C | 0.5MHCl,20°C | 1MHCl,20°C | 1MHCl,50°C |
| Example 2 | 752mins | 560mins | 325mins | 125mins |
| Example 3 | 488mins | 400mins | 264mins | 88mins |
| Example 4 | 1020mins | 850mins | 765mins | 690mins |
| Example 5 | 690mins | 490mins | 300mins | 110mins |
| Example 6 | 510mins | 430mins | 286mins | 98mins |
| Comparative example 1 | - | - | - | - |
As can be seen from Table 3, the vegetable oil-based epoxy resin prepared by the invention has the characteristic of quick degradation after the bisphenol curing agent containing the spiro bisborate group is added.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The bisphenol curing agent containing the spiro-bisborate group is characterized in that the bisphenol curing agent containing the spiro-bisborate group is prepared from 4-hydroxyphenylboric acid and pentaerythritol according to a molar ratio of 2-2.2:1, and the structure of the bisphenol curing agent containing the spiro-bisborate group is shown as a formula (I):
2. A method for preparing a bisphenol curative containing spiro-bisborate groups as claimed in claim 1, comprising the steps of:
mixing 4-hydroxyphenylboric acid, pentaerythritol and absolute ethyl alcohol, then heating for reaction, and performing rotary evaporation to obtain the bisphenol curing agent containing spiro bisborate groups.
3. The method for preparing bisphenol curing agent containing spiro-bisborate group according to claim 2, wherein the molar volume ratio of pentaerythritol to absolute ethanol is 1mol:0.5-1L, the heating reaction temperature is 50-70 ℃, and the heating reaction time is 12-24h.
4. A method for preparing a vegetable oil-based epoxy resin using the bisphenol curative containing spiro-bisborate groups of claim 1, comprising the steps of:
uniformly stirring and mixing epoxidized soybean oil, bisphenol curing agent containing spiro bisborate groups, curing agent, catalyst and absolute ethyl alcohol, heating and reacting under the condition of negative pressure, defoaming, and thermally drying to obtain the vegetable oil-based epoxy resin.
5. The method for preparing vegetable oil based epoxy resin of claim 4, wherein the curing agent comprises one of bisphenol F, bisphenol A, bisphenol S, and the catalyst comprises one of imidazole, acrylic anhydride, aniline, benzyl dimethylamine, phenol.
6. The method for preparing the vegetable oil-based epoxy resin according to claim 4, wherein the mole volume ratio of the epoxidized soybean oil to the bisphenol curing agent containing the spiro-bisborate group, the curing agent and the absolute ethyl alcohol is that the epoxy soybean oil to the bisphenol curing agent containing the spiro-bisborate group is that the curing agent is that the absolute ethyl alcohol=1 mol:0-2mol:1-1.5L, and the catalyst is used in an amount of 0-20% of the weight of the epoxy soybean oil.
7. The method for preparing vegetable oil-based epoxy resin according to claim 4, wherein the pressure of the heating reaction under the negative pressure condition is 0.1-0.5 MPa, the heating temperature is 70-100 ℃, and the heating time is 30-60min.
8. The method for preparing a vegetable oil based epoxy resin of claim 4, wherein the temperature of the heat bake is 120-160 ℃ for 6 hours.
9. A vegetable oil-based epoxy resin prepared by the method of preparing a vegetable oil-based epoxy resin of any one of claims 4-8.
10. Use of the vegetable oil-based epoxy resin of claim 9 as an adhesive.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003292581A (en) * | 2002-04-08 | 2003-10-15 | Hokko Chem Ind Co Ltd | Epoxy resin curing accelerator |
| WO2018045866A1 (en) * | 2016-09-09 | 2018-03-15 | 翁秋梅 | Dynamic polymer having hybridized cross-linked network and use thereof |
| CN115612054A (en) * | 2022-09-30 | 2023-01-17 | 河南城建学院 | Dynamic cross-linked polyurethane material and synthesis method thereof |
| CN116082628A (en) * | 2022-12-26 | 2023-05-09 | 江西科技师范大学 | Bio-based phenol-oxygen resin and preparation method and application thereof |
| CN117105202A (en) * | 2023-08-25 | 2023-11-24 | 三明学院 | Cardanol and boron dual-modified phenolic resin-based materials and their preparation methods and applications |
| CN117672610A (en) * | 2023-11-14 | 2024-03-08 | 江苏赛德电气有限公司 | Fire-resistant communication cable for radiation-resistant nuclear power plants and preparation method thereof |
-
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- 2024-08-23 CN CN202411170930.1A patent/CN119080810B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003292581A (en) * | 2002-04-08 | 2003-10-15 | Hokko Chem Ind Co Ltd | Epoxy resin curing accelerator |
| WO2018045866A1 (en) * | 2016-09-09 | 2018-03-15 | 翁秋梅 | Dynamic polymer having hybridized cross-linked network and use thereof |
| CN115612054A (en) * | 2022-09-30 | 2023-01-17 | 河南城建学院 | Dynamic cross-linked polyurethane material and synthesis method thereof |
| CN116082628A (en) * | 2022-12-26 | 2023-05-09 | 江西科技师范大学 | Bio-based phenol-oxygen resin and preparation method and application thereof |
| CN117105202A (en) * | 2023-08-25 | 2023-11-24 | 三明学院 | Cardanol and boron dual-modified phenolic resin-based materials and their preparation methods and applications |
| CN117672610A (en) * | 2023-11-14 | 2024-03-08 | 江苏赛德电气有限公司 | Fire-resistant communication cable for radiation-resistant nuclear power plants and preparation method thereof |
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