CN102206324B - Full-biobased epoxy resin composition and condensate - Google Patents
Full-biobased epoxy resin composition and condensate Download PDFInfo
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Abstract
The invention discloses a full-biobased epoxy resin condensate. The condensate is prepared by the following components in part by weight: 100 parts of abietyl-based epoxy resin base material, 50 to 300 parts of tung oil anhydride and 1 to 15 parts of catalyst, has the characteristics of higher mechanical property, high ultraviolet resistance, high aging resistance and the like and is particularly suitable for preparing biobased composite material matrix resin and outdoor electric insulation materials. The invention also discloses a preparation method for the full-biobased epoxy resin condensate. The preparation method has a simple preparation process, is high in operability and process controllability and is easy to implement industrially. The invention also discloses a full-biobased epoxy resin composition and application thereof. The full-biobased epoxy resin composition is suitable for preparing a weather resistant epoxy adhesive, epoxy resin paint and an epoxy resin coating and has a good application prospect.
Description
Technical field
The invention belongs to bio-based thermosetting resin field, particularly a kind of full bio-based composition epoxy resin and cured article thereof.
Background technology
Epoxy resin is widely used in the every field of national economy such as space flight and aviation, building traffic and electronic apparatus because of its excellent mechanical property, thermal property, corrosion resistance nature etc.But epoxy resin commonly used is raw material with petroleum base compounds such as dihydroxyphenyl propane or Bisphenol F all generally, contains structural unit such as aromatic series phenyl ring because of it and causes the ageing-resistant and uvioresistant performance of epoxy resin commonly used relatively poor, exists technical problem.
At present, outdoor weathe resistance epoxy resin master prepares with petroleum base aliphatics ring compound and epoxy chloropropane.Though this based epoxy resin does not have the better weather ability owing to not containing phenyl ring in the chemical structure, is difficult to large-scale application because of it costs an arm and a leg, and exists technological deficiency.
Because being on the rise of the exhausted day by day and problem of environmental pollution of petroleum resources; Research and develop environmentally friendly bio-based materials in order to replace existing petrochemical materials; Having protection environment and the double effects that economizes on resources, is a focus of at present domestic and international investigation of materials.Developed countries such as the U.S., Japan, European Union and organizing have all formulated the development that relevant laws and regulations are used for promoting and promoting the bio-based product in succession.With Japan is example, their clear and definite regulation in " the biotechnology strategy outline " put into effect in the recent period, to make to the year two thousand twenty Japan's consumption all plastics 20% from renewable resources.The planning of China's Eleventh Five-Year Plan also spells out, and greatly develop renewable resources, enlarges the research and the throughput of bio-based product.Just in the end of the year 2009; Premier Wen Jiabao is to world's attest; To on basis in 2005, reduce 40%～45% to the year two thousand twenty China per GDP CO2 emissions, a large amount of uses of bio-based materials will be important means that realizes " energy-saving and emission-reduction " and development " low-carbon economy ".It is thus clear that, be raw material with the regeneration biological resource, research and development novel high-performance material is complied with era development trend, meets national strategy demand, and important application value and vast potential for future development are arranged.
Rosin is nontoxic, tasteless, is a kind of important natural reproducible resource of China.China produces rosin 50～600,000 ton per year, is the maximum country of rosin output in the world, has the power to make decision of world's rosin price.Rosin is mainly by various isomerized sylvic acid C
19H
29COOH forms with a small amount of neutral substance, and wherein sylvic acid is a staple, accounts for more than 90% of its total amount.Two keys in the sylvic acid and carboxyl isoreactivity functional group conveniently carry out addition; Esterification; The reaction of number of chemical such as condensation; Its huge hydrogen phenanthrene ring structure has higher mechanics rigidity, can match in excellence or beauty with petroleum base aliphatics or aromatic series ring-type monomer, is applied to the Polymer Synthesizing field so rosin and verivate thereof have been used as the surrogate of some industrial chemicals.Application number is that the one Chinese patent application of 02149777.X has been introduced the method for using acrylic acid rosin and epichlorohydrin reaction to prepare rosin acrylic acid 2-glycidyl ester type epoxy resin; Application number is a kind of three-glycidyl ester epoxy resin based on maleopimaric anhydride and epoxy chloropropane for the 01108250.X one Chinese patent application discloses; Application number is that 200710032534.2 one Chinese patent application and application number are that 200810198059.0 one Chinese patent application provides a kind of method of using polymerized rosin and formaldehyde modified rosin to prepare epoxy resin respectively.But because huge hydrogen phenanthrene ring structure causes the general fragility of above-mentioned epoxy resin cured product bigger in the rosin, its over-all properties needs further to improve and improve.For this reason; Application number is that 200910038741.8 one Chinese patent application and application number are that 200910042321.7 one Chinese patent application has been introduced respectively again and utilized diglycidylether and dodecyl succinic anhydride etc. to contain the method for the compound of flexible chain to the acrylic acid rosin and epoxy resin modification, and the result is greatly improved the flexility of its cured product.
Tung oil is a kind of fatty acid triglycercide mixture that China special product oil plant seeds-the tung oil seed is squeezed, and has been widely used in fields such as medicine, chemical industry and coating at present.Tung oil acid anhydride is to utilize eleostearic acid and maleic anhydride to carry out the anhydrides compound for preparing after the D-A addition, is the fabulous epoxy resin toughener of a kind of performance.
In the above-mentioned prior art, epoxy resin commonly used adopts the petroleum base compound as raw material, and raw material is Nonrenewable resources, exists environmental benefit difference and the ageing-resistant and relatively poor technical problem of uvioresistant performance; The outdoor weathe resistance epoxy resin that adopts petroleum base aliphatics ring compound and epoxy chloropropane to prepare though have the better weather ability, is difficult to large-scale application owing to costing an arm and a leg, and exists technological deficiency.Simultaneously in the document and patent about epoxy resin in the past, also do not see and use bio-based epoxy monomer (or prepolymer) and bio-based solidifying agent to prepare the report of full bio-based epoxy resin cured product simultaneously.
Summary of the invention
The invention provides a kind of full bio-based composition epoxy resin and application thereof, be applicable to preparation Weather-resistant epoxy sizing agent, epoxy resin-based paint and epoxypaint.
The present invention also provides a kind of preparation method of full bio-based epoxy resin cured product, and its preparation technology is simple, workable, controllable process property is good, is easy to industrializing implementation.
The present invention also provides a kind of full bio-based epoxy resin cured product; Adopt the bio-based tung oil acid anhydride that rosinyl epoxy resin is cured; Prepare full bio-based epoxy resin cured product; Overcome from molecular structure that common rosin basic ring epoxy resins cured article fragility is big, the not good shortcoming of over-all properties, made the full bio-based epoxy resin cured product that makes have mechanical property preferably, good uvioresistant performance and excellent characteristics such as ageing-resistant performance.
The present invention also provides a kind of application of full bio-based epoxy resin cured product, is particularly useful for making composite matrix resin and outdoor electrical insulating material.
A kind of full bio-based composition epoxy resin, form by the raw material of following weight part:
Rosinyl epoxy resin 100 weight parts;
Tung oil acid anhydride 50～300 weight parts;
Catalyzer 1～15 weight part.
Described rosinyl epoxy resin is one or more in the rosinyl epoxy monomer; Described rosinyl epoxy monomer is preferably the monomer of formula I structure, formula II structure, formula III structure, formula IV structure or formula V structure:
Wherein, the rosinyl epoxy monomer of formula I structure is prepared through a series of existing chemical reactions by rosin derivative maleopimaric anhydride and epoxy chloropropane, and specifically preparing process can be the one Chinese patent application of 01108250.X with reference to application number;
The rosinyl epoxy monomer of formula II structure is prepared through a series of existing chemical reactions by acrylic acid modified rosin and epoxy chloropropane, and specifically preparing process can be the one Chinese patent application of 02149777.X with reference to application number;
The rosinyl epoxy monomer of formula III structure is prepared through a series of existing chemical reactions by maleopimaric acid imide diprotic acid and epoxy chloropropane; Concrete preparation process is that the Chinese patent of ZL200410098973.X obtains the maleopimaric acid imide diprotic acid through maleopimaric anhydride after through reaction with reference to the patent No. earlier, refers again to application number and be 201010225279.5 one Chinese patent application, and the maleopimaric acid imide diprotic acid of 100 weight parts and the epoxy bromopropane of 60～80 weight parts are mixed; After adding the catalyzer cetyl trimethylammonium bromide of 2～8 weight parts again; At 80～100 ℃ of reaction 4h～6h, be cooled to 60 ℃～70 ℃, add the sodium hydroxide of 15～25 weight parts; Continue reaction 3～5 hours; Remove by filter the NaCl of generation, excessive epoxy chloropropane is reclaimed in underpressure distillation, crude product water/ether system extraction; Vacuum-drying obtains the rosinyl epoxy monomer of formula III structure;
The rosinyl epoxy monomer of formula IV structure is prepared through a series of existing chemical reactions by polymerized rosin and epoxy chloropropane, specifically prepares process and can be with reference to application number 200710032534.2 one Chinese patent application;
The rosinyl epoxy monomer of formula V structure is prepared through a series of existing chemical reactions by formaldehyde modified rosin and epoxy chloropropane, specifically prepares process and can be with reference to application number 200810198059.0 one Chinese patent application.
Described tung oil acid anhydride adopts commercially available product, and its outward appearance is yellow or pale brown look thick liquid, and the weight percentage of acid anhydrides is greater than 13% in the preferred tung oil acid anhydride; 25 ℃ viscosity is 2000～8000mPas.Owing to contain longer aliphatics segment in the tung oil acid anhydride; In the solidification process, tung oil acid anhydride and catalyzer can make the epoxide group on the rosinyl epoxy monomer carry out ring-opening reaction and crosslinking reaction, and it is after solidifying with inflexible rosinyl epoxy monomer; Can reduce the cross-linking density of cured article; Increase the distance between the cross-linking set, thereby reduce the fragility of cured article, improve the comprehensive use properties of rosinyl epoxy resin cured product.
Described catalyzer can be selected one or more in imdazole derivatives, tertiary amine, quaternary ammonium salt, boron trifluoride complex, the metal halide for use; In preferred 1-methyl-2-ethyl imidazol(e), triethylamine, tetramethyl ammonium chloride, etamon chloride, the boron trifluoride ethyl ether complex one or more.
The preparation method of described full bio-based composition epoxy resin is: rosinyl epoxy resin, tung oil acid anhydride and catalyzer are mixed by proportioning, obtain full bio-based composition epoxy resin.
Described full bio-based composition epoxy resin can be applicable to prepare Weather-resistant epoxy sizing agent, epoxy resin-based paint and epoxypaint, has a good application prospect.Use like the Weather-resistant epoxy sizing agent; After rosinyl epoxy resin, 50～300 weight part tung oil acid anhydrides and 1～15 weight part catalyst mix with 100 weight parts, just can be used as the Weather-resistant epoxy sizing agent, smear required sticky position; After waiting to solidify, just has bonding strength preferably.
Described full bio-based composition epoxy resin can obtain full bio-based epoxy resin cured product after solidifying.
Described full bio-based composition epoxy resin prepares the method for full bio-based epoxy resin cured product, may further comprise the steps:
Rosinyl epoxy resin, tung oil acid anhydride and catalyst mix are obtained mixture after evenly; Mixture at 60 ℃～120 ℃ following Procuring 0.5h～4h, at 140 ℃～200 ℃ following after fixing 10min～6h, is obtained full bio-based epoxy resin cured product again.
Not containing aromatic series ring-type monomer (like phenyl ring, dihydroxyphenyl propane) etc. in the full bio-based epoxy resin cured product of the present invention easily by destructive structural units such as ultraviolet ray, heat energy, is a kind of pure fat based epoxy resin.The present invention utilizes flexible tung oil acid anhydride to solidify inflexible rosinyl epoxy monomer; Can reduce the cross-linking density of cured article; Increase the distance between the cross-linking set; Overcome from molecular structure that common rosin basic ring epoxy resins cured article fragility is big, the not good shortcoming of over-all properties, made that this full bio-based epoxy resin cured product has the excellent comprehensive performance.The full bio-based epoxy resin cured product of the present invention can be widely used in preparation composite matrix resin and outdoor electrical insulating material.
Compared with prior art, advantage of the present invention and beneficial effect are following:
(1) prescription of full bio-based epoxy resin cured product of the present invention and preparation method just so far, also do not see the document and the patent report that utilize bio-based solidifying agent solidified biological basic ring epoxy resins to prepare epoxy resin cured product;
(2) rosin and tung oil all belong to China's characteristic cheapness, renewable resources is easy to get; Through rosin (being the rosinyl epoxy monomer) alternative petroleum base aliphatics or the aromatic series ring-type monomer after the modification; Carry out preparing tung oil acid anhydride after the D-A addition through eleostearic acid and maleic anhydride; On the one hand, main raw material all adopts renewable resources, has good environmental benefit; On the other hand, the present invention provides new approach for their deep processing and high value added utilization;
(3) the present invention uses the bio-based tung oil acid anhydride that rosinyl epoxy resin is cured; Rosinyl epoxy resin, tung oil acid anhydride and catalyst combination have been given play to excellent performance together; The gained cured article is better flexible; Avoided the fragility of rosin and epoxy resin, and this cured article has good uvioresistant performance, excellent ageing-resistant performance and good mechanical performance, can prepare outdoor electrical insulating material, Weather-resistant epoxy sizing agent and epoxy resin-based paint etc.;
(4) the full bio-based epoxy resin cured product of the present invention preparation method, its preparation technology is simple, workable, controllable process property is good, is easy to industrializing implementation.
Embodiment
Embodiment 1
(1) maleopimaric anhydride 400 gram, epoxy chloropropane 300 grams and water 18 grams are mixed, add 8 gram 4 bromides, 80 ℃ of reactions 1 hour down; The remaining epoxy chloropropane of reaction is reclaimed in underpressure distillation, adds 50 milliliters of toluene then, and is 170 to restrain Pottasium Hydroxide 100 ℃ of following minutes 4 times equivalent adding total amounts; Keep reaction 2 hours; Filter also washing to neutral, vacuum distillation recovered solvent obtains the light yellow collophony basic ring epoxy resins monomer of formula I structure;
The rosinyl epoxy monomer of formula I structure
(2) the rosinyl epoxy monomer 100 with above-mentioned formula I structure restrains, (available from Henan Lin Mei Science and Technology Ltd., wherein the weight percentage of acid anhydrides is 14% to tung oil acid anhydride 50 grams; 25 ℃ viscosity is 4000mPas) after and catalyzer 1-methyl-2-ethyl imidazol(e) 3 grams mix, obtain mixture;
(3) with said mixture 60 ℃ of following Procuring 4 hours, 140 ℃ of following after fixing 6 hours, obtain full bio-based epoxy resin cured product again.
Through test, the prepared full bio-based epoxy resin cured product that obtains has following performance: tensile strength: 46MPa; Tensile modulus: 2635MPa; Elongation at break: 6.8%.
Embodiment 2
(1) 100 gram maleopimaric anhydrides are dissolved in 150 milliliters of N, in the dinethylformamide, and add 46 gram para-amino benzoic acid, stirring at room is after 3 hours; Be warming up to 150 ℃ and stirred 4 hours, be cooled to room temperature, become the yellowish brown solid; The zero(ppm) water that adds 150 grams stirs, and has yellow mercury oxide to produce.Filter, washing, 60 ℃ of vacuum-drying 3 hours, with DMF and water recrystallization repeatedly, final product becomes the white powder solid, inserts in the vacuum drying oven 90 ℃ of vacuum-dryings 10 hours, obtains the maleopimaric acid imide diprotic acid, productive rate 86%.Under the nitrogen protection, maleopimaric acid imide diprotic acid that obtains and 40 gram epoxy bromopropanes addings are had in the churned mechanically there-necked flask, heating for dissolving becomes homogeneous phase; Add cetyl trimethylammonium bromide 3 and restrain, be cooled to 65 ℃, add 5 gram sodium hydroxide at every turn in 90 ℃ of reactions 5 hours; Totally three times, keep reaction 4 hours, remove by filter the NaCl of generation; Excessive epoxy chloropropane is reclaimed in underpressure distillation; The extraction of crude product water/ether system, 60 ℃ of vacuum-drying 12 hours obtains the rosinyl epoxy monomer of formula III structure;
The rosinyl epoxy monomer of formula III structure
(2) the rosinyl epoxy monomer 100 with above-mentioned formula III structure restrains, (available from Yangzhou Guang Run chemical industry ltd, wherein, the weight percentage of acid anhydrides is 13.6% to tung oil acid anhydride 100 grams; 25 ℃ viscosity is 6000mPas) and catalyzer etamon chloride 5 gram mix, obtain mixture;
(3) with said mixture 90 ℃ of following Procuring 2 hours, 200 ℃ of following after fixing 2 hours, obtain full bio-based epoxy resin cured product again.
Through test, the prepared full bio-based epoxy resin cured product that obtains has following performance: tensile strength: 28MPa; Tensile modulus: 1890MPa; Elongation at break: 15.2%.
Embodiment 3
(1) 480 gram addings have in the four-hole boiling flask of TM, whisking appliance and prolong and mix with epoxy chloropropane with formaldehyde modified rosin 100 gram; Add tetramethyl ammonium chloride 0.45 gram after being warming up to 85 ℃; Reacted 5 hours; The cooling back adds benzene 75 grams and sodium hydroxide 29 grams, and controlled temperature then reacted 3.5 hours at 70 ℃.Filter, wash to the halogen ion, removal of solvent under reduced pressure, 60 ℃ of vacuum-dryings obtained the rosinyl epoxy monomer of formula V structure in 6 hours;
The rosinyl epoxy monomer of formula V structure
(2) the rosinyl epoxy monomer 100 with above-mentioned formula V structure restrains, (available from Henan Lin Mei Science and Technology Ltd., wherein, the weight percentage of acid anhydrides is 13.1% to tung oil acid anhydride 300 grams; 25 ℃ viscosity is 4300mPas) and catalyst of triethylamine 1 gram mix, obtain mixture;
(3) with said mixture 120 ℃ of following Procuring 4 hours, 180 ℃ of following after fixing 4 hours, obtain full bio-based epoxy resin cured product again.
Through test, the prepared full bio-based epoxy resin cured product that obtains has following performance: tensile strength: 49MPa; Tensile modulus: 2900MPa; Elongation at break: 5.3%.
Embodiment 4
(1) polymerized rosin 100 grams and epoxy chloropropane 70 gram addings are had in the four-hole boiling flask of TM, whisking appliance and prolong, be warming up to 100 ℃, add tetramethyl ammonium chloride 0.1 gram reaction and be cooled to 50 ℃ after 4.5 hours; Add 75 gram benzene and 20 gram sodium hydroxide then, be warming up to 70 ℃ of reactions 2.5 hours, filter; Be washed with distilled water to the halogen ion; Remove and to desolvate, 60 ℃ of vacuum-drying 6 hours obtains the rosinyl epoxy monomer of formula IV structure;
The rosinyl epoxy monomer of formula IV structure
(2) the rosinyl epoxy monomer 100 with above-mentioned formula IV structure restrains, (available from Yangzhou Guang Run chemical industry ltd, wherein the weight percentage of acid anhydrides is 14.5% to tung oil acid anhydride 120 grams; 25 ℃ viscosity is 8000mPas) and catalyzer boron trifluoride ethyl ether complex 15 gram mix, obtain mixture;
(3) with said mixture 80 ℃ of following Procuring 2 hours, 140 ℃ of following after fixing 6 hours, obtain full bio-based epoxy resin cured product again.
Through test, the prepared full bio-based epoxy resin cured product that obtains has following performance: tensile strength: 18MPa; Tensile modulus: 1940MPa; Elongation at break: 25.3%.
Embodiment 5
(1) in 100 milliliters of four-hole bottles, add rosin acrylic acid 374 grams, 70 milliliters in epoxy chloropropane 224 grams, saleratus 411 grams, Tetrabutyl amonium bromide 7.5 grams and acetone were heated to 60 ℃ of back flow reaction 10 hours, and the pressurization of cooling back removes desolvates.Add the dissolving of 20 milliliters of toluene then, repeatedly washing with zero(ppm) water does not have cl ions to water layer and exists.Collect toluene layer, 80 ℃ of vacuum-dryings 4 hours, obtain the rosinyl epoxy monomer of formula II structure behind the removal solvent;
The rosinyl epoxy monomer of formula II structure
(2) the rosinyl epoxy monomer 100 with above-mentioned formula II structure restrains, (available from Yangzhou Guang Run chemical industry ltd, wherein the weight percentage of acid anhydrides is 13.8% to tung oil acid anhydride 90 grams; 25 ℃ viscosity is 6500mPas) and even by the catalyst mix that tetramethyl ammonium chloride 2 restrains and triethylamine 1 gram is formed, obtain mixture;
(3) with said mixture 100 ℃ of following Procuring 2 hours, 140 ℃ of following after fixing 6 hours, obtain full bio-based epoxy resin cured product again;
Through test, the prepared full bio-based epoxy resin cured product that obtains has following performance: tensile strength: 30MPa; Tensile modulus: 2100MPa; Elongation at break: 11.8%.
Embodiment 6
(1) prepare the rosinyl epoxy monomer of the formula I structure that is shown in the following figure and the rosinyl epoxy monomer of formula IV structure according to the preparation process among embodiment 1 and the embodiment 4 respectively:
The rosinyl epoxy monomer of the rosinyl epoxy monomer formula IV structure of formula I structure
(2) with each 50 gram of rosinyl epoxy monomer of the rosinyl epoxy monomer of formula I structure and formula IV structure, (available from Henan Lin Mei Science and Technology Ltd., wherein, the weight percentage of acid anhydrides is 13.5% to tung oil acid anhydride 100 grams; 25 ℃ viscosity is 4500mPas) and catalyzer etamon chloride 5 gram mix, obtain mixture;
(3) with said mixture 90 ℃ of following Procuring 2 hours, 180 ℃ of following after fixing 5 hours, obtain full bio-based epoxy resin cured product again.
Through test, the prepared full bio-based epoxy resin cured product that obtains has following performance: tensile strength: 36MPa; Tensile modulus: 2600MPa; Elongation at break: 7.8%.
Embodiment 7
(available from Henan Lin Mei Science and Technology Ltd., wherein, the weight percentage of acid anhydrides is 13.5% with rosinyl epoxy monomer, the 160 weight part tung oil acid anhydrides of 100 weight part formula I structures; 25 ℃ viscosity is 4500mPas) and 2 after weight part 1-methyl-the 2-ethyl imidazol(e) mixes, obtain full bio-based composition epoxy resin.
Said composition can be directly as weathe resistance epoxy resin lacquer or epoxypaint.Concrete operation method is: get full bio-based composition epoxy resin 10 grams, evenly be applied on 50 square centimeters of iron plates, put it in 120 ℃ the baking oven heating at last 4 hours, be cooled to room temperature, left standstill 2 hours.Through test, iron plate surface pencil hardness is 2H, xanthochromia not after natural being exposed to the sun 4 months, and it is 0 grade that cross-hatching records sticking power.Show that this bio-based composition epoxy resin can be used as the weathe resistance epoxy resin lacquer or epoxypaint uses.
Above-mentioned is to combine embodiment that the present invention is elaborated; But embodiment of the present invention is not restricted to the described embodiments, and other any change of under patent core guiding theory of the present invention, being done, replacement, combination simplification etc. are included within the protection domain of patent of the present invention.
Claims (8)
1. a full bio-based composition epoxy resin is characterized in that, is made up of the raw material of following weight part:
Rosinyl epoxy resin 100 weight parts;
Tung oil acid anhydride 50～300 weight parts;
Catalyzer 1～15 weight part;
Described rosinyl epoxy resin is one or more in the rosinyl epoxy monomer;
Described rosinyl epoxy monomer is the monomer of formula II structure, formula III structure, formula IV structure or formula V structure:
2. full bio-based composition epoxy resin according to claim 1 is characterized in that the weight percentage of acid anhydrides is greater than 13% in the described tung oil acid anhydride;
Described tung oil acid anhydride is 2000～8000mPas 25 ℃ viscosity.
3. full bio-based composition epoxy resin according to claim 1 is characterized in that described catalyzer is one or more in imdazole derivatives, tertiary amine, quaternary ammonium salt, boron trifluoride complex, the metal halide.
4. according to claim 1 or 3 described full bio-based composition epoxy resins; It is characterized in that described catalyzer is one or more in 1-methyl-2-ethyl imidazol(e), triethylamine, tetramethyl ammonium chloride, etamon chloride, the boron trifluoride ethyl ether complex.
5. according to the application of each described full bio-based composition epoxy resin of claim 1～4 in preparation Weather-resistant epoxy sizing agent, epoxy resin-based paint and epoxypaint.
6. prepare the method for full bio-based epoxy resin cured product according to each described full bio-based composition epoxy resin of claim 1～4, it is characterized in that, may further comprise the steps:
Rosinyl epoxy resin, tung oil acid anhydride and catalyst mix are obtained mixture after evenly; Mixture at 60 ℃～120 ℃ following Procuring 0.5h～4h, at 140 ℃～200 ℃ following after fixing 10min～6h, is obtained full bio-based epoxy resin cured product again.
7. the full bio-based epoxy resin cured product of method preparation according to claim 6.
8. the application of full bio-based epoxy resin cured product according to claim 7 in preparation composite matrix resin and outdoor electrical insulating material.
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| CN101307170A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Fire retardant phosphorus-containing epoxy powder composition |
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| CN111533713A (en) * | 2020-05-20 | 2020-08-14 | 中国林业科学研究院林产化学工业研究所 | Rosin-based epoxy monomer and preparation method and application thereof |
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