CN108192078B - Preparation method of bio-based flame-retardant epoxy resin and bio-based flame-retardant epoxy resin prepared by preparation method - Google Patents
Preparation method of bio-based flame-retardant epoxy resin and bio-based flame-retardant epoxy resin prepared by preparation method Download PDFInfo
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- 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
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
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- 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
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- 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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy 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
- C08G59/40—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
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
Abstract
The invention discloses a full-biobased flame-retardant epoxy resin, which is characterized in that 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and an epoxy group are introduced by utilizing an active group on gallic acid to obtain a biobased epoxy monomer, thereby replacing bisphenol A epoxy resin DGEBA used in general industry, synthesizing a high-activity biobased curing agent-difurfurylamine, and mixing and curing the biobased curing agent with the prepared epoxy monomer under a certain condition to obtain a full-biobased epoxy resin product with flame retardant property. The epoxy resin has the advantages of wide biological source, environmental protection, simpler reaction process, good flame retardant property, maximum limit oxygen index of 34 percent and maximum vertical combustion grade of V-0 grade. The invention discloses a preparation method of the compound.
Description
Technical Field
The invention relates to a full-bio-based flame-retardant epoxy resin, which is prepared by introducing phosphorus element into a bio-based epoxy monomer, so that the bio-based epoxy resin has good flame-retardant property.
Background
Petroleum-based plastics can provide various raw materials and products for various industries such as buildings, automobiles, mechanical manufacturing, electronic information and the like due to various excellent properties, and play an important role in modern social life, but in the face of the increasing problems of petroleum energy crisis and environmental pollution in the world, people begin to search for new materials which take biomass and renewable resources as raw materials and are manufactured to meet the requirements to replace petroleum-based materials. Most biological materials are non-toxic and harmless, have rich content, can relieve the pressure of energy exhaustion and pollution aggravation, reduce the dependence of the plastic industry on petroleum-based chemical product supply, and reduce the environmental pollution caused in the production process of high polymer materials. Currently, research on bio-based polymer materials is mainly limited to some natural polymers or thermoplastic materials such as starch plastics, cellulose-based materials, PHBV, PLA, PBS, bio-based PE, etc., and research on bio-based thermosetting resins is relatively rare.
The epoxy resin is one of the most widely used thermosetting resins, the global yield is about 200 million tons per year, wherein the bisphenol A epoxy resin accounts for more than 85 percent and is mainly prepared from 2 raw materials of bisphenol A and epichlorohydrin. Epichlorohydrin can be prepared from bio-based glycerol and has been industrialized, but more than 67% of bisphenol a is completely dependent on petrochemical resources at present. Meanwhile, bisphenol A has great threat to the health of living bodies, and the development of environment-friendly resin which can replace bisphenol A epoxy resin is significant. Meanwhile, the oxygen index of the epoxy resin is 19.8, the epoxy resin can be combusted in the air after being ignited, and the combustion speed is high, so that how to improve the flame retardant property of the epoxy resin and expand the application range of the epoxy resin is also a big subject of application type research.
The epoxy resin is subjected to flame retardant modification, and chemical elements with flame retardant property can be introduced into an epoxy resin curing system. There are generally two methods of introducing flame retardant elements into the curing system: reactive and non-reactive. The non-reactive type is that the substrate is treated by a physical mode, and the flame retardant is directly added into the flame-retardant substrate, the reaction method is simple and easy to implement, but the mechanical property of the material is reduced due to the incompatibility of the flame retardant and the substrate; the reactive type is that flame retardant elements are introduced into an epoxy molecular framework and are covalently linked to a polymer molecular chain, so that the migration of a flame retardant can be avoided, and the flame retardant efficiency is improved.
Gallic Acid (GA) is a hydrolyzed compound of natural plant polyphenol, the plant polyphenol has abundant content and wide source in plant, and the structure contains 1 carboxyl and 3 hydroxyl, so that polyphenol type epoxy resin can be synthesized, and the aromatic structure of the gallic acid can also endow the epoxy resin with good thermal mechanical property. Chinese patent CN 102276788A discloses an epoxy resin based on gallic acid and a preparation method thereof, wherein gallic acid, epoxy halogenated propane and a catalyst are mixed and then react for 2-5 h at 100-120 ℃, then the temperature is reduced to 20-40 ℃, an alkaline compound and water are added, the reaction is continued for 2-5 h, and the epoxy resin based on the gallic acid is obtained after washing, solvent removal and drying. However, excess epihalohydrin tends to not react completely with gallic acid and tends to react with the acid to produce epoxy oligomers rather than epoxy monomers. Patent CN106519712A discloses a high-performance fully-bio-based epoxidized soybean oil resin, which is prepared by curing epoxidized soybean oil and polyamide 1010 prepolymer in the presence of a catalyst, has the advantages of tensile strength of 5-38.5MPa, breaking secondary length of 55-356 percent and excellent mechanical properties. The monomers used to prepare the polyamide 1010 prepolymer, namely sebacic acid and decanediamine, are also derived from renewable resources and are used as curing agents for epoxidized soybean oil. However, since vegetable oil bases contain a long aliphatic chain, the heat stability is inferior to that of aromatic group-containing epoxy resins. US patent WO2016172353a1 discloses a process for the preparation of an epoxy resin from vanillin. Firstly, Schiff base is used for reaction, and then the vanillin based epoxy resin is prepared by epoxypropyl. The obtained epoxy monomer has high activity and can be used as a resin coating. However, the epoxy monomer has a small number of epoxy groups, resulting in a low crosslinking density of the final cured product.
The invention provides a preparation method of a full-bio-based flame-retardant epoxy resin, and the raw material is derived from gallic acid, is a polyphenol compound existing in the nature, is widely present in plants such as rheum palmatum, swamp mahogany, dogwood and the like, and thus meets the standards of environmental protection and energy conservation. Phosphorus element, aromatic structure and a plurality of epoxy groups in the epoxy monomer, so that the thermal stability of the finally prepared epoxy resin is greatly improved compared with the industrial epoxy resin, and the limited oxygen index can reach more than 30 percent.
Disclosure of Invention
The invention aims to solve the problems of poor flame retardance, toxic raw materials and non-regenerability of the traditional synthetic resin, and provides a preparation method of a full-bio-based flame-retardant epoxy resin. The method has the advantages of cheap and easily-obtained raw materials, simple reaction process, no need of too harsh reaction conditions, more epoxy monomer epoxy groups, improvement of the cross-linking density of the epoxy resin, contribution to improvement of the thermal stability of the material due to the aromatic structure, and equivalent furan diamine curing activity as a curing agent to that of an industrially common curing agent. The introduction of phosphorus element effectively improves the flame retardant property. In order to achieve the above object, the technical solution of the present invention is as follows:
a preparation method of full-bio-based flame-retardant epoxy resin is characterized in that gallic acid is used as an initial raw material, is subjected to allylation, is subjected to addition reaction with 9, 10-dihydro-9-oxa-10-phospha-10-oxide (DOPO), is subjected to oxidation reaction to introduce an epoxy group, and is mixed and solidified with difurfuryl amine prepared from furfuryl amine under the heating condition to obtain a final product, wherein the synthesis of the bio-based epoxy monomer and a curing agent comprises the following steps:
step 1, adding a solvent, potassium carbonate and gallic acid into a flask, strongly stirring for 5-20 min, then slowly adding a solution of allyl bromide within 20-60 min, heating the mixture to 50-80 ℃, keeping the temperature for 20-48 h, filtering, carrying out rotary evaporation on the obtained solution, finally dissolving a crude product in dichloromethane, washing with saturated saline solution, carrying out rotary evaporation on a dichloromethane layer to obtain a refined product, and carrying out vacuum drying for 7-15 h at 50-80 ℃ to obtain a product 1: 3,4, 5-triallyl benzoate; the molar ratio of the gallic acid to the potassium carbonate is 1: 5-11, and the molar ratio of the gallic acid to the allyl bromide is 1: 6-12; the selected solvent is one of tetrahydrofuran, acetone, dichloromethane or diethyl ether;
the reaction is as follows:
step 2, adding 9, 10-dihydro-9-oxa-10-phospha-10-oxide and a solvent into a round-bottom flask with a condenser tube, heating the flask to 60-100 ℃ in an argon atmosphere, completely dissolving the 9, 10-dihydro-9-oxa-10-phospha-10-oxide, adding the product 1 into the flask within 30-80 min, keeping the reaction mixture at the temperature for 10-40 h, cooling to room temperature, filtering to obtain a product, washing for 2-5 times by using a mixed solvent, and then drying for 3-8 h in vacuum at 80-140 ℃ to obtain a product 2: DOPO-based 3,4, 5-triallyloxybenzoate; the molar ratio of the product 1 to the 9, 10-dihydro-9-oxa-10-phospha-10-oxide is 1: 1-2.2; the mixed solvent is a mixture of two solvents of xylene or tetrahydrofuran and dichloromethane or acetone in a volume ratio of 1: 1; (ii) a
The reaction is as follows:
step 3, adding the solution of the product 2, m-chloroperoxybenzoic acid and 4,4' -thiobis (6-tert-butyl-m-cresol) into a flask, reacting for 40-60 h at the temperature of 20-50 ℃, then cooling to 0-minus 10 ℃, keeping the temperature for 3-10 h, filtering to remove filter residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution and saturated sodium chloride aqueous solution in turn, removing residual water in the organic phase by anhydrous magnesium sulfate, then carrying out rotary evaporation, dissolving the obtained solid in 5ml dichloromethane, pouring into 10 times of cold methanol, filtering to obtain precipitate, and performing vacuum drying at the temperature of 20-50 ℃ for 40-60 hours to obtain DOPO-based 3,4, 5-tricyclic ethoxy benzoate, wherein the molar ratio of the product 2 to m-chloroperoxybenzoic acid is 1: 9-12, and the molar ratio of the product 2 to 4,4' -thiobis (6-tert-butyl-m-cresol) is 3-6: 1; the solvent of the solution of the product 2 is one of tetrahydrofuran, acetone, dichloromethane or diethyl ether;
the reaction is as follows:
step 4, adding furfuryl amine into a round bottom flask with a reflux condenser tube, cooling to-5 ℃, dropwise adding 10-20 w% of hydrochloric acid, heating to 20-35 ℃, stirring for 10-30 min, adding acetone into the mixture, raising the temperature to 30-60 ℃, adding a certain amount of acetone, reacting for 5-10 days, adding acetone, cooling the mixture to 20-30 ℃, adding 100-200 ml of deionized water, adjusting the pH to 8-13 with 15 wt% of NaOH solution, extracting the mixture with ethyl acetate for 2-5 times, washing an organic phase with a sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, and removing ethyl acetate by rotary evaporation to obtain a bio-based curing agent, namely furan dimethylamine, wherein the molar ratio of furfuryl amine to hydrochloric acid is 1: 2-4, and the molar ratio of furfuryl amine to acetone added three times is 1: 2-4: 0.1-0.4;
the structure of the product obtained is as follows:
and 5, stirring the phosphorus-containing epoxy monomer obtained in the step 3 at the temperature of 30-80 ℃ for 8-30 min, adding the bio-based curing agent furan dimethylamine obtained in the step 4, wherein the mass ratio of the phosphorus-containing epoxy monomer to the bio-based curing agent furan dimethylamine is 1: 2-4, stirring for 3-8 min, pouring into a preheated mold, curing for 4h at the temperature of 80 ℃, and curing for 10h at the temperature of 150 ℃ to obtain the full bio-based flame-retardant epoxy resin product.
A full bio-based flame-retardant epoxy resin product prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the raw materials of the epoxy resin prepared by the invention are all derived from renewable resources, the epoxy resin is cheap, environment-friendly and energy-saving, and the whole reaction process is simple and low in toxicity;
(2) gallic acid is used as a raw material for preparing the epoxy monomer, the aromatic structure of the gallic acid is favorable for improving the thermal stability of the material, a plurality of functional groups are also favorable for introducing epoxy groups, and the crosslinking density of the epoxy resin is improved;
(3) phosphorus element is introduced by utilizing addition reaction of a P-H bond of DOPO and a double bond, so that the flame retardant property of the epoxy resin is improved;
Detailed Description
The following examples are used to illustrate the preparation method of the all-bio-based flame-retardant epoxy resin of the present invention. The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
Example 1:
(1) a sealed flask was charged with 20ml of tetrahydrofuran, 0.088mol of potassium carbonate, and 0.0176mol of gallic acid, and vigorously stirred for 5 min. Then, the solution of allyl bromide was added slowly over 20 min. The mixture was heated to 50 ℃ and held at this temperature for 20 h. The obtained product is filtered to remove impurities in the solution and is rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated in a rotary evaporation way to obtain a refined product, and the refined product is dried in vacuum for 7 hours at the temperature of 50 ℃ to obtain a product 1.
(2) 0.0176mol DOPO, 30ml tetrahydrofuran, was added to a round bottom flask with a condenser tube and heated to 60 ℃ under argon. After complete dissolution of DOPO, 0.0176mol of product 1 are added within 30min, and the reaction mixture is held at this temperature for 10 h. After cooling to room temperature, the product was filtered, washed 2 times with tetrahydrofuran/xylene (1: 1) and then dried under vacuum at 80 ℃ for 3h to give product 2.
(3) A tetrahydrofuran solution (30ml) of a product 2(0.0176mol), 0.1584mol of m-chloroperoxybenzoic acid and 0.00587mol of 4,4' -thiobis (6-tert-butyl-m-cresol) are added into a flask, the mixture is reacted for 40h at 20 ℃, then the mixture is cooled to 0 ℃, the temperature is kept for 3h, filter residue is removed by filtration, the filtrate is washed by a 10% sodium sulfite solution, a 5% sodium carbonate solution and saturated saline solution in sequence, residual water in an organic phase is removed by anhydrous magnesium sulfate, rotary evaporation is carried out, the obtained solid is dissolved in 5ml of dichloromethane, the obtained solid is poured into 10 times of cold methanol and filtered to obtain precipitate, and the precipitate is dried for 40h in vacuum at 20 ℃ to obtain the phosphorus-containing epoxy monomer.
(4)0.1mol of furfurylamine was added to a round-bottomed flask with a reflux condenser and cooled to-5 ℃. 10 w% hydrochloric acid (0.2mol) was added dropwise. Then the temperature was raised to 20 ℃ and stirred for 10 min. 0.2mol of acetone are added to the mixture. The temperature was heated to 30 ℃. 0.01mol of acetone is added. After 5 days of reaction, 0.01mol of acetone was added. The mixture was cooled to 20 ℃ and 100ml of deionized water was added. The pH was adjusted to 8 with 15% by weight NaOH solution and the mixture was extracted 2 times with ethyl acetate. Washing the organic phase with saline solution, drying with anhydrous magnesium sulfate, and rotary evaporating to remove ethyl acetate to obtain the bio-based curing agent.
(5) Finally, the phosphorus-containing epoxy monomer is stirred for 8min at 30 ℃, a bio-based curing agent (the proportion is 1: 2w/w) is added, the mixture is stirred for 3min, and the mixture is poured into a preheated mold and is stirred for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 305 ℃, and the carbon residue rate at 800 ℃ is 32%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 27.3%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-1 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 2:
(1) a sealed flask was charged with 20ml of methylene chloride, 0.088mol of potassium carbonate and 0.0176mol of gallic acid, and vigorously stirred for 20 min. Then, a solution of allyl bromide in methylene chloride was added slowly over 60 min. The mixture was heated to 80 ℃ and held at this temperature for 48 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated by rotary evaporation to obtain a refined product, and the refined product is dried under vacuum at the temperature of 80 ℃ for 15 hours to obtain a product 1.
(2) 0.0176mol DOPO, 80ml methylene chloride, was added to a round bottom flask with a condenser tube and the flask was heated to 100 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 were added within 80min, and the reaction mixture was held at this temperature for 40 h. After cooling to room temperature, the product was filtered, washed 5 times with a mixed xylene/tetrahydrofuran solution (1: 1) and then dried under vacuum at 140 ℃ for 8h to give product 2.
(3) A solution of product 2(0.0176mol) in methylene chloride (80ml), 0.01584mol of m-chloroperoxybenzoic acid, 0.00587mol of 4,4' -thiobis (6-tert-butyl-m-cresol) were added to the flask. Reacting at 50 deg.C for 60h, cooling to-10 deg.C, maintaining at the temperature for 10h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, drying under vacuum at 50 ℃ for 60 h.
(4) Furfuryl amine (0.1mol) was charged to a round bottom flask with reflux condenser and cooled to 5 ℃. 20 w% hydrochloric acid (0.2mol) was added dropwise. Then the temperature was raised to 35 ℃ and stirred for 30 min. 0.2mol of acetone are added to the mixture. The temperature was increased to 60 ℃. 0.01mol of acetone is added. After 10 days of reaction, 0.01mol of acetone was added. The mixture was cooled to 30 ℃ and 200ml of deionized water was added. The pH was adjusted to 13 with 15% by weight NaOH solution and the mixture was extracted 5 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 30min at 80 ℃, a bio-based curing agent (the proportion is 1: 4w/w) is added, the mixture is stirred for 8min, and the mixture is poured into a preheated mold and is stirred for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 308 ℃, and the carbon residue rate at 800 ℃ is 33.2%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 27.5%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-1 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 3:
(1) a sealed flask was charged with 30ml of acetone, 0.088mol of potassium carbonate and 0.0176mol of gallic acid, and vigorously stirred for 15 min. Then, an acetone solution of allyl bromide was slowly added over 40 min. The mixture was heated to 60 ℃ and held at this temperature for 30 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated by rotary evaporation to obtain a refined product, and the refined product is dried under vacuum at 70 ℃ for 10 hours to obtain a product 1.
(2) 0.0176mol DOPO, 50ml acetone were added to a round bottom flask with a condenser tube and the flask was heated to 80 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 were added within 50min, and the reaction mixture was held at this temperature for 30 h. After cooling to room temperature, the product was filtered, washed 3 times with xylene/tetrahydrofuran (1: 1) and then dried under vacuum at 100 ℃ for 5h to give product 2.
(3) The flask was charged with a solution of product 2(0.0176mol) in acetone (50ml), 0.1584mol of m-chloroperoxybenzoic acid, 0.00587mol of 4,4' -thiobis (6-tert-butyl-m-cresol). Reacting at 30 deg.C for 50h, cooling to-5 deg.C, maintaining at the temperature for 7h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, vacuum drying is carried out for 50h at the temperature of 30 ℃, and the product 2 is obtained.
(4) Furfuryl amine (0.1mol) was charged to a round bottom flask with reflux condenser and cooled to 0 ℃.15 w% hydrochloric acid (0.2mol) was added dropwise. Then the temperature was raised to 30 ℃ and stirred for 20 min. 0.2mol of acetone are added to the mixture. The temperature was increased to 40 ℃. 0.01mol of acetone is added. After 7 days of reaction, 0.01mol of acetone was added. The mixture was cooled to 25 ℃ and 150ml of deionized water was added. The pH was adjusted to 10 with 15% by weight NaOH solution and the mixture was extracted 3 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 20min at 60 ℃, the bio-based curing agent (the proportion is 1: 3) is added, the mixture is stirred for 5min, and the mixture is poured into a preheated mold and is heated for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 302 ℃, and the carbon residue rate at 800 ℃ is 31.2%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 27.1%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-1 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 4:
(1) a sealed flask was charged with 20ml of tetrahydrofuran, 0.1936mol of potassium carbonate, and 0.0176mol of gallic acid, and vigorously stirred for 5 min. Then, a solution of allyl bromide (0.2112mol) in tetrahydrofuran was slowly added over 20 min. The mixture was heated to 50 ℃ and held at this temperature for 20 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated in a rotary evaporation way to obtain a refined product, and the refined product is dried in vacuum for 7 hours at the temperature of 50 ℃ to obtain a product 1.
(2) A round bottom flask with a condenser was charged with 0.03872mol dopo, 30ml tetrahydrofuran and the flask was heated to 60 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 are added within 30min, and the reaction mixture is held at this temperature for 10 h. After cooling to room temperature, the product was filtered, washed 2 times with tetrahydrofuran/xylene (1: 1) and then dried under vacuum at 80 ℃ for 3h to give product 2.
(3) The flask was charged with a solution of product 2(0.0176mol) in tetrahydrofuran (30ml), 0.2112mol of m-chloroperoxybenzoic acid, 0.002933mol of 4,4' -thiobis (6-tert-butyl-m-cresol). Reacting at 20 deg.C for 40h, cooling to 0 deg.C, maintaining at the temperature for 3h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, vacuum drying at 20 ℃ for 40 h.
(4)0.1mol of furfurylamine was added to a round-bottomed flask with a reflux condenser and cooled to-5 ℃. 10 w% hydrochloric acid (0.4mol) was added dropwise. Then the temperature was raised to 20 ℃ and stirred for 10 min. 0.4mol of acetone are added to the mixture. The temperature was increased to 30 ℃. 0.04mol of acetone are added. After 5 days of reaction, 0.04mol of acetone was added. The mixture was cooled to 20 ℃ and 100ml of deionized water was added. The pH was adjusted to 8 with 15% by weight NaOH solution and the mixture was extracted 2 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 8min at 30 ℃, a bio-based curing agent (the proportion is 1: 2) is added, the mixture is stirred for 3min, and the mixture is poured into a preheated mold and is stirred for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 312 ℃, and the carbon residue rate at 800 ℃ is 35.3%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 28.2%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy on a V-O scale, 130.0mm × 12.7mm × 3.2mm length × width × thickness.
Example 5:
(1) a sealed flask was charged with 20ml of methylene chloride, 0.1936mol of potassium carbonate and 0.0176mol of gallic acid, and vigorously stirred for 20 min. Then, a solution of allyl bromide (0.2112mol) in dichloromethane was slowly added over 60 min. The mixture was heated to 80 ℃ and held at this temperature for 48 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated by rotary evaporation to obtain a refined product, and the refined product is dried under vacuum at the temperature of 80 ℃ for 15 hours to obtain a product 1.
(2) A round bottom flask with a condenser was charged with 0.03872mol dopo, 80ml dichloromethane and the flask was heated to 100 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 were added within 80min, and the reaction mixture was held at this temperature for 40 h. After cooling to room temperature, the product was filtered, washed 5 times with a mixed xylene/tetrahydrofuran solution (1: 1) and then dried under vacuum at 140 ℃ for 8h to give product 2.
(3) A solution of product 2(0.0176mol) in methylene chloride (80ml), 0.2112mol of m-chloroperoxybenzoic acid, 0.002933mol of 4,4' -thiobis (6-tert-butyl-m-cresol) were added to the flask. Reacting at 50 deg.C for 60h, cooling to-10 deg.C, maintaining at the temperature for 10h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, drying under vacuum at 50 ℃ for 60 h.
(4) Furfuryl amine (0.1mol) was charged to a round bottom flask with reflux condenser and cooled to 5 ℃. 20 w% hydrochloric acid (0.4mol) was added dropwise. Then the temperature was raised to 35 ℃ and stirred for 30 min. 0.4mol of acetone are added to the mixture. The temperature was increased to 60 ℃. 0.04mol of acetone are added. After 10 days of reaction, 0.04mol of acetone was added. The mixture was cooled to 30 ℃ and 200ml of deionized water was added. The pH was adjusted to 13 with 15% by weight NaOH solution and the mixture was extracted 5 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 30min at 80 ℃, a bio-based curing agent (the proportion is 1: 4) is added, the stirring is carried out for 8min, and the mixture is poured into a preheated mold and is stirred for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 305 ℃, and the carbon residue rate at 800 ℃ is 31.2%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 27.2%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-1 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 6:
(1) a sealed flask was charged with 30ml of acetone, 0.1936mol of potassium carbonate and 0.0176mol of gallic acid, and vigorously stirred for 15 min. Then, a solution of allyl bromide (0.2112mol) in acetone was slowly added over 40 min. The mixture was heated to 60 ℃ and held at this temperature for 30 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated by rotary evaporation to obtain a refined product, and the refined product is dried under vacuum at 70 ℃ for 10 hours to obtain a product 1.
(2) A round bottom flask with a condenser was charged with 0.03872mol dopo, 50ml acetone and the flask was heated to 80 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 were added within 50min, and the reaction mixture was held at this temperature for 30 h. After cooling to room temperature, the product was filtered, washed 3 times with xylene/tetrahydrofuran (1: 1) and then dried under vacuum at 100 ℃ for 5h to give product 2.
(3) The flask was charged with a solution of product 2(0.0176mol) in acetone (50ml), 0.2112mol of m-chloroperoxybenzoic acid, 0.002933mol of 4,4' -thiobis (6-tert-butyl-m-cresol). Reacting at 30 deg.C for 50h, cooling to-5 deg.C, maintaining at the temperature for 7h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, vacuum drying is carried out for 50h at the temperature of 30 ℃, and the product 2 is obtained.
(4) Furfuryl amine (0.1mol) was charged to a round bottom flask with reflux condenser and cooled to 0 ℃.15 w% hydrochloric acid (0.4mol) was added dropwise. Then the temperature was raised to 30 ℃ and stirred for 20 min. 0.4mol of acetone are added to the mixture. The temperature was increased to 40 ℃. 0.04mol of acetone are added. After 7 days of reaction, 0.04mol of acetone was added. The mixture was cooled to 25 ℃ and 150ml of deionized water was added. The pH was adjusted to 10 with 15% by weight NaOH solution and the mixture was extracted 3 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 20min at 60 ℃, the bio-based curing agent (the proportion is 1: 3) is added, the mixture is stirred for 5min, and the mixture is poured into a preheated mold and is heated for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 315 ℃, and the carbon residue rate at 800 ℃ is 34%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 27.8%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-0 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 7:
(1) a sealed flask was charged with 20ml of tetrahydrofuran, 0.1408mol of potassium carbonate, and 0.0176mol of gallic acid, and vigorously stirred for 5 min. Then, a solution of allyl bromide (0.176mol) was added slowly over 20 min. The mixture was heated to 50 ℃ and held at this temperature for 20 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated in a rotary evaporation way to obtain a refined product, and the refined product is dried in vacuum for 7 hours at the temperature of 50 ℃ to obtain a product 1.
(2) A round bottom flask with a condenser was charged with 0.0264mol DOPO, 30ml tetrahydrofuran and the flask was heated to 60 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 are added within 30min, and the reaction mixture is held at this temperature for 10 h. After cooling to room temperature, the product was filtered, washed 2 times with tetrahydrofuran/xylene (1: 1) and then dried under vacuum at 80 ℃ for 3h to give product 2.
(3) The flask was charged with a solution of product 2(0.0176mol) in tetrahydrofuran (30ml), 0.1936mol of m-chloroperoxybenzoic acid, 0.00352mol of 4,4' -thiobis (6-tert-butyl-m-cresol). Reacting at 20 deg.C for 40h, cooling to 0 deg.C, maintaining at the temperature for 3h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, vacuum drying at 20 ℃ for 40 h.
(4)0.1mol of furfurylamine was added to a round-bottomed flask with a reflux condenser and cooled to-5 ℃. 10 w% hydrochloric acid (0.3mol) was added dropwise. Then the temperature was raised to 20 ℃ and stirred for 10 min. 0.3mol of acetone are added to the mixture. The temperature was increased to 30 ℃. 0.03mol of acetone is added. After 5 days of reaction, 0.03mol of acetone was added. The mixture was cooled to 20 ℃ and 100ml of deionized water was added. The pH was adjusted to 8 with 15% by weight NaOH solution and the mixture was extracted 2 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 8min at 30 ℃, a bio-based curing agent (the proportion is 1: 2) is added, the mixture is stirred for 3min, and the mixture is poured into a preheated mold and is stirred for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 301 ℃, and the carbon residue rate at 800 ℃ is 33%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 27.5%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-1 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 8:
(1) the sealed flask was charged with 20ml of dichloromethane, 0.: 1408mol of potassium carbonate and 0.0176mol of gallic acid, and stirring vigorously for 20 min. Then, a solution of allyl bromide (0.176mol) in methylene chloride was slowly added over 60 min. The mixture was heated to 80 ℃ and held at this temperature for 48 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated by rotary evaporation to obtain a refined product, and the refined product is dried under vacuum at the temperature of 80 ℃ for 15 hours to obtain a product 1.
(2) A round bottom flask with a condenser was charged with 0.0264mol DOPO, 80ml methylene chloride and the flask was heated to 100 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 were added within 80min, and the reaction mixture was held at this temperature for 40 h. After cooling to room temperature, the product was filtered, washed 5 times with a mixed xylene/tetrahydrofuran solution (1: 1) and then dried under vacuum at 140 ℃ for 8h to give product 2.
(3) A solution of product 2(0.0176mol) in methylene chloride (80ml), 0.1936mol of m-chloroperoxybenzoic acid, 0.00352mol of 4,4' -thiobis (6-tert-butyl-m-cresol) were charged into the flask. Reacting at 50 deg.C for 60h, cooling to-10 deg.C, maintaining at the temperature for 10h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, drying under vacuum at 50 ℃ for 60 h.
(4) Furfuryl amine (0.1mol) was charged to a round bottom flask with reflux condenser and cooled to 5 ℃. 20 w% hydrochloric acid (0.3mol) was added dropwise. Then the temperature was raised to 35 ℃ and stirred for 30 min. 0.3mol of acetone are added to the mixture. The temperature was increased to 60 ℃. 0.03mol of acetone is added. After 10 days of reaction, 0.03mol of acetone was added. The mixture was cooled to 30 ℃ and 200ml of deionized water was added. The pH was adjusted to 13 with 15% by weight NaOH solution and the mixture was extracted 5 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 30min at 80 ℃, a bio-based curing agent (the proportion is 1: 4) is added, the stirring is carried out for 8min, and the mixture is poured into a preheated mold and is stirred for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 311 ℃, and the carbon residue rate at 800 ℃ is 35.2%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 28.1%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy of V-0 grade, 130.0mm × 12.7mm × 3.2mm in length × width × thickness.
Example 9:
(1) a sealed flask was charged with 30ml of acetone, 0.1408mol of potassium carbonate and 0.0176mol of gallic acid, and vigorously stirred for 15 min. Then, a solution of allyl bromide (0.176mol) in acetone was slowly added over 40 min. The mixture was heated to 60 ℃ and held at this temperature for 30 h. The product obtained is filtered and rotary evaporated. Finally, the crude product was dissolved in dichloromethane and washed with saturated brine. The dichloromethane layer is evaporated by rotary evaporation to obtain a refined product, and the refined product is dried under vacuum at 70 ℃ for 10 hours to obtain a product 1.
(2) 0.0264mol DOPO, 50ml acetone were added to a round bottom flask with a condenser and the flask was heated to 80 ℃ under argon atmosphere. After complete dissolution of DOPO, 0.0176mol of product 1 were added within 50min, and the reaction mixture was held at this temperature for 30 h. After cooling to room temperature, the product was filtered, washed 3 times with xylene/tetrahydrofuran (1: 1) and then dried under vacuum at 100 ℃ for 5h to give product 2.
(3) The flask was charged with a solution of product 2(0.0176mol) in acetone (50ml), 0.1936mol of m-chloroperoxybenzoic acid, 0.00352mol of 4,4' -thiobis (6-tert-butyl-m-cresol). Reacting at 30 deg.C for 50h, cooling to-5 deg.C, maintaining at the temperature for 7h, filtering to remove residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution, saturated saline solution, removing residual water in organic phase with anhydrous magnesium sulfate, and rotary steaming. The resulting solid was dissolved in 5ml of dichloromethane, poured into 10 times of cold methanol and filtered to obtain a precipitate. Finally, vacuum drying is carried out for 50h at the temperature of 30 ℃, and the product 2 is obtained.
(4) Furfuryl amine (0.1mol) was charged to a round bottom flask with reflux condenser and cooled to 0 ℃.15 w% hydrochloric acid (0.3mol) was added dropwise. Then the temperature was raised to 30 ℃ and stirred for 20 min. 0.3mol of acetone are added to the mixture. The temperature was increased to 40 ℃. 0.03mol of acetone is added. After 7 days of reaction, 0.03mol of acetone was added. The mixture was cooled to 25 ℃ and 150ml of deionized water was added. The pH was adjusted to 10 with 15% by weight NaOH solution and the mixture was extracted 3 times with ethyl acetate. The organic phase was washed with brine, dried over anhydrous magnesium sulfate, and ethyl acetate was removed by rotary evaporation.
Finally, the phosphorus-containing epoxy monomer is stirred for 20min at 60 ℃, the bio-based curing agent (the proportion is 1: 3) is added, the mixture is stirred for 5min, and the mixture is poured into a preheated mold and is heated for 4h at 80 ℃ and 10h at 150 ℃.
Thermogravimetric analysis is carried out on the sample, the heating rate is 10 ℃/min, the initial decomposition temperature is 312 ℃, and the carbon residue rate at 800 ℃ is 34.8%.
According to GB/T2046.2-2009, the limiting oxygen index is characterized by a limiting oxygen index instrument, and the limiting oxygen index is 28%.
An CZF-3 type horizontal and vertical combustion instrument is adopted, and the specification of the sample strip is as follows: the sample was rated for flame retardancy on a V-O scale, 130.0mm × 12.7mm × 3.2mm length × width × thickness.
The mixture ratio of the raw materials is changed to prepare a series of full-bio-based flame-retardant epoxy resins, and the indexes are shown in table 1:
table 1:
Claims (2)
1. the preparation method of the full-bio-based flame-retardant epoxy resin is characterized by comprising the following steps of:
step 1, adding a solvent, potassium carbonate and gallic acid into a flask, strongly stirring for 5-20 min, then slowly adding a solution of allyl bromide within 20-60 min, heating the mixture to 50-80 ℃, keeping the temperature for 20-48 h, filtering the obtained product to remove impurities, carrying out rotary evaporation on the solution to remove the solvent to obtain a crude product, dissolving the crude product in dichloromethane, washing the crude product with a saturated sodium chloride aqueous solution, carrying out rotary evaporation on a dichloromethane layer to obtain a refined product, and carrying out vacuum drying for 7-15 h at 50-80 ℃ to obtain a product 1: 3,4, 5-triallyloxybenzoic acid ester; the molar ratio of the gallic acid to the potassium carbonate is 1: 5-11, and the molar ratio of the gallic acid to the allyl bromide is 1: 6-12; the solvent is one of tetrahydrofuran, acetone, dichloromethane or diethyl ether;
step 2, adding 9, 10-dihydro-9-oxa-10-phospha-10-oxide and a solvent into a round-bottom flask with a condenser tube, heating the flask to 60-100 ℃ in an argon atmosphere, completely dissolving the 9, 10-dihydro-9-oxa-10-phospha-10-oxide, adding the product 1 into the flask within 30-80 min, keeping the reaction mixture at the temperature for 10-40 h, cooling to room temperature, filtering to obtain a product, washing with a mixed solvent, and performing vacuum drying at 80-140 ℃ for 3-8 h to obtain a product 2: DOPO-based 3,4, 5-triallyloxybenzoate; the molar ratio of the product 1 to the 9, 10-dihydro-9-oxa-10-phospha-10-oxide is 1: 1-2.2; the mixed solvent is a mixture of two solvents of xylene or tetrahydrofuran and dichloromethane or acetone in a volume ratio of 1: 1;
step 3, adding the solution of the product 2, m-chloroperoxybenzoic acid and 4,4' -thiobis (6-tert-butyl-m-cresol) into a flask, reacting for 40-60 h at the temperature of 20-50 ℃, then cooling to 0-minus 10 ℃, keeping the temperature for 3-10 h, filtering to remove filter residue, washing the filtrate with 10% sodium sulfite solution, 5% sodium carbonate solution and saturated sodium chloride aqueous solution in turn, removing residual water in the organic phase by anhydrous magnesium sulfate, then carrying out rotary evaporation, dissolving the obtained solid in dichloromethane, pouring into cold methanol with the volume 10 times that of the mixture, filtering to obtain a precipitate, and performing vacuum drying to obtain phosphorus-containing epoxy monomer DOPO-based 3,4, 5-tricycloethoxybenzoic acid ester, wherein the molar ratio of the product 2 to m-chloroperoxybenzoic acid is 1: 9-12, and the molar ratio of the product 2 to 4,4' -thiobis (6-tert-butyl-m-cresol) is 3-6: 1; the solvent of the product 2 solution is one of tetrahydrofuran, acetone, dichloromethane or diethyl ether;
step 4, adding furfuryl amine into a round-bottom flask with a reflux condenser tube, cooling to-5 ℃, dropwise adding 10-20 w% of hydrochloric acid, then heating to 20-35 ℃, stirring for 10-30 min, adding acetone into the mixture, raising the temperature to 30-60 ℃, adding acetone, reacting for 5-10 days, then completing, adding acetone for the third time, cooling the mixture to 20-30 ℃, adding deionized water, adjusting the pH to 8-13 with 15 wt% of NaOH solution, extracting the mixture with ethyl acetate, washing an organic phase with sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, and removing ethyl acetate by rotary evaporation to obtain a bio-based curing agent, namely furan dimethylamine, wherein the molar ratio of the furfuryl amine to the hydrochloric acid is 1: 2-4, and the molar ratio of the furfuryl amine to the acetone added for the third time is 1: 2-4: 0.1-0.4;
and 5, stirring the phosphorus-containing epoxy monomer obtained in the step 3 at the temperature of 30-80 ℃ for 8-30 min, adding the bio-based curing agent furan dimethylamine obtained in the step 4, wherein the mass ratio of the phosphorus-containing epoxy monomer to the bio-based curing agent furan dimethylamine is 1: 2-4, stirring for 3-8 min, pouring into a preheated mold, curing for 4h at the temperature of 80 ℃, and curing for 10h at the temperature of 150 ℃ to obtain the full bio-based flame-retardant epoxy resin product.
2. A fully bio-based flame retardant epoxy resin made by the method of claim 1.
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| CN110483562A (en) * | 2018-08-20 | 2019-11-22 | 南京大学 | A kind of more aromatic ring flame retardant epoxy monomers of boron N structure and its preparation method and purposes |
| JP7081441B2 (en) * | 2018-10-24 | 2022-06-07 | 日本ゼオン株式会社 | Method for Producing Esters and Allyl Ethers Using Fluorine-Containing Cyclic Glycol as Raw Material |
| CN109942795B (en) * | 2019-02-12 | 2021-03-19 | 中南民族大学 | Gallic acid-based waterborne phosphorus-containing epoxy curing agent and preparation method thereof |
| CN111285827A (en) * | 2019-12-08 | 2020-06-16 | 南京工业大学 | Preparation method of novel difurane compound |
| CN111205437B (en) * | 2020-02-26 | 2022-07-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method of biological basic characteristic type flame-retardant epoxy resin |
| CN111333880B (en) * | 2020-04-21 | 2022-04-22 | 万华化学集团股份有限公司 | Super water-absorbing polymer and preparation method thereof |
| CN113736410B (en) * | 2020-05-28 | 2023-01-31 | 上海乘鹰新材料有限公司 | High-humidity-heat-resistant composite adhesive applied to cold-stamping formed aluminum and preparation method thereof |
| CN112552482B (en) * | 2020-11-25 | 2022-11-22 | 广东工业大学 | Bio-based phosphaphenanthrene biphenyl type epoxy resin as well as preparation method and application thereof |
| WO2022127640A1 (en) * | 2020-12-16 | 2022-06-23 | Covestro Deutschland Ag | Process for synthesis of furan-based diamines |
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| Multi-functionalization of gallic acid. Synthesis of a novel bio-based epoxy resin;Aouf C, et al.;《European Polymer Journal》;20121208;第49卷;全文 * |
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| CN108192078A (en) | 2018-06-22 |
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