CN111732607A - Carboxylic acid compound containing phosphorus, nitrogen and boron, preparation method thereof, and preparation method and application of flame-retardant epoxy resin - Google Patents
Carboxylic acid compound containing phosphorus, nitrogen and boron, preparation method thereof, and preparation method and application of flame-retardant epoxy resin Download PDFInfo
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- CN111732607A CN111732607A CN202010609427.7A CN202010609427A CN111732607A CN 111732607 A CN111732607 A CN 111732607A CN 202010609427 A CN202010609427 A CN 202010609427A CN 111732607 A CN111732607 A CN 111732607A
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention relates to the technical field of materials, in particular to a carboxylic acid compound containing phosphorus, nitrogen and boron, a preparation method thereof, a preparation method of flame-retardant epoxy resin and application of the flame-retardant epoxy resin. The carboxylic acid compound has a molecular structure containing phosphaphenanthrene, triazinetrione, boric acid or organic boric acid group and carboxyl, and the molecular structure has two forms of TMDB-1 and TMDB-2, and specifically comprises the following components: TMDB-1:
TMDB‑2：
wherein R1 and R2 are any one of hydroxyl, alkyl and aryl. The carboxylic acid containing phosphorus, nitrogen and boron of the invention is combinedThe material is a reactive halogen-free flame retardant, which not only solves the problem of harm of halogen-containing flame retardant to human body and environment, but also overcomes the influence of additive flame retardant on the physical and mechanical properties of epoxy resin matrix. The carboxylic acid compound of the invention endows an epoxy/anhydride system with excellent flame retardant and smoke suppression performances, and simultaneously can improve the mechanical properties to a certain extent, and the flexural modulus and the flexural strength of the flame-retardant epoxy resin are improved.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a carboxylic acid compound containing phosphorus, nitrogen and boron, a preparation method thereof, a preparation method of flame-retardant epoxy resin and application of the flame-retardant epoxy resin.
Background
The epoxy resin has excellent adhesive property, better corrosion resistance, excellent physical and mechanical properties and electrical insulation property, so that the epoxy resin is widely applied to the fields of adhesive coatings, electronics and electrics, chemistry and chemical engineering, mechanical manufacturing, transportation and the like, and is one of the most widely applied thermosetting resins at present. However, epoxy resin is a flammable material like other high molecular materials, and after being ignited, the epoxy resin will be violently burned and release a large amount of heat, thereby generating dense smoke and toxic gases, and easily causing huge casualties and property loss. Therefore, the improvement of the flame retardant property of the epoxy resin has important significance for improving the fire safety coefficient and widening the application field of the epoxy resin.
With the increase of global environmental awareness, the use of halogen-containing flame retardants is gradually restricted. In addition, since the additive flame retardant is merely physically blended in the resin matrix, the overall performance of the epoxy resin is deteriorated, and the flame retardant is precipitated from the surface of the matrix with the increase of the service time, so that the flame retardant performance is reduced and the environment is polluted. In order to reduce the negative influence of the flame retardant on the comprehensive performance of the epoxy resin matrix, the research on designing and developing a flame-retardant curing agent or co-curing agent with reactivity becomes a hotspot for the flame-retardant modification research of the epoxy resin.
Chinese patent CN 106749413B discloses a reactive flame retardant containing phosphorus, nitrogen and sulfur, which is added into an epoxy resin matrix, improves the flame retardant effect of the epoxy resin and keeps the thermal stability and mechanical properties of the epoxy resin. However, the reactive flame retardant is developed based on amine design, and the prepared reactive flame retardant is finally used for an epoxy resin/amine system. In addition to amine curing agents, anhydrides are another important and widely used epoxy resin curing agent, and have better comprehensive properties than amine cured epoxy resins, such as low toxicity, low initial viscosity, long pot life, low water absorption, excellent electrical insulation and transparency, and the like, so the anhydrides are preferably used in many important applications of epoxy resins, especially in electronic equipment. Nowadays, electronic products are highly integrated, and fire caused by overheating of the electronic products is more and more. Therefore, the research on the flame retardant modification of the anhydride curing epoxy resin is particularly important. Although the existing preparation methods basically solve the problem of flammability of an epoxy/anhydride system, the flame retardant efficiency is low, the smoke suppression performance is poor, the addition amount is increased, the process forming performance is inevitably reduced, and meanwhile, the mechanical property of a matrix is deteriorated to a certain extent by adding a large amount of flame retardant.
Disclosure of Invention
One of the purposes of the invention is to provide a carboxylic acid compound containing phosphorus, nitrogen and boron, which is a reactive halogen-free flame retardant, has higher flame retardant efficiency, is applied to an epoxy resin/anhydride system, endows the epoxy resin with excellent flame retardant and smoke suppression performances, and can also basically keep the original physical and mechanical properties of the epoxy resin, such as heat resistance, mechanical properties and the like.
The invention also aims to provide a preparation method of the carboxylic acid compound containing phosphorus, nitrogen and boron, which has the advantages of simple reaction process, mild conditions, no generation of toxic and harmful substances in the synthesis process, economy, environmental protection and low cost.
The invention also aims to provide a preparation method of the flame-retardant epoxy resin, wherein the carboxylic acid compound containing phosphorus, nitrogen and boron is used as a flame retardant, so that the original physical and mechanical properties of the epoxy resin, such as heat resistance, mechanical property and the like, can be basically maintained while the epoxy resin is endowed with excellent flame retardance and smoke suppression properties.
The fourth purpose of the invention is to provide application of the flame-retardant epoxy resin.
The scheme adopted by the invention for realizing one of the purposes is as follows: a carboxylic acid compound containing phosphorus, nitrogen and boron, wherein the molecular structure of the carboxylic acid compound contains phosphaphenanthrene, triazinetrione, boric acid or organic boric acid group and carboxyl, and the molecular structure of the carboxylic acid compound has two forms of TMDB-1 and TMDB-2, and the carboxylic acid compound specifically comprises the following components:
TMDB-1：
TMDB-2：
wherein R1 and R2 are any one of hydroxyl, alkyl and aryl.
The second scheme adopted by the invention for achieving the purpose is as follows: the preparation method of the carboxylic acid compound containing phosphorus, nitrogen and boron is characterized in that trihydroxyethyl isocyanurate, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and boric acid or organic boric acid are used as raw materials and are synthesized through esterification and addition reaction.
Preferably, the method comprises two esterification reactions and one addition reaction, and comprises the following specific steps:
(1) esterification reaction: mixing trihydroxyethyl isocyanurate, maleic anhydride and a proper amount of solvent a according to a certain proportion, heating to 85-95 ℃, and continuously stirring for 2-4 hours in a nitrogen atmosphere;
(2) addition reaction: adding a certain amount of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a solvent a into the reaction liquid in the step (1) in batches, heating to 110 ℃ and reacting for 8-9 h;
(3) esterification reaction: dissolving boric acid or organic boric acid in a solvent a, adding the boric acid or organic boric acid into the mixture obtained in the step (2), and continuing to react for 2-3 h;
(4) impurity removal and purification: and (4) removing the solvent a from the solution after the reaction in the step (3), and washing and drying the obtained crude product to obtain a white solid product.
Preferably, in the steps (1) to (3), when TMDB-1 is synthesized, the molar ratio of trishydroxyethyl isocyanurate, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, boric acid or organic boric acid is 1: (2-2.1): (2-2.1): (1-1.05); when TMDB-2 is synthesized, the molar ratio of the trihydroxyethyl isocyanurate to the maleic anhydride to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the boric acid or the organic boric acid is 1: (1-1.05): (1-1.05): (2-2.1).
Preferably, in the step (3), the organic boric acid is any one of methyl boric acid, ethyl boric acid, phenyl boric acid, 3-methyl phenyl boric acid, 2-furan boric acid and 3-furan boric acid.
Preferably, in the steps (1) to (4), the solvent a is dioxane; in the step (4), the crude product is washed by deionized water.
The scheme adopted by the invention for realizing the third purpose is as follows: the preparation method of the flame-retardant epoxy resin adopts the carboxylic acid compound as a flame retardant, and the epoxy resin and the flame retardant are mixed according to the mass ratio of 10: (1-5) uniformly mixing at 130-150 ℃, adding an anhydride curing agent and an accelerator into the mixed solution when the temperature of the mixture is cooled to 60-80 ℃, uniformly stirring the mixture, and defoaming; and finally, curing the mixed solution, wherein the curing system is 100 ℃/(3-4 h) +130 ℃/(2-3 h) +180 ℃/(1-2 h) +200 ℃/(1-2 h).
Preferably, the epoxy resin is any one of E-53, E-51 and E-44 bisphenol A type glycidyl ether epoxy resin.
Preferably, the acid anhydride curing agent is at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride; the accelerator is any one of tertiary amine, imidazole or quaternary ammonium salt. Preferably, the accelerator is a tertiary amine such as triethylamine, N-dimethylbenzylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, imidazole or a quaternary ammonium salt.
The scheme adopted by the fourth invention for realizing the purpose is as follows: the flame-retardant epoxy resin prepared by the preparation method of the flame-retardant epoxy resin is applied to the fields of electronics, electrics, aerospace and transportation.
The invention has the following advantages and beneficial effects:
(1) the phosphorus-nitrogen-boron-containing carboxylic acid compound is a reactive halogen-free flame retardant, on one hand, the harm of the halogen-containing flame retardant to human bodies and the environment is solved, and on the other hand, the influence of an additive flame retardant on the physical and mechanical properties of an epoxy resin matrix is overcome.
(2) The carboxylic acid compound of the present invention has high flame retardant efficiency, and the cured product can pass UL-94V-0 rating with only 15.1 wt% TMDB added.
(3) The carboxylic acid compound of the present invention has a good smoke suppressing effect, and the total smoke release amount during combustion of the cured product is reduced by 47.2% compared to a pure epoxy resin system when only 15.1 wt% of TMDB is added.
(4) The carboxylic acid compound of the invention can endow an epoxy/anhydride system with excellent flame retardant and smoke suppression performances, simultaneously improve the mechanical properties to a certain extent, improve the flexural modulus and the flexural strength of the flame-retardant epoxy resin, and can meet the application in the flame-retardant field with higher requirements on the mechanical properties.
(5) The synthesis of the carboxylic acid compound adopts cheap industrial raw materials, the reaction process is simple, the condition is mild, no toxic and harmful substances are generated in the synthesis process, and the preparation method is economic, environment-friendly and low in cost.
(6) The flame-retardant epoxy resin disclosed by the invention adopts the carboxylic acid compound as the flame retardant, so that the bending modulus and the bending strength of the flame-retardant epoxy resin are improved, the application in the flame-retardant field with higher requirements on mechanical properties can be met, and the flame-retardant epoxy resin can be applied to the fields of electronics, electrics, aerospace, transportation and the like, such as sealants, packaging materials of integrated circuits, matrix materials of composite materials and the like.
Drawings
FIG. 1 shows TMDB and THEIC in example 2 of the present invention1H NMR spectra and of TMDB and DOPO31A P NMR spectrum;
FIG. 2 is an infrared spectrum of a synthetic raw material and TMDB of example 2 of the present invention.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
The invention discloses a preparation method of a phosphorus-nitrogen-boron-containing carboxylic acid compound, which comprises the steps of two-step esterification reaction, one-step addition reaction and preparation of flame-retardant epoxy resin. The carboxylic acid compound is synthesized by taking trihydroxyethyl isocyanurate (THEIC), Maleic Anhydride (MAH), DOPO and Boric Acid (BA) as raw materials. The flame retardant has high flame retardant efficiency and good smoke suppression effect, can endow an epoxy/anhydride system with excellent flame retardant and smoke suppression performance at a low addition amount, can improve the mechanical property of an epoxy resin matrix to a certain extent by adding the flame retardant, effectively overcomes the defect that an epoxy resin/anhydride condensate is flammable, and has potential application value in related fields of electronics and electricity, aerospace, transportation and the like.
[ example 1 ]
100g of epoxy resin (E-51) and 84.7g of methyltetrahydrophthalic anhydride were initially stirred in a 250mL round-bottomed flask at room temperature for 10 min. Then 0.2g of 2,4, 6-tri (dimethylaminomethyl) phenol is added and stirred for 10min, and then vacuum defoamation is carried out for 5 min. And finally, quickly pouring the mixed solution into a preheated mold, and curing in an oven, wherein the curing system is 100 ℃/4h +130 ℃/2h +180 ℃/2h +200 ℃/2 h. After the resin was cured, samples were prepared according to the test standards and the resulting samples were designated EP, which is a control sample without the addition of flame retardant.
[ example 2 ]
To a 500mL three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and thermometer was added 78.3g of THEIC, 58.8g of MAH and 60mL of dioxane, and the mixture was stirred at a constant speed. The reaction was warmed to 85 ℃ under nitrogen atmosphere and reacted for 2 h. Then 129.6g of DOPO and 100mL of dioxane were added to the reaction solution in portions over 30 min. The mixture was further heated to reflux and held for 8 h. Then, 20mL of dioxane solution containing 18.5g of BA was added to the reaction mixture, and the reaction was continued for 3 hours. After the reaction was completed, the solution was distilled to remove dioxane. Then the crude product is treatedThe product is washed five times with deionized water and dried under vacuum at 80 ℃ for 24h to finally obtain a white solid product, namely TMDB. A small amount of the powder was subjected to NMR and IR spectroscopy, and the results are shown in FIGS. 1 and 2. The hydrogen atoms of different chemical environments of TMDB in the hydrogen spectrogram all correspond to each other, and a single peak appears in the phosphorus spectrogram. 3427, 1740 and 1693, 1435, 1200cm in the infrared spectrum of TMDB-1The characteristic absorption peaks of-OH and C-O, B-O-C, P-O bond are respectively at the position. The above results indicate that the phosphorus nitrogen boron-containing carboxylic acid is successfully synthesized.
100g of epoxy resin (E-51) and 14.6g of the carboxylic acid compound flame retardant prepared in this example were added to a 250mL round-bottomed flask, and after stirring at 140 ℃ for 1 hour, heating was stopped, and when the mixture temperature was cooled to 75 ℃, 79.5g of methyltetrahydrophthalic anhydride and 0.2g of 2,4, 6-tris (dimethylaminomethyl) phenol were added to the mixed solution, and after stirring for 10 minutes, defoaming was performed in vacuo for 5 minutes. And finally, quickly pouring the mixed solution into a preheated mold, and curing in an oven, wherein the curing system is 100 ℃/4h +130 ℃/2h +180 ℃/2h +200 ℃/2 h. After the resin was cured, specimens were prepared according to the test standards, and the specimens obtained were designated EP-1 and had a flame retardant content of 7.5% by weight.
[ example 3 ]
To a 500mL three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and thermometer was added 78.3g of THEIC, 58.8g of MAH and 60mL of dioxane, and the mixture was stirred at a constant speed. The reaction was warmed to 95 ℃ under nitrogen atmosphere and reacted for 2 h. Then 129.6g of DOPO and 100mL of dioxane were added to the reaction solution in portions over 30 min. The mixture was further heated to reflux and held for 8 h. Then, 20mL of dioxane solution containing 18.5g of BA was added to the reaction mixture, and the reaction was continued for 3 hours. After the reaction was completed, the solution was distilled to remove dioxane. The crude product was washed five times with deionized water and dried under vacuum at 80 ℃ for 24h to give the final product TMDB as a white solid.
100g of epoxy resin (E-51) and 30.8g of the carboxylic acid compound flame retardant prepared in this example were added to a 250mL round-bottomed flask, and after stirring at 140 ℃ for 1 hour, heating was stopped, and when the temperature of the mixture was cooled to 75 ℃, 73.7g of methyltetrahydrophthalic anhydride and 0.2g of 2,4, 6-tris (dimethylaminomethyl) phenol were added to the mixed solution, and after stirring for 10 minutes, vacuum defoaming was performed for 5 minutes. And finally, quickly pouring the mixed solution into a preheated mold, and curing in an oven, wherein the curing system is 100 ℃/4h +130 ℃/2h +180 ℃/2h +200 ℃/2 h. After the resin was cured, a sample was prepared according to the standard, and the obtained sample was designated as EP-2, and the flame retardant content was 15.1 wt%.
[ example 4 ]
To a 500mL three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and thermometer was added 78.3g of THEIC, 58.8g of MAH and 60mL of dioxane, and the mixture was stirred at a constant speed. The reaction was warmed to 90 ℃ under nitrogen atmosphere and reacted for 2 h. Then 129.6g of DOPO and 100mL of dioxane were added to the reaction solution in portions over 30 min. The mixture was further heated to reflux and held for 8 h. Then, 20mL of dioxane solution containing 18.5g of BA was added to the reaction mixture, and the reaction was continued for 3 hours. After the reaction was completed, the solution was distilled to remove dioxane. The crude product was washed five times with deionized water and dried under vacuum at 80 ℃ for 24h to give the final product TMDB as a white solid.
100g of epoxy resin (E-51) and 48.8g of the carboxylic acid compound flame retardant prepared in this example were added to a 250mL round-bottomed flask, and after stirring at 140 ℃ for 1 hour, heating was stopped, and when the temperature of the mixture was cooled to 75 ℃, 67.3g of methyltetrahydrophthalic anhydride and 0.2g of 2,4, 6-tris (dimethylaminomethyl) phenol were added to the mixed solution, and stirred for 10 minutes, followed by vacuum deaeration for 5 minutes. And finally, quickly pouring the mixed solution into a preheated mold, and curing in an oven, wherein the curing system is 100 ℃/4h +130 ℃/2h +180 ℃/2h +200 ℃/2 h. After the resin was cured, specimens were prepared according to the test standards, and the obtained specimens were designated EP-3, and the flame retardant content was 22.6% by weight.
The specimens prepared in examples 1 to 4 were subjected to Limit Oxygen Index (LOI), flame retardancy grade (UL-94), cone calorimetry, bending properties and dynamic thermo-mechanical analysis tests with reference to the standards, and the test results are shown in Table 1
The technical scheme adopted by the embodiment is that the flame retardant performance and the bending performance are carried out according to the following standards:
the limiting oxygen index is determined according to the following test criteria: GB 2406-80;
the flame retardant rating is determined according to the following test criteria: ASTM D3801;
the flexural properties were determined according to the test standards: GB/T2567-.
TABLE 1 flame-retardant, smoke-suppressing, mechanical and heat-resistant Properties test results of flame-retardant epoxy resins
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A carboxylic acid compound containing phosphorus, nitrogen and boron, characterized in that: the carboxylic acid compound has a molecular structure containing phosphaphenanthrene, triazinetrione, boric acid or organic boric acid group and carboxyl, and the molecular structure has two forms of TMDB-1 and TMDB-2, and specifically comprises the following components:
TMDB-1：
TMDB-2：
wherein R1 and R2 are any one of hydroxyl, alkyl and aryl.
2. A method for producing a carboxylic acid compound containing phosphorus, nitrogen and boron according to claim 1, characterized in that: the material is composed of trihydroxyethyl isocyanuric ester, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, boric acid or organic boric acid through esterification and addition reaction.
3. The method for producing a carboxylic acid compound containing phosphorus, nitrogen and boron according to claim 2, characterized in that: comprises two steps of esterification reaction and one step of addition reaction, and comprises the following specific steps:
(1) esterification reaction: mixing trihydroxyethyl isocyanurate, maleic anhydride and a proper amount of solvent a according to a certain proportion, heating to 85-95 ℃, and continuously stirring for 2-4 hours in a nitrogen atmosphere;
(2) addition reaction: adding a certain amount of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a solvent a into the reaction liquid in the step (1) in batches, heating to 110 ℃ and reacting for 8-9 h;
(3) esterification reaction: dissolving boric acid or organic boric acid in a solvent a, adding the boric acid or organic boric acid into the mixture obtained in the step (2), and continuing to react for 2-3 h;
(4) impurity removal and purification: and (4) removing the solvent a from the solution after the reaction in the step (3), and washing and drying the obtained crude product to obtain a white solid product.
4. The method of producing a carboxylic acid compound containing phosphorus, nitrogen and boron according to claim 3, characterized in that: in the steps (1) to (3), when TMDB-1 is synthesized, the molar ratio of trishydroxyethyl isocyanurate, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, boric acid, or organic boric acid is 1: (2-2.1): (2-2.1): (1-1.05); when TMDB-2 is synthesized, the molar ratio of the trihydroxyethyl isocyanurate to the maleic anhydride to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the boric acid or the organic boric acid is 1: (1-1.05): (1-1.05): (2-2.1).
5. The method of producing a carboxylic acid compound containing phosphorus, nitrogen and boron according to claim 3, characterized in that: in the step (3), the organic boric acid is any one of methyl boric acid, ethyl boric acid, phenylboronic acid, 3-methyl phenylboronic acid, 2-furanboronic acid and 3-furanboronic acid.
6. The method of producing a carboxylic acid compound containing phosphorus, nitrogen and boron according to claim 3, characterized in that: in the steps (1) to (4), the solvent a is dioxane; in the step (4), the crude product is washed by deionized water.
7. A preparation method of flame-retardant epoxy resin is characterized by comprising the following steps: using the carboxylic acid compound according to claim 1 or the carboxylic acid compound produced by the production method according to any one of claims 2 to 6 as a flame retardant, an epoxy resin and the flame retardant are mixed in a mass ratio of 10: (1-5) uniformly mixing at the temperature of 130-150 ℃, adding an anhydride curing agent and an accelerant into the mixed solution when the temperature of the mixture is cooled to 60-80 ℃, and then uniformly stirring the mixture and defoaming; and finally, curing the mixed solution, wherein the curing system is 100 ℃/(3-4 h) +130 ℃/(2-3 h) +180 ℃/(1-2 h) +200 ℃/(1-2 h).
8. The method for preparing a flame retardant epoxy resin according to claim 7, characterized in that: the epoxy resin is any one of E-53, E-51 and E-44 bisphenol A glycidyl ether epoxy resin.
9. The method for preparing a flame retardant epoxy resin according to claim 7, characterized in that: the acid anhydride curing agent is at least one of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride; the accelerator is any one of tertiary amine, imidazole or quaternary ammonium salt.
10. The use of the flame retardant epoxy resin prepared by the method of any one of claims 7 to 9 in the fields of electronics, electrics, aerospace, transportation and transportation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277995A (en) * | 2021-05-25 | 2021-08-20 | 江苏集萃先进高分子材料研究所有限公司 | Preparation method of flame-retardant synergist of piperazine borate and imidazole borate |
| CN113603864A (en) * | 2021-09-08 | 2021-11-05 | 江南大学 | Photocuring phosphorus-nitrogen flame-retardant acrylic resin and photocuring coating prepared from same |
| CN115785788A (en) * | 2023-01-29 | 2023-03-14 | 江苏零界科技集团有限公司 | Environment-friendly paint for wooden products and preparation method thereof |
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| CN113603864A (en) * | 2021-09-08 | 2021-11-05 | 江南大学 | Photocuring phosphorus-nitrogen flame-retardant acrylic resin and photocuring coating prepared from same |
| CN115785788A (en) * | 2023-01-29 | 2023-03-14 | 江苏零界科技集团有限公司 | Environment-friendly paint for wooden products and preparation method thereof |
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