CN111732607B - 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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- CN111732607B CN111732607B CN202010609427.7A CN202010609427A CN111732607B CN 111732607 B CN111732607 B CN 111732607B CN 202010609427 A CN202010609427 A CN 202010609427A CN 111732607 B CN111732607 B CN 111732607B
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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 thereof. The carboxylic acid compound contains phosphaphenanthrene, triazinetrione, boric acid or organic boric acid groups and carboxyl in a molecular structure, and the molecular structure of the carboxylic acid compound has two forms of TMDB-1 and TMDB-2, and the specific steps are as follows: TMDB-1:TMDB‑2：wherein R1 and R2 are any one of hydroxyl, alkyl and aryl. The phosphorus-nitrogen-boron-containing carboxylic acid compound is a reactive halogen-free flame retardant, so that the harm of the halogen-containing flame retardant to human bodies and the environment is solved, and the influence of the additive flame retardant on the physical and mechanical properties of an epoxy resin matrix is overcome. The carboxylic acid compound of the invention can give the epoxy/anhydride system excellent flame retardance and smoke suppression performance, and can improve the mechanical property to a certain extent, and the flexural modulus and 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 thereof.
Background
The epoxy resin has excellent adhesive property, better corrosion resistance, excellent physical and mechanical properties and electrical insulation properties, so that the epoxy resin is widely applied to the fields of adhesive coating, electronics and electricity, chemical industry, mechanical manufacturing, transportation and the like, and is one of the most widely applied thermosetting resins at present. However, epoxy resins, like other polymeric materials, are flammable materials that burn vigorously and release a large amount of heat after being ignited, producing smoke and toxic gases, which can easily cause significant 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 increasing awareness of environmental protection throughout the world, halogen-containing flame retardants are increasingly being restricted. In addition, since the additive type flame retardant is physically blended in the resin matrix, it may cause deterioration of the overall performance of the epoxy resin, and at the same time, the flame retardant may be precipitated from the surface of the matrix with the increase of the use time to cause deterioration of the flame retardant performance and environmental pollution. In order to reduce the negative influence of the flame retardant on the comprehensive performance of the epoxy resin matrix, a flame retardant curing agent or a co-curing agent with reactivity is designed and developed to become a research hot spot for flame retardant modification 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, and can improve the flame retardant effect of the epoxy resin and simultaneously maintain 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 class of epoxy resin curing agents which are more applied, and have better comprehensive properties than amine curing epoxy resins, such as low toxicity, low initial viscosity, long pot life, low water absorption, excellent electrical insulation and transparency, and the like, so that the anhydrides are preferentially selected for use in a plurality of important applications of the epoxy resins, particularly in electronic equipment. Today, electronic products are highly integrated, and fire hazards caused by overheating thereof are becoming more and more frequent. Therefore, the research on flame retardant modification of anhydride-cured epoxy resin is particularly important. In the existing preparation methods, although the inflammability of an epoxy/anhydride system is basically solved, the flame retardant efficiency is lower, the smoke suppression performance is poorer, the process formability is inevitably reduced due to the fact that the addition amount is increased, and meanwhile, the mechanical property of a matrix is deteriorated to a certain extent due to the fact that a large amount of flame retardant is added.
Disclosure of Invention
The invention aims 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, and can basically maintain the original physical and mechanical properties of the epoxy resin, such as heat resistance, mechanical properties and the like, while endowing the epoxy resin with excellent flame retardant and smoke suppression properties.
The second purpose of the invention is to provide a preparation method of the carboxylic acid compound containing phosphorus, nitrogen and boron, which has the advantages of simple reaction process, mild condition, no generation of toxic and harmful substances in the synthesis process, economy, environmental protection and low cost.
The invention further 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 excellent flame retardance and smoke suppression performance of the epoxy resin are provided, and meanwhile, the original physical and mechanical properties such as heat resistance and mechanical properties of the epoxy resin can be basically maintained.
The fourth object of the invention is to provide an application of the flame-retardant epoxy resin.
The scheme adopted by the invention for achieving one of the purposes is as follows: a carboxylic acid compound containing phosphorus, nitrogen and boron contains phosphaphenanthrene, triazinetrione, boric acid or organic boric acid groups and carboxyl in the molecular structure, and the molecular structure of the carboxylic acid compound 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 scheme adopted by the invention for achieving the second purpose is as follows: the preparation method of the carboxylic acid compound containing phosphorus, nitrogen and boron is characterized in that the carboxylic acid compound is synthesized by taking trihydroxyethyl isocyanuric ester, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and boric acid or organic boric acid as raw materials through esterification and addition reaction.
Preferably, the method comprises a two-step esterification reaction and a one-step addition reaction, and comprises the following specific steps:
(1) Esterification reaction: mixing the trihydroxyethyl isocyanurate, the maleic anhydride and a proper amount of solvent a according to a certain proportion, heating to 85-95 ℃, and continuously stirring for 2-4 h under the 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 100-110 ℃ and reacting for 8-9h;
(3) Esterification reaction: dissolving boric acid or organic boric acid in the solvent a, adding the solution into the mixture in the step (2), and then continuing to react for 2-3 hours;
(4) Impurity removal and purification: and (3) 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 mole ratio of the tri-hydroxyethyl isocyanurate, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, boric acid or organoboric acid is 1: (2-2.1): (2-2.1): (1-1.05); when TMDB-2 was synthesized, the molar ratio of tris-hydroxyethyl isocyanurate, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, boric acid or organoboric acid was 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 with deionized water.
The scheme adopted by the invention for achieving 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 mass ratio of the epoxy resin to the flame retardant is 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 ℃, and then uniformly stirring the mixture and defoaming; finally, the mixed solution is cured, and 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 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. 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 for realizing the fourth purpose of the invention is as follows: the flame-retardant epoxy resin prepared by the preparation method 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, so that the harm of the halogen-containing flame retardant to human bodies and the environment is solved, and the influence of the additive flame retardant to 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 the UL-94V-0 rating when only 15.1wt% TMDB is added.
(3) The carboxylic acid compound of the present invention has a good smoke suppressing effect, and when only 15.1wt% TMDB is added, the total smoke release amount of the cured product when burned is reduced by 47.2% compared with that of a pure epoxy resin system.
(4) The carboxylic acid compound of the invention can improve the mechanical property to a certain extent while endowing the epoxy/anhydride system with excellent flame retardance and smoke suppression performance, and the flexural modulus and flexural strength of the flame-retardant epoxy resin are improved, thereby being capable of meeting the application in the flame-retardant field with higher requirements on the mechanical property.
(5) The synthesis of the carboxylic acid compound adopts low-cost 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 and environment-friendly and has low cost.
(6) The flame-retardant epoxy resin adopts the carboxylic acid compound as the flame retardant, improves the flexural modulus and the flexural strength of the flame-retardant epoxy resin, can meet the application in the flame-retardant field with higher requirements on mechanical properties, and can be used in the fields of electronics, electrics, aerospace, transportation and the like, such as sealant, packaging materials of integrated circuits, matrix materials of composite materials and the like.
Drawings
FIG. 1 shows TMDB, THEIC according to embodiment 2 of the invention 1 H NMR spectrum, TMDB and DOPO 31 P NMR spectrum;
FIG. 2 is an infrared spectrum of the synthetic raw material and TMDB of example 2 of the present invention.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
The invention discloses a preparation method of a phosphorus-nitrogen-boron-containing carboxylic acid compound, which comprises the preparation steps of two-step esterification reaction, one-step addition reaction and preparation of flame-retardant epoxy resin. The carboxylic acid compound is synthesized by using tris (hydroxyethyl) isocyanurate (THEIC), maleic Anhydride (MAH), DOPO and Boric Acid (BA) as raw materials. The flame retardant has higher flame retardant efficiency and good smoke suppression effect, can endow an epoxy/anhydride system with excellent flame retardant and smoke suppression performance when the addition amount is low, can improve the mechanical property of an epoxy resin matrix to a certain extent, effectively solves the defect of inflammability of epoxy resin/anhydride cured products, and has potential application value in the related fields of electronics, electrics, 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 10min. Then 0.2g of 2,4, 6-tris (dimethylaminomethyl) phenol was added thereto, stirred for 10 minutes, and then vacuum defoamed for 5 minutes. Finally, the mixed solution is quickly poured into a preheated mold and is cured in an oven with a curing system of 100 ℃/4h+130 ℃/2h+180 ℃/2h+200 ℃/2h. After curing the resin, samples were prepared according to the test standard, and the obtained samples were designated as EP, which is a control sample to which no flame retardant was added.
[ example 2 ]
In a 500mL three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and thermometer, 78.3g THEIC, 58.8g MAH and 60mL dioxane were added and stirred at constant speed. The reaction was warmed to 85 ℃ under nitrogen atmosphere and reacted for 2h. 129.6g DOPO and 100mL dioxane were then added in portions to the reaction solution over 30 minutes. The mixture was further heated to reflux and held for 8h. Then, 20mL of dioxane solution in which 18.5g of BA was dissolved was added to the reaction mass, 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 more times with deionized water and dried under vacuum at 80 ℃ for 24 hours to finally obtain a white solid product, namely the final product TMDB. The results of the NMR and IR analyses are shown in FIGS. 1 and 2. The hydrogen atoms of different chemical environments of TMDB in the hydrogen spectrogram are corresponding, and a single peak appears in the phosphorus spectrogram. 3427, 1740 and 1693, 1435, 1200cm in the infrared spectrum of TMDB -1 The characteristic absorption peaks of-OH, c= O, B-O-C, P =o bonds, respectively. 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, 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, stirred for 10 minutes, and then vacuum defoamed for 5 minutes. Finally, the mixed solution is quickly poured into a preheated mold and is cured in an oven with a curing system of 100 ℃/4h+130 ℃/2h+180 ℃/2h+200 ℃/2h. After curing the resin, samples were prepared according to the test standard, the sample obtained being designated EP-1 and the flame retardant content being 7.5% by weight.
[ example 3 ]
In a 500mL three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and thermometer, 78.3g THEIC, 58.8g MAH and 60mL dioxane were added and stirred at constant speed. The reaction was warmed to 95 ℃ under nitrogen atmosphere and reacted for 2h. 129.6g DOPO and 100mL dioxane were then added in portions to the reaction solution over 30 minutes. The mixture was further heated to reflux and held for 8h. Then, 20mL of dioxane solution in which 18.5g of BA was dissolved was added to the reaction mass, 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 more times with deionized water and dried under vacuum at 80 ℃ for 24 hours to finally obtain a white solid product, namely the final product TMDB.
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 bottom flask, after stirring at 140℃for 1 hour, heating was stopped, 73.7g of methyltetrahydrophthalic anhydride and 0.2g of 2,4, 6-tris (dimethylaminomethyl) phenol were added to the mixed solution after cooling the mixture to 75℃and stirring for 10 minutes, and vacuum deaeration was carried out for 5 minutes. Finally, the mixed solution is quickly poured into a preheated mold and is cured in an oven with a curing system of 100 ℃/4h+130 ℃/2h+180 ℃/2h+200 ℃/2h. After curing the resin, samples were prepared according to the standard, the sample obtained being designated EP-2 and the flame retardant content being 15.1% by weight.
[ example 4 ]
In a 500mL three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and thermometer, 78.3g THEIC, 58.8g MAH and 60mL dioxane were added and stirred at constant speed. The reaction was warmed to 90 ℃ under nitrogen atmosphere and reacted for 2h. 129.6g DOPO and 100mL dioxane were then added in portions to the reaction solution over 30 minutes. The mixture was further heated to reflux and held for 8h. Then, 20mL of dioxane solution in which 18.5g of BA was dissolved was added to the reaction mass, 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 more times with deionized water and dried under vacuum at 80 ℃ for 24 hours to finally obtain a white solid product, namely the final product TMDB.
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 bottom flask, after stirring at 140℃for 1 hour, heating was stopped, and when the mixture temperature 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, stirred for 10 minutes, and then vacuum defoamed for 5 minutes. Finally, the mixed solution is quickly poured into a preheated mold and is cured in an oven with a curing system of 100 ℃/4h+130 ℃/2h+180 ℃/2h+200 ℃/2h. After curing the resin, a sample was prepared according to the test standard, the sample obtained being designated EP-3 and the flame retardant content being 22.6% by weight.
The test results are shown in Table 1 by performing Limiting Oxygen Index (LOI), flame retardant rating (UL-94), cone calorimeter, bending property and dynamic thermo-mechanical analysis test on the test pieces prepared in examples 1 to 4 with reference to the standard
The technical scheme adopted by the embodiment is that the flame retardant property and the bending property are carried out according to the following standards:
the test criteria according to which limiting oxygen index is determined are: GB 2406-80;
the test standards according to which the flame retardant rating is determined are: ASTM D3801;
the test criteria on which the flexural properties were determined were: GB/T2567-2008.
TABLE 1 flame retardant, smoke suppression, mechanical and Heat resistance test results of flame retardant epoxy resin
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (10)
1. A carboxylic acid compound containing phosphorus, nitrogen and boron, which is characterized in that: the carboxylic acid compound contains phosphaphenanthrene, triazinetrione, boric acid or organic boric acid groups and carboxyl in a molecular structure, and the molecular structure is TMDB-1, and specifically comprises the following steps:
TMDB-1：
；
wherein R1 and R2 are any one of hydroxyl, alkyl and aryl.
2. A process for producing a phosphorus-nitrogen-boron-containing carboxylic acid compound as claimed in claim 1, wherein: is synthesized by taking trihydroxyethyl isocyanuric acid ester, maleic anhydride, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, boric acid or organic boric acid as raw materials through esterification and addition reaction.
3. The method for producing a phosphorus-nitrogen-boron-containing carboxylic acid compound according to claim 2, characterized in that: comprises two-step esterification reaction and one-step addition reaction, and comprises the following specific steps:
(1) Esterification reaction: mixing the trihydroxyethyl isocyanurate, the maleic anhydride and a proper amount of solvent a according to a certain proportion, heating to 85-95 ℃, and continuously stirring for 2-4 h under the 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 100-110 ℃ and reacting for 8-9h;
(3) Esterification reaction: dissolving boric acid or organic boric acid in the solvent a, adding the solution into the mixture in the step (2), and then continuing to react for 2-3 hours;
(4) Impurity removal and purification: and (3) 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. A process for producing a phosphorus-nitrogen-boron-containing carboxylic acid compound according to claim 3, wherein: in the steps (1) - (3), when TMDB-1 is synthesized, the mole ratio of the tri-hydroxyethyl isocyanurate, the maleic anhydride, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the boric acid or the organic boric acid is 1: (2-2.1): (2-2.1): (1-1.05).
5. A process for producing a phosphorus-nitrogen-boron-containing carboxylic acid compound according to claim 3, wherein: in the step (3), the organic boric acid is any one of methyl boric acid, ethyl boric acid, phenylboric acid, 3-methylphenylboric acid, 2-furanboric acid and 3-furanboric acid.
6. A process for producing a phosphorus-nitrogen-boron-containing carboxylic acid compound according to claim 3, wherein: in the steps (1) - (4), the solvent a is dioxane; in the step (4), the crude product is washed with deionized water.
7. A preparation method of flame-retardant epoxy resin is characterized in that: the carboxylic acid compound according to claim 1 or the carboxylic acid compound according to any one of claims 2 to 6 is used as a flame retardant, and the epoxy resin and the flame retardant are mixed in a 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 ℃, 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, wherein: the epoxy resin is any one of E-53, E-51 and E-44 bisphenol A type glycidyl ether epoxy resin.
9. The method for preparing a flame retardant epoxy resin according to claim 7, wherein: the 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. Use of the flame retardant epoxy resin prepared by the method for preparing flame retardant epoxy resin according to any one of claims 7-9 in the fields of electronics, electrics, aerospace and transportation.
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| CN113603864B (en) * | 2021-09-08 | 2022-05-17 | 江南大学 | Photocuring phosphorus-nitrogen flame-retardant acrylic resin and photocuring coating prepared from same |
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