CN112126196A - Intermediate-temperature fast-curing flame-retardant epoxy resin composition and flame-retardant prepreg - Google Patents
Intermediate-temperature fast-curing flame-retardant epoxy resin composition and flame-retardant prepreg Download PDFInfo
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- C08G59/14—Polycondensates modified by chemical after-treatment
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- 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
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Abstract
The invention discloses a medium-temperature fast-curing flame-retardant epoxy resin composition and a flame-retardant prepreg, wherein the composition comprises bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame-retardant epoxy resin, modified inorganic flame-retardant filler, dicyandiamide curing agent and modification promoter, the resin composition is a low-temperature curing and normal-temperature storage composition, has the advantages of no halogen, environmental protection, high-efficiency flame retardance, low smoke generation, low smoke toxicity and low heat release, can be cured in 5-10 minutes at 150 ℃ by adopting the modification promoter, meanwhile, the flame-retardant prepreg laminated board has an ultra-long effective storage period at normal temperature, the storage period at 25 ℃ exceeds 30 days, and the flame-retardant prepreg laminated board has the characteristics of medium-temperature quick curing, long effective storage period at normal temperature, long operation time, no halogen, environmental protection, low smoke generation, low smoke toxicity, low heat release and the like, and meets the requirements of the flame retardant grade of EN45545/R1/HL3 in rail transit and the flame retardant grade of FAR 25.853 as an internal material of an aircraft cabin.
Description
Technical Field
The invention relates to the technical field of environment-friendly flame-retardant epoxy resin compositions and flame-retardant prepreg manufacturing, in particular to an environment-friendly flame-retardant epoxy resin composition capable of being rapidly cured at a medium temperature, and more particularly relates to a flame-retardant prepreg prepared from the composition.
Background
The flame-retardant prepreg prepared from the flame-retardant epoxy resin is mainly used for manufacturing flame-retardant composite material products, and the flame-retardant composite material with low smoke quantity, low smoke toxicity and low heat release is widely applied to the fields of rail transit interior trim and structural parts, new energy automobile battery boxes and cockpit parts, ship interior trim and cabin structural parts, airplane interior trim, airplane seats, electronic and electrical appliance shells and parts and the like.
A modification method is not described in the conventional epoxy resin composition adopting a modified imidazole accelerator, but an unmodified imidazole accelerator is directly adopted, the effective period of an epoxy resin composition prepared by the imidazole accelerator does not exceed 15 days at normal temperature, when the epoxy resin composition is produced by a solvent method, a volatile solvent is baked at high temperature at the rear end, a prepreg made of the epoxy resin composition is easy to lose efficacy under the condition that the imidazole accelerator is not modified, particularly, the effective period of less than 15 days at the storage period of 25 ℃ at normal temperature is only needed, the prepreg made of the epoxy resin composition cannot be transported at normal temperature in summer, and the prepreg made of the epoxy resin composition is not suitable for manufacturing large-scale composite material products when the temperature of a production workshop in summer is about 40 ℃, and is often paved in the production process of large-scale composite material part products with complex structures, such as large-scale rail transit carriages, ships, airplanes, buses and the like It takes a long time. Meanwhile, the prepreg produced by the epoxy resin composition containing solvent diluents such as acetone does not accord with the latest environmental protection regulation, so that the prepreg produced by the epoxy resin composition contains VOC, the solvent is easy to volatilize during high-temperature curing, and the high porosity is generated to damage the mechanical property of a composite material product and the body health of production staff.
The curing time of the prepreg produced by the conventional medium-temperature curing epoxy resin composition is usually several hours, the molding period is long, the production efficiency is low, the rapid development of the fields of the traditional sports equipment industry, automobile light weight, rail transit and the like enables the large-scale use of the fiber reinforced resin matrix composite material to be possible, the existing medium-temperature curing prepreg has the defects of long curing time of a resin matrix, low production efficiency, incapability of large-scale mass production and incapability of meeting the downstream rapidly-increased mass production requirement, so that the product can be well and rapidly cured at the medium temperature of 120-150 ℃, can be completely cured at the temperature of 150 ℃ within 5 minutes, and can solve the problem of high-efficiency mass production.
Disclosure of Invention
In order to effectively solve the technical problems, the flame-retardant epoxy resin composition and the flame-retardant prepreg which are rapidly cured at medium temperature provided by the invention can meet the technical requirements, and the specific technical scheme is as follows:
the medium-temperature fast-curing flame-retardant epoxy resin composition is composed of bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame-retardant epoxy resin, modified inorganic flame-retardant filler, dicyandiamide curing agent and modification accelerator, wherein the components are set according to the following mass:
bisphenol F epoxy resin: 30 to 80 parts by weight of
Phenolic epoxy resin: 20 to 70 parts of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 20 to 40 parts of
Modified inorganic flame-retardant filler: 50 to 100 parts of
Dicyandiamide curing agent: 2 to 10 parts by weight of
Modification accelerator: 5-20 parts.
In one preferred scheme, the components are set according to the following mass fractions:
bisphenol F epoxy resin: 30 to 70 parts of
Phenolic epoxy resin: 25 to 70 parts of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 22 to 40 parts of
Modified inorganic flame-retardant filler: 53 to 95 parts by weight of a stabilizer
Dicyandiamide curing agent: 2 to 8 parts of
Modification accelerator: 5-17 parts.
In one preferred scheme, the components are set according to the following mass fractions:
bisphenol F epoxy resin: 30 to 70 parts of
Phenolic epoxy resin: 25 to 70 parts of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 22 to 38 parts by weight of
Modified inorganic flame-retardant filler: 53 to 90 parts by weight of a stabilizer
Dicyandiamide curing agent: 2 to 8 parts of
Modification accelerator: 10-17 parts;
or the composition consists of bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame-retardant epoxy resin, modified inorganic flame-retardant filler, dicyandiamide curing agent and modified accelerator, wherein:
bisphenol F epoxy resin: 56 portions of
Phenolic epoxy resin: 41 portions of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 25 portions of
Modified inorganic flame-retardant filler: 60 portions of
Dicyandiamide curing agent 8 parts
Modification accelerator: 15 parts.
In one preferred scheme, the preparation method comprises the following steps of:
(1) synthesis of hexa [4- (N-phenylamino-DOPO-methine) phenoxy ] -cyclotriphosphazene (DOPO-PCP): adding a certain amount of p-hydroxybenzaldehyde, Triethylamine (TEA) and Tetrahydrofuran (THF) into a reaction kettle, dissolving a certain amount of Hexachlorocyclotriphosphazene (HCCP) into the THF, slowly dropwise adding the solution into the reaction kettle by using a constant-pressure dropping funnel, carrying out reflux reaction for 24 hours, adding water after the reaction is finished, carrying out rotary evaporation to separate out a solid, filtering and drying to obtain a crude product of hexa-p-formyl phenoxy cyclotriphosphazene (HAPCP), wherein the yield is 95%;
(2) refluxing a certain amount of HAPCP refined by ethyl acetate recrystallization, aniline and 1, 4-dioxane in a reaction kettle for 24h, adding water after reaction, filtering and drying precipitated solid to obtain hexa- (p-N-phenylmethyliminophenoxy) cyclotriphosphazene (HPA-PCP) with a yield of 91.3%;
(3) adding a certain amount of HPA-PCP and DOPO into a reaction kettle containing a certain amount of 1, 4-dioxane, refluxing for 24 hours, concentrating, pouring into a proper amount of ethanol, precipitating a large amount of white solid, ultrasonically washing for many times, and then drying in vacuum to obtain DOPO-PCP white powder, wherein the yield is 86.2%, and the melting point is 161-162.5 ℃;
(4) and mixing the cyclotriphosphazene-DOPO flame retardant with bisphenol F epoxy resin at 165 ℃ until the cyclotriphosphazene-DOPO flame retardant is completely dissolved into a uniform transparent substance, thus preparing the reactive cyclotriphosphazene-DOPO flame retardant epoxy resin.
In one preferred scheme, the preparation of the modified inorganic flame-retardant filler comprises the following steps: one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and zirconium phosphate are mixed, and the specific formula is as follows:
(1) drying the inorganic filler in a drying oven at 110 ℃ for 10h, and cooling to room temperature for later use;
(2) weighing KH550 with a certain mass, dripping 90% ethanol water solution with a certain volume, and stirring for 30min for later use. Weighing phosphate in a certain proportion to KH550, and dissolving in deionized water in a certain volume;
(3) adding inorganic filler into deionized water to prepare 5% slurry, heating and stirring in a magnetic stirrer for 10min, sequentially dripping KH550 and phosphate solution, and stirring at 40 deg.C for 30 min;
(4) and after the reaction is finished, cooling to room temperature and filtering, washing with water and ethanol for 5 times respectively to obtain a filter cake, drying for 10 hours at 110 ℃, naturally cooling to room temperature, grinding the filter cake into powder, and sieving with a 1250-mesh sieve to obtain the modified inorganic flame-retardant filler powder.
In one preferred embodiment, the preparation of the modification promoter:
one or more of PN-23, PN-23J, PN-31, PN-31J, PN-40, PN-40J, PN-50, PH-H, PN-R, PN-F, MY-24, MY-HK-1, AH-123, AH-124, AH-154, AH-203, ADH, VDH, VDH-J, UDH, UDH-J, N-12, MY-25 and MY-H are mixed, and the specific formula is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of borate stabilizer to form a resin mixture containing the stabilizer, then adding the ajinomoto latent curing agent into the resin mixture containing the borate stabilizer, stirring at a low speed by a double-planetary power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by a water cooling device, stirring for not less than 1 hour to prepare into paste, and uniformly wrapping the latent curing agent by the resin mixture containing the borate stabilizer to prepare the modification promoter.
In a preferred embodiment, the flame-retardant prepreg is prepared from the flame-retardant epoxy resin composition cured rapidly at a medium temperature, and the flame-retardant prepreg is a fiber prepreg containing no VOC, and specifically comprises the following components:
(1) the fiber is one or more of carbon fiber, glass fiber, basalt fiber, Kevlar fiber, quartz fiber, alumina fiber and the like with good flame-retardant and high-temperature-resistant performance;
(2) the fiber-containing prepreg is prepared from the flame-retardant epoxy resin composition quickly cured at medium temperature by a hot melting method, wherein the melting temperature and the coating temperature of the resin are not more than 80 ℃, and the impregnation temperature is not more than 100 ℃.
The invention has the beneficial effects that:
the invention provides a preparation method of a flame-retardant epoxy resin composition capable of being cured at low temperature and stored at normal temperature, a modification method of an inorganic flame-retardant filler and a normal-temperature storage modification method of a low-temperature curing agent, in particular to a low-temperature cured and normal-temperature stored composition of a resin composition, which has the advantages of no halogen, environmental protection, high-efficiency flame retardance, low smoke generation, low smoke toxicity and low heat release, can be rapidly cured at 150 ℃ for 5-10 minutes by adopting a modification promoter, and simultaneously has an ultra-long effective storage period at normal temperature, wherein the storage period at 25 ℃ is more than 30 days. The flame-retardant prepreg laminated board made of the resin meets the flame-retardant standard of UL94-V0, meets the requirement of the highest flame-retardant grade of European standard EN45545-2/R1/HL3 in the rail transit industry, and simultaneously meets the requirement of the FAR 25.853 flame-retardant fire-proof test of the interior material of the aircraft cabin.
The flame-retardant prepreg laminated board prepared from the mixture has the characteristics of medium-temperature quick curing, long effective period of normal-temperature storage, long operation time, no halogen, environmental protection, low smoke generation amount, low smoke toxicity, low heat release and the like, and meets the requirements of the flame retardant grade of EN45545/R1/HL3 in rail transit and the flame retardant grade of FAR 25.853 as an internal material of an airplane cabin.
Detailed Description
Example 1:
the medium-temperature fast-curing flame-retardant epoxy resin composition disclosed in the embodiment comprises bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame-retardant epoxy resin, modified inorganic flame-retardant filler, dicyandiamide curing agent and modification accelerator, wherein the components are set according to the following mass:
bisphenol F epoxy resin: 30 to 80 parts by weight of
Phenolic epoxy resin: 20 to 70 parts of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 20 to 40 parts of
Modified inorganic flame-retardant filler: 50 to 100 parts of
Dicyandiamide curing agent: 2 to 10 parts by weight of
Modification accelerator: 5-20 parts.
In the present embodiment, it is preferred that,
preparing cyclotriphosphazene-DOPO flame-retardant epoxy resin:
(1) synthesis of hexa [4- (N-phenylamino-DOPO-methine) phenoxy ] -cyclotriphosphazene (DOPO-PCP): adding a certain amount of p-hydroxybenzaldehyde, Triethylamine (TEA) and Tetrahydrofuran (THF) into a reaction kettle, dissolving a certain amount of Hexachlorocyclotriphosphazene (HCCP) into the THF, slowly dropwise adding the solution into the reaction kettle by using a constant-pressure dropping funnel, carrying out reflux reaction for 24 hours, adding water after the reaction is finished, carrying out rotary evaporation to separate out a solid, filtering and drying to obtain a crude product of hexa-p-formyl phenoxy cyclotriphosphazene (HAPCP), wherein the yield is 95%;
(2) refluxing a certain amount of HAPCP refined by ethyl acetate recrystallization, aniline and 1, 4-dioxane in a reaction kettle for 24h, adding water after reaction, filtering and drying precipitated solid to obtain hexa- (p-N-phenylmethyliminophenoxy) cyclotriphosphazene (HPA-PCP) with a yield of 91.3%;
(3) adding a certain amount of HPA-PCP and DOPO into a reaction kettle containing a certain amount of 1, 4-dioxane, refluxing for 24 hours, concentrating, pouring into a proper amount of ethanol, precipitating a large amount of white solid, ultrasonically washing for many times, and then drying in vacuum to obtain DOPO-PCP white powder, wherein the yield is 86.2%, and the melting point is 161-162.5 ℃;
(4) and mixing the cyclotriphosphazene-DOPO flame retardant with bisphenol F epoxy resin at 165 ℃ until the cyclotriphosphazene-DOPO flame retardant is completely dissolved into a uniform transparent substance, thus preparing the reactive cyclotriphosphazene-DOPO flame retardant epoxy resin.
Preparing modified inorganic flame-retardant filler: one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and zirconium phosphate are mixed, and the specific formula is as follows:
(1) drying the inorganic filler in a drying oven at 110 ℃ for 10h, and cooling to room temperature for later use;
(2) weighing KH550 with a certain mass, dripping 90% ethanol water solution with a certain volume, and stirring for 30min for later use. Weighing phosphate in a certain proportion to KH550, and dissolving in deionized water in a certain volume;
(3) adding inorganic filler into deionized water to prepare 5% slurry, heating and stirring in a magnetic stirrer for 10min, sequentially dripping KH550 and phosphate solution, and stirring at 40 deg.C for 30 min;
(4) and after the reaction is finished, cooling to room temperature and filtering, washing with water and ethanol for 5 times respectively to obtain a filter cake, drying for 10 hours at 110 ℃, naturally cooling to room temperature, grinding the filter cake into powder, and sieving with a 1250-mesh sieve to obtain the modified inorganic flame-retardant filler powder.
Preparing a modified accelerator:
one or more of PN-23, PN-23J, PN-31, PN-31J, PN-40, PN-40J, PN-50, PH-H, PN-R, PN-F, MY-24, MY-HK-1, AH-123, AH-124, AH-154, AH-203, ADH, VDH, VDH-J, UDH, UDH-J, N-12, MY-25 and MY-H are mixed, and the specific formula is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of borate stabilizer to form a resin mixture containing the stabilizer, then adding the ajinomoto latent curing agent into the resin mixture containing the borate stabilizer, stirring at a low speed by a double-planetary power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by a water cooling device, stirring for not less than 1 hour to prepare into paste, and uniformly wrapping the latent curing agent by the resin mixture containing the borate stabilizer to prepare the modification promoter.
Example 2:
in this embodiment, the flame retardant epoxy resin composition cured at medium temperature quickly is composed of bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame retardant epoxy resin, modified inorganic flame retardant filler, dicyandiamide curing agent and modification promoter, wherein the components of bisphenol F epoxy resin are set according to the following mass: 30 to 70 parts of
Phenolic epoxy resin: 25 to 70 parts of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 22 to 40 parts of
Modified inorganic flame-retardant filler: 53 to 95 parts by weight of a stabilizer
Dicyandiamide curing agent: 2 to 8 parts of
Modification accelerator: 5-17 parts.
In the present embodiment, it is preferred that,
preparing cyclotriphosphazene-DOPO flame-retardant epoxy resin:
(1) synthesis of hexa [4- (N-phenylamino-DOPO-methine) phenoxy ] -cyclotriphosphazene (DOPO-PCP): adding a certain amount of p-hydroxybenzaldehyde, Triethylamine (TEA) and Tetrahydrofuran (THF) into a reaction kettle, dissolving a certain amount of Hexachlorocyclotriphosphazene (HCCP) into the THF, slowly dropwise adding the solution into the reaction kettle by using a constant-pressure dropping funnel, carrying out reflux reaction for 24 hours, adding water after the reaction is finished, carrying out rotary evaporation to separate out a solid, filtering and drying to obtain a crude product of hexa-p-formyl phenoxy cyclotriphosphazene (HAPCP), wherein the yield is 95%;
(2) refluxing a certain amount of HAPCP refined by ethyl acetate recrystallization, aniline and 1, 4-dioxane in a reaction kettle for 24h, adding water after reaction, filtering and drying precipitated solid to obtain hexa- (p-N-phenylmethyliminophenoxy) cyclotriphosphazene (HPA-PCP) with a yield of 91.3%;
(3) adding a certain amount of HPA-PCP and DOPO into a reaction kettle containing a certain amount of 1, 4-dioxane, refluxing for 24 hours, concentrating, pouring into a proper amount of ethanol, precipitating a large amount of white solid, ultrasonically washing for many times, and then drying in vacuum to obtain DOPO-PCP white powder, wherein the yield is 86.2%, and the melting point is 161-162.5 ℃;
(4) and mixing the cyclotriphosphazene-DOPO flame retardant with bisphenol F epoxy resin at 165 ℃ until the cyclotriphosphazene-DOPO flame retardant is completely dissolved into a uniform transparent substance, thus preparing the reactive cyclotriphosphazene-DOPO flame retardant epoxy resin.
Preparing modified inorganic flame-retardant filler: one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and zirconium phosphate are mixed, and the specific formula is as follows:
(1) drying the inorganic filler in a drying oven at 110 ℃ for 10h, and cooling to room temperature for later use;
(2) weighing KH550 with a certain mass, dripping 90% ethanol water solution with a certain volume, and stirring for 30min for later use. Weighing phosphate in a certain proportion to KH550, and dissolving in deionized water in a certain volume;
(3) adding inorganic filler into deionized water to prepare 5% slurry, heating and stirring in a magnetic stirrer for 10min, sequentially dripping KH550 and phosphate solution, and stirring at 40 deg.C for 30 min;
(4) and after the reaction is finished, cooling to room temperature and filtering, washing with water and ethanol for 5 times respectively to obtain a filter cake, drying for 10 hours at 110 ℃, naturally cooling to room temperature, grinding the filter cake into powder, and sieving with a 1250-mesh sieve to obtain the modified inorganic flame-retardant filler powder.
Preparing a modified accelerator:
one or more of PN-23, PN-23J, PN-31, PN-31J, PN-40, PN-40J, PN-50, PH-H, PN-R, PN-F, MY-24, MY-HK-1, AH-123, AH-124, AH-154, AH-203, ADH, VDH, VDH-J, UDH, UDH-J, N-12, MY-25 and MY-H are mixed, and the specific formula is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of borate stabilizer to form a resin mixture containing the stabilizer, then adding the ajinomoto latent curing agent into the resin mixture containing the borate stabilizer, stirring at a low speed by a double-planetary power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by a water cooling device, stirring for not less than 1 hour to prepare into paste, and uniformly wrapping the latent curing agent by the resin mixture containing the borate stabilizer to prepare the modification promoter.
Example 3:
in this embodiment, the composition is composed of bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame retardant epoxy resin, modified inorganic flame retardant filler, dicyandiamide curing agent and modification promoter, wherein:
bisphenol F epoxy resin: 56 portions of
Phenolic epoxy resin: 41 portions of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 25 portions of
Modified inorganic flame-retardant filler: 60 portions of
Dicyandiamide curing agent 8 parts
Modification accelerator: 15 parts.
The flame-retardant prepreg prepared from the medium-temperature fast-curing flame-retardant epoxy resin composition is a VOC-free fiber prepreg, and specifically comprises the following components:
(1) the fiber is one or more of carbon fiber, glass fiber, basalt fiber, Kevlar fiber, quartz fiber, alumina fiber and the like with good flame-retardant and high-temperature-resistant performance;
(2) the fiber-containing prepreg is prepared from the flame-retardant epoxy resin composition quickly cured at medium temperature by a hot melting method, wherein the melting temperature and the coating temperature of the resin are not more than 80 ℃, and the impregnation temperature is not more than 100 ℃. .
Compared with the traditional processing technology, the invention has the following differences:
the flame-retardant epoxy resin composition cured at low temperature and stored at normal temperature and the flame-retardant prepreg prepared from the same provided by the embodiment adopt the modified accelerator, can be cured rapidly at 150 ℃ for 5-10 minutes at medium temperature to be completely cured, and have an ultra-long effective storage period at normal temperature, wherein the storage period at 25 ℃ is more than 30 days.
The flame-retardant prepreg laminated board made of the resin meets the flame-retardant standard of UL94-V0, meets the requirement of the highest flame-retardant grade of European standard EN45545-2/R1/HL3 in the rail transit industry, and simultaneously meets the requirement of the FAR 25.853 flame-retardant fire-proof test of the interior material of the aircraft cabin.
The flame-retardant composite material prepared from the flame-retardant prepreg has the characteristics of medium-temperature quick curing, long normal-temperature storage validity period, long operation time, no halogen, environmental protection, low smoke generation amount, low smoke toxicity, low heat release and the like, and meets the requirements of the flame-retardant grade of EN45545/R1/HL3 in rail transit and the flame-retardant grade of FAR 25.853 as an internal material of an airplane cabin.
The present invention is not limited to the above embodiments, and various embodiments using the same principle and method to achieve the same technical effects are the same as the present patent.
Claims (7)
1. The medium-temperature fast-curing flame-retardant epoxy resin composition is characterized by consisting of bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame-retardant epoxy resin, modified inorganic flame-retardant filler, dicyandiamide curing agent and modification accelerator, wherein the components are set according to the following mass:
bisphenol F epoxy resin: 30 to 80 portions of
Phenolic epoxy resin: 20 to 70 portions of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 20 to 40 portions of
Modified inorganic flame-retardant filler: 50 to 100 portions of
Dicyandiamide curing agent: 2 to 10 portions of
Modification accelerator: 5 to 20 portions.
2. An intermediate-temperature fast-curing flame-retardant epoxy resin composition according to claim 1, wherein the components are set in the following mass fractions:
bisphenol F epoxy resin: 30 to 70 portions of
Phenolic epoxy resin: 25 to 70 portions of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 22 to 40 portions of
Modified inorganic flame-retardant filler: 53 to 95 portions of
Dicyandiamide curing agent: 2 to 8 portions of
Modification accelerator: 5 to 17 portions.
3. An intermediate-temperature fast-curing flame-retardant epoxy resin composition according to claim 2, wherein the components are set in the following mass fractions:
bisphenol F epoxy resin: 30 to 70 portions of
Phenolic epoxy resin: 25 to 70 portions of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 22 to 38 portions of
Modified inorganic flame-retardant filler: 53 to 90 portions of
Dicyandiamide curing agent: 2 to 8 portions of
Modification accelerator: 10-17 parts;
or the composition consists of bisphenol F epoxy resin, novolac epoxy resin, cyclotriphosphazene-DOPO flame-retardant epoxy resin, modified inorganic flame-retardant filler, dicyandiamide curing agent and modified accelerator, wherein:
bisphenol F epoxy resin: 56 portions of
Phenolic epoxy resin: 41 portions of
cyclotriphosphazene-DOPO flame retardant epoxy resin: 25 portions of
Modified inorganic flame-retardant filler: 60 portions of
Dicyandiamide curing agent 8 parts
Modification accelerator: 15 parts.
4. An intermediate-temperature fast-curing flame-retardant epoxy resin composition according to claim 1, wherein a cyclotriphosphazene-DOPO flame-retardant epoxy resin is prepared:
(1) synthesis of hexa [4- (N-phenylamino-DOPO-methine) phenoxy ] -cyclotriphosphazene (DOPO-PCP): adding a certain amount of p-hydroxybenzaldehyde, Triethylamine (TEA) and Tetrahydrofuran (THF) into a reaction kettle; dissolving a certain amount of Hexachlorocyclotriphosphazene (HCCP) in Tetrahydrofuran (THF), slowly dripping into a reaction kettle by using a constant-pressure dropping funnel, and carrying out reflux reaction for 24 hours; after the reaction is finished, adding water, carrying out rotary evaporation to separate out a solid, filtering and drying to obtain a crude product of hexa-p-formyl phenoxy cyclotriphosphazene (HAPCP), wherein the yield is 95%;
(2) refluxing a certain amount of HAPCP refined by ethyl acetate recrystallization, aniline and 1, 4 dioxane in a reaction kettle for 24 hours; after the reaction, water is added, and the precipitated solid is filtered and dried to obtain hexa- (p-N-phenylmethyliminophenoxy) cyclotriphosphazene (HPA-PCP), wherein the yield is 91.3%;
(3) adding a certain amount of HPA-PCP and DOPO into a reaction kettle filled with a certain amount of 1, 4 dioxane, refluxing for 24h, concentrating, pouring into a proper amount of ethanol, and separating out a large amount of white solid; carrying out ultrasonic treatment and water washing for multiple times, and then carrying out vacuum drying to obtain DOPO-PCP white powder, wherein the yield is 86.2%, and the melting point is 161-162.5 ℃;
(4) and mixing the cyclotriphosphazene-DOPO flame retardant with bisphenol F epoxy resin at 165 ℃ until the cyclotriphosphazene-DOPO flame retardant is completely dissolved into a uniform transparent substance, thus preparing the reactive cyclotriphosphazene-DOPO flame retardant epoxy resin.
5. An intermediate-temperature fast-curing flame-retardant epoxy resin composition according to claim 1, wherein the modified inorganic flame-retardant filler is prepared by: one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and zirconium phosphate are mixed, and the specific formula is as follows:
(1) drying the inorganic filler in a drying oven at 110 ℃ for 10h, and cooling to room temperature for later use;
(2) weighing KH550 with a certain mass, dripping 90% ethanol water solution with a certain volume, and stirring for 30min for later use. Weighing phosphate in a certain proportion to KH550, and dissolving in deionized water in a certain volume;
(3) adding inorganic filler into deionized water to prepare 5% slurry, heating and stirring in a magnetic stirrer for 10min, sequentially dripping KH550 and phosphate solution, and stirring at 40 deg.C for 30 min;
(4) and after the reaction is finished, cooling to room temperature and filtering, respectively washing with water and ethanol for 5 times to obtain a filter cake, drying for 10 hours at 110 ℃, naturally cooling to room temperature, grinding the filter cake into powder, and sieving with a 1250-mesh sieve to obtain the modified inorganic flame-retardant filler powder.
6. An intermediate-temperature fast-curing flame-retardant epoxy resin composition according to claim 1, wherein a modification accelerator is prepared:
one or more of PN-23, PN-23J, PN-31, PN-31J, PN-40, PN-40J, PN-50, PH-H, PN-R, PN-F, MY-24, MY-HK-1, AH-123, AH-124, AH-154, AH-203, ADH, VDH, VDH-J, UDH, UDH-J, N-12, MY-25 and MY-H are mixed, and the specific formula is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of borate stabilizer to form a resin mixture containing the stabilizer, then adding the ajinomoto latent curing agent into the resin mixture containing the borate stabilizer, stirring at a low speed by a double-planetary power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by a water cooling device, stirring for not less than 1 hour to prepare into paste, and uniformly wrapping the latent curing agent by the resin mixture containing the borate stabilizer to prepare the modification promoter.
7. A flame-retardant prepreg prepared from the medium-temperature fast-curing flame-retardant epoxy resin composition according to claim 1, wherein the flame-retardant prepreg is a VOC-free fiber prepreg, and the following components are adopted:
(1) the fiber is one or more of carbon fiber, glass fiber, basalt fiber, Kevlar fiber, quartz fiber, alumina fiber and the like with good flame-retardant and high-temperature-resistant performance;
(2) the fiber-containing prepreg is prepared from the flame-retardant epoxy resin composition quickly cured at medium temperature by a hot melting method, wherein the melting temperature and the coating temperature of the resin are not more than 80 ℃, and the impregnation temperature is not more than 100 ℃.
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