CN112143174A - Low-temperature-cured normal-temperature-stored flame-retardant epoxy resin composition and flame-retardant prepreg - Google Patents
Low-temperature-cured normal-temperature-stored flame-retardant epoxy resin composition and flame-retardant prepreg Download PDFInfo
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Abstract
The invention discloses a flame-retardant epoxy resin composition and a flame-retardant prepreg which are cured at low temperature and stored at normal temperature, wherein the composition is a low-temperature curing normal-temperature storage composition consisting of bisphenol F epoxy resin, novolac epoxy resin, phosphorus-silicon-boron flame retardant, modified inorganic flame-retardant filler and modified low-temperature curing latent curing agent, 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 low temperature by adopting the modified low-temperature curing agent, and has an ultra-long effective storage period at normal temperature; the flame-retardant composite board made of the flame-retardant prepreg has the characteristics of high low-temperature curing speed, complete curing within 4 hours at 80 ℃, normal-temperature storage period of more than 30 days, long operation time, no halogen, environmental protection, no VOC, 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 airplane cabin.
Description
Technical Field
The invention relates to the technical field of low-temperature curing and normal-temperature storage flame-retardant epoxy resin compositions and flame-retardant prepreg manufacturing, in particular to a low-temperature curing and normal-temperature storage flame-retardant epoxy resin composition, 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.
When the epoxy resin composition is produced by adopting a solvent method, the solvent is volatilized by baking at a high temperature at the rear end, the prepreg made of the epoxy resin composition is easy to lose efficacy under the condition that the latent curing agent is not modified, particularly, the storage period at the normal temperature of 25 ℃ is only about 15 days, the prepreg made of the epoxy resin composition cannot be transported at the normal temperature in summer, when the temperature of the prepreg made of the epoxy resin composition is about 40 ℃, the working time of continuous operation cannot exceed 48 hours, and the prepreg is not suitable for manufacturing large-scale composite material products, and the manufacturing processes such as ply laying and the like in the production process of large-scale composite material part products with complex structures, such as large-scale rail transportation carriages, ships, airplanes, buses and the like, need to spend more than 48 hours. Meanwhile, the prepreg produced by the epoxy resin composition containing solvents 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 temperature of the prepreg produced by the conventional epoxy resin composition is usually more than 120 ℃, so that the problems that a high-cost high-temperature-resistant mold is required to be used, an autoclave cannot be used for curing when a large-sized composite material product with a complex structure is manufactured, and a low-cost oven or a baking room capable of curing at a low temperature of 70-90 ℃ is required to be used for curing.
Disclosure of Invention
In order to effectively solve the technical problems, the flame-retardant epoxy resin composition cured at low temperature and stored at normal temperature and the flame-retardant prepreg provided by the invention can meet the technical requirements, and the specific technical scheme is as follows: ring (C)
The flame-retardant epoxy resin composition is composed of bisphenol F epoxy resin, novolac epoxy resin, phosphorus-silicon-boron flame retardant, modified inorganic flame-retardant filler and modified low-temperature curing latent curing agent, 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
Phosphorus silicon boron flame retardant: 20 to 40 parts of
Modified inorganic flame-retardant filler: 50 to 100 parts of
Modified low-temperature curing latent curing agent: 10-35 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: 24 to 70 parts of
Phosphorus silicon boron flame retardant: 22 to 40 parts of
Modified inorganic flame-retardant filler: 50 to 100 parts of
Modified low-temperature curing latent curing agent: 10-25 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: 24 to 60 parts of
Phosphorus silicon boron flame retardant: 20 to 30 parts of
Modified inorganic flame-retardant filler: 50 to 95 parts by weight of a surfactant
Modified low-temperature curing latent curing agent: 10-20 parts;
or the composition consists of bisphenol F epoxy resin, novolac epoxy resin, phosphorus silicon boron flame retardant, modified inorganic flame retardant filler and modified low-temperature curing latent curing agent, wherein:
bisphenol F epoxy resin: 30 portions of
Phenolic epoxy resin: 25 portions of
Phosphorus silicon boron flame retardant: 25 portions of
Modified inorganic flame-retardant filler: 55 portions of
Modified low-temperature curing latent curing agent: and 20 parts.
In one preferred scheme, the preparation of the phosphorus-silicon-boron flame retardant comprises the following steps:
(1) carrying out addition reaction with C = C of vinyl trimethoxy silane by utilizing the reaction activity of P-H in DOPO to obtain trimethoxy silane (PSi) with DOPO on a lateral group;
(2) hydrolyzing Si-OCH3 of vinyltrimethoxysilane, and then performing dehydration condensation reaction with boric acid B (OH)3 to prepare Borosiloxane (BSi);
(3) vinyl trimethoxy silane reacts with boric acid B (OH)3 to obtain a BSi intermediate, and then reacts with DOPO to obtain the flame retardant PsiB.
In one preferred scheme, the preparation of the phosphorus-silicon-boron flame retardant comprises the following steps:
(1) carrying out addition reaction with C = C of vinyl trimethoxy silane by utilizing the reaction activity of P-H in DOPO to obtain trimethoxy silane (PSi) with DOPO on a lateral group;
(2) hydrolyzing Si-OCH3 of vinyltrimethoxysilane, and then performing dehydration condensation reaction with boric acid B (OH)3 to prepare Borosiloxane (BSi);
(3) the DOPO and the vinyltrimethoxysilane are subjected to addition reaction to obtain a PSi intermediate, and then the PSi intermediate reacts with boric acid B (OH)3 to obtain a flame retardant PSiB. A
In one preferred scheme, the preparation of the modified inorganic flame-retardant filler comprises the following steps: mixing one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and low-melting-point inorganic powder, wherein the specific contents are 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, dropwise adding 90% ethanol aqueous solution with a certain volume, stirring for 30min for later use, weighing phosphate with a certain proportion to the KH550, and dissolving in deionized water with 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 latent curing agent is prepared by:
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 description is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of stabilizer to form a resin mixture containing the stabilizer, then adding the latent curing agent into the resin mixture containing the stabilizer, stirring at a low speed by using a double-planet power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by using a water cooling device, stirring for not less than 1 hour to prepare a paste, uniformly coating the latent curing agent with the resin mixture containing the stabilizer, and preparing the modified low-temperature curing latent curing agent.
The flame-retardant prepreg prepared from the low-temperature cured normal-temperature stored flame-retardant epoxy resin composition is a VOC-free fiber prepreg, and comprises the following specific components in percentage by weight:
(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 which is cured at low temperature and stored at normal 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 composition which is cured at low temperature and stored at normal temperature and has the advantages of no halogen, environmental protection, high-efficiency flame retardance, low smoke generation, low smoke toxicity and low heat release, and can be rapidly cured at low temperature and has an ultra-long effective storage period at normal temperature by adopting the modified low-temperature curing agent;
the flame-retardant prepreg laminated board prepared from 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 flame-retardant and fireproof test of an interior material FAR 25.853 of an aircraft cabin.
Detailed Description
Example 1:
the flame-retardant epoxy resin composition cured at low temperature and stored at normal temperature disclosed in the embodiment comprises bisphenol F epoxy resin, novolac epoxy resin, phosphorus-silicon-boron flame retardant, modified inorganic flame-retardant filler and modified low-temperature curing latent curing agent, 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
Phosphorus silicon boron flame retardant: 20 to 40 parts of
Modified inorganic flame-retardant filler: 50 to 100 parts of
Modified low-temperature curing latent curing agent: 10-35 parts.
In the present embodiment, it is preferred that,
preparing a phosphorus-silicon-boron flame retardant:
(1) carrying out addition reaction with C = C of vinyl trimethoxy silane by utilizing the reaction activity of P-H in DOPO to obtain trimethoxy silane (PSi) with DOPO on a lateral group;
(2) hydrolyzing Si-OCH3 of vinyltrimethoxysilane, and then performing dehydration condensation reaction with boric acid B (OH)3 to prepare Borosiloxane (BSi);
(3) vinyl trimethoxy silane reacts with boric acid B (OH)3 to obtain a BSi intermediate, and then reacts with DOPO to obtain the flame retardant PsiB.
Preparing modified inorganic flame-retardant filler:
mixing one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and low-melting-point inorganic powder, wherein the specific contents are 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, dropwise adding 90% ethanol aqueous solution with a certain volume, stirring for 30min for later use, weighing phosphate with a certain proportion to the KH550, and dissolving in deionized water with 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 latent curing agent:
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 description is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of stabilizer to form a resin mixture containing the stabilizer, then adding the latent curing agent into the resin mixture containing the stabilizer, stirring at a low speed by using a double-planet power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by using a water cooling device, stirring for not less than 1 hour to prepare a paste, uniformly coating the latent curing agent with the resin mixture containing the stabilizer, and preparing the modified low-temperature curing latent curing agent.
Example 2:
in the embodiment, the flame-retardant epoxy resin composition cured at low temperature and stored at normal temperature comprises the following components in parts by mass:
bisphenol F epoxy resin: 30 to 70 parts of
Phenolic epoxy resin: 24 to 70 parts of
Phosphorus silicon boron flame retardant: 22 to 40 parts of
Modified inorganic flame-retardant filler: 50 to 100 parts of
Modified low-temperature curing latent curing agent: 10-25 parts.
In the present embodiment, it is preferred that,
preparing a phosphorus-silicon-boron flame retardant:
(1) carrying out addition reaction with C = C of vinyl trimethoxy silane by utilizing the reaction activity of P-H in DOPO to obtain trimethoxy silane (PSi) with DOPO on a lateral group;
(2) hydrolyzing Si-OCH3 of vinyltrimethoxysilane, and then performing dehydration condensation reaction with boric acid B (OH)3 to prepare Borosiloxane (BSi);
(3) the DOPO and the vinyltrimethoxysilane are subjected to addition reaction to obtain a PSi intermediate, and then the PSi intermediate reacts with boric acid B (OH)3 to obtain a flame retardant PSiB.
Preparing modified inorganic flame-retardant filler:
mixing one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and low-melting-point inorganic powder, wherein the specific contents are 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, dropwise adding 90% ethanol aqueous solution with a certain volume, stirring for 30min for later use, weighing phosphate with a certain proportion to the KH550, and dissolving in deionized water with 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 latent curing agent:
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 description is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of stabilizer to form a resin mixture containing the stabilizer, then adding the latent curing agent into the resin mixture containing the stabilizer, stirring at a low speed by using a double-planet power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by using a water cooling device, stirring for not less than 1 hour to prepare a paste, uniformly coating the latent curing agent with the resin mixture containing the stabilizer, and preparing the modified low-temperature curing latent curing agent.
Example 3:
this example sets forth that the composition consists of bisphenol F epoxy resin, novolac epoxy resin, phosphorus silicon boron flame retardant, modified inorganic flame retardant filler, and modified low temperature curing latent curing agent, wherein:
bisphenol F epoxy resin: 30 portions of
Phenolic epoxy resin: 25 portions of
Phosphorus silicon boron flame retardant: 25 portions of
Modified inorganic flame-retardant filler: 55 portions of
Modified low-temperature curing latent curing agent: and 20 parts.
The flame-retardant prepreg prepared from the low-temperature cured and normal-temperature stored flame-retardant epoxy resin composition is a VOC-free fiber prepreg, and is specifically as follows:
(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 which is cured at low temperature and stored at normal 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 composite material made of the flame-retardant prepreg material has the characteristics of high low-temperature curing speed, complete curing within 4 hours at 80 ℃, long normal-temperature storage period of more than 30 days, long operation time, no halogen, environmental friendliness, no VOC, 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 for rail transit and the flame-retardant grade of FAR 25.853 for materials in aircraft cabins.
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 (8)
1. The flame-retardant epoxy resin composition is characterized by consisting of bisphenol F epoxy resin, novolac epoxy resin, phosphorus-silicon-boron flame retardant, modified inorganic flame-retardant filler and modified low-temperature curing latent curing agent, 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
Phosphorus silicon boron flame retardant: 20 to 40 portions of
Modified inorganic flame-retardant filler: 50 to 100 portions of
Modified low-temperature curing latent curing agent: 10 to 35 portions.
2. The low-temperature-curing room-temperature-storage 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: 24 to 70 portions of
Phosphorus silicon boron flame retardant: 22 to 40 portions of
Modified inorganic flame-retardant filler: 50 to 100 portions of
Modified low-temperature curing latent curing agent: 10 to 25 portions.
3. The low-temperature-curing room-temperature-storage 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: 24 to 60 portions of
Phosphorus silicon boron flame retardant: 20 to 30 portions of
Modified inorganic flame-retardant filler: 50 to 95 portions of
Modified low-temperature curing latent curing agent: 10-20 parts;
or the composition consists of bisphenol F epoxy resin, novolac epoxy resin, phosphorus silicon boron flame retardant, modified inorganic flame retardant filler and modified low-temperature curing latent curing agent, wherein:
bisphenol F epoxy resin: 30 portions of
Phenolic epoxy resin: 25 portions of
Phosphorus silicon boron flame retardant: 25 portions of
Modified inorganic flame-retardant filler: 55 portions of
Modified low-temperature curing latent curing agent: and 20 parts.
4. The low-temperature-curing ambient-storage flame-retardant epoxy resin composition according to claim 1, wherein the phosphorus-silicon-boron flame retardant is prepared by:
(1) carrying out addition reaction with C ═ C of vinyl trimethoxy silane by utilizing the reaction activity of P-H in DOPO to obtain trimethoxy silane (PSi) with DOPO on the side group;
(2) hydrolyzing Si-OCH3 of vinyltrimethoxysilane, and then performing dehydration condensation reaction with boric acid B (OH)3 to prepare Borosiloxane (BSi);
(3) vinyl trimethoxy silane reacts with boric acid B (OH)3 to obtain a BSi intermediate, and then reacts with DOPO to obtain the flame retardant PsiB.
5. The low-temperature-curing ambient-storage flame-retardant epoxy resin composition according to claim 1, wherein the phosphorus-silicon-boron flame retardant is prepared by:
(1) carrying out addition reaction with C ═ C of vinyl trimethoxy silane by utilizing the reaction activity of P-H in DOPO to obtain trimethoxy silane (PSi) with DOPO on the side group;
(2) hydrolyzing Si-OCH3 of vinyltrimethoxysilane, and then performing dehydration condensation reaction with boric acid B (OH)3 to prepare Borosiloxane (BSi);
(3) the DOPO and the vinyltrimethoxysilane are subjected to addition reaction to obtain a PSi intermediate, and then the PSi intermediate reacts with boric acid B (OH)3 to obtain a flame retardant PSiB.
6. The low-temperature-curing ambient-storage flame-retardant epoxy resin composition according to claim 1, wherein the modified inorganic flame-retardant filler is prepared by: mixing one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and low-melting-point inorganic powder, wherein the specific contents are 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, dropwise adding 90% ethanol aqueous solution with a certain volume, stirring for 30min for later use, weighing phosphate with a certain proportion to the KH550, and dissolving in deionized water with 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.
7. The low-temperature-curing ambient-storage flame-retardant epoxy resin composition according to claim 1, wherein a latent curing agent 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 description is as follows:
firstly, mixing a certain amount of bisphenol F epoxy resin and a certain amount of stabilizer to form a resin mixture containing the stabilizer, then adding the latent curing agent into the resin mixture containing the stabilizer, stirring at a low speed by using a double-planet power stirrer, controlling the temperature in the stirrer to be not higher than 30 ℃ by using a water cooling device, stirring for not less than 1 hour to prepare a paste, uniformly coating the latent curing agent with the resin mixture containing the stabilizer, and preparing the modified low-temperature curing latent curing agent.
8. The flame-retardant prepreg prepared from the low-temperature-cured normal-temperature-stored 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 as follows:
(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 which is cured at low temperature and stored at normal 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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| CN113667266A (en) * | 2021-09-10 | 2021-11-19 | 四川玄武岩纤维新材料研究院(创新中心) | Thermosetting resin flame-retardant composition and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113667266A (en) * | 2021-09-10 | 2021-11-19 | 四川玄武岩纤维新材料研究院(创新中心) | Thermosetting resin flame-retardant composition and preparation method and application thereof |
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