CN112375242A - Preparation method of quickly-formed ultrathin flame-retardant composite material plate - Google Patents
Preparation method of quickly-formed ultrathin flame-retardant composite material plate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The invention provides a preparation method of a quickly-formed ultrathin flame-retardant composite material plate. The method is characterized in that: adopting isocyanate and DOPO to carry out flame-retardant modification on the general epoxy resin step by step, introducing oxazolidinone nitrogen heterocycle and phosphorus-containing phenanthrene heterocycle structures into a molecular structure, and preparing flame-retardant heat-resistant epoxy resin; dicyandiamide is used as a curing agent, and modified organic urea and imidazole are compounded to be used as an accelerant to prepare a rapid forming curing system. Adding liquid epoxy resin and a fast forming curing system master batch into the modified epoxy resin to prepare a resin system for the prepreg; and finally, compounding the composite material with reinforcing fibers or fabrics to prepare a prepreg, and preparing the ultrathin composite material plate by rapid compression molding. The prepreg can realize rapid molding at 150 ℃/5min, the flame retardant rating of a composite material plate (0.3mm) can reach UL 94V-0 level, and the high glass transition temperature and the good toughness are favorable for high-temperature demolding of a workpiece without warping, and can adapt to the production cost and the production speed of high-yield automatic manufacturing.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a preparation method of a quickly-formed ultrathin flame-retardant composite material plate.
Background
The carbon fiber composite material is really applied to the fields of electronic appliances, lithium battery shells, new energy automobiles and the like, and has to be suitable for the production cost and the production speed of high-yield automatic manufacturing, and higher requirements on the forming efficiency and the flame retardant grade are provided. Most of curing temperatures of the existing carbon fiber/epoxy resin-based flame-retardant prepreg are difficult to realize the technical requirement of rapid molding, the application cost of the composite material is greatly improved, and the practical application of the composite material in the field is limited.
The improvement of the flame retardant property of the composite material is realized by introducing elements such as nitrogen, phosphorus, silicon and the like into a resin system through a chemical modification or physical blending method, but the method can reduce groups capable of generating crosslinking reaction and reduce crosslinking density, so that the curing rate of a resin matrix is reduced and the glass transition temperature is reduced.
Patent CN106687495A discloses an epoxy resin composition for fiber-reinforced composite materials, a method for producing the epoxy resin composition for fiber-reinforced composite materials, a prepreg, and a honeycomb panel. According to the invention, the amino-terminated liquid rubber modified phosphorus-containing epoxy resin is used for preparing the composite material with excellent flame retardant property, but the resin system has long curing time (130 ℃/2h) and is difficult to meet the technical requirement of rapid molding of the composite material.
Patent CN106349650A discloses an epoxy resin composition and a preparation method thereof, and a prepreg and a composite material preparation method, wherein dicyandiamide is used as an epoxy resin curing agent, modified imidazole or modified amine is used as an accelerator, and the prepreg resin cured at 150 ℃/5min is obtained, but the prepreg has short storage period and poor flame retardant property, and cannot meet the requirement of the composite material on high flame retardant property.
Disclosure of Invention
In order to solve the technical problems of high flame retardant property and rapid forming process of the conventional carbon fiber/epoxy resin-based prepreg, the invention provides a preparation method of a rapid-forming ultrathin flame-retardant composite plate, which is characterized in that isocyanate and DOPO are used for modifying general epoxy resin to prepare phosphorus-nitrogen flame-retardant epoxy resin, a regulation and control technology of a rapid curing system is used as an auxiliary technology, and the preparation method is applied to a prepreg resin system.
To this end, the invention comprises the following steps:
(1) preparing phosphorus-nitrogen flame-retardant epoxy resin: placing isocyanate and epoxy resin in a reaction kettle at 160-180 ℃, reacting for 2-4 h under the action of a catalyst, then cooling to 130-150 ℃, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and continuing to react for 3-5 h to prepare the phosphorus-nitrogen flame retardant epoxy resin. Wherein, relative to 100 parts by weight of epoxy resin, the dosage of isocyanate is 5-20 parts by weight, the dosage of catalyst is 0.1-2 parts by weight, and the dosage of DOPO is 40-60 parts by weight;
(2) preparation of prepreg resin system: and (2) adding liquid epoxy resin and a rapid forming and curing system into the phosphorus-nitrogen flame-retardant epoxy resin obtained in the step (1) to prepare a resin system for the prepreg. The amount of the liquid epoxy resin is 25-45 parts by weight, the amount of the curing agent of the rapid prototyping curing system is 5-10 parts by weight, and the amount of the accelerator of the rapid prototyping curing system is 2-6 parts by weight, relative to 100 parts by weight of the phosphorus-nitrogen flame-retardant epoxy resin;
(3) and (3) compounding the resin system with the reinforced fiber or fabric to prepare a prepreg, and curing according to the process of 150 ℃/5min to prepare the rapidly-formed ultrathin flame-retardant composite material plate (0.3 mm).
Preferably, the epoxy resin reacted with isocyanate is one or a combination of bisphenol A epoxy resin, novolac epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin and bisphenol S epoxy resin.
Preferably, the catalyst is one or a combination of several of imidazole, imidazole derivatives, tertiary amine salts, quaternary ammonium salts, quaternary phosphonium salts, metal halides, metal organic compounds, Lewis acid and alkali complexes, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, triphenylphosphonium and other quaternary phosphonium salts.
Preferably, the isocyanate is one or a combination of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Preferably, the liquid epoxy resin is one or a combination of bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD type epoxy resin and alicyclic epoxy resin.
Preferably, the curing agent of the rapid prototyping curing system is one or two of dicyandiamide and modified dicyandiamide
Preferably, the accelerator of the rapid prototyping curing system is formed by compounding a modified organic urea accelerator and an imidazole accelerator in a mass ratio of 1: 1-5: 1.
The invention has the beneficial effects that:
(1) the phosphorus-nitrogen flame-retardant epoxy resin is prepared by molecular structure design, an oxazolidinone nitrogen heterocycle and a phosphorus-containing phenanthrene heterocycle structure are introduced into a molecular main chain, and the high flame-retardant property of the epoxy resin is realized by a phosphorus-nitrogen synergistic flame-retardant effect; and the amine curing agent with higher nitrogen content is arranged in the rapid curing system, so that the phosphorus-nitrogen synergistic flame retardant effect is enhanced, and the flame retardant grade of a resin system is further improved, thereby realizing the high flame retardant property of the ultrathin composite material plate (0.3 mm).
(2) The rigid five-membered ring of the oxazolidinone is introduced into the main chain of the epoxy resin molecule, so that on one hand, the glass transition temperature of a cured product can be improved, the high-temperature thermal demolding of the ultrathin composite material plate is realized, and the production efficiency is improved. On the other hand, by reasonably controlling the raw material proportion and the synthesis process route, the oxazolidinone structure can become a linear chain extender of the epoxy resin, the distance between rigid crosslinking points in a cured material crosslinking network can be increased, the toughness of the resin is well improved, and the composite material plate is ensured not to generate warpage after high-temperature demolding.
(3) The rapid curing system of the invention takes dicyandiamide as a curing agent and the modified urea and the modified imidazole are compounded as an accelerant, thereby greatly shortening the gel time of the resin, realizing the rapid curing of the composite material plate at 150 ℃/5min and not influencing the storage period of the prepreg at room temperature.
Detailed Description
The invention will now be further illustrated by reference to the following examples:
example 1
Putting diphenylmethane diisocyanate and bisphenol A epoxy resin into a reaction kettle at 160 ℃, reacting for 2h under the action of an imidazole catalyst, then cooling to 130 ℃, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and continuing to react for 3h to prepare the phosphorus-nitrogen flame-retardant epoxy resin. Wherein, relative to 100 weight portions of bisphenol A type epoxy resin, the dosage of the diphenylmethane diisocyanate is 5 weight portions, the dosage of the imidazole catalyst is 0.1 weight portion, and the dosage of the DOPO is 40 weight portions. And adding 25 parts by weight of liquid bisphenol A glycidyl ether, 5 parts by weight of dicyandiamide curing agent, 1 part by weight of modified organic urea accelerator and 1 part by weight of imidazole accelerator into 100 parts by weight of phosphorus-nitrogen flame-retardant epoxy resin obtained in the step, thereby preparing the resin system for the prepreg with excellent manufacturability. The resin system and the reinforced fiber or fabric are compounded to prepare the prepreg, the prepreg is cured according to the process of 150 ℃/5min, the thickness of a pressed plate is 0.3mm, the limited oxygen index, the flame retardant grade and the glass transition temperature of the composite material plate are respectively tested, and the results are shown in table 1.
Example 2
The mixture of toluene diisocyanate, novolac epoxy resin and o-cresol epoxy resin is placed in a reaction kettle at 170 ℃ to react for 3 hours under the action of a metal organic compound catalyst, then the temperature is reduced to 140 ℃, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) is added to continue to react for 4 hours, and the phosphorus-nitrogen flame retardant epoxy resin is prepared. Wherein the amount of the toluene diisocyanate is 12.5 parts by weight, the amount of the organometallic compound catalyst is 1 part by weight, and the amount of the DOPO is 50 parts by weight, relative to 100 parts by weight of the mixture of the novolac epoxy resin and the o-cresol epoxy resin. And adding 35 parts by weight of liquid bisphenol F glycidyl ether, 7.5 parts by weight of modified dicyandiamide, 3 parts by weight of modified organic urea accelerator and 1 part by weight of imidazole accelerator to 100 parts by weight of the phosphorus-nitrogen flame-retardant epoxy resin obtained in the step to prepare the resin system for the prepreg with excellent manufacturability. The resin system and the reinforced fiber or fabric are compounded to prepare the prepreg, the prepreg is cured according to the process of 150 ℃/5min, the thickness of a pressed plate is 0.3mm, the limited oxygen index, the flame retardant grade and the glass transition temperature of the composite material plate are respectively tested, and the results are shown in table 1.
Example 3
Placing hexamethyl diisocyanate and bisphenol S epoxy resin in a reaction kettle at 180 ℃, reacting for 4h under the action of quaternary phosphonium salt catalysts such as triphenylphosphine and the like, then cooling to 150 ℃, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and continuing to react for 5h to prepare the phosphorus-nitrogen flame-retardant epoxy resin. Wherein, relative to 100 weight portions of bisphenol S type epoxy resin, the dosage of hexamethyl diisocyanate is 20 weight portions, the dosage of quaternary phosphonium salt catalysts such as triphenylphosphine and the like is 2 weight portions, and the dosage of DOPO is 60 weight portions. And adding 45 parts by weight of liquid alicyclic epoxy resin, 10 parts by weight of dicyandiamide curing agent, 5 parts by weight of modified organic urea accelerator and 1 part by weight of imidazole accelerator to 100 parts by weight of phosphorus-nitrogen flame-retardant epoxy resin obtained in the step to prepare the resin system for the prepreg with excellent manufacturability. The resin system and the reinforced fiber or fabric are compounded to prepare the prepreg, the prepreg is cured according to the process of 150 ℃/5min, the thickness of a pressed plate is 0.3mm, the limited oxygen index, the flame retardant grade and the glass transition temperature of the composite material plate are respectively tested, and the results are shown in table 1.
Comparative example 1
Putting diphenylmethane diisocyanate and bisphenol A epoxy resin into a reaction kettle at 160 ℃, and reacting for 2h under the action of imidazole catalysts to prepare the oxazolidone modified nitrogen-containing epoxy resin. Wherein, relative to 100 weight portions of bisphenol A type epoxy resin, the dosage of the diphenylmethane diisocyanate is 5 weight portions, and the dosage of the imidazole catalyst is 0.1 weight portion. To 100 parts of the modified epoxy resin obtained in the above step, 25 parts of liquid bisphenol a glycidyl ether, 5 parts of dicyandiamide curing agent, 1 part of modified organic urea accelerator, and 1 part of imidazole accelerator were added to prepare a resin system for prepreg having excellent manufacturability. The resin system and the reinforced fiber or fabric are compounded to prepare the prepreg, the prepreg is cured according to the process of 150 ℃/5min, the thickness of a pressed plate is 0.3mm, the limited oxygen index, the flame retardant grade and the glass transition temperature of the composite material plate are respectively tested, and the results are shown in table 1.
Comparative example 2
9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and bisphenol A epoxy resin are placed in a reaction kettle at 130 ℃ to react for 3 hours under the action of imidazole catalysts to prepare the modified phosphorus-containing epoxy resin. Wherein, relative to 100 parts of bisphenol A type epoxy resin, the dosage of the imidazole catalyst is 0.1 part by weight, and the dosage of DOPO is 40 parts by weight. To 100 parts of the modified epoxy resin obtained in the above step, 25 parts of liquid bisphenol a glycidyl ether, 5 parts of dicyandiamide curing agent, 1 part of modified organic urea accelerator, and 1 part of imidazole accelerator were added to prepare a resin system for prepreg having excellent manufacturability. The resin system and the reinforced fiber or fabric are compounded to prepare the prepreg, the prepreg is cured according to the process of 150 ℃/5min, the thickness of a pressed plate is 0.3mm, the limited oxygen index, the flame retardant grade and the glass transition temperature of the composite material plate are respectively tested, and the results are shown in table 1.
TABLE 1 Properties of the composites of the different examples
Compared with a comparative example, the flame retardant grade of the 0.3mm ultrathin composite material plate prepared in the example can reach UL 94V-0, the limiting oxygen index is higher than 38%, the glass transition temperature is higher than 160 ℃, and the composite material can be subjected to high-temperature demoulding without warping. In the comparative example 1, the composite material plate prepared by the oxazolidone modified nitrogen-containing epoxy resin has a flame retardant rating of only UL 94V-2 and a limited oxygen index of only 33 percent although the glass transition temperature is higher, and the requirement of the thin-wall composite material on high flame retardant property is difficult to meet; in the composite material plate prepared by adopting the DOPO modified phosphorus-containing epoxy resin in the comparative example 2, the flame retardant grade is UL 94V-1, the limiting oxygen index is 35 percent, the flame retardant grade is lower, the glass transition temperature is 145 ℃, and the high-temperature thermal demolding of the composite material is difficult to realize. The invention finally solves the technical problems of the carbon fiber prepreg in the aspects of high flame retardant property and rapid molding process, and widens the application field of the carbon fiber composite material.
Claims (7)
1. A preparation method of a quickly-formed ultrathin flame-retardant composite material plate is characterized by comprising the following steps:
(1) preparing phosphorus-nitrogen flame-retardant epoxy resin: placing isocyanate and epoxy resin in a reaction kettle at 160-180 ℃, reacting for 2-4 h under the action of a catalyst, then cooling to 130-150 ℃, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and continuing to react for 3-5 h to prepare the phosphorus-nitrogen flame retardant epoxy resin. Wherein, relative to 100 parts by weight of epoxy resin, the dosage of isocyanate is 5-20 parts by weight, the dosage of catalyst is 0.1-2 parts by weight, and the dosage of DOPO is 40-60 parts by weight;
(2) preparation of prepreg resin system: and (2) adding liquid epoxy resin and a rapid forming and curing system into the phosphorus-nitrogen flame-retardant epoxy resin obtained in the step (1) to prepare a resin system for the prepreg. The amount of the liquid epoxy resin is 25-45 parts by weight, the amount of the curing agent of the rapid prototyping curing system is 5-10 parts by weight, and the amount of the accelerator of the rapid prototyping curing system is 2-6 parts by weight, relative to 100 parts by weight of the phosphorus-nitrogen flame-retardant epoxy resin;
(3) and (3) compounding the resin system and the reinforced fiber fabric to prepare a prepreg, and curing according to the process of 150 ℃/5min to prepare the rapidly-formed ultrathin flame-retardant composite material plate (0.3 mm).
2. The production method according to claim 1, characterized in that: the epoxy resin reacted with the isocyanate is one or a combination of bisphenol A epoxy resin, novolac epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin and bisphenol S epoxy resin.
3. The production method according to claim 1, characterized in that: the catalyst is one or a combination of more of imidazole, imidazole derivatives, tertiary amine salts, quaternary ammonium salts, quaternary phosphonium salts, metal halides, metal organic compounds, Lewis acid and alkali complexes, benzyl triphenyl phosphonium chloride, benzyl triphenyl phosphonium bromide, triphenyl phosphonium and other quaternary phosphonium salts.
4. The production method according to claim 1, characterized in that: the isocyanate is one or a combination of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
5. The production method according to claim 1, characterized in that: the liquid epoxy resin is one or a combination of bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol AD type epoxy resin and alicyclic epoxy resin.
6. The production method according to claim 1, characterized in that: the curing agent of the rapid prototyping curing system is one or two compositions of dicyandiamide and modified dicyandiamide.
7. The production method according to claim 1, characterized in that: the accelerator of the rapid prototyping curing system is prepared by compounding a modified organic urea accelerator and an imidazole accelerator in a mass ratio of 1: 1-5: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
| CN114149657A (en) * | 2021-12-28 | 2022-03-08 | 珠海宏昌电子材料有限公司 | Low dielectric loss and high CTI epoxy resin composition and application thereof |
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| CN105924674A (en) * | 2016-06-02 | 2016-09-07 | 沈阳化工大学 | Epoxy resin flame retardant containing phosphorus and nitrogen and preparation method of epoxy resin flame retardant |
| CN106987013A (en) * | 2017-05-17 | 2017-07-28 | 中威北化科技有限公司 | The preparation method for the intermediate temperature setting epoxy prepreg that glass transition temperature is improved |
| CN108530874A (en) * | 2017-03-02 | 2018-09-14 | 北京化工大学 | A kind of preparation method of high temperature tough epoxy resin and its rapid shaping carbon fiber prepreg |
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| CN105924674A (en) * | 2016-06-02 | 2016-09-07 | 沈阳化工大学 | Epoxy resin flame retardant containing phosphorus and nitrogen and preparation method of epoxy resin flame retardant |
| CN108530874A (en) * | 2017-03-02 | 2018-09-14 | 北京化工大学 | A kind of preparation method of high temperature tough epoxy resin and its rapid shaping carbon fiber prepreg |
| CN106987013A (en) * | 2017-05-17 | 2017-07-28 | 中威北化科技有限公司 | The preparation method for the intermediate temperature setting epoxy prepreg that glass transition temperature is improved |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113621230A (en) * | 2021-09-01 | 2021-11-09 | 广东华彩复合材料有限公司 | Epoxy resin composite material for high-transparency prepreg and preparation method thereof |
| CN114149657A (en) * | 2021-12-28 | 2022-03-08 | 珠海宏昌电子材料有限公司 | Low dielectric loss and high CTI epoxy resin composition and application thereof |
| CN114149657B (en) * | 2021-12-28 | 2023-01-17 | 珠海宏昌电子材料有限公司 | Epoxy resin composition with low dielectric loss and high CTI (comparative tracking index) and application thereof |
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| CN112375242B (en) | 2022-03-22 |
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Effective date of registration: 20220629 Address after: 264211 Room 802, carbon fiber industrial park, caomiaozi Town, Lingang Economic and Technological Development Zone, Weihai City, Shandong Province Patentee after: Shandong Guangxuan New Material Co.,Ltd. Address before: 213164 A211, Changzhou Advanced Material Research Institute, 520 Avenue, Changzhou science and Education City, 18 Wujin Road, Wujin, Changzhou, Jiangsu Patentee before: CHANGZHOU INSTITUTE OF ADVANCED MATERIAL OF BEIJING University OF CHEMICAL TECHNOLOGY |