CN111393804B - Epoxy resin composition, preparation method thereof and fiber prepreg prepared from epoxy resin composition - Google Patents
Epoxy resin composition, preparation method thereof and fiber prepreg prepared from epoxy resin composition Download PDFInfo
- Publication number
- CN111393804B CN111393804B CN202010322319.1A CN202010322319A CN111393804B CN 111393804 B CN111393804 B CN 111393804B CN 202010322319 A CN202010322319 A CN 202010322319A CN 111393804 B CN111393804 B CN 111393804B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- epoxy
- stirring
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
-
- 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
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an epoxy resin composition, a preparation method thereof and a fiber prepreg prepared from the epoxy resin composition. The epoxy resin composition includes: at least one epoxy resin; at least one hardener which is a compound containing phenolic hydroxyl functional groups; at least one catalyst; in particular, the adhesive also comprises at least one toughening agent which is a reaction product of polyether amine and hydantoin type epoxy resin. The epoxy resin composition is suitable for hot-melt prepreg and has the characteristics of good toughness, rapid forming and long-term storage stability.
Description
Technical Field
The invention relates to the field of fiber reinforced composite materials, in particular to an epoxy resin composition, a preparation method thereof and a fiber prepreg prepared from the epoxy resin composition.
Background
With the increasing prominence of the world energy crisis and the environmental protection problem, the new energy electric automobile also becomes an important component of low-carbon economy. The power battery is used as the heart of the new energy electric vehicle, and the higher endurance mileage is one of the important considered indexes. The battery case is as bearing and protection device of battery assembly, adopts steel and aluminium or aluminum alloy to make mostly, leads to its quality big, greatly increased the dead weight of battery case assembly and car, causes the car to go in-process energy consumption to increase, has influenced the continuation of the journey mileage.
In order to reduce the weight of the battery box of the new energy electric vehicle, the development trend of the battery box of the new energy electric vehicle is inevitable by adopting a lightweight high-strength fiber reinforced composite material to replace a traditional metal material. Epoxy resin is used as a matrix material of a fiber reinforced composite material, has very excellent comprehensive performance, and is widely used for preparing fiber reinforced prepregs. The traditional epoxy resin composition used for the prepreg has the defects of long curing period and poor storage stability, and cannot meet the molding efficiency and quality stability of the new energy electric vehicle battery box. In addition, the traditional epoxy resin composition has low impact strength, so that the toughness of the traditional epoxy resin composition is insufficient, and the high-temperature and low-temperature cracking performance of the epoxy resin composition is influenced. Therefore, there is a need for an epoxy resin composition for preparing a fiber prepreg, which is suitable for a hot-melt prepreg and has characteristics of flame retardancy, rapid molding, and long-term storage stability.
Disclosure of Invention
The invention aims to provide an epoxy resin composition which is suitable for a hot-melt prepreg and has the characteristics of good toughness, quick forming, long storage period and stable storage.
The present invention provides an epoxy resin composition comprising: at least one epoxy resin; at least one hardener which is a compound containing phenolic hydroxyl functional groups; at least one catalyst; in particular, the adhesive also comprises at least one toughening agent, wherein the toughening agent is a reaction product of polyetheramine and hydantoin type epoxy resin; the epoxy resin composition also comprises at least one flame retardant, wherein the flame retardant is one or more of melamine cyanurate salt and epoxy resin coated ammonium polyphosphate; the toughening agent is prepared by reacting trifunctional polyether amine with the molecular weight of 2000-10000 and hydantoin type epoxy resin with the epoxy equivalent of 100-190g/eq at 100-150 ℃ for 2-4h, wherein the molar ratio of amino in the polyether amine to epoxy in the hydantoin type epoxy resin is 1-4; the epoxy resin composition comprises the following components in percentage by mass: 15 to 60 percent of epoxy resin, 15 to 40 percent of hardener, 0.5 to 5 percent of catalyst, 10 to 25 percent of flame retardant and 5 to 20 percent of toughener; wherein the molar ratio of epoxy groups in the epoxy resin to hydroxyl groups in the hardener is 1.
Optionally, the molar ratio of epoxy groups in the epoxy resin to hydroxyl groups in the hardener is 1.
Optionally, the epoxy resin comprises the following components in percentage by mass: 10 to 40 percent of bisphenol A type glycidyl ether epoxy resin and 5 to 20 percent of novolac epoxy resin.
Optionally, the bisphenol A type glycidyl ether epoxy resin is one or more of bisphenol A type glycidyl ether epoxy resins with epoxy equivalent weight of 160-280 g/eq;
the novolac epoxy resin is one or more of linear novolac epoxy resin with epoxy equivalent of 160-200g/eq and o-cresol novolac epoxy resin with epoxy equivalent of 160-200 g/eq.
Optionally, the hardener is one or more of a linear phenol-formaldehyde resin, a linear bisphenol a-formaldehyde resin, and a linear o-cresol-formaldehyde resin, wherein the hydroxyl equivalent weight of each of the linear phenol-formaldehyde resin, the linear bisphenol a-formaldehyde resin, and the linear o-cresol-formaldehyde resin is 100-150g/eq.
Optionally, the catalyst is one or more of imidazole compounds, 1, 8-diazabicycloundecen-7-ene and quaternary phosphonium salt compounds.
On the other hand, the invention also provides a preparation method of the epoxy resin composition, which comprises the following steps:
adding epoxy resin and a toughening agent into a reaction kettle, heating, controlling the temperature of the reaction kettle at 80-100 ℃, and mixing and stirring for 10-20 minutes at 100-300 rpm;
adding the flame retardant into a reaction kettle, and stirring and dispersing for 10-20 minutes at the stirring speed of 1000-1300 rpm to obtain a homogeneous mixture;
adding a hardening agent into the mixture, mixing and stirring at 700-900 rpm, and continuing to mix and stir for 20-40 minutes after the hardening agent is fully dissolved;
finally adding the catalyst, keeping the temperature at 80-100 ℃, and stirring for 15-30 minutes under the condition that the stirring speed is 700-900 rpm to obtain the fully mixed epoxy resin composition.
Finally, the invention also provides a fiber prepreg comprising fibers and the epoxy resin composition.
In the invention, the toughening agent is added, so that the toughness of the epoxy resin composition is greatly improved and the high-low temperature cracking resistance is improved under the condition of not changing the mechanical strength and the heat resistance. Compared with the traditional dicyandiamide curing system, the hardener containing the phenolic hydroxyl functional group has higher reaction activity, and the epoxy functional group in the epoxy resin and the phenolic hydroxyl group in the hardener are promoted to react by adding the catalyst, so that the curing period is shortened. The epoxy resin composition is suitable for long-term storage and has high stability. The fiber prepreg prepared from the epoxy resin composition is suitable for a hot-melt prepreg, has the characteristics of stability, good flame retardance and higher forming efficiency during storage, and can be used for preparing power batteries, energy storage batteries and other lithium battery outer boxes and module supports of new energy vehicles. The preparation method of the epoxy resin composition is simple, low in cost, convenient to operate and convenient in source of reaction raw materials, can complete the preparation process in general equipment, and is beneficial to realizing industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In order to explain the technical means of the present invention, the following description will be given by way of specific examples.
In one embodiment of the present invention, an epoxy resin composition includes: at least one epoxy resin. At least one hardener which is a compound containing phenolic hydroxyl functional groups. At least one catalyst. Particularly, the epoxy resin toughening agent also comprises at least one toughening agent, wherein the toughening agent is a compound obtained by chain extension modification of the epoxy resin.
In the embodiment of the invention, the toughening agent is added, so that the toughness of the epoxy resin composition is greatly improved and the high-low temperature cracking resistance is improved under the condition of not changing the mechanical strength and the heat resistance. The epoxy resin composition of the present invention. Compared with the traditional dicyandiamide curing system, the hardener containing the phenolic hydroxyl functional group has higher reaction activity, and the epoxy functional group in the epoxy resin and the phenolic hydroxyl group in the hardener are promoted to react by adding the catalyst, so that the curing period is shortened. The epoxy resin composition is suitable for long-term storage and has high stability.
In some embodiments of the invention, the toughening agent is prepared by reacting trifunctional polyether amine with molecular weight of 2000-10000 and hydantoin type epoxy resin with epoxy equivalent of 100-190g/eq at 100-150 ℃ for 2-4h, wherein the molar ratio of amino in the polyether amine to epoxy in the hydantoin type epoxy resin is 1. By adding the toughening agent and introducing the flexible chain segment, the toughness of the epoxy resin composition is greatly improved and the high-low temperature cracking resistance is improved under the condition of not changing the mechanical strength and the heat resistance of the conventional epoxy resin composition.
In some embodiments of the present invention, the epoxy resin composition further comprises at least one flame retardant, which is one or more of melamine cyanurate salt, epoxy resin-encapsulated ammonium polyphosphate. By adding the flame retardant, the flame retardant has excellent flame retardant property.
In some embodiments of the present invention, the epoxy resin composition comprises the following components in percentage by mass: 15 to 60 percent of epoxy resin, 15 to 40 percent of hardener, 0.5 to 5 percent of catalyst, 10 to 25 percent of flame retardant and 5 to 20 percent of toughening agent. Wherein the molar ratio of epoxy groups in the epoxy resin to hydroxyl groups in the hardener is 1 to 1.1, and further the molar ratio of epoxy groups in the epoxy resin to hydroxyl groups in the hardener is 1. By adjusting the percentage of each component in the epoxy resin composition, the storage time of the epoxy resin composition is prolonged under the condition of keeping the existing viscosity, and the storage stability is ensured.
In some embodiments of the present invention, the epoxy resin comprises the following components in percentage by mass: 10 to 40 percent of bisphenol A type glycidyl ether epoxy resin and 5 to 20 percent of novolac epoxy resin.
In some embodiments of the present invention, the bisphenol a type glycidyl ether epoxy resin is one or more of bisphenol a type glycidyl ether epoxy resins having an epoxy equivalent weight of 160 to 280 g/eq. The novolac epoxy resin is one or more of linear novolac epoxy resin with epoxy equivalent of 160-200g/eq and o-cresol novolac epoxy resin with epoxy equivalent of 160-200 g/eq. The viscosity of the epoxy resin composition is controlled within a standard range by selecting an epoxy resin having an epoxy equivalent of the above-mentioned range value.
In some embodiments of the invention, the hardener is one or more of a linear phenol formaldehyde resin, a linear bisphenol a formaldehyde resin, a linear o-cresol formaldehyde resin, wherein the hydroxyl equivalent weight of each of the linear phenol formaldehyde resin, the linear bisphenol a formaldehyde resin, and the linear o-cresol formaldehyde resin is from 100 to 150g/eq.
In some embodiments of the present invention, the catalyst is one or more of imidazoles, 1, 8-diazabicycloundec-7-ene, and quaternary phosphonium compounds, which promote the ring opening of the epoxy group in the epoxy resin, and then react with the phenolic hydroxyl group in the hardener, thereby shortening the reaction time.
In another aspect, an embodiment of the present invention provides a method for preparing an epoxy resin composition, including the steps of:
adding epoxy resin and a toughening agent into a reaction kettle, heating, controlling the temperature of the reaction kettle at 80-100 ℃, and mixing and stirring at 100-300 rpm for 10-20 minutes and 200rpm for 10 minutes. Then adding the flame retardant into a reaction kettle, and stirring at a stirring dispersion speed of 1000rpm-1300rpm for 10-20 minutes to obtain a homogeneous mixture. Then adding the hardener into the mixture, mixing and stirring at 700-900 rpm, and continuing to mix and stir for 20-40 minutes after the hardener is fully dissolved. Finally adding a catalyst, keeping the temperature at 80-100 ℃, and stirring for 15-30 minutes under the condition that the stirring speed is 700-900 rpm to obtain the fully mixed epoxy resin composition.
In this embodiment, the catalyst is added at the end of 80-100 ℃ to catalyze the reaction of the epoxy resin and the hardener, thereby avoiding the self-reaction of the catalyst and the hardener. The preparation method of the epoxy resin composition is simple, low in cost, convenient to operate and convenient in reaction raw material source, can finish the preparation process in general equipment, and is favorable for realizing industrial production.
Finally, an embodiment of the invention provides a fiber prepreg, which comprises the epoxy resin composition and fibers of the embodiment, and the fiber prepreg is used for preparing outer boxes and module supports of power batteries, energy storage batteries and other lithium batteries of new energy vehicles. The fiber prepreg has the characteristics of stability, good flame retardance and higher molding efficiency during storage.
The invention is further illustrated by the following examples, in which,
the epoxy resin A is a bisphenol A type epoxy resin having an epoxy equivalent of 187
The epoxy resin B is D.E.N.TM438 phenolic aldehyde epoxy resin purchased from Dow chemical
The epoxy resin C is a bisphenol A type epoxy resin having an epoxy equivalent of 475g/eq
Hardener A is a Linear phenol Formaldehyde resin with a hydroxyl equivalent weight of 106
Hardener B is a 120 hydroxyl equivalent linear ortho-cresol formaldehyde resin
Hardener C is dicyandiamide having a particle size of about 10 microns
The flame retardant A was 1250 mesh melamine cyanurate salt (MCA)
The fire retardant B is 1250-mesh epoxy resin coated ammonium polyphosphate
Catalyst A is 2-methylimidazole
Catalyst B is DBU (1, 8-diazabicycloundec-7-ene)
Catalyst C is an organic urea UR300 having a particle size of about 10 microns
The toughening agent A is an epoxy resin modified compound
The preparation method of the toughening agent A comprises the following steps: according to the molar ratio of the epoxy groups to the amino hydrogen groups of 5:1, 139g/eq epoxy equivalent of hydantoin type epoxy resin and polyether polyamine (C)
T-5000), vacuumizing, introducing nitrogen for protection, heating to 120 ℃, reacting for 3 hours, and cooling to 25 ℃ to obtain a toughening agent A with the epoxy equivalent of 410g/eq
Example 1
This example is used to illustrate an epoxy resin composition and a method for preparing the same disclosed in the present invention, and the method comprises the following steps:
adding 29.9g of epoxy resin A,10g of epoxy resin B and 11g of toughening agent A into a reaction kettle, heating and controlling the kettle temperature at 90 ℃, mixing and stirring at 200rpm for 10 minutes, then adding 5g of flame retardant A and 15g of flame retardant B into the reaction kettle, and stirring and dispersing at 1200rpm for 15 minutes to obtain a homogeneous mixture. And adding 27.6g of hardening agent A into the mixture, mixing and stirring at 800rpm, continuing mixing and stirring for 30 minutes after the hardening agent A is fully dissolved, finally adding 1.5g of catalyst A, and stirring for 20 minutes under the condition of keeping the temperature and the stirring speed unchanged to obtain a fully mixed composition.
Example 2
This example is used to illustrate an epoxy resin composition and a method for preparing the same disclosed in the present invention, and the method comprises the following steps:
adding 28.3g of epoxy resin A,10g of epoxy resin B and 11g of toughening agent A into a reaction kettle, heating and controlling the kettle temperature at 90 ℃, mixing and stirring for 10 minutes at 200rpm, adding 5g of flame retardant A and 15g of flame retardant B into the reaction kettle, and stirring and dispersing for 15 minutes at 1200rpm to obtain a homogeneous mixture. Then adding 29.2g of hardening agent B into the mixture, mixing and stirring at 800rpm, continuing to mix and stir for 30 minutes after the hardening agent B is fully melted, finally adding 1.5g of catalyst A, and stirring for 20 minutes under the condition of keeping the temperature and the stirring speed unchanged to obtain a fully mixed composition.
Example 3
This example is used to illustrate an epoxy resin composition and a method for preparing the same disclosed in the present invention, and the method comprises the following steps:
adding 29.9g of epoxy resin A,10g of epoxy resin B and 11g of toughening agent A into a reaction kettle, heating and controlling the kettle temperature at 90 ℃, mixing and stirring at 200rpm for 10 minutes, then adding 5g of flame retardant A and 15g of flame retardant B into the reaction kettle, and stirring and dispersing at 1200rpm for 15 minutes to obtain a homogeneous mixture. And adding 27.6g of hardening agent A into the mixture, mixing and stirring at 800rpm, continuing to mix and stir for 30 minutes after the hardening agent A is fully dissolved, finally adding 1.5g of catalyst B, and stirring for 20 minutes under the condition of keeping the temperature and the stirring speed unchanged to obtain a fully mixed composition.
Example 4
This example is used to illustrate an epoxy resin composition and a method for preparing the same disclosed in the present invention, and the method comprises the following steps:
adding 29.9g of epoxy resin A,16g of epoxy resin B and 5g of toughening agent A into a reaction kettle, heating and controlling the kettle temperature at 90 ℃, mixing and stirring at 200rpm for 10 minutes, then adding 5g of flame retardant A and 15g of flame retardant B into the reaction kettle, and stirring at 1200rpm for 15 minutes to obtain a homogeneous mixture. And adding 28.6g of hardening agent A into the mixture, mixing and stirring at 800rpm, continuing mixing and stirring for 30 minutes after the hardening agent A is fully dissolved, finally adding 1.5g of catalyst B, and stirring for 20 minutes under the condition of keeping the temperature and the stirring speed unchanged to obtain a fully mixed composition.
Comparative example 1
Adding 29.9g of epoxy resin A and 10g of epoxy resin B into a reaction kettle, heating and controlling the kettle temperature at 90 ℃, mixing and stirring at 200rpm for 10 minutes, then adding 5g of flame retardant A and 15g of flame retardant B into the reaction kettle, and stirring and dispersing at 1200rpm for 15 minutes to obtain a homogeneous mixture. Then adding 22.6g of hardening agent A into the mixture, mixing and stirring at 800rpm, continuing to mix and stir for 30 minutes after the hardening agent A is fully dissolved, finally adding 1.5g of catalyst A, and stirring for 20 minutes under the condition of keeping the temperature and the stirring speed unchanged to obtain a fully mixed composition.
Comparative example 2
Adding 36.6g of epoxy resin A and 38.6g of epoxy resin C into a reaction kettle, heating and controlling the kettle temperature at 80 ℃, mixing and stirring at 200rpm, adding 5g of flame retardant A,15g of flame retardant B,3.8g of hardener C and 1g of catalyst C into the reaction kettle after the epoxy resin C is fully melted, and stirring and dispersing at 1200rpm for 30 minutes to obtain a fully mixed composition.
Performance testing
The implementation cases 1 to 4 and the comparison cases 1 and 2 are compared according to the following standards or test methods for the relevant performance:
(1) The viscosity at 70 ℃ is measured using GB/T10247.
(2) Gelation time: the composition was poured into a 170 ℃ hot plate and the time from the start of pouring to drawing was measured.
(3) Glass transition temperature: the composition was poured into a hot plate at 170 ℃ and cured for 5min to give a cured mass, which was tested using differential scanning calorimetry ISO 11357-2 at a scanning speed of 10 ℃/min.
(4) Bending property: the composition is heated to 100 ℃, poured into a heated mould with fixed specification, put into an oven with 170 ℃ for curing for 5min to prepare a sample bar with certain specification, and the bending property is measured according to ISO 178 (test speed 2 mm/min) by adopting Instron 5566.
(5) Impact strength: the composition is heated to 100 ℃, then poured into a heated mould with a fixed specification, put into an oven with the temperature of 170 ℃ for curing for 5min to prepare a sample bar with a certain specification, and the impact strength is measured according to GB/T2571.
(6) Change of viscosity: after the composition was stored at 40 ℃ for 30 days, the viscosity at 70 ℃ was measured.
(7) Flame retardant properties: heating the composition to 100 ℃, pouring the composition into a heated mould with a fixed specification, putting the heated mould into an oven with a temperature of 170 ℃ for curing for 5min to prepare a sample strip with a certain specification, and preparing the sample strip with a flame retardant property of 2mm according to GB 2408-2008.
The test results obtained are filled in Table 1.
TABLE 1
From the test results in table 1, it can be seen that the epoxy resin composition prepared by the present invention has the following advantages compared with the prior art: the reaction speed is accelerated, the bending strength is increased, the bending modulus is increased, and the impact strength is improved. The storage stability is good.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the embodiments or equivalent replacements of some technical features may still be made. Such modifications and substitutions do not substantially depart from the spirit and scope of the embodiments of the present invention, and are intended to be included within the scope of the present invention.
Claims (7)
1. An epoxy resin composition comprising: at least one epoxy resin; at least one hardener which is a compound containing phenolic hydroxyl functional groups; at least one catalyst; the epoxy resin toughening agent is characterized by also comprising at least one toughening agent, wherein the toughening agent is a reaction product of polyetheramine and hydantoin type epoxy resin; the flame retardant is one or more of melamine cyanurate salt and epoxy resin coated ammonium polyphosphate; the toughening agent is prepared by reacting trifunctional polyether amine with the molecular weight of 2000-10000 and hydantoin type epoxy resin with the epoxy equivalent of 100-190g/eq at 100-150 ℃ for 2-4h, wherein the molar ratio of amino in the polyether amine to epoxy in the hydantoin type epoxy resin is 1-4; the epoxy resin composition comprises the following components in percentage by mass: 15 to 60 percent of epoxy resin, 15 to 40 percent of hardener, 0.5 to 5 percent of catalyst, 10 to 25 percent of flame retardant and 5 to 20 percent of toughener; wherein the molar ratio of epoxy groups in the epoxy resin to hydroxyl groups in the hardener is 1.
2. The epoxy resin composition as claimed in claim 1, wherein the epoxy resin comprises the following components in percentage by mass: 10 to 40 percent of bisphenol A type glycidyl ether epoxy resin and 5 to 20 percent of novolac epoxy resin.
3. The epoxy resin composition according to claim 2,
the bisphenol A type glycidyl ether epoxy resin is one or more of bisphenol A type glycidyl ether epoxy resins with the epoxy equivalent of 160-280 g/eq;
the novolac epoxy resin is one or more of linear novolac epoxy resin with epoxy equivalent of 160-200g/eq and o-cresol novolac epoxy resin with epoxy equivalent of 160-200 g/eq.
4. The epoxy resin composition of claim 1, wherein the hardener is one or more of a linear phenol formaldehyde resin, a linear bisphenol a formaldehyde resin, a linear o-cresol formaldehyde resin, wherein the hydroxyl equivalent weight of the linear phenol formaldehyde resin, linear bisphenol a formaldehyde resin, and linear o-cresol formaldehyde resin are each 100 to 150g/eq.
5. The epoxy resin composition of claim 1, wherein the catalyst is one or more of an imidazole compound, 1, 8-diazabicycloundecen-7-ene, and a quaternary phosphonium salt compound.
6. The process for producing the epoxy resin composition according to any one of claims 1 to 5, comprising the steps of:
adding epoxy resin and a toughening agent into a reaction kettle, heating, controlling the temperature of the reaction kettle at 80-100 ℃, and mixing and stirring for 10-20 minutes at 100-300 rpm;
adding the flame retardant into a reaction kettle, and stirring at a dispersion speed of 1000-1300 rpm for 10-20 minutes to obtain a homogeneous mixture;
adding a hardening agent into the mixture, mixing and stirring at 700-900 rpm, and continuing to mix and stir for 20-40 minutes after the hardening agent is fully dissolved;
finally adding a catalyst, keeping the temperature at 80-100 ℃, and stirring for 15-30 minutes under the condition that the stirring speed is 700-900 rpm to obtain the fully mixed epoxy resin composition.
7. A fiber prepreg comprising fibers and the epoxy resin composition according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010322319.1A CN111393804B (en) | 2020-04-22 | 2020-04-22 | Epoxy resin composition, preparation method thereof and fiber prepreg prepared from epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010322319.1A CN111393804B (en) | 2020-04-22 | 2020-04-22 | Epoxy resin composition, preparation method thereof and fiber prepreg prepared from epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111393804A CN111393804A (en) | 2020-07-10 |
| CN111393804B true CN111393804B (en) | 2023-03-28 |
Family
ID=71426738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010322319.1A Active CN111393804B (en) | 2020-04-22 | 2020-04-22 | Epoxy resin composition, preparation method thereof and fiber prepreg prepared from epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111393804B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114902919A (en) * | 2022-06-07 | 2022-08-16 | 广东省农业科学院水稻研究所 | Silk seedling rice planting and cultivating method |
| CN115260708A (en) * | 2022-07-19 | 2022-11-01 | 广东茂化研绿色发展有限公司 | Modified carbon black master batch and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2086719A1 (en) * | 1992-08-13 | 1994-02-14 | Harold G. Waddill | Heimd-containing polyetheramine curative for flexible, toughened products |
| CN101341181A (en) * | 2005-12-22 | 2009-01-07 | 陶氏环球技术公司 | A curable epoxy resin composition and laminates made therefrom |
| WO2017019677A1 (en) * | 2015-07-30 | 2017-02-02 | Dow Global Technologies Llc | Epoxy thermoset materials and the use thereof |
| CN109593323A (en) * | 2018-12-18 | 2019-04-09 | 杭州之江新材料有限公司 | A kind of adduct of polyethers amine-epoxy and preparation method thereof and the good single-component epoxy composition and preparation method thereof of storage |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090099312A1 (en) * | 2007-10-15 | 2009-04-16 | Carl Duane Weber | Amine terminated tougheners for epoxy resin based adhesives and materials |
| CN104136479B (en) * | 2011-12-20 | 2017-03-22 | 陶氏环球技术有限责任公司 | For the toughner of epoxy thermosetting material |
-
2020
- 2020-04-22 CN CN202010322319.1A patent/CN111393804B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2086719A1 (en) * | 1992-08-13 | 1994-02-14 | Harold G. Waddill | Heimd-containing polyetheramine curative for flexible, toughened products |
| CN101341181A (en) * | 2005-12-22 | 2009-01-07 | 陶氏环球技术公司 | A curable epoxy resin composition and laminates made therefrom |
| WO2017019677A1 (en) * | 2015-07-30 | 2017-02-02 | Dow Global Technologies Llc | Epoxy thermoset materials and the use thereof |
| CN109593323A (en) * | 2018-12-18 | 2019-04-09 | 杭州之江新材料有限公司 | A kind of adduct of polyethers amine-epoxy and preparation method thereof and the good single-component epoxy composition and preparation method thereof of storage |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111393804A (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2574054C2 (en) | Epoxy resin-based curable compositions and composite materials obtained therefrom | |
| CN111393804B (en) | Epoxy resin composition, preparation method thereof and fiber prepreg prepared from epoxy resin composition | |
| US20030064228A1 (en) | Epoxy resin composition for fibre-reinforced composite material | |
| KR20130062915A (en) | Epoxy resin compositions comprising poly(propylene oxide) polyol as toughening agent | |
| CN106632993A (en) | Resin composition and application thereof | |
| CN111087761A (en) | Epoxy resin and preparation method thereof | |
| CN103819898B (en) | High temperature resistant cyanate ester resin formula for carbon fiber complex core and preparation method thereof | |
| CN111139021B (en) | Low-temperature-curable high-adhesion heat-resistant cyanate ester adhesive and preparation method thereof | |
| JP6995779B2 (en) | Curable epoxy resin composition and fiber reinforced composite material using it | |
| DE60032624T2 (en) | FOR VARIABLE TEMPERATURES, CURABLE COMPOSITION | |
| CN106047271B (en) | A kind of low dielectric cyanate ester adhesive and preparation method thereof | |
| CN114621717B (en) | Epoxy foundry AB adhesive with high temperature resistance and good chemical stability and preparation method thereof | |
| JP6927891B2 (en) | Epoxy resin system with stable high glass transition temperature for producing composite materials | |
| CN112778697B (en) | Crystalline thermoplastic epoxy resin condensate and preparation method thereof | |
| CN104448240A (en) | Blending method of epoxy resin moderate temperature curing for carbon fiber prepreg | |
| KR20140148081A (en) | Low temperature curing epoxy resin composition, prepreg using the same, and low temperature curing fiber reinforced polymer composites laminating the prepreg | |
| CN115109385A (en) | Epoxy resin composition for prepreg and preparation method thereof | |
| CN108250396B (en) | Environment-friendly high-strength impact-resistant molding compound and preparation method thereof | |
| CN104312104A (en) | Low-dielectric and high-strength epoxy resin composite material and preparation method thereof | |
| Chen et al. | Polymer matrix materials | |
| JPS61138622A (en) | Fiber-reinforced composite material, and cured product produced therefrom | |
| CN114736488B (en) | Preparation method of high-compression-resistance fireproof composite epoxy foam | |
| CN112266740B (en) | High-low temperature resistant modified cyanate ester structure adhesive film and preparation method and application thereof | |
| TWI836179B (en) | Epoxy resin compositions, prepregs and fiber reinforced composite materials for fiber reinforced composite materials | |
| RU2777895C2 (en) | Epoxy binder, prepreg based on it, and product made of it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230506 Address after: 528000, First Floor, Building E8, No. 6 Xi'an Road, Xicheng Community, Danzao Town, Nanhai District, Foshan City, Guangdong Province (Residence Declaration) Patentee after: Guangdong Zhongshenhui New Material Technology Co.,Ltd. Address before: 523000 Room 101, No.3, Jinshan 2nd Street, Rome, Qingxi Town, Dongguan City, Guangdong Province Patentee before: GUANGDONG ZHONGSEN INDUSTRIAL DEVELOPMENT CO.,LTD. |