CN108264729B - Epoxy resin composition, epoxy resin mixture, preparation method of epoxy resin mixture, epoxy resin prepreg and composite material - Google Patents
Epoxy resin composition, epoxy resin mixture, preparation method of epoxy resin mixture, epoxy resin prepreg and composite material Download PDFInfo
- Publication number
- CN108264729B CN108264729B CN201611264550.XA CN201611264550A CN108264729B CN 108264729 B CN108264729 B CN 108264729B CN 201611264550 A CN201611264550 A CN 201611264550A CN 108264729 B CN108264729 B CN 108264729B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- weight
- parts
- resin composition
- modified
- 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
- 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
-
- 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
- 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
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to the field of composite materials, in particular to an epoxy resin composition, a composite material and a preparation method thereof. The total weight of the epoxy resin composition is 100 parts by weight, the epoxy resin composition comprises 40-50 parts by weight of epoxy resin, 6-10 parts by weight of toughening modified epoxy resin, 2-6 parts by weight of curing agent, 1-4 parts by weight of accelerator and 30-50 parts by weight of flame retardant, wherein the flame retardant comprises ammonium polyphosphate and melamine cyanurate, and the weight ratio of the ammonium polyphosphate to the melamine cyanurate is 1: 0.5-1. The epoxy resin composition and the composite material have good flame retardant property and lower smoke density during combustion.
Description
Technical Field
The invention relates to the field of composite materials, in particular to an epoxy resin composition, an epoxy resin mixture, a preparation method of the epoxy resin mixture, an epoxy resin prepreg and a composite material.
Background
The epoxy resin has good mechanical property, adhesive property, chemical stability and electrical insulation property, so that the epoxy resin can be widely applied to the fields of traffic, energy, aerospace, electronics, machinery, paint and the like as a composite material resin matrix, an electronic packaging material and the like.
However, epoxy resins have flammable properties, and thus, with the increasing use of epoxy resins, the epoxy resins also pose a greater fire risk, and therefore, it is very important to find a flame retardant which is suitable for epoxy resins and has better flame retardant properties.
Although there are many types of flame retardants, halogen-based flame retardants are mainly used in a wide range of applications. The halogen flame retardant can cause the problem of dioxin in the combustion process, can also generate bromine free radicals and further generate hydrogen bromide compounds, and the compounds can exert the flame retardant effect and have the harm of irritation and the like if being inhaled by a human body. Therefore, the research of halogen-free flame retardant is very important.
In addition, it has been investigated that many death events are not caused by burning, but are caused by suffocation of people due to smoke toxic gas released during a fire, and further death occurs. However, most of the existing researches on the flame retardant focus on the flame retardant performance, and the density of smoke generated by combustion is rarely researched.
Disclosure of Invention
The invention aims to overcome the problems that the existing flame retardant is not high enough in flame retardant property and/or is not concerned about smoke density, and provides an epoxy resin composition, an epoxy resin mixture, a preparation method of the epoxy resin mixture, an epoxy resin prepreg and a composite material. The epoxy resin composition has better flame retardant property and lower smoke density during combustion.
To this end, according to a first aspect of the present invention, there is provided an epoxy resin composition, wherein the epoxy resin composition comprises 40 to 50 parts by weight of an epoxy resin, 6 to 10 parts by weight of a toughening-modified epoxy resin, 2 to 6 parts by weight of a curing agent, 1 to 4 parts by weight of an accelerator, and 30 to 50 parts by weight of a flame retardant, based on 100 parts by weight of the total weight of the epoxy resin composition, wherein the flame retardant comprises a polyphosphoric acid amine and melamine cyanurate, and the weight ratio of the polyphosphoric acid amine to the melamine cyanurate is 1: 0.5-1.
According to a second aspect of the present invention, there is provided a method for preparing an epoxy resin mixture, wherein the epoxy resin mixture is prepared from the epoxy resin composition of the present invention, the method comprising the steps of:
(1) grinding optional liquid epoxy resin, a curing agent and an accelerator to obtain a grinding material;
(2) melting optional semisolid and/or solid epoxy resin, optional novolac epoxy resin, toughening modified epoxy resin and a flame retardant to obtain lava material;
(3) stirring and mixing the lava material obtained in the step (2) and the grinding material obtained in the step (1) at the temperature of 55-80 ℃,
wherein at least one of said liquid epoxy resin and said semi-solid and/or solid epoxy resin is present in combination with an optional novolac epoxy resin as epoxy resin raw material.
According to a third aspect of the present invention there is provided an epoxy resin mixture prepared according to the method of the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided an epoxy resin prepreg obtained by impregnating a reinforcement with an epoxy resin mixture, which is the epoxy resin mixture of the third aspect of the present invention.
According to a fifth aspect of the present invention, there is provided a composite material obtained by curing the epoxy resin prepreg of the fourth aspect of the present invention.
By applying the technical scheme of the invention, when the flame retardant obtained by mutually matching the ammonium polyphosphate and the melamine cyanurate according to a specific proportion is used for the epoxy resin composition, the flame retardant has the properties of excellent flame retardant property and low smoke density during combustion, and the mechanical property of the prepared composite material is not influenced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, an epoxy resin composition is provided, wherein the epoxy resin composition comprises 40 to 50 parts by weight of an epoxy resin, 6 to 10 parts by weight of a toughening modified epoxy resin, 2 to 6 parts by weight of a curing agent, 1 to 4 parts by weight of an accelerator, and 30 to 50 parts by weight of a flame retardant, based on 100 parts by weight of the total weight of the epoxy resin composition, wherein the flame retardant comprises a polyphosphoric acid amine and a melamine cyanurate, and the weight ratio of the polyphosphoric acid amine to the melamine cyanurate is 1: 0.5-1.
Preferably, the epoxy resin composition comprises 45-50 parts by weight of epoxy resin, 7-9 parts by weight of toughening modified epoxy resin, 2-5.5 parts by weight of curing agent, 1-3 parts by weight of accelerator and 35-45 parts by weight of flame retardant, based on 100 parts by weight of the total weight of the epoxy resin composition.
According to the epoxy resin composition of the present invention, when the weight ratio of the polyphosphoric acid amine and the melamine cyanurate meets the above requirements, it is possible to achieve better flame retardant performance and smoke density performance, and it is further preferable that the weight ratio of the polyphosphoric acid amine and the melamine cyanurate is 1: 0.6-0.85.
According to the epoxy resin composition of the present invention, preferably, the polyphosphoric acid amine is a modified polyphosphoric acid amine obtained by a melamine formaldehyde resin or a silane pretreatment. More preferably, the polyphosphoric acid amine is modified polyphosphoric acid amine coated with melamine formaldehyde resin or silane.
The epoxy resin composition comprises 85-95 wt% of the modified polyphosphoric acid amine and 5-15 wt% of melamine formaldehyde resin or silane.
The modified polyphosphoric acid amine is commercially available, and when the modified polyphosphoric acid amine is obtained by coating polyphosphoric acid amine with melamine formaldehyde resin, the modified polyphosphoric acid amine can be modified polyphosphoric acid amine with a trademark of APP-262 of Puseofu (Qingyuan) phosphorus chemical company Limited, modified polyphosphoric acid amine with a trademark of APP-232 of Puseofu (Qingyuan) phosphorus chemical company Limited, modified polyphosphoric acid amine with a trademark of JLS-PNA of Jieisi chemical industry of Hangzhou, and modified polyphosphoric acid amine with a trademark of JLS-ES-10 of Jieisi chemical industry of Hangzhou, for example.
When the modified polyphosphate is a modified polyphosphate obtained by coating polyphosphate with silane, preferably, the silane may be selected from various common silanes that can be used as silane coupling agents, for example, may be selected from one or more of aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, mercaptopropyltri (ethyl) oxysilane, ethylenediamine propyltriethoxysilane, and ethylenediamine propylmethyldimethoxysilane; the modified polyphosphoric acid amine is, for example, a modified polyphosphoric acid amine commercially available from guan raw new materials, guan, under the brand number NP-35.
According to the epoxy resin composition, the particle size D50 of the polyphosphoric acid amine is 10-25 mu m, and the particle size D50 of the melamine cyanurate is less than or equal to 10 mu m.
In the present invention, when the polyphosphoric acid amine is present in the form of a modified polyphosphoric acid amine, the particle size, the amount, etc. of the polyphosphoric acid amine defined in the present invention are calculated as the modified polyphosphoric acid amine, that is, the particle size D50 of the modified polyphosphoric acid amine is 10 to 25 μm, and the weight ratio of the modified polyphosphoric acid amine to the melamine cyanurate is 1: 0.5-1, preferably 1: 0.6-0.85.
According to the epoxy resin composition of the present invention, the epoxy resin may be an epoxy resin conventionally used for epoxy resin composites in the art. In preferred aspects, the inventors of the present invention have found that the viscosity of the resulting epoxy resin mixture and the mechanical properties of the resulting composite material can be optimized when liquid epoxy resins, solid and/or semi-solid epoxy resins and optionally novolac epoxy resins are used in combination with each other. Thus, according to a preferred embodiment of the present invention, the epoxy resin comprises a liquid epoxy resin, a solid and/or semi-solid epoxy resin and optionally a novolac epoxy resin.
According to the epoxy resin composition of the present invention, preferably, the weight ratio of the liquid epoxy resin, the solid and/or semisolid epoxy resin and the novolac epoxy resin in the epoxy resin is 1: 1.2-2.5: 0-1. The novolac epoxy resin may be selectively added due to its high cost. The inventors of the present invention have found that a higher effect can be achieved also by compounding the liquid epoxy resin with a solid and/or semisolid epoxy resin, and in this case, it is further preferable that the content ratio of the liquid epoxy resin to the solid and/or semisolid epoxy resin is 1: 1.5-2. When a novolac epoxy resin is added, the novolac epoxy resin is further preferably used in an amount of: the content ratio of the liquid epoxy resin to the novolac epoxy resin is 1: 0.36-0.72.
According to the epoxy resin composition of the present invention, the liquid epoxy resin is preferably a bisphenol a type liquid epoxy resin. The bisphenol A type liquid epoxy resin can be a bisphenol A type liquid epoxy resin which is conventional in the field, and preferably has a viscosity of 10000-18000cps, more preferably 12000-15000cps at 25 ℃, an epoxy equivalent of 170-200g/eq, preferably 180-190g/eq, and a density of 1.1-1.2g/cm3(at 25 ℃), preferably 1.14 to 1.18g/cm3。
According to the epoxy resin composition of the present invention, in order to further optimize the viscosity of the obtained epoxy resin mixture and the mechanical properties of the obtained composite material, preferably, the solid and/or semisolid epoxy resin is bisphenol a type solid and/or semisolid epoxy resin, and the bisphenol a type semisolid epoxy resin and the bisphenol a type solid epoxy resin are both included in the epoxy resin system, and the weight ratio of the bisphenol a type semisolid epoxy resin to the bisphenol a type solid epoxy resin is 1: 1-3, more preferably 1: 1.5-2.5.
According to the epoxy resin composition of the present invention, the bisphenol A type solid epoxy resin may be a bisphenol A type solid epoxy resin which is conventional in the art, and preferably, the bisphenol A type solid epoxy resin has an epoxy equivalent of 430-520g/eq, preferably 450-500g/eq, a softening point at 25 ℃ of 60-80, preferably 64-74, and a density of 1.14-1.22g/cm3(at 25 ℃), preferably 1.16 to 1.2g/cm3。
According to the epoxy resin composition of the present invention, the bisphenol A type semisolid epoxy resin can be a bisphenol A type semisolid epoxy resin which is conventional in the art, and preferably, the bisphenol A type semisolid epoxy resin has an epoxy equivalent of 200-300g/eq, preferably 230-270g/eq, and a specific gravity of 1.16-1.2 at 20 ℃.
According to the epoxy resin composition of the present invention, the novolac epoxy resin can be novolac epoxy resin which is conventional in the art, preferably, the novolac epoxy resin has an epoxy equivalent of 150-220g/eq, preferably 170-190g/eq, and a density of 1.1-1.2g/cm3(at 25 ℃), preferably 1.14 to 1.18g/cm3。
According to the epoxy resin composition of the present invention, the toughening-modified epoxy resin may be various epoxy resins having toughening properties by modifying the epoxy resin in the art, and may be selected from one or more of dimer acid-modified epoxy resin, rubber-modified epoxy resin (such as nitrile rubber-modified epoxy resin), phenoxy-modified epoxy resin, and urethane-modified epoxy resin, for example.
According to the epoxy resin composition of the present invention, preferably, the toughening modified epoxy resin is selected from any one of the following toughening modified epoxy resins having specific epoxy equivalent and viscosity: the nitrile rubber modified epoxy resin has the epoxy equivalent of 325-375g/eq and the viscosity of 300000-600000cp at 25 ℃; the dimer acid modified epoxy resin has an epoxy equivalent of 550-600g/eq and a viscosity of 45000-65000cp at 50 ℃; and phenoxy modified epoxy resin with the epoxy equivalent of 185-190g/eq and the viscosity of 2000-5000cp at 25 ℃, wherein the phenoxy resin segment accounts for 20-45 wt% of the phenoxy modified epoxy resin.
According to the epoxy resin composition of the present invention, the curing agent may be a curing agent conventionally used in epoxy resin compositions in the art, preferably a dicyandiamide-based curing agent, most preferably dicyandiamide. The particle size of the curing agent preferably satisfies D98 ≦ 10 μm.
In the present invention, the method for determining the particle diameters D50 and D98 may include: the method adopts an American Macchick S3500 type granularity tester for testing, and the testing conditions are as follows: 0.1g of the powder was weighed out into a 10ml beaker and dispersed ultrasonically for 10 min.
According to the epoxy resin composition of the present invention, the accelerator may be an accelerator conventionally used in epoxy resin compositions in the art, preferably an organic urea accelerator. More preferably, the accelerator is selected from one or more of 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea (diuron), phenyldimethylurea, 2,4 toluene bisdimethylurea, and 2,4 methyl bisdimethylurea, and the 2,4 toluene bisdimethylurea may be a mixture of 2,4 toluene bisdimethylureas mixed together in multiple isomers of 2,4 toluene bisdimethylurea. The grain size of the accelerator preferably satisfies D98 ≦ 50 μm.
According to the epoxy resin composition of the present invention, the epoxy resin composition may further include optional auxiliary materials, for example, an internal mold release agent (which may be included in an amount of 4 to 10 wt% with respect to the epoxy resin composition), a color paste (which may be included in an amount of 0.1 to 1.5 wt% with respect to the epoxy resin composition), and the like.
According to a second aspect of the present invention, there is provided a method for preparing an epoxy resin mixture, wherein the epoxy resin mixture is prepared from the epoxy resin composition of the present invention, the method comprising the steps of:
(1) grinding optional liquid epoxy resin, a curing agent and an accelerator to obtain a grinding material;
(2) melting optional semisolid and/or solid epoxy resin, optional novolac epoxy resin, toughening modified epoxy resin and a flame retardant to obtain lava material;
(3) stirring and mixing the lava material obtained in the step (2) and the grinding material obtained in the step (1) at the temperature of 55-80 ℃,
wherein at least one of said liquid epoxy resin and said semi-solid and/or solid epoxy resin is present in combination with an optional novolac epoxy resin as epoxy resin raw material.
According to the preparation method of the present invention, in a preferred case, the liquid epoxy resin, the semi-solid and/or solid epoxy resin is combined with an optional novolac epoxy resin as an epoxy resin raw material.
According to the preparation method of the present invention, the selection and the amount of various materials can be found in the epoxy resin composition of the first aspect of the present invention, and the details thereof are not repeated herein.
In step (1), the grinding may be performed in a manner conventional in the art, the main purpose of the grinding is to sufficiently mix the materials, the grinding may be performed in a three-roll grinder, and a specific grinding method may be a conventional operation, which is not described herein again.
In step (1), the materials are mixed at room temperature (usually 10-30 ℃) before the grinding, and are stirred uniformly (the stirring time can be 0.5-2h), and the temperature is controlled during the stirring process so that the temperature is maintained in the range of 10-30 ℃.
In the step (2), the temperature of the melting may be 80 to 100 ℃.
In step (3), the temperature is controlled by a water bath, and the stirring time is preferably 20 to 50 minutes, more preferably 25 to 40 minutes.
In the step (3), in order to mix the lava material obtained in the step (2) and the millbase phase obtained in the step (1) under stirring at 55-80 ℃ (preferably 60-70 ℃), preferably, before mixing under stirring, the lava material obtained in the step (2) is separately subjected to a water bath standing so that its temperature reaches 55-80 ℃ (preferably 60-70 ℃), and then the millbase obtained in the step (1) is continuously added under the water bath and mixed under stirring.
According to a third aspect of the present invention there is provided an epoxy resin mixture prepared according to the method of the second aspect of the present invention. The epoxy resin mixture prepared from the epoxy resin composition has proper viscosity, and can be tightly adhered with the reinforcement after being pressed into a resin sheet in the process of preparing the prepreg. The viscosity of the epoxy resin mixtures of the present invention at 80 ℃ is typically 15000-50000cp, preferably 20000-30000 cp.
According to a fourth aspect of the present invention, there is provided an epoxy resin prepreg obtained by combining an epoxy resin mixture with a reinforcement, the epoxy resin mixture being the epoxy resin mixture of the third aspect of the present invention. The preparation process of the epoxy resin prepreg provided by the invention is only required to adopt the conventional process method provided by the invention. For example, the process may include: preheating the epoxy resin mixture resin at 75-90 ℃ for 1-2.5 h; transferring the preheated resin between two layers of release paper, and pressing the resin into a 0.1-1.5mm sheet by using a double-roller open mill; tearing the release paper at one side or two sides as required, laying a layer of glass fiber cloth on the resin sheet, and sequentially laying a plurality of layers of resin sheets and glass fiber cloth according to the required layers; cutting into proper size to obtain the epoxy resin prepreg.
According to the epoxy resin prepreg of the present invention, the reinforcement may be various conventional reinforcements, the reinforcement may be woven cloth or woven cloth, and the material of the woven cloth or woven cloth may be one or more of carbon fiber, glass fiber, aramid fiber, aromatic polyamide fiber and basalt fiber, and most preferably glass fiber. The weight ratio of the epoxy resin mixture to the reinforcement in the epoxy resin prepreg is not particularly limited, and may be, for example, 1: 0.43 to 2.3, preferably 1: 0.82-1.5. The pore size of the reinforcement is not particularly limited, and may be larger than the particle size of the material used in the present application, for example, larger than 50 μm, preferably larger than 200 μm.
According to a fifth aspect of the present invention, there is provided a composite material obtained by curing the epoxy resin prepreg of the fourth aspect of the present invention.
According to the composite material of the present invention, the method for curing the epoxy resin prepreg to obtain the composite material is not particularly limited, and may be a method conventional in the art, for example, a method of vacuum-laminating the prepreg may be used. The specific method can comprise the following steps: removing air from the epoxy resin prepreg (the epoxy resin prepreg can be cut and laid as required before), then placing the epoxy resin prepreg on a mould (the mould can be coated with a release agent in advance), laying a layer of macroporous isolation film and a glue absorption felt on the upper surface of the prepreg, and combining and filling a vacuum bag; then connecting the vacuum bag with a vacuum pumping system, putting the vacuum bag into an oven for hot-pressing curing, and continuously pumping vacuum in the hot-pressing curing process; the thermocompression curing may include: baking at 60-80 deg.C for 30-60 min, and baking at 105-125 deg.C for 60-90 min.
The composite material prepared by using the epoxy resin composition as a raw material can keep good mechanical property, has excellent flame retardance and has low smoke density during combustion.
The present invention will be described in detail below by way of examples. In the following examples, the viscosity was measured by means of a rotational viscometer (manufactured by Brookfield company, USA, RVDV-2T-TH brand), the epoxy equivalent was measured by means of a potentiometric autotitrator (manufactured by Gekko instruments, Jiangsu Jiangyan, ZDDY-2008 brand), the density was measured according to the method prescribed in GB/T12007.5-1989, the particle diameter was measured according to the method prescribed in GB/T19077-.
Example 1
(1) Preparing an epoxy resin composition comprising:
16 parts by weight of a liquid bisphenol A epoxy resin having a viscosity of 13800cps at 25 ℃, an epoxy equivalent of 186g/eq and a density of 1.16g/cm3)，
11 parts by weight of a bisphenol A type semi-solid epoxy resin (epoxy equivalent of 253g/eq, specific gravity at 20 ℃ C. of 1.18),
21 parts by weight of a bisphenol A type solid epoxy resin (epoxy equivalent: 482g/eq, 25 ℃ softening point: 69, 25 ℃ density: 1.18 g/cm)3)，
7 parts by weight of a nitrile rubber-modified epoxy resin (epoxy equivalent 358g/eq, viscosity at 25 ℃ 480000 mPa.s; manufactured by Jiadada New Material Co., Ltd., brand 861340),
5 parts by weight of dicyandiamide curing agent (particle diameter D98 ═ 10 μm),
2.5 parts by weight of a 2, 4-toluene bisdimethylurea promoter (isomer grade, CVC USA, U24M brand, D98 ═ 44 μm),
21.5 parts by weight of melamine formaldehyde resin-coated ammonium polyphosphate particles (particle size D50 is 12 μm, wherein the melamine formaldehyde resin content is 11% by weight, the ammonium polyphosphate content is 89% by weight, the manufacturer is Puseofu phosphorus chemical Co., Ltd., trade name is APP-262),
16 parts by weight of melamine cyanurate (particle size D50 of 9 μm, manufactured by Prosefuran (Qingyuan) phosphorus chemical Co., Ltd., under the designation MCA-25).
(2) Preparation of epoxy resin mixture:
the bisphenol A type liquid epoxy resin, the curing agent and the accelerator are mixed at room temperature, stirred uniformly by a stirrer and controlled in temperature, and then ground by a three-roll grinder to obtain the grinding material.
Melting bisphenol A type semi-solid epoxy resin, bisphenol A type solid epoxy resin and toughening modified epoxy resin at 90 ℃, uniformly stirring by using a stirrer, then adding melamine polyphosphate particles coated by melamine formaldehyde resin and melamine cyanurate, and uniformly stirring at 90 ℃ to obtain the lava material.
The obtained rock slurry was left to stand in a water bath at 70 ℃ for 30 minutes, and then the obtained abrasive was added thereto and stirred uniformly by a stirrer to obtain a resin mixture.
(3) Preparing an epoxy resin prepreg and a composite material:
taking the components in a weight ratio of 1: 1.04 and glass fiber cloth (check cloth, gram weight is 800g), and placing the epoxy resin mixture at 80 ℃ for 1.5h for preheating; transferring the preheated resin between two layers of release paper, and pressing the epoxy resin mixture into a 0.4mm slice by using a double-roller open mill; tearing a layer of release paper, laying a layer of glass fiber cloth on the resin sheet, and flattening; cut to the appropriate size (e.g., 15mm by 15mm) to obtain epoxy prepregs.
Wiping the mold and coating a release agent, then removing air from the obtained epoxy resin prepreg, placing the epoxy resin prepreg on the mold, laying a layer of macroporous isolation film and a glue absorption felt on the upper surface of the prepreg, combining and filling the prepreg into a vacuum bag. And connecting the vacuum bag with a vacuum pumping system, putting the vacuum bag into an oven for hot-pressing curing, and continuously pumping vacuum in the hot-pressing curing process, wherein the hot-pressing curing process comprises the steps of firstly baking at 75 ℃ for 40 minutes and then baking at 115 ℃ for 70 minutes.
Example 2
(1) Preparing an epoxy resin composition comprising:
17.5 parts by weight of a liquid bisphenol A epoxy resin (having a viscosity of 13800cps at 25 ℃, an epoxy equivalent of 186g/eq, and a density of 1.16 g/cm)3)，
11 parts by weight of a bisphenol A type semi-solid epoxy resin (epoxy equivalent of 253g/eq, specific gravity at 20 ℃ C. of 1.18),
16.5 parts by weight of a bisphenol A type solid epoxy resin (epoxy equivalent: 482g/eq, 25 ℃ softening point: 69, 25 ℃ density: 1.18 g/cm)3)，
8 parts by weight of dimer acid-modified epoxy resin (epoxy equivalent of 580g/eq, viscosity at 50 ℃ of 52000 cps; manufactured by Shanghai Zhongsi industries Co., Ltd., ERS-172),
4.5 parts by weight of a dicyandiamide curing agent (particle diameter D98 ═ 10 μm),
2 parts by weight of a 2, 4-methyldimethylurea accelerator (manufactured by Degussa, trade name: UR500, particle size: D98 ═ 10 μm),
22 parts by weight of melamine formaldehyde resin-coated ammonium polyphosphate particles (particle size D50 is 12 μm, wherein the melamine formaldehyde resin content is 11% by weight, the ammonium polyphosphate content is 89% by weight, the manufacturer is Puseofu phosphorus chemical Co., Ltd., trade name is APP-262),
18.5 parts by weight of melamine cyanurate (particle size D50 ═ 2 μm, Prosefuran (Qingyuan) phosphorus chemical Co., Ltd., trade name MCA-10).
Step (2) and step (3) were carried out with reference to example 1.
Example 3
(1) Preparing an epoxy resin composition comprising:
18 times ofLiquid bisphenol A epoxy resin (viscosity 13800cps at 25 deg.C, epoxy equivalent 186g/eq, density 1.16 g/cm)3)，
9 parts by weight of a bisphenol A type semi-solid epoxy resin (epoxy equivalent of 253g/eq, specific gravity at 20 ℃ C. of 1.18),
22 parts by weight of a bisphenol A type solid epoxy resin (epoxy equivalent: 482g/eq, 25 ℃ softening point: 69, 25 ℃ density: 1.18 g/cm)3)，
9 parts by weight of phenoxy modified epoxy resin (epoxy equivalent is 188g/eq, viscosity at 25 ℃ is 3900cps, the content of phenoxy resin chain segments is 30% by weight, the manufacturer is of the national chemistry, and the brand is pe 30);
5.5 parts by weight of a dicyandiamide curing agent (particle diameter D98 ═ 10 μm),
1.5 parts by weight of a 2, 4-toluene bisdimethylurea promoter (isomer grade, CVC USA, U24M brand, D98 ═ 44 μm),
21.5 parts by weight of melamine formaldehyde resin-coated ammonium polyphosphate particles (particle size D50 is about 20 μm, wherein the content of the melamine formaldehyde resin is 10% by weight, the content of the ammonium polyphosphate is 90% by weight, the manufacturer is Puseofu phosphorus chemical Co., Ltd., trade name APP-263),
13.5 parts by weight of melamine cyanurate (particle size D50 ═ 4 μm, from Puseofu phosphorus chemical Co., Ltd., under the designation MCA-8).
Step (2) and step (3) were carried out with reference to example 1.
Example 4
The procedure of example 1 was followed, except that the melamine formaldehyde resin-coated ammonium polyphosphate particles were replaced with ammonium polyphosphate of the same mass (particle size D50 of about 18 μm, manufactured by Possefuran (Qingyuan) phosphorus chemical Co., Ltd., brand name APP-223).
Example 5
The procedure of example 1 was followed, except that the epoxy resin composition further included a novolac epoxy resin (epoxy equivalent: 178g/eq), specifically, 5 parts by weight of the novolac oxygen-containing resin, 8 parts by weight of the bisphenol a type semi-solid epoxy resin, 19 parts by weight of the bisphenol a type solid epoxy resin, and the same materials as in example 1 were used, except that the amount of the other materials was the same as in example 1.
Example 6
The procedure of example 1 was followed, except that 11 parts by weight of the bisphenol A type semi-solid epoxy resin and 21 parts by weight of the bisphenol A type solid epoxy resin were replaced with 32 parts by weight of the bisphenol A type semi-solid epoxy resin, and the same materials as in example 1 were used.
Example 7
The procedure of example 1 was followed, except that 11 parts by weight of the bisphenol A type semi-solid epoxy resin and 21 parts by weight of the bisphenol A type solid epoxy resin were replaced with 32 parts by weight of the bisphenol A type solid epoxy resin, and the same materials as in example 1 were used.
Comparative example 1
The procedure of example 1 was followed except that melamine cyanurate was not added thereto, and melamine formaldehyde resin-coated ammonium polyphosphate particles were used in an amount of 37.5 parts by weight.
Comparative example 2
The procedure of example 1 was followed except that melamine formaldehyde resin-coated ammonium polyphosphate particles were not added thereto and melamine cyanurate was used in an amount of 37.5 parts by weight.
Comparative example 3
The procedure of example 1 was followed except that 21.5 parts by weight of melamine formaldehyde resin-coated ammonium polyphosphate particles and 16 parts by weight of melamine cyanurate were replaced with 37.5 parts by weight of an aluminum hydroxide flame retardant (made by Middling aluminum, trade name H-WF-25).
Test example
The composites obtained in examples 1 to 7 and comparative examples 1 to 3 and the intermediate materials in the preparation were tested as follows:
(1) viscosity of the resin mixture
The viscosity (cp) of the resin mixture at 80 ℃ was measured using a rotational viscometer (Brookfield company, manufacturer, brand RVDV-2T-TH) and the results are reported in Table 1.
(2) Setting time of the resin mixture
1g of the resin mixture was sampled, and the setting time at 110 ℃ was measured using a plate heater (a' b "means a minute and b seconds), and the results are shown in Table 1.
(3) Flame retardant Property test of composite Material
The flame retardant properties of the composite were measured according to the method specified in the UL94 standard, and the results are shown in Table 1.
(4) Smoke Density testing of composites
The test was performed according to ASTM E662-15a specific optical density test method for smoke production of solid materials. Specifically, the sample is dried for 24 hours at the temperature of 60 ℃ and is placed for 48 hours under the conditions of the temperature of 23 ℃ and the humidity of 50%; the sample was then placed in a sealed oven under a radiant heat source of 2.5w/cm2Under the conditions of (1), the specific optical density Ds of the smoke at the 4 th minute is measured by the light beam attenuation test in the ignition flame mode and the non-ignition flame mode respectively4The results are shown in Table 1.
Ds in the mode with pilot flame, as specified by the ASTM E662 standard4Ds of less than or equal to 100 in a non-pilot flame mode4When the flame is less than or equal to 100, the standard is passed, and Ds is in a mode with pilot flame4Ds > 100 and/or in non-pilot flame mode4If > 100, the standard is failed.
(5) Mechanical testing of composite materials
The tensile strength, flexural strength and flexural modulus of the composite material were tested according to the methods specified in GB/T1447-.
TABLE 1
As can be seen from Table 1, the composite materials according to the invention all achieve V-0 flame retardancy and pass the smoke density test specified in the ASTM E662 standard; while the comparative example had a significant decrease in flame retardant performance when the flame retardant ingredients were changed and did not pass the smoke density test specified in astm e662 standard. In addition, the viscosity and the solidification time of the resin mixture can be controlled within a proper range, and better mechanical properties such as tensile strength, bending modulus, impact toughness and the like can be ensured.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. An epoxy resin composition is characterized in that the epoxy resin composition comprises 40-50 parts by weight of epoxy resin, 6-10 parts by weight of toughening modified epoxy resin, 2-6 parts by weight of curing agent, 1-4 parts by weight of accelerator and 30-50 parts by weight of flame retardant, wherein the flame retardant comprises ammonium polyphosphate and melamine cyanurate, and the weight ratio of the ammonium polyphosphate to the melamine cyanurate is 1: 0.5 to 1;
wherein the ammonium polyphosphate is modified ammonium polyphosphate obtained by coating pretreatment of melamine formaldehyde resin;
based on the total weight of the modified ammonium polyphosphate, the content of the ammonium polyphosphate is 85-95 wt%, and the content of the melamine formaldehyde resin is 5-15 wt%.
2. The epoxy resin composition of claim 1, wherein the weight ratio of the ammonium polyphosphate to the melamine cyanurate is from 1: 0.6-0.85.
3. The epoxy resin composition of claim 1, wherein the particle size of the ammonium polyphosphate D50 is 10-25 μm, and the particle size of the melamine cyanurate D50 is 10 μm or less.
4. The epoxy resin composition of claim 1, wherein the epoxy resin comprises a liquid epoxy resin, a solid and/or semi-solid epoxy resin, and optionally a novolac epoxy resin.
5. The epoxy resin composition according to claim 1 or 4, wherein the weight ratio of the liquid epoxy resin, the solid and/or semi-solid epoxy resin and the novolac epoxy resin in the epoxy resin is 1: 1.2-2.5: 0-1.
6. The epoxy resin composition of claim 1, wherein the toughening-modified epoxy resin is selected from one or more of a dimer acid-modified epoxy resin, a rubber-modified epoxy resin, a phenoxy-modified epoxy resin, and a urethane-modified epoxy resin.
7. The epoxy resin composition according to claim 1, wherein the curing agent is a dicyandiamide-based curing agent; the accelerator is an organic urea accelerator.
8. The epoxy resin composition according to claim 7, wherein the accelerator is preferably one or more of 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, phenyldimethylurea, and 2, 4-tolylene bis (dimethylurea).
9. A method for preparing an epoxy resin mixture, wherein the epoxy resin mixture is prepared from the epoxy resin composition as claimed in any one of claims 1 to 8, and the method comprises the following steps:
(1) grinding optional liquid epoxy resin, a curing agent and an accelerator to obtain a grinding material;
(2) melting optional semisolid and/or solid epoxy resin, optional novolac epoxy resin, toughening modified epoxy resin and a flame retardant to obtain molten materials;
(3) stirring and mixing the molten material obtained in the step (2) and the grinding material obtained in the step (1) at the temperature of 55-80 ℃,
wherein at least one of said liquid epoxy resin and said semi-solid and/or solid epoxy resin is present in combination with an optional novolac epoxy resin as epoxy resin raw material.
10. The method according to claim 9, wherein in step (3), the temperature is controlled by a water bath, and the stirring time is 20 to 50 minutes.
11. An epoxy resin mixture prepared according to the process of claim 9 or 10.
12. An epoxy resin prepreg obtained by impregnating a reinforcement with an epoxy resin mixture according to claim 11.
13. A composite material obtained by curing the epoxy resin prepreg according to claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611264550.XA CN108264729B (en) | 2016-12-30 | 2016-12-30 | Epoxy resin composition, epoxy resin mixture, preparation method of epoxy resin mixture, epoxy resin prepreg and composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611264550.XA CN108264729B (en) | 2016-12-30 | 2016-12-30 | Epoxy resin composition, epoxy resin mixture, preparation method of epoxy resin mixture, epoxy resin prepreg and composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108264729A CN108264729A (en) | 2018-07-10 |
| CN108264729B true CN108264729B (en) | 2020-02-07 |
Family
ID=62755286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611264550.XA Active CN108264729B (en) | 2016-12-30 | 2016-12-30 | Epoxy resin composition, epoxy resin mixture, preparation method of epoxy resin mixture, epoxy resin prepreg and composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108264729B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2580283B (en) | 2018-08-03 | 2022-02-23 | Gurit Uk Ltd | Fire-retardant epoxide resins and use thereof |
| CN111662530A (en) * | 2019-03-07 | 2020-09-15 | 华东理工大学华昌聚合物有限公司 | Halogen-free flame-retardant epoxy resin system for prepreg and preparation method thereof |
| CN110305590B (en) * | 2019-07-25 | 2021-05-18 | 黑龙江省科学院石油化学研究院 | Flame-retardant epoxy resin adhesive and preparation method thereof |
| CN112552644A (en) * | 2020-11-20 | 2021-03-26 | 姜宏宇 | Composite epoxy resin and preparation method thereof |
| CN113278395B (en) * | 2021-04-12 | 2022-03-18 | 广东博汇新材料科技股份有限公司 | Pre-forming glue spraying composition and preparation method thereof |
| CN113736132B (en) * | 2021-10-21 | 2023-06-06 | 东莞市鼎泰鑫电子有限公司 | Low-density epoxy foaming grinding wheel and preparation method thereof |
| CN115652467A (en) * | 2022-10-10 | 2023-01-31 | 南通强生石墨烯科技有限公司 | Heat-resistant flame-retardant functional fiber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850520A (en) * | 2012-08-30 | 2013-01-02 | 西南石油大学 | Toughening-antiflaming type epoxy resin and preparation method thereof |
| CN103275304A (en) * | 2013-06-07 | 2013-09-04 | 连云港神鹰碳纤维自行车有限责任公司 | Preparation method of medium temperature curing heat-melting epoxy resin system for domestic carbon fiber bicycle |
| CN104119639A (en) * | 2013-04-24 | 2014-10-29 | 台光电子材料(昆山)有限公司 | Halogen-free resin composition, and copper foil substrate and printed circuit board applying it |
| CN105315620A (en) * | 2015-11-27 | 2016-02-10 | 四川迪弗电工科技有限公司 | Epoxy resin-enhanced laminated insulating profile and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611264550.XA patent/CN108264729B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850520A (en) * | 2012-08-30 | 2013-01-02 | 西南石油大学 | Toughening-antiflaming type epoxy resin and preparation method thereof |
| CN104119639A (en) * | 2013-04-24 | 2014-10-29 | 台光电子材料(昆山)有限公司 | Halogen-free resin composition, and copper foil substrate and printed circuit board applying it |
| CN103275304A (en) * | 2013-06-07 | 2013-09-04 | 连云港神鹰碳纤维自行车有限责任公司 | Preparation method of medium temperature curing heat-melting epoxy resin system for domestic carbon fiber bicycle |
| CN105315620A (en) * | 2015-11-27 | 2016-02-10 | 四川迪弗电工科技有限公司 | Epoxy resin-enhanced laminated insulating profile and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108264729A (en) | 2018-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108264729B (en) | Epoxy resin composition, epoxy resin mixture, preparation method of epoxy resin mixture, epoxy resin prepreg and composite material | |
| AU2016380284B2 (en) | Multifunctional surfacing material with burn-through resistance | |
| CN106751527B (en) | Self-adhering-type halogen-free flameproof epoxy prepreg composite material and preparation method | |
| EP1716201B1 (en) | Fire retardant compositions using siloxanes | |
| EP0471375B1 (en) | Low fuming phenolic resin prepreg and process for producing the same | |
| WO2011126070A1 (en) | Resin composition, prepreg and laminate | |
| CN106739289B (en) | A kind of preparation method of Halogen, High Tg CCL | |
| EP2892948A1 (en) | Toughening masterblends | |
| CN110894341A (en) | Halogen-free flame-retardant epoxy prepreg and composite material thereof | |
| EP2665761B1 (en) | High performance thermoset useful for electrical laminate, high density interconnect and interconnect substrate applications | |
| US20220298295A1 (en) | Epoxy resin systems | |
| JPWO2002050153A1 (en) | Flame-retardant epoxy resin composition, prepreg and fiber-reinforced composite material using the same | |
| CN111718561A (en) | Halogen-free flame-retardant epoxy resin composition | |
| CN115197537A (en) | Flame-retardant epoxy resin composition, prepreg, fiber-reinforced composite material and preparation | |
| JP2004175925A (en) | Prepreg and laminate | |
| CN112375468B (en) | Surface protection material for engine containing ring | |
| US12006430B2 (en) | Fire-retardant resins and composite materials | |
| CA3123577A1 (en) | Flame-retardant epoxy composition and method of using the same | |
| EP3976712A1 (en) | Fire-retardant resins and composite materials | |
| KR940001169B1 (en) | Epoxy resin composition | |
| JPS6058419A (en) | Epoxy resin composition for carbon fiber reinforcement | |
| JP2006077202A (en) | Flame-retardant prepreg | |
| BR112020004861B1 (en) | EPOXY RESIN SYSTEM | |
| KR20160046087A (en) | Epoxy Resin Compositions for Prepreg Having Halogen Free and Flame Retardant | |
| JPH01278524A (en) | Epoxy resin composition |
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 |