CN108264729A - A kind of composition epoxy resin and epoxy resin composition and preparation method thereof and epoxy prepreg and composite material - Google Patents
A kind of composition epoxy resin and epoxy resin composition and preparation method thereof and epoxy prepreg and composite material Download PDFInfo
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- CN108264729A CN108264729A CN201611264550.XA CN201611264550A CN108264729A CN 108264729 A CN108264729 A CN 108264729A CN 201611264550 A CN201611264550 A CN 201611264550A CN 108264729 A CN108264729 A CN 108264729A
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- 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
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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
- 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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- 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
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- 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
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- 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
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- 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
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Abstract
The present invention relates to field of compound material, and in particular, to a kind of composition epoxy resin and composite material and preparation method thereof.The total weight of the composition epoxy resin is 100 parts by weight meters, the composition epoxy resin includes the epoxy resin of 40 50 parts by weight, the Toughening Modification of Epoxy of 6 10 parts by weight, the curing agent of 26 parts by weight, the accelerating agent of 14 parts by weight and the fire retardant of 30 50 parts by weight, wherein described fire retardant includes polyphosphoric acid amine and melamine cyanurate, and the polyphosphoric acid amine and the weight ratio of the melamine cyanurate are 1：0.5‑1.The composition epoxy resin and composite material of the present invention has preferable flame retardant property, and in burning with relatively low smoke density.
Description
Technical field
The present invention relates to field of compound material, and in particular, to a kind of composition epoxy resin and epoxy resin composition
And preparation method thereof and epoxy prepreg and composite material.
Background technology
Epoxy resin has good mechanical property, bond properties, chemical stability and electrical insulation capability, makes it as multiple
Laminate resin matrix, electronic package material etc. obtain extensively in fields such as traffic, the energy, aerospace, electronics, machinery, coating
General application.
But epoxy resin has inflammable performance, therefore more and more extensive with the use of epoxy resin, also brings
The fire risk of bigger, thus find it is a kind of suitable for epoxy resin and fire retardant with preferable flame retardant property be
It is very important.
Although the type of present fire retardant is various, the wider mainly halogenated flame retardant of application.Halogenated flame retardant exists
The problem of bioxin can be brought in combustion process, bromine free radical can be also generated, further generate the compound of bromination hydrogen species, such
Compound is while flame retardant efficiency is played, if human body sucks, also irritant can wait harm.Therefore halogen-free flame retardants is ground
Studying carefully seems critically important.
In addition, according to investigations, when fire occurs, many death incidents, which are not due to burn, to be caused, but the cigarette released
Poison gas causes people to suffocate, and further causes death.But effect is mostly concentrated on flame retardant property by the existing research to fire retardant
On, and the smoke density seldom generated to burning is studied.
Invention content
The purpose of the present invention is overcome existing fire retardant performance not high enough and/or ask smoke density concern is insufficient
Topic provides a kind of composition epoxy resin and epoxy resin composition and preparation method thereof and epoxy prepreg and compound
Material.The composition epoxy resin of the present invention has preferable flame retardant property, and in burning with relatively low smoke density.
For this purpose, according to the first aspect of the invention, a kind of composition epoxy resin is provided, wherein, with the epoxy resin
The total weight of composition is 100 parts by weight meters, which includes the epoxy resin of 40-50 parts by weight, 6-10 weights
Measure the fire-retardant of the Toughening Modification of Epoxy of part, the curing agent of 2-6 parts by weight, the accelerating agent of 1-4 parts by weight and 30-50 parts by weight
Agent, wherein the fire retardant includes polyphosphoric acid amine and melamine cyanurate, and the polyphosphoric acid amine and the melamine
The weight ratio of cyanurate is 1：0.5-1.
According to the second aspect of the invention, a kind of preparation method of epoxy resin composition is provided, wherein, the epoxy
Resin compound is prepared using the composition epoxy resin of the present invention as raw material, and the preparation method includes the following steps：
(1) optional liquid epoxies and curing agent and accelerating agent are ground to obtain abrasive；
(2) by optional semisolid and/or solid epoxy, optional novolac epoxy resin and toughening modifying asphalt mixtures modified by epoxy resin
Fat and fire retardant melting, obtain lava material；
(3) lava material obtained by step (2) and abrasive obtained by step (1) are stirred at 55-80 DEG C,
Wherein described liquid epoxies and the semisolid and/or solid epoxy at least there are it is a kind of with it is optional
Novolac epoxy resin combination is as epoxy source material.
According to the third aspect of the invention we, the epoxy that a kind of method according to a second aspect of the present invention is prepared is provided
Resin compound.
According to the fourth aspect of the invention, a kind of epoxy prepreg is provided, wherein, which leads to
It crosses and obtains epoxy resin composition dipping reinforcement, the epoxy resin composition is the epoxy resin of third aspect present invention
Mixture.
According to the fifth aspect of the invention, a kind of composite material is provided, wherein, the composite material is by by the present invention the
The epoxy prepreg of four aspects cures to obtain.
Using above-mentioned technical proposal of the present invention, by by polyphosphoric acid amine and melamine cyanurate with specific ratio phase
Mutually coordinate obtained fire retardant for smoke density to be relatively low with excellent fireproof performance during composition epoxy resin and during burning
Property, and do not interfere with the mechanical property of preparation-obtained composite material.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood to comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It between the endpoint value of a range and individual point value and can be individually combined with each other between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, a kind of composition epoxy resin is provided, wherein, with the composition epoxy resin
Total weight for 100 parts by weight meters, which includes the epoxy resin of 40-50 parts by weight, 6-10 parts by weight
Toughening Modification of Epoxy, the curing agent of 2-6 parts by weight, the accelerating agent of 1-4 parts by weight and 30-50 parts by weight fire retardant,
Described in fire retardant include polyphosphoric acid amine and melamine cyanurate, and the polyphosphoric acid amine and the melamine cyanurate
The weight ratio of salt is 1：0.5-1.
Preferably, it is counted by 100 parts by weight of the total weight of the composition epoxy resin, which includes
The epoxy resin of 45-50 parts by weight, the Toughening Modification of Epoxy of 7-9 parts by weight, the curing agent of 2-5.5 parts by weight, 1-3 weight
The accelerating agent of part and the fire retardant of 35-45 parts by weight.
Composition epoxy resin according to the present invention, when the polyphosphoric acid amine and the weight of the melamine cyanurate
Preferable flame retardant property and smoke density performance can be thus achieved during than meeting above-mentioned requirements, it is further preferred that the polyphosphoric acid
The weight ratio of amine and the melamine cyanurate is 1：0.6-0.85.
Composition epoxy resin according to the present invention, in situations where it is preferred, the polyphosphoric acid amine is through melamine first
The modified polyphosphoric acid amine that urea formaldehyde or silane pretreatment obtain.It is highly preferred that the polyphosphoric acid amine is with melamino-formaldehyde tree
The modified polyphosphoric acid amine that fat or silane are coated polyphosphoric acid amine.
Composition epoxy resin according to the present invention, on the basis of the weight of the modified polyphosphoric acid amine, wherein polyphosphoric acid
The content of amine is 85-95 weight %, and the content of melamine resin or silane is 5-15%.
The modified polyphosphoric acid amine is commercially available, when the modified polyphosphoric acid amine will be poly- for melamine resin
During the modified polyphosphoric acid amine that phosphamide is coated, the modified polyphosphoric acid amine for example can be general plug furan (Qingyuan City) phosphatization
Learn the modified polyphosphoric acid amine that Co., Ltd's trade mark is APP-262, Presafer's trade mark is APP-232
Modified polyphosphoric acid amine, the Hangzhou Jie Ersi chemical industry trade mark be the modified polyphosphoric acid amine of JLS-PNA and the Hangzhou Jie Ersi chemical industry trades mark
Modified polyphosphoric acid amine for JLS-ES-10.
When the modified polyphosphoric acid amine that the modified polyphosphoric acid amine is coated polyphosphoric acid amine for silane, preferably
Ground, the silane can be selected from the various common silane that may be used as silane coupling agent, such as can be selected from three second of aminopropyl
Oxysilane, glycydoxy trimethoxy silane, methacryloxypropyl trimethoxy silane, vinyl
Triethoxysilane, vinyltriethoxysilane, mercapto propyl front three (second) oxysilane, ethylenediaminepropyltriethoxysilane
With it is one or more in ethylenediamine hydroxypropyl methyl dimethoxysilane；The modified polyphosphoric acid amine is, for example, commercially available from Guangzhou fine jade
The trade mark of former new material Co., Ltd is the modified polyphosphoric acid amine of NP-35.
Composition epoxy resin according to the present invention, D50=10-25 μm of the grain size of the polyphosphoric acid amine, the melamine
Grain size D50≤10 μm of amine cyanurate.
In the present invention, in the presence of polyphosphoric acid amine is in the form of modified polyphosphoric acid amine, the polyphosphoric acid of the invention limited
Grain size, dosage of amine etc. are calculated with modified polyphosphoric acid amine, i.e., D50=10-25 μm of the grain size of described modified polyphosphoric acid amine is described
The weight ratio of modified polyphosphoric acid amine and the melamine cyanurate is 1：0.5-1, preferably 1：0.6-0.85.
Composition epoxy resin according to the present invention, the epoxy resin can be this field routine for epoxy resin
The epoxy resin of composite material.In situations where it is preferred, it was found by the inventors of the present invention that when using liquid epoxies, solid
And/or semisolid epoxy resin and optional novolac epoxy resin can optimize gained epoxy resin when being used in conjunction with each other and mix
Close the viscosity of object and the mechanical property of gained composite material.Therefore, according to a kind of preferred technical solution of the present invention, the ring
Oxygen resin includes liquid epoxies, solid and/or semisolid epoxy resin and optional novolac epoxy resin.
Composition epoxy resin according to the present invention, it is preferable that liquid epoxies, solid described in the epoxy resin
And/or the weight ratio of semisolid epoxy resin and novolac epoxy resin is 1：1.2-2.5：0-1.Due to the novolac epoxy resin
Cost it is higher, therefore the novolac epoxy resin can be added selectively.It was found by the inventors of the present invention that by the Breakup of Liquid Ring
Oxygen resin can also realize higher effect with solid and/or the cooperation of semisolid epoxy resin, in this case, further preferably
Ground, the liquid epoxies are 1 with the content ratio of solid and/or semisolid epoxy resin：1.5-2.When addition epoxy novolac
During resin, the dosage of the novolac epoxy resin is more preferably：The content of the liquid epoxies and novolac epoxy resin
Than being 1：0.36-0.72.
Composition epoxy resin according to the present invention, the liquid epoxies are preferably bisphenol-A liquid epoxy resin.
The bisphenol-A liquid epoxy resin can be the bisphenol-A liquid epoxy resin of this field routine, described under preferable case
Bisphenol-A liquid epoxy resin is 10000-18000cps in 25 DEG C of viscosity, and more preferably 12000-15000cps, epoxy ought
It measures as 170-200g/eq, preferably 180-190g/eq, density can be 1.1-1.2g/cm3(at 25 DEG C), preferably 1.14-
1.18g/cm3。
Composition epoxy resin according to the present invention, in order to advanced optimize gained epoxy resin composition viscosity and
The mechanical property of gained composite material, under preferable case, the solid and/or semisolid epoxy resin for bisphenol A-type solid and/
Or semisolid epoxy resin, and consolidate simultaneously including bisphenol A-type semisolid epoxy resin and bisphenol A-type in epoxy-resin systems
The weight ratio of body epoxy resin, bisphenol A-type semisolid epoxy resin and bisphenol A-type solid epoxy is 1：1-3, more preferably
1：1.5-2.5.
Composition epoxy resin according to the present invention, the bisphenol A-type solid epoxy can be that this field is conventional
Bisphenol A-type solid epoxy, under preferable case, the epoxide equivalent of the bisphenol A-type solid epoxy is 430-520g/
Eq, preferably 450-500g/eq are 60-80, preferably 64-74, density 1.14-1.22g/cm in 25 DEG C of softening points3
(at 25 DEG C), preferably 1.16-1.2g/cm3。
Composition epoxy resin according to the present invention, the bisphenol A-type semisolid epoxy resin can be that this field is conventional
Bisphenol A-type semisolid epoxy resin, under preferable case, the epoxide equivalent of the bisphenol A-type semisolid epoxy resin is 200-
300g/eq, preferably 230-270g/eq are 1.16-1.2 in 20 DEG C of proportions.
Composition epoxy resin according to the present invention, the novolac epoxy resin can be the epoxy novolac of this field routine
Resin, under preferable case, the epoxide equivalent of the novolac epoxy resin is 150-220g/eq, preferably 170-190g/eq, close
Degree can be 1.1-1.2g/cm3(at 25 DEG C), preferably 1.14-1.18g/cm3。
Composition epoxy resin according to the present invention, the Toughening Modification of Epoxy can be this field it is various pass through by
Epoxy resin modification and the epoxy resin for making it have toughening performance, such as dimer acid modified epoxy resin, rubber can be selected from
Modified epoxy (such as acrylonitrile butadiene rubber modified epoxy resin), benzene oxygen modified epoxy and urethane-modified asphalt mixtures modified by epoxy resin
It is one or more in fat.
Composition epoxy resin according to the present invention, it is preferable that the Toughening Modification of Epoxy is selected from following several tools
There are any one of specific epoxide equivalent and the Toughening Modification of Epoxy of viscosity：Acrylonitrile butadiene rubber modified epoxy resin, epoxy
Equivalent is 325-375g/eq, is 300000-600000cp in 25 DEG C of viscosity；Dimer acid modified epoxy resin, epoxide equivalent
It is 45000-65000cp in 50 DEG C of viscosity for 550-600g/eq；And benzene oxygen modified epoxy, epoxide equivalent are
185-190g/eq is 2000-5000cp in 25 DEG C of viscosity, and wherein phenoxy resin segment accounts for containing for benzene oxygen modified epoxy
It measures as 20-45 weight %.
Composition epoxy resin according to the present invention, the curing agent can be this field conventionally used for epoxy composite
The curing agent of object, preferably dicyandiamide class curing agent, most preferably dicyandiamide.The grain size of the curing agent preferably satisfy D98≤
10μm。
In the present invention, the method for measuring grain size D50 and D98 can include：It is surveyed using strange gram of S3500 types granularity of american wheat
Examination instrument is tested, and test condition is：It weighs 0.1g powder and is put into ultrasonic disperse 10min in 10ml beakers.
Composition epoxy resin according to the present invention, the accelerating agent can be this field conventionally used for epoxy composite
The accelerating agent of object, preferably organic urea accelerating agent.It is highly preferred that the accelerating agent is selected from 3- (3,4- dichlorophenyl) -1,1- bis-
The double dimethyl ureas and 2 of methylurea (diuron), phenyl dimethylurea, 2,4 toluene, it is one or more in the double dimethyl ureas of 4 methyl, it is described
The double dimethyl ureas of 2,4 toluene can be the double dimethyl ureas of 2,4 toluene mixed with a variety of isomers of the double dimethyl ureas of 2,4 toluene
Mixture.The grain size of the accelerating agent preferably satisfies D98≤50 μm.
Composition epoxy resin according to the present invention, the composition epoxy resin can include optionally auxiliary with other
Material, such as inner pattern releasing agent applicable (content relative to the composition epoxy resin can be 4-10 weight %), color can be included
(content relative to the composition epoxy resin can be 0.1-1.5 weight %) etc..
According to the second aspect of the invention, a kind of preparation method of epoxy resin composition is provided, wherein, the epoxy
Resin compound is prepared using the composition epoxy resin of the present invention as raw material, and the preparation method includes the following steps：
(1) optional liquid epoxies and curing agent and accelerating agent are ground to obtain abrasive；
(2) by optional semisolid and/or solid epoxy, optional novolac epoxy resin and toughening modifying asphalt mixtures modified by epoxy resin
Fat and fire retardant melting, obtain lava material；
(3) lava material obtained by step (2) and abrasive obtained by step (1) are stirred at 55-80 DEG C,
Wherein described liquid epoxies and the semisolid and/or solid epoxy at least there are it is a kind of with it is optional
Novolac epoxy resin combination is as epoxy source material.
Preparation in accordance with the present invention, in situations where it is preferred, the liquid epoxies, the semisolid and/or
Solid epoxy is combined with optional novolac epoxy resin as epoxy source material.
Preparation in accordance with the present invention, the selection of various materials and dosage are referred to the ring of first aspect present invention
Epoxy resin composition, details are not described herein.
In step (1), the grinding can carry out in a manner that this field is conventional, and the main purpose of the grinding is
It is sufficiently mixed material, which can carry out in three Kun grinders, and specific grinding method can be routine operation, herein
It repeats no more.
In step (1), before the grinding, material (is first often referred to 10-30 DEG C) at room temperature and is mixed, and
And (mixing time can be 0.5-2h) is stirred evenly, and temperature is controlled in whipping process, it is made to maintain 10-30 DEG C of model
In enclosing.
In step (2), the temperature of the melting can be 80-100 DEG C.
In step (3), by water-bath temperature control, and preferably mixing time is 20-50 minutes, more preferably 25-40 minutes.
In step (3), in order to make lava material obtained by step (2) and abrasive obtained by step (1) mutually (excellent at 55-80 DEG C
Be selected as 60-70 DEG C) under be stirred, it is preferable that before being stirred, lava material list obtained by step (2) is solely first subjected to water
Bath is stood, so that its temperature reaches 55-80 DEG C (preferably 60-70 DEG C), then proceedes to add in step (1) institute under water-bath
It obtains abrasive and is stirred.
According to the third aspect of the invention we, the epoxy that a kind of method according to a second aspect of the present invention is prepared is provided
Resin compound.The epoxy resin composition that the composition epoxy resin of the present invention is prepared has suitable viscosity, can
It is pressed into when preparing prepreg after resin flake and is closely bonded with reinforcement.The epoxy resin composition of the present invention is at 80 DEG C
Under viscosity be usually 15000-50000cp, preferably 20000-30000cp.
According to the fourth aspect of the invention, a kind of epoxy prepreg is provided, wherein, which leads to
It crosses and is combined to obtain with reinforcement by epoxy resin composition, the epoxy resin composition is the epoxy of third aspect present invention
Resin compound.The preparation process of the epoxy prepreg of the present invention is using the conventional process of the present invention.For example,
The process can include：The epoxy resin composition resin is preheated into 1-2.5h at 75-90 DEG C；Preheated resin is turned
It moves on between two layers of release paper, resin is pressed into 0.1-1.5mm thin slices with two-roll mill；Tear one or both sides as needed
Release paper, in resin flake upper berth layer of glass cloth, and the number of plies as needed successively the multi-layer resinous thin slice of laying and
Glass fabric；Suitable dimension is cut into get to epoxy prepreg.
Epoxy prepreg according to the present invention, the reinforcement can be various conventional reinforcements, the enhancing
Body can be woven cloth or textile cloth, and the material of the woven cloth or textile cloth can be that carbon fiber, glass fibre, aramid fiber are fine
It ties up, is in aromatic polyamide fibre and basalt fibre one or more, most preferably glass fibre.The epoxy resin prepolymer
The weight ratio of leaching material epoxy resin mixture and the reinforcement is not particularly limited, such as can be 1：0.43-
2.3, preferably 1：0.82-1.5.There is no particular limitation in the aperture of the reinforcement, more than material used in this application
Grain size is greater than 50 μm, preferably greater than 200 μm.
According to the fifth aspect of the invention, a kind of composite material is provided, wherein, the composite material is by by the present invention the
The epoxy prepreg of four aspects cures to obtain.
Composite material according to the present invention, it is described that epoxy prepreg is cured to obtain the method for composite material without spy
Other restriction can be the method for this field routine, such as the method that pre-preg vacuum bag pressure may be used.Specific method can be with
Including：The epoxy prepreg is caught up with except air (can be cut as needed and laying) before, is then placed into
On mold (mold can coat releasing agent in advance), one layer of macropore isolation film is spread in prepreg upper surface and inhales rubber mat, combination
And fill vacuum bag；Vacuum bag is connected into pumped vacuum systems later, puts baking oven hot-press solidifying into, during the hot-press solidifying
Persistently vacuumize；The hot-press solidifying can include：It is first toasted 30-60 minutes at 60-80 DEG C, then at 105-125 DEG C
Baking 60-90 minutes.
Composition epoxy resin by using the present invention is the composite material that raw material is prepared, and can be kept preferable
Mechanical property, and with excellent flame retardant type and burning when smoke density it is relatively low.
The present invention will be described in detail by way of examples below.In the examples below, viscosity passes through rotary viscosity
Meter (producer of Brookfield companies of the U.S., the RVDV-2T-TH trades mark) measures, and epoxide equivalent passes through current potential autotitrator (Jiangsu
Producer of the earth instrument plant of Jiangyan City, the ZDDY-2008 trades mark) it measures, density method according to as defined in GB/T12007.5-1989 is surveyed
, grain size method according to as defined in GB/T 19077-2016 measures, softening point method according to as defined in GB/T12007.6-1989
It measures.
Embodiment 1
(1) prepare composition epoxy resin, which includes：
(25 DEG C of viscosity are 13800cps to the liquid bisphenol A epoxy resin of 16 parts by weight, epoxide equivalent 186g/eq, density
For 1.16g/cm3),
(epoxide equivalent 253g/eq is the bisphenol A-type semisolid epoxy resin of 11 parts by weight in 20 DEG C of proportions
1.18),
(epoxide equivalent 482g/eq, 25 DEG C of softening points are 69,25 DEG C close to the bisphenol A-type solid epoxy of 21 parts by weight
It spends for 1.18g/cm3),
(epoxide equivalent 358g/eq is the acrylonitrile butadiene rubber modified epoxy resin of 7 parts by weight in 25 DEG C of viscosity
480000mPa.s；Producer is preferred Di Da new materials company, the trade mark 861340),
The dicy-curing agent (D98=10 μm of grain size) of 5 parts by weight,
The 2 of 2.5 parts by weight, 4 toluene double dimethyl urea accelerating agent (isomers grade, CVC producers of the U.S., the U24M trades mark, grain sizes
D98=44 μm),
(grain size D50 is 12 μm, wherein trimerization to the polyphosphoric acid amine particle of the Melamino-formaldehyde resin encapsulated of 21.5 parts by weight
The content of cyanamide formaldehyde resin is 11 weight %, and the content of polyphosphoric acid amine is 89 weight %, and producer is general plug furan (Qingyuan City) phosphatization
Learn Co., Ltd, trade mark APP-262),
(grain size D50 is 9 μm to the melamine cyanurate of 16 parts by weight, and producer is limited for general plug furan (Qingyuan City) phosphorus chemistry
Company, trade mark MCA-25).
(2) epoxy resin composition is prepared：
Bisphenol-A liquid epoxy resin, curing agent and accelerating agent are mixed at room temperature, is stirred evenly and controlled with blender
Temperature processed, then with being ground to obtain abrasive in three-roll grinder.
By bisphenol A-type semisolid epoxy resin, bisphenol A-type solid epoxy, Toughening Modification of Epoxy at 90 DEG C
Melting, is stirred evenly with blender, then adds in the polyphosphoric acid amine particle of Melamino-formaldehyde resin encapsulated and melamine cyanogen
Lithate stirs evenly at 90 DEG C, obtains lava material.
After gained magma material is placed 30 minutes under 70 DEG C of water-baths, gained abrasive is added in, is stirred evenly, obtained with blender
To resin compound.
(3) epoxy prepreg and composite material are prepared：
It is 1 to take weight ratio：1.04 epoxy resin composition and glass fabric (woven roving, grammes per square metre 800g), by institute
It states epoxy resin composition and is positioned over 1.5h preheatings at 80 DEG C；Preheated resin is transferred between two layers of release paper, with double
The epoxy resin composition is pressed into 0.4mm thin slices by roller open mill；One layer of release paper is torn, in one layer of resin flake upper berth glass
Glass fiber cloth flattens；Suitable dimension (such as 15mm*15mm) is cut into, obtains epoxy prepreg.
By mold wiped clean and coated release agent, then gained epoxy prepreg is caught up with except air, and is positioned over
On mold, one layer of macropore isolation film is spread in prepreg upper surface and inhales rubber mat, combines and fills vacuum bag.Vacuum bag connection is taken out true
Empty set is united, and is put baking oven hot-press solidifying into, is persistently vacuumized during hot-press solidifying, and the process of hot-press solidifying is included first at 75 DEG C
Lower baking 40 minutes, is then toasted 70 minutes at 115 DEG C.
Embodiment 2
(1) prepare composition epoxy resin, which includes：
(25 DEG C of viscosity are 13800cps to the liquid bisphenol A epoxy resin of 17.5 parts by weight, epoxide equivalent 186g/eq, close
It spends for 1.16g/cm3),
(epoxide equivalent 253g/eq is the bisphenol A-type semisolid epoxy resin of 11 parts by weight in 20 DEG C of proportions
1.18),
(epoxide equivalent 482g/eq, 25 DEG C of softening points are 69,25 DEG C to the bisphenol A-type solid epoxy of 16.5 parts by weight
Density is 1.18g/cm3),
(epoxide equivalent 580g/eq is 52000cps in 50 DEG C of viscosity to the dimer acid modified epoxy resin of 8 parts by weight；
Producer be Shanghai Zhong Si Industrial Co., Ltd.s, trade mark ERS-172),
The dicy-curing agent (D98=10 μm of grain size) of 4.5 parts by weight,
The 2 of 2 parts by weight, (producer is Degussa to the double dimethyl urea accelerating agents of 4 methyl, trade mark UR500, grain size D98=10 μ
M),
(grain size D50 is 12 μm, wherein melamine to the polyphosphoric acid amine particle of the Melamino-formaldehyde resin encapsulated of 22 parts by weight
The content of amine-formaldehyde resins is 11 weight %, and the content of polyphosphoric acid amine is 89 weight %, and producer is general plug furan (Qingyuan City) phosphorus chemistry
Co., Ltd, trade mark APP-262),
(D50=2 μm of grain size, company have the melamine cyanurate of 18.5 parts by weight for general plug furan (Qingyuan City) phosphorus chemistry
Limit company, trade mark MCA-10).
Step (2) and step (3) are carried out with reference to embodiment 1.
Embodiment 3
(1) prepare composition epoxy resin, which includes：
(25 DEG C of viscosity are 13800cps to the liquid bisphenol A epoxy resin of 18 parts by weight, epoxide equivalent 186g/eq, density
For 1.16g/cm3),
9 parts by weight bisphenol A-type semisolid epoxy resin (epoxide equivalent 253g/eq, in 20 DEG C of proportions for 1.18),
(epoxide equivalent 482g/eq, 25 DEG C of softening points are 69,25 DEG C close to the bisphenol A-type solid epoxy of 22 parts by weight
It spends for 1.18g/cm3),
9 parts by weight benzene oxygen modified epoxy (epoxide equivalent 188g/eq, 25 DEG C of viscosity be 3900cps,
The content of middle phenoxy resin segment is 30 weight %；Producer is diligent abundant chemistry, trade mark pe30)；
The dicy-curing agent (D98=10 μm of grain size) of 5.5 parts by weight,
The 2 of 1.5 parts by weight, 4 toluene double dimethyl urea accelerating agent (isomers grade, CVC producers of the U.S., the U24M trades mark, grain sizes
D98=44 μm),
Polyphosphoric acid amine particle (about 20 μm of the grain size D50, wherein trimerization of the Melamino-formaldehyde resin encapsulated of 21.5 parts by weight
The content of cyanamide formaldehyde resin is 10 weight %, and the content of polyphosphoric acid amine is 90 weight %, and producer is general plug furan (Qingyuan City) phosphatization
Learn producer of Co., Ltd, trade mark APP-263),
(D50=4 μm of grain size, producer have the melamine cyanurate of 13.5 parts by weight for general plug furan (Qingyuan City) phosphorus chemistry
Limit company, trade mark MCA-8).
Step (2) and step (3) are carried out with reference to embodiment 1.
Embodiment 4
It is carried out according to the process of embodiment 1, the difference is that the polyphosphoric acid amine by the Melamino-formaldehyde resin encapsulated
Replacing with the polyphosphoric acid amines of phase homogenous quantities, (about 18 μm of grain size D50, producer are Presafer (Qingyuan) Phosphor Chemical Company Limited, board
Number be APP-223).
Embodiment 5
It is carried out according to the process of embodiment 1, the difference is that the composition epoxy resin further includes novolac epoxy resin
(epoxide equivalent 178g/eq), specifically, the dosage of the oxygen-containing resin of the phenolic aldehyde is 5 parts by weight, bisphenol A-type semisolid asphalt mixtures modified by epoxy resin
The dosage of fat is 8 parts by weight, and the dosage of bisphenol A-type solid epoxy is 19 parts by weight, the dosage of unclassified stores and embodiment 1
Identical, material uses material same as Example 1.
Embodiment 6
Carried out according to the process of embodiment 1, the difference is that by the bisphenol A-type semisolid epoxy resin of 11 parts by weight and
The bisphenol A-type solid epoxy of 21 parts by weight replaces with the bisphenol A-type semisolid epoxy resin of 32 parts by weight, and specific material is equal
Use material same as Example 1.
Embodiment 7
Carried out according to the process of embodiment 1, the difference is that by the bisphenol A-type semisolid epoxy resin of 11 parts by weight and
The bisphenol A-type solid epoxy of 21 parts by weight replaces with the bisphenol A-type solid epoxy of 32 parts by weight, and specific material makes
With material same as Example 1.
Comparative example 1
It is carried out according to the process of embodiment 1, the difference is that wherein and it is not added with melamine cyanurate, and trimerization
The dosage of the polyphosphoric acid amine particle of cyanamide formaldehyde resin cladding is 37.5 parts by weight.
Comparative example 2
It is carried out according to the process of embodiment 1, the difference is that wherein and being not added with the poly- of Melamino-formaldehyde resin encapsulated
Phosphamide particle, and the dosage of melamine cyanurate is 37.5 parts by weight.
Comparative example 3
It is carried out according to the process of embodiment 1, the difference is that by the Melamino-formaldehyde resin encapsulated of 21.5 parts by weight
Polyphosphoric acid amine particle and the melamine cyanurate of 16 parts by weight replace with the aluminium hydroxide fire retardant (producer of 37.5 parts by weight
For middle aluminium, trade mark H-WF-25).
Test case
Following test is done to the intermediate material in the composite material and preparation process obtained by embodiment 1-7 and comparative example 1-3：
(1) viscosity of resin compound
Resin compound is measured using rotational viscometer (Brookfield companies of the U.S. of producer, trade mark RVDV-2T-TH) to exist
Viscosity (cp) at 80 DEG C remembers result in table 1.
(2) the solidifyingization time of resin compound
1g resin compounds are sampled, (a ' b " refers to a points using solidifyingization time of the flat heater instrument measure at 110 DEG C
Clock b seconds), result is remembered in table 1.
(3) the flame retardant property test of composite material
The flame retardant property of composite material is measured according to method as defined in UL94 standards, result is remembered in table 1.
(4) the smoke density test of composite material
The specific optical density test method that cigarette is produced in test according to ASTM E662-15a solid materials carries out.Specifically, by sample
It is dried at a temperature of 60 DEG C for 24 hours, and 48h is placed under the conditions of 23 DEG C of temperature and humidity 50%；Then by sample in a sealing
Stove in, radiant heat source amount be 2.5w/cm2Under conditions of, there is pilot flame pattern and without under pilot flame pattern respectively
The beam attenuation test of progress, respectively by the specific optical density Ds of the 4th minute cigarette4Result remember in table 1.
According to the regulation of ASTME662 standards, as the Ds in the case where there is pilot flame pattern4≤ 100 and in no pilot flame mould
Ds under formula4It is by the standard, as the Ds in the case where there is pilot flame pattern when≤1004＞ 100 and/or in no pilot flame
Ds under pattern4It is not pass through the standard during ＞ 100.
(5) Mechanics Performance Testing of composite material
According to tensile strength, bending strength and the bending die of method test compound material as defined in GB/T 1447-2005
According to the impact flexibility of method test compound material as defined in GB/T 1451-2005, result is remembered in table 1 for amount.
Table 1
As it can be seen from table 1 the flame retardant property of composite material according to the present invention can reach V-0, and can lead to
Smoke density as defined in ASTME662 standards is crossed to test；And comparative example flame retardant property when changing flame retardant constituent significantly reduces,
And it is tested not over smoke density as defined in ASTME662 standards.In addition, the viscosity of resin compound according to the present invention and
The solidifyingization time can be controlled in suitable range, and can ensure preferable tensile strength, bending strength, bending modulus and
The mechanical properties such as impact flexibility.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature, in the case of no contradiction, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention no longer separately illustrate various combinations of possible ways.In addition, a variety of different implementations of the present invention
Arbitrary combination can also be carried out between mode, as long as its thought without prejudice to the present invention, it is public should to be equally considered as institute of the invention
The content opened.
Claims (14)
1. a kind of composition epoxy resin, which is characterized in that it is counted by 100 parts by weight of the total weight of the composition epoxy resin,
The composition epoxy resin includes the epoxy resin of 40-50 parts by weight, the Toughening Modification of Epoxy of 6-10 parts by weight, 2-6 weights
The curing agent, the accelerating agent of 1-4 parts by weight and the fire retardant of 30-50 parts by weight of part are measured, wherein the fire retardant includes polyphosphoric acid
Amine and melamine cyanurate, and the polyphosphoric acid amine and the weight ratio of the melamine cyanurate are 1：0.5-1.
2. composition epoxy resin according to claim 1, wherein, the polyphosphoric acid amine and the melamine cyanurate
The weight ratio of salt is 1：0.6-0.85.
3. composition epoxy resin according to claim 1 or 2, wherein, the polyphosphoric acid amine is through melamino-formaldehyde
The modified polyphosphoric acid amine that resin or silane pretreatment obtain.
4. composition epoxy resin according to claim 3, wherein, using the total weight of the modified polyphosphoric acid amine as base
Standard, the content of the polyphosphoric acid amine are 85-95 weight %, and the content of the melamine resin or silane is weighed for 5-15
Measure %.
5. composition epoxy resin according to claim 4, wherein, D50=10-25 μm of the grain size of the polyphosphoric acid amine,
Grain size D50≤10 μm of the melamine cyanurate.
6. composition epoxy resin according to claim 1, wherein, the epoxy resin includes liquid epoxies, consolidates
Body and/or semisolid epoxy resin and optional novolac epoxy resin.
7. the composition epoxy resin according to claim 1 or 6, wherein, it is liquid epoxies in the epoxy resin, solid
Body and/or the weight ratio of semisolid epoxy resin and novolac epoxy resin are 1：1.2-2.5：0-1.
8. composition epoxy resin according to claim 1, wherein, the Toughening Modification of Epoxy changes selected from dimeric dibasic acid
One in property epoxy resin, rubber modified epoxy resin, benzene oxygen modified epoxy and urethane-modified epoxy resin
Kind is a variety of.
9. composition epoxy resin according to claim 1, wherein, the curing agent is dicyandiamide class curing agent；It is described
Accelerating agent is organic urea accelerating agent, and preferably 3- (3,4- dichlorophenyl) -1,1- dimethyl ureas, phenyl dimethylurea, 2,4 toluene are double
It is one or more in dimethyl urea and the double dimethyl ureas of 2,4 methyl.
10. a kind of preparation method of epoxy resin composition, which is characterized in that the epoxy resin composition is with claim 1-
Composition epoxy resin in 9 described in any one is prepared for raw material, and the preparation method includes the following steps：
(1) optional liquid epoxies and curing agent and accelerating agent are ground to obtain abrasive；
(2) by optional semisolid and/or solid epoxy, optional novolac epoxy resin and Toughening Modification of Epoxy and
Fire retardant melts, and obtains lava material；
(3) lava material obtained by step (2) and abrasive obtained by step (1) are stirred at 55-80 DEG C,
At least there are a kind of and optional phenolic aldehyde for wherein described liquid epoxies and the semisolid and/or solid epoxy
Epoxy composite is as epoxy source material.
11. according to the method described in claim 10, wherein, in step (3), pass through water-bath temperature control, mixing time 20-50
Minute.
12. the epoxy resin composition that the method according to claim 10 or 11 is prepared.
13. a kind of epoxy prepreg, which is characterized in that the epoxy prepreg is by the way that epoxy resin composition is impregnated
Reinforcement obtains, and the epoxy resin composition is the epoxy resin composition described in claim 12.
14. a kind of composite material, which is characterized in that the composite material is by by the epoxy prepreg described in claim 13
Curing obtains.
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| 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 |
| CN113736132A (en) * | 2021-10-21 | 2021-12-03 | 东莞市鼎泰鑫电子有限公司 | Low-density epoxy foaming type grinding wheel and preparation method thereof |
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