CN106751527A - Self-adhering-type halogen-free flameproof epoxy prepreg composite and preparation method thereof - Google Patents
Self-adhering-type halogen-free flameproof epoxy prepreg composite and preparation method thereof Download PDFInfo
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- CN106751527A CN106751527A CN201611247954.8A CN201611247954A CN106751527A CN 106751527 A CN106751527 A CN 106751527A CN 201611247954 A CN201611247954 A CN 201611247954A CN 106751527 A CN106751527 A CN 106751527A
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
Abstract
The invention discloses a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite and preparation method thereof, the composite is the glued membrane being processed into by epoxy resin for prepreg matrix and the composite being combined into hot melt；Epoxy resin for prepreg matrix is made up of component A with B component；Component A includes：20~50 mass parts bisphenol A type epoxy resins, 5~10 mass parts polyfunctional epoxy resins, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts rubber-like toughener；B component includes：10~30 mass parts bisphenol A type epoxy resins, 3~10 mass parts curing agent, 3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents.The tack of materials is moderate, has good tack, toughness, fatigue resistance and is coated with processing performance, can be with honeycomb and foaming structure core self-adhesion；There is excellent flame retardant effect, moreover it is possible to the shortcoming that the poison gas for avoiding the use of halogen plain epoxy resin from causing discharges.
Description
Technical field
The present invention relates to field of composite material preparation, more particularly to a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite wood
Material and preparation method thereof.
Background technology
Epoxy/glass and epoxy/carbon-fiber composite material specific strength and specific modulus are high, and manufacturability is good and cost is relatively low
It is honest and clean, the fields such as Aero-Space, energy traffic and electric insulation are widely used at present, it is lighting, the work of aircraft component
The multi-selection in journey field and the high reliability of electrical equipment have made significant contribution.For example, Hexcel companies F155, M26T,
The trades mark such as M76 epoxy/glass and epoxy/carbon-fiber composite material are obtained greatly in Boeing and Airbus Aircraft radome and floor component
Amount application；FR-4 types epoxy/glass fiber composite material obtains batch application in high-performance electronic laminated plates；
The trades mark such as SynoliteTM1790-G-3 epoxy/glass fiber composite material has turned into the critical material of manufacture large fan blade.But
It is, ordinary epoxy resin poor toughness and inflammable that composite materials property prepared therefrom is not good enough and without fire resistance, nothing
Method meets the high-strength and high ductility of the fields such as Aero-Space proposition and fire savety requirement high.
It is well known that the sandwich structure that traditional prepreg is combined with honeycomb core is will by using the adhesive of film-form
Both form bonding, and from from the point of view of the lightweight of honeycomb core and reduction shaping cost, the above method has no advantage.Therefore have
People has the characteristic equal with adhesive by the resin that makes to be used in prepreg, without in order to bond prepreg and honeycomb core
Honeycomb interlayer panel can be molded into using glued membrane to be studied.Such as (the Japanese Unexamined Patent Publication 2001-31838 of referenced patent 1
Publication) it is described：Reacted with epoxy resin with polyisocyanate compounds in advance, resin viscosity is properly increased, after thus making shaping
Chamfering (prepreg resin a part flowing, between the panel and honeycomb containing prepreg formed resin cured matter) shape
Into good shape, so that honeycomb interlayer panel has good mechanical properties.Referenced patent 2 (201210211454.4) and
It is to improve the self-adhesion of prepreg using appropriate toughener is added in scheme disclosed in referenced patent 3 (201410417148.5)
Property, but fire retardant used is entirely bromine/stibium flame retardancy system in this two parts of schemes of patent, and consumption is big, is easily produced in combustion process
The substantial amounts of cigarette of life and poison gas, fire prevention gas defence security are poor.The solvent method processing that the prepreg is used simultaneously is obtained, solvent method
Environmental pollution is larger, while the volatilization and recovery of solvent cause very big energy consumption.
The content of the invention
Based on the problems of prior art, it is an object of the invention to provide a kind of preimpregnation of self-adhering-type halogen-free flameproof epoxy
Material composite and preparation method thereof, it has good tack, toughness, fatigue resistance and is coated with processing performance, is capable of achieving
With honeycomb and the self-adhesion of foaming structure core, with excellent flame retardant effect, moreover it is possible to effectively avoid halogen plain epoxy resin
The problem discharged using the poison gas for causing.The purpose of the present invention is achieved through the following technical solutions：
The embodiment of the present invention provides a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite, the composite be by by
Mass percent is 30~70% epoxy resin for prepreg the matrix glued membrane and 30~70% fibre reinforced materials that are processed into
The composite being combined into hot melt；
The epoxy resin for prepreg matrix is 100 by component A and B component in mass ratio:30~100:60 compositions；Its
In, the component A includes：20~50 mass parts bisphenol A type epoxy resins, 5~10 mass parts polyfunctional epoxy resins, 10~
30 mass parts phosphorous epoxy resins and 8~25 mass parts rubber-like toughener；B component includes：10~30 mass parts bisphenol A-type rings
Oxygen tree fat, 3~10 mass parts curing agent, 3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents.
The embodiment of the present invention also provides a kind of preparation method of self-adhering-type halogen-free flameproof epoxy prepreg composite, is used for
Composite of the present invention is prepared, including：
Step 1：Epoxy resin for prepreg matrix is prepared, by the A of epoxy resin for prepreg matrix, the formula of B component
Take each raw material；
Step 11：Prepare component A：20~50 mass parts bisphenol type epoxies of component A raw material are sequentially added in reactor
Resin, 5~10 mass parts polyfunctional epoxy resins, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts toughener,
Then abundant 50~120min of pre-polymerization at 120~200 DEG C, is obtained component A；
Step 12：Prepare B component：With high speed dispersor by 10~30 mass parts bisphenol type epoxy trees of B component raw material
Fat, 3~10 mass parts dicy-curing agents, 3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents are fully mixed
Ground 2~5 times in three-roll grinder after conjunction, B component is obtained；
Step 13：Prepare epoxy resin for prepreg matrix：To be added to after component A obtained above and B component preheating
In kneader, temperature control is 60~100 DEG C, and epoxy resin for prepreg matrix is obtained after fully mixing；
Step 2：Prepare composite：By mass percentage, epoxy resin for prepreg matrix obtained above be 30~
70%, fibre reinforced materials is 30~70%, the epoxy resin for prepreg matrix is machined into glued membrane by film, so
Afterwards, the glued membrane and fibre reinforced materials are combined into composite as self-adhering-type halogen-free flameproof epoxy using hot melt to presoak
Material composite.
As seen from the above technical solution provided by the invention, composite provided in an embodiment of the present invention, by ring
The adjustment of oxygen formula, is made in component A using the combination of bisphenol A type epoxy resin, polyfunctional epoxy resin and phosphorous epoxy resin
With, appropriate toughener is added, the viscosity to resin matrix is adjusted, while the toughness of resin is enhanced, with excellent
Be coated with manufacturability, it is achieved thereby that the self bonding of prepreg and honeycomb core.Used by ammonium polyphosphate flame retardant, molybdenum in B component
It is the NEW TYPE OF COMPOSITE fire retardant of Complex Smoke and nontoxic fire-retardant carbon forming agent composition, effectively avoids halogen plain epoxy resin
Use, therefore be not in the release of halogen poison gas in combustion process；Simultaneously by adding smoke suppressant and heavy carbon agent, reduce well
Smoke density, improves oxygen index (OI) and fire safety property coefficient.The self-adhering-type halogen-free flameproof epoxy composite material has excellent
Mechanical property, tensile strength >=600MPa, climbing drum peel strength >=30 (N.mm)/mm, 60 seconds vertical combustion length≤20mm, cigarette
Density≤150, oxygen index (OI) >=32.There is important popularizing application prospect in fields such as large aircraft, ship and high ferros, especially fit
It is interior together in ceilings of aircraft, luggage compartment and sidewall paneling, ship wallboard and cabinet and high ferro ceiling, door-plate and sidewall paneling etc.
Decorative element.
Specific embodiment
With reference to particular content of the invention, the technical scheme in the embodiment of the present invention is clearly and completely retouched
State, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made,
Belong to protection scope of the present invention.
The embodiment of the present invention provides a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite, the composite be by by
Mass percent is 30~70% epoxy resin for prepreg the matrix glued membrane and 30~70% fibre reinforced materials that are processed into
The composite being combined into hot melt；
The epoxy resin for prepreg matrix is 100 by component A and B component in mass ratio:30~100:70 compositions are (excellent
Choosing, component A is 100 with B component in mass ratio:35~100:60)；Wherein, the component A includes：20~50 mass parts are double
Phenol A types epoxy resin, 5~10 mass parts polyfunctional epoxy resins, 10~30 mass parts phosphorous epoxy resins and 8~25 mass
Part rubber-like toughener；B component includes：10~30 mass parts bisphenol A type epoxy resins, 3~10 mass parts curing agent, 3~10
Mass parts curing accelerator, 20~50 mass parts composite flame-retardant agents.
In the component A of above-mentioned composite, the bisphenol type epoxy is the bisphenol A-type ring that epoxide number is 0.42~0.56
One or more in oxygen tree fat；The multifunction group epoxy be one kind in the epoxy resin that epoxide number is 0.70~0.90 or
It is several；The phosphorous epoxy resin is one or more in the epoxy resin that phosphorus content is 3%~8%；
The rubber-like toughener be end carboxyl nitrile rubber, containing carboxyl acrylic resin, terminal hydroxy group nitrile rubber and
At least one in core-shell polymer.
In above-mentioned rubber-like toughener, core-shell polymer is with polybutadiene rubber, butadiene-styrene rubber or polymethyl siloxane
It is soft core, the polymer with polymethyl methacrylate as duricrust.
In the B component of above-mentioned composite, the bisphenol type epoxy is the bisphenol A-type ring that epoxide number is 0.42~0.56
One or more in oxygen tree fat；The multifunction group epoxy be one kind in the epoxy resin that epoxide number is 0.70~0.90 or
It is several；The phosphorous epoxy resin is one or more in the epoxy resin that phosphorus content is 3%~8%；
The curing agent be dicyandiamide, glyoxaline compound, imidazoles-metallic salt complex compound or carbamide compounds in extremely
Few one kind；
The accelerator is at least one in imidazoles, imidazoles-metallic salt complex compound or ureas accelerator；
The composite flame-retardant agent is by APP, metal molybdenum system smoke suppressant or fire-retardant carbon forming agent according to 2:1:1 or 1:1:1
(i.e. the amount of APP is other two sums to mass ratio composition, or three's equal proportion is added.
In above-mentioned composite, component A is obtained by the following manner：
20~50 mass parts bisphenol A type epoxy resins, 5~10 mass parts multifunction group epoxies are sequentially added in reactor
Resin, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts toughener, the then abundant pre-polymerization 50 at 120~200 DEG C
~120min, that is, be obtained component A.
In above-mentioned composite, B component is obtained by the following manner：
With high speed dispersor by 10~30 mass parts bisphenol A type epoxy resins, 3~10 mass parts dicy-curing agents, 3~
10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents grind 2~5 times after being sufficiently mixed in three-roll grinder,
B component is obtained.
The embodiment of the present invention also provides a kind of preparation method of self-adhering-type halogen-free flameproof epoxy prepreg composite, is used for
Above-mentioned composite is prepared, including：
Step 1：Epoxy resin for prepreg matrix is prepared, by the A of epoxy resin for prepreg matrix, the formula of B component
Take each raw material；
Step 11：Prepare component A：20~50 mass parts bisphenol type epoxies of component A raw material are sequentially added in reactor
Resin, 5~10 mass parts polyfunctional epoxy resins, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts toughener,
Then abundant 50~120min of pre-polymerization at 120~200 DEG C, is obtained component A；
Step 12：Prepare B component：With high speed dispersor by 10~30 mass parts bisphenol type epoxy trees of B component raw material
Fat, 3~10 mass parts dicy-curing agents, 3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents are fully mixed
Ground 2~5 times in three-roll grinder after conjunction, B component is obtained；
Step 13：Prepare epoxy resin for prepreg matrix：To be added to after component A obtained above and B component preheating
In kneader, temperature control is 60~100 DEG C, and epoxy resin for prepreg matrix is obtained after fully mixing；
Step 2：Prepare composite：By mass percentage, epoxy resin for prepreg matrix obtained above be 30~
70%, fibre reinforced materials is 30~70%, the epoxy resin for prepreg matrix is machined into glued membrane by film, so
Afterwards, the glued membrane and fibre reinforced materials are combined into composite as self-adhering-type halogen-free flameproof epoxy using hot melt to presoak
Material composite.
The width and thickness of glued membrane pass through fibre reinforced materials in the step of above method 2 breadth and prepreg epoxy
Resin matrix cubage and obtain；
Fibre reinforced materials used is in glass fabric, carbon cloth, aryl fiber cloth in the step of above method 2
Any one.
Self-adhering-type halogen-free flameproof epoxy prepreg composite of the invention, with good tack, toughness, antifatigue
Property and be coated with processing performance, be capable of achieving the self-adhesion with honeycomb and foaming structure core；Halogen-free flame retardants, smoke suppressant and into charcoal simultaneously
Agent collocation is used, not only with excellent flame retardant effect, moreover it is possible to the poison for effectively avoiding the use of halogen plain epoxy resin from causing
The shortcoming of gas release, can have important popularizing application prospect in fields such as large aircraft, ship and high ferros.
Composite of the invention is described in further detail below in conjunction with specific embodiment.
Self-adhering-type halogen-free flameproof epoxy prepreg of the invention：To be resin base through toughness reinforcing and flame-retardant modified compound prescription
Body, with continuous glass-fiber, carbon is fine or aramid fabric as reinforcing material, after hot melt is presoaked again through press hot pressing, vacuum
Bag forming or autoclave process combining are prepared from.
Self-adhering-type halogen-free flameproof epoxy composite material of the present invention contains the component of following mass percentage content：
Epoxy resin for prepreg matrix：30%~70%
Fibre reinforced materials：30%~70%
Wherein epoxy resin for prepreg matrix includes the component of A, B two, and wherein A, B component include following mass fraction respectively
Raw material：
Component A：
Bisphenol A type epoxy resin：30~80；
Polyfunctional epoxy resin：5~10；
Phosphorous epoxy resin：10~30；
Toughener：8~25；
B component
Curing agent：3~10；
Curing accelerator：3~10；
Composite flame-retardant agent：20~50.
In above-mentioned A, B component, bisphenol type epoxy be in the bisphenol A type epoxy resin that epoxide number is 0.20~0.55 extremely
Lack one or more.Consider mechanical property and prepreg is coated with processing performance, epoxide number is preferably 0.20~0.45 ring
Oxygen tree fat, consumption is preferably 30~80 mass parts.
The epoxide number of multifunction group epoxy is at least one or several in 0.70~0.90 resin, and the phosphorus of phosphorous epoxy contains
Amount is at least one or several in 3%~8% resin.
Composite flame-retardant agent constitutes mixing by ammonium polyphosphate flame retardant, molybdenum system Complex Smoke and nontoxic fire-retardant carbon forming agent
Thing, its consumption is 20~50 mass parts, amount ranges preferably 20~40 mass parts.If consumption is less than 20 mass parts, composite wood
The fire resistance of material is substantially deteriorated.
Toughener is selected from end carboxyl nitrile rubber, containing carboxyl acrylic resin, terminal hydroxy group nitrile rubber or core-shell polymer
(being soft core with polybutadiene rubber, butadiene-styrene rubber or polymethyl siloxane, with polymethyl methacrylate as duricrust) at least
One kind, toughener consumption is 8~25 mass parts, and preferably consumption is 10~18 mass parts, and optimal consumption is 8~15 mass
Part.If consumption is less than 8 mass parts, it will cause solidfied material toughening effect drastically to weaken；If consumption is more than 25 mass parts, will
Solidfied material heat resistance and mechanical property can be caused to drastically reduce.
The consumption of curing accelerator be 3~10 mass parts, if consumption be less than 3 mass parts, it is necessary to hardening time it is long, such as
Fruit consumption is higher than 10 mass parts, and the Storage period of resin can be greatly shortened.Curing accelerator is imidazoles, imidazoles-metallic salt network
Compound or ureas accelerator etc..In order to ensure that resin has preferable storage stability, preferably curing accelerator is ureas promotion
Agent, is chosen in particular from N, N- dimethyl urea groups toluene, N, N "-(4- methyl isophthalic acids, 3- phenylenes) double (N ', N '-dimethyl ureas) or N,
N ' '-(- 4,1- the phenylenes of methylene two) two (N ', at least one in N '-dimethyl urea.
Reinforcing material is selected from the one-way tape or woven cloth of glass fibre, carbon fiber or aramid fiber.
Curing agent is selected from ethylenediamine, dicyandiamide, 4 ' 4- MDAs, 4 ' 4- DADPSs, 3 ' 3- diaminos
One or more in base diphenyl sulphone (DPS).
The preparation method of self-adhering-type halogen-free flameproof epoxy prepreg composite of the present invention, comprises the following steps：
Step 1, epoxy resin for prepreg is prepared, it is specific as follows：
11. sequentially add 20~50 mass parts bisphenol A type epoxy resins, 5~10 mass parts polyfunctional groups in reactor
Epoxy resin, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts toughener, it is then fully pre- at 120~200 DEG C
Poly- 50~120min, that is, be obtained component A.
12. with high speed dispersor by 10~30 mass parts bisphenol A type epoxy resins, 3~10 mass parts dicy-curing agents,
3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents grind 2~5 after being sufficiently mixed in three-roll grinder
Time, that is, B component is obtained.
13rd, will be added in kneader (temperature control 60~100 DEG C between) after A and the preheating of the components of B two and fully mix
Obtain epoxy resin for prepreg matrix afterwards.
Step 2, self-adhering-type halogen-free flameproof epoxy prepreg composite is prepared, it is specific as follows：
Epoxy resin is machined to the certain thickness glued membrane of the one fixed width (width and thickness of glued membrane by 21. by film
Calculated by the breadth and prepreg resin content of glass fabric and obtained).
Glued membrane and glass fabric are combined into epoxy glass prepreg composite by 22. using hot melt.
Self-adhering-type halogen-free flameproof epoxy prepreg laying is carried out according to thickness requirement, afterwards by self-adhering-type halogen-free flameproof epoxy
The folded block of prepreg is put into solidification of the autoclave in 80~200 DEG C of solidification temperature, 0.1~3MPa after being put into press or vacuum coater
Curing molding under pressure, solidification temperature temperature is preferably 110~160 DEG C, and solidifying pressure is preferably 0.1~0.7MPa, processes
Mechanics Performance Testing is carried out to laminate.Laying is carried out to prepreg and aluminium honeycomb core as requested, by press or vacuum packet
Autoclave is put into after covering solidify obtaining honeycomb sandwich structure, for testing combustibility.
Prepreg is prepared using hot melt, and the volatile content of prepreg is 0~1 ﹪, and epoxy resin-base content is 30
~70%, preferably 35~50%；Prepreg at room temperature (15~30 DEG C) it is soft, viscosity is moderate, is suitable at room temperature paving by hand
Cover.
Self-adhering-type halogen-free flameproof epoxy composite material tensile strength of the invention >=600MPa, climbing drum peel strength >=30
(N.mm)/mm, 60 seconds vertical combustion length≤20mm, smoke density≤150, oxygen index (OI) >=32.In large aircraft, ship and high ferro
There is important popularizing application prospect Deng field, be particularly suitable for ceilings of aircraft, luggage compartment and sidewall paneling, ship wallboard and cupboard
The built-in trim such as cabinet and high ferro ceiling, door-plate and sidewall paneling.
Self-adhering-type halogen-free flameproof epoxy prepreg composite property method of testing is as follows：
Mechanical performance：The standards of ASTM D 3039 are pressed using the universal testing machines of INSTRON 3365 (Instron companies of the U.S.)
The tensile property of test material；By the compression performance of the Standards for Testing Materials of ASTM D 6641；By ASTM D790 standard testing materials
The bending property of material；By the interlaminar shear strength of ASTM D2344 Standards for Testing Materials.
Flame retardant test：Smoke density, oxygen index (OI) and toxicity gas are carried out to honeycomb sandwich construction according to TB/3237-2010 standards
Body analysis test；According to DIN5510-2:Burning grade separation and the molten drop classification of 2009 pairs of prepreg pressing plates are tested.
Embodiment 1：
10 mass parts E44 (epoxide number 0.44), 25 mass parts E20 (epoxide number 0.20), 8 matter are sequentially added in reactor
Amount part AG-80 (epoxide number 0.80), 15 mass parts phosphorous epoxy resins (phosphorous 3.1%) and 10 mass parts liquid end carboxyl butyronitriles
Rubber, then the pre-polymerization 90min at a temperature of 160 DEG C, that is, be obtained component A；With high speed dispersor by 15 mass parts E51 (epoxide numbers
0.51) three after, 8 mass parts dicy-curing agents, 5 mass parts curing accelerators and 35 mass parts composite flame-retardant agents are sufficiently mixed
Ground in roller mill 3 times, that is, B component is obtained.It is in mass ratio：100：30 take A, B component, after component A and B component preheating
It is added in kneader (temperature control is at 80 DEG C) after fully mixing and obtains epoxy resin for prepreg matrix.
With above-mentioned epoxy resin as matrix, SW200C types (crowfoot satin line, thickness 0.21mm, the face of ZhongCai Science Nan Bo institutes
Weight 220g/m2) glass cloth is reinforcing material, and resin content 50% is obtained using the continuous film of hot melt, compound and winding process
Flame retardant epoxy glass prepreg composite.The folded block of certain number of plies epoxy glass prepreg is coated with by thickness design requirement (to draw
It is 2mm to stretch and compress laminate thickness used；Bending and laminate thickness used by interlayer shear are 3mm), using press hot pressing work
Skill obtains self-adhering-type halogen-free flameproof epoxy glass prepreg laminate samples in 0.7MPa/125 DEG C of condition solidification.By standard requirement
(being tiled 2 layers according to thickness requirement) coats autoclave forming process and solidify under the conditions of 0.7MPa/125 DEG C and obtain oneself with vacuum bag
The battenboard of viscous type halogen-free flameproof epoxy glass prepreg honeycomb sandwich structure is (beautiful using the universal testing machines of INSTRON 3365
Instron companies of state) press the tensile property of the Standards for Testing Materials of ASTM D 3039；By the Standards for Testing Materials of ASTM D 6641
Compression performance；By the bending property of the Standards for Testing Materials of ASTM D 790；Cut by the interlayer of the Standards for Testing Materials of ASTM D 2344
Shearing stress；The analysis test of smoke density, oxygen index (OI) and poisonous gas is carried out to honeycomb sandwich construction according to TB/3237-2010 standards；
According to DIN5510-2:The burning grade separation damage envelope of 2009 pairs of prepreg pressing plates is tested.Obtained in the present embodiment
Composite typical performance is shown in Table 1.
Embodiment 2：
Understood with the contrast of embodiment 1, in epoxy resin for prepreg preparation process, by the epoxy resin B component of embodiment 2
The mass parts of middle composite flame-retardant agent are reduced to 25 mass parts, in mass ratio for：100：50 take A, B component, remaining condition with reality
Apply example 1 identical.Reinforcing material used and prepreg resin content, sample making course, method of testing and relevant parameter in embodiment 2
It is same as Example 1.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Embodiment 3：
Understood with the contrast of embodiment 1, in epoxy resin for prepreg preparation process, by the epoxy resin B component of embodiment 3
The mass parts of middle composite flame-retardant agent increase to 45 mass parts, in mass ratio for：100：70 take A, B component, remaining condition with reality
Apply example 1 identical.Reinforcing material used, prepreg resin content, sample making course, method of testing and relevant parameter in embodiment 3
It is same as Example 1.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Embodiment 4：
Understood with the contrast of embodiment 1, in prepreg recombination process, by the weight epoxy percentage composition of embodiment 4 drop
As little as 40%, epoxy resin for prepreg preparation process is same as Example 1.Reinforcing material used, sample preparation in embodiment 4
Journey, method of testing and relevant parameter are also same as Example 1.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Embodiment 5：
Understood with the contrast of embodiment 1, in prepreg recombination process, the epoxy resin content of embodiment 5 improved to 60%,
Epoxy resin for prepreg preparation process is same as Example 1.Reinforcing material used, sample making course, method of testing in embodiment 5
And relevant parameter is also same as Example 1.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Embodiment 6：
Understood with the contrast of embodiment 1, in epoxy resin for prepreg preparation process, by the epoxy resin component A of embodiment 6
Middle toughener mass parts are reduced to 3 mass parts, and remaining condition is same as Example 1.It is reinforcing material used in embodiment 6, pre-
Leaching material resin content, sample making course, method of testing and relevant parameter are also same as Example 1.It is combined obtained in the present embodiment
Material typical performance is shown in Table 1.
Embodiment 7：
Understood with the contrast of embodiment 1, in epoxy resin for prepreg preparation process, by the epoxy resin component A of embodiment 7
Middle toughener mass parts are improved to 15 mass parts, in mass ratio for：100：60 take A, B component, remaining condition with the phase of embodiment 1
Together.In embodiment 7 reinforcing material used, prepreg resin content, sample making course, method of testing and relevant parameter also with implementation
Example 1 is identical.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Embodiment 8：
Understand that in prepreg recombination process, embodiment 8 is replaced by ZhongCai Science with reinforcing material with the contrast of embodiment 1
The EW110 of Nan Bo institutes, epoxy resin for prepreg preparation process is same as Example 1.Prepreg resin content in embodiment 8,
Sample making course, method of testing and relevant parameter are also same as Example 1.Composite typical performance is shown in obtained in the present embodiment
Table 1.
Embodiment 9：
Understand that in prepreg recombination process, embodiment 9 is replaced by ZhongCai Science with reinforcing material with the contrast of embodiment 1
The EW220 of Nan Bo institutes, epoxy resin for prepreg preparation process is same as Example 1.Prepreg resin content in embodiment 9,
Sample making course, method of testing and relevant parameter are also same as Example 1.Composite typical performance is shown in obtained in the present embodiment
Table 1.
Embodiment 10：
Understand that in prepreg recombination process, embodiment 9 is replaced by toray with reinforcing material with the contrast of embodiment 1
T300 carbon fiber twill weave cloth, epoxy resin for prepreg preparation process is same as Example 1.Prepreg tree in embodiment 10
Fat content, sample making course, method of testing and relevant parameter are also same as Example 1.Composite allusion quotation obtained in the present embodiment
Type performance is shown in Table 1.
Embodiment 11：
Understood with the contrast of embodiment 1, in sample making course, the difference of embodiment 11 is that honeycomb sandwich structure is used
Prepreg overlay be 1 layer.Epoxy resin for prepreg preparation process, prepreg recombination process, method of testing in embodiment 11
And relevant parameter is same as Example 1.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Embodiment 12：
Understood with the contrast of embodiment 1, in sample making course, the difference of embodiment 12 is that honeycomb sandwich structure is used
Prepreg overlay be 3 layers.Epoxy resin for prepreg preparation process, prepreg recombination process, method of testing in embodiment 12
And relevant parameter is same as Example 1.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Comparative example 1：
On the basis of the mass parts of F type epoxy resin, in 100L reactors, 20 mass parts butanone are added, be warming up to 40
~60 DEG C, then add while stirring 100 mass parts F51 (epoxide number 0.51), 20 mass parts E types epoxy (epoxide number 0.40),
25 mass parts CTPBs, 15 mass parts tetrabromobisphenol As, 15 mass parts 4,4- MDAs, 10 mass parts
N, N- diethyl diphenyl urea and 5 mass parts antimony oxides, are sufficiently stirred for 30 minutes, that is, fire retarding epoxide resin combination is obtained
Thing.
With above-mentioned epoxy resin as matrix, with EW110C types (crowfoot satin line, thickness 0.11mm, the heavy 110g/m in face2) glass
Cloth is reinforcing material, and flame retardant epoxy glass prepreg is obtained through continuous dipping, drying and winding process using solution cement-dipping method.Press
Thickness
Design requirement is coated with the folded block of certain number of plies epoxy glass prepreg, using press heat pressing process at 0.4MPa/125 DEG C
Condition solidification obtains flame retardant epoxy glass fiber composite material.Composite typical performance is shown in Table 1 obtained in the present embodiment.
Comparative example 2：
On the basis of the mass parts of F epoxy resin, in 100L reactors, 30 mass parts ethyl acetate are added, be warming up to
40~60 DEG C, 100 mass parts F51 epoxies (epoxide number 0.51), 20 mass parts E type epoxy (epoxide numbers are then added while stirring
0.4), 20 mass parts contain carboxyl acrylic resin, 15 mass parts tetrabromobisphenol As, the 4- DADPSs of 15 mass parts 4 ', 5 matter
Amount part N, N '-diethyl diphenyl urea and 3 mass parts antimony oxides, are sufficiently stirred for 30 minutes, that is, fire retarding epoxide resin is obtained
Composition.
With above-mentioned epoxy resin as matrix, with EW250F types (eight pieces of satin weaves, thickness 0.25mm, the heavy 300g/m2 in face) glass
Cloth is reinforcing material, and flame retardant epoxy glass prepreg is obtained through continuous dipping, drying and winding process using solution cement-dipping method.Press
Thickness design requirement is coated with the folded block of certain number of plies epoxy glass prepreg, using press heat pressing process in 0.8MPa/140 DEG C of condition
Solidification obtains flame retardant epoxy glass fiber composite material.Composite typical performance of the invention is shown in Table 1.
Table 1 is the self-adhering-type flame retardant epoxy prepreg composite performance of various embodiments of the present invention
Indicate：Resin content is % in table；Tensile strength, compressive strength, bending strength and interlaminar shear strength unit are
MPa；The unit of stretch modulus, modulus of compressibility and bending modulus is GPa；Sandwich laying refers to honeycomb sandwich structure one side prepreg
Laying number；Climbing drum peel strength unit is (N.mm)/mm；Maximum smoke density when smoke density refers to 4S；Oxygen index (OI) is %；HBr gas
Body is poisonous gas index after composite burning, and unit is ppm；Vertical combustion refers to 6S vertical combustions, and unit is mm.
Knowable to the results of property of comparative example 1 and 2, although certain fire-retardant effect can be played using bromine/stibium flame retardancy system
Really, but the burst size of poisonous gas is exceeded after composite burning, and vertical combustion is destructive higher, therefore can not rise
To good flame retardant effect.Knowable to from embodiment 1-12 results of property, good resistance can be played using Halogenless composite fire retardant
Fuel efficiency really, therefore the present invention using by ammonium polyphosphate flame retardant, molybdenum system Complex Smoke and nontoxic fire-retardant carbon forming agent constitute it is new
Type composite flame-retardant agent, effectively avoids the use of halogen plain epoxy resin, therefore is not in halogen poison gas in combustion process
Release；Simultaneously by adding smoke suppressant and heavy carbon agent, smoke density is reduced well, improve oxygen index (OI) and fire savety system
Number.The present invention adds appropriate toughener, and the viscosity to resin matrix is adjusted, and not only increases toughness and the paving of resin
Coating process, and realize the self bonding of prepreg and honeycomb core.Self-adhering-type halogen-free flameproof epoxy prepreg composite has
There are excellent mechanical property, tensile strength >=600MPa, climbing drum peel strength >=25 (N.mm)/mm, 60 seconds vertical combustion length
≤ 20mm, smoke density≤150, oxygen index (OI) >=32.The composite has important in fields such as large aircraft, ship and high ferros
Popularizing application prospect, is particularly suitable for ceilings of aircraft, luggage compartment and sidewall paneling, ship wallboard and cabinet and high ferro smallpox
The built-in trim such as plate, door-plate and sidewall paneling.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
Should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (9)
1. a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite, it is characterised in that the composite is by by quality hundred
Divide the glued membrane and 30~70% fibre reinforced materials hot melt being processed into than the epoxy resin for prepreg matrix for 30~70%
The composite that method is combined into；
The epoxy resin for prepreg matrix is 100 by component A and B component in mass ratio:35~100:70 compositions；Wherein,
The component A includes：20~50 mass parts bisphenol A type epoxy resins, 5~10 mass parts polyfunctional epoxy resins, 10~30
Mass parts phosphorous epoxy resin and 8~25 mass parts rubber-like toughener；B component includes：10~30 mass parts bisphenol type epoxies
Resin, 3~10 mass parts curing agent, 3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents.
2. a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 1, it is characterised in that described
In component A, the bisphenol type epoxy is one or more in the bisphenol A type epoxy resin that epoxide number is 0.42~0.56；Institute
It is one or more in the epoxy resin that epoxide number is 0.70~0.90 to state multifunction group epoxy；The phosphorous epoxy resin is
Phosphorus content is one or more in 3%~8% epoxy resin；
The rubber-like toughener be end carboxyl nitrile rubber, containing carboxyl acrylic resin, terminal hydroxy group nitrile rubber and nucleocapsid
At least one in polymer.
3. a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 2, it is characterised in that described
It with polybutadiene rubber, butadiene-styrene rubber or polymethyl siloxane is soft core that core-shell polymer is, is with polymethyl methacrylate
The polymer of duricrust.
4. a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 1 and 2, it is characterised in that
In the B component, the bisphenol type epoxy is the one kind or several in the bisphenol A type epoxy resin that epoxide number is 0.42~0.56
Kind；The multifunction group epoxy is one or more in the epoxy resin that epoxide number is 0.70~0.90；The phosphorous epoxy
Resin is one or more in the epoxy resin that phosphorus content is 3%~8%；
The curing agent is at least in dicyandiamide, glyoxaline compound, imidazoles-metallic salt complex compound or carbamide compounds
Kind；
The accelerator is at least one in imidazoles, imidazoles-metallic salt complex compound or ureas accelerator；
The composite flame-retardant agent is 2 by APP, metal molybdenum system smoke suppressant or fire-retardant carbon forming agent in mass ratio：1：1 or 1：1：1
Composition.
5. a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 1 and 2, it is characterised in that
The component A is obtained by the following manner：
20~50 mass parts bisphenol A type epoxy resins, 5~10 mass parts multifunction group epoxy trees are sequentially added in reactor
Fat, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts toughener, then at 120~200 DEG C abundant pre-polymerization 50~
120min, that is, be obtained component A.
6. a kind of self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 1 and 2, it is characterised in that
The B component is obtained by the following manner：
With high speed dispersor by 10~30 mass parts bisphenol A type epoxy resins, 3~10 mass parts dicy-curing agents, 3~10 matter
Amount part curing accelerator, 20~50 mass parts composite flame-retardant agents grind 2~5 times after being sufficiently mixed in three-roll grinder, that is, make
Obtain B component.
7. a kind of preparation method of self-adhering-type halogen-free flameproof epoxy prepreg composite, it is characterised in that for preparing right
It is required that the composite described in 1 to 6 any one, including：
Step 1：Epoxy resin for prepreg matrix is prepared, is taken respectively by the formula of the A of epoxy resin for prepreg matrix, B component
Raw material；
Step 11：Prepare component A：20~50 mass parts bisphenol type epoxy trees of component A raw material are sequentially added in reactor
Fat, 5~10 mass parts polyfunctional epoxy resins, 10~30 mass parts phosphorous epoxy resins and 8~25 mass parts toughener, so
Abundant 50~120min of pre-polymerization at 120~200 DEG C, is obtained component A afterwards；
Step 12：Prepare B component：With high speed dispersor by 10~30 mass parts bisphenol A type epoxy resins of B component raw material, 3~
10 mass parts dicy-curing agents, 3~10 mass parts curing accelerators, 20~50 mass parts composite flame-retardant agents be sufficiently mixed after
Ground 2~5 times in three-roll grinder, B component is obtained；
Step 13：Prepare epoxy resin for prepreg matrix：Kneading will be added to after component A obtained above and B component preheating
In machine, temperature control is 60~100 DEG C, and epoxy resin for prepreg matrix is obtained after fully mixing；
Step 2：Prepare composite：By mass percentage, epoxy resin for prepreg matrix obtained above is 30~70%,
Fibre reinforced materials is 30~70%, and the epoxy resin for prepreg matrix is machined into glued membrane by film, then, will
The glued membrane and fibre reinforced materials are combined into composite as self-adhering-type halogen-free flameproof epoxy prepreg and answer using hot melt
Condensation material.
8. the preparation method of self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 7, its feature exists
In the width and thickness of glued membrane are contained by the breadth and epoxy resin for prepreg matrix of fibre reinforced materials in the step 2
Amount is calculated and obtained.
9. the preparation method of the self-adhering-type halogen-free flameproof epoxy prepreg composite according to claim 7 or 8, its feature
It is that fibre reinforced materials used is any one in glass fabric, carbon cloth, aryl fiber cloth in the step 2.
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| CN109553789A (en) * | 2017-09-27 | 2019-04-02 | 洛阳尖端技术研究院 | A kind of prepreg, composite material and preparation method and application |
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| CN113956820A (en) * | 2021-11-30 | 2022-01-21 | 世晨材料技术(上海)有限公司 | High-temperature-resistant epoxy adhesive tape and preparation method thereof |
| CN114179462A (en) * | 2022-02-16 | 2022-03-15 | 北京玻钢院复合材料有限公司 | Self-adhesive composite material honeycomb plate and preparation method thereof |
| CN115197537A (en) * | 2022-04-27 | 2022-10-18 | 道生天合材料科技(上海)股份有限公司 | Flame-retardant epoxy resin composition, prepreg, fiber-reinforced composite material and preparation |
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