CN109438918A - A kind of fibre reinforced composites and preparation method thereof - Google Patents
A kind of fibre reinforced composites and preparation method thereof Download PDFInfo
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- CN109438918A CN109438918A CN201811013055.0A CN201811013055A CN109438918A CN 109438918 A CN109438918 A CN 109438918A CN 201811013055 A CN201811013055 A CN 201811013055A CN 109438918 A CN109438918 A CN 109438918A
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Abstract
The invention discloses a kind of fibre reinforced composites and preparation method thereof, which includes the component of following parts by weight: 10~50 parts of epoxy resin；0.1~2 part of photoinitiator；5~10 parts of toughener；10~25 parts of fire retardant；0~15 part of fire retarding synergist；15~35 parts of reinforcing fiber.The fibre reinforced composites mechanical property and excellent flame retardancy.
Description
Technical field
The present invention relates to fibre reinforced composites technical field more particularly to a kind of fibre reinforced composites and its systems
Preparation Method.
Background technique
Fibre reinforced composites are answered by high intensity, high-modulus, continuous fiber or discontinuous fibre and resin matrix
It closes.The effect of resin matrix is that load is effectively transmitted to reinforced phase by interface, and reinforced phase can be whisker, fiber
Deng resin matrix is not primary load bearing phase.The effect of fiber be subject to by resin matrix transmitting Lai payload, be belong to master hold
Power phase.When material receives biggish stress, some fibers for having crackle may be first short, but resin matrix can hinder crackle to expand
Exhibition disease changes direction of crack propagation.Reinforcing fiber materials, such as glass fibre, carbon fiber, basalt fibre, aramid fiber, nylon
At least one of fiber, polyphenylene sulfide fibre, ultra high molecular weight polyethylene fiber, polyimide fiber etc., with resin matrix
Received and distributed the moulding process such as paste, vacuum diversion, resin transfer molding, winding, pultrusion, molding, vacuum bag pressure, autoclave and
The composite material of formation.Since fibre reinforced composites have a characteristic that (1) specific gravity is small, light-weight；(2) specific strength ratio
Modulus is high；(3) designability is strong, and processing technology is good；(4) fatigue crack-resistant performance is good；(5) durability, anticorrosive and radiation
Performance is good；(6) low thermal coefficient of expansion；(7) thermal capacity is small；(8) breach security is high.These features make FRP material be development
Modern industry, national defence and the indispensable basic material of science and technology and new technology revolution are rely the important substance base of development
Plinth, composite material have become the important leading material of field of new materials.The weight of aerospace craft is every to reduce 1 kilogram, so that it may make
Carrier rocket mitigates 500 kilograms.Present F1 (world's First-order equation championship) racing car, vehicle body major part structure are all increased with fiber
Strong composite material, the big attraction of the one of top-end sports cars is also the whole body using carbon fiber, to improve pneumatic property and structural strength.May be used also
As aircraft construction material, electromagnetic shielding except bodies substitute materials such as electric material, artificial ligaments, and for manufacturing outside rocket
The cores building block such as shell, power ship, industrial robot, leaf springs of car and drive shaft.
The advantages that light curing compound material is fast with its curing rate, energy saving, pollution is few has been used for every field.Photocuring
Material it is applied widely, be applied to laminated material, aeronautical glasses, pressure sensitive adhesive, the bonding of optical material, encapsulating material
Deng, it may also be used for information technology field, such as the biologies such as fiber optic protection and coloring, magnetic medium, optical medium and photocuring dental filling
And the fields such as medical application medical material.With the development of photo-curing material and technology, the application range of light curing compound material
It will continue to expand.
The main performance and effect of resin matrix in fiber-reinforced resin matrix compound material are as follows: 1. fiber is bonded it is integral
And position of fibers is fixed, load is transmitted between the fibers, and makes load equalization；2. determining some performances of composite material, such as
Heat resistance, cutting performance, medium-resistance of composite material etc.；3. determining the moulding technique and technological parameter of composite material
Selection；4. protecting the fibers from various damages；5. resin matrix is to composite material such as lateral performance, longitudinal performance, compressibility
The mechanical properties such as energy, fatigue behaviour, fracture toughness also have a certain impact.It is closed very much so developing suitable reisn base material
Key.
The flame retardant property of general polymer composite is poor, and the combustibility of composite material refers to the heat of material combustion
Amount release and flame extend situation.With aircraft, high-speed rail, car be equal to people's lives very close to the vehicles development,
And composite material on a vehicle inside and outside is decorated with and the application of stressed member, requires the flame retardant property of composite material more next
Higher, critical evaluation index includes: that surface flame extends, the intensity of a fire extends (heat release), smoke density, flue gas toxity etc..It is multiple
The flame retardant property of condensation material is mainly obtained by addition fire retardant.The fire retardant that China uses at present is mainly with organic halogen system
Based on fire retardant, although it is good with organic polymer compatibility, good flame retardation effect, additive amount is seldom, to the other performance of material
Very little is influenced, but smoke amount is larger in combustion, and releases toxic, corrosive hydrogen halide.In order to prevent
Burn secondary disaster brought by the smog generated, and people more and more pay attention to the use of bittern-free flame-proof material, seeks comprehensive
The good efficient halogen-free anti-inflaming system of energy is particularly important problem to exploitation halogen-free flame-retardant composite material.
Therefore, it develops with good fire retardant performance and preparation process is simple, fiber of low energy consumption, high efficiency and environmental protection
Enhancing composite material is a critically important research direction.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of fibre reinforced composites and its systems
Preparation Method, the fibre reinforced composites mechanical property and excellent flame retardancy.
The purpose of the present invention adopts the following technical scheme that realization:
A kind of fibre reinforced composites, the component including following parts by weight:
10~50 parts of epoxy resin；
0.1~2 part of photoinitiator；
5~10 parts of toughener；
10~25 parts of fire retardant；
0~15 part of fire retarding synergist；
15~35 parts of reinforcing fiber.
Further, the fibre reinforced composites include the component of following parts by weight: 20 parts of epoxy resin, light draws
0.15 part of agent, 5 parts of toughener, 15 parts of fire retardant, 15 parts of reinforcing fiber of hair；Alternatively,
40 parts of epoxy resin, 0.45 part of photoinitiator, 5 parts of toughener, 15 parts of fire retardant, 15 parts of reinforcing fiber；Alternatively,
30 parts of epoxy resin, 0.33 part of photoinitiator, 5 parts of toughener, 10 parts of fire retardant, 5 parts of fire retarding synergist, enhancing is fine
15 parts of dimension；Alternatively,
20 parts of epoxy resin, 0.15 part of photoinitiator, 5 parts of toughener, 10 parts of fire retardant, 5 parts of fire retarding synergist, enhancing is fine
15 parts of dimension.
Further, the epoxy resin is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, shrink
At least one of glycerol amine epoxy resin, cycloaliphatic epoxy resin, glycolylurea epoxide resin.
Further, the photoinitiator is at least one of salt compounded of iodine, sulfosalt, luxuriant molysite.
Further, the toughener is epoxidation end hydroxy butadiene, hydroxyl terminated butadiene acrylonitrile copolymer, terminal hydroxy group
At least one of polybutadiene, hydroxyl terminated butyl nitrile (HTBN) rubber.
Further, the fire retardant is phosphate, DOPO type phosphorous epoxy resin, melamine phosphate, polyphosphoric acid
At least one of ammonium, melamine cyanurate, hypo-aluminum orthophosphate, calcium hypophosphite, sodium hypophosphite.
Further, the fire retarding synergist be zinc borate, triazine carbon forming agent, magnesium hydroxide, in aluminium hydroxide at least
It is a kind of.
Further, the reinforcing fiber be glass fibre, basalt fibre, carbon fiber, aramid fiber, nylon fiber,
At least one of polyphenylene sulfide fibre, ultra high molecular weight polyethylene fiber, polyimide fiber.
The present invention also provides a kind of preparation methods of fibre reinforced composites as described above, include the following steps:
The ratio investment reaction in parts by weight of epoxy resin, photoinitiator, toughener, fire retardant and fire retarding synergist is held
In device, the first preset time is stirred under the conditions of preset rotation speed to being uniformly mixed, obtains the first intermediate, the preset rotation speed is
2000~5000 revs/min, first preset time is 15~45 minutes；
The reinforcing fiber and first intermediate are subjected to the second preset time of dipping, obtain the second intermediate, institute
Stating the second preset time is 5~20 minutes；
Second intermediate is placed under ultraviolet light and irradiates, solidify, obtains the fibre reinforced composites.
Further, the preset rotation speed is 2500~3500 revs/min, and first preset time is 30 minutes；And/
Or,
Second preset time is 8 minutes.
Compared with prior art, the beneficial effects of the present invention are:
(1) physical and mechanical property, processing performance, the appearance for the fibre reinforced composites that the present invention is prepared
It can good, excellent flame retardancy.Elongation at break up to 3.5%, tensile strength up to 69MPa, impact strength up to 70MPa,
Bending strength is up to 135MPa, and for bending modulus up to 7.1MPa, flame retardant property meets UL94-V0 grade.
(2) preparation process of fibre reinforced composites of the invention is simple, low energy consumption, high-efficiency environment friendly.It can widely answer
For various composite wire slots, decorative panel for building, rail traffic inside gadget, yacht inside gadget, interior of aircraft composite material
Pipeline and the structural member of every field etc..
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
Fibre reinforced composites provided in an embodiment of the present invention include the component of following parts by weight: epoxy resin 10~
50 parts；0.1~2 part of photoinitiator；5~10 parts of toughener；10~25 parts of fire retardant；0~15 part of fire retarding synergist；Reinforcing fiber
15~35 parts.
As preferred embodiment, the fibre reinforced composites include the component of following parts by weight: asphalt mixtures modified by epoxy resin
20 parts of rouge, 0.15 part of photoinitiator, 5 parts of toughener, 15 parts of fire retardant, 15 parts of reinforcing fiber.
40 parts of epoxy resin, 0.45 part of photoinitiator, 5 parts of toughener, 15 parts of fire retardant, 15 parts of reinforcing fiber.
30 parts of epoxy resin, 0.33 part of photoinitiator, 5 parts of toughener, 10 parts of fire retardant, 5 parts of fire retarding synergist, enhancing is fine
15 parts of dimension.
20 parts of epoxy resin, 0.15 part of photoinitiator, 5 parts of toughener, 10 parts of fire retardant, 5 parts of fire retarding synergist, enhancing is fine
15 parts of dimension.
As preferred embodiment, the epoxy resin is glycidyl ether type epoxy resin, glycidol esters ring
At least one of oxygen resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin, glycolylurea epoxide resin.
Cycloaliphatic epoxy resin includes 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters, bis- ((3,4- epoxies
Cyclohexyl) methyl) adipate ester, 3,4- epoxycyclohexyl-methyl acrylate, 1,2- epoxy -4- vinyl cyclohexane, 4- second
One such or a variety of mixing such as alkenyl -1- cyclohexene dicyclic oxide, dicyclopentadiene dicyclic oxide.Glycidol
Ether epoxy resin includes bis-phenol A glycidyl ether epoxy resin, hydrogenated bisphenol A diglycidyl ether epoxy resin, Bisphenol F shrink
Glycerin ether epoxy resin, resorcinol tetraglycidel ether epoxy resin, line style novolac glycidyl ethers epoxy resin, bisphenol S contracting
At least one of water glycerin ether epoxy resin, bisphenol-A D tetraglycidel ether epoxy resin etc..Ethylene oxidic ester epoxy resin packet
Tetrahydrophthalic acid bisglycidyl ester, hexamethylene-1,2- dicarboxylic acids 2-glycidyl ester, 7-oxa-bicyclo[4.1.0-1 4,5- are included,
At least one of 2- dicarboxylic acid diglycidyl ester.Glycidyl amine epoxy resin includes 4.4- diaminodiphenylmethane four
At least one of glycidyl amine (TGDDM), triglycidyl group para-aminophenol (TGPAP).Glycolylurea epoxide resin is point
Contain a kind of glycidyl amine type epoxy resin of glycolylurea ring (five yuan of diazacyclos), most commonly dimethyl sea in minor structure
Because of epoxy resin.
As preferred embodiment, the photoinitiator is at least one of salt compounded of iodine, sulfosalt, luxuriant molysite.
As preferred embodiment, the toughener is epoxidation end hydroxy butadiene, end hydroxy butadiene third
At least one of alkene nitrile, end hydroxy butadiene, hydroxyl terminated butyl nitrile (HTBN) rubber.Epoxidation terminal hydroxy liquid polybutadiene, English
Text is abbreviated as EHTPB, is to introduce epoxy group in end hydroxy butadiene macromolecular, not only effectively improves macromolecular pole
Property, and the epoxy group introduced is as reactive functional groups, can with generated in cross linking of epoxy resin solidification process it is active
Further crosslinking occurs for hydrogen, improves the mechanical property of epoxy resin cured product, adhesive strength and heat resistance.In addition, because introducing ring
Oxygen groups make directly mix with epoxy resin under toughener EHTPB room temperature, just have without pre-reaction extraordinary compatible
Property.
Hydroxyl terminated butadiene acrylonitrile copolymer, english abbreviation HTBN, due to introducing itrile group, thus butyronitrile hydroxyl liquid in strand
Body rubber other than the general characteristic with end hydroxy butadiene, also have good oil resistivity, cementability, resistance to ag(e)ing,
Resistance to low temperature.Hydroxyl terminated butadiene acrylonitrile copolymer, which is mainly reacted using terminal hydroxy group characteristic with molecule bifunctional, carries out chain
Extension, and then be crosslinked, generate flexible long-chain polymer.
Terminal hydroxy liquid polybutadiene, english abbreviation HTPB are a kind of liquid telechelic polymer, are a kind of new liquids
Rubber.The solidfied material of three-dimensional net structure can be generated in reaction.The solidfied material has excellent mechanical property, especially has water-fast
Solution, acid and alkali-resistance, wear-resisting, low temperature resistant and excellent electrical insulating property.
Carboxyl end group liquid nitrile rubber, english abbreviation CTBN, the both ends of strand are active function groups carboxyls, are passed through
Carboxyl reacts with epoxy resin, to realize the modification to epoxy resin, toughening modifying significant effect.At certain opposite point
Within the scope of protonatomic mass, the relative molecular mass of CTBN is bigger, and toughening effect is better.
As preferred embodiment, the fire retardant is phosphate, DOPO type phosphorous epoxy resin, melamine phosphorus
At least one of hydrochlorate, ammonium polyphosphate, melamine cyanurate, hypo-aluminum orthophosphate, calcium hypophosphite, sodium hypophosphite.It can manage
Solution, DOPO type phosphorous epoxy resin is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified epoxy.
Phosphate is applied in epoxy resin, has good compatibility and can reduce resin viscosity, so that resin system
Good to the wellability of fiber, simultaneously because phosphate high-purity, the transparency, when exclusive use, can make anti-flaming transparent asphalt mixtures modified by epoxy resin
Resin system promotes the translucency of resin, improves curing rate.Phosphate flame retardant may is that (english abbreviation is triethyl phosphate
TEP), tributyl phosphate (english abbreviation TBP), tricresyl phosphate (butoxyethyl group) ester (english abbreviation TBEP), tricresyl phosphate are different
(english abbreviation is for propyl phenyl ester (english abbreviation IPPP), di (isooctyl) phosphate (english abbreviation P204), triphenyl phosphate
TPP), triphenyl phosphite (english abbreviation TPP), tricresyl phosphate (english abbreviation TCP), trimethyl phosphate (English
Be abbreviated as TMP), one benzene diisodecyl ester (english abbreviation PDDP) of phosphorous acid, (english abbreviation is one isodecyl ester of phosphorous acid hexichol
DPDP), diisooctyl phenyl phosphite (english abbreviation PDOP), diisooctyl phenyl phosphite (english abbreviation PDOP),
At least one in the different monooctyl ester (english abbreviation DPOP) of phosphorous acid hexichol one, one benzene diisodecyl ester (english abbreviation PDDP) of phosphorous acid
Kind.
DOPO is new flame retardant intermediate, and P-H key is contained in structure, to alkene, epoxy bond and the great activity of carbonyl,
It can react and generate many derivatives.DOPO and its derivative are due to containing cyclohexyl biphenyl and phenanthrene ring structure in molecular structure, especially
Side phosphorus group is introduced in a manner of cyclic annular O=P-O key, than general, cyclic organophosphorus ester thermal stability and chemistry be not steady
Qualitative height, flame retardant property are more preferable.DOPO and DOPO and the derivative of epoxy resin pre-reaction can be used as response type and additive flame
Agent is fired, it is the fire retardant Halogen of synthesis, smokeless, nontoxic, it does not migrate, flame retardant property is lasting.When this kind of epoxy resin is ignited,
The oxyacid for generating phosphorus is decomposed, this kind of acid can be catalyzed hydroxy-containing compounds generation heat absorption and be dehydrated into carbon reaction, water and coke are generated,
Hydroxy-containing compounds charing the result is that in its Surface Creation graphite-like coke layer, the layer of charcoal is fire retardant, heat-insulated, oxygen barrier.Meanwhile by
In the poor thermal conductivity of coke layer, reduce the heat for being transferred to substrate, substrate thermal decomposition slows down.In addition, hydroxy compounds is de-
The water system endothermic reaction, and the water vapour for being dehydrated formation can dilute the concentration of oxygen and imflammable gas in atmosphere again, facilitate
Interrupt burning.Phosphoric acid further can also form polyphosphoric acid by dehydration esterification, and polyphosphoric acid is a glassy molten mass, is covered in burning
Body surface, prevents oxygen close and volatile materials release is to prevent to burn.In one embodiment of the present of invention, DOPO is used
When by DOPO and epichlorohydrin reaction, then reacted with hydroquinone, be added in epoxy resin the formation phosphorous resistance of response type
Agent is fired, there is low volatility, low pollution has good intermiscibility with epoxy resin, and it is saturating to form reaction-type flame-retarding after addition
Ming tree resin system, does not influence translucency, maintains the good mechanical property of resin system admittedly since fire retardant participates in reaction.
Melamine phosphate is a kind of expansion type flame retardant of Nitrogen-and Phosphorus-containing structure.Under the fire retardant high temperature (such as 300
Degree) decompose the phosphoric acid that releases and can form the covering effect of protective film on the surface of combustible polymers, reduce oxygen into
Enter.Meet different flame retardant ratings to nitrogen by adjusting the fire-retardant intramolecular N content of monomer and phosphorus content using nitrogen phosphorus cooperative flame retardant
With the requirement of the different content of phosphorus.Melamine phosphate halogen type fire retardant different from the past, it is processed in epoxy resin
It is corrosion-free to equipment and mold in journey；Fine and close expansion carbon-coating is generated when burning and reaches the fire-retardant performance of heat-insulated isolation air, no
Irritant hydrogen halide and burning black smoke can be generated, is a kind of fire retardant of ideal environment-friendly type.
Ammonium polyphosphate is also known as ammonium polyphosphate or polycondensation ammonium phosphate (abbreviation APP), is a kind of Quadrafos containing N and P.Its
Contain two kinds of phosphorus, nitrogen elements in molecule simultaneously, during fire-retardant, phosphorus, nitrogen have cooperative flame retardant effect, thus flame retardant effect is excellent
In single phosphonium flame retardant or single nitrogenous flame ratardant.Ammonium polyphosphate is added in epoxy resin with phosphorus content is big, nitrogen content is high, hot
Stability is good, hygroscopicity is small, good dispersion, toxicity is low, presses down the features such as cigarette.
Melamine cyanurate (MCA) is a kind of nitrogenous efficient halogen-free environmental protection fire retarding agent.When 300 DEG C or less heated
Highly stable, 350 DEG C or so start to distil, and about 440~450 DEG C of whens start to decompose.Nitrogen content is high, and when high temperature is dehydrated into charcoal, fires
Nitrogen, carbon dioxide and water are discharged when burning.Its fire retardant mechanism are as follows: distillation heat absorption and gas phase are fire-retardant.
Hypo-aluminum orthophosphate, calcium hypophosphite and sodium hypophosphite fire retardant are the fire retardant novel as one kind of base using phosphate, tool
There is higher thermal stability, there is preferable mechanical performance and preferable anti-marquis's property in process, contain phosphatic ring
Higher anti-flammability is presented in epoxy resin composition, since phosphate phosphorus content is high, heat liberation rate, heat release rate and the heat generated when burning after addition
Amount is sharply reduced, and the neat coal amout after burning increases, and has many advantages, such as that thermal stability is good, water solubility is small, antiflaming effect is big, Neng Gouqu
Obtain very high flame retardant effect.
As preferred embodiment, the fire retarding synergist is zinc borate, triazine carbon forming agent, magnesium hydroxide, hydrogen-oxygen
Change at least one of aluminium.Triazine carbon forming agent is mainly used for the charcoal source of halogen-free expansion fire retardant.With traditional Pentaerythritols
Carbon forming agent is compared, and water solubility is extremely low, is not migrated, and carbon-forming performance is excellent, can be with other additive compounds at halogen-free expanded flame-retardant
Agent.
As preferred embodiment, the reinforcing fiber be glass fibre, basalt fibre, carbon fiber, aramid fiber,
At least one of nylon fiber, polyphenylene sulfide fibre, ultra high molecular weight polyethylene fiber, polyimide fiber.It is understood that
, reinforcing fiber refers to by glass fibre, basalt fibre, carbon fiber, aramid fiber, nylon fiber, polyphenylene sulfide fibre, surpasses
Chopped strand yarn made by least one of high molecular weight polyethylene fiber, polyimide fiber etc., continuous fiber yarn, fibre
Tie up at least one of woven cloth, fibrofelt and surface felt.
The present invention also provides a kind of preparation methods of fibre reinforced composites as described above, include the following steps:
The ratio investment reaction in parts by weight of epoxy resin, photoinitiator, toughener, fire retardant and fire retarding synergist is held
In device, the first preset time is stirred under the conditions of preset rotation speed to being uniformly mixed, obtains the first intermediate, the preset rotation speed is
2000~5000 revs/min, first preset time is 15~45 minutes；
The reinforcing fiber and first intermediate are subjected to the second preset time of dipping, obtain the second intermediate, institute
Stating the second preset time is 5~20 minutes；
Second intermediate is placed under ultraviolet light and irradiates, solidify, obtains the fibre reinforced composites.
As preferred embodiment, the preset rotation speed is 2500~3500 revs/min, and first preset time is
30 minutes.Second preset time is 8 minutes.
Embodiment 1
The fibre reinforced composites of the embodiment include the component of following parts by weight: bis-phenol A glycidyl ether
15 parts of epoxy resin (E51), 3,4- 5 parts of epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters (2021P), 4,4- diformazans
Base -0.15 part of hexafluorophosphoric acid of diphenyl iodine father-in-law, 5 parts of epoxidation terminal hydroxy liquid polybutadiene (EHTPB), the phosphorous epoxy of DOPO type
10 parts of resin, 5 parts of melamine cyanurate (MCA), 15 parts of glass fibre.
The fibre reinforced composites of the present embodiment the preparation method is as follows: by bis-phenol A glycidyl ether epoxy resin, 3,
4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters, 4,4- dimethyl diphenyl iodine father-in-law hexafluorophosphoric acid, epoxidation end
Liquid hydroxyl polybutadiene, DOPO type phosphorous epoxy resin, melamine cyanurate ratio investment in parts by weight have disk
In the mixing vessel of formula high speed disperser blender, 30 minutes are stirred under the conditions of 3000 revs/min to being uniformly mixed, obtains the
One intermediate.The glass fibre and first intermediate are carried out dipping 8 minutes by ratio in parts by weight, are obtained in second
Mesosome.Extra resin is squeezed out after second intermediate is taken out to drain, and is irradiated, is solidified under ultraviolet light, obtains the fibre
Dimension enhancing composite material.
Embodiment 2
The fibre reinforced composites of the embodiment include the component of following parts by weight: 4.4- diamino hexichol first
20 parts of four glycidyl amine of alkane (TGDDM), 3,4- 20 parts of epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters (2021P),
0.45 part of triphenyl sulfosalt, 5 parts of hydroxyl terminated butyl nitrile (HTBN) rubber (CTBN), 5 parts of phosphate, 5 parts of ammonium polyphosphate, hypo-aluminum orthophosphate
5 parts, 15 parts of basalt fibre.
The fibre reinforced composites of the present embodiment the preparation method is as follows: 4.4- diaminodiphenylmethane four is shunk sweet
Oleyl amine, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters, triphenyl sulfosalt ratio in parts by weight put into band
In the mixing vessel for having disc type high speed disperser blender, then in parts by weight ratio investment hydroxyl terminated butyl nitrile (HTBN) rubber,
Phosphate, ammonium polyphosphate, hypo-aluminum orthophosphate stir 30 minutes to being uniformly mixed under the conditions of 3000 revs/min, obtain among first
Body.The basalt fibre and first intermediate are carried out dipping 8 minutes by ratio in parts by weight, are obtained among second
Body.Extra resin is squeezed out after second intermediate is taken out to drain, and is irradiated, is solidified under ultraviolet light, obtains the fiber
Enhance composite material.
Embodiment 3
The fibre reinforced composites of the embodiment include the component of following parts by weight: 3,4- epoxycyclohexyl first
20 parts of base -3,4- epoxycyclohexyl formic acid esters (2021P), poly- [(2- Oxyranyle) -1,2- cyclohexanediol] 2- ethyl -2-
(3150) 30 parts of (methylol) -1,3-PD ether (3:1), 0.33 part of diphenyl iodine hexafluorophosphate, terminal hydroxy group polybutadiene
5 parts of alkene acrylonitrile, 5 parts of ammonium polyphosphate, 5 parts of melamine cyanurate, 5 parts of aluminium hydroxide, 15 parts of carbon fiber.
The fibre reinforced composites of the present embodiment the preparation method is as follows: by 3,4- epoxycyclohexyl-methyl -3,4- ring
Oxygen hexahydrobenzoid acid ester (2021P), poly- [(2- Oxyranyle) -1,2- cyclohexanediol] 2- ethyl -2- (methylol) -1,3- third
Glycol ethers (3:1) (3150), diphenyl iodine hexafluorophosphate ratio investment in parts by weight are stirred with disc type high speed disperser
It mixes in the mixing vessel of device, ratio adds hydroxyl terminated butadiene acrylonitrile copolymer, ammonium polyphosphate, melamine cyanogen in parts by weight
Lithate, aluminium hydroxide stir 30 minutes to being uniformly mixed under the conditions of 3000 revs/min, obtain the first intermediate.By weight
The carbon fiber and first intermediate are carried out dipping 8 minutes by number ratio, obtain the second intermediate.It will be in described second
Mesosome squeezes out extra resin after taking out and drains, and irradiates, solidifies under ultraviolet light, obtains the fibre reinforced composites.
Embodiment 4
The fibre reinforced composites of the embodiment include the component of following parts by weight: 4,5- 7-oxa-bicyclo[4.1.0-
1,2- (186) 10 parts of dicarboxylic acid diglycidyl ester, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters
10 parts of (2021P), 0.15 part of triphenyl sulfosalt, 5 parts of epoxidation terminal hydroxy liquid polybutadiene (EHTPB), ammonium polyphosphate 5
Part, 5 parts of melamine polyphosphate, 5 parts of magnesium hydroxide, 15 parts of aramid fiber.
The fibre reinforced composites of the present embodiment the preparation method is as follows: by 4,5- 7-oxa-bicyclo[4.1.0-1,2- dioctyl phthalate
2-glycidyl ester (186), 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters (2021P), triphenyl sulfosalt
Ratio investment is in the mixing vessel of disc type high speed disperser blender in parts by weight, and ratio adds ring in parts by weight
Aoxidize terminal hydroxy liquid polybutadiene (EHTPB), 5 parts of ammonium polyphosphate, melamine polyphosphate, magnesium hydroxide, 3000 turns/
30 minutes are stirred under the conditions of minute to being uniformly mixed, and obtain the first intermediate.In parts by weight ratio by the aramid fiber with
First intermediate carries out dipping 8 minutes, obtains the second intermediate.Extra tree is squeezed out after second intermediate is taken out
Rouge drains, and irradiates, solidifies under ultraviolet light, obtains the fibre reinforced composites.
Embodiment 5
The fibre reinforced composites of the embodiment include the component of following parts by weight: glycolylurea epoxide resin 10
Part, 3,4- 10 parts of epoxycyclohexyl-methyl -3,4- epoxycyclohexyl formic acid esters (2021P), diphenyl iodine hexafluorophosphate 0.1
Part, diphenyl-(4- phenyl sulphur) 0.05 part of phenyl sulfonium hexafluorophosphate, 5 parts of hydroxyl terminated butyl nitrile (HTBN) rubber (CTBN) and DOPO
5 parts of type phosphorous epoxy resin, 5 parts of ammonium polyphosphate (APP), 5 parts of zinc borate, 15 parts of nylon fiber.
The fibre reinforced composites of the present embodiment the preparation method is as follows: by glycolylurea epoxide resin, 3,4- epoxy hexamethylene
Ylmethyl -3,4- epoxycyclohexyl formic acid esters (2021P), diphenyl iodine hexafluorophosphate, diphenyl-(4- phenyl sulphur) phenyl
Sulfonium hexafluorophosphate ratio investment in parts by weight is in the mixing vessel of disc type high speed disperser blender.In parts by weight
Ratio puts into hydroxyl terminated butyl nitrile (HTBN) rubber (CTBN) and DOPO type phosphorous epoxy resin again, ammonium polyphosphate (APP), zinc borate,
30 minutes are stirred under the conditions of 3000 revs/min to being uniformly mixed, and obtain the first intermediate.Ratio in parts by weight is by the Buddhist nun
Imperial fiber and first intermediate carry out dipping 8 minutes, obtain the second intermediate.It is squeezed out after second intermediate is taken out
Extra resin drains, and irradiates, solidifies under ultraviolet light, obtains the fibre reinforced composites.
Embodiment 6
The fibre reinforced composites of the embodiment include the component of following parts by weight: 3,4- epoxycyclohexyl first
10 parts of base -3,4- epoxycyclohexyl formic acid esters (2021P), four glycidyl amine of 4.4- diaminodiphenylmethane (TGDDM) AG80
5 parts, (128) 5 parts of bis-phenol A glycidyl ether epoxy resin, 0.3 part of triphenyl sulfosalt and diphenyl-(4- phenyl sulphur) phenyl
0.5 part of sulfonium hexafluorophosphate, 5 parts of epoxidation terminal hydroxy liquid polybutadiene (EHTPB), 5 parts of ammonium polyphosphate (APP), melamine
5 parts of amine cyanurate (MCA), 3 parts of sodium hypophosphite, 2 parts of triazine carbon forming agent, 15 parts of ultra high molecular weight polyethylene fiber.
The fibre reinforced composites of the present embodiment the preparation method is as follows: by 3,4- epoxycyclohexyl-methyl -3,4- ring
Oxygen hexahydrobenzoid acid ester (2021P), four glycidyl amine of 4.4- diaminodiphenylmethane (TGDDM) AG80, bisphenol-A glycidol
Ether epoxy resin (128), triphenyl sulfosalt and diphenyl-(4- phenyl sulphur) phenyl sulfonium hexafluorophosphate ratio in parts by weight
Investment is in the mixing vessel of disc type high speed disperser blender, and ratio adds epoxidation terminal hydroxy liquid in parts by weight
Polybutadiene (EHTPB), ammonium polyphosphate (APP), melamine cyanurate (MCA), sodium hypophosphite, triazine carbon forming agent,
30 minutes are stirred under the conditions of 3000 revs/min to being uniformly mixed, and obtain the first intermediate.Ratio in parts by weight is by the superelevation
Molecular weight polyethylene fiber and first intermediate carry out dipping 8 minutes, obtain the second intermediate.By second intermediate
Extra resin is squeezed out after taking-up to drain, and is irradiated, is solidified under ultraviolet light, obtains the fibre reinforced composites.
Comparative example
The fibre reinforced composites of the embodiment include the component of following parts by weight: bis-phenol A glycidyl ether
(128) 30 parts of epoxy resin, (6110) 10 parts of cycloaliphatic epoxy resin, 0.3 part of triphenyl sulfosalt, 10 parts of phosphate, hydrogen-oxygen
Change 5 parts of aluminium, 15 parts of carbon fiber.
The fibre reinforced composites of the present embodiment the preparation method is as follows: by bis-phenol A glycidyl ether epoxy resin
(128), cycloaliphatic epoxy resin (6110), triphenyl sulfosalt ratio investment in parts by weight are stirred with disc type high speed disperser
It mixes in the mixing vessel of device, ratio adds phosphate, aluminium hydroxide in parts by weight, stirs under the conditions of 3000 revs/min
To being uniformly mixed, the first intermediate is obtained within 30 minutes.In parts by weight ratio by the carbon fiber and first intermediate into
Row dipping 8 minutes, obtains the second intermediate.It squeezes out extra resin after second intermediate is taken out to drain, in ultraviolet light
Lower irradiation, solidification, obtain the fibre reinforced composites.
According to GBT 1449-2005 fibre reinforced plastics bending property test method come in embodiment 1-6 and comparative example
Bending property is tested.The comprehensive performance of embodiment 1-6 and the fibre reinforced composites in comparative example is shown in Table 1.
Table 1 is embodiment 1-6 and the all-round property testing data of the dimension enhancing composite material of comparative example
| Sample number into spectrum | 1 | 2 | 3 | 4 | 5 | 6 | Comparative example |
| Curing time (min) | 30 | 20 | 20 | 15 | 15 | 15 | 20 |
| Elongation at break | 3.3% | 3.5% | 3.6% | 3.8% | 3.2% | 3.5% | 2% |
| Tensile strength | 69 | 68 | 67 | 65 | 65 | 69 | 52 |
| Impact strength | 65 | 67 | 69 | 68 | 66 | 70 | 59 |
| Bending strength | 130 | 135 | 132 | 130 | 124 | 128 | 105 |
| Bending modulus | 6.3 | 6.6 | 6.2 | 7.1 | 5.8 | 6.5 | 5.8 |
| Anti-flammability | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
As can be seen from the above table, the comprehensive performance of the fibre reinforced composites of embodiment 1-6 is apparently higher than comparative example, table
Reveal preferable mechanical property and flame retardant property.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of fibre reinforced composites, which is characterized in that the component including following parts by weight:
10~50 parts of epoxy resin；
0.1~2 part of photoinitiator；
5~10 parts of toughener；
10~25 parts of fire retardant；
0~15 part of fire retarding synergist；
15~35 parts of reinforcing fiber.
2. fibre reinforced composites as described in claim 1, which is characterized in that the component including following parts by weight: ring
20 parts of oxygen resin, 0.15 part of photoinitiator, 5 parts of toughener, 15 parts of fire retardant, 15 parts of reinforcing fiber；Alternatively,
40 parts of epoxy resin, 0.45 part of photoinitiator, 5 parts of toughener, 15 parts of fire retardant, 15 parts of reinforcing fiber；Alternatively,
30 parts of epoxy resin, 0.33 part of photoinitiator, 5 parts of toughener, 10 parts of fire retardant, 5 parts of fire retarding synergist, reinforcing fiber 15
Part；Alternatively,
20 parts of epoxy resin, 0.15 part of photoinitiator, 5 parts of toughener, 10 parts of fire retardant, 5 parts of fire retarding synergist, reinforcing fiber 15
Part.
3. fibre reinforced composites as claimed in claim 1 or 2, which is characterized in that the epoxy resin is glycidol
Ether type epoxy resins, glycidyl ester epoxy resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin, glycolylurea ring
At least one of oxygen resin.
4. fibre reinforced composites as claimed in claim 1 or 2, which is characterized in that the photoinitiator is salt compounded of iodine, sulphur
At least one of salt, luxuriant molysite.
5. fibre reinforced composites as claimed in claim 1 or 2, which is characterized in that the toughener is epoxidation end hydroxyl
At least one of base polybutadiene, hydroxyl terminated butadiene acrylonitrile copolymer, end hydroxy butadiene, hydroxyl terminated butyl nitrile (HTBN) rubber.
6. fibre reinforced composites as claimed in claim 1 or 2, which is characterized in that the fire retardant be phosphate,
DOPO type phosphorous epoxy resin, melamine phosphate, ammonium polyphosphate, melamine cyanurate, hypo-aluminum orthophosphate, hypophosphorous acid
At least one of calcium, sodium hypophosphite.
7. fibre reinforced composites as claimed in claim 1 or 2, which is characterized in that the fire retarding synergist is boric acid
At least one of zinc, triazine carbon forming agent, magnesium hydroxide, aluminium hydroxide.
8. fibre reinforced composites as claimed in claim 1 or 2, which is characterized in that the reinforcing fiber be glass fibre,
Basalt fibre, carbon fiber, aramid fiber, nylon fiber, polyphenylene sulfide fibre, ultra high molecular weight polyethylene fiber, polyamides are sub-
At least one of amine fiber.
9. a kind of preparation method of the fibre reinforced composites as described in claim any one of 1-8, which is characterized in that including such as
Lower step:
Epoxy resin, photoinitiator, toughener, fire retardant and fire retarding synergist ratio in parts by weight are put into reaction vessel
It is interior, the first preset time is stirred under the conditions of preset rotation speed to being uniformly mixed, and obtains the first intermediate, the preset rotation speed is
2000~5000 revs/min, first preset time is 15~45 minutes；
The reinforcing fiber and first intermediate are subjected to the second preset time of dipping, obtain the second intermediate, described the
Two preset times are 5~20 minutes；
Second intermediate is placed under ultraviolet light and irradiates, solidify, obtains the fibre reinforced composites.
10. the preparation method of fibre reinforced composites as claimed in claim 9, which is characterized in that the preset rotation speed is
2500~3500 revs/min, first preset time is 30 minutes；And/or
Second preset time is 8 minutes.
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| CN110540707A (en) * | 2019-09-14 | 2019-12-06 | 福建师范大学 | Multi-element flame-retardant polypropylene material and preparation method thereof |
| CN110713697A (en) * | 2019-09-26 | 2020-01-21 | 江苏恒神股份有限公司 | OoA process prepreg meeting EN45545 flame-retardant standard |
| CN114957919A (en) * | 2022-06-13 | 2022-08-30 | 广州睿洁科技有限公司 | High-reflection heat-insulation glass fiber reinforced plastic and preparation method thereof |
| CN115011018A (en) * | 2022-06-23 | 2022-09-06 | 青岛优派普环保科技股份有限公司 | PE gas pipe and preparation method thereof |
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