CN109912954A - A kind of unsaturated-resin-glass fibre-graphene composite material and preparation method thereof - Google Patents
A kind of unsaturated-resin-glass fibre-graphene composite material and preparation method thereof Download PDFInfo
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- CN109912954A CN109912954A CN201910226328.8A CN201910226328A CN109912954A CN 109912954 A CN109912954 A CN 109912954A CN 201910226328 A CN201910226328 A CN 201910226328A CN 109912954 A CN109912954 A CN 109912954A
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Abstract
The invention belongs to resin materials to prepare technical field, and in particular to a kind of unsaturated-resin-glass fibre-graphene composite material and preparation method thereof.Graphene and glass fibre are used cooperatively by the present invention, for promoting the wearability of unsaturated-resin material.Embodiment also indicates that composite material described in above scheme uses DIN abrasion machine, is 0.2~0.5mm by GB9867-88 standard testing attrition value3, the liquid of resistance to petroleum industry conveying abrasion, can be used as transport pipeline or tank body prepares material.
Description
Technical field
The invention belongs to resin materials to prepare technical field, and in particular to a kind of unsaturated-resin-glass fibre-graphene
Composite material and preparation method.
Background technique
Unsaturated-resin refers to the high score containing unsaturated double-bond generated by binary acid and dihydric alcohol through polycondensation reaction
Sub- compound, such compound have preferable heat resistance, higher tensile strength, compressive strength and bending strength, simultaneously
Also there is excellent water-fast, acid-proof alkaline, be a kind of widely used high molecular material.It is continuous with industrial technology
Development, every field need to be continuously improved to the performance of material, for this purpose, researcher carries out unsaturated-resin using fibrous material
Performance improvement, and small, the higher composite material of intensity with density has been obtained, but the wear-resisting property of composite material is undesirable, shadow
The service life of composite material is rung.
Summary of the invention
The purpose of the present invention is to provide a kind of unsaturated-resin-glass fibre-graphene composite material and its preparation sides
Method, unsaturated-resin composite material provided by the invention have excellent wear-resisting property, and service life is longer, can be used as petroleum fortune
Defeated pipeline material or tank body materials'use.
To achieve the goals above, the invention provides the following technical scheme:
The present invention provides a kind of unsaturated-resin-glass fibre-graphene composite material, the group including following mass parts
Point: 100 parts of unsaturated-resin matrix, 0.1~0.3 part of graphene and 10~20 parts of glass fibre.
Preferably, the graphene includes modified graphene or redox graphene；
The modified graphene changes graphene raw material by dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane
Property obtains.
Preferably, the preparation method of the modified graphene includes:
Graphene raw material, dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane are mixed, mixture is obtained；
The mixture is successively carried out to ultrasonic mixing, stands heat preservation, cooling, separation and drying, obtains modified graphene.
Preferably, the glass fibre is obtained by glass fibre raw material by roughening treatment and/or sensitization-activation processing.
Preferably, the roughening treatment coarsening solution includes sodium hydroxide solution, and the temperature of roughening treatment is 50~65 DEG C,
The time of roughening treatment is 25~35min.
Preferably, the sensitization-activation processing sensitizing solution includes SnCl2Solution, the temperature of sensitization is 30~40 DEG C, quick
The time of change is 15~25min.
Preferably, the sensitization-activation processing activating solution includes PdCl2Solution, the temperature of activation is 25~35 DEG C, living
The time of change is 15~25min.
The present invention also provides unsaturated-resin described in above-mentioned technical proposal-glass fibre-graphene composite material systems
Preparation Method, comprising the following steps:
(1) the mixing melt that raw material and graphene are prepared including unsaturated-resin matrix is provided；
(2) the mixing melt of the step (1) is mixed with glass fibre, obtains pouring material；
(3) pouring material of the step (2) is successively poured and is solidified, obtain unsaturated-resin-glass fibre-stone
Black alkene composite material.
Preferably, in the step (1), when graphene is modified graphene, the preparation method for mixing melt includes:
Unsaturated-resin matrix is prepared into raw material mixed melting, obtains resin melt；
The resin melt is mixed with modified graphene dispersion liquid, obtains mixing melt.
Preferably, in the step (1), when graphene is redox graphene, the preparation method for mixing melt includes:
Prepare raw material, propylene glycol monomethyl ether, diethanol amine, acetum and the water of unsaturated-resin matrix are mixed, obtained
Resin melt containing reducing agent；
The resin melt containing reducing agent is mixed with graphene oxide, mixing melt is obtained after heat preservation.
Unsaturated-resin-glass fibre-graphene composite material provided by the invention, the component including following mass parts:
100 parts of unsaturated-resin matrix, 0.1~0.3 part of graphene and 10~20 parts of glass fibre.The present invention is with graphene and glass fibers
Dimension is composite fortifier, promotes the wear-resisting energy of unsaturated-resin composite material.Embodiment the result shows that, insatiable hunger provided by the invention
DIN abrasion machine is utilized with resin-glass fibre-graphene composite material, by its wearability of GB9867-88 standard testing, abrasion
Value is 0.2~0.5mm3。
Specific embodiment
The present invention provides a kind of unsaturated-resin-glass fibre-graphene composite material, the group including following mass parts
Point: 100 parts of unsaturated-resin matrix, 0.1~0.3 part of graphene and 10~20 parts of glass fibre.
In terms of mass parts, unsaturated-resin-glass fibre-graphene composite material provided by the invention includes unsaturated tree
100 parts of aliphatic radical body.In the present invention, the unsaturated-resin matrix prepare raw material preferably include unsaturated-resin, UV resin,
Initiator, polymerization inhibitor and fire retardant, the unsaturated-resin, UV resin, initiator, the mass ratio of polymerization inhibitor and fire retardant are preferred
It is 100: (13~16): (1.5~3): (0.4~0.6): (2~3), more preferably 100: (14~15): (2~2.5): (0.4
~0.5): (2~2.5) are further preferably 100: 13: 2.5: 0.5: 2.5.
In the present invention, the unsaturated-resin preferably includes bisphenol A-type polyester resin, and the UV resin is preferably the trade mark
For 9893 UV resin；The initiator preferably includes peroxidized t-butyl perbenzoate；The polymerization inhibitor preferably includes 1,4-benzoquinone；
The fire retardant preferably includes magnesia.The present invention is to the unsaturated-resin, UV resin, initiator, polymerization inhibitor and fire retardant
Source there is no particular/special requirement, using commercial product well known to those skilled in the art.
In the present invention, the initiator can promote the cross-linking and curing reaction of unsaturated-resin, form macromolecular structure
Material, and polymerization inhibitor can then stop the polymerization of unsaturated-resin, prevent unsaturated-resin from excessively polymerizeing, and the two is with cooperation
Condition is provided with to obtain the heat-resisting preferable and higher unsaturated-resin composite material of intensity.The present invention utilizes fire retardant, is promoted
The flame retardant property of composite material, to ensure safety that composite material uses.
On the basis of 100 mass parts of the unsaturated-resin matrix, unsaturated-resin-glass fibers provided by the invention
Dimension-graphene composite material includes 0.1~0.3 part of graphene, preferably 0.12~0.25 part, is further preferably 0.15~0.20
Part.In the present invention, the graphene preferably includes modified graphene or redox graphene.
In the present invention, the modified graphene is preferably by dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane
Graphene raw material modification is obtained.The present invention is preferably by dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane to stone
Black alkene raw material is modified, and improves the compatibility of graphene and unsaturated-resin matrix, graphene is evenly distributed on not
In saturated resin matrix.
In the present invention, the preparation method of the modified graphene preferably includes:
Graphene raw material, dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane are mixed, mixture is obtained；
The mixture is successively carried out to ultrasonic mixing, stands heat preservation, cooling, separation and drying, obtains modified graphene.
The present invention preferably mixes graphene raw material, dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane, obtains
To mixture.In the present invention, 2 μm of the preferred < of the diameter of the graphene raw material, more preferably 0.1~1.5 μm；The graphite
The thickness of alkene raw material is preferably 1~5nm, more preferably 2~3nm, and the specific surface area of the graphene raw material is preferably 400~
500m2/ g, more preferably 450~500m2/g；The density of the graphene raw material is preferably 2~2.25g/cm3；The graphene
The preferred > 3000W/mK of the thermal coefficient of raw material, the preferred > 10 of the electric conductivity of the graphene raw material7S/m。
In the present invention, the graphene raw material, the matter of dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane
Amount is than preferably 1: (0.4~0.5): (400~500), more preferably 1: 0.5: (450~500).
After obtaining mixture, the present invention preferably carries out ultrasonic mixing to the mixture, and the power of the ultrasonic mixing is excellent
It is selected as 80~120kW, more preferably 100~105kW；The time of the ultrasonic mixing is preferably 1~1.5h, more preferably 1~
1.2h。
After ultrasonic mixing, the present invention preferably carries out standing heat preservation to the material after ultrasonic mixing, so that mixed material is abundant
Contact promotes the graft reaction of dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane on the surface of graphene；It is described quiet
The temperature for setting heat preservation is preferably 70~75 DEG C, and more preferably 72~75 DEG C；The time for standing heat preservation is preferably 20~for 24 hours, it is more excellent
It is selected as 22~for 24 hours.
After standing heat preservation, the present invention preferably cools down the material stood after keeping the temperature, and the mode of the cooling is preferably
Temperature fall；The outlet temperature of the cooling is preferably room temperature.
After cooling, the present invention is preferably separated by solid-liquid separation material after cooling, obtains solid material.In the present invention, institute
The mode for stating separation of solid and liquid is preferably centrifuged.The present invention does not have particular/special requirement to the specific embodiment of the centrifugation, using this
Known to the technical staff of field.
After obtaining solid material, the present invention is preferably dried the solid material, obtains modified graphene.The drying
Mode is preferably dried in vacuo.The present invention does not have particular/special requirement to the vacuum drying specific embodiment, can remove solid
Liquid impurity in material obtains the modified graphene of powdery.
The present invention is modified graphene raw material using dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane,
It can be improved dispersibility of the graphene in unsaturated-resin, to resistance to thermal energy, the intensive properties for improving unsaturated-resin composite material
It can be advantageous with elasticity modulus.
In the present invention, when the graphene is redox graphene, the redox graphene is preferably by aoxidizing
Graphene restores to obtain through propylene glycol monomethyl ether, diethanol amine and acetum.System of the present invention to the redox graphene
Preparation Method does not have particular/special requirement, using well known to those skilled in the art.
On the basis of 100 mass parts of the unsaturated-resin matrix, unsaturated-resin-glass fibers provided by the invention
It includes 10~20 parts of glass fibre, preferably 12~17 parts, more preferably 14~15 that dimension-graphene composite material, which prepares raw material,
Part.In the present invention, the glass fibre preferably includes the component of following mass content: SiO252~57%, Al2O318~
22%, MgO 10~15%, remaining is Na2O and CaO.The present invention does not have particular/special requirement to the size of the glass fibre, uses
It is well known to those skilled in the art.
In the present invention, the glass fibre preferably passes through roughening treatment and/or sensitization-activation by glass fibre raw material
Reason obtains.
In the present invention, the mode of the roughening treatment preferably includes: by glass fibre raw material successively in aqueous acetone solution
It cleans in distilled water, then the glass fibre after cleaning is immersed in coarsening solution, after the completion of immersion, then carried out with distilled water
Cleaning removes coarsening solution.
The present invention first successively cleans glass fibre raw material in aqueous acetone solution and distilled water, to remove glass fibers
The impurity in dimension table face.In the present invention, the mass concentration of the aqueous acetone solution is preferably 35~45%, more preferably 37~
43%, it is further preferably 40%.The present invention does not have particular/special requirement to the dosage of the aqueous acetone solution, and glass fibre raw material can be made to soak
Bubble.In the present invention, the glass fibre raw material impregnates in aqueous acetone solution.In the present invention, glass fibre
The time impregnated in aqueous acetone solution is preferably 15~25min, more preferably 17~23min, is further preferably 20min.This hair
The bright cleaning way to the distilled water does not have particular/special requirement, can remove the remaining aqueous acetone solution of fiberglass surfacing.
After distilled water cleaning, the glass fibre after cleaning is preferably immersed in coarsening solution by the present invention.In the present invention, institute
It states roughening treatment and preferably includes sodium hydroxide solution with coarsening solution, the concentration of the coarsening solution is preferably 35~45g/L, more preferably
It is further preferably 40g/L for 37~43g/L；The temperature of roughening treatment is preferably 50~65 DEG C, and more preferably 53~62 DEG C, then it is excellent
It is selected as 55~60 DEG C；The time of roughening treatment is preferably 25~35min, more preferably 27~33min, is further preferably 30min.
The present invention is preferably by the strong basicity of coarsening solution and the aluminium oxide of fiberglass surfacing and/or aoxidizes pasc reaction, into
And obtain the glass fibre of roughing in surface；So that glass fibre is preferably combined with unsaturated-resin, glass fibre is given full play to
Humidification.
In the present invention, the processing mode of the glass fibre raw material further includes sensitization-activation processing.In the present invention,
The mode of the sensitization-activation processing preferably includes: glass fibre raw material being put into sensitizing solution and is impregnated, is then washed with water；
Glass fibre after cleaning is put into activating solution and is impregnated, then is washed with water, sensitization-activation glass fibre is obtained.The present invention is logical
It is sensitization plays-to be activated, increase the roughness on glass fibre raw material surface, improves the knot between glass fibre and unsaturated-resin
Close intensity.
In the present invention, the sensitization-activation processing preferably includes SnCl with sensitizing solution2Solution, the SnCl2Solution
Concentration is preferably 25~35g/L, more preferably 27~33g/L, is further preferably 30g/L；In the present invention, to keep stannous chloride steady
It is fixed to exist, preferably in SnCl2Hydrochloric acid is added in solution, the dosage of the hydrochloric acid is using dosage well known to those skilled in the art
It can.In the present invention, the temperature of sensitization is preferably 30~40 DEG C, and more preferably 32~37 DEG C, be further preferably 33~35 DEG C；Sensitization
Time be preferably 15~25min, more preferably 17~23 DEG C, be further preferably 18~21 DEG C.
In the present invention, the sensitization-activation processing preferably includes PdCl with activating solution2Solution, the PdCl2Solution
Concentration is preferably 0.05~0.15g/L, more preferably 0.08~0.12g/L, is further preferably 0.1g/L；The temperature of activation is preferably
25~35 DEG C, more preferably 27~32 DEG C are further preferably 30 DEG C；The time of activation is preferably 15~25min, more preferably 17~
23 DEG C, be further preferably 18~21 DEG C.
In the present invention, sensitization-activation processing can improve firmness of the glass fibre in conjunction with other components, make glass fibers
The humidification of dimension can be not fully exerted.
In the present invention, the roughening treatment and sensitization-activation processing can be used alone, and can also be combined；When combination, first will
Glass fibre raw material carries out roughening treatment, then carries out being sensitized-being activated again.
The present invention also provides unsaturated-resin described in above-mentioned technical proposal-glass fibre-graphene composite material systems
Preparation Method, comprising the following steps:
(1) the mixing melt that raw material and graphene are prepared including unsaturated-resin matrix is provided；
(2) the mixing melt of the step (1) is mixed with glass fibre, obtains pouring material；
(3) pouring material of the step (2) is successively poured and is solidified, obtain unsaturated-resin-glass fibre-stone
Black alkene composite material.
The present invention provides the mixing melt that raw material and graphene are prepared including unsaturated-resin matrix.In the present invention, institute
State graphene be modified graphene when, it is described mixing melt preparation method preferably include:
Unsaturated-resin matrix is prepared into raw material mixed melting, obtains resin melt；
The resin melt is mixed with modified graphene dispersion liquid, obtains mixing melt.
The present invention does not have particular/special requirement to the temperature and time of the mixed melting, can obtain resin melt.At this
In invention, the modified graphene dispersion liquid preferably includes modified graphene and acetone, the use of the modified graphene and acetone
Amount is than preferably 0.8~1.2g: 1L, more preferably 1.0~1.2: 1L.In the present invention, the modified graphene dispersion liquid is excellent
It gated and mixed modified graphene with acetone, then carry out ultrasound and obtain.The present invention to the specific implementation parameter of the ultrasound without
Particular/special requirement can make graphene uniform dispersion in acetone.
In the present invention, the mode that the resin melt is mixed with modified graphene dispersion liquid preferably adds resin melt
Enter into modified graphene dispersion liquid.The present invention does not have particular/special requirement to the adding manner of the resin melt, using this field
Known to technical staff.
After mixing, the present invention is preferably stirred mixed material, and to obtain, modified graphene is evenly dispersed to be mixed
Close melt.In the present invention, it is excellent to preferably include the slow stirring and fast stirring, the rate stirred slowly successively carried out for the stirring
It is selected as 200~300r/min, more preferably 220~240r/min；Slowly the time stirred is preferably 10~15min, more preferably
11~13min；The rate stirred fastly is preferably 600~700r/min, more preferably 640~670r/min；It stirs fastly
Time is preferably 20~30min, more preferably 25min.
In the present invention, performance is poured for raising mixing melt, the stirring preferably carries out under conditions of heat preservation.?
In the present invention, the temperature of the heat preservation is preferably 60~65 DEG C, and more preferably 62~64 DEG C.
In the present invention, when the graphene is redox graphene, the preparation method of the mixing melt is preferably wrapped
It includes:
Prepare raw material, propylene glycol monomethyl ether, diethanol amine, acetum and the water of unsaturated-resin matrix are mixed, obtained
Resin melt containing reducing agent；
The resin melt containing reducing agent is mixed with graphene oxide, mixing melt is obtained after heat preservation.
The present invention mixes prepare raw material, propylene glycol monomethyl ether, diethanol amine, acetum and the water of unsaturated-resin matrix
It closes, obtains the resin melt containing reducing agent.In the present invention, the unsaturated-resin matrix prepares raw material, propylene glycol monomethyl ether
Mass ratio with diethanol amine is preferably 50: (20~28): (10~12), more preferably 50: 25: 10.5.In the present invention, institute
The mass concentration for stating acetum is preferably 20~25%, and more preferably 20%；The water is preferably distilled water.The present invention is to institute
The dosage for stating acetum and water does not require, and each component can be made evenly dispersed.
In the present invention, the unsaturated-resin matrix prepares raw material, propylene glycol monomethyl ether, diethanol amine, acetum
Preferably included with the hybrid mode of water: unsaturated-resin matrix first being prepared into raw material heating melting, then by propylene glycol monomethyl ether,
Diethanol amine, acetum and water are successively added in melting charge.In the present invention, the temperature of the melting is preferably 80~85
DEG C, more preferably 80 DEG C；The addition manner of the diethanol amine is preferably added dropwise, and the speed of the dropwise addition is preferably 200~
500g/min, more preferably 350~400g/min.After diethanol amine is added dropwise, melting of the present invention preferably to addition diethanol amine
Material is stirred, and the time of the stirring is preferably 1.5~2h, more preferably 2h.
Before adding acetum, the present invention is preferably by the greenhouse cooling of melting charge to 58~62 DEG C, and more preferably 60 DEG C.?
In the present invention, the addition manner of the acetum is preferably added dropwise, and the speed of the dropwise addition is preferably 200~500g/min,
More preferably 350~400g/min.After acetum is added dropwise, the present invention is preferably stirred the melting charge of addition acetic acid, institute
The time for stating stirring is preferably 25~35min, more preferably 28~32min.
The present invention does not have particular/special requirement to the addition manner of the water, using well known to those skilled in the art.Add
After adding water, the present invention is preferably stirred the melting charge after addition water, to promote the uniform mixing of each component.The present invention is to institute
The speed and time for stating stirring do not have particular/special requirement, using well known to those skilled in the art.
After obtaining the resin melt containing reducing agent, the present invention mixes the resin melt containing reducing agent with graphene oxide
It closes, mixing melt is obtained after heat preservation.The present invention does not have particular/special requirement to the source of the graphene oxide, can be this field skill
Commercial product known to art personnel can also make by oneself to obtain.In embodiments of the present invention, the graphene oxide preferably is selected from obtained
It arrives, the preparation method of the graphene oxide preferably improves Hummers method.
The present invention does not have particular/special requirement to the addition manner of the graphene oxide, and use is well known to those skilled in the art
?.In the present invention, the mixing of the resin melt and graphene oxide containing reducing agent preferably carries out under ultrasound condition,
The frequency of the ultrasound is preferably 80~120kW, more preferably 90~100kW；The time of the ultrasound is preferably 1~1.5h,
More preferably 1~1.2h.In the present invention, the ultrasound preferably carries out under heat-retaining condition, and the temperature of the heat preservation is preferably
60~65 DEG C, more preferably 60~62 DEG C.
After ultrasound, the present invention preferably keeps the temperature the material after ultrasound, so that graphene oxide and propylene glycol monomethyl ether, two
Ethanol amine, acetic acid reaction generate redox graphene.In the present invention, in insulating process, reducing agent in resin melt with
Graphite oxide alkene reaction, and other components in resin melt and it is not involved in redox reaction, thus finally obtain including not
The mixture of saturated resin matrix and graphene.In the present invention, the temperature of the heat preservation is preferably 60~65 DEG C, more preferably
60~62 DEG C；The time of the heat preservation is preferably 3~4h, more preferably 3~3.5h.
After heat preservation, the present invention preferably carries out ultrasound again to the material after heat preservation, to improve the uniformity of material component.Institute
Stating frequency ultrasonic again is preferably 80~120kW, more preferably 90~100kW；Ultrasonic time again is preferably 1~
1.5h, more preferably 1h.
Again after ultrasound, the present invention is preferably filtered the material after ultrasound again, to obtain mixing melt.The present invention
There is no particular/special requirement to the specific embodiment of the filtering, using well known to those skilled in the art.
After obtaining mixing melt, the present invention mixes the mixing melt with glass fibre, obtains pouring material.In the present invention
In, glass fibre is preferably added in mixing melt by the mixing, is then stirred.Specific implementation of the present invention to the stirring
Mode does not have particular/special requirement, and glass fibre can be made to come into full contact with melt is mixed, and obtains the uniform pouring material of component.
After obtaining pouring material, the pouring material is successively poured and is solidified by the present invention, obtains unsaturated-resin-glass
Fiber-graphene composite material.In the present invention, the temperature poured is preferably 55~65 DEG C, and more preferably 57~60 DEG C.
When pouring, the present invention preferably vibrates the pouring material poured to mold, the gas in pouring material is discharged, improves insatiable hunger
With the uniformity of resin composite materials mechanical property.The present invention does not have particular/special requirement to the mode for pouring and vibrating, and uses
It is well known to those skilled in the art.The present invention does not have particular/special requirement with mold to described pour, according to actual needs, selection
The mold of suitable dimension.In embodiments of the present invention, the test sample is preferably dimensioned to be outer diameter 10cm, wall thickness 1cm,
The tubular material of length 50cm.
After pouring, the present invention preferably solidifies the material after pouring, it is described solidify preferably include successively to carry out it is solidifying
Glue, solidification and curing three phases, the time of the gel is preferably 25~35min, more preferably 27~30min.After gel,
Gel masses enter solidification stages, and the time of the solidification stages is preferably 20~for 24 hours, more preferably 22~for 24 hours.After solidification,
The present invention preferably demoulds the material after solidification, is then cured.In the present invention, the time of the curing is preferably
10~25 days, more preferably 15~21 days.
In the present invention, the gel, solidification and curing preferably carry out under normal temperature conditions.In the present invention, described normal
The temperature of temperature is preferably 15~30 DEG C, and more preferably 20~25 DEG C.
In the present invention, in the above specific embodiment, unless otherwise specified, the reagent is those skilled in the art
Well known commercial product.
In order to further illustrate the present invention, below with reference to embodiment to a kind of unsaturated-resin-glass provided by the invention
Fiber-graphene composite material and preparation method thereof is described in detail, but cannot be interpreted as them to protect the present invention
The restriction of range.
Embodiment 1
1 part of graphene raw material, 0.5 part of dicyclohexylcarbodiimide and 500 parts of 3- aminopropyl triethoxysilanes are mixed,
Disperse 5h using ultrasonic disperse machine, kept the temperature at 75 DEG C for 24 hours, is centrifuged after cooling, washing, vacuum drying, obtains modified graphene.
The modified graphene of 0.1g (0.1 part) is added portionwise in the acetone soln of 1L, it is right in Ultrasound Instrument to place it in
Mixed liquor is ultrasonically treated, and graphene dispersing solution is obtained.
Into 90g unsaturated-resin, successively addition accounts for the UV resin of unsaturated-resin quality 15%, accounts for unsaturated-resin matter
The peroxidized t-butyl perbenzoate of amount 2% accounts for the 1,4-benzoquinone of unsaturated-resin quality 0.5% and accounts for unsaturated-resin quality
2.5% MgO, stirring forms melt under heated condition.
Gained melt 100g is added in the dispersion liquid containing 0.1 part of graphene, using blender, in the item of 200r/min
Under part, 15min is mixed slowly, then under conditions of 600r/min, quickly stirs 30min, obtains resin melt, is placed at 60 DEG C
It keeps the temperature spare.
Glass fibre 15g is put into the acetone soln that 50mL mass fraction that temperature is 30 DEG C is 40% and impregnates 20min,
Oil removing wash with distilled water；Glass fibre after oil removing is soaked in the sodium hydroxide roughening solution that 50mL concentration is 40g/L
30min, temperature maintain 60 DEG C, finally clean.
The glass fibre being roughened is put into 50mL sensitizing solution the (SnCl of 30g/L at 35 DEG C2Solution), it impregnates
20min, it is rear to clean；Glass fabric after sensitization is put into activating solution (the 0.1g/L Pd Cl of 50mL2Solution) in, 30
20min is kept in DEG C, finally wash with distilled water, completes the roughening treatment of glass fibre.
The glass fibre of 10g roughing in surface is added in the compound melt of graphene-unsaturated-resin, after mixing evenly,
It pours into mold, bubble is discharged using vibratory drilling method in casting process；After pouring successively by 30min gel, for 24 hours solidification and 20 days
After curing three phases, one is demoulded, and obtains heat-resisting unsaturated-resin composite material.Composite material obtained by the present embodiment is outer diameter
10cm, wall thickness 1cm, the tubular material of length 50cm.
Embodiment 2
Graphene oxide is prepared using Hummers method is improved；3g graphite powder and 1g sodium nitrate are added, the dense sulphur of 69mL is housed
In the three-necked flask of acid, it is slowly added to 12g potassium permanganate under stirring in ice-water bath, in 10 DEG C or less reaction 1h；It is warming up to 35 DEG C
Left and right continues to stir 2h；It is slowly added to 120mL deionized water；Temperature of reaction system is increased to 95 DEG C or so, maintains 30min,
A large amount of distilled water dilutions are added, pour into 30%H2O2It generates to no bubble, filters while hot, and with dilute hydrochloric acid (HCl and water volume
Than being 1: 10) filter cake is washed, until without SO in filtrate4 2-(BaCl2Detection), it is dried to obtain graphite oxide；Graphite oxide is dissolved in
In water, ultrasound 1h, is allowed to be completely dispersed, obtains graphene oxide under 100kW；By graphene oxide with 1: 50 mass ratio and silicon
The mixing of alkane coupling agent, obtains graphene oxide dispersion, for use；
After 90g unsaturated-resin is heated into molten condition, successively addition accounts for the benzoyl peroxide of unsaturated-resin quality 2%
T-butyl formate, the 1,4-benzoquinone for accounting for unsaturated-resin quality 0.5% and the MgO for accounting for unsaturated-resin quality 2.5%, stir evenly
Resin melt is formed afterwards.100g unsaturated-resin melt and 25g propylene glycol monomethyl ether are added in three-necked flask, are warming up to 80
DEG C, under stirring, 10.5g diethanol amine is slowly added dropwise with the speed of 200g/min, reacts 2h；Then 60 DEG C are cooled to, with 200g/
The acetum that the speed of min is added dropwise 20% reacts 30min, is then slowly added to appropriate distilled water with the speed of 200g/min,
Quickly stir to get the resin melt containing reducing agent；
The graphene oxide of 0.15g is added in the resin melt containing reducing agent, 1h is stirred by ultrasonic, is kept the temperature at 60 DEG C
3h then proceedes to ultrasonic 30min, filtering, obtain mixing melt, be placed at 60 DEG C keep the temperature it is spare.
The modified glass fibre (method of modifying is with embodiment 1) of 15g is placed in the above-mentioned tree containing reducing agent being prepared
In rouge melt, sufficiently infiltrates, obtain pouring material.
Pouring material is poured into mold, bubble is discharged using vibratory drilling method in casting process；It is successively solidifying by 30min after pouring
After glue, for 24 hours solidification and 20 days curing three phases, one is demoulded, and obtains unsaturated-resin-glass fibre-graphene composite wood
Material.
Embodiment 3
Unsaturated-resin-glass fibre-graphene composite material is prepared according to the method for embodiment 1, the difference is that,
Graphene and glass fibre are without any modification.
Embodiment 4
Unsaturated-resin-glass fibre-graphene composite material is prepared according to the method for embodiment 3, the difference is that,
Graphene additive amount is 0.2g (0.2 part), and the additive amount of glass fibre is 20 parts.
Embodiment 5
Unsaturated-resin-glass fibre-graphene composite material is prepared according to the method for embodiment 1, the difference is that,
Graphene additive amount is 0.17g (0.17 part), and the additive amount of glass fibre is 15 parts, and wherein glass fibre is by glass fibre original
Material only carries out roughening treatment.
Performance characterization and result
According to " GB/T 1040.5-2008 " (experimental condition of Unidirectional Fiber-reinforced Composite) standard, testing example
The performance of 1~5 gained test sample, test result are as shown in table 1.
Unsaturated-resin-glass fibre-graphene composite material the performance test results obtained by 1 Examples 1 to 5 of table
By the test result of table 1 it is found that present invention gained unsaturated-resin-glass fibre-graphene composite material is being protected
On the substrate for holding excellent heat-resisting and strength character, wear-resisting property also with higher, can resist the liquid such as petroleum impact and
Friction, security performance and service life are obviously improved, and can be used as petroleum transportation tubing or tank body materials'use；It expands not
The application field of saturated resin composite material；The elasticity modulus of composite material is high, and complete performance is more preferable, can be prepared into tubulose profile
It uses.
As seen from the above embodiment, the present invention can improve the wearability of unsaturated-resin using graphene and glass fibre
Can, the decline of gained worn composite rate is obvious.
The present invention is lacked using method addition graphene, dosage caused by avoiding graphene from adhering in agitating device is first mixed,
It ensure that the precision of graphene additive amount.In the present invention, the graphene of the dosage and glass fibre mating reaction improve
Wearability, strength character, elasticity modulus, high temperature resistance and the heating conduction of unsaturated-resin material, gained composite material
Thermal coefficient it is low, thermal insulation property is more preferable, and processability is higher, be more suitable for being prepared into can-like or tubular material, be applied to petroleum
Production industry.
Production method of the present invention is simple and easy, prepared unsaturated-resin composite material keep its density it is small, plus
Under the premise of work performance is good, intensity and elasticity modulus are bigger, and thermal insulation is more preferable.
Further, modified graphene and redox graphene provided by the invention can make the property for not protecting resin material
It is bigger amplitude to be promoted；And the roughening of glass fibre can more promote glass fiber reinforcement to act on relative to existing glass fibre
Performance.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of unsaturated-resin-glass fibre-graphene composite material, the component including following mass parts: unsaturated-resin
100 parts of matrix, 0.1~0.3 part of graphene and 10~20 parts of glass fibre.
2. unsaturated-resin-glass fibre-graphene composite material as described in claim 1, which is characterized in that the graphite
Alkene includes modified graphene or redox graphene；
The modified graphene is by dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane modified to graphene raw material
It arrives.
3. unsaturated-resin-glass fibre-graphene composite material as described in claim 1, which is characterized in that the modification
The preparation method of graphene includes:
Graphene raw material, dicyclohexylcarbodiimide and 3- aminopropyl triethoxysilane are mixed, mixture is obtained；
The mixture is successively carried out to ultrasonic mixing, stands heat preservation, cooling, separation and drying, obtains modified graphene.
4. unsaturated-resin-glass fibre-graphene composite material as described in claim 1, which is characterized in that the glass
Fiber is obtained by glass fibre raw material by roughening treatment and/or sensitization-activation processing.
5. unsaturated-resin-glass fibre-graphene composite material as claimed in claim 4, which is characterized in that the roughening
Processing coarsening solution includes NaOH solution or potassium hydroxide solution；The temperature of roughening treatment be 50~65 DEG C, roughening treatment when
Between be 25~35min.
6. unsaturated-resin-glass fibre-graphene composite material as described in claim 4 or 5, which is characterized in that described
Sensitization-activation processing sensitizing solution includes SnCl2Solution, the temperature of sensitization are 30~40 DEG C, the time of sensitization is 15~
25min。
7. unsaturated-resin-glass fibre-graphene composite material as described in claim 4 or 5, which is characterized in that described
Sensitization-activation processing activating solution includes PdCl2Solution, the temperature of activation are 25~35 DEG C, the time of activation is 15~
25min。
8. any one of claim 1~7 unsaturated-resin-glass fibre-graphene composite material preparation method, including
Following steps:
(1) the mixing melt that raw material and graphene are prepared including unsaturated-resin matrix is provided；
(2) the mixing melt of the step (1) is mixed with glass fibre, obtains pouring material；
(3) pouring material of the step (2) is successively poured and is solidified, obtain unsaturated-resin-glass fibre-graphene
Composite material.
9. preparation method as claimed in claim 8, which is characterized in that in the step (1), graphene is modified graphene
When, the preparation method for mixing melt includes:
Unsaturated-resin matrix is prepared into raw material mixed melting, obtains resin melt；
The resin melt is mixed with modified graphene dispersion liquid, obtains mixing melt.
10. preparation method as claimed in claim 8, which is characterized in that in the step (1), graphene is oxygen reduction fossil
When black alkene, the preparation method for mixing melt includes:
Prepare raw material, propylene glycol monomethyl ether, diethanol amine, acetum and the water of unsaturated-resin matrix are mixed, obtained containing also
The resin melt of former agent；
The resin melt containing reducing agent is mixed with graphene oxide, mixing melt is obtained after heat preservation.
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| CN112248594A (en) * | 2020-09-09 | 2021-01-22 | 周晓燕 | Wear-resistant composite building template |
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| KR20180042978A (en) * | 2016-10-19 | 2018-04-27 | 인하대학교 산학협력단 | Graphene oxide synthesized from pitch-based carbon fiber and manufacturing method thereof |
| CN109016577A (en) * | 2018-07-06 | 2018-12-18 | 黄河科技学院 | The production and stress measuring method of glass fiber reinforcement unsaturated-resin plate |
| CN109111694A (en) * | 2018-07-06 | 2019-01-01 | 黄河科技学院 | The production and stress measuring method of glass fiber reinforced epoxy resin plate |
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| KR20180042978A (en) * | 2016-10-19 | 2018-04-27 | 인하대학교 산학협력단 | Graphene oxide synthesized from pitch-based carbon fiber and manufacturing method thereof |
| CN109016577A (en) * | 2018-07-06 | 2018-12-18 | 黄河科技学院 | The production and stress measuring method of glass fiber reinforcement unsaturated-resin plate |
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