CN108997606A - A kind of high-strength vehicle door-plate and preparation method thereof - Google Patents
A kind of high-strength vehicle door-plate and preparation method thereof Download PDFInfo
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- CN108997606A CN108997606A CN201810335180.7A CN201810335180A CN108997606A CN 108997606 A CN108997606 A CN 108997606A CN 201810335180 A CN201810335180 A CN 201810335180A CN 108997606 A CN108997606 A CN 108997606A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The present invention relates to field of automobile, more particularly to a kind of high-strength vehicle door-plate, the automobile door plate includes core material and the wear-resistant coating for being coated on core surfaces, it is in terms of 100 by the weight of epoxy resin, the core material is by including that the raw material of following parts by weight is made: 100 parts of epoxy resin, 30~50 parts of reinforcing fiber, 5~42 parts of amino modified silica 1,3~10 parts of foaming agent, 2~6 parts of chain extender, 1~5 part of surfactant, 5~15 parts of curing agent, 60~180 parts of organic solvent.High-strength vehicle door-plate prepared by the present invention has the characteristics that light weight, intensity are high and soundproof effect is good, additionally it is possible to play the role of buffering external force, improve the stability of automobile in the process of moving.
Description
Technical field
The present invention relates to field of automobile, and in particular to a kind of high-strength vehicle door-plate and preparation method thereof.
Background technique
In recent years, automotive light weight technology has become the emphasis direction of automotive field development instantly, and Lightweight Technology can not only
It the problem of enough its environmental pollutions of effective solution, realizes the target of energy-saving and emission-reduction, also largely reduces automobile manufacture
Cost has very big economic benefit for present used automobile.
Currently, the method for automotive light weight technology mainly includes the section using light material and reduction door-plate.Reduce door-plate
Section namely reduces the thickness of door-plate, although can reduce the overall weight of automobile, it can also cause automobile door plate is strong
Degree reduces, and in collision, can generate serious deformation, reduce the safety of automobile.Using light material refer to using light weight,
The steel material of the current car door of the big material substitution of intensity, currently, common light material has aluminium alloy extrusions, high-strength complex
Resin and carbon fibre material.Wherein, high-intensity resin relies on itself small specific gravity, sound-insulating and heat-insulating, corrosion-resistant, absorption impact energy
Amount, many advantages, such as specific strength is high, at low cost, easy processing, good decorating effect, already as light material in automotive light weight technology
Development trend.
There is epoxy resin after solidification good physics, chemical property to have relative to metal and nonmetallic materials
Surface deformation shrinking percentage is small, and product size stability is good, and hardness is high, the preferable feature of flexibility, and with relative to alkali and greatly
The stable feature of partial solvent, but the strain that the intensity of epoxy resin also is not enough to that automobile is supported to generate when running at high speed
Power is easy to produce the phenomenon that car door deforms, safety coefficient is low, and existing skill when galloping especially collides
The soundproof effect of epoxy resin is poor in art.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, an object of the present invention is to provide a kind of high-strength vehicle door-plate,
It has the characteristics that lightweight, intensity are high and soundproof effect is good.
The second object of the present invention is to provide a kind of preparation method of high-strength vehicle door-plate.
To achieve the goals above, the present invention provides a kind of high-strength vehicle door-plate, the automobile door plate include core material and
It is coated on the wear-resistant coating of core surfaces, is in terms of 100 by the weight of epoxy resin, the core material is by the original including following parts by weight
Material is made: 100 parts of epoxy resin, 30~50 parts of reinforcing fiber, 5~42 parts of amino modified silica 1,3~10 parts of foaming agent,
2~6 parts of chain extender, 1~5 part of surfactant, 5~15 parts of curing agent, 60~180 parts of organic solvent.
In the present invention, core material using fiber forced foamed epoxy resin as automobile door plate, foaming epoxy resin core material
Compared with existing steel core material, have the characteristics that light weight, the quality of automobile can be greatly lowered, reduces automobile in form
The resistance generated in the process reduces the oil consumption of automobile, plays the role of energy saving.
By the way that reinforcing fiber is added in the epoxy, can be improved the mechanical strength of epoxy resin, by by whisker with
SiO 2 powder is compound, makes silica-filled interfibrous gap, to improve the intensity of epoxy resin.Changed by amino
A large amount of amido functional group is contained on the surface of property silica, can react with the functional group on epoxy molecule chain,
Make to connect between improved silica and epoxy resin with the formation of chemical bond, to make to have between silica and epoxy resin
There is very high binding force, and can be uniformly dispersed in epoxy resin, the strong of epoxy-resin systems can not only be significantly improved
Degree, while also improving the uniformity of epoxy resin.It is used in mixed way by foaming epoxy resin and foaming agent, epoxy can be generated
Resin foam, epoxy foams have good soundproof effect, additionally it is possible to play the role of buffering external force, improve automobile and be expert at
Stability during sailing.
Through the above technical solutions, the automobile door plate prepared in the present invention is using fibre modification foaming epoxy resin as core
Material can not only improve the mechanical strength of epoxy resin, and in epoxy resin bubble presence, significantly reduce the weight of core material
Amount, additionally it is possible to absorb extraneous sound, play the role of sound insulation.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In order to improve the intensity of epoxy resin and obtain lightweight and the good epoxy resin of soundproof effect, mention in the present invention
A kind of fiber forced foamed epoxy resin is supplied, by including that following raw material is made: epoxy resin, reinforcing fiber, amino modified two
Silica, foaming agent, chain extender, surfactant, curing agent, organic solvent.
According to the present invention, by the way that reinforcing fiber is added in the epoxy, it can be improved the mechanical strength of epoxy resin, lead to
It crosses whisker and amino modified SiO 2 powder is compound, makes amino modified silica-filled interfibrous gap, to mention
The intensity of high epoxy resin.According to the present invention, amino modified silica surface contains a large amount of amido functional group, can
It reacts, makes between amino modified silica and epoxy resin with chemical bond with the functional group on epoxy molecule chain
Connection is formed, to make that there is very high binding force between amino modified silica and epoxy resin, and can uniformly be divided
It dissipates in the epoxy, the intensity of epoxy-resin systems can not only be significantly improved, while also improving the uniform of epoxy resin
Property.
According to the present invention, by the way that epoxy resin and foaming agent to be used in mixed way, epoxy foams, asphalt mixtures modified by epoxy resin can be generated
Fat vacuole foam has good soundproof effect, additionally it is possible to play the role of buffering external force, improve the stabilization of automobile in the process of moving
Property.
In the present invention, fiber forced foamed epoxy resin has the characteristics that light weight compared with steel core material, is applied
In the car, the quality of automobile can be greatly lowered, reduce the resistance that automobile generates during form, reduce the oil of automobile
Consumption, plays the role of energy saving.
According to the present invention, wherein the content of each substance is an important factor for influencing Properties of Epoxy Resin, under preferable case, with
On the basis of 100 parts by weight of epoxy resin, the feedstock composition includes: the epoxy resin of 100 parts by weight, 30~50 weight
Part reinforcing fiber, the amino modified silica of 15~42 parts by weight, the foaming agent of 3~10 parts by weight, 2~6 parts by weight
Chain extender, the surfactant of 1~5 parts by weight, the curing agent of 5~15 parts by weight, 60~180 parts by weight organic solvent.
According to the present invention, in order to advanced optimize the bulk properties of epoxy resin, under preferable case, with the epoxy resin
On the basis of 100 parts by weight, the feedstock composition includes: the enhancing fibre of the epoxy resin of 100 parts by weight, 35~45 parts by weight
Dimension, the amino modified silica of 20~30 parts by weight, the foaming agent of 3~10 parts by weight, the chain extender of 2~6 parts by weight, 1~5
The surfactant of parts by weight, the curing agent of 5~15 parts by weight, 100~150 parts by weight organic solvent.
According to the present invention, in order to make between epoxy resin and epoxy resin and amino modified silica between have it is good
The good degree of cross linking, under preferable case, the epoxy resin is selected from melamine epoxy resin, phenol aldehyde type epoxy resin, bisphenol A-type
Epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bis-phenol H-type epoxy resin, polyfunctional glycidyl ether's type ring
At least one of oxygen resin, multifunctional glycidyl amine type epoxy resin.
According to the present invention, wherein the main function of reinforcing fiber be improve epoxy resin bending modulus and shock resistance it is strong
It spends, under preferable case, the reinforcing fiber is selected from calcium sulfate crystal whiskers, alumina whisker, silicon carbide whisker, carbonization boron whisker, two
At least one of zirconium oxide whisker, aluminium nitride whisker, ZnOw, magnesium sulfate crystal whisker and silicon nitride crystal whisker.
According to the present invention, in order to advanced optimize the intensity of epoxy resin, under preferable case, the diameter of the reinforcing fiber
For 50~150nm, length is 3~12 μm.
According to the present invention, thermal decomposition can occur at high temperature and form bubble in epoxy inner for foaming agent, thus
Foaming epoxy resin is formed, since carburizing reagent can occur at high temperature for epoxy resin, foaming agent selected by the present invention
Decomposition temperature should be lower than epoxy resin carburizing temperature.Under preferable case, the foaming agent is selected from sodium bicarbonate, 4,4- oxygen
Generation double benzene sulfonyl hydrazide, azodicarbonamide, N, at least one of N '-dinitrosopentamethlyene tetramine.
In the case of, according to the invention it is preferred to, the chain extender in aliphatic diol, aromatic diol at least one
Kind.Wherein the aliphatic diol is selected from ethylene glycol, 1,3 butylene glycol, 1,10- certain herbaceous plants with big flowers glycol, 1,4- cyclohexanediol, 1,8- pungent two
Alcohol, neopentyl glycol, 2- methyl-1,3-propanediol, 2,4- diethyl -1,5- pentanediol and 3- methyl-1, in 5- pentanediol extremely
Few one kind；Wherein the aromatic diol is selected from hydroquinone double hydroxyethyl ether and/or resorcinol double hydroxyethyl ether.
In the case of, according to the invention it is preferred to, the surfactant is selected from dodecyl alcohol polyoxyethylene ether sodium sulfate, ten
Dialkyl group ammonium sulfate, lauryl sodium sulfate, dodecyl benzene sulfonic acid, sodium secondary alkyl sulfonate, fatty alcohol sodium isethionate, N-
Lauroyl musculamine acid sodium, coconut acyl methyl taurine sodium, α-sodium olefin sulfonate, in dodecyl phosphide ester triethanolamine at least
It is a kind of.
According to the present invention, wherein there is no special requirement to the type of organic solvent, if can dissolved epoxy be
Can, under preferable case, the organic solvent is selected from acetone, n,N-Dimethylformamide, N-Methyl pyrrolidone, N, N- dimethyl
Acetamide, dimethyl acetamide, methylene chloride, triethyl phosphate, acetone, chloroform, toluene, ethyl alcohol, acetic acid, acetic acid second
At least one of ester, formic acid, chloroform, tetrahydrofuran, atoleine and dimethyl sulfoxide.
In the case of, according to the invention it is preferred to, the curing agent is selected from ethylenediamine, hexamethylene diamine, methyl cyclohexyl diamine, Isosorbide-5-Nitrae-fourth
Diamines, 1,5- pentanediamine, 2- methyl-1,5- pentanediamine, 2- butyl -2- ethyl -1,5- pentanediamine, 1,6- hexamethylene diamine, 2,2,4-
Trimethylhexane diamine, 2,4,4- trimethylhexane diamine, 1,8- octamethylenediamine, 2- methyl-1,8- octamethylenediamine, 1,9-nonamethylene diamine, 1,10-
Decamethylene diamine, 1,11- hendecane diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, 1,14- tetradecane diamines, 1,15-
Pentadecane diamines, 2- methyl -2,4-PD, 1,16- hexadecane diamines and 1,18-1,14- octadecamethylene diamine, dimethyl sulphur-based first
At least one of phenylenediamine.
Meanwhile a kind of preparation method of epoxy resin fiber forced foamed according to the present invention being also provided in the present invention, it wraps
Include following steps:
(1) first part's epoxy resin, surfactant, foaming agent and first part's chain extender is organic in first part
It is uniformly mixed in solvent, 30~180min is reacted at 50~80 DEG C, obtains polymer emulsion；
(2) second part epoxy resin, reinforcing fiber, amino modified silica, second are added in polymer emulsion
Then part chain extender and second part organic solvent react 60~120min at 60~90 DEG C, add curing agent, mix
Uniformly, pre-product is obtained；
(3) by pre-product at 100~300MPa, after temperature keeps the temperature 5~10min under conditions of being 100~200 DEG C, drop
Temperature drop normal pressure and temperature normal pressure, obtains fiber forced foamed epoxy resin.
Preferably, in order to further control the expansion rate of foaming agent, the high-temperature process specifically comprises the processes of: will produce in advance
Object is warming up to 100~200 DEG C at 100~300MPa, with the rate of 2~5 DEG C/min, after keeping the temperature 5~10min, with 3~
System is depressurized to normal pressure by the rate of 10MPa/min, is then cooled to room temperature, and core material is obtained.
In the case of, according to the invention it is preferred to, the weight ratio of first part's epoxy resin and second part epoxy resin
For (3~4): 1.
In the case of, according to the invention it is preferred to, the weight ratio of first part's chain extender and the second part chain extender
For (0.5~2): 1.
In the case of, according to the invention it is preferred to, the weight of first part's organic solvent and the second part organic solvent
Amount is than being (1.4~3.33): 1.
In the present invention, epoxy resin, surfactant, foaming agent and chain extender are subjected to pre-polymerization in organic solvent first
Reaction, so that foaming agent is covered by inside epoxy resin prepolymer, it is then again that second part epoxy resin and enhancing is fine
The reaction was continued in organic solvent for dimension, amino modified silica and second part chain extender, generates epoxy resin, and will enhancing
Fiber is coated in epoxy resin, plays the role of reinforced epoxy.Amino modified silica can be with epoxy resin table
The functional group in face chemically reacts, and in the form of chemical bond in conjunction with epoxy resin, not only increases silica and ring
The binding force of oxygen resin, while the dispersing uniformity of silica in the epoxy is improved, significantly improve epoxy resin
Intensity.The present invention finally carries out high-temperature process to epoxy resin, on the one hand, the progress of curing reaction can be made, on the other hand,
It decomposes foaming agent at high temperature, forms porous structure in epoxy inner.
Epoxy resin containing foaming agent is carried out pyrolysis by the present invention at high temperature, in order to improve epoxy resin
Stability avoids local heating, and epoxy inner is caused the different phenomenon of pore opening occur.By epoxy resin in high pressure
Lower carry out thermal response, makes epoxy resin by stronger external pressure, slows down the evolution of gas in epoxy resin, reduces point of foaming agent
Speed is solved, the generating rate of bubble is reduced, improves the uniformity of pore opening, makes foaming epoxy resin that there is uniform internal junction
Structure.
The density for the fiber forced foamed epoxy resin being prepared according to the above method is 38.69~46.25kg/m3。
The present invention also provides a kind of high-strength vehicle door-plate, the automobile door plate includes core material and is coated on core surfaces
Wear-resistant coating, the core material use fiber forced foamed epoxy resin according to the present invention.
The present invention does not require the type of wear-resistant coating particularly, can be in the prior art for protecting automobile core material
Wear-resistant coating.It is described wear-resisting on the basis of 100 parts by weight of epoxy resin in a preferred embodiment of the invention
Coating include: the epoxy resin of 100 parts by weight, the butyl methacrylate of 30~58 parts by weight, 5~15 parts by weight oxygen reduction
Graphite alkene, the levelling agent of 2~6 parts by weight, 10~18 parts by weight curing agent.
Preferably, the levelling agent is selected from dimethyl silicone polymer and/or polymethylphenylsiloxane；The curing agent can
With using the aforementioned described curing agent of the present invention, the epoxy resin can be using the aforementioned described curing agent of the present invention.
In yet another embodiment of the present invention, the high-strength vehicle door-plate the preparation method is as follows:
(1) prepared by core material: the core material uses fiber forced foamed epoxy resin according to the present invention, preparation side
Method is referring to the present invention previously with regard to the description of the preparation method of fiber forced foamed epoxy resin.；
(2) wear-resistant coating sprays: by epoxy resin, butyl methacrylate, redox graphene, levelling agent, wetting
Agent, curing agent are uniformly mixed in organic solvent, form coating emulsion, coating emulsion is then sprayed on core surfaces, are solidified
Afterwards, wear-resistant coating is formed.
Under optimum condition, the curing process are as follows: 30~60min of solidified forming at 80~150 DEG C.
In the present invention, core material using fiber forced foamed epoxy resin as automobile door plate, foaming epoxy resin core material
Compared with existing steel core material, have the characteristics that light weight, the quality of automobile can be greatly lowered, reduces automobile in form
The resistance generated in the process reduces the oil consumption of automobile, plays the role of energy saving.
According to the present invention, by the way that reinforcing fiber is added in the epoxy, it can be improved the mechanical strength of epoxy resin, lead to
It crosses whisker and amino modified SiO 2 powder is compound, makes amino modified silica-filled interfibrous gap, to mention
The intensity of high epoxy resin.Amino modified silica surface contains a large amount of amido functional group, can be with epoxy resin
Functional group on strand reacts, and makes to connect between amino modified silica and epoxy resin with the formation of chemical bond,
To make that there is very high binding force between amino modified silica and epoxy resin, and asphalt mixtures modified by epoxy resin can be uniformly dispersed in
In rouge, the intensity of epoxy-resin systems can not only be significantly improved, while also improving the uniformity of epoxy resin.Pass through epoxy
Resin is used in mixed way with foaming agent, can generate epoxy foams, and epoxy foams have good soundproof effect, moreover it is possible to
Enough play the role of buffering external force, improves the stability of automobile in the process of moving.
The present invention will be described in detail by way of examples below.In following embodiment, various kinds is tested using drainage
The density of product.According to the tensile property of the method test each sample of GB/T1447-2005.According to the method for GB/T1449-2005
Survey the examination bending property of each sample.According to the elongation at break of the method test each sample of GB/T1040.1-2006.According to GB/
The impact flexibility of the method test each sample of T1451-2005.According to the suction of the method test each sample of GB/T18696.2-2002
Sonic system number.Test sample is that diameter is 7.8cm, and with a thickness of the disk of 1.2cm, test frequency range is 100~2500Hz.
Embodiment 1
(1) fiber forced foamed epoxy resin preparation:
A, by 80g melamine epoxy resin, 2g dodecyl alcohol polyoxyethylene ether sodium sulfate, the double benzene of 5g 4,4- oxo
Sulfohydrazide and 3g benzenediol double hydroxyethyl ether are uniformly mixed in 70g n,N-Dimethylformamide, react 90min at 60 DEG C,
Obtain polymer emulsion；
B, 20g melamine epoxy resin, 45g alumina whisker (diameter 100nm, length are added in polymer emulsion
Degree is 5 μm), the amino modified silica of 30g, 2g benzenediol double hydroxyethyl ether and 50g n,N-Dimethylformamide, then exist
90min is reacted at 75 DEG C, adds 10g dimethythiotoluene diamine, is uniformly mixed, obtains pre-product；
C, by pre-product at 200MPa, 150 DEG C are warming up to the rate of 3 DEG C/min, after keeping the temperature 5min, with 10MPa/
System is depressurized to normal pressure by the rate of min, is then cooled to room temperature, and fiber forced foamed epoxy resin is obtained；
(2) preparation of high-strength vehicle door-plate:
Using aforementioned fiber forced foamed epoxy resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer
Step includes: by 100g melamine epoxy resin, 45g butyl methacrylate, 8g redox graphene, 4g polymethyl-benzene
Radical siloxane, 15g dimethythiotoluene diamine are uniformly mixed in n,N-Dimethylformamide, form coating emulsion, then will
Coating emulsion is sprayed on core surfaces, solidifies 45min at 120 DEG C, forms wear-resistant coating.
Embodiment 2
(1) fiber forced foamed epoxy resin preparation:
A, by 80g glycidol type epoxy resin, 3g sodium secondary alkyl sulfonate, 2g azodicarbonamide and 4g 1,8- pungent two
Alcohol is uniformly mixed in 100g dimethyl acetamide, is reacted 120min at 60 DEG C, is obtained polymer emulsion；
B, 20g glycidol type epoxy resin, 35g carbonization boron whisker (diameter 80nm, length are added in polymer emulsion
Degree is 5 μm), the amino modified silica of 25g, 2g 1, then 8- ethohexadiol and 50g dimethyl acetamide are reacted at 80 DEG C
65min adds 2,2,4- trimethylhexane diamine of 8g, is uniformly mixed, obtains pre-product；
C, by pre-product at 220MPa, 200 DEG C are warming up to the rate of 2 DEG C/min, after keeping the temperature 5min, with 5MPa/min
Rate system is depressurized to normal pressure, then cool to room temperature, obtain fiber forced foamed epoxy resin, i.e. core material；
(2) preparation of high-strength vehicle door-plate:
Using aforementioned fiber forced foamed epoxy resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer
Step includes: by 100g glycidol type epoxy resin, 30g butyl methacrylate, 12g redox graphene, the poly- first of 3g
Base phenyl siloxane, 16g 2,2,4- trimethylhexane diamine are uniformly mixed in dimethyl acetamide, form coating emulsion, then
Coating emulsion is sprayed on core surfaces, in 100 DEG C of solidified forming 60min, forms wear-resistant coating.
Embodiment 3
(1) fiber forced foamed epoxy resin preparation:
A, by 80g bisphenol A type epoxy resin, 3g dodecyl benzene sulfonic acid, 8g sodium bicarbonate and the double hydroxyl second of 2g resorcinol
Base ether is uniformly mixed in 70g toluene, is reacted 45min at 75 DEG C, is obtained polymer emulsion；
B, 20g bisphenol A type epoxy resin, 40g aluminium nitride whisker (diameter 80nm, length are added in polymer emulsion
Be 8 μm), the amino modified silica of 20g, 2g resorcinol double hydroxyethyl ether and 30g toluene, then reacted at 65 DEG C
120min adds 12g methyl cyclohexyl diamine, is uniformly mixed, obtains pre-product；
C, by pre-product at 150MPa, 100 DEG C are warming up to the rate of 5 DEG C/min, after keeping the temperature 10min, with 8MPa/
System is depressurized to normal pressure by the rate of min, is then cooled to room temperature, and fiber forced foamed epoxy resin, i.e. core material are obtained；
(2) preparation of high-strength vehicle door-plate:
Using aforementioned fiber forced foamed epoxy resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer
Step includes: by 100g bisphenol A type epoxy resin, 50g butyl methacrylate, 12g redox graphene, 3g polymethyl-benzene
Radical siloxane, 12g methyl cyclohexyl diamine are uniformly mixed in toluene, form coating emulsion, coating emulsion is then sprayed on core
Material surface solidifies 30min at 120 DEG C and forms wear-resistant coating.
Embodiment 4
(1) fiber forced foamed epoxy resin preparation:
A, by 80g bis-phenol H-type epoxy resin, 5g dodecyl phosphide triethanolamine, 3g 4,4- oxobenzenesulfonyl hydrazide and
5g 3- methyl-1,5- pentanediol are uniformly mixed in 70g dimethyl sulfoxide, react 180min at 50 DEG C, obtain polymer cream
Liquid；
B, 20g bis-phenol H-type epoxy resin, 50g silicon carbide whisker (diameter 50nm, length are added in polymer emulsion
Be 3 μm), the amino modified silica of 15g, 2g 3- methyl-1,5- pentanediol and 50g dimethyl sulfoxide, it is then anti-at 90 DEG C
60min is answered, 5g hexamethylene diamine is added, is uniformly mixed, obtains pre-product；
C, by pre-product at 300MPa, 150 DEG C are warming up to the rate of 5 DEG C/min, after keeping the temperature 10min, with 5MPa/
System is depressurized to normal pressure by the rate of min, is then cooled to room temperature, and fiber forced foamed epoxy resin, i.e. core material are obtained；
(2) preparation of high-strength vehicle door-plate:
Using aforementioned fiber forced foamed epoxy resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer
Step includes: by 100g bis-phenol H-type epoxy resin, 58g butyl methacrylate, 5g redox graphene, 6g poly dimethyl
Siloxanes, 18g hexamethylene diamine are uniformly mixed in dimethyl sulfoxide, form coating emulsion, coating emulsion is then sprayed on core material
Surface solidifies 60min at 80 DEG C and forms wear-resistant coating.
Embodiment 5
(1) fiber forced foamed epoxy resin preparation:
A, by 80g phenol aldehyde type epoxy resin, 1g lauryl sodium sulfate, 10g N, N '-dinitrosopentamethlyene tetramine
With 1g 1,10- certain herbaceous plants with big flowers glycol is uniformly mixed in 50g ethyl acetate, reacts 30min at 80 DEG C, obtain polymer emulsion；
B, 20g phenol aldehyde type epoxy resin, 30g magnesium sulfate crystal whisker (diameter 150nm, length are added in polymer emulsion
Be 12 μm), the amino modified silica of 42g, 2g 1, then the pure and mild 10g ethyl acetate of 10- certain herbaceous plants with big flowers two reacts at 60 DEG C
120min adds 2,2,4- trimethylhexane diamine of 15g, is uniformly mixed, obtains pre-product；
C, by pre-product at 100MPa, 200 DEG C are warming up to the rate of 3 DEG C/min, after keeping the temperature 5min, with 3MPa/min
Rate system is depressurized to normal pressure, then cool to room temperature, obtain fiber forced foamed epoxy resin, i.e. core material；
(2) preparation of high-strength vehicle door-plate:
Using aforementioned fiber forced foamed epoxy resin as core material, in core surfaces spraying abrasion-proof layer, spraying abrasion-proof layer
Step includes: by 100g phenol aldehyde type epoxy resin, 30g butyl methacrylate, 15g redox graphene, 2g poly dimethyl
Siloxanes, 10g 2,2,4- trimethylhexane diamine are uniformly mixed in ethyl acetate, coating emulsion are formed, then by coating emulsion
Core surfaces are sprayed on, solidify 30min at 150 DEG C, form wear-resistant coating.
Comparative example 1
According to the method for embodiment 3, the difference is that, do not add enhancing fibre in the preparation of fiber forced foamed epoxy resin
Dimension.
Comparative example 2
According to the method for embodiment 3, the difference is that, SiO 2 powder is used in fiber forced foamed epoxy resin preparation
Substitute amino modified silica.
Comparative example 3
According to the method for embodiment 3, the difference is that, amino modified two are not added in fiber forced foamed epoxy resin preparation
Silica.
Comparative example 4
According to the method for embodiment 3, the difference is that, fiber forced foamed epoxy resin core material is prepared using one-step method, is had
Steps are as follows for body:
(1) fiber forced foamed epoxy resin preparation:
By 100g bisphenol A type epoxy resin, 3g dodecyl benzene sulfonic acid, 8g sodium bicarbonate, 4g resorcinol double hydroxyethyl
Ether, 40g aluminium nitride whisker (diameter 80nm, length are 8 μm) and the amino modified silica of 20g mix in 180g toluene
It is even, 45min is reacted at 75 DEG C, adds 12g methyl cyclohexyl diamine, is uniformly mixed, obtains pre-product；
By pre-product at 150MPa, 80 DEG C are warming up to the rate of 5 DEG C/min, after keeping the temperature 10min, with 8MPa/min's
System is depressurized to normal pressure by rate, is then cooled to room temperature, and fiber forced foamed epoxy resin, i.e. core material are obtained；
(2) preparation of high-strength vehicle door-plate:
By 100g epoxy resin, 50g butyl methacrylate, 12g redox graphene, 3g polymethyl-benzene base silicon oxygen
Alkane, 12g methyl cyclohexyl diamine are uniformly mixed in toluene, form coating emulsion, coating emulsion is then sprayed on core surfaces,
After solidification, wear-resistant coating is formed.
Comparative example 5
According to the method for embodiment 3, the difference is that, the decomposable process of foaming agent carries out under normal pressure, and steps are as follows:
(1) fiber forced foamed epoxy resin preparation:
A, by 80g bisphenol A type epoxy resin, 3g dodecyl benzene sulfonic acid, 8g sodium bicarbonate and the double hydroxyl second of 2g resorcinol
Base ether is uniformly mixed in 150g toluene, is reacted 45min at 75 DEG C, is obtained polymer emulsion；
B, be added in polymer emulsion 20g epoxy resin, 40g aluminium nitride whisker (diameter 80nm, length be 8 μm),
The amino modified silica of 20g, 2g resorcinol double hydroxyethyl ether and 30g toluene, then react 120min at 65 DEG C, then plus
Enter 12g methyl cyclohexyl diamine, is uniformly mixed, obtains pre-product；
C, pre-product is handled into 40min at 80 DEG C, then cooled to room temperature, obtain fiber forced foamed epoxy resin,
That is core material；
(2) preparation of high-strength vehicle door-plate:
By 100g epoxy resin, 50g butyl methacrylate, 12g redox graphene, 3g polymethyl-benzene base silicon oxygen
Alkane, 12g methyl cyclohexyl diamine are uniformly mixed in toluene, form coating emulsion, coating emulsion is then sprayed on core surfaces,
After solidification, wear-resistant coating is formed.
The performance table of each fiber forced foamed epoxy resin in 1 Examples 1 to 5 of table and comparative example 1~5
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of high-strength vehicle door-plate, the automobile door plate includes core material and the wear-resistant coating for being coated on core surfaces, spy
Sign is that the core material is made of feedstock composition, on the basis of 100 parts by weight of epoxy resin, the feedstock composition
It include: the epoxy resin of 100 parts by weight, the reinforcing fiber of 30~50 parts by weight, the amino modified titanium dioxide of 15~42 parts by weight
Silicon, the foaming agent of 3~10 parts by weight, the chain extender of 2~6 parts by weight, the surfactant of 1~5 parts by weight, 5~15 parts by weight
Curing agent, 60~180 parts by weight organic solvent.
2. high-strength vehicle door-plate according to claim 1, wherein on the basis of 100 parts by weight of epoxy resin, institute
State the ammonia that feedstock composition includes: the epoxy resin of 100 parts by weight, the reinforcing fiber of 35~45 parts by weight, 20~30 parts by weight
Base improved silica, the foaming agent of 3~10 parts by weight, the chain extender of 2~6 parts by weight, 1~5 parts by weight surfactant,
The organic solvent of the curing agent of 5~15 parts by weight, 100~150 parts by weight.
3. high-strength vehicle door-plate according to claim 1, wherein the epoxy resin is selected from melamine epoxy tree
Rouge, phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bis-phenol H-type epoxy
At least one of resin, polyfunctional glycidyl ether's type epoxy resin, multifunctional glycidyl amine type epoxy resin.
4. high-strength vehicle door-plate according to claim 1, wherein the reinforcing fiber is selected from calcium sulfate crystal whiskers, oxidation
Al whisker, silicon carbide whisker, carbonization boron whisker, zirconium dioxide whisker, aluminium nitride whisker, ZnOw, magnesium sulfate crystal whisker and
At least one of silicon nitride crystal whisker.
5. high-strength vehicle door-plate according to claim 1, wherein the foaming agent is selected from sodium bicarbonate, 4,4- oxo
Double benzene sulfonyl hydrazides, azodicarbonamide, N, at least one of N '-dinitrosopentamethlyene tetramine.
6. high-strength vehicle door-plate according to claim 1, which is characterized in that the surfactant is selected from dodecyl
Alcohol polyethenoxy ether sodium sulfate, ammonium lauryl sulfate, lauryl sodium sulfate, dodecyl benzene sulfonic acid, sodium secondary alkyl sulfonate,
Fatty alcohol sodium isethionate, N- lauroyl musculamine acid sodium, coconut acyl methyl taurine sodium, α-sodium olefin sulfonate, dodecyl
At least one of phosphide ester triethanolamine；And/or
The chain extender is selected from aliphatic diol and/or aromatic diol.
7. high-strength vehicle door-plate according to claim 1, which is characterized in that by the weight of epoxy resin be 100 in terms of, institute
State the substance that wear-resistant coating includes following parts by weight: 100 parts of epoxy resin, 30~58 parts of butyl methacrylate, reduction-oxidation
5~15 parts of graphene, 2~6 parts of levelling agent, 10~18 parts of curing agent.
8. the preparation method of high-strength vehicle door-plate as claimed in any of claims 1 to 7, which is characterized in that packet
Include following steps:
(1) prepared by core material:
A, by first part's epoxy resin, surfactant, foaming agent and first part's chain extender in first part's organic solvent
In be uniformly mixed, at 50~80 DEG C react 30~180min, obtain polymer emulsion；
B, second part epoxy resin and reinforcing fiber, amino modified silica, second part are added in polymer emulsion
Then chain extender and second part organic solvent react 60~120min at 60~90 DEG C, curing agent is then added, and mixing is equal
It is even, obtain pre-product；
C, pre-product high-temperature process: is kept the temperature into 5~10min under conditions of 100~300MPa of pressure, temperature are 100~200 DEG C
Afterwards, decrease temperature and pressure obtains core material to normal temperature and pressure；
(2) in core surfaces spraying of wearable coating.
9. the preparation method of high-strength vehicle door-plate according to claim 8, wherein in step C, the high-temperature process
Specifically comprises the processes of: by pre-product at 100~300MPa, 100~200 DEG C are warming up to the rate of 2~5 DEG C/min, heat preservation 5
After~10min, system is depressurized to by normal pressure with the rate of 3~10MPa/min, then cools to room temperature, obtains core material.
10. the preparation method of high-strength vehicle door-plate according to claim 9, wherein the spraying work of the wear-resistant coating
Skill are as follows: by epoxy resin, butyl methacrylate, redox graphene, levelling agent, wetting agent, curing agent in organic solvent
In be uniformly mixed, formed coating emulsion, coating emulsion is then sprayed on core surfaces, after solidification, formed wear-resistant coating.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765285A (en) * | 2004-10-27 | 2006-05-03 | 乐金电子(天津)电器有限公司 | Vacuum cleaner truckle |
| CN1929990A (en) * | 2004-02-02 | 2007-03-14 | L&L产品公司 | Improvements in or relating to composite materials |
-
2018
- 2018-04-16 CN CN201810335180.7A patent/CN108997606A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1929990A (en) * | 2004-02-02 | 2007-03-14 | L&L产品公司 | Improvements in or relating to composite materials |
| CN1765285A (en) * | 2004-10-27 | 2006-05-03 | 乐金电子(天津)电器有限公司 | Vacuum cleaner truckle |
Non-Patent Citations (1)
| Title |
|---|
| 伍方: "环氧树脂-石墨烯/氧化石墨烯防腐耐磨复合涂层的界面调控及其性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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