CN108690326A - A kind of light-high-strength automobile side door-plate and preparation method thereof - Google Patents
A kind of light-high-strength automobile side door-plate and preparation method thereof Download PDFInfo
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- CN108690326A CN108690326A CN201810335179.4A CN201810335179A CN108690326A CN 108690326 A CN108690326 A CN 108690326A CN 201810335179 A CN201810335179 A CN 201810335179A CN 108690326 A CN108690326 A CN 108690326A
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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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- C08J9/00—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
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- 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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- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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Abstract
The present invention relates to field of automobile, more particularly to a kind of light-high-strength automobile side door-plate and preparation method thereof, the light-high-strength automobile side door-plate, the light-high-strength automobile side door-plate includes core material and is coated on the wear-resistant coating of core surfaces, the core material is made of feedstock composition, on the basis of 100 parts by weight of the epoxy resin, the feedstock composition includes:0~15 parts by weight of amino modified silica 1 that 5~20 parts by weight of amino modified silica that 100 parts by weight of epoxy resin, 25~50 parts by weight of reinforcing fiber, grain size are 50~100 nanometers, grain size are 100~300 nanometers, 3~10 parts by weight of foaming agent, 2~6 parts by weight of chain extender, 1~5 parts by weight of surfactant, 5~15 parts by weight of curing agent, 60~180 parts by weight 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 light-high-strength automobile side door-plate and its preparation side
Method.
Background technology
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 making
Cost has prodigious economic benefit for present used automobile.
Currently, the method for automotive light weight technology includes mainly the section using light material and reduction door-plate.Reduce door-plate
Section namely reduces the thickness of door-plate, although the overall weight of automobile can be reduced, it can also cause automobile door plate is strong
Degree reduces, and in collision, will produce serious deformation, reduces 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 proportion, 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.
Epoxy resin after epoxy resin cure has good physics, chemical property, it is to metal and nonmetallic materials
Surface have deformation retract rate small, product size stability is good, and hardness is high, and flexibility is preferable, steady to alkali and most of solvent
Fixed feature, but the intensity of epoxy resin is also not enough to the adaptability to changes that support automobile is generated when running at high speed, in automobile height
When speed traveling especially collides, the phenomenon that car door is broken easily is generated, safety coefficient is low, and prior art epoxy resin
Soundproof effect it is poor.
Invention content
Of the existing technology in order to overcome the problems, such as, an object of the present invention is to provide a kind of light-high-strength automobile side
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 light-high-strength automobile side door-plate.
To achieve the goals above, the present invention provides a kind of light-high-strength automobile side door-plate, the automobile side door-plate packet
Core material and the wear-resistant coating for being coated on core surfaces are included, the core material is made of feedstock composition, with 100 weight of the epoxy resin
On the basis of measuring part, the feedstock composition includes:100 parts by weight of epoxy resin, 25~50 parts by weight of reinforcing fiber, grain size 50
~100 nanometers of 5~20 parts by weight of amino modified silica, the amino modified silica 10 that grain size is 100~300 nanometers
~15 parts by weight, 3~10 parts by weight of foaming agent, 2~6 parts by weight of chain extender, 1~5 parts by weight of surfactant, curing agent 5~
15 parts by weight, 60~180 parts by weight of organic solvent.
Through the above technical solutions, the present invention has the following technical effects:
In the present invention, the core material using fiber forced foamed epoxy resin as complex automobile door plate, foam asphalt mixtures modified by epoxy resin
Fat core material has the characteristics that light weight compared with existing steel core material, and the quality of automobile can be greatly lowered, and reduces automobile
The resistance generated during form reduces the oil consumption of automobile, plays the role of energy saving.
By the compound of reinforcing fiber and large-sized improved silica, enhancing bone can be formed in epoxy inner
Frame improves the mechanical strength of epoxy resin, and the improved silica compared with small particle can fill up the hole in epoxy resin, improves
The compactness of epoxy resin, to improve the mechanical strength of epoxy resin.
It is used in mixed way by foaming epoxy resin and foaming agent, epoxy foams can be generated, epoxy foams are not
The propagation that can only stop sound can also reduce impact of the external force to car body, to play buffering external force, damping and sound insulation drop
The effect made an uproar improves the stability of automobile in the process of moving, improves automobile comforts of use.
Specific implementation mode
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, carry in the present invention
A kind of fiber forced foamed epoxy resin composite material is supplied, the fiber forced foamed epoxy resin composite material is by raw material group
It closes object to be made, on the basis of 100 parts by weight of the epoxy resin, the feedstock composition includes:100 parts by weight of epoxy resin,
5~20 parts by weight of amino modified silica that 25~50 parts by weight of reinforcing fiber, grain size are 50~100 nanometers, grain size 100
~300 nanometers of 0~15 parts by weight of amino modified silica 1,3~10 parts by weight of foaming agent, 2~6 parts by weight of chain extender, table
1~5 parts by weight of face activating agent, 5~15 parts by weight of curing agent, 60~180 parts by weight of organic solvent.
According to the present invention, by the way that the different amino modified silica of two kinds of grain sizes to be used in combination, the ammonia of greater particle size
Base improved silica can coordinate with reinforcing fiber, form enhancing skeleton in epoxy inner, the amino compared with small particle changes
Property silica can fill up the hole in epoxy resin, the compactness of epoxy resin be improved, to improve the machine of epoxy resin
Tool intensity.
According to the present invention, a large amount of amido functional group is contained on the surface of amino modified silica, can be with epoxy resin
Functional group on strand reacts, and the formation between modified amido improved silica and epoxy resin with chemical bond is made to connect
It connects, to improve the binding force between silica and epoxy resin, and can be uniformly dispersed in epoxy resin, it can not only
The intensity of epoxy-resin systems is enough significantly improved, while also improving the uniformity of epoxy resin.
It according to the present invention, is used in mixed way by foaming epoxy resin and foaming agent, the quality of material entirety can be reduced, also
Epoxy foams can be generated, can stop the propagation of external force and sound, to play buffering external force, damping and sound insulation and noise reduction
Effect.
According to the present invention, in order to advanced optimize the bulk properties of epoxy resin, under preferable case, with the weight of epoxy resin
Amount is 100 meters, is made of the raw material including following parts by weight:100 parts by weight of epoxy resin, 25~50 parts by weight of reinforcing fiber,
5~20 parts by weight of amino modified silica that grain size is 50~100 nanometers, amino modified two that grain size is 100~300 nanometers
10~15 parts by weight of silica, 2~6 parts by weight of chain extender, 1~5 parts by weight of surfactant, are consolidated 3~10 parts by weight of foaming agent
5~15 parts by weight of agent, 60~180 parts by weight of organic solvent.
According to the present invention, the amino of amino modified silica surface can be with the functional group of epoxy resin surface
Learn reaction, thus on silica surface the content of amino be also influence silica and epoxy resin conjugation factor it
One, the content of amino is low, then the binding force of silica and epoxy resin can be caused high;The content of amino is high, and can be to epoxy
The functional group of resin surface, which causes, to be consumed excessively, and the degree of cross linking of epoxy resin is made to reduce.Under preferable case, the grain size is
The amino content of 100~300 nanometers of amino modified silica surface is 0.5~1.1mmol/g;It is further preferred that institute
The amino content for stating the amino modified silica that grain size is 50~100 nanometers is 0.3~0.6mmol/g.
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, reinforcing fiber can improve the folding strength and impact strength of epoxy resin, under preferable case,
The reinforcing fiber is selected from calcium sulfate crystal whiskers, alumina whisker, silicon carbide whisker, carbonization boron whisker, zirconium dioxide whisker, nitridation
At least one of al 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
It it is 50~150 nanometers, length is 3~12 microns.
According to the present invention, foaming agent can occur thermal decomposition and form bubble in epoxy inner at high temperature, to
Foaming epoxy resin is formed, since carburizing reagent can occur at high temperature for epoxy resin, the foaming agent selected by the present invention
Decomposition temperature should be less than epoxy resin carburizing temperature.Under preferable case, the foaming agent is selected from the double benzene sulphurs of 4,4- oxos
Hydrazides, azodicarbonamide, N, at least one of N '-dinitrosopentamethlyene tetramines.
In the case of, according to the invention it is preferred to, the chain extender is selected from aliphatic diol, aromatic diol, amido chain extender
At least one of, the aliphatic diol is selected from ethylene glycol, 1,3-BDO, 1,10- certain herbaceous plants with big flowers glycol, Isosorbide-5-Nitrae-cyclohexanediol, 1,
8- ethohexadiols, neopentyl glycol, 2- methyl-1,3-propanediols, 2,4- diethyl -1,5- pentanediols and 3- methyl-1s, 5- pentanediols
At least one of.
Under preferable case, the aromatic diol is selected from hydroquinone double hydroxyethyl ether and/or resorcinol double hydroxyethyl
Ether.
Under preferable case, the surfactant is selected from dodecyl alcohol polyoxyethylene ether sodium sulfate, dodecyl sulphate
Ammonium, lauryl sodium sulfate, dodecyl benzene sulfonic acid, sodium secondary alkyl sulfonate, fatty alcohol sodium isethionate, N- lauroyl musculamines
At least one of sour sodium, coconut acyl methyl taurine sodium, α-sodium olefin sulfonate, dodecyl phosphide ester triethanolamine.
The present invention does not have the type of organic solvent special requirement, as long as being capable of dissolved epoxy, preferably feelings
Under condition, the organic solvent is selected from acetone, n,N-Dimethylformamide, N-Methyl pyrrolidone, n,N-dimethylacetamide, two
Methylacetamide, dichloromethane, triethyl phosphate, acetone, chloroform, toluene, ethyl alcohol, acetic acid, ethyl acetate, formic acid, chlorine
At least one of imitative, tetrahydrofuran, atoleine and dimethyl sulfoxide (DMSO).
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- pentanediamines, 2- methyl-1s, 5- pentanediamines, 2- butyl -2- ethyl -1,5- pentanediamines, 1,6- hexamethylene diamines, 2,2,4-
Trimethylhexane diamine, 2,4,4- trimethylhexane diamines, 1,8- octamethylenediamines, 2- methyl-1s, 8- octamethylenediamines, 1,9-nonamethylene diamine, 1,10-
Decamethylene diamine, 1,11- hendecanes diamines, 1,12- dodecamethylene diamines, 1,13- tridecane diamines, 1,14- tetradecanes diamines, 1,15-
Pentadecane diamines, 2- methyl -2,4-PD, 1,16- hexadecanes diamines and 1,18-1,14- octadecamethylene diamines, dimethyl sulphur-based first
At least one of phenylenediamine.
It is 40.16~51.95kg/m according to the fiber forced foamed epoxy resin density that the above method is prepared3。
Meanwhile a kind of system of fiber forced foamed epoxy resin composite material according to the present invention is also provided in the present invention
Preparation Method includes the following steps:
(1) it is 100~300 nanometers amino modified by epoxy resin, surfactant, foaming agent, reinforcing fiber, grain size
Silica and first part's chain extender are uniformly mixed in organic solvent, and 30~180min is then reacted at 50~80 DEG C,
Obtain complex emulsions;
(2) amino modified silica and the second part chain extension that grain size is 50~100 nanometers are added in complex emulsions
Then agent reacts 60~120min at 60~90 DEG C, adds curing agent, be uniformly mixed, obtain pre-product;
(3) pre-product is heat-treated:By pre-product in the case where pressure is 100~300MPa, temperature is 130~200 DEG C
5~25min is handled, after then cooling to room temperature, obtains fiber forced foamed epoxy resin composite material.
According to the present invention, first by epoxy resin, surfactant, foaming agent, reinforcing fiber, amino modified silica
Prepolymerization reaction is carried out in organic solvent with chain extender, passes through the cooperation of large-sized amino modified silica and reinforcing fiber
It uses, enhancing skeleton can be formed in epoxy inner, improve the toughness and intensity of epoxy resin, and foaming agent is coated on
Epoxy inner, adds the amino modified silica of small particle, and the modification of small particle is made to be distributed in epoxy resin
In the gap in portion, the compactness of epoxy resin is improved, to improve the intensity of epoxy resin.
According to the present invention curing process and pore-forming reaction are carried out at the same time by being heat-treated to pre-product.Due to producing in advance
Contain curing agent and foaming agent in object simultaneously, curing agent can make epoxy resin be cured reaction at high temperature, and foaming agent
It can decompose at high temperature, porous structure is formed in epoxy inner.
Under the conditions of, according to the invention it is preferred to, the weight ratio of first part's chain extender and second part chain extender is (1
~2.5):1.
According to the present invention, performed polymer is subjected to pyrolysis under high pressure, makes performed polymer by stronger external pressure, slows down
The effusion of gas in performed polymer, reduces the decomposition rate of foaming agent, reduces the generating rate of bubble, improves the uniform of pore opening
Property, make foaming epoxy resin that there is uniform internal structure.
In order to further increase the uniformity of foaming epoxy resin composite material inner air vent, it is preferred that the pre-product into
Row process of thermal treatment is:By pre-product at 100~300MPa, 130~200 DEG C are warming up to the rate of 2~5 DEG C/min,
After keeping the temperature 5~15min, system is depressurized to by normal pressure with the rate of 3~10MPa/min, then keep the temperature 0~20min, be subsequently cooled to
Room temperature obtains fiber forced foamed epoxy resin composite material.
The present invention does not have the preparation method of amino modified silica special requirement, can be according to prior art preparation
It obtains.
In an embodiment of the invention, the preparation method of the amino modified silica, includes the following steps:
Esters of silicon acis is hydrolyzed in alkaline solution and generates nano silicon dioxide, by silica and silane coupling agent row heating in the solution
Reflux, that is, generate amino modified silica.
Wherein, the grain size of the nano silicon dioxide depends on the pH value of alkaline solution, and the pH value of solution is bigger, generation
The grain size of nano silicon dioxide is also bigger, under preferable case, the pH most 8~10.8 of the alkaline solution.It is further preferred that
The silane coupling agent is KH550.It is further preferred that 80~120 DEG C of the temperature being heated to reflux, the time is 6~10h.
The density for the fiber forced foamed epoxy resin composite material being prepared according to the above method is 38.69~
46.25kg/m3。
The present invention also provides a kind of light-high-strength automobile side door-plate, the automobile side door-plate includes core material and is coated on core
The wear-resistant coating on material surface, the core material use fiber forced foamed epoxy resin composite material according to the present invention.
The present invention does not require the type of wear-resistant coating particularly, can be to be used to protect automobile core material in the prior art
Wear-resistant coating.
It is the wear-resistant coating packet in terms of 100 by the weight of epoxy resin in the preferred embodiment of the present invention
Include the raw material of following parts by weight:100 parts by weight of epoxy resin, 30~58 parts by weight of butyl methacrylate, reduction-oxidation graphite
0.01~0.1 parts by weight of alkene, 2~6 parts by weight of levelling agent, 10~18 parts by weight of 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 aforementioned described asphalt mixtures modified by epoxy resin of the present invention may be used in the epoxy resin
Fat.
In yet another embodiment of the present invention, the preparation method of the light-high-strength automobile side door-plate is as follows:
(1) prepared by core material:The core material uses fiber forced foamed epoxy resin composite material according to the present invention,
Preparation method is referring to the present invention previously with regard to the description of the preparation method of fiber forced foamed epoxy resin composite material.;
(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 cured
Afterwards, wear-resistant coating is formed.
The present invention does not have the curing process of coating emulsion special requirement, can be the common work of epoxy resin cure
Skill, such as can cure 30min at 120 DEG C.
According to the present invention, the core material using fiber forced foamed epoxy resin as composite material automobile door-plate, foam ring
Oxygen resin core material has the characteristics that light weight compared with existing steel core material, and the quality of automobile can be greatly lowered, and reduces
The resistance that automobile generates during form reduces the oil consumption of automobile, plays the role of energy saving.In addition, by epoxy
Reinforcing fiber and large-sized amino modified silica are added in resin, enhancing skeleton can be formed in epoxy inner,
The mechanical strength of epoxy resin is improved, the amino modified silica compared with small particle can fill up the hole in epoxy resin, carry
The compactness of high epoxy resin, to improve the mechanical strength of epoxy resin.Contained by the surface of amino modified silica
A large amount of amido functional group can react with the functional group on epoxy molecule chain, make amino modified silica with
It is connected with the formation of chemical bond between epoxy resin, to make that there is very high binding force between silica and epoxy resin,
And can be uniformly dispersed in epoxy resin, the intensity of epoxy-resin systems can not only be significantly improved, is also improved simultaneously
The uniformity of epoxy resin.It is used in mixed way by foaming epoxy resin and foaming agent, epoxy foams, asphalt mixtures modified by epoxy resin can be generated
Fat vacuole foam can not only stop the propagation of sound, can also reduce impact of the external force to car body, to play buffering external force, damping
With the effect of sound insulation and noise reduction, the stability of automobile in the process of moving is improved, automobile comforts of use are improved.
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.The tensile property of each sample is tested according to the method for GB/T1447-2005.According to the method for GB/T1449-2005
Survey the examination bending property of each sample.The elongation at break of each sample is tested according to the method for GB/T1040.1-2006.According to GB/
The impact flexibility of the method test each sample of T1451-2005.The suction of each sample is tested according to the method for GB/T18696.2-2002
Sonic system number.Test sample is a diameter of 7.8cm, and thickness is the disk of 1.2cm, test frequency ranging from 100~2500Hz.
Embodiment 1
(1) preparation of amino modified silica:
The preparation of amino modified silica A:The sodium hydrate aqueous solution for being 8 in 500mLpH by 50g tetraethyl orthosilicates
In be uniformly mixed, 120min is then stood at 30 DEG C, centrifuge washing obtains nano silicon dioxide, by the nano silicon dioxide
It is uniformly mixed in toluene with Silane coupling agent KH550, then flow back at 100 DEG C 8h, and it is 50 nanometers to obtain grain size, surface ammonia
Base content is the amino modified silica of 0.45mmol/g;
The preparation of amino modified silica B:50g tetraethyl orthosilicates is water-soluble for 9.5 sodium hydroxide in 500mLpH
It is uniformly mixed in liquid, 120min is then stood at 30 DEG C, centrifuge washing obtains the silica that grain size is 50 nanometers, by institute
It states nano silicon dioxide to be uniformly mixed in toluene with Silane coupling agent KH550, then flow back at 85 DEG C 8h, obtains grain size and is
200 nanometers, surface amino groups content is the amino modified silica of 0.8mmol/g;
(2) prepared by fiber forced foamed epoxy resin:By 100g melamine epoxies resin, 2g dodecyl alcohol polyoxy second
Alkene ether sodium sulfate, 5g4,4- oxobenzenesulfonyl hydrazide, 32g alumina whiskers (a diameter of 100 nanometers, length is 5 microns), 12g
Amino modified silica B and 3g benzenediol double hydroxyethyl ethers are uniformly mixed in 120gN, dinethylformamide, at 60 DEG C
Lower reaction 90min, obtains complex emulsions;Add amino modified silica A, 2g the benzenediol double hydroxyethyls of 12g in complex emulsions
Ether is uniformly mixed in 150gN, dinethylformamide, is then reacted 90min at 75 DEG C, is added 10g dimethyl sulphur-based first
Phenylenediamine is uniformly mixed, obtains pre-product;
By pre-product at 200MPa, 130 DEG C are warming up to the rate of 3 DEG C/min, after keeping the temperature 5min, with 10MPa/min
Rate system is depressurized to normal pressure, then cool to room temperature, obtain fiber forced foamed epoxy resin, i.e. core material;
(3) preparation of light-high-strength automobile side door-plate:
By 100g epoxy resin, 45g butyl methacrylates, 5g redox graphenes, 4g polymethylphenylsiloxane,
15g dimethythiotoluene diamines are uniformly mixed in n,N-Dimethylformamide, are formed coating emulsion, are then sprayed coating emulsion
Core surfaces are coated in, cure 30min at 120 DEG C, form the wear-resistant coating that thickness is 20 microns.
Embodiment 2
(1) preparation of amino modified silica:
The preparation of amino modified silica A:The sodium hydrate aqueous solution for being 8 in 500mLpH by 38g tetraethyl orthosilicates
In be uniformly mixed, 120min is then stood at 30 DEG C, centrifuge washing obtains nano silicon dioxide, by the nano silicon dioxide
It is uniformly mixed in toluene with Silane coupling agent KH550, then flow back at 90 DEG C 8h, and it is 50 nanometers to obtain grain size, surface ammonia
Base content is the amino modified silica of 0.41mmol/g;
The preparation of amino modified silica B:The sodium hydroxide water for being 10.3 in 800mLpH by 55g tetraethyl orthosilicates
It is uniformly mixed in solution, 120min is then stood at 30 DEG C, centrifuge washing obtains the silica that grain size is 50 nanometers, will
The nano silicon dioxide is uniformly mixed with Silane coupling agent KH550 in toluene, and then flow back at 100 DEG C 6h, obtains grain
Diameter is 250 nanometers, and surface amino groups content is the amino modified silica of 0.6mmol/g;
(2) prepared by fiber forced foamed epoxy resin:
By 100g glycidol types epoxy resin, 3g sodium secondary alkyl sulfonate, 6g azodicarbonamides, 40g carbonization boron whiskers
(a diameter of 80 nanometers, length is 5 microns), the amino modified silica B and 4g1 of 15g, 8- ethohexadiols are in 100g dimethylacetamides
It is uniformly mixed in amine, reacts 120min at 60 DEG C, obtain complex emulsions;The amino modified dioxies of 10g are added in complex emulsions
SiClx A, 2g1,8- ethohexadiols and 50g dimethylacetylamides, then react 65min at 90 DEG C, add 8g2,2,4- front threes
Base hexamethylene diamine is uniformly mixed, obtains pre-product;
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'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;
(3) preparation of light-high-strength automobile side door-plate:
Using aforementioned fiber forced foamed epoxy resin composite material as core material, in core surfaces spraying abrasion-proof layer, spraying
The step of wearing layer includes:By 100g epoxy resin, 30g butyl methacrylates, 2g redox graphenes, 3g polymethyl-benzene
Radical siloxane, 16g2,2,4- trimethylhexane diamines are uniformly mixed in dimethylacetylamide, form coating emulsion, then will be applied
Layer Emulsion Spraying cures 30min in core surfaces at 120 DEG C, forms the wear-resistant coating that thickness is 20 microns.
Embodiment 3
(1) preparation of amino modified silica:
The preparation of amino modified silica A:55g tetraethyl orthosilicates is water-soluble for 8.5 sodium hydroxide in 800mLpH
It is uniformly mixed in liquid, 120min is then stood at 30 DEG C, centrifuge washing obtains nano silicon dioxide, by the nanometer titanium dioxide
Silicon is uniformly mixed with Silane coupling agent KH550 in toluene, and then flow back at 120 DEG C 8h, and it is 100 nanometers to obtain grain size, table
Face amino content is the amino modified silica of 0.52mmol/g;
The preparation of amino modified silica B:The sodium hydroxide water for being 10.3 in 500mLpH by 38g tetraethyl orthosilicates
It is uniformly mixed in solution, 120min is then stood at 30 DEG C, centrifuge washing obtains nano silicon dioxide, by the nano-silica
SiClx is uniformly mixed with Silane coupling agent KH550 in toluene, and then flow back at 100 DEG C 10h, and it is 250 nanometers to obtain grain size,
Surface amino groups content is the amino modified silica of 0.8mmol/g;
(2) prepared by fiber forced foamed epoxy resin:By 100g bisphenol A type epoxy resins, 3g dodecyl benzene sulfonic acid, 8g
Azodicarbonamide, 40g aluminium nitride whiskers (a diameter of 80 nanometers, length is 8 microns), the amino modified silica B and 2g of 10g
Resorcinol double hydroxyethyl ether is uniformly mixed in 150g toluene, is reacted 45min at 75 DEG C, is obtained complex emulsions;Compound
Amino modified silica A, 2g the resorcinol double hydroxyethyl ethers of 15g and 30g toluene are added in lotion, is then reacted at 65 DEG C
120min adds 12g methyl cyclohexyl diamines, is uniformly mixed, obtains pre-product;
By pre-product at 150MPa, 200 DEG C are warming up to the rate of 5 DEG C/min, after keeping the temperature 10min, with 8MPa/min
Rate system is depressurized to normal pressure, then cool to room temperature, obtain fiber forced foamed epoxy resin, i.e. core material;
(3) preparation of light-high-strength automobile side door-plate:
By 100g epoxy resin, 50g butyl methacrylates, 3g redox graphenes, 3g polymethylphenylsiloxane,
12g methyl cyclohexyl diamines are uniformly mixed in toluene, form coating emulsion, coating emulsion is then sprayed on core surfaces,
Cure 30min at 120 DEG C, forms the wear-resistant coating that thickness is 20 microns.
Embodiment 4
(1) preparation of amino modified silica:
The preparation of amino modified silica A:75g tetraethyl orthosilicates is water-soluble for 8 sodium hydroxide in 1000mLpH
It is uniformly mixed in liquid, 120min is then stood at 30 DEG C, centrifuge washing obtains nano silicon dioxide, by the nanometer titanium dioxide
Silicon is uniformly mixed with Silane coupling agent KH550 in toluene, and then flow back at 80 DEG C 10h, and it is 50 nanometers to obtain grain size, surface
Amino content is the amino modified silica of 0.3mmol/g;
The preparation of amino modified silica B:35g tetraethyl orthosilicates is water-soluble for 8.5 sodium hydroxide in 500mLpH
It is uniformly mixed in liquid, 120min is then stood at 30 DEG C, centrifuge washing obtains the silica that grain size is 50 nanometers, by institute
It states nano silicon dioxide to be uniformly mixed in toluene with Silane coupling agent KH550, then flow back at 90 DEG C 6h, obtains grain size and is
100 nanometers, surface amino groups content is the amino modified silica of 0.5mmol/g;
(2) prepared by fiber forced foamed epoxy resin:By 100g bis-phenol H-types epoxy resin, three second of 5g dodecyls phosphide
Hydramine, 3g4,4- oxobenzenesulfonyl hydrazide, 50g silicon carbide whiskers (a diameter of 50 nanometers, length is 3 microns), 10g are amino modified
Silica B and 5g3- methyl-1,5- pentanediols are uniformly mixed in 180g dimethyl sulfoxide (DMSO)s, react 180min at 50 DEG C,
Obtain complex emulsions;Amino modified silica A, 2g3- methyl-1s of 20g, 5- pentanediols and 50g bis- are added in complex emulsions
Then methyl sulfoxide reacts 60min at 90 DEG C, add 5g hexamethylene diamines, is uniformly mixed, obtains pre-product;
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/min
Rate system is depressurized to normal pressure, then cool to room temperature, obtain fiber forced foamed epoxy resin, i.e. core material;
(3) preparation of light-high-strength automobile side door-plate:
By 100g epoxy resin, 58g butyl methacrylates, 1g redox graphenes, 6g dimethyl silicone polymers,
18g hexamethylene diamines are uniformly mixed in dimethyl sulfoxide (DMSO), form coating emulsion, coating emulsion is then sprayed on core surfaces,
Cure 30min at 120 DEG C, forms the wear-resistant coating that thickness is 20 microns.
Embodiment 5
(1) preparation of amino modified silica:
The preparation of amino modified silica A:20g tetraethyl orthosilicates is water-soluble for 8.5 sodium hydroxide in 500mLpH
It is uniformly mixed in liquid, 120min is then stood at 30 DEG C, centrifuge washing obtains the silica that grain size is 50 nanometers, by institute
It states nano silicon dioxide to be uniformly mixed in toluene with Silane coupling agent KH550, then flow back at 120 DEG C 8h, obtains grain size
It it is 100 nanometers, surface amino groups content is the amino modified silica of 0.6mmol/g;
The preparation of amino modified silica B:The sodium hydroxide water for being 10.8 in 600mLpH by 60g tetraethyl orthosilicates
It is uniformly mixed in solution, 120min is then stood at 30 DEG C, centrifuge washing obtains the silica that grain size is 50 nanometers, will
The nano silicon dioxide is uniformly mixed with Silane coupling agent KH550 in toluene, and then flow back at 80 DEG C 10h, obtains grain
Diameter is 300 nanometers, and surface amino groups content is the amino modified silica of 1.1mmol/g;
(2) prepared by fiber forced foamed epoxy resin:By 100g phenol aldehyde type epoxy resins, 1g lauryl sodium sulfate,
10gN, N '-dinitrosopentamethlyene tetramine, 25g magnesium sulfate crystal whiskers (a diameter of 150 nanometers, length is 12 microns), 10g ammonia
Base improved silica B and 1g1,10- certain herbaceous plants with big flowers glycol are uniformly mixed in 60g ethyl acetate, react 30min at 80 DEG C, obtain
Complex emulsions;20g amino modified silica A, 2g1 are added in complex emulsions, then 10- certain herbaceous plants with big flowers glycol reacts at 60 DEG C
120min, adds 15g2, and 2,4- trimethylhexane diamines are uniformly mixed, obtain pre-product;
By pre-product at 100MPa, 150 DEG C are warming up to the rate of 3 DEG C/min, after keeping the temperature 5min, with 3MPa/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;
(3) preparation of light-high-strength automobile side door-plate:
By 100g epoxy resin, 30g butyl methacrylates, 10g redox graphenes, 2g dimethyl silicone polymers,
10g2,2,4- trimethylhexane diamines are uniformly mixed in ethyl acetate, form coating emulsion, coating emulsion is then sprayed on core
Material surface cures 30min at 120 DEG C, forms the wear-resistant coating that thickness is 20 microns.
Comparative example 1
According to the method for embodiment 1, the difference is that, amino modified silica is substituted using amino modified silica A
B。
Comparative example 2
According to the method for embodiment 1, the difference is that, amino modified silica is substituted using amino modified silica B
A。
Comparative example 3
According to the method for embodiment 1, the difference is that, use grain size to substitute amino modified dioxy for 50 nanometers of silica
SiClx A;Grain size is used to substitute amino modified silica B for 200 nanometers of silica.
Comparative example 4
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) preparation method of amino modified silica is the same as embodiment 3;
(2) prepared by fiber forced foamed epoxy resin:By 100g bisphenol A type epoxy resins, 3g dodecyl benzene sulfonic acid, 8g
Azodicarbonamide, 40g aluminium nitride whiskers (a diameter of 80 nanometers, length is 8 microns), the amino modified silica B and 2g of 10g
Resorcinol double hydroxyethyl ether is uniformly mixed in 150g toluene, is reacted 45min at 75 DEG C, is obtained complex emulsions;Compound
Amino modified silica A, 2g the resorcinol double hydroxyethyl ethers of 15g and 30g toluene are added in lotion, is then reacted at 65 DEG C
120min adds 12g methyl cyclohexyl diamines, is uniformly mixed, obtains pre-product;
By pre-product at 200 DEG C, after keeping the temperature 50min, then cools to room temperature, obtains fiber forced foamed epoxy resin,
That is core material;
(3) preparation method of light-high-strength automobile side door-plate is the same as embodiment 3.
The performance table of each product in 1 Examples 1 to 5 of table and comparative example 1~4
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, 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, belongs to
Protection scope of the present invention.
Claims (9)
1. a kind of light-high-strength automobile side door-plate, the automobile side door-plate includes core material and is coated on the wear-resisting painting of core surfaces
Layer, which is characterized in that the core material is made of feedstock composition, on the basis of 100 parts by weight of the epoxy resin, the raw material
Composition includes:100 parts by weight of epoxy resin, 25~50 parts by weight of reinforcing fiber, grain size are 50~100 nanometers amino modified
5~20 parts by weight of silica, 0~15 parts by weight of amino modified silica 1 that grain size is 100~300 nanometers, foaming agent 3
~10 parts by weight, 2~6 parts by weight of chain extender, 1~5 parts by weight of surfactant, 5~15 parts by weight of curing agent, organic solvent 60
~180 parts by weight.
2. light-high-strength automobile side door-plate according to claim 1, wherein by the weight of epoxy resin be 100 in terms of, institute
Stating feedstock composition includes:100 parts by weight of epoxy resin, 30~40 parts by weight of reinforcing fiber, the ammonia that grain size is 50~100 nanometers
10~15 parts by weight of base improved silica, grain size be 100~300 nanometers 0~15 parts by weight of amino modified silica 1,
It is 5~8 parts by weight of foaming agent, 2~6 parts by weight of chain extender, 1~5 parts by weight of surfactant, 5~15 parts by weight of curing agent, organic
100~150 parts by weight of solvent.
3. light-high-strength automobile side door-plate according to claim 1, wherein the epoxy resin is selected from melamine rings
Oxygen resin, phenol aldehyde type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bis-phenol H-type
At least one of epoxy resin, polyfunctional glycidyl ether's type epoxy resin, multifunctional glycidyl amine type epoxy resin.
4. light-high-strength automobile side door-plate according to claim 1, wherein it is brilliant that the reinforcing fiber is selected from calcium sulfate
Palpus, alumina whisker, silicon carbide whisker, carbonization boron whisker, zirconium dioxide whisker, aluminium nitride whisker, ZnOw, magnesium sulfate
At least one of whisker and silicon nitride crystal whisker.
5. light-high-strength automobile side door-plate according to claim 1, wherein the foaming agent is selected from sodium bicarbonate, 4,
4- oxobenzenesulfonyl hydrazide, azodicarbonamide, N, at least one of N '-dinitrosopentamethlyene tetramines.
6. light-high-strength automobile side door-plate as claimed in any of claims 1 to 5, wherein be with epoxy resin
On the basis of 100 parts by weight, the wear-resistant coating includes the substance of following parts by weight:100 parts by weight of epoxy resin, methacrylic acid
30~58 parts by weight of butyl ester, 0.01~0.1 parts by weight of redox graphene, 2~6 parts by weight of levelling agent, curing agent 10~18
Parts by weight.
7. light-high-strength automobile side door-plate according to claim 6, wherein the levelling agent is selected from polydimethylsiloxanes
Alkane and/or polymethylphenylsiloxane.
8. a kind of preparation method of light-high-strength automobile side door-plate as claimed in any of claims 1 to 7, special
Sign is, includes the following steps:
(1) prepared by core material:By epoxy resin, surfactant, foaming agent, reinforcing fiber, the ammonia that grain size is 100~300 nanometers
Base improved silica and first part's chain extender are uniformly mixed in organic solvent, then at 50~80 DEG C reaction 30~
180min obtains complex emulsions;Amino modified silica, the enhancing that grain size is 50~100 nanometers are added in complex emulsions
Then fiber and second part chain extender react 60~120min at 60~90 DEG C, add curing agent, be uniformly mixed, obtain
To pre-product;
Pre-product is heat-treated:Pre-product handles in the case where pressure is 100~300MPa, temperature is 75~120 DEG C to 5~
25min after then cooling to room temperature, obtains fiber forced foamed epoxy resin composite, i.e. core material;
(2) wear-resistant coating sprays:By epoxy resin, butyl methacrylate, redox graphene, levelling agent, wetting agent, consolidate
Agent is uniformly mixed in organic solvent, forms coating emulsion, coating emulsion is then sprayed on core surfaces, after solidification, shape
At wear-resistant coating.
9. the preparation method of light-high-strength automobile side door-plate according to claim 8, wherein the pre-product carries out heat
The technique of processing is:By pre-product at 100~300MPa, 75~120 DEG C are warming up to the rate of 2~5 DEG C/min, heat preservation 5
After~15min, system is depressurized to by normal pressure with the rate of 3~10MPa/min, then keep the temperature 0~20min, then cooled to room temperature.
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