CN107459773A - The preparation method of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite - Google Patents
The preparation method of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite Download PDFInfo
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- CN107459773A CN107459773A CN201610400046.1A CN201610400046A CN107459773A CN 107459773 A CN107459773 A CN 107459773A CN 201610400046 A CN201610400046 A CN 201610400046A CN 107459773 A CN107459773 A CN 107459773A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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Abstract
The present invention relates to a kind of preparation method of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.The present invention handles glass fibre by silane coupler, and Nano diamond is after surface carboxyl groups, chloride, then polyamine is introduced thereon, prepares the Nano diamond for carrying amino group.Supersonic oscillations and high-speed stirred, Nano diamond is set to be scattered in epoxy resin-base, solidified using amine curing agent, glass fibre using the epoxide resin polymer that obtains containing Nano diamond as matrix and Jing Guo coupling agent treatment is compound, forms the multi-dimensional hybrid composite structure being connected with covalent bond.The present invention prepares convenient, improve Nano diamond in the epoxy scattered, using Nano diamond link come Strengthening and Toughening epoxy resin, improve the adhesion strength with glass fibre basal plane, so as to improve the overall performance of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite, the application of glass fibre, Nano diamond and epoxy resin is widened.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of glass fibre/Nano diamond/epoxy resin is more
Tie up the preparation method of hybrid composite.
Background technology
Epoxy resin is a kind of thermoset oligomer, poor performance.In addition to the stabilizer as polyvinyl chloride, do not have
Direct use value.But after it and curing agent carry out curing reaction formation three-dimensional crosslinked network structure, then show one
The excellent performance of series.So the chemical reactivity of curing agent and epoxy resin is the basis of epoxy resin application, core.
Epoxy resin behavior in the curing process and Solidified enzyme depend greatly on curing agent performance and it
Interact between resin and rationally coordinate, and these depend on the molecular structure of curing agent.Therefore, asphalt mixtures modified by epoxy resin is studied
Apply is exactly the problem of solidification for studying epoxy resin to a certain extent fat.
Recently as the discovery and application of the development of nanometer material science, especially carbon nanomaterial such as CNT,
Nano level diamond is gradually recognized and applied as another new carbon nanomaterial.Because Nano diamond has
Have excellent biocompatibility, dimensionally stable ' property, electrical insulating property, high temperature resistant, high pressure and chemical stability, oneself is through being answered at present
For many aspects, such as the additive of lubricating oil or polymer composite, pharmaceutical carrier and cell marking.But
As in composite, because the surface energy of Nano diamond is higher, easily reunite, it is difficult in the polymer uniformly
It is scattered.How dispersed Nano diamond and to strengthen the combination between Nano diamond and matrix material interface, be to improve
The key of composite properties.The excellent properties of glass fiber compound material obtain extensive use in every profession and trade.Can
With using using the respective excellent mechanical property modified epoxy of glass fibre and Nano diamond, preparing glass fibre/receive
Rice diamond/epoxy resin multi-dimensional hybrid composite, it is anticipated that glass fibre/Nano diamond/epoxy resin mixes multiple
The prospect of condensation material will be boundless.
The content of the invention
It is an object of the invention to provide a kind of good dispersion, the firm glass fibre/Nano diamond/ring of interfacial adhesion
The preparation method of oxygen tree fat multi-dimensional hybrid composite.
The preparation method of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite proposed by the present invention, it is
After Nano diamond surface is carried out into carboxylated, chloride, diamine or polyamine with feature structure are introduced, obtains surface
Graft type Nano diamond with amino.Supersonic oscillations and high-speed stirred, make Nano diamond be scattered in epoxy resin-matrix
In body, solidified using aliphatic polyol amine curing agent, the epoxide resin polymer to obtain containing Nano diamond is used as matrix
It is compound by certain way with glass fibre, the multi-dimensional hybrid composite structure being connected with covalent bond is eventually formed, then glass fibers
Peacekeeping Nano diamond surface will be wound with substantial amounts of polymer.It is comprised the following steps that：
(1) by 1~1 × 10230min in the aqueous solution for the silane coupler that the glass fibre that g is dried is immersed in 5%, after taking-up again
It is put into 120 DEG C of baking oven and toasts 2h, remove the moisture on glass fibre, obtains the glass fibre of silane coupler processing；Will
Nano diamond 1~1 × 102G and acid with strong oxidizing property 1~1 × 104ML is mixed, and it is small that 1~80 is handled under 1 ~ 120kHz ultrasonic waves
When, 25~120 DEG C are then heated to, stirs simultaneously back flow reaction 1~80 hour, ultra porous membranes are filtered, washed repeatedly to solution
In neutrality, it is dried in vacuo 1~48 hour at a temperature of 25~200 DEG C, the Nano diamond being acidified；
(2) by the Nano diamond 1~1 × 10 of acidifying obtained by step (1)2G and acylating reagent l0~1 × 104G, with 1 ~
After 120kHz ultrasonications 0.1 ~ 10 hour, 25~220 DEG C are heated to, simultaneously back flow reaction 0.5~100 hour is stirred, filters
And washing removes acylating reagent, the Nano diamond being acylated repeatedly；
(3) by acylated Nano diamond 1~1 × 10 obtained by step (2)2G and diamine or polyamine 10~1 × 104G, with 1 ~
100kHz ultrasonications 1~100 hour, then reacted 0.5~100 hour at a temperature of 25~200 DEG C, filter and wash repeatedly
Wash, be dried in vacuo 1~48 hour at a temperature of 25 ~ 200 DEG C, obtain the graft type Nano diamond that surface carries amino；
(4) surface obtained by step (3) is carried to the Nano diamond 1~1 × 10 of amino2G and epoxy resin 10~1 × 104G,
After being warming up to resin matrix melting, uniform and bubble removing, while carry out chemical crosslink reaction under vacuum is dispersed with stirring, is obtained
To the epoxide resin polymer containing Nano diamond；
(5) matrix and step will be used as using the epoxide resin polymer 20g-25g for containing Nano diamond obtained by step (4)
(1) the glass fibre 20g-100g mechanical mixtures of the silane coupler processing obtained by, at 60~100 DEG C, ultrasonic wave disperses 1~12
Hour, 40 ~ 50g aliphatic polyol amine curing agent is added, system cured above is poured into mould, bubble removing under vacuum condition,
The curing molding at 100 ~ 250 DEG C, obtain containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
2. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that Nano diamond described in step (1) using Detonation Process obtain, including average grain diameter be 10 nanometers,
30 nanometers, 50 nanometers, 80 nanometers, any of 100 nanometers.
3. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that silane coupler described in step (1) be KH550, KH560, KH570, KH792, DL602 or
Any of DL171.
4. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that acid with strong oxidizing property described in step (1) is 0.1~70% weight acid concentration nitric acid, 1~100% weight
Measure acid concentration sulfuric acid, 1/100~100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100~100/1 mol ratio nitric acid
With sulfuric acid mixed solution, 1/100~100/1 mol ratio potassium permanganate and nitric acid mixed solution, 1/100~100/1 mol ratio mistake
Hydrogen oxide and sulfuric acid mixture liquid, 1/100~100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution, 1/100~100/1 mol ratio
It is any in hydrogen peroxide and nitric acid mixed liquor or 15~95% weight concentration hydrogenperoxide steam generators.
5. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that acylating reagent described in step (2) be thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride,
It is any in phosphorus tribromide, phosphorus pentabromide or thionyl bromide.
6. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that diamine described in step (3) be ethylenediamine, polyethyene diamine, 1,2- propane diamine, 1,3- propane diamine,
1,2- butanediamine, 1,3- butanediamine, hexamethylene diamine, p-phenylenediamine, m-phenylene diamine (MPD), m-xylene diamine, diaminodiphenyl-methane, Meng
Alkane diamines, divinyl propylamine, diaminodiphenyl-methane, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon
It is any in diamine or 13 carbon diamines；The polyamine is fourth triamine, N- aminoethyl piperazines, dicyandiamide, adipic acid two
Hydrazides, N, N- dimethyl dipropyl triamine, TEPA, diethylenetriamine, triethylene tetramine, pentaethylene hexamine or six ethene
It is any in seven amine.
7. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that epoxy resin described in step (4) is glycidol ethers, glycidol lipid, glycidyl amine
It is any in class, alicyclic ring class, epoxidation of olefins class, acid imide epoxy resin or glycolylurea epoxide resin.
8. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that aliphatic polyol amine curing agent described in step (5) is ethylenediamine, diethylene triamine, triethylene
Tetramine, TEPA, dipropylenetriamine, dimethylamine propylamine, diethyl amino propylamine, trimethylhexamethylenediamine, two are
Base triamine, diamines, trimethyl mixture one or several kinds of in diamines, diethylamine, polyether diamine.
9. the system of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1
Preparation Method, it is characterised in that glass fibre described in step (5) is continuous glass fibre, staple glass fibre or glass fabric
Any of.
Preparation method provided by the invention is simple and easy, and gained is glass that surface is connected to Epoxy/nano diamond
Glass fiber multi-dimensional hybrid compound.The amino group on Nano diamond surface by with epoxy resin produce chemical crosslink reaction,
Nano diamond is set to turn into a part for epoxy-resin systems, then the glass fibre by being handled with silane coupler with certain side
Formula is compound, froth in vacuum, obtains containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.Due to nanogold
The effect of hard rock modified epoxy, the boundary strength between matrix resin and glass fibre is added, there is composite
Good interlaminar shear strength.
The present invention is to introduce the amino group with feature structure in Nano diamond, and silane is carried out to fiberglass surfacing
Coupling agent treatment, chemical crosslink reaction is carried out using this structure and epoxy resin, then Nano diamond and fiberglass surfacing will
Substantial amounts of polymer is wound with, because polymer has the characteristic of affinity and Nano diamond in itself to matrix resin, so as to
The shortcomings that improving interlaminar shear strength deficiency etc. of glass fibre, this multi-dimensional hybrid compound have interfacial adhesion firmly, intensity
The multiple performances such as toughness is good, easy solidification, make the comprehensive mechanical property of composite be improved significantly.Therefore, the present invention has
Important science and technology value and actual application value.
Brief description of the drawings
Fig. 1 is the Nano diamond transmission electron microscope picture that a kind of average grain diameter is 10 nanometers.
Embodiment
The following examples are the further explanations to the present invention, rather than limit the scope of the present invention.
Embodiment l：It is initial original by 10 nanometers of Nano diamond and glass fibre of average grain diameter prepared by Detonation Process
Material, silane coupler processing is carried out to glass fibre, Nano diamond is acidified, chloride, after amination, by nanogold
Hard rock and liquid bisphenol A type epoxy resin（E-51）Chemical crosslink reaction is carried out, then must arrive surface and be connected to liquid bisphenol A type ring oxygen
The Nano diamond of resin, then it is compound in a certain way with the glass fibre of Silane coupling agent KH550 processing, obtain containing glass
Glass fiber/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1)：In the mono- neck round-bottom flasks of 250mL for having been loaded with agitator, add Nano diamond raw material 1g and
100mL, 60% weight concentration concentrated nitric acid, add and be heated to 25 DEG C after 1 hour through 60kHz ultrasonications, stir and flow back down
Reaction 24 hours, filtered with the poly- inclined tetrafluoroethene milipore filters of 1.2 μm of ψ, wash 3-10 time repeatedly with deionized water to neutrality, 80 DEG C
After vacuum drying 48 hours, Carboxylation Nano diamond is obtained.The 1.1g glass fibres dried are immersed in 5% silane idol
Join 30min in the agent KH550 aqueous solution, placed into after taking-up in 120 DEG C of baking oven and toast 2h, remove the moisture on glass fibre
Obtain the glass fibre of coupling agent treatment；
Step (2)：In the 250mL three neck round bottom of agitator is had been loaded with, the nanometer Buddha's warrior attendant of acidifying obtained by step (1) is added
Stone 1g and thionyl chloride 10g, handled through following condition：After 100Hz ultrasonications 1 hour, 80 DEG C are heated to, stirs and returns
Reaction 100 hours is flowed down, filters and washing removes thionyl chloride repeatedly, obtain the Nano diamond of chloride；
Step (3)：In the 250mL three neck round bottom of agitator is had been loaded with, nanometer Buddha's warrior attendant acylated obtained by step (2) is added
Stone 1g and 12 carbon diamine 10g, flask are handled through following condition：After 100kHz ultrasonications 1 hour, at 200 DEG C
Stirring reaction 0.5 hour, filter and remove unreacted reactant and byproduct of reaction, after being washed with deionized 3-10 times repeatedly, 80 DEG C
Vacuum drying 48 hours, obtain the Nano diamond that surface carries amino；
Step (4)：In the 250mL three neck round bottom of agitator is had been loaded with, step (3) amidized Nano diamond is added
1g and liquid bisphenol A types epoxy resin (E-51) 20g, heats and stirs, after 60kHz ultrasonications 2 hours, at 240 DEG C
Lower reaction 12 hours, obtains to surface and is connected to the Nano diamond of liquid bisphenol A types epoxy resin (E-51)；
Step (5)：Surface is taken to be connected to the Nano diamond compound 20g and step (1) of liquid bisphenol A types epoxy resin (E-51)
The glass fibre 1g of Silane coupling agent KH550 processing de-bubble under vacuum, is molded under 10MPa with compound at 150 DEG C
Type obtains containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Embodiment 2：The Nano diamond that the average grain diameter prepared using Detonation Process is 30 nanometers enters as initial raw material to glass fibre
The processing of row silane coupler, Nano diamond is acidified, chloride, amination, by Nano diamond and liquid bisphenol A types
Epoxy resin（E-54）Chemical crosslink reaction is carried out, then must arrive surface and be connected to liquid bisphenol A type epoxy resin（E-54）Nanometer
Diamond, then the glass fibre of its processing with silane coupler KH560 is compound in a certain way, obtain containing glass fibre/receive
Rice diamond/epoxy resin multi-dimensional hybrid composite
Step (1)：In the mono- neck round-bottom flasks of 500mL for having been loaded with agitator, addition Nano diamond raw material 1g and 200mL,
98% concentrated sulfuric acid solution, flask are handled through following condition：Add and 80 DEG C are heated to after 2 hours through 70kHz ultrasonications, stirring
And the lower reaction 80 hours that flows back, filtered with 1.2 μm of poly- inclined tetrafluoroethene milipore filters of ψ, wash 3-10 times repeatedly with deionized water extremely
Neutrality, after 100 DEG C are dried in vacuo 24 hours, obtain Carboxylation Nano diamond；The 20g glass fibres dried are immersed in 5%
Silane coupler KH560 the aqueous solution in 30min, placed into after taking-up in 120 DEG C of baking oven and toast 2h, remove glass fibre
On moisture obtain the glass fibre of coupling agent treatment；
Step (2)：In the 500mL three neck round bottom of agitator is had been loaded with, the nanometer Buddha's warrior attendant of acidifying obtained by step (1) is added
Stone 1g and trichlorine sulfoxide 10g, flask are handled through following condition：After 120Hz ultrasonications 10 hours, 25 DEG C are heated to, is stirred
Mix and the lower reaction 48 hours that flows back, repeatedly suction filtration and washing remove three toraks, obtain the Nano diamond of chloride；
Step (3)：In the 500mL three neck round bottom of agitator is had been loaded with, nanometer Buddha's warrior attendant acylated obtained by step (2) is added
Stone 1g and 12 carbon diamine 10g, flask are handled through following condition：After 100kHz ultrasonications 1 hour, at 200 DEG C
Stirring reaction 0.5 hour, filter and remove unreacted reactant and byproduct of reaction, after being washed with deionized 3-10 times repeatedly, 80 DEG C
Vacuum drying 48 hours, obtain the Nano diamond that surface carries amino；
Step (4)：In the 500mL three neck round bottom of agitator is had been loaded with, step (3) amidized Nano diamond is added
1g and liquid bisphenol A types epoxy resin (E-54) 20g, heats and stirs, after 60kHz ultrasonications 2 hours, at 240 DEG C
Lower reaction 12 hours, obtains to surface and is connected to the Nano diamond of liquid bisphenol A types epoxy resin (E-54)；
Step (5)：Surface is taken to be connected to the Nano diamond compound 20g and step (1) of liquid bisphenol A types epoxy resin (E-54)
The glass fibre 20g of coupling agent treatment is compound at 100 DEG C, de-bubble under vacuum, under 8MPa compression molding contained
Glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Embodiment 3：The Nano diamond that the average grain diameter prepared using Detonation Process is 50 nanometers enters as initial raw material to glass fibre
Row silane coupler processing, by Nano diamond is acidified, chloride, after amination, by Nano diamond and liquid bisphenol A
Type epoxy resin（E-44）Chemical crosslink reaction is carried out, then must arrive surface and be connected to liquid bisphenol A type epoxy resin（E-44）Receive
Rice diamond, then the glass fibre of its processing with silane coupler KH570 is compound in a certain way, obtain containing glass fibre/
Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1)：In the mono- neck round-bottom flasks of 500mL for having been loaded with agitator, add Nano diamond raw material 9.8g and
250mL, volume ratio 2：1 concentrated nitric acid and concentrated sulfuric acid mixed liquor, flask are handled through following condition：With 120kHz ultrasonications
25 DEG C are heated to after 80 hours, is stirred and the lower reaction 80 hours that flows back, is filtered, spent with the poly- inclined tetrafluoroethene milipore filters of 1.2 μm of ψ
Ionized water washs to neutrality repeatedly, after 25 DEG C are dried in vacuo 48 hours, obtains Carboxylation Nano diamond；100g is dried
Glass fibre is immersed in 30min in the 5% silane coupler KH570 aqueous solution, places into 120 DEG C of baking oven and dries after taking-up
Roasting 2h, remove the glass fibre that the moisture on glass fibre obtains coupling agent treatment；
Step (2)：In the 500mL three neck round bottom equipped with magnetic agitation rotor, the nanometer of acidifying obtained by step (1) is added
Diamond 9.8g and phosphorus pentachloride 100g, flask are handled through following condition：After 120Hz ultrasonications 1 hour, 25 are heated to
DEG C, stir and the lower reaction 100 hours that flows back, repeatedly suction filtration and washing except repeatedly phosphorus pentachloride is removed, obtain the nanogold of chloride
Hard rock；
Step (3)：In the 500mL three neck round bottom equipped with magnetic agitation rotor, acylated nanogold obtained by step (2) is added
Hard rock 9.8g and TEPA 50g, flask are handled through following condition：After 100kHz ultrasonications 1 hour, flask is 25
Reacted 24 hours at DEG C, filter and remove unreacted reactant and byproduct of reaction, after being washed with deionized repeatedly repeatedly, 200 DEG C true
Sky is dried 1 hour, obtains the Nano diamond that surface carries amino；
Step (4)：In the 500mL three neck round bottom of agitator is had been loaded with, step (3) amidized Nano diamond is added
9.8g and liquid bisphenol A types epoxy resin (E-44) 100g, heats and stirs, after 80kHz ultrasonications 2 hours, 240
Reacted 12 hours at DEG C, obtain to surface and be connected to the Nano diamond of liquid bisphenol A types epoxy resin (E-44)；
Step (5)：Surface is taken to be connected to the Nano diamond compound 25g and step (1) of liquid bisphenol A types epoxy resin (E-44)
The glass fibre 100g of silane coupler processing is compound at 100 DEG C, de-bubble under vacuum, the compression molding under 13MPa
Obtain containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Embodiment 4：The Nano diamond that the average grain diameter prepared using Detonation Process is 80 nanometers enters as initial raw material to glass fibre
Row silane coupler processing, by Nano diamond is acidified, chloride, after amination, by Nano diamond and liquid bisphenol A
Type epoxy resin（E-44）Chemical crosslink reaction is carried out, then must arrive surface and be connected to liquid bisphenol A type epoxy resin（E-44）Receive
Rice diamond, then the glass fibre of its processing with silane coupler KH792 is compound in a certain way, obtain containing glass fibre/
Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1)：In the mono- neck round-bottom flasks of 500mL for having been loaded with agitator, add Nano diamond raw material 9.8g and
250mL, volume ratio 2：1 concentrated nitric acid and concentrated sulfuric acid mixed liquor, flask are handled through following condition：With 60kHz ultrasonications
25 DEG C are heated to after 40 hours, is stirred and the lower reaction 80 hours that flows back, is filtered, spent with the poly- inclined tetrafluoroethene milipore filters of 1.2 μm of ψ
Ionized water washs to neutrality repeatedly, after 25 DEG C are dried in vacuo 48 hours, obtains Carboxylation Nano diamond；60g is dried
Glass fibre is immersed in 30min in the 5% silane coupler KH792 aqueous solution, places into 120 DEG C of baking oven and dries after taking-up
Roasting 2h, remove the glass fibre that the moisture on glass fibre obtains coupling agent treatment；
Step (2)：In the 500mL three neck round bottom equipped with magnetic agitation rotor, the nanometer of acidifying obtained by step (1) is added
Diamond 9.8g and phosphorus pentachloride 100g, flask are handled through following condition：After 60Hz ultrasonications 1 hour, 25 are heated to
DEG C, stir and the lower reaction 100 hours that flows back, repeatedly suction filtration and washing except repeatedly phosphorus pentachloride is removed, obtain the nanogold of chloride
Hard rock；
Step (3)：In the 500mL three neck round bottom equipped with magnetic agitation rotor, acylated nanogold obtained by step (2) is added
Hard rock 9.8g and TEPA 50g, flask are handled through following condition：After 100kHz ultrasonications 1 hour, flask is 25
Reacted 24 hours at DEG C, filter and remove unreacted reactant and byproduct of reaction, after being washed with deionized repeatedly repeatedly, 200 DEG C true
Sky is dried 1 hour, obtains the Nano diamond that surface carries amino；
Step (4)：In the 500mL three neck round bottom of agitator is had been loaded with, step (3) amidized Nano diamond is added
9.8g and liquid bisphenol A types epoxy resin (E-44) 100g, heats and stirs, after 80kHz ultrasonications 2 hours, 240
Reacted 12 hours at DEG C, obtain to surface and be connected to the Nano diamond of liquid bisphenol A types epoxy resin (E-44)；
Step (5)：Surface is taken to be connected to the Nano diamond compound 25g and step (1) of liquid bisphenol A types epoxy resin (E-44)
Silane coupler processing glass fibre 60g it is compound at 100 DEG C, de-bubble under vacuum, under 13MPa compression molding obtain
To containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Embodiment 5：The Nano diamond that the average grain diameter prepared using Detonation Process is 100 nanometers is initial raw material, to glass fibre
Silane coupler processing is carried out, it is after amination, Nano diamond and liquid is double by Nano diamond is acidified, chloride
Phenol A type epoxy resin（E-51）Chemical crosslink reaction is carried out, then must arrive surface and be connected to liquid bisphenol A type epoxy resin（E-51）'s
Nano diamond, then it is compound in a certain way with the glass fibre of silane coupler DL602 processing, obtain containing glass fibers
Dimension/Nano diamond/epoxy resin multi-dimensional hybrid composite.
Step (1)：In the mono- neck round-bottom flasks of 500mL for having been loaded with agitator, add Nano diamond raw material 9.8g and
250mL, volume ratio 2：1 concentrated nitric acid and concentrated sulfuric acid mixed liquor, flask are handled through following condition：With 120kHz ultrasonications
25 DEG C are heated to after 80 hours, is stirred and the lower reaction 80 hours that flows back, is filtered, spent with the poly- inclined tetrafluoroethene milipore filters of 1.2 μm of ψ
Ionized water washs to neutrality repeatedly, after 25 DEG C are dried in vacuo 48 hours, obtains Carboxylation Nano diamond；80g is dried
Glass fibre is immersed in 30min in the 5% silane coupler DL602 aqueous solution, places into 120 DEG C of baking oven and dries after taking-up
Roasting 2h, remove the glass fibre that the moisture on glass fibre obtains coupling agent treatment；
Step (2)：In the 500mL three neck round bottom equipped with magnetic agitation rotor, the nanometer of acidifying obtained by step (1) is added
Diamond 9.8g and phosphorus pentachloride 100g, flask are handled through following condition：After 120Hz ultrasonications 1 hour, 25 are heated to
DEG C, stir and the lower reaction 100 hours that flows back, repeatedly suction filtration and washing except repeatedly phosphorus pentachloride is removed, obtain the nanogold of chloride
Hard rock；
Step (3)：In the 500mL three neck round bottom equipped with magnetic agitation rotor, acylated nanogold obtained by step (2) is added
Hard rock 9.8g and TEPA 50g, flask are handled through following condition：After 60kHz ultrasonications 5 hours, flask is 25
Reacted 24 hours at DEG C, filter and remove unreacted reactant and byproduct of reaction, after being washed with deionized repeatedly repeatedly, 200 DEG C true
Sky is dried 1 hour, obtains the Nano diamond that surface carries amino；
Step (4)：In the 500mL three neck round bottom of agitator is had been loaded with, step (3) amidized Nano diamond is added
9.8g and liquid bisphenol A types epoxy resin (E-51) 100g, heats and stirs, after 80kHz ultrasonications 2 hours, 240
Reacted 12 hours at DEG C, obtain to surface and be connected to the Nano diamond of liquid bisphenol A types epoxy resin (E-51)；
Step (5)：Surface is taken to be connected to the Nano diamond compound 25g and step (1) of liquid bisphenol A types epoxy resin (E-51)
Silane coupler processing glass fibre 80g it is compound at 100 DEG C, de-bubble under vacuum, under 13MPa compression molding obtain
To containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
The above-mentioned description to embodiment is to understand for the ease of those skilled in the art and apply this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, the improvement made to the present invention and modification all should be in the guarantors of the present invention
Within the scope of shield.
Claims (9)
- A kind of 1. preparation method of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite, it is characterised in that tool Body step is as follows：(1) by 1~1 × 10230min in the aqueous solution for the silane coupler that the glass fibre that g is dried is immersed in 5%, after taking-up again It is put into 120 DEG C of baking oven and toasts 2h, remove the moisture on glass fibre, obtains the glass fibre of silane coupler processing；Will Nano diamond 1~1 × 102G and acid with strong oxidizing property 1~1 × 104ML is mixed, and it is small that 1~80 is handled under 1 ~ 120kHz ultrasonic waves When, 25~120 DEG C are then heated to, stirs simultaneously back flow reaction 1~80 hour, ultra porous membranes are filtered, washed repeatedly to solution In neutrality, it is dried in vacuo 1~48 hour at a temperature of 25~200 DEG C, the Nano diamond being acidified；(2) by the Nano diamond 1~1 × 10 of acidifying obtained by step (1)2G and acylating reagent l0~1 × 104G, with 1 ~ 120kHz After ultrasonication 0.1 ~ 10 hour, 25~220 DEG C are heated to, stirred and back flow reaction 0.5~100 hour, filter and repeatedly Washing removes acylating reagent, the Nano diamond being acylated；(3) by acylated Nano diamond 1~1 × 10 obtained by step (2)2G and diamine or polyamine 10~1 × 104G, with 1 ~ 100kHz ultrasonications 1~100 hour, then reacted 0.5~100 hour at a temperature of 25~200 DEG C, filter and wash repeatedly Wash, be dried in vacuo 1~48 hour at a temperature of 25 ~ 200 DEG C, obtain the graft type Nano diamond that surface carries amino；(4) surface obtained by step (3) is carried to the Nano diamond 1~1 × 10 of amino2G and epoxy resin 10~1 × 104G, After being warming up to resin matrix melting, uniform and bubble removing, while carry out chemical crosslink reaction under vacuum is dispersed with stirring, is obtained To the epoxide resin polymer containing Nano diamond；(5) matrix and step will be used as using the epoxide resin polymer 20g-25g for containing Nano diamond obtained by step (4) (1) the glass fibre 20g-100g mechanical mixtures of the silane coupler processing obtained by, at 60~100 DEG C, ultrasonic wave disperses 1~12 Hour, 40 ~ 50g aliphatic polyol amine curing agent is added, system cured above is poured into mould, bubble removing under vacuum condition, The curing molding at 100 ~ 250 DEG C, obtain containing glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite.
- 2. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that Nano diamond described in step (1) is obtained using Detonation Process, including average grain diameter is 10 nanometers, 30 receive Rice, 50 nanometers, 80 nanometers, any of 100 nanometers.
- 3. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that silane coupler described in step (1) is in KH550, KH560, KH570, KH792, DL602 or DL171 It is any.
- 4. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that acid with strong oxidizing property described in step (1) is 0.1~70% weight acid concentration nitric acid, 1~100% weight acid Concentration sulphuric acid, 1/100~100/1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1/100~100/1 mol ratio nitric acid and sulphur Sour mixed solution, 1/100~100/1 mol ratio potassium permanganate and nitric acid mixed solution, 1/100~100/1 mol ratio peroxidating Hydrogen and sulfuric acid mixture liquid, 1/100~100/1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution, 1/100~100/1 mol ratio peroxide Change any in hydrogen and nitric acid mixed liquor or 15~95% weight concentration hydrogenperoxide steam generators.
- 5. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that acylating reagent described in step (2) is thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, tribromo Change any in phosphorus, phosphorus pentabromide or thionyl bromide.
- 6. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that diamine described in step (3) is ethylenediamine, polyethyene diamine, 1,2- propane diamine, 1,3- propane diamine, 1,2- Butanediamine, 1,3- butanediamine, hexamethylene diamine, p-phenylenediamine, m-phenylene diamine (MPD), m-xylene diamine, diaminodiphenyl-methane, Meng's alkane two Amine, divinyl propylamine, diaminodiphenyl-methane, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon binary It is any in amine or 13 carbon diamines；The polyamine be fourth triamine, N- aminoethyl piperazines, dicyandiamide, adipic dihydrazide, N, N- dimethyl dipropyl triamine, TEPA, diethylenetriamine, triethylene tetramine, pentaethylene hexamine or the amine of six ethene seven In it is any.
- 7. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that epoxy resin described in step (4) is glycidol ethers, glycidol lipid, glycidol amine, fat It is any in ring class, epoxidation of olefins class, acid imide epoxy resin or glycolylurea epoxide resin.
- 8. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that aliphatic polyol amine curing agent described in step (5) be ethylenediamine, diethylene triamine, triethylene tetramine, Base three of TEPA, dipropylenetriamine, dimethylamine propylamine, diethyl amino propylamine, trimethylhexamethylenediamine, two Amine, diamines, trimethyl mixture one or several kinds of in diamines, diethylamine, polyether diamine.
- 9. the preparation side of glass fibre/Nano diamond/epoxy resin multi-dimensional hybrid composite according to claim 1 Method, it is characterised in that glass fibre described in step (5) is in continuous glass fibre, staple glass fibre or glass fabric It is any.
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| CN113004660A (en) * | 2021-03-22 | 2021-06-22 | 惠州市纵胜电子材料有限公司 | Processing technology of epoxy glass fiber board |
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| CN102276795A (en) * | 2011-06-22 | 2011-12-14 | 同济大学 | Preparation method of glass fiber/carbon nanotube/epoxy resin multi-dimensional hybrid composite material |
| CN104261385A (en) * | 2014-09-25 | 2015-01-07 | 鄂尔多斯市君实科技有限责任公司 | Modified carbon material as well as preparation method and application thereof |
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| CN102276795A (en) * | 2011-06-22 | 2011-12-14 | 同济大学 | Preparation method of glass fiber/carbon nanotube/epoxy resin multi-dimensional hybrid composite material |
| CN104261385A (en) * | 2014-09-25 | 2015-01-07 | 鄂尔多斯市君实科技有限责任公司 | Modified carbon material as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113004660A (en) * | 2021-03-22 | 2021-06-22 | 惠州市纵胜电子材料有限公司 | Processing technology of epoxy glass fiber board |
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