CN106916334B - A kind of preparation method of epoxidation nano-particle - Google Patents
A kind of preparation method of epoxidation nano-particle Download PDFInfo
- Publication number
- CN106916334B CN106916334B CN201710259227.1A CN201710259227A CN106916334B CN 106916334 B CN106916334 B CN 106916334B CN 201710259227 A CN201710259227 A CN 201710259227A CN 106916334 B CN106916334 B CN 106916334B
- Authority
- CN
- China
- Prior art keywords
- nano
- particle
- epoxidation
- epoxy resin
- ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention prepares the nano-particles such as epoxy carbon nano tube, graphene by ball mill method with low cost, contamination-free manner, solves the problems, such as that nano-particle is difficult in practical applications and disperses, easily reunites.Using nano-particles such as epoxy resin surface modified carbon nano-tube, graphenes, realize fine dispersion of the nano-particle in epoxy resin-base, epoxidation nano-particle can effectively improve the mechanical property and curing action of resin matrix simultaneously, and the research and application to nano-particle epoxy matrix composite have great directive significance.
Description
Technical field
The invention belongs to nano-material modified research fields, more particularly to prepare epoxidised nanometer material by ball-milling method
Material, to improve the dispersibility and compatibility of nano-particle in the epoxy.
Background technology
Nano-particle have grain size is small, large specific surface area, interior atoms ordered arrangement and possess some new physicochemical properties,
Unique bulk effect and skin effect are showed, the fullerene of zero dimension, one-dimensional carbon nanotube, two-dimensional graphene are all gathered around
There are respective unique performance characteristics, has the foreground of being widely applied.After carbon nanotube discovery, 2004, Manchester, England
Two scientist An Deliegaimu of university (Andre Geim) and Ke Siteyanuowo disappear love (Konstantin
Novoselov) it is found that the two-dimension nano materials graphene of single layer structure, graphene have extremely light, pole by adhesive tape stripping method
Thin and high intensity, and as hot spot new in scientific research.Graphene thickness in monolayer is about 0.334nm, perfect stone
Black alkene structural theory fracture strength is more than 100GPa, rupture modulus 1000GPa, is intensity highest in the material having found at this stage
's.Either one-dimensional carbon nanotube or two-dimensional graphene can rely on lower when being applied to structural composite material
Loading makes basis material intensity obtain significant raising, therefore is had broad application prospects in field of compound material.But
In practical application, nano material is difficult to be dispersed among solvent, between the tangling phenomenon and graphene sheet layer of carbon pipe by force
Van der Waals force makes graphene be easy to happen π-π stackings, and apparent reunion occurs in solution or solid phase, and the presence of aggregate can cause
Sample stress raisers, and influence its mechanical performance.
In order to solve the problems, such as difficult dispersion, easily reunion during nano-particle use, by taking graphene as an example, need to be directed to specific
Use condition selects suitable modification medium to be modified processing to graphene, and modified graphene can not only obtain and base
Body material more preferably compatibility can also increase graphene film interlamellar spacing due to the presence of modification medium, provide the row of piece interlayer
Repulsion avoids agglomeration.Lee(Lee W,Lee J U,Jung B M,et al.Simultaneous
enhancement of mechanical,electrical and thermal properties of graphene oxide
paper by embedding dopamine[J].Carbon,2013,65:Oxygen 296-304.) is modified by dopamine modification
Graphite alkene is prepared for the dopamine modified graphene of favorable dispersibility in aqueous solution, relies on the good film forming of dopamine
Property, it can be with the uniform complete graphene film material of preparation structure, and improve the thermal stability and mechanical performance of graphene.
Wan(Wan Y J,Tang L C,Gong L X,et al.Grafting of epoxy chains onto graphene
oxide for epoxy composites with improved mechanical and thermal
properties.Carbon,2014,69:467-480.) by bisphenol A type epoxy resin DGEBA modified graphene oxides and answer
For in epoxy matrix composite, the intensity and modulus of composite material can be significantly improved.Medhekar(Medhekar N V,
Ramasubramaniam A,Ruoff R S,et al.Hydrogen bond networks in graphene oxide
composite paper:structure and mechanical properties[J].Acs Nano,2010,4(4):
2300-2306.) etc. its performance is studied to control graphene oxide (GO) piece interlayer hydrogen bond quantity by changing water content
Change, the increase of water content makes piece interlamellar spacing increase, and oxygen-containing functional group is connect by hydrogen bond with hydrone, between oxygen-containing functional group
Hydrogen bond connection and the variation of its hydrogen bond quantity, thus probe into influence of the water content to graphene sheet layer mechanical property.Gao
(Gao Y,Liu L Q,Zu S Z,et al.The effect of interlayer adhesion on the
mechanical behaviors of macroscopic graphene oxide papers[J].ACS nano,2011,5
(3):2134-2141.) the shadow that oxidized graphite flake interlayer is added to its mechanical property by probing into the small molecules such as glutaraldehyde (GA)
It rings.Park has studied bivalent metal ion (Ca2+、Mg2+) influence to graphene oxide performance, when bivalent metal ion is added
Can then it make just when the increase of piece interlamellar spacing can be caused to lead to mechanical properties decrease when between graphene oxide layer, but being located at lamella edge
Property and intensity increase.GO-PVA, GO-PMMA, GO-PAA, GO-PEi, GO-PCDO etc. are to the study on the modification of graphene oxide also phase
After report, the mechanical performance for the enhancing graphene that these modifications can be in various degree, such as intensity, toughness, rigidity.But these are modified
All it is to be carried out by substrate of graphene oxide, and graphene oxide preparation process is complex, and low yield, of high cost, it is difficult to
Meets the needs of graphene use of large-scale production.In order to give full play to the advantage in nano material mechanics performance, it is applied to ring
Superior mechanical performance is obtained in oxygroup composite material, it would be highly desirable to exploitation it is a kind of it is good with epoxy resin compatibility, easily dispersion and
Has the preparation method of the modified Nano particle of large-scale production foreground.
Invention content
The cheap untreated carbon Guan Yuanguan of present invention use, (original graphite obtains graphite oxide after strong oxidizer is handled
), montmorillonite or nano-silicon dioxide particle be raw material, provide hyperbaric environment and carbon source by carbon dioxide, complete to nanometer
Particle surface functionalization, and two-dimensional nano particle is made to realize stripping in mechanical milling process, increase containing for nanoparticle surface
Oxygen number of functional groups meets the primary condition of modified-reaction, realizes epoxy resin to the in-situ modified of nano-particle.Pass through control
The conditions such as rate of charge, rotational speed of ball-mill, temperature, pressure, time in reaction process, it is inexpensive, pollution-free, prepare one on a large scale
Kind epoxidation nano-particle solves the problems, such as difficulty dispersion when applied to epoxy matrix composite, easily reunites, to prepare high-performance
The research of nano-particle reinforced epoxy based composites provides feasible program.
To achieve the above object, the present invention provides a kind of preparation method of epoxidation nano-particle, particular technique content
It is as follows：
By nano-particle, dry ice, organic solvent proportionally 1g:(30-70g):(20-50mL) is added in ball grinder,
Ball-milling treatment 12h under 300-600rpm rotating speeds, temperature is 30-60 DEG C in tank when mechanical milling process is stablized, pressure 1-15MPa；With
The carbon dioxide gas generated by dry ice sublimation in ball grinder slow release tank is opened afterwards, and 1-20g epoxy resin is added and is rubbed
That mass ratio 1:The intermediate phase medium of (1-2) is eventually adding 1-5g catalyst, continues the ball-milling treatment under 300-600rpm rotating speeds
12h；Products therefrom removes upper liquid after standing, filter and cleaned repeatedly with acetone three times, vacuum drying is finally produced afterwards for 24 hours
The nano-particle of object epoxidation modification.
Wherein, nano-particle is in graphene, carbon nanotube, montmorillonite, nano-silicon dioxide particle, Nano diamond
It is one or more of；Organic solvent is one kind in acetone, ethyl alcohol, DMF；Epoxy resin is polyfunctionality diglycidyl ether type epoxy
One kind in resin, polyfunctionality glycidyl ester type epoxy resin, active epoxy diluent, intermediate phase medium are isophorone
One kind in diisocyanate (IPDI), silane coupling agent 3-aminopropyltriethoxysilane (KH550)；Catalyst is February
One kind in dilaurylate, NaOH aqueous solutions.
The present invention effect be：1) using the carbon Guan Yuanguan of low cost, graphite oxide, (original graphite is by strong oxidizer
Obtained after reason), montmorillonite or nano-silicon dioxide particle be raw material, high productivity prepares epoxidised nano-particle, with satisfaction
The demand of epoxy matrix composite large-scale use；2) carry out modified Nano particle using epoxy resin, answered with improving nano-particle
For the compatibility in epoxy matrix composite, solve the problems, such as that dispersion is difficult；3) epoxidised nano-particle is added to epoxy
In resin matrix, prepared composite material can obtain higher mechanical strength and modulus, while resin system vitrifying turns
Temperature increases.
Below in conjunction with table, present disclosure is described in detail with specific implementation mode.Table 1 is in each embodiment
The mass fraction of used each concrete component, table 2 are that embodiment and the test result of comparative example sample compare.
Specific implementation method
Ball-milling treatment is carried out to sample using planetary ball mill in embodiment, ball grinder selects stainless cylinder of steel, and has
Good air-tightness and resistance to pressure.Nano-particle-polymer matrix composites resin adhesive liquid is swept in the TAQ20 differentials of TA companies of the U.S.
It retouches on calorimeter just non-isothermal DSC to test, nano-particle-polymer matrix composites resin pours building body according to GB/T2567-
2008 requirements prepare sample, and stretching and the crooked test of casting matrix are carried out on SUNS universal testing machines.
Embodiment of the present invention is further illustrated with embodiment below, but the present invention is not limited to following embodiments.Under
Experimental method described in embodiment is stated, is conventional method unless otherwise specified；The reagent and material, unless otherwise specified,
Commercially obtain.
Embodiment 1
By nano-particle, dry ice, organic solvent proportionally 1g:30g:20mL is added in ball grinder, in 300rpm rotating speeds
Lower ball-milling treatment 12h, temperature is 30 DEG C in tank when mechanical milling process is stablized, pressure 5MPa.Then turn on ball grinder slow release
10g epoxy resin and molal weight is added than 1 in the carbon dioxide gas generated by dry ice sublimation in tank:1 interphase is situated between
Matter is eventually adding 1g catalyst, continues the ball-milling treatment 12h under 300rpm rotating speeds.Products therefrom removes upper liquid, mistake after standing
It filters and is cleaned repeatedly with acetone three times, vacuum drying obtains the nano-particle of final product epoxidation modification afterwards for 24 hours.
Wherein, nano-particle is graphite oxide, and organic solvent is acetone；Epoxy resin selects active epoxy diluent butyl
Glycidol ether BGE, intermediate phase medium select silane coupling agent 3-aminopropyltriethoxysilane (KH550), catalyst choosing
Use dibutyl tin laurate.
1) by product as being stood in acetone soln, the time that sedimentation occurs is observed and recorded.2) high-performance epoxy is selected
Resin A component is blended standby resin adhesive liquid with curing agent B component, while the epoxidation nano-particle for adding 0.5wt% is uniformly mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the heating of 10 DEG C/min speed under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of scanning range measures resin adhesive liquid curing exotherm curve.3) it will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of national standard GB/T2567-2008 defined sizes, bending sample molds,
The curing process of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h cures, and taking-up batten is polishing to standard size after being cooled to room temperature
After carry out Mechanics Performance Testing.4) in the enterprising Mobile state heat analysis test of the Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The bis- cantilever modes of Shi Caiyong, air atmosphere, specimen size are 60 × 10 × 3.5mm, and amplitude is 5 μm, test frequency 1Hz, is risen
Warm rate is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
The selection of specific raw material and process conditions are as shown in table 1 in embodiment, sedimentation experiment result, DSC exothermic peak temperatures,
In storage modulus, glass transition temperature, resin-cast body tensile strength, bending strength, stretch modulus, bending modulus such as table 2
It is shown.
Comparative example 1
Be added closed ball milling tank after dry ice, carbon dioxide gas slowly released, make in tank for nitrogen dioxide atmosphere but
Pressure is normal atmosphere (An) 0.1MPa, and other conditions are consistent with step and embodiment 1.When pressure is relatively low, graphite-structure can not
Fully stripping, agglomeration is serious, and then influences to react with epoxy resin, causes the final sample to fail fully to realize epoxy
Change, rapid sedimentation in organic solvent, the phenomenon that mechanical property is poor and discreteness is big occurs
Embodiment 2
By nano-particle, dry ice, organic solvent proportionally 1g:60g:20mL is added in ball grinder, in 600rpm rotating speeds
Lower ball-milling treatment 12h, temperature is 60 DEG C in tank when mechanical milling process is stablized, pressure 12MPa.Then turn on ball grinder slow release
10g epoxy resin and molal weight is added than 1 in the carbon dioxide gas generated by dry ice sublimation in tank:1 interphase is situated between
Matter is eventually adding 1g catalyst, continues the ball-milling treatment 12h under 600rpm rotating speeds.Products therefrom removes upper liquid, mistake after standing
It filters and is cleaned repeatedly with acetone three times, vacuum drying obtains the nano-particle of final product epoxidation modification afterwards for 24 hours.
Wherein, nano-particle is carbon nanotube, and organic solvent is acetone；Epoxy resin selects bisphenol A-type glycidol ether
DGEBA, intermediate phase medium select silane coupling agent 3-aminopropyltriethoxysilane (KH550), catalyst to select two bays
Sour dibutyl tin.
1) by product as being stood in acetone soln, the time that sedimentation occurs is observed and recorded.2) high-performance epoxy is selected
Resin A component is blended standby resin adhesive liquid with curing agent B component, while the epoxidation nano-particle for adding 0.5wt% is uniformly mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the heating of 10 DEG C/min speed under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of scanning range measures resin adhesive liquid curing exotherm curve.3) it will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of national standard GB/T2567-2008 defined sizes, bending sample molds,
The curing process of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h cures, and taking-up batten is polishing to standard size after being cooled to room temperature
After carry out Mechanics Performance Testing.4) in the enterprising Mobile state heat analysis test of the Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The bis- cantilever modes of Shi Caiyong, air atmosphere, specimen size are 60 × 10 × 3.5mm, and amplitude is 5 μm, test frequency 1Hz, is risen
Warm rate is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
The selection of specific raw material and process conditions are as shown in table 1 in embodiment, sedimentation experiment result, DSC exothermic peak temperatures,
In storage modulus, glass transition temperature, resin-cast body tensile strength, bending strength, stretch modulus, bending modulus such as table 2
It is shown.
Comparative example 2
Rotational speed of ball-mill is set as 100rpm, and other conditions are consistent with step and embodiment 1.Nano-particle can not under the slow-speed of revolution
Fully dispersed stripping, and then influence to react with epoxy resin, cause final sample to fail fully to realize epoxidation, occurs
It is settled rapidly in organic solvent, the phenomenon that mechanical property is poor and discreteness is big.
Embodiment 3
By nano-particle, dry ice, organic solvent proportionally 1g:40g:20mL is added in ball grinder, in 500rpm rotating speeds
Lower ball-milling treatment 12h, temperature is 50 DEG C in tank when mechanical milling process is stablized, pressure 10MPa.Then turn on ball grinder slow release
10g epoxy resin and molal weight is added than 1 in the carbon dioxide gas generated by dry ice sublimation in tank:1 interphase is situated between
Matter is eventually adding 1g catalyst, continues the ball-milling treatment 12h under 300rpm rotating speeds.Products therefrom removes upper liquid, mistake after standing
It filters and is cleaned repeatedly with acetone three times, vacuum drying obtains the nano-particle of final product epoxidation modification afterwards for 24 hours.
Wherein, nano-particle is graphite oxide, and organic solvent is acetone；Epoxy resin selects butyl glycidyl ether, in
Between phase medium select isophorone diisocyanate (IPDI), catalyst select dibutyl tin laurate.
1) by product as being stood in acetone soln, the time that sedimentation occurs is observed and recorded.2) high-performance epoxy is selected
Resin A component is blended standby resin adhesive liquid with curing agent B component, while the epoxidation nano-particle for adding 0.5wt% is uniformly mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the heating of 10 DEG C/min speed under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of scanning range measures resin adhesive liquid curing exotherm curve.3) it will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of national standard GB/T2567-2008 defined sizes, bending sample molds,
The curing process of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h cures, and taking-up batten is polishing to standard size after being cooled to room temperature
After carry out Mechanics Performance Testing.4) in the enterprising Mobile state heat analysis test of the Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The bis- cantilever modes of Shi Caiyong, air atmosphere, specimen size are 60 × 10 × 3.5mm, and amplitude is 5 μm, test frequency 1Hz, is risen
Warm rate is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
The selection of specific raw material and process conditions are as shown in table 1 in embodiment, sedimentation experiment result, DSC exothermic peak temperatures,
In storage modulus, glass transition temperature, resin-cast body tensile strength, bending strength, stretch modulus, bending modulus such as table 2
It is shown.
Comparative example 3
Catalyst dibutyltin dilaurylate is not added, and other conditions are consistent with step and embodiment 1.When no catalyst
When, nano-particle and epoxy resin reaction rate are slower, and then affect the comprehensive performance of epoxy matrix composite, epoxy resin
Low grafting rate resin solidification behavior, curing reaction exothermic peak temperature cannot be promoted higher.
Embodiment 4
By nano-particle, dry ice, organic solvent proportionally 1g:40g:20mL is added in ball grinder, in 500rpm rotating speeds
Lower ball-milling treatment 12h, temperature is 50 DEG C in tank when mechanical milling process is stablized, pressure 10MPa.Then turn on ball grinder slow release
10g epoxy resin and molal weight is added than 1 in the carbon dioxide gas generated by dry ice sublimation in tank:1 interphase is situated between
Matter is eventually adding 1g catalyst, continues the ball-milling treatment 12h under 300rpm rotating speeds.Products therefrom removes upper liquid, mistake after standing
It filters and is cleaned repeatedly with acetone three times, vacuum drying obtains the nano-particle of final product epoxidation modification afterwards for 24 hours.
Wherein, nano-particle is carbon nanotube, and organic solvent is acetone；Epoxy resin selects bisphenol A-type glycidol ether
DGEBA, intermediate phase medium select isophorone diisocyanate (IPDI), catalyst to select dibutyl tin laurate.
1) by product as being stood in acetone soln, the time that sedimentation occurs is observed and recorded.2) high-performance epoxy is selected
Resin A component is blended standby resin adhesive liquid with curing agent B component, while the epoxidation nano-particle for adding 0.5wt% is uniformly mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the heating of 10 DEG C/min speed under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of scanning range measures resin adhesive liquid curing exotherm curve.3) it will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of national standard GB/T2567-2008 defined sizes, bending sample molds,
The curing process of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h cures, and taking-up batten is polishing to standard size after being cooled to room temperature
After carry out Mechanics Performance Testing.4) in the enterprising Mobile state heat analysis test of the Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The bis- cantilever modes of Shi Caiyong, air atmosphere, specimen size are 60 × 10 × 3.5mm, and amplitude is 5 μm, test frequency 1Hz, is risen
Warm rate is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
The selection of specific raw material and process conditions are as shown in table 1 in embodiment, sedimentation experiment result, DSC exothermic peak temperatures,
In storage modulus, glass transition temperature, resin-cast body tensile strength, bending strength, stretch modulus, bending modulus such as table 2
It is shown.
Comparative example 4
Dry ice is not added, and is filled with the N of 8MPa into tank2, other conditions and step and embodiment 4 are unanimously.It can be observed
Gained polymer matrix composites performance decreased significantly, and the inert atmosphere of nitrogen reduces ball milling maximum system energy, while cannot carry
It is fully reacted with nano-particle for oxygen-containing carbon source.
Embodiment 5
By nano-particle, dry ice, organic solvent proportionally 1g:40g:20mL is added in ball grinder, in 500rpm rotating speeds
Lower ball-milling treatment 12h, temperature is 50 DEG C in tank when mechanical milling process is stablized, pressure 10MPa.Then turn on ball grinder slow release
10g epoxy resin and molal weight is added than 1 in the carbon dioxide gas generated by dry ice sublimation in tank:1 interphase is situated between
Matter is eventually adding 1g catalyst, continues the ball-milling treatment 12h under 300rpm rotating speeds.Products therefrom removes upper liquid, mistake after standing
It filters and is cleaned repeatedly with acetone three times, vacuum drying obtains the nano-particle of final product epoxidation modification afterwards for 24 hours.
Wherein, nano-particle is graphite oxide, and organic solvent is acetone；Epoxy resin selects active epoxy diluent butyl
Glycidol ether (BGE), intermediate phase medium silane coupling agent 3-aminopropyltriethoxysilane (KH550), catalyst are selected
Dibutyl tin laurate.
1) by product as being stood in acetone soln, the time that sedimentation occurs is observed and recorded.2) high-performance epoxy is selected
Resin A component is blended standby resin adhesive liquid with curing agent B component, while the epoxidation nano-particle for adding 0.5wt% is uniformly mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the heating of 10 DEG C/min speed under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of scanning range measures resin adhesive liquid curing exotherm curve.3) it will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of national standard GB/T2567-2008 defined sizes, bending sample molds,
The curing process of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h cures, and taking-up batten is polishing to standard size after being cooled to room temperature
After carry out Mechanics Performance Testing.4) in the enterprising Mobile state heat analysis test of the Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The bis- cantilever modes of Shi Caiyong, air atmosphere, specimen size are 60 × 10 × 3.5mm, and amplitude is 5 μm, test frequency 1Hz, is risen
Warm rate is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
The selection of specific raw material and process conditions are as shown in table 1 in embodiment, sedimentation experiment result, DSC exothermic peak temperatures,
In storage modulus, glass transition temperature, resin-cast body tensile strength, bending strength, stretch modulus, bending modulus such as table 2
It is shown.
Comparative example 5
Directly dissolve dispersion graphite oxide using butyl glycidyl ether BGE, do not additionally incorporate solvent, other conditions with
Step is consistent with embodiment 5.The mechanical property that polymer matrix composites can be observed is declined, while test data is discrete
Property bigger.Illustrate that the presence of organic solvent can help nano-particle being dispersed in entire resin system evenly.
Each group is grouped as and process conditions in 1 embodiment of table
The test result of 2 embodiment of table and each group sample performance in comparative example
Claims (3)
1. a kind of preparation method of epoxidation nano-particle, it is characterised in that：A, by nano-particle, dry ice, organic solvent according to
Ratio 1g:(30-70g):(20-50mL) is added in ball grinder, ball-milling treatment 12h, mechanical milling process under 300-600rpm rotating speeds
Temperature is 30-60 DEG C in tank when stablizing, pressure 1-15Mpa；B, it then turns in ball grinder slow release tank by dry ice sublimation
1-20g epoxy resin and molal weight is added than 1 in the carbon dioxide gas of generation:The intermediate phase medium of (1-2) finally adds
Enter 1-5g catalyst, continues the ball-milling treatment 12h under 300-600rpm rotating speeds；C, products therefrom removes upper liquid, mistake after standing
It filters and is cleaned repeatedly with acetone three times, vacuum drying obtains the nano-particle of final product epoxidation modification afterwards for 24 hours；It is wherein described
Intermediate phase medium is one kind in isophorone diisocyanate, 3-aminopropyltriethoxysilane.
2. a kind of preparation method of epoxidation nano-particle according to claim 1, it is characterised in that：Epoxy resin is more
One in degree of functionality diglycidyl ether type epoxy resin, polyfunctionality glycidyl ester type epoxy resin, active epoxy diluent
Kind is several；Nano-particle is one kind in graphene, carbon nanotube, montmorillonite, nano-silicon dioxide particle, Nano diamond
Or it is several.
3. a kind of preparation method of epoxidation nano-particle according to claim 1, it is characterised in that：Intermediate phase medium is
One kind in isophorone diisocyanate (IPDI), 3-aminopropyltriethoxysilane (KH550)；Catalyst is two bays
One kind in sour dibutyl tin, NaOH aqueous solutions, organic solvent are one in acetone, ethyl alcohol, n,N-Dimethylformamide (DMF)
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710259227.1A CN106916334B (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of epoxidation nano-particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710259227.1A CN106916334B (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of epoxidation nano-particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106916334A CN106916334A (en) | 2017-07-04 |
| CN106916334B true CN106916334B (en) | 2018-08-14 |
Family
ID=59568099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710259227.1A Active CN106916334B (en) | 2017-04-20 | 2017-04-20 | A kind of preparation method of epoxidation nano-particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106916334B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155024B (en) * | 2017-12-20 | 2020-08-28 | 中国科学院山西煤炭化学研究所 | Graphene/capacitance carbon electrode slurry and preparation method and application thereof |
| CN108911583A (en) * | 2018-08-17 | 2018-11-30 | 深圳市诚朗科技有限公司 | A kind of high strength epoxy resin concrete material and preparation method thereof |
| CN109810585A (en) * | 2018-12-28 | 2019-05-28 | 中国船舶重工集团公司第七二五研究所 | A kind of high humid and warm environment extra-weather-proof high compactness fluorine carbon finishing paint and preparation method thereof |
| CN111721495B (en) * | 2020-06-16 | 2022-02-08 | 中国人民解放军国防科技大学 | Novel particle of nano particle plane laser scattering experiment generates device |
| CN114714708B (en) * | 2022-05-09 | 2023-09-19 | 江苏耀鸿电子有限公司 | High-frequency copper-clad plate with PPO resin substrate and preparation method thereof |
-
2017
- 2017-04-20 CN CN201710259227.1A patent/CN106916334B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106916334A (en) | 2017-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106916334B (en) | A kind of preparation method of epoxidation nano-particle | |
| Wang et al. | Highly compressive boron nitride nanotube aerogels reinforced with reduced graphene oxide | |
| Zhao et al. | Interactive oxidation–reduction reaction for the in situ synthesis of graphene–phenol formaldehyde composites with enhanced properties | |
| Deetuam et al. | Synthesis of well dispersed graphene in conjugated poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate via click chemistry | |
| Wang et al. | Relationship between dispersion state and reinforcement effect of graphene oxide in microcrystalline cellulose–graphene oxide composite films | |
| Luo et al. | Bulk nanostructured materials based on two-dimensional building blocks: a roadmap | |
| Zhou et al. | Activation of boron nitride nanotubes and their polymer composites for improving mechanical performance | |
| CN110589786A (en) | Based on three-dimensional porous transition metal carbide Ti3C2MXene composite nano structure and general preparation method thereof | |
| CN109880294B (en) | Epoxy nanocomposite of tannic acid modified graphene oxide | |
| CN106744900A (en) | A kind of preparation method of polymolecularity Graphene | |
| CN110157931B (en) | Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
| CN107151011A (en) | Modified graphene and preparation method thereof | |
| CN109929141A (en) | A kind of graphene oxide and its epoxy nano composite material of polyethyleneimine-modified | |
| CN106145944A (en) | A kind of high connductivity, heat conduction and high strength carbon material film and preparation method thereof | |
| CN110117004A (en) | A kind of preparation method of redox graphene group compound film | |
| CN106009787A (en) | Graded dispersion method and device for preparing graphene-based waterborne dispersion liquid | |
| CN103922323A (en) | Method for preparing small-diameter graphene | |
| CN104609465B (en) | The method that a kind of Barium metatitanate. doping multi-walled carbon nano-tubes prepares hud typed high dielectric filler | |
| CN111232967A (en) | Preparation method of aminated graphene oxide | |
| Gao et al. | Polyhedral oligomeric silsesquioxane modified carbon nanotube hybrid material with a bump structure via polydopamine transition layer | |
| Dutta et al. | Laser induced incorporation of CNTs in graphene electrodes improves flexibility and conductivity | |
| Lin et al. | Polypyrrole nanotube/ferrocene-modified graphene oxide composites: From fabrication to EMI shielding application | |
| Shamsaei et al. | Graphene oxide-based mesoporous calcium silicate hydrate sandwich-like structure: synthesis and application for thermal energy storage | |
| US20210206644A1 (en) | Substituted graphane material with three-dimensional structure and preparation method thereof | |
| CN102219203B (en) | Three-dimensional nano-carbon material for composite strengthening, and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |