CN106916334A - A kind of preparation method of epoxidation nano-particle - Google Patents
A kind of preparation method of epoxidation nano-particle Download PDFInfo
- Publication number
- CN106916334A CN106916334A CN201710259227.1A CN201710259227A CN106916334A CN 106916334 A CN106916334 A CN 106916334A CN 201710259227 A CN201710259227 A CN 201710259227A CN 106916334 A CN106916334 A CN 106916334A
- Authority
- CN
- China
- Prior art keywords
- nano
- particle
- epoxidation
- ball
- epoxy resin
- 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.)
- Granted
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 with low cost, contamination-free manner by ball mill method, solves nano-particle difficult dispersion, the problem easily reunited in actual applications.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 field, epoxidised nanometer material is more particularly to prepared by ball-milling method
Material, to improve nano-particle dispersiveness and compatibility in the epoxy.
Background technology
Nano-particle has that particle diameter is small, specific surface area big, interior atoms ordered arrangement and possess some new physicochemical properties,
The bulk effect and skin effect of uniqueness are showed, the fullerene of zero dimension, one-dimensional CNT, the Graphene of two dimension are all gathered around
There are the performance characteristics of respective uniqueness, possess the prospect of being widely applied.After CNT finds, Manchester, England in 2004
Two scientist An Deliegaimu of university (Andre Geim) and Ke Siteyanuowo disappear love (Konstantin
Novoselov the two-dimension nano materials Graphene of single layer structure) is found that by adhesive tape stripping method, Graphene has extremely light, pole
Thin and high intensity, and focus new in turning into scientific research.Graphene thickness in monolayer is about 0.334nm, perfect stone
Black alkene structural theory fracture strength, more than 100GPa, rupture modulus 1000GPa, is intensity highest in the material having found at this stage
's.The Graphene of either one-dimensional CNT, or two dimension, when being applied to structural composite material, can rely on relatively low
Loading, makes matrix material intensity obtain significant raising, therefore had broad application prospects in field of compound material.But
In practical application, nano material is difficult to be dispersed among solvent, strong between the tangling phenomenon and graphene sheet layer of carbon pipe
Van der Waals force makes Graphene be susceptible to π-π stackings, occurs substantially to reunite in solution or solid phase, and the presence of aggregate can be caused
Sample stress raisers, and influence its mechanical performance.
In order to solve the problems, such as difficult dispersion during nano-particle use, easily reunite, by taking Graphene as an example, need to be for specific
Use condition selects suitable modification medium that treatment is modified to Graphene, and modified Graphene can not only be obtained and base
The more excellent compatibility of body material, can also increase graphene film interlamellar spacing, there is provided the row of piece interlayer due to the presence of modification medium
Repulsion, it is to avoid agglomeration occurs.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,2013,65:296-304.) it is modified come the oxygen that is modified by dopamine
Graphite alkene, is prepared for the dopamine modified graphene of favorable dispersibility in aqueous, relies on the good film forming of dopamine
Property, with the homogeneous complete graphene film material of preparation structure, and the heat endurance and mechanical performance of Graphene can be improve.
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.) pass through bisphenol A type epoxy resin DGEBA modified graphene oxides and answer
In for epoxy matrix composite, the intensity and modulus of composite 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. graphene oxide (GO) piece interlayer hydrogen bond quantity is controlled to study its performance by changing water content
Change, the increase of water content increases piece interlamellar spacing, and oxygen-containing functional group is connected by hydrogen bond with hydrone, between oxygen-containing functional group
Hydrogen bond connection and the change 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.) by probing into shadow of the small molecules such as glutaraldehyde (GA) the addition oxidized graphite flake interlayer to its mechanical property
Ring.Park have studied bivalent metal ion (Ca2+、Mg2+) influence to graphene oxide performance, when bivalent metal ion is added
Piece interlamellar spacing can be caused to increase when between graphene oxide layer causes mechanical properties decrease, but can then make during positioned at lamella edge just
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, such as mechanical performance of these modified enhancing Graphenes that can be different degrees of, intensity, toughness, rigidity.But these are modified
All it is to be carried out by substrate of graphene oxide, and graphene oxide preparation technology is complex, and low yield, high cost, it is difficult to
Meet the demand of Graphene use of large-scale production.In order to give full play to the advantage in nano material mechanics performance, ring is applied to
More excellent mechanical performance is obtained in epoxide composite, it would be highly desirable to exploitation it is a kind of it is good with epoxy resin compatibility, easily dispersion and
Possesses the preparation method of the modified Nano particle of large-scale production prospect.
The content of the invention
Using cheap untreated carbon Guan Yuanguan, graphite oxide, (original graphite is obtained the present invention by after strong oxidizer treatment
), 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 make two-dimensional nano particle realize peeling off 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.By control
The conditions such as rate of charge, rotational speed of ball-mill, temperature, pressure, time in course of reaction, it is inexpensive, pollution-free, prepare one on a large scale
Epoxidation nano-particle is planted, solves the problems, such as to be applied to difficult dispersion, easily reunion during epoxy matrix composite, be preparation 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, its 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 during mechanical milling process stabilization, and pressure is 1-15MPa；With
The carbon dioxide produced by dry ice sublimation in the slow toilet-cleaning jar of ball grinder is opened afterwards, is added 1-20g epoxy resin and is rubbed
That mass ratio 1:The middle 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, is finally produced after vacuum drying 24h
The nano-particle of thing epoxidation modification.
Wherein, nano-particle is in Graphene, CNT, montmorillonite, nano-silicon dioxide particle, Nano diamond
One or more；Organic solvent is the one kind in acetone, ethanol, DMF；Epoxy resin is polyfunctionality diglycidyl ether type epoxy
One kind in resin, polyfunctionality glycidyl ester type epoxy resin, active epoxy diluent, middle phase medium is isophorone
One kind in diisocyanate (IPDI), silane coupler APTES (KH550)；Catalyst is February
One kind in dilaurylate, the NaOH aqueous solution.
Effect of the invention is：1) using low cost carbon Guan Yuanguan, graphite oxide (original graphite by strong oxidizer at
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) modified Nano particle is carried out using epoxy resin, should to improve 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 is obtained in that mechanical strength and modulus higher, while resin system vitrifying turns
Temperature increases.
Below in conjunction with form, present disclosure is described in detail with specific embodiment.Table 1 is in each embodiment
The mass fraction of used each concrete component, table 2 is that embodiment is contrasted with the test result of comparative example sample.
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.
Just non-isothermal DSC test on calorimeter is retouched, 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 invention is not restricted to following examples.Under
Experimental technique described in embodiment is stated, unless otherwise specified, conventional method is；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 during mechanical milling process stabilization, and pressure is 5MPa.Ball grinder is then turned on slowly to discharge
The carbon dioxide produced by dry ice sublimation in tank, adds 10g epoxy resin and molal weight to compare 1:1 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
Filter and cleaned repeatedly with acetone three times, the nano-particle of final product epoxidation modification is obtained after vacuum drying 24h.
Wherein, nano-particle is graphite oxide, and organic solvent is acetone；Epoxy resin selects active epoxy diluent butyl
Glycidol ether BGE, middle phase medium selects silane coupler APTES (KH550), catalyst choosing
Use dibutyl tin laurate.
1) product is stood as in acetone soln, observes and record the time that sedimentation occurs.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 well mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the intensification speed of 10 DEG C/min under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of sweep limits determines resin adhesive liquid curing exotherm curve.3) will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of GB GB/T2567-2008 defined sizes, bending sample molds,
The curing process solidification of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h, 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 Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The double cantilever modes of Shi Caiyong, air atmosphere, specimen size is 60 × 10 × 3.5mm, and amplitude is 5 μm, and test frequency is 1Hz, is risen
Warm speed is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
In embodiment the selection of specific raw material and process conditions as shown in table 1, 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
Add closed ball milling tank after dry ice, carbon dioxide 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 cannot
Fully peel off, its agglomeration is serious, and then influence the reaction with epoxy resin, cause final sample to fail fully to realize epoxy
Change, occur in that rapid sedimentation, the phenomenon that mechanical property is poor and discreteness is big in organic solvent
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 during mechanical milling process stabilization, and pressure is 12MPa.Ball grinder is then turned on slowly to discharge
The carbon dioxide produced by dry ice sublimation in tank, adds 10g epoxy resin and molal weight to compare 1:1 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
Filter and cleaned repeatedly with acetone three times, the nano-particle of final product epoxidation modification is obtained after vacuum drying 24h.
Wherein, nano-particle is CNT, and organic solvent is acetone；Epoxy resin selects bisphenol A-type glycidol ether
DGEBA, middle phase medium selects silane coupler APTES (KH550), catalyst to select two bays
Sour dibutyl tin.
1) product is stood as in acetone soln, observes and record the time that sedimentation occurs.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 well mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the intensification speed of 10 DEG C/min under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of sweep limits determines resin adhesive liquid curing exotherm curve.3) will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of GB GB/T2567-2008 defined sizes, bending sample molds,
The curing process solidification of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h, 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 Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The double cantilever modes of Shi Caiyong, air atmosphere, specimen size is 60 × 10 × 3.5mm, and amplitude is 5 μm, and test frequency is 1Hz, is risen
Warm speed is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
In embodiment the selection of specific raw material and process conditions as shown in table 1, 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 cannot under the slow-speed of revolution
Fully dispersed stripping, and then the reaction with epoxy resin is influenceed, cause final sample to fail fully to realize epoxidation, occur in that
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 during mechanical milling process stabilization, and pressure is 10MPa.Ball grinder is then turned on slowly to discharge
The carbon dioxide produced by dry ice sublimation in tank, adds 10g epoxy resin and molal weight to compare 1:1 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
Filter and cleaned repeatedly with acetone three times, the nano-particle of final product epoxidation modification is obtained after vacuum drying 24h.
Wherein, nano-particle is graphite oxide, and organic solvent is acetone；Epoxy resin selects butyl glycidyl ether, in
Between phase medium select IPDI (IPDI), catalyst selects dibutyl tin laurate.
1) product is stood as in acetone soln, observes and record the time that sedimentation occurs.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 well mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the intensification speed of 10 DEG C/min under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of sweep limits determines resin adhesive liquid curing exotherm curve.3) will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of GB GB/T2567-2008 defined sizes, bending sample molds,
The curing process solidification of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h, 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 Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The double cantilever modes of Shi Caiyong, air atmosphere, specimen size is 60 × 10 × 3.5mm, and amplitude is 5 μm, and test frequency is 1Hz, is risen
Warm speed is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
In embodiment the selection of specific raw material and process conditions as shown in table 1, 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
Without catalyst dibutyltin dilaurylate, other conditions are consistent with step and embodiment 1.When without catalyst
When, nano-particle is slower with epoxy resin reaction rate, and then have impact on the combination property of epoxy matrix composite, epoxy resin
Low grafting rate can not promote resin solidification behavior, curing reaction exothermic peak temperature is 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 during mechanical milling process stabilization, and pressure is 10MPa.Ball grinder is then turned on slowly to discharge
The carbon dioxide produced by dry ice sublimation in tank, adds 10g epoxy resin and molal weight to compare 1:1 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
Filter and cleaned repeatedly with acetone three times, the nano-particle of final product epoxidation modification is obtained after vacuum drying 24h.
Wherein, nano-particle is CNT, and organic solvent is acetone；Epoxy resin selects bisphenol A-type glycidol ether
DGEBA, middle phase medium selects IPDI (IPDI), and catalyst selects dibutyl tin laurate.
1) product is stood as in acetone soln, observes and record the time that sedimentation occurs.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 well mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the intensification speed of 10 DEG C/min under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of sweep limits determines resin adhesive liquid curing exotherm curve.3) will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of GB GB/T2567-2008 defined sizes, bending sample molds,
The curing process solidification of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h, 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 Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The double cantilever modes of Shi Caiyong, air atmosphere, specimen size is 60 × 10 × 3.5mm, and amplitude is 5 μm, and test frequency is 1Hz, is risen
Warm speed is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
In embodiment the selection of specific raw material and process conditions as shown in table 1, 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
Without dry ice, and to being filled with the N of 8MPa in tank2, other conditions are consistent with step and embodiment 4.Can be observed
Gained polymer matrix composites performance is decreased obviously, and the inert atmosphere of nitrogen reduces ball milling maximum system energy, while can not carry
Fully reacted for oxygen-containing carbon source and nano-particle.
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 during mechanical milling process stabilization, and pressure is 10MPa.Ball grinder is then turned on slowly to discharge
The carbon dioxide produced by dry ice sublimation in tank, adds 10g epoxy resin and molal weight to compare 1:1 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
Filter and cleaned repeatedly with acetone three times, the nano-particle of final product epoxidation modification is obtained after vacuum drying 24h.
Wherein, nano-particle is graphite oxide, and organic solvent is acetone；Epoxy resin selects active epoxy diluent butyl
Glycidol ether (BGE), middle phase medium silane coupler APTES (KH550), catalyst is selected
Dibutyl tin laurate.
1) product is stood as in acetone soln, observes and record the time that sedimentation occurs.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 well mixed,
5-8mg resin adhesive liquids are weighed in aluminum cup, using differential scanning calorimeter in N2With the intensification speed of 10 DEG C/min under atmosphere
Rate carries out non-isothermal test, and 30-300 DEG C of sweep limits determines resin adhesive liquid curing exotherm curve.3) will be received containing 0.5wt%
The high performance resin glue of rice corpuscles is poured into the stretching of GB GB/T2567-2008 defined sizes, bending sample molds,
The curing process solidification of 90 DEG C/1h+120 DEG C/2h+150 DEG C/3h, 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 Q800 dynamic thermal analysis instrument of TA companies of the U.S., test
The double cantilever modes of Shi Caiyong, air atmosphere, specimen size is 60 × 10 × 3.5mm, and amplitude is 5 μm, and test frequency is 1Hz, is risen
Warm speed is 5 DEG C/min, and test scope is 30-200 DEG C, the storage modulus and glass transition temperature of determination sample.
In embodiment the selection of specific raw material and process conditions as shown in table 1, 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
Dispersion graphite oxide is directly dissolved using butyl glycidyl ether BGE, solvent is not it is possible to additionally incorporate, other conditions with
Step is consistent with embodiment 5.The mechanical property that polymer matrix composites can be observed has declined, while test data is discrete
Property is bigger.Illustrating the presence of organic solvent can help nano-particle being dispersed in whole resin system evenly.
Each group is grouped into and process conditions in the embodiment of table 1
The test result of each group sample performance in the embodiment of table 2 and comparative example
Claims (4)
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 during stabilization, and pressure is 1-15Mpa；B, then turn in the slow toilet-cleaning jar of ball grinder by dry ice sublimation
The carbon dioxide of generation, adds 1-20g epoxy resin and molal weight to compare 1:The middle phase medium of (1-2), finally adds
Enter 1-5g catalyst, continue the ball-milling treatment 12h under 300-600rpm rotating speeds；C, products therefrom remove upper liquid, mistake after standing
Filter and cleaned repeatedly with acetone three times, the nano-particle of final product epoxidation modification is obtained after vacuum drying 24h.
2. the preparation method of a kind of epoxidation nano-particle according to claim 1, it is characterised in that：Epoxy resin is many
In degree of functionality diglycidyl ether type epoxy resin, polyfunctionality glycidyl ester type epoxy resin, active epoxy diluent one
Plant or several；Nano-particle is the one kind in Graphene, CNT, montmorillonite, nano-silicon dioxide particle, Nano diamond
Or it is several.
3. the preparation method of a kind of epoxidation nano-particle according to claim 1, it is characterised in that：Middle phase medium is
One kind in IPDI (IPDI), APTES (KH550)；Catalyst is two bays
One kind in sour dibutyl tin, the NaOH aqueous solution, organic solvent is in acetone, ethanol, DMF (DMF)
Kind.
4. the preparation method of a kind of epoxidation nano-particle according to claim 1, it is characterised in that：Ball in mechanical milling process
Mill rotating speed is 100-600rpm, and temperature is 30-80 DEG C in ball milling system, and pressure is 1-15MPa.
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 true CN106916334A (en) | 2017-07-04 |
| CN106916334B 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155024A (en) * | 2017-12-20 | 2018-06-12 | 中国科学院山西煤炭化学研究所 | A kind of graphene/capacitance carbon electrode slurry and preparation method and application |
| 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 |
| CN111721495A (en) * | 2020-06-16 | 2020-09-29 | 中国人民解放军国防科技大学 | Novel particle of nano particle plane laser scattering experiment generates device |
| CN114714708A (en) * | 2022-05-09 | 2022-07-08 | 江苏耀鸿电子有限公司 | High-frequency copper-clad plate with PPO resin base material and preparation method thereof |
-
2017
- 2017-04-20 CN CN201710259227.1A patent/CN106916334B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108155024A (en) * | 2017-12-20 | 2018-06-12 | 中国科学院山西煤炭化学研究所 | A kind of graphene/capacitance carbon electrode slurry and preparation method and application |
| 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 |
| CN111721495A (en) * | 2020-06-16 | 2020-09-29 | 中国人民解放军国防科技大学 | Novel particle of nano particle plane laser scattering experiment generates device |
| 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 |
| CN114714708A (en) * | 2022-05-09 | 2022-07-08 | 江苏耀鸿电子有限公司 | High-frequency copper-clad plate with PPO resin base material and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106916334B (en) | 2018-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106916334B (en) | A kind of preparation method of epoxidation nano-particle | |
| JP6537553B2 (en) | Large scale production of graphene oxide for industrial applications | |
| EP3056469B1 (en) | Production method for graphene | |
| Shim et al. | Facile method to functionalize graphene oxide and its application to poly (ethylene terephthalate)/graphene composite | |
| 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 | |
| Zhou et al. | Activation of boron nitride nanotubes and their polymer composites for improving mechanical performance | |
| CN106744900A (en) | A kind of preparation method of polymolecularity Graphene | |
| WO2015099457A1 (en) | Production method for graphene | |
| CN110157931B (en) | Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
| Sumdani et al. | Recent advances of the graphite exfoliation processes and structural modification of graphene: a review | |
| CN103922323A (en) | Method for preparing small-diameter graphene | |
| CN109929141A (en) | A kind of graphene oxide and its epoxy nano composite material of polyethyleneimine-modified | |
| Saadatmandi et al. | Effective epoxy composite coating mechanical/fracture toughness properties improvement by incorporation of graphene oxide nano-platforms reduced by a green/biocompataible reductant | |
| Gao et al. | Polyhedral oligomeric silsesquioxane modified carbon nanotube hybrid material with a bump structure via polydopamine transition layer | |
| Chen et al. | Epoxy/ionic liquid-like mwcnts composites with improved processability and mechanical properties | |
| Dutta et al. | Laser induced incorporation of CNTs in graphene electrodes improves flexibility and conductivity | |
| Li et al. | Influence of silanized low‐dimensional carbon nanofillers on mechanical, thermomechanical, and crystallization behaviors of poly (L‐lactic acid) composites—A comparative study | |
| US20210206644A1 (en) | Substituted graphane material with three-dimensional structure and preparation method thereof | |
| CN111253710B (en) | High-damping graphene/polymer composite material and preparation method thereof | |
| CN106751263A (en) | Stannic oxide/graphene nano lamella strengthens the preparation method of polyvinyl alcohol composite material | |
| CN105542398A (en) | Nano core-shell particle and preparation method and application thereof | |
| Kong et al. | Fabrication and properties for novel graphene oxide powder with extra large interlayer spacing and high reactivity | |
| CN113004829A (en) | Electronic adhesive for packaging graphene-based semiconductor chip and preparation method thereof | |
| Luo et al. | Templating assembly of NIR light-actuated TPU/SCNT-C60 flexible structures with high conductivity and controllable recovery behavior |
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 |