CN108970556A - A kind of synthetic method of Lauxite nanosphere - Google Patents
A kind of synthetic method of Lauxite nanosphere Download PDFInfo
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- CN108970556A CN108970556A CN201810713736.1A CN201810713736A CN108970556A CN 108970556 A CN108970556 A CN 108970556A CN 201810713736 A CN201810713736 A CN 201810713736A CN 108970556 A CN108970556 A CN 108970556A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Abstract
The invention discloses a kind of synthetic methods of Lauxite nanosphere, comprising the following steps: mutually mixes compound surfactant, cosurfactant, oil in proportion with aqueous solution of urea, is configured to reverse micro emulsion；Formalin is added into the reverse micro emulsion, with strong acid for adjusting pH value, carries out resinification reaction；Reaction system obtains Lauxite nanosphere of the particle diameter distribution between 10 ~ 100 nm through demulsification, centrifugation, washing and freeze-drying.The specific surface area minimum for the nanosphere N2 adsorption measurement being prepared is in 730 m2·g‑1, total pore size volume minimum is in 0.59 cm3·g‑1.The electrode of nanosphere preparation, specific capacitance minimum is in 444 Fg‑1, 500 circle charge and discharge cycles after specific capacitance loss late be up to 1.5%, can be used as super capacitor material.Meanwhile when as gluing agent addition agent, the curing time of adhesive shortens, bonding strength improves, and burst size of methanal reduces.
Description
Technical field
The present invention relates to a kind of synthetic methods of Lauxite nanosphere, belong to polymer nano material preparation field.
Background technique
Polymer nano-microspheres are a kind of sizes in nanometer to the high molecular material between sub-micron, have specific surface area
Greatly, strong adsorption has the characteristics that responsiveness to temperature, pH value and changes of magnetic field, from first report in relation to nanosphere
Start, just people is caused widely to pay close attention to.The application for being proved nanosphere at present is almost related to all fields, in electrification
It learns, gas absorption and separation, Industrial Catalysis agent carrier, gluing agent addition agent and pharmaceutical engineering and Biochemical Engineering field are answered
With especially popular in recent years.
Mainly there is polystyrene for preparing the high molecular material of polymer nano-microspheres, polymethyl methacrylate, gather
Acrylamide and polyaniline etc., and use the rare report of Lauxite synthetic polymer nanosphere.Urea formaldehyde resin microsphere is general
It is synthesized using hydro-thermal method precipitation polymerization method, the partial size of microballoon is micron order.
Microemulsion is usually by surfactant, cosurfactant (usually alcohols), oily (usually hydrocarbon)
The transparent or semitransparent, low viscosity and isotropic thermodynamics spontaneously formed under ratio appropriate with water or aqueous solution is steady
Determine system.When selecting W/O microemulsion as the template for preparing nanosphere, when surfactant concentration is more than certain C MC(critical
Micellar concentration) when, it is formed by hydrophilic polar head " micro- pond " structure that the micella boundary layer of hydrophobic chain outwardly wraps up inwardly, these
" micro- pond " is separated from each other, referred to as dispersed phase.Since microemulsion belongs to thermodynamic stable system, micella structure under certain condition
At " micro- pond " have keep specific dimensions and pattern characteristic, that is, rupture after can it is spontaneous reconfigure and size and shape not
Become, and reactant is limited in reaction in " micro- pond " to also have " micro- pond " certain size and pattern, therefore again
" micro- pond " constructed by reverse micro emulsion is known as intelligent response device.Under the assistance of cosurfactant, " micro- pond " energy
Significant solubilising polar liquid (water or aqueous solution), the range scale in " micro- pond " are 5-100nm, size depend on Solubilization of Water or
The amount of aqueous solution, the two are proportional in a certain range；And the pattern (spherical or other shapes) in " micro- pond " and surface
The type of activating agent is related to concentration, i.e., can very easily make " micro- pond " by the type and concentration that change surfactant
With spherical morphology, thus monodisperse can be obtained by single-phase inverting type (W/O) the microemulsion system composition of adjusting completely and received
Meter level spherical shape reaction compartment, and ideal dispersed nano microballoon is prepared by template of this space.Urea, formaldehyde and promote to urinate
Addition occurs for plain formaldehyde and the catalyst of polycondensation reaction all has water solubility, can be solubilized into " micro- pond " and by " micro- pond "
Addition and polycondensation reaction are completed in the nano-level sphere reactor of building, therefore select single-phase Reverse Microemulsion System as ureaformaldehyde
The controllable preparation of resin nano microballoon is feasible.
Chinese patent ZL 201110272169.9 is reported a kind of to be closed under Action of Surfactant using urea and formaldehyde
At the method for urea formaldehyde resin microsphere, this method is not belonging to conversed phase micro emulsion copolymerization, and the particle diameter distribution of gained urea formaldehyde resin microsphere
In the micron-scale.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of existing technologies, a kind of Lauxite nanosphere is provided
Synthetic method, synthetic polymer microballoon be nanoscale Lauxite.
In order to solve the above technical problems, the present invention provides a kind of synthetic method of Lauxite nanosphere, feature exists
In, comprising the following steps:
(1) compound surfactant, cosurfactant, oil phase and aqueous solution of urea are mixed to get mixture in proportion,
The mixture is adjusted to set temperature in magnetic agitation, setting the magnetic agitation time then after, stop stirring, setting
Determine to keep the temperature at temperature, stand, is clarified, transparent reverse micro emulsion；
(2) formalin is added into the reverse micro emulsion, with strong acid for adjusting pH value, sets the magnetic agitation time then again
Afterwards, stop stirring, heat preservation stands progress resinification reaction, obtains reaction system；
(3) it is added demulsifier into above-mentioned reaction system, after supercentrifuge centrifugal treating, removes supernatant liquor, it is solid to obtain lower layer
Body；
(4) detergent is added in lower layer's solid, within the set time supersound washing, after supercentrifuge centrifugal treating, removal
Supernatant liquor, lower layer's solid vacuum freeze drying, obtains Lauxite nanosphere.
Preferably, compound surfactant is made of CTAB and Span85 in the step (1), CTAB and Span85's
Composition mass ratio is 1:3 ~ 1:10；In the step (1) cosurfactant be n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol,
The composition mass ratio of one of 1- octanol, complexed surfactant and cosurfactant is 1:5 ~ 1:8；The step (1)
Middle oil mutually includes one of pentane, hexamethylene, normal heptane, normal octane, n-hexane, complexed surfactant and helps surface living
Property agent mixture and oily phase composition mass ratio be one of 1:9,2:8,3:7,4:6,5:5,6:4,7:3,8:2 or 9:1；Institute
It states in step (1) aqueous solution of urea and adds deionized water to be formulated by analyzing pure urea, concentration is 20% ~ 50%, and composite surface is living
Property agent, the mixture of cosurfactant and oily phase and aqueous solution of urea composition mass ratio be 10:1 ~ 30:1；
Preferably, the magnetic agitation time set in the step (1) as 1 ~ 10 min, magnetic agitation rotating speed≤100 rpm, if
Determining holding temperature is 10 ~ 90 DEG C, stands 10 ~ 30 min；
Preferably, the concentration of formalin is 36% ~ 38% in the step (2)；Additional amount presses the molar ratio of formaldehyde and urea
0.4:1 ~ 2:1 addition；
Preferably, the strong acid is to analyze one of pure grade hydrochloric acid or formic acid；
Preferably, the pH value adjusting range is pH value≤5.0；Resinification reaction temperature and reverse phase are micro- in the step (2)
Set temperature is identical when lotion is kept the temperature, and is 10 ~ 90 DEG C；1 ~ 10 min of magnetic agitation in the step (2), magnetic agitation rotating speed≤
100 rpm, resinification reaction time are 6 ~ 12 h.
Preferably, demulsifier is deionized water in the step (3), and additional amount is until reverse micro emulsion is demulsified；It is described
The revolving speed of step (3) high speed centrifuge is 10 000 ~ 26 000 rpm.
Preferably, detergent is dehydrated alcohol and deionized water in the step (4), first uses dehydrated alcohol supersound washing extremely
It is 3 times few, then with deionized water supersound washing at least 3 times；Supersonic frequency≤40kHz in the step (4), supersound washing time is
5~20 min；The temperature of precooling process is less than -40 DEG C in the vacuum freeze drying, and the vacuum degree of lyophilization process is
0.01 ~ 0.1 mbar, freeze temperature are -40 ~ -60 DEG C, and the vacuum degree of parsing-desiccation process is 0.001 ~ 0.01 mbar, is lyophilized
Temperature -60 ~ -80 DEG C.
Advantageous effects of the invention: using synthetic method of the invention, it is poly- as Material synthesis using urea and formaldehyde
Object microballoon is closed, and by the control of the particle diameter distribution of polymer microballoon in nano-scale range, as natural nitrogenous polymer microsphere,
The nano-scale carbon microspherulite diameter range obtained using the nanosphere as precursor preparation is between 10 ~ 100 nm, N2 adsorption measurement
Specific surface area minimum in 730 m2·g-1, total pore size volume minimum is in 0.49 cm3·g-1, compared with Lauxite micron order microballoon
320 m of specific surface area of N2 adsorption measurement2·g-1With 0.28 cm of total pore size volume3·g-1It significantly increases, is inhaled as adsorbent material
Attached performance significantly improves.The electrode of nano-scale carbon microballoon preparation, specific capacitance minimum is in 444 Fg in electrochemical property test-1, 288 Fg of specific capacitance of carbosphere more nitrogenous than micron grade urea-formaldehyde resin resin-1Height, 500 enclose specific capacitance after charge and discharge cycles
Loss late is up to 1.5%, and carbosphere specific capacitance loss late 3.2% more nitrogenous than micron grade urea-formaldehyde resin is small, as supercapacitor
Material property is more preferable than Lauxite micron order carbosphere performance.It selects and is synthesized by formaldehyde with the proportion of the molar ratio 1:1 of urea
Microballoon particle size range 40 ~ 50 nm Lauxite as gluing agent addition agent, in 0.5% additive amount, adhesive
Curing time shorten 42%, the bonding strength of glued board improves 33%, and burst size of methanal reduces by 21%.
Detailed description of the invention
Fig. 1 is the TEM figure for the Lauxite nanosphere that the present invention synthesizes.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention
Technical solution, and not intended to limit the protection scope of the present invention.
Embodiment 1
1 g CTAB, 3 g Span85,20 g n-butanols and 216 g pentanes are added in 1 000 mL beakers, 24 g are added
The urea deionized water solution that concentration is 20%, at 10 DEG C of holding temperature, 10 rpm of magnetic agitation rotating speed, 1 min of magnetic agitation
Stop stirring afterwards, stands 10 min, clarified, transparent reverse micro emulsion.It is dense that 2.59 g are added dropwise into the reverse micro emulsion
The pure formalin of analysis that degree is 37%, the molar ratio of formaldehyde and urea is 0.4:1 at this time；In magnetic agitation with formic acid tune
After whole pH value is 1,10 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 1 min of magnetic agitation, and heat preservation is stood, and is carried out
6 h are reacted in resinification, and resinification reaction temperature is controlled at 10 DEG C.After resinification reaction end is demulsified with deionized water, with high speed
Centrifuge is centrifugated out lower layer's solid, 26 000 rpm of centrifuge speed；Lower layer's solid first uses dehydrated alcohol ultrasonic washing 3
It is secondary, then with deionized water ultrasonic washing 3 times, 10 kHz of ultrasonic frequency is still isolated with supercentrifuge each time after washing
Solid washs 5 min, 26 000 rpm of centrifuge speed every time.Last solid is in -40 DEG C of pre-freezes to complete ice knot；Distillation
Dryer section, vacuum degree 0.01 mbar, -40 DEG C of freeze temperature；Parsing-desiccation section, 0.001 mbar of vacuum degree, freeze temperature-
80 DEG C, Lauxite nanosphere is obtained, the particle size range of microballoon is in 10 ~ 20 nm.
Embodiment 2
1 g CTAB, 4 g Span85,30 g n-amyl alcohols and 140 g hexamethylenes are added in 1 000 mL beakers, are added 17.5
The urea deionized water solution that g concentration is 30%, at 20 DEG C of holding temperature, magnetic agitation rotating speed 20 rpm, magnetic agitation 2min
Stop stirring afterwards, stands 15min, clarified, transparent reverse micro emulsion.4.26 g concentration are added dropwise into the reverse micro emulsion
For the 37% pure formalin of analysis, the molar ratio of formaldehyde and urea is 0.6:1 at this time；It is adjusted in magnetic agitation with hydrochloric acid
After pH value is 2,20 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 2 min of magnetic agitation, and it is anti-to stand progress resinification
7 h are answered, resinification reaction temperature is controlled at 20 DEG C.Resinification reaction end be demulsified with deionized water after, with supercentrifuge from
The heart isolates lower layer's solid, 24 000 rpm of centrifuge speed；Lower layer's solid is first used dehydrated alcohol ultrasonic washing 3 times, then is used
Deionized water ultrasonic washing 3 times, 15 kHz of ultrasonic frequency still isolates solid with supercentrifuge each time after washing, often
Secondary washing 5 min, 24 000 rpm of centrifuge speed.Last solid is in -45 DEG C of pre-freezes to complete ice knot；Lyophilization section,
Vacuum degree 0.02 mbar, -45 DEG C of freeze temperature；Parsing-desiccation section, 0.002 mbar of vacuum degree, freeze temperature are obtained at -70 DEG C
Lauxite nanosphere is obtained, the particle size range of microballoon is in 20 ~ 30 nm.
Embodiment 3
1 g CTAB, 5 g Span85,42 g n-hexyl alcohols and 112 g normal heptanes are added in 1 000 mL beakers, 16 g are added
The urea deionized water solution that concentration is 40% stops stirring after 30 rpm of magnetic agitation rotating speed, 3 min of magnetic agitation, stands 20
Min is clarified, transparent reverse micro emulsion, and holding temperature is at 30 DEG C.6.92 g concentration are added dropwise into the reverse micro emulsion
For the 37% pure formalin of analysis, the molar ratio of formaldehyde and urea is 0.8:1 at this time；It is adjusted in magnetic agitation with formic acid
After pH value is 3,30 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 3 min of magnetic agitation, and heat preservation is stood, and is set
8 h of esterification reaction, resinification reaction temperature are controlled at 30 DEG C.Resinification reaction end be demulsified with deionized water after, with high speed from
Scheming is centrifugated out lower layer's solid, 22 000 rpm of centrifuge speed；Lower layer's solid first uses dehydrated alcohol ultrasonic washing 3
It is secondary, then with deionized water ultrasonic washing 3 times, 20 kHz of ultrasonic frequency is still isolated with supercentrifuge each time after washing
Solid washs 5 min, 22 000 rpm of centrifuge speed every time.Last solid is in -50 DEG C of pre-freezes to complete ice knot；Distillation
Dryer section, vacuum degree 0.03mbar, -50 DEG C of freeze temperature；Parsing-desiccation section, 0.003 mbar of vacuum degree, freeze temperature is -60
DEG C, Lauxite nanosphere is obtained, the particle size range of microballoon is in 30 ~ 40 nm.
Embodiment 4
1 g CTAB, 6 g Span85,56 g n-heptanols and 94.5 g normal octanes are added in 1 000 mL beakers, are added
The urea deionized water solution that 15.75 g concentration are 50%, at 40 DEG C of holding temperature, 40 rpm of magnetic agitation rotating speed, magnetic force is stirred
Stop stirring after mixing 4 min, stand 25 min, clarified, transparent reverse micro emulsion,.It is added dropwise into the reverse micro emulsion
The pure formalin of analysis that 10.64 g concentration are 37%, the molar ratio of formaldehyde and urea is 1:1 at this time；It is used in magnetic agitation
After hydrochloric acid adjustment pH value is 4,40 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 4 min of magnetic agitation, keeps the temperature, is quiet
It sets, carries out resinification and react 9 h, resinification reaction temperature is controlled at 40 DEG C.After resinification reaction end is demulsified with deionized water,
Lower layer's solid, 20 000 rpm of centrifuge speed are centrifugated out with supercentrifuge；Lower layer's solid first uses dehydrated alcohol ultrasonic
Wave washs 3 times, then with deionized water ultrasonic washing 3 times, 30 kHz of ultrasonic frequency still uses supercentrifuge each time after washing
Solid is isolated, washs 5 min, 20 000 rpm of centrifuge speed every time.Last solid is in -60 DEG C of pre-freezes to complete ice
Knot；Lyophilization section, vacuum degree 0.04 mbar, -55 DEG C of freeze temperature；Parsing-desiccation section, 0.004 mbar of vacuum degree, freeze-drying
Temperature obtains Lauxite nanosphere, the particle size range of microballoon is in 40 ~ 50 nm at -55 DEG C.
Embodiment 5
1 g CTAB, 7 g Span85,40 g 1- octanols and 48 g n-hexanes are added in 1 000 mL beakers, 9.6 g are added
The urea deionized water solution that concentration is 20%, at 50 DEG C of holding temperature, 50 rpm of magnetic agitation rotating speed, 5 min of magnetic agitation
Stop stirring afterwards, stands 30 min, clarified, transparent reverse micro emulsion.3.11g concentration is added dropwise into the reverse micro emulsion
For the 37% pure formalin of analysis, the molar ratio of formaldehyde and urea is 1.2:1 at this time；It is adjusted in magnetic agitation with formic acid
After pH value is 5,50 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 5 min of magnetic agitation, and heat preservation is stood, and is set
10 h of esterification reaction, resinification reaction temperature are controlled at 50 DEG C.Resinification reaction end be demulsified with deionized water after, with high speed from
Scheming is centrifugated out lower layer's solid, 18 000 rpm of centrifuge speed；Lower layer's solid first uses dehydrated alcohol ultrasonic washing 3
It is secondary, then with deionized water ultrasonic washing 3 times, 10 kHz of ultrasonic frequency is still isolated with supercentrifuge each time after washing
Solid washs 5 min, 18 000 rpm of centrifuge speed every time.Last solid is in -55 DEG C of pre-freezes to complete ice knot；Distillation
Dryer section, vacuum degree 0.05 mbar, -55 DEG C of freeze temperature；Parsing-desiccation section, 0.005 mbar of vacuum degree, freeze temperature-
60 DEG C, Lauxite nanosphere is obtained, the particle size range of microballoon is in 50 ~ 60 nm.
Embodiment 6
1 g CTAB, 8 g Span85,54 g n-butanols and 42 g hexamethylenes are added in 1 000 mL beakers, 10.5g is added
The urea deionized water solution that concentration is 30%, at 60 DEG C of holding temperature, 60 rpm of magnetic agitation rotating speed, 6 min of magnetic agitation
Stop stirring afterwards, stands 10 min, clarified, transparent reverse micro emulsion.It is dense that 5.96 g are added dropwise into the reverse micro emulsion
The pure formalin of analysis that degree is 37%, the molar ratio of formaldehyde and urea is 1.4:1 at this time；In magnetic agitation with hydrochloric acid tune
After whole pH value is 1,60 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 6 min of magnetic agitation, and heat preservation is stood, and is carried out
11 h are reacted in resinification, and resinification reaction temperature is controlled at 60 DEG C.After resinification reaction end is demulsified with deionized water, with high speed
Centrifuge is centrifugated out lower layer's solid, 16 000 rpm of centrifuge speed；Lower layer's solid first uses dehydrated alcohol ultrasonic washing 3
It is secondary, then with deionized water ultrasonic washing 3 times, 10 kHz of ultrasonic frequency is still isolated with supercentrifuge each time after washing
Solid washs 5 min, 16 000 rpm of centrifuge speed every time.Last solid is in -50 DEG C of pre-freezes to complete ice knot；Distillation
Dryer section, vacuum degree 0.06 mbar, -50 DEG C of freeze temperature；Parsing-desiccation section, 0.006 mbar of vacuum degree, freeze temperature-
70 DEG C, Lauxite nanosphere is obtained, the particle size range of microballoon is in 60 ~ 70 nm.
Embodiment 7
1 g CTAB, 9 g Span85,70 g n-amyl alcohols and 34.3 g normal heptanes are added in 1 000 mL beakers, are added 11.4
The urea deionized water solution that g concentration is 40%, at 70 DEG C of holding temperature, 70 rpm of magnetic agitation rotating speed, magnetic agitation 7
Stop stirring after min, stands 20min, clarified, transparent reverse micro emulsion.9.88 g are added dropwise into the reverse micro emulsion
The pure formalin of analysis that concentration is 37%, the molar ratio of formaldehyde and urea is 1.6:1 at this time；The formic acid in magnetic agitation
After adjustment pH value is 2,70 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 7 min of magnetic agitation, and heat preservation is stood, into
12 h are reacted in row resinification, and resinification reaction temperature is controlled at 70 DEG C.After resinification reaction end is demulsified with deionized water, with height
Fast centrifuge is centrifugated out lower layer's solid, 14 000 rpm of centrifuge speed；Lower layer's solid is first washed with dehydrated alcohol ultrasonic wave
It washs 3 times, then with deionized water ultrasonic washing 3 times, 10 kHz of ultrasonic frequency is still separated with supercentrifuge each time after washing
Solid out washs 5 min, 14 000 rpm of centrifuge speed every time.Last solid is in -40 DEG C of pre-freezes to complete ice knot；It rises
Magnificent dryer section, vacuum degree 0.01 mbar, -40 DEG C of freeze temperature；Parsing-desiccation section, 0.001 mbar of vacuum degree, freeze temperature
At -80 DEG C, Lauxite nanosphere is obtained, the particle size range of microballoon is in 70 ~ 80 nm.
Embodiment 8
1 g CTAB, 10 g Span85,88 g n-hexyl alcohols and 24.8 g normal octanes are added in 1 000 mL beakers, are added
The urea deionized water solution that 12.4 g concentration are 50%, at 80 DEG C of holding temperature, 80 rpm of magnetic agitation rotating speed, magnetic force is stirred
Stop stirring after mixing 8 min, stands 30 min, clarified, transparent reverse micro emulsion.It is added dropwise into the reverse micro emulsion
The pure formalin of analysis that 15.05 g concentration are 37%, the molar ratio of formaldehyde and urea is 1.8:1 at this time；In magnetic agitation
After being 3 with hydrochloric acid adjustment pH value, 80 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 8 min of magnetic agitation, keep the temperature,
It stands and carries out resinification 6 h of reaction, resinification reaction temperature is controlled at 80 DEG C.Resinification reaction end is demulsified with deionized water
Afterwards, lower layer's solid, 12 000 rpm of centrifuge speed are centrifugated out with supercentrifuge；Lower layer's solid is first super with dehydrated alcohol
Sonic washing 3 times, then with deionized water ultrasonic washing 3 times, 15 kHz of ultrasonic frequency still uses high speed centrifugation each time after washing
Machine isolates solid, washs 5 min, 12 000 rpm of centrifuge speed every time.Last solid is in -45 DEG C of pre-freezes to complete ice
Knot；Lyophilization section, vacuum degree 0.02 mbar, -45 DEG C of freeze temperature；Parsing-desiccation section, 0.002 mbar of vacuum degree, freeze-drying
Temperature obtains Lauxite nanosphere, the particle size range of microballoon is in 80 ~ 90 nm at -70 DEG C.
Embodiment 9
1 g CTAB, 5 g Span85,36 g n-heptanols and 98 g n-hexanes are added in 1 000 mL beakers, it is dense that 14 g are added
The urea deionized water solution for being 50% is spent, stops stirring after 90 rpm of magnetic agitation rotating speed, 9 min of magnetic agitation, stands 10
Min is clarified, transparent reverse micro emulsion, and holding temperature is at 90 DEG C.18.92 g concentration are added dropwise into the reverse micro emulsion
For the 37% pure formalin of analysis, the molar ratio of formaldehyde and urea is 2:1 at this time；PH is adjusted with formic acid in magnetic agitation
After value is 4,90 rpm of magnetic agitation rotating speed stops magnetic agitation after continuing 9 min of magnetic agitation, and heat preservation is stood, and carries out resin
Change 8 h of reaction, resinification reaction temperature is controlled at 90 DEG C.After resinification reaction end is demulsified with deionized water, high speed centrifugation is used
Machine is centrifugated out lower layer's solid, 10 000 rpm of centrifuge speed；Lower layer's solid is first used dehydrated alcohol ultrasonic washing 3 times,
It uses deionized water ultrasonic washing 3 times, 20 kHz of ultrasonic frequency, is still isolated each time after washing with supercentrifuge solid again
Body washs 5 min, 10 000 rpm of centrifuge speed every time.Last solid is in -50 DEG C of pre-freezes to complete ice knot；Distillation is dry
Dry section, vacuum degree 0.03 mbar, -50 DEG C of freeze temperature；Parsing-desiccation section, 0.003 mbar of vacuum degree, freeze temperature is -60
DEG C, Lauxite nanosphere is obtained, the particle size range of microballoon is in 90 ~ 100 nm.
Using synthetic method of the invention, using urea and formaldehyde as Material synthesis polymer microballoon, and by polymer microballoon
Particle diameter distribution control in nano-scale range, as natural nitrogenous polymer microsphere, with the nanosphere for forerunner's system
Standby obtained nano-scale carbon microspherulite diameter range is between 10 ~ 100nm, and the specific surface area minimum of N2 adsorption measurement is in 730m2·g-1, total pore size volume minimum is in 0.49cm3·g-1, compared with the specific surface area 320 of Lauxite micron order microballoon N2 adsorption measurement
m2·g-1With 0.28 cm of total pore size volume3·g-1It significantly increases, is significantly improved as adsorbent material absorption property.The nanoscale
The electrode of carbosphere preparation, specific capacitance minimum is in 444Fg in electrochemical property test-1, contain than micron grade urea-formaldehyde resin resin
288 Fg of specific capacitance of nitrogen carbosphere-1Height, 500 circle charge and discharge cycles after specific capacitance loss late be up to 1.5%, compare micron order
The nitrogenous carbosphere specific capacitance loss late 3.2% of Lauxite is small, as super capacitor material performance than Lauxite micron order carbon
Microballoon performance is more preferable.The particle size range of the microballoon for the proportion synthesis that the molar ratio of formaldehyde and urea is 1:1 is selected to make in 40 ~ 50nm
For common urea-formaldehyde resin adhesive additive, in 0.5% additive amount, the curing time of adhesive shortens 42%, glued board
Bonding strength improves 33%, and burst size of methanal reduces by 21%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of synthetic method of Lauxite nanosphere, which comprises the following steps:
(1) compound surfactant, cosurfactant, oil phase and aqueous solution of urea are mixed to get mixture in proportion,
The mixture is adjusted to set temperature in magnetic agitation, setting the magnetic agitation time then after, stop stirring, setting
Determine to keep the temperature at temperature, stand, is clarified, transparent reverse micro emulsion；
(2) formalin is added into the reverse micro emulsion, with strong acid for adjusting pH value, sets the magnetic agitation time then again
Afterwards, stop stirring, heat preservation is stood, and is carried out resinification reaction, is obtained reaction system；
(3) it is added demulsifier into above-mentioned reaction system, after supercentrifuge centrifugal treating, removes supernatant liquor, it is solid to obtain lower layer
Body；
(4) detergent is added in lower layer's solid, within the set time supersound washing, after supercentrifuge centrifugal treating, removal
Supernatant liquor, lower layer's solid vacuum freeze drying, obtains Lauxite nanosphere.
2. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that in the step (1)
Compound surfactant is made of CTAB and Span85, and the composition mass ratio of CTAB and Span85 are 1:3 ~ 1:10；
Cosurfactant is one of n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, 1- octanol in the step (1), is answered
The composition mass ratio for closing surfactant and cosurfactant is 1:5 ~ 1:8；
Oil mutually includes one of pentane, hexamethylene, normal heptane, normal octane, n-hexane, composite surface in the step (1)
The mixture of activating agent and cosurfactant and oily phase composition mass ratio are 1:9,2:8,3:7,4:6,5:5,6:4,7:3,8:2
Or one of 9:1；
Aqueous solution of urea adds deionized water to be formulated by analyzing pure urea in the step (1), and concentration is 20% ~ 50%, compound
The composition mass ratio of surfactant, the mixture of cosurfactant and oily phase and aqueous solution of urea is 10:1 ~ 30:1.
3. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that in the step (1)
Magnetic agitation rotating speed≤100 rpm set holding temperature as 10 ~ 90 DEG C, stood as 1 ~ 10 min the magnetic agitation time set
10~30 min。
4. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that in the step (2)
The concentration of formalin is 36% ~ 38%；Additional amount is added by molar ratio 0.4:1 ~ 2:1 of formaldehyde and urea.
5. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that the strong acid is analysis
One of pure grade hydrochloric acid or formic acid.
6. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that the pH value adjustment
Range is pH value≤5.0；
Set temperature is identical when resinification reaction temperature is kept the temperature with reverse micro emulsion in the step (2), is 10 ~ 90 DEG C；
1 ~ 10 min of magnetic agitation in the step (2), magnetic agitation rotating speed≤100 rpm, resinification reaction time are 6 ~ 12
h。
7. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that in the step (3)
Demulsifier is deionized water, and additional amount is until reverse micro emulsion is demulsified；
The revolving speed of step (3) the high speed centrifuge is 10 000 ~ 26 000 rpm.
8. the synthetic method of Lauxite nanosphere according to claim 1, which is characterized in that in the step (4)
Detergent is dehydrated alcohol and deionized water, is first used dehydrated alcohol supersound washing at least 3 times, then extremely with deionized water supersound washing
It is 3 times few；
Supersonic frequency≤40kHz in the step (4), supersound washing time are 5 ~ 20min；
The temperature of precooling process is less than -40 DEG C in the vacuum freeze drying, and the vacuum degree of lyophilization process is 0.01 ~
0.1 mbar, freeze temperature are -40 ~ -60 DEG C, and the vacuum degree of parsing-desiccation process is 0.001 ~ 0.01mbar, freeze temperature -60
~-80℃。
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