CN103708510B - A kind of preparation method of stratiform aluminum oxide micro-sphere - Google Patents
A kind of preparation method of stratiform aluminum oxide micro-sphere Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of stratiform aluminum oxide micro-sphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resin microsphere as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain alumina gel microballoon, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains stratiform aluminum oxide micro-sphere.Compared with prior art, the present invention adopts urea formaldehyde resin microsphere to be template, this Template preparation is easy, the present invention utilizes the ring opening of propylene oxide that aluminum ion generation hydroxyl is joined and oxygen connection is obtained by reacting alumina gel microballoon, stratiform aluminum oxide micro-sphere uniform particle sizes prepared by the present invention, shape is regular, and hardness is stronger, more resistance to grinding.
Description
Technical field
The present invention relates to a kind of preparation method of stratiform aluminum oxide micro-sphere, belong to the synthesis preparing technical field of compound.
Background technology
Aluminum oxide has the advantages such as high temperature resistant, corrosion-resistant and good insulating property, makes it obtain widespread use in fields such as catalysis industry, electronic industry, biological medicine, pottery, coating and optical materials.Because its specific surface area is comparatively large, the advantages such as good stability, the application in absorption is also very extensive.Stratiform aluminum oxide micro-sphere specific surface area is large, and pore volume is little, and high specific surface pore volume is than being more conducive to absorption, catalysis.
DaltonF.Cheng utilizes the surface property of polymethylmethacrylate and polystyrene successfully to prepare the aluminum oxide film of the hard, clear of 500nm-5 μm of thickness.This film is actual is the anodised aluminium of stratiform, demonstrates excellent tackyness and surperficial mechanical property.And smooth surface is transparent.
FerdiSchuth aluminum nitrate solution is as presoma, and carbon aerogels makes hard template, adopts nanometer teeming practice synthesis controllable bore diameter, the glass-clear aluminum oxide that specific surface area is large.
DongyuanZhao using bimodal mesoporous carbon as hard template, the aluminum oxide in the synthesizing ordered hole of method of combining nano casting.
WeiquanCai, in the ethanolic soln of P123, adopts the synthesizing ordered mesoporous aluminum oxide of method of EISA (evaporation-induced self-assembly) and other metal oxides (nickel, magnesium, the iron of alumina load, chromium, copper, cerium, lanthanum, yttrium, calcium, tin) etc.
But uncommon to the report of aluminum oxide micro-sphere, and rare especially to the report of stratiform aluminum oxide micro-sphere.
Summary of the invention
Object of the present invention be exactly provide that a kind of uniform particle sizes, shape are regular to overcome defect that above-mentioned prior art exists, hardness more by force, the preparation method of the stratiform aluminum oxide micro-sphere of more resistance to grinding.
Object of the present invention can be achieved through the following technical solutions:
A kind of preparation method of stratiform aluminum oxide micro-sphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resin microsphere as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain alumina gel microballoon, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains stratiform aluminum oxide micro-sphere.
The method comprises the following steps:
(1) urea and formaldehyde are obtained by reacting urea-formaldehyde resin precipitation in acidic aqueous solution, precipitate and dry to obtain urea formaldehyde resin microsphere with deionized water and washing with alcohol urea-formaldehyde resin;
(2) nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resin microsphere is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, obtain being adsorbed with aluminum ions urea formaldehyde resin microsphere;
(4) aluminum ions urea formaldehyde resin microsphere will be adsorbed with and be placed in propylene oxide steam ambient 4 ~ 5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in Aqueous Solutions of Polyethylene Glycol ultrasonic disperse;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, obtains stratiform aluminum oxide micro-sphere;
Urea described in step (1) and the mol ratio of formaldehyde are 2: 1, the structure of the urea formaldehyde resin microsphere now obtained is approximate linear structure, the pattern of urea formaldehyde resin microsphere is stratiform resin microsphere, because urea-formaldehyde resin itself is a kind of semicrystalline structure, reactive force between thread-like molecule is more weak, the pattern of final product crystallization is easily changed, therefore, the urea formaldehyde resin microsphere of synthesizing under this urea and formaldehyde ratio is the aluminum oxide micro-sphere that Template preparation goes out is stratiform aluminum oxide micro-sphere.
Described stratiform aluminum oxide micro-sphere diameter is 4 ~ 5 microns.
Acidic aqueous solution described in step (1) is hydrochloric acid soln.
Nine water aluminum nitrates described in step (2) and the proportionlity of dehydrated alcohol are: dissolve nine water aluminum nitrate 0.3 ~ 0.5 gram in every milliliter of dehydrated alcohol.
The time needed for absorption immersion described in step (3) is 10 ~ 14 hours, and the temperature that absorption is soaked is 25 ~ 35 DEG C.
The massfraction of the Aqueous Solutions of Polyethylene Glycol described in step (5) is 4 ~ 6%.
The time of the ultrasonic disperse described in step (5) is 1 ~ 2 hour.
The temperature program(me) of the roasting described in step (6) is 30 DEG C and arrives 200 DEG C through 480min, and 200 DEG C keep 120min, arrive 350 DEG C through 120min, and 350 DEG C keep 60min, arrive 450 DEG C, then drop to room temperature through 120min.
Compared with prior art, the present invention has the following advantages and beneficial effect:
A () the present invention adopts urea formaldehyde resin microsphere to be template, this Template preparation is easy;
B the mol ratio of () urea of the present invention and formaldehyde is 2: 1, the pattern of the urea formaldehyde resin microsphere prepared is stratiform resin microsphere, therefore be stratiform aluminum oxide micro-sphere as the aluminum oxide micro-sphere that Template preparation goes out, the hardness of stratiform aluminum oxide micro-sphere is stronger, more resistance to grinding;
C () the present invention utilizes the ring opening of propylene oxide that aluminum ion generation hydroxyl is joined and oxygen connection is obtained by reacting alumina gel microballoon;
D stratiform aluminum oxide micro-sphere uniform particle sizes prepared by () the present invention, shape is regular.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the stratiform aluminum oxide micro-sphere that 20 times are amplified;
Fig. 2 is the SEM figure of the stratiform aluminum oxide micro-sphere that 10 times are amplified.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
In the beaker of the 100mL of 40mL distilled water, after adding the dissolving of 2.25g urea, then stir after respectively adding 1.5mL formaldehyde, finally add the hydrochloric acid of 0.2mL.Leave standstill and when solution reaction generates the state of cloud white, to continue reaction suction filtration after ten minutes, use a small amount of deionized water and ethanol to wash respectively and obtain urea-formaldehyde resin precipitation for three times.Urea formaldehyde resin microsphere after separation under room temperature dry 5 hours, and then 70 DEG C of dry 24h in an oven, obtain urea formaldehyde resin microsphere.
Take 4g nine water aluminum nitrate and be placed in beaker containing 10ml dehydrated alcohol, magnetic agitation makes nine water aluminum nitrates dissolve completely.Prepared urea formaldehyde resin microsphere is put in the ethanolic soln of aluminum nitrate, absorption immersion 12 hours.Filtration gains are placed in propylene oxide steam ambient 4 hours by filtering mixt.Taking out renders in the Aqueous Solutions of Polyethylene Glycol of 5%, and ultrasonic disperse filtered after 1 hour.Filtration product is placed in air at room temperature and dries, and finally calcines, and during calcining, program temperature is 30 DEG C and arrives 200 DEG C through 480min, and 200 DEG C keep 120min, arrive 350 DEG C through 120min, and 350 DEG C keep 60min, 120min to arrive 450 DEG C, then drop to room temperature.Then stratiform aluminum oxide micro-sphere is obtained.Shape as shown in Figure 1.
Experiment embodiment 2
A kind of preparation method of stratiform aluminum oxide micro-sphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resin microsphere as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain urea-formaldehyde resin-alumina gel complex microsphere, then complex microsphere is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains stratiform aluminum oxide micro-sphere.
The method comprises the following steps:
(1) urea and formaldehyde with mol ratio be 2: 1 ratio in acidic aqueous solution (hydrochloric acid soln), be obtained by reacting urea-formaldehyde resin precipitation, precipitate by deionized water and washing with alcohol and dry and obtain urea formaldehyde resin microsphere;
(2) with the ratio of dissolving nine water aluminum nitrate 0.4 gram in every milliliter of dehydrated alcohol, nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resin microsphere renders to absorption immersion in the ethanolic soln of aluminum nitrate, and absorption soak time is 12 hours, and absorption soaking temperature is 30 DEG C, obtains being adsorbed with aluminum ions urea formaldehyde resin microsphere;
(4) aluminum ions urea formaldehyde resin microsphere will be adsorbed with and be placed in propylene oxide steam ambient 4 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection, obtain urea-formaldehyde resin-alumina gel complex microsphere;
(5) urea-formaldehyde resin-alumina gel complex microsphere is placed in the Aqueous Solutions of Polyethylene Glycol ultrasonic disperse 1 hour that massfraction is 5%;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, temperature program(me) during roasting is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, arrive 350 DEG C through 120min, 350 DEG C keep 60min, arrive 450 DEG C through 120min, then drop to room temperature, obtain stratiform aluminum oxide micro-sphere.
Obtained stratiform aluminum oxide micro-sphere diameter is 4 ~ 5 microns.
Embodiment 3
A kind of preparation method of stratiform aluminum oxide micro-sphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resin microsphere as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain urea-formaldehyde resin-alumina gel complex microsphere, then complex microsphere is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains stratiform aluminum oxide micro-sphere.
The method comprises the following steps:
(1) urea and formaldehyde with mol ratio be 2: 1 ratio in acidic aqueous solution (hydrochloric acid soln), be obtained by reacting urea-formaldehyde resin precipitation, precipitate by deionized water and washing with alcohol and dry and obtain urea formaldehyde resin microsphere;
(2) with the ratio of dissolving nine water aluminum nitrate 0.3 gram in every milliliter of dehydrated alcohol, nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resins microballoon is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, absorption soak time is 10 hours, and absorption soaking temperature is 25 DEG C, obtains being adsorbed with aluminum ions urea formaldehyde resin microsphere;
(4) aluminum ions urea formaldehyde resin microsphere will be adsorbed with and be placed in propylene oxide steam ambient 4.5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection, obtain urea-formaldehyde resin-alumina gel complex microsphere;
(5) urea-formaldehyde resin-alumina gel complex microsphere is placed in the Aqueous Solutions of Polyethylene Glycol ultrasonic disperse 1.5 hours that massfraction is 4%;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, temperature program(me) during roasting is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, arrive 350 DEG C through 120min, 350 DEG C keep 60min, arrive 450 DEG C through 120min, then drop to room temperature, obtain stratiform aluminum oxide micro-sphere.
Obtained stratiform aluminum oxide micro-sphere diameter is 4 ~ 5 microns.
Embodiment 4
A kind of preparation method of stratiform aluminum oxide micro-sphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resin microsphere as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain urea-formaldehyde resin-alumina gel complex microsphere, then complex microsphere is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains stratiform aluminum oxide micro-sphere.
The method comprises the following steps:
(1) urea and formaldehyde with mol ratio be 2: 1 ratio in acidic aqueous solution (hydrochloric acid soln), be obtained by reacting urea-formaldehyde resin precipitation, precipitate by deionized water and washing with alcohol and dry and obtain urea formaldehyde resin microsphere;
(2) with the ratio of dissolving nine water aluminum nitrate 0.5 gram in every milliliter of dehydrated alcohol, nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resin microsphere is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, absorption soak time is 14 hours, and absorption soaking temperature is 35 DEG C, obtains being adsorbed with aluminum ions urea formaldehyde resin microsphere;
(4) aluminum ions urea formaldehyde resin microsphere will be adsorbed with and be placed in propylene oxide steam ambient 5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection, obtain urea-formaldehyde resin-alumina gel complex microsphere;
(5) urea-formaldehyde resin-alumina gel complex microsphere is placed in the Aqueous Solutions of Polyethylene Glycol ultrasonic disperse 2 hours that massfraction is 6%;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, temperature program(me) during roasting is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, arrive 350 DEG C through 120min, 350 DEG C keep 60min, arrive 450 DEG C through 120min, then drop to room temperature, obtain stratiform aluminum oxide micro-sphere.
Obtained stratiform aluminum oxide micro-sphere diameter is 4 ~ 5 microns.
The above-mentioned description to embodiment can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (7)
1. the preparation method of a stratiform aluminum oxide micro-sphere, it is characterized in that, take aluminum nitrate as aluminium source, utilize urea formaldehyde resin microsphere as template, Al adsorption ion, makes to be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection, obtains alumina gel microballoon under the effect of propylene oxide ring-opening reaction, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains stratiform aluminum oxide micro-sphere;
The method comprises the following steps:
(1) urea and formaldehyde are obtained by reacting urea-formaldehyde resin precipitation in acidic aqueous solution, precipitate and dry to obtain urea formaldehyde resin microsphere with deionized water and washing with alcohol urea-formaldehyde resin;
(2) nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resin microsphere is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, obtain being adsorbed with aluminum ions urea formaldehyde resin microsphere;
(4) aluminum ions urea formaldehyde resin microsphere will be adsorbed with and be placed in propylene oxide steam ambient 4 ~ 5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction in urea formaldehyde resin microsphere and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in Aqueous Solutions of Polyethylene Glycol ultrasonic disperse;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, obtains stratiform aluminum oxide micro-sphere; Urea described in step (1) and the mol ratio of formaldehyde are 2:1;
Described stratiform aluminum oxide micro-sphere diameter is 4 ~ 5 microns.
2. the preparation method of a kind of stratiform aluminum oxide micro-sphere according to claim 1, is characterized in that, the acidic aqueous solution described in step (1) is hydrochloric acid soln.
3. the preparation method of a kind of stratiform aluminum oxide micro-sphere according to claim 1, is characterized in that, nine water aluminum nitrates described in step (2) and the proportionlity of dehydrated alcohol are: dissolve nine water aluminum nitrate 0.3 ~ 0.5 gram in every milliliter of dehydrated alcohol.
4. the preparation method of a kind of stratiform aluminum oxide micro-sphere according to claim 1, is characterized in that, the time needed for absorption immersion described in step (3) is 10 ~ 14 hours, and the temperature that absorption is soaked is 25 ~ 35 DEG C.
5. the preparation method of a kind of stratiform aluminum oxide micro-sphere according to claim 1, is characterized in that, the massfraction of the Aqueous Solutions of Polyethylene Glycol described in step (5) is 4 ~ 6%.
6. the preparation method of a kind of stratiform aluminum oxide micro-sphere according to claim 1, is characterized in that, the time of the ultrasonic disperse described in step (5) is 1 ~ 2 hour.
7. the preparation method of a kind of stratiform aluminum oxide micro-sphere according to claim 1, it is characterized in that, the temperature program(me) of the roasting described in step (6) is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, 350 DEG C are arrived through 120min, 350 DEG C keep 60min, arrive 450 DEG C, then drop to room temperature through 120min.
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| CN1113922A (en) * | 1994-06-02 | 1995-12-27 | 中国科学院化学研究所 | Porous oxide micro-balls with uniform granule size and preparing method |
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| CN1113922A (en) * | 1994-06-02 | 1995-12-27 | 中国科学院化学研究所 | Porous oxide micro-balls with uniform granule size and preparing method |
Non-Patent Citations (3)
| Title |
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| 以无机铝盐为前驱体用溶胶凝胶法合成中孔氧化铝;郝志显等;《物理化学学报》;20071231;第23卷(第3期);289-294 * |
| 新型氧化铝空心球的制备及表征;庞利萍等;《物理化学学报》;20081231;第24卷(第6期);1115-1119 * |
| 脲醛树脂基炭微球的制备及其形貌控制研究;王大林;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20120615(第6期);26、81-83 * |
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