CN107344118A - One kind prepares the controllable TiO of porous resin microsphere surface growth morphology2Method - Google Patents
One kind prepares the controllable TiO of porous resin microsphere surface growth morphology2Method Download PDFInfo
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- CN107344118A CN107344118A CN201710637867.1A CN201710637867A CN107344118A CN 107344118 A CN107344118 A CN 107344118A CN 201710637867 A CN201710637867 A CN 201710637867A CN 107344118 A CN107344118 A CN 107344118A
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- tio
- porous resin
- microsphere
- porous
- microballoon
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- 239000004005 microsphere Substances 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 8
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 isopropyl ester Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/51—
-
- B01J35/647—
Abstract
The present invention relates to one kind to prepare the controllable TiO of porous resin microsphere surface growth morphology2Method, using porous resin microballoon as matrix, pass through water-heat process on its surface and grow inorganic semiconductor TiO2, porous resin microballoon/TiO is prepared2Complex microsphere.The TiO of porous resin microsphere surface2Pattern can carry out Effective Regulation by adjusting resin pore passage structure, titanium source dosage, reaction time etc..Porous resin microballoon/TiO2Complex microsphere has the porous high-specific surface area and TiO of resin microsphere matrix concurrently2The catalysis characteristics of material, i.e. absorption are with the obvious advantage with degrading, and therefore, have broad application prospects in environmentology field.
Description
Technical field
The invention belongs to new material technology field, is related to one kind and prepares the controllable TiO of porous resin microsphere surface growth morphology2
Method, specifically using porous resin microballoon as matrix, by water-heat process in the controllable TiO of its surface growth morphology2, so as to
Prepare porous resin microballoon/TiO2The method of complex microsphere.
Background technology
In recent years, TiO2Report in terms of control preparation is of common occurrence, sheet, spherical, bar-shaped, hollow, mesoporous, flowers etc.
The TiO of pattern2It can be all made by the regulation and control of synthetic method and process conditions, its application study in terms of dyestuff degraded is limited
In its high-specific surface area and the contradiction of high efficiente callback efficiency.Researcher is had found in quartz glass (ZL201410346487.9), ITO
Or TiO can be realized in FTO electro-conductive glass (ZL201210358379.4), ceramic bases (ZL201310422337.7)2Burr
Or the guiding growth of flowers, this high-specific surface area supported titanium2Presented in photoelectric conversion and dyestuff degraded application aspect good
Good effect.With the continuous development of material preparation technology and enriching constantly for material category, using resin microsphere as matrix, with
TiO2For dressing agent complex microsphere by more and more extensive concern.TiO is deposited or is coated with present on polymer microballoon surface2
Method be mainly first synthetic polymer microballoon or micro-capsule, then TiO is coated by sol-gel process on its surface2
(ZL201110150864.8, CN201110150864.8, CN201611120277.3).There is not yet in porous polymer microsphere
The controllable TiO of surface growth morphology2The relevant report of (bar-shaped, near-spherical).
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that one kind prepares porous resin microsphere surface growth morphology
Controllable TiO2Method, this method realizes TiO using porous resin microballoon as matrix, using hydro-thermal method on its surface2Nanometer rods,
TiO2The controllable growth of microballoon, different-shape porous resin microballoon/TiO is prepared2Complex microsphere.
Technical scheme
One kind prepares the controllable TiO of porous resin microsphere surface growth morphology2Method, it is characterised in that step is as follows：
Step 1：Porous resin microballoon is added into titanium source solution, the stainless of polytetrafluoroethyllining lining is transferred to after ultrasonic disperse
In steel hydrothermal reaction kettle, the mass ratio of wherein porous resin microballoon and titanium source solution is 1:10~15；
The titanium source solution is：It is 50~200g/L's using the mass concentration that concentration is prepared as 4~6mol/L hydrochloric acid solutions
Titanium source solution；
Step 2：The stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining is placed in high temperature oven, is to slowly warm up to 180
~220 DEG C, react 4~12h；
Step 3：After reaction terminates, the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining is naturally cooled into room temperature, water
Wash product and be centrifuged, obtain porous resin microsphere/TiO2Complex microsphere.
The titanium source is tetrabutyl titanate or tetraisopropyl titanate.
The porous resin microballoon is cross-linked styrene class, esters of acrylic acid or vinyl cyanide porous polymer microsphere or more
Hole magnetic composite microsphere.
The porous resin microballoon average pore size is more than 20nm.
Beneficial effect
One kind proposed by the present invention prepares the controllable TiO of porous resin microsphere surface growth morphology2Method, with porous resin
Microballoon is matrix, grows inorganic semiconductor TiO by water-heat process on its surface2, porous resin microballoon/TiO is prepared2It is multiple
Close microballoon.The TiO of porous resin microsphere surface2Pattern can be by adjusting resin pore passage structure, titanium source dosage, reaction time etc.
Carry out Effective Regulation.Porous resin microballoon/TiO2Complex microsphere has the porous high-specific surface area and TiO of resin microsphere matrix concurrently2Material
The catalysis characteristics of material, i.e. absorption are with the obvious advantage with degrading, and therefore, have broad application prospects in environmentology field.
This area load TiO2Magnetic composite microsphere in terms of Degradation of Organo-pollutants in Water with Photo-catalysis have three
Clear superiority：(1) TiO of surface spikes shape or flowers shape2With high specific surface area and good photoelectricity conducting power；(2)
Carrier of photocatalyst microspherulite diameter is larger, has easy enrichment, repeat performance；(3) there is pore polymer microsphere surface pair
Pollutant equally has high adsorption capacity, and can play and act synergistically with catalyst.
Brief description of the drawings
Fig. 1 is porous resin microballoon/TiO made from different growth times2Complex microsphere：4h(A)；6h(B)；8h(C)；
10h(D)；12h(E)；
Fig. 2 is porous magnetic resin microsphere/TiO prepared by different titanium source dosages2Complex microsphere:Butyl titanate dosage point
It is not：2g(A)；3g(B)；4g(C)；5g(D)；6g(E)
Embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
Embodiment 1：Porous resin microballoon/TiO2The preparation of complex microsphere
The tetrabutyl titanate solution that mass concentration is 100g/L is prepared, wherein solvent is that the hydrochloric acid that concentration is 5mol/L is molten
Liquid；Porous poly- (styrene-divinylbenzene) microballoons of 3.0g are added in the above-mentioned tetrabutyl titanate solution of 30g, and ultrasound point
Dissipate.Solution after will be scattered is transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, then hydrothermal reaction kettle is placed in
In high temperature oven, 180 DEG C are to slowly warm up to, after reacting 12h, naturally cools to room temperature, product is washed and is centrifuged, produce
Porous poly- (styrene-divinylbenzene) microballoon/TiO2Complex microsphere.
Embodiment 2：Porous resin microballoon/TiO2The preparation of complex microsphere
The tetraisopropyl titanate solution that mass concentration is 100g/L is prepared, wherein solvent is that concentration is molten for 5mol/L hydrochloric acid
Liquid；Porous poly- (GMA-divinylbenzene) microballoons of 2.5g are added to the above-mentioned tetraisopropyl titanates of 30g
In solution, and ultrasonic disperse.Solution after will be scattered is transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, then will
Hydrothermal reaction kettle is placed in high temperature oven, is to slowly warm up to 200 DEG C, after reacting 6h, naturally cools to room temperature, is washed product and is passed through
Centrifuge, produce porous poly- (GMA-divinylbenzene) microballoon/TiO2Complex microsphere.
Embodiment 3：Porous resin microballoon/TiO2The preparation of complex microsphere
The tetrabutyl titanate solution that mass concentration is 100g/L is prepared, wherein solvent is that concentration is 4mol/L hydrochloric acid solutions；
Porous poly- (GMA-divinylbenzene) microballoons of 3.0g are added to the above-mentioned tetrabutyl titanate solution of 30g
In, and ultrasonic disperse.Will it is scattered after solution be transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, then by hydro-thermal
Reactor is placed in high temperature oven, is to slowly warm up to 220 DEG C, after reacting 9h, naturally cools to room temperature, washes product and through centrifugation
Separation, produces porous poly- (GMA-divinylbenzene) microballoon/TiO2Complex microsphere.
Embodiment 4：Porous resin microballoon/TiO2The preparation of complex microsphere
The tetrabutyl titanate solution that mass concentration is 100g/L is prepared, wherein solvent is that concentration is 6mol/L hydrochloric acid solutions；
Porous poly- (styrene-divinylbenzene) microballoons of 2.5g are added in the above-mentioned tetrabutyl titanate solution of 30g, and ultrasonic disperse.
Solution after will be scattered is transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, then hydrothermal reaction kettle is placed in into high temperature
In baking oven, 220 DEG C are to slowly warm up to, after reacting 4h, naturally cools to room temperature, product is washed and is centrifuged, produce porous
Poly- (styrene-divinylbenzene) microballoon/TiO2Complex microsphere.
Embodiment 5：Porous resin microballoon/TiO2The preparation of complex microsphere
The tetraisopropyl titanate solution that mass concentration is 100g/L is prepared, wherein solvent is that concentration is molten for 4mol/L hydrochloric acid
Liquid；Porous poly- (GMA-GDMA) microballoons of 2.2g are added to the above-mentioned titaniums of 33g
In sour four isopropyl ester solutions, and ultrasonic disperse.The stainless steel hydro-thermal that solution after will be scattered is transferred to polytetrafluoroethyllining lining is anti-
Answer in kettle, then hydrothermal reaction kettle be placed in high temperature oven, be to slowly warm up to 200 DEG C, after reacting 10h, naturally cool to room temperature,
Washing product is simultaneously centrifuged, and it is micro- to produce porous poly- (GMA-GDMA)
Ball/TiO2Complex microsphere.
Embodiment 6：Porous resin microballoon/TiO2The preparation of complex microsphere
The tetraisopropyl titanate solution that mass concentration is 50g/L is prepared, wherein solvent is that concentration is 6mol/L hydrochloric acid solutions；
Porous poly- (styrene-divinylbenzene) microballoons of 3.0g are added in the above-mentioned tetraisopropyl titanate solution of 33g, and ultrasound point
Dissipate.Solution after will be scattered is transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, then hydrothermal reaction kettle is placed in
In high temperature oven, 200 DEG C are to slowly warm up to, after reacting 8h, naturally cools to room temperature, product is washed and is centrifuged, produce
Porous poly- (styrene-divinylbenzene) microballoon/TiO2Complex microsphere.
Claims (4)
1. one kind prepares the controllable TiO of porous resin microsphere surface growth morphology2Method, it is characterised in that step is as follows：
Step 1：Porous resin microballoon is added into titanium source solution, the stainless steel water of polytetrafluoroethyllining lining is transferred to after ultrasonic disperse
In thermal response kettle, the mass ratio of wherein porous resin microballoon and titanium source solution is 1:10~15；
The titanium source solution is：The titanium source for being 50~200g/L using the mass concentration that concentration is prepared as 4~6mol/L hydrochloric acid solutions
Solution；
Step 2：The stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining is placed in high temperature oven, is to slowly warm up to 180~220
DEG C, react 4~12h；
Step 3：After reaction terminates, the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining is naturally cooled into room temperature, washing production
Thing is simultaneously centrifuged, and obtains porous resin microsphere/TiO2Complex microsphere.
2. according to claim 1 prepare the controllable TiO of porous resin microsphere surface growth morphology2Method, its feature exists
In：The titanium source is tetrabutyl titanate or tetraisopropyl titanate.
3. according to claim 1 prepare the controllable TiO of porous resin microsphere surface growth morphology2Method, its feature exists
In：The porous resin microballoon is cross-linked styrene class, esters of acrylic acid or vinyl cyanide porous polymer microsphere or porous magnetic
Property complex microsphere.
4. according to claim 3 prepare the controllable TiO of porous resin microsphere surface growth morphology2Method, its feature exists
In：The porous resin microballoon average pore size is more than 20nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710637867.1A CN107344118B (en) | 2017-07-31 | 2017-07-31 | TiO with controllable surface growth morphology for preparing porous resin microspheres2Method (2) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710637867.1A CN107344118B (en) | 2017-07-31 | 2017-07-31 | TiO with controllable surface growth morphology for preparing porous resin microspheres2Method (2) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107344118A true CN107344118A (en) | 2017-11-14 |
| CN107344118B CN107344118B (en) | 2020-05-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201613A (en) * | 2019-06-10 | 2019-09-06 | 东莞东阳光科研发有限公司 | A kind of Magnetic Polystyrene Microsphere and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549204A (en) * | 2014-12-23 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| CN105129849A (en) * | 2015-09-17 | 2015-12-09 | 上海大学 | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof |
-
2017
- 2017-07-31 CN CN201710637867.1A patent/CN107344118B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104549204A (en) * | 2014-12-23 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Preparing method and application of titanium dioxide/carbon nano-micro spherical powder |
| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| CN105129849A (en) * | 2015-09-17 | 2015-12-09 | 上海大学 | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JILIANG YIN ETAL.: "Preparation of PS/TiO2 core-shell microspheres and TiO2 hollow shells", 《JOURNAL OF MATERIALS SCIENCE》 * |
| 王宽等: "二氧化钛/聚合物复合微球的制备及聚合物表面性质的影响研究", 《化工技术与开发》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110201613A (en) * | 2019-06-10 | 2019-09-06 | 东莞东阳光科研发有限公司 | A kind of Magnetic Polystyrene Microsphere and preparation method thereof |
| CN110201613B (en) * | 2019-06-10 | 2021-09-14 | 东莞东阳光科研发有限公司 | Polystyrene magnetic microsphere and preparation method thereof |
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