CN108456277A - A kind of molecular imprinted polymer on surface material of redox graphene - Google Patents
A kind of molecular imprinted polymer on surface material of redox graphene Download PDFInfo
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- CN108456277A CN108456277A CN201711481943.0A CN201711481943A CN108456277A CN 108456277 A CN108456277 A CN 108456277A CN 201711481943 A CN201711481943 A CN 201711481943A CN 108456277 A CN108456277 A CN 108456277A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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Abstract
The invention discloses a kind of molecular imprinted polymer on surface materials that reduction-oxidation graphite is dilute.The molecular imprinted polymer on surface material that the reduction-oxidation graphite of the present invention is dilute is using redox graphene as carrier, using 4 nitrophenoxy acids as template molecule, methacrylate is function monomer, and ethylene glycol dimethacrylate is crosslinking agent, is prepared using surface molecule print technology.The molecular imprinted polymer on surface material of the redox graphene of the present invention can increase the specific surface area and recognition site of imprinted material, and it can be effectively reduced the resistance to mass tranfer that template molecule is adsorbed and is desorbed in the polymeric material, to achieve the purpose that shorten the response time, improve detection sensitivity.
Description
Technical field
The present invention relates to a kind of graphene polymeric materials, and in particular to a kind of surface molecule print that reduction-oxidation graphite is dilute
Polymer material.
Background technology
The synthesis of reduction-oxidation graphite dilute (RGO) is by being heated also in graphene oxide (GO) under alkaline condition hydrazine solution
Original obtains.The structure of RGO and GO has identical point：Unique bi-dimensional cellular shape lattice structure has stable carbon in structural unit
Hexatomic ring however compared with GO, the oxygen-containing functional group of RGO is few, at the same RGO have better thermal stability, more preferably electricity is urged
Change activity.In order to further develop the composite material of RGO, expand the application range of RGO, researcher passes through chemical polymerization, voltolisation
It the methods of closes and to prepare the research of the polymer composites of RGO these composite materials and can assign more preferably solvent-dispersible, more
Good electric conductivity and mechanical performance etc., in addition, in order to further increase the selectivity of composite material, increase method sensitivity and
Accelerate to combine speed, molecular imprinting technology can be applied to the preparation of RGO composite materials.
Molecular imprinting technology is that the work(with fixed hole size, three-dimensional structure is prepared as template using target molecule
It can polymer.Wherein the surface molecule print method based on nano material can not only increase specific surface area and the identification of imprinted material
Site, and it can be effectively reduced the resistance to mass tranfer that template molecule is adsorbed and is desorbed in the polymeric material, shorten to reach
Response time, the purpose for improving detection sensitivity.In surface molecule print method, need to select different loads according to different
Body, such as the molecularly imprinted material on surface carrier of document report have silica, carbon nanotube, quantum dot.
Invention content
The purpose of the present invention is to provide being carrier one is redox graphene, using 4- nitrophenoxy acids as template point
Son, methacrylate are function monomer, and ethylene glycol dimethacrylate is crosslinking agent, are prepared using surface molecule print technology
Obtained molecular imprinted polymer on surface material.
The present invention adopts the following technical scheme that realization:A kind of molecular imprinted polymer on surface material that reduction-oxidation graphite is dilute
Material, preparation process are as follows：
(1) the dilute 10-20 mass parts of graphite oxide are added in the water of 200-400 mass parts, then ultrasonic 2h is added
0.1-0.5 mass parts hydrazine hydrate solution, 1.5-5 mass parts concentrated ammonia liquor, 0.5-1.2 mass parts aerosils continue ultrasound
1-2h obtains dispersion liquid；By dispersion liquid, heating stirring 0.5-2h is filtered then with clear water washing 2-3 times at 95-105 DEG C,
It is dried in vacuo at 60 DEG C, redox graphene is made；
(2) 0.3-0.7 mass parts 4- nitrophenols, the methanol of 35-60 mass parts, 90-110 mass parts step (1) are made
Redox graphene, the 1-4 mass parts methacrylic acids obtained is added in reaction vessel, then 2-5 matter is added in magnetic agitation 2h
Measure part ethylene glycol dimethacrylate, 25-55 mass parts azodiisobutyronitriles；It is filled with nitrogen in the reaction vessel, keeps 15-
25min seals container, starts to react 28-36h in 60-65 DEG C of water-bath；Reaction terminates, product solvent Soxhlet extraction
Method removes 4- nitrophenoxy acids, dry, and the dilute molecular imprinted polymer on surface material of reduction-oxidation graphite is made.
Further, after step (1) the dispersion liquid heating stirring, sodium bicarbonate 0.2-0.5 mass parts, then ultrasound is added
0.5h。
Preferably, the volume fraction of step (1) described hydrazine hydrate solution is 75-85%.
Preferably, the mass fraction of step (1) described concentrated ammonia liquor is 28.5-32.5%.
Preferably, step (2) described solvent is normal propyl alcohol and acetic acid according to volume ratio 8:2 are mixed to prepare.
The molecular imprinted polymer on surface material of the redox graphene of the present invention can increase the ratio table of imprinted material
Area and recognition site, and it can be effectively reduced the resistance to mass tranfer that template molecule is adsorbed and is desorbed in the polymeric material, from
And achievees the purpose that shorten the response time, improves detection sensitivity.
Specific implementation mode
With reference to embodiment, the present invention will be further described.
Embodiment 1 realizes the present invention using following steps：
(1) dilute 10 mass parts of graphite oxide are added in the water of 200 mass parts, then 0.13 mass is added in ultrasonic 2h
Concentrated ammonia liquor that hydrazine hydrate solution that part volume fraction is 85%, 5 mass parts mass fractions are 28.5%, 0.5 mass parts gas phase two
Silica continues ultrasound 1h, obtains dispersion liquid；By dispersion liquid at 95-105 DEG C heating stirring 1h, then with clear water wash 2-3
It is secondary, it filters, is dried in vacuo at 60 DEG C, redox graphene is made；
(2) by oxygen reduction made from 0.4 mass parts 4- nitrophenols, the methanol of 38 mass parts, 100 mass parts steps (1)
Graphite alkene, 4 mass parts methacrylic acids are added in reaction vessel, then 2.5 mass parts dimethyl propylenes are added in magnetic agitation 2h
Olefin(e) acid glycol ester, 28 mass parts azodiisobutyronitriles；It is filled with nitrogen in the reaction vessel, keeps 18min, container is sealed,
Start to react 28h in 60-65 DEG C of water-bath；Reaction terminates, and (it is normal propyl alcohol and acetic acid according to body to use solvent to product solvent
Product ratio 8:2 are mixed to prepare) soxhlet extraction removing 4- nitrophenoxy acids, it is dry, the dilute surface molecular print of reduction-oxidation graphite is made
Mark polymer material.
Embodiment 2 realizes the present invention using following steps：
(1) dilute 20 mass parts of graphite oxide are added in the water of 400 mass parts, then 0.5 mass parts are added in ultrasonic 2h
Concentrated ammonia liquor that hydrazine hydrate solution that volume fraction is 75%, 1.5 mass parts mass fractions are 32.5%, 1.2 mass parts gas phases two
Silica continues ultrasound 2h, obtains dispersion liquid；By dispersion liquid at 95-105 DEG C heating stirring 2h, be added 0.4 mass of sodium bicarbonate
Part, then ultrasound 0.5h, it is then washed 2-3 times with clear water, filters, be dried in vacuo at 60 DEG C, redox graphene is made；
(2) by oxygen reduction made from 0.6 mass parts 4- nitrophenols, the methanol of 55 mass parts, 110 mass parts steps (1)
Graphite alkene, 2 mass parts methacrylic acids are added in reaction vessel, then 4.5 mass parts dimethyl propylenes are added in magnetic agitation 2h
Olefin(e) acid glycol ester, 47 mass parts azodiisobutyronitriles；It is filled with nitrogen in the reaction vessel, keeps 25min, container is sealed,
Start to react 36h in 60-65 DEG C of water-bath；Reaction terminates, and (it is normal propyl alcohol and acetic acid according to body to use solvent to product solvent
Product ratio 8:2 are mixed to prepare) soxhlet extraction removing 4- nitrophenoxy acids, it is dry, the dilute surface molecular print of reduction-oxidation graphite is made
Mark polymer material.
Claims (5)
1. a kind of molecular imprinted polymer on surface material that reduction-oxidation graphite is dilute, which is characterized in that its preparation process is as follows：
(1) the dilute 10-20 mass parts of graphite oxide are added in the water of 200-400 mass parts, then 0.1- is added in ultrasonic 2h
0.5 mass parts hydrazine hydrate solution, 1.5-5 mass parts concentrated ammonia liquor, 0.5-1.2 mass parts aerosils continue ultrasound 1-2h,
Obtain dispersion liquid；By dispersion liquid, heating stirring 0.5-2h is filtered, then with clear water washing 2-3 times at 60 DEG C at 95-105 DEG C
Redox graphene is made in vacuum drying；
(2) 0.3-0.7 mass parts 4- nitrophenols, the methanol of 35-60 mass parts, 90-110 mass parts step (1) is obtained
Redox graphene, 1-4 mass parts methacrylic acids are added in reaction vessel, then 2-5 mass parts are added in magnetic agitation 2h
Ethylene glycol dimethacrylate, 25-55 mass parts azodiisobutyronitriles；It is filled with nitrogen in the reaction vessel, keeps 15-
25min seals container, starts to react 28-36h in 60-65 DEG C of water-bath；Reaction terminates, product solvent Soxhlet extraction
Method removes 4- nitrophenoxy acids, dry, and the dilute molecular imprinted polymer on surface material of reduction-oxidation graphite is made.
2. the dilute molecular imprinted polymer on surface material of reduction-oxidation graphite according to claim 1, which is characterized in that institute
After stating step (1) dispersion liquid heating stirring, sodium bicarbonate 0.2-0.5 mass parts, then ultrasound 0.5h are added.
3. the dilute molecular imprinted polymer on surface material of reduction-oxidation graphite according to claim 1, which is characterized in that step
Suddenly the volume fraction of (1) described hydrazine hydrate solution is 75-85%.
4. the dilute molecular imprinted polymer on surface material of reduction-oxidation graphite according to claim 1, which is characterized in that step
Suddenly the mass fraction of (1) described concentrated ammonia liquor is 28.5-32.5%.
5. the dilute molecular imprinted polymer on surface material of reduction-oxidation graphite according to claim 1, which is characterized in that step
Suddenly (2) described solvent is normal propyl alcohol and acetic acid according to volume ratio 8:2 are mixed to prepare.
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| CN201711481943.0A CN108456277A (en) | 2017-12-30 | 2017-12-30 | A kind of molecular imprinted polymer on surface material of redox graphene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909311A (en) * | 2020-07-06 | 2020-11-10 | 国家粮食和物资储备局科学研究院 | Zearalenone functionalized graphene surface molecularly imprinted material and preparation method thereof |
| CN111905701A (en) * | 2020-07-06 | 2020-11-10 | 国家粮食和物资储备局科学研究院 | Application of zearalenone functionalized graphene surface molecular imprinting material |
| WO2022007704A1 (en) * | 2020-07-06 | 2022-01-13 | 国家粮食和物资储备局科学研究院 | Zearalenone functionalized graphene surface molecularly imprinted material, preparation method therefor and use thereof |
| CN114487051A (en) * | 2021-12-23 | 2022-05-13 | 宁波职业技术学院 | Reduced graphene oxide molecularly imprinted composite material for electrode and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909311A (en) * | 2020-07-06 | 2020-11-10 | 国家粮食和物资储备局科学研究院 | Zearalenone functionalized graphene surface molecularly imprinted material and preparation method thereof |
| CN111905701A (en) * | 2020-07-06 | 2020-11-10 | 国家粮食和物资储备局科学研究院 | Application of zearalenone functionalized graphene surface molecular imprinting material |
| WO2022007704A1 (en) * | 2020-07-06 | 2022-01-13 | 国家粮食和物资储备局科学研究院 | Zearalenone functionalized graphene surface molecularly imprinted material, preparation method therefor and use thereof |
| CN114487051A (en) * | 2021-12-23 | 2022-05-13 | 宁波职业技术学院 | Reduced graphene oxide molecularly imprinted composite material for electrode and preparation method thereof |
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Application publication date: 20180828 |