CN107141398B - A kind of preparation method and application of 4,4 '-Bisphenol F molecularly imprinted polymers - Google Patents
A kind of preparation method and application of 4,4 '-Bisphenol F molecularly imprinted polymers Download PDFInfo
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- CN107141398B CN107141398B CN201710279666.9A CN201710279666A CN107141398B CN 107141398 B CN107141398 B CN 107141398B CN 201710279666 A CN201710279666 A CN 201710279666A CN 107141398 B CN107141398 B CN 107141398B
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- bisphenol
- molecularly imprinted
- imprinted polymers
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- adsorption
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003480 eluent Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 238000011069 regeneration method Methods 0.000 claims abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229940106691 bisphenol a Drugs 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000011800 void material Substances 0.000 claims description 3
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000004576 sand Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 125000002133 (4-hydroxy-3-iodo-5-nitrophenyl)acetyl group Chemical group OC1=C(C=C(C=C1I)CC(=O)*)[N+](=O)[O-] 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000001439 Opuntia Species 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 alkenyl benzene Chemical compound 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A kind of preparation method and application of 4,4 '-Bisphenol F molecularly imprinted polymers: template molecule, function monomer are dissolved in pore-foaming agent, crosslinking agent and initiator are added; it is sealed after letting nitrogen in and deoxidizing, constant temperature polymerize under nitrogen protection, and obtained pale white solid polymer is pulverized and sieved; with eluent template molecule and acetic acid; filtering, it is dry, obtain one kind 4; 4 '-Bisphenol F molecularly imprinted polymers; it is applied to the selective removal of 4,4 '-Bisphenol Fs in water, removal rate reaches 90.7%.The method of the present invention reaction condition is mild, it is easy to operate, at low cost, the 4 of preparation, 4 '-Bisphenol F molecularly imprinted polymers have to 4, the high selectivity of 4 '-Bisphenol Fs and regeneration reusability, stability is high, and adsorption capacity is big, 4 suitable for water, the separation and enrichment of 4,4 '-Bisphenol F of trace in the quick removal and sample analysis pre-treatment of 4 '-Bisphenol Fs.
Description
Technical field
The invention belongs to environment functional material preparation and its application fields, are related to a kind of 4,4 '-Bisphenol F molecular engrams polymerization
The preparation of object and the method for going the applications such as 4,4 '-Bisphenol Fs in water removal.
Background technique
Bisphenol F (BPF) has 4,4 '-, 2, and 4 '-, 2,2 '-three kinds of isomers, wherein 4,4 '-Bisphenol Fs (4,4 '-BPF)
Performance is preferable, and application prospect is good.But Bisphenol F easily exists in water body, can cause to surface water, underground water even drinking water etc.
Certain pollution, while the Bisphenol F for entering human body is taken in and accumulated by food chain, organism endocrine system can also be caused centainly
It influences.Therefore, Bisphenol F in water removal how quickly, efficiently and selectively to be gone to seem extremely important.Remove organic pollutants
Method have chemical oxidization method, biological degradation method and adsorption separation method etc., wherein adsorption separation method it is easy to operate with its, it is quick,
Low consumption and the characteristics such as without secondary pollution are widely adopted.Molecular imprinting technology using object as template molecule, by covalently or
Non-covalent bond effect power and function monomer interact in pore-foaming agent, and eluted template molecule is formed with specific after cross-linked polymeric
Group arrangement and space size and shape 3 D stereo rigid polymer (Molecular imprinted polymers,
MIPs), energy specific recognition template molecule and the like.Due to MIPs have predetermined identity, prepare it is simple, at low cost
Honest and clean, the features such as stability is good, in complex system the removal of target compound, Selective Separation, enrichment and in terms of
It is widely used.Currently, having some reports for going 4,4 '-Bisphenol Fs in water removal about bisphenol A molecular engram polymer, but yet
The not strong, rate of adsorption that there are adsorbent specificities is slowly, adsorbent reactivation and reusability be not good enough, preparation process is complicated and prepares
The disadvantages of at high cost.Moreover, the adsorbent material of Bisphenol F and application in water removal is gone also to be rarely reported.Therefore, it is a kind of right to need to research and develop
Bisphenol F large amount of adsorption, the adsorbent material that selectivity is high, reproducibility is good are for going Bisphenol F in water removal.
Summary of the invention
The object of the invention
The present invention is directed to overcome the deficiencies of the prior art and provide a kind of preparation of 4,4 '-Bisphenol F molecularly imprinted polymers and
The method for going the applications such as 4,4 '-Bisphenol Fs in water removal.
Technical solution of the present invention
1. the preparation method and application of 4,4 '-Bisphenol F molecularly imprinted polymer of one kind, technical solution are as follows:
(1) described 4, the particle sizes of 4 '-Bisphenol F molecularly imprinted polymers is 48~80 μm, specific surface area is 50~
120m2/ g, polymeric inner have mesoporous and micropore and deposit, and aperture is 1~20nm；
(2) described 4, the preparation method of 4 '-Bisphenol F molecularly imprinted polymers, comprising the following steps:
By template molecule, function monomer is scattered in the reactor equipped with pore-foaming agent, and 3~4h is sufficiently stirred at room temperature, to
After template molecule and the abundant self assembly of function monomer, crosslinking agent and initiator are added, is ultrasonically treated 15~20min, logical nitrogen removes
It is sealed after 20~40min of oxygen, react 18 in 55~65 DEG C~for 24 hours, it is cooled to room temperature after reaction, it is poly- to obtain pale white solid
Object is closed, pale white solid polymer is pulverized and sieved, the particle that 48~80 μm of collection cut size, with the methanol-of volume ratio 4~9: 1
Acetic acid mixture soxhlet type 12~for 24 hours, remove the template molecule and pore-foaming agent in particle, then the first with volume ratio 1~2: 1
Alcohol-ultrapure water mixed liquid dipping stirs 10~30min, removes acetic acid, filtering, and gained filter cake is dried in vacuo at 50~60 DEG C
Afterwards to get a kind of 4,4 '-Bisphenol F molecularly imprinted polymers；
The template molecule is 4,4 '-Bisphenol Fs, and function monomer is methacrylic acid, 4-vinylpridine, methacrylic acid
At least one of methyl esters, crosslinking agent are ethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, diethyl
At least one of alkenyl benzene, initiator are at least one of azodiisobutyronitrile, benzoyl peroxide, and the pore-foaming agent is
The mixture of acetonitrile and chloroform, wherein the molar ratio of acetonitrile and chloroform is 1~3: 1；
The template molecule, function monomer, crosslinking agent, pore-foaming agent and initiator mass ratio be 1: 1~5: 15~30: 40
~120: 0.05~0.4；
(3) described 4,4 '-Bisphenol F molecularly imprinted polymers investment is contained in the aqueous solution of 4,4 '-Bisphenol Fs, 10~40
2~6h is impregnated at DEG C and reaches adsorption saturation, and the 4 of adsorption saturation, 4 '-Bisphenol F molecularly imprinted polymers are moved into sieve
In the void column of plate, going out adsorbed 4 with eluent, eluent is concentrated by evaporation and 4,4 '-Bisphenol Fs is precipitated by 4 '-Bisphenol Fs, then
It is washed with deionized, dries to get 4,4 '-Bisphenol Fs of recycling are arrived；It is separately washed with deionized and has eluted 4,4 '-is bis-
The 4 of phenol F, 4 '-Bisphenol F molecularly imprinted polymers, then at 50-60 DEG C be dried under vacuum to constant weight after, namely regenerated 4,4 '-bis-phenols
F molecularly imprinted polymer, the absorption for 4,4 '-Bisphenol Fs in next water；
The concentration for containing 4,4 '-Bisphenol Fs in 4,4 '-Bisphenol F aqueous solutions is 50~600mg/L, 4,4 '-Bisphenol F molecules
The investment concentration of imprinted polymer is 5~10g/L, absorption of 4, the 4 '-Bisphenol F molecularly imprinted polymers in water 4,4 '-Bisphenol Fs
Amount is 320~580mg/g；
The elution is with the eluant, eluent of 5~10 times of column bed volumes at 15~55 DEG C, with 100~300mL/ (m2·s)
Section flow elute 4,4 '-Bisphenol F molecularly imprinted polymers adsorbed 4,4 '-Bisphenol Fs, the eluant, eluent be volume ratio 5~
15: 1 methanol-water solution.
2. according to 1, it is preferable that the particle size of described 4,4 '-Bisphenol F molecularly imprinted polymers is 61~75 μm,
Specific surface area is 60~100m2/ g, polymeric inner have mesoporous and micropore and deposit, and aperture is 6~12nm.
3. according to 1, it is preferable that the quality of the template molecule, function monomer, crosslinking agent, pore-foaming agent and initiator
Than being 1: 2~4: 20~25: 60~100: 0.1~0.25.
4. according to 1, it is preferable that the elution be with the eluant, eluents of 6~8 times of column bed volumes 40~50 DEG C, with
200~250mL/ (m2S) section flow elutes 4,4 '-Bisphenol F molecularly imprinted polymers adsorbed 4, and 4 '-Bisphenol Fs are described
Eluant, eluent is the methanol-water solution of volume ratio 9~11: 1.
Technical characterstic and effect of the invention
(1) compared with common other adsorbents such as active carbon, ion exchange resin, prepared by the present invention 4,4 '-Bisphenol Fs
Containing with 4 inside molecularly imprinted polymer, the functional group and 4 of 4 '-Bisphenol F molecule phenolic hydroxyl group phase separations, 4 '-Bisphenol F molecules
The imprinted cavity that size of three-dimensional space, shape match, therefore adsorptive selectivity is high, adsorption capacity is big, and reusability is good, fits
Separation and enrichment for 4,4 '-Bisphenol F of trace in the quick removal and sample analysis pre-treatment of in water 4,4 '-Bisphenol Fs.
(2) the method for the present invention reaction condition is mild, easy to operate, at low cost.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of prepared 4,4 '-Bisphenol F molecularly imprinted polymers.Fig. 1 (left side) and Fig. 1 (right side) points
It is not exaggerated 10,000 times and 100,000 times.Fig. 1 observation discovery: prepared 4,4 '-Bisphenol F molecularly imprinted polymers are in spherical
Cross-linked polymer, though there are some agglomerations, general levels and three-dimensional sense are stronger.
Fig. 2 is the infrared spectrogram of three kinds of polymer, and a is the molecularly imprinted polymer for not eluting 4,4 '-Bisphenol Fs, b is to wash
Molecularly imprinted polymer, c after de- 4,4 '-Bisphenol F molecules are non-molecularly imprinted polymer.As shown in Figure 2,3437cm-1Place for-
The stretching vibration peak of OH, 2956cm-1、1452cm-1、1385cm-1Place is-CH3Characteristic absorption peak, 1728cm-1Place is C=O
Stretching vibration peak, 1631cm-1Place is the stretching vibration peak of C=C.Fig. 2 a 1512cm-1There is the asymmetric of phenyl ring and stretches in place
Vibration absorption peak does not appear on Fig. 2 b, c, and comparison shows that 4,4 '-Bisphenol F of template molecule has been eluted in Fig. 2 b.Fig. 2 b, c
Peak shape it is almost the same, demonstrate again that 4, the 4 '-Bisphenol F of template molecule in imprinted polymer has been eluted completely.
Fig. 3 is that 4,4 '-Bisphenol F molecularly imprinted polymers (are abbreviated as 4,4 '-BPF-MIPS, full text expression is same), it is overstepping one's bounds
Sub- imprinted polymer (is abbreviated as NIPS, full text expression is same) in function monomer and crosslinking agent quality compare 4,4 '-BPF (write a Chinese character in simplified form
It is 4,4 '-Bisphenol Fs, full text expression is same) adsorbance Q (4,4 '-Bisphenol F molecularly imprinted polymer of mg 4,4 '-Bisphenol Fs/g).
Fig. 4 is that function monomer and crosslinking agent quality compare the polymerization of 4,4 '-Bisphenol F molecular engrams in 4,4 '-Bisphenol F molecularly imprinted polymers
Imprinting factor α (the Q of objectMIPs/QNIPs), imprinting factor shows 4,4 '-Bisphenol F molecularly imprinted polymer trace binding site numbers
How much.Found out by Fig. 3,4, when the mass ratio of function monomer and crosslinking agent is 1: 3,1: 5,1: 6,1: 7,1: 8,1: 9,4,4 '-
Bisphenol F molecularly imprinted polymer adsorbance is respectively 111.2,127,148.6,186.2,166.8,152.3mg/g, imprinting factor
Respectively 1.36,1.44,1.60,1.97,1.68,1.43, this shows the function monomer of 4,4 '-Bisphenol F molecularly imprinted polymers
Suitable quality ratio with crosslinking agent is 1: 7.
Fig. 5 is 4,4 '-BPF-MIPSAnd NIPSTo the adsorption equilibrium thermoisopleth of 4,4 '-BPF at 25 DEG C.As shown in Figure 5,
4,4 '-BPF-MIPs and NIPs increase the equilibrium adsorption capacity of 4,4 '-BPF as the concentration C e of 4,4 '-BPF in water increases
Greatly, while 4,4 '-BPF-MIPs are significantly greater than NIPs to the equilibrium adsorption capacity of 4,4 '-BPF to the equilibrium adsorption capacity of 4,4 '-BPF,
And the difference of the adsorbance both within the scope of a certain concentration, in water 4, the concentration C e of 4 '-BPF increases and increases.This shows 4,
It has been generated in the 4 ' holes-BPF-MIPs to template molecule 4,4 '-BPF have the active bound site of high-affinity and specific recognition
Point, and NIPs does not contain the imprinted cavity and recognition site to match with 4,4 '-BPF form size of template molecule, belongs to non-choosing
Selecting property bonding action.
Fig. 6 is 4,4 '-BPF-MIPSWith NIPSTo the isothermal adsorption kinetic curve of 4,4 '-BPF at 25 DEG C.It can by Fig. 6
See, 4,4 '-BPF-MIPSWith NIPSBeing adsorbed in the 100min initially contacted for 4,4 '-BPF is absorbed quickly, and 4,4 '-
BPF-MIPSTo the absorption ratio NIP of 4,4 '-BPFSFaster, they reach adsorption equilibrium in 200min, 300min respectively.
Fig. 7 is 4,4 '-BPF-MIPSAnd NIPSComparison to the selective absorption of 4,4 '-BPF, bisphenol-A, phenol.By Fig. 7
As it can be seen that 4,4 '-BPF-MIPSNIPs, and 4 are all larger than to the adsorbance of 4,4 '-BPF, bisphenol-A, phenol, 4 '-BPF-MIPs to 4,
The adsorbance of 4 '-BPF is to adsorb bisphenol-A, 1.86 and 3.82 times of phenol, but NIPs is to 4,4 '-BPF and bisphenol-A but phase respectively
Almost.This shows 4, and 4 '-BPF-MIPs have a highly selective recognition capability to 4,4 '-BPF, and NIPSThere is no Selective recognition
Ability.
Fig. 8 is 4,4 '-BPF-MIPSFollow bad access times.To the adsorbance of 4,4 '-BPF with number is recycled
Increase only slight decline, 4,4 '-BPF-MIPSAbsorption regeneration is reused 8 times, 4,4 '-BPF-MIPSTo 4,4 '-BPF's
Adsorbance is 166.7mg/g, only reduces 9.5%, this shows 4,4 '-BPF-MIPSWith good stable regenerability.
Fig. 9 is 4, the 4 '-BPF aqueous solutions of 20mL, 20mg/L through 20mg 4,4 '-BPF-MIPS4,4 '-in the water of absorption front and back
The liquid chromatogram of BPF changes of contents.As seen from Figure 9, through 4,4 '-BPF-MIPSAfter absorption, 4 in water, the content of 4 '-BPF is only
For 0.023mg, 94% is reduced, shows 4,4 '-BPF-MIPSTo in water 4, the removal effect of 4 '-BPF is significant.
Specific embodiment
Content for a better understanding of the present invention is described in further details the present invention below with reference to embodiment.
Embodiment 1
The preparation of 1.4,4 '-Bisphenol F molecularly imprinted polymers
4,4 '-Bisphenol F of 0.8g template molecule, 2.4g bi-functional monomer methacrylic acid and 100mL are added in conical flask
Pore-foaming agent acetonitrile vibrates 4h at 25 DEG C after mixing, makes template molecule and the abundant self assembly of function monomer, states then up
16.8g crosslinking agent ethylene glycol dimethacrylate and 100mg initiator azodiisobutyronitrile are sequentially added in solution, at ultrasound
20min is managed, is sealed after letting nitrogen in and deoxidizing 25min, after thermal polymerization for 24 hours in 60 DEG C of waters bath with thermostatic control, takes out pale white solid polymerization
Object pulverizes and sieves, and takes the particle between 48~80 μm of partial size, with acetic acid/methanol volume ratio 1: 9 acetate-methanol mixed liquor rope
Family name extracts 18h, until extracting solution can't detect 4,4 '-Bisphenol F of template molecule with high performance liquid chromatograph (HPLC), then uses volume
Methanol-ultrapure water mixed liquid dipping than 1.5: 1 stirs 30min, removes acetic acid, filtering, and gained filter cake vacuum at 60 DEG C is done
To get a kind of 4,4 '-Bisphenol F molecularly imprinted polymers after dry.As control, template molecule 4 is not added in a manner described, 4 '-is bis-
Phenol F preparation gained is non-molecularly imprinted polymer (NIPs).
The method that 4,4 '-Bisphenol Fs in water removal were evaluated and gone to the absorption property of 2.4,4 '-Bisphenol F molecularly imprinted polymers
(1) adsorption isotherm experiment: 4 are accurately weighed, 4 '-BPF-MIPSAnd NIPSEach 200mg is placed in conical flask, respectively plus
Enter 4,4 '-BPF aqueous solution 200mL of 50,100,200,300,400,500,600mg/L, constant temperature oscillation adsorbs 6h at room temperature, reaches
To after static adsorption equilibria, supernatant is taken to cross 0.45 μm of filter membrane, is measured 4 in supernatant with HPLC, the concentration of 4 '-BPF, and calculate
Adsorption capacity.Fig. 5 the result shows that, 4,4 '-BPF-MIPSTo the adsorbance of 4,4 '-BPF with the increasing of 4,4 '-BPF initial concentrations
Add and increase, and no matter high concentration region or low concentration region, 4,4 '-BPF-MIPSIt is obviously big to the adsorbance of 4,4 '-BPF
In NIPS, 4,4 '-BPF-MIPSSaturated adsorption capacity reach 436.4mg/g, show 4,4 '-BPF-MIPSThere is big for inside
Imprinted cavity and trace binding site are measured, good adsorption effect is shown to 4,4 '-BPF.
(2) the adsorption kinetic data: 4 are accurately weighed, 4 '-BPF-MIPSAnd NIPSEach 200mg is placed in 250mL round-bottomed flask
In, be separately added into 200mL, the 4 of 200mg/L, 4 '-BPF aqueous solutions, at room temperature constant temperature oscillation 20,40,60,80,100,200,
300,0.45 μm of filter membrane of separately sampled mistake when 400min, with 4 in HPLC measurement supernatant, the concentration of 4 '-BPF calculates absorption and holds
Amount.Fig. 6 the result shows that, the incipient stage 4,4 '-BPF-MIPSIt is very big to the rate of adsorption of 4,4 '-BPF, with prolonging for adsorption time
The long rate of adsorption is gradually steady, lasts 95% (175.8mg/g) that 100min reaches saturated extent of adsorption, lasts 200min and reach
Adsorption saturation, saturated extent of adsorption 184.8mg/g.
(3) adsorptive selectivity is tested: accurately weighing 4,4 '-BPF-MIPSAnd NIPSEach 200mg is placed in conical flask, respectively
Be added 150mL, the 4 of 200mg/L, 4 '-Bisphenol Fs, bisphenol-A and phenol mixed aqueous solution, at room temperature constant temperature oscillation absorption 6h after, take
Supernatant crosses 0.45 μm of filter membrane, is measured 4 in supernatant with HPLC, the concentration of 4 '-BPF, and calculate adsorption capacity.Fig. 7 result table
It is bright, 4,4 '-BPF-MIPSAnd NIPSTo in water 4, the removal rate of 4 '-BPF is respectively 90.7% and 39.8%, 4,4 '-BPF-MIPS
To the removal rate 48.7%, 23.7% of bisphenol-A in water and phenol, illustrate 4,4 '-BPF-MIPSContain and 4,4 '-BPF points inside
The hole that size of three-dimensional space, shape and the functional group of son match, 4,4 '-BPF-MIPSHave to 4,4 '-BPF
Selective recognition.
(4) reproducibility is tested: containing in the 4 of 200mg/L, 4 '-BPF aqueous solutions in 200mL, 200mg 4,4 '-is added
BPF-MIPS, and 6h is vibrated in constant-temperature table, after reaching adsorption equilibrium, with 4 in HPLC measurement supernatant, 4 '-BPF's is dense
Degree, and calculate adsorption capacity.The 4 of adsorption saturation, 4 '-Bisphenol F molecularly imprinted polymers are moved into the void column with sieve plate, are used
The eluant, eluent of 7 times of column bed volumes at 45 DEG C, with 230mL/ (m2S) 4,4 '-Bisphenol F molecularly imprinted polymers are eluted to be inhaled
Attached 4,4 '-Bisphenol Fs, the eluant, eluent are the methanol-water solution of volume ratio 10: 1, and eluent is concentrated by evaporation to precipitation 4,4 '-
Bisphenol F is washed with deionized, dries be precipitated 4, and 4 '-Bisphenol Fs are to get 4, the 4 '-Bisphenol Fs for arriving recycling；In addition spend from
Sub- water washing has eluted 4,4 '-Bisphenol F molecularly imprinted polymers of 4,4 '-Bisphenol Fs, is dried under vacuum to constant weight then at 55 DEG C
Afterwards, 4,4 '-namely regenerated Bisphenol F molecularly imprinted polymers, the absorption for 4,4 '-Bisphenol Fs in next water.Fig. 8 result table
Bright: 4,4 '-Bisphenol F molecularly imprinted polymers are used through 8 adsorption/desorption regeneration cycles, 4,4 '-BPF-MIPSTo 4,4 '-BPF
Adsorbance only reduce 9.5%, this shows 4,4 '-BPF-MIPSWith good and stable regenerability.
Embodiment 2
For operating procedure with embodiment 1, difference is that adsorbate is bisphenol-A aqueous solution, and 4,4 '-Bisphenol F molecules print is made
Mark polymer is 108.2mg/g to the adsorbance of bisphenol-A.
Embodiment 3
For operating procedure with embodiment 1, difference is that adsorbate is phenol solution, and 4,4 '-Bisphenol F molecular engrams are made
The adsorbance of polymer Pyrogentisinic Acid is 48.6mg/g.
To sum up embodiment 1-3's the result shows that, adsorbance of 4, the 4 '-Bisphenol F molecularly imprinted polymers to 4,4 '-Bisphenol Fs
Maximum takes second place to the adsorbance of bisphenol-A, and the adsorbance of Pyrogentisinic Acid is minimum.
Claims (4)
1. 4,4 '-Bisphenol F molecularly imprinted polymer of one kind, it is characterised in that:
Described 4,4 '-Bisphenol F molecularly imprinted polymers are by 4,4 '-Bisphenol F of template molecule, function monomer methacrylic acid, crosslinking
Agent ethylene glycol dimethacrylate, initiator azodiisobutyronitrile, pore-foaming agent acetonitrile are prepared, the template molecule, function
Can monomer, crosslinking agent, pore-foaming agent and initiator mass ratio be 1: 3: 21: 99: 0.125；
Described 4,4 '-Bisphenol F molecularly imprinted polymers are in spherical cross-linked polymer, and particle size is 61~75 μm, compare table
Area is 60~100m2/ g, polymeric inner have mesoporous and micropore and deposit, and aperture is 6~12nm；
Described 4,4 '-Bisphenol F molecularly imprinted polymers have high selection recognition capability to 4,4 '-Bisphenol Fs, the suction to 4,4 '-BPF
Attached amount is to adsorb bisphenol-A, 1.86 times and 3.82 times of phenol respectively；
Described 4,4 '-Bisphenol F molecularly imprinted polymers reach 436.4mg/g to the saturated adsorption capacity of 4,4 '-BPF；
When described 4,4 '-Bisphenol F molecularly imprinted polymers adsorb 4, the 4 '-BPF aqueous solution of 200mg/L, absorption 100min reaches
To the 95% of saturated extent of adsorption, it is 175.8mg/g, lasts 200min and reach adsorption saturation, saturated extent of adsorption 184.8mg/g；
Described 4,4 '-Bisphenol F molecularly imprinted polymers have good and stable regenerability, follow through 8 adsorption/desorption regeneration
Ring uses, and only reduces 9.5% to the adsorbance of 4,4 '-BPF.
2. a kind of preparation method of 4,4 '-Bisphenol F molecularly imprinted polymers as described in claim 1, it is characterised in that: by mould
Plate molecule, function monomer are scattered in the reactor equipped with pore-foaming agent, 3~4h are sufficiently stirred at room temperature, to template molecule and function
Crosslinking agent and initiator can be added after the abundant self assembly of monomer, be ultrasonically treated 15~20min, after 20~40min of letting nitrogen in and deoxidizing
Sealing, in 55~65 DEG C react 18~for 24 hours, be cooled to room temperature after reaction, obtain pale white solid polymer, by pale
Solid polymer pulverizes and sieves, the particle that 65~71 μm of collection cut size, with the methanol-acetic acid mixed liquor Soxhlet of volume ratio 4~9: 1
Extracting 12~for 24 hours, remove the template molecule and pore-foaming agent in particle, then the ultrapure water mixed liquid of methanol-with volume ratio 1~2: 1
10~30min of soaking and stirring, removes acetic acid, filtering, gained filter cake be dried in vacuo at 50~60 DEG C after to get a kind of 4,4 '-
Bisphenol F molecularly imprinted polymer.
3. by described in claim 1 a kind of 4, aqueous solution of the 4 '-Bisphenol F molecularly imprinted polymers processing containing 4,4 '-Bisphenol Fs
Method, it is characterized in that: by described 4, in aqueous solution of the 4 '-Bisphenol F molecularly imprinted polymers investment containing 4,4 '-Bisphenol Fs, 10
2~6h is impregnated at~40 DEG C and reaches adsorption saturation, and the 4 of adsorption saturation, 4 '-Bisphenol F molecularly imprinted polymers are moved into band
Have in the void column of sieve plate, goes out adsorbed 4 with eluent, eluent is concentrated by evaporation and 4,4 '-bis-phenols are precipitated by 4 '-Bisphenol Fs
F, then be washed with deionized, dry to get 4,4 '-Bisphenol Fs of recycling are arrived；It is separately washed with deionized and has eluted 4,
The 4 of 4 '-Bisphenol Fs, 4 '-Bisphenol F molecularly imprinted polymers, then at 50-60 DEG C be dried under vacuum to constant weight after, namely regenerated 4,
4 '-Bisphenol F molecularly imprinted polymers, the absorption for 4,4 '-Bisphenol Fs in next water；
The concentration for containing 4,4 '-Bisphenol Fs in 4,4 '-Bisphenol F aqueous solutions is 50~600mg/L, 4,4 '-Bisphenol F molecular engrams
The investment concentration of polymer is 5~10g/L, and 4,4 '-Bisphenol F molecularly imprinted polymers are to the adsorbance of in water 4,4 '-Bisphenol Fs
320~580mg/g；
The elution is with the eluant, eluent of 5~10 times of column bed volumes at 15~55 DEG C, with 100~300mL/ (m2S) section is flowed
Amount 4,4 '-Bisphenol F molecularly imprinted polymers adsorbed 4 of elution, 4 '-Bisphenol Fs, the eluant, eluent are volume ratio 5~15: 1
Methanol-water solution.
4. according to claim 3 a kind of 4, the processing of 4 '-Bisphenol F molecularly imprinted polymers contains the aqueous solution of 4,4 '-Bisphenol Fs
Method, it is characterised in that: the elution be with the eluant, eluents of 6~8 times of column bed volumes at 40~50 DEG C, with 200~
250mL/(m2S) section flow elutes 4,4 '-Bisphenol F molecularly imprinted polymers adsorbed 4,4 '-Bisphenol Fs, the elution
Agent is the methanol-water solution of volume ratio 9~11: 1.
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