CN105498728B - A kind of phthalic acid two（2- ethylhexyls）The preparation and application of ester surface molecule print magnetic Nano material - Google Patents
A kind of phthalic acid two（2- ethylhexyls）The preparation and application of ester surface molecule print magnetic Nano material Download PDFInfo
- Publication number
- CN105498728B CN105498728B CN201510963533.4A CN201510963533A CN105498728B CN 105498728 B CN105498728 B CN 105498728B CN 201510963533 A CN201510963533 A CN 201510963533A CN 105498728 B CN105498728 B CN 105498728B
- Authority
- CN
- China
- Prior art keywords
- dehp
- ethylhexyls
- ester
- solution
- phthalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 21
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 title claims description 34
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims abstract description 37
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000011553 magnetic fluid Substances 0.000 claims abstract description 4
- 150000003022 phthalic acids Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- 229920000151 polyglycol Polymers 0.000 claims abstract 2
- 239000010695 polyglycol Substances 0.000 claims abstract 2
- 239000003643 water by type Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- OUUJNAYUKRAPFD-UHFFFAOYSA-N [N].N.O Chemical compound [N].N.O OUUJNAYUKRAPFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052603 melanterite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 238000001994 activation Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000005415 magnetization Effects 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 14
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical group CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/203—Equilibration or regeneration
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The present invention relates to a kind of phthalic acids two（2 ethylhexyls）Ester（DEHP）The preparation and application of surface molecule print magnetic Nano material, belong to technical field of nano material；Preparation method：In N2Protection is lower to be stirred by ultrasonic, toward Fe (NO3)3、FeSO4Mixed liquor in add in polyglycol solution, adjust pH, cotton-shaped magnetic fluid separated with magnet and is scattered in ethyl alcohol, is uniformly mixed with the acetone soln of tetraethoxysilane, add in concentrated ammonia liquor, form black gel；After gel aging, drying, Fe is obtained3O4‑SiO2Material；DEHP is taken to be dissolved in methanol with phenyltrimethoxysila,e, activated Fe is added in after oscillation3O4‑SiO2Material, tetraethoxysilane and acetic acid, are stirred at room temperature；It cleans, after Magneto separate, is dried in vacuo through chloroform, obtain DEHP trace magnetic Nano materials, average grain diameter is about 33 nm, and saturation magnetization is 14.9 emug‑1；The material is added in environmental water sample or drink sample containing DEHP, can efficiently concentrating DEHP, processing speed is fast, selectivity is good；Material is reusable repeatedly.
Description
Technical field
The present invention relates to the preparations and application of a kind of nano material, and in particular to a kind of phthalic acid two（2- ethyl hexyls
Base）The preparation method of ester surface molecule print magnetic Nano material and the material are in solution example（Such as environmental water sample, beverage
Sample etc.）Middle trace phthalic acid two（2- ethylhexyls）Application in ester separation and concentration, belongs to technical field of composite materials.
Background technology
Phthalic acid two（2- ethylhexyls）Ester（DEHP）It is a kind of plasticizer largely used.Research shows that DEHP
Water body, soil, air and food, beverage have been widely present in it, in vegetables.Since DEHP is incretion interferent and carcinogenic
Object, the analysis method and removal technology of the O-phthalic acids plasticizer including DEHP have become has become ring in recent years
The research hotspot in the fields such as border, food, health.
The content of DEHP is usually in micro or even trace level in the samples such as environmental water sample, beverage, it is necessary to using existing
It is measured for instrument analysis technology.The detection method of DEHP, mainly including spectrophotometry, fluorescent spectrometry, gas phase
Chromatography, liquid chromatography, chromatography mass spectrometry etc..Since DEHP contents are low, and matrix composition is complicated, need to often use separation rich
Collection technology, to improve the concentration of DEHP and eliminate the interference of sample matrices ingredient.Traditional method for separating and concentrating such as liquid-liquid extraction
Deng there are the defects of cumbersome, poor reproducibility, the not high rate of recovery.Solid Phase Extraction is a kind of newer Sample Pretreatment Technique,
Have the characteristics that easy to operate, enrichment times are high, can be combined with a variety of analytical instrument, application is very extensive.But common solid phase extraction
It draws materials poor selectivity, crosses that column is slow, easily block, the operating time is long（When especially handling bulk sample）.Therefore, it is necessary to develop
Solid Phase Extraction material to improve the selectivity of Solid Phase Extraction, and accelerates analyze speed.
Molecular imprinting technology is the important channel for improving Solid Phase Extraction material selectivity.Molecular engram material system is with specific
Target molecule is made for template, and selective suction-operated can be generated to the target molecule in sample solution.Magnetic Nano material
Not only surface area is big for material, but also due to that with paramagnetism, can realize that quick solid-liquid is separated by externally-applied magnetic field.Magnetic material
The common ferroso-ferric oxide of material, but its nano particle diameter is small, easily reunites.With coated with silica ferriferrous oxide nano-particle,
Both its reunion can be prevented, also surface-functionalized is provided a convenient for its.
Invention content
The present invention is directed to overcome the deficiencies in the prior art, with the composite material of coated with silica ferroso-ferric oxide（Fe3O4-
SiO2）For carrier, DEHP is template molecule, phenyltrimethoxysila,e（PTMS）For function monomer, using surface molecule print
Sol-gel method in technology prepares high selectivity and the nanoscale phthalic acid two of superparamagnetism（2- ethyl hexyls
Base）Ester imprinted magnetic material；Using the material as solid phase extraction adsorbents, realize to the trace in environmental water sample, drink sample
Measure phthalic acid two（2- ethylhexyls）The highly selective fast separating concentration of ester substantially increases the effect of sample pre-treatments
Rate.
To solve the above-mentioned problems, the technical solution adopted in the present invention is：
A kind of phthalic acid two（2- ethylhexyls）The preparation method of ester surface molecule print magnetic Nano material, including
Following steps：
（1）Take 3.33 g polyethylene glycol（PEG）It is dissolved in 30 mL ultra-pure waters；Take 2.86 g FeSO4·7H2O and 8.10 g
Fe(NO3)3·9H2O is dissolved in 75 mL ultra-pure waters, is uniformly mixed so as to obtain brown solution；After PEG solution therewith mixing, protected in nitrogen
Ammonium hydroxide is slowly added under shield and adjusts pH to 11-12, is stirred in ultrasound；Cotton-shaped magnetic fluid is separated with magnet, with 200
ML deionized waters are cleaned 2 times, are cleaned 2 times with 150 mL, 95% ethyl alcohol, and are settled to 100 mL with the dispersion of 95% ethyl alcohol, are obtained molten
Liquid A；
（2）Take 15 mL tetraethoxysilanes（TEOS）It is dissolved in 30 mL acetone, adds in 0.45 mL concentrated hydrochloric acids and 1.2 mL
Ultra-pure water in 58 DEG C of water-baths after 3 h of heating stirring, obtains solution B；Solution B with A is uniformly mixed under ultrasound, is rapidly joined
6.0 mL concentrated ammonia liquors, stir evenly, and form black gel；After black gel is placed in 30 min of ventilation aging, done in vacuum
Dry 24 h at 60 DEG C in dry case；Grinding crosses 400 mesh sieve, obtains powdered Fe3O4—SiO2Composite material；
（3）Above-mentioned material is activated to 4 h at normal temperatures with 10% hydrochloric acid, it is neutrality to be washed with deionized water to solution；
（4）Take 4 mL phthalic acids two（2- ethylhexyls）Ester is dissolved in 10 mL methanol with 5mL phenyltrimethoxysila,es
In, 3 h of concussion reaction；Add in the 1.0 g Fe that activation process is crossed3O4—SiO2, 1.0 mol/L vinegar of 1 mL TEOS and 2 mL
Acid stirs 18 h at room temperature；
（5）It is washed with toluene, until supernatant can't detect phthalic acid two with gas chromatography-mass spectrography（2- ethyls
Hexyl）Until ester；Vacuum drying, obtains phthalic acid two（2- ethylhexyls）Ester surface molecule print magnetic Nano material.
A kind of phthalic acid two（2- ethylhexyls）The application process of ester surface molecule print magnetic Nano material, including
Following steps：
（1）50 mg materials are added into the solution that 100 mL contain a certain concentration DEHP（Environmental water sample, drink sample
Deng）In, it is 7 to adjust pH value, and 20 min are vibrated under 200 rpm；
（2）The material for having adsorbed DEHP with magnet from solution is separated, then adds 5 mL chloroforms, 300
5 min of oscillation desorption under rpm；
（3）The content of DEHP in eluent is measured with gas chromatograph-mass spectrometer.
The beneficial effects of the invention are as follows：
（1）Magnetic Nano material prepared by the present invention is with Fe3O4-SiO2For carrier, DEHP is template, phenyl trimethoxy
Silane is function monomer, and using the sol-gel method in surface molecule print technology, preparation process is simple, quick, reliable；
（2）The phthalic acid two that preparation method of the present invention obtains（2- ethylhexyls）Ester surface molecule print magnetic Nano
The average grain diameter of material is about 33 nm, and saturation magnetization is 14.9 emug-1, and with superparamagnetism；
（3）Material prepared by the present invention not only has specific recognition ability to DEHP, but also possesses superparamagnetism and nanometer material
The high surface area of material can carry out fast separating concentration using externally-applied magnetic field to the DEHP in complex matrices solution.Meanwhile material is inhaled
Attached capacity is big, good, reusable 8 times selective；
（4）Material prepared by the present invention is used for the Solid Phase Extraction of DEHP in solution, the rate of adsorption is fast, strong antijamming capability,
Greatly accelerate sample handling processes, efficiently concentrating DEHP significantly improves the sensitivity that instrument detects DEHP.
Specific embodiment
The present invention is described in further details below by example, these examples are only used for illustrating the present invention, and unlimited
The scope of the present invention processed.
Embodiment 1
（1）Take 3.33 g polyethylene glycol（PEG）It is dissolved in 30 mL ultra-pure waters.Take 2.86 g FeSO4·7H2O and 8.10 g
Fe(NO3)3·9H2O is dissolved in 75 mL ultra-pure waters, is uniformly mixed so as to obtain brown solution.After PEG solution therewith mixing, protected in nitrogen
Ammonium hydroxide is slowly added under shield and adjusts pH to 11-12, is stirred in ultrasound.Cotton-shaped magnetic fluid is separated with magnet, with 200
ML deionized waters are cleaned 2 times, are cleaned 2 times with 150 mL, 95% ethyl alcohol, and are settled to 100 mL with the dispersion of 95% ethyl alcohol, are obtained molten
Liquid A.
（2）15 mL TEOS is taken to be dissolved in 30 mL acetone, 0.45 mL concentrated hydrochloric acids and 1.2 mL ultra-pure waters are added in, at 58 DEG C
Heating stirring in water-bath.After 3 h, solution B is obtained.Solution B with A is uniformly mixed under ultrasound, rapidly joins 6.0 mL concentrated ammonia liquors,
It stirs evenly, forms black gel.After black gel is placed in 30 min of ventilation aging, done in vacuum drying chamber 60 DEG C
Dry 24 h.Grinding crosses 200 mesh sieve, obtains powdered Fe3O4-SiO2Composite material.
（3）Above-mentioned material is activated to 4 h at normal temperatures with 10% hydrochloric acid, it is neutrality to be washed with deionized water to solution.
（4）Take 4 mL phthalic acids two（2- ethylhexyls）Ester is dissolved in 10 mL methanol with 5mL phenyltrimethoxysila,es
In, 3 h of concussion reaction.Add in the activated Fe of 1.0 g3O4-SiO2, 1.0 mol/L acetic acid of 1 mL TEOS and 2 mL, room temperature
18 h of lower stirring.
（5）It is washed with toluene, until supernatant can't detect phthalic acid two with gas chromatography-mass spectrography（2- ethyls
Hexyl）Until ester.Vacuum drying, obtains phthalic acid two（2- ethylhexyls）Ester surface molecule print magnetic Nano material is put down
Equal grain size is about 33 nm.
Embodiment 2
Indices experiment is carried out to 1 resulting materials of embodiment.
50 mg embodiments, 1 resulting materials are added to the solution that 100 mL of different pH values contain 1 mg/L DEHP
In, investigate influence of the pH values to DEHP adsorption effects.The result shows that pH in 7 or so the rate of recovery close to 100%, therefore other suctions
Attached experiment carries out in neutral conditions.
100 mL that 50 mg embodiments, 1 resulting materials are added to pH=7 contain in the solution of 1 mg/L DEHP, investigate
Influence of the adsorption time to DEHP adsorption effects.The result shows that after 20 min, reach adsorption equilibrium.
50 mg embodiments, 1 resulting materials are added in the solution of different initial DEHP concentration, in constant temperature oscillator
Adsorb 3h at 25 DEG C, the adsorbance of research material is fitted by adsorption isotherm with the variation of DEHP initial concentrations,
It is 30.7 mg/g to the saturated extent of adsorption of DEHP that material, which is calculated,.
Select dibutyl phthalate（DBP）, di-n-octyl phthalate（DNOP）Absorption examination is carried out for competitor
It tests, research material is to the adsorptive selectivity of DEHP.The result shows that relative to DBP, DNOP, the trace coefficient of material is respectively
4.9th, 5.3, illustrate that imprinted material has the function of DEHP excellent specific recognition.
Test influence of the variation of externally-applied magnetic field to material magnetization intensity.It was found that the intensity of magnetization with externally-applied magnetic field enhance and
Increase, saturation magnetization are 14.9 emug-1, and B-H loop crosses origin, shows good superparamagnetism.
Embodiment 3
1 resulting materials of embodiment are used for the Solid phase extraction separation enrichment of trace DEHP in solution.
50 mg materials are added into the solution that 100 mL contain a certain concentration DEHP（Environmental water sample, drink sample etc.）In,
It is 7 to adjust pH value, and 20 min are vibrated under 200 rpm.The material for having adsorbed DEHP is separated with magnet, then adds 5 mL
Chloroform, 5 min of oscillation desorption under 300 rpm, the content of DEHP in eluent is measured with gas chromatograph-mass spectrometer, is counted
Calculate the rate of recovery.
Reusable 8 times of material.
Claims (1)
1. a kind of phthalic acid two（2- ethylhexyls）The preparation method of ester DEHP surface molecule print magnetic Nano materials,
It is characterized in that：Include the following steps：
（1）3.33 g polyethylene glycol is taken to be dissolved in 30 mL ultra-pure waters；Take 2.86 g FeSO4·7H2O and 8.10 g Fe
(NO3)3·9H2O is dissolved in 75 mL ultra-pure waters, is uniformly mixed so as to obtain brown solution；After polyglycol solution therewith mixing, in nitrogen
Ammonium hydroxide is slowly added under protection and adjusts pH to 11-12, is stirred in ultrasound；Cotton-shaped magnetic fluid is separated with magnet, with 200
ML deionized waters are cleaned 2 times, are cleaned 2 times with 150 mL, 95% ethyl alcohol, and are settled to 100 mL with the dispersion of 95% ethyl alcohol, are obtained molten
Liquid A；
（2）15 mL tetraethoxysilanes is taken to be dissolved in 30 mL acetone, add in 0.45 mL concentrated hydrochloric acids and 1.2 mL ultra-pure waters, in
In 58 DEG C of water-baths after 3 h of heating stirring, solution B is obtained；Solution B with A is uniformly mixed under ultrasound, rapidly joins the dense ammonia of 6.0 mL
Water stirs evenly, and forms black gel；After black gel is placed in 30 min of ventilation aging, in 60 DEG C in vacuum drying chamber
Lower 24 h of drying；Grinding crosses 400 mesh sieve, obtains powdered Fe3O4-SiO2Composite material；
（3）Above-mentioned material is activated to 4 h at normal temperatures with 10% hydrochloric acid, it is neutrality to be washed with deionized water to solution；
（4）Take 4 mL phthalic acids two（2- ethylhexyls）Ester is dissolved in 5mL phenyltrimethoxysila,es in 10 mL methanol,
3 h of concussion reaction；Add in the 1.0 g Fe that activation process is crossed3O4-SiO2, 1 mL tetraethoxysilanes and 2 mL 1.0
Mol/L acetic acid stirs 18 h at room temperature；
（5）It is washed with toluene, until supernatant can't detect phthalic acid two with gas chromatography-mass spectrography（2- ethylhexyls）
Until ester；Vacuum drying, obtains phthalic acid two（2- ethylhexyls）Ester surface molecule print magnetic Nano material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510963533.4A CN105498728B (en) | 2015-12-21 | 2015-12-21 | A kind of phthalic acid two（2- ethylhexyls）The preparation and application of ester surface molecule print magnetic Nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510963533.4A CN105498728B (en) | 2015-12-21 | 2015-12-21 | A kind of phthalic acid two（2- ethylhexyls）The preparation and application of ester surface molecule print magnetic Nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105498728A CN105498728A (en) | 2016-04-20 |
| CN105498728B true CN105498728B (en) | 2018-07-03 |
Family
ID=55707261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510963533.4A Expired - Fee Related CN105498728B (en) | 2015-12-21 | 2015-12-21 | A kind of phthalic acid two（2- ethylhexyls）The preparation and application of ester surface molecule print magnetic Nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105498728B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106970215B (en) * | 2017-03-26 | 2018-10-12 | 合肥学院 | A kind of preparation method of the Fe3O4@PEG@SiO2 artificial antibodies of detection thifensulfuronmethyl |
| CN109092254B (en) * | 2018-08-16 | 2021-09-21 | 广东工业大学 | Preparation and application method of double-virtual-template phthalate molecularly imprinted magnetic material |
| CN110215909A (en) * | 2019-05-14 | 2019-09-10 | 江苏大学 | A kind of preparation method detecting dioctyl phthalate imprinted material |
| CN112007621A (en) * | 2020-06-23 | 2020-12-01 | 广东工业大学 | Preparation and application methods of tetracycline antibiotic multi-template molecularly imprinted magnetic composite material |
| CN113791061B (en) * | 2021-09-15 | 2024-03-12 | 合肥海关技术中心 | Method for rapidly detecting myclobutanil residues in food and magnetic surface molecular imprinting adsorbent used by same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004049805A1 (en) * | 2004-10-12 | 2006-04-13 | Universität Dortmund | Process for the preparation of molecularly imprinted polymers for the recognition of target molecules |
| CN102604008B (en) * | 2012-03-15 | 2014-07-09 | 江南大学 | Preparation method of pefloxacin surface molecular imprinting polymer and application thereof |
| CN104069818B (en) * | 2014-06-27 | 2016-06-22 | 中国科学技术大学 | The preparation method of the radial magnetic core-shell mesoporous silicon material of phenyl functionalization |
| CN104892868B (en) * | 2015-05-14 | 2017-09-12 | 江苏科技大学 | A kind of specific adsorption DEHP Silica Surface molecularly imprinted polymer and preparation method and application |
-
2015
- 2015-12-21 CN CN201510963533.4A patent/CN105498728B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105498728A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105498728B (en) | A kind of phthalic acid two（2- ethylhexyls）The preparation and application of ester surface molecule print magnetic Nano material | |
| CN108620048B (en) | Preparation method and application of polyethyleneimine modified magnetic microspheres | |
| CN105664861B (en) | A kind of magnetism covalent organic framework nanocomposite and preparation method and application | |
| CN105879842B (en) | A kind of magnetism PAFs solid extracting agents and its preparation method and application | |
| CN109092254B (en) | Preparation and application method of double-virtual-template phthalate molecularly imprinted magnetic material | |
| CN109589931A (en) | A kind of magnetism covalent organic framework compound solid phase extraction adsorbents and preparation method | |
| CN103041773A (en) | Magnetic carbon nanotube composite material and preparation method and application thereof | |
| CN111650320B (en) | Detection method and kit for quinolone veterinary drugs based on magnetic solid-phase extraction | |
| CN109400889B (en) | Magnetic modified metal organic porous material and preparation and application thereof | |
| CN114409913B (en) | Magnetic metal organic framework material and preparation method and application thereof | |
| Liu et al. | The determination of pesticides in tea samples followed by magnetic multiwalled carbon nanotube-based magnetic solid-phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry | |
| CN104193875B (en) | The preparation method of stilboestrol magnetic molecularly imprinted polymer and application thereof | |
| CN109354657B (en) | Preparation and application methods of alkylphenol composite template molecularly imprinted polymer modified magnetic graphene oxide | |
| CN112808256A (en) | Magnetic core-shell mesoporous surface molecularly imprinted composite nanomaterial and preparation method thereof | |
| CN109839466A (en) | A method of testing melamine content in milk powder is detected based on three-dimensional magnetic molecularly imprinted polymer | |
| CN106397692B (en) | A kind of magnetic molecularly imprinted nano material and preparation method thereof | |
| CN113061216A (en) | Magnetic molecularly imprinted polymer for simultaneously extracting multiple cephalosporin antibiotics and preparation method and application thereof | |
| CN110161136B (en) | Method for determining persistent organic pollutants in water by using tablet bubbling to assist dispersion magnetic solid-phase extraction | |
| Jiao et al. | Fabrication of polypyrrole-coated magnetic particles for quinone extraction from fine atmospheric particulate matter | |
| Zhang et al. | Preparation of magnetic zeolitic imidazolate framework-67 composites for the extraction of phthalate esters from environmental water samples | |
| CN111715198B (en) | Magnetic fullerene nano material and application thereof in magnetic dispersion solid-phase extraction of methyl methoxyacrylate pesticides | |
| CN109456438A (en) | A kind of magnetic blotting material and preparation method thereof | |
| CN109621889A (en) | The preparation method of mesoporous magnetism silicon substrate Microcystin adsorbent | |
| CN110412156B (en) | Method for determining polychlorinated biphenyl in soil | |
| CN108435150B (en) | Thiophilic magnetic bead and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180703 |