CN102702429A - Method for preparing bisphenol A molecularly imprinted polymer - Google Patents
Method for preparing bisphenol A molecularly imprinted polymer Download PDFInfo
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- CN102702429A CN102702429A CN2012102021272A CN201210202127A CN102702429A CN 102702429 A CN102702429 A CN 102702429A CN 2012102021272 A CN2012102021272 A CN 2012102021272A CN 201210202127 A CN201210202127 A CN 201210202127A CN 102702429 A CN102702429 A CN 102702429A
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Abstract
The invention discloses a method for preparing a bisphenol A molecularly imprinted polymer. The method comprises the following steps of: adding bisphenol A, a functional monomer and porogen into a conical flask to ensure that the bisphenol A and the functional monomer are fully reacted, wherein the functional monomer is 2- vinylpyridine, and alpha-methacrylic acid, the porogen is chloroform and methylbenzene, the polarity of the chloroform and methylbenzene is low, and hydrogen bonds are not easily formed; adding initiator and a cross-linking agent, fully mixing and performing ultrasonic processing, introducing nitrogen to remove dissolved oxygen, and transferring into a thermostat water bath in a sealing state and performing thermal polymerization; and after reaction, taking out the obtained product, cooling to room temperature to obtain colloidal polymer, screening the colloidal polymer by using a 200-mesh molecular sieve, performing Soxhlet extraction by using acetic acid-methanol, washing the extract by using methanol, and drying under vacuum to obtain the bisphenol A molecularly imprinted polymer. The prepared bisphenol A molecularly imprinted polymer has the characteristics of specific adsorption to specific organic pollutant bisphenol A in industrial wastewater, high selectivity on a sample and high speed, accuracy and efficiency in enrichment and purification.
Description
Technical field
The invention belongs to the molecularly imprinted polymer field, particularly a kind of method for preparing microsphere filters out the best-of-breed functionality monomer, synthesizes the nano material that dihydroxyphenyl propane is had highly selective.
Background technology
Dihydroxyphenyl propane (Bisphenol A, CAS 80-05-7 are a kind of environment incretion interferents BPA), be mainly used in to produce polycarbonate and epoxy resin, and be a kind of important chemical material.The mass production of dihydroxyphenyl propane and widespread use consequently all detect in water, settling, soil and atmospheric environment.At present; The mensuration of dihydroxyphenyl propane mainly adopts chromatography, enzyme process and immunization etc.; The tolerance range of these analytical technologies, sensitivity are all very high, but that it requires pre-treatment of sample is very high, need be from the matrix sample of complicacy with target compound high efficiency extraction, the purifying of lower concentration with concentrate; And instrument costs an arm and a leg, and process is complicated, and is consuming time longer.Therefore demand urgently developing a kind of scene fast, accurately, the effective ways of trace amount of bisphenol A in the simple determination waste water.
Development in recent years is molecular imprinting (molecularly imprinted technology faster; MIT) more and more receive publicity; This technological core is preparation molecularly imprinted polymer (molecularly imprinted polymer; MIP), this polymkeric substance has special identification and binding ability as a kind of emerging artificial affinity media to specific template molecule.According to bibliographical information, people have adopted traditional method to synthesize the molecularly imprinted polymer that is used to discern dihydroxyphenyl propane, and the microcosmic molecular mechanisms of action of molecularly imprinted polymer material is studied.But it is block that the polymkeric substance of this method gained is, and particle is bigger, and easy grinding does not sieve; And identification specificity and the susceptibility research in specific environment is then reported seldom about bisphenol A molecular engram polymer.
Summary of the invention
The objective of the invention is to overcome the above problem that prior art exists, a kind of preparation method of bisphenol A molecular engram polymer is provided.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention realizes through following technical scheme:
A kind of preparation method of bisphenol A molecular engram polymer may further comprise the steps:
Step 1) adds 1-2mmol dihydroxyphenyl propane, 3-5mmol function monomer and pore-creating agent in Erlenmeyer flask, vibration 3-5h fully acts on dihydroxyphenyl propane and function monomer; Wherein function monomer is 2-vinylpyridine (2-Vpy), α-Jia Jibingxisuan (MAA), and pore-creating agent is chloroform, the toluene of the less and difficult formation hydrogen bond of polarity;
Step 2) add initiator and linking agent again, supersound process 1-60min behind the thorough mixing, logical nitrogen 1-30min removes dissolved oxygen, and sealed state moves into 20-90 ℃ of thermostat water bath thermopolymerization down;
Take out behind the step 3) reaction 22-25h and be cooled to room temperature, make the colloidal polymkeric substance, behind the 200 order molecular sieves, extract 24-72h with acetic acid-methyl alcohol Suo Shi excessively, use methanol wash 12-36h again, vacuum-drying makes the dihydroxyphenyl propane imprinted polymer.
Further; In the Erlenmeyer flask of 150mL, add 1mmol (228mg) dihydroxyphenyl propane, 4mmol (0.42mL) 2-vinylpyridine and 50mL toluene in the step 1; 4h vibrates under room temperature; Dihydroxyphenyl propane and 2-vinylpyridine are fully acted on, add 20mmol again and gather trimethylammonium vinylformic acid glycerine ester and 50mg ethylene glycol dimethacrylate.
Further, with supersound process 15-20min behind the mixed solution thorough mixing of processing, logical nitrogen 5-10min removes dissolved oxygen in the step 2, and sealed state moves into 60 ℃ of thermostat water bath thermopolymerizations down.
Preferably, the initiator described in the step 2 is Diisopropyl azodicarboxylate (AIBN).
Preferably, the linking agent described in the step 2 is for gathering the mixture of trimethylammonium vinylformic acid glycerine ester (TRIM) and ethylene glycol dimethacrylate (EGDMA).
Preferably, take out behind the reaction 24h in the step 3 and be cooled to room temperature.
Further, after the colloidal polymkeric substance is crossed 200 order molecular sieves in the step 3, extract 24-48h with acetic acid-methyl alcohol Suo Shi, wherein acetic acid, methyl alcohol volume ratio are 1: 9, use methanol wash 24h again, vacuum-drying.
The invention has the beneficial effects as follows:
The microballoon method is a kind of novel preparation method who develops in recent years, the molecularly imprinted polymer of gained uniform particles not only thus, and surface-area is big, and controlled amount.
The bisphenol A molecular engram polymer that the present invention makes has specific absorption to specific organic pollutant dihydroxyphenyl propane in the trade effluent, and sample is had the selectivity height, can be fast, accurately, the characteristics that purify of efficiently concentrating.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention, understands technique means of the present invention in order can more to know, and can implement according to the content of specification sheets, below with preferred embodiment of the present invention and conjunction with figs. specify as after.Embodiment of the present invention is provided by following examples and accompanying drawing thereof in detail.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
The ratio of Fig. 1 linking agent and template molecule is the sem photograph of 15: 1 o'clock thus obtained microspheres;
The ratio of Fig. 2 linking agent and template molecule is the sem photograph of 20: 1 o'clock thus obtained microspheres;
The ratio of Fig. 3 linking agent and template molecule is the sem photograph of 25: 1 o'clock thus obtained microspheres;
The ratio of Fig. 4 linking agent and template molecule is the sem photograph of 30: 1 o'clock thus obtained microspheres;
Fig. 5 molecularly imprinted polymer and blank polymkeric substance are to the combination thermo-isopleth of dihydroxyphenyl propane;
Fig. 6 vinylpyridine molecularly imprinted polymer and α-Jia Jibingxisuan molecularly imprinted polymer are to the curve of adsorption kinetics of BPA
Embodiment
Below with reference to accompanying drawing and combine embodiment, specify the present invention.
In the 150mL Erlenmeyer flask, add 1mmol (228mg) dihydroxyphenyl propane, 4mmol (0.42mL) 2-vinylpyridine and 50mL toluene, the 4h that under room temperature, vibrates fully acts on dihydroxyphenyl propane and 2-vinylpyridine; Add 20mmol again and gather trimethylammonium vinylformic acid glycerine ester and 50mg Diisopropyl azodicarboxylate, supersound process 20min behind the thorough mixing, logical nitrogen 10min removes dissolved oxygen, and sealed state moves into 60 ℃ of thermostat water bath thermopolymerizations down.Take out behind the 24h and be cooled to room temperature, make the colloidal polymkeric substance, behind the 200 order molecular sieves, extract 48h excessively with 1: 9 (v/v) acetic acid-methyl alcohol 200mL Suo Shi, again with methyl alcohol 200mL washing 24h, vacuum-drying, resulting polymers is a molecularly imprinted polymer.
In the 150mL Erlenmeyer flask, add 1mmol (228mg) dihydroxyphenyl propane, 4mmol (0.42mL) α-Jia Jibingxisuan (MAA) and 50mL toluene, the 4h that under room temperature, vibrates fully acts on dihydroxyphenyl propane and 2-vinylpyridine; Add 20mmol again and gather trimethylammonium vinylformic acid glycerine ester and 50mg Diisopropyl azodicarboxylate, supersound process 20min behind the thorough mixing, logical nitrogen 10min removes dissolved oxygen, and sealed state moves into 60 ℃ of thermostat water bath thermopolymerizations down.Take out behind the 24h and be cooled to room temperature, make the colloidal polymkeric substance, behind the 200 order molecular sieves, extract 48h excessively with 1: 9 (v/v) acetic acid-methyl alcohol 200mL Suo Shi, again with methyl alcohol 200mL washing 24h, vacuum-drying, resulting polymers is a molecularly imprinted polymer.
Embodiment 3
In the 150mL Erlenmeyer flask, add 1mmol (228mg) dihydroxyphenyl propane, 4mmol (0.42mL) 2-vinylpyridine and 50mL chloroform, the 4h that under room temperature, vibrates fully acts on dihydroxyphenyl propane and 2-vinylpyridine; Add 20mmol again and gather trimethylammonium vinylformic acid glycerine ester and 50mg Diisopropyl azodicarboxylate, supersound process 20min behind the thorough mixing, logical nitrogen 10min removes dissolved oxygen, and sealed state moves into 60 ℃ of thermostat water bath thermopolymerizations down.Take out behind the 24h and be cooled to room temperature, make the colloidal polymkeric substance, behind the 200 order molecular sieves, extract 48h excessively with 1: 9 (v/v) acetic acid-methyl alcohol 200mL Suo Shi, again with methyl alcohol 200mL washing 24h, vacuum-drying, resulting polymers is a molecularly imprinted polymer.
Embodiment 4
In order to seek the suitable crosslinking agent consumption, on template molecule and 1: 4 basis of function monomer mol ratio, change the ratio 15: 1,20: 1,25: 1,30: 1 of linking agent and template molecule, the sem photograph of thus obtained microsphere is with reference to Fig. 1-shown in Figure 4.Can find out that when the ratio of linking agent and template molecule was 20: 1, the monodispersity effect of thus obtained microsphere was best.
Embodiment 5
Accurately take by weighing molecularly imprinted polymer and blank polymkeric substance 50mg respectively; Place 10mL tool plug Erlenmeyer flask; Adding 0 (1mmol/L dihydroxyphenyl propane toluene solution 5mL, 25 ℃ of vibration 24h get the centrifugal 10min of 1mL supernatant liquid 10000r/min in constant temperature oscillator; Get upper strata centrifugate 0.6mL, the content of high-performance liquid chromatogram determination dihydroxyphenyl propane.Thereby the concentration of dihydroxyphenyl propane in the solution when calculating adsorption equilibrium, according to the binding capacity Q of the concentration change Units of Account quality polymkeric substance of dihydroxyphenyl propane in the solution before and after combining, replicate(determination) 3 times is averaged.This is for measuring the bisphenol A molecular engram polymer absorption property.With reference to shown in Figure 5; Relatively the combination thermo-isopleth of molecularly imprinted polymer and blank polymkeric substance can be known; Increase along with initial concentration; Molecularly imprinted polymer and blank polymkeric substance all increase the binding capacity of substrate, but molecularly imprinted polymer to the binding capacity of template molecule always significantly greater than blank polymkeric substance.In this explanation trace process, trace hole that template molecule stays in the molecular imprinting polymerization and the active binding site on the hole have determined height avidity and the specific recognition property of molecular imprinting polymerization to template molecule.
The dihydroxyphenyl propane toluene solution of getting 50mg bisphenol A molecular engram polymer and 5mL concentration and be 0.1mmol/L mixes, and measures the binding capacity of dihydroxyphenyl propane on molecularly imprinted polymer and blank polymkeric substance respectively in different time.Shown in accompanying drawing 6,2-vinylpyridine molecularly imprinted polymer is very fast in the adsorption rate of preceding 10min, and adsorptive capacity has accounted for 67% of total adsorptive capacity, and after this adsorption rate is slack-off, is adsorbed on about 180min to reach capacity.And α-Jia Jibingxisuan molecularly imprinted polymer particle does not have 2-vinylpyridine molecularly imprinted polymer good to the adsorption effect of template molecule, and adsorption rate is also slower, only reaches 51% of total adsorptive capacity in preceding 10min internal adsorption amount, does not reach balance yet at 180min.The result shows that dihydroxyphenyl propane adsorbs the bonded rapid speed on molecularly imprinted polymer, can satisfy the needs of environmental monitoring field field quick detection.
Embodiment 7
With the compound phenol of the bisphenol A molecular engram polymer of embodiment 1 preparation and BPA structural similitude, tetrabromo-bisphenol uniform mixing as substrate; Take by weighing molecularly imprinted polymer and each 50mg of blank polymkeric substance and place 10mL tool plug Erlenmeyer flask; The substrate toluene solution that adds 5mL 0.1mmol/L; Draw the adsorption liquid sample behind the 24h in centrifuge tube, get the 0.6mL supernatant liquid after 10000r/min is centrifugal, the content of high-performance liquid chromatogram determination substrate.Binding capacity Q and Static Adsorption partition ratio KD according to the concentration change Units of Account quality polymkeric substance of dihydroxyphenyl propane in the solution before and after combining.The result is as shown in the table, and bisphenol A molecular engram polymer has shown in fact specific selectivity clearly to the dihydroxyphenyl propane molecule.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. the preparation method of a bisphenol A molecular engram polymer is characterized in that, may further comprise the steps:
Step 1) adds 1-2mmol dihydroxyphenyl propane, 3-5mmol function monomer and pore-creating agent in Erlenmeyer flask, vibration 3-5h fully acts on dihydroxyphenyl propane and function monomer;
Step 2) add initiator and linking agent again, supersound process 1-60min behind the thorough mixing, logical nitrogen 1-30min removes dissolved oxygen, and sealed state moves into 20-90 ℃ of thermostat water bath thermopolymerization down;
Take out behind the step 3) reaction 22-25h and be cooled to room temperature, make the colloidal polymkeric substance, behind the 200 order molecular sieves, extract 24-72h with acetic acid-methyl alcohol Suo Shi excessively, use methanol wash 12-36h again, vacuum-drying makes the dihydroxyphenyl propane imprinted polymer.
2. the preparation method of bisphenol A molecular engram polymer according to claim 1, it is characterized in that: the function monomer described in the step 1 is 2-vinylpyridine (2-Vpy) or α-Jia Jibingxisuan (MAA).
3. the preparation method of bisphenol A molecular engram polymer according to claim 1, it is characterized in that: the pore-creating agent described in the step 1 is chloroform or toluene.
4. according to the preparation method of claim 1,2 or 3 described bisphenol A molecular engram polymers; It is characterized in that: in the Erlenmeyer flask of 150mL, add 1mmol (228mg) dihydroxyphenyl propane, 4mmol (0.42mL) 2-vinylpyridine and 50mL toluene in the step 1; 4h vibrates under room temperature; Dihydroxyphenyl propane and 2-vinylpyridine are fully acted on, add 20mmol again and gather trimethylammonium vinylformic acid glycerine ester and 50mg ethylene glycol dimethacrylate.
5. the preparation method of bisphenol A molecular engram polymer according to claim 1; It is characterized in that: in the step 2 with supersound process 15-20min behind the mixed solution thorough mixing of processing; Logical nitrogen 5-10min removes dissolved oxygen, and sealed state moves into 60 ℃ of thermostat water bath thermopolymerizations down.
6. the preparation method of bisphenol A molecular engram polymer according to claim 1, it is characterized in that: the initiator described in the step 2 is Diisopropyl azodicarboxylate (AIBN).
7. the preparation method of bisphenol A molecular engram polymer according to claim 1 is characterized in that: the linking agent described in the step 2 is for gathering the mixture of trimethylammonium vinylformic acid glycerine ester (TRIM) and ethylene glycol dimethacrylate (EGDMA).
8. the preparation method of bisphenol A molecular engram polymer according to claim 1 is characterized in that: take out behind the reaction 24h in the step 3 and be cooled to room temperature.
9. the preparation method of bisphenol A molecular engram polymer according to claim 1; It is characterized in that: after the colloidal polymkeric substance is crossed 200 order molecular sieves in the step 3, extract 24-48h with acetic acid-methyl alcohol Suo Shi, wherein acetic acid, methyl alcohol volume ratio are 1: 9; Use methanol wash 24h again, vacuum-drying.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911306A (en) * | 2012-10-10 | 2013-02-06 | 肇庆学院 | Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres |
| CN102921391A (en) * | 2012-11-20 | 2013-02-13 | 红云红河烟草(集团)有限责任公司 | Preparation method of adsorbent for effectively reducing phenol content in cigarette smoke |
| CN103071469A (en) * | 2013-02-06 | 2013-05-01 | 江苏南大金山环保科技有限公司 | Pyridinium group-containing moderate-polarity skeleton adsorption resin and preparation method thereof |
| CN104892839A (en) * | 2015-06-23 | 2015-09-09 | 嘉兴学院 | Surface molecular imprinting polyion liquid of reduced graphene oxide for detecting bisphenol A and preparation method and application of surface molecular imprinting polyion liquid |
| CN104974348A (en) * | 2014-04-02 | 2015-10-14 | 中国科学院大连化学物理研究所 | Bisphenol A half-covalent molecular imprinting spongy mesoporous silicon as well as preparation and application thereof |
| CN105085813A (en) * | 2014-05-05 | 2015-11-25 | 中国科学院大连化学物理研究所 | Bisphenol type substituted template molecularly imprinted polymer and preparation therefor and application thereof |
| CN107141398A (en) * | 2017-04-21 | 2017-09-08 | 湘潭大学 | A kind of preparation method and application of 4,4 ' Bisphenol F molecularly imprinted polymers |
| CN109142328A (en) * | 2017-12-27 | 2019-01-04 | 安徽理工大学 | For detecting magnetic quantum dot molecular engram material and the application of bisphenol-A |
| CN109232823A (en) * | 2018-08-14 | 2019-01-18 | 桂林理工大学 | A kind of preparation method of abietyl TDI type polyurethane molecular engram microsphere |
| CN109265727A (en) * | 2018-08-14 | 2019-01-25 | 桂林理工大学 | A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere |
| CN109369951A (en) * | 2018-08-14 | 2019-02-22 | 桂林理工大学 | A kind of preparation method of abietyl IPDI type polyurethane molecular engram microsphere |
| CN110918073A (en) * | 2019-11-22 | 2020-03-27 | 山东农业大学 | Preparation method and application of magnetic MOF-based bisphenol A molecularly imprinted high-selectivity nanocomposite |
| CN110980893A (en) * | 2019-11-05 | 2020-04-10 | 同济大学 | Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method |
| CN113171763A (en) * | 2021-05-24 | 2021-07-27 | 河南师范大学 | Method for preparing bisphenol A surface molecularly imprinted polymer in aqueous phase by taking MIL-100(Fe) as carrier |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
-
2012
- 2012-06-19 CN CN2012102021272A patent/CN102702429A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177500A (en) * | 2007-10-30 | 2008-05-14 | 湖北出入境检验检疫局检验检疫技术中心 | Method for preparing bisphenol A molecular engram polymer |
Non-Patent Citations (3)
| Title |
|---|
| 杨本晓 等: "双酚A分子印迹聚合物的制备及其吸附机制初探", 《南京大学学报（自然科学版）》 * |
| 杨本晓等: "双酚A分子印迹聚合物的制备及其在环境监测中的应用初探", 《河南科学》 * |
| 林福华 等: "双酚A分子印迹聚合物为萃取介质搅拌饼固相萃取的制备及其萃取性能研究", 《分析化学》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102911306A (en) * | 2012-10-10 | 2013-02-06 | 肇庆学院 | Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres |
| CN102911306B (en) * | 2012-10-10 | 2014-08-06 | 肇庆学院 | Bisphenol-A and nonylphenol double-template molecularly imprinted polymeric microspheres |
| CN102921391A (en) * | 2012-11-20 | 2013-02-13 | 红云红河烟草(集团)有限责任公司 | Preparation method of adsorbent for effectively reducing phenol content in cigarette smoke |
| CN103071469A (en) * | 2013-02-06 | 2013-05-01 | 江苏南大金山环保科技有限公司 | Pyridinium group-containing moderate-polarity skeleton adsorption resin and preparation method thereof |
| CN103071469B (en) * | 2013-02-06 | 2015-02-18 | 江苏南大金山环保科技有限公司 | Pyridinium group-containing moderate-polarity skeleton adsorption resin and preparation method thereof |
| CN104974348A (en) * | 2014-04-02 | 2015-10-14 | 中国科学院大连化学物理研究所 | Bisphenol A half-covalent molecular imprinting spongy mesoporous silicon as well as preparation and application thereof |
| CN104974348B (en) * | 2014-04-02 | 2017-07-21 | 中国科学院大连化学物理研究所 | A kind of spongy mesoporous silicon of covalent molecule trace of bisphenol-A half and its preparation and application |
| CN105085813A (en) * | 2014-05-05 | 2015-11-25 | 中国科学院大连化学物理研究所 | Bisphenol type substituted template molecularly imprinted polymer and preparation therefor and application thereof |
| CN105085813B (en) * | 2014-05-05 | 2017-01-25 | 中国科学院大连化学物理研究所 | Bisphenol type substituted template molecularly imprinted polymer and preparation therefor and application thereof |
| CN104892839A (en) * | 2015-06-23 | 2015-09-09 | 嘉兴学院 | Surface molecular imprinting polyion liquid of reduced graphene oxide for detecting bisphenol A and preparation method and application of surface molecular imprinting polyion liquid |
| CN107141398A (en) * | 2017-04-21 | 2017-09-08 | 湘潭大学 | A kind of preparation method and application of 4,4 ' Bisphenol F molecularly imprinted polymers |
| CN109142328A (en) * | 2017-12-27 | 2019-01-04 | 安徽理工大学 | For detecting magnetic quantum dot molecular engram material and the application of bisphenol-A |
| CN109232823A (en) * | 2018-08-14 | 2019-01-18 | 桂林理工大学 | A kind of preparation method of abietyl TDI type polyurethane molecular engram microsphere |
| CN109265727A (en) * | 2018-08-14 | 2019-01-25 | 桂林理工大学 | A kind of preparation method of abietyl HDI type polyurethane molecular engram microsphere |
| CN109369951A (en) * | 2018-08-14 | 2019-02-22 | 桂林理工大学 | A kind of preparation method of abietyl IPDI type polyurethane molecular engram microsphere |
| CN109232823B (en) * | 2018-08-14 | 2020-11-24 | 桂林理工大学 | Preparation method of rosin-based TDI (toluene diisocynate) type polyurethane molecularly imprinted microspheres |
| CN109369951B (en) * | 2018-08-14 | 2020-11-24 | 桂林理工大学 | Preparation method of rosin-based IPDI polyurethane molecularly imprinted microspheres |
| CN109265727B (en) * | 2018-08-14 | 2020-11-24 | 桂林理工大学 | Preparation method of rosin-based HDI polyurethane molecularly imprinted microspheres |
| CN110980893A (en) * | 2019-11-05 | 2020-04-10 | 同济大学 | Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method |
| CN110980893B (en) * | 2019-11-05 | 2021-06-04 | 同济大学 | Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method |
| CN110918073A (en) * | 2019-11-22 | 2020-03-27 | 山东农业大学 | Preparation method and application of magnetic MOF-based bisphenol A molecularly imprinted high-selectivity nanocomposite |
| CN113171763A (en) * | 2021-05-24 | 2021-07-27 | 河南师范大学 | Method for preparing bisphenol A surface molecularly imprinted polymer in aqueous phase by taking MIL-100(Fe) as carrier |
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Application publication date: 20121003 |