CN110452319B - Preparation method and application of dendrimer functional polymer - Google Patents

Preparation method and application of dendrimer functional polymer Download PDF

Info

Publication number
CN110452319B
CN110452319B CN201810427916.3A CN201810427916A CN110452319B CN 110452319 B CN110452319 B CN 110452319B CN 201810427916 A CN201810427916 A CN 201810427916A CN 110452319 B CN110452319 B CN 110452319B
Authority
CN
China
Prior art keywords
polymer
dendrimer
pdvb
extraction
microspheres
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.)
Active
Application number
CN201810427916.3A
Other languages
Chinese (zh)
Other versions
CN110452319A (en
Inventor
黄超囡
李云
陈吉平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201810427916.3A priority Critical patent/CN110452319B/en
Publication of CN110452319A publication Critical patent/CN110452319A/en
Application granted granted Critical
Publication of CN110452319B publication Critical patent/CN110452319B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/32—Bonded phase chromatography
    • B01D15/325—Reversed phase
    • 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
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B01D15/363—Anion-exchange
    • 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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • B01J20/287—Non-polar phases; Reversed phases
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention provides a preparation method and application of a novel dendrimer functionalized polymer. Firstly, a Pickering polymerization method is adopted to prepare a polymer with uniform particle size and regular shape, and then a stepwise grafting method is adopted to modify the surface of the polymer with the dendritic macromolecule with the cationic functional group. The preparation method fully utilizes the branch structure and high functional group density of the dendrimer, and greatly improves the ion exchange capacity and the extraction efficiency of the material. The preparation method of the dendrimer functional polymer provided by the invention is simple and convenient, has the advantages of fast reaction, short period and high ion exchange capacity, has strong selectivity and extraction capability on the acidic non-steroidal anti-inflammatory drug, solves the problems of poor selectivity and low recovery rate of the traditional extraction material, and can be used for enriching and purifying the acidic non-steroidal anti-inflammatory drug in a complex matrix.

Description

Preparation method and application of dendrimer functional polymer
Technical Field
The invention relates to preparation and application of a novel dendrimer functional polymer selective for an acidic non-steroidal anti-inflammatory drug, and belongs to the field of novel chromatographic materials and sample pretreatment.
Background
Non-steroidal anti-inflammatory drugs (NSAIDs) are a class of drugs with anti-inflammatory, analgesic and antipyretic effects and are widely used by humans and livestock. There is evidence that this class of drugs has great nephrotoxicity, for example bal irises in south asia die largely of renal failure due to consumption of bovine carcasses with residual diclofenac (a chemttrust report (2014)). Nonsteroidal anti-inflammatory drugs can also increase cardiovascular adverse events and complications (Pharmaceuticals 3(2010) 2146-2162). Due to large use amount and large side effect of the medicaments, the method is particularly important for accurately and quickly detecting the non-steroidal anti-inflammatory drugs in complex samples.
Due to the low drug content in biological and environmental samples (ng mL)-1～μg mL-1) And contains many interfering substances, so that the enrichment and purification of the sample are key steps for sample preparation. The solid phase extraction technology has the advantages of diversity of adsorbent materials, good recovery rate, small using amount of organic solvent and the like, and is the most common sample pretreatment technology. Conventional solid phase extraction materials typically have only one chromatographic retention mode-reverse phase (e.g., C18, St-DVB) or ion exchange (ion exchange resins) with poor selectivity. The mixed-mode adsorbent integrates the reverse phase effect and the ion exchange effect, improves the selectivity and the retention capacity of a target analyte, can effectively remove impurities, and obtains high sensitivity and low background interference.
Increasing the site of action of the mixed mode sorbent material can improve the selectivity and extraction efficiency of the sorbent material. The dendrimer is a highly branched and radial novel functional macromolecule, has a nano cavity and abundant active sites inside, has a functional group capable of being modified at the periphery, and has potential application in the aspects of nano catalysis, drug transportation, chemical sensors, sewage treatment, membrane materials and the like. The application of the dendrimer to the solid phase extraction technology can obviously improve the action sites of the material. In the current literature reports, no report exists that resorcinol diglycidyl ether and methylamine are used as functional monomers, and a stepwise grafting method is adopted to modify dendritic macromolecules on the surface of a polymer to be used as a reversed phase/anion exchange mixed mode adsorbent to enrich and purify acidic nonsteroidal anti-inflammatory drugs in a complex sample.
Disclosure of Invention
The invention aims to provide a preparation method of a dendrimer functional polymer with ultrahigh selectivity on acidic non-steroidal anti-inflammatory drugs.
A method for preparing a dendrimer functionalized polymer, the method comprising the steps of:
step one, preparing PDVB-SiO by Pickering emulsion polymerization method2(nanosilica-stabilized polydivinylbenzene) composite microspheres;
step two, the obtained PDVB-SiO2Soaking composite microsphere in hydrofluoric acid to remove nano SiO2Separating to obtain PDVB microspheres;
step three, grafting the dendritic macromolecule on the surface of the polymer by adopting a step-by-step reaction
(1) Dispersing PDVB microspheres in methanol, wherein the concentration of PDVB is 0.05-0.1 g/mL; adding resorcinol diglycidyl ether, reacting for 3-5 h at 60-80 ℃, washing, and drying in vacuum to obtain a dendrimer modified polymer (G0.5-ED) with epoxy terminal functional groups;
(2) dispersing the obtained G0.5-ED in ethanol, wherein the concentration of the G0.5-ED is 0.05-0.1G/mL; adding methylamine, reacting for 3-5 h at 60-80 ℃, washing, and drying in vacuum to obtain a dendrimer modified polymer (G1-AD) with an amino-terminated functional group;
(3) repeating the steps (1) and (2) to obtain dendritic macromolecular functional polymers of different generations;
step four, quaternary ammonification reaction of epoxy end group
Dispersing the obtained dendrimer functional polymer Gn-ED (n is m-0.5, m is an integer more than or equal to 1) with the terminal functional group being epoxy in ethanol, wherein the Gn-ED concentration is 0.05-0.1 g/mL; adding a tertiary amine compound (preferably N, N-dimethylethanolamine), and reacting at 60-80 ℃ for 3-5 h to obtain the dendrimer functional polymer Gm-QD (m is an integer more than or equal to 1) with the end group of a quaternary ammonium group.
The Pickering emulsion polymerization method adopts nano SiO2As an emulsifier, diethylaminoethyl methacrylate (DEAEMA) is used as a monomer; divinyl benzene is used as a crosslinking agent; azodiisobutyronitrile is used as an initiator; toluene and 1-dodecanol are taken as pore-foaming agents and are subjected to polymerization reaction for 12-36h at 50-70 ℃; the molar ratio of the 1-dodecanol to the toluene is 1: 4-5; nano SiO2The mass ratio of the oil phase to the oil phase (the oil phase is a mixed solution of diethylaminoethyl methacrylate, divinylbenzene, toluene, 1-dodecanol and azobisisobutyronitrile) is 1-4 percent;
the molar ratio of the monomer to the cross-linking agent to the pore-forming agent to the initiator is 1: 1-5: 2-8: 0.02-0.1.
In the second step, the particle size of the PDVB microspheres is preferably 15-35 μm.
In the second step, the method preferably further comprises the following extraction steps of the PDVB microspheres: soxhlet extraction is carried out by taking one or more of methanol, acetonitrile, ethanol and acetone as an extraction solvent at the temperature of 80-120 ℃ to remove unreacted substances and oligomers in the polymer;
in the second step, the mass concentration of the hydrofluoric acid is preferably 20-40%, and one or two of methanol and acetone solvents are not added or can be added.
In the third step (1), the volume solubility of the resorcinol diglycidyl ether in the total reactants is preferably 5 to 15 percent;
in the third step (2), the preferable volume concentration of the methylamine in the total reactants is 5-20%;
in the fourth step, the concentration of the tertiary amine compound in the total reactants is preferably 5-15%.
The invention also provides the dendrimer functional polymer prepared by the method.
The invention also provides the application of the dendrimer functional polymer as an adsorbent material with a reversed phase/anion exchange mixed mode in selectively enriching and purifying trace acidic organic matters in complex samples; the acidic organic substance comprises an acidic non-steroidal anti-inflammatory drug.
The dendrimer functional polymer is used as a filler of a solid phase extraction column.
Preferably, the sample comprises an extraction solution of a liquid sample and a solid sample; the liquid sample comprises drinking water, milk, river water, sewage, blood and urine; the solid sample comprises bottom mud, soil and meat.
The dendrimer modified polymer has high selectivity on acidic non-steroidal anti-inflammatory drugs such as salicylic acid, ibuprofen, naproxen, ketoprofen and diclofenac, can adsorb the drugs from a solution, and retains a target substance by removing adsorbed interfering substances through selecting a proper leaching condition. The compound is used as a sample pretreatment material, so that the target compound can obtain high recovery rate and ultrahigh purification effect.
Because of adopting the modification of the dendrimer, the ion exchange capacity of the adsorbent is greatly increased, and the adsorption capacity is enhanced. Because the dendrimer modified polymer has a reverse phase and ion exchange dual retention mechanism as the adsorbent, the interference substances can be removed and only the target analyte can be retained by selecting a proper leaching condition, and the problems of low recovery rate and poor purification effect of the traditional polymer are solved.
The invention has the advantages that: provides a preparation method and application of a novel high-capacity dendrimer functional polymer. The stepwise grafting method is adopted to modify the surface of the polymer with different generations of dendritic macromolecules, and the high branch structure and high-density active sites of the dendritic macromolecules are fully utilized to increase the adsorption sites of the material, so that the adsorption efficiency and selectivity are improved. The dendrimer functional polymer is used as the solid phase extraction column filler, so that the acidic non-steroidal anti-inflammatory drug in the complex matrix can be separated and purified, the matrix interference can be effectively reduced, and the complex sample can be rapidly and accurately detected.
Description of the drawings:
FIG. 1 is a schematic of the synthesis of a polymer;
figure 2 is an elution profile for basic (carbamazepine and amitriptyline), neutral (hydrocortisone) and acidic (ibuprofen) drugs.
Detailed Description
① dissolving a monomer, a cross-linking agent and an initiator in a pore-forming agent to prepare a solution A, introducing nitrogen into the solution A, removing oxygen molecules in the solution A preferably for 15min, wherein the molar ratio of the monomer, the cross-linking agent, the pore-forming agent and the initiator is 1: 1-5: 2-8: 0.02-0.1, the monomer is preferably diethylaminoethyl methacrylate (DEAEMA), the cross-linking agent is preferably divinylbenzene, the initiator is preferably azobisisobutyronitrile, the pore-forming agent is preferably toluene and 1-dodecanol, wherein the molar ratio of the 1-dodecanol to the toluene is 1: 4-5, and the SiO is 1-dodecanol2The particle size is less than 50 nm.
② mixing nano SiO2Dispersing into deionized waterIn the specification, called as dispersion B, nano SiO2The mass concentration is 3-15 mg mL-1(preferably at a concentration of 12 mg/mL). Then, 3-5 mL of the solution A was added to 10mL of the dispersion B, and the mixture was homogenized and dispersed at 6000rpm for 1 min. Introducing nitrogen for 2min, discharging oxygen molecules in the system, and sealing. And carrying out polymerization reaction on the obtained Pickering emulsion at 50-70 ℃ for 12-36 h.
③ after the reaction is finished, obtaining white polymer and SiO by centrifugal separation or suction filtration2Composite material (PDVB-SiO)2)。
④ PDVB-SiO obtained2And soaking the composite material in hydrofluoric acid for 12-24 h, and separating to obtain white polymer microspheres (PDVB).
⑤, sieving and settling to obtain the polymer microspheres with the particle size of 15-35 mu m.
⑥ the obtained material is subjected to Soxhlet extraction by using one or more of methanol, acetonitrile, ethanol and acetone as an extraction solvent, wherein the extraction temperature is 80-120 ℃, and unreacted substances and oligomers in the polymer are removed.
⑦ A stepwise reaction is used to modify the dendrimer
PDVB is dispersed in 90% methanol, and the concentration of the PDVB is 0.05-0.1 g/mL. Adding resorcinol diglycidyl ether to react at 60-80 ℃ for 3-5 h to obtain a dendrimer modified polymer (G0.5-ED) with an epoxy terminal functional group, washing the G0.5-ED with methanol and acetone, and drying in vacuum.
Then, dispersing G0.5-ED in ethanol, wherein the concentration of the G0.5-ED is 0.05-0.1G/mL. Adding methylamine solution to react for 3-5 h at 60-80 ℃ to obtain the dendrimer modified polymer (G1-AD) with the terminal functional group being amino, washing G1-AD with methanol and acetone, and drying in vacuum. Repeating the two steps of reactions to obtain polymers functionalized by different generations of dendritic macromolecules;
⑧ Quaternary amination of epoxy end groups
And (2) dispersing the prepared dendritic macromolecular functional polymer Gn-ED (n is m-0.5, m is an integer more than or equal to 1) with the epoxy end in a 70% ethanol solution, wherein the Gn-ED concentration is 0.05-0.1 g/mL. Adding N, N-dimethylethanolamine to react for 3-5 h at the temperature of 60-80 ℃ to obtain a high-capacity dendrimer functional polymer Gm-QD (m is an integer more than or equal to 1) with a quaternary ammonium group as a terminal group.
The optimal conditions for preparing the dendrimer functional polymer are that in the step ①, the functional monomer is diethylaminoethyl methacrylate, the crosslinking agent is divinylbenzene, the initiator is azobisisobutyronitrile, the molar ratio of the monomer to the crosslinking agent to the pore-forming agent to the initiator is 1: 4: 6.5: 0.07, and the molar ratio of 1-dodecanol to toluene in the pore-forming agent is 1: 4.7.
Example 1
10mmol (2.0mL) of diethylaminoethyl methacrylate, 40mmol (5.66mL) of divinylbenzene and 115mg of azobisisobutyronitrile were dissolved in a porogen solution containing toluene (5.68mL) and 1-dodecanol (2.12g) to prepare a solution A, and then nitrogen was passed through the solution A for 15min to remove oxygen molecules. 120mg of SiO with a particle size of 12nm2Dispersing into 10mL water, and performing ultrasonic treatment for 10min to obtain nanometer SiO2Dispersing, then adding 4mL of solution A, stirring by adopting a homogenizer at 6000rpm for 1min, introducing nitrogen for 2min to remove air above the system, sealing, and carrying out polymerization reaction on the obtained Pickering emulsion for 24h at 60 ℃. After the reaction is finished, performing suction filtration, then sieving the reaction product through a 400-mesh stainless steel sieve, and then precipitating the reaction product twice with acetone for 10min each time to obtain a polymer PDVB-SiO with the particle size of 15-35 mu m2. Then taking 2g of PDVB-SiO2Soaking the substrate in 10mL of 40% hydrofluoric acid for 24h to remove SiO on the surface2Obtaining the PDVB microspheres. Suction filtration and washing with deionized water to neutrality. Soxhlet extracting with methanol as extraction solvent for 24 hr, and drying in vacuum oven at 60 deg.C for 12 hr.
2.0G of PDVB was dispersed in 20mL of 90% methanol, 2.5mL of resorcinol diglycidyl ether was added and reacted at 80 ℃ for 3 hours to give a dendrimer-modified polymer whose terminal functional group was epoxy (G0.5-ED), and the G0.5-ED was washed with methanol and acetone and dried under vacuum. Then, G0.5-ED (2.0G) was dispersed in 20mL of ethanol, 5mL of methylamine solution was added and reacted at 80 ℃ for 3 hours to obtain a dendrimer-modified polymer (G1-AD) whose terminal functional group was an amine group, and G1-AD was washed with methanol and acetone and dried in vacuo. Repeating the two steps of reactions to obtain polymers functionalized by different generations of dendritic macromolecules;
dispersing 2.0g Gn-ED (N is m-0.5, m is an integer more than or equal to 1) of the prepared dendrimer functional polymer with the epoxy terminal into 20mL of 70% ethanol solution, adding 2.5mLN and N-dimethylethanolamine, and reacting at 80 ℃ for 3h to obtain the dendrimer functional polymer Gm-QD with the terminal group of a quaternary ammonium group, wherein m is an integer more than or equal to 1. The results of the specific surface area and pore volume of the dendrimer functionalized polymers of different generations are shown in Table 1.
Example 2
50mg of PDVB was loaded into a 3-mL SPE cartridge, equilibrated with 5mL methanol and 5mL deionized water, and 7mg ibuprofen was dissolved and loaded in 30mL 10mM phosphate buffer (pH 7.0). Draining for 30min, eluting with 5mL of methanol, eluting ibuprofen with 5mL of 1% formic acid in methanol, collecting the eluate, diluting with methanol/water (1:1), diluting to 250mL, measuring with high performance liquid chromatography, and calculating ion exchange capacity. The ion exchange capacity of G1-QD, G2-QD, G3-QD, G4-QD and G5-QD was measured in the same manner as that of PDVB. The results of ion exchange capacity of the dendrimer functionalized polymers of different generations are shown in Table 1.
TABLE 1 measurement results of specific surface area, pore volume and ion exchange capacity of dendrimer functional polymers of different generations
Figure BDA0001652623070000071
From table 1, it can be seen that as the dendrimer grows in the polymer pore channels, (1) the specific surface area and pore volume of the polymer gradually decrease, (2) the ion exchange capacity of the material gradually increases until the ion exchange capacity of the fourth generation dendrimer modified polymer (G4-QD) is maximized, and the ion exchange capacity of G5-QD is decreased compared with G4-QD. Therefore, G4-QD was chosen as the packing for the solid phase extraction column.
Example 3
200mg of G4-QD was loaded into a 3-mL SPE cartridge, equilibrated with 5mL methanol and 5mL 10mM phosphate buffer solution, and 10mL 5. mu.g mL-1Of Carbamazepine (CAZ), Amitriptyline (AMI), Hydrocortisone (HYC) and Ibuprofen (IBP) (pH 7.0)At a rate of 1mL min-1Is loaded at the speed of (2). Draining for 30min, eluting with 5mL of methanol, eluting with 5mL of 1% formic acid solution in methanol, collecting the eluted solution and the eluate, drying with nitrogen gas, diluting to 0.5mL, and analyzing with HPLC-UV. The flow curves of the different substances are shown in fig. 2, and it can be seen from fig. 2 that Carbamazepine (CAZ), Amitriptyline (AMT) and Hydrocortisone (HYC) can be eluted from the solid phase extraction column with 2mL of methanol, while ibuprofen can be eluted only by using a methanol solution containing formic acid, which indicates that the dendrimer functional polymer can selectively retain acidic ibuprofen by selecting appropriate conditions.

Claims (11)

1. A preparation method of a dendrimer functional polymer is characterized by comprising the following steps: the method comprises the following steps:
step one, diethylaminoethyl methacrylate (DEAEMA) is used as a monomer; PDVB-SiO prepared by Pickering emulsion polymerization method2Compounding the microspheres;
step two, the obtained PDVB-SiO2Soaking composite microsphere in hydrofluoric acid to remove nano SiO2Separating to obtain PDVB microspheres;
step three, grafting the dendritic macromolecule on the surface of the polymer by adopting a step-by-step reaction
(1) Dispersing PDVB microspheres in methanol, wherein the concentration of PDVB is 0.05-0.1 g/mL; adding resorcinol diglycidyl ether, reacting for 3-5 h at 60-80 ℃, washing, and drying in vacuum to obtain a polymer G0.5-ED modified by a dendritic macromolecule with an epoxy terminal functional group;
(2) dispersing the obtained G0.5-ED in ethanol, wherein the concentration of the G0.5-ED is 0.05-0.1G/mL; adding methylamine, reacting for 3-5 h at 60-80 ℃, washing, and drying in vacuum to obtain a dendrimer modified polymer G1-AD with an amino terminal functional group;
(3) repeating the steps (1) and (2) to obtain a dendritic macromolecular functional polymer with an epoxy terminal functional group;
step four, quaternary ammonification reaction of epoxy end group
Dispersing the obtained dendritic macromolecular functional polymer Gn-ED with the epoxy terminal functional group in ethanol, wherein the Gn-ED concentration is 0.05-0.1 g/mL; adding a tertiary amine compound, and reacting at 60-80 ℃ for 3-5 h to obtain a dendrimer functional polymer Gm-QD with the end group being a quaternary ammonium group; wherein n = m-0.5, and m is an integer of 1 or more.
2. The method of claim 1, wherein:
the Pickering emulsion polymerization method adopts nano SiO2As an emulsifier, diethylaminoethyl methacrylate (DEAEMA) is used as a monomer; divinyl benzene is used as a crosslinking agent; azodiisobutyronitrile is used as an initiator; toluene and 1-dodecanol are taken as pore-foaming agents and are subjected to polymerization reaction for 12-36h at 50-70 ℃; the molar ratio of the 1-dodecanol to the toluene is 1: 4-5;
the molar ratio of the monomer to the cross-linking agent to the pore-forming agent to the initiator is 1: 1-5: 2-8: 0.02-0.1.
3. The method of claim 1, wherein:
in the second step, the particle size of the PDVB microspheres is 15-35 mu m.
4. The method of claim 1, wherein: in the second step, the method also comprises the following extraction steps of the PDVB microspheres: soxhlet extraction is carried out by taking one or more of methanol, acetonitrile, ethanol and acetone as an extraction solvent at the extraction temperature of 80-120 ℃ to remove unreacted substances and oligomers in the polymer.
5. The method of claim 1, wherein: in the second step, the mass concentration of the hydrofluoric acid is 20-40%.
6. The method of claim 5, wherein: and in the second step, one or two of methanol and acetone solvents are added.
7. The method of claim 1, wherein:
in the third step (1), the volume concentration of the resorcinol diglycidyl ether in the total reactants is 5-15%;
in the third step (2), the volume concentration of the methylamine in the total reactants is 5-20%.
8. The method of claim 1, wherein: in the fourth step, the volume concentration of the tertiary amine compound in the total reactants is 5-15%.
9. A dendrimer functionalized polymer prepared by the method according to any one of claims 1 to 8.
10. Use of the dendrimer functionalized polymer according to claim 9 as a reverse phase/anion exchange mixed mode adsorbent material for the selective enrichment of trace acidic organics in purified samples, said acidic organics comprising acidic non-steroidal anti-inflammatory drugs.
11. Use according to claim 10, characterized in that: the sample comprises a liquid sample and an extraction solution of a solid sample; the liquid sample comprises drinking water, milk, river water, sewage, blood and urine; the solid sample comprises bottom mud, soil and meat.
CN201810427916.3A 2018-05-07 2018-05-07 Preparation method and application of dendrimer functional polymer Active CN110452319B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810427916.3A CN110452319B (en) 2018-05-07 2018-05-07 Preparation method and application of dendrimer functional polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810427916.3A CN110452319B (en) 2018-05-07 2018-05-07 Preparation method and application of dendrimer functional polymer

Publications (2)

Publication Number Publication Date
CN110452319A CN110452319A (en) 2019-11-15
CN110452319B true CN110452319B (en) 2020-05-05

Family

ID=68472089

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810427916.3A Active CN110452319B (en) 2018-05-07 2018-05-07 Preparation method and application of dendrimer functional polymer

Country Status (1)

Country Link
CN (1) CN110452319B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114573823B (en) * 2020-12-02 2023-03-31 中国科学院大连化学物理研究所 Tree-shaped molecule functionalized mesoporous material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102941130A (en) * 2012-10-31 2013-02-27 浙江大学 Preparation method of quaternized carbon nanotube agglomerated anionic chromatographic packing material
CN104941611A (en) * 2015-06-02 2015-09-30 浙江大学 Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing
CN105396628A (en) * 2015-12-06 2016-03-16 杭州飞山浩科技有限公司 Preparation method of polyethylene polyamine graft-modified polystyrene-divinyl benzene ion chromatographic packing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102941130A (en) * 2012-10-31 2013-02-27 浙江大学 Preparation method of quaternized carbon nanotube agglomerated anionic chromatographic packing material
CN104941611A (en) * 2015-06-02 2015-09-30 浙江大学 Preparation method of novel grafting high-capacity dendrimer ion chromatography stationary phase stuffing
CN105396628A (en) * 2015-12-06 2016-03-16 杭州飞山浩科技有限公司 Preparation method of polyethylene polyamine graft-modified polystyrene-divinyl benzene ion chromatographic packing

Also Published As

Publication number Publication date
CN110452319A (en) 2019-11-15

Similar Documents

Publication Publication Date Title
Liang et al. Molecularly imprinted phloroglucinol–formaldehyde–melamine resin prepared in a deep eutectic solvent for selective recognition of clorprenaline and bambuterol in urine
Cai et al. Application of deep eutectic solvents in chromatography: A review
Wang et al. Enhanced binding capacity of boronate affinity adsorbent via surface modification of silica by combination of atom transfer radical polymerization and chain-end functionalization for high-efficiency enrichment of cis-diol molecules
Peng et al. Molecularly imprinted polymer for solid-phase extraction of rutin in complicated traditional Chinese medicines
Cong et al. Preparation of porous sulfonated poly (styrene-divinylbenzene) microspheres and its application in hydrophilic and chiral separation
Chen et al. Molecularly imprinted polymer microspheres for solid‐phase extraction of protocatechuic acid in Rhizoma homalomenae
Zhu et al. Using ionic liquid monomer to improve the selective recognition performance of surface imprinted polymer for sulfamonomethoxine in strong polar medium
Jiang et al. Small organic molecular imprinted materials: their preparation and application
Lian et al. Selective detection of chloramphenicol based on molecularly imprinted solid-phase extraction in seawater from Jiaozhou Bay, China
CN109206623A (en) Hydrophily GMA-DVB polymer microballoon and preparation method thereof and ion chromatographic column
Lyu et al. Preparation of ionic liquid mediated molecularly imprinted polymer and specific recognition for bisphenol A from aqueous solution
CN111659356B (en) Preparation and application of polyethyleneimine modified reversed phase/strong anion exchange mixed mode polymer
Chi et al. Preparation of phenyl-boronic acid polymer monolith by initiator-free ring-opening polymerization for microextraction of sulfamethoxazole and trimethoprim from animal-originated foodstuffs
CN110452319B (en) Preparation method and application of dendrimer functional polymer
Ma et al. Preparation of molecularly imprinted polymer monolith with an analogue of thiamphenicol and application to selective solid-phase microextraction
CN104788602A (en) Phenylboronic acid-modified covalent affinity hypercrosslinked resin, and preparation method and application thereof
Wang et al. A study of the precipitation polymerization of bisphenol A-imprinted polymer microspheres and their application in solid-phase extraction
CN109632985B (en) Method for detecting bisphenol compounds and derivatives thereof based on extraction technology of metal organic framework nano materials
CN108178810B (en) Preparation and application of reversed phase/anion exchange mixed mode polymer
Cui et al. Cellulose-incorporated imprinted materials with amphiphilic crosslinking structure for selective adsorption of bisphenol A
Liu et al. Preparation of reversed-phase/boronate affinity mixed-mode restricted access materials with zwitterionic polymer outer layers and its extraction properties
Ji et al. Superhydrophilic molecularly imprinted polymers based on a single cross-linking monomer for the recognition of iridoid glycosides in Di-huang pills
CN102527334B (en) Solid phase extraction column with functionalized multi-walled carbon nanotube substrate, and preparation method thereof
Zhang et al. Facile one-pot preparation of chiral monoliths with a well-defined framework based on the thiol–ene click reaction for capillary liquid chromatography
Yu et al. RECENT DEVELOPMENT AND APPLICATION OF MONOLITHIC COLUMNS.

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant