CN110452319A - A kind of preparation method and applications of dendrimer functionalized polymer - Google Patents
A kind of preparation method and applications of dendrimer functionalized polymer Download PDFInfo
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Abstract
The present invention provides a kind of preparation method and applications of the polymer of novel tree-like macromolecular functionalization.First using pik woods polymerization preparation uniform particle sizes, the polymer of regular shape, then using gradually grafting method in dendrimer of the polymer surfaces modification with Cationic functional groups.The preparation method take full advantage of dendrimer branched structure and high functional group densities, greatly improve the ion exchange capacity and extraction efficiency of material.The preparation method of dendrimer functionalized polymer provided by the invention is easy, reaction is fast, period is short, ion exchange capacity is high, there is very strong selectivity and extracting power to acid non-steroidal anti-inflammatory drugs, solve that traditional extraction material selectivity is poor simultaneously, the low problem of the rate of recovery can be used for being enriched with and purifying the faintly acid non-steroidal anti-inflammatory drugs in complex matrices.
Description
Technical field
The present invention relates to one kind to polymerize the selective novel tree-like macromolecular functionalization of acid non-steroidal anti-inflammatory drugs
The preparation and application of object, belong to chromatography new material and sample pre-treatments field.
Background technique
Non-steroidal anti-inflammatory drugs (non-steroid anti-inflammatory drugs, NSAIDs) is a kind of with anti-
Scorching, analgesic and antipyretic effect drug, is widely applied by the mankind and livestock.Evidence suggests such drugs to have very big kidney poison
Property, such as the cinereous vulture in South Asia remain the ox corpse of Diclofenac and largely die of kidney failure (A CHEM due to having eaten
Trust report(2014)).Non-steroidal anti-inflammatory drugs can also increase Cardia cevent and complication
(Pharmaceuticals 3(2010)2146-2162).Since the usage amount of such drug is big, side effect is big, therefore to complexity
The accurate quick detection of non-steroidal anti-inflammatory drugs is particularly important in sample.
Due to content very low (ng mL of the drug in biology and environmental sample-1~μ g mL-1), simultaneously containing many dry
Substance is disturbed, therefore the enrichment and purification of sample are the committed steps of sample preparation.Since solid phase extraction techniques have adsorbent material
Expect the advantages that diversity, the rate of recovery are good, consumption of organic solvent is few, is most common Sample Pretreatment Technique.Traditional solid phase extraction
Drawing materials, (ion is handed over for usually only a kind of chromatography retained-mode-inverting function (such as C18, St-DVB) or ion exchange
Change resin), poor selectivity.Mixed mode adsorbent integrates inverting function and ion exchange, improves to target point
The selectivity and reserve capability for analysing object can more effectively remove impurity, obtain highly sensitive and low background interference.
The action site for increasing mixed mode sorbent material can improve the selectivity and extraction efficiency of sorbent material.
Dendrimer is a kind of new function macromolecule highly branched, radially, and inside has lar nanometric cavities and work abundant
Property site, periphery has the functional group that can modify, in nano-catalytic, medicament transport, chemical sensor, sewage treatment, membrane material
Material etc. has potential application.Dendrimer can be significantly improved to the action site of material applied to solid phase extraction techniques.
In current document report, does not have also using resorcinolformaldehyde resin and methylamine as function monomer, pass through what is be gradually grafted
Method, it is multiple as reverse phase/anion exchange mixed mode adsorbent enrichment and purification in polymer surfaces modification dendrimer
The report of acid non-steroidal anti-inflammatory drugs in miscellaneous sample.
Summary of the invention
The object of the present invention is to provide a kind of dendrimer function to acid non-steroidal anti-inflammatory drugs with very high selectivity
The preparation method of energy fluidized polymer.
A kind of preparation method of dendrimer functionalized polymer, the described method comprises the following steps:
Step 1: preparing PDVB-SiO using Pickering emulsion polymerization2(the stable poly- diethyl of nano silica
Alkenyl benzene) complex microsphere;
Step 2: by gained PDVB-SiO2Complex microsphere removes Nano-meter SiO_2 with hydrofluoric acid dips2, isolated PDVB is micro-
Ball;
Step 3: being grafted dendrimer in polymer surfaces using step-reaction
(1) in methyl alcohol by the dispersion of PDVB microballoon, the concentration of PDVB is 0.05~0.1g/mL;Resorcinol two is added to contract
Water glycerin ether, in 60~80 DEG C of 3~5h of reaction, washing, vacuum drying obtain the dendrimer that functional end-group is epoxy and repair
The polymer (G0.5-ED) of decorations;
(2) in ethanol by gained G0.5-ED dispersion, the concentration of G0.5-ED is 0.05~0.1g/mL;Methylamine is added, in
60~80 DEG C of 3~5h of reaction, washing, vacuum drying obtain the polymer that the dendrimer that functional end-group is amido is modified
(G1-AD);
(3) described in repeating (1) and (2), the dendrimer functionalized polymer of different algebra is obtained;
Step 4: epoxy-terminated season aminating reaction
By dendrimer functionalized polymer Gn-ED that gained functional end-group is epoxy, (n=m-0.5, m are >=1
Integer) to disperse in ethanol, Gn-ED concentration is 0.05~0.1g/mL;Tertiary amine compound (preferably N, N- dimethyl second is added
Hydramine), in 60~80 DEG C of 3~5h of reaction, obtaining dendrimer functionalized polymer Gm-QD that end group is quaternary ammonium group, (m is
>=1 integer).
The Pickering emulsion polymerization is with Nano-meter SiO_22For emulsifier, with diethylaminoethyl methacrylate
It (DEAEMA) is monomer;Using divinylbenzene as crosslinking agent;Using azodiisobutyronitrile as initiator;It is with toluene and 1- lauryl alcohol
Pore-foaming agent, in 50~70 DEG C of polymerization reaction 12-36h;The molar ratio of the 1- lauryl alcohol and toluene is 1:4~5;Nano-meter SiO_22With
(oil is mutually diethylaminoethyl base ethyl ester, divinylbenzene, toluene, 1- lauryl alcohol and azodiisobutyronitrile mixing to oily phase
Solution) mass ratio be 1%~4%;
The monomer, crosslinking agent, pore-foaming agent, initiator molar ratio be 1:1~5:2~8:0.02~0.1.
In step 2, the partial size of the PDVB microballoon is preferably 15~35 μm.
In step 2, it is also preferable to include carry out following extracting for gained PDVB microballoon: using methanol, acetonitrile, second
One of alcohol, acetone or more than one solution are Extraction solvent, and soxhlet type, extraction temperature is 80~120 DEG C, are removed poly-
Close unreacted substance and oligomer in object;
In step 2, the mass concentration of the preferably described hydrofluoric acid is 20%~40%, is added without or in which can be added methanol
Or one of acetone solvent or two kinds.
In step 3 (1), volume solubility of the preferably described resorcinolformaldehyde resin in total reactant be 5%~
15%;
In step 3 (2), volumetric concentration of the preferably described methylamine in total reactant is 5%~20%;
In step 4, concentration of the preferred tertiary amine compound in total reactant is 5~15%.
The present invention also provides the dendrimer functionalized polymers that the above method is prepared.
The present invention also provides above-mentioned dendrimer functionalized polymers as reverse phase/anion exchange mixed mode absorption
Application of the agent material in the trace Acidic organic matter in selective enrichment purification complex sample;The Acidic organic matter includes acid
Property non-steroidal anti-inflammatory drugs.
Filler of the dendrimer functionalized polymer as solid-phase extraction column.
Preferably, the sample includes the extraction solution of fluid sample and solid sample;The fluid sample includes drinking
Water, milk, river water, sewage, blood, urine;The solid sample includes bed mud, soil, meat.
The polymer of dendrimer modification of the present invention is fragrant to salicylic acid, brufen, naproxen, Ketoprofen, double chlorine
The acidity non-steroidal anti-inflammatory drugs such as acid has very high selectivity, such drug can be adsorbed from solution, suitable by selecting
Elution condition removes the interfering substance of absorption and retains object.It is used as sample pretreatment material, targeted can be made to close
Object obtains the clean-up effect of high-recovery and superelevation.
Due to modifying using dendrimer, the ion exchange capacity of adsorbent, adsorption capacity enhancing are significantly increased.
Since the polymer of dendrimer modification has reverse phase and the dual retention mechanism of ion exchange as adsorbent, closed by selection
Suitable elution condition, can remove interfering substance and only retain target analytes, overcome the traditional polymer rate of recovery it is low, purification
The problem of effect difference.
The invention has the advantages that provide a kind of novel high-capacity dendrimer functionalized polymer preparation method and
Using.The dendrimer for modifying different algebra in polymer surfaces using gradually grafting method takes full advantage of tree-shaped big point
The hyperbranched structure of son, high density active site increase the adsorption site of material, improve adsorption efficiency and selectivity.It will tree
Shape macromolecular functionalized polymer can isolate and purify the acid non-steroidal anti-inflammatory in complex matrices as solid phase extraction column stuffing
Medicine can effectively reduce matrix interference, can rapidly and accurately detect to complex sample.
Detailed description of the invention:
Fig. 1 is the synthesis schematic diagram of polymer;
Fig. 2 is washing for alkaline (carbamazepine and amitriptyline), neutral (hydrocortisone) and acid (brufen) drug
De- curve.
Specific embodiment
1. monomer, crosslinking agent and initiator are dissolved in pore-foaming agent, it is prepared into solution A, nitrogen is led into solution A;, excellent
15min is selected, the oxygen molecule in solution A is removed;Monomer, crosslinking agent, pore-foaming agent, initiator molar ratio be 1:1~5:2~8:
0.02~0.1;Monomer is preferably diethylaminoethyl methacrylate (DEAEMA);Crosslinking agent is preferably divinylbenzene;Draw
Sending out agent is preferably azodiisobutyronitrile;Pore-foaming agent is preferably toluene and 1- lauryl alcohol, wherein the molar ratio of 1- lauryl alcohol and toluene
For 1:4~5;SiO2Partial size is less than 50nm.
2. by Nano-meter SiO_22It is distributed in deionized water, referred to as dispersion liquid B, Nano-meter SiO_22Mass concentration is 3~15mg mL-1(preferred concentration 12mg/mL).Then 3~5mL solution A, 6000rpm homogenate dispersion 1min are added into 10mL dispersion liquid B.
It is sealed after oxygen molecule in logical nitrogen 2min discharge system.By obtained Pickering lotion in 50~70 DEG C of polymerization reactions 12
~36h.
3. after reaction, using centrifuge separation or filtering, white polymer and SiO are obtained2Composite materials (PDVB-
SiO2)。
4. obtained PDVB-SiO2Composite material hydrofluoric acid dips 12~for 24 hours, isolated white polymer microballoon
(PDVB)。
5. screening, sedimentation obtain the polymer microballoon that partial size is 15~35 μm.
6. obtained material uses one of methanol, acetonitrile, ethyl alcohol, acetone or more than one mixed liquor to extract
Solvent carries out soxhlet type, and extraction temperature is 80~120 DEG C, removes unreacted substance and oligomer in polymer.
7. modifying dendrimer using step-reaction
PDVB is dispersed in 90% methanol, the concentration of PDVB is 0.05~0.1g/mL.Addition resorcinol two shrinks sweet
Oily ether obtains the polymer (G0.5- that the dendrimer that functional end-group is epoxy is modified in 60~80 DEG C of 3~5h of reaction
ED), with methanol and acetone washing G0.5-ED, and in vacuum drying.
Then in ethanol by G0.5-ED dispersion, the concentration of G0.5-ED is 0.05~0.1g/mL.Be added methylamine solution in
60~80 DEG C of 3~5h of reaction obtain the polymer (G1-AD) that the dendrimer that functional end-group is amido is modified, use methanol
With acetone washing G1-AD, and in vacuum drying.Above-mentioned two-step reaction is repeated, different algebra dendrimer functionalization are obtained
Polymer;
8. epoxy-terminated season aminating reaction
By dendrimer functionalized polymer Gn-ED that the end being prepared is epoxy, (n=m-0.5, m are >=1
Integer) it is dispersed in 70% ethanol solution, Gn-ED concentration is 0.05~0.1g/mL.Be added N, N- dimethylethanolamine in 60~
80 DEG C of 3~5h of reaction, obtaining the high capacity dendrimer functionalized polymer Gm-QD that end group is quaternary ammonium group, (m is >=1
Integer).
Wherein, the optimum condition of dendrimer functionalized polymer is prepared are as follows: 1. middle function monomer is in above-mentioned steps
Diethylaminoethyl methacrylate, crosslinking agent are divinylbenzene, and initiator is azodiisobutyronitrile, monomer: crosslinking agent: are caused
Hole agent: initiator molar ratio is 1:4:6.5:0.07, and the molar ratio of 1- lauryl alcohol and toluene is 1:4.7 in pore-foaming agent.
Embodiment 1
By 10mmol (2.0mL) methacrylic acid diethyllaminoethyl ester, 40mmol (5.66mL) divinylbenzene and
115mg azodiisobutyronitrile is dissolved into the porogen solutions of (5.68mL) and 1- lauryl alcohol (2.12g) containing toluene, is prepared into
Then solution A leads to nitrogen 15min into solution A and removes oxygen molecule.By the SiO of 120mg partial size 12nm2It is distributed in 10mL water,
Ultrasonic 10min makes Nano-meter SiO_22Then 4mL solution A is added in dispersion, stir 1min using refiner 6000rpm, then lead to nitrogen
Sealed after air above 2min removing system, by obtained Pickering lotion 60 DEG C of polymerization reactions for 24 hours.Reaction terminates
After filter, then cross 400 mesh stainless steels sieve, then twice with acetone sedimentation, each 10min, obtaining partial size is 15~35 μm poly-
Close object PDVB-SiO2.Then 2gPDVB-SiO is taken2For 24 hours with the hydrofluoric acid dips of 10mL 40%, the SiO on surface is removed2It obtains
PDVB microballoon.It filters, and is washed with deionized to neutrality.Using methanol as Extraction solvent, Soxhlet extraction for 24 hours, then in vacuum
60 DEG C of dry 12h in drying box.
2.0gPDVB is dispersed in 20mL90% methanol, it is anti-in 80 DEG C that 2.5mL resorcinolformaldehyde resin is added
3h is answered, the polymer (G0.5-ED) that the dendrimer that functional end-group is epoxy is modified is obtained, with methanol and acetone washing
G0.5-ED, and be dried in vacuo.Then G0.5-ED (2.0g) is dispersed in 20mL ethyl alcohol, 5mL methylamine solution is added in 80 DEG C
3h is reacted, the polymer (G1-AD) that the dendrimer that functional end-group is amido is modified is obtained, with methanol and acetone washing
G1-AD, and be dried in vacuo.Above-mentioned two-step reaction is repeated, the polymer of different algebra dendrimer functionalization is obtained;
By the end being prepared be epoxy dendrimer functionalized polymer 2.0g Gn-ED (n=m-0.5, m are
>=1 integer) it is dispersed in 20mL70% ethanol solution, 2.5mLN is added, N- dimethylethanolamine is held in 80 DEG C of reaction 3h
Base is the dendrimer functionalized polymer Gm-QD of quaternary ammonium group, (m is >=1 integer).The dendrimer function of different algebra
The specific surface area and pore volume of energy fluidized polymer the results are shown in Table 1.
Embodiment 2
50mgPDVB is packed into 3-mL SPE column tube, 5mL methanol and 5mL deionized water balance is first used, 7mg brufen is used
The phosphate buffer (pH 7.0) of 30mL 10mM dissolves and loading.30min is drained, is eluted with 5mL methanol, then uses 5mL
The methanol solution of 1% formic acid elutes brufen, collects elution solution, is diluted with methanol/water (1:1), constant volume to 250mL, with height
Effect liquid phase chromatogram measurement, calculates ion exchange capacity.The ion exchange capacity of G1-QD, G2-QD, G3-QD, G4-QD and G5-QD
Measuring method is identical as PDVB's.The ion exchange capacity of the dendrimer functionalized polymer of different algebra the results are shown in Table 1.
Specific surface area, pore volume and the ion exchange capacity of the dendrimer functionalized polymer of the different algebra of table 1 are surveyed
Determine result
Pass through table 1, it can be seen that as dendrimer is grown in polymer duct, the specific surface area of (1) polymer
It is gradually reduced with pore volume, the ion exchange capacity of (2) material gradually increases, until the polymerization of forth generation dendrimer modification
The ion exchange capacity of object (G4-QD) is maximum, and the ion exchange capacity of G5-QD is declined compared with G4-QD.So selection
Filler of the G4-QD as solid-phase extraction column.
Embodiment 3
200mg G4-QD is packed into 3-mL SPE column tube, it is first flat with 5mL methanol and 5mL 10mM phosphate buffer solution
Weighing apparatus, by 5 μ g mL of 10mL-1Carbamazepine (CAZ), amitriptyline (AMI), hydrocortisone (HYC) and brufen (IBP)
Phosphate buffer (pH 7.0) is with 1mL min-1Speed loading.30min is drained, is first eluted with 5mL methanol, then uses 5mL
The methanol solution of 1% formic acid elutes, and collects eluent solution and eluent, and every milliliter is used as one section and slips part, is dried with nitrogen, is settled to
0.5mL is analyzed with HPLC-UV.The elution curve of different material is shown in Fig. 2, can be incited somebody to action with 2mL methanol as seen in Figure 2
Carbamazepine (CAZ), amitriptyline (AMT) and hydrocortisone (HYC) are eluted from solid-phase extraction column, and must be used
Methanol solution containing formic acid can just elute brufen, and as a result explanation is by selecting suitable condition, dendrimer function
It can the acid brufen of the fluidized polymer property of can choose reservation.
Claims (10)
1. a kind of preparation method of dendrimer functionalized polymer, it is characterised in that: the described method comprises the following steps:
Step 1: preparing PDVB-SiO using Pickering emulsion polymerization2Complex microsphere;
Step 2: by gained PDVB-SiO2Complex microsphere removes Nano-meter SiO_2 with hydrofluoric acid dips2, isolated PDVB microballoon;
Step 3: being grafted dendrimer in polymer surfaces using step-reaction
(1) in methyl alcohol by the dispersion of PDVB microballoon, the concentration of PDVB is 0.05~0.1g/mL;Addition resorcinol two shrinks sweet
Oily ether, in 60~80 DEG C of 3~5h of reaction, washing, vacuum drying obtain what the dendrimer that functional end-group is epoxy was modified
Polymer (G0.5-ED);
(2) in ethanol by gained G0.5-ED dispersion, the concentration of G0.5-ED is 0.05~0.1g/mL;Methylamine is added, in 60~
80 DEG C of 3~5h of reaction, washing, vacuum drying obtain the polymer (G1- that the dendrimer that functional end-group is amido is modified
AD);
(3) described in repeating (1) and (2), the dendrimer functionalized polymer of different algebra is obtained;
Step 4: epoxy-terminated season aminating reaction
By dendrimer functionalized polymer Gn-ED that gained functional end-group is epoxy (n=m-0.5, m be >=1 it is whole
Number) to disperse in ethanol, Gn-ED concentration is 0.05~0.1g/mL;Tertiary amine compound is added, in 60~80 DEG C of 3~5h of reaction,
Obtain the dendrimer functionalized polymer Gm-QD (integer that m is >=1) that end group is quaternary ammonium group.
2. according to the method described in claim 1, it is characterized by:
The Pickering emulsion polymerization is with Nano-meter SiO_22For emulsifier, with diethylaminoethyl methacrylate (DEAEMA)
For monomer;Using divinylbenzene as crosslinking agent;Using azodiisobutyronitrile as initiator;Using toluene and 1- lauryl alcohol as pore-foaming agent,
In 50~70 DEG C of polymerization reaction 12-36h;The molar ratio of the 1- lauryl alcohol and toluene is 1:4~5;
The monomer, crosslinking agent, pore-foaming agent, initiator molar ratio be 1:1~5:2~8:0.02~0.1:.
3. according to the method described in claim 1, it is characterized by:
In step 2, the partial size of the PDVB microballoon is 15-35 μm.
4. according to the method described in claim 1, it is characterized by: in step 2, further include gained PDVB microballoon is carried out with
The step of lower extracting: use one of methanol, acetonitrile, ethyl alcohol, acetone or more than one mixed liquor for Extraction solvent progress
Soxhlet type, extraction temperature are 80~120 DEG C, remove unreacted substance and oligomer in polymer.
5. according to the method described in claim 1, it is characterized by: the mass concentration of the hydrofluoric acid is 20% in step 2
~40%, it is added without or in which can be added one of methanol or acetone solvent or two kinds.
6. according to the method described in claim 1, it is characterized by:
In step 3 (1), volume solubility of the resorcinolformaldehyde resin in total reactant is 5%~15%;
In step 3 (2), volumetric concentration of the methylamine in total reactant is 5%~20%.
7. according to the method described in claim 1, it is characterized by: tertiary amine compound is dense in total reactant in step 4
Degree is 5~15%.
8. the dendrimer functionalized polymer that any one of claim 1-7 the method is prepared.
9. dendrimer functionalized polymer is as reverse phase/anion exchange mixed mode absorption according to claim 8
Application of the agent material in the trace Acidic organic matter in selective enrichment purification sample, the Acidic organic matter include acid non-
Steroidal anti-inflammatory medicine.
10. application according to claim 9, it is characterised in that: the sample includes mentioning for fluid sample and solid sample
Take solution;The fluid sample includes drinking water, milk, river water, sewage, blood, urine;The solid sample include bed mud,
Soil, meat.
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