CN105037602B - Surface phenolic group modified resin and preparation method thereof - Google Patents
Surface phenolic group modified resin and preparation method thereof Download PDFInfo
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- CN105037602B CN105037602B CN201510519768.4A CN201510519768A CN105037602B CN 105037602 B CN105037602 B CN 105037602B CN 201510519768 A CN201510519768 A CN 201510519768A CN 105037602 B CN105037602 B CN 105037602B
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Abstract
The present invention relates to a kind of surface phenolic group modified resin and preparation method thereof.Styrene divinylbenzene resin is prepared with monomer styrene and cross-linker divinylbenzene, in a manner of being bonded step by step, nitration styrene divinylbenzene resin is obtained in styrene divinylbenzene resin surface bond nitro, then amination styrene divinylbenzene resin is obtained by reduction reaction, last conversion surfaces amino obtains surface phenolic group modified resin.Phenolic group modified process for preparing resins in surface of the present invention is simple, degree of functionalization controllability is high, by the content for accurately controlling filler surface phenolic hydroxyl group, obtain the resin modified material with faintly acid group, it is big to the extraction selectivity height of polar compound, adsorption capacity in water available for solid phase extraction filler.
Description
Technical field
The present invention relates to chemical example pre-treatment field, more particularly to a kind of modified resin chromatograph packing material is especially a kind of
Surface phenolic group modified resin and preparation method thereof.
Background technology
Sample Pretreatment Technique has the component of strong effect power according to SPE general principle with stationary phase in sample
Retain on solid-phase extraction column, and the component weaker with stationary phase active force flows out solid-phase extraction column quickly, so as to reach separation
Purpose.
Polymer filler due to suitable pore size and distribution, particle uniformly and present single dispersing and be easy into
Row chemical modification, sample pre-treatments field is widely used at present.Polymer filler has stronger bear to the sample that is separated
Loading capability and higher chromatogram capacity；In addition, polymer filler also has good acid and alkali resistance, can be in extensive pH models
Enclose interior use；Also, its favorable reproducibility, long lifespan.
Organic polymeric solid phase fiber material is that matrix carries out modification with poly- reduction reaction resin (PS), in recent years,
Constantly there is new high-crosslinking-degree polymer resin SPE material to launch, such as containing phenolic hydroxyl group, methylol, benzoyl and
Adjacent carboxylbenzoyl, sulfonic group etc..These modified resins have good hydrophily, energy during polar compound in extraction water
Obtain the higher rate of recovery.
Prior art CN201510015754.9 discloses a kind of phenolic hydroxyl group modification polymeric adsorbent, by the polyphenyl of chloromethylation
After diene-divinylbenzene microspheres are swelled in nitrobenzene, phenol, anhydrous zinc chloride are added, heating stirring is handed over after friedel-craft occurs
Connection reaction, phenolic hydroxyl group modification polymeric adsorbent is obtained after washing, by the polyphenyl of chloromethylation diene-divinylbenzene microspheres
Phenolic hydroxyl group is introduced, improves its adsorption efficiency and selectivity to Stibene-glucoside in the fleece-flower root.Prior art
CN201210469755.7 discloses a kind of phenolic hydroxy group super high cross-linked adsorbing resin, by chloromethylated polystyrene resin in nitre
Fully it is swelled in base benzene or o-nitroethylbenzene or o-dichlorohenzene, adds phenol and fourier catalyst, be progressively warming up to 100-180
DEG C, Friedel-Crafts reactions are carried out, washs with ethanol or acetone, after drying in the having of obtained phenolic hydroxy group functional group
The Hypercrosslinked polystyrene polymeric adsorbent of isopolarity, big to Ethanol Adsorption capacity, adsorptive selectivity is good.
However, reaction temperature height needed for the phenolic group modified resin of surface, time length are prepared in the prior art, and resin surface
The content of phenolic hydroxyl group be difficult to control.
The content of the invention
The present invention in view of the shortcomings of the prior art, on the one hand provides a kind of surface phenolic hydroxyl group functionalization controllable degree high table
Face phenolic group modified resin, styrene divinylbenzene resin is prepared with monomer styrene and cross-linker divinylbenzene,
In a manner of being bonded step by step, nitration styrene divinylbenzene is obtained in styrene divinylbenzene resin surface bond nitro
Resin, then obtains amination styrene divinylbenzene resin by reduction reaction, and last conversion surfaces amino obtains surface
Phenolic group modified resin, wherein, the surface phenolic hydroxyl group substitution value is 0.6-1.5mmol/g.
In embodiments of the present invention, the surface phenolic hydroxyl group substitution value can be specifically 0.6-0.9mmol/g or 0.9-
1.5mmol/g, preferably 0.9-1.2mmol/g.
Preferably, the dosage of crosslinking agent is in mass ratio monomer and the 70-80% of crosslinking agent total amount.It is high in the present invention to hand over
Crushing resistance is strong when joining the modified resin of agent dosage as chromatograph packing material, easily elutes, and has higher sample recovery rate.
Preferably, the surface phenolic group modified resin specific surface area is 500-800m2/ g, aperture 7-10nm, particle diameter
For 40-60 μm.
Preferably, it is described to obtain nitration styrenedivinyl in styrene divinylbenzene resin surface bond nitro
Benzene resin includes：Styrene divinylbenzene resin, alkyl solvents, concentrated nitric acid, the concentrated sulfuric acid are mixed by a certain percentage, stirred
Under the conditions of at a temperature of about 40 DEG C reaction 2-4h obtain nitration styrene divinylbenzene resin；The alkyl solvents are selected from dichloro
One or more in methane, dichloroethanes, diiodomethane, ethylidene periodide, n-hexane.
It is furthermore preferred that the ratio of the concentrated nitric acid, the concentrated sulfuric acid and styrene divinylbenzene resin is respectively (in mass ratio
Meter)：0.25-0.6:1 and 0.2-0.5:1.
Preferably, it is described amination styrene divinylbenzene resin is obtained by reduction reaction to include：Nitration benzene second
Alkene divinylbenzene resin carries out reduction reaction with reducing agent under acid condition (such as hydrochloric acid or acetic acid), at a temperature of about 65 DEG C
3-6h is stirred, obtains amination styrene divinylbenzene resin；The reducing agent is selected from iron powder, frerrous chloride, zinc powder, chlorination
One or more in stannous, glass putty etc..
In embodiments of the present invention, hydrazine hydrate, vulcanized sodium or sodium disulfide etc. and nitration styrene can also be used
Divinylbenzene resin carries out reduction reaction.
In a specific embodiment, the reducing agent uses frerrous chloride and iron powder, the frerrous chloride, iron powder
Ratio with nitration styrene divinylbenzene resin is respectively (counting in mass ratio)：1-1.5:1 and 0.2-0.5:1.
Specifically, by nitration styrene divinylbenzene resin 100g, 700-1000mL solvent, 60-100mL acetic acid,
10-30mL deionized waters, 100-150g frerrous chlorides, 20-50g reduced iron powders, react under agitation at a temperature of about 65 DEG C
3-6h, obtain amination styrene divinylbenzene resin；The solvent is the one or more in methanol, ethanol, n-hexane.
In a specific embodiment, the reducing agent uses iron powder, the iron powder and nitration styrene diethyl
The ratio of alkenyl benzene resin is (counting in mass ratio)：0.4-0.8:1.
Specifically, by nitration styrene divinylbenzene resin 100g, 700-1000mL solvent, 60-100mL acetic acid,
10-30mL deionized waters, 40-80g reduced iron powders, 3-6h are reacted at a temperature of about 65 DEG C under agitation, obtains amination benzene
Ethene divinylbenzene resin；The solvent is the one or more in methanol, ethanol, n-hexane.
Preferably, the conversion surfaces amino, which obtains surface phenolic group modified resin, includes：By amination styrene diethyl
Alkenyl benzene resin, ethanol-water mixed solvent, the concentrated sulfuric acid, sodium nitrite in aqueous solution hybrid reaction, then flowed back in the mixed solvent
Dehydration, obtains surface phenolic hydroxyl group resin chromatography filler.
In a specific embodiment, the concentrated sulfuric acid, sodium nitrite in aqueous solution and amination styrene divinyl
The ratio of base benzene resin is respectively (counting in mass ratio)：0.5-0.8:1 and 0.1-0.3:1.
The present invention also provides a kind of preparation method of surface phenolic group modified resin, comprises the following steps：
(1) styrene divinylbenzene resin is prepared with monomer styrene and cross-linker divinylbenzene；
(2) by styrene divinylbenzene resin made from step (1), alkyl solvents, concentrated nitric acid, the concentrated sulfuric acid is by certain ratio
Example mixing, reaction 2-4h obtains nitration styrene divinylbenzene resin at a temperature of about 40 DEG C under agitation；The alkane
One or more of the based solvent in dichloromethane, dichloroethanes, diiodomethane, ethylidene periodide, n-hexane；
(3) by nitration styrene divinylbenzene resin made from step (2) and reducing agent in acid condition (such as hydrochloric acid
Or acetic acid) under carry out reduction reaction, stir 3-6h at a temperature of about 65 DEG C, obtain amination styrene divinylbenzene resin；
One or more of the reducing agent in iron powder, frerrous chloride, zinc powder, stannous chloride, glass putty etc.；
(4) by amination styrene divinylbenzene resin made from step (3), ethanol-water mixed solvent, the concentrated sulfuric acid,
Sodium nitrite in aqueous solution hybrid reaction, then in the mixed solvent reflux dewatering, obtain surface phenolic group modified resin.
Preferably, in the step (1), dosage of crosslinking agent is in mass ratio monomer and the 70-80% of crosslinking agent total amount.
Preferably, in the step (2), the ratio point of the concentrated nitric acid, the concentrated sulfuric acid and styrene divinylbenzene resin
(it Wei not count in mass ratio)：0.25-0.6:1 and 0.2-0.5:1.
Preferably, in the step (3), the reducing agent uses frerrous chloride and iron powder, the frerrous chloride, iron powder with
The ratio of nitration styrene divinylbenzene resin is respectively (counting in mass ratio)：1-1.5:1 and 0.2-0.5:1.
Specifically, by nitration styrene divinylbenzene resin 100g, 700-1000mL solvent, 60-100mL acetic acid,
10-30mL deionized waters, 100-150g frerrous chlorides, 20-50g reduced iron powders, react under agitation at a temperature of about 65 DEG C
3-6h, obtain amination styrene divinylbenzene resin；The solvent is the one or more in methanol, ethanol, n-hexane.
Preferably, in the step (3), the reducing agent uses iron powder, the iron powder and nitration styrene divinyl
The ratio of base benzene resin is (counting in mass ratio)：0.4-0.8:1.
Specifically, by nitration styrene divinylbenzene resin 100g, 700-1000mL solvent, 60-100mL acetic acid,
10-30mL deionized waters, 40-80g reduced iron powders, 3-6h are reacted at a temperature of about 65 DEG C under agitation, obtains amination benzene
Ethene divinylbenzene resin；The solvent is the one or more in methanol, ethanol, n-hexane.
Preferably, in the step (4), the concentrated sulfuric acid, sodium nitrite in aqueous solution and amination styrenedivinyl
The ratio of benzene resin is respectively (counting in mass ratio)：0.5-0.8:1 and 0.1-0.3:1.
In addition, the present invention also provides a kind of phenolic group modified resin in surface of the present invention answering in solid phase extraction filler
With the especially application in during the enrichment of polar substances is extracted.
Beneficial effect possessed by the present invention：
Surface phenolic group modified resin degree of functionalization controllability of the present invention is high, by accurately controlling filler surface phenolic hydroxyl group
Substitution value, obtain the resin modified material with faintly acid group, during for chromatograph packing material, it is high to polar substances selectivity,
Adsorption capacity is big；In addition, phenolic group modified process for preparing resins in surface of the present invention is simple, and compared with prior art, reaction temperature
Low, the reaction time is short, greatly reduces process costs, and beneficial to the Quality Control of filler, obtain the basically identical modified resin of property
Filler.
Brief description of the drawings
Fig. 1 solid-phase extraction column structural representations
The rate of recovery of Fig. 2 difference specific surface areas surface phenolic group modified resin for phenol sample
Fig. 3 hydroxyl modification resin adsorption amounts of the present invention and specific surface area relation curve
In figure, 1 is PA tube, and 2 be sieve plate, and 3 be filler, and 4 be interface
Embodiment
" phenolic hydroxyl group substitution value " of the present invention refers to the standby solid phase extraction filler surface phenolic hydroxy group functional group of institute of every restraint
MM number.
" styrene divinylbenzene resin " of the present invention refers to be gathered by what styrene and divinyl benzene crosslinked formed
Compound microballoon, also referred to as " styrene-divinyl benzene resin " or " styrene-divinylbenzene resin " or " styrenedivinyl
Benzene polymer " etc..
In " nitration styrene divinylbenzene resin " of the present invention, " amination styrene divinylbenzene resin "
Functionalizing group's nitro or amino bonded on the surface of styrene divinylbenzene resin.
" concentrated nitric acid " of the present invention can be the concentrated nitric acid that nitric acid mass fraction is 60-70%, refer in particular to nitric acid quality
Fraction is 65%, density 1.4g/cm3, molal weight be 16mol/L concentrated nitric acid；" concentrated sulfuric acid " of the present invention refers to sulphur
Sour mass fraction is more than or equal to 70% sulfuric acid solution, refers in particular to the sulfuric acid solution that sulfuric acid mass fraction is 97-99%.
" ratio " of the present invention is to count in mass ratio such as without specifically defined.
The error of the present invention for " about " referring to have ± 5% in the number range, e.g., from about 40 DEG C can represent 38-
42℃。
" degree of cross linking " of the present invention refer to crosslinking agent in mass ratio with crosslinking agent and the ratio of monomer total amount.
With reference to specific embodiment, the invention will be further described.
Embodiment 1：
The preparation of 80% degree of cross linking styrene divinylbenzene polymer (Archon)
Added in 1000mL four-hole boiling flasks at 450mL, 10%PVA22.5mL, 40 DEG C of running water and stir 1h, then be warming up to 60
DEG C, separately standby with oil phase, oil phase proportioning is 68g divinylbenzenes, and 17g styrene, 0.90g azo diethyl fourths are fine, 20g liquid stones
Wax.Oil phase is put at 60 DEG C, after standing 10min, stirring is opened, adjusts rotating speed, after being adapted to (38-75 μm) of the diameter of oil droplet,
80 DEG C are warming up to 1 DEG C~2 DEG C/min speed, 80 ± 1 DEG C of insulation 2h；85 DEG C of heating is further continued for, after 85 ± 1 DEG C are incubated 4h,
It is further continued for 95 DEG C of heating, 95 ± 1 DEG C of insulation 4h, discharging.
It is clear that hot water is washed till water, drains, and ethanol extracts three times, and screening (makes Archon particle diameter be 38-75 μm), and dress post petroleum ether carries
Pore-foaming agent is to without wax.
Embodiment 2：
The preparation of 70% degree of cross linking styrene divinylbenzene polymer (Archon)
Added in 1000mL four-hole boiling flasks at 450mL, 10%PVA22.5mL, 40 DEG C of running water and stir 1h, then be warming up to 60
DEG C, separately standby with oil phase, oil phase proportioning is 60g divinylbenzenes, and 25g styrene, 0.85g azo diethyl fourths are fine, 20g liquid stones
Wax.Oil phase is put at 60 DEG C, after standing 10min, stirring is opened, adjusts rotating speed, after being adapted to (38-75 μm) of the diameter of oil droplet,
80 DEG C are warming up to 1 DEG C~2 DEG C/min speed, 80 ± 1 DEG C of insulation 2h；85 DEG C of heating is further continued for, after 85 ± 1 DEG C are incubated 4h,
It is further continued for 95 DEG C of heating, 95 ± 1 DEG C of insulation 4h, discharging.
It is clear that hot water is washed till water, drains, and ethanol extracts three times, and screening (makes Archon particle diameter be 38-75 μm), and dress post petroleum ether carries
Pore-foaming agent is to without wax.
Embodiment 3：
1300mL dichloromethane is added in 2000mL four-hole boiling flasks, the Archon that 100g embodiments 1 or 2 are prepared, stir
Swelling 2h is mixed, the 50mL concentrated sulfuric acids that feed intake, 50mL concentrated nitric acid mixtures, is heated to 40 DEG C of back flow reaction 2h, is cooled down, filtering is washed with water
To neutrality, washed with methanol to filtrate without color, naturally dry.
Embodiment 4：
1300mL dichloroethanes is added in 2000mL four-hole boiling flasks, the Archon that 100g embodiments 1 or 2 are prepared, stir
Mix swelling 2h, the 40mL concentrated sulfuric acids that feed intake, 60mL concentrated nitric acid mixtures, be heated to 40 DEG C reaction 2.5h, cooling, filtering be washed with water to
Neutrality, washed with methanol to filtrate without color, naturally dry.
Embodiment 5：
The gained about 100g desciccates of above-described embodiment 3 or 4 are put into 2000mL there-necked flasks, addition 900mL methanol,
100mL acetic acid and 20mL deionized waters；2h is swelled, is fed intake：123.6g frerrous chlorides and 35.2g reduced iron powders, back flow reaction 4h；
Room temperature is cooled to, it is colourless (or 4h is boiled in the backflow of 1M HCl/waters solution) that 1M HCl/water solution, which is washed to filtrate, and deionized water is washed till
Neutrality, methanol are washed 3 times, dried.
Embodiment 6：
The gained about 100g desciccates of above-described embodiment 3 or 4 are put into 2000mL there-necked flasks, addition 900mL methanol,
100mL acetic acid and 20mL deionized waters；2h is swelled, is fed intake：60g reduced iron powders, back flow reaction 6h；It is cooled to room temperature, 1M HCl
It is colourless (or 4h is boiled in the backflow of 1M HCl/waters solution) that the aqueous solution, which is washed to filtrate, and deionized water is washed till neutrality, and methanol washs 3 times,
Dry.
Embodiment 7：
The gained about 100g desciccates of above-described embodiment 5 or 6 are put into 2000mL there-necked flasks, addition 600mL methanol,
600mL deionized waters and the 56g concentrated sulfuric acids；Ice bath is swelled 2h, and the aqueous solution of 14g natrium nitrosums is added dropwise with constant pressure funnel,
30min is dripped off, and is filtered out after stirring 2h, is collected in resin input 2000mL there-necked flasks, is added 600mL methanol and 600mL water, backflow
3h is reacted, is filtered out, water and methanol are respectively washed three times, are dried.
Embodiment 8：
Surface phenolic group modified resin made from embodiment 7 is weighed into 60mg, loads the 3mL PA tubes 1 with lower sieve plate 2
In, insert after upper sieve plate 2 and shaken uniformly with vibrating bed, is compacted with presser-into-rod, solid-phase extraction column structural representation is referring to accompanying drawing 1.
Embodiment 9：
The separation of different specific surface area surface phenolic group modified resin Pyrogentisinic Acid standard items and reagent sample
Prepare solution：50mg phenol Standard product water, which dissolves and is diluted to 50mL (1000ppm), takes 0.5mL l000ppm to mark
Product are accurate, are diluted with water and prepare 10ppm standard items.Methanol (analysis is pure), 5mol/L NAOH (weigh 2g NAOH and are dissolved in 10mL water
In), 5% ammonia/water solution (in 95mL water add 5mL ammoniacal liquor), 4% acetic acid methanol (in 100mL methanol plus in add 4mL second
Acid).
By preparation method of the embodiment of the present invention, the modified resin filler of different specific surface areas is prepared, obtains solid-phase extraction column,
Obtained each 3 of solid-phase extraction column is taken, is activated successively with 1mL methanol, 1mL 5mol/L NAOH, 1mL water, loading 3mL (10ppm
Phenol Standard product), pillar is flowed through with 4~5mL/min flow velocity, pillar is eluted successively with the ammoniacal liquor of 1mL 5%, 1mL methanol, is used
Methanol solutions of the 3mL containing 4% acetic acid is eluted, and eluent is dried up with nitrogen, methanol 1mL constant volumes, analyzed with HPLC.
Each 3 of the solid-phase extraction column of different specific surface areas obtained above is taken, successively with 1mL methanol, 1mL5mol/L
NAOH, 1mL water activate, and it is 10% that phenol Standard product to concentration is added in loading 300mL water samples, with 4~5mL/min flow velocity stream
Pillar is crossed, pillar is eluted successively with the ammoniacal liquor of 1mL 5%, 1mL methanol, is eluted with methanol solutions of the 3mL containing 4% acetic acid, eluent
Dried up, methanol 1mL constant volumes, analyzed with HPLC with nitrogen.Recovery of the phenolic group modified resin in surface of the present invention for phenol sample
For rate referring to table 1 and accompanying drawing 2, testing result takes 3 average values.
Table 1：The rate of recovery of the different specific surface area surface phenolic group modified resins for phenol sample
From the testing result of above-mentioned table 1, with the increase of specific surface area, the rate of recovery of standard items and actual sample increases
Add, after reaching certain numerical value, the rate of recovery declines on the contrary.When specific surface area is less than 420m2During/g, the rate of recovery less than 70%, when than
Surface area is 890m2During/g, to the rate of recovery of actual sample less than 70%, and when specific surface area is in about 500-800m2/ g, especially
It is 560-735m2It is relatively gentle to the growth trend of the rate of recovery of sample during/g and big for the rate of recovery of actual sample
In 80%.Therefore, preferential in actual applications from specific surface area is 500-800m2/ g modified resin.
Embodiment 10：
The absorption property of phenolic group modified resin in surface of the present invention
The accurate resin 60mg for weighing the present invention and being prepared, is placed in conical flask, the phenol for adding concentration known is water-soluble
Liquid, room temperature concussion 12h, adsorbance, testing result ginseng are calculated according to the weight of the change in concentration of the front and rear sample of absorption and resin
It is shown in Table 2 and accompanying drawing 3.
Table 2：The absorption property of surface of embodiment of the present invention phenolic group modified resin
From the result of above-mentioned table 2, surface its surface of phenolic group modified resin obtained using preparation method of the present invention
Phenolic hydroxyl group substitution value is controllable, and is between 0.9-1.2mmol/L, is particularly concentrated between 1.0-1.1.In addition, by accompanying drawing 2
Understood with table 2, it is directly proportional between resin specific surface area and adsorbance in the case that surface phenolic hydroxyl group substitution value is essentially identical,
With the increase of specific surface area, the adsorbance of resin shows a rising trend.Further, since surface phenolic hydroxyl group substitution value is controllable, resin
Absorption property be directly associated with specific surface area, the difficulty of filler Quality Control is reduced, by detecting specific surface area i.e. can be known
The adsorbance of resin.
The above described is only a preferred embodiment of the present invention, not make any form to technical scheme
On limitation.Any simply modification, the equivalent variations that every technical spirit according to the present invention is made to above example are with repairing
Decorations, in the range of still falling within technical scheme.
Claims (10)
1. a kind of surface phenolic group modified resin, styrene diethyl is prepared with monomer styrene and cross-linker divinylbenzene
Alkenyl benzene resin, in a manner of being bonded step by step, nitration benzene second is obtained in styrene divinylbenzene resin surface bond nitro
Alkene divinylbenzene resin, amination styrene divinylbenzene resin, last conversion surfaces are then obtained by reduction reaction
Amino obtains surface phenolic group modified resin, wherein, the surface phenolic hydroxyl group substitution value is 0.6-1.5mmol/g.
2. phenolic group modified resin in surface as claimed in claim 1, it is characterised in that：Surface phenolic hydroxyl group substitution value is 0.9-
1.2mmol/g。
3. phenolic group modified resin in surface as claimed in claim 1, it is characterised in that：The surface phenolic group modified resin ratio
Surface area is 500-800m2/ g, aperture 7-10nm, particle diameter are 40-60 μm.
4. phenolic group modified resin in surface as claimed in claim 1, it is characterised in that：The dosage of crosslinking agent is in mass ratio
The 70-80% of monomer and crosslinking agent total amount.
5. a kind of preparation method of surface phenolic group modified resin, comprises the following steps：
(1) styrene divinylbenzene resin is prepared with monomer styrene and cross-linker divinylbenzene；
(2) styrene divinylbenzene resin, alkyl solvents, concentrated nitric acid, the concentrated sulfuric acid made from step (1) are mixed by a certain percentage
Close, reaction 2-4h obtains nitration styrene divinylbenzene resin at a temperature of about 40 DEG C under agitation；The alkyl is molten
One or more of the agent in dichloromethane, dichloroethanes, diiodomethane, ethylidene periodide, n-hexane；
(3) nitration styrene divinylbenzene resin made from step (2) is reduced in acid condition with reducing agent
Reaction, stirs 3-6h at a temperature of about 65 DEG C, obtains amination styrene divinylbenzene resin；The reducing agent is selected from iron
One or more in powder, frerrous chloride, zinc powder, stannous chloride, glass putty；
(4) by amination styrene divinylbenzene resin, ethanol-water mixed solvent, the concentrated sulfuric acid, nitrous made from step (3)
Acid sodium aqueous solution hybrid reaction, then in the mixed solvent reflux dewatering, obtain surface phenolic group modified resin；
" about " refer to that there is ± 5% error in the number range described in step (2) and (3).
6. preparation method as claimed in claim 5, it is characterised in that：In the step (1), dosage of crosslinking agent is in mass ratio
The 70-80% of monomer and crosslinking agent total amount.
7. preparation method as claimed in claim 5, it is characterised in that：In the step (2), the concentrated nitric acid, the concentrated sulfuric acid with
The ratio of styrene divinylbenzene resin is respectively：0.25-0.6:1 and 0.2-0.5:1.
8. preparation method as claimed in claim 5, it is characterised in that：In the step (3), the reducing agent uses protochloride
Iron and iron powder, the ratio of the frerrous chloride, iron powder and nitration styrene divinylbenzene resin are respectively：1-1.5:1 He
0.2-0.5:1；
Or in the step (3), the reducing agent uses iron powder, the iron powder and nitration styrene divinylbenzene tree
The ratio of fat is：0.4-0.8:1.
9. preparation method as claimed in claim 5, it is characterised in that：In the step (4), the concentrated sulfuric acid, natrium nitrosum
The ratio of the aqueous solution and amination styrene divinylbenzene resin is respectively：0.5-0.8:1 and 0.1-0.3:1.
A kind of 10. chromatograph packing material, it is characterised in that：Including the surface phenolic group modified tree as described in claim any one of 1-4
The surface phenolic group modified resin that fat or the preparation method as described in claim any one of 5-9 are prepared.
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| CN106366221A (en) * | 2016-08-07 | 2017-02-01 | 刘天泽 | Preparation method for amino-functionalized macroporous styrene resin with large specific surface |
| WO2018031853A1 (en) | 2016-08-12 | 2018-02-15 | Akron Polymer Systems, Inc. | Optical compensation film having reversed wavelength dispersion |
| KR102450677B1 (en) * | 2016-08-12 | 2022-10-04 | 아크론 폴리머 시스템즈, 인코포레이티드 | Method for producing styrene nitride-based fluoropolymer |
| EP3496941B1 (en) | 2016-08-12 | 2023-06-14 | Akron Polymer Systems, Inc. | Multilayer optical compensation film having reversed wavelength dispersion |
| CN107793514B (en) * | 2017-11-29 | 2020-08-07 | 中国科学院青岛生物能源与过程研究所 | Functionalized ultrahigh cross-linked resin and preparation method thereof |
| CN114057914A (en) * | 2021-11-03 | 2022-02-18 | 上海海智维医药科技有限公司 | Novel bifunctional group modified ultrahigh cross-linked resin and preparation technology thereof |
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