CN109847715A - A kind of preparation method of amide group modified polystyrene system super high cross-linked adsorbing resin - Google Patents
A kind of preparation method of amide group modified polystyrene system super high cross-linked adsorbing resin Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of amide group modified polystyrene crosslinked resin.Method includes the following steps: water phase and oil, which are mixed suspension polymerization, is prepared ester group modification of precursor resin, sweller is added in precursor resin and lewis acid catalyst carries out Friedel-Crafts reaction and obtains post-crosslinking resin, aminating agent is added in post-crosslinking resin and carries out aminating reaction, crosslinked resin is prepared.Double bond containing esters monomer is introduced in preparation method of the invention, improves the polarity of resin, resin micropore and mesoporous number are increased by Fu Ke cross-linking reaction, generates amide group by introducing aminating agent, the specific surface area of adsorbent is up to 900 ~ 1500 m21.012 ~ 1.412 cm of/g, Kong Rong3/ g, 1 ~ 20 nm of average pore size are easy to form hydrophobic forces and hydrogen bond action with adsorbent in absorption, to improve the absorption property of resin, and preparation process is simple, reaction condition is easily controllable, can industrialized production.
Description
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of amide group modified styrene superhigh cross-linking absorption
The preparation method of resin.
Background technique
5 hydroxymethyl furfural (5-hydroxymethylfurfural, abbreviation 5-HMF) is that one kind contains aldehyde radical, hydroxyl simultaneously
The polyfunctional compound of methyl isoreactivity group can occur to add the reaction such as hydrogen, oxidation, esterification, halogenation, polymerization, hydrolysis, be
A kind of important biomass platform chemicals.5 hydroxymethyl furfural is also used as synthesizing the original of a variety of high added value compounds
Material, is widely used in the fields such as synthetic polymer, drug, resin, plastics, fuel additive.Such as 5 hydroxymethyl furfural quilt
It is obtained after oxidation 2,5-furandicarboxylic acid (FDCA), FDCA is widely used in synthesizing polyester material, to get rid of polyester product and original
Material depends on the situation of petroleum resources unduly.5 hydroxymethyl furfural can produce C by reacting back end hydrogenation with condensation of acetone9-C17's
Alkane fuel, component is similar to ordinary diesel oil, can be directly used for common engine, and substitute petroleum fuel.
The preparation method of 5 hydroxymethyl furfural mainly passes through monosaccharide or polysaccharide and is dehydrated under the action of acid catalyst at present
It arrives.After decades of development, the yield that sugared degradation prepares 5 hydroxymethyl furfural is continuously improved, but obtained 5 hydroxymethyl furfural
It is not easy to be separated, reason is that 5 hydroxymethyl furfural is easy to happen polymerization in acid condition and generates humin, also Yi Fasheng
Hydrolysis generates levulic acid and formic acid.Therefore in the production process of 5 hydroxymethyl furfural, 5 hydroxymethyl furfural is isolated in time
It is particularly important.The separation method for being usually used in separating 5 hydroxymethylfurfurals at present includes distillation, solution extraction, UF membrane, absorption
Deng since 5 hydroxymethyl furfural boiling point is higher, there is the disadvantages of energy consumption is high, complex process in distillation separation；Solution extraction then needs
Quantity of solvent is big, and the time is long；For UF membrane due to expensive, film is easily contaminated and is not widely used；Adsorption separation process is based on
Adsorbent is different to the active force of different adsorbates；Adsorption separating method is easy to operate, at low cost, it is considered to be most promising
One of separation method.The key of adsorbing separation is to select suitable adsorbent, and common adsorbent has zeolite, active carbon, ion
Exchanger resin, hypercrosslinked polymeric resin etc., active carbon and zeolite are a kind of non-specific adsorption agent, can not be selected in aqueous solution
5 hydroxymethyl furfural is adsorbed to property, and when ion exchange resin treatment is lived again, can generate a large amount of acidic and alkaline waste water, these disadvantages are all
The extensive use of active carbon, zeolite, ion exchange resin industrially is limited to a certain extent.Super high cross-linked adsorbing resin is
Skeleton structure with rigidity, and have stable physicochemical properties, higher mechanical strength, be easy to recycling utilization etc.
Feature is a kind of NEW TYPE OF COMPOSITE functional material, and the skeleton structure of super high cross-linked adsorbing resin is most of at present is with polystyrene
It is main, because the strong-hydrophobicity of polystyrene makes it need to be pre-processed with polar reagent before use, increase answering for operation
Polygamy and expense, while being the super high cross-linked adsorbing resin of skeleton structure to the biggish polar substances of solubility using polystyrene
Adsorbance is less than normal, and the yield of target product is relatively low in desorption process, and operate it is very complicated, be unfavorable for actual production benefit
With.Prior art CN201410171630.5 discloses a kind of preparation side of the superhigh cross-linking type absorption resin of acetamido modification
Method and its application, the resin are monomer as skeleton using styrene, are successively modified by amination and two step of acetylation, obtained tree
Rouge Pyrogentisinic Acid has preferable Selective adsorption, however the preparation method is adsorbed in resin preparation process still in Fu Ke post-crosslinking
Using chloromethyl methyl ether as chloromethylation reagents, chloromethyl methyl ether has intense irritation, severe toxicity, volatile and carcinogenic etc. lack
Point, there are more serious security risks, and the actual industrial metaplasia for being unfavorable for post-crosslinking resin produces and application.But also it needs stringent
The chlorine mass percentage in resin is controlled, and the resin specific surface area and Kong Rongjun that obtain after amidation are reduced, and influence to inhale
Attached performance.
Therefore, need to develop it is a kind of with high-adsorption-capacity, green preparation that is cheap, being easy the adsorbing medium lived again
Technique.
Summary of the invention
The present invention is to overcome above-mentioned defect in the prior art, provides a kind of amide group modified polystyrene system superelevation
The preparation method of cross-linked adsorbing resin introduces ester functional groups using the double bond effect of esters monomer, recycles Friedel-Crafts reaction system
Standby to obtain post-crosslinking resin, amide group modified polystyrene super high cross-linked adsorbing resin is prepared in post-crosslinking resin amination,
Further increase resin micropore and mesoporous number.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of amide group modified polystyrene crosslinked resin, comprising the following steps:
S1. the preparation of precursor resin: water phase and oil are mixed into suspension polymerization, ester group modification of precursor tree is prepared
Rouge, wherein the water phase be the aqueous solution containing dispersing agent, oil mutually be double bond containing esters monomer, styrene monomer, initiator,
The mixture of pore-foaming agent, crosslinking agent, reaction temperature are 50 DEG C~90 DEG C, reaction time 5~for 24 hours, in oily phase styrene monomer with
The mass ratio of double bond containing esters monomer is 1:0.01~100；
S2. the preparation of post-crosslinking resin: be added in the precursor resin of S1 preparation sweller and lewis acid catalyst into
Post-crosslinking resin is prepared in row Friedel-Crafts reaction, and wherein reaction temperature is 40~100 DEG C, 6~14h of reaction time；
S3. the preparation of crosslinked resin: aminating agent is added in the post-crosslinking resin prepared in S2 and carries out aminating reaction, preparation
Crosslinked resin is obtained, wherein aminating reaction temperature is 95~150 DEG C, and the aminating reaction time is 8~14h.
Polystyrene super high cross-linked adsorbing resin is modified by the present invention, and precursor resin is by introducing double bond containing esters
The amount of monomer, esters monomer can be adjusted arbitrarily in a certain range, on the one hand provide largely can modification group, another party
Face, esters monomer, which is uniformly distributed, be evenly distributed in Modified with Polar Monomer group can also in super high cross-linked adsorbing resin, reach
Introduce largely can modification group purpose, improve the polarity of resin.
Wherein the mass ratio of oily phase styrene monomer and double bond containing esters monomer can be 1:0.01,1:0.25 in S1,
1:4,1:14 or 1:100.
The suspended double bond and neighbouring phenyl ring that post-crosslinking resin is prepared by resin matrix occur Friedel-Crafts reaction and generate newly
Cross-bridge and crosslink sites increase resin micropore and mesoporous number.
The preparation of crosslinked resin is by introducing aminating agent to the modified super high cross-linked adsorbing resin internal pore structure of ester group
It carries out Modified with Polar Monomer and forms amide functional group, while also size distribution is regulated and controled.
The preparation method not only simple process, and the specific surface area of obtained hypercrosslinked polymeric resin and mechanical strength are after
It is improved after the effect of crosslinking.In addition to this, which avoids during post-crosslinking reaction using chloromethyl first
The toxic reagents such as ether are a kind of environmentally protective preparation processes.
The amide group modified polystyrene crosslinked resin that the present invention is prepared absorption when not only can be adsorbed
Substance forms hydrophobic forces, while can also form Hyarogen-bonding, promotes to inhale by hydrophobic effect and hydrogen bond action collaboration
The promotion of attached capacity.
Preferably, double bond containing esters monomer described in S1 is methyl methacrylate, methyl acrylate, methacrylic acid
One or more of butyl ester, glycidyl methacrylate, hydroxy-ethyl acrylate.
Preferably, the mass ratio of styrene monomer and double bond containing esters monomer is 1:0.1~20 in oil phase described in S1.
When the mass ratio of styrene monomer and double bond containing esters monomer is too low, esters monomer containing double bond is excessive, partially ester containing double bond
The meeting homopolymerization of class monomer forms polyacrylate polymers, can block the pore structure of super high cross-linked adsorbing resin.Work as styrene monomer
When excessively high with the mass ratio of double bond containing esters monomer, esters monomer containing double bond is very few, and base can largely be modified by being unable to reach introducing
The purpose of group.
Preferably, the mass ratio of the gross mass and crosslinking agent of double bond containing esters monomer and styrene monomer described in S1 is
The mass ratio of 1:0.1~10, the gross mass and initiator of double bond containing esters monomer and styrene monomer is 50~200:1, is contained
The mass ratio of the esters monomer of double bond and the gross mass of styrene monomer and pore-foaming agent is 1:0.25~8.
It is limiting in range, cross-linking process tends to form short chain, has closer structure, so that resin be made to possess more
Big specific surface area and Kong Rong and smaller aperture.However crosslinking agent and monomer compared conference and hinder super high cross-linked adsorbing resin
The stretching, extension of internal reticular structure, causes specific surface area to decline.In addition, the specific surface area of super high cross-linked adsorbing resin, Kong Rong and hole
After diameter is gradually increased to maximum value with the increase of pore agent content.With continuing growing for pore agent content, copolymerization will lead to
Object rigidity is insufficient and generates collapse hole phenomenon, and the specific surface area of resin is caused to be gradually reduced, and Kong Rong and aperture gradually increase.
It is highly preferred that the mass ratio of the gross mass and crosslinking agent of double bond containing esters monomer and styrene monomer is 1:0.2
~2, the mass ratio of the gross mass and initiator of double bond containing esters monomer and styrene monomer is 50:1, double bond containing esters list
The mass ratio of the gross mass and pore-foaming agent of body and styrene monomer is 1:0.5~8.
In specific implementation, crosslinking agent described in S1 is preferably Triallyl isocyanurate, divinylbenzene, diisocyanate
One or more of ester；
Initiator described in S1 be preferably one of azodiisobutyronitrile, benzoyl peroxide, dilauroyl peroxide or
It is several；
Pore-foaming agent described in S1 is preferably one or more of benzene,toluene,xylene, normal heptane, butyl acetate.
Preferably, the mass ratio of water phase described in S1 and oily phase is 1~4:1.
Preferably, in water phase described in S1, the mass fraction of dispersing agent is 0.5%~5%.In specific implementation, institute in S1
Stating dispersing agent is preferably one or more of gelatin, polyvinyl alcohol, carboxymethyl cellulose, polyacrylic acid, hydroxypropyl cellulose.
In specific implementation, lewis acid catalyst described in S2 can be preferably FeCl3, ZnCl2, AlCl3, SnCl4,
One or more of TiCl4.
Preferably, the mass ratio of precursor resin described in S2 and Lewis acid catalyst is 1:0.1~10.
It is highly preferred that the mass ratio of precursor resin described in S2 and Lewis acid catalyst is 1:0.2~5.
Preferably, precursor resin described in S2 and the solid-to-liquid ratio of sweller are 1:5~30g/mL.In specific implementation, this hair
Bright sweller is preferably one or more of 1,2- dichloroethanes, ethyl alcohol, methylene chloride, chlorobenzene.
It is highly preferred that precursor resin described in S2 and the solid-to-liquid ratio of sweller are 1:5~20g/mL.
Preferably, aminating agent described in S3 is one of polyethylene polyamine, diethylenetriamine, triethylene tetramine, aniline
Or it is several.
Preferably, post-crosslinking resin described in S3 and the solid-to-liquid ratio of aminating agent are 1:1~30g/mL.
It is highly preferred that post-crosslinking resin described in S3 and the solid-to-liquid ratio of aminating agent are 1:1~15g/mL.
The absorption resin that the present invention is prepared can be applied to the Adsorption of many kinds of substance, be particularly suitable for absorption 5-
Hydroxymethylfurfural, resin specific surface area are 900~1500m21.012~1.412cm of/g, Kong Rongwei3/ g, average pore size be 1~
20nm。
Specific adsorption mechanism are as follows: absorption resin can not only pass through phenyl ring in skeleton structure and 5 hydroxymethyl furfural
Furan nucleus forms hydrophobic forces, and can form hydrogen bond by the hydroxyl and aldehyde radical of amide group and 5 hydroxymethyl furfural and make
Firmly, hydrophobic effect and hydrogen bond action collaboration promote the promotion of 5 hydroxymethyl furfural adsorption capacity.Further, in desorption process
In, Hyarogen-bonding also plays a key effect in 5 hydroxymethyl furfural desorption process, can promote the elution of 5 hydroxymethyl furfural
Yield is higher than 99.3%, realizes efficiently separating for 5 hydroxymethyl furfural.Further, Hyarogen-bonding is in 5 hydroxymethyl furfural
It also plays a key effect in desorption process, so that the elution yield of 5 hydroxymethyl furfural is higher than 99.3%, realizes to 5- hydroxyl first
Base furfural efficiently separates.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of preparation method of amide group modified polystyrene crosslinked resin, which passes through
Double bond containing esters monomer is introduced in phenylethylene resin series, improves the polarity of resin, is increased by Fu Ke cross-linking reaction
Resin micropore and mesoporous number generate amide group by introducing aminating agent, the specific surface area of adsorbent up to 900~
1500m21.012~1.412cm of/g, Kong Rongwei3/ g, average pore size are 1~20nm, are easy to be formed with adsorbent in absorption
Hydrophobic forces and hydrogen bond action, to improve the absorption property of resin, and preparation process is simple, reaction condition is easy to control
System, can industrialized production.
Detailed description of the invention
Fig. 1 is the IR Characterization map of amide group modified polystyrene system super high cross-linked adsorbing resin in embodiment 1.
Specific embodiment
In order to become apparent from, completely describe technical solution of the present invention, further specifically below by way of specific embodiment
The bright present invention, it should be understood that described herein the specific embodiments are only for explaining the present invention, is not intended to limit the present invention,
Various changes can be carried out in the range of right of the present invention limits.The source for preparing raw material of the invention does not have special limit
System is commercially available.
Embodiment 1
A kind of preparation method of amide group modified polystyrene crosslinked resin, comprising the following steps:
S1. the preparation of precursor resin: water phase is added in 500mL three-necked flask, and oily phase is added into water phase, is passed through nitrogen
5min adjusts revolving speed 160rpm, is warming up to 80 DEG C of reaction 8h, is successively rinsed with hot water, industrial alcohol to cleaning solution and is clarified, then rope
Family name's extracting is placed on 45 DEG C for 24 hours and is dried under vacuum to constant weight, obtains premise resin, and wherein water phase is the polyvinyl alcohol containing 0.5%
With 3 drop methylene blues, water phase quality is 240g, and oily phase composition is styrene monomer 4g, hydroxy-ethyl acrylate 16g, crosslinking agent two
Vinyl benzene 20g, pore-foaming agent toluene 20g and normal heptane 20g, initiator benzoyl peroxide 0.4g；
The preparation of S2 post-crosslinking resin: 120mL sweller is added in the precursor resin into S1 and impregnates 18h, 2g is being added
Catalyst adjusts revolving speed and arrives 160rpm, is warming up to 90 DEG C of reaction 12h, generation Friedel-Crafts reaction, after reaction by product with anhydrous
Ethyl alcohol and 1% hydrochloric acid solution are alternately rinsed to cleaning solution and are clarified, then soxhlet type is placed on 45 DEG C for 24 hours and is dried under vacuum to perseverance
Weight, obtains ester group modified polystyrene-divinylbenzene post-crosslinking resin, wherein ester group modified polystyrene-two
The quality of vinyl benzene resin is 10g, and sweller 1,2- dichloroethanes, catalyst is anhydrous ferric chloride；
S3. the preparation of crosslinked resin: ester group modified polystyrene-divinylbenzene post-crosslinking resin 5g in S2 is taken
It is added in 150mL three-necked flask, adds 60mL aminating agent soaked overnight, adjustings revolving speed is 160rpm, at 130 DEG C of Yu Wendu instead
10h is answered, the hydrochloric acid solution of product dehydrated alcohol and 1% is alternately rinsed to cleaning solution clarify after reaction, then Soxhlet is taken out
It mentions and is placed on 45 DEG C for 24 hours and is dried under vacuum to constant weight, obtain amide group modified polystyrene system super high cross-linked adsorbing resin, wherein
Aminating agent is diethylenetriamine.
Embodiment 2
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
Its difference is that the amount of the polyethylene of dispersing agent alcohol in S1 in water phase is 1.0%, and the quality of styrene monomer is 16g in oily phase,
The quality of hydroxy-ethyl acrylate is 4g.
Embodiment 3
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
Its difference is that double bond containing esters monomer is glycidyl methacrylate in S1.
Embodiment 4
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
Its difference is, the carboxymethyl cellulose that the dispersing agent in S1 in water phase is 5%, styrene monomer 2g, metering system in oily phase
Sour methyl esters 28g, crosslinking agent diisocyanate 10g, pore-foaming agent toluene 20g and heptane 20g, initiator dilauroyl peroxide 0.4g；
Catalyst is 5g zinc chloride in S2；Aminating agent is polyethylene polyamine in S3.
Embodiment 5
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
Its difference is, the gelatin that the dispersing agent in S1 in water phase is 1%, styrene monomer 8g, methyl acrylate 2g, crosslinking in oily phase
Agent Triallyl isocyanurate 10g, pore-foaming agent toluene 30g and normal heptane 30g, initiator azodiisobutyronitrile 0.2g；In S2
Sweller is chlorobenzene, and catalyst is 5g zinc chloride；Aminating agent is aniline in S3.
Embodiment 6~12
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
It is distinguished technological parameter and is shown in Table 1, and wherein A is the mass ratio of S1 water phase with oily phase, and B is styrene monomer in S1 oil phase and contains double bond
Esters monomer mass ratio, C be S2 in precursor resin and Lewis acid catalyst mass ratio, D be precursor resin and sweller
Solid-to-liquid ratio (g/mL).
Table 1
| Project | A | B | C | D |
| Embodiment 6 | 1:1 | 1:100 | 1:0.1 | 1:5 |
| Embodiment 7 | 4:1 | 1:100 | 1:0.1 | 1:5 |
| Embodiment 8 | 1:1 | 1:0.01 | 1:0.1 | 1:5 |
| Embodiment 9 | 1:1 | 1:20 | 1:0.1 | 1:5 |
| Embodiment 10 | 1:1 | 1:0.1 | 1:0.1 | 1:5 |
| Embodiment 11 | 1:1 | 1:100 | 1:10 | 1:5 |
| Embodiment 12 | 1:1 | 1:100 | 1:0.1 | 1:30 |
Comparative example 1
A kind of preparation method of phenylethylene resin series, comprising the following steps:
Water phase is added in 500mL three-necked flask, oil is added and mixes, is passed through nitrogen 5min, adjusts revolving speed 160rpm, rises
Temperature is successively rinsed to clarification, then soxhlet type with hot water, industrial alcohol be placed on 45 for 24 hours after reaction to 80 DEG C of reaction 8h
DEG C it is dried under vacuum to constant weight, obtains phenylethylene resin series, wherein water phase is to contain 0.75% polyvinyl alcohol and 3 drop methylene
Indigo plant, water phase quality be 240g, oily phase composition be styrene monomer 20g, cross-linker divinylbenzene 20g, pore-foaming agent toluene 20g and
Normal heptane 20g, initiator benzoyl peroxide 0.4g.
Comparative example 2
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
Its difference is that the esters monomer in S1 in oily phase is ethyl acetate.
Comparative example 3~10
A kind of preparation method of amide group modified styrene super high cross-linked adsorbing resin, it is substantially the same manner as Example 1,
It is distinguished technological parameter and is shown in Table 2, and wherein A is the mass ratio of S1 water phase with oily phase, and B is styrene monomer in S1 oil phase and contains double bond
Esters monomer mass ratio, C be S2 in precursor resin and lewis acid catalyst mass ratio, D be S3 in post-crosslinking resin
With the solid-to-liquid ratio (g/mL) of aminating agent.
Table 2
| Project | A | B | C | D |
| Comparative example 3 | 1:2 | 1:100 | 1:0.1 | 1:1 |
| Comparative example 4 | 5:1 | 1:20 | 1:0.1 | 1:1 |
| Comparative example 5 | 1:1 | 1:110 | 10:1 | 1:1 |
| Comparative example 6 | 1:1 | 110:1 | 10:1 | 1:1 |
| Comparative example 7 | 1:1 | 1:100 | 1:9 | 1:1 |
| Comparative example 8 | 1:1 | 1:100 | 11:1 | 1:1 |
| Comparative example 9 | 1:1 | 1:100 | 10:1 | 1:0.5 |
| Comparative example 10 | 1:1 | 1:100 | 10:1 | 1:31 |
Performance detection and interpretation of result
IR Characterization is carried out to the polystyrene super high cross-linked adsorbing resin of amide modifications made from embodiment 1, wherein red
For the outer instrument used that characterizes for Fourier transformation infrared spectrometer (TENSOR27, BRUKER, German), measurement wave number is 4000
~400cm-1, characterization result is as shown in Figure 1.It will be seen from figure 1 that-NH stretching vibration appears in 3454cm-1Near；?
2926cm-1Caused by the vibration peak that place occurs is the telescopic band as C-H group；1698cm-1The vibration peak at place shows as imines C
=N and amide C=O stretching vibration；Vibration peak is in 1017cm-1For C-O-C group.In addition, the presence of C=C group by
1608,1507 and 1454cm-1Locate the presence at peak to confirm.The presence at phenyl ring peak can be in 1576 and 1608cm-1It is true nearby
It is fixed.
To the specific surface area of polystyrene super high cross-linked adsorbing resin made from above-described embodiment and comparative example, Kong Rong, put down
It is detected in equal aperture；
Wherein detecting instrument are as follows: specific surface and Porosimetry (ASIQMO002-2, Quantachrome, USA)；
Detection method are as follows: before analysis, first deaerate at 363K resin 10h；Specific surface area, Kong Rong and mesoporous pore size distribution
Brunauer-Emmett-Teller (BET) model, Langmuir model and Barrett-Joyner-Halenda is respectively adopted
(BJH) model calculates.
Specific surface area, Kong Rong, the testing result of average pore size of resin are as shown in table 3.
To resin made from embodiment and comparative example to the carry out adsorption/desorption of 5 hydroxymethyl furfural；
Wherein adsorption method specifically: resin is placed in Soxhlet extractor and extracts 20h, then repeatedly with acetone and distilled water
It rinses；1g resin is weighed again to be placed in 100mL conical flask, 5g/L 5 hydroxymethyl furfural aqueous solution is added, and is placed in 25 DEG C, oscillation
240min is vibrated in the shaken cultivation case that frequency is 120rpm, after being saturated adsorption equilibrium, filtering, by amide group modified polyphenyl second
Alkene system super high cross-linked adsorbing resin is separated with aqueous solution.
Desorption method specifically: weigh 1g absorption 5 hydroxymethyl furfural saturated resin and be placed in 100mL conical flask, be added
20mL ethanol solution is placed in 25 DEG C, vibrates 60min in the shaken cultivation case that frequency of oscillation is 120rpm, after stripping equilibria,
Filtering, amide group modified polystyrene system super high cross-linked adsorbing resin is separated with aqueous solution.
The adsorption capacity and elution yield of 5 hydroxymethyl furfural are shown in Table 3.
Table 3
From table 3 it can be seen that using resin specific surface area obtained by preparation method of the invention for 900~1500m2/
1.012~1.412cm of g, Kong Rongwei3/ g, average pore size are 1~20nm, are up to the adsorption capacity of 5 hydroxymethyl furfural
The elution yield of 298mg/g dried resin, 5 hydroxymethyl furfural is higher than 99.3%, is significantly better than comparative example.Preparation of the invention
Method can not only realize efficiently separating for 5 hydroxymethyl furfural, and preparation process is simple, and reaction condition is easily controllable, can industry
Metaplasia produces.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to this
The restriction of the embodiment of invention.It will be appreciated by those skilled in the art that can also make on the basis of the above description other
Various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., the protection scope of the claims in the present invention should be included in
Within.
Claims (10)
1. a kind of preparation method of amide group modified polystyrene crosslinked resin, which comprises the following steps:
S1. the preparation of precursor resin: mixing suspension polymerization for water phase and oil and ester group modification of precursor resin be prepared,
Wherein the water phase is the aqueous solution containing dispersing agent, and oil is mutually double bond containing esters monomer, styrene monomer, initiator, cause
Hole agent, crosslinking agent mixture, reaction temperature is 50 DEG C ~ 90 DEG C, reaction time 5 ~ for 24 hours, in oily phase styrene monomer with containing double
The mass ratio of the esters monomer of key is 1:0.01 ~ 100；
S2. the preparation of post-crosslinking resin: being added sweller in the precursor resin of S1 preparation and lewis acid catalyst carries out Fu
Gram reaction, post-crosslinking resin is prepared, wherein reaction temperature be 40 ~ 100 DEG C, 6 ~ 14h of reaction time；
S3. the preparation of crosslinked resin: aminating agent is added in the post-crosslinking resin prepared in S2 and carries out aminating reaction, is prepared into
To crosslinked resin, wherein aminating reaction temperature is 95 ~ 150 DEG C, and the aminating reaction time is 8 ~ 14h.
2. preparation method as described in claim 1, which is characterized in that double bond containing esters monomer described in S1 is methacrylic acid
One of methyl esters, methyl acrylate, butyl methacrylate, glycidyl methacrylate, hydroxy-ethyl acrylate are several
Kind.
3. preparation method as described in claim 1, which is characterized in that styrene monomer and double bond containing ester in oil phase described in S1
The mass ratio of class monomer is 1:0.1 ~ 20.
4. preparation method as claimed in claim 3, which is characterized in that double bond containing esters monomer and styrene monomer described in S1
Gross mass and crosslinking agent mass ratio be 1:0.1 ~ 10, the gross mass and initiation of double bond containing esters monomer and styrene monomer
The mass ratio of agent is 50 ~ 200:1, and the mass ratio of the gross mass and pore-foaming agent of double bond containing esters monomer and styrene monomer is 1:
0.25~8。
5. the preparation method as described in claim 1 ~ 4 any one, which is characterized in that the mass ratio of water phase described in S1 and oily phase
For 1 ~ 4:1.
6. preparation method as described in claim 1, which is characterized in that lewis acid catalyst described in S2 is FeCl3、ZnCl2、
AlCl3、SnCl4、TiCl4One or more of.
7. preparation method as claimed in claim 6, which is characterized in that the quality of precursor resin described in S2 and Lewis acid catalyst
Than for 1:0.1 ~ 10.
8. preparation method as claimed in claim 6, which is characterized in that precursor resin described in S2 and the solid-to-liquid ratio of sweller are 1:
5~30g/mL。
9. preparation method as described in claim 1, which is characterized in that aminating agent described in S3 is polyethylene polyamine, divinyl three
One or more of amine, triethylene tetramine, aniline.
10. preparation method as claimed in claim 9, which is characterized in that the solid-to-liquid ratio of post-crosslinking resin described in S3 and aminating agent
For the g/mL of 1:1 ~ 30.
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| CN112646132A (en) * | 2020-12-09 | 2021-04-13 | 济南大学 | Hypercrosslinked microporous polymer with high hydrogen storage performance and preparation method thereof |
| CN113019473A (en) * | 2021-03-06 | 2021-06-25 | 凯瑞环保科技股份有限公司 | Preparation method of anion exchange resin |
| CN114014966A (en) * | 2021-09-28 | 2022-02-08 | 广东工业大学 | Amide group modified ultrahigh cross-linked adsorption resin and preparation method and application thereof |
| CN114671970A (en) * | 2022-03-29 | 2022-06-28 | 中国科学院广州能源研究所 | Method for removing cane molasses pigment by using ultrahigh cross-linked adsorption resin |
| CN115634673A (en) * | 2022-12-07 | 2023-01-24 | 盱眙凹土能源环保材料研发中心 | Preparation method of ultrahigh cross-linked resin for bilirubin adsorption and blood perfusion |
| CN115945181A (en) * | 2023-03-13 | 2023-04-11 | 中国科学院过程工程研究所 | Multistage pore size distribution high specific surface area adsorption resin, preparation method and application thereof |
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| CN117383767A (en) * | 2023-12-08 | 2024-01-12 | 中国科学院大学 | Method for deeply purifying total organic carbon in high-salinity water |
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Application publication date: 20190607 |