CN108948255A - A kind of styrene resin and preparation method thereof - Google Patents
A kind of styrene resin and preparation method thereof Download PDFInfo
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- CN108948255A CN108948255A CN201810797152.7A CN201810797152A CN108948255A CN 108948255 A CN108948255 A CN 108948255A CN 201810797152 A CN201810797152 A CN 201810797152A CN 108948255 A CN108948255 A CN 108948255A
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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Abstract
The present invention discloses a kind of styrene resin and preparation method, i.e. with styrene, divinylbenzene is that phenylethylene resin bead synthesized by raw material is raw material, 25-60 DEG C of temperature of control, it is swollen phenylethylene resin bead sufficiently in sweller, phenylethylene resin bead after resulting swelling is added in a kettle, then solvent is sequentially added, crosslinking agent haloform and catalyst, then heat to 40-120 DEG C of progress cross-linking reaction, obtained reaction solution filtering, pickling removes catalyst, filter cake after obtaining pickling successively carries out washing 3-5 times with dehydrated alcohol and distilled water, then controlled at 105 DEG C, pressure is dried for 0.1Mpa, up to styrene resin.Its uniform particle sizes is 100-300 μm, has high specific surface area, and specific surface area reaches as high as 900m2/ g reaches as high as 105mg/g to the adsorbance of phenol in ethanol solution.
Description
Technical field
The present invention relates to a kind of styrene resin and preparation method thereof is proposed, belong to filed of functional.
Background technique
Macroporous ion-exchange resin is a kind of high molecular material with space net structure, is widely used in sewage treatment, naturally
Purification of products, pharmaceutical engineering etc..The most common macroreticular resin is phenylethylene resin bead, it mainly by two methods prepare and
At.
1) styrene is made up of suspension polymerisation in the presence of solvent with divinylbenzene.Have with product made from this method
There is certain specific surface area (usually in 500m2/ g or less).It is modified sometimes through further function base to regulate and control the pole of resin
Property.
2) it is prepared by the secondary cross-linking method of phenylethylene resin bead (also known as " post-crosslinking method ").Pass through a kind of this side
Method can prepare the resin of high-specific surface area, and (specific surface area is up to 700m2/ g, He Ping Lin, the yellow strong ion exchange of text and suction
The Shanghai attached resin [M]: the publication of education of science and technology of Shanghai society, 1992.), but need to use strong carcinogenic crosslinking agent (chloromethyl first
Ether).U.S. patent Nos US4543365 discloses a kind of suspended double bond using in the more vinyl aromatic monomers of high-content,
The method for improving adsorbent crosslinking degree, obtained adsorbent specific surface area are 100m2/ g or so, and the technique still will make
It is volatile with nitrobenzene etc., the stronger solvent of toxicity, therefore there are safeties for preparation process, while last handling process technique is multiple
It is miscellaneous.
In conclusion at present for the phenylethylene resin bead preparation process of high-specific surface area due to using strong carcinogenic crosslinking
Agent (chloromethyl methyl ether) and there are safety issues, while there is also the technologies such as the process is more complicated, post-reaction treatment difficulty to ask
Topic.
Summary of the invention
An object of the present invention be in order to solve the phenylethylene resin bead preparation process of above-mentioned high-specific surface area due to
Using strong carcinogenic crosslinking agent (chloromethyl methyl ether) there are safety issue and there is also the process is more complicated, after reaction
It manages the technical problem of difficulty etc. and a kind of preparation method of styrene resin is provided, the preparation method is due to avoiding conventional crosslinking
The use of chloromethyl methyl ether in method, simultaneously because post-reaction treatment technique is relatively simple, therefore the preparation method has production
Process safety, it is easy to operate, it is convenient to carry out the advantages that.
The second object of the present invention is to provide above-mentioned preparation method a kind of resulting styrene resin, the styrene resin fat granule
Diameter is uniform, and partial size is 100-300 μm, and has high specific surface area, and highest specific surface area is up to 900m2/ g, therefore have
There is high adsorbance, can be used as absorption resin and use；Simultaneously because the halogen on resin matrix is influenced by phenyl ring, have very
High reactivity can be changed into other functional groups such as amido, hydroxyl, further apply by further reacting
The fields such as ion exchange, pharmaceutical synthesis carrier.
Technical principle of the invention
The reaction equation schematic diagram of the preparation process of styrene resin of the invention as shown in Figure 1, wherein X be Cl or
Br is under the effect of the catalyst, to lead to synthesized by raw material based on phenylethylene resin bead by styrene, divinylbenzene
Cross special crosslinking agent haloform (i.e. CHX in Fig. 13) method that is crosslinked, finally big in phenylethylene resin bead
Phenyl ring on strand is chained up by halogenated methylene, obtained styrene resin.
Above-mentioned resulting styrene resin not only has big specific surface area (more than 500m2/ g, reaches as high as 900m2/
G), it is used as absorption resin；And the halogen in the halogenated methylene on the styrene resin formed is due to the shadow by phenyl ring
It rings, there is very high reactivity, other functional groups such as amido, hydroxyl can be changed by further reacting, it can be into
One step is applied to the fields such as ion exchange, pharmaceutical synthesis carrier.
Technical solution of the present invention
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), phenylethylene resin bead is added in sweller, under the conditions of magnetic agitation, controls 25-60 DEG C of immersion 6- of temperature
For 24 hours, preferably 12h, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:
The ratio of 10-100, preferably 1:20-50 calculate；
The phenylethylene resin bead is using styrene-divinylbenzene as the microballoon of skeleton, and preferably Shanghai is radically reformed resin
The partial size of Co., Ltd's production is 100-300 μm, specific surface area≤400m2/ g using styrene-divinylbenzene as skeleton
Microballoon；
The sweller be tetrahydrofuran, ethylene glycol and N, one or more of N- dimethylformamide mixing and
At；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 40-120 DEG C of progress cross-linking reaction 5-20h, be preferably warming up to 80-120 DEG C into
Row cross-linking reaction 12h, obtains reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:5-
50:1-6:0.1-0.5 the ratio of preferably 1:10-40:1-5:0.1-0.5 calculates；
The solvent is that one or more of petroleum ether, hexamethylene and hexahydrotoluene mix；
The crosslinking agent be haloform, the haloform be chloroform, bromoform or chloroform and
The mixture of bromoform；
The catalyst is one or more of alchlor, ferric trichloride, boron trifluoride and zinc dichloride
It mixes, preferably alchlor or ferric trichloride；
(3), the resulting reaction solution of step (2) is filtered, the diluted hydrochloric acid aqueous solution or dilute sulfuric acid that resulting filter cake is 1 with pH
Aqueous solution, which is washed, does not have catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3-5 times with dehydrated alcohol and distilled water, then by the filter cake after washing controlled at 105 DEG C, pressure
It is dried for 0.1Mpa to get styrene resin.
Above-mentioned resulting styrene resin, uniform particle sizes, partial size are 100-300 μm, have high specific surface area, therefore have
There are high adsorbance, specific surface area 550-900m2/ g, preferably 750-900m2/ g, at normal temperature preferred styrene resin
When rouge Pyrogentisinic Acid is adsorbed, adsorbance 81-105mg/g, preferably adsorbance are 101-105mg/g.
Above-mentioned resulting styrene resin reaches as high as 900m due to having big specific surface area2/ g is conducive to absorption point
Organic substance in chaotropic phase or gas phase, therefore can be used as absorption resin and use；Simultaneously because the halogen that resin group includes
With high reactivity, it can be changed into other functional groups such as amido, hydroxyl by further reacting, yin can be synthesized
A variety of polymer-function materials such as ion exchange resin, hydroxy resin.Applied to fields such as ion exchange, pharmaceutical synthesis carriers.
Advantageous effects of the invention
A kind of preparation method of styrene resin of the invention, due in preparation process based on phenylethylene resin bead,
Method by being crosslinked is chained up the phenyl ring on the macromolecular chain in phenylethylene resin bead by halogenated methylene, therefore
The use of chloromethyl methyl ether in customary preparation methods is avoided, therefore production process is safe and reliable, last handling process is simple.
Further, the preparation method of a kind of styrene resin of the invention, since preparation process is by styrene resin
Macromolecular chain is crosslinked together by halogenated methylene chain, and contains halogen element on methylene, it can be changed into amido, hydroxyl
Other groups such as base, for fields such as ion exchange, pharmaceutical synthesis carriers.
Further, the resulting styrene resin of the preparation method of styrene resin of the invention, uniform particle sizes are 100-
300 μm, with high specific surface area, therefore adsorbance with higher, Pyrogentisinic Acid is adsorbed at normal temperature, adsorbance
105mg/g is reached as high as, i.e. every gram of styrene resin adsorbing phenol is up to 105 milligrams.
Detailed description of the invention
The reaction equation schematic diagram of the preparation process of Fig. 1, styrene resin of the invention.
The scanning electron microscope (SEM) photograph of Fig. 2, the resulting styrene resin of the embodiment of the present invention 1.
Specific embodiment
Technical solution of the present invention is further described below with reference to embodiment and in conjunction with attached drawing, but the present invention is not limited to
Listed embodiment should also include other any well known changes in interest field of the presently claimed invention.
The measurement of the specific surface area of the resulting styrene resin of the present invention, inhales according to national standard GB/T 19587-2004 gas
Attached BET method measurement solid matter specific surface area is using U.S. Micromeritics Instrument Corporation's
The full-automatic surface analysis instrument of Micromeritics ASAP2020 measures；
The adsorbance of the resulting styrene resin Pyrogentisinic Acid of the present invention measuring method (reference literature Kawamura Y,
Mitsuhashi M,Tanibe H,et al.Adsorption of Metal Ions on Polyaminated Highly
Porous Chitosan Chelating Resin[J].Industrial&Engineering Chemistry Research,
1993,32 (2): the absorption quantity measuring method in 386-391.), steps are as follows:
The resulting styrene resin of the O.lg present invention is added in the ethanol solution for configuring the phenol that 30mL concentration is 100mg/L,
Oscillation 12h, which adsorb, at room temperature reaches saturation, then calculates the concentration (c of the phenol after saturation is adsorbed in ethanol solution1,
Mg/L), the adsorbance (A, mg/g) of macropore styrene resin Pyrogentisinic Acid of the invention is calculated according to the following formula:
Wherein m=0.1g.
Raw material used in each embodiment and equipment are commercially available if not refering in particular in the present invention.
Method in following embodiments is unless otherwise instructed the conventional method of this field.
Embodiment 1
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 25 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is using styrene-divinylbenzene as the microballoon of skeleton, and partial size is 100-300 μm,
Shanghai radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 80 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
1:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake with the aqueous hydrochloric acid solution that pH is 1 washed to
There is no catalyst in efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to carry out washing 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
8h is dried to get styrene resin in 0.1Mpa.
Using high-new that jade-like stone cause S-3400N type scanning electron microscope produced of Hitachi to 1 gained of above-described embodiment
Styrene resin be scanned, resulting scanning electron microscope (SEM) photograph as shown in Fig. 2, from figure 2 it can be seen that its uniform particle sizes,
Between 100-300 μm.
Above-mentioned resulting styrene resin after measured, specific surface area 600m2/ g, the adsorbance of Pyrogentisinic Acid are 78mg/g.
Embodiment 2
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 200g sweller, under the conditions of magnetic agitation, controls 25 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:20
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is N, N- dimethylformamide；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 80 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
1:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake with the aqueous sulfuric acid that pH is 1 washed to
There is no catalyst in efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 4 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
700m2/ g, the adsorbance of Pyrogentisinic Acid are 69mg/g.
Embodiment 3
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 30 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 80 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
1:0.3 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the diluted hydrochloric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 4 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
800m2/ g, the adsorbance of Pyrogentisinic Acid are 81mg/g.
Embodiment 4
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 25 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is ethylene glycol；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 80 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:30:
2:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the diluted hydrochloric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
600m2/ g, the adsorbance of Pyrogentisinic Acid are 86mg/g.
Embodiment 5
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 30 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 40 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:30:
2:0.2 ratio calculate；
The solvent is hexamethylene；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the diluted hydrochloric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 5 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
650m2/ g, the adsorbance of Pyrogentisinic Acid are 79mg/g.
Embodiment 6
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 30 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 80 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:30:
2:0.1 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is ferric trichloride；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the diluted hydrochloric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 4 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
800m2/ g, the adsorbance of Pyrogentisinic Acid are 88mg/g.
Embodiment 7
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 500g sweller, under the conditions of magnetic agitation, controls 25 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:50
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 90 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:30:
2:0.1 ratio calculate；
The solvent is hexahydrotoluene；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake with pH be 1 diluted hydrochloric acid aqueous solution aqueous solution into
Row washing does not have catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
850m2/ g, the adsorbance of Pyrogentisinic Acid are 91mg/g.
Embodiment 8
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, control temperature 45 C leaching
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is N, N- dimethylformamide；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 120 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
1:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
900m2/ g, the adsorbance of Pyrogentisinic Acid are 105mg/g.
Embodiment 9
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, control temperature 60 C leaching
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 100 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
1:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 5 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
800m2/ g, the adsorbance of Pyrogentisinic Acid are 103mg/g.
Embodiment 10
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, control temperature 50 C leaching
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；The sweller is N, N- dimethylformamide；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 85 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:30:
2:0.3 ratio calculate；
The solvent is hexahydrotoluene；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the diluted hydrochloric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 4 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
750m2/ g, the adsorbance of Pyrogentisinic Acid are 101mg/g.
Embodiment 11
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 40 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 70 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
3:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step how many 3 times with dehydrated alcohol and distilled water, then by the filter cake after washing controlled at 105 DEG C, pressure
Power is that 12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
700m2/ g, the adsorbance of Pyrogentisinic Acid are 90mg/g.
Embodiment 12
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 40 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 120 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
5:0.2 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
800m2/ g, the adsorbance of Pyrogentisinic Acid are 93mg/g.
Embodiment 13
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 40 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is tetrahydrofuran；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 100 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:
1:0.5 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is bromoform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 4 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
600m2/ g, the adsorbance of Pyrogentisinic Acid are 82mg/g.
Embodiment 14
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 300g sweller, under the conditions of magnetic agitation, controls 35 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:30
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is ethylene glycol；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 100 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:40:
1:0.5 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
850m2/ g, the adsorbance of Pyrogentisinic Acid are 82mg/g.
Embodiment 15
A kind of styrene resin, is prepared by a method comprising the following steps:
(1), 10g phenylethylene resin bead is added in 200g sweller, under the conditions of magnetic agitation, controls 35 DEG C of temperature leachings
12h is steeped, is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:20
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton, on
Sea radically reform resin Co., Ltd production；
The sweller is N, N- dimethylformamide；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, is then sequentially added
Solvent, crosslinking agent and catalyst then heat to 80 DEG C of progress cross-linking reaction 12h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, by quality
Than calculating, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:10:
2:0.4 ratio calculate；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor；
(3), the resulting reaction solution of step (2) is filtered, resulting filter cake is washed with the dilute sulfuric acid aqueous solution that pH is 1
There is no catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repeat according to
It is secondary to be carried out washing step 3 times with dehydrated alcohol and distilled water, be then controlled at 105 DEG C, pressure by the filter cake after washing
12h is dried to get styrene resin in 0.1Mpa.
After measured, uniform particle sizes, between 100-300 μm, specific surface area is above-mentioned resulting styrene resin
550m2/ g, the adsorbance of Pyrogentisinic Acid are 66mg/g.
In conclusion the preparation method of styrene resin of the invention, since the crosslinking agent used in preparation process is halogen
For methylene, therefore safe preparation process is controllable, and last handling process is simple, meanwhile, further resulting styrene resin bead
Diameter is uniform, is 100-300 μm, simultaneously because containing halogen element on resin matrix, it can be changed into other bases such as amido, hydroxyl
Group, for fields such as ion exchange, pharmaceutical synthesis carriers.Further, resulting phenylethylene resin bead specific surface with higher
Product, specific surface area 550-900m2/ g, preferably 750-900m2/ g, preferred styrene resin Pyrogentisinic Acid carries out at normal temperature
When absorption, adsorbance 81-105mg/g, preferably adsorbance are 101-105mg/g.More preferably specific surface area is 900m2/
G, the adsorbance to phenol in ethanol solution are 105mg/g.
The above content is only basic explanation and preferred embodiment of the invention, and is appointed made by technical solution according to the present invention
What equivalent transformation, is within the scope of protection of the invention.
Claims (10)
1. a kind of preparation method of styrene resin, which comprises the following steps:
(1), phenylethylene resin bead is added in sweller, under the conditions of magnetic agitation, controls 25-60 DEG C of immersion 6-24h of temperature,
It is swollen phenylethylene resin bead sufficiently, the phenylethylene resin bead after being swollen；
The dosage of above-mentioned phenylethylene resin bead and sweller, calculates in mass ratio, phenylethylene resin bead: sweller 1:10-100
Ratio calculate；
The phenylethylene resin bead is 100-300 μm of partial size using styrene-divinylbenzene as the microballoon of skeleton；
The sweller is tetrahydrofuran, ethylene glycol and N, and one or more of N- dimethylformamide mixes；
(2), the phenylethylene resin bead after step (1) resulting swelling is added in a kettle, then sequentially add solvent,
Crosslinking agent and catalyst then heat to 40-120 DEG C of progress cross-linking reaction 5-20h, obtain reaction solution；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in above-mentioned cross-linking reaction, is counted in mass ratio
It calculates, that is, phenylethylene resin bead used in the phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:5-50:1-
6:0.1-0.5 ratio calculate；
The solvent is that one or more of petroleum ether, hexamethylene and hexahydrotoluene mix；
The crosslinking agent is the mixture of chloroform, bromoform or chloroform and bromoform；
The catalyst is the mixing of one or more of alchlor, ferric trichloride, boron trifluoride and zinc dichloride
It forms；
(3), the resulting reaction solution of step (2) is filtered, the aqueous hydrochloric acid solution or dilute sulfuric acid aqueous solution that resulting filter cake is 1 with pH
Being washed does not have catalyst into efflux, the filter cake after obtaining pickling；
(4), the filter cake after step (3) resulting pickling is successively washed with dehydrated alcohol and distilled water, repetition is successively used
Dehydrated alcohol and distilled water carry out washing step 3-5 times, are then controlled at 105 DEG C, pressure by the filter cake after washing
The styrene resin that 0.1Mpa is dried to get macropore.
2. a kind of preparation method of styrene resin as described in claim 1, it is characterised in that:
In step (1): control 25-60 DEG C of immersion 12h of temperature, the dosage of phenylethylene resin bead and sweller calculate in mass ratio,
Phenylethylene resin bead: sweller 1:20-50；
The sweller is tetrahydrofuran, ethylene glycol or N, N- dimethylformamide
In step (2): control cross-linking reaction 12h；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in cross-linking reaction, calculates in mass ratio,
Phenylethylene resin bead used in phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:10-40:1-5:
0.1-0.5；
The catalyst is alchlor or ferric trichloride.
3. a kind of preparation method of styrene resin as described in claim 1, it is characterised in that:
In step (1): control 45-60 DEG C of immersion 12h of temperature, the dosage of phenylethylene resin bead and sweller calculate in mass ratio,
Phenylethylene resin bead: sweller 1:30；
The sweller is tetrahydrofuran, ethylene glycol or N, N- dimethylformamide
In step (2): being warming up to 85-120 DEG C of progress cross-linking reaction 12h；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in cross-linking reaction, calculates in mass ratio,
Phenylethylene resin bead used in phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20-30:1-2:
0.2-0.3；
The solvent is petroleum ether or hexahydrotoluene；
The crosslinking agent is chloroform or bromoform；
The catalyst is alchlor.
4. a kind of preparation method of styrene resin as claimed in claim 3, it is characterised in that:
In step (1): control temperature 45 C impregnates 12h；
The sweller is N, N- dimethylformamide；
In step (2): being warming up to 120 DEG C of progress cross-linking reaction 12h；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in cross-linking reaction, calculates in mass ratio,
Phenylethylene resin bead used in phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:1:0.2；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor.
5. a kind of preparation method of styrene resin as claimed in claim 3, it is characterised in that:
In step (1): control temperature 60 C impregnates 12h；
The sweller is tetrahydrofuran；
In step (2): being warming up to 100 DEG C of progress cross-linking reaction 12h；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in cross-linking reaction, calculates in mass ratio,
Phenylethylene resin bead used in phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:20:1:0.2；
The solvent is petroleum ether；
The crosslinking agent is chloroform；
The catalyst is alchlor.
6. a kind of preparation method of styrene resin as described in claim 1, it is characterised in that:
In step (1): control temperature 50 C impregnates 12h；
The sweller is N, N- dimethylformamide
In step (2): being warming up to 85 DEG C of progress cross-linking reaction 12h；
The amount of phenylethylene resin bead, solvent, crosslinking agent and catalyst after swelling used in cross-linking reaction, calculates in mass ratio,
Phenylethylene resin bead used in phenylethylene resin bead after preparing swelling: solvent: crosslinking agent: catalyst 1:30:2:0.3；
The solvent is hexahydrotoluene；
The crosslinking agent is bromoform；
The catalyst is alchlor.
7. a kind of preparation method of styrene resin as described in claim 1-6 is any, it is characterised in that:
Phenylethylene resin bead described in step (1) is the partial size 100-300 μ using styrene-divinylbenzene as the microballoon of skeleton
M, Shanghai radically reform resin Co., Ltd production.
8. such as a kind of resulting styrene resin of any preparation method of claim 1-6.
9. a kind of styrene resin as claimed in claim 8, it is characterised in that its specific surface area is 550-900m2/ g, partial size are
100-300μm。
10. a kind of styrene resin as claimed in claim 9, it is characterised in that its specific surface area is 750-900m2/g。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111948323A (en) * | 2020-08-26 | 2020-11-17 | 浙江中环瑞蓝科技发展有限公司 | Pretreatment device and content determination method for volatile organic gas |
| CN112023900A (en) * | 2020-08-07 | 2020-12-04 | 万华化学集团股份有限公司 | Preparation method of secondary cross-linked resin adsorbent and secondary cross-linked resin adsorbent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088600A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN102294228A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102294229A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102295724A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula for hypercrosslinked styrene macroporous adsorbent and process route thereof |
| CN102600810A (en) * | 2012-03-23 | 2012-07-25 | 南开大学 | Mesoporous adsorbent resin with uniform pore size and large specific surface area and preparation method and application thereof |
-
2018
- 2018-07-19 CN CN201810797152.7A patent/CN108948255A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088600A (en) * | 2006-06-12 | 2007-12-19 | 天津协成昌国际贸易有限公司 | Prepn and product of adsorbing material |
| CN102294228A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102294229A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula of ultrahigh cross-linked styrene macroporous adsorbent and process route thereof |
| CN102295724A (en) * | 2010-06-24 | 2011-12-28 | 于杰 | Synthesis formula for hypercrosslinked styrene macroporous adsorbent and process route thereof |
| CN102600810A (en) * | 2012-03-23 | 2012-07-25 | 南开大学 | Mesoporous adsorbent resin with uniform pore size and large specific surface area and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023900A (en) * | 2020-08-07 | 2020-12-04 | 万华化学集团股份有限公司 | Preparation method of secondary cross-linked resin adsorbent and secondary cross-linked resin adsorbent |
| CN112023900B (en) * | 2020-08-07 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method of secondary cross-linked resin adsorbent and secondary cross-linked resin adsorbent |
| CN111948323A (en) * | 2020-08-26 | 2020-11-17 | 浙江中环瑞蓝科技发展有限公司 | Pretreatment device and content determination method for volatile organic gas |
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Application publication date: 20181207 |