CN106188406A - The technique of chloromethylation without dichloroethanes prepares the method for gel strong basic anion-exchange resin - Google Patents
The technique of chloromethylation without dichloroethanes prepares the method for gel strong basic anion-exchange resin Download PDFInfo
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- CN106188406A CN106188406A CN201610588581.4A CN201610588581A CN106188406A CN 106188406 A CN106188406 A CN 106188406A CN 201610588581 A CN201610588581 A CN 201610588581A CN 106188406 A CN106188406 A CN 106188406A
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- chloromethylation
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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Abstract
The present invention relates to ion exchange resin field.The technique of chloromethylation without sweller prepares the method for gel strong basic anion-exchange resin, the method comprises the following steps: 1) add formaldehyde, dimethoxym ethane and methanol in a kettle., it is slowly added dropwise chlorosulfonic acid and controls reactor temperature and be not more than 30 DEG C, fabricated in situ chloromethyl ether；2) adding Archon in chloromethyl ether prepared by above-mentioned method, and add Lewis acid catalyst and carry out chloromethylation, chloromethylation temperature is 10 ~ 60 DEG C, and the time is 2 ~ 48 hrs；3) the chlorine ball that prepared by above-mentioned method adds organic solvent and carries out swelling, is subsequently adding aminating agent, and aminating reaction temperature is 30 60 DEG C, and the time is 30 min 24 hrs, and the excess percentage of aminating agent is 10 300%.This method eliminates the health environment hidden danger that original chloromethylation technique uses sweller to cause.Strong basic anion-exchange resin prepared by this invention is compared with original technique has more preferable resistance to infiltration cycles impact property.
Description
Technical field
The present invention relates to ion exchange resin field.
Background technology
The initial preparation of industrialization of anion exchange resin uses chloromethyl ether (to see as chloromethylation raw material
SaKabe H. Ind. Health, 1973 11:45 and Leong B. K. J. Arch. Environ. Health 1971
22:663), there is strong carcinogenecity in chloromethyl ether.The application in actual production of this raw material is restricted.(Pascu D.V,
Antal. A. RO., 84283. 1984) document reports employing paraformaldehyde, chlorosulfonic acid and sweller as chloromethylation
The Cholromethylation method of raw material, the method is also applied in industrialized production.Common sweller be oxolane and
Dichloroethanes.Wherein oxolane has stimulation and anesthetic action, can cause liver, renal damage after suction.Its LD50 is 2050
2850 mg/ Kg(rat orals).Dichloroethanes belongs to high toxicity, and its LD50 is 670 mg/ Kg(rat orals), 2800 mg/
Kg(rabbit percutaneous).Its application on commercial production should be reduced from the point of view of environment and health as far as possible.
Strong-base anion-exchange resin prepared by technique without dichloroethanes, has not only stopped high environmental pollution from technique
The use of organic solvent.And resin prepared by the method has more preferable application performance.
The impact of resistance to infiltration cycles is the important parameter of evaluating resin mechanical strength.After the chloromethylation technique adjustment of the present invention
The resistance to infiltration cycles impact parameter of the resin of preparation and have sweller technique to compare to improve further.
Summary of the invention
It is an object of the invention to provide one and prepare gel strong alkali anion exchange tree without dichloroethanes chloromethylation technique
The method of fat, this method eliminatess the health environment hidden danger that original chloromethylation technique uses sweller to cause.This invention system
Standby strong basic anion-exchange resin is compared with original technique has more preferable resistance to infiltration cycles impact property.
In order to realize above-mentioned purpose, present invention employs following technical scheme:
The technique of chloromethylation without sweller prepares the method for gel strong basic anion-exchange resin, and the method includes following step
Rapid:
1) chloromethyl ether synthesis
Add formaldehyde, dimethoxym ethane and methanol in a kettle., be slowly added dropwise chlorosulfonic acid and control reactor temperature and be not more than 30
DEG C, fabricated in situ chloromethyl ether；
2) chloromethylation prepares chlorine ball
Chloromethyl ether prepared by above-mentioned method adds Archon, and adds Lewis acid catalyst and carry out chloromethylation, chloromethane
Glycosylation reaction temperature is 10 ~ 60 DEG C, and the time is 2 ~ 48 hrs；
3) aminating reaction
Chlorine ball prepared by above-mentioned method adds organic solvent and carries out swelling, is subsequently adding aminating agent, and aminating reaction temperature is 30-
60 DEG C, the time is 30 min-24 hrs, and the excess percentage of aminating agent is 10-300%.
Archon is unfunctionalized high molecular polymer, and its preparation uses process for suspension polymerization.Gelling anionic exchange tree
Fat uses gel-type Archon.As preferably, described Archon selects styrene-divinylbenzene beads, and monomer is styrene mutually
Divinylbenzene mixture, divinylbenzene plays the effect of cross-linking agent.The degree of cross linking is 1 ~ 10%, and Archon particle size range is 100 ~ 1000
um.Archon polymeric reaction temperature is 60-95 DEG C and carries out 2-14 hrs, and preferred temperature range is 80 90 DEG C and carries out 4-10
hrs.As further preferably, the described Archon degree of cross linking is 2 ~ 8%, and Archon particle size range is 250 ~ 800 um.
Formaldehyde is gas at ambient temperature.Skin and mucosa to human body have strong impulse and toxicity (LD50
800 mg/ Kg(rat orals), 2700 mg/ Kg(rabbit percutaneous)).Be not suitable for using directly from the point of view of economy and environment
Connecing and transport in gaseous form, appropriate mode is transport paraformaldehyde.But paraformaldehyde is when reactor feed, charge pipe
During charging, solid material difficulty is relatively big, and is unfavorable for that reaction system seals.Relatively reasonable mode is arranged to methanol solution, just
In being fed by pipeline.As preferably, described formaldehyde uses the mode of paraformaldehyde methanol solution to add, paraformaldehyde methanol
The mass concentration of solution is 10 ~ 55%.
In chloromethylation step, Archon is formed by chloromethylation reagents activation that have can the chlorine ball of activated group.Industry
Production use chloromethyl ether as chloromethylation reagents.Chloromethyl ether has strong impulse and carcinogenecity to human body.It is not suitable for
Firsthand mode obtains, and preferred scheme is fabricated in situ.As preferably, the method for chloromethyl ether synthesis is as follows, in reaction
Still adds paraformaldehyde solution, dimethoxym ethane and methanol, is slowly added dropwise chlorosulfonic acid and controls reactor temperature and be not more than 30 DEG C；
By adding total amount volume percentage paraformaldehyde solution 20 ~ 40%, dimethoxym ethane 8 ~ 15%, methanol 10 ~ 20%, chlorosulfonic acid 25 ~ 50%.
As preferably, the catalyst of described chloromethylation includes in zinc chloride, aluminum chloride, stannic chloride and iron chloride
One or more；Further preferably, Lewis acid is iron chloride, and the iron chloride storing mode as catalyst is solid storage and joins
Making solution and preserving preferred ferric chloride concn is 5-80%, and preferred ferric chloride concn is 30-50%.
Chloromethylation temperature affects diffusion velocity and the response speed of chloromethylation reagents.Chloromethylation temperature is 10
~60℃.Along with the rising of reaction temperature, response speed is accelerated, and preferred chloromethylation temperature range is 30 ~ 60 DEG C.
The chloromethylation time is for affect chloromethylation exchange capacity.The exchange capacity of chloromethylation is in time
Gather way and gradually slow down.But the secondary crosslinking of resin is gradually increased along with the increase in response time.The chloromethylation time is
2- 48 hrs.The preferably chloromethylation time is 3-7.5 hrs.
As preferably, described swelling organic solvent selects the one or many in benzene, acetone, dimethoxym ethane and carbon tetrachloride
Kind；Further preferably, swelling organic solvent selects dimethoxym ethane.
As preferably, described aminating agent selects trimethylamine, triethylamine, tri-n-butylamine, dimethyl propanol amine, methyl diethanol
One or more in amine, dimethylethanolamine, dimethylamine and diethylamine；Further preferably, aminating agent selects trimethylamine or dimethyl
Ethanolamine.Gel highly basic I type and II type anion exchange resin can be prepared respectively.
As preferably, described amination temperature is 30-50 DEG C, and the aminating reaction time is 1-6 hrs.
The excess percentage of amine of the present invention is 10-300%.When excess percentage is relatively low, reach the temperature needed for target exchange capacity
Spend higher, the time is longer.When excess percentage is higher, waste raw material.
Aminating reaction needs to reclaim solvent and the amine of excess from the point of view of economical and environmentally friendly after terminating, as preferably,
Described aminating reaction is recovered by distillation solvent and the amine of excess after terminating.
Chloromethylation is for swollen the solvent such as oxolane and dichloroethanes of swelling Archon.This solvent is possible not only to
Preferable swelling Archon, carries out chloromethylation, can reduce again the concentration of chloromethyl ether in reaction system, reduces and reveals wind
Danger.But this kind of sweller there is also healthy hidden danger.The most do not use sweller, it is to avoid this hidden danger.
Gel highly basic I type prepared by the present invention has the whole ball rate of anion exchange resin to be not less than 95%, chlorine type moisture
Being 42 54%, volume-exchange amount is more than 1.3 eq/ L, and weight exchange capacity is more than 3.7 eq/ Kg.Higher degree of crosslinking highly basic I type
Anion exchange resin, its resistance to infiltration cycles impact (100 circulation) is not less than 90%.
The whole ball rate of gel highly basic II type anion exchange resin prepared by the present invention is not less than 95%, and moisture is
45 51%, volume-exchange amount is more than 1.3 eq/ L, and weight exchange capacity is more than 3.3 eq/ Kg..
Detailed description of the invention
Should be understood that invention as described herein is not limited to ad hoc approach, scheme and reagent, because these alterable,
It is also to be understood that say that the term being is only used for describing the purpose of specific embodiments herein, it is not intended to limit the present invention's
Scope.Unless otherwise defined, whole scientific and technical terminology the most used herein has the common skill with the technical field of the invention
Art personnel are generally understood that identical connotation.The practice or test of the present invention can use close with those described herein
Or any method of equivalent or material.
Whole publications that are herein cited or that mention, go out including patent, patent application and other patents and non-patent
Version thing is expressly incorporated herein by reference at least its purpose being cited: include such as in order to disclosure and description can be used for this
The method of bright material.The most never it is construed as an admission that publication and other lists of references (include only in technology " background parts "
Any list of references quoted) for relative to the prior art of the present invention or such as making the present invention not have due to existing invention
There is the qualification early than the disclosure.
Skilled artisan will appreciate that numerical value presented herein is approximation.Generally unless otherwise stated, term
Such as " about " and in " about " include 20% in the value of place, more preferably in 10% even more preferably in 5%.
Embodiment 1: prepare gel highly basic I type anion exchange resin without dichloroethanes technique
Deionized water (1000 mL), polyvinyl alcohol (2.1 g), sodium chloride (32.3 g) and sodium nitrite is added in reactor
(0.02 g), is heated to 88 DEG C, is designated as aqueous phase.Styrene (679.65g), divinylbenzene (39.55 g) and t-butyl peroxy-
2 ethyl hexanoic acid (1.1 g) mixes, and is designated as monomer phase.Monomer is added in aqueous phase, 82 DEG C of insulation 4 hrs, then heats up
To 88 DEG C, it is incubated 1.5 hrs.Cool to room temperature.
Paraformaldehyde solution (57.4mL), dimethoxym ethane (23.8 mL) and methanol (28 mL).It is slowly added dropwise chlorosulfonic acid
(77mL) and control reactor temperature and be not more than 30 DEG C.Add Archon (50 g, 5.5% DVB, 250 800 um), stir 10
Min, adds 40% ferric chloride (3.4 mL) solution.30 DEG C of insulation 6 hrs.It is slowly added dropwise 77 mL methanol, is cooled to less than 25
℃.Three times are washed with methanol (86 mL).
Chlorine ball, water (86 mL), 47% liquid caustic soda (18 mL) and dimethoxym ethane (76mL) is added in reactor.Add 50% front three
Amine aqueous solution (51mL) is also incubated 3 hrs.It is set to distillation state.Still-process is slowly added dropwise water to keep mobility.Heat up
15 min it are incubated during to 98-100 DEG C.It is cooled to less than 50 DEG C.Water washing resin is 7 to pH.Drip 32% hydrochloric acid solution
(21mL).Water washing resin is 7 to pH.Preparing resin volume is 218mL, and the expansion factor of resin is 4.35.
The test result of the product of this embodiment gained is shown in Table 1:
The test result of the highly basic I type resin of table 1. embodiment 1 gained
| Parameter | Unit | |
| Whole ball rate | % | 99 |
| Moisture | % | 44.0 |
| Volume-exchange amount | eq/ L | 1.51 |
| Weight exchange capacity | eq/ Kg | 3.70 |
Embodiment 2: prepare gel highly basic II type anion exchange resin without dichloroethanes technique
Paraformaldehyde solution (62mL), dimethoxym ethane (26 mL) and methanol (30 mL).It is slowly added dropwise chlorosulfonic acid (83mL) and controls
Reactor temperature is not more than 30 DEG C.Add Archon (50 g, 2% DVB, 250 800 um), stir 10 min, add 40% 3
Iron chloride (3.4 mL) solution.30 DEG C of insulation 5 hrs.It is slowly added dropwise 77 mL methanol, is cooled to less than 25 DEG C.With methanol (86
ML) washing three times.
Chlorine ball, water (86 mL), 47% liquid caustic soda (18 mL) and dimethoxym ethane (76mL) is added in reactor.Add dimethyl
Ethanolamine solutions (62mL) 48 DEG C insulation 2 hrs.It is cooled to 30 DEG C and drips 50% trimethylamine (10 mL), 40 DEG C of insulations 3
hrs.It is set to distillation state.Still-process is slowly added dropwise water to keep mobility.It is warming up to insulation 15 when 98-100 DEG C
min.It is cooled to less than 50 DEG C.Water washing resin is 7 to pH.Drip 32% hydrochloric acid solution (21mL).Water washing resin is 7 to pH.
Preparing resin volume is 250mL, and the expansion factor of resin is 5.0.
The test result of the product of this embodiment gained is shown in Table 2:
The test result of the highly basic II type resin of table 2 embodiment 2 gained
| Parameter | Unit | |
| Whole ball rate | % | 100 |
| Moisture | % | 46.86 |
| Volume-exchange amount | eq/ L | 1.27 |
| Weight exchange capacity | eq/ Kg | 3.32 |
Comparative example 1: have dichloroethanes technique to prepare gel highly basic I type anion exchange resin
Paraformaldehyde solution (41mL), dimethoxym ethane (17 mL) dichloroethanes (50 mL) and methanol (20 mL).It is slowly added dropwise chlorine sulphur
Acid (50mL) also controls reactor temperature and is not more than 30 DEG C.Add Archon (50 g, 5.5% DVB, 250 800 um), stirring
10 min, add 40% ferric chloride (3.4 mL) solution.30 DEG C of insulation 4 hrs.It is slowly added dropwise 55 mL methanol, is cooled to little
In 25 DEG C.Three times are washed with methanol (86 mL).
Chlorine ball, water (86 mL), 47% liquid caustic soda (18 mL) and dimethoxym ethane (76mL) is added in reactor.Add 50% front three
Amine aqueous solution (51mL), 40 DEG C of insulation 3 hrs.It is set to distillation state.Still-process is slowly added dropwise water to keep mobility.
It is warming up to when 98-100 DEG C be incubated 15 min.It is cooled to less than 50 DEG C.Water washing resin is 7 to pH.Drip 32% hydrochloric acid solution
(21mL).Water washing resin is 7 to pH.Preparing resin volume is 250mL, and the expansion factor of resin is 5.0.
The test result of the product of this embodiment gained is shown in Table 3:
The test result of table 3 embodiment 3 gained resin
| Parameter | Unit | |
| Whole ball rate | % | 99 |
| Moisture | % | 43.9 |
| Volume-exchange amount | eq/ L | 1.35 |
| Weight exchange capacity | eq/ Kg | 3.35 |
Test example: resistance to infiltration cycles shock-testing
Resistance to infiltration cycles shock measurement method is as follows: measures 10 mL resins, is transformed into chlorine type.Sieve takes 600 um above sections, really
In guarantor's sample, < 500 um are less than 2%.Measure 2.5 mL resins and load circulation exchange column.Select 15% sodium hydroxide solution and
20% sodium chloride solution.It is circulated test, altogether 100 circulations.After cycle period terminates, collect all from circulation exchange
Granule in post.Whole ball rate after record infiltration cycles operation is that resistance to infiltration cycles impacts (100 cycle).
The embodiment 1 without dichloroethanes and the gel highly basic I type anion having the comparative example 1 of dichloroethanes to prepare is used to hand over
Changing the resistance to infiltration cycles impact of resin, (100 cycle) the results are shown in Table 4, is 96% and 92%.Chloromethane without dichloroethanes is described
Resin prepared by base technique has more preferable mechanical strength.
Table 4 uses resistance to infiltration cycles impact (100 cycle) of the resin of embodiment 1 and embodiment 3 preparation
| Parameter | Unit | Embodiment 1 | Comparative example 1 |
| Resistance to infiltration cycles impact (100 cycle) | % | 96 | 92 |
Claims (10)
1. the method preparing gel strong basic anion-exchange resin without dichloroethanes chloromethylation technique, it is characterised in that the method
Comprise the following steps:
1) chloromethyl ether synthesis
Add formaldehyde, dimethoxym ethane and methanol in a kettle., be slowly added dropwise chlorosulfonic acid and control reactor temperature and be not more than 30
DEG C, fabricated in situ chloromethyl ether；
2) chloromethylation prepares chlorine ball
Chloromethyl ether prepared by above-mentioned method adds Archon, and adds Lewis acid catalyst and carry out chloromethylation, chloromethane
Glycosylation reaction temperature is 10 ~ 60 DEG C, and the time is 2 ~ 48 hrs；
3) aminating reaction
Chlorine ball prepared by above-mentioned method adds organic solvent and carries out swelling, is subsequently adding aminating agent, and aminating reaction temperature is 30-
60 DEG C, the time is 30 min-24 hrs, and the excess percentage of aminating agent is 10-300%.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: Archon selects styrene-divinylbenzene beads, and the degree of cross linking is 1 ~ 10%, and Archon particle size range is 100 ~
1000 um。
The technique of chloromethylation without dichloroethanes the most according to claim 2 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: the Archon degree of cross linking is 2 ~ 8%, and Archon particle size range is 250 ~ 800 um.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: formaldehyde uses the mode of paraformaldehyde methanol solution to add, and the mass concentration of paraformaldehyde methanol solution is
10~55%。
The technique of chloromethylation without dichloroethanes the most according to claim 4 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: by adding total amount volume percentage paraformaldehyde solution 25 ~ 40%, dimethoxym ethane 10 ~ 15%, methanol 10 ~
20%, chlorosulfonic acid 30 ~ 50%.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: the catalyst of chloromethylation include the one in zinc chloride, aluminum chloride, stannic chloride and iron chloride or
Multiple；Preferably, Lewis acid is iron chloride, and iron chloride mass concentration is 5 ~ 80%, and preferred ferric chloride concn is 30 ~ 50%.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: swelling organic solvent selects one or more in benzene, acetone, dimethoxym ethane and carbon tetrachloride；Preferably, molten
Swollen organic solvent selects dimethoxym ethane.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: aminating agent selects trimethylamine, triethylamine, tri-n-butylamine, dimethyl propanol amine, methyl diethanolamine, dimethyl
One or more in ethanolamine, dimethylamine and diethylamine；Preferably, aminating agent selects trimethylamine or dimethylethanolamine.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares the side of gel strong basic anion-exchange resin
Method, it is characterised in that: amination temperature is 30-50 DEG C, and the aminating reaction time is 1-6 hrs.
The technique of chloromethylation without dichloroethanes the most according to claim 1 prepares gel strong basic anion-exchange resin
Method, it is characterised in that: aminating reaction is recovered by distillation solvent and the amine of excess after terminating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535302A (en) * | 2018-10-31 | 2019-03-29 | 南京工程学院 | A kind of preparation method of the polyaniline-modified ion exchange resin of high temperature resistant |
| CN113248781A (en) * | 2021-05-24 | 2021-08-13 | 井冈山大学 | Green recycling method for non-metal materials in circuit board waste |
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| CN105367689A (en) * | 2015-12-22 | 2016-03-02 | 漂莱特（中国）有限公司 | Gel-type strong-base anion exchange resin |
| CN105399888A (en) * | 2015-12-22 | 2016-03-16 | 漂莱特（中国）有限公司 | Uranium adsorption resin |
| CN105418819A (en) * | 2015-12-22 | 2016-03-23 | 漂莱特（中国）有限公司 | Preparation method for gel-type strongly-alkaline anion exchange resin |
| CN105524202A (en) * | 2015-12-22 | 2016-04-27 | 漂莱特（中国）有限公司 | Preparation method of uranium absorption resin |
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2016
- 2016-07-22 CN CN201610588581.4A patent/CN106188406A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367689A (en) * | 2015-12-22 | 2016-03-02 | 漂莱特（中国）有限公司 | Gel-type strong-base anion exchange resin |
| CN105399888A (en) * | 2015-12-22 | 2016-03-16 | 漂莱特（中国）有限公司 | Uranium adsorption resin |
| CN105418819A (en) * | 2015-12-22 | 2016-03-23 | 漂莱特（中国）有限公司 | Preparation method for gel-type strongly-alkaline anion exchange resin |
| CN105524202A (en) * | 2015-12-22 | 2016-04-27 | 漂莱特（中国）有限公司 | Preparation method of uranium absorption resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535302A (en) * | 2018-10-31 | 2019-03-29 | 南京工程学院 | A kind of preparation method of the polyaniline-modified ion exchange resin of high temperature resistant |
| CN109535302B (en) * | 2018-10-31 | 2021-06-01 | 南京工程学院 | Preparation method of high-temperature-resistant polyaniline modified ion exchange resin |
| CN113248781A (en) * | 2021-05-24 | 2021-08-13 | 井冈山大学 | Green recycling method for non-metal materials in circuit board waste |
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Application publication date: 20161207 |