CN1157190A - Weak-base anion-exchange resin and preparing method thereof - Google Patents
Weak-base anion-exchange resin and preparing method thereof Download PDFInfo
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- CN1157190A CN1157190A CN96101131A CN96101131A CN1157190A CN 1157190 A CN1157190 A CN 1157190A CN 96101131 A CN96101131 A CN 96101131A CN 96101131 A CN96101131 A CN 96101131A CN 1157190 A CN1157190 A CN 1157190A
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Abstract
The present invention relates to a weak-base anion-exchange resin. Its exchange capacity is 2.40-4.10 meq/g dry resin, and its preparation method is characterized by using acylated aromatic three-dimensional copolymer and paraformaldehyde, ammonium salt and amine salt, and making them pass through Mannich reaction. Said invention is simple in reaction process, and its raw materials are cheap. It avoids the use of high toxic monochloro-methylether type compounds, so that it can reduce the harm to operators.
Description
The present invention relates to weak-base anion-exchange resin and preparation method thereof.
Usually preparation anion exchange resin is to adopt the chloro alkyl ether, under the Fu Shi catalyst action, make the EVA that contains chloromethyl as chloromethylether with the three-dimensional EVA reaction that contains aromatic proton, make a kind of anion exchange resin through amination then, because chloromethylether has high toxicity and carries out secondary cross-linking easily resin exchange capacity is reduced in the above-mentioned method for making, in recent years, U.S.3843566 has reported with the aromatic of 1-chloro-4-methyl-benzene class and polyenoid monomer (as divinylbenzene) and has made the EVA that contains chloromethyl by copolymerization, make a kind of anion exchange resin through amination then, but because when containing 1-chloro-4-methyl-benzene and divinylbenzene and in water, carrying out suspension polymerisation, the bead polymerization body has foamed phenomenon, and the granular EVA homogeneity that obtains is poor.
US 3,791, and 996 have reported on the aromatic proton EVA and to introduce the acid amides methyl, and the acid amides methyl adds water decomposition and obtains carrying out secondary or three grades of changes with formic acid and formalin behind the amine methyl EVA then, and this method complex process is wayward.
The present invention foamed phenomenon occurs when having overcome the problem of using toxic raw material chloromethylether in the prior art and suspension polymerisation and a kind of method for preparing weak-base anion-exchange resin simple and easy to control is provided.
The present invention is used, and to contain the three-dimensional EVA of aromatic proton be by aromatic series mono-vinyl compound and the many vinyl compounds of crosslinking agent, carries out suspension polymerization and obtain in aqueous medium.
Weak-base anion-exchange resin of the present invention has following structure:
The exchange capacity of this weak-base anion-exchange resin is the 2.40-4.10meq/g dried resin.
The method for making of weak-base anion-exchange resin of the present invention step is in the following order carried out:
1, the preparation of the three-dimensional EVA of acyl group aromatic proton
With aromatic series mono-vinyl compound and the many vinyl compounds of crosslinking agent by weight (80～99): (20～1), that carries out in aqueous medium that suspension polymerization obtains gel structure or loose structure contains the three-dimensional EVA of aromatic proton.Described aromatic series mono-vinyl compound is a styrene, vinyltoluene, ethyl styrene or naphthalene ethene.Described crosslinking agent is many vinyl compounds, as divinylbenzene, and divinyl ethylo benzene, divinyl toluene, divinyl naphthalene.
Above-mentioned three-dimensional EVA through swelling agent swelling 1-5 hour, is carried out the Fu Shi reaction with acylting agent in the presence of catalyst, reaction temperature 20-80 ℃, reaction time 1-5 hour, obtain the three-dimensional EVA of acyl group aromatic series.Described swelling agent is a carbon disulfide, heptane, cyclohexane, nitrobenzene, 1-nitropropane, 2-nitropropane or dinitro benzene.
Described catalyst is an aluminum trichloride (anhydrous), and anhydrous zinc chloride or anhydrous stannic chloride, catalyst amount are that 100 gram EVAs use the 100-500 gram.Described acylting agent is chloroacetic chloride or acetic anhydride.The three-dimensional EVA of acylting agent and aromatic proton, mol ratio is 0.5-4,
2, primary, the preparation of secondary, tertiary amine-type anion exchange resin:
With the three-dimensional EVA of the acyl group aromatic series that obtains in 1 and paraformaldehyde and ammonium salt ammonium chloride or amine salt is that methylamine hydrochloride or dimethylamine hydrochloride carry out Mannich reaction 4-10 hour at 60-120 ℃, obtains primary respectively, the second month in a season, tertiary amine-type anion exchange resin.
Weak-base anion-exchange resin of the present invention, exchange capacity are the 2.4-4.10meq/g dried resin.
Raw material used in the present invention is cheap, and course of reaction is easy, and mild condition is easy to control, has avoided the crosslinked problem of two degree, and gained anion exchange resin cost is low.Avoided using the high toxicity compound of chloromethyl ether and so on, can reduce the harm healthy greatly operating personnel.
It below is the detailed description of embodiments of the invention.Embodiment 1,
Restrain porous type styrene one divinylbenzene EVA (weight ratio 92: 8) swellings after 2 hours at 400 milliliters of curing carbon blacks with 52; slowly add the 140g aluminum trichloride (anhydrous); then maintain the temperature at and slowly drip acetic anhydride 50g in the 10-30 ℃ of scope; after dripping end of a period, stirred 4 hours down, boil off carbon disulfide at 40 ℃; to fully stir in the last solid impouring mixture of ice and water; filter and respectively give a baby a bath on the third day after its birth time, wash with water at last to neutrality with acid, alkali, after the drying 70 restrain the acyl group products.
Getting the above-mentioned acetyl group cross-linked polystyrene beads bodies of 12 grams restrains dimethylamine hydrochlorides with 5 gram paraformaldehydes and 7 and carries out Mannich reaction at 90 ℃; react that to obtain 16 gram nitrogen contents in 4 hours be 5.15% primary amine type anion exchange resin, recording its exchange capacity is the 3.73meq/g dried resin.Embodiment 2,
Acetyl group product 12 gram of getting embodiment 1 and 5 gram paraformaldehydes and 6 gram methylamine hydrochlorides 90 ℃ down reaction 6 hours 15.6 gram nitrogen contents are 5.20% secondary amine type anion exchange resin, recording its exchange capacity is the 3.75meq/g dried resin.Embodiment 3,
The acetyl group EVAs of getting 12 gram embodiment 1 and 5 gram paraformaldehydes and 5 gram ammonium chlorides react and obtained 14.8 in 8 hours to restrain nitrogen contents be 4.45% primary amine type anion exchange resin under 90 ℃, and recording its exchange capacity is the 3.10meq/g dried resin.Embodiment 4,
With 52 gram pearl crosslinked polystyrenes (4% is crosslinked) swellings 2 hours in 400 milliliters of carbon disulfide, add aluminum trichloride (anhydrous) and acetic anhydride, press embodiment 1 similar processing thereafter, 73 restrain acyl group copolymerization pearl bodies.
Get the above-mentioned products of 12 grams and 5 gram paraformaldehydes and 7 gram dimethylamine hydrochlorides and carry out Mannich reaction and get 16.4 to restrain nitrogen contents be 5.60% tertiary amine-type anion exchange resin, exchange capacity is the 4.03meq/g dried resin.Embodiment 5,
Changing EVA into the degree of cross linking is 20% porous type crosslinked polystyrene, and obtaining 14.0 gram nitrogen contents at last by embodiment 4 similar processing is 3.35% tertiary amine-type anion exchange resin, and exchange capacity is the 2.40meg/g dried resin.
Claims (8)
1, a kind of anion exchange resin is characterized in that described anion exchange resin is alkalescent, and its structural formula is as follows:
Described Capacity of Basic Anion Exchange Resin is the 2.40-4.10meq/g dried resin.
2, a kind of preparation method of anion exchange resin is characterized in that step is carried out in the following order:
(1) preparation of the three-dimensional EVA of acyl group aromatic proton
By aromatic series mono-vinyl compound and many vinyl compounds, that carries out in aqueous medium that suspension polymerization obtains gel structure or loose structure contains the three-dimensional EVA of aromatic proton,
Above-mentioned three-dimensional EVA through swelling agent swelling 1-5 hour, is carried out the Fu Shi reaction with acylting agent in the presence of catalyst, reaction temperature 20-80 ℃, reaction time 1-5 hour, obtain the three-dimensional EVA of acyl group aromatic series.
(2) primary, the preparation of the second month in a season, tertiary amine-type anion exchange resin
The three-dimensional EVA of the acyl group aromatic series that obtains in (1) and paraformaldehyde and ammonium salt or amine salt are carried out Mannich reaction 4-10 hour at 60-120 ℃, obtain primary respectively, the second month in a season, tertiary amine-type weak-base anion-exchange resin.
3, the preparation method of a kind of anion exchange resin according to claim 2 is characterized in that described acylting agent and three-dimensional EVA are 0.5-4 in molar ratio.
4,, it is characterized in that described swelling agent is a carbon disulfide, heptane, cyclohexane, nitrobenzene, 1-nitropropane, 2-nitropropane or dinitro benzene according to the preparation method of the described a kind of anion exchange resin of claim 2.
5,, it is characterized in that described catalyst is aluminum trichloride (anhydrous), anhydrous zinc chloride or anhydrous stannic chloride according to the preparation method of the described a kind of anion exchange resin of claim 2.
6,, it is characterized in that described acylting agent is chloroacetic chloride or acetic anhydride according to the preparation method of the described a kind of anion exchange resin of claim 2.
7,, it is characterized in that described ammonium salt is an ammonium chloride according to the preparation method of the described a kind of anion exchange resin of claim 2.
8,, it is characterized in that described amine salt is methylamine hydrochloride and dimethylamine hydrochloride according to the preparation method of the described a kind of anion exchange resin of claim 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96101131A CN1053394C (en) | 1996-02-12 | 1996-02-12 | Weak-base anion-exchange resin and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN96101131A CN1053394C (en) | 1996-02-12 | 1996-02-12 | Weak-base anion-exchange resin and preparing method thereof |
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| CN1157190A true CN1157190A (en) | 1997-08-20 |
| CN1053394C CN1053394C (en) | 2000-06-14 |
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| CN96101131A Expired - Fee Related CN1053394C (en) | 1996-02-12 | 1996-02-12 | Weak-base anion-exchange resin and preparing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500430A (en) * | 2011-10-19 | 2012-06-20 | 厦门大学 | Modified anion exchange resin with double long carbon chains and preparation method and application thereof |
| CN104098750A (en) * | 2013-04-10 | 2014-10-15 | 中国科学院宁波材料技术与工程研究所 | Aromatic polymer anion exchange resin with side chain containing sulfonamide quaternary ammonium salt, and preparation method and application thereof |
| CN106554285A (en) * | 2016-11-27 | 2017-04-05 | 天津市职业大学 | A kind of production method of perovskite solar cell with methyl ammonium halide |
| CN106748803A (en) * | 2016-11-27 | 2017-05-31 | 天津市职业大学 | A kind of production method of LITHIUM BATTERY methyl ammonium halide |
-
1996
- 1996-02-12 CN CN96101131A patent/CN1053394C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500430A (en) * | 2011-10-19 | 2012-06-20 | 厦门大学 | Modified anion exchange resin with double long carbon chains and preparation method and application thereof |
| CN102500430B (en) * | 2011-10-19 | 2013-07-24 | 厦门大学 | Modified anion exchange resin with double long carbon chains and preparation method and application thereof |
| CN104098750A (en) * | 2013-04-10 | 2014-10-15 | 中国科学院宁波材料技术与工程研究所 | Aromatic polymer anion exchange resin with side chain containing sulfonamide quaternary ammonium salt, and preparation method and application thereof |
| CN106554285A (en) * | 2016-11-27 | 2017-04-05 | 天津市职业大学 | A kind of production method of perovskite solar cell with methyl ammonium halide |
| CN106748803A (en) * | 2016-11-27 | 2017-05-31 | 天津市职业大学 | A kind of production method of LITHIUM BATTERY methyl ammonium halide |
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| CN1053394C (en) | 2000-06-14 |
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