CN104744615B - Preparation method of perfluorinated quaternary ammonium type strong base anion exchange resin - Google Patents
Preparation method of perfluorinated quaternary ammonium type strong base anion exchange resin Download PDFInfo
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- CN104744615B CN104744615B CN201310756127.1A CN201310756127A CN104744615B CN 104744615 B CN104744615 B CN 104744615B CN 201310756127 A CN201310756127 A CN 201310756127A CN 104744615 B CN104744615 B CN 104744615B
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Abstract
The invention provides a preparation method of perfluorinated quaternary ammonium type strong base anion exchange resin. The preparation method is characterized by preparing the strong base anion exchange resin by adopting chloromethyl polystyrene to react with perfluorinated tertiary amine and trimethylamine simultaneously. The preparation method has the beneficial effects that the compatibility between aminating agents and chloromethylated beads is improved, the efficiency of aminating reaction is improved, the binding force of bonds between alkylbenzylamine and alkyl N-C is reinforced, amino is not easy to fall of, and the resin can be used at a higher temperature; by introducing fluorine-containing groups, the corrosion resistance of a resin insert is reinforced and the surface of the sphere is protected, thus prolonging the service life and expanding the application range of the resin.
Description
Technical field
The present invention relates to a kind of preparation method of strong-base anion-exchange resin, particularly a kind of perfluor quaternary ammonium type highly basic
The preparation method of property anion exchange resin.
Background technology
By quaternary ammonium group it is bonded on macromolecular scaffold i.e. can obtain strong alkali resin.Strong basic anion-exchange resin can be used for
The aspects such as water process, the purification of material, concentration, separation, the transformation of substance ion composition, the decolouring of material and catalyst, but
The temperature in use of strong basic anion-exchange resin particularly hydroxyl type resin is only limitted to less than 60 DEG C, so limit highly basic it is cloudy from
The range of application of sub-exchange resin
There is thermal degradation and mainly have two approach in strong basic anion-exchange resin, one is that amido comes off, i.e. benzyl and amido
Between key be broken from I, catabolite is the mixture of tertiary amine and alcohol；Two is the key between alkylbenzylamine and one of alkyl N-C
It is broken from II, product is alcohol or its oxide and tertiary amine weak base resin, and the probability of three alkyl is identical, therefore has highly basic
The suppression ratio total exchange amount of exchange capacity is fast.
Russian Patent SU675056 discloses the 2-mercaptobenzimidazole that 2% is introduced in chloromethyl polystyrene resin
(age resistor B), then prepares strong basic anion-exchange resin with trimethylamine reaction again, can improve the heat endurance of resin.Institute
The anion exchange resin of synthesis has the heat endurance higher than general strong base negative resin, and its chlorine type is heated to 300 DEG C of weight
It is 4.5% to lose, and general negative resin weightlessness 10% at 150 DEG C.
JP0175041 is prepared for the amine type strong base anion exchangers of triethyl group two for having tricyclic structure, is heated in boiling water
Certain hour exchange capacity holding 93%, and the exchange capacity holding 80% after the heating of corresponding front three amine type exchanger.
What Mitsubishi chemical company had been succeeded in developing between phenyl ring and quaternary nitrogen atoms containing long chain hydrocarbon groups or benzyl oxide alkyl
Polystyrene strong basic anion-exchange resin.The quaternary ammonium group that it contains is relatively stable when being heated, and temperature can still be grown when being 90 DEG C
Phase uses.
Above prior art process flow is long, and yield is low, the problem of mechanical strength of resin reduction after high cost, and long-term use,
Have impact on the using effect in commercial plant.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of system of perfluor quaternary ammonium type anion exchange resin
Preparation Method.
A kind of preparation method of perfluor quaternary ammonium type anion exchange resin, using chloromethylated polystyrene with it is complete
Fluorine tertiary amine and trimethylamine simultaneous reactions prepare strong basic anion-exchange resin.
A kind of preparation method of perfluor quaternary ammonium type anion exchange resin, fluorine-containing part structural formula is as follows：
N=1-9
A kind of preparation method of perfluor quaternary ammonium type anion exchange resin, comprises the following steps：
Chloromethylated polystyrene spheroid is swollen in 2-5 times of (weight ratio) trimethylamine aqueous solution, is optimized for 3 times of (weight
Than), add the perfluoro tertiary amines of the 10-50 (wt%) of chloromethylated polystyrene spheroid percent；(45 are optimized in 40 DEG C -70 DEG C
DEG C) stirring reaction 10-20h, (being optimized for 15h), the prepared perfluor quaternary ammonium type anion exchange resin of reaction end.
Chloromethylated polystyrene spheroid can be used commercially available prod, such as chlorine of Anhui Samsung resin Science and Technology Ltd. production
Ball.
Perfluoro tertiary amines series, including：Perfluoro triethylamine, perfluamine, perfluorotributylamine, perfluor triamylamine, perfluor ring
Ether etc..It is preferred that perfluoro triethylamine, perfluamine, perfluorotributylamine.
Beneficial effects of the present invention：
1) using perfluoro tertiary amines and trimethylamine simultaneously as aminating agent, fluorine element has hydro-oleophobicity to the present invention simultaneously,
Improved compatibility between aminating agent and chlorine ball, improve the efficiency of aminating reaction, made between alkylbenzylamine and alkyl N-C
The adhesion enhancing of key, also makes amino difficult for drop-off, resin is used at higher temperatures.
2) introducing of fluoro-containing group, strengthens resin matrix corrosion resistance, and spherome surface is protected, makes so as to extend
With the life-span, the range of application of the resin is expanded.
Specific embodiment
Following examples are only to further illustrate the present invention, are not limitation the scope of protection of the invention.
Chloromethylated polystyrene spheroid can be used commercially available prod, such as chlorine of Anhui Samsung resin Science and Technology Ltd. production
Ball.
100Kg chloromethylated polystyrene spheroids are added in 500L reactors, 300Kg trimethylamine aqueous solutions are swollen in
In, the perfluoro triethylamine of 30Kg is added, in 45 DEG C of stirring reaction 15h, reaction terminates, and perfluor quaternary ammonium type strong alkalinity anion is obtained
Exchanger resin.
Embodiment 2
100Kg chloromethylated polystyrene spheroids are added in 500L reactors, 200Kg trimethylamine aqueous solutions are swollen in
In, the perfluoro triethylamine of 10Kg is added, in 40 DEG C of stirring reaction 20h, reaction terminates, and perfluor quaternary ammonium type strong alkalinity anion is obtained
Exchanger resin.Products obtained therefrom numbering is SX-2.
Embodiment 3
100Kg chloromethylated polystyrene spheroids are added in 500L reactors, 500Kg trimethylamine aqueous solutions are swollen in
In, the perfluoro triethylamine of 50Kg is added, in 70 DEG C of stirring reaction 10h, reaction terminates, and perfluor quaternary ammonium type strong alkalinity anion is obtained
Exchanger resin.Products obtained therefrom numbering is SX-3.
Embodiment 4
Perfluoro tertiary amines select perfluamine, the other the same as in Example 1.Products obtained therefrom numbering is SX-4.
Embodiment 5
Perfluoro tertiary amines select perfluamine, the other the same as in Example 2.Products obtained therefrom numbering is SX-5.
Embodiment 6
Perfluoro tertiary amines select perfluamine, the other the same as in Example 3.Products obtained therefrom numbering is SX-6.
Embodiment 7
Perfluoro tertiary amines select perfluorotributylamine, the other the same as in Example 1.Products obtained therefrom numbering is SX-7
Embodiment 8
It is added without perfluoro tertiary amines, the other the same as in Example 1.Products obtained therefrom numbering is SX-8
With FTIS, pressing potassium bromide troche does infrared spectrum analysis to synthesized each resin.By anti-
The infrared spectrum of product is answered to understand：SX1-SX8 is in 1370cm-1Nearby there are C-N stretching vibration absworption peaks, in 1640cm-1Near
There are N-H symmetric vibration absworption peaks, illustrate to introduce tertiary amine group in the skeleton of polystyrene resin；In 1220cm-1With
1260cm-1It is strong bimodal in appearance, it is the stretching vibration absworption peak of quaternary ammonium salt, in 1235cm in the collection of illustrative plates of SX1-SX7 samples-1It is attached
Closely there is CF2, CF3Stretching vibration peak, 660cm-1Nearby there is CF2CF3Absworption peak, illustrate with the presence of perfluoro tertiary amines group；So
Quaternary ammonium salt is have also been introduced in the skeleton of polystyrene resin, so this patent product generates the quaternary ammonium salt and front three of perfluoro tertiary amines
The mixture of the quaternary ammonium salt of amine.
Embodiment 9
The final resin in 10g embodiments is taken, is placed in 1000ml water, 95 DEG C of temperature is incubated 100h, detects highly basic group
Capacity, calculates highly basic group loss late %
| Production code member | Highly basic group loss late % |
| SX-1 | 3.2 |
| SX-2 | 6.8 |
| SX-3 | 2.1 |
| SX-4 | 4.2 |
| SX-5 | 7.8 |
| SX-6 | 2.9 |
| SX-7 | 2.6 |
| SX-8 | 17.2 |
Claims (2)
1. a kind of preparation method of perfluor quaternary ammonium type anion exchange resin, it is characterised in that comprise the following steps：Chlorine
Methylated Polystyrene spheroid is swollen in 2-5 times of (weight ratio) trimethylamine aqueous solution, adds chloromethylated polystyrene spheroid
The perfluoro tertiary amines of percent 10-50 (wt%)；In 40 DEG C of -70 DEG C of stirring reaction 10-20h, reaction terminates, and perfluor quaternary ammonium type is obtained
Strong-base anion-exchange resin.
2. a kind of preparation method of perfluor quaternary ammonium type anion exchange resin, it is characterised in that chloromethylation polyphenyl second
Alkene prepares strong basic anion-exchange resin with perfluoro tertiary amines and trimethylamine simultaneous reactions；Wherein perfluoro tertiary amines are serial, including：Perfluor
Triethylamine, perfluamine, perfluorotributylamine, perfluor triamylamine.
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| CN201310756127.1A CN104744615B (en) | 2013-12-25 | 2013-12-25 | Preparation method of perfluorinated quaternary ammonium type strong base anion exchange resin |
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| CN104744615B true CN104744615B (en) | 2017-05-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993286A (en) * | 1973-01-10 | 1974-09-05 | ||
| JPS5422310A (en) * | 1977-07-20 | 1979-02-20 | Henkel Kgaa | Process for preparing acyloin |
| SU958428A1 (en) * | 1980-11-14 | 1982-09-15 | Предприятие П/Я А-7815 | Process for producing polymeric optical analyzer of ammoia in gas phase |
| CN103008007A (en) * | 2012-12-10 | 2013-04-03 | 厦门大学 | Resin-type solid base catalyst for synthesis of propylene glycol ether and preparation method and application thereof |
-
2013
- 2013-12-25 CN CN201310756127.1A patent/CN104744615B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4993286A (en) * | 1973-01-10 | 1974-09-05 | ||
| JPS5422310A (en) * | 1977-07-20 | 1979-02-20 | Henkel Kgaa | Process for preparing acyloin |
| SU958428A1 (en) * | 1980-11-14 | 1982-09-15 | Предприятие П/Я А-7815 | Process for producing polymeric optical analyzer of ammoia in gas phase |
| CN103008007A (en) * | 2012-12-10 | 2013-04-03 | 厦门大学 | Resin-type solid base catalyst for synthesis of propylene glycol ether and preparation method and application thereof |
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| CN104744615A (en) | 2015-07-01 |
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Effective date of registration: 20200331 Address after: 313000 1-B, building 1, No. 656, Qixing Road, high tech Zone, Wuxing District, Huzhou City, Zhejiang Province Patentee after: Huzhou Qiqi Electromechanical Technology Co., Ltd Address before: 225300 No. 108 Mingzhu Avenue, Yonganzhou Town, Gaogang District, Taizhou City, Jiangsu Province Patentee before: Luo Sanjie |
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