CN104262207B - A kind of preparation method of sulfonic fluoropolymer compounds - Google Patents
A kind of preparation method of sulfonic fluoropolymer compounds Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of sulfonic fluoropolymer compounds, comprise the steps: 1) substitution reaction: with CnF2n+1(CH2)mI is raw material, and substitution reaction occurs in a solvent with rhodanide, generates CnF2n+1(CH2)mSCN；2) oxidation reaction: by step 1) gained CnF2n+1(CH2)mOxidized dose of SCN oxidation, obtaining formula is CnF2n+1(CH2)mSO3The fluorochemical of H.Using the method for the invention, gained intermediate product yield is high, and purity is high, thus high yield, the high-purity for end-product provides condition, and by-product is few, and production cost is low, dangerous little, easily realizes industrialized production.
Description
Technical field
The present invention relates to the preparation method of a kind of sulfonic fluoropolymer compounds, belong to fluorochemical surface and live
Technical field prepared by property agent.
Background technology
Since the 1950's, perfluoro caprylic acid (ammonium) (PFOA) and perfluoro octyl sulfonic acid
(ammonium) (PFOS) is the fluorine-containing surfactant being most widely used, and PFOA/PFOS is extensive
In hundreds of chemical industry, mechanical industry and daily perfluorinate chemical product.But
PFOA/PFOS stabilizer pole, will not be degraded, and once emitting will in nature forever
Remote exist, affect environment, and cause liver, reproduction, growth, hereditary and immune etc.
Toxicity.Therefore the research of PFOA/PFOS succedaneum becomes current common Jiao paid close attention in the world
Point.
In prior art, the preparation side of the fluorine-containing surfactant of this kind of replacement PFOA/PFOS
Method is mainly electrofluorination method and the telomerization method Han halothane test.Simons etc. are in patent
US2519983 describes the corresponding hydrocarbon acyl fluorides of employing and acyl chlorides is raw material, be first converted into
Perfluoroacyl fluoride, then hydrolyze, distill and i.e. obtain containing carboxylic acid fluoride.But product prepared by electrofluorination method
Purity is the highest.
Du Pont's patent US3132185, US3226449, US3234294 describe another kind
The preparation method of fluorine-containing emulsifier, will tetrafluoroethene and iodine pentafluoride and iodine one system of reacting
Standby perfluor iodoethane, and react with tetrafluoroethene as telogen, prepare perfluoroalkyl iodides,
Then perfluoroalkyl iodides is prepared perfluor carboxylic with oleum, sulfur trioxide or chlorosulfonic acid process
Acid.But the method is owing to directly using strong oxidizer oxidation perfluoroalkyl iodides, and corrosivity is strong,
The spent acid waste liquid simultaneously produced is the most.
The most also there is the report of fluorine-containing emulsifier using photooxidation method to prepare perfluor ethers, as
CN101648122B, fluorine-containing emulsifier prepared by this method owing to being a kind of mixture,
Single compound is can not show a candle in stability.
Therefore, finding a kind of corrosivity little, produce waste liquid less, product purity is high, stable
The preparation method of the fluorine-containing surfactant that property is good is significant.
Summary of the invention
For the technological deficiency of above-mentioned existence, the present invention provides a kind of sulfonic fluoropolymer compounds
Preparation method, gained intermediate product yield is high, and purity is high, thus be end-product high yield,
High-purity provides condition, and by-product is few, and production cost is low, dangerous little, easily realizes work
Industry metaplasia is produced.
For above-mentioned purpose, the present invention adopts the following technical scheme that
The preparation method of a kind of sulfonic fluoropolymer compounds, comprises the steps:
1) substitution reaction:
With CnF2n+1(CH2)mI is raw material, and substitution reaction occurs in a solvent with rhodanide,
Generate CnF2n+1(CH2)mSCN；
2) oxidation reaction:
By step 1) gained CnF2n+1(CH2)mOxidized dose of SCN oxidation, obtaining formula is
CnF2n+1(CH2)mSO3The sulfonic fluoropolymer compounds of H；
In formula, n, m are the positive integer of ＞ 0, and n < 8, m < 7, n+m < 11.
Use preparation method of the present invention, in building-up process, it is not necessary to use corrosivity too strong
Oxidant, the waste liquid of generation is less, and the poisonous and harmful substance of discharge is few, and is easily handled,
Production cost is low, dangerous little, easily realizes industrialized production.Products obtained therefrom purity is high,
Good stability, beneficially enterprise are promoted.
In step 1) in substitution reaction, described rhodanide is selected from containing SCN-The nothing of ion
Machine salt, preferably KSCN, NaSCN, Fe (SCN)3Or Ca (SCN)2In one or both
Above.
In step 1) in substitution reaction, described solvent is organic alcohols or organic acid ester, excellent
Select in methanol, ethanol, propanol, isobutanol, ethyl acetate, methyl acetate or butyl acetate
One or more.More preferably ethyl acetate or ethanol.
In step 1) in substitution reaction, described CnF2n+1(CH2)mI and solvent molar ratio 1:
15-40, preferably 1:18-35.
As the preferred embodiment of the present invention, when solvent is ethanol, described
CnF2n+1(CH2)mI and ethanol mol ratio are 1:33-35；When solvent is ethyl acetate, institute
State CnF2n+1(CH2)mI and ethyl acetate mol ratio are 1:18-19.
In step 1) in substitution reaction, temperature 60-120 DEG C, preferably 100-110 DEG C；Reaction
Pressure 0.2-0.3MPa；Response time 8-10h.
Use step 1 of the present invention) described process conditions, substitution reaction efficiency is high, and conversion ratio can
Reaching 100%, yield can reach 97.2%-98.7%, and purity is up to 99.4%-99.8%.
In step 2) in oxidation reaction, described oxidant is selected from O2, mass concentration 50%H2O2,
Na2O2, K2O2, HNO3, mass concentration 50% oleum or KMnO4In one
Or it is two or more.Preferably O2, mass concentration 50%H2O2Or mass concentration 50% oleum.
In step 2) in oxidation reaction, described CnF2n+1(CH2)mI and oxidant mol ratio 1:
1-15, preferably 1:1-10.
As the preferred embodiment of the present invention, when oxidant is mass concentration 50%H2O2
Time, described CnF2n+1(CH2)mI and H2O2Mol ratio is 1:9-10；When oxidant is quality
During concentration 50% oleum, described CnF2n+1(CH2)mI and oleum mol ratio are 1:
1-1.5。
As the present invention another preferred embodiment, when oxidant is O2Time, also can be direct
Hydroxide is added, such as NaOH, KOH, (NH in oxidation reaction system4) OH or
LiOH, and solvent, it is C that reaction obtains formulanF2n+1(CH2)mSO3The fluorine-containing chemical combination of M
Thing；
In formula, n, m are the positive integer of ＞ 0, and n < 8, m < 7, n+m < 11；M be Na,
K、NH4Or Li.
Described catalyst is CuCl2, described CnF2n+1(CH2)mI and catalyst molar ratio are 1:
0.008-0.009, described reaction system pressure is 0.15-0.25MPa.
In step 2) in oxidation reaction, described oxidation reaction condition: temperature 0～150 DEG C, tool
The temperature range that temperature is suitable for according to different oxidants.Such as use O2, temperature model
Being trapped among 0～100 DEG C, preferable temperature is at 50～60 DEG C；Use H2O2, temperature range exists
30～100 DEG C, preferable temperature is at 80～90 DEG C；Using oleum, temperature range exists
120～125 DEG C.The most dated at this.
In preparation method of the present invention, described preferred followingization of sulfonic fluoropolymer compounds
Compound:
| n | m | Compound |
| 2 | 6 | C2F3(CH2)6SO3M |
| 3 | 5 | C3F5(CH2)5SO3M |
| 4 | 4 | C4F9(CH2)4SO3M |
| 4 | 2 | C4F9(CH2)2SO3M |
| 5 | 3 | C5F11(CH2)3SO3M |
| 6 | 2 | C6F13(CH2)2SO3M |
| 6 | 4 | C6F13(CH2)4SO3M |
| 7 | 1 | C7F15CH2SO3M |
Further it is preferably as follows compound:
| n | m | Compound |
| 4 | 4 | C4F9(CH2)4SO3M |
| 4 | 2 | C4F9(CH2)2SO3M |
| 6 | 2 | C6F13(CH2)2SO3M |
| 6 | 4 | C6F13(CH2)4SO3M |
Preparation method of the present invention also includes the post processing to crude product, and this area can be used conventional
Method, such as neutralization, washing, sucking filtration, decompression distillation etc., with specific reference to different oxidants,
Select the processing mode being suitable for.
Use the preparation method of sulfonic fluoropolymer compounds of the present invention, gained intermediate product
CnF2n+1(CH2)mSCN yield is high, and purity is high, thus is the high yield of end-product, high-purity
Offer condition, and by-product is few, production cost is low, dangerous little, easily realizes industry metaplasia
Produce.Gained sulfonic fluoropolymer compounds has the structure similar with PFOA/PFOS, contains simultaneously
Fluorine carbonic acid is less than 11, can substitute PFOA/PFOS, as a new generation's fluorine-containing surfactant.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
Embodiment 1 C6F13(CH2)2SO3The preparation of H
1) substitution reaction
In the stirred autoclave of 5L, add 474g C6F13(CH2)2I, 107g KSCN,
1.6Kg ethanol, under 0.2Mpa pressure, reaction temperature 110 DEG C, react 8 hours, be cooled to
Room temperature, filters and separates solid salt, and rectification under vacuum removing ethanol, through washing, separatory, cooling
Deng solid C6F13(CH2)2SCN 398g, yield 98.3%, through gas chromatographic detection purity
99.6%.
2) oxidation reaction
In the flask of 5L, add 300g step 1) in prepared C6F13(CH2)2SCN,
Add 50%H2O2650g, flask band magnetic stirring apparatus, condensation reflux unit, tail gas is passed through
Strong acid heat treated.Reaction temperature 85～90 DEG C, react 20 hours, and decompression is distilled off it
In moisture and H2O2, then rectification under vacuum oxidation product, obtain C6F13(CH2)2SO3H
305g, is 98.8% through chromatography purity, yield 96.0%.
Embodiment 2 C6F13(CH2)2SO3NH4Preparation
1) substitution reaction
In the stirred autoclave of 5L, add 474g C6F13(CH2)2I, 90g NaSCN,
1.6Kg ethyl acetate, under 0.2Mpa pressure, reaction temperature 110 DEG C, react 10 hours, fall
Warm to room temperature, filter and separate solid salt, rectification under vacuum removing ethyl acetate, through washing, point
Liquid, cooling waits to obtain solid C6F13(CH2)2SCN 396g, yield 97.7%, examine through gas chromatogram
Survey purity 99.8%.
2) oxidation reaction adds 300g step 1 in the there-necked flask of 5L) prepare
C6F13(CH2)2SCN, is slowly added dropwise the oleum 480g of mass concentration 50%, three mouthfuls of burnings
Bottle belt stirrer, condensation reflux unit, tail gas alkali liquor absorption.Reaction temperature 120～125 DEG C,
Reacting 12 hours, cooling adds ammonia and neutralizes, washing material 4 times, and sucking filtration obtains white
Crystal C6F13(CH2)2SO3NH4326g, yield 98.9%, it is dissolved in containing in fluorous solvent
Carry out chromatography purity 99.6%.
Embodiment 3 C4F9(CH2)2SO3NH4Preparation
1) in the stirred autoclave of 5L, 375g C is added4F9(CH2)2I, 107g KSCN,
1.6Kg ethanol, under 0.2Mpa pressure, reaction temperature 110 DEG C, react 8 hours, be cooled to
Room temperature, filters and separates solid salt, and rectification under vacuum removing ethanol, through washing, separatory, cooling
Deng solid C4F9(CH2)2SCN 302g, yield 98.7%, through gas chromatographic detection purity
99.7%.
2) oxidation reaction adds 300g step 1 in the there-necked flask of 5L) prepare
C4F9(CH2)2SCN, be slowly added dropwise add mass concentration 50% oleum 480g, three
Mouth flask belt stirrer, condensation reflux unit, tail gas alkali liquor absorption.Reaction temperature
120～125 DEG C, reacting 12 hours, cooling adds ammonia and neutralizes, and washing material 4 times is taken out
Filter, obtains white crystal C4F9(CH2)2SO3 NH4327g, yield 96.4%, it is molten
Xie Yu carries out chromatography purity 99.2% containing in fluorous solvent.
Embodiment 4 C6F13(CH2)4SO3The preparation of H
1) substitution reaction
In the stirred autoclave of 5L, add 502g C6F13(CH2)4I, 107g KSCN,
1.6Kg ethyl acetate, under 0.25Mpa pressure, reaction temperature 105 DEG C, react 10 hours,
It is cooled to room temperature, filters and separate solid salt, rectification under vacuum removing ethyl acetate, through washing,
Separatory, cooling waits to obtain solid C6F13(CH2)4SCN 421g, yield 97.2%, through gas chromatogram
Detection purity 99.8%.
2) oxidation reaction
In the flask of 5L, add 320g step 1) in prepared C6F13(CH2)4SCN,
Add 50%H2O2650g, flask band magnetic stirring apparatus, condensation reflux unit, tail gas is passed through
Strong acid heat treated.Reaction temperature 80～85 DEG C, react 24 hours, and decompression is distilled off it
In moisture and H2O2, then rectification under vacuum oxidation product, obtain C6F13(CH2)4SO3H
333g, is 99.5% through chromatography purity, yield 98.8%.
Embodiment 5 C4F9(CH2)4SO3The preparation of Na
1) substitution reaction
In the stirred autoclave of 5L, add 403g C4F9(CH2)4I, 107g KSCN,
1.6Kg ethyl acetate, under 0.25Mpa pressure, reaction temperature 110 DEG C, react 10 hours,
It is cooled to room temperature, filters and separate solid salt, rectification under vacuum removing ethyl acetate, through washing,
Separatory, cooling waits to obtain solid C4F9(CH2)4SCN 326g, yield 98.5%, through gas chromatogram
Detection purity 99.4%.
2) oxidation reaction
By 300g step 1) the middle C prepared4F9(CH2)4SCN joins the stainless steel reaction of 5L
In still, it is subsequently adding 40gNaOH, 1.5gCuCl2, 450g deionized water, it is warming up to 55 DEG C,
It is slowly introducing O2, keep reactor pressure at 0.2Mpa, react 24 hours.The product that will obtain
Wash 4 times, sucking filtration, obtain white crystal C4F9(CH2)4SO3Na 265g, yield 77.3%,
It is dissolved in containing fluorous solvent carries out chromatography purity 97.6%.
In like manner, NaOH is replaced with KOH, (NH4) OH or LiOH, can be prepared into respectively
To C4F9(CH2)4SO3K、C4F9(CH2)4SO3(NH4)、C4F9(CH2)4SO3Li。
Although, the most with a general description of the specific embodiments the present invention is made
Detailed description, but on the basis of the present invention, it can be made some modifications or improvements, this
Will be apparent to those skilled in the art.Therefore, without departing from present invention spirit
On the basis of these modifications or improvements, belong to the scope of protection of present invention.
Claims (6)
1. the preparation method of a sulfonic fluoropolymer compounds, it is characterised in that include as follows
Step:
1) substitution reaction:
With CnF2n+1(CH2)mI is raw material, and substitution reaction occurs in a solvent with rhodanide,
Generate CnF2n+1(CH2)mSCN；
2) oxidation reaction:
By step 1) gained CnF2n+1(CH2)mOxidized dose of SCN oxidation, obtaining formula is
CnF2n+1(CH2)mSO3The sulfonic fluoropolymer compounds of H；
In formula, n, m are the positive integer of ＞ 0, and n < 8, m < 7, n+m < 11；
In step 1) in substitution reaction, described CnF2n+1(CH2)mI and solvent molar ratio 1:
15-40；
In step 1) in substitution reaction, temperature 60-120 DEG C, reaction pressure 0.2-0.3MPa,
Response time 8-10h；
In step 2) in oxidation reaction, described oxidant is selected from O2, mass concentration 50%H2O2,
One or more in mass concentration 50% oleum；
In step 2) in oxidation reaction, when oxidant is O2Time, oxidation reaction need to be at hydrogen-oxygen
Compound and catalyst CuCl2In the presence of carry out；
In step 2) in oxidation reaction, described CnF2n+1(CH2)mI and oxidant mol ratio 1:
1-15。
Preparation method the most according to claim 1, it is characterised in that in step 1) take
In generation reaction, described rhodanide is selected from KSCN, NaSCN, Fe (SCN)3Or Ca (SCN)2
In one or more.
Preparation method the most according to claim 1, it is characterised in that in step 1)
In substitution reaction, described solvent selected from methanol, ethanol, propanol, isobutanol, ethyl acetate,
One or more in methyl acetate or butyl acetate.
Preparation method the most according to claim 1, it is characterised in that in step 2)
In oxidation reaction, when oxidant is O2Time, in oxidation reaction system add hydroxide and
Catalyst, it is C that reaction obtains formulanF2n+1(CH2)mSO3The fluorochemical of M；
Wherein, n, m are the positive integer of ＞ 0, and n < 8, m < 7, n+m < 11；M be Na,
K、NH4Or Li.
Preparation method the most according to claim 4, it is characterised in that in step 2)
In oxidation reaction, described CnF2n+1(CH2)mI and catalyst molar ratio are 1:0.008-0.009.
Preparation method the most according to claim 4, it is characterised in that in step 2)
In oxidation reaction, described reaction system pressure is 0.15-0.25MPa.
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|---|---|---|---|---|
| US4784809A (en) * | 1986-06-27 | 1988-11-15 | E. I. Du Pont De Nemours And Company | Process for preparing perfluoroalkyl-alkyl sulfonic acid compounds |
| CN1239948A (en) * | 1996-12-13 | 1999-12-29 | 纳幕尔杜邦公司 | Fluorinated alkylthiocyanate process |
| CN102320909A (en) * | 2011-07-18 | 2012-01-18 | 浙江工业大学 | Synthesis method of alpha-ketone thiocyanate compound |
-
2014
- 2014-08-19 CN CN201410409058.1A patent/CN104262207B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4784809A (en) * | 1986-06-27 | 1988-11-15 | E. I. Du Pont De Nemours And Company | Process for preparing perfluoroalkyl-alkyl sulfonic acid compounds |
| CN1239948A (en) * | 1996-12-13 | 1999-12-29 | 纳幕尔杜邦公司 | Fluorinated alkylthiocyanate process |
| CN102320909A (en) * | 2011-07-18 | 2012-01-18 | 浙江工业大学 | Synthesis method of alpha-ketone thiocyanate compound |
Non-Patent Citations (3)
| Title |
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| Synthesis of 2,2,2-TrifluoroethanesulfonicA cid;Chaiyun Bunyagidj et al;《J. Org. Chem》;19811231;第46卷;3335-3336 * |
| Szonyi, F.;Cambon, A..Functionalization of 2-perfluoroalkylethyl iodides via phase transfer catalysis. Importance of this technique in the perfluoroalkyl series.《Journal of Fluorine Chemstry》.1989,第42卷 * |
| 全氟和多氟烷基磺酸的研究 Ⅳ.3-氧杂多氟烷烃磺酸酯的合成及其硫-氧和碳-氧键的断裂;陈庆云等;《化学学报》;19820430(第04期);337-352 * |
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