CN1295256C - High-molecular polymer containing perfluoro alkyl sulfimine side-chain and its synthesizing method - Google Patents
High-molecular polymer containing perfluoro alkyl sulfimine side-chain and its synthesizing method Download PDFInfo
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- CN1295256C CN1295256C CNB2004100613844A CN200410061384A CN1295256C CN 1295256 C CN1295256 C CN 1295256C CN B2004100613844 A CNB2004100613844 A CN B2004100613844A CN 200410061384 A CN200410061384 A CN 200410061384A CN 1295256 C CN1295256 C CN 1295256C
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Abstract
The present invention discloses a high molecular polymer containing a perfluoro alkylsulfimine side chain. A structural formula of the present invention discloses in the specification, wherein PO is polyphosphazene, crosslinked polystyrene or polystyrene provided with an alkyl group side chain; Rf is a perfluoroalkyl group of C1 to C8. In a synthesizing method of the present invention, a high molecular polymer is chlorosulfonated, and a thiophenesulfonyl chloride group is connected to a benzene ring; then, the high molecular polymer reacts with perfluoro-sulfamide to obtain the high molecular polymer containing a perfluoro alkyl sulfimine side chain. The used polymer is poly-phenol oxygen phosphonitrile, the crosslinked polystyrene and the polystyrene provided with the alkyl group long side chain. The high molecular polymer obtained by the present invention has strong acidity and good thermal stability, has a good catalyzing effect on esterification reaction, Dies-Alder reaction, Friedel-Crafts reaction, etc. and can be repeatedly used. Thus, the high molecular polymer has potential application value at aspects of being used as a green organic synthesis catalyst and an electrolyte material. The present invention has the advantages of simple synthesizing method and low cost and is favorable to industrialization production.
Description
Technical field
The present invention relates to a class sulfimide high molecular polymer, be specifically related to contain the high molecular polymer and the synthetic method thereof of perfluoroalkyl sulfimide side chain.Such high molecular polymer is a strongly-acid, can be used as supported acid catalyst and electrolyte.
Background technology
Because it is easily separated that macromolecule load catalyst has with reactant, product, the advantage that can be repeatedly used is compared with homogeneous catalyst and to be had bigger superiority.Therefore, catalyst cupport is had great importance to polymer carrier.The more highly acidic resin of research is a sulfonate resin now, but its thermotolerance is relatively poor, has limited its use range.Simultaneously, the report of introducing on a small quantity polymer lateral chain about trifluoromethanesulp-onyl-onyl imide is arranged also, but its synthetic be the method that adopts monomer polymerization.Pertinent literature is referring to 1) Hofmann, M.A.; Ambler, C.M.; Maher, A.E.; Chalkova, E.; Zhou, X.Y.; Lvov, S.N.; Allcock, H.R.Macromolecules 2002,35, and 6490.2) Thomas, B.H.; Shafer, G.; Ma, J.J.; Tu, M.H.; DesMarteau, D.D.J.Fluorine Chem.2004,125,1231.3) Feiring, A.E.; Choi, S.K.; Doyle, M.; Wonchoba, E.R.Macromolecules 2000,33, and 9262.
Summary of the invention
The object of the present invention is to provide a kind of high molecular polymer and synthetic method thereof that contains perfluoroalkyl sulfimide side chain.This high molecular polymer has high thermostability, can be used as solid acid catalyst and electrolyte.Its synthetic method is simple, cost is low, helps suitability for industrialized production.
The high molecular polymer that contains perfluoroalkyl sulfimide side chain provided by the invention, its structural formula is:
Wherein, PO is poly phenol oxygen phosphonitrile, crosslinked polystyrene or the polystyrene with benzene alkyl group side chain, and this benzene alkyl group side chain is connected on the high molecular phenyl ring of polystyrene; R
fBe C
1～C
8Perfluoroalkyl, when PO was the poly phenol oxygen phosphonitrile, perfluoroalkyl sulfimide side chain was connected on the phenyl ring of poly phenol oxygen phosphonitrile; When PO was crosslinked polystyrene, perfluoroalkyl sulfimide side chain was connected on the benzene ring of polystyrene; When PO is when having the polystyrene of benzene alkyl group side chain, perfluoroalkyl sulfimide side chain is connected on the phenyl ring of this benzene alkyl group side chain.
Above-mentioned synthesis method for high molecular polymer the steps include:
(1) poly phenol oxygen phosphonitrile, crosslinked polystyrene or polystyrene with the long side chain of alkyl are dissolved in the chloroform, stir down in ice-water bath and add chlorsulfonic acid, the mass ratio of chlorsulfonic acid and above-mentioned polymkeric substance is 2: 1-3: 1; Reacted 4～8 hours down in 60～80 ℃, the reaction back adds excessive thionyl chloride, mixture is poured in the frozen water after reaction is finished again, and the solid of separating out is washed with distilled water to neutrality, and drying under reduced pressure obtains pale solid then;
(2) above-mentioned pale solid is dissolved in the chloroform, add perfluor sulfonyl amine again, the mass ratio of perfluor sulfonyl amine and pale solid is 1.2: 1-1.5: 1, drip triethylamine again, the mass ratio of triethylamine and pale solid is 1: 1.5-1: 1, reacted 24～48 hours down in 50～80 ℃; After finishing, reaction, obtains yellow solid after the vacuum-drying with hydrochloric acid and water washing.
The present invention compares with existing sulfonate resin, because the introducing of perfluoroalkyl sulfimide base has strengthened its thermostability, the influence of the strong electron-withdrawing group on N atom both sides very easily dissociates hydrogen on the N and shows stronger acidity, and its acidity is stronger than sulfonate resin.For esterification, the Dies-Alder reaction, the Friedel-Crafts reaction waits all good catalytic effect.The present invention can be dissolved in except that the poly phenol oxygen phosphazene compound the intensive polar solvents such as acetonitrile, and the polystyrene compound does not dissolve in most organic solvents.The high molecular polymer that the present invention obtains all has very strong acidity and good thermostability, for esterification, and the Dies-Alder reaction, the Friedel-Crafts reaction waits all good catalytic effect, and can be repeatedly used.So, have the potential using value aspect green organic catalyst compound and electrolyte.
Synthetic method of the present invention directly adopts the commercialization polymkeric substance, inserts the sulfimide group by two-step reaction on side chain.This method is simple, cost is low, helps suitability for industrialized production.
Description of drawings
Fig. 1 is a perfluor sulfonyl imines poly phenol oxygen phosphonitrile IR spectrum;
Fig. 2 is a perfluor sulfonyl imines poly phenol oxygen phosphonitrile
1The HNMR spectrum
Fig. 3 is a perfluor sulfonyl imines poly phenol oxygen phosphonitrile
19The FNMR spectrum
Fig. 4 is the TGA figure of perfluor sulfonyl imines poly phenol oxygen phosphonitrile;
Fig. 5 is perfluor sulfonyl imines poly phenol oxygen phosphonitrile DSC figure;
Fig. 6 is the SEM figure of perfluor sulfonyl imines polystyrene;
Fig. 7 is the SEM figure of perfluor sulfonyl imines benzene alkyl group side chain polystyrene.
Embodiment
The high molecular general building-up reactions equation of such perfluoroalkyl sulfimide is as follows:
Wherein, PO is poly phenol oxygen phosphonitrile, crosslinked polystyrene or the polystyrene with benzene alkyl group side chain; R
fBe C
1～C
8Perfluoroalkyl.
Perfluoroalkyl sulfimide side chain poly phenol oxygen phosphonitrile and fluorine-containing sulfimide side chain polystyrene, its structural formula is respectively:
R
fBe C
1～C
8Perfluoroalkyl.
Structural characterization: adopt Varian Mercury VX-300 nuclear-magnetism that polymkeric substance is carried out
1The HNMR test adopts INOVA-600 to carry out
19The FNMR test; Adopt Brucker EQUINOX infrared spectrometer to carry out infrared test, molecular weight determination is carried out in Agilent 1100 gel infiltration looks shop, PerkinElmer TGA 7, DSC 7 Thermo Systems carry out thermal performance test, Quanta 200 scanning electronic microscope (SEM).
Embodiment 1: all alkyl fluorine sulfimide side chain poly phenol oxygen phosphonitrile synthetic
(1). the chlorosulphonation of poly phenol oxygen phosphonitrile
Take by weighing 1.24g poly phenol oxygen phosphonitrile, add the 6ml chloroform.Stirring makes it dissolving, under condition of ice bath, add the 2.48g chlorsulfonic acid then, behind 60 ℃ of reaction 4h, add the 5.5ml thionyl chloride, continue reaction 1h, mixture is poured in a large amount of frozen water, separate out solid, with this solid with a large amount of distilled water washs to neutral, drying under reduced pressure then, obtain white solid 1.87g, i.e. poly phenol oxygen phosphonitrile after the chlorosulphonation.
(2). the reaction of polyphenyl SULPHURYL CHLORIDE phosphonitrile and perfluor sulfonyl amine
Take by weighing the poly phenol oxygen phosphonitrile after the 1.30g chlorosulphonation, add 5ml chloroform and 1.56g perfluoro-methyl sulphonamide, slowly drip the 1.3g triethylamine then, in 50 ℃ of reactions 24 hours.After having reacted, use dilute hydrochloric acid, deionized water wash, vacuum-drying, dialysis purification obtain yellow solid 2.63g.Structural characterization:
IR:3204cm
-1The peak, for the absorption peak of sulfimide N-H, at 1000-500cm
-1Between the serial absorption peak of C-F is arranged, see Fig. 1.
1Near the H NMR:8.9ppm peak is the peak that N goes up the H that connects, and sees Fig. 2.
19F NMR:-80.8 ,-113.5 ,-121.6 ,-126.2ppm sees Fig. 3.
TGA, dsc analysis the results are shown in Figure 4, Fig. 5.As seen polymkeric substance just begins to decompose at 180 ℃, and its thermostability is good than sulfonate resin.
Embodiment 2: all alkyl fluorine sulfimide side chain crosslinked polystyrene synthetic
(1) take by weighing crosslinked polystyrene 20g, add 1,2-ethylene dichloride 40ml adds the 60g chlorsulfonic acid, reacts 6 hours down in 80 ℃.Reaction is poured mixture in the frozen water into after finishing, and the washing solid is extremely neutral, vacuum-drying, and the gained solid is used SOCl again
2Handle chlorosulphonation polystyrene 33.6g.
(2) get above-mentioned 4.90g chlorosulphonation polystyrene, 6.86g perfluor sulfonyl amine (C
4F
9SO
2NH
2), at 25mlCH
2ClCH
2In the Cl solvent, drip triethylamine (7g), temperature is controlled at 80 ℃, reacted 48 hours, and after having reacted, with the rare HCl of 50ml, the 50ml chloroform, the 250ml deionized water washes successively, extracting and purifying, drying under reduced pressure then.Product is 9.68g.
The result of structural characterization: SEM test shows the vesicular structure (Fig. 6) of perfluor sulfonyl imines polystyrene.
Embodiment 3: contain the synthetic of benzene alkyl group side chain polystyrene all alkyl fluorine sulfimide
(1) take by weighing the uncrosslinked side chain polystyrene 10g that contains, add 10ml 1, the 2-ethylene dichloride adds the 25g chlorsulfonic acid then, and in 60 ℃ of reactions 8 hours down, the reaction later stage adds 14ml SOCl
2, after reaction finishes mixture is poured in the frozen water, the washing solid is to neutral, vacuum-drying, the chlorosulphonation polymer.
(2) take by weighing chlorosulphonation polymer 5.0g, 7.5g perfluor sulfonyl amine (C
8F
17SO
2NH
2) adding 25ml CH
2ClCH
2Cl slowly drips triethylamine 7.5g, and temperature is controlled at 60 ℃, reacts 40 hours, after having reacted, uses rare HCl, chloroform, and deionized water washes successively, extracting and purifying, drying under reduced pressure gets product 11.6g then.
The result of structural characterization: SEM test shows the vesicular structure (Fig. 7) of perfluor sulfonyl imines benzene alkyl group side chain polystyrene.
Embodiment 4: catalysis butyl benzoate synthetic
Above-mentioned perfluoroalkyl sulfimide polymkeric substance, phenylformic acid with 10% mole: propyl carbinol (1: 2 mol ratio) is dissolved in the 20ml hexanaphthene, reflux water-dividing reaction 4 hours.Behind the filtration catalizer, through extract, wash, separate butyl benzoate, productive rate 96%.Catalyzer is reused 5 times, and is active constant.
Embodiment 5: catalysis Diels-Alder reaction
Above-mentioned perfluoroalkyl sulfimide polymkeric substance, cyclopentadiene with 2% mole: methyl vinyl ketone (1.2: 1 mol ratios) and 10ml CH
2Cl
2Solvent adds at the bottom of the 25ml garden in the flask, at room temperature reacts 6 hours.Behind the filtration catalizer, through extract, wash, separate adduct, productive rate is 99%.Catalyzer is reused 5 times, and is active constant.
Embodiment 6: catalysis Friedel-Crafts alkylated reaction
Above-mentioned perfluoroalkyl sulfimide polymkeric substance, Resorcinol with 10% mole: the trimethyl carbinol (1: 2 mol ratio), 25ml toluene add at the bottom of the 50ml garden in the flask, 100 ℃ of reactions 5 hours.Behind the filtration catalizer, through extract, wash, separate substitution product.The selectivity of single tertiary butyl substitution product reaches 60%, and catalyzer is reused 5 times, and is active constant.
Claims (2)
1, the high molecular polymer that contains perfluoroalkyl sulfimide side chain, its structural formula is:
Wherein, PO is poly phenol oxygen phosphonitrile, crosslinked polystyrene or the polystyrene with benzene alkyl group side chain, and this benzene alkyl group side chain is connected on the high molecular phenyl ring of polystyrene; R
fBe C
1～C
8Perfluoroalkyl; When PO was the poly phenol oxygen phosphonitrile, perfluoroalkyl sulfimide side chain was connected on the phenyl ring of poly phenol oxygen phosphonitrile; When PO was crosslinked polystyrene, perfluoroalkyl sulfimide side chain was connected on the benzene ring of polystyrene; When PO is when having the polystyrene of benzene alkyl group side chain, perfluoroalkyl sulfimide side chain is connected on the phenyl ring of this benzene alkyl group side chain.
2, the described synthesis method for high molecular polymer of claim 1 the steps include:
(1) poly phenol oxygen phosphonitrile, crosslinked polystyrene or polystyrene with the long side chain of alkyl are dissolved in the chloroform, stir down in ice-water bath and add chlorsulfonic acid, the mass ratio of chlorsulfonic acid and above-mentioned polymkeric substance is 2: 1-3: 1; Reacted 4～8 hours down in 60～80 ℃, the reaction back adds excessive thionyl chloride, mixture is poured in the frozen water after reaction is finished again, and the solid of separating out is washed with distilled water to neutrality, and drying under reduced pressure obtains pale solid then;
(2) above-mentioned pale solid is dissolved in the chloroform, add perfluor sulfonyl amine again, the mass ratio of perfluor sulfonyl amine and pale solid is 1.2: 1-1.5: 1, drip triethylamine again, the mass ratio of triethylamine and pale solid is 1: 1.5-1: 1, reacted 24～48 hours down in 50～80 ℃; After finishing, reaction, obtains yellow solid after the vacuum-drying with hydrochloric acid and water washing.
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| US8759578B2 (en) | 2010-05-26 | 2014-06-24 | Mitsubishi Materials Corporation | Method for manufacturing fluorine-containing imide compound |
| CN103509153B (en) * | 2012-06-15 | 2016-05-25 | 华中科技大学 | A kind of polymer list ionic electrolytes and preparation method thereof |
| CN103638972B (en) * | 2013-12-10 | 2016-01-20 | 王金明 | A kind of Catalysts and its preparation method of lactate synthesis Trifluoroacetic Acid Ethyl Ester |
| CN103804713B (en) * | 2014-02-19 | 2016-05-18 | 华中农业大学 | The acid resin of a kind of porous perfluoroalkyl sulfimide and application thereof |
| CN104592454A (en) * | 2014-12-29 | 2015-05-06 | 徐虎林 | Preparation method of sulfonated polyphosphazene copolymer proton exchange membrane material and sulfonated polyphosphazene copolymer proton exchange membrane |
| WO2017015996A1 (en) * | 2015-07-28 | 2017-02-02 | 东莞市凯欣电池材料有限公司 | Phosphonitrile fluoroalkyl sulfimide alkali metal salt and electrolyte solution containing the metal salt |
| CN108912335A (en) * | 2018-05-04 | 2018-11-30 | 惠州市大道新材料科技有限公司 | Application in phosphonitrile polyanion alkali metal salt and preparation method thereof and nonaqueous electrolytic solution |
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| CN1475471A (en) * | 2003-06-27 | 2004-02-18 | 中国科学院上海有机化学研究所 | 1-aryl-2 perluoro or polyfluoro phenyl ethylene and its derirative, its synthesis and application |
| CN1496372A (en) * | 2001-03-12 | 2004-05-12 | ��ѧ����������ҵ�� | High polymer-supported arylbis(perfluoroalkylsulfonyl)-methane |
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| CN1475471A (en) * | 2003-06-27 | 2004-02-18 | 中国科学院上海有机化学研究所 | 1-aryl-2 perluoro or polyfluoro phenyl ethylene and its derirative, its synthesis and application |
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Assignee: Wuhan Jinghe Chemical Co., Ltd. Assignor: Huazhong University of Science and Technology Contract fulfillment period: 2009.4.8 to 2015.4.8 contract change Contract record no.: 2009420010027 Denomination of invention: High-molecular polymer containing perfluoro alkyl sulfimine side-chain and its synthesizing method Granted publication date: 20070117 License type: Exclusive license Record date: 2009.6.5 |
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