CN1640895A - High-molecular polymer containing perfluoro alkyl sulfimine side-chain and its synthesizing method - Google Patents

Abstract

The present invention discloses one kind of polymer containing perfluoroalkyl sulfonyl imido side chain. It is synthesized through chlorosulfonating one of polyhydroxy ether phosphonitrile, crosslinked polystyrene and polystyrene with alkyl long side chain; grafting sulfuryl chloride group to the benzene ring; and final reaction with perfluoro sulfonamide. The obtained polymer containing perfluoroalkyl sulfonyl imido side chain has strong acidity and excellent heat stability, and excellent catalyzing effect on esterification, Dies-Alder reaction, Friedel-Crafts reaction, etc., and may be reused. Therefore, the present invention has latent value in use as green organic synthesis catalyst and electrolyte material. It has simple synthesis and low cost, and is favorable to industrial production.

Description

The high molecular polymer and the synthetic method thereof that contain perfluoroalkyl sulfimide side chain

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.

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 polyphosphonitrile, crosslinked polystyrene or the polystyrene with alkyl group side chain; R _fBe C ₁～C ₈Perfluoroalkyl.

Above-mentioned synthesis method for high molecular polymer the steps include:

(1) polyphosphonitrile, 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 polyphosphonitrile 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 polyphosphonitrile IR spectrum;

Fig. 2 is a perfluor sulfonyl imines polyphosphonitrile ¹The HNMR spectrum

Fig. 3 is a perfluor sulfonyl imines polyphosphonitrile ¹⁹The FNMR spectrum

Fig. 4 is the TGA figure of perfluor sulfonyl imines polyphosphonitrile;

Fig. 5 is perfluor sulfonyl imines polyphosphonitrile DSC figure;

Fig. 6 is the SEM figure of perfluor sulfonyl imines polystyrene;

Fig. 7 is the SEM figure of perfluor sulfonyl imines alkyl group side chain polystyrene.

Embodiment

The high molecular general building-up reactions equation of such perfluoroalkyl sulfimide is as follows:

Wherein, PO is polyphosphonitrile, crosslinked polystyrene or the polystyrene with alkyl group side chain; R ^fBe C ₁～C ₈Perfluoroalkyl.

Perfluoroalkyl sulfimide side chain polyphosphonitrile 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 polyphosphonitrile 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 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 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-Craffs 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 polyphosphonitrile, crosslinked polystyrene or the polystyrene with alkyl group side chain; R _fBe C ₁～C ₈Perfluoroalkyl.

2, the described synthesis method for high molecular polymer of claim 1 the steps include:

(1) polyphosphonitrile, 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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