CN1389486A - Fluororesin containing sulfonyl structure and its pnepn. and use - Google Patents

Abstract

The invention relates to a fluorine resin containing a sulfone group structure which is excellent in corrosion resistance, wear resistance, oil repellency and dirt resistance, high temperature resistance, electrical insulation performance and processing performance, a production method and its application. The fluororesin with a sulfone group structure has the following structural formula: wherein, n=5-6000; R or R ¹ = aromatic group or an aromatic group substituted by R ² or R ³ , and the aromatic group may be a benzene ring , biphenyl ring, substituted benzene ring, etc. R ² or R ³ = hydrogen, perfluoroalkyl, alkyl or other inert substituents. Its weight average molecular weight _Mw is 2000-900000. It is polymerized separately from the polymer monomer bis(trifluoroethyleneoxy)diaryl sulfoxide or bis(trifluoroethyleneoxy)diarylsulfone. It can be used as a surface coating film material for metal material substitutes, eating utensils, sanitary appliances, medical appliances, etc.

Description

Fluorine resin containing sulfone group structure, production method and use thereof

technical field

The present invention relates to a kind of fluorine resin containing sulfone group structure, its production method and its use. Specifically, it relates to a fluorine resin containing a sulfone group structure excellent in corrosion resistance, wear resistance, oil repellency and stain resistance, high temperature resistance, electrical insulation performance and processability, a production method and its use.

Background technique

Due to the excellent thermal stability, corrosion resistance, electrical insulation, low surface tension and other properties of fluororesin, it has been widely used in all walks of life in national defense, industry and life (JP-A-60-234618 bulletin, Japanese Patent Publication No. 7-55182). However, due to the poor processability of the conventional fluororesin in the past, and the defects of the specific use performance caused by it, it has brought inconvenience to the practical application. For example, the patent application with the Chinese Publication No. CN1265942A is an improvement aimed at the defect that the high molecular weight of the fluororesin is difficult to form a uniform and smooth coating film through the coating; its technical points are limited to the existing fluorine resin. Resin compounding cannot fundamentally overcome the defects of uneven coating and poor wear resistance caused by high molecular weight. Similarly, Chinese patent CN1019081B’s technical solution for improving the wear resistance of fluororesin coatings is to compound polyamide resin, polyimide resin, polyphenylene sulfide resin, poly Ethersulfone resins or their mixtures. Although this type of method can play a certain role, its process is complex, and the conventional fluororesin used cannot achieve good results due to its inherent defects.

Contents of the invention

The object of the present invention is to provide a kind of fluororesin with sulfone group structure which is excellent in corrosion resistance, wear resistance, oil repellency, anti-pollution, high temperature resistance, electrical insulation performance and processability.

Another object of the present invention is to provide a method for producing a sulfone group-containing structure-containing fluororesin having excellent properties as described above.

The object of the present invention also provides the application of the fluororesin containing the sulfone group structure which is excellent in the above-mentioned various characteristics, and the fluororesin containing the sulfone group structure of the present invention can be conveniently used as a coating material in various fields of national defense, industry and life , especially for the coating of polysulfone materials in the food hygiene industry.

In order to overcome the above-mentioned technical defects in the past, the present invention obtains a resin with ideal properties, so that it is suitable for use as a surface coating material for cooking utensils such as pots, steamers, and rice cookers, industrial utensils, and appliances in the field of electrical machinery, especially The surface coating resin of polymer polysulfone and polyether materials is based on a new type of fluorine-containing polymer developed by Dow Corporation in the United States since the early 1990s, and a new type of polymer unit is molecularly designed. body, and through appropriate polymerization conditions, a fluororesin containing a sulfone group structure can be obtained.

The molecular structure general formula of the fluororesin monomer containing sulfone group structure of the present invention is: CF ₂ =CF-ORS(O) _m -R ¹ -O-CF=CF ₂ , the fluororesin containing sulfone group structure of the present invention It is a chain-shaped or body-shaped polymer obtained by the cyclodimerization reaction of the above-mentioned fluororesin monomer under heat, and has the following structural formula:

Among them, n=5-6000, m=1, 2; R or R ¹ = aromatic group or aromatic group substituted by R ² or R ³ , the aromatic group can be benzene ring, biphenyl ring, substituted benzene ring etc. R ² or R ³ = hydrogen, perfluoroalkyl, alkyl or other inert substituents. Its weight average molecular weight _Mw is 2000-900000.

One of the manufacturing methods of fluororesin monomers provided by the present invention is to use trifluorovinyloxy bromoaromatic compounds, such as 4-(trifluorovinyloxy) bromoaromatic compounds (2), or other positions with inert The Grignard reagent of the trifluorovinyloxy group ^R2 or ^R3 substituted bromoaromatic compound is reacted with thionyl chloride and further obtained by oxidation reaction. Wherein the Grignard reagent system of the trifluorovinyloxy group R ² or R substituted bromoaromatic compound ( ² ) is made with reference to the U.S. "Macromolecules" magazine (DWSmith, Jr.; Babb, DA Macromolecules 1996,29,852- 860). This document is to use p-bromoaryl phenol as starting raw material, and alkali (such as KOH) in DMSO solvent, with toluene as azeotrope, after several hours of water removal, add 1 to the reaction system that is basically anhydrous, 2-Dibromotetrafluoroethane to give 4-(1-bromotetrafluoroethoxy)bromobenzene (1). Compound 1 can be obtained in pure form by distillation under reduced pressure. The pure compound 1 is debrominated and fluorinated with zinc powder under the condition of reflux in acetonitrile solvent to obtain 4-(trifluorovinyloxy) R ² or R ³ substituted bromoaromatic compound (2). Compound 2 was treated with magnesium to obtain the corresponding Grignard reagent.

In an organic solvent, the Grignard reagent of the above-mentioned trifluorovinyloxy ^R2 or ^R3 substituted bromine aromatic compound, that is, the ^R2 or/and ^R3 substituted or unsubstituted trifluorovinyloxy bromide aromatic compound The Grignard reagent is added to thionyl chloride, and the molar ratio of Grignard reagent to thionyl chloride can vary between 1-4:1, preferably between 1.8-2.4:1. The organic solvent is preferably anhydrous tetrahydrofuran or anhydrous ether; of course, the thionyl dihalide can be thionyl chloride, thionyl bromide or thionyl iodide, etc. The reaction temperature can be varied between -70°C and reflux temperature, and the reaction time is 1 hour to 200 hours. The preferred temperature range is between -10°C and 70°C, and the preferred time is between 4 hours and 48 hours. After the reaction, the reaction is treated with an oxidizing agent to obtain two-trifluoroethyleneoxy bis (R ² or/and R ³ substituted aryl) sulfoxides. When the Grignard reagent reacts, the ideal way is to keep the reaction solution at about 0°C during the dropwise addition stage. After the dropwise addition is completed, slowly raise the temperature to make it react under reflux for 10 hours. When the organic solvent is tetrahydrofuran, it is 65°C. . When the aryl group is phenyl, 4,4'-(trifluoroethyleneoxy)diphenylsulfoxide (3) is obtained, and compound 3 is treated and oxidized with an oxidizing agent to obtain 4,4'-trifluoroethyleneoxydiarylsulfone. The reaction formula is as follows:

Commonly used oxidants include hydrogen peroxide, organic peroxyacid, chromic acid, permanganate or selenium dioxide, etc. Other oxidation methods such as catalytic oxidation and electrolytic oxidation can also be used for oxidation. A better way is to use hydrogen peroxide as oxidant and organic acid as solvent, or use organic peroxyacid as oxidant and chemical liquid capable of dissolving compound 3 as solvent. The reaction time is generally 1-100 hours, preferably 4-48 hours.

Another method for producing fluororesin monomers is to use 4,4'-(dihydroxy)bis(R ² or R ³ to replace aryl)sulfone, 4,4'-(dihydroxy)bis(R ² or R ³ Substituted aryl)sulfoxide or other 4,4'-(dihydroxy)bis( ^R2 or ^R3 substituted aryl)sulfones with inert substituents ^R2 or ^R3 , 4,4'-(dihydroxy ) When two (R ² or ^R substituted aryl) sulfoxides are starting materials, react with a base to obtain phenoxide. The base can be organic base or inorganic base ^, preferably potassium hydroxide, sodium ^hydroxide and other inorganic bases. Between 0.1-10:1, the preferred range of molar ratio is between 2-4:1. After obtaining the phenoxide, use 1,2-dibromotetrafluoroethane and 4,4'-dihydroxybis( ^R2 or ^R3 substituted aryl)sulfone in a molar ratio of 2:1 for fluoroalkylation , to obtain 4,4'-bis(1-bromotetrafluoroethoxy)bis(R ² or R ³ substituted aryl)sulfone (5). Compound 5 is treated in a polar solvent such as acetonitrile, when the molar ratio of zinc is 1:1-2, the reaction temperature is preferably in a reflux state. When the solvent is acetonitrile, the reaction temperature is preferably 82 ° C. Reaction 3-120 After hours, the monomer can be obtained, for example, compound 4 can be obtained when the aryl is phenyl. For example, when aryl is phenyl, the reaction formula is as follows:

The preferred method is to select a polar aprotic solvent such as dimethyl sulfoxide (DMSO), and add an azeotrope of water such as benzene, toluene, xylene, etc. to it, and the reaction device is equipped with a Dunsta water separator . In the process of reacting with alkali to obtain phenate, water and azeotrope are evaporated together. When standing for stratification, because of the large proportion of water, the lower layer is water and the upper layer is azeotrope, and the azeotrope can be returned to the reaction bottle. In order to achieve the purpose of circulating water removal. The effect of the water removal step is to remove the water that can cause side reactions, so as not to generate a kind of sulfone such as 4,4'-two (tetrafluoroethoxy) two (R ² or ^R substituted aryl) sulfone, so that the product rate drops. This step is not necessary to obtain the product, and can be skipped if the yield is not considered. When using 1,2-dibromotetrafluoroethane for fluoroalkylation reaction, the reaction temperature can be selected between -10-180°C, and the best practice is to control the temperature between 0-30°C during the dropping stage After the dropwise addition is completed, the temperature is controlled between 20-40°C.

The fluorine resin containing sulfone group structure of the present invention is composed of the above-mentioned polymer monomer 4,4'-(trifluoroethyleneoxy)bis(R ² or R ³ substituted aryl)sulfoxide (3) or 4,4 '-(trifluoroethyleneoxy)bis(R ² or R ³ substituted aryl)sulfone (4), obtained by thermal cyclopolymerization. The polymerization temperature is carried out between 120-280°C, preferably between 160-220°C. The polymerization method can be bulk polymerization or solution polymerization. When solution polymerization is adopted, the solution used is generally 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3- Aproton scavengers such as triethylbenzene or polyhalogenated aromatic compounds. When the monomers of the present invention are polymerized, no catalyst or initiator is required, and thus, the resulting polymer is free of impurities. What the present invention obtains is a kind of polymer of chain shape or body type, and the polyreaction of general monomer is as follows:

Compared with conventional fluororesins, the fluororesin monomer involved in the present invention has two structural features. One is that there is a trifluorovinyl aryl ether (TFVE) structure in the monomer. Due to the strong electron-attracting force of the fluorine atom, the electron cloud of the C-F bond is greatly biased towards the F atom, so that the electrons in the outer shell of the F atom tend to be saturated, so the F on the double bond is not attractive to the electron cloud of the π bond , but a repulsive force. The stress on this double bond is greater compared to hydrogen bonded olefins. Therefore, the π bond is very unstable, and it is easy to undergo cyclodimerization reaction under the condition of heating.

When there are two or more of the above-mentioned trifluorovinyl ether (TFVE) structures in the polymer monomer, a chain or body polymer is obtained after a cyclodimerization reaction occurs under heat. The main chain of the obtained polymer contains aryl ether group and perfluorocyclobutyl group. The perfluorocyclobutyl structure endows the polymer with the excellent properties of general fluorine-containing polymers, that is, excellent electrical insulation performance, thermal stability and chemical stability. At the same time, the main chain of this type of polymer also contains aryl ether groups, which makes this type of thermoplastic polymer and thermosetting prepolymer soluble in various organic solvents, thus having good processing performance.

Another feature of the present invention is that a sulfonyl structure or a sulfinyl structure is compounded in the polymer monomer, and there are sulfonyl or sulfinyl groups on the main chain of the polymer thus obtained, thus also compounding general polyphenylsulfone or properties of polysulfoxide materials. Therefore, in terms of performance, the fluororesin containing sulfone group structure of the present invention has better wear resistance than a composite fluororesin coating in Chinese Patent No. CN1019081B. In addition, due to its excellent thermal stability and chemical stability, polyphenylsulfone resin has been used as a substitute for metal materials, and is widely used in eating utensils, sanitary equipment, medical equipment, etc. However, its surface properties are poor, so its oil repellency, stain resistance and wear resistance are poor. The present invention can be used as the surface coating film material of such eating utensils, sanitary appliances, and medical appliances to achieve the purpose of oil repellency and antifouling. , due to its good processability and phenylsulfone group in its structure, it has good combination with the substrate of polyphenylsulfone resin, making this type of film layer difficult to foam.

The use of the fluororesin with a sulfone group structure of the present invention is flexible and changeable. Different processes can be selected according to specific usage conditions.

In application, the fluororesin high polymer containing sulfone group structure of the present invention can be dissolved in a specific solvent, and coated by a conventional spraying method, and then, the desired film-forming coating can be obtained after the solvent is volatilized. In order to get a better film-forming effect, oligomers with a low molecular weight (molecular weight between 2000-10000) can also be coated on the application object, and then the temperature is raised to allow further curing reaction.

In addition, the polymer monomer of the present invention can be compounded with other polymer monomers containing trifluorovinylaryl ether structure to obtain copolymers with different ratios. For example, it can be copolymerized with a trifluorovinyl aryl ether monomer containing a silicon oxygen chain (according to Polym. Polymer with cyclobutyl structure. The ratio of the two polymer monomers can be selected according to specific usage conditions. The mole percentage of monomers in the polymers of this invention can vary from 5% to 95%. Typically, the mole percent of monomers in the polymers of the present invention is from 30% to 70%.

In order to obtain a thermosetting resin with better thermal stability, the polymer monomer of the present invention can be co-prepolymerized with a trifluorovinyl ether (TFVE) monomer with trifunctionality to obtain a low molecular weight (3000-20000) of prepolymers. The molecular mole percentage of the polymer monomer of the present invention and the thermosetting polymer monomer can also vary from 30% to 99% according to specific usage conditions. Typically, the mole percent of monomers in the polymers of the present invention is from 60% to 96%. After the prepolymer is coated on the application object, it can be heated to a certain temperature to cross-link and solidify to form a film.

best practice

The present invention will be described below through specific examples. All examples are only illustrative of the present invention, not limiting thereof.

Embodiment 1: Taking p-bromophenol as starting material to synthesize 4,4'-trifluorovinyl ether diphenyl sulfone

Add 1007.33 grams (5.82 moles) of p-bromophenol, 373.79 grams (5.82 moles) of potassium hydroxide, 3.2 liters of dimethyl sulfoxide, and 0.8 liters of toluene in a 5-liter three-necked flask equipped with a Dunnite water separator . The temperature of the mixture was raised to 110° C. and kept for 24 hours to remove water in the reaction system. It was then cooled to room temperature and 1665 g (6.4 moles) of 1,2-dibromotetrafluoroethane was added slowly at 30°C over four hours to keep the temperature below 35°C. After the addition was completed, the reaction solution was reacted at 20° C. for 20 hours. The reaction solution was diluted with water to terminate the reaction, extracted with dichloromethane, the organic layer was washed three times with distilled water, and dried over magnesium sulfate. Remove solvent, under the condition of reduced pressure, collect the cut when 105-107 ℃ under the pressure of 20mm mercury column, be 4-(1-bromotetrafluoroethoxy) bromobenzene (1), obtain 1477.9 grams of product (product The rate is 72%) and the related data are as follows: ¹ H NMR (400MHz, CDCl ₃ ): δ7.06 (2H, d, J=8.4Hz), 7.45 (2H, d, J=8.8Hz); ¹⁹ F NMR ( 376MHz, CDCl3): δ-86.60(t, J=4.57Hz), -68.58(t, J=4.57Hz); IR: 1592, 1484(Ar), 1328, 1201, 1164, 1132, 1099, 1012, 933cm ^-1 ; MS m/z (%): 354(46), 352(100), 351(39), 157(25), 155(25), 63(40), 50(27).

1477.9 grams of compound obtained in the previous step reaction was slowly added to a three-necked flask equipped with 3.5 liters of acetonitrile solution and 302 grams of zinc powder under nitrogen protection, and the reaction solution was refluxed for 10 hours, then the acetonitrile was distilled off, extracted three times with n-hexane, The solvent was spin-dried, and the product was evaporated under reduced pressure to obtain 843.5 g of a fraction at 70-72° C. under a pressure of 20 mm Hg (yield 79.4%), which was 4-(trifluoroethyleneoxy)bromobenzene 2. The spectral data are as follows: ¹ H NMR (400MHz, CDCl ₃ ): δ6.95 (2H, d, J=8.7Hz), 7.43 (2H, d, J=8.7Hz); ¹⁹ F NMR (376MHz, CDCl ₃ ): δ-119.8 (1F, cis-CF=CF ₂ , F _a ), -126.7 (1F, trans-CF=CF ₂ , F _b ), -134.9 (1F, CF=CF ₂ , Fc); IR: 1832(CF=CF ₂ ), 1592, 1482(Ar), 1318, 1288, 1200, 1165, 1143, 1074, 1015, 822cm ^-1 ; MS m/z(%): 254(72), 253(12) , 173(51), 157(36), 155(40), 63(16), 50(72).

Slowly add 100.6 grams of the above compound 2 dropwise to 11.6 grams of magnesium chips and 600 ml of anhydrous tetrahydrofuran. After the magnesium chips have basically disappeared, 23.8 grams of thionyl chloride are added dropwise to the Grignard reagent. After reacting at room temperature for 10 hours, the reaction was continued for 10 hours under reflux. After post-treatment, 32 grams (40%) of 4,4'-trifluoroethyleneoxydiphenyl sulfoxide (3) was obtained, and the compound 3 was dissolved in acetic acid, and oxidized with hydrogen peroxide to obtain 4,4' - Trifluoroethyleneoxydiphenylsulfone (4) 30.6 g (95%). Compound (4) has a melting point of 67-69°C. The spectra of compounds 3 and 4 are as follows:

Compound 3: ¹ H NMR (400MHz, CDCl ₃ ): δ7.25 (2H, d), 7.68 (2H, d); ¹⁹ FNMR (376 MHz, CDCl ₃ ): δ-119.5 (1F, cis-CF=CF ₂ , F _a ), -126.6 (1F, trans-CF=CF ₂ , F _b ), -134.5 (1F, CF=CF ₂ , Fc); IR: 1834 (CF=CF ₂ ), 1591, 1482 (Ar) , 1325(S=O), 1274, 1203, 1165, 1143, 1074, 1015, 835, 789, 556cm ^-1 ; MS m/z(%): 394(56), 346(100), 297(47) , 249(17), 221(48), 205(45), 189(40), 174(34), 152(85), 124(41), 76(63), 63(27), 50(50) ; Elemental analysis (W%): Molecular formula is the theoretical element content (W%) of the compound 3 of C ₁₆ H ₈ O ₃ F ₆ S: C, 48.69; H, 2.03; Carry out elemental analysis, actual result is as follows: C, 49.02; H, 2.23%.

Compound 4: ¹ H NMR (400MHz, CDCl ₃ ): δ7.23 (2H, d), 7.98 (2H, d); ¹⁹ FNMR (376 MHz, CDCl ₃ ): δ-119.5 (1F, cis-CF=CF ₂ , F _a ), -126.6 (1F, trans-CF=CF ₂ , F _b ), -134.5 (1F, CF=CF ₂ , Fc); IR: 1834 (CF=CF ₂ ), 1591, 1492 (Ar) , 1325 (S=O), 1274, 1203, 1158, 1142, 1108, 1073, 1011, 837, 789, 556 cm ^-1 ; MS m/z (%): 410 (80), 313 (33), 237 ( 49), 221(44), 173(56), 168(100), 152(21), 76(92), 63(16), 50(51); elemental analysis (W%): molecular formula is C ₁₆ H The theoretical element content (W%) of compound 4 of ₈ O ₄ F ₆ S is: C, 46.83, H, 1.95; the actual results of elemental analysis are as follows: C, 46.94; H, 2.13%.

Embodiment 2: Taking 4,4'-diphenol base diphenyl sulfone as starting material synthesis

                                                                                   

Add 500.54 grams (2.0 moles) of 4,4'-dihydroxydiphenylsulfone, 112.2 grams (2.0 moles) of potassium hydroxide, and 3.2 liters of dimethyl sulfoxide, 0.8 L of toluene. The temperature of the mixture was raised to 110°C and maintained for 24 hours to remove water in the reaction system. It was then cooled to room temperature, and 1143.12 g (4.4 moles) of 1,2-dibromotetrafluoroethane was slowly added at 30°C, and the addition was completed within 3 hours to keep the temperature below 35°C. After the addition was completed, the reaction solution was reacted at 20° C. for 20 hours. The reaction solution was diluted with water to terminate the reaction, extracted with dichloromethane, the organic layer was washed three times with distilled water, and the solvent was spin-dried to obtain a yellow solid. Recrystallized three times from a mixture of petroleum ether and ethyl acetate to obtain 863.36 g (yield: 71%) of a white needle-like solid with a melting point of 140-142°C. The white solid was measured as 4,4'-bis(1-bromotetrafluoroethoxy)diphenylsulfone (5), and its spectral data were as follows: Compound 4: ¹ H NMR (400MHz, CDCl ₃ ): δ7. 23 (2H, d), 7.98 (2H, d); ¹⁹ F NMR (376MHz, CDCl ₃ ): δ-86.60 (t, J=4.57Hz), -68.58 (t, J=4.57Hz); IR: 1591 , 1492(Ar), 1324(S=O), 1276, 1201, 1158, 1108, 1011, 837, 789, 556cm ^-1 ; MS m/z(%): 610(13, m+2), 608( 22), 321(100), 319(97.3), 289(11.1), 287(11.9), 181(17.2), 179(17.9), 131(8.2), 129(8.7), 95(11.6), 63( 12.7), 50 (6.8); Elemental analysis (W%): molecular formula is C ₁₆ H ₈ O ₄ F ₈ SBr The theoretical element content (W%) of _compound 5 is: C, 31.58, H, 1.32; Analysis, the actual results are as follows: C, 31.82; H, 1.55.

Add 863.36 grams of the above compound (5) and 102.15 grams (1.56 moles) of zinc powder into a 5-liter three-necked flask, and add 3.6 liters of acetonitrile as a solvent, and reflux for 24 hours under the protection of nitrogen. The acetonitrile was distilled off and the product was extracted from the solid residue with dichloromethane. Dichloromethane was spun out, and recrystallized with petroleum ether and ethyl acetate to obtain 378.43 g (65% yield) of white crystals. Its melting point is 67-69°C, and the rest of the spectrogram data is also consistent with compound (4), which is compound (4).

Embodiment 3: the bulk polymerization of polymer monomer 4

Take 5 grams of the above-mentioned compound 4, put it in a glass bottle, and under the protection of nitrogen gas, heat up to above the melting point, and it becomes molten. At this point, the magnet in the bottle started to stir, and the temperature was raised to 160°C and kept for 10 hours, then raised to 220°C and kept for 10 hours. During the heat preservation process, the polymerized liquid solidifies due to the increase in the degree of polymerization.

The obtained polymer was tested for properties, and the results were as follows: GPC analysis with THF as the solvent showed that _Mw = 33600, _Mn = 12760, _Mw / _Mn = 2.63; DSC test showed that _Tg = 128°C ; TGA test shows that in a nitrogen atmosphere, T _d (onset) = 516 ° C, while in an air atmosphere, T _d (onset) = 501 ° C. This result shows that the fluororesin having a sulfone group structure of the present invention is excellent in thermal stability.

Embodiment 4: the bulk polymerization of polymer monomer 4

Take 5 grams of the above-mentioned compound 4, dissolve it in 1,2,3-triethylbenzene, raise the temperature to 160°C, keep it for 10 hours, then raise the temperature to 210°C, and keep it for 12 hours. At this time, high molecular weight polymers were precipitated. The properties of the polymer were tested, and the results were as follows: GPC analysis with THF as the solvent showed that _Mw = 39630, _Mn = 23750, _Mw / _Mn = 1.67; DSC test showed that _Tg = 129°C ; TGA test shows that in nitrogen atmosphere, T _d (onset) = 518 ° C, and in air atmosphere, T _d (onset) = 503 ° C.

Claims (10)

1, a kind of fluoro-resin that contains the sulfuryl structure is that the general formula of molecular structure by fluororesin monomer is CF ₂=CF-O-R-S (O) _m-R ¹-O-CF=CF ₂Monomer be heated that what take place to obtain behind the cyclisation dimerization reaction is the polymkeric substance of a kind of chain or build, wherein m=1 or 2, R or R ¹=aromatic group or R is arranged ², R ³The aromatic group that replaces, R ²Or R ³=hydrogen, perfluoroalkyl, alkyl or other inert substituent.

2, a kind of fluoro-resin that contains the sulfuryl structure as claimed in claim 1 is characterized in that the described fluoro-resin that contains the sulfuryl structure has following structural formula:

Wherein n=5-6000, R or R ¹As claimed in claim.

3, a kind of fluoro-resin that contains the sulfuryl structure as claimed in claim 1 or 2 is characterized in that described aromatic group can be phenyl ring or cyclohexyl biphenyl.

4, a kind of fluoro-resin that contains the sulfuryl structure as claimed in claim 1 or 2, it is characterized in that the described fluoro-resin system of sulfuryl structure that contains is by polymer monomer 4,4 '-(trifluoro-ethylene oxygen base) thionyl benzene or 4,4 '-(trifluoro-ethylene oxygen base) sulfobenzide is polymerized respectively.

5, a kind of fluoro-resin production method that contains the sulfuryl structure as claimed in claim 1 is characterized in that described a kind of fluoro-resin that contains the sulfuryl structure is by following 1) and 3) or 2) and 3) method make respectively:

1) trifluoro vinyl oxygen base bromine (R ²Or/and R ³Replacing) Grignard reagent of aromatic compound adds and is dissolved with in the organic solvent of dihalide sulfoxide, and temperature of reaction is between-70 ℃ and reflux temperature, and reaction obtains 4,4 '-(trifluoro-ethylene oxygen base) two (R ²Or R ³The aryl that replaces) sulfoxide, this reaction product promptly gets 4,4 '-(trifluoro-ethylene oxygen base) two (R through the oxidation means ²Or R ³The aryl that replaces) sulfone.

2) with 4,4 '-(dihydroxyl) two (R ²Or R ³The aryl that replaces) when sulfoxide is starting raw material, 4,4 '-(dihydroxyl) two (R ²Or R ³The aryl that replaces) sulfone and organic bases or mineral alkali mol ratio are 1: the 0.1-10 reaction, obtain phenates, and use 1 again, the 2-dibromotetrafluoroethane carries out the fluoroalkylation reaction, obtains 4,4 '-two (1-bromine tetrafluoro oxyethyl groups), two (R ²Or R ³Substituted aryl) sulfone, 4,4 '-two (1-bromine tetrafluoro oxyethyl groups), two (R ²Or R ³Substituted aryl) sulfone is handled under conditions suitable with the active metal, carries out the dehalogenation reaction, promptly gets 4,4 '-(trifluoro-ethylene oxygen base) two (R ²Or R ³The aryl that replaces) sulfone.

3) by polymer monomer 4,4 '-(trifluoro-ethylene oxygen base) two (R ²Or R ³The aryl that replaces) sulfoxide or 4,4 '-(trifluoro-ethylene oxygen base) two (R ²Or R ³The aryl that replaces) sulfone is respectively at 150-250 ℃, and polyreaction 10-25 hour,

6, a kind of fluoro-resin production method that contains the sulfuryl structure as claimed in claim 5 is characterized in that described 1) in the method, organic solvent is anhydrous tetrahydro furan or anhydrous ether.

7, as claim 5 or 6 described a kind of fluoro-resin production methods that contain the sulfuryl structure, it is characterized in that described 1) in the method, described dihalide sulfoxide is thionyl chloride, dibromo sulfoxide or diiodo-sulfoxide.

8, as claim 5,6 or 7 described a kind of fluoro-resin production methods that contain the sulfuryl structure, it is characterized in that described 1) in the method, these oxidation means can adopt electrochemical oxidation process or carry out oxidation with oxygenant, and the oxygenant that is adopted generally is hydrogen peroxide, organic peroxide acid, chromic acid, permanganate or tin anhydride.

9, a kind of fluoro-resin production method that contains the sulfuryl structure as claimed in claim 5 is characterized in that described 2) in the method, the dehalogenation reaction be with metallic zinc in acetonitrile, under reflux temperature, carry out.

10, a kind of as claim 1,2,3,4,5, the 6 or 7 described purposes that contain the fluoro-resin of sulfuryl structure, it is characterized in that this fluoro-resin that contains the sulfuryl structure can be used for all trades and professions of national defence, industry and life as coated material, especially for filming of polysulfone material in the dietetic hygiene industry or polyarylether material apparatus.