CN1179987C - Fluororesin containing sulfonyl structure and its pnepn. and use - Google Patents
Fluororesin containing sulfonyl structure and its pnepn. and use Download PDFInfo
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- CN1179987C CN1179987C CNB021360049A CN02136004A CN1179987C CN 1179987 C CN1179987 C CN 1179987C CN B021360049 A CNB021360049 A CN B021360049A CN 02136004 A CN02136004 A CN 02136004A CN 1179987 C CN1179987 C CN 1179987C
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Abstract
The present invention relates to a fluororesin containing a sulfonyl structure and a preparing method and the application thereof, and the fluororesin has good corrosion resisting performance, good abrasive resisting performance, good oil and dirt resisting performance, good high temperature resisting performance, good electrical insulation performance and good processing performance. The fluororesin containing a sulfonyl structure has the following structural formula, wherein n is from 5 to 6000; R or R<1> is an aromatic group or an R2 or R3 substituted aromatic group; the aromatic group can be a benzene ring, a biphenyl ring, a substituted phenyl ring, etc. R2 or R3 is hydrogen, full-flourin alkyl, and alkyl or other inert substituted groups. The weight average molecular weight Mw is from 2000 to 900. The fluororesin is formed by the respective polymerization of polymer monomers two portions of (trifluoroethene oxyl) diaryl sulfoxide or two portions of (trifluoroethene oxyl) diaryl sulfone. The fluororesin can be used as membrane material coated on surface layers for metal material substitutes, food and drink utensils, sanitary apparatus, medical utensils, etc.
Description
Technical field
The present invention relates to fluoro-resin that a class contains the sulfuryl structure, manufacture method and uses thereof.In detail, relate to a kind of erosion resistance, wear resistance, refuse all good fluoro-resin that contains the sulfuryl structure of oily pollution resistance, high thermal resistance, electrical insulation capability and processing characteristics, manufacture method and uses thereof.
Background technology
Because fluoro-resin has excellent thermostability, erosion resistance, electrical insulating property, low performances such as surface tension, all trades and professions (spy opens clear 60-234618 communique, special fair 7-55182 communique) that have been widely used in national defence, industry and lived.But because conventional fluoro-resin poor processability in the past, and the defective of bringing concrete use properties thus, brought inconvenience to practical application.For example, Chinese publication number is applying for a patent of CN1265942A, forms even and level and smooth film this defective because of high molecular by coating is extremely difficult at always fluoro-resin exactly, and the improvement of carrying out; Its technical essential only limits to existing fluoro-resin is carried out composite, can not fundamentally overcome the defective that the coating of bringing because of high molecular is unsmooth and wear no resistance.With it similarly, be for Chinese patent CN1019081B number that composite in fluoro-resin have polyamide resin, polyimide resin, polyphenylene sulfoether resin, polyethersulfone resin or their mixture to the technical scheme that improves the fluorine resin coating material wear resistance.Though these class methods can be played a role, its complex process, and the conventional fluoro-resin that is adopted is because itself institute's inherent defective can not play good effect.
Summary of the invention
The purpose of this invention is to provide a class erosion resistance, wear resistance, refuse all good fluoro-resin that contains the sulfuryl structure of oily pollution resistance, high thermal resistance, electrical insulation capability and processing characteristics.
Another purpose of the present invention provides the manufacture method of all good fluoro-resin that contains the sulfuryl structure of above-mentioned various characteristics.
The object of the invention also provides the purposes of all good fluoro-resin that contains the sulfuryl structure of above-mentioned various characteristics, the fluoro-resin that contains the sulfuryl structure of the present invention can be easily in all trades and professions of national defence, industry and life as coated material, especially for filming of polysulfone material apparatus in the dietetic hygiene industry.
The present invention is in order to overcome above-mentioned technological deficiency always, obtain resin with ideal performance, to be suitable for use as cooking appliances such as pot, steamer, cooker, industrial appliance, and the surface coating material of electrical machinery field apparatus etc., the top layer coated with resins of particularly high molecular polysulfones and polyethers material, a class novel fluoropolymers of developing from the early 1990s with U.S. Dow company is a starting point, molecular designing goes out the new polymer monomer of a class, through suitable polymerizing condition, obtain containing the fluoro-resin of sulfuryl structure.
The general formula of molecular structure that contains the fluororesin monomer of sulfuryl structure of the present invention is: CF
2=CF-O-R-S (O)
m-R
1-O-CF=CF
2, the fluoro-resin that contains the sulfuryl structure of the present invention is to be heated by above-mentioned fluororesin monomer that what take place to obtain behind the cyclisation dimerization reaction is the polymkeric substance of a kind of chain or build, has following structural formula:
Or
Wherein, n=5-6000, m=1,2; R or R
1=aromatic group or R
2Or R
3The aromatic group that replaces, described aromatic group can be a phenyl ring, cyclohexyl biphenyl, substituted benzene ring etc.R
2Or R
3=hydrogen, perfluoroalkyl, alkyl or other inert substituent.Its weight-average molecular weight M
wBe 2000-900000.
One of fluororesin monomer manufacture method provided by the present invention is with trifluoro vinyl oxygen base bromine aromatic compound, as 4-(trifluoro vinyl oxygen base) bromine aromatic compound (2), or the trifluoro vinyl oxygen base R of inert substituent is arranged on other
2Or R
3The Grignard reagent of the bromine aromatic compound that replaces and thionyl chloride reaction further obtain through oxidizing reaction.This trifluoro vinyl oxygen base R wherein
2Or R
3The Grignard reagent system of the bromine aromatic compound (2) that replaces makes (D.W.Smith, Jr. with reference to U.S.'s " macromole " magazine; Babb, D.A.Macromolecules 1996,29,852-860).The document is that using bromine aromatic group phenol is starting raw material, with alkali (as KOH) in the DMSO solvent, be azeotrope with toluene, through after a few hours dewater, add 1 toward substantially anhydrous reaction system, the 2-dibromotetrafluoroethane obtains 4-(1-bromine tetrafluoro oxyethyl group) bromobenzene (1).Compound 1 can be by obtaining pure product with underpressure distillation.Pure compound 1 under the reflux conditions, is sloughed the bromine fluorine with zinc powder in acetonitrile solvent, promptly obtain 4-(trifluoro vinyl oxygen base) R
2Or R
3The bromine aromatic compound (2) that replaces.Compound 2 usefulness magnesium are handled, and get corresponding Grignard reagent.
In organic solvent, above-mentioned trifluoro vinyl oxygen base R
2Or R
3The Grignard reagent of the bromine aromatic compound that replaces, i.e. R
2Or/and R
3Replace or the Grignard reagent of unsubstituted trifluoro vinyl oxygen base bromine aromatic compound adds the dihalide sulfoxide, the mol ratio of Grignard reagent and thionyl chloride can be at 1-4: variation between 1, and preferably at 1.8-2.4: between 1.This organic solvent preferably adopts anhydrous tetrahydro furan or anhydrous ether; Certainly, described dihalide sulfoxide can be thionyl chloride, dibromo sulfoxide or diiodo-sulfoxide etc.Temperature of reaction can change between-70 ℃ and reflux temperature, and the reaction times is 1 hour to 200 hours.Temperature range is between-10 ℃ to 70 ℃ preferably, and the time is at 4 hours to 48 hours preferably, and the reaction back obtains two-trifluoro-ethylene oxygen base, two (R with the oxidizer treatment oxidation
2Or/and R
3Substituted aryl) sulfoxide.During the Grignard reagent reaction, the ideal way is in the dropping stage, and reaction solution is maintained about 0 ℃, dropwises, and slowly heats up, and makes it to react 10 hours under the backflow attitude, when organic solvent is tetrahydrofuran (THF) is 65 ℃.When aryl obtains 4,4 '-(trifluoro-ethylene oxygen base) thionyl benzene (3) during for phenyl, compound 3 usefulness oxidizer treatment oxidations get 4,4 '-trifluoro-ethylene oxygen base diaryl sulfone.Reaction formula is as follows:
Oxygenant commonly used has hydrogen peroxide, organic peroxide acid, chromic acid, permanganate or tin anhydride etc., and also available other mode of oxidizing carries out oxidation such as catalyzed oxidation, electrolytic oxidation.Mode is to use hydrogen peroxide as oxidant preferably, makes solvent with organic acid, perhaps makes oxygenant with organic peroxide acid, makes solvent with the chemical liquid of energy dissolved compound 3.Reaction times better is to select for use 4-48 hour generally at 1-100 hour.
The manufacture method of another fluororesin monomer is with 4,4 '-(dihydroxyl) two (R
2Or R
3Substituted aryl) sulfone, 4,4 '-(dihydroxyl) two (R
2Or R
3Substituted aryl) on sulfoxide or other positions inert substituent R is arranged
2Or R
34,4 '-(dihydroxyl) two (R
2Or R
3Substituted aryl) sulfone, 4,4 '-(dihydroxyl) two (R
2Or R
3When substituted aryl) sulfoxide is starting raw material,, obtain phenates with alkali reaction.This alkali can better be to use mineral alkalis such as potassium hydroxide, sodium hydroxide with organic bases or mineral alkali, itself and 4,4 '-(dihydroxyl) two (R
2Or R
3Substituted aryl) mol ratio of sulfone is at 0.1-10: between 1, preferable molar ratio range is 2-4: between 1.After obtaining phenates, with 1,2-dibromotetrafluoroethane and 4,4 '-dihydroxyl, two (R
2Or R
3Substituted aryl) sulfone, mol ratio are 2: 1, carry out the fluoroalkylation reaction, can obtain 4,4 '-two (1-bromine tetrafluoro oxyethyl groups), two (R
2Or R
3Substituted aryl) sulfone (5).As in the acetonitrile, be 1 with the mol ratio of zinc: handle during 1-2, temperature of reaction is preferably reflux state to compound 5 in polar solvent, and when solvent was acetonitrile, the reaction preferred temperature was 82 ℃, reacts promptly to get monomer in 3-120 hour, obtains compound 4 during for phenyl as aryl.Is example as aryl during for phenyl, and reaction formula is as follows:
The preferable practice is, selects polar aprotic solvent such as dimethyl sulfoxide (DMSO) (DMSO) for use, and adds the azeotrope of entry such as benzene,toluene,xylene etc. therein, and reaction unit is equipped with the Deng Sita water trap.Obtaining in the process of phenates with alkali reaction, water steams with azeotrope, and during standing demix, because of the proportion of water is bigger, lower floor is a water, and the upper strata is an azeotrope, and azeotrope can be back in the reaction flask, to reach the purpose that circulation dewaters.The effect of the step that dewaters is, can cause that the water of side reaction is removed, in order to avoid generate a kind of as 4,4 '-two (tetrafluoro oxyethyl groups), two (R
2Or R
3Substituted aryl) sulfone descends productive rate.This step is not to be obtain product essential, as not considering productive rate, can skip over.With 1, the 2-dibromotetrafluoroethane carries out fluoroalkylation when reaction, and temperature of reaction can be selected between-10-180 ℃, and preferable way is in the dropping stage, and temperature is controlled between 0-30 ℃, dropwises, and temperature is controlled between 20-40 ℃.
The fluoro-resin system of sulfuryl structure that contains of the present invention is by above-mentioned polymer monomer 4,4 '-(trifluoro-ethylene oxygen base) two (R
2Or R
3Substituted aryl) sulfoxide (3) or 4,4 '-(trifluoro-ethylene oxygen base) two (R
2Or R
3Substituted aryl) sulfone (4), the cyclopolymerization reaction obtains by being heated.Polymerization temperature carries out between 120-280 ℃, and the better polymerization temperature is between 160-220 ℃.Polymerization methods can adopt mass polymerization or solution polymerization mode, and when adopting the solution polymerization mode, the solution of employing is generally 1,1, and 1,2, non-proton trapping agent such as 3-triethylbenzene or many halogen substituted aromatics.During monomer polymerization of the present invention, do not need catalyzer or initiator, thereby resulting polymers is free from foreign meter.What the present invention obtained is the polymkeric substance of a kind of chain or build, and general monomeric polyreaction is as follows:
Compared to the fluoro-resin of routine, fluororesin monomer involved in the present invention has the two-part structure feature.Trifluoro vinyl aryl ethers (TFVE) structure is arranged in this monomer of the first.Because the strong electrophilic power of fluorine atom, make the electronic cloud of C-F key be partial to the F atom significantly, thereby make F atom out-shell electron be tending towards state of saturation, thereby the F on two key shows for π bonding electron cloud is not magnetism, but a kind of repulsive force.Compare with hydrogen bonding alkene, the stress of this pair key is bigger.Therefore this π key is very unstable, under the situation of being heated, the cyclisation dimerization reaction takes place easily.
When two or more above-mentioned trifluoro vinyl ethers (TFVE) structure is arranged in the polymer monomer, be heated behind the generation cyclisation dimerization reaction, what obtain is the polymkeric substance of a kind of chain or build.Contain aryl ether group and perfluorocyclobutanearyl on the main polymer chain that obtains.The perfluorocyclobutanearyl structure is given this polymkeric substance excellent properties that general fluoropolymer is had, promptly outstanding electrical insulation capability, thermostability and chemical stability.Simultaneously, also contain aryl ether group on such main polymer chain, this structure makes such thermoplastic polymer and thermoset prepolymer can be dissolved in the multiple organic solvent, thereby has good processing properties.
Another feature of the present invention is, compound alkylsulfonyl structure or sulfinyl structure have alkylsulfonyl or sulfinyl in this polymer monomer on the main polymer chain that obtains thus, thereby also compound general Polyphenylene Sulfone or polysulfoxides properties of materials.Therefore, on performance, the fluoro-resin that contains the sulfuryl structure of the present invention, a kind of compound fluorine resin coating material than Chinese patent CN1019081B number has more excellent wear resisting property.In addition, the Polyphenylene Sulfone resin is widely used for aspects such as food service items, health equipment, medical apparatus because its excellent thermostability and chemical stability have been used as the metallic substance substitute.But its surface property is poor, therefore it refuses oily resistance to soiling, wear resistance is relatively poor, the present invention can be used as the top layer coat film material of these food service items, health equipment, medical apparatus, refuse oily antifouling purpose to play, because its processibility is good, benzene sulfuryl group is arranged in the structure,, make that such rete is difficult for bubbling so have good binding with the ground of Polyphenylene Sulfone resin.
The use of the fluoro-resin that contains the sulfuryl structure of the present invention is flexible, changeable.Can comply with concrete service condition, select different technology for use.
During application, the fluoro-resin superpolymer that contains the sulfuryl structure of the present invention can be dissolved in the specific solvent, apply, thereafter, treat that solvent evaporates goes out, promptly get required film forming applicator with conventional spraying method.Be the De Gengjia film-formation result, also oligopolymer that can molecular weight is not too high (molecular weight is between 2000-10000) is coated to application and gets on, and heats up then, makes it to carry out further curing reaction.
In addition, polymer monomer of the present invention can be compound with other the polymer monomer that contains trifluoro vinyl aryl oxide structure, obtains not multipolymer on year-on-year basis.As can with a kind of trifluoro vinyl aryl ethers monomer that contains the silica chain (according to Polym.Prepr., 39,1998,609 reports) copolymerization, obtain containing on the main chain polymkeric substance of silica chain, alkylsulfonyl and perfluorocyclobutanearyl structure.The ratio of two kinds of polymer monomers can be selected for use according to concrete service condition.The molar percentage of polymer monomer of the present invention can change between 5% to 95%.Routinely, the molar percentage of polymer monomer of the present invention is 30% to 70%.
For obtaining the better thermosetting resin of thermostability, polymer monomer of the present invention and trifluoro vinyl ethers (TFVE) monomer with three-functionality-degree can be carried out common pre-polymerization, obtain the performed polymer of lower molecular weight (3000-20000).The monomeric molecule molar percentage of polymer monomer of the present invention and thermosetting polymer also can be complied with concrete service condition, changes between 30% to 99%.Routinely, the molar percentage of polymer monomer of the present invention is 60% to 96%.This performed polymer being coated to after application gets on, can be warmed up to certain temperature, make it the crosslinking curing film forming.
Most preferred embodiment
Below by specific embodiment, the present invention will be described.All embodiment only are to explanation of the present invention, are not intended to limit.
Embodiment 1: be that starting raw material synthesizes 4,4 '-trifluoro-ethylene ether sulfobenzide with the p bromophenol
The p bromophenol that in 5 liters of three-necked bottles that Deng Shi tower water trap is housed, adds 1007.33 grams (5.82 moles), the potassium hydroxide of 373.79 grams (5.82 moles), 3.2 liters of methyl-sulphoxides, 0.8 liter toluene.Mixed solution is warmed up to 110 ℃, keeps 24 hours, to remove the water in the reaction system.Cool to room temperature adds 1 of 1665 grams (6.4 moles) at leisure in the time of 30 ℃ then, and the 2-dibromotetrafluoroethane finishes interpolation in four hours, so that temperature remains on below 35 ℃.Interpolation finishes, and reaction solution was reacted 20 hours in the time of 20 ℃.The dilute with water reaction solution, termination reaction is used dichloromethane extraction, and organic layer is given a baby a bath on the third day after its birth inferior with distilled water, use dried over mgso.Remove solvent, under the condition of decompression, the cut when collecting under the 20mm mercurypressure 105-107 ℃ is 4-(1-bromine tetrafluoro oxyethyl group) bromobenzene (1), and it is as follows to obtain 1477.9 its related datas of gram product (productive rate is 72%):
1H NMR (400MHz, CDCl3): δ 7.06 (2H, d, J=8.4Hz), 7.45 (2H, d, J=8.8Hz);
19F 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
-1MS m/z (%): 354 (46), 352 (100), 351 (39), 157 (25), 155 (25), 63 (40), 50 (27).
Reaction of last step gained compound 1477.9 grams are slowly joined the three-necked bottle that 3.5 liters of acetonitrile solutions and 302 gram zinc powders are housed under the nitrogen protection; this reaction solution was refluxed 10 hours; then acetonitrile is steamed; with n-hexane extraction three times; be spin-dried for solvent; under reduced pressure steam product, cut 843.5 grams (productive rate 79.4%) 70-72 ℃ time the under the 20mm mercurypressure, this product is 4-(trifluoro-ethylene oxygen base) bromobenzene 2.Its spectral data is as follows:
1H NMR (400MHz, CDCl
3): δ 6.95 (2H, d, J=8.7Hz), 7.43 (2H, d, J=8.7Hz);
19F 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
-1MS m/z (%): 254 (72), 253 (12), 173 (51), 157 (36), 155 (40), 63 (16), 50 (72).
Slowly drip in the anhydrous tetrahydro furan of 11.6 gram magnesium chips and 600ml after 100.6 gram above-claimed cpds 2 treat that magnesium chips disappears substantially, in this Grignard reagent, drip 23.8 thionyl chlorides that restrain.After 10 hours, under the backflow situation, continue reaction ten hours in normal-temperature reaction.Through aftertreatment, get 32 grams (40%) 4,4 '-trifluoro-ethylene oxygen base thionyl benzene (3) is dissolved in this compound 3 in the acetate, with hydrogen peroxide it is carried out oxidation, gets 4,4 '-trifluoro-ethylene oxygen base sulfobenzide (4) 30.6 grams (95%).The fusing point of compound (4) is 67-69 ℃.Compound 3 and 4 spectrogram are as follows:
Compound 3:
1H NMR (400MHz, CDCl
3): δ 7.25 (2H, d), 7.68 (2H, d);
19FNMR (376MHz, 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
-1MS 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); Ultimate analysis (W%): molecular formula is C
16H
8O
3F
6The theoretical constituent content (W%) of the compound 3 of S is: C, 48.69; H, 2.03; Carry out ultimate analysis, actual result is as follows: C, 49.02; H, 2.23%.
Compound 4:
1H NMR (400MHz, CDCl
3): δ 7.23 (2H, d), 7.98 (2H, d);
19FNMR (376MHz, 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), 1274,1203,1158,1142,1108,1073,1011,837,789,556cm
-1MS m/z (%): 410 (80), 313 (33), 237 (49), 221 (44), 173 (56), 168 (100), 152 (21), 76 (92), 63 (16), 50 (51); Ultimate analysis (W%): molecular formula is C
16H
8O
4F
6The theoretical constituent content (W%) of the compound 4 of S is: C, 46.83, H, 1.95; Carry out ultimate analysis, actual result is as follows: C, 46.94; H, 2.13%.
Embodiment 2: with 4,4 '-diphenylol sulfobenzide is that starting raw material is synthetic
4,4 '-trifluoro-ethylene ether sulfobenzide
In 5 liters of three-necked bottles that Deng Shi tower water trap is housed, add 4 of 500.54 grams (2.0 moles), 4 '-dihydroxy diphenylsulphone, the potassium hydroxide of 112.2 grams (2.0 moles), 3.2 liters of methyl-sulphoxides, 0.8 liter toluene.Mixed solution is warmed up to 1102, keeps 24 hours, to remove the water in the reaction system.Cool to room temperature adds 1 of 1143.12 grams (4.4 moles) at leisure in the time of 30 ℃ then, and the 2-dibromotetrafluoroethane finishes interpolation in 3 hours, so that temperature remains on below 35 ℃.Interpolation finishes, and reaction solution was reacted 20 hours in the time of 20 ℃.The dilute with water reaction solution, termination reaction is used dichloromethane extraction, and organic layer is given a baby a bath on the third day after its birth inferior with distilled water, be spin-dried for solvent, gets yellow solid.With sherwood oil and ethyl acetate mixed solution recrystallization three times, white needles solid 863.36 grams (productive rate 71%), fusing point is 140-142 ℃.Record i.e. 4,4 '-two (the 1-bromine tetrafluoro oxyethyl group) sulfobenzide (5) of this white solid, its spectral data is as follows: compound 4:
1H NMR (400MHz, CDCl
3): δ 7.23 (2H, d), 7.98 (2H, d);
19F 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
-1MS 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); Ultimate analysis (W%): molecular formula is C
16H
8O
4F
8SBr
2The theoretical constituent content (W%) of compound 5 be: C, 31.58, H, 1.32; Carry out ultimate analysis, actual result is as follows: C, 31.82; H, 1.55.
The zinc powders of above-claimed cpd (5) 863.36 gram and 102.15 grams (1.56 moles) are added in 5 liters the three-necked bottle, and add 3.6 liters acetonitrile and make solvent, under protection of nitrogen gas, refluxed 24 hours.Steam acetonitrile, product is extracted in solid slag with methylene dichloride.Screw out methylene dichloride, make recrystallization, get 378.43 gram (productive rate is 65%) white crystals with sherwood oil and ethyl acetate.Its fusing point is 67-69 ℃, and all the other spectral datas also coincide with compound (4), are compound (4).
Embodiment 3: the mass polymerization of polymer monomer 4
Get 5 gram above-claimed cpds 4, be positioned in the vial, under logical nitrogen protection, be warmed up to more than the fusing point, be molten.At this moment, the magneton in the bottle begins to stir, and temperature is raised to 160 ℃, keeps 10 hours, is warmed up to 220 ℃ then, keeps 10 hours.In insulating process, carry out the polymeric fraction because polymerization degree rising is solidified.
Resulting polymers is carried out performance test, and the result is as follows: be that solvent is made gpc analysis with THF, the result is M
w=33600, M
n=12760, M
w/ M
n=2.63; Do the DSC test, obtain T
g=128 ℃; Do the TGA test and show T in nitrogen atmosphere
d℃ (onset)=516, and in air atmosphere, T
d℃ (onset)=501.This result shows, the thermostability of the fluoro-resin that contains the sulfuryl structure of the present invention is fabulous.
Embodiment 4: the mass polymerization of polymer monomer 4
Get 5 gram above-claimed cpds 4, be dissolved in 1,2, in the 3-triethylbenzene, be warmed up to 160 ℃, kept 10 hours, be warmed up to 210 ℃ then, kept 12 hours.At this moment, there is high molecular weight polymers to separate out.This polymkeric substance is carried out performance test, and the result is as follows: be that solvent is made gpc analysis with THF, the result is M
w=39630, M
n=23750, M
w/ M
n=1.67; Do the DSC test, obtain T
g=129 ℃; Do the TGA test and show T in nitrogen atmosphere
d℃ (onset)=518, and in air atmosphere, T
d℃ (onset)=503.
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
2Being heated, what take place to obtain behind the cyclisation dimerization reaction is the polymkeric substance of a kind of chain or build, wherein m=2, R or R
1=aromatic group.
2, a kind of fluoro-resin that contains the sulfuryl structure as claimed in claim 1 is characterized in that having following structural formula:
Wherein n=1-6000, R or R
1According to claim 1.
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 is phenyl ring or cyclohexyl biphenyl.
4, a kind of fluoro-resin that contains the sulfuryl structure as claimed in claim 1 or 2 is characterized in that the described fluoro-resin system that contains the sulfuryl structure by polymer monomer 4, and 4 '-(trifluoro-ethylene oxygen base) sulfobenzide is polymerized.
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 of sulfuryl structure that contains is by following 1) and 3) method make:
1) adding of the Grignard reagent of trifluoro vinyl oxygen base bromine aromatic compound is dissolved with in the organic solvent of dihalide sulfoxide, between temperature of reaction-70 ℃ and the reflux temperature, the mol ratio of above-mentioned Grignard reagent and dihalide sulfoxide is 1-4: 1, obtained 4 in reaction times 1-200 hour, 4 '-(trifluoro-ethylene oxygen base) diaryl sulphoxide, the same court product promptly gets 4,4 '-(trifluoro-ethylene oxygen base) diaryl sulfone through oxidation;
2) by polymer monomer 4,4 '-(trifluoro-ethylene oxygen base) diaryl sulfone is respectively at 150-250 ℃, 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 dibromo iodine sulfoxide.
8, 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, these oxidation means adopt electrochemical oxidation process or use the oxygenant oxidation, and described oxygenant 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 is to carry out in acetonitrile He under the reflux temperature with metallic zinc.
10, 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 is used for the coated material of all trades and professions of national defence, industry and life, especially for filming of polysulfone material in the dietetic hygiene industry or polyarylether material apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021360049A CN1179987C (en) | 2002-07-12 | 2002-07-12 | Fluororesin containing sulfonyl structure and its pnepn. and use |
Applications Claiming Priority (1)
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| JP2019510335A (en) * | 2015-12-04 | 2019-04-11 | ソルヴェイ（ソシエテ アノニム） | Dielectric insulation method for electroactive components |
| CN116515114A (en) * | 2023-04-28 | 2023-08-01 | 珠海万通特种工程塑料有限公司 | Polymerization method of aromatic sulfone polymer |
| CN116535649A (en) * | 2023-04-28 | 2023-08-04 | 珠海万通特种工程塑料有限公司 | Aromatic sulfone polymer and polymerization method and application thereof |
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