CN100334120C - Fluororesin containing heterocycle structure and its prepn. and use - Google Patents
Fluororesin containing heterocycle structure and its prepn. and use Download PDFInfo
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- CN100334120C CN100334120C CNB021360057A CN02136005A CN100334120C CN 100334120 C CN100334120 C CN 100334120C CN B021360057 A CNB021360057 A CN B021360057A CN 02136005 A CN02136005 A CN 02136005A CN 100334120 C CN100334120 C CN 100334120C
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Abstract
The present invention relates to fluororesin containing a heterocycle structure. The fluororesin has the following general formula of a monomeric molecule structure: Q-(O-CF=CF2)x or Q-(R-O-CF=CF2)x; after a ring type di-polymerization reaction happens by heating, a kind of chain type or body type polymer is obtained, wherein Q a heterocyclic compound with a substituent group R1 or R2 or without the substituent group; R is an aromatic group and an inert substituted group such as an R1 or R2=H, C1-12 alkane chain, C<1 to 12> amido, a C<1 to 5> oxyalkyl group, halogen, etc; x is equal to 1 or 2 or 3 or 4 or 5 or 6. The heterocycle can be pyrimidine or pyridinium or sym-triazine or pyrazole or pyrrole or phenoxazine or thiophene or phenothiazine or piperidine, etc. The fluororesin is prepared by a bulk polymerisation method or a solution polymerization method. The fluororesin is used as surface coating materials of appliances in the fields of cooking devices, industrial appliances and electric appliances. The coating material can be decomposed.
Description
Technical field
The present invention relates to fluoro-resin and manufacture method thereof that a class contains heterocycle structure.In detail, the present invention relates to a class electrical insulation capability, erosion resistance, refuse the fluoro-resin that contains heterocycle structure that oily pollution resistance, high thermal resistance, processing characteristics are all good and can degrade in a particular manner, this fluoro-resin can be easily for using conventional fluoro-resin.
Background technology
Always, 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.
In addition, fluoro-resin is to have excellent chemical stability, thermostability, weathering resistance etc. compared to the feature of other type of resin.These advantages in some applications, or in some stage of using, have but become the obstacle in using conversely.For example, when the application task of fluoro-resin is finished, people wish and can reclaim these resins, perhaps make it degraded.But because the above-mentioned advantage of fluoro-resin makes to reclaim or degrade to be difficult to carry out.In other some are used, as the top layer coat of hardware the time, when the rete of fluoro-resin partly is damaged, and can't restore by the mode of repairing the time, must peel off filming, recoat the overlay film layer again.At this moment, under the situation of not damaging ground, peel off the rete of fluoro-resin, for existing fluorine resin material difficulty beyond doubt.
The research of Biodegradable polymeric material is known already, as 219 pages of biological medicine investigation of materials (J.Biomed.Mater.Res.) 1978 the 12nd phases disclose, but present range of application is still narrower, mainly be to be applied to the polymer drug field, seldom be conceived to material environment friendly and reclaim this respect.
Summary of the invention
The object of the present invention is to provide a class electrical insulation capability, erosion resistance, refuse the fluoro-resin that oily pollution resistance, high thermal resistance, processing characteristics are all good and can degrade in a particular manner, contain heterocycle structure.Make its can be easily in all trades and professions of national defence, industry and life as coated material, and finishing using, can successfully degrade in a particular manner, be a kind of coated material of environment-friendly and green type.
Another purpose of the present invention provides the above-mentioned manufacture method that contains the fluoro-resin of heterocycle structure.
The present invention is in order to overcome above-mentioned technological deficiency always, obtain resin with ideal performance, to be suitable for use as the surface coating material of cooking appliance, industrial appliance, electrical machinery field apparatus etc., and this clad material can be degraded in a particular manner, be able to smooth recovery, meet modern's environmental protection ideas.A class novel fluoropolymers one perfluorocyclobutanearyl (PFCB) polymer monomer of developing from the early 1990s based on U.S. Dow company, introducing can be with the group of ad hoc fashion degraded, molecular designing goes out the new polymer monomer of a class, and this monomer is the crosslinked fluoro-resin that obtains containing heterocycle structure under suitable polymerizing condition.
The fluoro-resin that contains heterocycle structure of the present invention is that introduce on the main chain of fluoro-resin can be with the group of ad hoc fashion degraded, and the introducing of this group, to the not influence of general property of fluoro-resin.
The general formula of molecular structure that contains the fluororesin monomer of heterocycle structure of the present invention is Q-(O-CF=CF
2) x or Q-(R-O-CF=CF
2) x, what obtain behind the generation cyclisation dimerization reaction that is heated is the polymkeric substance of a kind of chain or build, wherein, Q has substituent R
1Or/and R
2Or not to be with substituent heterogeneous ring compound, R be aromatic group, R
1Or R
2=H, C
1-12Alkane chain, C
1-12Amido, C
1-5Alkoxyl group, inert substituents such as halogen; X=1,2,3,4,5 or 6.Described heterocycle can be pyrimidine, pyridine, s-triazine, pyrazoles, pyrroles, azophenlyene, thiophene, thiodiphenylamine or piperidines etc.As introduce the derivative of biodegradable but generally very stable heterogeneous ring compound miazines.N=6-30000 wherein, R
1Or R
2=H, C
1-12Alkane chain, C
1-12Amido, C
1-5Alkoxyl group, inert substituents such as perfluor chain or halogen.Above-mentioned heterogeneous ring compound, the malconformation as the conjugated Cloud Distribution of pyrimidine makes it aspect thermostability and chemical stability, not as good as in phenyl ring, but when 4,6 introduced fluorine-containing chain after, make that these malconformation obtain coordinating, be tending towards balanced, chemical property is also more stable.
Contain pyridine in the polymkeric substance of the present invention, heterocycle structure such as pyrimidine or s-triazine, should assorted nuclear nitrogen unit have a pair of lone-pair electron, can form hydrogen bond with special microorganism or some groups in the katalaze enzyme, by this combination, stable polymer is weakened gradually, thereby degraded successfully, and the condition of a this Degradation all is difficult to run in application, can not become the obstacle of application.
The use that the present invention contains the heterocycle structure fluoro-resin is flexible, and is changeable.Can comply with concrete service condition, select different technology for use.
One base polymer monomer of fluoro-resin of the present invention is such synthetic, with the p bromophenol is starting raw material, with alkali (as KOH) in the DMSO solvent, with toluene is azeotrope, 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.Compound 1 under the reflux conditions, with the zinc powder reaction, is sloughed the bromine fluorine in acetonitrile solvent, promptly obtain trifluoro vinyl to bromophenyl ether (2).Compound 2 usefulness magnesium are handled, and get corresponding Grignard reagent.The method for making of this 4-(trifluoro-ethylene oxygen base) bromobenzene (2) and Grignard reagent thereof is to make (D.W.Smith, Jr. with reference to U.S.'s " macromole " magazine; Babb, D.A.Macromolecules 1996,29,852-860).
With molecular formula is 4-CF
2CFOC
6H
4The MgBr Grignard reagent is added dropwise in the solution that is dissolved with the heterogeneous ring compound XmQ that dihalo-or many halogen replaces, m=2-3 wherein, and X is a halogen, Q is as mentioned above.This Grignard reagent 4-CF
2CFOC
6H
4The molar ratio range of the heterogeneous ring compound XmQ that MgBr and dihalo-or many halogen replace is at 1.6-8: between 1, better scope is at 2-4: between 1.In organic solvent and-75 ℃ to the reflux temperature reaction obtained 4,6-two (4-trifluoro-ethylene oxygen base) phenyl QR in 2-80 hour
1R
2, the preferable reaction times is at 6-24 hour.The organic solvent that adopts is good with the anhydrous solution of ethers such as tetrahydrofuran (THF) (THF), ether generally.Reaction system can have metal catalyst catalysis preferable, as the compound as catalyst with nickelous (Ni).With the dihalo-pyrimidine is example, and preferable way is in the dropping stage, and reaction solution is kept about 0 ℃, dropwises, and slowly heats up, and makes it to react 10 hours under reflux temperature, obtains 4,6-two (4-trifluoro-ethylene oxygen base) phenyl heterocycles.Is example as heterocycle during for pyrimidine, obtains compound 3 in the reaction formula.In addition, also above-mentioned Grignard reagent can be added dropwise to be in-temperature of 78-0 ℃ under, be dissolved with in the solution of boric acid three esters, reacted 1-80 hour, 4-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide.This reaction preferred temperature is between-70 ℃ to-50 ℃; The preferable reaction times is 5-20 hour; Preferred solvents is to adopt anhydrous tetrahydro furan or anhydrous ether kind solvent; Described boric acid three esters are with trimethyl borate, and triethyl borate or tripropoxy-boron are for well.In organic solvent, should-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide and 4,6-dichloro R
1R
2The Q heterocyclic compound reaction that replaces 1-80 hour, the recommendation response time is 5-40 hour; Get final product polymer monomer 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R
1R
2The Q heterogeneous ring compound that replaces, typical reaction formula is as follows:
Wherein, preferred solvents is to adopt two facies pattern solvents, and better solvent is the Na with benzene or its homologue and 2M
2CO
3The two phase liquid of solution composition; Reaction system can adopt catalyzer, and preferable catalyzer is to make catalyzer with the zeroth order organic palladium.Catalyzer and (trifluoro-ethylene oxygen base) phenyl-boron dihydroxide, 4,6-dichloro R
1R
2The mol ratio of the Q heterogeneous ring compound that replaces is 0-0.5: 0.8-2: 1, and with 0.05-0.2: 1 for well.
The synthetic method of the another kind of polymer monomer of the present invention is to be R with the molecular formula
3 gQR
1R
2Dihydroxyl or polyhydric R
1And R
2The heterogeneous ring compound that replaces is a starting raw material, as 3, the 5-dihydroxy-pyridine, 4, the 6-dihydroxy-pyrimidine, and 2,4, the molten grade of 6-trihydroxy-s-triazine had been equipped with in the three-necked bottle of water trap, with monovalence metal hydroxides azeotropic reaction 5-24 hour, it is 1 that mol ratio is followed successively by: during 0.5-2, obtaining molecular formula is R
4 gQR
1R
2Ether salt is equipped with the azeotrope of water in this reaction system, be preferably with benzene, and toluene, dimethylbenzene by circulation method, reach the purpose that dewaters as azeotrope.Be good with polar aprotic solvent generally, the volume ratio of azeotrope and solvent is generally at 0.05-8: between 1, be preferably 1: between the 2-6.The effect of the step that dewaters is, can cause that the water of side reaction is removed, and avoids productive rate to descend.Dewatering finishes, and molecular formula is R
4 gQR
1R
21 of ether salt and 2-6 times molar weight, 2-dibromotetrafluoroethane are carried out fluoroalkylation reaction 1-20 hour at normal temperatures,, the product of this reaction is handled in organic solvent with the zinc of 2-6 times of molar weight, promptly gets polymer monomer 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R
1R
2The Q heterogeneous ring compound that replaces, wherein R
3=OH, R
4=OK or ON a represent radicals R
3, R
4The g=2 of number, 3, or 4, reaction formula is as follows:
In above-mentioned two monomeric synthesis materials of the present invention, 4,6-dichloro pyrimidine and 4, the 6-dihydroxy-pyrimidine, available 2,4,6-trichloropyrimidine and 2,4,6-trihydroxy-pyrimidine substitute respectively, with the monomer of synthetic three-functionality-degree.And substituting group can reasonably be introduced according to practical situations, with the effect that obtains imagining in the position on 2,5 of above-mentioned pyrimidine or other heterogeneous ring compound ring.R as implied above
1Or R
2=hydrogen, the alkane chain, the amido substituting group, the ether substituting group, or halogenic substituent etc.The malconformation of the conjugated Cloud Distribution of heterogeneous ring compound pyrimidine makes it aspect thermostability and chemical stability, and is too late in phenyl ring, but when 4,6 introduced fluorine-containing chain after, make that these malconformation obtain coordinating, be tending towards balanced, chemical property is also more stable.
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, is example with following reaction formula:
Wherein n is between 6 to 30000.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.
Contain pyridine in the polymer monomer of the present invention, heterocycle structure such as pyrimidine or s-triazine, should assorted nuclear nitrogen unit have a pair of lone-pair electron, can form hydrogen bond with special microorganism or some groups in the katalaze enzyme, by this combination, stable polymer is weakened gradually, thereby degraded successfully, and the condition of a this Degradation all is difficult to run in application, can not become the obstacle of application.
The fluoro-resin that the present invention contains heterocycle structure is by above-mentioned 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R
1R
2The Q heterogeneous ring compound polymer monomer that replaces, the cyclopolymerization reaction obtains by being heated.Described monomer can be 4,6-two (4-trifluoro-ethylene oxygen base phenyl) pyrimidine, 4,6-trifluoro-ethylene oxygen yl pyrimidines or 2,4,6-trifluoro-ethylene oxygen yl pyrimidines etc.Polymerization temperature carries out between 120-280 ℃, and the better polymerization temperature is between 150-200 ℃.Polymerization methods can adopt mass polymerization or solution polymerization mode, when adopting the solution polymerization mode, solution is generally had two requirements, for liquid, boiling point is higher than 120 ℃ down for one, normal temperature, be preferably and be higher than 160 ℃, as 1,2, the 3-Three methyl Benzene, 1,2, the 4-Three methyl Benzene, 1,2,3-triethylbenzene or phenyl polyhalide etc. are not caught the high boiling solvent of proton.Owing to when polymer monomer of the present invention carries out polymerization, do not need catalyzer or initiator, thereby resulting polymers is free from foreign meter, the purity height.
During application, the fluoro-resin superpolymer that contains heterocycle 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 (weight-average molecular weight is preferably between 6000-20000 between 2000-100000) is coated to application and gets on, and heats up then, make it to carry out further curing reaction, with crosslinked film forming.
In addition, the fluororesin polymer monomer that contains heterocycle structure 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, heterocycle structure and perfluorocyclobutanearyl structure.The two mol ratio can change between 1: 99 to 99: 1, and preferable ratio is to change between 10: 90 to 90: 10.
For obtaining the hot resin of the better thermosetting of thermostability, can have the three-functionality-degree polymer monomer and carry out pre-polymerization of the present invention, obtain the performed polymer of lower molecular weight (molecular weight is preferably molecular weight between 7000 to 30000 between 1000-100000).This performed polymer being coated to after application gets on, can be warmed up to certain temperature, make it the crosslinking curing film forming.Similarly, the monomer that the present invention has two functionality can be used with the monomer with three-functionality-degree, and mol ratio can change between 1: 100 to 500: 1, and preferable ratio is between 30: 70 to 98: 2, select different proportionings for use, can get the polymkeric substance of degree of crosslinking in various degree.
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 1,5-dimethyl 4,6 with the p bromophenol
-two (4-trifluoro-ethylene ether) phenyl pyrimidine (3)
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.Spin off 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%):
1HNMR (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.) ,-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, this Grignard reagent is added dropwise in the tetrahydrofuran solution of trimethyl borates of 41.5 grams that are in-65 ℃.After reaction 10 hours, be raised to 20 ℃, add the hydrochloric acid termination reaction, use dichloromethane extraction.Spin off methylene dichloride, the gained solid is carried out recrystallization, obtain combining the look solid.4-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide 42.7 gram of this comprehensive look put into be dissolved with 500ml toluene, 180ml1M NaCO
3In the solution, make catalyzer, under the backflow situation, continue reaction ten hours with four (triphenyl phosphorus) palladium.Through aftertreatment, get 31.6 grams 4,6-two (4-trifluoro-ethylene oxygen base) phenyl pyrimidine (3).The fusing point of compound 3 is 67.5-68.5 ℃, and remainder data is as follows:
Compound 3:
1H NMR (400MHz, CDCl
3): δ 7.26 (2H on the phenyl ring, d), 8.03 (1H on the pyrimidine ring on the C-5, S), 8.12 (2H on the phenyl ring, d), 9.31 (H on the pyrimidine ring on the C-2, S);
19F NMR (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:1838 (CF=CF
2), 1596,1508 (Ar), 1321,1276,1137,834,772,522cm
-1MS m/z (%): 424 (100), 396 (10), 327 (59), 230 (72), 203 (11), 176 (7), 101 (12), 88 (10), 75 (9), 50 (3); Ultimate analysis (W%): molecular formula is C
20H
10O
2F
6N
2The theoretical constituent content (W%) of compound 3 be: C, 56.60, H, 2.36, N, 6.61; Carry out ultimate analysis, actual result is as follows: C, 56.84; H, 2.54; N, 6.47.
Embodiment 2: with 4-methyl 3, the 5-dihydroxy-pyridine is the synthetic 4-methyl 3,5 of starting raw material
-two (trifluoro-ethylene ether) pyridines (5)
The 4-methyl 3 that in 5 liters of three-necked bottles that Deng Shi tower water trap is housed, adds 250 grams (2.0 moles), 5-dihydroxy-pyridine, the potassium hydroxide of 112.2 grams (2.0 moles), 3.2 liters of methyl-sulphoxides, 0.8 liter toluene.Mixed solution stirs and is warmed up to 110 ℃, 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 625.8 grams (65%).Recording this white solid is 4-methyl 3,5-two (1-bromine tetrafluoro oxyethyl group) pyridine (4), and its spectral data is as follows:
1H NMR (400MHz, CDCl
3): δ 1.78 (3H, s), 8.87 (2H, s);
19F NMR (376MHz, CDCl
3): δ-86.60 (t, J=4.57Hz) ,-68.58 (t, J=4.57Hz); IR:1695,1602,1276,1235,1201,1158,1108,1011,820,667cm
-1MS m/z (%): 483 (72), 469 (50), 454 (100), 442 (40), 389 (56), 249 (65), 222 (37), 179 (17.9), 136 (8.2), 129 (8.7), 96 (11.6), 77 (43), 50 (36); Ultimate analysis (W%): molecular formula is C
10H
5O
2F
8NBr
2The theoretical constituent content (W%) of compound 4 be: C, 24.84, H, 1.03, N, 2.90; Carry out ultimate analysis, actual result is as follows: C, 24.78; H, 1.34; N, 2.87.
The zinc powders of above-claimed cpd (4) 625.8 gram and 92.6 grams (1.43 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 224.7 gram (productive rate is 61%) white crystal compounds (5) with sherwood oil and ethyl acetate.Its fusing point is 63-65 ° of c, and all the other spectral datas are as follows:
1H NMR (400MHz, CDCl
3); δ 1.77 (3H, s), 8.91 (2H, s);
19F NMR (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:1838 (CF=CF
2), 1696,1608,1321,1276,1137,857,772cm
-1MS m/z (%): 285 (70), 258 (100), 189 (59), 148 (43), 136 (31), 77 (41), 50 (3); Ultimate analysis (W%): molecular formula is C
10H
5O
2F
6The theoretical constituent content (W%) of the compound 5 of N is: C, 42.11, H, 1.75, N, 4.91; Carry out ultimate analysis, actual result is as follows: C, 42.32; H, 1.81; N, 4.94.
Embodiment 3: with 2,4,6-three chloro-1,3,5-s-triazine are that starting raw material is synthetic
2,4,6-three (4-trifluoro-ethylene ether phenyl) s-triazine (6)
4-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide 42.7 grams of the comprehensive look of above-mentioned gained preferred embodiment 1 gained are put into 2,4,6-three chloro-1,3, the 500ml toluene of 5-s-triazine, 180ml 1M NaCO
3In the solution, make catalyzer, under the backflow situation, continue reaction ten hours with four (triphenyl phosphorus) palladium.Through aftertreatment, get 27.6 grams 2,4,6-three (4-trifluoro-ethylene oxygen base) phenyl s-triazine (6).The fusing point of compound 6 is 83.5-85.5 °, and all the other spectral datas are as follows:
1H NMR (400MHz, CDCl
3): δ 7.26 (6H, d, J=8.4Hz), 7.95 (6H, d, J=8.8Hz);
19F NMR (376MHz, CDCl
3): δ-119.4 (1F, cis-CF=CF
2, F
a) ,-126.5 (1F, trans-CF=CF
2, F
b) ,-134.6 (1F, CF=CF
2, Fc); IR:1838 (CF=CF
2), 1696,1321,1276,1137,857,772cm
-1MS m/z (%): 597 (100), 424 (63), 397 (51), 251 (15) 200 (43), 173 (13), 84 (9); Ultimate analysis (W%): molecular formula is C
27H
12O
3F
9N
3The theoretical constituent content (W%) of compound 6 be: C, 54.27, H, 2.01, N, 7.04; Carry out ultimate analysis, actual result is as follows: C, 54.65; H, 2.11; N, 7.29.
Embodiment 4: the mass polymerization of polymer monomer 3
Get 5 gram above-claimed cpds 4, be positioned in the vial, under logical nitrogen protection, be warmed up to 70 ℃ more than the fusing point, this compound 4 is molten.At this moment, the magneton in the bottle begins to stir, and temperature is raised to 150 ℃, keeps 10 hours, is warmed up to 200 ℃ then, keeps 10 hours.In insulating process, carry out the polymeric fraction and solidify owing to the polymerization degree raises.
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=35600, M
n=12860, M
w/ M
n=2.77; Do the DSC test, obtain T
g=105 ℃; Do the TGA test and show T in nitrogen atmosphere
d℃ (onset)=427, and in air atmosphere, T
d℃ (onset)=406.This result shows that fluoro-resin of the present invention still keeps good thermostability.
Embodiment 5: 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 150 ℃, kept 10 hours, be warmed up to 200 ℃ then, kept 12 hours.Stop to stir, at this moment, have 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=39350, M
n=23950, M
w/ M
n=1.63; Do the DSC test, obtain T
g=106 ℃; Do the TGA test and show T in nitrogen atmosphere
d℃ (onset)=428, and in air atmosphere, T
d(onset)=407 ° c.
Embodiment 6: the pre-polymerization and the application of thermoplastic polymer monomer 4 and thermosetting polymer monomer 6: get 5 above-mentioned polymer monomers 4 of gram and 6 (mol ratio is about 75: 25) of 2 gram thermosetting polymer monomers, be dissolved in 1,2, in the 3-triethylbenzene, be warmed up to 160 ℃, kept 8 hours.The high-molecular weight prepolymer is separated out, this prepolymer is carried out performance test, the result is as follows: be that solvent is made gpc analysis with THF, the result is M
w=15630, M
n=8750, M
w/ M
n=1.79.This prepolymer solid is ground,, be coated on the clean ground, then this ground plate was suspended in 200 ℃ the baking oven baking 10 hours, obtain one deck and apply and film uniformly by electrostatic spraying.
Claims (7)
1, a kind of fluoro-resin that contains heterocycle structure has following structural formula:
, n=6-30000 wherein, y=0 or 1, Q have substituent R
1Or/and R
2Or not to be with substituent heterogeneous ring compound, R be aromatic group, R
1Or R
2Be selected from H, C
1-12Alkane chain, C
1-12Amido, C
1-5The inert substituent of alkoxy or halogen; Described heterocycle is pyrimidine, pyridine, s-triazine, pyrazoles, pyrroles, azophenlyene, thiophene, thiodiphenylamine or piperidines;
Be perfluorocyclobutanearyl.
2, a kind of fluoro-resin that contains heterocycle structure as claimed in claim 1 is characterized in that the described fluoro-resin system that contains heterocycle structure is Q-(O-CF=CF by general formula of molecular structure
2)
xOr Q-(R-O-CF=CF
2)
xFluororesin monomer, be heated a kind of chain that obtains behind the cyclisation dimerization reaction or the polymkeric substance of build take place, wherein, R and Q are according to claim 1.
3, a kind of a kind of manufacture method that contains the fluoro-resin of heterocycle structure as claimed in claim 1 is characterized in that by following 1) and 4), 2) and 4) or 3) and 4) method form:
1) in organic solvent and-65 ℃ to reflux temperature, molecular formula is 4-CF
2CFOC
6H
4The heterogeneous ring compound XmQ reaction that the Grignard reagent of MgBr splashes into dihalo-or the replacement of many halogen obtained 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R in 2-80 hour
1R
2The Q heterogeneous ring compound that replaces, the mol ratio of Grignard reagent and XmQ is 1.6-8: 1;
2) in organic solvent and under-78～0 ℃ the temperature, molecular formula is 4-CF
2CFOC
6H
4The Grignard reagent of MgBr and the reaction of boric acid three esters 1-80 hour get 4-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide; This compound is done in the presence of the catalyzer at the zeroth order organic palladium again, with 4, and 6-dichloro R
1R
2The Q heterogeneous ring compound reaction that replaces obtained 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R in 1-80 hour
1R
2The Q heterogeneous ring compound that replaces, catalyzer and 4-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide, 4 wherein, 6-dichloro R
1R
2The mol ratio of the Q heterogeneous ring compound that replaces is 0-0.5: 0.8-2: 1;
3) in organic solvent, molecular formula is R
3GQR
1R
2Dihydroxyl or polyhydric R
1And R
2The heterogeneous ring compound and the monovalence metal hydroxides mol ratio that replace are 1: during 0.5-2 and azeotropic reacted 5-24 hour and dewater, obtaining molecular formula is R
4GQR
1R
2Ether salt; 1 of this ether salt and 2-6 times of molar weight, 2-dibromotetrafluoroethane are carried out fluoroalkylation reaction 1-20 hour at normal temperatures, and the product of this reaction is handled in organic solvent with the zinc of 2-6 times of molar weight, promptly gets polymer monomer 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R
1R
2The Q heterogeneous ring compound that replaces;
4) in organic solvent or during organic solvent-free and under 120-280 ℃, 4,6-two (4-trifluoro-ethylene oxygen base) phenyl R
1R
2The Q heterocyclic compound that replaces carries out mass polymerization or solution polymerization, and polymerization reaction time is 10-50 hour:
M=2-3 wherein, X is a halogen, R
3=OH, R
4=OK or ONa, g=2,3 or 4, R
1, R
2With Q according to claim 1.
4, a kind of manufacture method that contains the fluoro-resin of heterocycle structure as claimed in claim 3 is characterized in that described boric acid three esters are trimethyl borates, triethyl borate or tripropoxy-boron.
5, a kind of manufacture method that contains the fluoro-resin of heterocycle structure as claimed in claim 3 is characterized in that described polymerization temperature is at 150-200 ℃.
6, a kind of manufacture method that contains the fluoro-resin of heterocycle structure as claimed in claim 3 is characterized in that described solution polymerization is at 1,1 or 1,2, carries out in the 3-triethylbenzene organic solvent.
7, a kind of manufacture method that contains the fluoro-resin of heterocycle structure as claimed in claim 3 is characterized in that described method 2) in, catalyzer and 4-(trifluoro-ethylene oxygen base) phenyl-boron dihydroxide, 4,6-dichloro R
1R
2The mol ratio of the Q heterogeneous ring compound that replaces is 0.05-0.2: 1: 1.
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063117A (en) * | 1990-12-03 | 1992-07-29 | W·L·戈尔及合伙人有限公司 | Dioxole/TFE copolymer composites |
| US5811034A (en) * | 1997-10-23 | 1998-09-22 | Ppg Industries, Inc. | 7-methylidene-5-oxo-furo fused naphthopyrans |
| WO1999067228A1 (en) * | 1998-06-24 | 1999-12-29 | Aventis Pharmaceuticals Products Inc. | Fluorophenyl resin compounds |
-
2002
- 2002-07-12 CN CNB021360057A patent/CN100334120C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063117A (en) * | 1990-12-03 | 1992-07-29 | W·L·戈尔及合伙人有限公司 | Dioxole/TFE copolymer composites |
| US5811034A (en) * | 1997-10-23 | 1998-09-22 | Ppg Industries, Inc. | 7-methylidene-5-oxo-furo fused naphthopyrans |
| WO1999067228A1 (en) * | 1998-06-24 | 1999-12-29 | Aventis Pharmaceuticals Products Inc. | Fluorophenyl resin compounds |
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