CN101445511A - Perfluor cyclobutyl arylene oligopolymer, preparation method thereof by using iterative coupled reaction and usage - Google Patents
Perfluor cyclobutyl arylene oligopolymer, preparation method thereof by using iterative coupled reaction and usage Download PDFInfo
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- CN101445511A CN101445511A CNA2008102079120A CN200810207912A CN101445511A CN 101445511 A CN101445511 A CN 101445511A CN A2008102079120 A CNA2008102079120 A CN A2008102079120A CN 200810207912 A CN200810207912 A CN 200810207912A CN 101445511 A CN101445511 A CN 101445511A
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Abstract
The invention provides a perfluor cyclobutyl arylene oligopolymer and a preparation method thereof by using iterative Suzuki coupled reaction. An intermediate 3 of the iterative Suzuki coupled reaction is firstly prepared, aryl boric acid and the intermediate 3 have the Suzuki coupled reaction, and one perfluor cyclobutyl arylene unit is introduced into the reaction product; the product is deacidized to be boric acid which then has the Suzuki coupled reaction with the intermediate 3, and the perfluor cyclobutyl arylene unit is introduced. The Suzuki coupled reaction and the reaction of deacidizing the product to be the boric acid are repeatedly carried out, so that the perfluor cyclobutyl arylene oligopolymer containing the exact number of perfluor cyclobutyl arylene units is prepared. The obtained oligopolymer contains an active reaction terminal group and can further react to prepare functional oligopolymer or polymer containing perfluor cyclobutyl arylene structure.
Description
Technical field
The present invention relates to perfluorocyclobutanearyl (perfluorocyclobutyl, PFCB) preparation method of aryl ethers oligopolymer and use iterative Suzuki coupled.
Background technology
The perfluorocyclobutanearyl aryl-ether polymkeric substance is by the researchist of DOW Chemical (Dow Chemical Co.) the new fluoropolymer of a class in exploitation in 1993.This class fluoropolymer is usually by trifluoro vinyl (trifluorovinyl, TFVE) the aryl ethers monomer is between 150 ℃ to 250 ℃ temperature, [2 π+2 π] thermal cyclization polymerization taking place generate, need not any initiator or catalyzer, does not have micromolecular compound simultaneously and emit.As a kind of novel fluoropolymer, not only have the traditional premium properties of fluoropolymer based on the polymkeric substance of perfluorocyclobutanearyl aryl-ether, as heat/oxidative stability and chemical resistance etc., and have good solution processing characteristics.
Because the essence of polymerization process has statistical, generally the polymkeric substance of gained is the mixture of the polymer molecule of various molecular weights.When using as body, the polymkeric substance of polymolecularity has its advantage; But as theoretical investigation, scientist has the polymkeric substance of accurate molecular weight always in pursuit, because have the model that the polymkeric substance of accurate molecular weight can be used as its polydisperse polymer, non uniform homologue, carries out the research of polymer property.Simultaneously, has the detailed sign of polymkeric substance of accurate molecular weight usually than being easier to.Oligopolymer has accurate structure, can carry out the research of polymer property as the model of its polydisperse polymer, non uniform homologue.
The monomeric polymerization of trifluoro vinyl aryl ethers has progressively polymeric essence, therefore the common molecular weight distribution broad of perfluorocyclobutanearyl aryl-ether polymkeric substance that obtains; And be difficult to effectively reduce molecular weight distribution, obtain monodispersed polymkeric substance by changing polymerizing condition.The perfluorocyclobutanearyl aryl-ether oligopolymer is as the model of the homologue of perfluorocyclobutanearyl aryl-ether polymkeric substance, and it is characterized research with character, will help the further understanding to the perfluorocyclobutanearyl aryl-ether polymer property.
Development along with organic synthesis technology, modern methodology of organic synthesis is learned and is provided strong means to obtain required oligopolymer by polystep reaction, and wherein iteration reaction (iterative reaction) is proved to be a kind of method of efficient production oligopolymer.Shown in the iteration reaction down, the monomer M that contains two nonreactive functional groups X and Y changes two active compounds into, and one is that end group X is converted into active function groups X ', and another is that end group Y is converted into active function groups Y '.These two kinds of activatory compound reactions generate dimer XMMY, emit a part X ' Y ' simultaneously.Also contain the nonreactive functional groups in the monomer in the dimer, repeat this process and just can access the tetramer.Repeat this process, molecular length just can double at every turn.
Wherein oligomer represents oligopolymer.
The perfluorocyclobutanearyl aryl-ether oligopolymer is connected to form by a plurality of perfluorocyclobutanearyl aryl-ether units, and each unit is connected with covalent linkage by phenyl ring.The linked reaction of catalytic organic boronic acid derivative of palladium and Organohalogen compounds, i.e. Suzuki coupling is the most reliable and one of the reaction that forms of carbon-carbon bond easily.The present invention uses the thought of iteration reaction, designs a kind of intermediate that contains perfluorocyclobutanearyl aryl-ether unit, can carry out the Suzuki linked reaction with aryl boric acid, introduces a perfluorocyclobutanearyl aryl-ether unit; The product of gained can be reduced to aryl boric acid again once more, carries out the Suzuki linked reaction with intermediate once more, introduces a perfluorocyclobutanearyl aryl-ether unit in product once more.Product repeats to carry out the reaction that Suzuki reacts and be reduced to boric acid with intermediate, it is the Suzuki linked reaction of iteration, repeat to introduce perfluorocyclobutanearyl aryl-ether unit, thereby preparation contains the perfluorocyclobutanearyl aryl-ether oligopolymer of accurate perfluorocyclobutanearyl aryl-ether unit number.And the oligopolymer of gained contains the active reaction end group, can be as the synthetic building block of perfluorocyclobutanearyl aryl-ether polymkeric substance, and further preparation contains the oligopolymer or the polymkeric substance of perfluorocyclobutanearyl aryl-ether.Perfluorocyclobutanearyl aryl-ether oligopolymer and polymkeric substance not only have high heat/oxidative stability, well chemical resistance, outstanding mechanical property and outstanding premium propertiess such as weathering resistance, and have good solution processibility, be applied in the type materials such as optics, aeroplane dope, Organic Light Emitting Diode and battery electrolyte.
Summary of the invention
The objective of the invention is to utilize the thought of iteration reaction,, prepare a kind of iteration Suzuki coupling intermediate that contains perfluorocyclobutanearyl aryl-ether unit by molecular designing; Utilize aryl boric acid to carry out iterative Suzuki coupled with intermediate, preparation contains the perfluorocyclobutanearyl aryl-ether oligopolymer of accurate perfluorocyclobutanearyl aryl-ether unit number.And the oligopolymer of gained contains active end group, and further prepared in reaction contains the oligopolymer or the polymkeric substance of perfluorocyclobutanearyl aryl-ether structure.
The object of the present invention is to provide a kind of Suzuki linked reaction of using iteration to prepare the method for perfluorocyclobutanearyl aryl-ether oligopolymer.
Purpose of the present invention also provides a kind of iteration Suzuki coupling intermediate and a series of perfluorocyclobutanearyl aryl-ether oligopolymer that contains active end group that contains perfluorocyclobutanearyl aryl-ether unit.
Another object of the present invention provides a kind ofly utilizes the reaction of the active end group that oligopolymer contains to prepare the purposes that contains perfluorocyclobutanearyl aryl-ether oligopolymer or polymkeric substance.
Method of the present invention can be from p bromophenol, synthetic contain perfluorocyclobutanearyl aryl-ether unit to the intermediate of bromine two amido borines 3 as iterative Suzuki coupled; Contain R
1Remove the protection of two amido borines after substituent aryl boric acid 4 and the intermediate 3 generation Suzuki linked reactions and be reduced to boric acid; The Suzuki linked reaction takes place with intermediate 3 in gained boric acid once more, removes the protection of two amido borines then and is reduced to boric acid.Repeat this process, promptly the Suzuki linked reaction of iteration is synthesized the perfluorocyclobutanearyl aryl-ether oligopolymer that contains accurate perfluorocyclobutanearyl aryl-ether unit number n.Its mesoboric acid carries out the Suzuki linked reaction with intermediate 3 each time, can introduce a perfluorocyclobutanearyl aryl-ether unit in product; And the product of gained can be reduced to boric acid, carries out the Suzuki linked reaction with intermediate 3 once more, introduces perfluorocyclobutanearyl aryl-ether unit; Constantly repeat the Suzuki linked reaction and remove protective reaction, just can constantly introduce perfluorocyclobutanearyl aryl-ether unit, obtain containing the perfluorocyclobutanearyl aryl-ether oligopolymer of accurate perfluorocyclobutanearyl aryl-ether unit number.The active end group R that resulting perfluorocyclobutanearyl aryl-ether oligopolymer contains
1Or R
2Can further react, preparation contains the oligopolymer or the polymkeric substance of perfluorocyclobutanearyl aryl-ether structure.
Described 3 and 4 structural formulas are as follows:
Perfluorocyclobutanearyl aryl-ether oligopolymer provided by the present invention has following structure:
R wherein
1Be any substituting group that can be compatible with the Suzuki linked reaction, recommendation-F ,-OCF=CF
2, C
1～C
4Alkyl, C
1～C
4Alkoxyl group or phenyl;
R
2For :-B (OH)
2,
Or
The scope of n is 1～10 integer; The scope of m is 10～1000 integer;
Represent cis or transconfiguration.
Preparation process of the present invention is recommended as follows:
1. the preparation of iterative Suzuki coupled intermediate 3
Reaction formula is as follows:
In the above-mentioned reaction formula, reflux represents to reflux, and DMSO represents dimethyl sulfoxide (DMSO), and toluene represents toluene, and △ represents heating.
Starting material compound 1,2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 is recommended and can be prepared by following method: (1) is under atmosphere of inert gases, with dimethyl sulfoxide (DMSO) (DMSO) and toluene is solvent, p bromophenol and KOH reacted under the condition of refluxing toluene 24～48 hours, after removing the water that is generated reaction system is cooled to below 30 ℃, add (recommending to drip) exsiccant 1, the 2-dibromotetrafluoroethane also keeps temperature of reaction system to be lower than 30 ℃.Then reaction system was stirred 6～12 hours at 30 ℃～50 ℃, through extraction, dry, filter, concentrate and step such as underpressure distillation obtains 4-bromo-(2-bromine tetrafluoro oxyethyl group base) benzene.The reinforced mol ratio of described p bromophenol and KOH is 1:1, p bromophenol and 1, the reinforced mol ratio of 2-dibromotetrafluoroethane is 1:(1.1～1.5).(2) under atmosphere of inert gases, activatory Zn powder is put into the exsiccant reaction flask, add a certain amount of acetonitrile as solvent.Under the condition that acetonitrile refluxes, resulting 4-bromo-in the step (1) (2-bromine tetrafluoro oxyethyl group base) benzene is added (recommending to drip) in reaction system, keep reaction system to reflux then 4～12 hours, after filtration, concentrate and step such as underpressure distillation obtains 4-bromine (trifluoro-ethylene oxygen base) benzene.The reinforced mol ratio of described 4-bromo-(2-bromine tetrafluoro oxyethyl group base) benzene and Zn is 1:(1～1.5), the reinforced pass of 4-bromo-(2-bromine tetrafluoro oxyethyl group base) benzene and acetonitrile is 1mol/1000mL.
(3) under atmosphere of inert gases, resulting 4-bromine in the step (2) (trifluoro-ethylene oxygen base) benzene is carried out thermal cyclization reaction, behind the rapid column chromatography purifying, obtain 1,2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1.Temperature of reaction is 150 ℃～250 ℃, and the reaction times is 12～24 hours.Be reflected in the body and carry out.
By 1,2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 further prepares the bromo boric acid 2 that contains the perfluorocyclobutanearyl aryl-ether structure and the method for the bromo two amido borines 3 that contain the perfluorocyclobutanearyl aryl-ether structure is as follows: (4) are under atmosphere of inert gases, n-Butyl Lithium is added (recommending to drip) to 1, in the tetrahydrofuran solution of 2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1.React after 1～2 hour, boric acid ester is added (recommending to drip) in reaction system, reaction (recommending to stir) 6～12 hours.Add the hydrochloric acid soln acidifying after replying room temperature, through extraction, dry, filter, concentrate and the rapid column chromatography purifying after obtain containing the bromo boric acid 2 of perfluorocyclobutanearyl aryl-ether structure.N-Butyl Lithium and 1, the mol ratio of 2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 is (1～1.2): 1.Used boric acid ester is trimethyl borate or triisopropyl borate ester, boric acid ester and 1, and the mol ratio of 2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 is (1.5～3): 1.Temperature of reaction is-65 ℃～-80 ℃.
(5) under atmosphere of inert gases, with bromo boric acid 2 and 1,8-two amido naphthalenes refluxed in solvent 2～12 hours, removed the water that dereaction generated simultaneously, obtained containing the bromo two amido borines 3 of perfluorocyclobutanearyl aryl-ether structure behind concentrated and rapid column chromatography purifying.Bromo boric acid 2 and 1, the mol ratio of 8-two amido naphthalenes is 1:(1～1.5); The solvent of reaction is recommended as toluene or dimethylbenzene.
2. the preparation of perfluorocyclobutanearyl aryl-ether oligopolymer
Reaction formula is as follows:
(1) under atmosphere of inert gases, will contain R
1Substituent aryl boric acid 4 carries out the Suzuki linked reaction with bromo two amido borines 3, through extraction, dry, filter, concentrate and the rapid column chromatography purifying after obtain containing two amido borines 5 of perfluorocyclobutanearyl aryl-ether structure.Boric acid 4 is recommended as (1～5) with the mol ratio of bromo two amido borines 3: 1.The Suzuki linked reaction recommends to use for example four (triphen phosphino-) palladium or two (tri-tert phosphino-) palladium of Pd (0) catalyzer.The mol ratio of Pd (0) catalyzer and bromo two amido borines 3 is recommended as (0.03～0.05): 1.The used alkali of Suzuki linked reaction is yellow soda ash, salt of wormwood, cesium carbonate and cesium fluoride for example.The mol ratio of alkali and bromo two amido borines 3 is recommended as (1～5): 1.The used solvent of Suzuki linked reaction be recommended as toluene or tetrahydrofuran (THF) respectively with the mixed solvent of water.
(2) two amido borines 5 and excessive acid-respons (recommending to stir) 12～24 hours, through extraction, dry, filter, concentrate and the rapid column chromatography purifying after obtain containing the boric acid 6 of perfluorocyclobutanearyl aryl-ether structure.Sulfuric acid or hydrochloric acid are recommended in acid.Solvent is recommended tetrahydrofuran (THF) or methylene dichloride.
(3) boric acid 6 carries out the Suzuki linked reaction with bromo two amido borines 3, obtains perfluorocyclobutanearyl aryl-ether dimer 7; 7 with acid-respons be reduced to boric acid 8, carry out the Suzuki linked reaction with bromo two amido borines 3 once more, obtain perfluorocyclobutanearyl aryl-ether tripolymer 9.
Two amido borines are reduced to boric acid once more, boric acid repeats to carry out the Suzuki coupling with bromo two amido borines 3 and remove the amido reaction, can introduce a perfluorocyclobutanearyl aryl-ether unit at every turn, obtain containing the perfluorocyclobutanearyl aryl-ether oligopolymer of accurate perfluorocyclobutanearyl aryl-ether unit number n.The Suzuki linked reaction can be with reference to aforementioned with the reaction conditions that is reduced to boric acid.
R described in the perfluorocyclobutanearyl aryl-ether oligopolymer of the present invention
1Or R
2Substituting group can further react, and contains the functional oligomer or the polymkeric substance of perfluorocyclobutanearyl aryl-ether structure as reaction building block preparation.Concrete example application is as follows:
1. perfluorocyclobutanearyl aryl-ether trimer 10 prepares perfluorocyclobutanearyl aryl-ether oligopolymer 11 by the end group thermal cyclization reaction:
R
1For trifluoro-ethylene oxygen base, under atmosphere of inert gases, perfluorocyclobutanearyl aryl-ether tripolymer 10 carries out thermal cyclization and poly-reaction, generates perfluorocyclobutanearyl aryl-ether 7 polymers 11.Temperature of reaction is 150 ℃～250 ℃, and the reaction times is 12～24 hours, and solvent for use is a phenyl ether.
2. the perfluorocyclobutanearyl aryl-ether oligopolymer contains the unitary polymkeric substance of perfluorocyclobutanearyl by the prepared in reaction of end group:
(1) boric acid 12 and excessive hydrogen peroxide reaction (recommending to stir) 12～24 hours, through extraction, dry, filter, concentrate and the rapid column chromatography purifying after obtain containing the phenol 13 of perfluorocyclobutanearyl aryl-ether structure.Hydrogen peroxide is recommended the concentration with 30%.Solvent is recommended tetrahydrofuran (THF) or methylene dichloride.
(2) in the presence of triethylamine with the phenol 13 and methacrylic chloride generation esterification of gained in the step (1), after filtration, concentrate and the rapid column chromatography purifying after obtain containing two unitary methacrylate monomer 14 of PFCB.Described phenol 13 is 1:(1～2 with the reinforced mol ratio of methacrylic chloride), phenol 13 is 1:(1～2 with the reinforced mol ratio of triethylamine).Temperature of reaction is 0 ℃, and the reaction times is 1～3 hour.Solvent is recommended methylene dichloride or 1-butanone.
(3) monomer 14 of gained carries out free radical body or solution polymerization in the step (2) under the initiation of traditional radical polymerization initiator, precipitates in precipitation agent, obtains containing the unitary polymethacrylate polymkeric substance 15 of PFCB through filtration and drying.Described monomer 14 is 100/1～25/1 with the reinforced mol ratio of radical initiator, and temperature of reaction is 50～70 ℃, and the reaction times is 1～24 hour.Radical polymerization initiator is recommended Diisopropyl azodicarboxylate, benzoyl peroxide, the peroxide-3,5,5 Trimethylhexanoic acid tert-butyl ester or tert-butyl peroxide, and solvent for use is recommended toluene, methyl-phenoxide or phenyl ether.
(4) number-average molecular weight (M that contains the unitary polymethacrylate polymkeric substance 15 of PFCB of gained in the step (3)
n) scope be 10,000 to 1,000,000g/mol, molecular weight distribution (M
w/ M
n) be 1.4-4.0.Polymkeric substance 15 has higher thermostability, can potentially use as a kind of heat resistance synthetic glass, for example M
n=80,300g/mol, M
w/ M
n=1.58 polymkeric substance, its second-order transition temperature (T
g) be 193.3 ℃.
Above-mentioned all boric acid is obtained by the rapid column chromatography separation as reaction intermediate, is not further purified direct use.The boric acid end-group structure is confirmed by nuclear magnetic resonance spectrum, infrared spectra; The structure of the compound that all the other are new is confirmed by nuclear magnetic resonance spectrum, infrared spectra and mass spectrum; The structure of all polymkeric substance is confirmed by nuclear magnetic resonance spectrum, infrared spectra and gel chromatography.
Perfluorocyclobutanearyl aryl-ether oligopolymer of the present invention contains active end group, can be as the synthetic building block of perfluorocyclobutanearyl aryl-ether polymkeric substance, further preparation contains the functional oligomer or the polymkeric substance of perfluorocyclobutanearyl aryl-ether, can be applied to prepare optical material, aeroplane dope, Organic Light Emitting Diode or battery proton exchange membrane material.
The invention provides a kind of new perfluorocyclobutanearyl aryl-ether oligopolymer and the method for using iterative Suzuki coupled to prepare.This method has at first prepared iterative Suzuki coupled intermediate 3, and it contains 1,8-two amido naphthalene boronic acids blocking groups.1,8-two amido naphthalene boronic acids blocking groups can be avoided the side reaction in the cross-coupling reaction effectively, and can remove with acid easily after reaction finishes, and are reduced to boric acid.Intermediate 3 carries out the Suzuki linked reaction with aryl boric acid, in product, introduce a perfluorocyclobutanearyl aryl-ether unit, and can be reduced to boric acid easily, and further repeat the Suzuki linked reaction with intermediate 3, constantly in product, introduce perfluorocyclobutanearyl aryl-ether unit.Use iterative Suzuki coupled to prepare the perfluorocyclobutanearyl aryl-ether oligopolymer, only need preparation intermediate 3, just can utilize the preparation of Suzuki linked reaction to contain the oligopolymer of specific perfluorocyclobutanearyl aryl-ether unit number n easily.Reaction conditions is simple, the reaction intermediate stable in properties; The polarity of each step product differs bigger, is easy to separate, and is suitable for a large amount of preparations.And the unitary number n of the contained perfluorocyclobutanearyl of oligopolymer can be by accurately controlling with the Suzuki linked reaction number of times of intermediate 3.
The oligopolymer of gained contains the active reaction end group, and active end group can further carry out functional oligomer or the polymkeric substance that prepared in reaction contains the perfluorocyclobutanearyl aryl-ether structure.
Embodiment:
Can further understand the present invention by following examples, but not limit the scope of the invention.
1.4-bromo-(2-bromine tetrafluoro oxyethyl group base) benzene is synthetic
(173g 1mol) and methyl-sulphoxide (700mL), stirs and makes the phenol dissolving to add p bromophenol in the 1000mL three-necked bottle of water trap and reflux condensing tube is housed.Behind oil pump decompression 30min, with nitrogen in solution bubbling 30min to remove the oxygen in the solution.Under nitrogen protection, add potassium hydroxide (68g, 1mol, 82%).In solution, behind the bubbling 30min, add the new toluene (200mL) that steams with nitrogen.Under nitrogen protection, heating up refluxes system, constantly divides the water layer that goes in the water trap.Reflux approximately behind the 24h, when no longer including water layer in the water trap, stop heating, the room temperature cooling.After treating the system cool to room temperature, remove water trap fast, change the exsiccant constant pressure funnel.Reaction system is put into ice-water bath, slowly drip 1 with dropping funnel, (130mL 1.1mol), keeps temperature of reaction system to be lower than 30 ℃ to the 2-dibromotetrafluoroethane, and 4h dropwises.The question response system is replied room temperature, is warming up to 30 ℃ and stirs 8h, is warming up to 50 ℃ then and stirs 6h.
After the room temperature cooling, use the B suction filtration, wash the salt of generation with small amount of acetone.Add 500mL water in the filtrate, tell lower floor's organic phase, organic phase again with the 300mL washing once.Merge water, with n-hexane extraction (100mL * 6).Merge organic phase, use anhydrous magnesium sulfate drying.Suction filtration removes with Rotary Evaporators and to desolvate.Remaining black liquor underpressure distillation, the cut of 64 ℃/95Pa of collection gets the 260g colourless transparent liquid, and productive rate is 74%.
1H?NMR(300MHz，CDCl
3)：δ?7.12(d，J＝7.8Hz，2H)，7.53(d，J＝7.8Hz，2H).
19F?NMR(282MHz，CDCl
3)：δ-86.56(t，J＝3.95Hz，2F)，-68.54(t，J＝3.95Hz，2F).IR(KBr)：1586，1486，1329，1202，1163，1133，1098，1014，933，849，782，657cm
-1.
2.4-bromine (trifluoro-ethylene oxygen base) benzene is synthetic
On the three-necked bottle of 1000mL, reinstall the stream prolong, and the adding zinc powder (39.1g, 0.60mol).After substituting nitrogen with oil pump, with gas fire baking, inflated with nitrogen afterwards.Triplicate.Behind the cool to room temperature, add the new acetonitrile 500mL that steams.Adding 4-bromo-(2-bromine tetrafluoro oxyethyl group base) benzene in dropping funnel (174.5g, 0.50mol).Oil bath is warmed up to 110 ℃ refluxes acetonitrile.Slowly drip 4-bromo-(2-bromine tetrafluoro oxyethyl group base) benzene then, in 4h, dropwise.In the dropping process, acetonitrile refluxes violent.Dropwise, at 110 ℃ of reaction 10h.Stop heating, the room temperature cooling is left standstill.Generate ground salt and be deposited in the three-necked bottle bottom, inclining supernatant liquid; Remaining reactants adds washing, with n-hexane extraction (100mL * 3), and the organic phase anhydrous magnesium sulfate drying.Merge organic phase, remove with rotary evaporation and desolvate, the remaining liq underpressure distillation, the cut of collection boiling point 42 ℃/95 Pa obtains the 96.7g colourless transparent liquid, productive rate 77%.
1H?NMR(300MHz，CDCl
3)：δ?6.99(d，J＝8.4Hz，2H)，7.48(d，J＝8.4Hz，2H).
19F?NMR(282MHz，CDCl
3)：δ-134.32(dd，J＝58，106Hz，1F)，-125.94(dd，J＝95，106Hz，1F)，-119.05(dd，J＝58，95Hz，1F).IR(KBr)：1833，1585，1458，1317，1284，1197，1168，1142，1071，1012，824cm
-1.
3.1,2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 synthetic
(50g 20mmol), substitutes after the nitrogen three times with behind the nitrogen bubble 20min, puts into 200 ℃ of oil baths and stirs 24h to add 4-bromine (trifluoro-ethylene oxygen base) benzene in 250mL exsiccant three-necked bottle.After the room temperature cooling, underpressure distillation, the cut of 198 ℃/70Pa of collection boiling point obtains the 43g colourless transparent liquid, and productive rate is 86%.
1H?NMR(300MHz，CDCl
3)：δ?7.03(d，J＝8.4Hz，4H)，7.46(d，J＝8.4Hz，4H).
19F?NMR(282MHz，CDCl
3)：δ-131.89，-131.78，-131.44，-130.70，-130.65，-129.92，-129.20，-128.40，-127.16.IR(KBr)：1584，1486，1312，1204，1012，963，824cm
-1.
4.Suzuki linked reaction intermediate 3 is synthetic
The decompression of 250mL three-necked bottle oil pump is roasting with gas fire, charges into nitrogen, triplicate after the room temperature cooling.(25.3g 50mmol) and behind the THF (100mL), puts into the dry ice-propanone bath to add 1.Behind the cooling 20min, slow Dropwise 35 mL n-Butyl Lithium (55mmol).Dropwising the back keeps low temperature to stir 2h.Slowly drip triisopropyl borate ester (17.5mL, 75mmol) after, keep low temperature 1h.Treat that cryostat replys room temperature naturally, stirring is spent the night.Reaction solution is poured in the 200mL 2M HCl solution, with extracted with diethyl ether (50mL * 3).Merge organic phase, use anhydrous magnesium sulfate drying.Behind the suction filtration with rotary evaporation remove desolvate faint yellow sticky solid 2.Rapid column chromatography (sherwood oil: obtain the yellow sticky solid of 7.8g after the ethyl acetate=4:1), be not further purified.In 50mL exsiccant three-necked bottle, add boric acid 2 (1.03g, 2.1mmol) and 1,8-two amido naphthalenes (0.34g, 2.1mmol), substitute nitrogen three times after, add the new toluene that steams of 20mL, use nitrogen bubble 20min.Be warming up to refluxing toluene, tell the water of generation with water trap.Behind the reaction 2h, the room temperature cooling.Except that desolvating, (normal hexane: ethyl acetate=20:1), obtain white sticky solid 1.03g, productive rate is 83% to rapid column chromatography with rotary evaporation.
1H NMR (300MHz, CDCl
3): δ 5.98 (s, 2H), 6.42 (d, J=6.6Hz, 2H), 7.01-7.21 (m, 8H), 7.46 (d, J=8.1Hz, 2H), 7.62 (d, J=7.2Hz, 2H).
19F NMR (282MHz, CDCl3): δ-132.15 ,-131.97 ,-131.41 ,-131.34 ,-130.59 ,-129.85 ,-129.26 ,-128.98 ,-128.47 ,-128.12 ,-127.04.
13C NMR (75MHz, CDCl
3): δ 106.1,117.6, and 117.9,118.0,118.3,119.8,119.9,120.4,127.6,129.9,132.79,133.1,136.3,140.8,151.5,154.0.IR (KBr): 3421,3055,2976,1629,1603,1492,1411,1310,1203,1086,1012,962,819,763cm
-1.MS (MALDI) m/z:592.5.HRMS:C
26H
16BBrF
6N
2O
2Calculated value 592.0392 (measured value 592.0393)
5. compound 13 is synthetic
The 250mL three-necked bottle that reflux condensing tube is housed is dried with gas fire, substitute add behind the nitrogen boric acid 12 (2.18g, 10mmol) and compound 3 (5.92g, 10mmol).Add Pd (PPh after substituting nitrogen three times
3)
4(0.34g 0.3mmol), substitutes nitrogen three times.Add the new toluene 50mL that steams, nitrogen bubble 30min.Will be with the K of nitrogen bubble
2CO
3(6.85g, 50mmol) aqueous solution 10mL joins in the three-necked bottle, is warming up to 90 ℃ of reaction 12h.Reaction finishes the back and adds 50mL water, with ethyl acetate extraction (50mL * 3), uses anhydrous magnesium sulfate drying.Remove with rotary evaporation behind the suction filtration and desolvate, (normal hexane: ethyl acetate=20:1) obtain faint yellow solid 4.25g, productive rate is 62% to rapid column chromatography.
1H NMR (300MHz, CDCl
3): δ 5.97 (s, 2H), 6.41 (d, J=6.9Hz, 2H), 7.05-7.21 (m, 10H), 7.49-7.56 (m, 4H), 7.63 (d, J=8.1Hz, 2H).
19F NMR (282MHz, CDCl
3): δ-134.39 (dd, J=59,111Hz, 1F) ,-131.69--128.20 (m, 6F) ,-126.75 (dd, J=91,111Hz, 1F) ,-119.82 (dd, J=59,91Hz, 1F).
13C NMR (75MHz, CDCl
3): δ 106.2,116.3, and 117.7,118.1,118.5,118.9,120.1,127.6,128.3,128.5,133.1,136.3,136.8,137.1,137.3,140.8,152.0,154.2,154.6.IR (KBr): 3422,3041,2978,1833,1629,1602,1493,1411,1313,1276,1198,1168,1140,1085,962,819,764cm
-1.MS (MALDI) m/z:686.7.HRMS:C
34H
20BF
9N
2O
3Calculated value 686.1423 (measured value 686.1421).
6. perfluorocyclobutanearyl aryl-ether dimer 15 is synthetic
(3.43mmol 5mmol) is dissolved among the 20mL THF, adds the stirring of the 1mL vitriol oil and spends the night with compound 13.Add 20mL water, with ethyl acetate extraction (30mL * 3), anhydrous magnesium sulfate drying.Rotary evaporation removes and desolvates behind the suction filtration.(normal hexane: ethyl acetate=3:1) obtain purple solid 14 is not further purified rapid column chromatography.The 250mL three-necked bottle that reflux condensing tube is housed is dried with coal gas, substitute add behind the nitrogen boric acid 14 and compound 3 (2.96g, 5mmol).Add Pd (PPh after substituting nitrogen three times
3)
4(0.17g 0.15mmol), substitutes nitrogen three times.Add the new toluene 50mL that steams, nitrogen bubble 30min.Will be with the K of nitrogen bubble
2CO
3(3.4g, 25mmol) aqueous solution 10mL joins in the three-necked bottle, is warming up to 90 ℃ of reaction 12h.Reaction finishes the back and adds 50mL water, with ethyl acetate extraction (50mL * 3), uses anhydrous magnesium sulfate drying.Remove with rotary evaporation behind the suction filtration and desolvate, (normal hexane: ethyl acetate=20:1) obtain faint yellow solid 2.58g, productive rate is 65% to rapid column chromatography.
1H NMR (300MHz, CDCl
3): δ 5.98 (s, 2H), 6.40 (d, J=6.9Hz, 2H), 7.05-7.24 (m, 14H), 7.48-7.51 (m, 8H), 7.63 (d, J=7.8Hz, 2H).
19F NMR (282MHz, CDCl
3): δ-134.41 (dd, J=59,111Hz, 1F) ,-131.76--128.10 (m, 12F) ,-126.78 (dd, J=91,111Hz, 1F) ,-119.83 (dd, J=59,91Hz, 1F).
13C NMR (75MHz, CDCl
3): δ 106.1,116.2, and 117.8,118.6,128.2,128.5,133.1,136.2,137.0,140.8,152.0,154.1,154.6.IR (KBr): 3428,3043,2977,2871,1832,1629,1602,1494,1411,1312,1277,1198,1168,1141,962,820,765cm
-1.MS (MALDI) m/z:1032.2.HRMS:C
50H
28BF
15N
2O
5Calculated value 1032.1852 (measured value 1032.1852).
7. perfluorocyclobutanearyl aryl-ether tripolymer 10 is synthetic
(1.03g 1mmol) is dissolved among the 20mL THF, adds the stirring of the 1mL vitriol oil and spends the night with compound 15.Add 20mL water, with ethyl acetate extraction (30mL * 3), anhydrous magnesium sulfate drying.Rotary evaporation removes and desolvates behind the suction filtration.(normal hexane: ethyl acetate=3:1) obtain purple solid 16 is not further purified rapid column chromatography.The 250mL three-necked bottle that reflux condensing tube is housed is dried with gas fire, substitute add behind the nitrogen boric acid 16 and compound 3 (0.592g, 1mmol).Add Pd (PPh after substituting nitrogen three times
3)
4(0.03g 0.03mmol), substitutes nitrogen three times.Add the new toluene 50mL that steams, nitrogen bubble 30min.Will be with the K of nitrogen bubble
2CO
3(0.685g, 5mmol) aqueous solution 10mL joins in the three-necked bottle, is warming up to 90 ℃ of reaction 12h.Reaction finishes the back and adds 50mL water, with ethyl acetate extraction (50mL * 3), uses anhydrous magnesium sulfate drying.Remove with rotary evaporation behind the suction filtration and desolvate, (normal hexane: ethyl acetate=20:1) obtain faint yellow solid 0.82g, productive rate is 60% to rapid column chromatography.
1H NMR (300MHz, CDCl
3): δ 5.98 (s, 2H), 6.40 (d, J=6.9Hz, 2H), 7.05-7.24 (m, 18H), 7.48-7.50 (m, 12H), 7.63 (d, J=8.4Hz, 2H).
19F NMR (282MHz, CDCl
3): δ-134.42 (dd, J=59,111Hz, 1F) ,-131.75--128.10 (m, 18F) ,-126.77 (dd, J=91,111Hz, 1F) ,-119.83 (dd, J=59,91Hz, 1F).
13C NMR (75MHz, CDCl
3): δ 106.1,116.2, and 117.8,118.6,128.2,128.5,133.1,136.2,137.0,140.8,152.0,154.1,154.6.IR (KBr): 3432,3044,2977,2870,1833,1629,1602,1495,1410,1309,1198,1168,1141,1119,962,821,765cm
-1.MS (MALDI) m/z:1378.3.HRMS:C
66H
36BF
21N
2O
7Calculated value 1378.2280 (measured value 1378.2272).
8. the thermal cyclization dimerization reaction of perfluorocyclobutanearyl aryl-ether tripolymer 10
(200mg) places the exsiccant reaction tubes with compound 10, substitutes nitrogen three times.After adding the 2mL phenyl ether, place 180 ℃ oil bath to stir 24h.Rapid column chromatography obtains white solid 103mg, and productive rate is 52%.
1H NMR (300MHz, CDCl
3): δ 5.97 (s, 4H), 6.40 (d, J=6.6Hz, 4H), 7.05-7.23 (m, 36H), 7.47-7.50 (m, 24H), 7.63 (d, J=7.8Hz, 4H).
19F NMR (282MHz, CDCl
3): δ-131.76 ,-131.46 ,-130.59 ,-129.89 ,-129.14 ,-128.99 ,-128.36 ,-128.20.
13C NMR (75MHz, CDCl
3): δ 106.1,117.7,118.0,118.5,128.2,128.3,133.1,136.9,137.2,140.8,152.1.IR (KBr): 3439,2975,2856,1629,1602,1495,1410,1304,1265,1198,1118,961,821,765cm
-1.MS (MALDI) m/z:2756.2.HRMS:C
132H
72B
2F
42N
4O
14Calculated value 2756.4561 (measured value 2756.4566).
9. compound 17 is synthetic
(600mg 0.66mmol) is dissolved in the 20mL tetrahydrofuran (THF), stirs the hydrogen peroxide that is added dropwise to 5mL30% down with compound 16.React after 12 hours, remove with rotary evaporation and desolvate, (normal hexane: ethyl acetate=5:1) obtain white sticky solid 535mg, productive rate is 92% to rapid column chromatography.
1H?NMR(300MHz，CDCl
3)：δ?4.82(s，1H)，6.77(d，J＝6.0Hz，2H)，7.08(d，J＝9.6Hz，2H)，7.24-7.36(m，8H)，7.48-7.50(m，8H).
19F?NMR(282MHz，CDCl
3)：δ-134.42(dd，J＝56，111Hz，1F)，-132.16--128.34(m，12F)，-126.77(dd，J＝94，111Hz，1F)，-119.83(dd，J＝56，94Hz，1F).IR(KBr)：3386，2980，1606，1508，1496，1313，1277，1198，1141，962，825cm
-1.
13C?NMR(75MHz，CDCl
3)：δ?116.1，116.2，116.3，118.5，118.9，120.0，120.5，128.3，128.5，129.8，136.9，137.1，146.0，152.0，154.7.
10. contain the synthetic of the unitary methacrylate monomer 18 of PFCB
With 17 (500mg 0.57mmol) places the exsiccant three-necked bottle, add the dissolving of 20mL methylene dichloride after, add triethylamine (0.1mL, 0.72mmol).Reaction flask is put into ice-water bath, slowly drip methacrylic chloride (0.1mL, 0.96mmol).Dropwise the back and stir 1h in ice-water bath, suction filtration is removed the salt of generation, removes with rotary evaporation and desolvates.Rapid column chromatography (normal hexane: after the ethyl acetate=50:1), obtain 448mg (83%) 18, be colourless transparent liquid.
1H?NMR(300MHz，CDCl
3)：δ?2.04(s，3H)，5.76(s，1H)，6.33(s，1H)，7.08-7.23(m，12H)，6.48-7.50(m，8H).
19F?NMR(282MHz，CDCl
3)：δ-134.40(dd，J＝57，108Hz，1F)，-131.84--128.36(m，12F)，-126.79(dd，J＝96，108Hz，1F)，-119.85(dd，J＝57，96Hz，1F).IR(KBr)：2928，1740，1636，1606，1316，1278，1198，1121，1016，962，824cm
-1.
13C?NMR(75MHz，CDCl
3)：δ?18.3，116.3，118.5，119.2，119.7，122.8，122.9，127.6，128.3，128.5，135.6，136.8，137.3，147.9，148.1，149.9，152.1，171.3.
11. the radical polymerization of monomer 18
Monomer 18 (200mg) and AIBN (5mg) are added in the exsiccant reaction tubes, substitute nitrogen three times.Add the new toluene (1mL) that steams, put into liquid nitrogen freezing, the 5min that bleeds, inflated with nitrogen thaws.Circulate after three times, reaction tubes is put into 70 ℃ of oil baths at once, stir 2h.Reaction tubes is taken out from oil bath, put into liquid nitrogen cancellation reaction.After rising again, add 1mL THF dilution, solution is splashed in the 100mL methyl alcohol precipitate, obtain the white solid powder behind the suction filtration.Post precipitation once more, vacuum-drying 24h obtains 125mg white polymer powder, and yield is 63%.
GPC：M
n＝11，800g/mol，M
w/M
n＝2.27.
1H?NMR(300MHz，CDCl
3)：δ?1.17-1.78(m)，7.17-7.40(m).
19F?NMR(282MHz，CDCl
3)：δ-134.84，-131.44--127.84，-126.02，-120.23.FT-IR(KBr)：2930，1744，1607，1497，1315，1199，1007，961，852cm
-1。
Claims (9)
1. perfluorocyclobutanearyl aryl-ether oligopolymer is characterized in that structural formula is as follows:
R wherein
1Be-F ,-OCF=CF
2, C
1～C
4Alkyl, C
1～C
4Alkoxyl group or phenyl;
R
2For :-B (OH)
2,
Or
The scope of n is 1～10 integer; The scope of m is 10～1000 integer;
Represent cis or transconfiguration.
2. the intermediate of a perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1 is characterized in that structural formula is as follows:
3. the preparation method of a perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1 is characterized in that being made by following method:
(1) under atmosphere of inert gases, n-Butyl Lithium is added to 1, in the tetrahydrofuran solution of 2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1, react after 1～2 hour, boric acid ester is added drop-wise in the reaction system, reacted 6～12 hours, and added the hydrochloric acid soln acidifying after the answer room temperature, after separating, obtain containing the bromo boric acid 2 of perfluorocyclobutanearyl aryl-ether structure; Described n-Butyl Lithium and 1, the mol ratio of 2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 is (1～1.2): 1, boric acid ester and 1, the mol ratio of 2-two (4-bromophenyl) trans-1,1,2,2,3,4-Hexafluorocyclobutane 1 is (1.5～3): 1, temperature of reaction is-65 ℃～-80 ℃;
(2) under atmosphere of inert gases, with bromo boric acid 2 and 1,8-two amido naphthalenes refluxed in solvent 2～12 hours, remove the water that dereaction generated simultaneously, after separation and purification, obtain containing the bromo two amido borines 3 of perfluorocyclobutanearyl aryl-ether structure, described bromo boric acid 2 and 1, the mol ratio of 8-two amido naphthalenes is 1:(1～1.5); Reaction solvent is toluene or dimethylbenzene;
(3) under atmosphere of inert gases, will contain R
1Substituent aryl boric acid 4 carries out the Suzuki linked reaction with bromo two amido borines 3, obtains containing two amido borines 5 of perfluorocyclobutanearyl aryl-ether structure after separation and purification, and described boric acid 4 is (1～5) with the mol ratio of bromo two amido borines 3: 1;
(4) two amido borines 5 removed amido in 12～24 hours with excessive acid-respons, obtained containing the boric acid 6 of perfluorocyclobutanearyl aryl-ether structure through separation; Boric acid 6 carries out the Suzuki linked reaction with bromo two amido borines 3, obtains containing two amido borines of two perfluorocyclobutanearyl aryl-ether units;
(5) two amido borane reductions of gained are boric acid, carry out the Suzuki linked reaction with bromo two amido borines 3 once more, obtain containing two amido borines of three perfluorocyclobutanearyl aryl-ether units; Two amido borines are reduced to boric acid once more, boric acid repeats to carry out the Suzuki coupling with bromo two amido borines 3 and remove the amido reaction, can introduce a perfluorocyclobutanearyl aryl-ether unit at every turn, obtain the described perfluorocyclobutanearyl aryl-ether oligopolymer that contains accurate perfluorocyclobutanearyl aryl-ether unit number n of claim 1, n according to claim 1;
Described 1～6 structural formula is as follows:
R in the formula
1According to claim 1.
4. the preparation method of a perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1, it is characterized in that preparing bromo boric acid 2 used boric acid esters is trimethyl borate or triisopropyl borate ester.
5. the preparation method of a perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1 is characterized in that the used transition-metal catalyst of Suzuki linked reaction is a zero valent palladium catalyst; The mol ratio of zero valent palladium catalyst and bromo two amido borines 3 is (0.03～0.05): 1.
6. the preparation method of a perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1 is characterized in that described Suzuki linked reaction is to react under the effect of solvent neutralization bases, and described alkali is yellow soda ash, salt of wormwood, cesium carbonate or cesium fluoride; The mol ratio of described alkali and bromo two amido borines 3 is (1～5): 1; Described solvent be toluene or tetrahydrofuran (THF) respectively with the mixed solvent of water.
7. the preparation method of a perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1 is characterized in that it is sulfuric acid or hydrochloric acid that two amido borines remove the used acid of amido reaction; Used solvent is tetrahydrofuran (THF) or methylene dichloride.
8. the purposes of class perfluorocyclobutanearyl aryl-ether oligopolymer as claimed in claim 1, it is characterized in that prepared perfluorocyclobutanearyl aryl-ether oligopolymer contains active end group, can be as the synthetic building block of perfluorocyclobutanearyl aryl-ether polymkeric substance, further preparation contains the functional oligomer or the polymkeric substance of perfluorocyclobutanearyl aryl-ether.
9. the purposes of class perfluorocyclobutanearyl aryl-ether polymerization as claimed in claim 8 polymers is characterized in that being used to prepare optical material, aeroplane dope, Organic Light Emitting Diode or battery proton exchange membrane material.
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| CN104109229A (en) * | 2013-04-19 | 2014-10-22 | 中国科学院上海有机化学研究所 | Low-dielectric constant polymer containing binaphthyl and hexafluorocyclobutyl ether units and its preparation method and use |
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| US5225515A (en) * | 1991-04-17 | 1993-07-06 | The Dow Chemical Company | Poly(aryl ether) polymers containing perfluorocyclobutane rings |
| US6649715B1 (en) * | 2000-06-27 | 2003-11-18 | Clemson University | Fluoropolymers and methods of applying fluoropolymers in molding processes |
| US6953653B2 (en) * | 2001-08-30 | 2005-10-11 | Clemson University | Fluoropolymer compositions, optical devices, and methods for fabricating optical devices |
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| CN104109229A (en) * | 2013-04-19 | 2014-10-22 | 中国科学院上海有机化学研究所 | Low-dielectric constant polymer containing binaphthyl and hexafluorocyclobutyl ether units and its preparation method and use |
| WO2014169651A1 (en) * | 2013-04-19 | 2014-10-23 | 中国科学院上海有机化学研究所 | Low dielectric constant polymer containing dinaphthyl and hexafluorocyclobutyl ether unit, preparation method and use |
| US9518151B2 (en) | 2013-04-19 | 2016-12-13 | Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences | Low dielectric constant polymer containing dinaphthyl and hexafluorocyclobutyl ether unit, preparation method and use |
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| CN117264316A (en) * | 2023-08-24 | 2023-12-22 | 江苏海聚新材料科技有限公司 | Antistatic polyolefin composition and preparation method thereof |
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