CN101362691B - Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application - Google Patents
Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application Download PDFInfo
- Publication number
- CN101362691B CN101362691B CN200810200128A CN200810200128A CN101362691B CN 101362691 B CN101362691 B CN 101362691B CN 200810200128 A CN200810200128 A CN 200810200128A CN 200810200128 A CN200810200128 A CN 200810200128A CN 101362691 B CN101362691 B CN 101362691B
- Authority
- CN
- China
- Prior art keywords
- perfluorocyclobutanearyl
- ether unit
- preparation
- unitary
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 Cc1ccc(*)cc1 Chemical compound Cc1ccc(*)cc1 0.000 description 5
- QTJSTTBYEOELOW-UHFFFAOYSA-N Cc(cc1)ccc1ON Chemical compound Cc(cc1)ccc1ON QTJSTTBYEOELOW-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a function acrylic ester monomer containing perfluor cyclobutyl aryl ether unit, a preparation method and the application thereof. The preparation method comprises a three-step reactions: firstly, thermal cyclization reaction is carried out between trifluoro vinyl aryl ether and trifluoro vinyl (4-methoxyphenyl) ether to produce perfluor cyclobutyl aryl ether, and then methyl is removed to obtain phenol containing perfluor cyclobutyl aryl ether unit, finally, by esterification, acrylic ester monomer containing perfluor cyclobutyl aryl ether unit is obtained. The monomercan be used for preparing polyacrylate polymer containing perfluor cyclobutyl aryl ether unit.
Description
Technical field
The present invention relates to contain functional acrylic esters monomers, preparation method and the purposes of perfluorocyclobutanearyl (PFCB) aryl-ether unit.
Background technology
Perfluorocyclobutanearyl aryl-ether aryl ethers polymkeric substance is by the researchist of DOW Chemical (Dow Chemical Co.) one type of new fluoropolymer in exploitation in 1993.Usually (trifluorovinyl, TFVE) [2 π+2 π] thermal cyclization polymerization takes place and generates between 150 ℃ to 250 ℃ temperature this type fluoropolymer in the aryl ethers monomer, need not any initiator or catalyzer, does not have micromolecular compound simultaneously and emits by trifluoro vinyl.As a kind of novel fluoropolymer, not only have the traditional premium properties of fluoropolymer based on the polymkeric substance of PFCB, like heat/oxidative stability and chemical resistance etc., and have good solution processing performance.
In recent years the research based on the polymkeric substance of PFCB mainly being concentrated on uses different trifluoro vinyl aryl ethers monomers to carry out thermal cyclization the polymerization synthetic different homopolymer and the random copolymers that are connected by PFCB.Yet, owing to 150 ℃ of higher relatively polymerization temperatures (>) and unique polymerization mechanism, the design of the functional group of connection trifluoro vinyl and synthetic being restricted in the monomer, the type of polymer based on PFCB that document is reported is less.Simultaneously, be difficult to general commercial monomer introduced in the trifluoro vinyl aryl ethers monomer obtaining compound fluoropolymer, be restricted based on the range of application of the polymkeric substance of PFCB.
The PFCB unit is incorporated in the general commercial polymer, and the polymkeric substance of the novel PFCB of containing of gained will not only keep the performance of commercial polymer, and have the premium properties of PFCB aryl ethers polymkeric substance, thereby expand the range of application based on the polymkeric substance of PFCB.Based on this, the present invention has synthesized and has contained that PFCB is unitary to gather (methyl) acrylic ester monomer, and has carried out radical polymerization and active free radical polymerization, obtains the novel unitary polyacrylic polymer of PFCB that contains.
Summary of the invention
The objective of the invention is to through molecular designing; Through stable covalent linkage perfluorocyclobutanearyl (PFCB) unit is introduced in the acrylate monomer; Prepare the novel unitary acrylate monomer of PFCB that contains; And utilize free radical polymerisation process, prepare the novel unitary polyacrylate polymers of PFCB that contains.
The object of the invention is further described and is provided the unitary acrylate monomer of a kind of PFCB of containing;
The object of the invention also provides a kind of above-mentioned PFCB of containing the preparation method of unitary acrylate monomer;
Another object of the present invention provides the purposes of the unitary acrylate monomer of a kind of above-mentioned PFCB of containing, and prepares the novel unitary polyacrylate polymers of PFCB that contains.
Content of the present invention is to be raw material with the phenol that contains para-orienting group, and preparation contains the unitary acrylate functional monomer of PFCB.This functional monomer and common acrylic ester monomer through radical polymerization or the copolymerization of active free radical polymerization method, obtain containing the unitary polyacrylate polymers of PFCB.It is characterized in that this functional monomer direct polymerization can obtain containing the unitary polyacrylate polymers of PFCB; And the unitary content of PFCB can prepare the different polyacrylate polymers of a series of PFCB unit content thus through changing functional monomer and the common monomeric control recently that feeds intake in the polymkeric substance.
The unitary acrylate monomer of the novel PFCB of containing provided by the present invention has following structure:
Wherein R is C
1～C
4Alkyl.
Preparation process of the present invention is following:
In the above-mentioned reaction formula, reflux representes to reflux, and DMSO representes DMSO 99.8MIN., and toluene representes toluene, and Δ is represented heating, and r.t. representes room temperature, and 2-butanone representes 2-butanone.
(1) under atmosphere of inert gases; With DMSO 99.8MIN. (DMSO) and toluene is solvent; The phenol 5 that contraposition contains substituent R reacted under the condition of refluxing toluene 24～48 hours with KOH; After removing the water that is generated reaction system is cooled to below 30 ℃, slowly drips exsiccant 1, the 2-dibromotetrafluoroethane also keeps temperature of reaction system to be lower than 30 ℃.After dropwising reaction system was stirred 12 hours at 50 ℃, through extraction, dry, filter, concentrate and step such as underpressure distillation obtains contraposition R substituted (2-bromine tetrafluoro oxyethyl group base) benzene 6.Described phenol 5 is 1/1 with the reinforced mol ratio of KOH, phenol 5 and 1, and the reinforced mol ratio of 2-dibromotetrafluoroethane is 1/1.1.
(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 product 6 in the step (1) slowly is added drop-wise in the reaction system, reduction reaction takes place with Zn in compound 6 immediately.After dropwising, keep reaction system to reflux 4～12 hours, through filtering, concentrate and step such as underpressure distillation obtaining the substituted trifluoro-ethylene oxygen of contraposition R base benzene 1.Said compound 6 is 1/1 with the reinforced mol ratio of Zn, and compound 6 is 1mol/1000mL with the reinforced relation of acetonitrile.
(3) under atmosphere of inert gases,, behind the rapid column chromatography purifying, obtain containing the unitary compound 2 of PFCB with resulting trifluoro vinyl phenyl ether 1 and trifluoro vinyl (4-p-methoxy-phenyl) ether generation thermal cyclization reaction in the step (2).Said compound 1 is 1/1 with the reinforced mol ratio of trifluoro vinyl (4-p-methoxy-phenyl) ether, and temperature of reaction is 150 ℃～250 ℃, and the reaction times is 12～24 hours.Be reflected in body or the solvent and carry out, solvent is a phenyl ether.
(4) under atmosphere of inert gases and 0 ℃, the dichloromethane solution of boron tribromide slowly is added drop-wise in the dichloromethane solution of resultant compound 2 in the step (3) demethylation reaction takes place.After dropwising, replied stirring at room 1～3 hour.Through extraction, dry, filter, concentrate and the rapid column chromatography purifying after obtain containing the unitary phenol 3 of PFCB.Said compound 2 is 3/1～1/1 with the reinforced mol ratio of boron tribromide.
(5) in the presence of triethylamine with the phenol of gained in the step (4) 3 and acrylate chloride or methacrylic chloride generation esterification, through filtering, obtaining containing PFCB unitary (methyl) acrylate monomer 4 behind the concentrated and rapid column chromatography purifying.Said phenol 3 is 1 with the reinforced mol ratio of (methyl) acrylate chloride: (1～3), phenol 3 is 1 with the reinforced mol ratio of triethylamine: (1～3).Temperature of reaction is 0 ℃, and the reaction times is 0.5～2 hour.
(6) preparedly in the step (5) contain PFCB unitary (methyl) acrylate monomer 4 under the initiation of traditional radical initiator; Carry out radical body or solution polymerization; In precipitation agent, precipitate, through filtering and drying obtains containing that PFCB is unitary gathers (methyl) acrylic polymer.Said monomer 4 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.
Used solvent comprises 2-butanone, chloroform, methylene dichloride and THF in the step of the present invention (5).
Used radical initiator comprises Diisopropyl azodicarboxylate, Lucidol in the step of the present invention (6), the peroxide-3,5,5 Trimethylhexanoic acid tert-butyl ester and tert-butyl peroxide, and solvent for use comprises toluene, methyl-phenoxide and phenyl ether.All new small molecules All new compounds are confirmed by nuclear magnetic resonance spectrum, ir spectra and mass spectrum.
The structure of all polymkeric substance is confirmed by nuclear magnetic resonance spectrum, ir spectra and gel chromatography, and partial results is seen the specific embodiment part.The polymkeric substance that for example synthesizes following structure
Embodiment:
Can further understand the present invention through following examples, but not be restriction scope of the present invention.
Synthesizing of embodiment 1 4-methyl-(2-bromine tetrafluoro oxyethyl group base) benzene 7
In the 1000mL three-necked bottle of water trap and reflux condensing tube is housed, add p-cresol (108g, 1mol) and methyl-sulphoxide (DMSO) (700mL), stir and to make the phenol dissolving.Behind oil pump decompression 30min, with nitrogen in solution bubbling 30min to remove the oxygen in the solution.Under nitrogen protection, add Pottasium 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 and removes the water layer 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 tap 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 filtrating, 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.Get the 218g colourless transparent liquid behind the remaining liquid rapid column chromatography (normal hexane), productive rate is 76%.
1H?NMR(300MHz，CDCl
3)：δ2.36(s，3H)，7.11(d，J＝8.7Hz，2H)，7.19(d，J＝8.7Hz，2H).
19F?NMR(282MHz，CDCl
3)：δ-86.41(t，J＝5.2Hz，2F)，-86.41(t，J＝5.2Hz，2F).IR(KBr)：3040，2929，1957，1508，1329，1220，1196，1164，1102，1020，932，844，780cm
-1.
Synthesizing of embodiment 2 trifluoro vinyls (4-aminomethyl phenyl) ether 8
On the three-necked bottle of 1000mL, reinstall the stream prolong, and the adding zinc powder (40g, 0.72mol).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 600mL that steams.Adding compound 7 in tap funnel (156g, 0.55mol).Oil bath is warmed up to 110 ℃ refluxes acetonitrile.Slowly drip compound 7 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, and with n-hexane extraction (100mL * 3), organic phase is used anhydrous magnesium sulfate drying.Merge organic phase, remove with rotary evaporation and desolvate, remaining liq rapid column chromatography (normal hexane) obtains the 71.34g colourless transparent liquid, productive rate 69%.
1H?NMR(300MHz，CDCl
3)：δ2.33(s，3H)，6.99(d，J＝8.1Hz，2H)，7.16(d，J＝8.1Hz，2H).
19FNMR(282MHz，CDCl
3)：δ-134.05(dd，J＝57，108Hz，1F)，-127.61(dd，J＝99，108Hz，1F)，-120.64(dd，J＝57，99Hz，1F).IR(KBr)：3039，2929，1833，1611，1508，1312，1277，1194，1168，1139，1018，820cm
-1.
Synthesizing of embodiment 3 compounds 9
(18.8g, 100mmol) (20.4g 100mmol), substitutes nitrogen three times afterwards with behind the nitrogen bubble 20min, puts into 180 ℃ of oil baths and stirs 24h with trifluoro vinyl (4-p-methoxy-phenyl) ether in 250mL exsiccant three-necked bottle, to add compound 8.After the room temperature cooling, rapid column chromatography obtains the 18.82g colourless transparent liquid, and productive rate is 48%.
1H NMR (300MHz, CDCl
3): δ 2.31 (s, 3H), 3.79 (s, 3H), 6.83 (d, J=7.2Hz, 2H), 7.03-7.13 (m, 6H).
19F NMR (282MHz, CDCl
3): δ-131.83 ,-131.63 ,-131.30 ,-131.03 ,-130.39 ,-130.25 ,-129.81 ,-129.59 ,-129.46 ,-129.02 ,-128.78 ,-128.67 ,-127.51.
13C NMR (75MHz, CDCl
3): δ 20.6,55.6,114.6,117.3,118.2,119.9,123.0,130.1,134.8,135.1,146.1,150.4,157.0.IR (KBr): 3006,2956,2840,1611,1507,1466,1319,1249,1193,1118,1036,962,829cm
-1.MS (EI) m/z (%relativeintensity): 65 (26), 77 (45), 91 (60), 107 (26), 123 (50), 157 (22), 204 (33), 224 (25), 392 (100) .HRMS:C
18H
14F
6O
3Calculated value 392.0847 (measured value 392.0865).
Synthesizing of embodiment 4 compounds 10
(10g 25.5mmol) puts into the exsiccant 250mL three-necked bottle that tap funnel is housed, and adds the dissolving of 150mL methylene dichloride, in tap funnel, adds BBr with compound 9
3(6mL, 50mL dichloromethane solution 24mmol).Reaction flask is put into ice-water bath, slowly drip BBr
3Solution, 1h dropwises.After in ice-water bath, stirring 0.5h, stirring at room 1h.Add ethanol cancellation reaction.After rotary evaporation removed and desolvates, rapid column chromatography obtained the transparent liquid of 8.77g brown, and productive rate is 91%.
1H NMR (300MHz, CDCl
3): δ 2.32 (s, 3H), 6.76 (d, J=7.5Hz, 2H), 7.03-7.13 (m, 6H).
19F NMR (282MHz, CDCl
3): δ-131.82 ,-131.62 ,-131.33 ,-131.17 ,-131.03 ,-130.38 ,-130.23 ,-129.78 ,-129.55 ,-129.42 ,-128.99 ,-128.76 ,-127.51.
13C NMR (75 MHz, CDCl
3): δ 20.6,115.1,116.1,118.1,120.2,123.2,130.1,134.9,145.9,150.2,153.1.IR (KBr): 3361,3040,2928,1610,1508,1452,1319,1194,1171,1019,963,831cm
-1.MS (EI) m/z (%relative intensity): 65 (100), 91 (95), 109 (54), 143 (34), 190 (29), 378 (70) .HRMS:C
17H
12F
6O
3Calculated value 378.0691 (measured value 378.0679).
Synthesizing of embodiment 5 monomers 11
With 10 (5g 13mmol) places the exsiccant three-necked bottle, add the dissolving of 50mL butanone after, add triethylamine (1.8mL, 13mmol).Reaction flask is put into ice-water bath, slowly drip methacrylic chloride (1.3mL, 13mmol).Dropwise the back and in ice-water bath, stir 1h, suction filtration is removed the salt of generation, removes with rotary evaporation and desolvates.Rapid column chromatography (normal hexane: behind the ETHYLE ACETATE=50:1), obtain 5.2g (90%) 11, be colourless transparent liquid.
1H NMR (300MHz, CDCl
3): δ 2.05 (s, 3H), 2.32 (s, 3H), 5.77 (s, 1H), 6.34 (s, 1H), 7.01-7.19 (m, 8H).
19F NMR (282MHz, CDCl
3): δ-132.30 ,-131.92 ,-131.62 ,-131.18 ,-130.87 ,-130.12 ,-129.53 ,-129.23 ,-128.74 ,-128.43 ,-127.28.
13C NMR (75MHz, CDCl
3): δ 18.3,20.8, and 118.0,118.4,119.2,119.5,121.3,122.7,122.8,127.0; 127.5,129.9,130.1,130.2,134.9,135.2,135.6,165.6.IR (KBr): 2930,1740,1638; 1610,1503,1319,1267,1188,1124,1016,963,817cm
-1.MS (EI) m/z (%relativeintensity): 65 (5), 69 (100), 77 (2), 91 (11), 109 (7), 278 (6), 446 (1) .HRMS:C
21H
16F
6O
4Calculated value 446.0953 (measured value 446.0964). ultimate analysis calculated value (Anal.Calcd.) C
21H
16F
6O
4: C, 56.51%; H, 3.61%. measured value (Found): C, 55.67%; H, 3.49%.
Synthesizing of embodiment 6 monomers 12
With 10 (5g 13mmol) places the exsiccant three-necked bottle, add the dissolving of 50mL butanone after, add triethylamine (1.8mL, 13mmol).Reaction flask is put into ice-water bath, slowly drip acrylate chloride (1.1mL, 14mmol).Dropwise the back and in ice-water bath, stir 1h, suction filtration is removed the salt of generation, removes with rotary evaporation and desolvates.Rapid column chromatography (normal hexane: behind the ETHYLE ACETATE=50:1), obtain 5.2g (92%) 12, be colourless transparent liquid.
1H NMR (300MHz, CDCl
3): δ 2.32 (s, 3H), 6.02 (d, J=10.8Hz, 1H), 6.30 (dd, J=10.8,17.1Hz, 1H), 6.60 (d, J=17.1Hz, 1H), 6.98-7.21 (m, 8H).
19F NMR (282MHz, CDCl
3): δ-132.50 ,-132.01 ,-131.61 ,-131.14 ,-130.94 ,-130.88 ,-130.78 ,-130.18 ,-130.08 ,-129.58 ,-129.25 ,-128.79 ,-128.49 ,-127.30.
13C NMR (75MHz, CDCl
3): δ 20.6,117.9,118.3,119.2,119.4,122.6,122.7,127.6,130.1,132.9,134.8,135.1,164.2.IR (KBr): 2927,1749,1636,1610,1503,1318,1266,1179,1146,1017,961,818cm
-1.MS (EI) m/z (% relative intensity): 55 (100), 65 (8), 77 (4), 91 (14), 107 (2), 432 (7) .HRMS:C
20H
14F
6O
4Calculated value 432.0796 (measured value 432.0797).
The radical polymerization of embodiment 7 monomers 11
Monomer 11 (2g) and AIBN (10mg) are added in the exsiccant reaction tubes, substitute nitrogen three times.Add the new toluene (4mL) 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 1h.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 1.63g white polymer powder, and yield is 81.6%.
GPC：M
n＝37,000g/mol，M
w/M
n＝2.46.
1H?NMR(300MHz，CDCl
3)：δ1.36-1.47(m)，2.25(s)，6.97-7.04(m).
19F?NMR(282MHz，CDCl
3)：δ-133.06，-132.50，-131.61，-131.49，-131.11，-130.93，-130.69，-130.14，-129.54，-129.27，-128.96，-128.75，-128.47，-128.14.FT-IR(KBr)：2929，1751，1610，1503，1318，1197，1104，962，818cm
-1.
The radical polymerization of embodiment 8 monomers 12
Monomer 12 (1g) and BPO (10mg) 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 12h.Reaction tubes is taken out from oil bath, put into liquid nitrogen cancellation reaction.After rising again, add 5mL THF dilution, solution is splashed into 150mL methyl alcohol/H
2Deposition obtains the white solid powder among the O (v:v=1:1) behind the suction filtration.Post precipitation once more, vacuum-drying 24h obtains 0.626g white polymer powder, and yield is 62.6%.
GPC：M
n＝22,600g/mol，M
w/M
n＝1.99.
1H?NMR(300MHz，CDCl
3)：δ1.60(s)，2.24(s)，2.32(s)，6.95-7.02(m).
19F?NMR(282MHz，CDCl
3)：δ-132.99，-132.54，-131.64，-131.52，-131.00，-130.85，-130.72，-130.20，-130.06，-129.54，-129.21，-128.76，-128.41，-127.45.FT-IR(KBr)：2929，1758，1610，1504，1318，1178，1132，962，818cm
-1.
Claims (8)
1. one type of function methyl acrylic ester monomer that contains perfluorocyclobutanearyl aryl-ether unit is characterized in that having following chemical structure:
Wherein R is C
1～C
4Alkyl.
2. monomeric preparation method of function methyl acrylic ester who contains perfluorocyclobutanearyl aryl-ether unit as claimed in claim 1 is characterized in that being made by following method:
(1) in solvent-free body or in the organic solvent phenyl ether, will contain substituent trifluoro vinyl phenylate 1 of R and trifluoro vinyl (4-p-methoxy-phenyl) ether generation thermal cyclization reaction 12～24 hours, and generate and contain the unitary compound 2 of perfluorocyclobutanearyl; Said compound 1 is 1: 1 with the mol ratio of trifluoro vinyl (4-p-methoxy-phenyl) ether, and temperature of reaction is 150 ℃～250 ℃;
(2) under atmosphere of inert gases and 0 ℃, the dichloromethane solution of boron tribromide slowly is added drop-wise in the dichloromethane solution of compound 2 demethylation reaction takes place, compound 2 is 3～1: 1 with the mol ratio of boron tribromide; After dropwising, returned back to stirring at room 1～3 hour; Through extraction, dry, filter, concentrate and the rapid column chromatography purifying after obtain containing the unitary phenol 3 of perfluorocyclobutanearyl;
(3) in the presence of triethylamine with 0 ℃ the time, with phenol 3 and methacrylic chloride generation esterification 0.5～2 hour; Through filter, concentrate and the rapid column chromatography purifying after obtain containing the methacrylate monomers 4 of perfluorocyclobutanearyl aryl-ether unit; Said phenol 3 is 1 with the mol ratio of methacrylic chloride: (1～3), and phenol 3 is 1 with the mol ratio of triethylamine: (1～3);
Said compound 1,2,3 and 4 structural formula are following:
Wherein R according to claim 1.
3. the monomeric preparation method of function methyl acrylic ester who contains perfluorocyclobutanearyl aryl-ether unit as claimed in claim 2 is characterized in that employed demethylation reagent is boron tribromide among the preparation method.
4. the monomeric preparation method of function methyl acrylic ester who contains perfluorocyclobutanearyl aryl-ether unit as claimed in claim 2 is characterized in that the used solvent of esterification comprises 2-butanone, chloroform, methylene dichloride or THF among the preparation method.
5. one type of monomeric purposes of function methyl acrylic ester that contains perfluorocyclobutanearyl aryl-ether unit as claimed in claim 1 is characterized in that being used to prepare the polyacrylate polymers that contains perfluorocyclobutanearyl aryl-ether unit.
6. purposes as claimed in claim 5; It is characterized in that described preparation method is following: contain the unitary methyl acrylic ester monomer of perfluorocyclobutanearyl under the initiation of radical initiator; Carry out radical body or solution polymerization; In precipitation agent, precipitate, obtain containing the unitary polymethacrylate polymkeric substance of perfluorocyclobutanearyl through filtration and drying; The said mol ratio that contains unitary methyl acrylic ester monomer of perfluorocyclobutanearyl and radical initiator is 100～25: 1, and temperature of reaction is 50～70 ℃, and the reaction times is 1～24 hour.
7. a purposes as claimed in claim 6 is characterized in that described radical initiator is Diisopropyl azodicarboxylate, Lucidol, the peroxide-3,5,5 Trimethylhexanoic acid tert-butyl ester or tert-butyl peroxide.
8. a purposes as claimed in claim 7 is characterized in that the described scope that contains the number-average molecular weight of the unitary polymethacrylate polymkeric substance of perfluorocyclobutanearyl is 10,000 to 500,000g/mol, and MWD is 1.4-4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810200128A CN101362691B (en) | 2008-09-19 | 2008-09-19 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810200128A CN101362691B (en) | 2008-09-19 | 2008-09-19 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101362691A CN101362691A (en) | 2009-02-11 |
| CN101362691B true CN101362691B (en) | 2012-08-29 |
Family
ID=40389324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810200128A Active CN101362691B (en) | 2008-09-19 | 2008-09-19 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101362691B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865066B (en) * | 2014-03-06 | 2017-04-19 | 中国科学院上海有机化学研究所 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
| CN104262617B (en) * | 2014-09-25 | 2017-05-10 | 广西大学 | Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator |
| CN105924601B (en) * | 2016-05-26 | 2018-07-10 | 中国科学院上海有机化学研究所 | It can the directly phenolic resin of the aryl of ether containing trifluoro vinyl of heat cure, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5426164A (en) * | 1992-12-24 | 1995-06-20 | The Dow Chemical Company | Photodefinable polymers containing perfluorocyclobutane groups |
-
2008
- 2008-09-19 CN CN200810200128A patent/CN101362691B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5426164A (en) * | 1992-12-24 | 1995-06-20 | The Dow Chemical Company | Photodefinable polymers containing perfluorocyclobutane groups |
Non-Patent Citations (1)
| Title |
|---|
| Liang Tong et al.."Synthesis and characterization of perfluorocyclobutyl aryl ether-based amphiphilic diblock copolymer".《Polymer》.2008,第49卷4534-4540. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101362691A (en) | 2009-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20100018533A (en) | Low molecular weight brominated polymers and their use in thermoplastic formulations | |
| JP2010024231A (en) | New phosphorus-based biphenol, and method for producing derivative thereof | |
| CN101805279A (en) | Preparation method of atorvastatin calcium | |
| CN101362691B (en) | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application | |
| CN104860808B (en) | Two fluorine monomers containing tetraphenyl ethylene group and be used for preparing poly aryl ether ketone polymer | |
| EP1460057B1 (en) | Perfluoroadamantyl acrylate compound and intermediate therefor | |
| CN109134384A (en) | A kind of preparation method of aggregation-induced emission hydrogen-bonded polymer network | |
| JP5102863B2 (en) | Ligand synthesis | |
| CN109456435B (en) | Synthetic method of perfluorocyclobutyl polyarylether containing heteronaphthalene biphenyl structure | |
| CN1953963B (en) | Process for producing cyclic N-hydroxyimide compound | |
| CN1696094A (en) | Method for preparing 4,4'-dihydroxy benzophenone | |
| CN101445511B (en) | Perfluor cyclobutyl arylene oligopolymer, preparation method thereof by using iterative coupled reaction and usage | |
| EA018583B1 (en) | Group 3 post-metallocene complexes based on bis(naphthoxy)pyridine and bis(naphthoxy)thiophene ligands for the ring-opening polymerisation of polar cyclic monomers | |
| KR20180129767A (en) | Process for producing 2-hydrazinobenzothiazole derivative | |
| JP5269444B2 (en) | Solid Lewis acid catalyst and method for producing Diels-Alder adduct using the same | |
| CN113583245B (en) | Hyperbranched poly (benzoic acid ester) and preparation method and application thereof | |
| CN104262617A (en) | Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator | |
| JP3595094B2 (en) | Heat resistant poly-α, α-difluoro-paraxylylene film | |
| WO2022266820A1 (en) | Hyperbranched polybenzoate, and preparation method therefor and use thereof | |
| CN110627628A (en) | Beta-iodo-difluoropropanone derivative and preparation method thereof | |
| JP5603041B2 (en) | (Hetero) Diels-Alder Reaction Catalyst, Method for Producing Dihydropyran Compound and Diels-Alder Reaction Adduct Using the Same | |
| JP2585422B2 (en) | 1- (2-Haloethoxy) -4- (2-alkoxyethyl) dialkylbenzenes, intermediates for synthesis thereof, and methods for producing them | |
| CN102174135B (en) | Gem dinitro-modified polystyrene as well as preparation method thereof and binding agent comprising same | |
| CN110078922A (en) | A method of polysulfones is synthesized using the homogeneous allyl substitution reaction of palladium chtalyst | |
| Ghelfi et al. | Atom transfer radical cyclization of O-allyl-2, 2-dichlorohemiacetal acetates: an expedient method to dichloro-γ-lactones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |