CN101225035B - Biphenol monomer containing anthracene benzophenone substituent as well as preparation method and use thereof - Google Patents
Biphenol monomer containing anthracene benzophenone substituent as well as preparation method and use thereof Download PDFInfo
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- CN101225035B CN101225035B CN2008100503170A CN200810050317A CN101225035B CN 101225035 B CN101225035 B CN 101225035B CN 2008100503170 A CN2008100503170 A CN 2008100503170A CN 200810050317 A CN200810050317 A CN 200810050317A CN 101225035 B CN101225035 B CN 101225035B
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Abstract
The invention relates to a bisphenol monomer containing anthracene ketone substituent and the preparation method and application, belonging to the technical field of macromolecular materials. The bisphenol monomer containing anthracene ketone substituent is a new compound which is denominated as 4-(2, 6-hydroxyphenoxy phenyl) carbonyl-9-anthracene and of which the preparation method comprises three reaction steps: acylation, preparing semi-finished product containing methoxy group, and attaining bisphenol monomer. The double phenol monomer synthesizes with the double fluorine monomer polymerization to obtain polyetheretherketone resin. The homopolymers and the copolymers are polymers with auto heat cross-bonding property and outstanding optical property, capable of controlling the cross-bonding density through the control of the ratio of mixture of monomers. The the preparation method for the bisphenol monomer containing anthracene ketone substituent has both the proccessibility of the thermoplastic resin and the high thermal stability and corrosion resistance of thermosetting resin.
Description
Technical field
The invention belongs to the technical field that belongs to macromolecular material and preparation method thereof.Be particularly related to that to contain the anthracene benzophenone substituent 2,6-dihydroxy-benzene phenolic compound and synthetic method thereof and by it in the synthetic application that contains in the anthracene benzophenone polyaryletherketone resinous materials.
Background technology
The fire-resistant high-performance macromolecular material is the focus and the forward position research topic of field of polymer technology in recent years.A lot of thermoplastic resins such as polymeric amide, polyethersulfone, polyarylether, polyaryletherketone all have high thermostability, good excellent performances such as mechanical property, in a lot of fields important application prospects are being arranged.The polyaryletherketone base polymer contains rigidity, stable on heating phenylene and flexibility, stable on heating ehter bond in molecular structure, show high thermotolerance and high physical and mechanical properties.Wherein, with the PES of ICI company, PEEK, PEK and the polyphenylene thioether PPS S that developed afterwards, polyketone thioether PKS is representative, has showed important use value.
The prior art close with the present invention can be with reference to " SCI ", and 2005,26 (3), 586.Along with the introducing of rigid structure side group in the molecular structure, as introducing 2-(4-Phenoxyphenyl)-1,4-dihydroxy-benzene, the raising of polymkeric substance thermotolerance.But they also exist deficiency, be exactly the synthetic method relative complex,, do not have sufficiently high chemoresistance ability by its prepared high-performance line polymer, there is not good solvent resistivity, the easy optical property of dissolving, swelling or the excellence breaking, do not possess etc. in solvent.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the problem that prior art exists, the at first synthetic biphenol monomer that contains anthracene benzophenone group; Carry out the polymkeric substance that polycondensation makes the self-crosslinkable that contains side group anthracene benzophenone accordingly with the biphenol monomer and second monomer, the 3rd monomer that contain anthracene benzophenone group again.In polymkeric substance, introduce crosslinkable anthracene benzophenone group with the polyaryletherketone structural similitude, that can utilize anthracene nucleus is beneficial to thermostability that bridging property comes impact polymer, heat cross-linking, cross-linking radiation etc., and then makes polymkeric substance in high temperature, high irradiation field very wide application prospect be arranged.Simultaneously, embody 2-(4-Phenoxyphenyl)-1, the optical property of the not available excellence of 4-dihydroxy-benzene, and then very wide application prospect is arranged at optical field.
The structure that contains the substituent biphenol monomer of anthracene benzophenone of the present invention is:
Called after 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene.
Biphenol monomer of the present invention is new compound.This compound is introduced the big side group that contains anthracene benzophenone structure in bis-phenol, can increase the molecule chain rigidity, improves its temperature classification.Biphenol monomer of the present invention can carry out polycondensation with second kind of monomer, the third monomer or the 4th kind of monomer etc., prepares the homopolymer and the multipolymer of the polyaryletherketone that contains side group anthracene benzophenone group, polyarylether etc.Anthracene benzophenone structure has controlled self-crosslinking and excellent optical property, and this structure is introduced polymkeric substance, makes polymkeric substance have self heat cross-linking and excellent optical.
The preparation method who contains the substituent biphenol monomer of anthracene benzophenone of the present invention has acylations, preparation to contain the intermediate product of methoxyl group and make three reactions steps of diphenol monomer;
1, with anthracene, fluorobenzoyl chloride and methylene chloride are joined reaction system, add Zinc Chloride Anhydrous under the stirring at room, system refluxed 8～12 hours, steaming vibrating dichloromethane, discharging is used alkali liquid washing in water, vacuum-drying, ethyl alcohol recrystallization gets light yellow Fu Shi acylations product, called after 9-(4-fluorobenzene acyl group) anthracene; Wherein anthracene, be 1: 1～1.2: 4～6 to the mol ratio of fluorobenzoyl chloride, Zinc Chloride Anhydrous, the amount ratio of anthracene and methylene chloride is 1mol: 2000～6000ml.
2, with above-mentioned Fu Shi acylations product and 2,6-syringol, catalyzer anhydrous K
2CO
3With solvent N, dinethylformamide (DMF) or N, N-N,N-DIMETHYLACETAMIDE (DMAc), band aqua toluene is put into the container that nitrogen port, water-taker, reflux condensing tube are housed, refluxing toluene band water 1～2 hour is got rid of toluene, and the solvent refluxing reaction is 4～6 hours then, discharging in sour water, sedimentation and filtration, washing, drying.The chromatographic column eluent methylene chloride, the intermediate product that contains methoxyl group that distillation concentrates, vacuum-drying gets light yellow solid, called after 4-(2,6-dimethoxy Phenoxyphenyl) carbonyl-9-anthracene.Fu Shi acylations product, 2 wherein, the molar ratio of 6-syringol and Anhydrous potassium carbonate is 1: 1: 1.03～1.05.Solvent bank aqua consumption is every 0.1mol Fu Shi acylations product solubilizing agent 50～120mL, band aqua 15～30mL.
3, in the container of logical nitrogen, the above-mentioned intermediate product that contains methoxyl group is dissolved in the mixing solutions of hydroiodic acid HI and Glacial acetic acid, reaction system refluxed 4～8 hours; Contain intermediate product, the hydroiodic acid HI of methoxyl group, the amount ratio of Glacial acetic acid is 0.01mol: 10～30mL: 50～100mL; Cool to room temperature, solution pour in the frozen water, get faint yellow precipitation, filter, and washing, vacuum-drying, the toluene recrystallization gets faint yellow solid, called after 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene.Productive rate 65～85%.
The present invention contains the preparation method of the substituent biphenol monomer of anthracene benzophenone, is to be that starting raw material begins to synthesize with anthracene, finally spends etherification reaction and is prepared into needed biphenol monomer.This monomer synthetic method is simpler with respect to traditional diazonium salt reaction, and productive rate is higher.
The monomer 4-(2 that makes according to above-mentioned synthetic method, 6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, can and second monomer, the 3rd monomer carry out the polymkeric substance that polycondensation makes the self-crosslinkable that contains side group anthracene benzophenone accordingly, as the polyarylether of self-crosslinkable, polyaryletherketone, polyethersulfone, polyethers nitrile etc.
The purposes that contains the substituent biphenol monomer of anthracene benzophenone of the present invention is to carry out polycondensation with two fluorine monomers or two chlorine monomer, the polyaryletherketone resinoid that contains anthracene benzophenone group of preparation homopolymerization; Perhaps carry out polycondensation with other biphenol monomers or with two chlorine monomers and other biphenol monomers, the polyaryletherketone resinoid that contains anthracene benzophenone group of preparation copolymerization with two fluorine monomers.
It is concrete that to prepare the synthetic method of polymkeric substance such as polyaryletherketone, polyarylether by 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene as follows:
Synthetic method 1:(homopolymer)
With 4-(2; 6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, two fluorine monomer or two chlorine monomer, catalyzer Anhydrous potassium carbonate, solvent N; N-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone, water liquid benzene or toluene; join in the container that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed; under the nitrogen protection; reflux, band water 1.5～2h.Be warming up to 150～160 ℃ after getting rid of the band aqua, reaction 6～8h.In product impouring sour water, pulverize, filter with pulverizer, solid is directly boiled, filters with methyl alcohol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain refining homopolymer.
Wherein, the mol ratio of catalyzer, two fluorine monomer or two chlorine monomer and 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene is 1.03～1.05: 1: 1; Solvent, band aqua consumption are every 0.01mol 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, solubilizing agent 20～30mL, band aqua 10～15mL.Described pair of fluorine monomer or two chlorine monomer comprise 4,4-difluorodiphenyl base ketone, 1,4-two (4-fluorobenzene carbonyl) benzene or 4,4 '-dichloro diphenyl sulfone or decafluorobiphenyl or 2,6-two fluorobenzene cyanogen or other two fluorine monomers.
Synthetic method 2:(homogeneous multipolymer)
Two fluorine monomers or two chlorine monomer, biphenol monomer, catalyzer Anhydrous potassium carbonate, solvent N-Methyl pyrrolidone or tetramethylene sulfone, water liquid benzene or toluene are joined in the container that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed, under nitrogen protection, band water 1.5～2h refluxes; Wherein, biphenol monomer is n with the mol ratio of two fluorine monomers: 1, (0＜n＜1), and the mol ratio of catalyzer and biphenol monomer is 1.03～1.05: 1, and solvent, band aqua consumption are every 0.01mol biphenol monomer, add solvent 20～30mL, band aqua 10～15mL; After getting rid of toluene, be warmed up to 160～200 ℃, continue reaction 4～8 hours;
Then 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, water liquid benzene or toluene are put in the reaction system, refluxed and be with water 1.5～2 hours, again 140～170 ℃ of reactions 4～8 hours; Wherein, the mol ratio of 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene and biphenol monomer is 1-n: n, and band aqua consumption is every 0.01mol 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, adds band aqua 10～15mL; Last discharging through pulverizing, washing, drying, obtains the multipolymer that purified anthracene benzophenone group homogeneous distributes in acidic aqueous solution;
Described pair of fluorine monomer or two chlorine monomer comprise 4,4 '-difluorodiphenyl base ketone, 4,4 '-dichloro diphenyl sulfone, 1,4-two (4-fluorobenzene carbonyl) benzene, decafluorobiphenyl, 2,6-difluorobenzonilyile or other two fluorine monomers; Described biphenol monomer comprises 2,2-two (4-hydroxyphenyl) propane, 4,4 '-dihydroxy diphenylsulphone, Resorcinol, Resorcinol, 2,2-two (4-hydroxyphenyl) HFC-236fa, m-trifluoromethylphenyl Resorcinol or 3,5-two trifluoromethyl Resorcinol.
Synthetic method 3:(random copolymers)
With 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene and two fluorine monomers or two chlorine monomer, biphenol monomer, catalyzer Anhydrous potassium carbonate, solvent N-Methyl pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc) or tetramethylene sulfone, water liquid benzene or toluene join in the container that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed.Under nitrogen protection, band water 1.5～2h refluxes.After getting rid of benzene or toluene, be warmed up to 140～170 ℃, continue reaction 4～12h.Last discharging through pulverizing, washing, drying, gets needed anthracene benzophenone group random distribution in the lateral polymkeric substance of molecular chain in acidic aqueous solution.
Wherein, biphenol monomer and two fluorine monomers or the monomeric mol ratio n of two chlorine: 1 (0＜n＜1); The mol ratio of biphenol monomer and 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene is n: 1-n; Catalyzer by amount of substance be biphenol monomer and 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene amount of substance and 1.03～1.05 times; The two fluorine monomers of every 0.01mol add solvent 20～30mL, band aqua 10～15mL.Described pair of fluorine monomer or two chlorine monomer comprise 4,4 '-difluorodiphenyl base ketone or 4,4 '-dichloro diphenyl sulfone or 1,4-two (4-fluorobenzene carbonyl) benzene or decafluorobiphenyl or 2,6-difluorobenzonilyile or other two fluorine monomers; Described biphenol monomer comprises 2,2-two (4-hydroxyphenyl) propane, 4,4 '-dihydroxy diphenylsulphone, Resorcinol, Resorcinol, 2,2-two (4-hydroxyphenyl) HFC-236fa, m-trifluoromethylphenyl Resorcinol or 3,5-two trifluoromethyl Resorcinol.
With 4-(2 of the present invention, 6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene can carry out polycondensation with two fluorine monomers or two chlorine monomer or with two fluorine monomers and biphenol monomer or two chlorine monomer and biphenol monomer, prepares the homopolymer and the multipolymer of the polyaryletherketone that contains side group anthracene benzophenone group, polyarylether etc.These homopolymer and multipolymer are the polymkeric substance that a class has self heat cross-linking and excellent optical, and can be by the control monomer blends cross-linking density of controlling polymers recently, had the high thermal stability, erosion resistance of the processability of thermoplastic resin and thermosetting resin etc. concurrently.
Description of drawings
Fig. 1 is the infrared spectrum of the sample that makes of the embodiment of the invention one.
Fig. 2 is the infrared spectrum of the polymkeric substance that makes of the embodiment of the invention nine.
Fig. 3 is the uv atlas of the polymkeric substance that makes of the embodiment of the invention nine.
Embodiment
Embodiment one:
The first step: with anthracene (17.8g, 0.1mol), to fluorobenzoyl chloride (15.8g, 0.1mol), methylene dichloride makees solvent and join container (three-necked flask) reaction system, adds Zinc Chloride Anhydrous (54.4g under the stirring at room, 0.4mol), (anthracene, be 1: 1: 4 to the mol ratio of fluorobenzoyl chloride, Zinc Chloride Anhydrous, the amount ratio of anthracene and methylene chloride is 1mol: 2000ml), system refluxed 8 hours, steaming vibrating dichloromethane, discharging is used the alkali lye repetitive scrubbing, vacuum-drying in water.Ethyl alcohol recrystallization gets light yellow solid, called after 9-(4-fluorobenzene acyl group) anthracene.
Second step: with above-mentioned Fu Shi acylations product (30g, 0.1mol) with 2, the 6-syringol (15.4g, 0.1mol), anhydrous K
2CO
3(14.21g, 0.103mol) and N, dinethylformamide (DMF) or N,N-dimethylacetamide (DMAc) are (120mL), toluene (30mL) is put into the container (three-necked flask) that nitrogen port, water-taker, reflux condensing tube are housed, refluxing toluene band water 1～2 hour.Fu Shi acylations product, 2 wherein, the molar ratio of 6-syringol and Anhydrous potassium carbonate is 1: 1: 1.03.Get rid of toluene, the DMF back flow reaction is 4～6 hours then, discharging in sour water, sedimentation and filtration, washing, drying.Chromatographic column eluent methylene chloride, distillation concentrate the lurid intermediate product that contains methoxyl group, vacuum-drying.Called after 4-(2,6-dimethoxy Phenoxyphenyl) carbonyl-9-anthracene.
The 3rd step: in the container (three-necked flask) of logical nitrogen, (4.34g 0.01mol) is dissolved in the mixing solutions of hydroiodic acid HI (10mL) and Glacial acetic acid (50mL), and reaction system refluxed 4 hours with the above-mentioned intermediate product that contains methoxyl group.The amount ratio of 4-(2,6-dimethoxy Phenoxyphenyl) carbonyl-9-anthracene, hydroiodic acid HI, Glacial acetic acid is 0.01mol: 10mL: 50mL.Cool to room temperature, solution pour in the frozen water, get faint yellow precipitation, filter, and washing, vacuum-drying, the toluene recrystallization gets faint yellow solid, called after 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene.Productive rate 65～85%.
The infrared spectrum of 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene product is seen Fig. 1.
Embodiment two:
The first step: with anthracene (17.8g, 0.1mol), to fluorobenzoyl chloride (18.96g, 0.12mol), methylene dichloride makees solvent and joins container (three-necked flask) reaction system, slowly add Zinc Chloride Anhydrous (81.6g under the stirring at room, 0.6mol), (anthracene, it is 1: 1.2: 6 to the mol ratio of fluorobenzoyl chloride, Zinc Chloride Anhydrous, the amount ratio of anthracene and methylene chloride is 1mol: 6000ml), system refluxed 12 hours, steaming vibrating dichloromethane, discharging is used the alkali lye repetitive scrubbing, vacuum-drying in water.Ethyl alcohol recrystallization gets light yellow solid, English simple called after 9-(4-fluorobenzene acyl group) anthracene.
Second step: with above-mentioned Fu Shi acylations product (30g, 0.1mol) with 2, the 6-syringol (15.4g, 0.1mol), anhydrous K
2CO
3(14.49g, 0.105mol) and N, N dimethyl formamide (DMF) (or N,N-dimethylacetamide DMAc) is (50mL), toluene (15mL) is put into the container (three-necked flask) that nitrogen port, water-taker, reflux condensing tube are housed, refluxing toluene band water 1～2 hour.(Fu Shi acylations product, 2 wherein, the molar ratio of 6-syringol and Anhydrous potassium carbonate is 1: 1: 1.05.Get rid of toluene, the DMF back flow reaction is 4～6 hours then, discharging in sour water, sedimentation and filtration, washing, drying.Chromatographic column eluent methylene chloride, distillation concentrate the lurid intermediate product that contains methoxyl group, vacuum-drying.Called after 4-(2,6-dimethoxy Phenoxyphenyl) carbonyl-9-anthracene.
The 3rd step: in the container (three-necked flask) of logical nitrogen, (4.34g 0.01mol) is dissolved in the mixing solutions of hydroiodic acid HI (30mL) and Glacial acetic acid (100mL), and reaction system refluxed 4～8 hours with the above-mentioned intermediate product that contains methoxyl group.The amount ratio of 4-(2,6-dimethoxy Phenoxyphenyl) carbonyl-9-anthracene, hydroiodic acid HI, Glacial acetic acid is 0.01mol: 30mL: 100mL.Cool to room temperature, solution pour in the frozen water, get faint yellow precipitation, filter, and washing, vacuum-drying, the toluene recrystallization gets faint yellow solid, called after 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene.Productive rate 65～85%.
Embodiment three
With 4-(2; 6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene (4.06g; 10mmol), 4; 4 '-difluorodiphenyl base ketone (2.18g; 10mmol), Anhydrous potassium carbonate (1.422g) and N,N-dimethylacetamide (20ml), toluene (10ml) join in the container (three-necked flask) that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed, under the nitrogen protection; reflux, band water 1.5h.Be warming up to 150 ℃ after getting rid of benzene, reaction 6h in product impouring sour water, pulverizes, filters with pulverizer, solid is directly boiled, filters with methyl alcohol, repeat 5 times, boil, filter with distilled water again, repeat 5 times, dry in baking oven, obtain refining homopolymer, productive rate is 92%.
Embodiment four:
With 4-(2; 6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene (4.06g; 10mmol), 4; 4 '-difluorodiphenyl base ketone (2.18g; 10mmol), Anhydrous potassium carbonate (1.449g) and N, dinethylformamide (30ml), toluene (15ml) join in the container (three-necked flask) that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed, under the nitrogen protection; reflux, band water 2h.Be warming up to 160 ℃ after getting rid of benzene, reaction 8h in product impouring sour water, pulverizes, filters with pulverizer, solid is directly boiled, filters with methyl alcohol, repeat 5 times, boil, filter with distilled water again, repeat 5 times, dry in baking oven, obtain refining homopolymer, productive rate is 92%.
Embodiment five:
Identical with the method for embodiment three, four, just with 4,4 '-difluorodiphenyl base ketone makes 1 into, 4-two (4-fluorobenzene carbonyl) benzene or 2,6-two fluorobenzene cyanogen or other two fluorine monomers, perhaps changing N,N-dimethylacetamide is N-Methyl pyrrolidone or tetramethylene sulfone, toluene changes benzene into, and remaining method is complete in also accessing needed poly aryl ether ketone polymer.
Embodiment six:
With 4,4 '-difluorodiphenyl base ketone (4.36g, 20mmol), 2,2-two (4-hydroxyphenyl) propane (4.104g, 18mmol), Anhydrous potassium carbonate (2.898g), N-Methyl pyrrolidone (NMP) (54ml), toluene (27ml) joins in the container (three-necked flask) that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed.Refluxing toluene band water 1.5h.After getting rid of toluene, be warmed up to 160 ℃, continue reaction 4h.(0.812g, 2mmol), band aqua toluene (2ml) is put in the reaction system refluxing toluene band water 1.5h with 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene then.After getting rid of toluene, again 140 ℃ of reactions 4 hours.Last discharging through pulverizing, methyl alcohol and deionized water repetitive scrubbing, drying, obtains the poly (aryl ether ketone) copolymer that purified anthracene benzophenone group homogeneous distributes in acidic aqueous solution, productive rate is 93%.
Embodiment seven:
With 4,4 '-difluorodiphenyl base ketone (4.36g, 20mmol), 2,2-two (4-hydroxyphenyl) propane (4.104g, 18mmol), Anhydrous potassium carbonate (2.843g), N-Methyl pyrrolidone (NMP) (36ml), toluene (18ml) joins in the container (three-necked flask) that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed.Refluxing toluene band water 2h.After getting rid of toluene, be warmed up to 200 ℃, continue reaction 8h.(0.812g, 2mmol), band aqua toluene (3ml) is put in the reaction system refluxing toluene band water 2h with 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene then.After getting rid of toluene, again 170 ℃ of reactions 8 hours.Last discharging through pulverizing, methyl alcohol and deionized water repetitive scrubbing, drying, obtains the poly (aryl ether ketone) copolymer that purified anthracene benzophenone group homogeneous distributes in acidic aqueous solution, productive rate is 92%.
Embodiment eight
Identical with the method for embodiment six, seven, just with 4,4 '-difluorodiphenyl base ketone changes into 4,4 '-dichloro diphenyl sulfone or difluoro diketone or decafluorobiphenyl or 2,6-difluorobenzonilyile, perhaps with 2,2-two (4-hydroxyphenyl) propane makes Resorcinol or Resorcinol or 2 into, 2-two (4-hydroxyphenyl) HFC-236fa or other biphenol monomer, and perhaps changing N-Methyl pyrrolidone is tetramethylene sulfone, toluene changes benzene into, and remaining method is complete in also accessing the polymkeric substance such as polyaryletherketone that anthracene benzophenone homogeneous distributes.
Embodiment nine:
With 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene (0.812g, 2mmol) with Resorcinol (1.98g, 18mmol), 4,4 '-difluorodiphenyl base ketone (4.36g, 20mmol), Anhydrous potassium carbonate (2.898g), N-Methyl pyrrolidone (NMP) (60ml), toluene (20ml) joins in the container (three-necked flask) that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed.Under nitrogen protection, band water 1.5h refluxes.After getting rid of toluene, be warmed up to 140 ℃, continue reaction 12h.Last discharging through pulverizing, methyl alcohol and deionized water repetitive scrubbing, drying, gets needed anthracene benzophenone group random distribution in the lateral poly (aryl ether ketone) copolymer of molecular chain in acidic aqueous solution, productive rate is 94%.Recording second-order transition temperature through DSC is 128 ℃.
The anthracene benzophenone group random distribution that makes is seen Fig. 2 and Fig. 3 respectively in the infrared spectrum and the uv atlas of the lateral poly (aryl ether ketone) copolymer of molecular chain.
Embodiment ten:
With 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene (0.812g, 2mmol) with Resorcinol (1.98g, 18mmol), 4,4 '-difluorodiphenyl base ketone (4.36g, 20mmol), Anhydrous potassium carbonate (2.843g), N-Methyl pyrrolidone (NMP) (40ml), toluene (30ml) joins in the container (three-necked flask) that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed.Under nitrogen protection, band water 2h refluxes.After getting rid of toluene, be warmed up to 170 ℃, continue reaction 4h.Last discharging through pulverizing, methyl alcohol and deionized water repetitive scrubbing, drying, gets needed anthracene benzophenone group random distribution in the lateral poly (aryl ether ketone) copolymer of molecular chain in acidic aqueous solution, productive rate is 94%.
Embodiment 11:
Identical with the method for embodiment nine, ten, just change 4,4 '-difluorodiphenyl base ketone is 4,4 '-dichloro diphenyl sulfone or difluoro diketone or decafluorobiphenyl or 2, the 6-difluorobenzonilyile, perhaps changing Resorcinol is 2,2-two (4-hydroxyphenyl) propane or Resorcinol or 2,2-two (4-hydroxyphenyl) HFC-236fa or other biphenol monomer, perhaps changing N-Methyl pyrrolidone is N-N-N,N-DIMETHYLACETAMIDE or tetramethylene sulfone, toluene changes benzene into.Remainder method together, also can access needed anthracene benzophenone group random distribution in multipolymers such as the lateral polyaryletherketones of molecular chain entirely.
Embodiment 12:
Just change biphenol monomer and 4-(2 among the embodiment three to 11,6-dihydroxyl Phenoxyphenyl) the amount of substance ratio that feeds intake of carbonyl-9-anthracene and two fluorine monomers (or two chlorine monomer) is n: 1-n: 1 (0＜n＜1) can both obtain the multipolymer of a series of desired anthracene benzophenone group different contents.
Claims (6)
1. one kind contains the substituent biphenol monomer of anthracene benzophenone, it is characterized in that structure is:
Called after 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene.
2. the preparation method who contains the substituent biphenol monomer of anthracene benzophenone of a claim 1 is characterized in that, has acylations, preparation to contain the intermediate product of methoxyl group and make three reactions steps of diphenol monomer;
Said acylations, be with anthracene, fluorobenzoyl chloride and methylene chloride are joined reaction system, add Zinc Chloride Anhydrous under the stirring at room, system refluxed 8～12 hours, steaming vibrating dichloromethane, discharging are used alkali liquid washing in water, vacuum-drying, ethyl alcohol recrystallization get light yellow Fu Shi acylations product; Wherein, anthracene, be 1: 1～1.2: 4～6 to the mol ratio of fluorobenzoyl chloride, Zinc Chloride Anhydrous, the amount ratio of anthracene and methylene chloride is 1mol: 2000～6000ml;
Said preparation contains the intermediate product of methoxyl group, is with above-mentioned Fu Shi acylations product and 2,6-syringol, catalyzer anhydrous K
2CO
3With solvent N, dinethylformamide or N, the N-N,N-DIMETHYLACETAMIDE, band aqua toluene is put into the container that nitrogen port, water-taker, reflux condensing tube are housed, refluxing toluene band water 1～2 hour is got rid of toluene, and the solvent refluxing reaction is 4～6 hours then, discharging in sour water, sedimentation and filtration, washing, drying; The chromatographic column eluent methylene chloride, the intermediate product that contains methoxyl group that distillation concentrates, vacuum-drying gets light yellow solid; Fu Shi acylations product, 2 wherein, the molar ratio of 6-syringol and Anhydrous potassium carbonate is 1: 1: 1.03～1.05, solvent, band aqua consumption are every 0.1mol Fu Shi acylations product solubilizing agent 50～120mL, band aqua 15～30mL;
The said diphenol monomer that makes is that the intermediate product that will contain methoxyl group is dissolved in the mixing solutions of hydroiodic acid HI and Glacial acetic acid in the container of logical nitrogen, and reaction system refluxed 4～8 hours; Contain intermediate product, the hydroiodic acid HI of methoxyl group, the amount ratio of Glacial acetic acid is 0.01mol: 10～30mL: 50～100mL; Cool to room temperature, solution pour in the frozen water, get faint yellow precipitation, filter, and washing, vacuum-drying, the toluene recrystallization gets faint yellow solid 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene.
3. the purposes that contains the substituent biphenol monomer of anthracene benzophenone of a claim 1, be with 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene carries out polycondensation with two fluorine monomers or two chlorine monomer, the polyaryletherketone resinoid that contains anthracene benzophenone group of preparation homopolymerization; Perhaps carry out polycondensation with other biphenol monomers or with two chlorine monomers and other biphenol monomers, the polyaryletherketone resinoid that contains anthracene benzophenone group of preparation copolymerization with two fluorine monomers.
4. according to the described purposes that contains the substituent biphenol monomer of anthracene benzophenone of claim 3, it is characterized in that, the polyaryletherketone resinoid that contains anthracene benzophenone group of said preparation homopolymerization, detailed process is, with 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, two fluorine monomers or two chlorine monomer, the catalyzer Anhydrous potassium carbonate, solvent N, N-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone, water liquid benzene or toluene, join the nitrogen port is housed, mechanical stirring, thermometer, in the container of water-taker and reflux condensing tube, under the nitrogen protection, reflux, band water 1.5～2 hours, be warming up to 150～160 ℃ after getting rid of the band aqua, reacted 6～8 hours; In product impouring sour water, pulverize, filter with pulverizer, solid is directly boiled, filters with methyl alcohol or acetone boiling method, repeat 5～6 times, boil, filter with distilled water again, repeat 5～6 times, in baking oven, dry, obtain refining homopolymer;
Wherein, catalyzer, two fluorine monomer or two chlorine monomer and 4-(2,6-dihydroxyl Phenoxyphenyl) mol ratio of carbonyl-9-anthracene is 1.03～1.05: 1: 1, solvent, band aqua consumption are every 0.01mol 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, solubilizing agent 20～30mL, band aqua 10～15mL; Described pair of fluorine monomer is 4,4 '-difluorodiphenyl base ketone, 1,4-two (4-fluorobenzene carbonyl) benzene or 2,6-two fluorobenzene cyanogen; Described pair of chlorine monomer is 4,4 '-dichloro diphenyl sulfone.
5. according to the described purposes that contains the substituent biphenol monomer of anthracene benzophenone of claim 3, it is characterized in that the polyaryletherketone resinoid that contains anthracene benzophenone group of said preparation copolymerization comprises the multipolymer that preparation anthracene benzophenone group homogeneous distributes; Detailed process is,
Two fluorine monomers or two chlorine monomer, biphenol monomer, catalyzer Anhydrous potassium carbonate, solvent N-Methyl pyrrolidone or tetramethylene sulfone, water liquid benzene or toluene are joined in the container that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed, under nitrogen protection, reflux and be with water 1.5～2 hours; Wherein, biphenol monomer is n: 1,0＜n＜1 with two fluorine monomers or the monomeric mol ratio of two chlorine, the mol ratio of catalyzer and biphenol monomer is 1.03～1.05: 1, solvent, band aqua consumption are every 0.01mol biphenol monomer, add solvent 20～30mL, band aqua 10～15mL; After getting rid of toluene, be warmed up to 160～200 ℃, continue reaction 4～8 hours;
Then 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, water liquid benzene or toluene are put in the reaction system, refluxed and be with water 1.5～2 hours, again 140～170 ℃ of reactions 4～8 hours; Wherein, the mol ratio of 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene and biphenol monomer is 1-n: n, and band aqua consumption is every 0.01mol 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene, adds band aqua 10～15mL; Last discharging through pulverizing, washing, drying, obtains the multipolymer that purified anthracene benzophenone group homogeneous distributes in acidic aqueous solution;
Described pair of fluorine monomer is 4,4 '-difluorodiphenyl base ketone, 1,4-two (4-fluorobenzene carbonyl) benzene or 2,6-difluorobenzonilyile; Described pair of chlorine monomer is 4,4 '-dichloro diphenyl sulfone; Described biphenol monomer is 2,2-two (4-hydroxyphenyl) propane, 4,4 '-dihydroxy diphenylsulphone, Resorcinol, Resorcinol, 2,2-two (4-hydroxyphenyl) HFC-236fa, m-trifluoromethylphenyl Resorcinol or 3,5-two trifluoromethyl Resorcinol.
6. according to the described purposes that contains the substituent biphenol monomer of anthracene benzophenone of claim 3, it is characterized in that, the polyaryletherketone resinoid that contains anthracene benzophenone group of said preparation copolymerization comprises that preparation anthracene benzophenone group random distribution is in the lateral polymkeric substance of molecular chain; Detailed process is,
With 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene and two fluorine monomers or two chlorine monomer, biphenol monomer, catalyzer Anhydrous potassium carbonate, solvent N-Methyl pyrrolidone or N,N-dimethylacetamide or tetramethylene sulfone and water liquid benzene or toluene join in the container that nitrogen port, mechanical stirring, thermometer, water-taker and reflux condensing tube are housed; Under nitrogen protection, reflux and be with water 1.5～2 hours; After getting rid of the band aqua, be warmed up to 140～170 ℃, continue reaction 4～12 hours; Last discharging through pulverizing, washing, drying, gets needed anthracene benzophenone group random distribution in the lateral polymkeric substance of molecular chain in acidic aqueous solution;
Wherein, biphenol monomer and two fluorine monomers or the monomeric mol ratio n of two chlorine: 1,0＜n＜1; The mol ratio of biphenol monomer and 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene is n: 1-n; Catalyzer by amount of substance be biphenol monomer and 4-(2,6-dihydroxyl Phenoxyphenyl) carbonyl-9-anthracene amount of substance and 1.03～1.05 times; The two fluorine monomers of every 0.01mol or two chlorine monomer add solvent 20～30mL, band aqua 10～15mL; Described pair of fluorine monomer is 4,4 '-difluorodiphenyl base ketone, 1,4-two (4-fluorobenzene carbonyl) benzene or 2,6-difluorobenzonilyile; Described pair of chlorine monomer is 4,4 '-dichloro diphenyl sulfone; Described biphenol monomer is 2,2-two (4-hydroxyphenyl) propane, 4,4 '-dihydroxy diphenylsulphone, Resorcinol, Resorcinol, 2,2-two (4-hydroxyphenyl) HFC-236fa, m-trifluoromethylphenyl Resorcinol or 3,5-two trifluoromethyl Resorcinol.
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| EP0268112A2 (en) * | 1986-11-20 | 1988-05-25 | Asahi Kasei Kogyo Kabushiki Kaisha | A novel aromatic polyether and a process for producing a polyether |
| US5120818A (en) * | 1985-06-21 | 1992-06-09 | Amoco Corporation | Chain-extended poly(aryl ether ketones) |
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| US5120818A (en) * | 1985-06-21 | 1992-06-09 | Amoco Corporation | Chain-extended poly(aryl ether ketones) |
| EP0268112A2 (en) * | 1986-11-20 | 1988-05-25 | Asahi Kasei Kogyo Kabushiki Kaisha | A novel aromatic polyether and a process for producing a polyether |
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| 付长清等.聚芳醚酮酮、聚芳醚醚酮酮无规共聚物的合成与性能研究.江西师范大学学报（自然科学版）29 5.2005,29(5),377-380. |
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