CN101463128B - Polyarylether polymer containing amino-benzene lateral group and method for synthesizing the same - Google Patents
Polyarylether polymer containing amino-benzene lateral group and method for synthesizing the same Download PDFInfo
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- CN101463128B CN101463128B CN2008100517169A CN200810051716A CN101463128B CN 101463128 B CN101463128 B CN 101463128B CN 2008100517169 A CN2008100517169 A CN 2008100517169A CN 200810051716 A CN200810051716 A CN 200810051716A CN 101463128 B CN101463128 B CN 101463128B
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Abstract
The invention discloses polyarylether polymers containing aminophenyl lateral group and a synthesis method thereof, and belongs to the technical fields of high molecular materials and synthesis thereof. The polymers comprise polyether ether ketone containing 4-aminophenyl lateral group, the polyether ether ketone containing the aminophenyl lateral group, polyether ether naphtonone containing the aminophenyl lateral group, polyether ether sulfone containing the aminophenyl lateral group or sulfonated polyether ether ketone containing the aminophenyl lateral group; the polymers are prepared by polycondensation reaction of 4-aminophenyl hydroquinone monomer and difluoro monomer or dichloro monomer. In the synthesis method, a functional amino is introduced into a molecular structure of the polyarylether ketone (sulfone) to obtain a novel soluble polyarylether ketone (sulfone) containing the amino. The materials of the series have the advantages of high thermal stability, good film forming property, good reaction cross-linking property and good functionality. Moreover, the amino as a latent reaction cross-linking point can cause the materials of the series to have a plurality of advantages.
Description
Technical field
The invention belongs to macromolecular material and synthetic technical field thereof, is that the raw material synthetic contains polymkeric substance such as the polyaryletherketone of amino-benzene lateral group or polyether sulphone with 4-aminophenyl-Resorcinol monomer particularly.
Background technology
Along with the emergence of development of modern science and technology and high-tech industry, special engineering plastics more and more is subjected to the attention and the favor of national governments, businessman with its high performance price ratio, the high additional output value.Polyarylether 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 PES, PEEK, the PEK of ICI company and the polyphenylene thioether PPS S that developed afterwards, polyketone thioether PKS is representative, has showed important use value.Crystallinity polyethers same type of material thermotolerance height wherein, but the forming process difficulty of material; And the poor solvent resistance of the amorphous polysulfones material of moulding handling ease, thus polyetherketone (sulfone) class material being carried out the modification application is hot research in recent years.
Because amino has high reaction activity and high, therefore polymkeric substance is carried out the extensive concern that modification causes people with amino, will have the amino (NH of high reaction activity
2) introduce in the molecular structure of polyether sulphone, the polyether sulphone that obtains the amino-terminated polyether sulphone of the novel speciality polymer of a class and contain active lateral group, for amino-terminated polyether sulphone, when improving amino content, can reduce the molecular weight of prepolymer, material is become fragile, and when polymericular weight increases, active end group content will reduce, therefore, the polyether sulphone that contains active lateral group is more paid close attention to, introduce active lateral group two kinds of approach are arranged: the one, back grafting, the 2nd, utilize the monomer that contains active group directly synthetic, these two kinds of method synthetic amino-polyether sulfone primary structures are as follows at present:
Because amino is positioned on the main chain in this base polymer, and is sterically hindered bigger, reduce amino activity, influence is reaction further.
Summary of the invention
The technical problem to be solved in the present invention is to design and synthesize polyaryletherketone (sulfone) polymkeric substance that contains amino-benzene lateral group.The present invention adopts 4-aminophenyl-Resorcinol and two halogen monomers to carry out polycondensation, prepare polymkeric substance such as a series of polyaryletherketones that contain amino-benzene lateral group, polyether sulphone, they are high-performance polymer materials that a class has high thermal stability, good filming and cross-linking reaction and good function.
The polyarylether polymer that contains amino-benzene lateral group of the present invention is polyether-ether-ketone, the polyether ether ketone ketone that contains amino-benzene lateral group, the polyethers ether naphthalenone that contains amino-benzene lateral group that contain the 4-amino-benzene lateral group, contain the polyether ethersulfone of amino-benzene lateral group or contain the sulfonated polyether-ether-ketone of amino-benzene lateral group; Their structural formula is respectively
N=80~220 wherein.
The sulfonated polyether-ether-ketone that contains amino-benzene lateral group among the present invention is a kind of proton conduction membrane material that is used for proton conduction membrane cell (PEMFC), has low water swelling ratio, high elongation at break and tensile strength characteristics; Can direct pouring shop film.
Polyaryletherketone (sulfone) base polymer that contains amino-benzene lateral group of the present invention is to use 4-aminophenyl Resorcinol monomer and two fluorine or two chlorine monomer to carry out polycondensation to make.Detailed process is as follows.
A kind of synthetic method that contains the polyarylether polymer of amino-benzene lateral group is a reactant with 4-aminophenyl Resorcinol and two halogen monomer, is solvent with tetramethylene sulfone or N-Methyl pyrrolidone, is azeotropy dehydrant with toluene or dimethylbenzene; With 4-aminophenyl Resorcinol and equimolar pair of halogen monomer, put into the reaction vessel that mechanical stirring and water-taker are housed with the azeotropy dehydrant of the Anhydrous potassium carbonate of 1.05~1.2 times of 4-aminophenyl Resorcinol quality, 4 times of solvents, solvent volume 20% to the reactant quality, logical nitrogen, being warmed up to azeotropy dehydrant refluxes, reacted 1.5~4 hours, get rid of azeotropy dehydrant, be warmed up to 180~190 ℃ and continue reaction 4~9 hours; The polymers soln that obtains is separated out in deionized water, through pulverizing, washing, drying obtains containing the polyarylether polymer of amino-benzene lateral group structure.
Described raw material 4-aminophenyl Resorcinol, its structure is:
The two halogen monomers of described raw material can be two fluorine monomers or two chlorine monomer, and concrete is 4,4 '-difluorodiphenyl base ketone, 1,4-two (4-fluorobenzene carbonyl) benzene, 1,4-two (4-fluorobenzene carbonyl) naphthalene or 4,4 '-dichloro diphenylmethyl sulfone; Or hexafluoro bisphenol-a and 4,4 '-difluoro benzophenone and 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene.
The present invention will have functional amino (NH by containing amino Resorcinol
2) introduce in the molecular structure of polyaryletherketone (sulfone), obtain the novel solubility of a class and contain amino polyaryletherketone (sulfone).The existing high thermal stability of this series material (higher thermotolerance), second-order transition temperature is all more than 200 ℃, has good filming again, adopt the polymeric film of the method preparation of solvent shop film to have good flexible, be difficult for being fractureed, and cross-linking reaction (referring to the acid ion alkali ion key between the sulfamide groups in the embodiment 7 synthetic multipolymers) and good function (referring to accompanying drawing 3).In addition, amino can make this series material that plurality of advantages is arranged, for example prepare the graft type interpenetrating(polymer)networks thermosetting material, curable epoxide material of polyetherketone (sulfone) and polyimide etc. as a potential chemical reaction cross-linking set.This series polymer is that high performance engineering plastics and functional polymer are in the special copolymer of one.
Description of drawings
Fig. 1 is the infrared spectrum of 4-aminophenyl Resorcinol.
Fig. 2 is a 4-aminophenyl Resorcinol
1H NMR spectrogram.
Fig. 3 is infrared figure before and after the amino-benzene lateral group polyethers ether naphthalenone grafting of the present invention.
Fig. 4 is the hot weightless picture under the amino-benzene lateral group polyethers ether naphthalenone condition of nitrogen gas of the present invention.
Fig. 5 is the hot weightless picture under the amino-benzene lateral group polyethers ether naphthalenone air conditions of the present invention.
Embodiment
Embodiment 1:
The raw material that the present invention adopts---contain the monomeric synthetic method of aminophenyl Resorcinol, can divide three-step reaction to carry out:
The first step reaction:
With the 4-N-methyl-p-nitroaniline is raw material, raw material, ethanol, water are joined among the container D, heated mechanical stirs, and drops to room temperature after the dissolving, adds hydrochloric acid, reacted 0.5~1 hour, with concentration is that the sodium nitrite in aqueous solution of 12~35g/ml splashes in the reaction system, and controlled temperature is at 0~10 ℃, and dropping time and reaction times amount to 2~6 hours, make intermediate product A, wherein raw material, concentrated hydrochloric acid, Sodium Nitrite, ethanol, hydromassage you than being 1: 4~6: 1: 5~100: 5~100.
The reaction of second step:
In container E, add benzoquinones, sodium bicarbonate and water, the powerful stirring, 3~15 ℃ of controlled temperature are poured intermediate product A in batches into or are splashed in the system, and dropping time and reaction times amount to 4~6 hours, filter, and washing obtains intermediate product B; Wherein benzoquinones, sodium bicarbonate, water and feed molar ratio are 0.5~1.2: 2.5~10: 10~100: 1; The intermediate product B here is 4-aminophenyl-benzoquinone.
Three-step reaction:
In intermediate product B, zinc powder, your ratio 1: 6~10: 5~25 adding container F of hydromassage, mechanical stirring drips concentrated hydrochloric acid, and dropping time and reaction times amount to 4~8 hours, and controlled temperature is at 80~100 ℃, and filtered while hot obtains thick product; Wherein the molar ratio of hydrochloric acid and raw material is 8~15: 1, and water and alcohol mixeding liquid (volume ratio is 9: 1) recrystallization obtains wine-colored 4-aminophenyl-Resorcinol.
Show that by the nucleus magnetic resonance of Fig. 1 and Fig. 2 and the analytical results of infrared spectrum institute's synthetic compound is 4-aminophenyl-Resorcinol.Its productive rate is 50~60%, tests fusing point at 174~176 ℃ through DSC.
To restrain (0.01mol) by the 4-aminophenyl Resorcinol 2.0122 that embodiment 1 method makes, 4,4 '-difluoro benzophenone, 2.1820 grams (0.01mol) and 1.6585 Anhydrous potassium carbonates that restrain, 22.5ml tetramethylene sulfone, 20ml toluene is put into the there-necked flask of the 100ml that water-taker is housed, logical nitrogen is warmed up to refluxing toluene and stirs, and refluxes 1.5~2 hours, get rid of toluene, be warmed up to 180 ℃, about 180 ℃, continue reaction 4~5 hours, polymeric solution is separated out in water, through pulverizing, washing, drying obtains having the brown ceramic powder of the polyether-ether-ketone of 4-aminophenyl structure.It is 203 ℃ that DSC records second-order transition temperature.Molecular formula is as follows:
N=100~220 wherein.
Embodiment 3
Method is with embodiment 2, monomeric amount is enlarged ten times reacts: 4-aminophenyl Resorcinol 20.122 grams (0.1mol), 4,4 '-difluoro benzophenone, 21.820 grams (0.1mol) and 16.5852 Anhydrous potassium carbonates that restrain, the 230ml tetramethylene sulfone, 60ml toluene is put into the there-necked flask of the 500ml that water-taker is housed, logical nitrogen, being warmed up to refluxing toluene stirs, refluxed 3~4 hours, and got rid of toluene, be warmed up to 190 ℃, about 190 ℃, continue reaction 7~9 hours, polymeric solution is separated out in water, through pulverizing washing, drying is had the brown ceramic powder of the polyether-ether-ketone of 4-aminophenyl structure equally.
Method is with embodiment 2, and with 4,4 '-difluoro benzophenone changes 1 into, 4-two (4-fluorobenzene carbonyl) benzene, and other condition is identical, obtains containing amino polyether ether ketone ketone, and second-order transition temperature is 204 ℃.Molecular formula is as follows:
N=90~200 wherein.
Method is with embodiment 2, and with 4,4 '-difluoro benzophenone changes 1 into, 4-two (4-fluorobenzene carbonyl) naphthalene, and solvent changes N-Methyl pyrrolidone into, and solvent changes dimethylbenzene into, and other condition is identical, obtains containing amino polyethers ether naphthalenone, and second-order transition temperature is 224 ℃.Molecular formula is as follows:
N=80~200 wherein.
By the infrared figure of Fig. 3 as can be seen before the amino-benzene lateral group polyethers ether naphthalenone graft reaction at 3400cm
-1There is obvious amino absorption peak at the place, and peak disappearance herein after connecing, simultaneously at 1728cm
-1The absorption peak of imido grpup appears in the place, illustrates that graft reaction carries out smoothly.Find out the polymkeric substance heat decomposition temperature all more than 400 ℃ from Fig. 4 and Fig. 5 nitrogen, airborne hot weightless picture, illustrate that amino-benzene lateral group polyethers ether naphthalenone of the present invention has good thermostability.
Method is with embodiment 2, and with 4,4 '-difluoro benzophenone changes 4 into, 4 '-dichloro diphenylmethyl sulfone, and other condition is identical, obtains containing amino polyether ethersulfone, and second-order transition temperature is 220 ℃.Molecular formula is as follows:
N=90~200 wherein.
Embodiment 7
Will be by 4-aminophenyl Resorcinol 0.4024 gram (0.002mol) that makes among the embodiment 1; hexafluoro bisphenol-a 6.0521g (0.018mol); 4; 4 '-difluoro benzophenone, 2.1820 grams (0.01mol); 1; 4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene 4.2229g (0.01mol) and 3.312 Anhydrous potassium carbonates that restrain, the 22.5ml tetramethylene sulfone, 25ml toluene is put into the there-necked flask of the 100ml that water-taker is housed; logical nitrogen; be warmed up to refluxing toluene and stir, refluxed 1.5~2 hours, get rid of toluene; be warmed up to 180 ℃; about 180 ℃, continue reaction 4~8 hours, polymeric solution is separated out in water, through pulverizing; washing; drying obtains containing the sulfonated polyether-ether-ketone of amino-benzene lateral group, and it is 174 ℃ that DSC records second-order transition temperature.Molecular formula is as follows:
0.4≤x≤0.5 wherein.
Embodiment 8
With the stirring and dissolving under 60 ℃ of conditions of the polymkeric substance among the embodiment 5, add the 4-chloride anhydride step by step behind the one-tenth transparent and homogeneous solution, stir stoichiometric pyridine of adding and diacetyl oxide after one day, continue to stir one day, discharging through pulverizing, is washed drying in ethanol.It is 209 ℃ that DSC records second-order transition temperature.Molecular formula is as follows:
N=80~200 wherein.
Claims (2)
1. polyarylether polymer that contains amino-benzene lateral group, it is characterized in that, the described polyarylether polymer that contains amino-benzene lateral group is polyether-ether-ketone, the polyether ether ketone ketone that contains amino-benzene lateral group, the polyethers ether naphthalenone that contains amino-benzene lateral group that contain the 4-amino-benzene lateral group, contain the polyether ethersulfone of amino-benzene lateral group or contain the sulfonated polyether-ether-ketone of amino-benzene lateral group; Their structural formula is respectively
N=80~220 wherein.
2. the synthetic method of the polyarylether polymer that contains amino-benzene lateral group of a claim 1 is a reactant with 4-aminophenyl Resorcinol and two halogen monomer, is solvent with tetramethylene sulfone or N-Methyl pyrrolidone, is azeotropy dehydrant with toluene or dimethylbenzene; With 4-aminophenyl Resorcinol and equimolar pair of halogen monomer, put into the reaction vessel that mechanical stirring and water-taker are housed with the azeotropy dehydrant of the Anhydrous potassium carbonate of 1.05~1.2 times of 4-aminophenyl Resorcinol quality, 4 times of solvents, solvent volume 20% to the reactant quality, logical nitrogen, being warmed up to azeotropy dehydrant refluxes, reacted 1.5~4 hours, get rid of azeotropy dehydrant, be warmed up to 180~190 ℃ and continue reaction 4~9 hours; The polymers soln that obtains is separated out in deionized water, through pulverizing, washing, drying obtains containing the polyarylether polymer of amino-benzene lateral group structure; Described pair of halogen monomer is 4,4 '-difluorodiphenyl base ketone, 1,4-two (4-fluorobenzene carbonyl) benzene, 1,4-two (4-fluorobenzene carbonyl) naphthalene or 4,4 '-dichloro diphenylmethyl sulfone; Two halogen monomers or hexafluoro bisphenol-a and 4,4 '-difluoro benzophenone and 1,4-two (3-sodium sulfonate group-4-fluoro-benzoyl) benzene.
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CN103242530B (en) * | 2013-05-07 | 2015-02-04 | 吉林大学 | Amido bond phenylboronic acid ester-containing polyether sulphone polymer and preparation method thereof |
CN103804680B (en) * | 2014-02-27 | 2015-10-28 | 吉林大学 | Crystal type sulfonated polyether ketone, polyetherketoneetherketoneketone and preparation method thereof |
CN103923318B (en) * | 2014-04-24 | 2016-05-25 | 吉林大学 | A kind of containing amino crosslinkable polyether sulphone and its production and use |
CN105097294B (en) * | 2015-09-18 | 2017-08-29 | 吉林大学 | A kind of polyarylether/ionic liquid composite membrane for ultracapacitor and preparation method thereof |
CN105348512B (en) * | 2015-11-09 | 2017-11-14 | 吉林大学 | A kind of polyarylether material containing acid imide side base and preparation method thereof |
CN107663272A (en) * | 2016-11-18 | 2018-02-06 | 中国科学院海洋研究所 | A kind of Pyrogentisinic Acid base polyether-ether-ketone resin in the wear-resisting composite coating of marine corrosion environment and preparation method thereof |
DE102018119446A1 (en) * | 2018-08-09 | 2020-02-13 | Carl Freudenberg Kg | Crosslinking of polyaryl ether ketones |
CN117004024A (en) * | 2023-09-04 | 2023-11-07 | 吉林大学 | Amino polyarylether epoxy curing agent and preparation method thereof |
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US4016211A (en) * | 1974-07-04 | 1977-04-05 | Snam Progetti S.P.A. | Stabilized polyglycol for high temperatures |
CN1696091A (en) * | 2005-04-26 | 2005-11-16 | 吉林大学 | Method phenyl paradioxybenzene, synthetic method and application in synthesizing polymeric material |
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US4016211A (en) * | 1974-07-04 | 1977-04-05 | Snam Progetti S.P.A. | Stabilized polyglycol for high temperatures |
CN1696091A (en) * | 2005-04-26 | 2005-11-16 | 吉林大学 | Method phenyl paradioxybenzene, synthetic method and application in synthesizing polymeric material |
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