CN102634034B - Preparation method for modified polyarylether - Google Patents
Preparation method for modified polyarylether Download PDFInfo
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- CN102634034B CN102634034B CN201210078458.XA CN201210078458A CN102634034B CN 102634034 B CN102634034 B CN 102634034B CN 201210078458 A CN201210078458 A CN 201210078458A CN 102634034 B CN102634034 B CN 102634034B
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Abstract
The invention discloses a preparation method for modified polyarylether, which includes: dissolving polyarylether and hydroxyl polymer into solvent, adding deprotonation agent, carrying out a stirring action for 1-48 hours at the temperature of 10-220 DEG C, terminating the reaction, pouring reaction liquid into precipitator or directly evaporating to lead a product to be separated out, and filtering, crushing, washing and drying the product, so that the modified polyarylether is obtained. The preparation method leads the polyarylether and the hydroxyl polymer to realize trans-etherification under the action of the deprotonation agent, so that the modified polyarylether with ether bond chaining between the hydroxyl polymer and the polyarylether is obtained. The preparation method is simple in operation, low in reaction temperature, high in efficiency, easy in product separation, easily controllable in molecular weight and hydroxyl polymer chain content, the solvent can be recycled after separation, and a preparation process is low in cost and environmental pollution, less in side reaction, high in yield and easy in large-scale production application. The prepared modified polyarylether has the advantages of high chemical stability, high heat stability, high pH (potential of hydrogen) stability, high disinfectant resistance and the like, and serves as important raw materials for high-performance engineering plastics and functional polymer materials.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of preparation method of modified polyarylether.
Background technology
Polyarylether is the high performance engineering plastics that a class main chain contains phenylate structure, good mechanical property, there is the performances such as good insulativity, thermotolerance, chemical resistance, resistance to sterilization, be widely used as numerous areas such as aerospace, electronic apparatus, coating, water treatment, battery, medical materials.But, due to the rigidity of polyarylether backbone structure, make its processing treatment more difficult, also poor with the consistency of other polymkeric substance, the particularly strong-hydrophobicity of itself, makes its resistance to crocking and biocompatibility poor, has limited effect and the scope of its application.
Because the main chain phenylate key of polyarylether is comparatively stable, also directly polyarylether is not carried out the report of modification by ether exchange process, conventional method of modifying mainly contains two kinds at present: a kind of is to introduce other molecular chain or active group by the copolymerization process of monomer, and another kind is by the phenyl ring on main chain is activated or functionalization.Chinese patent CN1989174 discloses a kind of polysulfones polyether block copolymer and synthetic method thereof, the method is the monomer of aliphatic polyether and polysulfones to be carried out under the high temperature of 230 DEG C to copolymerization, the condition harshness of reaction, pre-treatment to raw material and feed ratio require very strict, and the length of polysulfones segment and the bad control of molecular weight of product; Chinese patent CN101864070A discloses a kind of soluble poly aromatic ether and synthetic method thereof with high glass-transition temperature, by with the copolymerization of large volume diphenol monomer, prepare the soluble poly aromatic ether of high glass-transition temperature, but the temperature of its polyreaction is high, energy consumption is large, also high to equipment requirements; Chinese patent CN1680461, by the sulfurization of chlorsulfonic acid, has prepared the modified polyarylether that can be used as ionic exchange film for fuel cell material, but due to the severe corrosive of chlorsulfonic acid, high to equipment requirements, seriously polluted to environment.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of simple to operate, efficiency is high, energy consumption is low, cost is low, pollute less, the preparation method of modified polyarylether that yield is high.
The technical solution used in the present invention is:
The preparation method of a kind of modified polyarylether providing, comprises the steps:
Polyarylether and hydroxyl polymer-containing are dissolved in solvent, add proton-removed agent, stirring reaction termination reaction after 1～48 hour at 10～220 DEG C of temperature, reaction solution is poured in precipitation agent or directly evaporating solvent product is separated out, by this product after filtration, pulverize, washing, dry, obtain modified polyarylether.
Described polyarylether refers to the polymkeric substance that contains phenylate structure, has following structural formula:
Wherein:
R1 is:
R2 is:
R3 is:
In formula, a+b=1; 0≤a≤1,0≤b≤1; N is more than or equal to 1 integer.
Specifically, mainly comprise the polymkeric substance of following structure and the multipolymer of any two kinds of polymkeric substance below:
Polysulfones
Polyethersulfone
Polyether sulphone
PEKK
Polyether-ether-ketone
Polyetherketone
Hexafluoro bisphenol-a base polyethersulfone
Phenolphthalein polyethersulfone
Phenolphthalein base polyetherketone
Diazanaphthalene biphenyl base polyethersulfone
Diazanaphthalene biphenyl base polyetherketone
From the mechanism of reaction, as long as polymkeric substance contains hydroxyl, just can realize the ether exchange reaction with polyarylether.
Hydroxyl polymer-containing of the present invention is the polymkeric substance that at least contains a hydroxyl, includes but not limited to polyoxyethylene glycol, monohydroxy polyoxyethylene glycol, polypropylene glycol, PEP-101, hydroxy-terminated polytetrahydrofuran, hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group polyethylene, hydroxy'terminated butadiene nitrile rubber, liquid end hydroxy styrene-butadiene rubber, hydroxy-terminated polybutadienes, hydroxyl terminated polyisoprene, polyvinyl alcohol or ethylene-vinyl alcohol copolymer etc.
In the process of reaction, the effect of proton-removed agent is mainly to remove the proton on hydroxyl in hydroxyl polymer-containing, so as long as have the material of certain Deprotonation energy power can serve as proton-removed agent of the present invention.
Proton-removed agent of the present invention is a kind of or any two or more mixture in basic metal, alkalimetal oxide, alkaline carbonate, alkali metal hydroxide, alkalimetal hydride or alkali metal alcoholates.
Described basic metal is selected from lithium, sodium, potassium or rubidium.
Described proton-removed agent includes but not limited to lithium, sodium, potassium, rubidium, sodium oxide, potassium oxide, salt of wormwood, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium hydride, potassium hydride KH, sodium methylate, sodium ethylate, potassium methylate, n-Butyl Lithium or tert-butyl lithium etc.
Precipitation agent of the present invention is a kind of or any two or more mixture in water, alcohol or ether.
Described alcohol is selected from methyl alcohol, ethanol, Virahol, the trimethyl carbinol, propyl carbinol and ethylene glycol.
Described ether is selected from ether, t-butyl methyl ether, isopropyl ether and n-butyl ether.
The mass ratio of hydroxyl polymer-containing of the present invention and polyarylether is 0.05～4:1, and the mole ratio of described proton-removed agent and the hydroxyl of hydroxyl polymer-containing is 0.01～10:1.
Solvent of the present invention is a kind of or any two or more mixture in tetramethylene sulfone, dimethyl sulfoxide (DMSO), DMF, N,N-dimethylacetamide, tetrahydrofuran (THF) or N-Methyl pyrrolidone.
The present invention, after stirring reaction time enough, can reduce the speed of reaction greatly by cooling, thereby reaches the object of termination reaction; Also can after stirring reaction, add terminator termination reaction, to obtain better effect.Because the present invention's proton-removed agent used is the material with certain alkalescence, can make proton-removed agent inactivation by sour processing, reach the object of better termination reaction, acid all can be used as reaction terminating agent arbitrarily, and terminator of the present invention is any inorganic acid or organic acid.
Preparation method of the present invention utilizes the ether exchange reaction of the phenylate key of polyarylether and the hydroxyl of hydroxyl polymer-containing, its principle is: under the effect of the proton-removed agents such as basic metal, alkalimetal oxide, alkaline carbonate, alkali metal hydroxide, alkalimetal hydride or alkali metal alcoholates, the nucleophilic attack ability of the hydroxyl in hydroxyl polymer-containing strengthens, can carry out ether exchange reaction with phenylate key, thereby realize the covalency ehter bond link between polyarylether and hydroxyl polymer-containing.
Fig. 5 is shown in by the chemical reaction schematic diagram of this reaction.
In above-mentioned reaction equation,
represent polyarylether segment,
represent hydroxyl polymer-containing segment.
Can find out from reaction schematic diagram, reaction product is the mixture of polyarylether and polyarylether-hydroxyl polymer-containing multipolymer composition, and wherein polyarylether-hydroxyl polymer-containing multipolymer at least contains a polyarylether segment and a hydroxyl polymer-containing segment.By controlling the feed ratio of polyarylether and hydroxyl polymer-containing, can regulate the length of hydroxyl polymer-containing content and polyarylether segment; By changing the molecular weight of hydroxyl polymer-containing, can regulate the length of hydroxyl polymer-containing segment; By changing the structure of hydroxyl polymer-containing, can obtain the modified polyarylether of different performance and purposes.
The present invention makes the hydroxyl in hydroxyl polymer-containing realize covalency ehter bond with the ehter bond of polyarylether by ether exchange reaction to be connected, to obtain modified polyarylether, can improve solubility property and the processing characteristics of polyarylether; In addition, because hydroxyl polymer-containing range of choice is wide, can, according to different purposes, prepare different modified polyarylethers.Prepared modified polyarylether has the advantages such as good chemical stability, thermostability, pH stability, resistance to sterilization, is the important source material of high performance engineering plastics and functional high molecule material.
Superiority of the present invention also shows: preparation method of the present invention, and temperature of reaction is lower, and reaction conditions gentleness is easy and simple to handle, is easy to control, and side reaction is few;
By the polyarylether in change start material and the feed ratio of hydroxyl polymer-containing, can obtain different hydroxyl polymer-containing content and the modified polyarylether of polyarylether chain length again;
By changing the molecular weight of hydroxyl polymer-containing, can obtain the modified polyarylether of different hydroxyl polymer-containing chain lengths again;
Again, reaction raw materials used, for conventional material, easily obtains, and corrodibility is little, low for equipment requirements, and low price, pollutes few;
Again, product is easily isolated to, and yield is high, and solvent can use through partitioning cycle, makes preparation cost low, and environmental pollution is little.
Comprehensive, method provided by the invention is a kind of preparation method of the modified polyarylether that is easy to large-scale production application.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the prepared poly ethyldiol modified polysulfones of monohydroxy of embodiment 1;
Fig. 2 is the infrared spectrogram of the prepared poly ethyldiol modified polysulfones of monohydroxy of embodiment 1;
Fig. 3 is the thermogravimetric curve figure of the prepared poly ethyldiol modified polysulfones of monohydroxy of embodiment 1;
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of the prepared poly ethyldiol modified polyethersulfone of embodiment 2;
Fig. 5 is chemical reaction schematic diagram of the present invention.
Embodiment
Describe the present invention below in conjunction with embodiment and accompanying drawing, but this should be interpreted as to the scope of theme involved in the present invention only limits to following embodiment, all technology realizing based on following content all belong to the scope of protection of the invention.
The yield of reaction is to calculate according to formula below,
Wherein R represents the yield of reaction, W
modified polyaryletherrefer to the quality of modified polyarylether, W
polyaryletherrefer to the quality of the polyarylether in start material, W
hydroxyl polymer-containingrefer to the quality of hydroxyl polymer-containing in start material.
The Nomenclature Composition and Structure of Complexes of modified polyarylether is determined according to proton nmr spectra and infrared spectra.
In modified polyarylether, the content of hydroxyl polymer-containing segment is to obtain according to the peak area of hydroxyl polymer-containing segment in proton nmr spectra and the ratio of the peak area of polyarylether segment.
Embodiment 1: the preparation of the poly ethyldiol modified polysulfones of monohydroxy
The monohydroxy polyoxyethylene glycol (molecular weight is 5000g/mol) of 44.25g polysulfones and 20.00g (containing 4.00mmol hydroxyl) is joined in the tetrahydrofuran (THF) of 440.00g, at 50 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.11g sodium (4.78mmol) as proton-removed agent, stirring reaction 12 hours drips dilute hydrochloric acid termination reaction in reaction system at 20 DEG C.Reaction solution is poured in deionized water product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain the poly ethyldiol modified polysulfones of monohydroxy.Weigh and obtain 62.52g product, the yield of this reaction is 97.3%.
The hydrogen nuclear magnetic resonance spectrogram of the poly ethyldiol modified polysulfones of monohydroxy that this embodiment makes is shown in Fig. 1, and as can be seen from Figure 1, the strong absorption peak occurring at 3.65ppm is on monohydroxy polyoxyethylene glycol segment-OCH
2-key, this has proved that monohydroxy polyoxyethylene glycol is connected on polysulfones chain by covalent linkage.Meanwhile, according to the ratio of peak area, the content that can calculate polyoxyethylene glycol segment in this modification polysulfones is 31.1wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
The infrared spectrogram of the poly ethyldiol modified polysulfones of monohydroxy that this embodiment makes is shown in Fig. 2, as can be seen from Figure 2, and at 2870cm
-1and 1103cm
-1there is new obvious absorption peak in place, this is respectively in polyoxyethylene glycol segment-CH-stretching vibration absorption peak and-the asymmetric contraction vibration absorption peak of COC-, emerging 1040cm in addition
-1and 950cm
-1be the charateristic avsorption band of polyoxyethylene glycol segment, instruction book hydroxyl polyoxyethylene glycol is stably linked on polysulfones.
The poly ethyldiol modified polysulfones of monohydroxy that this embodiment makes is the mixture of polysulfones and polysulfones-polyethyleneglycol block copolymer composition, wherein polysulfones-polyethyleneglycol block copolymer comprises three block structures of the diblock structure of (A)-(B) and (A)-(B)-ρ-(A), wherein:
The repeating unit of block (A) is:
The repeating unit of block (B) is:
The structure of ρ is:
The thermogravimetric curve figure of the poly ethyldiol modified polysulfones of monohydroxy that this embodiment makes under nitrogen is shown in Fig. 3, as can be seen from Figure 3, the heat decomposition temperature of the poly ethyldiol modified polysulfones of this monohydroxy exceedes 300 DEG C, illustrate that it has good thermostability, this is conducive to actual use, is particularly applied to the occasion that needs sterilization or higher use temperature.
Embodiment 2: the preparation of poly ethyldiol modified polyethersulfone
The polyoxyethylene glycol (molecular weight is 10000g/mol) of 40.00g polyethersulfone and 18.00g (containing 3.60mmol hydroxyl) is joined in the tetramethylene sulfone of 440.00g, and at 40 DEG C, mechanical stirring makes it to dissolve completely for 6 hours, cool to room temperature.Add 0.18g (4.50mmol) potassium hydride KH as proton-removed agent, stirring reaction 1 hour drips Glacial acetic acid termination reaction in reaction system at 10 DEG C.Reaction solution is poured in methyl alcohol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain poly ethyldiol modified polyethersulfone.Weigh and obtain 57.13g product, the yield of this reaction is 98.5%.
The hydrogen nuclear magnetic resonance spectrogram of the poly ethyldiol modified polyethersulfone that this embodiment makes is shown in Fig. 4, and as can be seen from Figure 4, the strong absorption peak occurring at 3.51ppm is on polyoxyethylene glycol segment-OCH
2-key, this has proved that polyoxyethylene glycol is connected on polyethersulfone chain by covalent linkage.Meanwhile, according to the ratio of peak area, the content that can calculate polyoxyethylene glycol segment in this modified poly (ether-sulfone) is 29.4wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Poly ethyldiol modified polyethersulfone prepared by this embodiment is the mixture of polyethersulfone and polyethersulfone-polyethyleneglycol block copolymer composition, wherein polyethersulfone-polyethyleneglycol block copolymer is mainly three block structures of (B)-ρ-(A)-(B), wherein:
The repeating unit of block (A) is:
The repeating unit of block (B) is:
The structure of ρ is:
Embodiment 3: the preparation of polypropylene glycol modified polyether sulphone
The polypropylene glycol (molecular weight is 4000g/mol) of 40.00g polyether sulphone and 160.00g (containing 80.00mmol hydroxyl) is joined to the N of 1500.00g, in dinethylformamide, at 80 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 1.10g (8.00mmol) salt of wormwood as proton-removed agent, stirring reaction 18 hours at 220 DEG C, by being cooled to room temperature termination reaction.Reaction solution is poured in ether product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polypropylene glycol modified polyether sulphone.Weigh and obtain 180.80g product, the yield of this reaction is 90.4%.
The polypropylene glycol content that can calculate in this modified polyarylether sulfone by hydrogen nuclear magnetic resonance spectrogram is 78.8wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Polypropylene glycol modified polyether sulphone prepared by this embodiment is the mixture of polyether sulphone and polyether sulphone-polypropylene glycol segmented copolymer composition, wherein polyether sulphone-polypropylene glycol segmented copolymer is mainly three block structures of (B)-ρ-(A)-(B), wherein:
The repeating unit of block (A) is:
The repeating unit of block (B) is:
The structure of ρ is:
Embodiment 4: the preparation of PEP-101 modification phenolphthalein polyethersulfone
By the PEP-101 (F127 of 40.00g phenolphthalein polyethersulfone and 63.00g (containing 10.00mmol hydroxyl), triblock copolymer, two ends are polyoxyethylene glycol segments, centre is polypropylene glycol segment, molecular weight is 12600g/mol) join in the tetrahydrofuran (THF) of 1000.00g, at 40 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.24g (10.00mmol) sodium hydride and 0.62g (10.00mmol) sodium oxide as proton-removed agent, stirring reaction 48 hours at 40 DEG C, directly evaporating solvent is separated out product, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain PEP-101 modification phenolphthalein polyethersulfone.Weigh and obtain 99.70g product, the yield of this reaction is 96.8%.
Can calculate PEP-101 content in this modification phenolphthalein polyethersulfone by hydrogen nuclear magnetic resonance spectrogram is 60.2wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 5: the preparation of polydimethylsiloxane--modified hexafluoro bisphenol-a base polyethersulfone
The hydroxyl-terminated injecting two methyl siloxane (molecular weight is 2000g/mol) of 40.00g hexafluoro bisphenol-a base polyethersulfone and 20g (containing 20.00mmol hydroxyl) is joined to the N of 500.00g, in N-N,N-DIMETHYLACETAMIDE, at 80 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.59g (15.00mmol) potassium as proton-removed agent, stirring reaction 24 hours at 20 DEG C drips formic acid termination reaction in reaction system.Reaction solution is poured in Virahol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polydimethylsiloxane--modified hexafluoro bisphenol-a base polyethersulfone.Weigh and obtain 59.52g product, the yield of this reaction is 99.2%.
The content that can calculate PolydimethylsiloxaneChain Chain section in this modification hexafluoro bisphenol-a base polyethersulfone by hydrogen nuclear magnetic resonance spectrogram is 29.7wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 6: the preparation of polybutadiene-modified diazanaphthalene biphenyl base polyethersulfone
The hydroxy-terminated polybutadienes (molecular weight is 5000g/mol) of 40.00g diazanaphthalene biphenyl base polyethersulfone and 5.00g (containing 2.00mmol hydroxyl) is joined in the dimethyl sulfoxide (DMSO) of 400.00g, at 80 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.031g (0.50mmol) sodium oxide as proton-removed agent, stirring reaction 12 hours at 60 DEG C drips Glacial acetic acid termination reaction in reaction system.Reaction solution is poured in propyl carbinol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polybutadiene-modified diazanaphthalene biphenyl base polyethersulfone.Weigh and obtain 43.92g product, the yield of this reaction is 97.6%.
The content that can calculate the polybutadiene segments in this modification diazanaphthalene biphenyl base polyethersulfone by hydrogen nuclear magnetic resonance spectrogram is 11.2wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 7: the preparation of acrylonitrile butadiene rubber modified polyetherketone
The hydroxy'terminated butadiene nitrile rubber (molecular weight is 3000g/mol) of 40.00g polyetherketone and 10.00g (containing 6.60mmol hydroxyl) is joined in the N-Methyl pyrrolidone of 500.00g, at 80 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.13g (3.33mmol) sodium hydroxide as proton-removed agent, stirring reaction 30 hours at 60 DEG C drips dilute sulphuric acid termination reaction in reaction system.Reaction solution is poured in t-butyl methyl ether product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain acrylonitrile butadiene rubber modified polyetherketone.Weigh and obtain 47.55g product, the yield of this reaction is 95.1%.
The content that can calculate paracril segment in this modified polyether ketone by hydrogen nuclear magnetic resonance spectrogram is 17.9wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 8: the preparation of polyisoprene modified PEKK
The hydroxyl terminated polyisoprene (molecular weight is 2000g/mol) of 40.00g PEKK and 10.00g (containing 10.00mmol hydroxyl) is joined in the N-Methyl pyrrolidone of 500.00g, at 60 DEG C, mechanical stirring makes it to dissolve completely for 10 hours, cool to room temperature.Add 0.14g lithium (20.00mmol) as proton-removed agent, stirring reaction 24 hours at 30 DEG C drips propionic acid termination reaction in reaction system.Reaction solution is poured in isopropyl ether product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polyisoprene modified PEKK.Weigh and obtain 47.40g product, the yield of this reaction is 94.8%.
The content that can calculate polyisoprene segment in this modified polyether ketone ketone by hydrogen nuclear magnetic resonance spectrogram is 18.8wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 9: the preparation of poly ethyldiol modified polyether-ether-ketone
The polyoxyethylene glycol (molecular weight is 20000g/mol) of 40.00g polyether-ether-ketone and 2.00g (containing 0.20mmol hydroxyl) is joined to the N of 440.00g, in dinethylformamide, at 60 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.11g (2.00mmol) sodium methylate as proton-removed agent, stirring reaction 40 hours at 70 DEG C drips dilute phosphoric acid termination reaction in reaction system.Reaction solution is poured in methanol/water mixing solutions product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain poly ethyldiol modified polyether-ether-ketone.Weigh and obtain 41.33g product, the yield of this reaction is 98.4%.
The content that can calculate polyoxyethylene glycol segment in this modified polyetheretherketonefiber by hydrogen nuclear magnetic resonance spectrogram is 4.7wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 10: the preparation of polytetrahydrofuran modification diazanaphthalene biphenyl base polyetherketone
The hydroxy-terminated polytetrahydrofuran (molecular weight is 5000g/mol) of 40.00g diazanaphthalene biphenyl base polyetherketone and 25.00g (containing 10.00mmol hydroxyl) is joined to the N of 600.00g, in N-N,N-DIMETHYLACETAMIDE, at 50 DEG C, mechanical stirring makes it to dissolve completely for 6 hours, cool to room temperature.Add 2.52g potassium ethylate (30.00mmol) as proton-removed agent, stirring reaction 28 hours at 80 DEG C drips formic acid termination reaction in reaction system.Reaction solution is poured in the trimethyl carbinol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polytetrahydrofuran modification diazanaphthalene biphenyl base polyetherketone.Weigh and obtain 59.67g product, the yield of this reaction is 91.8%.
The content that can calculate polytetrahydrofuran segment in this modification diazanaphthalene biphenyl base polyetherketone by hydrogen nuclear magnetic resonance spectrogram is 36.6wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 11: the preparation of PE modified diazanaphthalene biphenyl base polyethersulfone ketone
The terminal hydroxy group polyethylene (molecular weight is 2000g/mol) of 40.00g diazanaphthalene biphenyl base polyethersulfone ketone (multipolymer of diazanaphthalene biphenyl base polyethersulfone and diazanaphthalene biphenyl base polyetherketone) and 10.00g (containing 10.00mmol hydroxyl) is joined in the mixing solutions of 500.00g dimethyl sulfoxide (DMSO) and tetramethylene sulfone, at 50 DEG C, mechanical stirring makes it to dissolve completely for 6 hours, cool to room temperature.Add 0.56g (10.00mmol) potassium hydroxide as proton-removed agent, stirring reaction 24 hours at 70 DEG C drips dilute acetic acid termination reaction in reaction system.Reaction solution is poured in ethanol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain PE modified diazanaphthalene biphenyl base polyethersulfone ketone.Weigh and obtain 49.35g product, the yield of this reaction is 98.7%.
The content that can calculate polyethylene segment in this modification diazanaphthalene biphenyl base polyethersulfone ketone by hydrogen nuclear magnetic resonance spectrogram is 16.9wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 12: the preparation of the liquid rubber modified polysulfones-polyethersulfone copolymer of butylbenzene
The liquid end hydroxy styrene-butadiene rubber (molecular weight is 3000g/mol) of 40.00g polysulfones-polyethersulfone copolymer and 5.00g (containing 3.40mmol hydroxyl) is joined to 400.00g N, in the mixing solutions of dinethylformamide and tetrahydrofuran (THF), at 60 DEG C, mechanical stirring makes it to dissolve completely for 8 hours, cool to room temperature.Add 0.16g potassium oxide (1.67mmol) as proton-removed agent, stirring reaction 36 hours at 60 DEG C drips rare nitric acid termination reaction in reaction system.Reaction solution is poured in ethylene glycol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain the liquid rubber modified polysulfones-polyethersulfone copolymer of butylbenzene.Weigh and obtain 43.61g product, the yield of this reaction is 96.9%.
The content that can calculate butylbenzene fluid rubber segment in this modification polysulfones-polyethersulfone copolymer by hydrogen nuclear magnetic resonance spectrogram is 10.4wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 13: the preparation of polypropylene glycol modified polyethersulfone-polyether-ether ketone copolymer
The polypropylene glycol (molecular weight is 1000g/mol) of 40.00g polyethersulfone-polyether-ether ketone copolymer and 30.00g (containing 60.00mmol hydroxyl) is joined to 700.00g N, in the mixing solutions of N-N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone, at 50 DEG C, mechanical stirring makes it to dissolve completely for 7 hours, cool to room temperature.Add 3.35g (39.00mmol) rubidium as proton-removed agent, stirring reaction 8 hours at 30 DEG C drips dilute sulphuric acid termination reaction in reaction system.Reaction solution is poured in the mixing solutions of water and ethanol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polypropylene glycol modified polyethersulfone-polyether-ether ketone copolymer.Weigh and obtain 67.41g product, the yield of this reaction is 96.3%.
The content that can calculate polypropylene glycol segment in this modified poly (ether-sulfone)-polyether-ether ketone copolymer by hydrogen nuclear magnetic resonance spectrogram is 42.1wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 14: the preparation of epoxy ethane-epoxy propane random copolymer modified polyether ketone ketone-polyether-ether ketone copolymer
The epoxy ethane-epoxy propane random copolymer (molecular weight is 10000g/mol) of 40.00g PEKK-polyether-ether ketone copolymer and 12.00g (containing 2.40mmol hydroxyl) is joined in the mixing solutions of 500.00g dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone, at 50 DEG C, mechanical stirring makes it to dissolve completely for 7 hours, cool to room temperature.Add 0.64g (6.00mmol) sodium carbonate as proton-removed agent, stirring reaction 12 hours at 120 DEG C drips dilute hydrochloric acid termination reaction in reaction system.Reaction solution is poured in n-butyl ether product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain epoxy ethane-epoxy propane random copolymer modified polyether ketone ketone-polyether-ether ketone copolymer.Weigh and obtain 51.58g product, the yield of this reaction is 99.2%.
The content that can calculate epoxy ethane-epoxy propane random copolymer segment in this modified polyether ketone ketone-polyether-ether ketone copolymer by hydrogen nuclear magnetic resonance spectrogram is 22.5wt%, this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 15: the preparation of poly ethyldiol modified phenolphthalein base polyetherketone
The polyoxyethylene glycol (molecular weight is 4000g/mol) of 40.00g phenolphthalein base polyetherketone and 18.00g (containing 9.00mmol hydroxyl) is joined in the mixing solutions of 500.00g N-Methyl pyrrolidone and tetramethylene sulfone, at 60 DEG C, mechanical stirring makes it to dissolve completely for 6 hours, cool to room temperature.Add 0.11g (13.50mmol) lithium hydride as proton-removed agent, stirring reaction 32 hours at 30 DEG C drips propionic acid termination reaction in reaction system.Reaction solution is poured in the mixing solutions of ethanol and ethylene glycol product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain poly ethyldiol modified phenolphthalein base polyetherketone.Weigh and obtain 54.40g product, the yield of this reaction is 93.8%.
The content that can calculate polyoxyethylene glycol segment in this modification phenolphthalein base polyetherketone by hydrogen nuclear magnetic resonance spectrogram is 30.6wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.Embodiment 16: the preparation of polyvinyl alcohol modification polyethersulfone
By 40.00g polyethersulfone and 20.00g(containing 454.55mmol hydroxyl) polyvinyl alcohol (molecular weight is 22000g/mol) join in the DMF of 600.00g, at 80 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 0.29g (4.55mmol) n-Butyl Lithium as proton-removed agent, stirring reaction 24 hours at 30 DEG C drips dilute hydrochloric acid termination reaction in reaction system.Reaction solution is poured into water product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain polyvinyl alcohol modification polyethersulfone.Weigh and obtain 55.50g product, the yield of this reaction is 92.5%.
The content that can calculate polyvinyl alcohol segments in this modified poly (ether-sulfone) by hydrogen nuclear magnetic resonance spectrogram is 31.2wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Embodiment 17: the preparation of ethylene-vinyl alcohol copolymer modified poly (ether-sulfone)
By 40.00g polyethersulfone and 20.00g(containing 323.94mmol hydroxyl) ethylene-vinyl alcohol copolymer (content of vinyl alcohol is 38wt%) join the N of 600.00g, in N-N,N-DIMETHYLACETAMIDE, at 80 DEG C, mechanical stirring makes it to dissolve completely for 5 hours, cool to room temperature.Add 1.04g (16.20mmol) tert-butyl lithium as proton-removed agent, stirring reaction 24 hours at 30 DEG C drips dilute hydrochloric acid termination reaction in reaction system.Reaction solution is poured into water product is separated out, by this product after filtration, pulverizing, washed with de-ionized water multipass, then dry and obtain ethylene-vinyl alcohol copolymer modified poly (ether-sulfone).Weigh and obtain 56.34g product, the yield of this reaction is 93.9%.
The content that can calculate ethylene-vinyl alcohol copolymer segment in this modified poly (ether-sulfone) by hydrogen nuclear magnetic resonance spectrogram is 32.7wt%, and this is consistent with feed ratio, illustrates that this reaction is very complete and reaction efficiency is very high.
Claims (9)
1. a preparation method for modified polyarylether, is characterized in that, comprises the steps:
Polyarylether and hydroxyl polymer-containing are dissolved in solvent, add proton-removed agent, stirring reaction termination reaction after 1～48 hour at 10～30 DEG C of temperature, reaction solution is poured in precipitation agent or directly evaporating solvent product is separated out, by this product after filtration, pulverize, washing, dry, obtain modified polyarylether; Described proton-removed agent is a kind of or any two or more mixture in basic metal, alkalimetal hydride.
2. the preparation method of modified polyarylether as claimed in claim 1, is characterized in that, described polyarylether refers to the polymkeric substance that contains phenylate structure, has following structural formula:
Wherein:
R1 is:
R2 is:
or
R3 is:
or
or
or
or
or
or
or
or
In formula, a+b=1; 0≤a≤1,0≤b≤1; N is more than or equal to 1 integer.
3. the preparation method of modified polyarylether as claimed in claim 1, it is characterized in that, described hydroxyl polymer-containing is polyoxyethylene glycol, monohydroxy polyoxyethylene glycol, polypropylene glycol, PEP-101, hydroxy-terminated polytetrahydrofuran, hydroxyl-terminated injecting two methyl siloxane, terminal hydroxy group polyethylene, hydroxy'terminated butadiene nitrile rubber, liquid end hydroxy styrene-butadiene rubber, hydroxy-terminated polybutadienes, hydroxyl terminated polyisoprene, polyvinyl alcohol or ethylene-vinyl alcohol copolymer.
4. the preparation method of modified polyarylether as claimed in claim 1, is characterized in that, described basic metal is selected from lithium, sodium, potassium and rubidium.
5. the preparation method of modified polyarylether as claimed in claim 1, is characterized in that, described precipitation agent is a kind of or any two or more mixture in water, alcohol or ether.
6. the preparation method of modified polyarylether as claimed in claim 5, is characterized in that, described alcohol is selected from methyl alcohol, ethanol, Virahol, the trimethyl carbinol, propyl carbinol or ethylene glycol; Described ether is selected from ether, t-butyl methyl ether, isopropyl ether or n-butyl ether.
7. the preparation method of modified polyarylether as claimed in claim 1, is characterized in that, described hydroxyl polymer-containing and the mass ratio of polyarylether are 0.05～4:1, and the mole ratio of described proton-removed agent and the hydroxyl of hydroxyl polymer-containing is 0.01～10:1.
8. the preparation method of modified polyarylether as claimed in claim 1, it is characterized in that, described solvent is a kind of or any two or more mixture in tetramethylene sulfone, dimethyl sulfoxide (DMSO), DMF, N,N-dimethylacetamide, tetrahydrofuran (THF) or N-Methyl pyrrolidone.
9. the preparation method of modified polyarylether as claimed in claim 1, is characterized in that, adds terminator termination reaction after described stirring reaction, and described terminator is any inorganic acid or organic acid.
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