CN110156994A - Poly- (ether ketone-benzimidazole) copolymer of one kind and preparation method thereof - Google Patents
Poly- (ether ketone-benzimidazole) copolymer of one kind and preparation method thereof Download PDFInfo
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- CN110156994A CN110156994A CN201910537236.1A CN201910537236A CN110156994A CN 110156994 A CN110156994 A CN 110156994A CN 201910537236 A CN201910537236 A CN 201910537236A CN 110156994 A CN110156994 A CN 110156994A
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Abstract
The present invention provides a kind of poly- (ether ketone-benzimidazole) copolymers, are related to technical field of polymer materials.Poly- (ether ketone-benzimidazole) copolymer provided by the invention has structure shown in formula I.Contain benzimidazole group and aromatic ether ketone structure in the repetitive unit of poly- (ether ketone-benzimidazole) copolymer provided by the invention simultaneously, both maintained poly(aryl ether ketone) can thermoplastic processing property, the performances such as the excellent chemical stability of polybenzimidazoles and higher glass transition temperature have been had both again, have potential application prospect in fields such as high-performance composite materials, medical material, clean energy resource materials as a new class of special polymer material.The present invention provides the preparation method of poly- (ether ketone-benzimidazole) copolymer, preparation method process provided by the invention is simple, easy to operate, low in cost.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of poly- (ether ketone-benzimidazole) copolymer and its
Preparation method.
Background technique
Polybenzimidazoles is a kind of excellent aromatic heterocycle polymer, has many advantages, such as high-strength, Gao Mo, high-fire resistance.In addition,
Polybenzimidazoles also has outstanding spinning properties and fabulous chemical stability and anti-flammability, in high-tech such as aerospaces
The civil fields such as field and fire-fighting, seawater cleaning and methanol direct fuel cell suffer from extensive use.Polybenzimidazoles is only
Strong hydrogen bond action assigns its excellent mechanical property between special rigid rod-shaped molecular structure and segment, but also due to its point
Sub- chain rigidity is too strong, and making it substantially can only be dissolved in a small number of strong acid such as methanesulfonic acid, and its fusing point is higher than thermal decomposition temperature,
It is difficult to carry out thermoplastic processing, limit its scope of application.
Poly(aryl ether ketone) is a kind of hemicrystalline high-performance polymer, has good mechanical properties, fatigue resistance, higher resistance to
Hot property and excellent electrical insulation properties.Different from polybenzimidazoles, poly(aryl ether ketone) can carry out thermoplastic processing, but its chemistry
The performances such as stability, glass transition temperature and anti-flammability are not as good as polybenzimidazoles.It is commercialized the glass transition of poly(aryl ether ketone)
Temperature is about 143 DEG C, and the contradiction between heat resistance and moulding processability limits further applying for poly(aryl ether ketone).
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of poly- (ether ketone-benzimidazole) copolymers and preparation method thereof.
Contain benzimidazole group and aromatic ether ketone in the repetitive unit of poly- (ether ketone-benzimidazole) copolymer provided by the invention simultaneously
Structure, not only maintained poly(aryl ether ketone) can thermoplastic processing property, but also had both the excellent chemical stability of polybenzimidazoles and compared with
The performances such as high glass transition temperature.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of poly- (ether ketone-benzimidazole) copolymers, have structure shown in formula I:
In formula I: Ar includes WithOne kind；N=20~1000.
The present invention provides the preparation methods of (ether ketone-benzimidazole) copolymer poly- described in above technical scheme, including with
Lower step:
Under protective atmosphere, 3,4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer are carried out under the action of polyphosphoric acids
Polymerization reaction obtains poly- (ether ketone-benzimidazole) copolymer；
The aromatic dicarboxilic acid monomer includes M-phthalic acid, terephthalic acid (TPA), 4,4 '-oxydibenzoic acids, 4,4 '-two
Carboxyl benzophenone, 4,4 '-Dicarboxy diphenylsulfones, (4- carboxyl phenyl) isopropyl alkane of 2,2- bis- and 2,2- bis- (4- carboxyl phenyl) hexafluoro
One of isopropyl alkane.
Preferably, the molar ratio of 3, the 4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer is 1:1.
Preferably, the total mass fraction of 3, the 4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer in polyphosphoric acids is
2~20%；The mass content of phosphorus pentoxide is 70~90% in the polyphosphoric acids.
Preferably, the polymerization reaction includes the first polymerization reaction and the second polymerization reaction successively carried out；Described first
The temperature of polymerization reaction is 120~160 DEG C, and the time is 1~5h；The temperature of second polymerization reaction is 180~220 DEG C, when
Between be 5~30h.
Preferably, 3, the 4- diaminodiphenyl ether is prepared by method comprising the following steps:
(1) under protective atmosphere, 5- chloro-2-nitroaniline, phenol and potassium carbonate carry out into ether in organic solvent and react,
Obtain 2- nitro -5- phenoxybenzamine；
(2) under protective atmosphere, the 2- nitro -5- phenoxybenzamine and hydrazine hydrate are gone back under the effect of the catalyst
Original reaction, obtains 3,4- diaminodiphenyl ether.
Preferably, the molar ratio of 5- chloro-2-nitroaniline and phenol is 1:1~1.05:1, the benzene in the step (1)
The molar ratio of phenol and potassium carbonate is 1:1~1:2.
Preferably, organic solvent is n,N-dimethylacetamide in the step (1)；The 5- chloro-2-nitroaniline with
The total mass fraction of phenol in organic solvent is 10~70%；The temperature at ether reaction is 130~200 DEG C, the time 5
~40h.
Preferably, the amount ratio of hydrazine hydrate and 2- nitro -5- phenoxybenzamine is 0.5~10mL in the step (2):
1g；The catalyst is palladium/carbon, and the mass ratio of the catalyst and 2- nitro -5- phenoxybenzamine is 1:10~1:1000.
Preferably, the solvent of reduction reaction is ethyl alcohol and/or Isosorbide-5-Nitrae-dioxane in the step (2)；The 2- nitro-
The concentration of 5- phenoxybenzamine in a solvent is 2~200g/L；The temperature of the reduction reaction is 80~120 DEG C, the time 10
~70h.
The present invention provides a kind of poly- (ether ketone-benzimidazole) copolymers, have structure shown in formula I.It is provided by the invention
Contain benzimidazole group and aromatic ether ketone structure in the repetitive unit of poly- (ether ketone-benzimidazole) copolymer simultaneously, both kept
Poly(aryl ether ketone) can thermoplastic processing property, and had both polybenzimidazoles excellent chemical stability and higher vitrifying turns
The performances such as temperature, as a new class of special polymer material in high-performance composite materials, medical material, clean energy resource material
There is potential application prospect in equal fields.Embodiment the result shows that, poly- (ether ketone-benzimidazole) copolymer tool provided by the invention
There is good thermoplastic processing, glass transition temperature is significantly higher than the glass transition temperature of commercialization poly(aryl ether ketone).
The present invention provides the preparation methods of above-mentioned poly- (ether ketone-benzimidazole) copolymer.Preparation side provided by the invention
Method process is simple, easy to operate, low in cost.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of poly- (ether ketone-benzimidazole) copolymer prepared by embodiment 2；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of poly- (ether ketone-benzimidazole) copolymer prepared by embodiment 2.
Specific embodiment
The present invention provides a kind of poly- (ether ketone-benzimidazole) copolymers, have structure shown in formula I:
In formula I: Ar includes WithOne kind；N=20~1000, preferably
100~900.
Contain benzimidazole group and fragrance on the main chain of poly- (ether ketone-benzimidazole) copolymer provided by the invention simultaneously
Ether ketone structure, combines the excellent properties of two kinds of high molecular materials of polyether-ketone and polybenzimidazoles, while solving polyether-ketone again
The problem of glass transition temperature is low and polybenzimidazoles processing difficulties.Poly- (ether ketone-benzimidazole) provided by the invention copolymerization
Object is with a wide range of applications in fields such as space flight, military affairs, electronics, fuel cell, nuclear energy and precision instruments.
The present invention provides the preparation methods of (ether ketone-benzimidazole) copolymer poly- described in above technical scheme, including with
Lower step:
Under protective atmosphere, 3,4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer are carried out under the action of polyphosphoric acids
Polymerization reaction obtains poly- (ether ketone-benzimidazole) copolymer；
The aromatic dicarboxilic acid monomer includes M-phthalic acid, terephthalic acid (TPA), 4,4 '-oxydibenzoic acids, 4,4 '-two
Carboxyl benzophenone, 4,4 '-Dicarboxy diphenylsulfones, (4- carboxyl phenyl) isopropyl alkane of 2,2- bis- and 2,2- bis- (4- carboxyl phenyl) hexafluoro
One of isopropyl alkane.
In the present invention, 3, the 4- diaminodiphenyl ether is preferably prepared by method comprising the following steps:
(1) under protective atmosphere, 5- chloro-2-nitroaniline, phenol and potassium carbonate carry out into ether in organic solvent and react,
Obtain 2- nitro -5- phenoxybenzamine；
(2) under protective atmosphere, the 2- nitro -5- phenoxybenzamine and hydrazine hydrate are gone back under the effect of the catalyst
Original reaction, obtains 3,4- diaminodiphenyl ether.
The present invention carries out into ether under protective atmosphere, by 5- chloro-2-nitroaniline, phenol and potassium carbonate in organic solvent
Reaction, obtains 2- nitro -5- phenoxybenzamine, reaction equation is as shown in Equation 1:
In the present invention, the molar ratio of the 5- chloro-2-nitroaniline and phenol is preferably 1:1~1.05:1, more preferably
For 1.02:1；The molar ratio of the phenol and potassium carbonate is preferably 1:1~1:2, more preferably 1:1.5；The potassium carbonate is preferred
For Anhydrous potassium carbonate.In the present invention, the organic solvent is preferably n,N-dimethylacetamide；The chloro- 2- nitrobenzene of 5-
Amine and the total mass fraction of phenol in organic solvent are preferably 10~70%, and more preferably 50~60%.In the present invention, on
The addition sequence for stating each raw material is preferred are as follows: first mixes 5- chloro-2-nitroaniline, phenol and organic solvent, then adds again
Enter potassium carbonate to be mixed.In the present invention, the mixing preferably carries out under stirring conditions, and the present invention is to the stirring
Speed and time do not require particularly, can guarantee that each component is sufficiently dissolved and is uniformly mixed.Of the invention specific real
It applies in example, it is preferred to use the three-necked flask equipped with water segregator is as the reaction vessel reacted at ether.
The present invention preferably first carries out water removal processing before carrying out into ether reaction, described to remove water process specifically: in the 5-
Toluene is added in the mixed solution that chloro-2-nitroaniline, phenol, potassium carbonate and organic solvent form, is then heated；It is described
The temperature of heating is preferably 90~125 DEG C, and more preferably 120 DEG C, the time is preferably 1~20h, more preferably 12h.Benefit of the invention
Azeotropic mixture is formed with toluene and water and removes moisture a small amount of in reaction system, and the water generated including phenol with carbonic acid nak response has
Micro-moisture and reaction vessel micro-moisture remained on surface in solvent.
After water process, reaction system heating react at ether by the present invention.In the present invention, it is described at ether reaction
Temperature is preferably 130~200 DEG C, and more preferably 150~160 DEG C, the time is preferably 5~40h, more preferably 20~30h.At this
In invention, described in ether reaction process, phenol and carbonic acid nak response generate phenol sylvite, the chlorine atom of 5- chloro-2-nitroaniline
It is combined into potassium chloride with the potassium ion of phenol sylvite, other parts are combined into ether.
After reacting at ether, the present invention preferably post-processes gained at ether reactant；The method of the post-processing is preferred
The following steps are included:
(a) by it is described be cooled to room temperature at ether reactant after pour into methanol aqueous solution, obtain yellow solid；
(b) by yellow solid first alcohol and water alternately washing filtering, crude product is obtained；
(c) recrystallization and decolorization will be successively carried out after crude product drying, Decolorization product is dried again, is obtained
2- nitro -5- phenoxybenzamine.
In the present invention, the volume ratio of first alcohol and water is preferably 1:4 in the methanol aqueous solution in the step (a)；It is described
Alternately the number of washing is preferably no less than three times in step (b).In the present invention, temperature dry in the step (c) is preferred
It is 60 DEG C；The solvent of the recrystallization is preferably ethanol solution；The decolorization is preferably active carbon with decolorising agent.
After obtaining 2- nitro -5- phenoxybenzamine, the present invention is under protective atmosphere, by the 2- nitro -5- phenoxy group benzene
Amine and hydrazine hydrate carry out reduction reaction under the effect of the catalyst, obtain 3,4- diaminodiphenyl ether, reaction equation is as shown in Equation 2:
In the present invention, the amount ratio of the hydrazine hydrate and 2- nitro -5- phenoxybenzamine is preferably 0.5~10mL:1g,
More preferably 4~6mL:1g；The catalyst is preferably palladium/carbon, the quality of the catalyst and 2- nitro -5- phenoxybenzamine
Than being preferably 1:10~1:1000.In the present invention, the solvent of the reduction reaction is preferably ethyl alcohol and/or Isosorbide-5-Nitrae-dioxy six
Ring；The concentration of the 2- nitro -5- phenoxybenzamine in a solvent is preferably 2~200g/L, more preferably 50~150g/L.This
Invention does not require the source of the hydrazine hydrate, catalysts and solvents particularly, using commercially available corresponding product；Its
In, in the specific embodiment of the invention, the purity of commercially available hydrazine hydrate is preferably 85%.
In the present invention, the temperature of the reduction reaction is preferably 80~120 DEG C, and more preferably 95 DEG C, the time is preferably
10~70h, more preferably 48h.In the present invention, the addition sequence of above-mentioned each raw material is preferred are as follows: sequentially adds 2- nitro -5- benzene
Oxygroup aniline, solvent and catalyst are mixed, and then heating reaches the temperature of the reduction reaction, and hydrazine hydrate is added.At this
In invention, the mixing preferably carries out under stirring conditions, and the time of the stirring is preferably 0.5h.The present invention is preferably with water
It closes the dioxane solution of hydrazine or hydrazine hydrate is added in the form of the ethanol solution of hydrazine hydrate, i.e., first by hydrazine hydrate and dioxane
Or ethyl alcohol mixing, the ethanol solution of the dioxane solution or hydrazine hydrate that form hydrazine hydrate add；The hydrazine hydrate and dioxy
The volume ratio of six rings is preferably 4:1.In the present invention, the hydrazine hydrate is added preferably in the form of dropwise addition, the dropwise addition when
Between preferably 6h；The time of the reduction reaction starts to calculate after being added dropwise with the hydrazine hydrate.In the present invention, described to go back
During original reaction, the nitro in 2- nitro -5- phenoxybenzamine structure is reduced to amino.
After reduction reaction, the present invention preferably post-processes gained reduction reaction liquid；The method of the post-processing is preferred
Are as follows: it is filtered after being cooled to room temperature the reduction reaction liquid, removes catalyst；Gained filtrate is poured into deionized water, is stirred
Under the conditions of solid is precipitated；It is dried after the washed filtering of obtained solid, obtains 3,4- diaminodiphenyl ether.The present invention is to described
The method of filtering does not require particularly, using method well known in the art.In the present invention, excellent in the deionized water
A small amount of acetic acid and NaHSO is added in choosing3, prevent product from aoxidizing.In the present invention, the washing detergent preferably go from
Sub- water；The present invention does not require the number of the washing particularly, and guarantee cleans up.In the present invention, described dry
Dry temperature is preferably 60 DEG C, and the time is preferably 10h；The drying carries out preferably in vacuum drying oven.
After obtaining 3,4- diaminodiphenyl ether, the present invention is under protective atmosphere, by 3,4- diaminodiphenyl ether and fragrance two
Carboxylic acid monomer carries out polymerization reaction under the action of polyphosphoric acids, obtains poly- (ether ketone-benzimidazole) copolymer, reaction equation such as formula
Shown in 3:
In the present invention, the molar ratio of 3, the 4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer is preferably 1:1.At this
In invention, the total mass fraction of 3, the 4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer in polyphosphoric acids is preferably 2~
20%, more preferably 8~15%；The mass content of phosphorus pentoxide is preferably 70~90% in the polyphosphoric acids, more preferably
It is 80%；The polyphosphoric acids is as catalyst and reaction medium.In the present invention, the addition sequence of above-mentioned each raw material is preferred
Are as follows: polyphosphoric acids and 3 is first added, 4- diaminodiphenyl ether carries out the first heating, dissolves 3,4- diaminodiphenyl ether sufficiently；It is cold
But to after room temperature, aromatic dicarboxilic acid monomer is added, carries out the second heating, is completely dissolved aromatic dicarboxilic acid monomer.In the present invention
In, the temperature of first heating is preferably 80 DEG C, and the time is preferably 4h；The temperature of second heating is preferably 100 DEG C, when
Between preferably 1h.The present invention adds aromatic dicarboxilic acid monomer after cooling to room temperature, avoids 3,4- diaminodiphenyl ether by oxygen
Change.
In the present invention, the polymerization reaction includes the first polymerization reaction and the second polymerization reaction successively carried out.At this
In invention, the temperature of first polymerization reaction is preferably 120~160 DEG C, and more preferably 150 DEG C, the time is preferably 1~5h,
More preferably 4h；The present invention is continuously heating to institute to gained mixed liquor preferably after the aromatic dicarboxilic acid monomer is completely dissolved
The temperature for stating the first polymerization reaction starts to carry out polymerization reaction.In the present invention, the temperature of second polymerization reaction is preferably
180~220 DEG C, more preferably 190 DEG C, the time is preferably 5~30h, more preferably 20h.The present invention divides the polymerization reaction
Two stages carry out, i.e. the first polymerization stage and the second polymerization stage are conducive to the steady progress of reaction；Wherein,
One polymerization stage be mainly aromatic dicarboxilic acid monomer carboxyl respectively with the phenoxy group of 3,4- diaminodiphenyl ether and one
Condensation reaction occurs for amino, is respectively formed benzophenone and amido bond；Second polymerization stage amido bond and adjacent amino are into one
Step condensation forms imidazole ring, and at desired temperatures with the extension of reaction time, the degree of polymerization further increases.
After polymerization reaction, the present invention preferably post-processes gained polymerization liquid；The method of the post-processing is preferred
Are as follows: it is poured into ice water after being cooled to room temperature gained polymerization liquid, sediment is precipitated；Again successively with sodium bicarbonate aqueous solution and
Water carries out washing to the sediment until neutral；Then washed product is dried, obtains poly- (ether ketone-benzimidazole) altogether
Polymers.In the present invention, the mass concentration of the sodium bicarbonate aqueous solution is preferably 2%；The temperature of the drying is preferably 60
DEG C, the time is preferably 10h.
The present invention provides the preparation methods of above-mentioned poly- (ether ketone-benzimidazole) copolymer.Preparation side provided by the invention
Method process is simple, easy to operate, low in cost.
Poly- (ether ketone-benzimidazole) copolymer provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Thin explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The synthesis of 3,4- diaminodiphenyl ether monomer
In the 500mL three-necked flask equipped with water segregator being completely dried, 36.24g is sequentially added under nitrogen protection
(0.21mol) 5- chloro-2-nitroaniline, 18.83g (0.2mol) phenol and 150mL DMAC (DMAC N,N' dimethyl acetamide).
At room temperature, magnetic agitation makes it completely dissolved, and 30.41g (0.22mol) Anhydrous potassium carbonate and 20mL toluene is then added.?
At room temperature, it is warming up to 120 DEG C of reaction 12h after stirred under nitrogen atmosphere 30min, then heats to 140 DEG C the reaction was continued for 24 hours.Instead
It after answering, is cooled to room temperature, and reaction solution is poured into 600mL methanol aqueous solution (volume ratio 1:4), it is solid to obtain a large amount of yellow
Body, repeatedly by product with the alternately washing filtering of first alcohol and water, obtained crude product is 10 hours dry in 60 DEG C of vacuum drying ovens.Most
Pure product need to be recrystallized in ethanol solution eventually, then use active carbon decolorization, finally be dried to get to product 2-
Nitro -5- phenoxybenzamine, yield: 70%.
In the 500mL three-necked flask being completely dried, 16g (0.08mol) 2- nitro -5- is sequentially added under nitrogen protection
Phenoxybenzamine, 150mL ethyl alcohol, 70mL1,4- dioxane and 1.0g palladium/carbon.At room temperature, magnetic agitation under nitrogen protection
It is warming up to 95 DEG C after 30min, the mixed solution of 80mL hydrazine hydrate and 20mL1,4- dioxane, blunting of attention drop is then added dropwise
Add, is added dropwise within about 6 hours, then keeps thermotonus 48h.After reaction, it is cooled to room temperature, filters off palladium removing/carbon；
Filtrate is poured into 2L deionized water and (a small amount of acetic acid and NaHSO are added in deionized water3, prevent product from aoxidizing), stirring
A large amount of solids are slowly precipitated down, is washed with deionized and filters repeatedly, obtained product is dry 10 in 60 DEG C of vacuum drying ovens
Hour, obtain 3,4- diaminodiphenyl ether monomer, yield: 65%.
Embodiment 2
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, and 1.55g (6mmol) 4,4'- oxydibenzoic acid is added, rises after nitrogen protection 0.5h
Temperature is completely dissolved acid to 100 DEG C of reaction 1h, is then warming up to 150 DEG C of reaction 4h, is continuously heating to 190 DEG C of reaction 20h.Reaction
After, reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the sediment being precipitated 2wt% carbonic acid
Hydrogen sodium water solution sufficiently washs, and is washed with water and washs to neutrality, be finally dried in vacuo 10 hours at 60 DEG C, obtains poly- (ether ketone-benzene
And imidazoles) copolymer, it is denoted as poly- (ether ketone-benzimidazole) copolymer (1).
The infrared spectroscopy (KBr tabletting) of synthesized poly- (ether ketone-benzimidazole) copolymer (1) is as shown in Figure 1, wherein exist
1630cm-1Peak at left and right is the stretching vibration peak of C=N and the characteristic peak of aromatic ketone on imidazole ring, and the characteristic peak of the two has weight
Close part；1240cm-1The peak at place is the C-O-C stretching vibration characteristic absorption peak of aromatic ether.Synthesized poly- (ether ketone-benzo miaow
Azoles) copolymer (1) hydrogen nuclear magnetic resonance spectrogram as shown in Fig. 2, 1~10 proton for respectively indicating different location in Fig. 2 structural formula,
The ownership of each proton peak and the structure of polymer are consistent in Fig. 2.By Fig. 1 and Fig. 2 it is found that the present invention successfully synthesizes poly- (ether ketone-
Benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (1) is in dimethyl sulfoxide, N, N- bis-
Good dissolubility is all had in methylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone and the concentrated sulfuric acid, but not
It is dissolved in the organic solvents such as chloroform, methanol, ethyl alcohol, tetrahydrofuran.The property phase that can only be dissolved in polybenzimidazoles in a small number of strong acid
Than poly- (ether ketone-benzimidazole) copolymer (1) that the present invention synthesizes has good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (1) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 72MPa, elongation at break 24%.It can
To find out, the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (1) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (1)
Temperature is 238 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
Embodiment 3
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, and 0.996g (6mmol) M-phthalic acid is added, is warming up to 100 after nitrogen protection 0.5h
DEG C reaction 1h be completely dissolved acid, be then warming up to 150 DEG C of reaction 4h, be continuously heating to 190 DEG C of reaction 20h.After reaction,
Reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the sediment being precipitated 2wt% sodium bicarbonate water
Solution sufficiently washs, and is washed with water and washs to neutrality, is finally dried in vacuo 10 hours at 60 DEG C, and poly- (ether ketone benzimidazole) is made
Copolymer is denoted as poly- (ether ketone benzimidazole) copolymer (2).
Pass through the infrared spectroscopy and hydrogen nuclear magnetic resonance spectrogram point to synthesized poly- (ether ketone-benzimidazole) copolymer (2)
Analysis shows that the present invention successfully synthesizes poly- (ether ketone-benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (2) is in dimethyl sulfoxide, N, N- bis-
Good dissolubility is all had in methylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone and the concentrated sulfuric acid, but not
It is dissolved in the organic solvents such as chloroform, methanol, ethyl alcohol, tetrahydrofuran.The property phase that can only be dissolved in polybenzimidazoles in a small number of strong acid
Than poly- (ether ketone-benzimidazole) copolymer (2) that the present invention synthesizes has good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (2) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 86MPa, elongation at break 18%.It can
To find out, the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (2) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (2)
Temperature is 271 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
Embodiment 4
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, and 0.996g (6mmol) terephthalic acid (TPA) is added, is warming up to 100 after nitrogen protection 0.5h
DEG C reaction 1h be completely dissolved acid, be then warming up to 150 DEG C of reaction 4h, be continuously heating to 190 DEG C of reaction 20h.After reaction,
Reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the sediment being precipitated 2wt% sodium bicarbonate water
Solution sufficiently washs, and is washed with water and washs to neutrality, is finally dried in vacuo 10 hours at 60 DEG C, and poly- (ether ketone benzimidazole) is made
Copolymer is denoted as poly- (ether ketone benzimidazole) copolymer (3).
Pass through the infrared spectroscopy and hydrogen nuclear magnetic resonance spectrogram point to synthesized poly- (ether ketone-benzimidazole) copolymer (3)
Analysis shows that the present invention successfully synthesizes poly- (ether ketone-benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (3) is in dimethyl sulfoxide, N, N- bis-
Good dissolubility is all had in methylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone and the concentrated sulfuric acid, but not
It is dissolved in the organic solvents such as chloroform, methanol, ethyl alcohol, tetrahydrofuran.The property phase that can only be dissolved in polybenzimidazoles in a small number of strong acid
Than poly- (ether ketone-benzimidazole) copolymer (3) that the present invention synthesizes has good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (3) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 102MPa, elongation at break 31%.
As can be seen that the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (3) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (3)
Temperature is 292 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
Embodiment 5
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, addition 1.620g (6mmol) 4,4 '-benzophenonedicarboxylic acid, after nitrogen protection 0.5h
Being warming up to 100 DEG C of reaction 1h is completely dissolved acid, is then warming up to 150 DEG C of reaction 4h, is continuously heating to 190 DEG C of reaction 20h.Instead
After answering, reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the sediment being precipitated 2wt% carbon
Sour hydrogen sodium water solution sufficiently washs, and is washed with water and washs to neutrality, is finally dried in vacuo 10 hours at 60 DEG C, poly- (ether ketone is made
Benzimidazole) copolymer, it is denoted as poly- (ether ketone benzimidazole) copolymer (4).
Pass through the infrared spectroscopy and hydrogen nuclear magnetic resonance spectrogram point to synthesized poly- (ether ketone-benzimidazole) copolymer (4)
Analysis shows that the present invention successfully synthesizes poly- (ether ketone-benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (4) is in dimethyl sulfoxide and N- methyl
Good dissolubility is all had in pyrrolidones and the concentrated sulfuric acid, but does not dissolve in n,N-Dimethylformamide, N, N- dimethyl second
The organic solvents such as amide, chloroform, methanol, ethyl alcohol, tetrahydrofuran.The property phase that can only be dissolved in polybenzimidazoles in a small number of strong acid
Than poly- (ether ketone-benzimidazole) copolymer (4) that the present invention synthesizes has good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (4) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 72MPa, elongation at break 11%.It can
To find out, the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (4) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (4)
Temperature is 280 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
Embodiment 6
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, and 1.836g (6mmol) 4,4 '-Dicarboxy diphenylsulfone is added, rises after nitrogen protection 0.5h
Temperature is completely dissolved acid to 100 DEG C of reaction 1h, is then warming up to 150 DEG C of reaction 4h, is continuously heating to 190 DEG C of reaction 20h.Reaction
After, reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the sediment being precipitated 2wt% carbonic acid
Hydrogen sodium water solution sufficiently washs, and is washed with water and washs to neutrality, be finally dried in vacuo 10 hours at 60 DEG C, poly- (ether ketone benzene is made
And imidazoles) copolymer, it is denoted as poly- (ether ketone benzimidazole) copolymer (5).
Pass through the infrared spectroscopy and hydrogen nuclear magnetic resonance spectrogram point to synthesized poly- (ether ketone-benzimidazole) copolymer (5)
Analysis shows that the present invention successfully synthesizes poly- (ether ketone-benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (5) is in dimethyl sulfoxide, N, N- bis-
Good dissolubility is all had in methylacetamide and N-Methyl pyrrolidone and the concentrated sulfuric acid, is partially soluble in N, N- dimethyl
Formamide, but insoluble in organic solvents such as chloroform, methanol, ethyl alcohol, tetrahydrofurans.A small number of strong acid can only be dissolved in polybenzimidazoles
In property compare, poly- (ether ketone-benzimidazole) copolymer (5) that the present invention synthesizes have good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (5) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 91MPa, elongation at break 19%.It can
To find out, the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (5) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (5)
Temperature is 287 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
Embodiment 7
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, and 1.704g (6mmol) 2,2- bis- (4- carboxyl phenyl) isopropyl alkane, nitrogen protection is added
100 DEG C of reaction 1h are warming up to after 0.5h is completely dissolved acid, is then warming up to 150 DEG C of reaction 4h, is continuously heating to 190 DEG C of reactions
20h.After reaction, reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the sediment being precipitated is used
5wt% sodium bicarbonate aqueous solution sufficiently washs, and is washed with water and washs to neutrality, is finally dried in vacuo 10 hours at 60 DEG C, is made
Poly- (ether ketone benzimidazole) copolymer is denoted as poly- (ether ketone benzimidazole) copolymer (6).
Pass through the infrared spectroscopy and hydrogen nuclear magnetic resonance spectrogram point to synthesized poly- (ether ketone-benzimidazole) copolymer (6)
Analysis shows that the present invention successfully synthesizes poly- (ether ketone-benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (6) is in dimethyl sulfoxide, N, N- bis-
Good dissolubility is all had in methylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone and the concentrated sulfuric acid, but
Insoluble in organic solvents such as chloroform, methanol, ethyl alcohol, tetrahydrofurans.The property in a small number of strong acid can only be dissolved in polybenzimidazoles
It compares, poly- (ether ketone-benzimidazole) copolymer (6) that the present invention synthesizes has good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (6) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 83MPa, elongation at break 17%.It can
To find out, the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (6) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (6)
Temperature is 254 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
Embodiment 8
The synthesis of poly- (ether ketone-benzimidazole) copolymer
50.0g polyphosphoric acids (P is sequentially added in the 100mL three-necked flask being completely dried2O5Content be 85%) and
1.20g (6mmol) 3,4- diaminodiphenyl ether is warming up to 80 DEG C of reaction 4h after logical nitrogen half an hour, makes 3,4- diamino hexichol
Ether sufficiently dissolves, and is cooled to room temperature again, and 2.352g (6mmol) 2,2- bis- (4- carboxyl phenyl) hexafluoro isopropyl alkane, nitrogen is added
Being warming up to 100 DEG C of reaction 1h after protection 0.5h is completely dissolved acid, is then warming up to 150 DEG C of reaction 4h, is continuously heating to 190 DEG C
React 20h.After reaction, reaction system is cooled to room temperature, is then poured slowly into 300mL ice water, the precipitating being precipitated
Object is sufficiently washed with 5wt% sodium bicarbonate aqueous solution, is washed with water and is washed to neutrality, is finally dried in vacuo 10 hours at 60 DEG C,
Poly- (ether ketone benzimidazole) copolymer is made, is denoted as poly- (ether ketone benzimidazole) copolymer (7).
Pass through the infrared spectroscopy and hydrogen nuclear magnetic resonance spectrogram point to synthesized poly- (ether ketone-benzimidazole) copolymer (7)
Analysis shows that the present invention successfully synthesizes poly- (ether ketone-benzimidazole) copolymer.
Dissolubility test result: synthesized poly- (ether ketone-benzimidazole) copolymer (7) is in dimethyl sulfoxide, N, N- bis-
Good dissolution is all had in methylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone and chloroform and the concentrated sulfuric acid
Property, it is partially soluble in tetrahydrofuran, but insoluble in organic solvents such as methanol, ethyl alcohol.It can only be dissolved in polybenzimidazoles a small number of strong
Property in acid is compared, and poly- (ether ketone-benzimidazole) copolymer (7) that the present invention synthesizes has good resolvability.
Poly- (ether ketone-benzimidazole) copolymer (7) is dissolved in dimethyl sulfoxide, be made mass concentration be 5% it is molten
Liquid is film-made using solution casting method, and measuring its tensile strength using tensilon is 121MPa, elongation at break 48%.
As can be seen that the present invention synthesized by poly- (ether ketone-benzimidazole) copolymer (7) have it is good can thermoplastic processing property.
Differential thermal analysis (DSC) test result: the glass transition of synthesized poly- (ether ketone-benzimidazole) copolymer (5)
Temperature is 264 DEG C, is significantly higher than the glass transition temperature (143 DEG C) of commercialization poly(aryl ether ketone).
As can be seen from the above embodiments, poly- (ether ketone-benzimidazole) copolymer provided by the invention combines polyether-ketone
With the excellent properties of two kinds of high molecular materials of polybenzimidazoles, while solving that polyether-ketone glass transition temperature is low and polyphenyl again
And the problem of imidazoles processing difficulties.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of poly- (ether ketone-benzimidazole) copolymer, which is characterized in that have structure shown in formula I:
In formula I: Ar includes One kind；N=20~1000.
2. the preparation method of (ether ketone-benzimidazole) copolymer poly- described in claim 1, which comprises the following steps:
Under protective atmosphere, 3,4- diaminodiphenyl ether and aromatic dicarboxilic acid monomer are polymerize under the action of polyphosphoric acids
Reaction, obtains poly- (ether ketone-benzimidazole) copolymer；
The aromatic dicarboxilic acid monomer includes M-phthalic acid, terephthalic acid (TPA), 4,4 '-oxydibenzoic acids, 4,4 '-dicarboxyls
Benzophenone, 4,4 '-Dicarboxy diphenylsulfones, (4- carboxyl phenyl) isopropyl alkane of 2,2- bis- and 2,2- bis- (4- carboxyl phenyl) hexafluoro isopropyl
One of alkane.
3. preparation method according to claim 2, which is characterized in that 3, the 4- diaminodiphenyl ether and aromatic dicarboxilic acid
The molar ratio of monomer is 1:1.
4. preparation method according to claim 2 or 3, which is characterized in that 3, the 4- diaminodiphenyl ether and fragrance two
Total mass fraction of the carboxylic acid monomer in polyphosphoric acids is 2~20%；The mass content of phosphorus pentoxide in the polyphosphoric acids
It is 70~90%.
5. preparation method according to claim 2, which is characterized in that the polymerization reaction includes that first successively carried out gathers
Close reaction and the second polymerization reaction；The temperature of first polymerization reaction is 120~160 DEG C, and the time is 1~5h；Described second
The temperature of polymerization reaction is 180~220 DEG C, and the time is 5~30h.
6. according to right want 2 described in preparation method, which is characterized in that 3, the 4- diaminodiphenyl ether is by including the following steps
Method be prepared:
(1) under protective atmosphere, 5- chloro-2-nitroaniline, phenol and potassium carbonate carry out into ether in organic solvent and react, and obtain
2- nitro -5- phenoxybenzamine；
(2) under protective atmosphere, the 2- nitro -5- phenoxybenzamine and hydrazine hydrate carry out restoring instead under the effect of the catalyst
It answers, obtains 3,4- diaminodiphenyl ether.
7. preparation method according to claim 6, which is characterized in that 5- chloro-2-nitroaniline and benzene in the step (1)
The molar ratio of phenol is 1:1~1.05:1, and the molar ratio of the phenol and potassium carbonate is 1:1~1:2.
8. preparation method according to claim 6, which is characterized in that organic solvent is N, N- diformazan in the step (1)
Yl acetamide；The 5- chloro-2-nitroaniline and the total mass fraction of phenol in organic solvent are 10~70%；It is described at ether
The temperature of reaction is 130~200 DEG C, and the time is 5~40h.
9. preparation method according to claim 6, which is characterized in that hydrazine hydrate and 2- nitro -5- benzene in the step (2)
The amount ratio of oxygroup aniline is 0.5~10mL:1g；The catalyst is palladium/carbon, the catalyst and 2- nitro -5- phenoxy group
The mass ratio of aniline is 1:10~1:1000.
10. preparation method according to claim 6, which is characterized in that the solvent of reduction reaction is second in the step (2)
Alcohol and/or 1,4- dioxane；The concentration of the 2- nitro -5- phenoxybenzamine in a solvent is 2~200g/L；The reduction
The temperature of reaction is 80~120 DEG C, and the time is 10~70h.
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| CN103059300B (en) * | 2013-01-23 | 2015-01-14 | 中国科学技术大学 | Polypyrron with sulfated side chain and preparation method of polypyrron |
| CN105131289A (en) * | 2015-08-24 | 2015-12-09 | 上海交通大学 | Novel sulfonated polybenzimidazole copolymer, crosslinked membrane, preparation method and application thereof |
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| JP2012163712A (en) * | 2011-02-04 | 2012-08-30 | Nippon Kayaku Co Ltd | Photosensitive resin composition, applications and usage thereof |
| CN103059300B (en) * | 2013-01-23 | 2015-01-14 | 中国科学技术大学 | Polypyrron with sulfated side chain and preparation method of polypyrron |
| CN105131289A (en) * | 2015-08-24 | 2015-12-09 | 上海交通大学 | Novel sulfonated polybenzimidazole copolymer, crosslinked membrane, preparation method and application thereof |
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