CN108752587A - A kind of sulfonated poly aryl ether ketone sulphones and preparation method thereof based on dinaphthol - Google Patents
A kind of sulfonated poly aryl ether ketone sulphones and preparation method thereof based on dinaphthol Download PDFInfo
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- CN108752587A CN108752587A CN201810410636.1A CN201810410636A CN108752587A CN 108752587 A CN108752587 A CN 108752587A CN 201810410636 A CN201810410636 A CN 201810410636A CN 108752587 A CN108752587 A CN 108752587A
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- dinaphthol
- ether ketone
- aryl ether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
Abstract
The present invention relates to a kind of sulfonated poly aryl ether ketone sulphones and preparation method thereof based on dinaphthol.The present invention is first with 4,4'- difluoro benzophenones and 4,4'- dihydroxydiphenylsulisomers prepare ABA type oligomer, again with the 1 of different proportion, 1'- union -2-naphthols and 4, the polycondensation reaction of 4'- difluoro benzophenones prepares the poly(aryl ether ketone) sulphones based on dinaphthol, and a series of sulfonated poly aryl ether ketone sulphones based on dinaphthol then are made come selective sulfonation resulting polymers with excessive chlorosulfonic acid.The content of dinaphthalene group in polymer is adjusted by adjusting the molar ratio of 1,1'- union -2-naphthols, and then adjusts the ion exchange membrane capacity of sulfonated products.Gained sulfonated polymer has good dissolubility in n,N-dimethylacetamide isopolarity aprotic solvent, can be formed a film with solution-cast, and obtained proton exchange membrane thermal stability is good, oxidation stability is good, and proton conductivity is high, mechanical property is good.
Description
Technical field
The present invention relates to a kind of sulfonated poly aryl ether ketone sulphones and preparation method thereof based on dinaphthol, belong to proton
Exchange field of membrane material.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFCs）It is a kind of device converting chemical energy to electric energy, there is transfer efficiency
High, the advantages that energy density is high, easy to operate, pollution-free.Proton exchange membrane is one of core component of PEMFCs, performance
Quality directly determines the quality of battery performance.Currently, the proton exchange membrane received significant attention is DuPont Corporation's production
Nafion membrane, have many advantages, such as higher proton conductivity and oxidation stability.However, Nafion membrane is due to production cost
Higher, the shortcomings of preparation process is complicated, mechanical performance is relatively low, fuel permeability is big, large-scale commercial applications application is restricted.Sulphur
It is one kind using polyarylether as the proton exchange membrane material of main chain to change polyarylether, has that preparation process is simple, raw material sources are abundant, heat
Excellent in stability, high mechanical strength, good chemical stability, therefore become the focus of people's research.Sulfonated polyether one
As can by two methods be made：（1）Direct polymerization method, such as Li Ye of sulfonated monomer et al.（Patent CN105524268B）
A kind of sulfonated polyether ketone copolymers of the group containing benzothiazole and preparation method thereof are disclosed, gained film has preferable size
Stability, lower methanol permeability and higher antioxidative stabilizer, but the molecular weight of this method resulting polymers and
Proton conductivity is relatively low；（2）Rear sulfonation method, such as that brightness of polymer et al.（Patent CN101434697B）Disclose a kind of base
In the side chain type sulphonation polyarylether ketone and preparation method thereof of naphthalene nucleus, the bisphenol A-type naphthalene of sulfonic acid containing dibutyl that sulfonation degree is 80%
Reunion aryl ether ketone（SNPAEK-80）Proton conductivity can reach 0.1S/cm at 60 degree, but the complexity used in this method is single
Body structure can increase production cost.Different polymer architectures have weight with sulfonation base content to the properties of gained proton exchange membrane
The influence wanted.Therefore, develop the sulfonated polyether proton exchange membrane material of excellent combination property have to the development of PEMFC it is important
Meaning.
Invention content
The present invention in order to overcome the deficiencies of the prior art, provides a kind of sulfonated poly aryl ether ketone sulphones based on dinaphthol
And preparation method, the compound have many advantages, such as excellent proton conductivity, mechanical strength, thermal stability, chemical stability, are
A kind of proton exchange membrane material with broad prospect of application.
To achieve the above object, the present invention is realised by adopting the following technical scheme：
A kind of sulfonated poly aryl ether ketone sulphones based on dinaphthol, structural formula are shown below：
M=10 ~ 200, n=0 ~ 200, x=1 ~ 2 in formula.
The preparation method of the above-mentioned sulfonated poly aryl ether ketone sulphones based on dinaphthol, detailed step are as follows：
（1）In polar non-solute, 4,4'- difluoro benzophenones, 4,4'- dihydroxydiphenylsulisomers, Anhydrous potassium carbonate are pressed 4
~10:1:1.5 ~ 5 molar ratio mixing, wherein the quality of polar non-solute be 4,4'- difluoro benzophenones quality 2 ~
10 times；Mixture is warming up to 80 ~ 120 DEG C under the protection of inert gas, is reacted 12 ~ 24 hours, is subsequently poured into water and is precipitated
Precipitation, purifies to obtain ABA type oligomer by column, reaction process is as follows：
。
（2）In polar non-solute, by 1,1'- union -2-naphthols, 4,4'- difluoro benzophenones, ABA type oligomer,
Anhydrous potassium carbonate presses 1:2~10:1~9:10 ~ 30 molar ratio mixing, and 4,4'-, 4 ~ 10 times of volumes of difluoro benzophenone are added
Toluene reacts 1 ~ 4 hour under the protection of inert gas at 140 ~ 150 DEG C, takes what reaction was generated out of by refluxing toluene
Then water steams toluene, then temperature is risen to 160 ~ 170 DEG C, react 12 ~ 24 hours, is subsequently poured into be precipitated in deionized water and sink
It forms sediment, after being collected by filtration and drying, obtains the poly(aryl ether ketone) sulphones based on dinaphthol, reaction process is as follows：
。
（3）It the above-mentioned poly(aryl ether ketone) sulphones based on dinaphthol is dissolved in halogenated alkane is configured to mass concentration and be
0.5 ~ 5% solution, then the halogenated alkane solution for the chlorosulfonic acid that mass concentration is 0.1 ~ 5%, chlorine in reactant is added dropwise into solution
The molar ratio of sulfonic acid and the dinaphthalene unit in polymer is 2 ~ 20:1, it then reacts 12 ~ 48 hours at room temperature, gained precipitation warp
Halogenated alkane washing is dissolved in polar non-solute afterwards three times, pours into after semi-permeable membrane dialysis three days in deionized water, so
After dry solution, obtained substance is the sulfonated poly aryl ether ketone sulphones based on dinaphthol, and reaction process is as follows：
。
The preparation method of sulfonated poly aryl ether ketone sulphones of the present invention based on dinaphthol, the aprotic, polar
Solvent is any one in DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO)
Kind.
The preparation method of sulfonated poly aryl ether ketone sulphones of the present invention based on dinaphthol, the halogenated alkane are
Any one in monochloro methane, dichloromethane, chloroform.
Sulfonated poly aryl ether ketone sulphones of the present invention based on dinaphthol can be used for preparing proton exchange membrane.
Preparation method of the present invention is preferred embodiment, the predictable reasonable temperature of those skilled in the art
Degree, time and other reaction conditions are invention which is intended to be protected, it is not limited to above-mentioned reaction condition.
The present invention is oligomeric by the way that 4,4'- difluoro benzophenones and 4,4' dihydroxydiphenyl sulfone are first prepared linear ABA type
Then object introduces containing non-coplanar 1,1'- union -2-naphthols are conjugated, finally sulfonation is carried out with chlorosulfonic acid, to introduce sulfonic group
Group.
Compared with prior art, the present invention has the advantages that：
（1）, raw material of the present invention be common industrial chemicals, be easy to get.
（2）, the non-coplanar binaphthyl structure of conjugation assign compound good dissolubility, film forming, thermal stability and machinery
Performance.
（3）, reacted using big 1, the 1'- union -2-naphthols of ABA type oligomer and steric hindrance, reduce the entanglement of strand,
Improve the molecular weight of product.
（4）, gained compound sulfonic group content can simply be controlled by the inventory of 1,1'- union -2-naphthols
System.
（5）, sulfonated poly aryl ether ketone sulfone proton exchange membrane of the gained based on dinaphthol have excellent proton conductivity.
Description of the drawings
Fig. 1 is the nuclear magnetic resonance spectroscopy of ABA type oligomer in the embodiment of the present invention.
Fig. 2 is the nuclear magnetic resonance spectroscopy of the poly(aryl ether ketone) sulphones based on dinaphthol in the embodiment of the present invention.
Fig. 3 is the infrared spectrogram of the poly(aryl ether ketone) sulphones based on dinaphthol in the embodiment of the present invention.
Fig. 4 is the nuclear magnetic resonance spectroscopy of the sulfonated poly aryl ether ketone sulphones based on dinaphthol in the embodiment of the present invention.
Fig. 5 is the infrared spectrogram of the sulfonated poly aryl ether ketone sulphones based on dinaphthol in the embodiment of the present invention.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The preparation of 1 ABA type oligomer of embodiment
By 1.7519 g（7.0 mmol）4,4' dihydroxydiphenyl sulfone, 12.2192 g（56.0 mmol）4,4'- difluorodiphenyl first
Ketone, 2.2000g potassium carbonate and 20mL n,N-dimethylacetamide are added in three-necked flask, under the protection of argon gas, are warming up to
80 DEG C, magnetic agitation is reacted 12 hours, is poured into be precipitated in deionized water by reaction solution after reaction and be precipitated, precipitation is collected by filtration
And it is dry, it is purified using column, obtains ABA type oligomer, yield 98%, hydrogen nuclear magnetic resonance modal data is：1H NMR
(400 MHz, CDCl3, ppm), 7.12 (m, 8H), 7.83 (s, 4H), 7.85 (s, 4H), 7.95 (s, 4H),
7.97 (s, 4H)。
The preparation of poly(aryl ether ketone) sulphones based on dinaphthol of the embodiment 2 containing 50mol% dinaphthalene groups
By 0.5727 g（2mmol）1,1'- union -2-naphthols, 1.3733 g（2mmol）ABA type oligomer and 16mL N, N- diformazans
Yl acetamide is added in three-necked flask, after dissolving, adds 1.0000 g potassium carbonate, 8mL toluene, under the protection of argon gas,
It is first reacted 2 hours at 140 DEG C, then steams toluene, then temperature is risen to 160 DEG C, react 24 hours, be subsequently poured into deionization
Precipitation is precipitated in water, collects precipitation and drying 24 hours in 80 DEG C of baking ovens, obtains containing 50mol% dinaphthalene groups based on connection
The poly(aryl ether ketone) sulphones of naphthols, yield 99%.Through characterizing, number-average molecular weight 51kDa, nuclear magnetic resonance spectroscopy
Data are：1H NMR (400 MHz, CDCl3, ppm), 6.79 (d, 4H), 7.05 (s, 2H), 7.10 (s, 2H),
7.25 (s, 2H), 7.43 (d, 2H), 7.56 (d, 4H), 7.68 (d, 2H), 7.83 (s, 2H), 7.94
(s, 1H);Infrared data is：FT-IR (cm-1) υ 3060, 1654, 1585, 1488, 1413, 1160, 1110,
1072, 1010, 930, 870, 833, 770, 692, 578。
The preparation of poly(aryl ether ketone) sulphones based on dinaphthol of the embodiment 3 containing 43mol% dinaphthalene groups
The inventory of 1,1'- union -2-naphthols in embodiment 2 is changed to 0.4075 g（1.72mmol）, ABA type oligomer feeds intake
Amount is changed to 1.5656 g（2.28mmol）, while the two compounds are added, 0.3753 g is added（1.72mmol）4,4'-
Difluoro benzophenone, remaining operation is same as Example 2, obtains the polyarylether based on dinaphthol containing 43mol% dinaphthalene groups
Ketone sulphones, yield 98%.Through characterization, number-average molecular weight 35kDa.
The preparation of poly(aryl ether ketone) sulphones based on dinaphthol of the embodiment 4 containing 35mol% dinaphthalene groups
The inventory of 1,1'- union -2-naphthols in embodiment 2 is changed to 0.4049 g（1.4mmol）, ABA type oligomer feeds intake
Amount is changed to 1.7854 g（2.6mmol）, while the two compounds are added, 0.3055 g is added（1.4mmol）4,4'- bis-
Fluorine benzophenone, remaining operation is same as Example 2, obtains the poly(aryl ether ketone) based on dinaphthol containing 35mol% dinaphthalene groups
Sulphones, yield 98%.Through characterization, number-average molecular weight 42kDa.
The preparation of sulfonated poly aryl ether ketone sulphones based on dinaphthol of the embodiment 5 containing 50mol% dinaphthalene groups
By 1.06 g of poly(aryl ether ketone) sulphones based on dinaphthol containing 50% dinaphthalene group of 2 gained of embodiment
（2.37mmol）It is added in the three-necked flask of 500 mL with 300 mL dichloromethane, then 1.6 mL chlorosulfonic acids is taken to be dissolved into 16mL
It in dichloromethane, is added drop-wise in three-necked flask with 1 drop/sec of speed, reacts 24 hours and precipitated under the protection of argon gas, sunk
It after shallow lake is washed three times with dichloromethane, is dissolved with n,N-dimethylacetamide, is subsequently poured into dialysis bag, dialysis three days is changed daily
Three times, finally, the substance in dialysis bag is dried for water, obtains the poly- virtue of the sulfonation based on dinaphthol containing 50mol% dinaphthalene groups
Ether ketone sulphones, yield 85%.The data of the nuclear magnetic resonance spectroscopy of the compound are：1H NMR (400 MHz, CDCl3,
Ppm), 7.15 (d, 2H), 7.22 (d, 2H), 7.79 (m, 2H), 7.98 (m, 2H)；Infrared data is：FT-IR
(cm-1) υ 3450, 1648, 1585, 1488, 1415, 1307, 1243, 1162, 1106, 1035, 930, 838,
770, 696, 580。
The preparation of sulfonated poly aryl ether ketone sulphones based on dinaphthol of the embodiment 6 containing 43mol% dinaphthalene groups
By 1.00 g of poly(aryl ether ketone) sulphones based on dinaphthol containing 43% dinaphthalene group of 3 gained of embodiment
（2.25mmol）It is added in the three-necked flask of 500 mL with 300 mL dichloromethane, then 1.3 mL chlorosulfonic acids is taken to be dissolved into 13mL
In dichloromethane, remaining operation is same as Example 5, obtains the poly- virtue of the sulfonation based on dinaphthol containing 43mol% dinaphthalene groups
Ether ketone sulphones, yield 82%.
The preparation of sulfonated poly aryl ether ketone sulphones based on dinaphthol of the embodiment 7 containing 35mol% dinaphthalene groups
By 1.05 g of poly(aryl ether ketone) sulphones based on dinaphthol containing 35% dinaphthalene group of 4 gained of embodiment
（2.38mmol）It is added in the three-necked flask of 500 mL with 300 mL dichloromethane, then 1.1 mL chlorosulfonic acids is taken to be dissolved into 11mL
In dichloromethane, remaining operation is same as Example 5, obtains the poly- virtue of the sulfonation based on dinaphthol containing 35mol% dinaphthalene groups
Ether ketone sulphones, yield 85%.
The preparation of sulfonated poly aryl ether ketone sulfone proton exchange membrane of the embodiment 8 based on dinaphthol
The sulfonated polyether based on dinaphthol containing 50mol%, 43mol%, 35mol% dinaphthalene group obtained in embodiment 5-7
Ketone sulphones respectively take 1 g to be dissolved completely in 20 mL n,N-dimethylacetamide, and ultrasonic deaeration, then pours and cast from water after filtering
On the glass plate of placing flat, dried 20 hours in 80 DEG C of baking ovens, after glass plate is cooled to room temperature, be immersed in from
1 hour in sub- water, film is taken off from glass plate, be immersed in 1mol/L sulfuric acid solution carry out acidification 1 hour, then spend from
Sub- water cleans sulfuric acid extra in film, obtains the sulfonated poly aryl ether ketone sulfone proton exchange membrane based on dinaphthol.Through characterization, ion
Exchange capacity is respectively 1.89mmol g-1、1.65mmol g-1、1.40mmol g-1；Proton conductivity under its 100% humidity of room temperature
Respectively 103mS cm-1、59mS cm-1、41mS cm-1；Tensile strength is respectively 11.5MPa, 17.8MPa, 22.6MPa.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (5)
1. a kind of sulfonated poly aryl ether ketone sulphones based on dinaphthol, it is characterised in that：Structural formula is as follows：
M=10 ~ 200, n=0 ~ 200, x=1 ~ 2 in formula.
2. a kind of method preparing the sulfonated poly aryl ether ketone sulphones based on dinaphthol as described in claim 1, feature
It is：Include the following steps：
（1）In polar non-solute, 4,4'- difluoro benzophenones, 4,4'- dihydroxydiphenylsulisomers, Anhydrous potassium carbonate are pressed 4
~10:1:1.5 ~ 5 molar ratio mixing, wherein the quality of polar non-solute be 4,4'- difluoro benzophenones quality 2 ~
10 times；Mixture is warming up to 80 ~ 120 DEG C under the protection of inert gas, is reacted 12 ~ 24 hours, is subsequently poured into water and is precipitated
Precipitation, purifies to obtain ABA type oligomer by column, reaction process is as follows：
；
（2）In polar non-solute, by 1,1'- union -2-naphthols, 4,4'- difluoro benzophenones, ABA type oligomer, anhydrous
Potassium carbonate presses 1:2~10:1~9:10 ~ 30 molar ratio mixing, and the toluene of 4,4'-, 4 ~ 10 times of volumes of difluoro benzophenone is added,
It under the protection of inert gas, is reacted 1 ~ 4 hour at 140 ~ 150 DEG C, the water for reacting generated is taken out of by refluxing toluene, then
Toluene is steamed, then temperature is risen to 160 ~ 170 DEG C, is reacted 12 ~ 24 hours, is subsequently poured into deionized water and precipitation is precipitated, filtering
After collecting and drying, the poly(aryl ether ketone) sulphones based on dinaphthol are obtained；
（3）It is 0.5 ~ 5% that the above-mentioned poly(aryl ether ketone) sulphones based on dinaphthol, which are dissolved in halogenated alkane to be configured to mass concentration,
Solution, then the halogenated alkane solution for the chlorosulfonic acid that mass concentration is 0.1 ~ 5% is added dropwise into solution, in reactant chlorosulfonic acid with
The molar ratio of dinaphthalene unit in polymer is 2 ~ 20:1, it then reacts 12 ~ 48 hours at room temperature, gained is precipitated through alkyl halide
Hydrocarbon washing is dissolved in polar non-solute afterwards three times, is poured into after semi-permeable membrane dialysis three days in deionized water, is then dried
Solution, obtained substance are the sulfonated poly aryl ether ketone sulphones based on dinaphthol.
3. the preparation method of the sulfonated poly aryl ether ketone sulphones as described in claim 2 based on dinaphthol, which is characterized in that
The polar non-solute is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl Asia
Any one in sulfone.
4. the preparation method of the sulfonated poly aryl ether ketone sulphones as described in claim 2 based on dinaphthol, which is characterized in that
The halogenated alkane is any one in monochloro methane, dichloromethane, chloroform.
5. a kind of sulfonated poly aryl ether ketone sulphones answering in proton exchange membrane based on dinaphthol as described in claim 1
With.
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Cited By (1)
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| CN115403764A (en) * | 2022-09-26 | 2022-11-29 | 福州大学 | Epoxy group-containing polyaryletherketone compound and preparation method thereof |
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| CN115403764B (en) * | 2022-09-26 | 2023-10-20 | 福州大学 | Polyaryletherketone compound containing epoxy group and preparation method thereof |
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