CN107722271A - The preparation and its application of the side chain type sulfonated polyimides of main chain group containing quinoxaline - Google Patents
The preparation and its application of the side chain type sulfonated polyimides of main chain group containing quinoxaline Download PDFInfo
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- CN107722271A CN107722271A CN201710981010.1A CN201710981010A CN107722271A CN 107722271 A CN107722271 A CN 107722271A CN 201710981010 A CN201710981010 A CN 201710981010A CN 107722271 A CN107722271 A CN 107722271A
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The method of PEM is prepared the invention discloses side chain type sulfonated polyimides of a kind of main chain group containing quinoxaline and preparation method thereof and using it, wherein, the architectural feature of the side chain type sulfonated polyimides is to contain quinoxaline group on main chain, and the linking group using ehter bond thereon or thioether bond as side chain, both the hydrophobicity of side chain flexibility and main chain had been ensure that, while there is higher molecular weight, excellent heat endurance and good hydrolytic stability again；Preparation technology of the present invention is simple, and reaction condition is easy to operate and control, suitable for industrialized production.The PEM prepared using the side chain type sulfonated polyimides of main chain group containing quinoxaline of the present invention has higher proton conductivity and excellent mechanical performance, has broad application prospects.
Description
Technical field
The present invention relates to polymeric material field, is specifically related to a kind of the side chain type sulfonated poly- of main chain group containing quinoxaline
The preparation method of imido preparation method and its PEM.
Background technology
Sulfonated polyimide is because with good physical and chemical stability, heat resistance, higher proton-conducting, being easy to make
The advantages that standby and cheap, it is considered to be very promising Proton Exchange Membrane Fuel Cells material.But this kind of polymer
Imide ring easily attacked by nucleopilic reagent, cause its hydrolytic stability bad.It can generally be improved by changing monomer structure
Its water resistance, wherein the sulfonated diamine monomer for introducing side chain type is a kind of very effective method.Document (ECS
Transactions 2008,12,5) report a kind of side chain type sulfonated polyimides connected by ehter bond, this polymer
With excellent hydrolytic stability (more than mechanical strength 500h is maintained in 130 DEG C of pressure (hydraulic) water).Document (Journal of
Power Sources 2011,196,1694) report a kind of preparation side using quinoxaline as the PEM of crosslinked group
Method, wherein quinoxaline structure has been incorporated on the side chain of polymer, the side-chain structure is caused to be unfavorable for strengthening macromolecular chain
It is flexible.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention proposes that a kind of side chain type sulfonated polyamides of main chain group containing quinoxaline is sub-
Amine and preparation method thereof, and apply the side chain type sulfonated polyimides of main chain group containing quinoxaline to prepare the side of PEM
Method.Quinoxaline group is incorporated on polymer molecule backbone, and using ehter bond or thioether bond as linking group, both ensure that side chain
Flexibility, the proton conductivity of polymer film can be increased again.
The technical proposal of the invention is realized in this way：
A kind of side chain type sulfonated polyimides of main chain group containing quinoxaline, including the sulfonation polyamides with logical formula (I) are sub-
Amine homopolymer (y=1) or sulfonated polyimide copolymer (0 ＜ y ＜ 1)：
Wherein, X represents O or S；
Wherein, R1-(SO3H)aIncluding：
R2Including：
R3Including：
N is positive integer；A=1 or 2 or 3；0 ＜ y≤1.
A kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline, including sulfonated polyimide are equal
The preparation method of the preparation method and sulfonated polyimide copolymer (0 ＜ y ＜ 1) of polymers (y=1), wherein described sulfonation gathers
The preparation method of acid imide homopolymer (y=1) comprises the following steps：
Under nitrogen protection, sulfonated diamine and a certain amount of organic weak base are dissolved in organic solvent, then addition and sulphur
Change the equimolar dianhydride monomer of diamines and a certain amount of organic monoacid, reaction system is reacted into 1-8h, Ran Hou at 80-140 DEG C
160-220 DEG C of reaction 8-24h, after reaction terminates, is down to 70-120 DEG C by system temperature, is subsequently poured into methanol, obtain thread
Product, through washing repeatedly after being dried in vacuum drying oven, obtain the sulfonated polyimide homopolymer；
The preparation method of described sulfonated polyimide copolymer (0 ＜ y ＜ 1) comprises the following steps：
Under nitrogen protection, sulfonated diamine, non-sulfonated diamines and a certain amount of organic weak base are dissolved in organic solvent, so
Addition and the equimolar dianhydride monomer of diamines (total amount of sulfonated diamine and non-sulfonated diamines) and organic monoacid afterwards, by reactant
80-140 DEG C of reaction 1-8h is tied up to, 8-24h is then reacted at 160-220 DEG C, after reaction terminates, system temperature is down to 70-120
DEG C, it is subsequently poured into methanol, obtains thread product, through washing repeatedly after being dried in vacuum drying oven, obtains the sulfonation polyamides
Imine copolymer.
Further, sulfonated diamine be 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides]-benzene sulfonic acid, 5- [2,
3- bis- (4- aminophenyls)-quinoxaline -6- epoxides] -2- toluene sulfonic acides, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6-
Epoxide] -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides] -5- (4- sulfonic groups-thiophenyl)
Benzene sulfonic acid, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides] -5- (4- sulfonic groups-phenoxy group) benzene sulfonic acid, 4- { 4-
[2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides] -3- sulfonic groups-phenoxy group } -1,3- benzenedisulfonic acids, 4- { 4- [2,3-
Two (4- aminophenyls)-quinoxaline -6- epoxides] -3- sulfonic groups-thiophenyl -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- amino
Phenyl)-quinoxaline -6- epoxides] -5- [1- methyl isophthalic acids-(4- sulfo groups phenyl) ethyl] benzene sulfonic acid, 4- [2,3- bis- (4- aminobenzenes
Base)-quinoxaline -6- epoxides] -3,4 '-disulfonic acid base biphenyl, 2- [2,3- bis--(4- aminophenyls)-quinoxaline -6- epoxides] -
5- (4- sulfonic groups-benzyl) benzene sulfonic acid, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls]-benzene sulfonic acid, 5- [2,3- bis-
(4- aminophenyls)-quinoxaline -6- sulfenyls] -2- toluene sulfonic acides, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulphur
Base] -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls] -5- (4- sulfonic groups-thiophenyl) benzene
Sulfonic acid, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls] -5- (4- sulfonic groups-phenoxy group) benzene sulfonic acid, 4- 4- [2,
3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls] -3- sulfonic groups-phenoxy group -1,3- benzenedisulfonic acids, 4- { 4- [2,3- bis-
(4- aminophenyls)-quinoxaline -6- sulfenyls] -3- sulfonic groups-thiophenyl -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- aminobenzenes
Base)-quinoxaline -6- sulfenyls] -5- [1- methyl isophthalic acids-(4- sulfo groups phenyl) ethyl] benzene sulfonic acid, 4- [2,3- bis- (4- aminobenzenes
Base)-quinoxaline -6- sulfenyls] -3,4 '-disulfonic acid base biphenyl, 2- [2,3- bis--(4- aminophenyls)-quinoxaline -6- sulfenyls] -
One kind in 5- (4- sulfonic groups-benzyl) benzene sulfonic acid.
Further, non-sulfonated diamines is 4,4 '-diaminodiphenyl ether, Isosorbide-5-Nitrae-two (3- amino-benzene oxygens) benzene, Isosorbide-5-Nitrae-two
(4- amino-benzene oxygens) benzene, 4,4 '-two (4- amino-benzene oxygens) biphenyl, 3,3 '-dimethyl -4,4 '-benzidine, 2,2 ' -
Dimethyl -4,4 '-benzidine, 2,2- bis- (4- aminophenyls) propane, 2,2 '-two (trifluoromethyl) -4,4 '-diaminourea
Biphenyl, 4,4 '-MDA, two (3- methyl -4- aminophenyls) methane, two (3,5- dimethyl -4- aminophenyls)
Methane, 9, one kind in 9 '-two (4- aminophenyls) fluorenes.
Further, dianhydride monomer is Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydrides, 4,4 '-dinaphthalene -1,1 ', 8,8 '-tetracarboxylic dianhydride,
4,4 '-dinaphthyl ether -1,1 ', 8,8 '-tetracarboxylic dianhydride, 4,4 '-dinaphthyl ketone -1,1 ', 8,8 '-tetracarboxylic dianhydride, biphenyl -4,4 '-two (4-
Oxo -1,8- naphthalic anhydride), -3, one kind in 4,9,10- tetracarboxylic dianhydrides.
Further, organic weak base is one kind in triethylamine, triethylene diamine, pyridine, N-methylmorpholine, isoquinolin；
Organic monoacid is one kind in formic acid, acetic acid, benzoic acid, phenylacetic acid, ethanedioic acid；Organic solvent is metacresol, 1- methylpyrroles
One kind in alkanone and DMA.
Further, mole addition of organic weak base is 2.0-4.0 times of the sulfonated diamine addition；Organic monoacid
Mole addition be 1.0-3.0 times of the dianhydride monomer addition.
Further, the total mass concentration of sulfonated diamine, non-sulfonated diamines and dianhydride monomer in the organic solvent
For 8-20%.
The present invention also provides a kind of side chain type sulfonated polyimides using main chain group containing quinoxaline and prepares proton exchange
The method of film, comprises the following steps：
The side chain type sulfonated polyimides of main chain group containing quinoxaline is dissolved in organic solvent, through filtering after-pouring in cleaning
Glass plate on, 2-8h is dried in 60-120 DEG C of convection oven, is then fully washed gained film in ethanol, and in temperature
For 60-90 DEG C, concentration is to soak 4-24h in 1.5-4.0mol/L hydrochloric acid solution, dries, obtains after being washed with deionized water to neutrality
To the side chain type sulfonated medlin proton exchange film of main chain group containing quinoxaline.
Further, organic solvent is one kind in metacresol, 1- methyl pyrrolidones and DMA.
Further, the mass concentration of the side chain type sulfonated polyimides of main chain group containing quinoxaline in organic solvent is
2-20%.
The beneficial effects of the invention are as follows：The present invention proposes a kind of side chain type sulfonated polyimides, contains quinoxaline on main chain
Group, and the linking group using ehter bond thereon or thioether bond as side chain, the hydrophobic of side chain flexibility and main chain was both ensure that
Property, while there is higher molecular weight, excellent heat endurance and good hydrolytic stability again；Main chain of the present invention contains quinoline
The preparation method of the side chain type sulfonated polyimides of quinoline group, technique is simple, and reaction condition is easily controllable, and resulting polymers can be made
Obtain the PEM of excellent performance.Prepared using the side chain type sulfonated polyimides of main chain group containing quinoxaline of the present invention
PEM has higher proton conductivity, excellent mechanical property and heat endurance, a kind of to have a extensive future
Proton exchange membrane material.
Brief description of the drawings
Fig. 1 is the synthetic route of the side chain type sulfonated polyimides of the group containing quinoxaline in preferred embodiment of the present invention；
Fig. 2 is the infrared spectrum of the side chain type sulfonated polyimides of the group containing quinoxaline in preferred embodiment of the present invention；
Fig. 3 is that the thermal weight loss of the side chain type sulfonated polyimides of the group containing quinoxaline in preferred embodiment of the present invention is bent
Line.
Embodiment
In order to be more clearly understood that the technology contents of the present invention, described in detail especially exemplified by following examples, its purpose is only
It is to be best understood from the protection domain that present disclosure is not intended to limit the present invention.
The present invention proposes a kind of side chain type sulfonated polyimides of main chain group containing quinoxaline, including with logical formula (I)
Sulfonated polyimide homopolymer (y=1) or sulfonated polyimide copolymer (0 ＜ y ＜ 1)：
Wherein, X represents O or S；
Wherein, R1-(SO3H)aIncluding：
R2Including：
R3Including：
N is positive integer；A=1 or 2 or 3；0 ＜ y≤1.
The present invention also proposes a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline, including sulphur
Change the preparation method of polyimides homopolymer (y=1) and the preparation method of sulfonated polyimide copolymer (0 ＜ y ＜ 1), it is closed
Into route as shown in figure 1, wherein, the preparation method of described sulfonated polyimide homopolymer (y=1) comprises the following steps：
Under nitrogen protection, sulfonated diamine and a certain amount of organic weak base are dissolved in organic solvent, then addition and sulphur
Change the equimolar dianhydride monomer of diamines and a certain amount of organic monoacid, reaction system is reacted into 1-8h, Ran Hou at 80-140 DEG C
160-220 DEG C of reaction 8-24h, after reaction terminates, is down to 70-120 DEG C by system temperature, is subsequently poured into methanol, obtain thread
Product, through washing repeatedly after being dried in vacuum drying oven, obtain the sulfonated polyimide homopolymer；
The preparation method of described sulfonated polyimide copolymer (0 ＜ y ＜ 1) comprises the following steps：
Under nitrogen protection, sulfonated diamine, non-sulfonated diamines and a certain amount of organic weak base are dissolved in organic solvent, so
Addition and the equimolar dianhydride monomer of diamines (total amount of sulfonated diamine and non-sulfonated diamines) and organic monoacid afterwards, by reactant
80-140 DEG C of reaction 1-8h is tied up to, 8-24h is then reacted at 160-220 DEG C, after reaction terminates, system temperature is down to 70-120
DEG C, it is subsequently poured into methanol, obtains thread product, through washing repeatedly after being dried in vacuum drying oven, obtains the sulfonation polyamides
Imine copolymer.
The present invention also proposes that a kind of side chain type sulfonated polyimides using main chain group containing quinoxaline prepares proton exchange
The method of film, comprises the following steps：
The side chain type sulfonated polyimides of main chain group containing quinoxaline is dissolved in organic solvent, is cast in after filtering clean
On net glass plate, 2-8h is dried in 60-120 DEG C of convection oven, then fully washs resulting film in ethanol, and
It it is 60-90 DEG C in temperature, concentration is to soak 4-24h in 1.5-4.0mol/L hydrochloric acid solution, is washed with deionized water to neutrality
Drying, obtains the side chain type sulfonated medlin proton exchange film of the group containing quinoxaline.
Below by way of specific embodiment, the preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline is entered
Row describes in detail：
Embodiment 1：A kind of synthesis of the side chain type sulfonated polyimides homopolymer of main chain group containing quinoxaline and proton are handed over
Change the preparation of film：
Under the protection of nitrogen and mechanical agitation, 4- [2,3- bis- (4- ammonia are added in the three-necked bottle dried to 250mL
Base phenyl)-quinoxaline -6- epoxides] -3,4 '-disulfonic acid base biphenyl 6.401g (10mmol), triethylamine 2.024-4.048g
(20-40mmol) and metacresol 45-115mL, it is preferred that the optimal addition in the present embodiment is respectively 3.036g
(30mmol) and 75mL.Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydride (10mmol) 2.682g and benzoic acid are added until completely dissolved
1.221-3.664g (10-30mmol), it is preferred that the optimal addition in the present embodiment is 2.907g (23.8mmol).In nitrogen
Under gas shielded, after reaction system first is warming up into 80-140 DEG C of reaction 1-8h, it is continuously heating to 160-220 DEG C and reacts 8-24h, it is excellent
Choosing, two temperature in the present embodiment are respectively 100 DEG C and 180 DEG C, and two times are respectively 4h and 20h.After reaction terminates,
System is cooled to 110 DEG C, reaction mixture is poured into 500mL methanol, obtained fibrous product is washed 3-5 times with methanol
Afterwards, the drying for standby at vacuum, 120 DEG C.
The sulfonated polyimide that experiment obtains is dissolved in metacresol, is made into the solution that mass concentration is 2-15%, it is excellent
Choosing, the best in quality concentration in the present embodiment is 10%.It is filtered, solution is cast on the glass plate of cleaning, in 60-
2-8h is dried in 120 DEG C of convection ovens, the temperature and time used in the present embodiment is respectively 100 DEG C and 4h.Film after drying
Fully washing in ethanol, it is then 60-90 DEG C in temperature, concentration is to soak 4-24h in 1.5-4.0mol/L hydrochloric acid solution,
Preferably, the condition that the present embodiment uses is respectively 80 DEG C, 3mol/L and 10h.Then it is washed with deionized water to neutrality and dries,
Obtain the side chain type sulfonated medlin proton exchange film of main chain group containing quinoxaline.
Embodiment 2：A kind of synthesis of the side chain type sulfonated polyimide copolymer of main chain group containing quinoxaline and proton are handed over
Change the preparation of film：
Under the protection of nitrogen and mechanical agitation, 4- [2,3- bis- (4- ammonia are added in the three-necked bottle dried to 250mL
Base phenyl)-quinoxaline -6- epoxides] -3,4 '-disulfonic acid base biphenyl 3.201g (5mmol), triethylamine is optimal in the present embodiment
Addition is respectively 1.619g (16mmol), metacresol 60mL.4,4 '-diaminodiphenyl ether is added until completely dissolved
1.001g (5mmol), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydride 2.682g (10 mmol), the optimal of benzoic acid in the present embodiment add
Dosage is 2.198g (18mmol).
Remaining experimentation is same as Example 1.
The preparation method of PEM is same as Example 1.
Embodiment 3：A kind of synthesis of the side chain type sulfonated polyimide copolymer of main chain group containing quinoxaline and proton are handed over
Change the preparation of film：
Under the protection of nitrogen and mechanical agitation, 4- [2,3- bis- (4- ammonia are added in the three-necked bottle dried to 250mL
Base phenyl)-quinoxaline -6- epoxides] -3,4 '-disulfonic acid base biphenyl 5.121g (8mmol), triethylamine is optimal in the present embodiment
Addition is respectively 2.267g (22.4mmol), metacresol 90mL.4,4 '-diaminodiphenyl ether is added until completely dissolved
0.801g (4mmol), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydride 3.218g (12 mmol), the optimal of benzoic acid in the present embodiment add
Dosage is 2.931g (24mmol).
Remaining experimentation is same as Example 1.
The preparation method of PEM is same as Example 1.
Embodiment 4：A kind of synthesis of the side chain type sulfonated polyimide copolymer of main chain group containing quinoxaline and proton are handed over
Change the preparation of film：
Under the protection of nitrogen and mechanical agitation, 4- [2,3- bis- (4- ammonia are added in the three-necked bottle dried to 250mL
Base phenyl)-quinoxaline -6- epoxides] -3,4 '-disulfonic acid base biphenyl 3.201g (5mmol), triethylamine is optimal in the present embodiment
Addition is respectively 1.518g (15mmol), metacresol 50mL.4,4 '-two (4- amino-benzene oxygens) are added until completely dissolved
Biphenyl 1.842g (5mmol), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydride 2.682g (10mmol), the benzoic acid in the present embodiment is most
Excellent addition is 1.832g (15mmol).
Remaining experimentation is same as Example 1.
The preparation method of PEM is same as Example 1.
Embodiment 5：A kind of synthesis of the side chain type sulfonated polyimide copolymer of main chain group containing quinoxaline and proton are handed over
Change the preparation of film：
Under the protection of nitrogen and mechanical agitation, 4- [2,3- bis- (4- ammonia are added in the three-necked bottle dried to 250mL
Base phenyl)-quinoxaline -6- epoxides] benzene sulfonic acid 2.907g (6mmol), the optimal addition of triethylamine is respectively in the present embodiment
1.396g (13.8mmol), metacresol 70mL.4,4 '-diaminodiphenyl ether 1.201g is added until completely dissolved
(6mmol), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidic dianhydride 3.218g (12mmol), the optimal addition of the benzoic acid in the present embodiment are
3.054g(25mmol)。
Remaining experimentation is same as Example 1.
The preparation method of PEM is same as Example 1.
Embodiment 6：A kind of synthesis of the side chain type sulfonated polyimide copolymer of main chain group containing quinoxaline and proton are handed over
Change the preparation of film：
Under the protection of nitrogen and mechanical agitation, 4- [2,3- bis- (4- ammonia are added in the three-necked bottle dried to 250mL
Base phenyl)-quinoxaline -6- epoxides] -3,4 '-disulfonic acid base biphenyl 3.201g (5mmol), triethylamine is optimal in the present embodiment
Addition is respectively 2.315g (13mmol), metacresol 75mL.4,4 '-diaminodiphenyl ether is added until completely dissolved
1.001g (5mmol), 3,4,9,10- tetracarboxylic dianhydride 3.923g (10 mmol), the optimal of benzoic acid in the present embodiment add
Dosage is 1.831g (15mmol).
Remaining experimentation is same as Example 1.
The preparation method of PEM is same as Example 1.
Table 1 below for the present invention using in 6 preferred embodiments obtained main chain group containing quinoxaline it is side chain type sulfonated
The PEM proton conductivity result in water at different temperatures prepared by polyimides, this is understood by result in table 1
A little PEMs are respectively provided with higher proton conductivity.
Table 1
Fig. 2 is the INFRARED SPECTRUM of the side chain type sulfonated polyimides of the group containing quinoxaline in 6 preferred embodiments of the invention
Scheme (protic state), wherein 1710cm-1And 1670cm-1The peak of left and right be imide ring characteristic absorption peak, 1090cm-1With
1017cm-1The peak of left and right be sulfonic acid group characteristic absorption peak, 1500cm-1The peak of left and right is the proton uptake peak of quinoxaline ring,
Wherein 1670cm-1The peak at place broadens, and to be due to that C=N on quinoxaline ring is almost identical with main chain C=0 absorption peak position draw
Rise.As seen from the figure, preparation method provided by the invention can successfully obtain the side chain type of described main chain group containing quinoxaline
Sulfonated polyimide.
Fig. 3 is the thermal weight loss of the side chain type sulfonated polyimides of the group containing quinoxaline in 6 preferred embodiments of the invention
Curve (protic state), the thermal weight loss from room temperature to 150 DEG C are due to the volatilization of moisture, and 300 DEG C to 450 DEG C of thermal weight loss is
Due to the decomposition of sulfonic acid group, and more than 500 DEG C of weightlessness is due to then the degraded of main polymer chain.As seen from the figure, in temperature
At up to 700 DEG C, this kind of polymer still has more than 30% Ash residue, shows that the polymer has excellent heat endurance.
To sum up, the present invention proposes side chain type sulfonated polyimides of a kind of main chain group containing quinoxaline and preparation method thereof
And the method for PEM is prepared using it, its architectural feature is that the side chain with sulfonic acid group passes through quinoxaline on main chain
The ehter bond or thioether bond of group are bridge joint group, have both increased the hydrophobicity of main chain, and in turn ensure that side chain flexibility.The present invention
Preparation method is easy to operate and control, suitable for industrialized production, obtained sulfonated polyimide have higher molecular weight with
And good hydrolytic stability, it is with a wide range of applications in PEM field.
Above example be referring to the drawings, to a preferred embodiment of the present invention will be described in detail, those skilled in the art
Member by above-described embodiment carry out various forms on modification or change, but without departing substantially from the present invention essence in the case of, all
Fall within the scope and spirit of the invention.
Claims (11)
- A kind of 1. side chain type sulfonated polyimides of main chain group containing quinoxaline, it is characterised in that described sulfonated polyimide For sulfonated polyimide homopolymer (y=1) or sulfonated polyimide copolymer (0 with logical formula (I)<y<1)：Wherein, X represents O or S；Wherein, R1-(SO3H)aIncluding：R2Including：R3Including：N is positive integer；A=1 or 2 or 3；0<y≤1.
- 2. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline as claimed in claim 1, its It is characterised by, the preparation method of described sulfonated polyimide homopolymer (y=1) comprises the following steps：Under nitrogen protection, sulfonated diamine and a certain amount of organic weak base are dissolved in organic solvent, then added and sulfonation two The equimolar dianhydride monomer of amine and a certain amount of organic monoacid, reaction system is reacted into 1-8h at 80-140 DEG C, then in 160- 220 DEG C of reaction 8-24h, after question response terminates, are down to 70-120 DEG C by system temperature, are subsequently poured into methanol, obtain thread production Thing, through washing repeatedly after being dried in vacuum drying oven, obtain the sulfonated polyimide homopolymer；Described sulfonated polyimide copolymer (0<y<1) preparation method comprises the following steps：Under nitrogen protection, sulfonated diamine, non-sulfonated diamines and a certain amount of organic weak base are dissolved in organic solvent, Ran Houjia Enter with diamines (total amount of sulfonated diamine and non-sulfonated diamines) equimolar dianhydride monomer and a certain amount of organic monoacid, will react System reacts 1-8h at 80-140 DEG C, then reacts 8-24 h at 160-220 DEG C, after question response terminates, system temperature is down to 70-120 DEG C, it is subsequently poured into methanol, obtains thread product, through washing repeatedly after being dried in vacuum drying oven, obtains the sulphur Change polyimide copolymer.
- 3. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline according to claim 2, Characterized in that, the sulfonated diamine is 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides]-benzene sulfonic acid, 5- [2,3- Two (4- aminophenyls)-quinoxaline -6- epoxides] -2- toluene sulfonic acides, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- oxygen Base] -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides] -5- (4- sulfonic groups-thiophenyl) benzene sulphur Acid, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- epoxides] -5- (4- sulfonic groups-phenoxy group) benzene sulfonic acid, 4- { 4- [2,3- Two (4- aminophenyls)-quinoxaline -6- epoxides] -3- sulfonic groups-phenoxy group -1,3- benzenedisulfonic acids, 4- { 4- [(the 4- ammonia of 2,3- bis- Base phenyl)-quinoxaline -6- epoxides] -3- sulfonic groups-thiophenyl -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- aminophenyls)-quinolines Quinoline -6- epoxides] -5- [1- methyl isophthalic acids-(4- sulfonic groups phenyl) ethyl] benzene sulfonic acid, 4- [2,3- bis- (4- aminophenyls)-quinolines Quinoline -6- epoxides] -3,4 '-disulfonic acid base biphenyl, 2- [2,3- bis--(4- aminophenyls)-quinoxaline -6- epoxides] -5- (4- sulfonic acid Base-benzyl) benzene sulfonic acid, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls]-benzene sulfonic acid, 5- [(the 4- aminobenzenes of 2,3- bis- Base)-quinoxaline -6- sulfenyls] -2- toluene sulfonic acides, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls] -1,3- benzene two Sulfonic acid, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls] -5- (4- sulfonic groups-thiophenyl) benzene sulfonic acid, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulfenyls] -5- (4- sulfonic groups-phenoxy group) benzene sulfonic acid, 4- { 4- [(the 4- aminobenzenes of 2,3- bis- Base)-quinoxaline -6- sulfenyls] -3- sulfonic groups-phenoxy group -1,3- benzenedisulfonic acids, 4- { 4- [2,3- bis- (4- aminophenyls)-quinolines Quinoline -6- sulfenyls] -3- sulfonic groups-thiophenyl -1,3- benzenedisulfonic acids, 2- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulphur Base] -5- [1- methyl isophthalic acids-(4- sulfonic groups phenyl) ethyl] benzene sulfonic acid, 4- [2,3- bis- (4- aminophenyls)-quinoxaline -6- sulphur Base] -3,4 '-disulfonic acid base biphenyl, 2- [2,3- bis--(4- aminophenyls)-quinoxaline -6- sulfenyls] -5- (4- sulfonic groups-benzyl) One kind in benzene sulfonic acid.
- 4. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline according to claim 2, Characterized in that, the non-sulfonated diamines is 4,4 '-diaminodiphenyl ether, Isosorbide-5-Nitrae-two (3- amino-benzene oxygens) benzene, (4- of Isosorbide-5-Nitrae-two Amino-benzene oxygen) benzene, 4,4 '-two (4- amino-benzene oxygens) biphenyl, 3,3 '-dimethyl -4,4 '-benzidine, 2,2 '-diformazan Base -4,4 '-benzidine, 2,2- bis- (4- aminophenyls) propane, 2,2 '-two (trifluoromethyl) -4,4 '-benzidines, 4,4 '-MDA, two (3- methyl -4- aminophenyls) methane, two (3,5- dimethyl -4- aminophenyls) methane, One kind in 9,9 '-two (4- aminophenyls) fluorenes.
- 5. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline according to claim 2, Characterized in that, the dianhydride monomer is Isosorbide-5-Nitrae, and 5,8- naphthalenetetracarbacidic acidic dianhydrides, 4,4 '-dinaphthalene -1,1 ', 8,8 '-tetracarboxylic dianhydride, 4, 4 '-dinaphthyl ether -1,1 ', 8,8 '-tetracarboxylic dianhydride, 4,4 '-dinaphthyl ketone -1,1 ', 8,8 '-tetracarboxylic dianhydride, (the 4- oxygen of biphenyl -4,4 '-two Generation -1,8- naphthalic anhydrides), one kind in -3,4,9,10- tetracarboxylic dianhydrides.
- 6. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline according to claim 2, Characterized in that, the organic weak base is one kind in triethylamine, triethylene diamine, pyridine, N-methylmorpholine, isoquinolin；Institute Organic monoacid is stated as one kind in formic acid, acetic acid, benzoic acid, phenylacetic acid, ethanedioic acid；The organic solvent is metacresol, 1- first One kind in base pyrrolidones and DMAC N,N' dimethyl acetamide.
- 7. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline according to claim 2, Characterized in that, mole addition of the organic weak base is 2.0-4.0 times of the sulfonated diamine addition；It is described organic weak Mole addition of acid is 1.0-3.0 times of the dianhydride monomer addition.
- 8. a kind of preparation method of the side chain type sulfonated polyimides of main chain group containing quinoxaline according to claim 2, Characterized in that, the total mass concentration of the sulfonated diamine, non-sulfonated diamines and dianhydride monomer in the organic solvent is 8-20%.
- 9. a kind of method that side chain type sulfonated polyimides using main chain group containing quinoxaline prepares PEM, its feature It is, comprises the following steps：By the side chain type sulfonated polyimides dissolving of main chain group containing quinoxaline described in claim 1 in organic solvent, warp After-pouring is filtered on the glass plate of cleaning, 2-8h is dried in 60-120 DEG C of convection oven, then by resulting film in second Fully washed in alcohol, and in temperature be 60-90 DEG C, concentration be 1.5-4.0mol/L hydrochloric acid solution in soak 4-24h, spend from Son is dried after being washed to neutrality, obtains the side chain type sulfonated medlin proton exchange film of main chain group containing quinoxaline.
- 10. the side chain type sulfonated polyimides according to claim 9 using main chain group containing quinoxaline prepares proton friendship The method for changing film, it is characterised in that described organic solvent is metacresol, 1- methyl pyrrolidones and N, N- dimethylacetamide One kind in amine.
- 11. the side chain type sulfonated polyimides according to claim 9 using main chain group containing quinoxaline prepares proton friendship The method for changing film, it is characterised in that the side chain type sulfonated polyimides of main chain group containing quinoxaline is in organic solvent Mass concentration is 2-20%.
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