CN103073702B - Polyimide with sulfonated side chain and preparation method thereof - Google Patents
Polyimide with sulfonated side chain and preparation method thereof Download PDFInfo
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Abstract
The invention provides polyimide with a sulfonated side chain. The content of sulfonic acid groups in polyimide is controllable. The polyimide with the sulfonated side chain can be used for preparing a proton exchange membrane with high conductivity, good mechanical performance and low price. The invention further provides a preparation method for polyimide with the sulfonated side chain. In addition, the invention further provides the proton exchange membrane.
Description
Technical field
The present invention relates to polymkeric substance and preparation field thereof, particularly relate to polyimide of a kind of pendant sulfonic acid and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) starts with its energy transformation ratio high and low temperature, the remarkable advantage such as pollution-free and be regarded as cleaning, the high efficient energy sources of 21st century.Proton exchange membrane is the key components of PEMFC, mainly plays a part proton conducting and isolates fuel and oxygenant.Proton exchange membrane conventional is at present the Nafion series perfluoro sulfonic acid membrane that du pont company produces, but perfluoro sulfonic acid membrane is expensive, therefore develops the focus that new cheap proton exchange membrane becomes research.Wherein the polyimide of pendant sulfonic acid has excellent mechanical performances and swelling resistance performance due to interaction strong between imide structure, therefore receives the concern of people.In document, the polyimide of pendant sulfonic acid is usually by aromatic diamine monomers (H
2n-Ar
1-NH
2) and side chain sulfonated aromatic diamine monomer (H
2n-Ar
s-NH
2) carry out polyimide polycondensation with dianhydride monomer and obtain (as YIN Y, FANG J, WATARI T, et al.Synthesis and properties of highly sulfonated proton conductingpolyimides from bis (3-sulfopropoxy) benzidine diamines [J] .Journal ofMaterials Chemistry, 2004,14 (6): 1062-1070; YASUDA T, LI Y, MIYATAKE K, et al.Synthesis and properties of polyimides bearing acidgroups on long pendant aliphatic chains [J] .Journal of Polymer SciencePart A:Polymer Chemistry, 2006,44 (13): 3995-4005.), reaction expression is as follows:
In the polyimide of the pendant sulfonic acid obtained like this, the sulfonic acid group of side chain and imide structure are on same polymerized unit, can weaken the hydrolytic resistance of imide structure.In addition, polyimide polycondensation temperature is very high, usually just can obtain the polymkeric substance of complete imidization at 200 ° of more than C, and solvent for use is generally pungency and the cresols of difficult removing; The synthesis of side chain sulfonated aromatic diamine monomer, purifying and preserve difficulty.
Summary of the invention
The technical problem to be solved in the present invention is polyimide providing a kind of pendant sulfonic acid and preparation method thereof, the sulfonic acid group content of described polyimide is controlled, and this polymkeric substance can be used in preparation specific conductivity high, good mechanical property, cheap proton exchange membrane.
In order to solve above technical problem, the invention provides the polyimide of the pendant sulfonic acid shown in a kind of formula I:
Wherein x=0.01 ~ 0.99; N is 1 ~ 400; Wherein Q can be H
+, the protonated salt of tertiary amine, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6; A
j1, A
j2be respectively di-carboxylic acid formed substituting group in one or more; A
kfor one or more in the substituting group that imide compound is formed.
Preferably, the protonated salt of described tertiary amine is HN
+(CH
3)
3or HN
+(CH
2cH
3)
3.
Preferably, described quaternary ammonium salt cationic is N
+(CH
3)
4or N
+(CH
2cH
3)
4.
Preferably, one or more in the substituting group shown in substituting group formula 1 ~ formula 13 that formed of described di-carboxylic acid:
Wherein, W is the substituting group shown in formula a ~ formula i:
Qa is the integer of 4 ~ 12; Qb is the integer of 1 ~ 5; Qc is the integer of 1 ~ 6; Qd is the integer of 1 ~ 10; Qe is the integer of 1 ~ 3; Qf is the integer of 2 ~ 12; Qg is the integer of 2 ~ 10.
Preferably, the substituting group that described imide compound is formed is one or more in the substituting group shown in formula 14-formula 19:
Wherein, Im is the substituting group shown in formula j ~ formula o:
Present invention also offers a kind of preparation method of polyimide of pendant sulfonic acid, comprising:
Pendant sulfonic acid monomer shown in formula II is mixed with dibasic carboxylic acid monomers, imide monomer and acid solvent, reacts 4 ~ 48 hours, obtain the polyimide of the pendant sulfonic acid shown in formula I.
Wherein, wherein Q can be H
+, the protonated salt of tertiary amine, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6.
Preferably, the protonated salt of described tertiary amine is HN
+(CH
3)
3or HN
+(CH
2cH
3)
3.
Preferably, described quaternary ammonium salt cationic is N
+(CH
3)
4or N
+(CH
2cH
3)
4.
According to the present invention, the preparation method of the polyimide of the pendant sulfonic acid shown in described formula I is specially: by the compound shown in foregoing formula II and dibasic carboxylic acid monomers, imide monomer and acid solvent add in the reaction flask of logical nitrogen, stirring reaction 4 ~ 48 hours under certain temperature of reaction, reacting liquor while hot is poured into suitable precipitation agent preferably in water, be settled out polymkeric substance, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, it is neutral that the dilute hydrochloric acid soaking at room temperature of resulting polymers 0.1mol/L is washed till washings with deionized water after 24 hours more repeatedly, namely vacuum-drying be able to H
+the polyimide of the pendant sulfonic acid that form exists, then will with H
+namely the polyimide of the pendant sulfonic acid that form exists is able to the polyimide of the pendant sulfonic acid that other cationic form exists with corresponding alkali neutralization.
According to the present invention, described dibasic carboxylic acid monomers be preferably in the dicarboxylic acid compound shown in formula 20 ~ formula 32 one or more, due to the carboxylic acid functional that acylation reaction can occur containing two described dibasic carboxylic acid monomers, can represent with AA type monomer.
Dicarboxylic acid compound shown in table 1 formula 20 ~ formula 32
Wherein, W is the substituting group shown in formula a ~ formula i.Qa is the integer of 4 ~ 12; Qb is the integer of 1 ~ 5; Qc is the integer of 1 ~ 6; Qd is the integer of 1 ~ 10; Qe is the integer of 1 ~ 3; Qf is the integer of 2 ~ 12; Qg is the integer of 2 ~ 10.
According to the present invention; described imide monomer is preferably one or more of the imide compound shown in formula 33 ~ formula 38; because two phenyl ring being only in molecule two ends in described imide compound acylation reaction can occur, can represent with BB type monomer.
Imide compound shown in table 2 formula 33 ~ formula 38
Wherein, Im is the substituting group shown in formula j ~ formula o.
According to the present invention, mole interpolation between the pendant sulfonic acid monomer shown in described formula II, dibasic carboxylic acid monomers, imide monomer is than being X
qBB: X
aA: X
bB, wherein X
qBB, X
aA, X
bBall be greater than zero and X
qBB+ X
bB=X
aA, acid solvent adds 2 ~ 4L by every moles of dicarboxylic acids present monomer.According to the present invention, the copolyreaction of described monomer is obtained by the formula acylation reaction of paying between carboxyl and aryl.Be preferably 60 ~ 150 DEG C according to temperature of reaction of the present invention, be more preferably 80 ~ 100 DEG C.
Described acid solvent is preferably P
2o
5/ polyphosphoric acid mixture, P
2o
5/ methanesulfonic acid mixture or trifluoromethanesulfonic acid, wherein P
2o
5/ polyphosphoric acid mixture can by document Baek, J.B., et al., Polymer, 44 (2003), 4135-4147 preparations, P
2o
5be 15% ~ 30% with the mass ratio of polyphosphoric acid; P
2o
5/ methanesulfonic acid mixture can by document Eaton, P.E., et al., Journal ofOrganic Chemistry, 38 (1973), 4071-4073 preparations, preferably commercially available Eton reagent (Eaton ' s reagent).
Present invention also offers a kind of proton exchange membrane.According to the present invention, described proton exchange membrane can use the polyimide of the pendant sulfonic acid shown in formula I to be prepared according to the preparation method about proton exchange membrane in " the preparation and application technology of ion-exchange membrane ".Proton exchange membrane prepared by the present invention is owing to employing the polyimide of the pendant sulfonic acid shown in formula I, simultaneously containing the sulfonic acid group of side chain and the imide structure of main chain, wherein sulfonic acid group provides high ionic conductivity and imide structure to provide the water swell resistance of film.Pendant sulfonic acid groups in the polyimide of pendant sulfonic acid prepared by the present invention and imide structure, respectively in different structural units (being respectively hydrophilic structural unit and non-hydrophilic structural unit), can not be hydrolyzed by available protecting imide structure.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
Further describe the present invention by the following examples.
Proton nmr spectra (
1h NMR) by AVANCE AV400, Bruker record, with heavy water (D
2o) or deuterated dimethyl sulfoxide (DMSO-d6, tetramethylsilane is interior mark) be solvent.Fourier transform infrared spectra (FTIR) is by Vector22, Bruker record.The molecular weight of polymkeric substance adopts general Ubbelohde viscometer method to characterize, and probe temperature is 30 ° of C, and solvent is 99% methylsulfonic acid, and polymer concentration is 0.3 gram/100 milliliters, and solution properties viscosity unit is dL/g.The proton conductivity of film measures at known four electrode models of the upper employing of PGSTAT302N type electrochemical workstation (MetrohmChina Ltd.), and probe temperature is 25 DEG C, and relative humidity is 100%.
The measuring method of the loading capacity (IEC) of film is the film sample (H cutting 3 × 3cm
+type cationic exchange membrane, dry film is heavily designated as W
dry), at the 1moldm of 100mL
-324h is soaked to make the H in film in NaCl solution
+completely by the Na in solution
+out, be then indicator with phenolphthalein, with standard NaOH solution, (concentration is designated as C in ion-exchange
naOH(mmol cm
-3)) being titrated to terminal, titration institute quota of expenditure NaOH solution volume is designated as V
naOH(cm
-3), IEC calculates as follows:
IEC＝C
NaOH×V
NaOH/W
dry。
Embodiment 1: the synthesis of imide monomer
Imide monomer is obtained by the condensation reaction between dianhydride compound and single fragrant ammoniate.The purity of dianhydride compound and single aromatic amine compound does not need very high, avoids in polyimide polycondensation synthesis of polyimides method and must use the dianhydride monomer of high purity (usually requiring that purity is greater than 99%) and the shortcoming of diaryl-amine monomer.Example is synthesized: successively by 1.0 moles 1 with a kind of imide monomer, 8-naphthalic anhydride (purity is 97%), the 4-amino-diphenylethers (purity is 97%) of 2.2 moles and the dimethyl formamide of 0.5 liter add in 1.0 liters of reaction flasks of logical nitrogen, mechanic whirl-nett reaction 6 hours at 160 DEG C, cooling post crystallization, filter, washing with alcohol, namely obtains the imide monomer (productive rate is 88%) that can be used for next step polymerization after vacuum-drying.Reaction formula is as follows:
Embodiment 2:
Successively by 1.00 moles 4, 4,-oxydibenzoic acid, the imide monomer of synthesis in 0.99 mole of embodiment 1, 0.01 mole 2, 2,-bis-(3-sulfonation propoxy-) biphenyl disodium and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, stirring reaction 48 hours at 80 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, it is neutral that the dilute hydrochloric acid soaking at room temperature of resulting polymers 0.1mol/L is washed till washings with deionized water after 24 hours more repeatedly, namely vacuum-drying be able to H
+the side chain that form exists is containing the polymkeric substance of sulfonic acid group.At 1716cm in infrared spectrum
-1with 1670cm
-1there is strong imide charateristic avsorption band and 1646cm in left and right
-1the carbonyl absorption peak of left and right and almost do not observe the absorption peak of carboxyl, shows the generation of polyamides glycosylation reaction and the introducing of imide structure unit; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
1h NMR (400MHz, DMSO-d6) δ (ppm): 8.5-7.0 (Ar-H), 4.16 (OCH
2), 2.42 (CH
2s), 1.95 (CH
2 cH 2 cH
2); The limiting viscosity of resulting polymers is 1.05dL/g simultaneously, is indicated as high-molecular weight polymer.
Wherein, described 2,2, the preparation method of-bis-(3-sulfonation propoxy-) biphenyl disodium is:
Successively by 1.0 moles 2,2 ,-dihydroxybiphenyl, the sodium tert-butoxide of 2.0 moles and the dimethyl sulfoxide (DMSO) of 2.5 liters add in 4.0 liters of reaction flasks of logical nitrogen, mechanic whirl-nett reaction 1 hour at 65 DEG C, add the 3-bromopropyl sodium sulfonate of 2.0 moles again, stirring reaction 24 hours at continuing 65 DEG C, underpressure distillation is except desolventizing, gained solid is the ethanol/water recrystallization of 95/5 through weight ratio, filter, namely 2 of sodium-salt form existence are able to after vacuum-drying, 2 ,-bis-(3-sulfonation propoxy-) biphenyl disodium
1h NMR (400MHz, D
2o) δ (ppm): 7.40(Ar-H4, t, 2H), 7.25(Ar-H6, d, 2H), 7.09-7.15(Ar-H3 & Ar-H5, m, 4H) and, 4.07(OCH
2, t, 4H), 2.72(CH
2s, t, 4H), 1.97(CH
2 cH 2 cH
2, m, 4H), confirm the structure of compound.Reaction formula is as follows:
Embodiment 3:
Successively by 1.00 moles 4, 4,-oxydibenzoic acid, the imide monomer of synthesis in 0.50 mole of embodiment 1, 0.50 mole 2, 2,-bis-(3-sulfonation propoxy-) biphenyl disodium (by the synthesis of embodiment 2 method) and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, stirring reaction 24 hours at 100 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, it is neutral that the dilute hydrochloric acid soaking at room temperature of resulting polymers 0.1mol/L is washed till washings with deionized water after 24 hours more repeatedly, namely vacuum-drying be able to H
+the side chain that form exists is containing the polymkeric substance of sulfonic acid group.At 1716cm in infrared spectrum
-1with 1670cm
-1there is strong imide charateristic avsorption band and 1646cm in left and right
-1the carbonyl absorption peak of left and right and almost do not observe the absorption peak of carboxyl, shows the generation of polyamides glycosylation reaction and the introducing of imide structure unit; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
1h NMR (400MHz, DMSO-d6) δ (ppm): 8.5-7.0 (Ar-H), 4.16 (OCH
2), 2.42 (CH
2s), 1.95 (CH
2 cH 2 cH
2); The limiting viscosity of resulting polymers is 2.05dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 4:
Successively by 1.00 moles 4, 4,-oxydibenzoic acid, the imide monomer of synthesis in 0.25 mole of embodiment 1, 0.75 mole 2, 2,-bis-(3-sulfonation propoxy-) biphenyl disodium (by the synthesis of embodiment 2 method) and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, stirring reaction 12 hours at 120 DEG C, reacting liquor while hot is poured in a large amount of deionized water and obtain polymkeric substance precipitation, it is neutral for filtering and being repeatedly washed till filtrate with deionized water, it is neutral that the dilute hydrochloric acid soaking at room temperature of resulting polymers 0.1mol/L is washed till washings with deionized water after 24 hours more repeatedly, namely vacuum-drying be able to H
+the side chain that form exists is containing the polymkeric substance of sulfonic acid group.At 1716cm in infrared spectrum
-1with 1670cm
-1there is strong imide charateristic avsorption band and 1646cm in left and right
-1the carbonyl absorption peak of left and right and almost do not observe the absorption peak of carboxyl, shows the generation of polyamides glycosylation reaction and the introducing of imide structure unit; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection by the ratio of integration structural unit more each than calculating gained,
1h NMR (400MHz, DMSO-d6) δ (ppm): 8.5-7.0 (Ar-H), 4.16 (OCH
2), 2.42 (CH
2s), 1.95 (CH
2 cH 2 cH
2); The limiting viscosity of resulting polymers is 1.31dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 5:
Getting resulting polymers in 1 gram of embodiment 4 is dissolved in 15 grams of N-Methyl pyrrolidone, be mixed with homogeneous solution, be applied on clean horizontal glass plate, at 60 DEG C, solvent flashing is after about 18 hours, by film after glass stripping, soak in the dilute hydrochloric acid of 1mol/L after 24 hours and namely obtain acid type proton exchange membrane.The loading capacity of gained film by determination of acid-basetitration be 2.13mmol/g and theoretical value closely (theoretical value is 2.16mmol/g).Room temperature proton conductivity reaches 0.15S/cm, far above business-like Nafion115 film (under same test condition, Nafion115 film quality electron conductivity is 0.09S/cm).
More than apply specific case to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (3)
1. the polyimide of the pendant sulfonic acid shown in a formula I:
Wherein x=0.01 ~ 0.99; N is 1 ~ 400; Wherein Q is H
+, the protonated salt of tertiary amine, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6; A
j1, A
j2be respectively di-carboxylic acid formed substituting group in one or more; A
kfor one or more in the substituting group that imide compound is formed;
The substituting group that described di-carboxylic acid is formed is one or more in the substituting group shown in formula 1 ~ formula 13:
Wherein, W is the substituting group shown in formula a ~ formula i:
Qa is the integer of 4 ~ 12; Qb is the integer of 1 ~ 5; Qc is the integer of 1 ~ 6; Qd is the integer of 1 ~ 10; Qe is the integer of 1 ~ 3; Qf is the integer of 2 ~ 12; Qg is the integer of 2 ~ 10;
The substituting group that described imide compound is formed is one or more in the substituting group shown in formula 14 ~ formula 19:
Wherein, Im is the substituting group shown in formula j ~ formula o:
2. the preparation method of the polyimide of a pendant sulfonic acid according to claim 1, it is characterized in that, dibasic carboxylic acid monomers, imide monomer, side chain sulfonated monomers and acid solvent are added the polyimide obtaining the pendant sulfonic acid shown in formula I in the reaction flask of logical nitrogen.
3. a cationic exchange membrane, is characterized in that, uses the polyimide of the pendant sulfonic acid described in claim 1 to be prepared from.
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| CN113150344B (en) * | 2021-04-21 | 2022-05-31 | 常州大学 | Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof |
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