CN103044292A - Sulfonated aromatic compound, polyketone with sulfonated aromatic groups and methods for preparing sulfonated aromatic compound and polyketone with sulfonated aromatic groups - Google Patents
Sulfonated aromatic compound, polyketone with sulfonated aromatic groups and methods for preparing sulfonated aromatic compound and polyketone with sulfonated aromatic groups Download PDFInfo
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- SUEKXDZEVKLTIT-LKSINWNRSA-N CC(CC1)C=CC1ONOC1=CC[C@H](C)C=C1 Chemical compound CC(CC1)C=CC1ONOC1=CC[C@H](C)C=C1 SUEKXDZEVKLTIT-LKSINWNRSA-N 0.000 description 1
- BSRJINZYPHZDPZ-UHFFFAOYSA-N Cc(cc1)cc(-c2ccccc2)c1O[N]Oc1ccc(C)cc1-c1ccccc1 Chemical compound Cc(cc1)cc(-c2ccccc2)c1O[N]Oc1ccc(C)cc1-c1ccccc1 BSRJINZYPHZDPZ-UHFFFAOYSA-N 0.000 description 1
- ZWPWLKXZYNXATK-UHFFFAOYSA-N Cc(cc1)ccc1C(c1ccc(C)cc1)=O Chemical compound Cc(cc1)ccc1C(c1ccc(C)cc1)=O ZWPWLKXZYNXATK-UHFFFAOYSA-N 0.000 description 1
- WEAYCYAIVOIUMG-UHFFFAOYSA-N Cc(cc1)ccc1S(c1ccc(C)cc1)(=O)=O Chemical compound Cc(cc1)ccc1S(c1ccc(C)cc1)(=O)=O WEAYCYAIVOIUMG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a sulfonated aromatic compound and a polyketone with sulfonated aromatic groups, wherein the polyketone is obtained by polymerization by taking the sulfonated aromatic compound as a monomer. The content of the sulfonated aromatic groups on the polyketone is controllable, and the polymer with sulfonated aromatic groups can be used for preparing a proton exchange membrane with high electric conductivity, good mechanical properties and low cost. The invention also provides methods for preparing the sulfonated aromatic compound and the polyketone with sulfonated aromatic groups. In addition, the invention further provides the proton exchange membrane.
Description
Technical field
The present invention relates to polymkeric substance and preparation field thereof, relate in particular to a kind of sulfonated aromatics and a kind of polyketone that contains sulfonated aromatic group and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) with its energy transformation ratio high and low temperature start, 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 isolation fuel and oxygenant.Proton exchange membrane commonly used is the Nafion series perfluoro sulfonic acid membrane that du pont company is produced at present, but perfluoro sulfonic acid membrane is expensive, therefore develops the focus that new cheap proton exchange membrane becomes research.Wherein the side chain sulfonated type polymkeric substance is positioned at side chain thereby can has simultaneously high proton conductivity and good swell-resistant owing to hydrophilic sulfonic acid functional group, so the preparation of side chain sulfonated type polymkeric substance receives people's concern.
Angle from the introducing mode of pendant sulfonic acid group, the pendant sulfonic acid group can the method by rear sulfonation reaction be introduced after polymkeric substance is synthetic, and the method for direct polymerization that also can be by sulfonated monomers is introduced. wherein the method for sulfonated monomers direct polymerization can accurately be controlled by the adding proportion of controlling sulfonated monomers content and the position of sulfonic acid group in the sulfonated polymer. but about side chain sulfonated aromatic monomer synthesize and the patent report of polymerization seldom.U.S. Patent Application No. 20050106469 has reported that side chain contains the polymerization of the aryl dihalo-monomer of sulfonate ester group, because the sulfonic acid group on the monomer exists with the form of alkyl sulfonate esters, so resulting polymers must just can obtain the ionic polymer that sulfonic acid group exists with ionic species through further hydrolysis.The coupling polymerization of the aryl dihalo-monomer of this patent description must carry out in the presence of a large amount of metallic reducing agents, metal catalyst and part in addition, and polymerizing condition is harsh, the polymerisate purifying complex.
Summary of the invention
The technical problem to be solved in the present invention is the sulfonated aromatic series polyketone that a kind of sulfonated aromatics is provided and obtains as monomer polymerization with this compound, described polyketone sulfonic acid group content is controlled, and this polymkeric substance that contains sulfonated aromatic group can be used in high, the good mechanical property of preparation specific conductivity, cheap proton exchange membrane.
In order to solve above technical problem, the invention provides a kind of suc as formula the sulfonated aromatic compound shown in the I:
Formula I
Wherein, wherein Q can be H
+, tertiary amine protonated salt, 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
Compound shown in the formula I is except having Ionized pendant sulfonic acid group; also has simultaneously aryl two symmetries, that the Fu Shi acylation reaction can occur in the contraposition position of ether oxygen base; therefore the diaryl monomer that can be used as pendant sulfonic acid participates in the polymerization of Fu Shi acylations, thereby is directly obtained the aromatic polymer of pendant sulfonic acid by sulfonated monomer polymerization.
The present invention also provides a kind of preparation method suc as formula the sulfonated aromatic compound shown in the I, it is characterized in that, comprising:
2,2`-dihydroxybiphenyl, sodium tert-butoxide, dimethyl sulfoxide (DMSO) are mixed, reacted 0.5~2 hour; Obtain the first intermediate product;
With described the first intermediate product and sulfonated reagent mix, etherification reaction occurs obtain the compound shown in the formula I.
Wherein said 2,2`-dihydroxybiphenyl, salt of wormwood, sulfonated reagent are (1~2) in molar ratio: (2~4): (2~4), and described 2, the mole/volume ratio of 2`-dihydroxybiphenyl and dimethyl sulfoxide (DMSO) is 1: 2.5;
Described sulfonated reagent is 2-bromotrifluoromethane sodium sulfonate, 3-bromopropyl sodium sulfonate, 4-brombutyl sodium sulfonate, 5-bromine amyl group sodium sulfonate or 6-bromine hexyl sodium sulfonate; Q is H
+, tertiary amine protonated salt, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6.
According to the present invention, described preparation method is specially: successively with 2,2`-dihydroxybiphenyl, sodium tert-butoxide and dimethyl sulfoxide (DMSO) add in the reaction flask of logical nitrogen, preferably 60~70 ℃ of lower stirring reactions 1 hour, add again sulfonated reagent, continued 60~70 ℃ of lower stirring reactions 24 hours, the underpressure distillation desolventizing, the gained solid is 95/5 ethanol/water recrystallization through weight ratio, filters, and namely is able to the sulfonation diaryl monomer that sodium-salt form exists after the vacuum-drying; The mol ratio of each material consumption is 2,2`-dihydroxybiphenyl: sodium tert-butoxide: sulfonated reagent=1: 2: 2; Every mole 2, the 2`-dihydroxybiphenyl adds 2.5 liters of dimethyl sulfoxide (DMSO); Described sulfonated reagent is 2-bromotrifluoromethane sodium sulfonate, 3-bromopropyl sodium sulfonate, 4-brombutyl sodium sulfonate, 5-bromine amyl group sodium sulfonate or 6-bromine hexyl sodium sulfonate.The sulfonation diaryl monomer that exists with sodium-salt form in addition can pass through H
+The type Zeo-karb is converted into H
+The sulfonation diaryl monomer that form exists is again with H
+The sulfonation diaryl monomer that form exists neutralizes with corresponding tertiary amine or alkali and namely is able to other positively charged ion such as protonated tertiary amine, Li
+, K
+, the sulfonation diaryl monomer that exists of the form such as quaternary ammonium salt cationic.
The building-up reactions formula is as follows:
Under alkaline condition, with sulfonated reagent and '-biphenyl diphenol reaction, etherification reaction occurs, make and form the side chain that contains sulfonic acid group on the cyclohexyl biphenyl.
According to the present invention, sulfonated aromatic compound shown in the use formula I prepares the polymkeric substance that side chain contains sulfonic acid group as monomer, because monomer itself is by sulfonated, so the quantity of sulfonic acid group is controlled, as long as adjust the consumption of monomer, just can control the quantity of sulfonic acid group, control molecular weight simultaneously.Because contain phenyl ring in the monomer molecule, so molecular weight is higher, mechanical property and heat resistance are better.In addition, the sulfonated aromatic compound preparation method shown in the formula I provided by the invention is simple, and the raw material of use is easy to get, and is with low cost, is fit to large-scale industrial production.
The present invention also provides the polyketone that contains sulfonated aromatic group shown in a kind of formula II:
Formula II
X=0.01~1.0 wherein; Y=0~0.99; X+y≤1; N is 1~220; Wherein, wherein Q can be H
+, tertiary amine protonated salt, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6; A
J1, A
J2Be respectively in the substituting group that diprotic acid forms one or more; A
kIn the substituting group that forms for polyarylate one or more; A
iIn the substituting group that forms for aromatic ether monoprotic acid one or more.
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 the substituting group formula 1~formula 13 of described diprotic acid formation:
-(CH
2)
qa- -(CH
2CH
2O)
qbCH
2CH
2- -CH
2O(CH
2CH
2O)
qcCH
2-
Formula 1 formula 2 formulas 3
Formula 4 formulas 5
Formula 6 formulas 7 formulas 8
Formula 9 formulas 10 formulas 11
Formula 12 formulas 13
Wherein, W is the substituting group shown in formula a~formula i:
Formula a formula b formula c formula d
Formula e formula f formula g formula h formula i
Qa is 4~12 integer; Qb is 1~5 integer; Qc is 1~6 integer; Qd is 1~10 integer; Qe is 1~3 integer; Qf is 2~12 integer; Qg is 2~10 integer.
Preferably, the substituting group of described polyarylate formation is one or more in the substituting group shown in formula 4, the formula 14~formula 33:
Formula 4 formulas 14
Formula 15 formulas 16
Formula 17 formulas 18 formulas 19
Formula 20 formulas 21
Formula 22 formulas 23 formulas 24
Formula 25 formulas 26 formulas 27
Formula 28 formulas 29
Formula 30
Formula 31
Formula 32 formulas 33
Wherein, W is the substituting group shown in formula a~formula i:
Formula a formula b formula c formula d
Formula e formula f formula g formula h formula i
Ra is 1~4 integer; Rb is 1~9 integer; Rc is 1~2 integer; Rd is 0~2 integer; Re is 0~2 integer; Qf is 2~12 integer; Qg is 2~10 integer.
Preferably, the substituting group that forms of described aromatic oxide monoprotic acid is formula 4, formula 14, formula 34~formula 41: shown in substituting group in one or more:
Formula 4 formulas 14 formulas 34
Formula 35 formulas 36 formulas 37
Formula 38 formulas 39
Formula 40 formulas 41
According to the present invention, the polyketone shown in the described formula II is actually a kind of random copolymers.Had the Sulfonated aromatic compound shown in the formula I, for reaction is more easily carried out, used the comonomer that contains ehter bond, because these comonomers that contain ehter bond easily obtain, wide material sources and cost are lower, easily carry out polyreaction with the compound shown in the formula I.
The present invention also provides a kind of preparation method who contains the polyketone of sulfonated aromatic group, comprising:
Compound shown in the formula I is provided;
Compound shown in the formula 1 is mixed with symmetrical diprotic acid, symmetrical aromatic oxide, acid solvent and/or aromatic oxide monoprotic acid, reacted 4~48 hours, obtain the polyketone that contains sulfonated aromatic group shown in the formula II.
According to the present invention, the preparation method of the polyketone that contains sulfonated aromatic group shown in the described formula II is specially: successively with compound and the symmetrical diprotic acid shown in the foregoing formula 1, symmetrical aromatic oxide and/or aromatic oxide monoprotic acid and acid solvent add in the reaction flask of logical nitrogen, stirring reaction is 4~48 hours under certain temperature of reaction, pour reacting liquor while hot into suitable precipitation agent preferably in the water, be settled out polymkeric substance, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group, again will be with H
+The side chain that form exists contains the polymkeric substance that side chain that the polymkeric substance of sulfonic acid group namely is able to other cationic form existence with corresponding alkali neutralization contains sulfonic acid group.
According to the present invention, described symmetrical diprotic acid is preferably one or more in the diprotic acid shown in formula 42~formula 54, because described dicarboxylic acid monomer contains two carboxylic acid functionals that acylation reaction can occur, can represent with AA type monomer.
Diprotic acid shown in table 1 formula 42~formula 55
Wherein, w is the substituting group shown in formula a~formula i.Qa is 4~12 integer; Qb is 1~5 integer; Qc is 1~6 integer; Qd is 1~10 integer; Qe is 1~3 integer; Qf is 2~12 integer; Qg is 2~10 integer.
According to the present invention; described polyarylate is preferably one or more in the polyarylate compound shown in formula 55~formula 75; because described polyarylate contains two or more stupid rings and forms; acylation reaction can occur in two phenyl ring that wherein only are in the molecule two ends, can represent with BB type monomer.
Aromatic oxide shown in table 2 formula 55~formula 75
Wherein, M is the substituting group shown in formula a~formula i; Ra is 1~4 integer; Rb is 1~9 integer; Rc is 1~2 integer; Rd is 0~2 integer; Re is 0~2 integer; Qf is 2~12 integer; Qg is 2~10 integer.
According to the present invention; described aromatic oxide monoprotic acid is preferably one or more in the aromatic oxide monoprotic acid shown in formula 76~formula 85; because described aryl ethers monoprotic acid monomer contains carboxyl and the aryl functional group that acylation reaction can occur simultaneously, can represent with AB type monomer
According to the present invention, the sulfonated aromatic compound monomer shown in the described formula I, AA type monomer, BB type monomer, AB type monomer be X in molar ratio
QBB: X
AA: X
BB: X
AB, X wherein
QBB, X
AA, X
BBAll greater than zero, X
ABGreater than zero or equal zero X
QBB+ X
AA+ X
BB+ X
AB=2, X
QBB+ X
BB=X
AA, 0.01≤X
QBB≤ 1,0≤X
AB≤ 1, the summation of the amount of every mole of AA type monomer and AB type monomer adds 2~4L acid solvent.According to the present invention; the copolyreaction of described monomer obtains by paying the formula acylation reaction; can know by monomer and condition control; acylation reaction occurs in monomer under the effect of trifluoromethanesulfonic acid; diprotic acid and/or monacid carboxyl are sloughed the hydrogen evolution water on an OH and the phenyl ring, and remaining carbonyl links to each other monomer.Be preferably 40~150 ℃ according to temperature of reaction of the present invention, more preferably 60~100 ℃.
Described acid solvent is preferably P
2O
5/ polyphosphoric acid mixture, P
2O
5/ methylsulfonic acid mixture or trifluoromethanesulfonic acid, wherein P
2O
5/ polyphosphoric acid mixture can be by document Baek, J.B., et al., Polymer, 44 (2003), 4135-4147 preparation, P
2O
5With the mass ratio of polyphosphoric acid be 15%~30%; P
2O
5/ methylsulfonic acid mixture can be by document Eaton, P.E., et al., Journal of Organic Chemistry, 38 (1973), 4071-4073 preparation, preferably commercially available Eton reagent (Eaton ' s reagent).
The present invention also provides a kind of proton exchange membrane, is prepared from by the polyketone that contains sulfonated aromatic group claimed in claim 5.According to the present invention, described proton exchange membrane can use the polyketone shown in the formula II to be prepared according to the preparation method about proton exchange membrane in " the preparation and application technology of ion-exchange membrane ".The proton exchange membrane of the present invention's preparation is owing to having used the polyketone shown in the formula II, and the sulfonic acid group that contains is more, has improved electric conductivity and the switching performance of proton exchange membrane.In addition, many phenyl ring and ehter bond in the polyketone molecular chain that the present invention uses are so not only possess intensity but also possess pliability.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
Further describe by the following examples the present invention.
Proton nmr spectra (
1H NMR) by AVANCE AV400, the Bruker record is with heavy water (D
2O) or deuterated dimethyl sulfoxide (DMSO-d6, tetramethylsilane are interior mark) be solvent.Fourier transform infrared spectra (FTIR) is by Vector 22, the Bruker record.The molecular weight of polymkeric substance adopts general Ubbelohde viscometer method to characterize, and probe temperature is 30 ℃, and solvent is 99% methylsulfonic acid, and polymer concentration is/100 milliliters of 0.3 grams, and solution properties viscosity unit is dL/g.The proton conductivity of film adopts known four electrode models to measure at PGSTAT302N type electrochemical workstation (Metrohm China Ltd.), and probe temperature is 25 ℃, and relative humidity is 100%.
Embodiment 1: sulfonation polyaryl monomer synthetic
Successively with 1.0 moles 2,2`-dihydroxybiphenyl, 2.0 moles sodium tert-butoxide and 2.5 liters dimethyl sulfoxide (DMSO) add in 4.0 liters of reaction flasks of logical nitrogen, 65 ℃ of lower mechanical stirring were reacted 1 hour, added 2.0 moles 3-bromopropyl sodium sulfonate again, continued 65 ℃ of lower stirring reactions 24 hours, the underpressure distillation desolventizing, the gained solid is 95/5 ethanol/water recrystallization through weight ratio, filters, and namely is able to 2 of sodium-salt form existence after the vacuum-drying, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-
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﹠amp; Ar-H5, m, 4H), 4.07 (OCH
2, t, 4H), 2.72 (CH
2S, t, 4H), 1.97 (CH
2 CH 2 CH
2, m, 4H), confirmed the structure of compound.Reaction formula is as follows:
The sulfonation polyaryl monomer of other different alkyl length is synthetic by similar method, and just with 2-bromotrifluoromethane sodium sulfonate, 4-brombutyl sodium sulfonate, 5-bromine amyl group sodium sulfonate and 6-bromine hexyl sodium sulfonate replace respectively 3-bromopropyl sodium sulfonate.
Embodiment 2:
Successively with 2 among 0.01 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 4 of mole, 4`-phenyl ether dioctyl phthalate, 0.99 2 of mole, 2`-dimethoxy-biphenyl and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 40 ℃ of lower stirring reactions 48 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.55dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 3:
Successively with 2 among 0.01 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 4 of mole, 4`-phenyl ether dioctyl phthalate, 0.99 2 of mole, 2`-dimethoxy-biphenyl and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 60 ℃ of lower stirring reactions 24 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.91dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 4:
Successively with 2 among 0.01 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 4 of mole, 4`-phenyl ether dioctyl phthalate, 0.99 2 of mole, 2`-dimethoxy-biphenyl and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 100 ℃ of lower stirring reactions 12 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 1.11dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 5:
Successively with 2 among 0.01 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 4 of mole, 4`-phenyl ether dioctyl phthalate, 0.99 2 of mole, 2`-dimethoxy-biphenyl and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 150 ℃ of lower stirring reactions 4 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.80dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 6:
Successively with 2 among 0.50 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 4 of mole, 4`-phenyl ether dioctyl phthalate, 0.50 2 of mole, 2 '-dimethoxy-biphenyl and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 100 ℃ of lower stirring reactions 12 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.75dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 7:
Successively with 2 among 1.00 moles the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 moles 4,4`-phenyl ether dioctyl phthalate and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 80 ℃ of lower stirring reactions 12 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.51dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 8:
Successively with 2 among 0.50 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 4 of mole, 4`-phenyl ether dioctyl phthalate, 0.50 the dibenzo hexaoxacyclooctadecane-6-6 and 4 of mole liter Eton reagent adds in the reaction flask of logical nitrogen, 60 ℃ of lower stirring reactions 24 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 1.20dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 9:
Successively with 2 among 0.50 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 1.00 moles sebacic acid, 0.50 mole dibenzo hexaoxacyclooctadecane-6-6 and 4 liter Eton reagent add in the reaction flask of logical nitrogen, 40 ℃ of lower stirring reactions 6 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.58dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 10:
Successively with 2 among 0.01 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 0.50 the sebacic acid of mole, 0.49 2 of mole, the 2`-dimethoxy-biphenyl, 1.00 the 3-phenoxy benzoic acid of mole and 6 liters of Eton reagent add in the reaction flask of logical nitrogen, 60 ℃ of lower stirring reactions 24 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.75dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 11:
Successively with 2 among 0.50 mole the embodiment 1, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, 0.50 mole sebacic acid, 3-phenoxy benzoic acid and 6 liters of Eton reagent of 1.00 moles add in the reaction flask of logical nitrogen, 60 ℃ of lower stirring reactions 24 hours, reacting liquor while hot poured in a large amount of deionized waters obtain polymer precipitation, it is neutral filtering and repeatedly being washed till filtrate with deionized water, it is neutral that resulting polymers is washed till washings with deionized water with the dilute hydrochloric acid soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to H
+The side chain that form exists contains the polymkeric substance of sulfonic acid group.Occur strong carbonyl absorption peak in the infrared spectrum and almost do not observe the absorption peak of carboxyl, show the generation of polyamides glycosylation reaction; Proton nmr spectra confirms the structure of resulting polymers and is conformed to expection than the ratio of calculating each structural unit of gained by integration; The limiting viscosity of resulting polymers is 0.79dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 12:
Get 1 the gram embodiment 6 in resulting polymers be dissolved in 9 the gram dimethyl formamides in, be mixed with homogeneous solution, be applied on the clean horizontal glass plate, 60 ℃ of lower solvent flashings are approximately after 10 hours, soak after 24 hours with film glass and in the dilute hydrochloric acid of 1mol/L namely to get the acid type proton exchange membrane.The room temperature proton conductivity reaches 0.1s/cm, is higher than business-like Nafion 117 films.
Above to a kind of sulfonated aromatics provided by the invention and a kind of polyketone that contains sulfonated aromatic group and preparation method thereof.Be described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
2. compound according to claim 1 is characterized in that, the protonated salt of described tertiary amine is HN
+(CH
3)
3Or HN
+(CH
2CH
3)
3
3. compound according to claim 1 is characterized in that, described quaternary ammonium salt cationic is N
+(CH
3)
4Or N
+(CH
2CH
3)
4
4. the preparation method suc as formula the sulfonated aromatics shown in the I is characterized in that, comprising:
2,2`-dihydroxybiphenyl, sodium tert-butoxide, dimethyl sulfoxide (DMSO) are mixed, reacted 0.5~2 hour; Obtain the first intermediate product;
With described the first intermediate product and sulfonated reagent mix, etherification reaction occurs obtain the compound shown in the formula I.
Wherein said 2,2`-dihydroxybiphenyl, salt of wormwood, sulfonated reagent are (1~2) in molar ratio: (2~4): (2~4), and described 2, the mole/volume ratio of 2`-dihydroxybiphenyl and dimethyl sulfoxide (DMSO) is 1: 2.5;
Described sulfonated reagent is 2-bromotrifluoromethane sodium sulfonate, 3-bromopropyl sodium sulfonate, 4-brombutyl sodium sulfonate, 5-bromine amyl group sodium sulfonate or 6-bromine hexyl sodium sulfonate; Q is H
+, tertiary amine protonated salt, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6.
5. the polyketone that contains sulfonated aromatic group shown in the formula II:
Formula II
X=0.01~1.0 wherein; Y=0~0.99; X+y≤1; N is 1~220; Wherein, wherein Q can be H
+, tertiary amine protonated salt, monovalent base metal ion or quaternary ammonium salt cationic; P is 3,4,5 or 6; A
J1, A
J2Be respectively in the substituting group that diprotic acid forms one or more; A
kIn the substituting group that forms for polyarylate one or more; A
iIn the substituting group that forms for aromatic ether monoprotic acid one or more.
6. the polyketone that contains sulfonated aromatic group according to claim 5 is characterized in that, one or more in the substituting group shown in substituting group formula 1~formula 13 that described diprotic acid forms:
-(CH
2)
qa- -(CH
2CH
2O)
qbCH
2CH
2- -CH
2O(CH
2CH
2O)
qcCH
2-
Formula 1 formula 2 formulas 3
Formula 4 formulas 5
Formula 6 formulas 7 formulas 8
Formula 9 formulas 10 formulas 11
Formula 12 formulas 13
Wherein, W is the substituting group shown in formula a~formula i:
Formula a formula b formula c formula d
Formula e formula f formula g formula h formula i
Qa is 4~12 integer; Qb is 1~5 integer; Qc is 1~6 integer; Qd is 1~10 integer; Qe is 1~3 integer; Qf is 2~12 integer; Qg is 2~10 integer.
7. the polyketone that contains sulfonated aromatic group according to claim 5 is characterized in that, the substituting group that described polyarylate forms is one or more in the substituting group shown in formula 4, the formula 14~formula 33:
Formula 4 formulas 14
Formula 15 formulas 16
Formula 17 formulas 18 formulas 19
Formula 20 formulas 21
Formula 22 formulas 23 formulas 24
Formula 25 formulas 26 formulas 27
Formula 28 formulas 29
Formula 30
Formula 31
Formula 32 formulas 33
Wherein, W is the substituting group shown in formula a~formula i:
Formula a formula b formula c formula d
Formula e formula f formula g formula h formula i
Ra is 1~4 integer; Rb is 1~9 integer; Rc is 1~2 integer; Rd is 0~2 integer; Re is 0~2 integer; Qf is 2~12 integer; Qg is 2~10 integer.
8. the polyketone that contains sulfonated aromatic group according to claim 5 is characterized in that, the substituting group that described aromatic ether monoprotic acid forms is formula 4, formula 14, formula 34~formula 41: shown in substituting group in one or more:
Formula 4 formulas 1 formula 34
Formula 35 formulas 36 formulas 37
Formula 38 formulas 39
Formula 40 formulas 41
9. a preparation method who contains the polyketone of sulfonated aromatic group claimed in claim 5 is characterized in that, comprising:
Compound shown in the formula I is provided;
Compound shown in the formula 1 is mixed with symmetrical diprotic acid, symmetrical aromatic oxide, acid solvent and/or aromatic oxide monoprotic acid, reacted 4~48 hours, obtain the polyketone that contains sulfonated aromatic group shown in the formula II.
10. a proton exchange membrane is characterized in that, is prepared from by the polyketone that contains sulfonated aromatic group claimed in claim 5.
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Cited By (3)
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CN103554446A (en) * | 2013-10-25 | 2014-02-05 | 武汉工程大学 | Semi-aromatic sulfonated polyether ketone and preparation method thereof |
CN103709379A (en) * | 2013-10-25 | 2014-04-09 | 武汉工程大学 | Aromatic sulfonated poly ketone and preparation method thereof |
WO2023185149A1 (en) * | 2022-03-28 | 2023-10-05 | 中国科学院深圳先进技术研究院 | Sulfonated benzene polyphenyl ionomer and method for preparing same, and proton exchange membrane |
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US20090111027A1 (en) * | 2007-10-26 | 2009-04-30 | Battelle Memorial Institute | Ionically conductive polymer for use in electrochemical devices |
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EP0688824A2 (en) * | 1994-06-24 | 1995-12-27 | Hoechst Aktiengesellschaft | Homogeneous polymer blends on the basis of sulphonated, aromatic polyetherketones |
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JP2007169175A (en) * | 2005-12-20 | 2007-07-05 | Lion Corp | Biphenyl ether derivative or its salt, and external preparation composition |
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CN103554446A (en) * | 2013-10-25 | 2014-02-05 | 武汉工程大学 | Semi-aromatic sulfonated polyether ketone and preparation method thereof |
CN103709379A (en) * | 2013-10-25 | 2014-04-09 | 武汉工程大学 | Aromatic sulfonated poly ketone and preparation method thereof |
CN103709379B (en) * | 2013-10-25 | 2015-12-02 | 武汉工程大学 | aromatic sulfonated polyketone and preparation method thereof |
CN103554446B (en) * | 2013-10-25 | 2016-04-13 | 武汉工程大学 | Semiaromatic sulfonated polyether ketone and preparation method thereof |
WO2023185149A1 (en) * | 2022-03-28 | 2023-10-05 | 中国科学院深圳先进技术研究院 | Sulfonated benzene polyphenyl ionomer and method for preparing same, and proton exchange membrane |
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