CN103073719A - Polybenzimidazole with sulfonated side chain and preparation method thereof - Google Patents

Polybenzimidazole with sulfonated side chain and preparation method thereof Download PDF

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CN103073719A
CN103073719A CN2013100252192A CN201310025219A CN103073719A CN 103073719 A CN103073719 A CN 103073719A CN 2013100252192 A CN2013100252192 A CN 2013100252192A CN 201310025219 A CN201310025219 A CN 201310025219A CN 103073719 A CN103073719 A CN 103073719A
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polybenzimidazole
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sulfonic acid
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徐铜文
张正辉
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University of Science and Technology of China USTC
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Abstract

The invention provides polybenzimidazole with a sulfonated side chain. The content of sulfonic acid groups in polybenzimidazole is controllable. The polybenzimidazole 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 polybenzimidazole with the sulfonated side chain. In addition, the invention further provides the proton exchange membrane.

Description

Polybenzimidazole of a kind of pendant sulfonic acid and preparation method thereof
Technical field
The present invention relates to polymkeric substance and preparation field thereof, relate in particular to polybenzimidazole of a kind of pendant sulfonic acid 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 and the methanol fuel rate of permeation is high, therefore develops the focus that new cheap proton exchange membrane becomes research.Wherein Sulfonated aromatic polymer such as polyetherketone, polyethersulfone, polyimide, polybenzimidazole etc. receive people's concern.Benzimidazole structure in the polybenzimidazole has certain alkalescence, can produce soda acid with sulfonic acid group and interact, and therefore Sulfonated polybenzimidazole has high swell-resistant, and the low advantages such as fuel permeability are very potential proton exchange membrane materials.
The polybenzimidazole of side chain sulfonation synthesizes first polybenzimidazole usually in the document, carry out again post-modification namely by alkaline metal hydride such as lithium hydride, active hydrogen on the p-poly-phenyls such as sodium hydride and the imidazoles main chain imidazoles unit nitrogen metallizes, again by nucleophilic substitution reaction (such as GLIPA X, EL HADDAD M, JONES D J, et al.Synthesis and characterisation of sulfonated polybenzimidazole:a highly conducting proton exchange polymer[J] .Solid State Ionics, 1997,97 (1 – 4): 323-331.) or ring-opening reaction (such as KAWAHARA M, RIKUKAWA M, SANUI K, et al.Synthesis and proton conductivity of sulfopropylated poly (benzimidazole) films[J] .Solid State Ionics, 2000,136 – 137:1193-1196.) introduce the pendant sulfonic acid group, react schematically as follows:
Figure BDA00002765951400021
Wherein the service requirements reaction system of alkaline metal hydride is strictly anhydrous, and reaction process is complicated in addition, is difficult to quantitatively carry out.The more important thing is by the quantity of the sulfonic acid group in the polybenzimidazole of the synthetic side chain sulfonation of these N-alkylation modification methods always less than the quantity of benzoglyoxaline group (in theory, most acid sulfonic acid group can be by the neutralization of the benzoglyoxaline group of alkalescence, cause the proton number that can dissociate to greatly reduce) and be difficult to accomplish the quantity of sulfonic acid group greater than the quantity of benzoglyoxaline group, this has caused low proton conductivity (to be usually less than 10 -3The S/cm magnitude) can not satisfy the requirement of Proton Exchange Membrane Fuel Cells.
Summary of the invention
Polybenzimidazole that provides a kind of pendant sulfonic acid and preparation method thereof is provided the technical problem to be solved in the present invention, the sulfonic acid group content of described polybenzimidazole is controlled, and this polymkeric substance 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 the polybenzimidazole of the pendant sulfonic acid shown in a kind of formula I:
Figure BDA00002765951400022
X=0.01～0.99 wherein; N is 1～400; 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 di-carboxylic acid forms one or more; A kBe in the substituting group of bisbenzimidazole compound formation 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 di-carboxylic acid formation:
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.
Preferably, the substituting group of described bisbenzimidazole compound formation is one or more in the substituting group shown in the formula 14-formula 18:
Figure BDA00002765951400042
Figure BDA00002765951400051
The present invention also provides a kind of preparation method of polybenzimidazole of pendant sulfonic acid, comprising:
Pendant sulfonic acid monomer shown in the formula II is mixed with di-carboxylic acid monomer, bisbenzimidazole monomer and acid solvent, reacted 4～48 hours, obtain the polybenzimidazole of the pendant sulfonic acid shown in the formula I.
Figure BDA00002765951400052
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
According to the present invention, the preparation method of the polybenzimidazole of the pendant sulfonic acid shown in the described formula I is specially: with the compound shown in the foregoing formula II and di-carboxylic acid monomer, bisbenzimidazole monomer 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 polybenzimidazole of the pendant sulfonic acid that form exists again will be with H +The polybenzimidazole of the pendant sulfonic acid that form exists namely is able to the polybenzimidazole of the pendant sulfonic acid of other cationic form existence with corresponding alkali neutralization.
According to the present invention, described di-carboxylic acid monomer is preferably one or more in the di-carboxylic acid compound shown in formula 19～formula 31, because described di-carboxylic acid monomer contains two carboxylic acid functionals that acylation reaction can occur, can represent with AA type monomer.
Di-carboxylic acid compound shown in table 1 formula 19～formula 31
Figure BDA00002765951400061
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 bisbenzimidazole monomer is preferably one or more of the bisbenzimidazole compound shown in formula 32～formula 36; owing to only being in two phenyl ring at molecule two ends in the described bisbenzimidazole compound acylation reaction can occur, can represent with BB type monomer.
Figure BDA00002765951400072
According to the present invention, the mole between the pendant sulfonic acid monomer shown in the described formula II, di-carboxylic acid monomer, bisbenzimidazole monomer adds than being X QBB: X AA: X BB, X wherein QBB, X AA, X BBAll greater than zero and X QBB+ X BB=X AA, acid solvent adds 2～8L by every moles of dicarboxylic acids present monomer.According to the present invention; the copolyreaction of described monomer is to obtain by the formula acylation reaction of paying between carboxyl and aryl; bisbenzimidazole monomer wherein obtains before polymerization, avoided in the polycondensation process of tetramines aromatic monomer and dianhydride monomer in the traditional method easily crosslinked shortcoming.Be preferably 60～150 ℃ according to temperature of reaction of the present invention, more preferably 80～100 ℃.
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.According to the present invention, described proton exchange membrane can use the polybenzimidazole of the pendant sulfonic acid shown in the formula I 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 polybenzimidazole of the pendant sulfonic acid shown in the formula I, contain simultaneously the sulfonic acid group of side chain and the benzimidazole structure of main chain, wherein sulfonic acid group provides high ionic conductivity and interaction of hydrogen bond between the sulfonic acid group of benzimidazole structure and side chain provides the water-fast swelling property of film.Prior, the quantity of sulfonic acid group can much larger than the quantity of benzoglyoxaline group, satisfy the requirement of Proton Exchange Membrane Fuel Cells so that higher proton conductivity to be provided in the proton exchange membrane of the present invention's preparation.
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 Vector22, 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 80 ℃, and relative humidity is 100%.
The measuring method of the loading capacity of film (IEC) is the film sample (H that cuts 3 * 3cm +Type cationic exchange membrane, dry film heavily are designated as W Dry), at the 1mol of 100mL dm -3Soak 24h in the NaCl solution so that the H in the film +Fully by the Na in the solution +Ion-exchange out, then take phenolphthalein as indicator, (concentration is designated as C with standard NaOH solution NaOH(mmol cm -3)) being titrated to terminal point, the quota of expenditure NaOH of titration institute liquor capacity is designated as V NaOH(cm -3), IEC calculates as follows:
IEC＝C NaOH×V NaOH/W dry。
Embodiment 1: bisbenzimidazole monomer synthetic
The example that synthesizes with a kind of bisbenzimidazole monomer: successively with 1.0 moles 3,3 ' N-Methyl pyrrolidone of p-diaminodiphenyl (purity is 97%), 2.0 moles 4-phenoxy group Benzoyl chloride (purity is 97%) and 0.5 liter adds in 1.0 liters of reaction flasks of logical nitrogen, 25 ℃ of lower mechanical stirring reactions are after 12 hours, be warmed up to 180 ℃ of lower reactions 4 hours, pour into after the cooling in rare NaOH aqueous solution, filter, water and ethanol repetitive scrubbing get bisbenzimidazole monomer (productive rate is 90%) and can be directly used in next step polymerization after the vacuum-drying.In the infrared spectrum at 1625cm -1The imidazoles charateristic avsorption band appears in (C=N, in strong), and reaction formula is as follows:
Figure BDA00002765951400101
Embodiment 2:
Successively with 1.00 moles 4,4`-phenyl ether dioctyl phthalate, 0.99 synthetic bisbenzimidazole monomer among the mole embodiment 1,0.01 2 of mole, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 80 ℃ 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 NaOH solution soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to Na +The side chain that form exists contains the polymkeric substance of sulfonic acid group.In the infrared spectrum at 1646cm -1About the carbonyl charateristic avsorption band occurs and almost do not observe the absorption peak of carboxyl, 1625cm -1About the imidazoles charateristic avsorption band appears, show the generation of polyamides glycosylation reaction and the introducing of benzimidazole unit; Proton nmr spectra confirms that the ratio that the structure of resulting polymers reaches by each structural unit of integration ratio calculating gained conforms to expection, 1H NMR (400 MHz, DMSO-d6) δ (ppm): 13.1 (N-H), 8.6-7.0 (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 1.85dL/g simultaneously, is indicated as high-molecular weight polymer.
Wherein, described 2, the preparation method of two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-is:
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 (400 MHz, 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:
Embodiment 3:
Successively with 1.00 moles 4,4`-phenyl ether dioctyl phthalate, 0.50 synthetic bisbenzimidazole monomer among the mole embodiment 1,0.50 2 of mole, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, method preparation according to embodiment 2, and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 100 ℃ 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 NaOH solution soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to Na +The side chain that form exists contains the polymkeric substance of sulfonic acid group.In the infrared spectrum at 1646cm -1About the carbonyl charateristic avsorption band occurs and almost do not observe the absorption peak of carboxyl, 1625cm -1About the imidazoles charateristic avsorption band appears, show the generation of polyamides glycosylation reaction and the introducing of benzimidazole unit; Proton nmr spectra confirms that the ratio that the structure of resulting polymers reaches by each structural unit of integration ratio calculating gained conforms to expection, 1H NMR (400 MHz, DMSO-d6) δ (ppm): 13.1 (N-H), 8.6-7.0 (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 2.15dL/g simultaneously, is indicated as high-molecular weight polymer.
Embodiment 4:
Successively with 1.00 moles 4,4`-phenyl ether dioctyl phthalate, 0.25 synthetic bisbenzimidazole monomer among the mole embodiment 1,0.75 2 of mole, two (3-sulfonation propoxy-) the biphenyl disodiums of 2`-, method preparation according to embodiment 2, and 4 liters of Eton reagent add in the reaction flask of logical nitrogen, 120 ℃ 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 NaOH solution soaking at room temperature of 0.1mol/L after 24 hours more repeatedly, and vacuum-drying namely is able to Na +The side chain that form exists contains the polymkeric substance of sulfonic acid group.In the infrared spectrum at 1646cm -1About the carbonyl charateristic avsorption band occurs and almost do not observe the absorption peak of carboxyl, 1625cm -1About the imidazoles charateristic avsorption band appears, show the generation of polyamides glycosylation reaction and the introducing of benzimidazole unit; Proton nmr spectra confirms that the ratio that the structure of resulting polymers reaches by each structural unit of integration ratio calculating gained conforms to expection, 1H NMR (400 MHz, DMSO-d6) δ (ppm): 13.1 (N-H), 8.6-7.0 (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 5:
Get 1 the gram embodiment 4 in resulting polymers be dissolved in 18 the gram N-Methyl pyrrolidone in, be mixed with homogeneous solution, be applied on the clean horizontal glass plate, 60 ℃ of lower solvent flashings are approximately after 18 hours, after on glass peeling off, immersion namely got the acid type proton exchange membrane after 24 hours in the dilute hydrochloric acid of 1mol/L with film.80 ℃ of proton conductivities reach 0.13S/cm, and the tensile strain rate of film before and after 80 ℃ of swellings is lower than 15% simultaneously.
More than used specific case principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out 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 (5)

1. the polybenzimidazole of the pendant sulfonic acid shown in the formula I:
Figure FDA00002765951300011
X=0.01～0.99 wherein; N is 1～400; 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 di-carboxylic acid forms one or more; A kBe in the substituting group of bisbenzimidazole compound formation one or more.
2. the polybenzimidazole of pendant sulfonic acid according to claim 1 is characterized in that, the substituting group that described di-carboxylic acid forms is one or more in the substituting group shown in formula 1～formula 13:
Figure FDA00002765951300012
Figure FDA00002765951300021
Wherein, W is the substituting group shown in formula a～formula i:
Figure FDA00002765951300022
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.
3. the polybenzimidazole of pendant sulfonic acid according to claim 1 is characterized in that, the substituting group of described bisbenzimidazole compound formation is one or more in the substituting group shown in formula 14～formula 18:
Figure FDA00002765951300023
Figure FDA00002765951300031
4. the preparation method of the polybenzimidazole of a pendant sulfonic acid claimed in claim 1, it is characterized in that, di-carboxylic acid monomer, bisbenzimidazole monomer, side chain sulfonated monomers and acid solvent are added the polybenzimidazole that obtains the pendant sulfonic acid shown in the formula I in the reaction flask that leads to nitrogen.
5. a cationic exchange membrane is characterized in that, right to use requires the polybenzimidazole of 1 described pendant sulfonic acid to be prepared from.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106255715A (en) * 2014-04-15 2016-12-21 西蒙·弗雷泽大学 The ionene that hydroxide is stable
CN108400362A (en) * 2018-02-05 2018-08-14 大连理工大学 A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof
CN113150344A (en) * 2021-04-21 2021-07-23 常州大学 Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005139318A (en) * 2003-11-07 2005-06-02 Toyobo Co Ltd Composition containing polybenzimidazole compound containing acid group
CN102731811A (en) * 2012-06-20 2012-10-17 中国科学技术大学 Homogeneous anion exchange membrane and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005139318A (en) * 2003-11-07 2005-06-02 Toyobo Co Ltd Composition containing polybenzimidazole compound containing acid group
CN102731811A (en) * 2012-06-20 2012-10-17 中国科学技术大学 Homogeneous anion exchange membrane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHENGHUI ZHANG ET AL: "Novel aromatic proton-exchange polyelectrolytes via polyacylation of pre-sulfonated monomers", 《J.MATER.CHEM》, 18 May 2012 (2012-05-18), pages 13996 - 14000 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106255715A (en) * 2014-04-15 2016-12-21 西蒙·弗雷泽大学 The ionene that hydroxide is stable
CN106255715B (en) * 2014-04-15 2020-01-17 西蒙·弗雷泽大学 Hydroxide-stabilized ionenes
CN108400362A (en) * 2018-02-05 2018-08-14 大连理工大学 A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof
CN113150344A (en) * 2021-04-21 2021-07-23 常州大学 Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof
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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