AU784308B2 - Composite polyamide reverse osmosis membrane and method for producing the same - Google Patents

Composite polyamide reverse osmosis membrane and method for producing the same Download PDF

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AU784308B2
AU784308B2 AU18307/01A AU1830701A AU784308B2 AU 784308 B2 AU784308 B2 AU 784308B2 AU 18307/01 A AU18307/01 A AU 18307/01A AU 1830701 A AU1830701 A AU 1830701A AU 784308 B2 AU784308 B2 AU 784308B2
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polyfunctional
tertiary amine
amine
tetramethyl
acid
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Jong Eun Kim
Wan Joo Kim
Ja Young Koo
Kee Seop Park
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Toray Chemical Korea Inc
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Saehan Industries Inc
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AUSTRALIA

Patents Act 1990 Saehan Industries Incorporation

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Invention Title: Composite polyamide reverse osmosis membrane and method for producing the same The following statement is a full description of this invention including the best method of performing it known to us:- .4 BA"CKGROUND OF THE INVENTION 1. £ieI'- f the inventicr The creszent invenz:Lon relates, in general, co a ncvel occereve-rse csmosL(-,ss membrane suitabl fo i nd us tril aaricltre or home use and a method for pror-ucing the Same.

2. DescricLtion of thle Prior Art is konthat di;ssolved Substances be secar=-a =d f om th ei so-,.Le nt s by use of var-ious types of se lective eCoe of 0 su ch membranes nciuding 1c~mico mmorne, utreilreto~ membranes and C Cr.-n us-e -ncr ever-se osmcos-*s sutal or inusrial a nd h ome ujse. What is involved in 20 t e a-Lna:-cL' of, brackish wat er or seawazerusn rere ocrncss1s membr-anes is literally a flerincou of salt -a=nd *:oss:§:eo ios orf moleculesz :ro stvwe: er by n~ ne a~vW a reverse osmcsJ s membrane wnercv zz::e wezo toses:nrucn~errecrae -W-i 23D n :e s~e n cz o ase 7-l the m e ,ra-ne. OSnC 1:c oS S 1-r wo aoans t rever-se osmosis process, ano te or c:Dncezrted the feed wa:er, the g-a- the= cs-ot I cpressure which mus: be overcome. Areverse oS-os;s r.=-m.rane, in order to be cc3 L me r c ia II V uSe fu 1 in d esa Ia: i-g bracki sh water or seawater on a large scale, must possess certain properties.

Ce s con croo-e-v is tna- the mem-ranes have a high- salt re. eticn cce:f c ri e n. r: fat, 3r th'.e desalin ated via-or zC be sutbl or man*,. cc~er: aoti r.s, ees osmosis membrane shoCUd haea sa:rjcincac;abillv or 97 Ancn: ncr-ncer.' o: a reve=rse O-sTOsis membrane i s t: h m;n snscsss hich flux ~tezectr~stc, tss evelv large a* nmcutCof wee -Z r C- a elatively low 13 ressures. iolv,-.-lu.::te mem'co-ne slnould be reeer hen 0 cllo,'f:ia~cf§ at a pressure or, 800 ao: Ce::on-S, S ree:.nreent ess tn~a: wn-cn go2 woul:d otebs e de-s-rs Ce= x3 n q eoot0 .fne rux an-- vz verco.4 One comrion t yco c: rev;e S osmosis r-rec-,or -ane i S a sIt-e me m.b rane c mnc r S: ccrtu.s support anid a thnn cc /amide fim rMe ote Co :r s s:cc Too c& 1 am-ide e: c ro o cv an..er.~ polymerization of a QPolyffunctional amine and a PCo-I un C zna cyl U..Pa.No. 4,27, o not ,aot dicoses a :r pr=C= an. Cc-~~e by ntacaI~v~~z~In f two P pr Ia r y amine sub s ti ctu enrts cont-Lai'n in a a rom atiC pclyf u nc tion al 'i with at least three acvl halide functional art ups-con aning aromatic acyl halides. in thie preferred ezomn, a -crous polysulfone supoort, is coated Wi th m-pih.env'enedAiamine in water. A"t-er rernova of excess m-p'henv! -nediam =nine Sol Iu io f f Co7 neC c a S: 0C rtZ tne coated succor:- i s ceee fx a Coh:o Crmecy c: e reacrion iS S2Cstact c -1.e te In s :nJu.

th-e Cadotte membrane as describ ed abocv,;e e xibs 7 Z 1 f-Iu x a nd s alt r eje ct iocn, v-mr 4.ou s a--c roa c h es hae beene taen to fL-urtLher improve th-e flux and salt-, reject- ion of: ccmco-.

polvarni'de reverse osmosis remranes. In addiCtion, otner 20 aoQ.roaches have been taken tlo imocroVe t-.e r e- s Cs ccn I.-e:7 N2 :nc~2> s*~L Tomashke issued in- Octo7,ber, 'jtee~s<~oe aaromatic polvamride mem-btr an.e foe y ccating a microporous support withl an acu,-ecus solu--icn comprisi ng aessentially aromatic Qo-lv/-funot-icnial colvamine ha vi .n a: least two am-Lne funot-ionalI groups aoan ami'ne sa-: ta liquiJd layer or. th ircoo(ssoot b' o the liquid layer with', an organi c solv,;ent sOlution of aaroma-ic amine-react ive reactant cor*Is-*ng a /oiyrnctic4 acv±1 halide or m~mx:-ure therec-f, wh~ere-n thle -aoLe reactant: has, on- t-t a-.eragce, atleas- aozct- 2-2a~ 2 g ro-ups per react-ant mlecule, and drying t-he Droduct- -I n oen a: o0-fu- 1- 1 y ~u so as to fo-rm a wat:er *pe r mea bIe m7.e 1b a stronc acid anod a t ecir I m~ c tec consistn of tra kim-;,s-n amehla.

.triethylamine, tr CrooVlamine; N-ai-kvl,,cvc 'oa -Johbatic ami.~ such. as Il- meth-y ioci de; N-a -a suc as bn cce i c2. I c Irva r ne-: a c o -Z V, ZZ- hydronie :c t ao rcov-.a= on -4um hydCAr 3" ben zvl al v1.'c--a n um hydroxides, su ch as be n zy1 rim e -v Iammc hydroxide, benzy~triethylamnoniu. hydroxfde and benzyltr 4proryamonijur hy-dr-oxide; and mixzures thereof.

3 in U.S. Par. No. 4, 983,291 to Chau al. there 'is disclosed a memb rn, 1:7-h coC-r oi Sze s an interfacialcc.mr~e cc2:on crus s C0. codn to z:hns pazent, saome- .~rn a ra arcae bye cm~n e S z: c rt wi an- aqcue c,:S so C. c o a oc va -Ine !-Ii cIh ma Y, i*f so desired, contai4n a polar aorotcic SCoUt-.en: not reacti2ve wi>the arnines, a compcund anrd a=rn acid acce-- -r The polyhydjric comt:Ccun, h-c' Ma%,icueenl n c backbocne alvoc aycoan :a acuCs solut jron in a amun:raninairo- 01-1 1.Thesur:c:o: ne cca7ed 02a c. oraOeo me suar mae ra jThe reu orosc s t eatze d with a h a cafbc1 cid,0 ov arm auve ne o1arbcxyli acid, am: e sal7- r cLs s ui acid, am_*n.'c acid, aminoic a s aI:, cco'vmeric aci'd and0 oanc ac Q t fc r e d f v c c fn r eerS e s cs 1's e-r a ne.

di -oe eci.

c.o, ya m id e tvYoe s ki .n eaier on a pocr ou s s, :_ort, said_4 mernorane b e 1*-1 r. c' coat a s ciu':i on a con-ainina a cor'-ccund having leas: tor=z,- ye amino groucs on the poro-us s-upporz and', thereafter, co-nzac:_-na a solution. B containing a polifurnctional ac-id halide with t coated layer of sol u t Ion A, wh er en th e difF e r en b Ce t-ween a solubility Parameter orf solution At and a solub -_it -,Ii Darameter of soUtiCon iS I S-1 Examol;:.es o -he solvenzt for solution A ar-e a mixed sol!ventE of wat-er ano4 an alcohol such as er-hanol, oropanol, b no C ntaol, -arnvl alcohcol1, isoamyi alC-cl, isotbu v 1 a I Cno± isooroovl alcohol, undecano- e-no:n± 2-vY- examno 1, octanol, ov ooh ex a.-l CrI alc-- oo, neooe nt-vl gi'vool-, U* a 21 7a I butano-L, alc:ho, ailao o, e-h'nylenel C~ y c anoC dieth-nyl1en7,e alc l etc;a a m _x ed sol ve n- of waeZn nroen ccmzcun rd s;-,cn as n:omtae formaimide, methylformamide,----------- dime :h 1 ~o r mam .je e thvl f o rmam e c. AS an Cx2-c or-0- tn*:e MLK ratZio o0 20 water and the oth*-er- s.o-Lve.nt of Slut-L n 7,h' zs e- a! be staes na: orw=r/et haro ca nb se-lectec n :eranqe of 60-90/4-0-10.

EL22 et her-e is cc.-pzs* rr e n av g a ghness i ar- leas-- 55 n.The polyamide type skin layer comprises the reaoT:_J Qto:c c a ,ocon hai amn arrups and a poiv::-. J:o ie Co--M0c urd- havinc a c Ji-4 halid e groups. p cc' r-n film may be formed by contacting a solut-ion contai'n-ig, for example, m-phenylenediamiLne wit,_h a porous polvsulfone suporting fi;lm so as to form a layer of Ln'e soluaion on the suoqortIna film, then contac- 'na cne f J± m w i zn a solu T:ion orf t r -mesov 1 chlor ide and ho Id I tnho _film in a hot dryer so that a polyvme r f~i 4I-s Z C on r the supporti_:no -nm ti surzace of thle polvami de type skin.

laver can alSo be rfo=e c w in quatr-efnar v a r~nu s a 17 an d *coated a z S o .a.Cr a oan C rme: D5 M± nw7aa,- ia: No_. 6, 0 63 2 7 to IaYu Koo who is an inv-otr ot the present invention, relates toC a oomps.~e Cl"~idCmemran naznchigh salz re'ectior and flux that is :the rea ction. product of pcivf'uno:I'onr.a' aie an I an- am -e e _zc:e r ea ;zctan.t s e Ie c e from..e group consisting o-f a pol funct iona I acv! halide, a poly/funoti*onal s:lC:-v -4id and a co:ina Isoovanaan aii Sn: a Lrsneo a a C oI S re a e ~c~e n s g for eq-_ _a to.

2 5 1:1, 8 SUMMARY OF THE INVENTION Therefore, it desirable that the present invention overcome the above problems encountered in the prior arts and to provide a composite polyamide reverse osmosis membrane having high salt rejection and flux.

It is also desirable that the present invention provide a method for producing a composite polyamide reverse osmosis membrane having high salt-rejection rate and high flux, even though adding a polyfunctional tertiary amine and an acid in a molar ratio that is less than 1:1 compared with conventional ones, after taking account of the fact that, when interfacial-polymerized a polyfunctional amine and an amine-reactive reactant, a polyfunctional tertiary amine and an acid is added into a molar ratio that is greater than or equal to 1:1, as disclosed in U.S. Pat. No. 6,063,278, yielded to the present inventors.

In accordance with one embodiment of the present invention, there is provided a composite polyamide reverse osmosis membrane comprising an interfacialpolymerization product of an aqueous polyfunctional amine solution and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a .:::polyfunctional isocyanate, on a porous support, said aqueous solution further comprising an additional substance selected from the group consisting of a 20 polyfunctional tertiary amine alone, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and a polyfunctional tertiary amine, and a mixture of a polar solvent, a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, said mixture of the polyfunctional tertiary amine salt and the free polyfunctional tertiary amine resulting from the reaction of polyfunctional 25 tertiary amine and acid in a molar ratio that is greater than 1:0 and less than 1:1.

In accordance with another embodiment of the present invention, there is provided a method for producing a composite polyamide reverse osmosis membrane Scomprising the following steps of: coating a porous support with an aqueous polyfunctional amine solution; and contacting the coated support with an aminereactive reactant-containing organic solvent solution to interfacially polymerize said polyfunctional amine with said amine-reactive reactant, thereby forming a polyamide layer on said porous support.

The present invention provides a composite polyamide reverse osmosis membrane comprising an interfacial-polymerization product of an aqueous polyfunctional amine solution and (ii) an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, on a porous support, said aqueous solution comprising a polyfunctional tertiary amine alone, or a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine resulting from the reaction of polyfunctional tertiary amine and acid in a molar ratio that is greater than 1:0 and less than 1:1;.

wherein the polyfunctional tertiary amine is selected from the group consisting of N, N,N',N'-tetramethyl-1,6-hexanediamine, N,N,NN'-tetramethyl- 1 ,4-butanediamine, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, N,NN'N'-tetramethyl- 1,3-butanediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl- 1,8-octanediamine, N,N,N,N-tetramethyl-1,7-heptanediamine, N,N,N',N'-tetramethyl- N, N,N',N'-tetraethyl-1,4- butanediamine, N, N,',N'-tetraethyl- 1,3-butanediamine, N,N,N,N'-tetraethyl-1,3-propanediamine, tetraethlyethylenediamine, N,N,N' N'-tetraethyl-1,n-cyclohexanediamine (wherein n is 2 tetramethyl-l,n-cyclohexanebis (methylamine) wherein n is 2 4).

The present invention also provides a composite polyamide reverse osmosis membrane comprising an interfacial-polymerization product of an aqueous polyfunctional amine solution and (ii) an organic solvent solution comprising 20 an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, on a porous support, said aqueous solution comprising one or more polar solvents, along with a polyfunctional tertiary amine alone, or a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine resulting from the reaction of polyfunctional tertiary amine and acid in a molar ratio that is greater than 1:0 and less than 1:1; wherein the polyfunctional tertiary amine is selected from the group consisting of N,N,N',N'-tetramethyl-l,6-hexanediamine, N, N,N',N'-tetramethyl-1,4butanediamine, N, N'-tetramethyl-2-butene-1,4-diamine, N N, N',N'-tetramethyl- 1,3-butanediamine tetramethyl-1,3-propanediamine, tetramethyl- 1,8-octanediamine, N,N,N'N'-tetramethyl-1,7-heptanediamine, pentanediamine, N,N,N',N'-tetraethy l -1,4-butanediamine, AN,N,NN'-tetraethyl-1, 3butanediamine, N,N,N',N'-tetraethyl-1,3-propanediamine, N,NN,N tetraethylethylenediamine, NN,N N'-tetraethyl-I,n-cyclohexanediamine (wherein n is 2 N,N,N',N'-tetramethyl-1,n-cyclohexanebis (methylamine) (wherein n is 2 4).

The present invention also provides a method for producing a composite polyamide reverse osmosis membrane, comprising the steps of: coating a porous support with an additional substance- containing aqueous polyfunctional amine solution to form a first liquid layer on said porous support, said additional substance being selected from the group consisting of a polyfunctional tertiary amine, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and a polyfunctional tertiary amine, and a mixture of a polar solvent, a polyfunctional tertiary amine salt and a free tertiary amine; coating the coated support with an aqueous polyfunctional amine solution to form a second liquid layer on said first liquid layer; contacting the twice-coated support with an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, so as to interfacial-polymerize said amine-reactive reactant with said polyfunctional amine, thereby forming a cross-linked polyamide layer on said porous support; and washing the product with water after drying.

The present invention further provides a method for producing a composite 20 polyamide reverse osmosis membrane, comprising the steps of; coating a porous support with one or more polar solvents-containing aqueous polyfunctional amine solution to form a first liquid layer on said porous support; coating the coated support with an aqueous polyfunctional amine solution 25 to form a second liquid layer on said first liquid layer, said aqueous polyfunctional amine solution comprising a polyfunctional tertiary amine alone, or a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine; contacting the twice-coated support with an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, so as to interfacial-polymerize said amine-reactive reactant with said polyfunctional amine, thereby forming a cross-linked polyamide layer on said porous support; and washing the product with water after drying.

DETAILED DESCRIPTION OF THE INVENTION The porous support used in the present invention is a microporous support formed of a general polymeric material containing pore sizes which are of sufficient size to permit the passage of permeate therethrough but not large enough so as to interfere with the bridging over of the ultrathin membrane formed thereon. The pore size of the support will generally range from 1 to 500 nanometers inasmuch as pores which are larger in diameter than 500 nanometers will permit the ultrathin film to sag into the pores, thus disrupting the flat sheet configuration desired. Examoles of microporous supports useful in the present invention include those made of a polysulfone, a poiyether, a polyimide, a polyamide, polypropylene and various halogenated polymers, such as polyvinylidene fluoride.

The thickness of the microporous suppor: is not critical to the present invention, however, generally, it is about 25-125 pm (more preferably, 40-75 p m) The polyfunctional amine reactant employed in interfacial pclyverization of the present invention is preferably an essentially monomeric amine having at least two amine functional groups. The amine functional group is typically a primary or secondary amine functional group.

Examples of suitable polyamines include metaphenylenediamine and para-phenylenediamine, and substituted derivatives thereof, wherein the substituen includes, e.g., an alkyl group, such as a methyl group or an ethyl group, an alkoxy group, such as a methoxy group or an ethoxy grc:uc, a hydroxy a- gru, a grod or oe atom.

Ad d Iiion aIM J e p 1 s o f sui--:abole pCcvamines d ~ue alkaniedi a mi_.n es such as 1, 3 -p ro pa n e diJami71e c yc 1o a 11pnac prirrarv d iam in e s, such as cyclohexane diamine, cycloaliphatic secondary diamines, such as piperazine or its derivatives, aromatic secondary amines, such a s N,N'dimethyl-1,3-phenylenediamine, N,N'-diphenylethyiene d_4amlne, benzidine, xvlyene diamine and derivatives thereof. Of 'er, the preferred polyamines are aromatic primary diamines, more preferably metapbhevlenediamine.

The colvfunct-onal amine is cresent in an aoueous so ro an amrn ontr oao:0.-0Wt%- (more referaLy", th-e acucus solution, and the 15 oH o f the aqueous solut Ion ranges 7 to 13. The pH can be adjusted by thle addition ofF an alkali'ne acid acceotor in an' amount ranging from 0.001 to 5 wt, of -he soluti on..

Exampoles of the acid acceptor include hydroxidaes, carboXylates, carbonates, borates, and phoschates of a'lkalim et:a Is, as wel IamS t r ia 1kyvlam in es aool:Ion -to n o amine, tne coucus solution frhr c~~ CofCamlre orac.:uo.ooami'ne sairt resltred* fro the rc:o o:f a PO:: n 7on a tetayaiewith- an acid or- a oz~n:o ert:iarv amine with an acid anhydride. The additrion of' such pclyfunctilonal tertiary. amine or its salt1 to the aqueous solution results in a flux increase of the resultant memorefne. At that time, the salt: of polv-funcz-ional tertiary amine may be added after the polyfunctional terti.ary ami~ne is mixed with the acid (or- acid an-hydri-de), or secarazely added to the aqueous solution.

Examples of the fir-st. class of ooly'uncional tertiary amine useful in the present invention i*nclude, but are not li4Mite to N, N, N'N' -zet-rainethyl-1, 6-hexan-ediam' re, N, N, N'N' -te-tramet~hv- 1,4-b-utan-edia-mi'-ne,

N,N,N'N'-

te~amehyl2-bten-l,4-diemn4 N, N, N' N" -tetrarethyl-l, 3bu ta ed i amrine, N, N, N' N' -tet rametyl-l1, 3-propanediamine, N NN NN' N N, N, N' N'-tetraethyl--, 3-butanediam-Iie, N, ,N,N -t-etrethyl- 1,3-propanediamine, N,N,N'N'--t:rat-viet.v/-ene- an.ine; wi17n N, N, N' N' -tetramethyl-, ,6-hexanediarnine, M, N, N'N' teturamethyl-l1,3-butzanedia-. ine-=, rr~Y-,3 procanediamin-E being pre:erred etC N, N, N'N' etr a m e-hy -1,6 hexanediarnine be-h:moe reereo Lx~~.nolesS- _=aescnd c~s o oIfn:oe are o: c, N, N, :errenIincccez-e:rie(w*-=-ei s -42, end N, N, N' N'-tetranethvl- 1, f-cyc'lohexanebis methylamine) (where4.n n is 2-4).

Exam~ples of thi-e third 'cs of polyfunct-ional tertiary amine include 1, 4-dirnetylpipera7z-ne.

Such polyfunctional tertiary amine is pref''erably present in the aquecu';-S solution' in an amount constituting about 0.5-6 w:--mreoaerbv 0.1-3 o h ~eu solution. Additicna>71, u±eo2yfunctional ami*ne and the polyfunctional tertiar; amin are present in the aqueous solution in a we':.h7 ratic range of about .51101 The salt: o f the poIyv u rc t .o na I t ertiary- am ine is obtained by reacting th*e pol yfunctional tetayamine with a acd (r aidanhy'ride) Examoles of acids suitable for use in the presenrt inventlon include aromatic sulfonic acid, 1- aliLhatic sulfonic aci-d, cvc-Loa ipoha t -c sulfonic acid, sulfuric acid, tr -'fuor'oace:±-c acid, n itc acid, hydr-ochloric ac-id, p 'osohorOic aci-df Ph-csOhic Ad aryl.' chcohor io acid carbxvc aidC and Mi*Xtu resz thereof.

The acid an"ycride i S ex e 7. I L -Ledr- by acet-ic anhydride, procionic anhydride, bul_,vric anhydr ide, he:<an-cio* anhvdr rde, b en zoi-*,c a nhyvd de, sufIcI anr.v jde and.C- mi-*-xtre t:nefeo 7 t-e cresen: nne:ownnt. c yuc:na, tert-'arv amlne and acl'd are simul-aneous v used as acd ves ,t-her molar iS creat-.er T:han 1:0 and less 2 5 than 1 I mcr--e pr ef er Ite moa ratio i s a -e a !-er tan 1: 0 and less than 9. Also, when the Po>/functional tertiary amine and the acid anhydride are simultaneously used as additives, their molar ratio is greater than 1:0 and less than 1:1. However, the molar ratio greater than and less than 1:5 results in excellent addition effects.

The polyfunctional tertiary amine salt in aqueous solution has contents of preferably 0.1-12 wt%, more preferably 0.1-9 wt%.

in addition to zte ooly.functional tertiary amine and/or the polyfuncticnal tertiary amnine salt, the aqueous pclyfunctional amine solution further comprises, one or more pclar solvents being selected from the group consisting of entylene glycol derivatives, propylene glycol derivatives, 1, 3-propanediol derivatives, sulfoxide derivatives, sulfone derivatves, nitrile derivatives, ketone derivatives, urea derivatives, and mixtures thereof. As will be seen bel-cw, the addition of the polar solvents to the solution results in a flux increase of the resultant membrane.

Examples cof ethylene glycol derivatives sui:table for use in the cresent invention include, but are not limited to, *2-me:hox'e~harol, 2-e:hcxyethancI, 2-'ropoxyet hanol, 2butoxyethanol, di (ethyleneglycol) -t-butylmethvl ether, dijechyLeneglycol)hexyl ether, (2-methoxy ethyl) ether, (2echcxveohyl) ether and so on. Examples of 1, 3-propane diol 2 ex 2afa1e inclide, t are not limited to, 1, 3-heptaneilol, 2-ethyl-i, 3-hexanediol, 1, 3-hexanediol and 1, 3-pentanediol.

Examoies of sulfoxide der-ivatives useful in the present invention include, but. are no: limi;ted to, dimethyl sulfoxde, tetramethylene sulfoxide, butyl suifoxide and methyiphenylI sulfoxide. The sulfone derivatives are exemplified by dimethylsulfone, tetramethylene sulfone, butyl sulf'one and so on.

Nizrile derivatives are prfrbyselected from r group consisti-,ng Of acetonitri- le and propionitrile.

Examples of urea derivatives include 1,3-dimethyl-2- .jndazol dinone, and ketone derivati-vesz include acetone, 2butanone, -hxroe -eao, -et-cec%,clohe xanone, and cvcloont.,..

The -n 7 re solvents :eac-ueous solution 1-3 oreferablv corszitute total amounts Of aboCut 0.01-8 Wt% of tea'oueou,-S cion Where an alkoxyethanol is used as a p~olar Solven~t, it preferably constitutes about 0.04-4.0 wt', of the acueous *solution. Where 1-pentanediol is used as a polar solvent, it p ref e ra bly c3nistz:itzu t es abo ut7 0.011 .0 w of t-ne acau eoCus solutiLon. W hee a but-l suif4 oxide- isusrasa oa s o Iventz:, i t p re e rab con Stiues a*-out- :i Ct% or: tne acueous solut-ion. Wh-ere a me suifxide is used as a oerscilven:-, it- preferably ccs -sabout 0.01-1.0 253 c..of the acuer -us scliut--on. Where a burP 1 :One is used as a polar solvent, it preferably constitutes about 0.01-1.0 wt% of the aauecus solution. Wher-e a ketone dierivative is used as a polar sovnt t preferably constitutes about 0.01-4.0 wt5 ofthe aqu-eous solution.

Insmlaeu diinmanner, the sumDoort is coat-ej wit Such polazr aovns alona with the polyfunctional t~tar- ne alone or ti '-Cemaxture of plfntoa tertiary amine salt and free polyfunctional tertiary amine, added to the aqueous polyfunctional amine solution. in a sequential addit-ion manner, the support is coaze,- o-lv :D.Lar so-lvent-added aqueous polyfunctional amine slto and then wit'zh aqueous polyfunctionial amine solution (1) coc s ng the o~yotIi:-7io .na I ter"iary ami'ne alon-e or the of zD 0>:r of oov cie tert:r. m7n 1al an 7 ry a Th e~ la: er m.a n.ne r naS mcr Th amierate reactant is present in ancr-' solvent solution immiscible with wate-r, and has contents of about 0.005-3 wtz-, preferably 0.01-0.5 Examples the organic solvent include hexane, cyclohexane, hectane, alkanes havi-no frm 8 to 12 ca=rbon atoms, and halogen:-atec hydrcarbons, such as thi O seri*es. ISO.:-A"P. solvent. used inth followina examoles is a mi--xt;ure of alkanes hv n.

c-.m to 12 car-bon- a, method for procuc-ro teco7moosr-'e r-ev.-erse om:~ membrane throuch interfacial-polymerizaion by a contact of an addition substance-conain4. aqueous polyfunctional amine solution wit-h an an amine reactive reactantcontaining organic solvent solution is as follows; In one embodiment, the method comprises the steps of coating a porous support with an additional substan-cecontaining aauecus polyfunctional amine solutt4n to frm a first liuid layer on said porous succort, said addi:L-on substance being selected from the group co-sisting of a polyfuncticnal tertiary amine, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and a polyfunctional tertiary amine, an.

mixture a cc-'1 Slve, a poly.unczonai tertiary amine salt and a free polyfunctior.al tertiary amine; (ii) coating the coated support wth an aaueous polyfunctional amine solution to form a second liq,-uid, layer on said first :liquid layer; (iii) contacting the twi an organic solvent solution comorising an amune-reacTave reactant selected from the group ccnslsting or a polyfunctional acyl halide, a polyfunctional sulfonyl halide, and a pclyfunctional isocvanate, so as to inerfacpolymerize said amn.ine-reactive reactant with aid polVfUnc:zonaI am-ine, thereby f o formin a crcss-lnked polyamide layer on the coro-us S20rt; and iv washn-,, o.,e In another embod1iment:, th-e m7,ethod,_ comprises the steps of coating a corous succorrr: wvith one or more crolar solvents -conta in ing acueous clvfurnctional amine s olut io n t o f orm a first lq u Jd lav e r o n sa.-'d su po rt; i coating the ooated support with an aqueous polyfunct-ional amine solution (1 comprising a polyfunctional tertiary amine alone or a mixture of polyfunctional tertiary amine salz and free polyfunczional te _arv amine to form a second liquid layer on. said fi*rst licuid layer; (i~i con-acting the twice-coated porous sucport- 4iha a:7~ C reac7oant-contai ni4ng or~ian_* s o I v ZS 0 U: zo_. 3, so as to -vmer- e: C d ae ie- recive reVtn I "n s ai-d oIyvun c t i cna:z amin, th.ereby fo rmi n a cross-' nk d ;D cpIoLv-aid e la-ver on sai z orous succ LV, a Lc av wa-hn :e 15 product with water a-'ter drying.

better uestnigof the cresent invention may be *obtained in lia:hzt o-f the following examples which are set forth to il lustrae buT- are nor- to be construed to limit the present inven:-ion.

*EXaM DT.

A 10 pam thi-k I mcroCoCr c us c- r Incucn 1:ne= wa n o-~ve sr: .Essee na acaue ou s sol Iu t Incr co ic 1.6 -4aminre MPD) and 0. 6 wt! N,N, N' -tetramethyl-1, 6-hexanediJamine (TMHD) for 4-0 seconis and then excess solu-icn is removed frmthe suc'ccrr cvl a o 11 ef. Th -e su-cppor t W a3C'_ dc Ce d i n 0. 1 wt% solution of trimesoyl chloride (TMC) in Isopar 0 solvent (Exxon Corp.) for 1 minute followed by draining the excess organic solution of-- the supportl. The resulting composite memtbrane was -i-ridfor about I minute and then rinsed in 0.2 wt% Na 2 CO: aoueous solution for 30 minutes at room temperature before the performance test. The performance of the reverse osmosis membrane was measured by passing an ac_=u sCIU-:icn con. 2000 cpm of- NeCI trouo the mermorane at ps_. As the result, the sa'l: rej-ction was 96.3 %and t~ lx.;s4.~a'd.

EXAMPLES 2-16 AND COMPARA.TIVJE EXAMPLE A The same procedure as set forth in Examcle 1 was carried out for each of Examples 2-16 and Comparar:Ive **Example A, except that the concentrations of MPD and T.MHD listed in Tatle 1 wer-e used insread of those in Example 1.

I Re on MDTH 2~ 4 0 I 3.

0.1 21.9 95.8 27, 2.2 9 E 7~.

0 -13 6.2 91 7 0.5 55.3 95.6 1 0.3 94.7 63.5 1.25 1.6 0.2 2S.1 I ,8 I j 042.1 3.6 j 4 13 .0 0.3 i 6.7 -3 0.3 4 2.0 0.6 3 9 9. 2.

2.0 92 EXAMPLE 17 The same procedure as set for h i Exam:olDIe 1 was reeated, excecto te:a- a mixtufe of 0 6 wr- TXHD an.d 0.06 wt% toluenesulfonic acid wSAi a uosed J o- or.> wt% TH. 2 aZc~ tIe reIx cf z re s a rnt mermrane were 3-.9 d c nd 97 e scec -7v EXAMPLES 18-25 AND COLMPAR.ATT EX>?LE 3 The same procedure as set forth in Example 1 was carried out for each of Examples 18-25 and Comparative Exarrle B, ex cect c a arous cccentrai"ns on f MP D, TMHD, aci d s Cluen s Sari a-d aceni7 acid- and acetic anr.:ore ~s lis~7=d in Ta-le 2, blw wre used instead of corns::e re vers e oss meSae a e S er c errne and the results are given in Table 2, below.

TABLE 2 EXAMPLE 26 0* The same procedure as set forth in Example 17 was repeated, efxcepn tnao 0.2 wt% 2 -ethyl-!, 3-hexanediol (EHD) was added to the aqueous solution containing MPD, TMHr) and TSA. The flu:, an.d :bN sal: re'ection of che resulvant membrane were 4Q.7 cf~d and 96.6 repectivelv.

EXAi'PLES 27-39 The same procedure as set forth in Example 1 was repeated for each of Examples 27-39, exceot that various concentrations of MK, DO>, TSA, AdOC and various organic solvents as liedi Ta 3 were used. The obtained reverse osmosis *emrae as measured fozr i :s performance and the re=slt-s are given in Table 3, below. (in Table 3, "MEE" stands for 2-methoxyethyle:her-; "BUT" stands for 1butanol1; "BE" stands for 2 bu;Itoxye!t-hanoI; "DEGEE" stands for diethyleneglycolethyl ether; "CYHE-X" stands fcor cyolohexane; and "DIMSO" stands for intvslode TABLE 3 -1 TSa Ac'H 0'-a icz S oive- z R-'-t at (M-v e 2 9_ i I. I I _9 6 3 3 I1 6 f 0 6 I 3 1j.6 [0 D 47 3E__ 1.61 i F SE [1.6 _F 1 3 9 1 i.6 1 1 U~ EXAMPLE Th-ie s a re orccedur-e as set- frh n 7. Y ce 2.was repeated, exc=ept 1.6 wt3- o rmeteochenvlenedcl,7iaine

(MPD)

an 05 wt z of: N ,N'N IN'z-tera etv-I I,6 n<e dI a m r.e w er e emplo ye d i4n s tea d of 1.6 -oi z o f r y Ie -e d Iami4n e _j a d 0 .6 w t of N, N' t=t-r amev-l6 ex. ed -eam Jne. Th'Ie f.lux andt the saltIz rejection ortz rslant membrane were 3L c fd anrd 9-.9 r. e c z v V EXAMPLZS 41-53 AND COMPARATIVE EXAMPLES C-F Jo.

.o The same procedure as set fcoh in Example i was repeated for each of Examples 41-53 and Compara:ive Exanples C-F, except that various concentrations of MD, amines and various organic solvents as listed in Table 4 were used instead of 1.6 wt% metaphenylene diamine (MPD) and 0. 6 wt% N, N, N' ,N'-tetramethyl-1, 6-hexanediamine (TMHD) The obtained reverse osmosis membrane was measured for its performance and the results are presented in Table 4, below.

TABLE 4 Exampne. I~*t 41 j19.0 96.6 1 42 F 1 T S EW 3) 2F 9. a 1 43 1.6 TY-5D F- 2 (1(i .3 96. 0 1 44 1. F AS +DMS (3 3 .6 4 1.6 1 MEu' 5. 1.6 I F D~ 33 4 ~rCom 1.6 3 TMED J_ 93.7 47' 1.6 THED EHD 28.4 92.4 zrox.. F TEA 14.9 j 96.3 TEA 94.5 48 I .6 TZ 10.5) D 2 96.5 3 49. 1 1 22.6 96.9 I3 E D (0.21 31. 97 .4 1.6 1 .11 1- 1 2 94.9 F F a. F .9 95.3 1,4. P 1.2) EH 14. 97.1 Accordingly, thusly prepared cooit rvre cs~i 24 membrane having high flux and excellent salt rejection can be used in industrial watercleaning systems or home purifiers, useful in the desalination of brackish water or seawater.

The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.

~Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

.ooo°i

Claims (16)

1. A composite polyamide reverse osmosis membrane comprising an interfacial-polymerization product of an aqueous polyfunctional amine solution and (ii) an organic solvent solution comprising an amine- reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, on a porous support, said aqueous solution comprising a polyfunctional tertiary amine alone, or a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine resulting from the reaction of polyfunctional tertiary amine and acid in a molar ratio that is greater than 1:0 and less than 1:1; wherein the polyfunctional tertiary amine is selected from the group consisting of N,N,N',N'-tetramethyl-1,6-hexanediamine, AN,N, N''-tetramethyl- 1,4-butanediamine, N, N,N',N'-tetramethyl-2-butene-l1,4-diamine, tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, AN,N, N'-tetramethyl-1,8-octanediamine, N,NNN-tetramethyl- 1,7- heptanediamine, N, N,N',N'-tetramethyl-1,5-pentanediamine, NN,N',N'- .:tetraethyl-1,4- butanediamine, A, NN',N'-tetraethyl-1,3-butanediamine, A, N,N'-tetraethyl-1,3-propanediamine, NNN', N'-tetraethlyethylenediamine, N,N,N',N'-tetraethyl-l,n-cyclohexanediamine (wherein n is 2 tetramethyl-l,n-cyclohexane bis (methylamine) wherein n is 2 4).
2. A composite polyamide reverse osmosis membrane comprising an I interfacial-polymerization product of an aqueous polyfunctional 25 amine solution and (ii) an organic solvent solution comprising an amine- reactive reactant selected from the group consisting of a polyfunctional *acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, on a porous support, said aqueous solution comprising one or more polar solvents, along with a polyfunctional tertiary amine alone, or a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine resulting from the reaction of polyfunctional tertiary amine and acid in a molar ratio that is greater than 1:0 and less than 1:1; wherein the polyfunctional tertiary amine is selected from the group consisting of N,N,N',N'-tetramethyl-1,6-hexanediamine, NN,N',N'-tetramethyl- 1,4-butanediamine, NN, ,N',N'-tetramethyl-2-butene-1,4-diamine, tetramethyl-l,3-butanediamine tetramethyl-1,3-propanediamine, tetramethyl- ,8-octanediamine, N,N,N',N'-tetramethyl-1,7- heptanediamine, N, N'-tetramethyl-1,5-pentanediamine, N,N, tetraethyl-1,4-butanediamine, N,N,N',N'-tetraethyl-1, 3-butanediamine, N,N, N',N'-tetraethyl-1,3-propanediamine, N, N, N, N tetraethylethylenediamine, N,N,N',N'-tetraethyl-l,n-cyclohexanediamine (wherein n is 2 N,N,N',N'-tetramethyl-1,n-cyclohexanebis (methylamine) (wherein n is 2 4).
3. The membrane as set forth in claim 1 or 2, wherein the polyfunctional tertiary amine is present in said aqueous solution in an amount constituting 0.05-6 wt% of said aqueous solution.
4. The membrane as set forth in claim 1 or 2, wherein the mixture of the 15 polyfunctional tertiary amine salt and the free polyfunctional tertiary amine is present in said aqueous solution in an amount constituting 0.1- 12 wt% of said aqueous solution.
5. The membrane as set forth in claim 1 or 2, wherein the polyfunctional amine has at least two primary or secondary amine functional groups.
6. The membrane as set forth in claim 1 or 2, wherein the polar solvent is selected from the group consisting of ethylene glycol derivatives, propylene glycol derivatives, 1,3-propanediol derivatives, sulfoxide 25 derivatives, nitrile derivatives, ketone derivatives, urea derivatives and mixtures thereof.
7. The membrane as set forth in claim 1 or 2, wherein the polar solvent is present in said aqueous solution in an amount constituting 0.01-8 wt% of said aqueous solution.
8. The membrane as set forth in claim 1 or 2, wherein the acid is selected from the group consisting of aromatic sulfonic acid, aliphatic sulfonic acid, cycloaliphatic sulfonic acid, sulfuric acid, trifluoroacetic acid, nitric acid, hydrochloric acid, phosphoric acid, alkyl phosphoric acid, aryl phosphoric acid, carboxylic acid and mixtures thereof.
9. The membrane as set forth in claim 1 or 2, wherein said acid is replaced with an acid anhydride.
10. The membrane as set forth in claim 10, wherein the acid anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, hexanoic anhydride, benzoic anhydride, sulfonic anhydride and mixtures thereof.
11. The membrane as set forth in claim 8, wherein the polyfunctional tertiary amine and the acid anhydride are mixed in a molar ratio that is greater than 1:0 and less than 1:0.5.
12. A method for producing a composite polyamide reverse osmosis 15 membrane, comprising the steps of; coating a porous support with an additional substance containing aqueous polyfunctional amine solution to form a first liquid layer on said porous support, said additional substance being selected from the group consisting of a polyfunctional tertiary amine, a mixture of a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine, a polar solvent and a polyfunctional tertiary amine, and a mixture "of a polar solvent, a polyfunctional tertiary amine salt and a free tertiary S: amine; contacting the coated support with an organic solvent solution 25 comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, so as to interfacial-polymerize said amine- reactive reactant with said polyfunctional amine, thereby forming a cross- linked polyamide layer on said porous support; and washing the product with water after drying.
13. A method for producing a composite polyamide reverse osmosis membrane, comprising the steps of; coating a porous support with one or more polar solvents-containing aqueous polyfunctional amine solution to form a first liquid layer on said porous support; coating the coated support with an aqueous polyfunctional amine solution to form a second liquid layer on said first liquid layer, said aqueous polyfunctional amine solution comprising a polyfunctional tertiary amine alone, a polyfunctional tertiary amine salt and a free polyfunctional tertiary amine; contacting the twice-coated support with an organic solvent solution comprising an amine-reactive reactant selected from the group consisting of a polyfunctional acyl halide, a polyfunctional sulfonyl halide and a polyfunctional isocyanate, so as to interfacial-polymerize said amine-reactive reactant with said polyfunctional amine, thereby forming a cross-linked polyamide layer on said porous support; and washing the product with water after drying.
14. The method as set forth in claim 12 or 13, wherein the mixture of the 15 polyfunctional tertiary amine salt and the free polyfunctional tertiary amine is obtained by mixing the polyfunctional tertiary amine with the acid or the acid anhydride in a molar ratio that is greater than 1:0 and less than 1:1.
15. A composite polyamide reverse osmosis membrane substantially as hereinbefore described with reference to the examples and/or the preferred embodiments and excluding, if any, comparative examples.
16. A method for producing a composite polyamide reverse osmosis 25 membrane substantially as hereinbefore described with reference to the examples and/or the preferred embodiments and excluding, if any, comparative examples. Dated this twenty-third day of December 2005 SAEHAN INDUSTRIES INCORPORATION Patent Attorneys for the Applicant:- F.B.RICE CO
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014054A1 (en) * 1979-01-10 1980-08-06 Midwest Research Institute Process for the production of a reverse osmosis membrane, reverse osmosis membrane thus produced, and use of such membrane in a desalination process
EP0316525A2 (en) * 1987-11-18 1989-05-24 The Dow Chemical Company Polyamide reverse osmosis membranes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014054A1 (en) * 1979-01-10 1980-08-06 Midwest Research Institute Process for the production of a reverse osmosis membrane, reverse osmosis membrane thus produced, and use of such membrane in a desalination process
EP0316525A2 (en) * 1987-11-18 1989-05-24 The Dow Chemical Company Polyamide reverse osmosis membranes

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