CA1267486A - Process for preparing sulfonated poly(aryl ether) resins - Google Patents
Process for preparing sulfonated poly(aryl ether) resinsInfo
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- CA1267486A CA1267486A CA000517951A CA517951A CA1267486A CA 1267486 A CA1267486 A CA 1267486A CA 000517951 A CA000517951 A CA 000517951A CA 517951 A CA517951 A CA 517951A CA 1267486 A CA1267486 A CA 1267486A
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- resin
- aryl ether
- silyl
- residuum
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Abstract
PROCESS FOR PREPARING
SULFONATED POLY(ARYL ETHER) RESINS
ABSTRACT OF THE DISCLOSURE
Poly(aryl ether) resins having repeat units of the structure -O-E-O-E'-wherein E is the residuum of a dihydric phenol and E' is the residuum of e benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and pars to the valence bonds, can be sulfonated by first reacting with a silyl halosulfonate, or the combination of a silyl halide and a halosulfonic acid, to form a resin having pendant silyl sulfonate groups, followed by the base cleavage of the silyl moiety to form the sulfonated resin. The sulfonated resins may be used to make membranes.
SULFONATED POLY(ARYL ETHER) RESINS
ABSTRACT OF THE DISCLOSURE
Poly(aryl ether) resins having repeat units of the structure -O-E-O-E'-wherein E is the residuum of a dihydric phenol and E' is the residuum of e benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and pars to the valence bonds, can be sulfonated by first reacting with a silyl halosulfonate, or the combination of a silyl halide and a halosulfonic acid, to form a resin having pendant silyl sulfonate groups, followed by the base cleavage of the silyl moiety to form the sulfonated resin. The sulfonated resins may be used to make membranes.
Description
48~i ~
PROCESS ~OR PREPARING
SULFONATED POLY(ARYL ETHER~ RESINS
FIELD OF THE INVENTION
Thls inventlon relstes to ~ novel process for sulfon~ting poly(sryl ether) re~ln~, and ln particul~r to using 8 silyl h~losulfonate or 8 comblnatlon of 8 h~losulfonlc acld ~nd ~ 311yl hallde as the sulfonating agent. The inventlon further relates to sulfonated polytaryl ether) reslns ~nd to membranes fsbrlcated therefrom.
BACKGROUND
Poly(~ryl ether) reslns sre ~ class of res~ns having a variety of uses ln formlng wlre coatings, wlre lnsulatlon, snd electrlc~l connectors. When ~ulEonated, ~hese resins can be used to form osmosls and reverse osmosls membr~nes useful ln processes to purlfy a wlde var~ety of liqulds, for example ln desallnatlon processes to purify sallne solutions such ~s seswater. A
represents~ive poly~aryl ether) resin ls a polysulfone hsvlng the repest unlt structure:
_ O~C, ~0-~ S02~-CH3 . n n can rsn8e ~rom 2 to 200 but 1s more typlcally 50 to 100. The ~bove polysulfone 1~ hereln sometimes reEerred to fl~ PSF.
PSF h~s been sul~Qnsted by a vsrie~y of methods. For example, an early method dlsclosed ln D~14,561 ,~.
U.S. P~tent 3,709,841 to Quen~in discloses sulfonRtion uslng hlorosulfonic acld:
PSF + ClSO3H ---~ PSF-SO3H ~ HCl (I) Thls method msy induce chaln cleav~ge, br~nching, or cross-linklng, however (Johnson et ~1, J. Pol~m.
Sci., Pol~m. Chem. Ed-, 22, 721, 1984). The reaction ls Qlso heterogeneous, which csn ~ffect reproductlbilty and the extent o~ sulfon~tion.
Noshay and Robeson (J. APP1. PolYm. Sci., 20, 1885, 1976) reported s milder sulfonstion process using ~ complex o~ SO3 wlth ~riethylphosphate, SO3-PO(OCH2CH3)3, which may minimize side reactions. This process is cumbersome, however, due to the reactivl~y and toxiclty cf SO3 and the exothermic reactlon of SO3 with triethylphosphate.
The sulfon~ted polysulfone is o~ten converted to the s~lt form for use in membranes by reaction with a base such ~s sodium hydroxide:
PSF-SO3H + NaOH ~ PSF-SO3Na + H2O
S~lts of sulfonated polysulfone sre disclosed, for exsmple, ln U.S. patent 3,875,096 eo Graefe et 81.
and in Johnson et ~1. snd Noshay et sl., supra.
Sever~l ~rticles hsve ~ppeared whlch report the sulfon~tlon o~ vsrlous org~nlc compounds using trimethylsilyl chlorosulfon~te ~s ~ sulfonatlng ~gent~ See Hofmann et fll., Synthesisr Sept., 1979, 699-700; Hofm~nn et ~1, Llebigs Ann. Chem., 1982, 282-297; Grlgnon-Dubol~ et ~1., J. Org2nomet~1.
Chem., 124, lq77, 135-142; Du~f~ut et 81., Bull.
D-14,561 . . . .
74~6 Soc, Chlm. Fr.~ 1963, 512-S17; Felix et ~1, Angew.
Chem. Int. Ed. ~ngl., 1~, l9~g, 402-403; ~nd Fellx et al, Angew. Chem. Int. Ed. Engl., 16, 1977, 488-489. None of these ~rticles dlscloses the sulfonstlon o~ ~ny polymer, however. Nor do ~ny of these arti~les su~gest using a combin~tlon o~
sllyl h~llde ~nd ~ h~losulfonlc acid ln Qny sulfona~ion procedure.
SVMMARY OF THE INVENTION
This lnventlon provldes in one ~spect novel processes of sulfon~ting poly(~ryl ether) resins gener~lly by (i) in ~ flrst step, m~klng an intermedi~te resln product by rescting a poly(aryl ether) resin wlth ~ sllyl h~losulfon~te or wlth the comblnation of ~ sllyl h~llde ~nd a halosulfonic ~cld, thereby formlng a poly(aryl ether~ resin having ~ portlon o~ repeat unl~s ln the resln bacXbone derivstized wlth pendant silyl sulfonate groups, followed by (li) ~e~ctlng the intermedi~te resln product thus formed w~th a base to cleave sllyl moieti~s ~rom the sllyl sulfon~te groups, thereby formlng 8 sulfon~te salt of æaid poly(aryl ether) res1n.
In snother sspect the invention provldes novel lntermedi~te resins per se, that ls poly~ryl ether) reslns h~vlng B portlQn of repest unlts in the re~ln backbone deriv~tlzed wlth pendant sllyl sulfonste groups extending from ~romstic rin8 port~ons of the unlts:
D-14,561 ~7 R O
~ ~ S~ -O-S--R O
,, where R i3 de1ned below.
The intermediate reslns c~n be formed by reacting a poly(sryl ether~ res~n with 8 silyl halosulfonate having the formul~
R O
11 , R - Sl-O-S-X
R O
wherein X i8 Cl, Br or I, prefersbly Cl, snd the R
groups, whlch csn be the same or different, ~re lnert organic rsdicals.
The intermedlste resins cen also be formed by reactlng the resin with ~ eombination of s halosulfonic ~cid ~o-9-x ~nd ~ ~ilyl h~lide h~ving the structure D-l4~56l 1~i7~6 - R - Sl - X
whereln X snd R ~re as defined above. Uslng this com~lnatlon to make the lntermedlate res1n is sometimes referred to herein 85 "in situ"
sulfonation, ln contrast to sulfonatlon employing preformed silyl halosulfonate.
The terms "combin~tion" and/or "sllyl halide/h~lo-~ulfonic ~cld combinatlon" are intended to denote that a silyl hallde and Q halosulfonic acid ar~ used together, belng provided to a solutlon o a poly(aryl ether) resln ~s a mixture or 8S
separate components.
The product formed from the reaction of a poly(aryl ether) resin with a silyl halosulfon~e or wlth a 8ilyl hallde/h~losulFonic acid combina~lon is herein reFerred to ~s an lntermediate or derivative, and is 8 poly~aryl ether) res~n h~vlng pendant sllyl sulfonste groups, R3-SiO-S02-, along the resln backbone. Bsse ~e.g., sodlum hydroxide in the Pollowing lllustratlon~ m~y then be added to cleave the 5ilyl molety, yieldlng the poly(aryl ether~
resin ln (sulfonQte) salt form, l.e., ~ resin havlng -S03M gr~ups whereln M 18 8 cation derived from the base ~s hereinaFter further disclosed snd descrlbed.
As a ~peclflc example, the following equatlons ~ and B de~cribe ~ procedure ~or sulfon~ting ~ccordlng to thl~ lnvention ln flow D-14,561 ,~
74~ti rh~rt form for 9 slngle repea~ unlt of PSF uslng trlmethyl~llyl chlorosulfonate ~s the sulfon~tlng agent, whereln Me denotes 8 methyl group.
/~) He3sl-so3-cl ~ ~C~0~502 II
Me -~ ~0~ C~O~S02~:~ + HCl Me S03 Sl~e3 III
M~
Mo 03Ns ~ H0-SiMc3~
The ssme result as sbove can be schieved lf, instead of u~lng trimethylsilyl chlorosulfonAte ~i.e. B 811yl ~ulÇonate), trlmethylsllyl chlorlde comblned wlth chlorosulfon1c acld ~l.e. a 8ilyl hallde/halosul~onlc acid combinstlon) is used.
Thus the sulfonated poly(aryl ether) resln~
snd lntermediate reslns provided by thls lnventlon can be produced ln ~ltu uslng ~ silyl/h~llde h~losulfonic ~cld comblnatiQn ~8 the sulfonatlng n8ent. The resln~ c~n al~o be ~ormed uslng ~ sllyl : D-14,561 7fl8 halosulfon~te as the sul~onatlng sgent, whlch ln turn can be pre~ormed as the re~ctlon product of a 8ilyl hal~de/halosulfonlc ~cld comblnatlon~ The sulfonatlng agents useful ln this lnvention thus form a fsmlly of functionaily equiv~lent re~ctants.
The present invention avoids ~ number o~
problems associQted wlth previously known sulfona~lon methods. For exsmple, the present sulfonatlnÆ agents generally re-~ult ln a homogeneous resction system, as opposed to the heterogeneous system which results from using a halosul~onic acld. When ~ halosulfonlc scld ~uoh 8S
chlorosulfonlc ~cid 1 dlssolved in 8 solution of poly(aryl ether) resln ~uch as PSF, a single phase reactlon solutlon ls lnitl~lly obtslned. As the resotion proceeds, however, two phases develop, one of whlch ls ~ thlck, rel~tlvely vlscous phase rlch ln sulfonsted polymer. Thls thlck phase ls dlfficult to stlr e~fectlvely and presents other processing problems lncluding dlfficult filtr~tlon.
By contr~st, when 8 811yl h~losulfon~te or ~ silyl hallde/h~losulfonlc flCid COmbillAtlOn 15 dissolved in 8 ~olutlon o polymer the homogeneous 801utlon lniti~lly obt~lned remalns ~s ~ homogeneous single pha~e throughout the course of the reaction whlch produces a 811yl sulfon~te polymer intermedlate. Addltlon o~ a bsse to cle~ve the 8ilyl moiety does not destroy the slngle phase, homogeneous nsture of the reactlon medlum, ~lthough turbldity may be observed. Stlrrlng and flltr~tlon ~re rel~tlvely f~clle~ It ls Eurther belleved that the better mlxlng achlevable ln ~ homogeneous D-14,561 ~ ~ ~'7~ 8 ~
re~ction system ~llows ~or more uniform distrlbutlon of sulfon~tion, slong the b~ckbone of the polymer, ~nd thus for ~ more unlform sulfon~ted polymer product, 8S opposed to less unlform sul~onation which may resul~ due to the grester dlfficulty of mixing in ~ heterogenou~ system. The homogenelty is belleved to be due to the 811yl molety which serves ~s ~ solubilizlng group and ~llows the silyl h~losulfon~te polymer derlv~tive to dissolve in the solvent used to d~ssolve the unsulfonsted polymer.
Importantly, the present sulfonating ~gen~s generslly result in less ch~in sc1ssion than that which results when uslng ~ halosulfonic acid alone.
Thus, in ~nother aspect this invention advantageously provldes hlgher molecul~r welght sul~onated polymers re~stive to those obtained by employ~ng chlorosulfonlc ~cid under identical reactlon condltlons. High moleculAr weight is an important feature needed to m~ke membranes having good mechanic~l strength for resistance to ~earlng and rupturing.
The ~billty o~ a 8ilyl hallde/halosul~onic acld combination to produce sulfonated poly~ryl ether) reslns havlng ~ higher molecular weight th~n those produced uslng chlorosulfonlc acid alone i~
particul~rly surprlslng. The r~action of A
poly(aryl ather) resin wlth a halosulfonlc ~cld ~lone produces one equlvalent of hydrogen halide, as exempllFled by re~ctlon (I), supr~. The reaction o~
~ poly(aryl ether) resln wlth ~ stlyl hsllde/halosul~onic acid combinatlon, by contrsst, produces two equlv~lents o~ hydrogen hallde as ~ollows D-14,561 - i9 -HO-S02-X + R3-Sl-X + PSF ~ PSF + 2HX
S1~2-~-Sl -R3 ye~ hlgher polymer molecul~r weights are obtAined than those obtsined by uslng a halosulfonic acid.
It was unexpected that higher molecula~ welghts could be obtained ~or a sulfonated resin in a reaction medium where double the amount of hydrogen hallde ls produced, and hence where greater acid clesvage of the resin would be expected to occur.
Also, the toxicity and exothermicity problems encountered from using the S03-phosphate process described above can be avoided when using the processes of thls lnvention.
The invention shall be further described and exemplified ln the ~ollow1ng detailed discussion.
DETAILED DISCUSSIO~
A. PolYaFxlether Resins The poly(aryl ether~ resins suitable for use ln thls lnvention are linear, thermoplastic poly~rylene polyethers containing recurring units of the following formul~:
-O-E-O-E'-wherein E ls the residuum of a dlhydrlc phenol, and E' is the reslduum of ~ benzenoid compound hRving ~n inert electron wlthdrawin~ group in at le~st one of the pos~tlons ortho ~nd para to the valence bonds;
both of s~ld residua ~re vslently bonded to the ethe~ oxygens throu~h ~romstlc carbon atoms. Such ~rom~tlc polyethers sre lncluded within the clQss o~
D-14,561 ~7~6 polysrylene polyether resins described ln, for ex~mple~ U.S. P~tents 3,264,536 ~nd 4,175,175. It ls preferred th~t the dlhydrlc phenol be ~ dlnucle~r phenol such ~s, for exsmple, the dihydroxy dlphenyl ~lkanes or the nuclear halogenated deriva~ives thereof, such ~9, for ex~mple, ~he
PROCESS ~OR PREPARING
SULFONATED POLY(ARYL ETHER~ RESINS
FIELD OF THE INVENTION
Thls inventlon relstes to ~ novel process for sulfon~ting poly(sryl ether) re~ln~, and ln particul~r to using 8 silyl h~losulfonate or 8 comblnatlon of 8 h~losulfonlc acld ~nd ~ 311yl hallde as the sulfonating agent. The inventlon further relates to sulfonated polytaryl ether) reslns ~nd to membranes fsbrlcated therefrom.
BACKGROUND
Poly(~ryl ether) reslns sre ~ class of res~ns having a variety of uses ln formlng wlre coatings, wlre lnsulatlon, snd electrlc~l connectors. When ~ulEonated, ~hese resins can be used to form osmosls and reverse osmosls membr~nes useful ln processes to purlfy a wlde var~ety of liqulds, for example ln desallnatlon processes to purify sallne solutions such ~s seswater. A
represents~ive poly~aryl ether) resin ls a polysulfone hsvlng the repest unlt structure:
_ O~C, ~0-~ S02~-CH3 . n n can rsn8e ~rom 2 to 200 but 1s more typlcally 50 to 100. The ~bove polysulfone 1~ hereln sometimes reEerred to fl~ PSF.
PSF h~s been sul~Qnsted by a vsrie~y of methods. For example, an early method dlsclosed ln D~14,561 ,~.
U.S. P~tent 3,709,841 to Quen~in discloses sulfonRtion uslng hlorosulfonic acld:
PSF + ClSO3H ---~ PSF-SO3H ~ HCl (I) Thls method msy induce chaln cleav~ge, br~nching, or cross-linklng, however (Johnson et ~1, J. Pol~m.
Sci., Pol~m. Chem. Ed-, 22, 721, 1984). The reaction ls Qlso heterogeneous, which csn ~ffect reproductlbilty and the extent o~ sulfon~tion.
Noshay and Robeson (J. APP1. PolYm. Sci., 20, 1885, 1976) reported s milder sulfonstion process using ~ complex o~ SO3 wlth ~riethylphosphate, SO3-PO(OCH2CH3)3, which may minimize side reactions. This process is cumbersome, however, due to the reactivl~y and toxiclty cf SO3 and the exothermic reactlon of SO3 with triethylphosphate.
The sulfon~ted polysulfone is o~ten converted to the s~lt form for use in membranes by reaction with a base such ~s sodium hydroxide:
PSF-SO3H + NaOH ~ PSF-SO3Na + H2O
S~lts of sulfonated polysulfone sre disclosed, for exsmple, ln U.S. patent 3,875,096 eo Graefe et 81.
and in Johnson et ~1. snd Noshay et sl., supra.
Sever~l ~rticles hsve ~ppeared whlch report the sulfon~tlon o~ vsrlous org~nlc compounds using trimethylsilyl chlorosulfon~te ~s ~ sulfonatlng ~gent~ See Hofmann et fll., Synthesisr Sept., 1979, 699-700; Hofm~nn et ~1, Llebigs Ann. Chem., 1982, 282-297; Grlgnon-Dubol~ et ~1., J. Org2nomet~1.
Chem., 124, lq77, 135-142; Du~f~ut et 81., Bull.
D-14,561 . . . .
74~6 Soc, Chlm. Fr.~ 1963, 512-S17; Felix et ~1, Angew.
Chem. Int. Ed. ~ngl., 1~, l9~g, 402-403; ~nd Fellx et al, Angew. Chem. Int. Ed. Engl., 16, 1977, 488-489. None of these ~rticles dlscloses the sulfonstlon o~ ~ny polymer, however. Nor do ~ny of these arti~les su~gest using a combin~tlon o~
sllyl h~llde ~nd ~ h~losulfonlc acid ln Qny sulfona~ion procedure.
SVMMARY OF THE INVENTION
This lnventlon provldes in one ~spect novel processes of sulfon~ting poly(~ryl ether) resins gener~lly by (i) in ~ flrst step, m~klng an intermedi~te resln product by rescting a poly(aryl ether) resin wlth ~ sllyl h~losulfon~te or wlth the comblnation of ~ sllyl h~llde ~nd a halosulfonic ~cld, thereby formlng a poly(aryl ether~ resin having ~ portlon o~ repeat unl~s ln the resln bacXbone derivstized wlth pendant silyl sulfonate groups, followed by (li) ~e~ctlng the intermedi~te resln product thus formed w~th a base to cleave sllyl moieti~s ~rom the sllyl sulfon~te groups, thereby formlng 8 sulfon~te salt of æaid poly(aryl ether) res1n.
In snother sspect the invention provldes novel lntermedi~te resins per se, that ls poly~ryl ether) reslns h~vlng B portlQn of repest unlts in the re~ln backbone deriv~tlzed wlth pendant sllyl sulfonste groups extending from ~romstic rin8 port~ons of the unlts:
D-14,561 ~7 R O
~ ~ S~ -O-S--R O
,, where R i3 de1ned below.
The intermediate reslns c~n be formed by reacting a poly(sryl ether~ res~n with 8 silyl halosulfonate having the formul~
R O
11 , R - Sl-O-S-X
R O
wherein X i8 Cl, Br or I, prefersbly Cl, snd the R
groups, whlch csn be the same or different, ~re lnert organic rsdicals.
The intermedlste resins cen also be formed by reactlng the resin with ~ eombination of s halosulfonic ~cid ~o-9-x ~nd ~ ~ilyl h~lide h~ving the structure D-l4~56l 1~i7~6 - R - Sl - X
whereln X snd R ~re as defined above. Uslng this com~lnatlon to make the lntermedlate res1n is sometimes referred to herein 85 "in situ"
sulfonation, ln contrast to sulfonatlon employing preformed silyl halosulfonate.
The terms "combin~tion" and/or "sllyl halide/h~lo-~ulfonic ~cld combinatlon" are intended to denote that a silyl hallde and Q halosulfonic acid ar~ used together, belng provided to a solutlon o a poly(aryl ether) resln ~s a mixture or 8S
separate components.
The product formed from the reaction of a poly(aryl ether) resin with a silyl halosulfon~e or wlth a 8ilyl hallde/h~losulFonic acid combina~lon is herein reFerred to ~s an lntermediate or derivative, and is 8 poly~aryl ether) res~n h~vlng pendant sllyl sulfonste groups, R3-SiO-S02-, along the resln backbone. Bsse ~e.g., sodlum hydroxide in the Pollowing lllustratlon~ m~y then be added to cleave the 5ilyl molety, yieldlng the poly(aryl ether~
resin ln (sulfonQte) salt form, l.e., ~ resin havlng -S03M gr~ups whereln M 18 8 cation derived from the base ~s hereinaFter further disclosed snd descrlbed.
As a ~peclflc example, the following equatlons ~ and B de~cribe ~ procedure ~or sulfon~ting ~ccordlng to thl~ lnvention ln flow D-14,561 ,~
74~ti rh~rt form for 9 slngle repea~ unlt of PSF uslng trlmethyl~llyl chlorosulfonate ~s the sulfon~tlng agent, whereln Me denotes 8 methyl group.
/~) He3sl-so3-cl ~ ~C~0~502 II
Me -~ ~0~ C~O~S02~:~ + HCl Me S03 Sl~e3 III
M~
Mo 03Ns ~ H0-SiMc3~
The ssme result as sbove can be schieved lf, instead of u~lng trimethylsilyl chlorosulfonAte ~i.e. B 811yl ~ulÇonate), trlmethylsllyl chlorlde comblned wlth chlorosulfon1c acld ~l.e. a 8ilyl hallde/halosul~onlc acid combinstlon) is used.
Thus the sulfonated poly(aryl ether) resln~
snd lntermediate reslns provided by thls lnventlon can be produced ln ~ltu uslng ~ silyl/h~llde h~losulfonic ~cld comblnatiQn ~8 the sulfonatlng n8ent. The resln~ c~n al~o be ~ormed uslng ~ sllyl : D-14,561 7fl8 halosulfon~te as the sul~onatlng sgent, whlch ln turn can be pre~ormed as the re~ctlon product of a 8ilyl hal~de/halosulfonlc ~cld comblnatlon~ The sulfonatlng agents useful ln this lnvention thus form a fsmlly of functionaily equiv~lent re~ctants.
The present invention avoids ~ number o~
problems associQted wlth previously known sulfona~lon methods. For exsmple, the present sulfonatlnÆ agents generally re-~ult ln a homogeneous resction system, as opposed to the heterogeneous system which results from using a halosul~onic acld. When ~ halosulfonlc scld ~uoh 8S
chlorosulfonlc ~cid 1 dlssolved in 8 solution of poly(aryl ether) resln ~uch as PSF, a single phase reactlon solutlon ls lnitl~lly obtslned. As the resotion proceeds, however, two phases develop, one of whlch ls ~ thlck, rel~tlvely vlscous phase rlch ln sulfonsted polymer. Thls thlck phase ls dlfficult to stlr e~fectlvely and presents other processing problems lncluding dlfficult filtr~tlon.
By contr~st, when 8 811yl h~losulfon~te or ~ silyl hallde/h~losulfonlc flCid COmbillAtlOn 15 dissolved in 8 ~olutlon o polymer the homogeneous 801utlon lniti~lly obt~lned remalns ~s ~ homogeneous single pha~e throughout the course of the reaction whlch produces a 811yl sulfon~te polymer intermedlate. Addltlon o~ a bsse to cle~ve the 8ilyl moiety does not destroy the slngle phase, homogeneous nsture of the reactlon medlum, ~lthough turbldity may be observed. Stlrrlng and flltr~tlon ~re rel~tlvely f~clle~ It ls Eurther belleved that the better mlxlng achlevable ln ~ homogeneous D-14,561 ~ ~ ~'7~ 8 ~
re~ction system ~llows ~or more uniform distrlbutlon of sulfon~tion, slong the b~ckbone of the polymer, ~nd thus for ~ more unlform sulfon~ted polymer product, 8S opposed to less unlform sul~onation which may resul~ due to the grester dlfficulty of mixing in ~ heterogenou~ system. The homogenelty is belleved to be due to the 811yl molety which serves ~s ~ solubilizlng group and ~llows the silyl h~losulfon~te polymer derlv~tive to dissolve in the solvent used to d~ssolve the unsulfonsted polymer.
Importantly, the present sulfonating ~gen~s generslly result in less ch~in sc1ssion than that which results when uslng ~ halosulfonic acid alone.
Thus, in ~nother aspect this invention advantageously provldes hlgher molecul~r welght sul~onated polymers re~stive to those obtained by employ~ng chlorosulfonlc ~cid under identical reactlon condltlons. High moleculAr weight is an important feature needed to m~ke membranes having good mechanic~l strength for resistance to ~earlng and rupturing.
The ~billty o~ a 8ilyl hallde/halosul~onic acld combination to produce sulfonated poly~ryl ether) reslns havlng ~ higher molecular weight th~n those produced uslng chlorosulfonlc acid alone i~
particul~rly surprlslng. The r~action of A
poly(aryl ather) resin wlth a halosulfonlc ~cld ~lone produces one equlvalent of hydrogen halide, as exempllFled by re~ctlon (I), supr~. The reaction o~
~ poly(aryl ether) resln wlth ~ stlyl hsllde/halosul~onic acid combinatlon, by contrsst, produces two equlv~lents o~ hydrogen hallde as ~ollows D-14,561 - i9 -HO-S02-X + R3-Sl-X + PSF ~ PSF + 2HX
S1~2-~-Sl -R3 ye~ hlgher polymer molecul~r weights are obtAined than those obtsined by uslng a halosulfonic acid.
It was unexpected that higher molecula~ welghts could be obtained ~or a sulfonated resin in a reaction medium where double the amount of hydrogen hallde ls produced, and hence where greater acid clesvage of the resin would be expected to occur.
Also, the toxicity and exothermicity problems encountered from using the S03-phosphate process described above can be avoided when using the processes of thls lnvention.
The invention shall be further described and exemplified ln the ~ollow1ng detailed discussion.
DETAILED DISCUSSIO~
A. PolYaFxlether Resins The poly(aryl ether~ resins suitable for use ln thls lnvention are linear, thermoplastic poly~rylene polyethers containing recurring units of the following formul~:
-O-E-O-E'-wherein E ls the residuum of a dlhydrlc phenol, and E' is the reslduum of ~ benzenoid compound hRving ~n inert electron wlthdrawin~ group in at le~st one of the pos~tlons ortho ~nd para to the valence bonds;
both of s~ld residua ~re vslently bonded to the ethe~ oxygens throu~h ~romstlc carbon atoms. Such ~rom~tlc polyethers sre lncluded within the clQss o~
D-14,561 ~7~6 polysrylene polyether resins described ln, for ex~mple~ U.S. P~tents 3,264,536 ~nd 4,175,175. It ls preferred th~t the dlhydrlc phenol be ~ dlnucle~r phenol such ~s, for exsmple, the dihydroxy dlphenyl ~lkanes or the nuclear halogenated deriva~ives thereof, such ~9, for ex~mple, ~he
2,2-bis(4-hydroxyphenyl)propane, 1,1-bist4-hydroxphenyl)2-phenyl ethane, or bls(4-hydroxyphenyl)methane. Bec~use ~he sulfonation ~eactlon ls electrophil~c, 8~ least one of the rings in the dlhydric dinuclear phenol is preferably "undeactivated", meaning that it is not substituted by deactlvat$ng, electron wlthdrawing -~
groups. The remainlng r~ng m~y contsin deactivatin~
groups. Other materials also termed approprl~tely bisphenols ~re also highly vflluable and preferred.
These m~terials ~re the blsphenols of a symmetrical or unsym~etrical ~oinlng group, 2s, for exsmple, ether oxygen (-O-), or hydrocarbon resldua in which the two phenollc nucle~ are ~oined to the same or dlfferent carbon atoms of the residue.
Such dlnucle~r phenol~ can be ch~rscterized as having the structure:
HO(Ar-R2-Ar)OH
whereln Ar is an ~romatlc group and prefer~bly is a phenylene group, Rl and R'l can be the same or dlfferent lnert substituent ~roups such ~s ~lkyl groups hflvlng from 1 to 4 carbons atoms, aryl, halogen atoms, i.e., ~luorine, chlorlne, bromine or D-14,561 1 2 6 7 ~ 8~ i !
lodlne, or alkoxyl r~dlcals hsvlng ~rom l to 4 ~arbon atoms, the o~s ~e ~ndependently ~ntegers having ~ v lue of fro~ ~ to 4, inelus~Ye, ~nd R2 15 representstive of a bond between sromat~c carbon a~oms flS ln dihydroxy-dlphenyl, or 15 a dlvalent rsdic~l, includlng ~or example, r~dlc~ls such ~s -O-, -S-, -5-5-, and divalent hydroo~rbon rsdicals suoh as ~lkylene, ~lkylldene, cyclo~lkylene, cycloalkylldene, or the halogen, alXyl, aryl or llke substituted alkylene, alkylldene ~nd cycloallphstlc radlcals as well as aromatlc radicals and rln~s fused to both Ar groups.
Examples o~ speclflc dihydrlc pol~nuclear phenols including ~mong others:
the bls-~hydroxyphenyl) alkanes such as 2,2-bis-(4-hydroxyphenyl)propana, 2,2-blst4-hydroxy-3,5 dlmethylphenyl)propane 2,4'-dlhydroxydlphenylmethane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bls~4-hydroxy-2,6-dlmethyl-3-methoxyphenyl)methane, l,l-bis-~4-hydroxy-phenyl)eth~ne, 1,2-bis-(4-hydroxyphenyl)ethane, l,l-bis-(4-hydroxy-2-chlorophenyl)eth~ne, 1,1-bi~-(3-methyl-4-hydroxyphenyl)propane, 1,3-bls-t3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bi 3 - ( 2-isopropyl-4-hydroxyphenyl)propQne, 2,2-bls-~4-hydroxy-naphthyl)propane, 2,2-bis-(4-hydroxyphenyl~pent~ne,
groups. The remainlng r~ng m~y contsin deactivatin~
groups. Other materials also termed approprl~tely bisphenols ~re also highly vflluable and preferred.
These m~terials ~re the blsphenols of a symmetrical or unsym~etrical ~oinlng group, 2s, for exsmple, ether oxygen (-O-), or hydrocarbon resldua in which the two phenollc nucle~ are ~oined to the same or dlfferent carbon atoms of the residue.
Such dlnucle~r phenol~ can be ch~rscterized as having the structure:
HO(Ar-R2-Ar)OH
whereln Ar is an ~romatlc group and prefer~bly is a phenylene group, Rl and R'l can be the same or dlfferent lnert substituent ~roups such ~s ~lkyl groups hflvlng from 1 to 4 carbons atoms, aryl, halogen atoms, i.e., ~luorine, chlorlne, bromine or D-14,561 1 2 6 7 ~ 8~ i !
lodlne, or alkoxyl r~dlcals hsvlng ~rom l to 4 ~arbon atoms, the o~s ~e ~ndependently ~ntegers having ~ v lue of fro~ ~ to 4, inelus~Ye, ~nd R2 15 representstive of a bond between sromat~c carbon a~oms flS ln dihydroxy-dlphenyl, or 15 a dlvalent rsdic~l, includlng ~or example, r~dlc~ls such ~s -O-, -S-, -5-5-, and divalent hydroo~rbon rsdicals suoh as ~lkylene, ~lkylldene, cyclo~lkylene, cycloalkylldene, or the halogen, alXyl, aryl or llke substituted alkylene, alkylldene ~nd cycloallphstlc radlcals as well as aromatlc radicals and rln~s fused to both Ar groups.
Examples o~ speclflc dihydrlc pol~nuclear phenols including ~mong others:
the bls-~hydroxyphenyl) alkanes such as 2,2-bis-(4-hydroxyphenyl)propana, 2,2-blst4-hydroxy-3,5 dlmethylphenyl)propane 2,4'-dlhydroxydlphenylmethane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bls~4-hydroxy-2,6-dlmethyl-3-methoxyphenyl)methane, l,l-bis-~4-hydroxy-phenyl)eth~ne, 1,2-bis-(4-hydroxyphenyl)ethane, l,l-bis-(4-hydroxy-2-chlorophenyl)eth~ne, 1,1-bi~-(3-methyl-4-hydroxyphenyl)propane, 1,3-bls-t3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bi 3 - ( 2-isopropyl-4-hydroxyphenyl)propQne, 2,2-bls-~4-hydroxy-naphthyl)propane, 2,2-bis-(4-hydroxyphenyl~pent~ne,
3,3-bls~4-hydroxyphenyl)pentane, D-14,561
4~6 2,2-bi~-(4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)phenylmethane, 2,2-bls-(4-hydroxyphenyl)-1-phenyl-propsne, 2,2-bi~-(4-hydroxyphenyl)1,1,1,3,3,3,-hexa~luoro-propane, snd the llke;
-~ di~hydroxyphenyl)ethers, such a~
bls-(4-hydroxyphenyl)ether, 4~2'- , 2,2'- , and 2,3 e -dihydroxyphenyl ether, 4,3'- ~nd 4,4'-dlhydroxyl-216-dimethyldiphenyl-ether, bls-(4-hydroxy-3-isobutylphenyl)ether, bis-~4-hydroxy-3-isopropylphenyl)ether, bls-(4 hydroxy-3-chlorophenyl)ether, bls-(4--hydroxy 3-1uorophenyl~ether, bis-(4 hydroxy-3-bromophenyl)ether, bis- (4--hydroxyn~phthyl)ether, bls-(4 hydroxy-3-chloronaphthyl)ether, and 4,4'-dihydroxyl-3,$-dimethoxydlphenyl ether.
Also pre~erred as useful dihydric phenols are the followin8:
HO ~ OH
HO ~ OH
D-14,561 ..
As herein used the E term de~lned as bein~
the "reslduum of the dihydrlc phenol" o~ course refers to the resldue of the dihydrlc phenol ~ter the removal of the two arom~tlc hydroxyl groups.
Thus as ls re~dlly seen these poly~rylene polyethers cont~in recurring groups of the residuum o~ the dihydric phenol snd the residuum of the benzenold compound bonded through ~romatic ether oxygen ~tomsO
Any dihalobenzenoid or dinitrobenzenold compound or mixtures thereof c~n be employed to form an E' benzenoid reslduum in thls lnvention, which compound or compounds has the two halogens or nitro-groups bonded to benzene rings having sn electron wlthdr~wing group ln ~t least one o~ the positlons ortho snd pars to the hslogen or nitro group. The dlhalobenzenold or dinitrobenzenoid compound can be either mononuclear where the halogens or nitro groups ~re attached to the same benzenoid rlng or polynuclear where they ~re attached to different benzenold rlngs, ~s long ~s there is an activ~ting electrorl withdr~wing group ln the ortho or para position of thst benzenoid nucleus~ Fluorine and chlorlne ~ubstltuted benzenold reactants ~re preferred, the ~luorine oompounds for ~ast reactlvlty ~nd the chlorine compounds for their inexpensiv~ness.
An electron withdrawing group can be employed ~s the activator group in these compounds.
It should be, of course, lnert under the reaction condition~, but otherwlse lts structure ls not critlcal. Preferred are the stron~ actl~tlng D-14,561 1~ ..
group~ such as the sulfone group ~-S-) bondlng two il halogen or nltro subst~tuted benzenoid nuclel as in the 4,4'-dichlorodiphenyl ~ulEone and 4,4'-difluorodiphenyl ~ulfone, although such other strong`withdrewlng groups hereinsf~er mentloned can also be used.
lt is preferred that the rinB contaln no electron supplytng groups on the same benzenoid nucleus as the halogen or nltro group; however, the presence of other groups on the nucleus or in the residuum o~ the compound can be toleratsd.
The activating group can be basically -:
either of two types:
(8) monovalent groups that actlvate one or more halogens or nltro-groups on the same ring such as another nitro or halo group, phenylsulfone, or alkyl~ulfone, cyano, trlfluoromethyl, nitroso, and hetero nitrogen, as in pyridine.
(b) dlvalent groups which can activate dlsplacement of halogens on two different rings, o Il such as the sul~one group -S-; the carbonyl group o O H
Il I
-C-; the vinylene group -C~C-; the sulfoxide group D-14,561 1 ~`7 ~fi - 1~
Il -S-; th~ ~zo group -N-N-; the saturuted fluoroc~rbon I
groups -C-, -CF2-CF2CF2-; organ1c phosphine oxides -P-:
where R3 is ~ hydrocarbon group, and the ethylidene group A-C-A where A csn be Il --C--hydrogen or halogen.
I~ deslred, the polymers msy be made with mixtures o~ two or more dlhalobenzenoid or dinl~robenzenoid compound~.. Thus, the E' residuum of the benzenoid compounds in the polymer structure may be the same or dlfferent.
Exsmples of benzenold compound~ which ~re useful ln contrlbuting E' resldua to a poly(aryl ether) resln are the following:
4,4'-dlchlorodiphenyl sulfone, 4,4'-dlfluorodlphenyl sulfone, 4, 4 ~ -bi5 t4-chloroPhenYlsulfonYl)biPhenYl~
4,4'-bls(4-fluorophenylsulfonyl)blphenyl, 4,4'-di~luorobenzophenone, 4,4'-dlchlorobenzophenon~, 4,4'-bis~4-~luorobenzoyl)benzene D-14~561 i74~i 4,4~-bis(4-chlorobenzoyl)benzene, 2,6-dlchlorobenzonitrtle, lsomers thereof, ~nd the like.
It ls seen al80 that as used herein, ~he E' term defined ~s being the "residuum of the benzenoid compound" refers to the aromatic or benzenoid residue of the compound sfter ~he remov~l of the halogen atom or nitro group on the benzenold nucleus.
The polyArylene polyethers of this invention are prepared by methods well known in the art as for tnstance the ~ubstantially equimol~r one-step reaction of ~ double alk~li metsl s~lt of dihydric phenol with a dlhalobenzenold compound in the presence of specific llquid organlc suloxide or sulfone solvents under substantl~lly snhydrous conditions. Catalysts are not necesssry for this reaction.
The polymers may also be prepared in a two-step proce~s in which a dihydric phenol is first converted in situ in the primary reactlon solvent to the alkali metal salt of the reaction with the alkali metal, the alkali met~l hydride, alkali metsl hydroxide, alkall ~et~l ~lkoxide o~ the ~lk~li met~l Alkyl compounds. PreEersbly, the slXali metal hydroxlde ls employed. After removing the water whlch is present or formed, in order to secure substantlally ~nhydrous conditions, the dialkali metal salts of the dlhydric phenol are ~dmixed and reacted with about ~tolchiometrlc quantities of the dihalobenzenoid or dinltrobenzenoid compound.
Addltionally, the polyethers may be prepared by the procedure descrlbed ~n, for example, D-14,561 U.S. Patent 4,176~222 ln whlch ~ substantl~lly equlmolar mlxture of at les~t one blsphenol And ~t lPast one dlh~lobenzenold sre he~ted ~t temper~tur~ of from ~bout 100 to sboue 490C wlth mlxture of ~odium csrbsnate or blcarbonate snd ~
second alkali metal c~rbonate or blcarbon~te h~vlng 8 hlgher ~tomlc number th~n that o sodiu~.
Further, the polyethers may be prep~red by the procedure described ln Csnsdian P~tent 84~,963 wherein the bisphenol and dlhalobenzenold c~mpount are hested ln the presence of pot~sslum carbonate uslng ~ hlgh boillng ~olvent such a~ diphenylsulfone or sul~ol~ne.
Preferred poly~rylene polyethers oE thi~
inventlon are ehose prepared uslng the dlhydrlc polynuclesr phenot~ o~ ths followlng type~, includlng the derivatlves thereo~ whlch are subQtltuted with inert substi~uent group~
~4 ~ a) HO ~ I ~ ~ OH
~4 ln whlch the R4 groups represent independently hydrogen, lower ~lkyl, ~ryl ~nd the h~logen substltuted groups thereoE, whlch c~n be the same or d~E~erent;
~-14,5~1 ~ti7 - la -(b) HO ~ OH
(c~ . HO ~ OH
~d) HO ~ O ~ OH
and substltuted derlvatlve~ thereof.
It 18 also contempl~ted in thls lnvention to use ~ mixture of two or more dlEferent dihydrlc phenols to accomplish the s~me ends 9S ebove. Thus when reflerred to ~bove the -E- reslduum ln the polymer structure can actually be the ~ame or dlf~erent ~romatlc resldu~ mlxture~ of polynuclear dlhydrlc phenol~ such as bln~ry mixtures of dlnuclear blsphenols ~re ~employed, e~ch rlng in one of the component dihydrlc phenols m~y be deactlvated 1~ deslred, sllowlng for the incorporatlon oE (dlfflcultly sul~onatsble) deact~vated unlts lnto the polymer b~ckbone.
Representstive of such deactlv~ted dihydrlc polynuclear phenol~ ~re those wherein the rings are connected by electron wlthdrawing groups, lncludlng dlhydrlc phenols ~uch a~
D 14,561 ~ 19 -HO~SOz~ SO~OH
O
~0~ S~
O
O
HO~ t~ , and t) O
~~C~o~
If such phenols having each rlng de~ctivsted ~re employed 1~ 1~ preferred thst ~hey be ll~lted to les~ than about 95 mole percent of the -E- unlts compr1slng th~ copolymer backbone~
The poly(aryl ether~) hsYe a reduced vlscoslty of Erom about 0.2 to about 2, prefersbly from ~bout 0.35 to about l~5 R~B mea~ured ln an Approprl~te solvent 5t an approprlste tempersture dependlng on the p~rtlcular po'lyether, ~uch ~ ln methylene chlor~de ~t 25C.
The pre~er~ed poly(sryl ethers) have one o~
more repeRt unlts or subunlt~ of the ~ormul~:
~o~ O~ SO~ , D-~4,561 ~0~0~502 ~~~52~52 ~~~S2~52~
H~ ~1~
~0~~~52 C~
t ~ ~o~S02~o~ S~J
~0~~52 D-14, S61 7~8~
The term "subunlt" me~ns th~t sny of the above, ln addl~ion to serving 8s an entire repest unit, can slso be cont~ined ~s psrt of ~ l~rger repeat unlt.
Polymers havlng repeat un~ts or subunits a illustr~ted ~bove are disclosed, for exAmple, ln U.S. patents 4,175,175; 4,320,224; 4,10B,837;
4,00g,149; 3,455,866; 3,518,067; 3,764,583;
3,400,065; 3,647,751; Europe2n pstent (EP) applic~-tlon number 81107193.5, published March 24, 1982 under the publication number 0047999; and EP
appllcstlon 80201194.0, publlshed June 3, 1981 under the publ~catlon number 0029S33.
~ or e~se of dlscussion PSF ls sometimes specific~lly referred to herein for purposes of exemplifylng the lnventlon. Such exemplificstion is not to be taken as limiting, however.
B Process Conditlons The sulfonatlon reactlon is conducted in suitable solvent, suitability being determined by the ability of he solvent to dissolve the polymer and the sulfonsting sgent snd by its lnertness to the sulfonatlng ~gent. Pre~erred ~re chloroallphatlc hydrocsrbons such as chloroform, methylene chlorlde, and 1,2-dlchloroethane.
Chlorin~ted sromstlc hydrocsrbons ~uch ~s chlorobenzene sre less deslrable slnce, although they csn be accept~ble to dlssolve the polymer, they can ~lso be reactive to the sul~onatlng agent. It 18 belleved that deactlvated aromatlc hydrocarbons such 8S tr~chlorobenzene snd nltrobenzene are ~uit~ble ~olvents.
~-14,561 3L~ ~7~ 6 The ~mount of solvent used to conduct the re~c~lon ls non-crlticsl although an amount o~
solvent should not ~e used that ls l~rge enough ~o dilute the re~ction mixture ~o ~he polnt ~hat the rate o~ re~ction is ~dversely slowed. The minimum amount oÇ solvent is thAt amoun~ which is su~flc~ent to ~ust dissolve the polymer and the sulfonatlng agent. When using chloroallph~ti~ hydroc~rbons such &S methylene chlorlde or 1,2-dichloroethane, ~n amount o~ solvent between 5 And 20 ml per gram o~
polymer, prefersbly between 10 snd lS ml per gram of polymer, may be employed.
The reaction is preferably conducted at sbout room temper~ture, say between ~bout 0C ~nd ~bout 35C. Conducting the reaction ~t hi~her temper~tures may increQse chain scission ~o unscceptable levels rel~tive to the smount of chain scission which occurs ~t lower temperstures. The reactlon m~y be conducted at temperstures lower thsn 0C althou~h the resction r~te msy decrease, necessitating conducting the resctlon ~or longer periods.
No speci~l pressure considerstions are re~ulred, the re~ction generally be~ng conducted ~t ~mblent pressure.
When msklng ~ sulfonated poly~ryl ether) resin uslng ~ 811yl hslide/hslosulfonic scid comblnstlon, the h~losulfonic ~cld csn be ~ny of the compoundæ hcvlng the ~ormul~
D-14,5Sl O
whereln X i8 Cl~ or Br or I, pre~erably Cl.
As previously noted the s~lyl h~llde ean be any compound havlng the structure R
R - Si - X
whereln X 18 hslogen selected from the group conslsting o~ Cl, ~r and I, preferably Cl. The R
groups can ln general be the same or dlfferent orgsnlc radlcals and be ~ny group whlch ls lnert, l.e. whlch 18 not reactive toward the polymer, which does not render the sulfonating agent ~nsoluble ~n the reaction medlum, and whlch preferably does not lnter~ere wlth base cleavage of the Si-0 bond. R
can, ~or ~xample, be:
~ llphatlc or cycloallphatlc alkyl or alkoxy hsvlng 1-10 carbon atoms, lncludlng methyl, ethyl, propyl, isopropyl, butyl, lsobutyl, cyclohexyl, and the alkoxy sn~lQgs thereof (e.g. methoxy, ethoxy etc.);
fluor~n~ted alkyl and cycloslkyl, cyanoQlkyl and cycloalkyl, and the llke;
sryl h~vlng 6 to 18 c~rbon atoms ~uch a~
phenyl or n~phthyl whereln said aryl group may optlon~lly be substltuted by one or more electron D~14,561 ~4 ~4 wlthdrawlng ~i.e. desctlv~ting) group~ ~uch 89 h~logen (F, Cl, Br or I), -N02, -CN, or -COR (R ~Cl_10 ~lkyl), Other sultable organic radicals include (siloxy or) ollgosiloxy groups oE the formula ~ R6 R t A
wher~ w lcl O to about 10 and the R~ group~ can be the ssme or tlffzrent and have the s~me mesning 8S
~or R ~bove.
Representstlve silyl halid2s lnclude the followlng:
chlorot~lmethylsilane chlorotrlethoxysll~ne chlo~otrlethylsll~ne chloroethoxydlme~hylsllane chlorotrlpropylsllane chloromethoxydlmethylsllan~
chlorotrimethoxy~ilsne tributylchloros~l~ne chlorodiethoxymethyl~ilane butylchlorodlmethylsllane chloropentamethyldi~lloxflne ~-14~5~1 chlorotriisopropylsil~ne chlorolsopropyldimethylsilane chloromethylbls(3,3,3-trlfluoropropyl)sil~ne tri-tert-butylchlorosil~ne chlorotriisopropoxysil~ne dlmethyldecylchlorosilsne 4-(chlorodimethylsllyl)butyronitrile tributoxychlorosll~ne 2-~chlorodimethylsllyl)proionitrile chlorotrihexyl~llane chlorodimethyl(m-nltrophenethyl)silane chlorodimethyl(2,3,4,5,6-penta~luoro-phenethyl)sll~ne chlorodimethyl[2,4,6-tris(l,l-dimethylethyl) phenoxy~sll~ne c:hlorodimethyl(~-nltropropoxy)silsne chloro~isooctyloxy)dimethylsil~ne The amount of halosulfonic acid employed can in general vsry from sbout ().OOS to About 2 moles per mole of polymer repeat unlts. The ~mount o~ sllyl hellde employed c~n Yary from about 0~50 to about 2 moles per mole of haloslllfonic acld, prefer~bly between about 0.9 snfl about 1.4 moles.
In a preferred embodiment mol~r equlvalents of 811yl h~losulfonste and hslosulfonlc ~cld are provlded to the re~ctlon medium. ~he mol~r ratlo of sulfon~ting ~gent to polymer repe~t unlts or subunlts can be sd~usted to schieve a desired de8ree of sulfonation. For purposes of deflnitlon, "degree o sulfon~tlon" 18 the number of indlvidual polymer repeat unlts -0-E-0-E'- whioh h~ve been sulfonsted D-14,561 ~6748~i . - 2~ -as a percentage of tha totsl number of polymer repest unlt~ Avsllable ln the re~ctlon mlxture solution cont~lnlng the reacting polymer. For example, a degree of sulfon~tion of ~bout 33 indlcates that sbout 1 out of every 3 polymer repea~
unlts has been ~ul~on~ted.
When making ~ aulfonated poly(~ryl ether) resln uslng a sllyl hslosulfonate, l.e. the resctlon product of a ~llyl hallde ~nd ~ halosulfonic acld, the ~ilyl halosulfonate can be ~ny compound havlng the structure R3 - Sl - - n x wherein X and R are 8S deflned above.
A~ lntlcated, the ~bove 511yl halosul~onates msy be ~yntheslzed by reactlng the correspondlng halosulfonic acld o Il .
with a ~llyl chlorlde ~-14,561 ., 2 ~ ~ 8 6 R3-Sl-Cl.
all symbols havlng the meanlngs prevlously ssslgned, followlng the genersl principle~ disclosed, for example, by Schmidt et al.,! Chem. Ber., 95, 47, (1962). Representstive silyl chlorldes sre the same as those enumerated supra, and the like.
The amount of silyl halosulfonate reacted w~th a poly(aryl ether) resin can range from about O.OOS to about 2 moles o$ sllyl h~losul~onate per mole o~ polymer repeat unlts -0-E-0-E'- depending on the degree of sulfonation deslred.
For ~ given reaction tlme, temperQture, Qnd concentr~tion of polymer repeat unlts, lncreas~ng the concentratlon of sul~onatlng sgent generslly lncreases the degree Oe sulfon~tlon. The number of moles oP sllyl halosulfonate used per mole of polymer repeat unlts -0-E-0-E'- can be increased beyond 2, but little advantage is to be gained.
Re~ctlon times c~n vary w~dely from fractions of an hour to as long as deslred and can be ~ncre~sed to lncrease the degree o~ sulfonatlon although, reactlon condltions otherwl~e ramainlng conxtant, the rate of sul~onation msy not lncrease linearly with resctlon tlme.
The sul~onating s8ent may be ~dded dlrectly to the re~ctlon mlxture or lt may flrst be dlssolved in ~ solvent, preferably the solvent used to dissolve the polymer. 8ecause the substltutlon reactlon gener~tes hydrogen hallde, lt is preferred to ~dd the sul~onatlng ~gent dropw1se to the dlssolved poly~er~ ~lthough the tlme fo~ addlt~on D-14,561 - 2~ -may vsry wldely from minutes to sever~l hours or more.
The reactlon may be conducted by dissolvlng polymer, e.g., as a powder, flu~f, or pellet ~n a ~olvent and charging the polymer ~olution and sulfonatlng sgent to Q suitable resction vessel which is non-corrosiYe to HCl. Adv~ntsgeously, the vessei may be gl8ss or gl~ss-lined or fabricated of a non-corrosive metal such as HASTELLOY (regis~ered trademark of the Cabot Corporation). The vessel should also be provlded wlth a mesns to effect mechsnic~l mixlng or ~tlrring. Although the reaction has not been found to be particularly .
exothermic or endothermic, heating snd/or cooling means may be deslrable. It can 81so be desirable to provlde means eor provldlng sn lnert ~tmosphere such ~s nltrogen or argon over the reaction solutlon~
Dry gas should be employed since excessive water or water vapor can lnterfere with the sulfonation.
Becaus~ HCl ls gener~ted ln situ by the reaction, provlsion for scrubbing or tr~pping HCl from the reactlon solution may 8'180 be employed. To removs HCl the means used ~o supply ~n lnert g~s atmosphere cRn be implemented to p8SS 8 gentle flow 0~ g8S over the surface of the re~ction solutlan or to sparge gas through the ~olution followed by scrubblng or trapping HCl ~rom the gaseous effluent, e.g. by passlng the e~luent through a solutlon o~
base.
In cases where a relstively volstile ~olvent such 8S methylene chloride is used to conduct the react1on a condenser provided wlth 8 D-14,561 7~
cool~nt such as dry ice/~cetone or chilled brine m~y be used to recondense solvent v~pors ~nd return them to the reactlon medlum.
A~ter havlng conducted the resctlon for the deslred perlod, ~n lntermedl~te 801utlon ls obtalned cont~ning the intermedlate product, ~ polymer hav~ng sllyl sulfon~te groups, ~or ex~mple in the case o~ PSF specific~lly prevlously lllustr~ted:
M
~0~SO~-M~ 03-Si(Me)3 whereln all symbols sre a~ prevlously de~lned. I~
deslred, the sllyl sulfona~e derlvative may be lsolsted, for exsmple, by coflgul~tion of the polymer in 8 nonsolvent such as methanol, acetone, or water~
Cle~vage o~ the 8ilyl group may be conducted by addlng base, yieldlng the desired sulfonated polymer produc. A ~olutlon of base ln 8n ~pproprlate 801vent 1~ sdded to the reactlon solutlon ~nd mechanical sgit~tion contlnued ~or a time ~uf~iclent to substan~i~lly co~plete the cleav~ge. Upon ~ddition of the base some turbldlty may be observed lnlti~lly 1~ the solvent in ~hich the base 18 dlssolved is one c~pable of coagulatlng the polymer, ~lthough ~ener~lly no precipltation occurs .
The b~se used to cle~ve the trlmethylsilyl group c~n be ~ny suituble organlc or inorg~nic b~se such B8 ~mmonium hydroxide or ~n alk~ll or ~lXallne D-14,561 ~L~ 4 esrth metal hydroxlde or alkoxide having 1-15 carbon atoms, preferably 1-3 csrbon atoms, lncludlng sod1um, llthium snd potassium hydroxide, sodlu~, lithium and pot~sslum methoxide, sodlum, 11thlum and potassium ethoxide snd the corresponding magnes~um, calclum, snd barlum hydroxides snd slkoxides, dissolved in 8 suitsble solvent such ~s an alcohol.
Bases such as alkali met~l amldes eg~ KNH2, NaNH2 or LlNH2 can also be employed, or ~he alkyl analogs such ~s NaNHR or NaNR2 where R is a Cl_l5 alkyl group. Inorg~nic hydrlde bases such as lithium, sodlum, or potsgsium hydride or calcium hydride may slso be used. Alkali metsl hydroxides and alkoxldes are preferred.
The base should be added preferably ln an amount sufficient to cleave pendant silyl groups and to neutralize any acld still present in solution.
An excess of base may be used, although any excess should be minlmized to svoid undue base cleavage of the resin chsln backbone. The b~lse cleav~ge of the silyl group ls conducted preferably wlth contlnuous mechanical stlrring for 8 time sufficient for the cleavage resctlon to reach subst~ntial completlon.
Depending on bsse concentration, polymer concentration, etc. gener~lly the b~se cleavage is substantlally complete wlthin flbout ~n hour slthough the cleavsge resctlon may be contlnued for lon~er lf des~red wlth care to avold chaln clesvage of the resln.
Adv~nt~geously, the cleavage reaction ylelds the sul~onated polymer ln salt form D-14,561 7~
M@~ SO -M t ~S02~.
M~
J
where M+ 1~ a cation ~e.g. NH4, Ns , Li , K+,Mg2+ C~2+ or ~a2+) derived from the base whlch cleaves the 5ilyl molety. The polymer s~lt csn be fabrlcated into a more useful asymmetrlc membr~ne and ~ membrane of superlor desslin~tion proper~le~ thsn membrane~ prepAred from the ~cid form of th~ polymer, ~ dlsclosed ln U.S. p~tent 3,875,096. The salt form i~ more stsble th~n the scld form~ especially at high temperatures, and prevents ~ny sel~ degrad~tlon whlch might otherwise occur due ltO the presence o~ acid~c sulfonic acld groups.
If it is desired, however, to fabricate membrane~ from the sulfonlc ~cld (-S03H) form of M
sulfonated p~ly(sryl ether) resln, or to ob~ain the acld form ~or ~ny other ~pplicatlon, the resln sulfonste salt can easlly be converted to the resin sulfonlc acid by slmply exposlng the sslt to 8 dllute solut~on of acld. Sult~ble ~clds are, ~or example, csrboxyllc ~cld~ such as acetlc scld, proplonlc ~cld, snd halogen~ed ~nalQgs thereof ~e.g., trlchlor~cetlc acid snd trifluoro~cetic ~cld), ~ulfonic acld~ such ~ p-toluenesulFonic ~cld, m~thflnesulEonlc acld, and halogenAted ~nalogs thereoE ~e.~., trlEluoromethAnesul~on1c acld, ~rlchloro~ethane~ul~onlc acld), und miner~l ~clds D-14,561 ~uch ~s hydrochlorlc, ~ulfurlc, and nltrlc acids.
The precedlng ~re representstive and by no mesns exh~ustive.
The s~lt c~n be converted to the ~cid followlng b~se cle~vsge of ~llyl groups and prlor to co~gulstion by ~dding ~cld ln R sultable solvent whlch 18 mlscible wlth the solvent in whi~h the resin s~lt ls dlssolved. Care should be tsken to add ~cld sufflcient not only to convert the salt but ~l~o to neutrallze ~ny base le~t over following the base cle~vage of 8ilyl groups. The resln should be washed following coagulstlon to remove any residual ~ree ~cld.
Alternatlvely, the resin salt can flrst be coagulated ~8 known in the 8rt by ~ddlng an excess o~ ~ nonsolvent (e.g. water, ~cetone, or an alcohol) to the resln s~lt ~olution obtained sfter b~se cleav~ge snd lsola~ed as by flltratlon. The res1n so isol~ted may then either be washed dlrectly wlth nonsolvent ~e.g. wster) acld solutlon or sosked therein. Conver~lon to the scld, by percolRtlng ~clt th~ough A sulEon~ted poly(aryl ether) resin salt obtsined ~s ~ ~iltrste, i~ fe~slble bec~use the flltra~e 18 generally a ~lu~fy po~ous product which allows e~flclent ~urf~ce cont~ct with the acid nonsolvent ~olution, ln the manner one regenerates sn lon exch~nge resln. So~king 1~ preferred, however.
Al~ernfltively, the resln ~alt c~n be coa~ulated, lsolated as by filtratlon, ~nd then redis~olved in fresh chloroallpha~lc hydrocsrbon solvent. Acid may be dlssolved in ~he ~olutlon to convert the salt~
D-14,561 -~74~16 The qu~ntity and concentr~tion of ~cid whlch should be added to ~ re~ln s~lt solution or used to w~sh or so~k ~ co~gul~ted resin salt is not critlc~l but may depend, to ~ome extent, on the degree of sul~onatlon. ~enerally, ~ mole r~tlo of acid to sulfon~te s~lt group~ o~ ~bout 10:1 i8 entirely sufficlent to convert substsnti~lly ~11 o~
the sulfonate salt groups to the ~cid form. Adding acid to 8 resin s~lt solutlon sufficlent to m~ke the solutlon lN (one normal), o~ less, in ~cid, or soaking or w~shing co~gulated polymer wlth 1~ (or less) concentrQtlons of ~cld will generally be sufflclent to e~ect converslon, reg~rdless of the degree of sulfonation. Acld solutions morP
concentr~ted than lN m~y be used although c~re should be t~ken to avoid acld cleav~ge of the resin, uncontrolled sulfonatlon when u~lng hlgh concentr~tlons of sulfurlc ~cid~ or undue oxidatlve de~radation when using high concentrations of nltric ~cld.
As-noted Above, co~gulation of the sul~onated resln ln elther ~cid or salt form, if deslred, mfly be effected by ~dding a solutlon of the resln, ln an Rmount sufficlent to effect coagul~tion, ~ny llquld whlch ls miscible therewith but whlch i8 not ~ 801vent for the sulfonated resin, ~s known ln the art.
Membr~nes c~n be fabrlc~ted ~rom sulfonated poly(aryl ether) resins produced ln ~ccordance with thls lnventlon, ~s well known ln the art, ~y by castlng ~ solutlon o~ resin onto ~ suitably ~h~ped surf~ce or substrste ~nd evsporatlng the solvent.
D-14,561 ~ 4 8 ~ `
Sultable solvents ~re, in gener~l, polar orgQnlc solvents ~uch ~ dlmethylormamlde, dlmethyl~ulfoxide, methylpyrrolldone, snd dlethylene glycol monoethyl ether, with dime~hylorm~mlde belng preferred. Relnforce~ mem~rAnes m~y be obtained by cQstlng onto a ~creen such ~ ~ woven fabric or grid. Such method~ have been dlsclosed snd exemplified, for inst~nce, in U.S. p~tents 3,709,841 ~nd 3,8~5,096.
The lnvention wlll be further explained snd described by means of the followlng exQmples which sre not to be t~ken ~5 limltlng:
C. EXPERIMENTAL
ExamPle 1 Forty grams of P-1700, the designatlon for ~ commercial polysulfone manufactured by Unlon Carbide Corpor~tlon, was dissolved in 300 ml of methylene chloride ~CH2C12). The ~olutlon was placed into a glass four neck fl~sk provided with a mech~nlcal ~tlrrer, thermometer, reflux condenser, ~nd nltrogen lnlet. Clrculation of nitrogen over the surfnce of the ~olutlon wa~ started Qnd malntQined throughout the experlment. A separ~te solution of 11.95 gms (0.0634 mole) of trlmethylsllyl chlorosulfonate ln 100 ml of methylene chloride W~8 prepared and added dropwise over ~ perlod of 10 mlnute~ to the stlrred polymer solution at room temperQture. Stlrrlng was contlnued overnlght (-20 hrs.). Twenty-flve gr~ms of ~ 25~ by weight solutlon of ~odlum methoxlde ln meth~nol were ~dded. Development of ~light D-14,561 turbidlty W&S observed~ However, no precipl~tion of polyme~ WBS observed~ After 1 addltional hour of stirrlng the reAction mixture was coagulated ln sn excess (5:1 by vol.) of methanol. The whlte fluffy precipitate was filtered ~nd wHshed once with wster ~nd once with methanol. Each wQsh consisted in a 5 minute sgi~atlon in a Waring blender with 2 liters of watèr or methanol.
The reduced vlscosities were:
0.37 dl/gms, (25C 0.2 gms/100 ml. ln N-methylpyrrolidone) for the starting materiPl, P-1700; and 1.12 dl/gm for the flnal sulfonated salt. A sulfur anqlysis indicated thst the material contalned 0.3083 SQ3Na units per repeat unlt of the polymer, i.e. a degree oF sulfonatlon of abou~
31~.
In comparison to the above result ~-he ef~ect of shorter reaction tlme i.e. the stirring perlod prior to the addltlon of ~he sodlum me~hoxide/methanol 801u~10n) iS shown ln ~he tabulatlon of reduced vlscosity ~RV) and de~ree of sulfonation that follows:
Tlme (Hrs.~ Rv~l) DeRree of Sul~onation ~(2) 4 0.98 14.54 1.03 13.78 ~1) 0.2 gmsllOO ml; 25C, N methylpyrrolldone (~MP).
~2) The two results ~re consldered essentlally ldentlcal, the discrepancy being due to experlmental errors inherent in the snalysis.
,561 ExamPle 2 The generzl procedure of exflmple 1 u~ing P-1700 was followed except that only 8.54gms (0.0453 moles) of (CH3)3SlS03Cl were employed. Also, the reactlon w~ performed at re~lux (-40C) for 4 hours only. The polymer w~s isolated ~s in example l. The sulfonated product h~d ~n RV of 1.15 (0.2 gm/lO0 ml, 25C, NMP ~nd lts degree of sulfon~tion was 3~.2~.
The result indicates that at higher temper~ture~ less of the expensive silyl reagent and shorter reAction times ~re requlred to ~chiev~ a comparsble degree of ~ul~onation. However, lf the re~ction i5 continued Rt reflux overnight (~20 hrs.) degr~datlon oF the polymer is observecl; the degraded ~,~terlal i8 more highly sulfon~ted. Thus, the degraded product hfld ~n RV of 0.58 snd the degree of ~ulfon~tion was 40.7~.
Exam~les 3-21 Additlonsl d~t~ snd results followlng the gener~l procedure of Example l and using reaction times, temper~tures snd amounts ~DE stsrting m~terl~ls ~s no~ed are presented in Table I.
D-14~561 3L~ 4 - _3_3 Conc. of CIS03-P- ~70n S I (CH3) 3 Reoct ~ on _ ~o l ~m~r Exp. (molo rsp0at tmol9/mol~ ~Ima Tcro. Da~ree of ~o. unlt/litor~ r~ t unit) (hrs.~ ~C) l2) RV~3~ Sulfonatlon ~O ~9 3. 0.11 0.10 ~ 25 0.~ 7.57 18S
4. 0.11 0.10 24 25 0.55 9.44 IB4
-~ di~hydroxyphenyl)ethers, such a~
bls-(4-hydroxyphenyl)ether, 4~2'- , 2,2'- , and 2,3 e -dihydroxyphenyl ether, 4,3'- ~nd 4,4'-dlhydroxyl-216-dimethyldiphenyl-ether, bls-(4-hydroxy-3-isobutylphenyl)ether, bis-~4-hydroxy-3-isopropylphenyl)ether, bls-(4 hydroxy-3-chlorophenyl)ether, bls-(4--hydroxy 3-1uorophenyl~ether, bis-(4 hydroxy-3-bromophenyl)ether, bis- (4--hydroxyn~phthyl)ether, bls-(4 hydroxy-3-chloronaphthyl)ether, and 4,4'-dihydroxyl-3,$-dimethoxydlphenyl ether.
Also pre~erred as useful dihydric phenols are the followin8:
HO ~ OH
HO ~ OH
D-14,561 ..
As herein used the E term de~lned as bein~
the "reslduum of the dihydrlc phenol" o~ course refers to the resldue of the dihydrlc phenol ~ter the removal of the two arom~tlc hydroxyl groups.
Thus as ls re~dlly seen these poly~rylene polyethers cont~in recurring groups of the residuum o~ the dihydric phenol snd the residuum of the benzenold compound bonded through ~romatic ether oxygen ~tomsO
Any dihalobenzenoid or dinitrobenzenold compound or mixtures thereof c~n be employed to form an E' benzenoid reslduum in thls lnvention, which compound or compounds has the two halogens or nitro-groups bonded to benzene rings having sn electron wlthdr~wing group ln ~t least one o~ the positlons ortho snd pars to the hslogen or nitro group. The dlhalobenzenold or dinitrobenzenoid compound can be either mononuclear where the halogens or nitro groups ~re attached to the same benzenoid rlng or polynuclear where they ~re attached to different benzenold rlngs, ~s long ~s there is an activ~ting electrorl withdr~wing group ln the ortho or para position of thst benzenoid nucleus~ Fluorine and chlorlne ~ubstltuted benzenold reactants ~re preferred, the ~luorine oompounds for ~ast reactlvlty ~nd the chlorine compounds for their inexpensiv~ness.
An electron withdrawing group can be employed ~s the activator group in these compounds.
It should be, of course, lnert under the reaction condition~, but otherwlse lts structure ls not critlcal. Preferred are the stron~ actl~tlng D-14,561 1~ ..
group~ such as the sulfone group ~-S-) bondlng two il halogen or nltro subst~tuted benzenoid nuclel as in the 4,4'-dichlorodiphenyl ~ulEone and 4,4'-difluorodiphenyl ~ulfone, although such other strong`withdrewlng groups hereinsf~er mentloned can also be used.
lt is preferred that the rinB contaln no electron supplytng groups on the same benzenoid nucleus as the halogen or nltro group; however, the presence of other groups on the nucleus or in the residuum o~ the compound can be toleratsd.
The activating group can be basically -:
either of two types:
(8) monovalent groups that actlvate one or more halogens or nltro-groups on the same ring such as another nitro or halo group, phenylsulfone, or alkyl~ulfone, cyano, trlfluoromethyl, nitroso, and hetero nitrogen, as in pyridine.
(b) dlvalent groups which can activate dlsplacement of halogens on two different rings, o Il such as the sul~one group -S-; the carbonyl group o O H
Il I
-C-; the vinylene group -C~C-; the sulfoxide group D-14,561 1 ~`7 ~fi - 1~
Il -S-; th~ ~zo group -N-N-; the saturuted fluoroc~rbon I
groups -C-, -CF2-CF2CF2-; organ1c phosphine oxides -P-:
where R3 is ~ hydrocarbon group, and the ethylidene group A-C-A where A csn be Il --C--hydrogen or halogen.
I~ deslred, the polymers msy be made with mixtures o~ two or more dlhalobenzenoid or dinl~robenzenoid compound~.. Thus, the E' residuum of the benzenoid compounds in the polymer structure may be the same or dlfferent.
Exsmples of benzenold compound~ which ~re useful ln contrlbuting E' resldua to a poly(aryl ether) resln are the following:
4,4'-dlchlorodiphenyl sulfone, 4,4'-dlfluorodlphenyl sulfone, 4, 4 ~ -bi5 t4-chloroPhenYlsulfonYl)biPhenYl~
4,4'-bls(4-fluorophenylsulfonyl)blphenyl, 4,4'-di~luorobenzophenone, 4,4'-dlchlorobenzophenon~, 4,4'-bis~4-~luorobenzoyl)benzene D-14~561 i74~i 4,4~-bis(4-chlorobenzoyl)benzene, 2,6-dlchlorobenzonitrtle, lsomers thereof, ~nd the like.
It ls seen al80 that as used herein, ~he E' term defined ~s being the "residuum of the benzenoid compound" refers to the aromatic or benzenoid residue of the compound sfter ~he remov~l of the halogen atom or nitro group on the benzenold nucleus.
The polyArylene polyethers of this invention are prepared by methods well known in the art as for tnstance the ~ubstantially equimol~r one-step reaction of ~ double alk~li metsl s~lt of dihydric phenol with a dlhalobenzenold compound in the presence of specific llquid organlc suloxide or sulfone solvents under substantl~lly snhydrous conditions. Catalysts are not necesssry for this reaction.
The polymers may also be prepared in a two-step proce~s in which a dihydric phenol is first converted in situ in the primary reactlon solvent to the alkali metal salt of the reaction with the alkali metal, the alkali met~l hydride, alkali metsl hydroxide, alkall ~et~l ~lkoxide o~ the ~lk~li met~l Alkyl compounds. PreEersbly, the slXali metal hydroxlde ls employed. After removing the water whlch is present or formed, in order to secure substantlally ~nhydrous conditions, the dialkali metal salts of the dlhydric phenol are ~dmixed and reacted with about ~tolchiometrlc quantities of the dihalobenzenoid or dinltrobenzenoid compound.
Addltionally, the polyethers may be prepared by the procedure descrlbed ~n, for example, D-14,561 U.S. Patent 4,176~222 ln whlch ~ substantl~lly equlmolar mlxture of at les~t one blsphenol And ~t lPast one dlh~lobenzenold sre he~ted ~t temper~tur~ of from ~bout 100 to sboue 490C wlth mlxture of ~odium csrbsnate or blcarbonate snd ~
second alkali metal c~rbonate or blcarbon~te h~vlng 8 hlgher ~tomlc number th~n that o sodiu~.
Further, the polyethers may be prep~red by the procedure described ln Csnsdian P~tent 84~,963 wherein the bisphenol and dlhalobenzenold c~mpount are hested ln the presence of pot~sslum carbonate uslng ~ hlgh boillng ~olvent such a~ diphenylsulfone or sul~ol~ne.
Preferred poly~rylene polyethers oE thi~
inventlon are ehose prepared uslng the dlhydrlc polynuclesr phenot~ o~ ths followlng type~, includlng the derivatlves thereo~ whlch are subQtltuted with inert substi~uent group~
~4 ~ a) HO ~ I ~ ~ OH
~4 ln whlch the R4 groups represent independently hydrogen, lower ~lkyl, ~ryl ~nd the h~logen substltuted groups thereoE, whlch c~n be the same or d~E~erent;
~-14,5~1 ~ti7 - la -(b) HO ~ OH
(c~ . HO ~ OH
~d) HO ~ O ~ OH
and substltuted derlvatlve~ thereof.
It 18 also contempl~ted in thls lnvention to use ~ mixture of two or more dlEferent dihydrlc phenols to accomplish the s~me ends 9S ebove. Thus when reflerred to ~bove the -E- reslduum ln the polymer structure can actually be the ~ame or dlf~erent ~romatlc resldu~ mlxture~ of polynuclear dlhydrlc phenol~ such as bln~ry mixtures of dlnuclear blsphenols ~re ~employed, e~ch rlng in one of the component dihydrlc phenols m~y be deactlvated 1~ deslred, sllowlng for the incorporatlon oE (dlfflcultly sul~onatsble) deact~vated unlts lnto the polymer b~ckbone.
Representstive of such deactlv~ted dihydrlc polynuclear phenol~ ~re those wherein the rings are connected by electron wlthdrawing groups, lncludlng dlhydrlc phenols ~uch a~
D 14,561 ~ 19 -HO~SOz~ SO~OH
O
~0~ S~
O
O
HO~ t~ , and t) O
~~C~o~
If such phenols having each rlng de~ctivsted ~re employed 1~ 1~ preferred thst ~hey be ll~lted to les~ than about 95 mole percent of the -E- unlts compr1slng th~ copolymer backbone~
The poly(aryl ether~) hsYe a reduced vlscoslty of Erom about 0.2 to about 2, prefersbly from ~bout 0.35 to about l~5 R~B mea~ured ln an Approprl~te solvent 5t an approprlste tempersture dependlng on the p~rtlcular po'lyether, ~uch ~ ln methylene chlor~de ~t 25C.
The pre~er~ed poly(sryl ethers) have one o~
more repeRt unlts or subunlt~ of the ~ormul~:
~o~ O~ SO~ , D-~4,561 ~0~0~502 ~~~52~52 ~~~S2~52~
H~ ~1~
~0~~~52 C~
t ~ ~o~S02~o~ S~J
~0~~52 D-14, S61 7~8~
The term "subunlt" me~ns th~t sny of the above, ln addl~ion to serving 8s an entire repest unit, can slso be cont~ined ~s psrt of ~ l~rger repeat unlt.
Polymers havlng repeat un~ts or subunits a illustr~ted ~bove are disclosed, for exAmple, ln U.S. patents 4,175,175; 4,320,224; 4,10B,837;
4,00g,149; 3,455,866; 3,518,067; 3,764,583;
3,400,065; 3,647,751; Europe2n pstent (EP) applic~-tlon number 81107193.5, published March 24, 1982 under the publication number 0047999; and EP
appllcstlon 80201194.0, publlshed June 3, 1981 under the publ~catlon number 0029S33.
~ or e~se of dlscussion PSF ls sometimes specific~lly referred to herein for purposes of exemplifylng the lnventlon. Such exemplificstion is not to be taken as limiting, however.
B Process Conditlons The sulfonatlon reactlon is conducted in suitable solvent, suitability being determined by the ability of he solvent to dissolve the polymer and the sulfonsting sgent snd by its lnertness to the sulfonatlng ~gent. Pre~erred ~re chloroallphatlc hydrocsrbons such as chloroform, methylene chlorlde, and 1,2-dlchloroethane.
Chlorin~ted sromstlc hydrocsrbons ~uch ~s chlorobenzene sre less deslrable slnce, although they csn be accept~ble to dlssolve the polymer, they can ~lso be reactive to the sul~onatlng agent. It 18 belleved that deactlvated aromatlc hydrocarbons such 8S tr~chlorobenzene snd nltrobenzene are ~uit~ble ~olvents.
~-14,561 3L~ ~7~ 6 The ~mount of solvent used to conduct the re~c~lon ls non-crlticsl although an amount o~
solvent should not ~e used that ls l~rge enough ~o dilute the re~ction mixture ~o ~he polnt ~hat the rate o~ re~ction is ~dversely slowed. The minimum amount oÇ solvent is thAt amoun~ which is su~flc~ent to ~ust dissolve the polymer and the sulfonatlng agent. When using chloroallph~ti~ hydroc~rbons such &S methylene chlorlde or 1,2-dichloroethane, ~n amount o~ solvent between 5 And 20 ml per gram o~
polymer, prefersbly between 10 snd lS ml per gram of polymer, may be employed.
The reaction is preferably conducted at sbout room temper~ture, say between ~bout 0C ~nd ~bout 35C. Conducting the reaction ~t hi~her temper~tures may increQse chain scission ~o unscceptable levels rel~tive to the smount of chain scission which occurs ~t lower temperstures. The reactlon m~y be conducted at temperstures lower thsn 0C althou~h the resction r~te msy decrease, necessitating conducting the resctlon ~or longer periods.
No speci~l pressure considerstions are re~ulred, the re~ction generally be~ng conducted ~t ~mblent pressure.
When msklng ~ sulfonated poly~ryl ether) resin uslng ~ 811yl hslide/hslosulfonic scid comblnstlon, the h~losulfonic ~cld csn be ~ny of the compoundæ hcvlng the ~ormul~
D-14,5Sl O
whereln X i8 Cl~ or Br or I, pre~erably Cl.
As previously noted the s~lyl h~llde ean be any compound havlng the structure R
R - Si - X
whereln X 18 hslogen selected from the group conslsting o~ Cl, ~r and I, preferably Cl. The R
groups can ln general be the same or dlfferent orgsnlc radlcals and be ~ny group whlch ls lnert, l.e. whlch 18 not reactive toward the polymer, which does not render the sulfonating agent ~nsoluble ~n the reaction medlum, and whlch preferably does not lnter~ere wlth base cleavage of the Si-0 bond. R
can, ~or ~xample, be:
~ llphatlc or cycloallphatlc alkyl or alkoxy hsvlng 1-10 carbon atoms, lncludlng methyl, ethyl, propyl, isopropyl, butyl, lsobutyl, cyclohexyl, and the alkoxy sn~lQgs thereof (e.g. methoxy, ethoxy etc.);
fluor~n~ted alkyl and cycloslkyl, cyanoQlkyl and cycloalkyl, and the llke;
sryl h~vlng 6 to 18 c~rbon atoms ~uch a~
phenyl or n~phthyl whereln said aryl group may optlon~lly be substltuted by one or more electron D~14,561 ~4 ~4 wlthdrawlng ~i.e. desctlv~ting) group~ ~uch 89 h~logen (F, Cl, Br or I), -N02, -CN, or -COR (R ~Cl_10 ~lkyl), Other sultable organic radicals include (siloxy or) ollgosiloxy groups oE the formula ~ R6 R t A
wher~ w lcl O to about 10 and the R~ group~ can be the ssme or tlffzrent and have the s~me mesning 8S
~or R ~bove.
Representstlve silyl halid2s lnclude the followlng:
chlorot~lmethylsilane chlorotrlethoxysll~ne chlo~otrlethylsll~ne chloroethoxydlme~hylsllane chlorotrlpropylsllane chloromethoxydlmethylsllan~
chlorotrimethoxy~ilsne tributylchloros~l~ne chlorodiethoxymethyl~ilane butylchlorodlmethylsllane chloropentamethyldi~lloxflne ~-14~5~1 chlorotriisopropylsil~ne chlorolsopropyldimethylsilane chloromethylbls(3,3,3-trlfluoropropyl)sil~ne tri-tert-butylchlorosil~ne chlorotriisopropoxysil~ne dlmethyldecylchlorosilsne 4-(chlorodimethylsllyl)butyronitrile tributoxychlorosll~ne 2-~chlorodimethylsllyl)proionitrile chlorotrihexyl~llane chlorodimethyl(m-nltrophenethyl)silane chlorodimethyl(2,3,4,5,6-penta~luoro-phenethyl)sll~ne chlorodimethyl[2,4,6-tris(l,l-dimethylethyl) phenoxy~sll~ne c:hlorodimethyl(~-nltropropoxy)silsne chloro~isooctyloxy)dimethylsil~ne The amount of halosulfonic acid employed can in general vsry from sbout ().OOS to About 2 moles per mole of polymer repeat unlts. The ~mount o~ sllyl hellde employed c~n Yary from about 0~50 to about 2 moles per mole of haloslllfonic acld, prefer~bly between about 0.9 snfl about 1.4 moles.
In a preferred embodiment mol~r equlvalents of 811yl h~losulfonste and hslosulfonlc ~cld are provlded to the re~ctlon medium. ~he mol~r ratlo of sulfon~ting ~gent to polymer repe~t unlts or subunlts can be sd~usted to schieve a desired de8ree of sulfonation. For purposes of deflnitlon, "degree o sulfon~tlon" 18 the number of indlvidual polymer repeat unlts -0-E-0-E'- whioh h~ve been sulfonsted D-14,561 ~6748~i . - 2~ -as a percentage of tha totsl number of polymer repest unlt~ Avsllable ln the re~ctlon mlxture solution cont~lnlng the reacting polymer. For example, a degree of sulfon~tion of ~bout 33 indlcates that sbout 1 out of every 3 polymer repea~
unlts has been ~ul~on~ted.
When making ~ aulfonated poly(~ryl ether) resln uslng a sllyl hslosulfonate, l.e. the resctlon product of a ~llyl hallde ~nd ~ halosulfonic acld, the ~ilyl halosulfonate can be ~ny compound havlng the structure R3 - Sl - - n x wherein X and R are 8S deflned above.
A~ lntlcated, the ~bove 511yl halosul~onates msy be ~yntheslzed by reactlng the correspondlng halosulfonic acld o Il .
with a ~llyl chlorlde ~-14,561 ., 2 ~ ~ 8 6 R3-Sl-Cl.
all symbols havlng the meanlngs prevlously ssslgned, followlng the genersl principle~ disclosed, for example, by Schmidt et al.,! Chem. Ber., 95, 47, (1962). Representstive silyl chlorldes sre the same as those enumerated supra, and the like.
The amount of silyl halosulfonate reacted w~th a poly(aryl ether) resin can range from about O.OOS to about 2 moles o$ sllyl h~losul~onate per mole o~ polymer repeat unlts -0-E-0-E'- depending on the degree of sulfonation deslred.
For ~ given reaction tlme, temperQture, Qnd concentr~tion of polymer repeat unlts, lncreas~ng the concentratlon of sul~onatlng sgent generslly lncreases the degree Oe sulfon~tlon. The number of moles oP sllyl halosulfonate used per mole of polymer repeat unlts -0-E-0-E'- can be increased beyond 2, but little advantage is to be gained.
Re~ctlon times c~n vary w~dely from fractions of an hour to as long as deslred and can be ~ncre~sed to lncrease the degree o~ sulfonatlon although, reactlon condltions otherwl~e ramainlng conxtant, the rate of sul~onation msy not lncrease linearly with resctlon tlme.
The sul~onating s8ent may be ~dded dlrectly to the re~ctlon mlxture or lt may flrst be dlssolved in ~ solvent, preferably the solvent used to dissolve the polymer. 8ecause the substltutlon reactlon gener~tes hydrogen hallde, lt is preferred to ~dd the sul~onatlng ~gent dropw1se to the dlssolved poly~er~ ~lthough the tlme fo~ addlt~on D-14,561 - 2~ -may vsry wldely from minutes to sever~l hours or more.
The reactlon may be conducted by dissolvlng polymer, e.g., as a powder, flu~f, or pellet ~n a ~olvent and charging the polymer ~olution and sulfonatlng sgent to Q suitable resction vessel which is non-corrosiYe to HCl. Adv~ntsgeously, the vessei may be gl8ss or gl~ss-lined or fabricated of a non-corrosive metal such as HASTELLOY (regis~ered trademark of the Cabot Corporation). The vessel should also be provlded wlth a mesns to effect mechsnic~l mixlng or ~tlrring. Although the reaction has not been found to be particularly .
exothermic or endothermic, heating snd/or cooling means may be deslrable. It can 81so be desirable to provlde means eor provldlng sn lnert ~tmosphere such ~s nltrogen or argon over the reaction solutlon~
Dry gas should be employed since excessive water or water vapor can lnterfere with the sulfonation.
Becaus~ HCl ls gener~ted ln situ by the reaction, provlsion for scrubbing or tr~pping HCl from the reactlon solution may 8'180 be employed. To removs HCl the means used ~o supply ~n lnert g~s atmosphere cRn be implemented to p8SS 8 gentle flow 0~ g8S over the surface of the re~ction solutlan or to sparge gas through the ~olution followed by scrubblng or trapping HCl ~rom the gaseous effluent, e.g. by passlng the e~luent through a solutlon o~
base.
In cases where a relstively volstile ~olvent such 8S methylene chloride is used to conduct the react1on a condenser provided wlth 8 D-14,561 7~
cool~nt such as dry ice/~cetone or chilled brine m~y be used to recondense solvent v~pors ~nd return them to the reactlon medlum.
A~ter havlng conducted the resctlon for the deslred perlod, ~n lntermedl~te 801utlon ls obtalned cont~ning the intermedlate product, ~ polymer hav~ng sllyl sulfon~te groups, ~or ex~mple in the case o~ PSF specific~lly prevlously lllustr~ted:
M
~0~SO~-M~ 03-Si(Me)3 whereln all symbols sre a~ prevlously de~lned. I~
deslred, the sllyl sulfona~e derlvative may be lsolsted, for exsmple, by coflgul~tion of the polymer in 8 nonsolvent such as methanol, acetone, or water~
Cle~vage o~ the 8ilyl group may be conducted by addlng base, yieldlng the desired sulfonated polymer produc. A ~olutlon of base ln 8n ~pproprlate 801vent 1~ sdded to the reactlon solutlon ~nd mechanical sgit~tion contlnued ~or a time ~uf~iclent to substan~i~lly co~plete the cleav~ge. Upon ~ddition of the base some turbldlty may be observed lnlti~lly 1~ the solvent in ~hich the base 18 dlssolved is one c~pable of coagulatlng the polymer, ~lthough ~ener~lly no precipltation occurs .
The b~se used to cle~ve the trlmethylsilyl group c~n be ~ny suituble organlc or inorg~nic b~se such B8 ~mmonium hydroxide or ~n alk~ll or ~lXallne D-14,561 ~L~ 4 esrth metal hydroxlde or alkoxide having 1-15 carbon atoms, preferably 1-3 csrbon atoms, lncludlng sod1um, llthium snd potassium hydroxide, sodlu~, lithium and pot~sslum methoxide, sodlum, 11thlum and potassium ethoxide snd the corresponding magnes~um, calclum, snd barlum hydroxides snd slkoxides, dissolved in 8 suitsble solvent such ~s an alcohol.
Bases such as alkali met~l amldes eg~ KNH2, NaNH2 or LlNH2 can also be employed, or ~he alkyl analogs such ~s NaNHR or NaNR2 where R is a Cl_l5 alkyl group. Inorg~nic hydrlde bases such as lithium, sodlum, or potsgsium hydride or calcium hydride may slso be used. Alkali metsl hydroxides and alkoxldes are preferred.
The base should be added preferably ln an amount sufficient to cleave pendant silyl groups and to neutralize any acld still present in solution.
An excess of base may be used, although any excess should be minlmized to svoid undue base cleavage of the resin chsln backbone. The b~lse cleav~ge of the silyl group ls conducted preferably wlth contlnuous mechanical stlrring for 8 time sufficient for the cleavage resctlon to reach subst~ntial completlon.
Depending on bsse concentration, polymer concentration, etc. gener~lly the b~se cleavage is substantlally complete wlthin flbout ~n hour slthough the cleavsge resctlon may be contlnued for lon~er lf des~red wlth care to avold chaln clesvage of the resln.
Adv~nt~geously, the cleavage reaction ylelds the sul~onated polymer ln salt form D-14,561 7~
M@~ SO -M t ~S02~.
M~
J
where M+ 1~ a cation ~e.g. NH4, Ns , Li , K+,Mg2+ C~2+ or ~a2+) derived from the base whlch cleaves the 5ilyl molety. The polymer s~lt csn be fabrlcated into a more useful asymmetrlc membr~ne and ~ membrane of superlor desslin~tion proper~le~ thsn membrane~ prepAred from the ~cid form of th~ polymer, ~ dlsclosed ln U.S. p~tent 3,875,096. The salt form i~ more stsble th~n the scld form~ especially at high temperatures, and prevents ~ny sel~ degrad~tlon whlch might otherwise occur due ltO the presence o~ acid~c sulfonic acld groups.
If it is desired, however, to fabricate membrane~ from the sulfonlc ~cld (-S03H) form of M
sulfonated p~ly(sryl ether) resln, or to ob~ain the acld form ~or ~ny other ~pplicatlon, the resln sulfonste salt can easlly be converted to the resin sulfonlc acid by slmply exposlng the sslt to 8 dllute solut~on of acld. Sult~ble ~clds are, ~or example, csrboxyllc ~cld~ such as acetlc scld, proplonlc ~cld, snd halogen~ed ~nalQgs thereof ~e.g., trlchlor~cetlc acid snd trifluoro~cetic ~cld), ~ulfonic acld~ such ~ p-toluenesulFonic ~cld, m~thflnesulEonlc acld, and halogenAted ~nalogs thereoE ~e.~., trlEluoromethAnesul~on1c acld, ~rlchloro~ethane~ul~onlc acld), und miner~l ~clds D-14,561 ~uch ~s hydrochlorlc, ~ulfurlc, and nltrlc acids.
The precedlng ~re representstive and by no mesns exh~ustive.
The s~lt c~n be converted to the ~cid followlng b~se cle~vsge of ~llyl groups and prlor to co~gulstion by ~dding ~cld ln R sultable solvent whlch 18 mlscible wlth the solvent in whi~h the resin s~lt ls dlssolved. Care should be tsken to add ~cld sufflcient not only to convert the salt but ~l~o to neutrallze ~ny base le~t over following the base cle~vage of 8ilyl groups. The resln should be washed following coagulstlon to remove any residual ~ree ~cld.
Alternatlvely, the resin salt can flrst be coagulated ~8 known in the 8rt by ~ddlng an excess o~ ~ nonsolvent (e.g. water, ~cetone, or an alcohol) to the resln s~lt ~olution obtained sfter b~se cleav~ge snd lsola~ed as by flltratlon. The res1n so isol~ted may then either be washed dlrectly wlth nonsolvent ~e.g. wster) acld solutlon or sosked therein. Conver~lon to the scld, by percolRtlng ~clt th~ough A sulEon~ted poly(aryl ether) resin salt obtsined ~s ~ ~iltrste, i~ fe~slble bec~use the flltra~e 18 generally a ~lu~fy po~ous product which allows e~flclent ~urf~ce cont~ct with the acid nonsolvent ~olution, ln the manner one regenerates sn lon exch~nge resln. So~king 1~ preferred, however.
Al~ernfltively, the resln ~alt c~n be coa~ulated, lsolated as by filtratlon, ~nd then redis~olved in fresh chloroallpha~lc hydrocsrbon solvent. Acid may be dlssolved in ~he ~olutlon to convert the salt~
D-14,561 -~74~16 The qu~ntity and concentr~tion of ~cid whlch should be added to ~ re~ln s~lt solution or used to w~sh or so~k ~ co~gul~ted resin salt is not critlc~l but may depend, to ~ome extent, on the degree of sul~onatlon. ~enerally, ~ mole r~tlo of acid to sulfon~te s~lt group~ o~ ~bout 10:1 i8 entirely sufficlent to convert substsnti~lly ~11 o~
the sulfonate salt groups to the ~cid form. Adding acid to 8 resin s~lt solutlon sufficlent to m~ke the solutlon lN (one normal), o~ less, in ~cid, or soaking or w~shing co~gulated polymer wlth 1~ (or less) concentrQtlons of ~cld will generally be sufflclent to e~ect converslon, reg~rdless of the degree of sulfonation. Acld solutions morP
concentr~ted than lN m~y be used although c~re should be t~ken to avoid acld cleav~ge of the resin, uncontrolled sulfonatlon when u~lng hlgh concentr~tlons of sulfurlc ~cid~ or undue oxidatlve de~radation when using high concentrations of nltric ~cld.
As-noted Above, co~gulation of the sul~onated resln ln elther ~cid or salt form, if deslred, mfly be effected by ~dding a solutlon of the resln, ln an Rmount sufficlent to effect coagul~tion, ~ny llquld whlch ls miscible therewith but whlch i8 not ~ 801vent for the sulfonated resin, ~s known ln the art.
Membr~nes c~n be fabrlc~ted ~rom sulfonated poly(aryl ether) resins produced ln ~ccordance with thls lnventlon, ~s well known ln the art, ~y by castlng ~ solutlon o~ resin onto ~ suitably ~h~ped surf~ce or substrste ~nd evsporatlng the solvent.
D-14,561 ~ 4 8 ~ `
Sultable solvents ~re, in gener~l, polar orgQnlc solvents ~uch ~ dlmethylormamlde, dlmethyl~ulfoxide, methylpyrrolldone, snd dlethylene glycol monoethyl ether, with dime~hylorm~mlde belng preferred. Relnforce~ mem~rAnes m~y be obtained by cQstlng onto a ~creen such ~ ~ woven fabric or grid. Such method~ have been dlsclosed snd exemplified, for inst~nce, in U.S. p~tents 3,709,841 ~nd 3,8~5,096.
The lnvention wlll be further explained snd described by means of the followlng exQmples which sre not to be t~ken ~5 limltlng:
C. EXPERIMENTAL
ExamPle 1 Forty grams of P-1700, the designatlon for ~ commercial polysulfone manufactured by Unlon Carbide Corpor~tlon, was dissolved in 300 ml of methylene chloride ~CH2C12). The ~olutlon was placed into a glass four neck fl~sk provided with a mech~nlcal ~tlrrer, thermometer, reflux condenser, ~nd nltrogen lnlet. Clrculation of nitrogen over the surfnce of the ~olutlon wa~ started Qnd malntQined throughout the experlment. A separ~te solution of 11.95 gms (0.0634 mole) of trlmethylsllyl chlorosulfonate ln 100 ml of methylene chloride W~8 prepared and added dropwise over ~ perlod of 10 mlnute~ to the stlrred polymer solution at room temperQture. Stlrrlng was contlnued overnlght (-20 hrs.). Twenty-flve gr~ms of ~ 25~ by weight solutlon of ~odlum methoxlde ln meth~nol were ~dded. Development of ~light D-14,561 turbidlty W&S observed~ However, no precipl~tion of polyme~ WBS observed~ After 1 addltional hour of stirrlng the reAction mixture was coagulated ln sn excess (5:1 by vol.) of methanol. The whlte fluffy precipitate was filtered ~nd wHshed once with wster ~nd once with methanol. Each wQsh consisted in a 5 minute sgi~atlon in a Waring blender with 2 liters of watèr or methanol.
The reduced vlscosities were:
0.37 dl/gms, (25C 0.2 gms/100 ml. ln N-methylpyrrolidone) for the starting materiPl, P-1700; and 1.12 dl/gm for the flnal sulfonated salt. A sulfur anqlysis indicated thst the material contalned 0.3083 SQ3Na units per repeat unlt of the polymer, i.e. a degree oF sulfonatlon of abou~
31~.
In comparison to the above result ~-he ef~ect of shorter reaction tlme i.e. the stirring perlod prior to the addltlon of ~he sodlum me~hoxide/methanol 801u~10n) iS shown ln ~he tabulatlon of reduced vlscosity ~RV) and de~ree of sulfonation that follows:
Tlme (Hrs.~ Rv~l) DeRree of Sul~onation ~(2) 4 0.98 14.54 1.03 13.78 ~1) 0.2 gmsllOO ml; 25C, N methylpyrrolldone (~MP).
~2) The two results ~re consldered essentlally ldentlcal, the discrepancy being due to experlmental errors inherent in the snalysis.
,561 ExamPle 2 The generzl procedure of exflmple 1 u~ing P-1700 was followed except that only 8.54gms (0.0453 moles) of (CH3)3SlS03Cl were employed. Also, the reactlon w~ performed at re~lux (-40C) for 4 hours only. The polymer w~s isolated ~s in example l. The sulfonated product h~d ~n RV of 1.15 (0.2 gm/lO0 ml, 25C, NMP ~nd lts degree of sulfon~tion was 3~.2~.
The result indicates that at higher temper~ture~ less of the expensive silyl reagent and shorter reAction times ~re requlred to ~chiev~ a comparsble degree of ~ul~onation. However, lf the re~ction i5 continued Rt reflux overnight (~20 hrs.) degr~datlon oF the polymer is observecl; the degraded ~,~terlal i8 more highly sulfon~ted. Thus, the degraded product hfld ~n RV of 0.58 snd the degree of ~ulfon~tion was 40.7~.
Exam~les 3-21 Additlonsl d~t~ snd results followlng the gener~l procedure of Example l and using reaction times, temper~tures snd amounts ~DE stsrting m~terl~ls ~s no~ed are presented in Table I.
D-14~561 3L~ 4 - _3_3 Conc. of CIS03-P- ~70n S I (CH3) 3 Reoct ~ on _ ~o l ~m~r Exp. (molo rsp0at tmol9/mol~ ~Ima Tcro. Da~ree of ~o. unlt/litor~ r~ t unit) (hrs.~ ~C) l2) RV~3~ Sulfonatlon ~O ~9 3. 0.11 0.10 ~ 25 0.~ 7.57 18S
4. 0.11 0.10 24 25 0.55 9.44 IB4
5. 0.11 0.~0 ~ 25 0.45 10.9
6. 0.11 0.~0 3 25 0.78 g.64 191
7. 0. i 1 0.40 24 25 0.92 180 15 B. 0.11 0.40 24 BC4 0.81 28.76 204 9. 0.1 t 0.50 ~ 25 0.72 12.47 190 10. O. I 1 0.50 24 25 0.8~ 22.8 211 I l . 0.11 0.60 ~ 25 O.B~ 19.6 I S6 12. 0. I 1 0.60 24 25 1.21 2~.B 215 13. 0. t 1 0.80 ~ 25 0.9~ 24.4 200 14. o. l 1 0.90 ~ 25 ~ .00 21.4 20 15. 0.22 0.40 2.5 40 0.s6 2S.94 16. 0.22 0.40 20 40 0.35(5) 33.~
17. 0.22 0.60 24 25 ~ .17 22.34 - -18. 0.22 0.70 22 ~5 1.16 ~7.9D 230 19. 0.22 0.~0 1 25 0.72 g.8 191 20. 0.22 0.~0 ~ 25 0.82 11.7 192 21. 0.22 0.~0 4 25 1.10 16.9 195 1. All experiments were per~ormed uslng the same bstch o~ UCC P-1700, RY(0.2g~100ml.
N-methylpyrolldone, 25C)z0.37.
2. All experlments in methylene ch~oride solv~nt either ~t room-temperature ~25G) or at re~lux ~40C), except where lndicsted otherwise.
3. RV's measured ln N-methylpyrolldone aS 25C
(0.2g/lOOml).
4. This experiment was performed ln 1,2-dlchloroethane.
S. Degr~dstlon due to prolonged high-temperRture tre~tment.
D-14,56l Example 22 Forty grams of dried P-1700 was dissolved ln 370 ml methylene ~hlor~de ln a 1,000 ml 3-nec~
flask fit~ed wlth mechanical stirrer, condense~, ~nd nltrogen sparge tube. The solution was purged with nltrogen for one hour ~nd trlmethylsilyl chloride (7~57 ~m, .0697 moles) W8S edded from ~n sdd~tion funnel over 5 minutes and rinsed ln wlth 15 ml of methylene chloride. Chlorosulfonic ~cid (7.39 gm, 0.0634 mole) was then added dropwise over one hour snd rlnsed ln wlth 15 ml of methylene chloride. The solution was ~hen stlrred ~t room temperature overnight. The reactlon solution was homogeneous throughout thls time. A 25~ solution (40 gm) oE
sodium methoxide ln methanol W8S ~dded to the reaction. After an hour t~e homogeneous solution was ~dded to a large excess o~ methanol in a blender to coagulate the polymer. The recovered polymer was washed with water snd methanol in the blender and dried in ~ vacuum oven. The polymer reduced viscosity (RV, 0.2% in NMP) was 0.98. Elemental ~nslysls g~ve 8.92~ ~ulfur ~nd 1.64~ sodium ~32.31L
degree of sul~onstlon~. The product glsss transition temperature wss 224C.
The polymer of this example exhiblted lmproved resistance to ~olvent~ such as acetonP, ethyl ~cetute, ~nd toluene, compared to polysul~one.
ExamPle 23 The sulfonation resctlon was repeated essentislly B~ ln Example 22 us~ng 40 gm (P-1700) polysulfone, 6.88 8m (0.0634 mole) trlmethylsllyl chlorlde, snd 7.39 gm ~0.0634 mole) chloroaulfonlc ~-14,S6~
67~&
~cid in 8 to~81 of 400 ml methylene chloride contsinlng 1.~ mmole ~29 mg) w~ter. A dry ice/~cetone condenser was used. A sample taXen 8f ter 4 hours gsve an RV of 0.80. After 22 hours ~t room temper~ture, the reaction was treated with base snd the polymer recovered, as in Example 22. The product h~d ~n RV = 1.14, S.85~ sulfur, end 1.50 sodium (30.8~ degree of sulfonation).
~omParatlve Example A
The sulfonatlon of Example 22 was repested wlthout trlmethylsilyl chlorlde. Thus, 40 gm of (P-1709) polysulfone ln 385 ml methylene chlorlde was reacted with 7.38 gm (0.0634 mole) chlorosulfonic acid (15 ml solvent rinse)~ The reaction w~s heterogeneous, having two distinct phsses. After 22 hours, the lower 2hase was thick and the stirrer w~s l~borlng. Sodlum methoxidelmeth~nol solution was added which caused partlal dissolution o the lower layer. The polymer was recovered 8~ in Ex~mple l, but was extremely dlfficult to ~llter because o~ the flneness of the particles. The recovered ~olymer h~d an RV of 0.61 and gave anslysis for 9.47~ sulEur ~nd 2.39~ sodium (nomlnally 43.9% degree of sulfonation). The polymer glass tr~nsltlon was 264C. A æAmple tsken a~ter 4 hours h~d an RV of 0.98.
Compflred to Examples 22 and 23, this Example illustrates that sulfonation wlth chlorosulEonlc acld results in ~n ~pparent good degree 9f ~ulfonation but can result in 8.
signlficAntly lower molecul~r weight product. The decreese ln molecular welght between 4 and 22 hours ~-14,~61 ~o ~as ~hown by B decresse in the RV) indlcates ch~in clea~Rge o$ the polymer. Thls Ex~mple ~lso lllustrates thRt chlorosulfonic scld slone results in ~ heterogenous, two-phsse system wherea~ ~n the presence of trimethylsilyl chloride the resctlon is homogeneous. -, comPar`~tive Ex~mPle ~
The sul~onation w~s repeated essenti~lly AS in Ex~mple 22 uslng 40 gm of (P-1700) polysulfone in 300 ml methylene chlorlde And addlng a solution of trlmethylsilyl chlorosulfonate (11.95 gm, 0.0634 mole, obt~lned from Fluka AG) in 100 ml methylene chlor1de over 10 minutes. A~ter s~lrring st room ~empersture overnight, the homogeneous re~ctlon medium w~s treated wlth sodium methoxide snd the polymer recovered ~s ln Exsmple 22. The po-Lymer RV
W8S ~ nd g~ve elemental snalysis ~or 8.86 sulfur ~nd 0.439 sodlum (31.0~ degree of sulfon~tion).
This Ex~mple illustrstas thst the use of trimethyl3ilyl chlorosulfon~te re~gent ~lso results in polymers wlth good molecul~r welght ~nd degrees of sulfon~t~on sim~lar to those obtalned ~n Ex~mples 22 ~nd 23. The ln situ process of Examples 22 snd 23 is~ however, less co~tly~
Ex~mPle 24 The resctlon wss repested essentlally ~s ln Ex~mple 22, except that the trimethylsilyl chloride (8.25 gm, 0.076 mole) ~n 25 ml methylene chlorSde wu~ fldded to the chlorosulfonic ~cld (7.39 gm, 0.0634) ln 25 ml solvent in ~n ~dditlon ~unnel.
D-14,561 2 ~
After 2 hours at room temper~ture thls mlxture wa5 then ~dded to polysulfone (40 gm) d1s301ved in 300 ml solvent. Af~er 22 hours, the homogeneous reaction medlum was treated with sodium methoxlde and the polymer recovered 8S ln Example 22. The polymer RV was.Ø96 ~nd elemental an~lysis g~ve
17. 0.22 0.60 24 25 ~ .17 22.34 - -18. 0.22 0.70 22 ~5 1.16 ~7.9D 230 19. 0.22 0.~0 1 25 0.72 g.8 191 20. 0.22 0.~0 ~ 25 0.82 11.7 192 21. 0.22 0.~0 4 25 1.10 16.9 195 1. All experiments were per~ormed uslng the same bstch o~ UCC P-1700, RY(0.2g~100ml.
N-methylpyrolldone, 25C)z0.37.
2. All experlments in methylene ch~oride solv~nt either ~t room-temperature ~25G) or at re~lux ~40C), except where lndicsted otherwise.
3. RV's measured ln N-methylpyrolldone aS 25C
(0.2g/lOOml).
4. This experiment was performed ln 1,2-dlchloroethane.
S. Degr~dstlon due to prolonged high-temperRture tre~tment.
D-14,56l Example 22 Forty grams of dried P-1700 was dissolved ln 370 ml methylene ~hlor~de ln a 1,000 ml 3-nec~
flask fit~ed wlth mechanical stirrer, condense~, ~nd nltrogen sparge tube. The solution was purged with nltrogen for one hour ~nd trlmethylsilyl chloride (7~57 ~m, .0697 moles) W8S edded from ~n sdd~tion funnel over 5 minutes and rinsed ln wlth 15 ml of methylene chloride. Chlorosulfonic ~cid (7.39 gm, 0.0634 mole) was then added dropwise over one hour snd rlnsed ln wlth 15 ml of methylene chloride. The solution was ~hen stlrred ~t room temperature overnight. The reactlon solution was homogeneous throughout thls time. A 25~ solution (40 gm) oE
sodium methoxide ln methanol W8S ~dded to the reaction. After an hour t~e homogeneous solution was ~dded to a large excess o~ methanol in a blender to coagulate the polymer. The recovered polymer was washed with water snd methanol in the blender and dried in ~ vacuum oven. The polymer reduced viscosity (RV, 0.2% in NMP) was 0.98. Elemental ~nslysls g~ve 8.92~ ~ulfur ~nd 1.64~ sodium ~32.31L
degree of sul~onstlon~. The product glsss transition temperature wss 224C.
The polymer of this example exhiblted lmproved resistance to ~olvent~ such as acetonP, ethyl ~cetute, ~nd toluene, compared to polysul~one.
ExamPle 23 The sulfonation resctlon was repeated essentislly B~ ln Example 22 us~ng 40 gm (P-1700) polysulfone, 6.88 8m (0.0634 mole) trlmethylsllyl chlorlde, snd 7.39 gm ~0.0634 mole) chloroaulfonlc ~-14,S6~
67~&
~cid in 8 to~81 of 400 ml methylene chloride contsinlng 1.~ mmole ~29 mg) w~ter. A dry ice/~cetone condenser was used. A sample taXen 8f ter 4 hours gsve an RV of 0.80. After 22 hours ~t room temper~ture, the reaction was treated with base snd the polymer recovered, as in Example 22. The product h~d ~n RV = 1.14, S.85~ sulfur, end 1.50 sodium (30.8~ degree of sulfonation).
~omParatlve Example A
The sulfonatlon of Example 22 was repested wlthout trlmethylsilyl chlorlde. Thus, 40 gm of (P-1709) polysulfone ln 385 ml methylene chlorlde was reacted with 7.38 gm (0.0634 mole) chlorosulfonic acid (15 ml solvent rinse)~ The reaction w~s heterogeneous, having two distinct phsses. After 22 hours, the lower 2hase was thick and the stirrer w~s l~borlng. Sodlum methoxidelmeth~nol solution was added which caused partlal dissolution o the lower layer. The polymer was recovered 8~ in Ex~mple l, but was extremely dlfficult to ~llter because o~ the flneness of the particles. The recovered ~olymer h~d an RV of 0.61 and gave anslysis for 9.47~ sulEur ~nd 2.39~ sodium (nomlnally 43.9% degree of sulfonation). The polymer glass tr~nsltlon was 264C. A æAmple tsken a~ter 4 hours h~d an RV of 0.98.
Compflred to Examples 22 and 23, this Example illustrates that sulfonation wlth chlorosulEonlc acld results in ~n ~pparent good degree 9f ~ulfonation but can result in 8.
signlficAntly lower molecul~r weight product. The decreese ln molecular welght between 4 and 22 hours ~-14,~61 ~o ~as ~hown by B decresse in the RV) indlcates ch~in clea~Rge o$ the polymer. Thls Ex~mple ~lso lllustrates thRt chlorosulfonic scld slone results in ~ heterogenous, two-phsse system wherea~ ~n the presence of trimethylsilyl chloride the resctlon is homogeneous. -, comPar`~tive Ex~mPle ~
The sul~onation w~s repeated essenti~lly AS in Ex~mple 22 uslng 40 gm of (P-1700) polysulfone in 300 ml methylene chlorlde And addlng a solution of trlmethylsilyl chlorosulfonate (11.95 gm, 0.0634 mole, obt~lned from Fluka AG) in 100 ml methylene chlor1de over 10 minutes. A~ter s~lrring st room ~empersture overnight, the homogeneous re~ctlon medium w~s treated wlth sodium methoxide snd the polymer recovered ~s ln Exsmple 22. The po-Lymer RV
W8S ~ nd g~ve elemental snalysis ~or 8.86 sulfur ~nd 0.439 sodlum (31.0~ degree of sulfon~tion).
This Ex~mple illustrstas thst the use of trimethyl3ilyl chlorosulfon~te re~gent ~lso results in polymers wlth good molecul~r welght ~nd degrees of sulfon~t~on sim~lar to those obtalned ~n Ex~mples 22 ~nd 23. The ln situ process of Examples 22 snd 23 is~ however, less co~tly~
Ex~mPle 24 The resctlon wss repested essentlally ~s ln Ex~mple 22, except that the trimethylsilyl chloride (8.25 gm, 0.076 mole) ~n 25 ml methylene chlorSde wu~ fldded to the chlorosulfonic ~cld (7.39 gm, 0.0634) ln 25 ml solvent in ~n ~dditlon ~unnel.
D-14,561 2 ~
After 2 hours at room temper~ture thls mlxture wa5 then ~dded to polysulfone (40 gm) d1s301ved in 300 ml solvent. Af~er 22 hours, the homogeneous reaction medlum was treated with sodium methoxlde and the polymer recovered 8S ln Example 22. The polymer RV was.Ø96 ~nd elemental an~lysis g~ve
8.56~ sulfur snd 1.07~ sodlum (24.9~ degre~ of sulfon2tion).
Premixlng the reegents thus slso results ln a homogeneous resction ~nd the final molecular welght ls comparable to those obtained ln Examples 22 and 23. The degree of sulfonation is somewhat less, however. Thls Exampte illustr~tes an alternative mode of practicing the lnvention, where~s Examples 22 flnd 23 lllustrate a preferred method o~ c~rrylng out the in sltu process.
D-14,561
Premixlng the reegents thus slso results ln a homogeneous resction ~nd the final molecular welght ls comparable to those obtained ln Examples 22 and 23. The degree of sulfonation is somewhat less, however. Thls Exampte illustr~tes an alternative mode of practicing the lnvention, where~s Examples 22 flnd 23 lllustrate a preferred method o~ c~rrylng out the in sltu process.
D-14,561
Claims (71)
1. A method of making a silyl sulfonate derivative of a poly(aryl ether) resin, comprising reacting a linear poly(aryl ether) resin, comprised of repeat units of the formula -O-E-O-E'-where E is the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, wherein both of said residua E and E' are bonded to ether oxygens through aromatic carbon atoms with an effective amount of a silyl halosulfonate and under reaction conditions sufficient to form acid derivative.
2. The method of claim 1, wherein said dihydric phenol residuum is a bisphenol residuum.
3. The method of claim 1, wherein said dihydric phenol is selected from the group consisting of D-14,561 in which the R4 groups represent independently hydrogen, lower alkyl, aryl and the halogen subutituted groups thereof.
4. The method of claim 1 wherein said benzenoid compound is selected from the group consisting of wherein Y is halogen or nitro.
D-14,561
D-14,561
5. The method of claim 4, wherein Y is F
or Cl.
or Cl.
6. The method of claim 1, wherein said poly(aryl ether) resin contains repeat units of subunits selected from the group consisting of:
D-14,561
D-14,561
7. The method of claim 6, wherein said poly(aryl ether) resin is a polysulfone.
3. The method of claim 1, wherein said poly(aryl ether) resin is reacted with said silyl halosulfonate at a temperature between about 0°C and about 35°C.
9. The method of claim 1, wherein said silyl halosulfonate has the structure wherein X is halogen selected from Cl, Br, and I and R is an inert organic radical.
10. The method of claim 9, wherein said silyl halosulfonate is trimethylsilyl chlorosulfonate.
D-14,561
D-14,561
11. The method of claim 1, wherein said poly(aryl ether) sealing is reacted with said halosulfonate in an inert chloroaliphatic hydraocarbon solvent.
12. The method of claim 1, wherein the amount of said silyl halosulfonate reacted with said poly(aryl ether) resin is between about 0.005 and about 2.0 moles per mole of repeat units -O-E-O-E'
13. A silyl sulfonate derivative of poly(aryl ether) according to the method of claim 1,
14. A method of sulfonating poly(aryl ether) resins, comprising:
A. making a silyl sulfonate derivative by reacting a linear poly(aryl ether) resin comprised of repeat units of the formula -O-E-O-E'-wherein the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, wherein both of said resida E and E' are bonded to ether oxygens through aromatic carbon atoms, with an effective amount of a silyl halosulfonate and under reaction conditions sufficient to form said derivative followed by B. reacting said derivative with base, thereby forming a sulfonate salt of said poly(aryl ethyl) resin.
D-14,561
A. making a silyl sulfonate derivative by reacting a linear poly(aryl ether) resin comprised of repeat units of the formula -O-E-O-E'-wherein the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, wherein both of said resida E and E' are bonded to ether oxygens through aromatic carbon atoms, with an effective amount of a silyl halosulfonate and under reaction conditions sufficient to form said derivative followed by B. reacting said derivative with base, thereby forming a sulfonate salt of said poly(aryl ethyl) resin.
D-14,561
15. The method of claim 14, wherein said dihydric phenol residuum is a bisphenol residuum.
16. The method of claim 14, wherein said dihydric phenol is selected from the group consisting of in which the R4 groups represent independently hydrogen, lower alkyl, aryl and the halogen substituted groups thereof.
17. The method of claim 14 wherein said benzenoid compound is selected from the group consisting of D-14,561 wherein Y is halogen or nitro.
18. The method of claim 17, wherein Y is F
or Cl.
or Cl.
19. The method of claim 14, wherein said poly(aryl ether) resin contains repeat units or subunits selected from the group consisting of:
D-14,561
D-14,561
20. The method of claim 19, wherein said poly(aryl ether) resin is a polysulfone.
D-14,561
D-14,561
21. The method of claim 14, wherein said poly(ayl ether) resin is reacted with said silyl halosulfonate at a temperature between about 0°C and about 35°C.
22. The method of claim 14, wherein the poly(aryl ether) resin is reacted with said silyl halosulfonate in an inert chloroaliphatic hydrocarbon solvent.
23. The method of claim 14, wherein said silyl halosulfonate has the structure wherein X is halogen selected From Cl, Br, and I and R is an inert organic radical.
24. The method of claim 23, wherein said silyl halosulfonate is trimethylsilyl chlorosulfonate.
25. The method of claim 14, wherein the amount of said silyl halosulfonate reacted with said poly(aryl ether) resin is between about 0.005 and about 2 moles per mole of repeat units -O-E-O-E'-D-14,561-
26. The method of claim 14, wherein said base is an alkali or alkaline earth metal hydroxide or an alkali metal alkoxide.
27. The method of claim 26 wherein said alkali metal is sodium, potassium or lithium.
28. The method of claim 26 wherein said alkali metal is oxide contains 1-15 carbon atoms.
29. The method of claim 28 wherein said alkali metal alkoxide contains 1-3 carbon-atoms,
30. The method of claim 29 wherein said alkali metal alkoxide is an alkali metal methoxide or ethoxide.
31. The method of claim 14, wherein said poly(aryl ether) resin sulfonate salt is exposed to acid, thereby converting said resin sulfonate salt to a resin sulfonic acid.
32. A method of making a silyl sulfonate derivative of a poly(aryl ether) resin, comprising reacting a linear poly(aryl ether) resin, comprised of repeat units of the formula -O-E-O-E'-where E is the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, wherein both of said residua E and E' are bonded to ether oxygens through aromatic carbon atoms with a combination of a silyl halide and a halosulfonic acid, each in an effective amount and under reaction conditions sufficient to form said derivative.
33. The method of claim 32, wherein dihydric phenol residuum is a phenol residuum.
34. The method of claim 32, wherein said dihydric phenol a selected from the group consisting of D-14,561 in which the R4 groups represent independently hydrogen, lower alkyl, aryl and the halogen substituted groups thereof.
35. The method of claim 32 wherein said benzenoid compound is selected from the group consisting of wherein Y is halogen or nitro.
36. The method of claim 35, wherein Y is F
37. A method of claim 32, wherein said poly(aryl ether) resin contains repeat units or subunits selected from the group consisting of:
D-14,561 D-14,561
D-14,561 D-14,561
38. The method of claim 37, wherein said poly(aryl ether) resin is a polysulfone.
39. The method of claim 32, wherein said poly(aryl ether) resin is reacted with said combination at a temperature between about 0°C and about 35°C.
40. The method of claim 38, wherein said silyl halide has the structure R3-Si-X
wherein X is halogen selected from Cl, Br, and I and the R groups independently are inert organic radicals.
wherein X is halogen selected from Cl, Br, and I and the R groups independently are inert organic radicals.
41. The methods of claim 40, wherein said silyl halide is trimethylsilyl chloride.
42. The method of claim 32, wherein said halosulfonic acid is chlorosulfonic acid.
43. The method of claim 32 wherein said poly(aryl ether) resin is reacted with said combination in an inert chloroaliphatic hydrocarbon solvent.
44. The method of claim 32, wherein an amount of said halosulfonic acid between 0.005 and about 2 moles per mole of repeat units -O-E-O-E'- is reacted with said poly(aryl ether) resin.
45. The method of claim 44, wherein an amount of said silyl halide between about 0.5 and D-14,561 about 2 moles per mole of said halosulfonic acid is reacted with said poly(aryl ether) resin.
46. A silyl sulfonate derivative of a poly(aryl ether) according to the method of claim 32.
47. A method of sulfonating poly(aryl ether) resins, comprising:
A. making a silyl sulfonate derivative by reacting a linear poly(aryl ether) resin comprised of repeat units of the formula -O-E-O-E'-where E is the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron with drawing group in at least one of the positions ortho and para to the valence bonds, wherein both of said residua E and E' are bonded to ether oxygens through aromatic carbon atoms, with a combination of a silyl halide and a halosulfonic acid each in an effective amount and under reaction conditions sufficient to form said derivative, followed by B. reacting said derivative with a base, thereby forming a sulfonate salt of said poly(aryl ether) resin.
A. making a silyl sulfonate derivative by reacting a linear poly(aryl ether) resin comprised of repeat units of the formula -O-E-O-E'-where E is the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron with drawing group in at least one of the positions ortho and para to the valence bonds, wherein both of said residua E and E' are bonded to ether oxygens through aromatic carbon atoms, with a combination of a silyl halide and a halosulfonic acid each in an effective amount and under reaction conditions sufficient to form said derivative, followed by B. reacting said derivative with a base, thereby forming a sulfonate salt of said poly(aryl ether) resin.
48. The method of claim 47, wherein said dihydric phenol residuum is a bisphenol residuum,
D-14,561 (a) (b) (c) (d) in which the R4 groups represent independently hydrogen, lower alkyl, aryl and the halogen substituted groups therof.
50. The method of claim 47 wherein said benzenoid compound is selected from the group consisting of D-14,561 wherein Y is halogen or nitro.
51. The method of claim 50, wherein Y is F
or Cl.
or Cl.
52. The method of claim 47, wherein said poly(aryl ether) resin contains repeat units or subunits selected from the group consisting of:
D-14,561
D-14,561
53. The method of claim 52, wherein said poly(aryl ether) resin is a poylsulfone.
54. The method of claim 47, wherein said poly(aryl ether) resin is reacted with said combination at a temperature between about 0°C and about 35°C.
55. The method of claim 47, wherein the poly(aryl ether) resin is reacted with said combination in an inert chloroaliphatic hydrocarbon solvent.
56. The method of claim 47, wherein said silyl halide has the structure.
D-14,561 R3-Si-X
wherein X is halogen selected From Cl, Br, and I and the R groups independently are inert organic radicals.
D-14,561 R3-Si-X
wherein X is halogen selected From Cl, Br, and I and the R groups independently are inert organic radicals.
57. The method of claim 56, wherein said silyl halide is trimethylsilyl chloride.
58. The method of claim 47, wherein said halosulfonic acid is chlorosulfonic acid.
59. The method of claim 47, wherein the amount of said halosulfonic acid reacted with said poly(aryl ether) resin is between about 0.005 and about 2.0 moles per mole of repeat units -O-E-O-E'-.
60. The method of claim 47, wherein the amount of said silyl halide reacted with acid.
poly(aryl ether) resin is between about 0.5 and about 2 moles per mole of said halolsulfonic acid.
poly(aryl ether) resin is between about 0.5 and about 2 moles per mole of said halolsulfonic acid.
61. The method of claim 47, wherein said base is an alkali or alkaline earth metal hydroxide or an alkali metal alkoxide.
62. The method of claim 61 wherein said alkali metal is sodium, potassium or lithium.
63. The method of claim 61 wherein said alkali metal alkoxide contains 1-15 carbon atoms.
64. The method of claim 63 wherein said alkali metal alkoxide contains 1-3 carbon-atoms.
D-14,561
D-14,561
65. The method of claim 64 wherein said alkali metal alkoxide is an alkali metal methoxide or ethoxide.
66. The method of claim 47, wherein said poly(aryl ether) resin sulfonic salt is exposed to acid, thereby converting said resin sulfonate salt to a resin sulfonic acid.
67. Linear poly(aryl ether) resins comprising repeat units or subunits of the formula -O-E-O-E'-wherein E is the residuum of a dihydric phenol and E' is the residuum of a benzenoid compound having an electron withdrawing group in at least one of the positions ortho and para to the valence bonds, both of said residua E and E' being bonded to ether oxygens through aromatic carbon atoms, and wherein a portion of said repeat units contain pendant silyl sulfonate groups having the structure D-14,561 wherein the R groups are the same or differ??t inert organic radicals.
68. The resins of claim 67, wherein said repeat units or subunits are selected from the group consisting of D-14,561
69. The resins of claim 67, wherein said' silyl sulfonate group is a trimethylsilyl chlorosulfonate group.
70. The method of claim 1, wherein the silyl halosulfonate is derived from the introduction of a silyl halide and a halosulfonic acid, as recited in claim 34.
71. The method of claim 14, wherein the silyl halosulfonate is derived from the introduction of a silyl halide and a halosulfonic acid, as recited in claim 47.
D-14,561
D-14,561
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000517951A CA1267486A (en) | 1986-09-11 | 1986-09-11 | Process for preparing sulfonated poly(aryl ether) resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000517951A CA1267486A (en) | 1986-09-11 | 1986-09-11 | Process for preparing sulfonated poly(aryl ether) resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1267486A true CA1267486A (en) | 1990-04-03 |
Family
ID=4133904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000517951A Expired CA1267486A (en) | 1986-09-11 | 1986-09-11 | Process for preparing sulfonated poly(aryl ether) resins |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1267486A (en) |
-
1986
- 1986-09-11 CA CA000517951A patent/CA1267486A/en not_active Expired
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