PROCESS FOR PREPARING SULFONATED POLY(ARYL ETHER) RESINS

PROCEDE POUR LA PREPARATION DE RESINES DE TYPE POLY (ARYLETHER)

English 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.

Claims

- 42 -
What is claimed is
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
<IMG>
D-14,561

- 43 -
<IMG>
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
<IMG>
wherein Y is halogen or nitro.
D-14,561

- 44 -
5. The method of claim 4, wherein Y is F
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:
<IMG>
D-14,561

- 45 -
<IMG>
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
<IMG>
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

- 46 -
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

- 47 -
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
<IMG>
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

- 48 -
<IMG>
wherein Y is halogen or nitro.
18. The method of claim 17, wherein Y is F
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:
<IMG>
D-14,561

- 49 -
<IMG>
20. The method of claim 19, wherein said
poly(aryl ether) resin is a polysulfone.
D-14,561

- 50 -
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
<IMG>
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-

- 51 -
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
D-14-561

- 52 -
-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
<IMG>
D-14,561

- 53 -
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
<IMG>
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

- 54 -
<IMG>
D-14,561

- 55 -
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.
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

- 56 -
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.
48. The method of claim 47, wherein said
dihydric phenol residuum is a bisphenol residuum,
D-14,561

- 57 -
(a) <IMG>
(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
<IMG>
D-14,561

- 58 -
<IMG>
wherein Y is halogen or nitro.
51. The method of claim 50, wherein Y is F
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:
<IMG>
D-14,561

- 59 -
<IMG>
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

- 60 -
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.
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

- 61 -
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

- 62 -
<IMG>
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
<IMG>
D-14,561

- 63 -
<IMG>
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

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:
CH3
_ 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
,~.

74
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
-- 4 --
R O
11
~ ~ 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
11
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
5 --
- 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
-- 7 --
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
- 10 -
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 !
- 11 -
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
- 12 -
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
..

- 13 -
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
CF3
I
groups -C-, -CF2-CF2CF2-; organ1c phosphine
CF3
oxides -P-:
R3
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
- 16 -
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

- 17 -
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~ ,
CH3
D-~4,561

- 20 -
~0~0~502
~~~52~52
~~~S2~52~
H3 0 0
H~ ~1~
~0~~~52
C~
t ~ ~o~S02~o~ S~J
CH3
~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
- 22 -
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

- 23 -
H0 - S - X
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

- 25 -
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 .
H0-S-X
with a ~llyl chlorlde
~-14,561
.,

2 ~ ~ 8 6
- 27 -
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~
- 29 -
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
- 30 -
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~
- 31 -
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

4 8
- 32 -
~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
- 33 -
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

- 35 -
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

374
- 36 -
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
- 37
TABLE 1
- _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

- 3B -
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~&
- 39 -
~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 ~
- 41 - -
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