1. US009040651B2
(12) United States Patent (10) Patent No.: US 9,040,651 B2
Lutz et al. (45) Date of Patent: May 26, 2015
(54) POLY(ARYL ETHER SULFONE) 5,663,275 A * 9/1997 Schmidhauser .............. 528/125
5,830,974 A * 11/1998 Schmidhauser et al. ...... 528/125COMPOSITION, AND METHOD OF MAKING 6,197,924 B1 3/2001 Takekoshi
:}; -
(75) Inventors: Eric Lee Lutz, Mount Vernon, IN (US); 6,228,970 B1 + 5/2001 sum, -- . . . . . . . . . . . . . . . . . . . . . 528/125
William Hoy Heath, Lake Jackson, TX (Continued)
(US); Roy Ray Odle, Mount Vernon, IN
(US); Thomas Link Guggenheim, FOREIGN PATENT DOCUMENTS
MountVernon, IN (US); JuanJustino EP ()043101 A1 1/1982
Rodriguez Ordonez, San Javier (ES); JP 05163352 A * 6/1993
Jose Roman Galdamez Pena, Fuente (Continued)
Alamo (ES)
(73) Assignee: SABIC GLOBAL TECHNOLOGIES OTHER PUBLICATIONS
B.V. (NL) MachineTranslation ofJP 05-163352, 2013.”
- - - - - International Search Report for International Application No. PCT/
(*) Notice: Subjectto any disclaimer,the term ofthis US2012/062353, International Application Filing Date Oct. 29,
patent is extended or adjusted under 35 2012, Date ofMailing Mar. 1, 2013, 5pages.
U.S.C. 154(b) by 15 days. Written Opinion for International Application No. PCT/US2012/
062353, InternationalApplicationFilingDate: Oct. 29, 2012, Dateof
(21) Appl. No.: 13/285,043 Mailing Mar. 1, 2013, 7 pages.
(22) Filed: Oct. 31, 2011 Primary Examiner–Liam J Heincer
(65) Prior Publication Data (74) Attorney, Agent, or Firm –Cantor Colburn LLP;
Diderico van Eyl
|US 2013/0109831 A1 May 2, 2013
(51) Int. Cl. (57) ABSTRACT
C08G 75/06) 2006.01 - -
C08G 75/23 § A poly(aryl ethersulfone) comprises units offormula (I):
C08G 65/40 (2006.01)
C08G 65/06) (2006.01) (I)
(52) U.S. CI. O
CPC ................ CO8G 75/23 (2013.01); CO8G 65/40 |
(2013.01); CO8G 65/4056 (2013.01); CO8G O—Ar"—O—Ar”—S–Arº
65/00(2013.01) |
(58) Field of Classification Search #
CPC ............................ C08G 65/40; CO8G 65/4056
USPC …~~~~… 528/174 wherein Ar" is a divalent Co-C1s aromatic group, Art is a
See application file forcomplete search history. divalentCo-Clsaromaticgroup,Ar’ isadivalentCo-Cls aro
ti d n is greater than 1:(56) References Cited mal1c group, and n 1s greater Unan 1;
|U.S. PATENT DOCUMENTS
3,795,660 A * 3/1974 Feasey et al. ................... 28/487
4,105,636 A * 8/1978 Taylor .......... ... 528/126
4,156,068 A * 5/1979 Hartmann ..................... 528/175
4,186,262 A * 1/1980 Freeman et al. . ... 528/125
4,239,678 A * 12/1980 Williams ...................... 524/1.59
4,273,712 A 6/1981 Williams, III
4,310,654 A 1/1982 Carnahan, Jr.
4,446,294 A * 5/1984 Rose et al. .................... 528/128
4,460,778 A * 7/1984 Brunelle ....................... 546/304
4,533,721 A * 8/1985 Kurosawa et al. ............ 528/174
4,562,243 A * 12/1985 Percec .......................... 528/174
4,595,760 A 6/1986 Brunelle
4,701,514 A * 10/1987 Percec .......................... 528/174
4,806,601 A * 2/1989 Percec .......................... 525/391
4,818,803 A * 4/1989 Harris ........................... 525/390
4,957,978 A * 9/1990 Harris ........................... 525/390
5,053,477 A * 10/1991 Kern et al. .................... 528/125
5,081,298 A 1/1992 Brunelle
5,084,530 A 1/1992 Matzner et al.
5,086,157 A * 2/1992 Reuter et al. .................. 528/171
5,116,975 A 5/1992 Brunelle
5,132,423 A 7/1992 Brunelle et al.
5,229,482 A * 7/1993 Brunelle ....................... 528/125
5,567,800 A * 10/1996 Hergenrother et al. ....... 528/.353
and a terminal group offormula (II) derived from a mono
functional phenoxide
(II)
wherein is X is a hydrogen atom or an organic substituent
having from 1 to20carbonatoms;whereinthepoly(arylether
sulfone) has a hydroxyl group content greaterthan0 and less
than 50parts permillion (ppm), based on the poly(aryl ether
sulfone)weight, a glass transitiontemperatureof180 to 290°
C., a weight average molecularweight of20,000 to 100,000,
a halogen content of greater than 0 and less than 3000 ppm
based on the poly(aryl ether sulfone) weight. The poly(aryl
ether sulfone) is free ofmethoxy groups.
8 Claims, 1 Drawing Sheet

2. US 9,040,651 B2
Page 2
(56) References Cited 2012/0029106 A1* 2/2012 Weber et al. .................. 521/180
2012/0130041 A1* 5/2012 Han et al. ..... ..., 528/125
|U.S. PATENT DOCUMENTS 2012/0149796 A1* 6/2012 Weber et al. .................. 521/180
7,125,954 B2 * 10/2006 Guggenheim et al. ........ 528/491 FOREIGN PATENT DOCUMENTS
7,273,919 B1* 9/2007 Steiger et al. ................. 528/373
7,772,435 B2 8/2010 Guggenheim et al. JP H05163352 6/1993
2002/0049286 A1 * 4/2002 Takekoshi ..................... 525/437 WO 2008059004 A1 5/2008
2003/0114639 A1 6/2003 Okamoto et al. WO WO 2009.022591 A1 * 2/2009
2007/0066741 A1* 3/2007 Donovan et al. .............. 524/430
2010/0204431 A1* 8/2010 Brunelle ............ , 528/170
2011/0311816 A1* 12/2011 Kanomata et al. ............ 428/402 * cited by examiner

3. U.S. Patent May 26, 2015 US 9,040,651 B2
Effect of PCP on MW
80 -r---->3
75 ºff--------------------------------------------------------------------------------------------------------------------------------------------------------------------|
3. & i
° 76 –:
§ i
º: 65 $
= i
60 4..…~~~~&Ti
55 r i
O 0.2 0.4 0.6 0.8 t $ 2
Mole 96 PCP
Fig. 1
Chlorine Reduction
PCP Charge (mole%)
Fig. 2

4. US 9,040,651 B2
1
POLY(ARYL ETHER SULFONE)
COMPOSITION, AND METHOD OF MAKING
BACKGROUND OF THE INVENTION
This invention relates to a poly(aryl ether sulfone) and a
method to synthesize thepoly(aryl ether sulfone).
Poly(aryl ether sulfone)s are typically linear, amorphous,
injection moldable polymers possessing a number of desir
able features such as excellent high temperature resistance,
good electricalproperties, and toughness. Due to theirexcel
lent properties, the poly(aryl ether sulfone)s can be used to
manufacture a variety of useful articles such as molded
articles, films, sheets, and fibers. Synthesis ofpoly(aryl ether
sulfones)canbedifficult—particularlywhentryingtocontrol
molecular weight. Molecular weight control has typically
been achieved through the rigorous use of stoichiometric
amounts but very small variations in the relative amounts of
the monomers can result in significant differencesin molecu
lar weight. This makes consistent synthesis in a manufactur
ing setting difficult.Additionally, thepolymerresulting from
stoichiometric control can have a less than desirable halogen
content, primarily resulting from the dihalodiaryl sulfone
monomer. Furthermore, known, ordinarypoly(aryl ethersul
fones) can contain methoxy groups and are made with reac
tive alkyl halide-containing materials such as methyl chlo
ride-materials that can raise regulatory and safety concerns.
For the foregoing reasons, there is a need to develop
improved, more robust synthetic methods thatdo not employ
reactive alkyl halide-containing materials such as methyl
chloride-materials and produce poly(aryl ether sulfones)
whicharestructurallydifferentfrompoly(arylethersulfones)
made using reactive alkyl halide-containing materials. Addi
tionally, there is a need to develop a poly(aryl ether sulfone)
that can be made without rigorous use of stoichiometric
amounts ofthemonomers needed to make thepoly(aryl ether
sulfone). Furthermore, there is a need to develop a poly(aryl
ether sulfone) having low halogen content.
BRIEF DESCRIPTION OF THE INVENTION
Theaforementionedneed is addressed, atleastinpart, by a
poly(aryl ether sulfone) comprising units offormula (I):
(I)
|
wherein Ar" is a divalent Co-Cls aromatic group, Art is a
divalentCo-Clsaromatic group,Ar’ isa divalentCo-Clsaro
matic group and n is greater than 1;
and a terminal group offormula (II) derived from a mono
functional phenoxide
(II)
10
15
20
25
30
35
40
45
50
55
60
65
2
wherein is X is a hydrogen atom or an organic substituent
having from 1 to 20 carbon atoms; further wherein the poly
(aryl ethersulfone) has a hydroxylgroupcontentgreaterthan
or equal to 0 and less than 50 parts per million (ppm), based
on thepoly(aryl ethersulfone)weight, a glass transition tem
peratureof180to 290°C.,aweightaveragemolecularweight
of20,000 to 100,000, anda halogen contentofgreater than0
and less than 3000ppm based on the poly(aryl ether sulfone)
weight. The poly(aryl ether sulfone) can have a thermal sta
bility factorgreater than orequal to 90%. Thepoly(aryl ether
sulfone) can have a yellowness index (YI) less than 120 after
anarticle madefromthepoly(arylethersulfone)isexposedto
a temperature of 200° C. in ambient air for 28 days. The
poly(aryl ether sulfone) is methoxy free.
Also disclosed herein is a method ofmaking thepoly(aryl
ether sulfone) comprising reacting a bishydroxy aromatic
compound with an aqueous mixture of an alkali metal
hydroxideto form a bis saltofthe bishydroxy aromatic com
pound; drying the bis salt ofthe bishydroxy aromatic com
pound to form a dry bis salt of the bishydroxy aromatic
compound; reacting the dry bis salt of the bishydroxy aro
matic compound with a dihalodiaryl sulfone in the presence
ofan organic solvent, an alkali metal carbonate, and a phase
transfercatalyst to form thepoly(aryl ethersulfone), wherein
amonofunctionalphenoxideis addedduringthemethod inan
amountsufficientto resultinapoly(arylethersulfone)having
a halogen content less than 3000 ppm based on the poly(aryl
ether sulfone) weight.
BRIEF DESCRIPTION OF THE FIGURES
FIGS. 1 and 2 graphically represent data presented in the
Examples.
DETAILED DESCRIPTION OF THE INVENTION
It has been discovered that a monofunctional phenoxide is
a highly effective terminating agent in poly(aryl ether sul
fone)synthesis.Themonofunctionalphenoxidehassufficient
reactivityto resultinapproximately90to 100%incorporation
in the poly(aryl ether sulfone), based on the total moles of
monofunctional phenoxide present. Additionally, little or no
side products comprising the monofunctional phenoxide are
detected. Additionally, the use of the monofunctional phe
noxide reduces the halogen content of the poly(aryl ether
sulfone). Use of the monofunctional phenoxide relieves the
need for tight stoichiometric control of the bis salt of the
bishydroxy aromatic compound andthedihalodiaryl sulfone.
Also, advantageously, the poly(aryl ether sulfones) do not
contain methoxygroups and arenotmadewith reactive alkyl
halide-containing materials such as methyl chloride.
In some embodiments thepoly(aryl ethersulfone)consists
essentially of units of formula (I) and terminal groups of
formula (II). “Consists essentially of as used in this context,
describes a polymer having less than 10 weight percent, or,
more specifically, less than 5 weight percent, or, even more
specifically, less than 3 weight percent, based on the total
weightofthepolymer, ofunitsand terminalgroupsotherthan
those described by formulas (I) and (II). In some embodi
mentsthepoly(arylethersulfone)consists ofunits offormula
(I) and terminal groups offormula (II).
In this specification and in theclaims, which follow, refer
ence will bemadeto a numberofterms which shall be defined
to have thefollowing meanings. Thesingular forms“a”,“an”
and “the include plural referents unless the context clearly
dictates otherwise. “Optional”or“optionally” means thatthe
subsequently described event or circumstance may or may

5. US 9,040,651 B2
3
not occur, and that the description includes instances where
the event occurs and instances where it does not.
Theterm“alkyl”asused in thevariousembodiments ofthe
present invention is intended to designate both linear alkyl,
branched alkyl, aralkyl, cycloalkyl, bicycloalkyl, tricy
cloalkyl and polycycloalkyl radicals containing carbon and
hydrogen atoms, and optionally containingatoms in addition
to carbon and hydrogen, for example atoms selected from
Groups 15, 16 and 17 ofthe Periodic Table. The term “alkyl”
also encompasses that alkyl portion of alkoxide groups. In
various embodiments normal and branched alkyl radicals are
those containing from 1 to about 32 carbon atoms, and
include as illustrative non-limiting examples C1-C32 alkyl
optionally substituted with oneormoregroups selected from
C1-C32 alkyl, Cs-C1s cycloalkyl or aryl; and Cs-C1s
cycloalkyl optionally substituted with one or more groups
selected from C1-C3, alkyl. Some particular illustrative
examples comprise methyl, ethyl, n-propyl, isopropyl, n-bu
tyl, sec-butyl, tertiary-butyl, pentyl, neopentyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl and dodecyl. Some illustrative
non-limiting examples of cycloalkyl and bicycloalkyl radi
cals include cyclobutyl, cyclopentyl, cyclohexyl, methylcy
clohexyl, cycloheptyl, bicycloheptyl and adamantyl. In vari
ousembodimentsaralkylradicalsarethosecontaining from 7
toabout 14carbonatoms;theseinclude,butarenotlimitedto,
benzyl, phenylbutyl, phenylpropyl, and phenylethyl. In vari
ous embodiments aryl radicals used in the various embodi
ments ofthepresent invention arethose substituted or unsub
stituted aryl or heteroaryl radicals containing from 6 to 18
ring carbon atoms. Some illustrative non-limiting examples
ofthese aryl radicals include Co-C1s aryl optionally substi
tuted with one or more groups selected from C-Cs, alkyl,
Cs-C1s cycloalkyl or aryl. Some particular illustrative
examples ofaryl radicals comprise substituted or unsubsti
tuted phenyl, biphenyl, toluoyl and naphthyl. Heteroaryl
groups comprise those containing from about 3 to about 10
ring carbon atoms, and include, but are not limited to, triazi
nyl, pyrimidinyl, pyridinyl, furanyl, thiazolinyl and quinoli
nyl. Aryl halides that are very active to reaction are also
included. Examples of such materials include 3,4-dinitro
chlorobenzene, 3,4-dinitrofluorobenzene, 2-fluoro-benzene
sulfonamide, and 4-fluorobenzenesulfonamide.
The term “methoxy free” means that the polymer, at least,
has structural unitsofFormula(I)thatdonotcontain methoxy
terminal groups and preferably that the entire polymer does
not contain any methoxy groups (structural units offormula
(I) and the polymer’s backbone do not have any methoxy
groups).
As discussed above thepoly(aryl ethersulfone) comprises
structuralunitsofformula(I)anda terminalgroupofformula
(II). Structuralgroups offormula (I)arederived fromabishy
droxy aromatic compound and a dihalodiaryl sulfone. Exem
plary bishydroxy aromatic compounds are HO—Ar’–OH
whereinAr" isdefinedasmentionedabove.Exemplarybishy
droxy compounds are represented by the formula (III):
wherein A' represents an aromatic group including, but not
limitedto,phenylene,biphenylene,naphthylene,andthelike.
In some embodiments E may be an alkylene or alkylidene
grouphaving up to 3 carbons including, methylene, ethylene,
ethylidene, propylene, propylidene, and isopropylidene.
(III)
10
15
20
25
30
35
40
45
50
55
60
65
4
Additionally, E can be sulfur, SO, SO’, or oxygen. Y' inde
pendently at each occurrence may be an inorganic atom
including, but not limited to, halogen (fluorine, bromine,
chlorine, iodine); an inorganic group containing more than
one inorganic atom including, but not limited to, nitro; an
organic group including, but not limited to, a monovalent
hydrocarbon group including, but not limited to, alkenyl,
allyl, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl, or an oxy
group including, but not limited to, OR* wherein R* is a
monovalenthydrocarbon group including, but not limited to,
alkyl, aryl,aralkyl,alkaryl, orcycloalkylwiththeproviso that
theoxygroup isnot amethoxygroup;itbeingonly necessary
thatY' beinerttoandunaffectedbythereactantsandreaction
conditions used to prepare the polymer. In some particular
embodiments Y' comprises a halo group or C-C, alkyl
group.Theletter“m”representsany integerfrom and includ
ing zero through the numberofreplaceable hydrogens on A'
available forsubstitution; andtheparameter“t”represents an
integer greater than or equal to one. The parameters “s” and
u”can bezero oran integergreaterthan orequal to 1. When
“s”is zero and “u” is one then a singlebond connects the two
A'groups.Thedefinitionsofthechemicalvariableinformula
(III)arechosensoastobeconsistentwiththedefinitionofAr"
in formula (I). The poly(aryl ether sulfone) can be a
homopolymer or a copolymer.
In bishydroxy aromatic monomers offormula (III) above,
whenmorethanoneY' substituentispresent,they maybethe
same or different. The positions ofthe hydroxyl groups and
Y' on the aromatic nuclear residues A" can be varied in the
ortho, meta, or para positions and the groupings can be in
vicinal,asymmetrical orsymmetrical relationship,wheretwo
ormore ringcarbon atoms ofthe aromatic residue are substi
tuted with Y' and hydroxyl groups. Exemplary monomers
include 4,4'-bisphenol, bisphenol A and combinations
thereof.
As mentioned above structural units of formula (I) are
derived from a bishydroxy aromaticcompound and a dihalo
diaryl sulfone. Exemplary dihalodiaryl sulfones are
X—Arº–SO2–Ar’—X whereinArº andArº aredefined as
mentioned above and X is a halogen. A wide variety ofdiha
lodiarylsulfone monomers may be used to prepare the poly
(aryl ether sulfone). Typically, sulfone-containing structural
units are derived from a dihalodiarylsulfone monomer which
bears halogen substituents reactive towards displacement by
phenoxide moieties (e.g. the phenoxide moieties present in
the disodium salt ofthe bishydroxy aromatic compound). In
some embodiments dihalodiarylsulfone comprises at least
one of a dichloro- or a difluorodiaryl sulfone. In some
embodiments the dihalodiarylsulfone comprises a dihalo
diphenylsulfone. In some embodiments the dihalodiarylsul
fone comprises a 4,4'-dihalodiarylsulfone, Illustrative
examples of 4,4'-dihalodiarylsulfones include 4,4'-dichlo
rodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'-bis(4
chlorophenyl sulfonyl)biphenyl and 4,4'-bis(4-fluorophenyl
sulfonyl)biphenyl. Without being bound by theory it is
believedthatthe halogen found inthepoly(aryl ethersulfone)
originates in the dihalodiaryl sulfone.
Theterminal groupofformula(II)is derived from amono
functional phenol. The term “monofunctional phenol” is
defined herein as a phenyl group with a single hydroxyl
group. The phenyl group may be further substituted with an
organic substituent having 1 to 20 carbon atoms. Exemplary
monofunctional phenols include phenol, p-t-butyl-phenol,
m-t-butyl-phenol, 4-hydroxybenzamide, 4-phenoxyphenol,
4-hydroxy-N,N-dimethylbenzamide, 4-ethynylphenol,
4-tert-butyl-2-methylphenol, 4-(2-phenylpropan-2-yl)phe

6. US 9,040,651 B2
5
nol, (4-hydroxyphenyl)(phenyl)methanone, methyl 4-hy
droxybenzoate, 4-(2,4-dimethylheptan-3-yl)phenol, para
cumyl phenol, 4-phenyl phenol, para methyl phenol, para
nonylphenols, o-t-butyl phenol, hydroxybenzoic acid esters,
and combinations thereof. In some embodiments the mono
functional phenol is selected from the group consisting of
phenol, para cumyl phenol, 4-phenyl phenol, and combina
tions thereof.
The terminal group of formula (II) can be present in an
amount of1 mol% to 10 mol %, based on the total number of
moles ofsulfone groups present in the polymer.
The poly(aryl ether sulfone) is made in a reaction mixture
comprising alkali metal salt of a bishydroxy aromatic com
pound(thebis saltofthebishydroxy compound), alkali metal
salt ofthe monofunctional phenol (the monofunctional phe
noxide), and a dihalodiarylsulfone monomer, an organic sol
ventandatleastonephasetransfercatalyst(hereinaftersome
times “PTC”). The alkali metal salt of the bishydroxy
aromatic compound is typically a sodium or potassium salt.
Sodium salts areoften used by reason oftheir availabilityand
relatively low cost. In one embodiment, the salts are formed
bycontactingabishydroxyaromaticcompoundwithanalkali
metalcarbonate. In anotherembodiment, thesalts areformed
bycontactingbishydroxy aromaticcompoundswith analkali
metal hydroxide.
The organicsolventhas low polarity. Thesolventcan have
a boiling point above about 150° C. in order to facilitate the
polymerization reaction, which typically requires tempera
tures of about 125° C. to about 250° C. Suitable solvents of
this type include, but are not limited to, ortho-dichloroben
zene, para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlo
robenzene, diphenyl sulfone, phenetole, anisole and vera
trole, andmixturesthereof. Insomeembodimentstheorganic
solventforms an azeotropewith water. In someembodiments
the organic solvent is ortho-dichlorobenzene.
The alkali metal carbonate can bepresent in an amount of
greaterthan0 to 10 weight percent, basedon thetotal weight
of the reaction mixture. In another embodiment, the alkali
metalcarbonate is present in an amountgreater than 0 to 1,2,
3,4,5,6,7,and 9weight9%. Inanotherembodiment,thealkali
metal carbonate is used in an amount greater than 0 to 1.5
weight percent. In some embodiments the alkali metal car
bonate is potassium carbonate.
Suitablephasetransfercatalysts include thosethataresub
stantially stable attemperatures required to effect reaction to
makethepoly(aryl ethersulfone)s. Substantiallystable in the
presentcontextmeansthatthePTCissufficiently stableatthe
temperatures needed to effect the desired polymerization
reactionatasyntheticallyusefulreactionrate. Differenttypes
ofphase transfer catalysts may be employed. They include
quaternary phosphonium salts ofthe type disclosed in U.S.
Pat. No. 4,273,712; N-alkyl-4-dialkylaminopyridinium salts
ofthe type disclosed in U.S. Pat. Nos. 4,460,778 and 4,595,
760; and guanidinium salts ofthe type disclosed in U.S. Pat.
Nos. 5,081,298, 5,116,975 and 5,132,423. Exemplary phase
transfer catalysts, by reason of their exceptional stability at
high temperatures and their effectiveness to produce high
molecularweightaromaticpolyetherpolymers in high yield,
comprise alpha-omega-bis(pentaalkylguanidinium)alkane
salts andhexaalkylguanidinium salts. Hexaalkylguanidinium
salts include, but are not limited to, hexaalkylguanidinium
halides and especially hexaalkylguanidinium chlorides.
Methods for employing guanidinium salts as catalysts are
disclosed, for example, in U.S. Pat. No. 5,229,482. In a par
ticular embodiment a catalyst comprising hexaethylguani
dinium chloride is employed.
5
10
15
20
25
30
35
40
45
50
55
60
65
6
The catalystcan bepresentin an amount ofabout0.5 mole
percentto about 10mole percentbased onthetotal amountof
alkali metal salt. The total amount of alkali metal salt is
defined herein as the total amount of the salts ofthe bishy
droxy aromatic compounds employed. Within this range the
catalyst can bepresent in an amount ofabout 1 mole percent
to about 4 mole percent, or, more specifically, about 2 mole
percent to about 4 mole percent.
The molar amount ofthe dihalodiarylsulfone is generally
atleast equivalenttoandpreferablyinexcessofthecombined
molar amounts ofthe bis salt ofthe bishydroxy compound
and the monofunctional phenoxide. More particularly, the
dihalodiarylsulfone:total his salt and monofunctional phe
noxide molar ratio is generally 1:0.96 to 1:1. In practice, it is
understood that calculated excesses may be subject to some
variability due to separation (fractionation) of the solvent
fromthesuspensionofthebisphenolate, asmay beevidenced
by comparing thepolymer’s actual degreeofpolymerization
that is obtained versus the degree ofpolymerization that is
predicted by the formula:
where R isthe molarratio ofthephenoxidetochloridemono
mers used to makethepolymer (withoutachain stopper), DP
is thedegreeofpolymerization, N_i isthenumberofmolesof
dihalodiarylsulfone monomer, Naa is the numberofmoles of
the his salt ofthe bishydroxy aromatic compound, and Na is
the number ofmoles ofthe monofunctional phenoxide.
The polymerization reaction temperature can be about
125° C. to about 250° C. Within this range the temperature
can be greater than or equalto 170° C. Also within this range
the temperature can be less than or equal to 185°C.
In one embodiment, the reagents employed: the phase
transfer catalyst, the alkali metal salt of the bishydroxy aro
matic compound, the dihalodiarylsulfone, monofunctional
phenoxide, and the solvent, are substantially dry. In the
present context “substantially dry” means that the reaction
mixture comprising the said reactantscontains at most about
100ppm byweightofwater. In someparticularembodiments
the amount ofwater in the reaction mixture is less than about
50 ppm, and in still other embodiments less than about 20
ppm. The proportion of water may be determined by any
convenientmeans andis typically determinedbyKarlFischer
coulometric titration. In some embodiments the amount of
water in the reaction mixture is determined indirectly by
measuringwatercontentofanover-head distillateorconden
sate. Dry catalyst may be employed which means that the
catalyst contains less than about 100 ppm water, or, more
specifically, less than about 50 ppm water, or, even more
specifically, less than about 30 ppm water.
Accordingly, the method for preparing the poly(aryl ether
sulfone)cancomprisereacting a bis hydroxyl aromaticcom
pound with an aqueous mixture ofan alkali metal hydroxide,
thereby forming a bis salt ofthe bishydroxy aromatic com
pound. Thebis saltis then dried to form a substantially drybis
salt(i.e., having awatercontent less than orequalto 100ppm,
or, more specifically, less than or equal to 50 ppm, based on
the total weight of the bis salt). The bis salt is then reacted
with a dihalodiaryl sulfone in the presence of an organic
solvent and a phase transfer catalyst. Monofunctional phe
noxide is added to the reaction in an amount sufficient to
result in a poly(aryl ether sulfone) having a halogen content
less than or equal to 3000 ppm, based on the total weight of
the poly(aryl ether sulfone). In some embodiments, a mono
functional phenol or monofunctional phenoxide is added to
the reaction ofthe bishydroxy aryl compound and the alkali

7. US 9,040,651 B2
7
metal hydroxide. In some embodiments the monofunctional
phenoxide is added after formation of the poly(aryl ether
sulfone).
The reaction mixture has a solids content ofgreater than 0
to less than 30 weight percent, based on the weight of the
poly(aryl ether sulfone), after the poly(aryl ethersulfone has
formed. The solidscontent canbegreater than0 and less than
or equal to 25 weight percent. In one embodiment the solids
content is 20 to 25 weight percent. In another embodiment,
thesolidscontentranges fromgreaterthan0toanupperrange
selected from the group of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25 weight
percent.
Following the achievement ofa desired molecular weight
the polymerization reaction may be quenched by addition of
a quenching agent. Suitablequenching agents typicallycom
prise at least one acidic compound, said acidic compound
being in solid, liquid, gaseous, or solution form. Suitable
acids include organic acids, particularly carboxylic acids
such as acetic acid, malic acid, oxalic acid, and the like.
Suitable acids also include inorganic acids such as phospho
rous acid, phosphoric acid, polyphosphoric acid, hypophos
phorous acid, sulfuric acid, hydrochloric acid, anhydrous
hydrochloricacid, and the like.Agaseous acid, such as anhy
drous hydrochloric acid, can be bubbled into the mixture
through a sparger or delivered as a solution in a convenient
solvent such as the same organic solvent as used in polymer
ization reaction. Mixtures comprising at least two acids may
also be employed.
The amount ofquenching agent used is an amount suffi
cient to end the polymerization reaction. In particular
embodiments the amount ofacid quenching agent used is at
least sufficientto reactwith thecalculated amountofphenox
ide end-groups that will be present for a given molecular
weight ofpoly(aryl ether sulfone) product. “Phenoxide end
groups” as used herein refers to the end groups that result
from the bis salt ofthe bishydroxy aromatic compound; this
term does not refer to the end groups which result from the
monofunctional phenoxide. Preferably the quantity of acid
added is greater than the calculated amount and moreprefer
ably about twice the calculated amount of phenoxide end
groups that will be present for a given molecular weight of
poly(aryl ether sulfone) product. The acid may be added
using any convenient protocol. In some embodiments the
amount ofacid added is in a range ofbetween about 0.02 to
about 0.21 millimoles (mmol) acid per gram ofpolymer or
between about 0.07 to about 0.21 mmol acid per gram of
polymer.
The poly(aryl ether sulfone)s may be isolated by conven
tional methods. These include, but are not limited to, one or
more steps of salt agglomeration, filtration, washing with
water, solvent removal, precipitation, drying and the like. In
some embodiments a reaction mixture comprising poly(aryl
ether sulfone) is combined with a non-solvent for the poly
(aryl ether sulfone) to effect precipitation ofthe polymer. In
another embodiment the polymer can be isolated by steps
which comprise total devolatilization, for example in a
devolatilizing extruder.
The poly(aryl ether sulfone) has a hydroxyl group (OH)
content ofgreater than orequal to 0 and less than orequal to
50 ppm, based on the weight ofthe poly(aryl ether sulfone).
Within this range the hydroxylgroupcontentcan be less than
orequal to 30ppm, or, more specifically, lessthan orequal to
20ppm, which is the current limitofdetection. The poly(aryl
ether sulfone) can have an OH content ranging from more
than 0 to a member selected from thegroup of 1, 2, 3, 4, 56,
7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24,
10
15
20
25
30
35
40
45
50
55
60
65
8
25, 26, 27, 28, 29,30, 31, 32,33, 3435, 36, 37, 38, 39, 40,41.
42,43,44,45,46,47,48,49, and less thanorequal to 50ppm.
Thepoly(aryl ethersulfone has a glass transition tempera
ture (Tg) of 180 to 290° C. Within this range the glass tran
sition temperature can be 215 to 285°C., specifically, 220 to
225° C., more specifically 220 to an upper range selected
from the group of 221, 222, 223, 224, and 225. The glass
transition temperatureis determined by differential scanning
calorimetry (DSC).
As noted, thepoly(arylethersulfone) has a weight average
molecularweights (Mw) ofat least 20,000 to 100,000 grams
per mole. Within this range the weight average molecular
weightcanbegreaterthanorequal to40,000.Also withinthis
rangetheweightaveragemolecularweightcanbelessthanor
equal to 60,000. Weight average molecularweights (Mº.)are
measured by gel permeation chromatography (GPC) versus
polystyrene standards and are expressed in grams per mole.
Thepoly(aryl ether sulfone) has a halogen content greater
than0 andlessthan or equal to 3000 ppm, based onpoly(aryl
ether sulfone) weight. Within this range the halogen content
can begreaterthanorequal to 900, or,greaterthanorequal to
1500. Also within this range the halogen content can be less
than or equal to 2500, or, less than or equal to 1500, or, less
thanorequal to900, or,less than orequal to 500ppm. In other
embodiments, the halogen content can be greater than 0 and
less than 400ppm, more than 0 and less than 300ppm, more
than 0 and less than 200 ppm, more than 0 and less than 100
ppm, and more than 0 and less than 50 ppm. The halogen is
selected from the group consisting of chlorine, bromine,
iodine, fluorine and combinations thereof. In some embodi
ments the halogen is chlorine.
The poly(aryl ether sulfone) can have a thermal stability
factor that is greater than or equal to 90%, or, greaterthan or
equal to 95%. Thermal stability factoris defined as thereten
tion ofmolecularweight, in percentageterms, afterexposure
to air at 200° C. for 28 days. Thus ifan amorphous polymer
retains 90% of its original molecular weight after being
exposed to air at 200° C. for 28 days then the polymer has a
thermal stability factor of90%.
Articles made from the poly(aryl ether sulfone) can have a
yellowness index (YI) ofless than 120afterbeingexposed to
air at a temperature of200° C. for 28 days.
The poly(aryl ether sulfone) described herein is an amor
phous thermoplastic. The term “amorphous,” when used to
define the poly(aryl ether sulfone) means that the poly(aryl
ether sulfone) does not exhibit a crystalline melting peak
whenthepoly(arylethersulfone)issubjectedto aDifferential
Scanning calorimeter (DSC) at 20°C./minute ramp rate.
The terminal groups of formula (II) are present in an
amount of 1 to 10 mol%, based on the total moles ofsulfone
(SO2)groups inthepoly(arylethersulfone). Withinthisrange
the amountofterminalgroups can begreaterthan orequal to
1 and less than or equal to 2, 3, 4, or 5.
As such, it can be useful and convenient to employ an
additional chain termination agent, to limit the molecular
weightoftheproductpoly(aryl ethersulfone). Thus, reaction
mixtures used in the preparation ofpoly(aryl ether sulfone)s
may optionally compriseat least onechain termination agent
in addition to the monofunctional phenoxide offormula (II).
Suitablechain termination agents include, butare not limited
to, all thosecomprising a single activated substituentcapable
ofbeing displaced by a phenoxide moiety derived from the
bis salt of the bishydroxy aromatic compound during the
polymerization process thereby end-capping the polymer
chain. In various embodiments suitable chain termination

8. US 9,040,651 B2
agents include, but are not limited to, alkyl halides such as
alkyl chlorides, and aryl halides including, but not limited to,
chlorides offormulas (VIII):
wherein the chlorine substituentis in the3-or4-position,and
Zº is a substituted or unsubstitutedalkyl or aryl group. Suit
able chain termination agents encompassed by generic for
mula (VIII) include 2-chlorobenzophenone, 4-chloroben
Zophenone, 2-chlorophenyl phenyl sulfone, 4-chlorophenyl
phenyl sulfone (CAS Registry No. 80-00-2) and the like.
(VIII)
Material
p-Cumyl phenol sodium
salt
10
15
4,4'-biphenol disodium
salt
Bisphenol-A disodium
10
make the poly(aryl ether sulfone). The poly(aryl ether sul
fone) has low halogen content. The poly(aryl ether sulfone)
exhibits a combination ofproperties that are useful and ben
eficial.
The composition and method are further illustrated by the
following non-limiting examples.
EXAMPLES
Thepurpose ofthese examples was to evaluatethe useofa
monofunctional phenoxide as a terminating agent and how
the use of monofunctional phenoxide affects the halogen
content, e.g., chlorine content, color thermal stability, haze,
molecular weight, and molecular weight retention of poly
(aryl ethersulfones). The examples used thematerials shown
in Table 1.
TABLE 1
Description Source
Suspended alkali salt in o
dichlorobenzene
Para-cumyl phenol was
manufactured by SABIC-IP and
converted to the sodium salt using
the method described below
4,4'-biphenol was manufactured by
Melog and convertedtothe
disodium salt using the method
described below
4,4'-bisphenol Awas manufactured
Dialkali salt suspended in o
dichlorobenzene
Dialkali salt suspended in o
salt dichlorobenzene by Hexion and converted to the
disodium salt using the method
described below
4,4'- Solid, used as received Ganesh Polychem
dichlorodiphenylsulfone
o-dichlorobenzene Liquid, contained less than Fisher Scientific
(ODCB) 20 ppm H2O
Hexaethylguanidinium Solution in o- Made as described below
chloride dichlorobenzene
Potassium carbonate Oven dried solid used as Armand
received.
BASF P3010 PPSU pellets, used as received BASF
BASF 9495.6367JO PPSU pellets, used as received BASF
BASF 86.663867.JO PPSU pellets, used as received BASF
BASF Ultrason E 2010 PES, used as received BASF
Solvay Udel PSU pellets, used as received Solvay
Solvay M10297T PPSU pellets, used as received Solvay
Solvay M100.82J PPSU pellets, used as received Solvay
Solvay Oct. 27, 2007 PPSU pellets, used as received Solvay
Solvay R5100NTAM667 PPSU pellets,used as received Solvay
Solvay R5800 PPSU pellets, used as received Solvay
Solvay R5000 old PPSU pellets, used as received Solvay
Solvay R5500 Black PPSU pellets, used as received Solvay
Solvay M07187T PPSU pellets, used as received Solvay
Jida PPSU PPSU pellets, used as received Jida/Degussa
U2 SLT 77-79 Polyetherimide pellets, used as SABIC
Other suitable chain-termination agents comprise activated
phthalimides, illustrative examples ofwhich include, but are
not limited to, chloro-N-arylphthalimides, chloro-N-alky
lphthalimides, 3-chloro-N-phenylphthalimide, 4-chloro-N
phenylphthalimide, 3-chloro-N-methylphthalimide and
4-chloro-N-methylphthalimide. Mixtures comprising two or
more chain termination agents can also be used.
Advantageously, the method and composition described
herein provides previously unavailable benefits. The poly
(aryl ether sulfone) is not made with reactive alkyl halide
containing materials such as methyl chloride-materials. The
poly(aryl ether sulfone) described herein are structurally dif
ferent from known poly(aryl ether sulfones). The poly(aryl
ether sulfone) described herein can be madewithout rigorous
use of stoichiometric amounts of the monomers needed to
55
60
65
received
Techniques and Procedures
Preparation ofhexaethylguanidinium chloridein o-dichlo
robenzene: Prepared in a manner according to U.S. Pat. No.
7,772.435.
Preparation of4,4'-biphenol disodium salt: A 2 liter three
neckround-bottomed flask was equipped with two thermom
eter adapters modified with a rubber septum—one of which
was penetrated by a stainless steel needle supplying nitrogen
and another sealing a glass siphon tube connected to a peri
staltic pump by Masterflex Chem-DuranceR tubing. The
third neck was fitted with a water-cooled condensersealed by
oil bubbler. The flask contained a magnetic stirrer. 1550 mil
liliters ofFisher OptimaR methanol was added and degassed
with nitrogen by submerged needle for 30minutes. Biphenol
(93.0991 g, 0.5 mol) was charged to the flask with a slight

9. US 9,040,651 B2
11
nitrogen purge and the mixture was allowed to degas for an
additional 10 minutes. A 1N sodium hydroxide Acculute (1
mol) was added to the mixture through a neck with sufficient
nitrogen purge to prevent entry ofoxygen and was stirred at
roomtemperature for30minutes.Anexotherm wasobserved.
Separately, 500milliliters ofo-dichlorobenzenewasaddedto
a 1 liter three-necked round-bottomed flask equipped with a
Dean-Stark trap (wrapped with heat tape) with graham con
denser attached and connected to an oil bubbler at the top of
the condenser, Teflon stopper equipped to the middle neck,
magneticstirrer,anda modifiedthermometeradaptersupply
ing nitrogen was added to the third neck. A needle with
nitrogensupplydegassedthe o-dichlorobenzene andflask for
30 minutes prior to being heated to 150° C. The methanolic
solution was dripped into the o-dichlorobenzene at a rate of
about 1 drop/secondwithaperistalticpump(approximately 3
to 5 milliliters/minute). The disodium salt precipitated upon
addition to the hoto-dichlorobenzene and theaddedmethanol
andwaterwas removed viadistillation. Uponcompletion250
millilitersofadditionaldegassedODCB was added tothesalt
suspension and was dried by azeotropic distillation at reflux
until the distillate contained less than 20 ppm water. Typi
cally, salt suspensions were allowed to cool overnight while
stirring which helped to decrease the particle size of the
biphenol disodium salt.
The salt suspension was transferred to a dry box main
tained undera nitrogen atmosphere where it was poured into
a 1 literglassjar, homogenized by a hand held homogenizer
and was left stirring under nitrogen by magnetic stir bar.
Preparation of p-cumyl phenol sodium salt: same
described for biphenol salt preparation but with use
p-cumyl phenol and 1 equivalent of NaOH per mol
p-cumyl phenol.
Preparation of bisphenol-A disodium salt: same as
describedforbiphenol saltpreparation butwithuseofbisphe
nol-A and 2 equivalents ofNaOH per mol ofbisphenol-A.
Potentiometric titration of phenolic salts: Phenolate per
cent solids were measured by potentiometric titration with a
Mettler-Toledo DL70 equipped with an auto sampler.
Samples were titrated with 0.1N or 1.0N HCl standardized
with tris(hydroxymethyl)aminomethane (THAM). 0.5
gram-1 gram ofstirredsaltsuspensionwasaddedto acupand
dissolved in 40 milliliters of a 50/50 (v/v) mix ofmethanol/
waterdiluent. HCl was titrated past the endpoint, and the 1”
derivative curve was used to identify exact endpoint for 9%
solids determination. Procedure was repeated threetimesand
then the results were averaged.
Laboratory polymerizations were performed by the fol
lowing procedure. In a nitrogen atmosphere, a 3-neck 250
milliliter flask was charged with solid 4,4'-dichlorodiphenyl
sulfone, 5 wt% suspension ofp-cumyl phenol sodium salt in
o-dichlorobenzene, suspension ofbisphenol-Adisodium salt
in o-dichlorobenzene, suspension of4,4'-biphenol disodium
salt in o-dichlorobenzene, solid K2COs and dry o-dichlo
robenzene. All suspensions were individually measured for
phenoxide contentby potentiometric titration with 0.1N HCl
in 50% (v/v) MeOH/H2O. Additionally attached to the flask
were a modified thermometer adapterwith septa, a glass rod
with Teflon blade, and a Dean Stark trap with Teflon stopper.
Nitrogen was supplied to the flaskby a stainless steel needle
through the septum and the stopper replaced by a water
cooled condenser when placed in a fume hood. Heat was
supplied by a temperature controlled oil bath at 200° C. and
the contents were azeotropically dried by removal of
o-dichlorobenzene until collected overheads were below 20
ppm H2O by Karl Fischer titration and the desired reaction
solids, typically 25-28% polymer, were reached. A 20 wt %
&lS
of
of
10
15
20
25
30
35
40
45
50
55
60
65
12
solution of catalyst (hexaethylguanadinium chloride) in
o-dichlorobenzene, typically 4 mol % with respectto dichlo
rodiphenyl sulfone, was slowly added to the flask by syringe
through the septum. Additional catalyst was added if the
reaction did not initiate. Upon reaction initiation, an exo
therm and a color change were observed and molecular
weight built immediately. Molecular weight was monitored
by gel permeation chromatography and adjustments were
made with suspended bisphenol-A salt in o-dichlorobenzene
(in the amounts shown in Table 6) until target molecular
weight was achieved.
After reaching molecular weight target, the polymer was
quenchedwithanexcessof85%HAPOaat 160°C.anddiluted
to 10%solids with regard to thepolymerwith o-dichloroben
zene. The reaction mixture was cooled and mixed with 100
milliliters of dichloromethane, washed twice with an equal
volume of deionized water to volume of solvent, and the
organic phase was then precipitated into an equal volume of
hexanes and placed in a vacuum oven at 130° C. at full
vacuum for 24 hours.
HalogenDetectionTechniques: to determinetheamountof
chlorine present in the polymer, the following techniques
were used.
Analysis 1: Lab samples and commercial samples were
used as received.
Analysis 2: A 10 wt % solution ofpolymer was made in
veratrole (o-dimethoxybenzene) and heated to 170° C. for
complete dissolution ofthe polymer. Sample was allowed to
completely cool beforethepolymersolutionwas precipitated
in aWaring 1 literblendercontaining300millilitersofmetha
mol. The polymer was isolated by vacuum filtration and
allowedtoairdrybeforebeingplacedinavacuum ovenatfull
vacuum at 150° C. overnight.
The chlorine (halogen) content ofthe polymer was deter
mined by measuring the total chlorine content ofthe sample
and the extractable chlorine content ofthe sample. The dif
ference betweenthetotal chlorinecontent and the extractable
chlorine content is defined as the polymer chlorine content.
Total chlorine content was measured using a Parr bomb.
0.2-0.4 grams of sample was placed into a combustion cup.
Powder samples were pressed into a pellet. 10 milliliters of
deionized water was added to the bottom of the Parr Bomb.
Ignition wires were placed in the Parr Bomb head so that the
wire ends were 5 to 7 millimeters above the combustion cup.
400 microliters ofbutanol was added to the combustion cup.
The Parrbomb was purged with oxygen for 15 to 30 seconds
at 5 atmospheres ofpressure and was slowly pressurized to
approximately 30 atmospheres of oxygen. The Parr bomb
was placed in a water bath and ignited for approximately 5
seconds. The apparatus was allowed to cool for 20 to 30
minutesremovedfrombath, anddried. 10millilitersofdeion
ized(DI)waterwasaddedthrougha reliefvalve.Thecontents
were transferredinto a50millilitervolumetric.Thebomband
bomb head were rinsed with DI water and poured into the
volumetric. The volumetric was then filled to the line with DI
water as needed. A blank was combusted and analyzed for
each set ofsamples analyzed and was performed as written
above without the addition ofpolymer to the system.
Extractable chlorine was determined by the following
method. 2.5 (+0.5) grams of sample was weighed into a 2
ounce glass sample bottle. The sample weight was recorded
on the bottle. 20 milliliters of methylene chloride or appro
priate organic solvent was added. The sample was shaken
until dissolved, but notless than 30 minutes. 15 milliliters of
DI waterwas added and shaken for a minimum of30 minutes
to extract the ions from the sample. The sample was allowed
to separate. Ifthe aqueous layerwasnotclearthen thesample

12. US 9,040,651 B2
17
dichlorodiphenyl sulfone, 5 wt % suspension of p-cumyl
phenol sodium salt in o-dichlorobenzene, a suspension of
4,4'-biphenol disodium salt in o-dichlorobenzene, solid
K2COs and dry o-dichlorobenzene. All suspensions were
individuallymeasured forphenoxidecontentbypotentiomet
ric titration with 0.1N HCl in 50% (v/v) MeOH/H2O. Addi
tionally attached to the flask was a modified thermometer
adapterwith septa, a glass rod withTeflon blade, and a Dean
Stark trap with Teflon stopper. Nitrogen was supplied to the
flask by a stainless steel needle through the septum and the
stopperreplacedbya water-cooled condenserwhen placed in
a fume hood. Heat was supplied by a temperature controlled
oil bathat200°C. and thecontents wereazeotropically dried
by removal of o-dichlorobenzene until collected overheads
were below 20 ppm H2O by Karl Fischer titration and the
desired reaction solids, typically 25–28% polymer, were
reached. A 20 wt % solution of catalyst (hexaethylguana
dinium chloride) in o-dichlorobenzene, typically 4 mol %
withrespecttodichlorodiphenylsulfone,wasslowly addedto
the flask by syringe through the septum. Additional catalyst
was added if the reaction did not initiate. Upon reaction
initiation, an exotherm and acolorchangewere observedand
molecular weight built immediately.
Results
0.5 mol % PCP
Charge %
(g) Solids Mass (g) mol eq
Example DCDPS 28.00 28.00 0.09751 1 0000
20 BP Salt 110.44 19.862 21.94 0.0953 0.9777
BPA Salt O Ilä. O O O
PCP Salt 2.28 5 0.114 0.00049 0.0050
K2CO3 2 2 0.0.1447 0.1484
HEGCl 5.16 20 1.032 0.00391 0.0401
ODCB 99.758
Our results show that Bisphenol-A salt does not need to be
present to methoxy free poly(aryl ether sulfone).
While the invention has been illustrated and described in
typical embodiments, it is not intended to be limited to the
details shown, since various modifications and substitutions
can be made without departing in any way from the spirit of
the present invention. As such, further modifications and
equivalents of the invention herein disclosed may occur to
persons skilled in the art using no more than routine experi
mentation, and all such modifications and equivalents are
believed to be within the spirit and scope ofthe invention as
defined by the following claims. All patents and published
articles cited herein are incorporated herein by reference.
The invention claimed is:
1. A method for preparing the poly(aryl ethersulfone),
comprising
reacting at least one bishydroxy aromatic compound with
an aqueous mixture ofalkali metal hydroxide, thereby
forming bis salt ofthe bishydroxy aromatic compound;
drying the bis salt ofthe bishydroxy aromatic compound,
thereby formingadrybissaltofthebishydroxyaromatic
compound;
reacting the dry bis salt of the bishydroxy aromatic com
pound with at leastone dihalodiaryl sulfonein thepres
ence of an organic solvent, an alkali metal carbonate,
and a phase transfer catalyst at a temperature of 125
185° C. thereby forming the poly(aryl ether sulfone)
wherein the organic solvent comprises ortho-dichlo
10
15
20
25
30
35
40
45
50
55
60
65
18
robenzene, para-dichlorobenzene, dichlorotoluene, 1,2,
4-trichlorobenzene, phenetole, anisole, veratrole, and
mixtures thereof;
wherein a monofunctional phenoxide is added during the
method in a sufficient amount to result in a poly(aryl
ether sulfone) having a halogen content less than 3000
parts per million, based on the poly(aryl ether sulfone)
weight.
2. The method of claim 1, wherein the monofunctional
phenoxide is added in situ when the at least one bishydroxy
aromatic compound reactswith theaqueous mixtureofalkali
metal hydroxide, prior to the formation ofthe bis salt ofthe
bishydroxy aromatic compound.
3. The method of claim 1, wherein the bis salt of the
bishydroxy aromatic compound is dried before the phase
transfer catalyst is added.
4. The method of claim 1, wherein the monofunctional
phenoxide is added after the poly(aryl ether sulfone) forms.
5. The method ofclaim 1, wherein the wherein the mono
functionalphenoxideis selected from thegroup consisting of
phenol, p-t-butyl-phenol, m-t-butyl-phenol, 4-hydroxyben
zamide, 4-phenoxyphenol, 4-hydroxy-N,N-dimethylbenza
mide, 4-ethynylphenol, 4-tert-butyl-2-methylphenol, 4-(2
phenylpropan-2-yl)phenol, (4-hydroxyphenyl)(phenyl)
methanone, methyl 4-hydroxybenzoate, 4-(2,4
dimethylheptan-3-yl)phenol, para cumyl phenol, 4-phenyl
phenol, para methyl phenol, para nonylphenols, o-t-butyl
phenol, hydroxy benzoic acid esters, and combinations
thereof.
6. The method of claim 1, wherein the monofunctional
phenoxide is selected from the group consisting of phenol,
para cumyl phenol, 4-phenyl phenol, and combinations
thereof.
7. The method ofclaim 1, wherein the dry bis salt ofthe
bishydroxy aromatic compound reacts with at least onediha
lodiaryl sulfone in the presence ofan organic solvent under
conditions where thesolvent-polymermixturehas a % solids
isgreaterthan 0and less than 25 weight9%, based onthe total
weight ofthe polymer and solvent mixture, and the reaction
occurs at a temperature of 170 to 185°C.
8. The method of claim 1, wherein the poly(aryl ether
sulfone) comprises units offormula (I):
(I)
|
wherein Ar" is a divalent Co-Cls aromatic group,Art is a
divalentCo-Clsaromaticgroup,Ar’isadivalentCo-C1s
aromatic group, and n is greater than 1;
and a terminal group offormula (II) derived from a mono
functional phenoxide
(II)
wherein X is a hydrogen atom or an organic substituent
having from 1 to 20 carbon atoms and wherein thepoly

13. US 9,040,651 B2
19
mer is methoxy free and the polymerhas an OH content
greater than 0 and less than 50 ppm, based on polymer
weight, aglass transition temperature of 180to 290°C.,
a molecular weightof20,000 to 100,000, and a halogen
content ofmore than 0 and less than 3000 ppm. 5
20