Note: Descriptions are shown in the official language in which they were submitted.
~7~
-- 1 --
CHAIN-EXTENDED POLY(A~YL ETHER KETONES)
FIE~D OF THE lNVENTION
This invention ls dirPc~ed to novel
crystRlllne chsin extended polymers containlng
segmen~s of crystalline poly(aryl ether ketones~.
The novel materials are essy to prepare and displa~
excellent toughness, fabricabllity, ~nd very good
h~gh temperature and 801vent resistance.
BACKGROUND OF THE INVENTION
O~er the yesrs, ~here has been deYeloped a
substant~al body of pAtent and other liters~ure
directed to the formation snd propertles of
poly(aryl ethers) (hereinafter c~lled "PA~"). Some
of the earliest work such as by Bonner, U.S. Patent
No. 3,065,205, ~nvolves the electrophilic aromatic
substitution (e.g. Frledel-Crsfts c~talyzed)
reaction of aromatic diacylhslides with
unsubstituted ar~matic compounds such ~s diphenyl
ether. The evolution of thls cl~ss to ~ much
broflder range ~f PAE's w~s ~chleved by Johnson e~
81., Journal of Polymer Science, ~-1, vol. 5, 1967,
pp. 2415-2427, Johnson et dl., U.S. P2tent Nos.
4,108,837 snd 4,175,175. Johnson e~ ~1. show that a
very bro~d rflnge of PAE csn be formed by the
nucleophillc aromatlc substltution (condensQtlon)
reaction of ~n activ~ted sromst~c dlhallde ~nd an
~romatic dlol. By thi~ method, JohnsDn et 81.
cre~ed ~ host o~ new P~E'~ ~ncludlng ~ broad class
of poly~aryl ether ketones), hereinaf~er c~lled
~PAEK'8".
;
~-14814
,
:":
~'
, .
7 ~ ~ ~3
In recent years, there h~s developed ~
~r~wing interest ln PAKs 85 evldenced ~y ~ahl D U ~ S .
P~ent No. 3,953,400; D~hl e~ ~1., U.S. Patent No.
3,956,240; Dshl, U.S. P~tent No. 4,247,682; Rose et
al., U.S. Pa~ent No. 4,320,224; M~tesc~, U.S D P~ent
No. 4,339,56~; A~w~od et ~1., P~lymer, 1981, vol 22,
August, pp. 1096-1103; Blundell et ~1., Polymer,
19~3 vol. 24, Au~ust, pp. 953-9S8, Atwo~d et al.,
Polymer Prepr~nts, 20, no. 1, Aprll 1979, pp.
191-194; ~nd Rueda et ~1., Polymer Gommun~cations,
1~83, vol. 24, September, pp. 253-260. In esrly to
mld-1970, Raychem Corp. commerclally lntroduced
PAEK cRlled STlLAN~, a polymer wh~se ~cronym ls
PEK, each ether and keto group being ~eparsted by
1,4-phenylene unlts. In 19~8, Imperi~l Ch2micsl
Industrles P~C (ICI) commerci~lized 8 PAEK under the
tr~demRrk Yictrex PEEK. As P~EK ls the ~cronym of
poly(aryl ether ketone), PEEK ls the scronym oE
poly~ether e~her ketone) ln whleh the l,4-phenylene
units ln the struc~ure Qre ~ssumed~
Thus PAE~s ~re well known; ghey c~n be
syntheslzed fr~m a v~rlety of ~ar~1ng mRteri~
~nd they c~n be m~de with dlfferent melting
temperstures ~nd moleculsr weigh~s. The PAEKs ~re
cryst~lline, and ~s shown by the Dahl ~nd Dahl et
al. patents, ~ t ~ufficlen~ly hlgh ~olecul~r
welghts they csn be tough, l.e. 3 ~hey exhiblt hlgh
v~lues (>50 ft-lb~/in2) ~n the tenslle imp~ct
test (ASTM D-1822). They hsve potential for ~ ~lde
~sr~ety of uses, but bec~use of ~he signiflcsn~ cost
~o m~nufec~ure them, they ~re expenslve polymer~.
~helr favorHble propertles clss~es them ln the upper
br~cket of engtneer~ng polymers.
D-14814
. . .
".,. - ,
~'~ 7
-- 3 --
PAE~'~ m&y be produced by ~he
Friedel-Crafts cstaly2ed reac~ion of ~romfl~lc
discylhsl~des with unsubs~ltuted ~rom~t~c compound~
~uch as dlphenyl e~her as described ln, for example,
U.S. Pstent No. 3,065,205. These processe are
generslly ~nexpensive processes; h~wever, ~he
poly~ers produced by ~hese processes have been
ststed by Dshl et ~1., uPra, to be brlttle ~nd
therm~lly unsta~le. The Dahl patents, ~uPr&,
allegedly depict more expensive processes for making
superlor PAEK's by Friedel-Cr~fts c~t~lysis. ~n
eontrast, PAEK's such as PEEK made by nucleophlllc
aromstic substieution react~ons gener~lly d~spl~y
good ~oughness and acceptable mechanical propertles.
THE ~NVENTION
The present ~nvention ls directed ~o ch~in
extended poly(Aryl ether ketone) polymers. Both the
prep~ratlon of the sterting poly(~ryl ether ketone)
segments and ~heir ~ubsequent coupl~ng wl~h ~
diphenol ~re performed vla the nuc~eophil~c route,
l.e. using a base ~nd ~n æprotic ~olven~. Products
hsving superlor toughness, ~ood f~brlcsb~ y, and
excellent solvent and tempere~ure resistance ~re
obtalned.
Thus, the present invention provides a poly-
(aryl ether ketone~ of the following formula:
~ ~ ~ ~ O ~ ~ O~t~ wherein
y is greater than one, and Ar is a residue of an
activated dihalo or dinitro aromatic compound selected
from one or more of the following:
~, .
- 3a -
ol- mi~tures thereof, and wherein m is 1 to 3, and each
n is independently at least 2.
The invention also provides a process for
preparing such compounds, comprising:
(a) reacting an excess of hydroquinone with
4,4'-dihalo or dinitro benzophenone in an aprotic solvent
to yield a hydroxyl-terminated intermediate, and
(b) further chain-extending the intermediate
obtained in step (a) with an activated aromatic dihalo
or dinitro compound which is different from 4,4'-dihalo
or dinitro benzophenone.
In another embodiment the invention provides
a poly(aryl ether ketone) of the following formula:
~o~Eo~o~c~c~ Ar ~0~
wherein n is at least 2, y is greater than 1 and Ar'
is a residue of a dipheno:L selected from one or more
of the following:
~C9 ~:0~ ~$
or mixtures thereof.
.
.
' . . ,,: .:: . .
. ..
,:, : .,
.
~ 7~
. c~
- 3b -
The invention also provides a process for
preparing such compounds, comprising:
(a) reacting an excess of 4,4'-dihalo or
dinitro benzophenone with hydroquinone in the presence
of an aprotic solvent to yield a dihalo or dinitro
terminated intermediate, and
(b) further chain-extending the intermediate
obtailled in step (a~ with an aromatic dihydroxy compound
which is different from hydroquinone.
The polymers of the inst~n~ inventlon ere
prepsred by the pr~cess ~hown ~n the equstions that
fol~w:
(n+l ) H~H ~ n~ b~se
a pr3t l c solvent;
he~t
(1) (2) (1)
~ ..
.
,
,- ." . . ... .
-
` - ~
H ~ ~ C ~ ~ H
~3~
The intermedi~te (3) csn be prepared ~t ~ny
des~red molecul~r weight. The hlgher ~he exce~s of
the hydroquinone r2~ct~nt, ~he lower the molecular
welght of the resulting precursor. Gener~lly, ~he
v~lue of n ls such th~t the intermedi~te h~s ~
molecular weigh~ of less than about 10,000. For the
second step, the dihydroxyl terminated precursor (3~
ls extended ~o the desired hlgh molecular weight "
pDly(aryl ether kek~nes) by condens~tion with ~ l~
differ2nt ~ctivated dihalosrom~tic compound, viz
y H ~ C ~ ~ H ~ y XArX base 3
~protic
n ~olvent;
he~t (11)
0 ~ 0 ~ 0 ~ 0-Ar3
(5)
In the formulse Ybove X denotes ~ halogen
such 8s ehlorine, fluorine, ~r bromine, or R nitro
group, Rnd Ar iS a divalent ~romatlc ~esidue
cont~ining activating ~roups ~n posi~ions or~ho
and/or p~r~ to the hslogen or nl~ro functl~ns with
the proviso th8t Ar ls not ~ residuum of
4,4'-dih810ben~0phenone.
It i~ to ~e noted that the 6teps depi~ted
in the equstions (I) ~nd (lI) c~n be perf~rm~d
elther with the l~ol~tlon of ~he intermediate (3),
or ln ~ one-pot operR~i~n ~n which ~he preparstlon
D-14814
' . .. : ~ -; , . ,
: - .. : . ., ~ ,
, . . .
;;.;.-....," . ~ .-
,; - ~ ,,, ,; .
of the precurs~r ls followed dlrec~ly by i~s
coupling ~o ehe ~inal copolymer (5). Obvlously,
mixtures of ~w~ or more coupl~ng ~gents of ~he
formula (4) can ~lso be used in the process ~f the
ins~ant ~nvention.
Any dihalobenzenoid or dinltrobenzenoid
compound or mixtures thereof cQn be employed in this
~nvention which compound or compounds h~ve the two
h~logens or nitro-groups bonded ~o benzene rings
h~ving an electron wlthdrawing ~roup ~n a~ least one
of the pos~tions ortho snd p~rs to the halogen ~r
nltro group. The dihalobenzen~id or
d~nitrobenzenold compound c~n be either mononucle~r
where the h~logens or nltro groups ~re ~ttached to
the same benzenoid ring or polynuclesr where they
are attached to dif~erent benzeno~d rinRs~ 8S lon~
as there is an actlvating electron withdr~wing group
in the ortho or parA posltion of that benzenoid
nucleus. Fluorine snd chlorine ~ubstltuted
benzenoid resctsn~s ere preÇerred; the fluor~ne
compounds for ~ast reactlyity snd the chlorine
compounds for their inexpensiveness. Fluorine
substituted benzenoid compounds ~re most preferred,
particulsrly when there is ~ trace of wster present
in the polymer~z3tlon reactlon ~y~tem. However,
thls w~ter content ~hould be mflineslned below ~bout
1~ and preferably below 0.5~ for best results.
An electron wlthdrsw~ng ~roup is employed
as the flctivator group ~n ~hese ccmpounds. It
should be, of course, inert under the resctlon
cond~ions, but otherwlse lts ~ruceure is not
; rltlcal. Preferred ~re the stron~ ~ctlv~t~ng
D-14814
. -.. ,. . ~ : , ,
. . ' ;
' .. :' '
. . , :. ,
-- 6
gr~ups such as the sulfone group ~-$-) bonding tW9
11
o
h310gen or nitro substi~uted benzenold nuclei ~s ln
the 4,4'-dlchlorodiphenyl sulfone And
4,4'-difluorodiphenyl sulfone, ~lthough such other
strong wi~hdr~wing groups herein~fter mentioned c~n
also be used wlth equal e~se.
The more powerful of the elec~ron
withdrswing groups give the fss~est ~e2ctions and
hence sre preferred. I~ is further preferred that
the ring con~in no electron supplyln~ groups on ~he
s~me ~enzenoSd nucleus as ~he h~logen or n~tro
~roup; however, the presence Qf other ~roups on the
nueleus or in ~he residuum of the compound can be
tolerated. Preferably, 811 of the ~ubsti~uents on
the benzenoid nucleus are elther hydrogen (~ero
electron wiihdrawing), or ~ther gr~up~ havin~ ~
positive sigma v~lue, as ~et forth ln J.F. Bunnett
~n Chem. Rev. 49, 273 (l9Sl) ~nd Quart. Rev., 12, 1
(1958). See also TQft, Steric Effects in orRanio
Chemistry, John W~ley ~ Sons (1956), ch~pter 13;
Chem, Rev., 53, 222; lACS, 74,3120; ~nd JACS, 75,
4231.
The sc~ivating group can be bss~cally
either of t~o types:
(a~ monoYalent groups that ~ctiv~te one or
more h~logens or n1tro-groups on the s~me ring ~ch
~s another nitro or h~lo group, phenyl~ulfone, or
alkylsulfone, cysno, trlfluoromethyl~ nltroso, ~nd
hetero nltr~en, ~s ln pyridine.
D-14814
., ::. . ...
,,, .,~ ,.... .
. . ;
, ... . ~ } . .. . . .
., : '
~ b~ dlv~lent groups which can sctiva~e
displ~cement of hslogens or ni~ro groups on ~wo
different rings,
o
.-
such ~s the sulfone group -S-; the csrbonyl group
o
0 H
., .
-C-; the vinylene group -C=C-; the sulfoxide grDup
o
-S-; the azo group -N=~-; the sstur~ted fluorocarbon
o
groups -CF2CF2-; organlc phosphine oxides -P-:
R2
where R2 is ~ hydrocarbon group, snd the
ethyl~dene group Xl-C-Xl where Xl can be
t~ .
hydrogen or hslogen, and Qctlvsting groups wl~hin
the nucleus which c~n ~ctiv~te h~logens or nitro
functlons on the same or ~d~ecen~ ring ~uch ~s ln
the csse with difluorobenzoquinone~ 1,4- or 1,5- or
, a -difluoroanthraqulnone, e~c.
The preferred coupl~ng a~ents ~re
represented by the formulae g6), (7), (8~ ~nd ~9
D-14814
: ,,, : .
: ,; . . .
. . . ~ ' b
: ~ . ' ' ":
' .,, .,, ' ":
'
.. ... . . .
- B -
F- ~ CO ~ CO -~ F F~O~CO~;t F
(6~ {7)
F~CO ~~ [ ~ CO~F Cl~S02~ Cl
m
(~) (9)
O O ~ O
.,
F~C~O ~C ~ C ~ (~
~9a)
wherein m ~s 1 to 3.
The most preferred coupling sæents ~re selected ~rom
the group of the difluoro-compoun~s (6~, (7), ~nd
(8) .
The molecular weight of the precursor ~3)
c~n vary ~rom as low 8S that of the dimer (l.e. when
n=2) to as high as ~bout~10,000.
An ~lterna~ive ~repar~lon o~ the coupled
poly(aryl ether ketones) o~ the instant lnvent~on
ln-~rol~Jes the inl~ial prepsr2tion ol~ 8
dihalo-terminated precursor (lO)-equatlor~
(n~l ) F~CO~ ~ b se
he~ t
~2~ (1) ~III)
}~CO~ O~C~F
(10)
D- 14814
, ,,:, ;,, . ~ . . :
- . . , :. . : ,
.. ,, .. ., :....... .. ..
," ,.,i,, . :: ,: ,,
:- , :
~: ". ~ :~
6~7~3
The moleculAr weight of (10) c~n be
oontrolled ln ~ m~nner slmll~r ~o th~t utlllzed for
the control of the molecul~r welght of (3).
Precursor (10) is condensed elther ~fter isolation
and purification or directly ~s prep~red, with ~
diphenol or a mixture of diphenols ~o glve the fin~l
copolymer-equation (IV).
b~s~,
Y ~ )~ 0~ 00~ F ~ y HO Ar'Oii ~
n~prot i c so I v6~nt;
eat
~10)
~lV)
CO ~ ~ ~ -O ~ -CO- ~ 0-Ar J 0
tl2)
In the formulae flbove the group Ar' is the
residue of ~ diphenol differen~ from hydroquinone.
The diphenol can be, for example, ~
dihydroxydlphenyl ~lkane or the nuclear halogenated
derivatives thereof, such ~s, for example, the
2,2-bis(4-hydroxyphenyl)propane ?
1,1-bis(4-hydroxyphenyl)2-phenyl eth~ne,
bis(4-hydroxyphenyl)me~hane, or their ohlorin~ted
~erivstlves contsining one or ewo chlorines on e~ch
Rromatlc ring. Other mater~ls ~lso termed
flpproprlately "blsphenols" ~re ~lso highly vAlu~ble
~nd preferred. These materials are the bisphenols
of ~ symmetrical or unsymmetrlcal joinln~ group, the
D-14814
,
- ';: '' ' " '
~ ~ 7 ~3~
- 10 -
l~tter, for example, belng ~n ether oxygen ~-O-) 9
O O
cArbonyl (-C-), sulfone (-S-), or hydrocarbon residue
o
in which the two phenolic nuclei ~re Joined to the
same or dlfferent carbon atoms of the residue.
Such dinuclear phenols can be chsracterized
as havlng the structure:
(Al)a (A2)b
HO(Ar-Rl -Ar)OH
wherein Ar is an sromstic group ~nd preferably is
phenylene group, Al ~nd A2 c~n be the same or
different inert subs~ituent groups such ~s alkyl
group5 hav~ng from 1 to 4 carbons atoms, h~logen
~toms, i.e., fluorine, chlorine, bromine or lodine,
or alkoxy radicals h~ving from 1 to 4 c~rbon atoms,
nd b are integers having ~ value of from 0 to 4,
lnclusive, and Rl is representstive of a bond
between aromatic c~rbon atoms ~s ln ~
dihydroxy-diphenyl~ such ~s 4,4', 3,3', or
4,3'-dihydroxydiphenyl; or ls a divalent r~dicsl,
o
..
~ncluding, for ex~mple, r~dic~ls such ~s ~C-, -O-,
-S-, -SO2, ~nd d~v~lent hydroc~rbon r~dicals such
~s alkylene, alkyl~dene, cycloalkylene,
cycloslXylldene, or the h~logen, ~lkyl, ~ryl or like
substituted alkylene, ~lkylldene ~nd cyclo~liph~tic
rsdicals or an sromatic ~dicsl; ~t m~y ~lso
represent rings fused ~o both ~r groups.
D-14814
.
. ~ .:, ,
: . ,,
,
3~
Examples of spec~fic dihydric polynuelear
phenols include ~mong others ~he bis-(hydroxyphenyl~
alkanes such ~s 2,2-bis-(4~hydroxyphenyl~prop~ne,
2,4'-dihydroxydiphenylmeth~ne,
bis-~2-hydroxyphenyl)meth~ne,
bls~(4-hydroxyphenyl)methane,
bls(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane,
1,1-bis-(4-hydroxyphenyl)eth~ne,
1,2-bis-(4-hydroxyphenyl)eth~ne,
1,1-bls-(4-hydroxy-2-chlorophenyl)ethane,
1,1-bis-~3-methyl-4-hydroxyphenyl)propane,
1,3-bis-(3-methyl-4-hydroxyphenyl)prop~ne,
2,2-bis-(3-phenyl-4-hydroxyphenyl~propane,
2,2-bis-(3-isopropyl-4-hydroxyphenyl)prop~ne,
2,2-bis-(2-isopropy~-4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxynaphthyl)prop~ne,
2,2-bis-(4-hydroxyphenyl)pent~ne,
3,3-bis-(4-hydroxyphenyl)pent~ne,
2,2-bis-(4-hydroxyphenyl)heptane,
bis-(4-hydroxyphenyl)phenylmeth~ne,
2,2-bis-(4-hydroxyphenyl)-1-phenyl-prop~ne,
2,2-bis-(4-hydroxyphenyl)1,1,1,3,3,3,-hexa~luoro-
prop~ne, and the like;
di(hydroxyphenyl)sulfones such as
bis-(4-hydroxyphenyl)sulfone~ 2,4'-dihydroxydiphenyl
sulfone, 5-chloro-2,4'-dihydroxydiphenyl sulfone,
5'-chloro-4,4'-dihydroxydiphenyl sulfone, ~nd ~he
like;
di(hydroxyphenyl)ethers such ~s
bis-(4-hydroxyphenyl)ether, the 4,3'-,
4,2'-2,2'-2,3'-,dihydroxydiphenyl ethe~s,
4,4'-dihydroxy-2,6-dlmethyldlphenyl
D-14814
,' , ~' ,
`: ,: ' " ' , ~
~3
- 12 -
ether,bls-(4^hydroxy-3-lsobu~ylphenyl~eLher,
bis-~4-hydroxy-3-isopropylphenyl)ether,
bis-~4-hydroxy-3-chlorophenyl)ether,
bis-(4-hydroxy-3-fluorophenyl)ether,
bis-(4-hydroxy-3-bromophenyl)ether,
bis-(4-hydroxynaphthyl~ether,
bis-(4-hydroxy-3-chloronaphthyl)ether, and
4,4'-dihydroxy-3,6-dimethoxydiphenyl ether.
di(hydroxydiphenyl)ketones such as the
4,3'-, 4,4'-, 4r2l, 2,2', and 2,3'-
dihydroxybenzophenones; dlhydroxy-diketones such ~s
1,4-bis(4'-hydroxybenzoyl)benzene,
4,4'-bls(4"-hydroxybenzoyl)d~phenyl ether,
1,3-bis(4'-hydroxybenzoyl)benzene; fused ring
polynuclear diphenols such ~s the
dihydroxynaphthalenes, dihydroxyanthracenes, and
dihydroxyphenanthrenes.
The preferred diphenolic coupling agents
correspond to the formul~e shown
H ~ O ~ OH HO ~ CO ~ CO ~ OH
(13) (14)
O O
H ~ ~ C ~ O HO- ~ SO ~ H
(15) (16)
H ~ H H ~ CO ~ H
~17) (~8)
Compounds (13, (14), (17) and (18) ~re most
preferred for the purposes of ~he pre~ent invention.
D-14814
.
.. ,
'.
~ 3
- ~3 -
The moleculsr we~ght of ~he precurs~r (lOj
can vary from 8S low ~s ~hat of ~he dimer ~i.e.
where n=~) ~o QS hlgh as ~bou~ 10,000.
Bo~h ~he precursors and the flnal p~lymers
~re prepsred ~n aolutlon, using the nucleophllic
polycondens2tion resc~ion.
European Psten~ Appllca~lon 125 ,816~k filed
Apr~l 19, 1~84, based for priori~y upon British
Patent Application 8,313,110, ~iled May 12, 1~83, ls
directed to a meth3d for increasing the mol2cular
weight by mel~ polymeri~ation of 8 poly(aryl ether)
such as PEEK.
The process of European Paten~ Applica~ion
125,816, provides ~ basis ~y melt polymeriz~t~on
sbove the crysta~llne melt~ng point of ~he poly~Rryl
et~er) to incre~se the molecular welght ~y ch~in
extension of pDlymer blocks. The appllcation
theorizes ~hat ~he proeedure can be used for maXlng
the block copolymers descrlbed ~n US. 4 D 052,365 and
4,268,635. Impticlt problems ~s~ocis~ed in the
process of ~his appllc~t~on ~re the dl~iculty ln
controlling the moleoular welght of ~he resulting
polymer and/or llmiting lsomeri2~ion ~nd the
problems associsted wit~ branching. The process of
this Europe~n ~pplic~tion would appesr to be
advanta~eous in making composites where ~he
linearlty and solu~lon pr~perties of ~he ~inal
polymer ~re not so crltie81.
The re~c~1ons ~re csrried out by he~tln~
mixture of the ssid monomers or precursor ~or
precursors) wlth ~he ~ppropriate monomers ~t ~
te~per~ture of from ~bout 100 to about 400~C. The
*published November 21, 1984. Related to Canadian
Patent 1,233,940 of March 8, 1988.
D-l4al4
`~ -
~:, ,, ~,: '' :
' "'~: ' . , : ' '
- 14 -
reactions are conducted in the presence of an alkali
metal c~rbonate or bicarbonate. Preferably a
mixture of alkali metal cRrbonates or bic~rbonates
is used. ~hen 8 mixture of ~lkali metal carbon~tes
or bic~rbon~tes is used, the mixture comprises
sod~um carbonate or bicarbonate wit~ ~ second ~lkali
metal carbon~te or bicarbonate wherein the &lkali
me~al of the second c~rbonate or bic~rbona~e has
highe~ Atomlc number ~han thst of sodium. The
amount of the second alkali metal carbonate or
bicArbonate ls such that ~here ls ~rom 0.01 to about
0.25 gram atoms of the second slksli met~l per gram
atom of sodium.
The higher alkali me~al carbonates or
bicflrbonates are thus selected from the group
consisting of potRssium, ~ubidium and cesium
c~rbonates and bic~rbonate~. Preferred combinations
~re sodium carbonate or bicarbonate with potassium
carbonflte or cesium carbonateO
The alk~li metal carbonstes or bicarbonates
should be snhydrous ~lthough, ~f hydrated salts are
employed, where the polymerization temperature i~
relatively low, e.B. 100 to 250C., the water should
be removedp e.g. by heating under reduced pressure,
prior to resching the polymerization temper~ture.
Where high polymerlzation temperstures
(>250C) ~re used, it is not necessary to
dehydrate the cArbonate or bicarbonate first ~s any
wster ~s driven off r~pidly before lt can adversely
affect ehe course of the polymerization re~ction.
The totsl amount of ~lkall metal oarbonAte
or bicarbonate employed should be such th~t there is
at-l~ast 1 ~tom of Alkali met~l for e~ch phenol
D-14814
,~ ., . . .:
'"~'."~ ' . " ' .
-: .
~Lr~ 3
- 15 -
group. Hence, when using the oligomeric dlphenols
of the inst~nt invention ~here shou~d be ~t leas~ 1
mole of carbonate, or 2 moles of bicarbonatei per
mole of the aromatic dlol.
An excess of osrbonate or blcarbonate may
be employed. ~ence there may be 1 ~o 1.2 atoms of
alkRli metal per phenol group. While the use of an
excess of carbona~e or bicarbona~e may give rise to
faster reactions, there is ~he ~t~endant risk of
clea~age of the resulting polymer, partlcularly when
using high temperatures and/or the more actlve
carbonates.
As stated ~bove the amount of the second
(higher) alkali metal carbonate or bicarbona~e
emp~oyed is such that there are 0.01 to about 0.25
grams atoms of the slkali metal of higher atomlc
number per gram atom of sodium.
Thus when using a mixture of csrbonates,
e.g. sodium carbon~te ~nd cesium carbon~te, there
should be 0.1 to about 20 moles of caesium carbonate
per 100 moles of sodium car~onate. L~kewise when
using a mixture of a bic~rbon~te and a carbonate,
e.g. sodium bicarbonate and potasslum carb~nate,
there should be 0.05 to 10 moles of potassium
carbonate per 100 moles of sodium bicarbonate.
A mixed carbonate, for example sodiu~ and
potassium carbonRte, may be employed as ~he second
alXali metal carbon~te. In thls oase, where one cf
the alkali metal atoms of the mixed carbon~te is
sodium, the ~mount of sodium in the mixed carbonste
should be ~dded to that in the sodium c~rbon~te when
determining the Amount of mixed carbonate to be
employed.
D-14814
. ..
~ . .. .
.: . ;; :. ..
.. . .
. . .
- 16 -
Preferably, from 0.005 to 0.1 gram atoms of
the alk~li met~l of the second ~lk~li met~l
carbonate or bicarbon~te per gram ~om of ~odium is
used.
Where the ollgomeric bisphenol or the
oligomeric dihaloben~enoid compound are employed,
they should be used in substantislly equimolar
amounts with respect to the monomeric
chain-extending reagen~. Excesses lead to ~he
production of lower molecular weight products.
However a slight excess, up to 5 mole ~ o$ any of
the re~gents may be employed if desired.
The re~ction is c~rried out 1n the presence
of an inert solvent.
Prefersbly the solvent employed ls an
~liphatic or aromatic sulfoxide or sulfone of the
~ormula
R - S~)x R'
where x ts 1 or 2 and R and R' are alkyl or ~ryl
8roUPs and may be the same or different. R and R'
may together form a d~valent r~dir~l. Preferred
solvents lnclude dimethyl sulfoxide, dimethyl
sulfone, sulfolane (1,1 dioxothiolan3, or aroma~ic
sulfones of the formul~:
R3~ ~R ~ 3
D-14814
.; " . ' '. , .' , :
,::
.. . ; :
- 17 -
where R2 ls a direct llnk, ~n oxygen atom or two
hydrogen atoms (one sttached to each benzPne rin~)
and R~ snd R'3, which mAy be the same or
different, sre hydrogen ~oms and alkyl or phenyl
groups. Ex~mples of su~h aromatic sulfones lnclude
dlphenylsulfone, dibenzothiophen dioxlde,
phenoxathiin dloxide ~nd 4-phenylsulfonyl biphenyl.
Diphenylsulfone is the pre~erred solven~. Other
solvents that msy be used include N,N'-dime~hyl
acet~mide, N,N-dime~hyl formamide and
N-methyl-2-pyrrolldone.
The polymeriz~tlon temper~ture is in the
rsnge of from abGut 100 to ~bout 400C ~nd will
depend on the nature of ~he reac~ants and ~he
solvent, if ~ny, employed. The preferred
tempersture is sbove 270C. The re~ctions sre
generslly performed under ~tmospheric pressure.
However, higher or lower pressures may be used.
For the production of some polymers, it may
be desir~ble to commence polymerization at one
tempersture, e.g. between 200 and 250C and to
incresse the temperature as polymerlzation ensues.
This is p~rticularly necessary when ~aking polymers
having only a low solubility in the solvent. Thus,
it is desir~ble to incre~se the temperature
progress~vely to maint~in the polymer in ~olution ~s
lts molecular weight increases.
To minimize cleavage re~ctions it ls
preferred th~t the m~xlmum polymerization
tempersture be below 350C.
The polymeriz3tion reac~1On msy be
terminated by mlxlng ~ suitable end capplng se~gent,
e.g. a mono or polyfunctionsl hslide such ~s methyl
D-14814
.
- 18 - -
chloride, ~-bu~yl chloride or
4,4'-dichlorodiphenylsulphQne with ~he reactlon
mixture at the polymerization temperature, heating
for ~ period of up to one hour ~t the polymerlzatlon
tempera~ure ~nd then discontinuing the
polymerization.
This invention is ~lso directed to an
~mpro~ed process for maXing t~e chain-extended
polymers in comp~rstively shorter reaction t~mes
overall than by uslng potQssium fluoride alone sr by
uslng a combination of sodium carbon~te or
bicarbonate and a second hlgher slkall metal
carbonate or bicarbonate.
Specific~lly, this process is directed to
preparing the poly(aryl ether ketone) precursors ~nd
the chain-extended polymers by the reaction of a
mixture of the hydroqulnone and
4,4'-difluorobenzophenone ~to make the precursor),
or the reaction of the precursor to make the
chain-extended polymer either one or both in the
presence of sodium carbonate ~ndlor b~carbonate sn
alkall metal hallde selected from potassium,
rubidium, or cesium fluoride or chlorlde, or
combinations thereof.
The reaction is carried out by heating a
mixture of the monomeric re~ctants or ~he block
precursor ~nd the monomeric coupling agent, as
described herein, ~t ~ temper~ture of from ~out 100
to ~bout 400C. The reaction is conducted ln the
presence of ~dded sodium carbonate and/or
blcarbonate and potassium, rubidium or ceslum
fluorldes or chlorides. The sodlum c~rbona~e or
D-14814
: . . .
-
:- .:. ,, ~ ..
: . :
. .
3~
- 19 - .
b~carbonate and the chloride and fluoride s21ts
should be anhydrous ~lthough, if hydrated ~lts ~re
employed, where the reactlon tempersture ~s
relstively lsw, e.g. 100 ~o 2509C., the w~er ~hould
be remove~, e.g. by he~t~ng under reduced pressure,
prlor ~o reAching ~he reactlon temper~ture.
Where high reaction temperatures ~>250~C)
are used, it ls not necessary to dehydrate the
carbonate or bicarbonate irst as any water ls
driven off rapidly before it can ~dversely affect
Che course of the reaction. Optionally, an
entrsin~ng orgRnic medium can be used ~o remove
water from the reacti~n such AS toluene, xylene,
chlorobenzene~ ~nd the like.
The total amount of sodium carbonate sr
bicarbonate and potassium, rubidium or ceslum
fluoride or chloride, or comblnations thereof
employed should be such th~t ~here i5 at least 1
atom of total alkali metal for each phenol group,
re~ardless of the anion (carbonate, bicarbonate or
halide).
Preferably, from ~bout 1 to about 1.2 atoms
of sodium for each phenol group is used. In ~no~her
preferred embodiment from 0.001 ~o about 0v5 ~toms
of alkali metal ~derived from a higher alkali metal
halide) is used for each phenol group.
~ he sodium carbon~te or blc~rbonate ~nd
potassium fluoride are used such that the r~io of
potassium to sodium therein is from about 0.001 ~o
About 0.5, prefersbly from ~bout 0.01 to about 0.25,
snd most preferably from ~bout 0.02 to ~bou~ 0.~0.
D-14814
. .
.
. . .~.
. .
,.
,;,. .. ~
~7~S33
- 20 -
An excess of ~otal alXsli met~l m~y be
employed. H~nce ~here m~y be sbout 1 tG 8bout 1 . 7
atoms of alkali metal per phenol ~roup. While the
use of a large excess of a1kAli metal may give rise
to faster reactions, ~here is the attendsnt risk of
cleavage of the resultlng polymer, particularly when
using high temperatures and/or the morP active
alkRli metal sRlts. Of course it is well known co
those skilled in ~he art that cesium is a more
active metal and poeasslum is a less active me~a~ so
that less cesium an~ more potassium are used.
Further~ the chloride salts are less aetive thsn the
fluoride salts so that more chloride and less
fluoride is used.
In the chain-extension process the
bisphenol ~nd the dihaloben2enoid compound, one o~
which is oligomeric, are employed in substflntially
equimolar amounts when max~mum molecular weight is
sought. However a slight excess, up to 5 mole ~, of
any of the reactants may be employed if desired. An
excess of one over the other leads to the production
of low molecular weight products.
The reaction are carried out in the
presence of an lnert solvent.
The reaction ~emper~ture ls in ~he range of
from about 100 to about 400C and w~ll depend on
the nature of the reac~ants flnd the solvent 9 if ~ny,
employed. The preferred temperature is above
250C. The reactions ~re preferably carried out Qt
ambient pressure. However, hlgher or lower pressure
can also be used. The reaction is gener~lly c~rried
out in an inert ~tmosphere.
D-14~14
.; ,
...
33
- 21 -
For ~he production of some chain-extended
polymers it may be desirable to commence reac~lon at
one temperature, e.g. between 20~ snd 250C and
increase the temperature as reaction ensues. Thls
is particulsrly necessary when m~king high molecular
weight polymers having only ~ low solublli~y ln the
solvent. Thus, there it is desirable to increase
the temperature progressively to maintain the
polymer ln solution as its molecular weight
increases
The polymers of this inven~ion may lnolude
mineral fillers such as carbonates including chalk,
calcite and dolomit2; silicates includlng mics,
talc, woll~s~onite; silicon dioxide; glass spheres;
glass powders; slumlnum; clay; quartz; and ~he
like. Also, reinforc~ng fibers such as fiberglass,
cArbon fibers, and the like may be used. The
polymers ~ay also ~nclude additives such as tltflnium
dioxide; thermal stabilizers, ultraviolet llght
stabilizers, plasticizers, ~nd the like.
The polymers of this inventlon may be
blended with one or more other polymers such as
polyaryl~tes, polysulfones, polyetherimides,
polyamideimides, polyimldes, polyphenylene sulfides,
2o1Yesters~ polycarbonates, polyamldes,
polyhydroxyethers, and the like.
The polymers of this lnvention may be
fabricated into any desired sh~pe, l.e., moldings,
coat$n~s, films, or fibers. They are partlcularly
desir~ble for use as electrical lnsulation for
electrlcal conductors.
D-14814
.
.
- ~2 -
Also, the polymers may be woven into
mono~ilament ~hreads whlch are then formed lnto
industri~l f~brics by methods well known ln the ~rt
as exemplified by U.S. Pa~ent 4~359>501. Further,
the polymers m~y be used ~o mold gears, be~rings and
the like.
ExamPles
The ~ollow~ng exsmples serve to give
specif~c illus~rations o~ the prac~ice of this
~nvention but they ~re not intended in any w~y to
lim~t the scope of this invent~on.
ExamPle 1
Preparation o~ Hydroxyl-terminsted Oligomer
HO ~ ~ C~ ~ O ~ O~
(3)
A 250 ml 3-neck flssk wi~h ~lanted side
arms f~tted with a Cl~isen ~rm, nltrogen inlet tube,
thermocouple probe, condenser, and stainless steel
stirrer w~s charged with difluorobenzophenone
(0.1104 mole, 24.09 gm), hydroquinone (0.115 mole,
12.66 gm), sodium carbonate (~.1173 moles, 12.43 gm,
ground and dried), ~nhydrous potass'lum Fluoride
(O . 0293 mole, 1. 70 g,m~ snd diphenyl sul~onP (lûO
gm) . The spparatus was ev~cuated ~nd filled with
argon by means oE ~ Firestone v~lve connected to the
top of the condenser. A flow o~ high purity
nitrogen was begun snd the oonnection to the
Firestone vslve W8S replaced with a bubbler. The
con~ents of the flask were heated carefully by means
D-14814
.
.
. . .
.
- 23 -
of a hea~ing mantle ~nd tempera~ure controller ~o
melt the diphenyl sulfQne. The re~ction mixture was
stlrr~d and heated to 200C and held 30 minutes,
held at 250C for 1 hour, ænd flnally ~ 270C for 2
hours. The reaction mixture w~s poured from the
reaction flask, cooled, ground to a fln~ powder, and
a sample refluxed successively twice with acet~ne,
once with 2% hydrochloric acid, once wi~h water, and
washed ~horoughly with ~cetone. The dried (120,
vacuum o~en) sample gave ~ reduced viscasity (1% in
conc. sulfuric acid, 25C) of 0.53 dlJ~m. B&sed on
reactant stoichiometry ~his oli~omer had th~
structure (3) RS depicted ~bove.
Example 2
Preparation of the oligomer (3) using a
slightly modified procedure.
The oligomer was prepared essentially as in
Example 1 except that less potasslum fluorid~
(0.01465 moles, 0.85 gm) was used ~nd the reaction
mixture was heated ~t 200C for 30 minutes, at 250C
for 1 hour, and then at 2goDc for 2 hours. The
lsolated oligomer had a reduced vlscosity of 0.51
dl/~m (concentr~ted sulfuric acid, lgm/100 ml ~t
25C)
Example 3
Coupling of the Hydroxyl-terminated
Precursors to Wigh Polymer.
The oligomer w~s prep~red essenti~lly by
the procedure of Example 1. When the 2 hour heating
period ~t 270~C W85 oomplete,
1,4-bis(4-fluorobenzoyl~benzene (0.005~ mole, 1.87
D-14814
.
. ...
.,.:, ' i .: .
::: ...... .
:,
.: ~.
~7~3~3
- ;2 ', -
gm, reeryst~ ed~ w~s added to the stirred
re~ction mixture along with 8.0 gm oE diphenyl
sulfone. The reac~ion mixture ~s ~hen hea~ed to
290~C, held 30 mlnutes, and then heated to 320~C.
Af~er 1.6 hours~ ~he Y~SCOUS re~c~on m~xture was
removed from the flask, cooled, ~nd ground. The
reaction mixture was refluxed successively (500 ml,
1 hr) with acetone (2X), w~terp 2S hydrochloric
acid, water~ and ~cetone and dried st 110-120C ln a
v~cuum oven overnight (~bou~ 12 hours).
The polymer had ~ reduced viscoslty (1~ ln
concentrated sulfuric acid at 25~C) of 1.10 dllgm.
The polymer was compression molded (20 mil)
and tested for tensile strength and modulus
according to ASTM-D-638, yield elongat~on and
elongation st break ~ccording to ASTM-D-633 and
pendulum impact strength according to ASTM-D-256.
The results were as follows:
Tensile modulus375,000 psi
Tens~le strength13,600 psi
Yield elongation 6.2
Bresk elongation 55~
Pendulum impact164 ft-lb/in3
Melt flow (lP) of the polymer WQS 2.48 dgm/min after
10 m~n at 400C.
Exsmple 4
The polymeriz~tion o~ Example 3 was
repeated using twice ~he amount of all ingredients
snd a 500 ml reac~ion flask. After 2 hours ~ 320D,
the polymerization was ~topped ~nd ~he recovered
polymer worked up as ln Exsmple 3. The p~lymer had
a reduced viscosity of 1.17 dl/gm. The eolYmer was
D-14814
.. . ' ':
-
q~
compression molded an~ tested as described lnExample 3. The results were as fsllows:
Tensile modulus337,000 psi
Tensile strength13,300 psl
Yield elongation 7.0
Break elongatlon 15.0~
Pendulum imp~ct140 f~-lb~in
xamPle 5
The react~on of Example 2 w~s repeat~d
using twice the smounts of all in~redlents (500 ml
fl~sk). After heatlng ~t 290C for 2 hours,
1~4-bis(4-fluorobenzoyl)benzene ~0.0115 mole, 3.71
gms, recrys~allized) was added to ~he reaction
mixture along with 10 gms of diphenylsulone. The
mixture was heated at 290C for 30 minutes and the
temperature raised to 320C. After 1.5 hours the
reaction mixture was removed and worked up as in
Ex~mple 3. The polymer had ~ reduced viscosity of
0.96 dl/gm (concentrated sulfuric ~cid, lgmllOO ml
a~ 25C). The polymer exhibited excellent melt flow
o~ 13.20 dgm/min ~t 400C sfter 10 minu~es (lP) ~nd
13.73 dgm/min after 30 minutes.
The polymer was compression molded ~nd
tested as described in Example 3. The results ~re
~s follows:
Tensile modulus3~4,000 psi
Tensile streng~h13,800 psi
Yield elongation 7.3
Break elong~tlo~ 11.3
Pendulum imp~ct 51 ft-lblln3
D-14814
,
- 2~ -
Example 6
The prep~r~tion of sever~lhydroxyl-terminated oligomers ls summarized in Table
I. The technique used W8S simil~r to th~t of
example 1.
TABLE I
Mole ratio of DP Mn~l) Reduced
4,4-difluoro- viscosity(2)
benzophenone/
hYdroquinone
0.98 99 14,300
0.97 66 9,500 ~.45
0.96 49 7,000 0.40
o~5 39 5,600
(1) Approximate number aver~ge molecular weight
values (calculated).
(2) Measured ~ 25C ln conc. H~S04 (1 gm of
polymer in 100 ml of acid~
ExamPle 7
The precursor and the chain-extended
poly(aryl ether) were prepsred using ~echniques
described in the foregoing exQmples. The lnitiR1
mole ratio of 4,4-difluorobenzophenone/hydroquinone
was 0.985, snd 4,4'-dichlorodiphenylsulfone was the
coupllng agent. The final polymer showed ~ reduced
viscostty in conc. H~S04 (1 gm of polymer/100 ml.
of acid, 25C) of 1.94.
D-14814
,' .
' :'
~:7G~3~;3
- - 27 -
Examples 8-10
Preparstion of halogen-terminated precursors and
thelr couPling with diphenols.
The experimen~al techniques were the same
as those used ln the exAmples above. The
experiments are summarized in Table II.
TABL II
~ole r~tio: 4,4-' Coupling Agent, RaJuoed
ExAmple difluoro mol~s ~is~osity
ben20phsnone/ t25C, conc.
hydroquinon~ H2S04;
I om/100 ml)
8 1.02 4,4-dihydroxyben~o- 0.16
phonone, 0.02 moles
9 1.02 4,4'-dihydroxydiph~nyl- 0. Ia
suIfone, 0.02 mol0s
1.02 ~,4'-biphenol, 0.02 moles O.BI
D-14814
.
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:,
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- 28 -
.
ExamPle 11
A 250 ml Ace Glass res~n ~ettle ~l~sk w~s
fitted with a head cont~ining a mechsnic~l stir~er,
a stainless steel g8S inlet tube, a ~tainles~ ~teel
thermocouple probe connected to ~ dig~tal
tempersture controller, and an adapter containing a
dropping funnel snd a Dean-St~ck trflp connected to
condenser. The flssk was ch~rged wlth 100 gms of
diphenyl sulfone, 12.66 gms (0.115 moles) of
hydroquinone, 24.59 gms (0.1127 moles~ of
4,4'-difluorobenzophenone, 9.325 gms (0.0880 moles)
of anhydrous sodium carbonate, 4.053 gms (0.0293
moles) of anhydrous potassium carbonate, ~nd 35 ml
of xylene.
The contents were hested to 200C with
stirring st~rted ~s ~oon as the m~ss becsme molten,
~nd maintalned there ~or one hour while sdding
xylene dropwise through the dropping funnel. It was
then he~ted to 250C and held there for ~bout 1/2
hour after wh~ch the xylene addition was stopped ~nd
1.119 gms (0.0035 moles) oÇ 1,4-bi~(p-fluorobenzoyl)
benzene (coupling agent) W8S added. The ~emperature
was raised ~o 3~0C ~n~ held there un~l molecular
weight w~s reached (about 2 hours ~n this case).
The ~olymer was isolated by pouring the
flask contents lnto ~ metsl p~n~ grinding the cooled
mass through B 2.0 micron screen, followed by reflux
extraction ~or one hour wi~h 600 ml of acetone
followed by filtr~tion ~nd two w~shes wlth ~cetone
on the funnel. The gr8nul8r materisl was then
reflux extracted with ~bout 600 ml o~ dis~illed
~-14814
- 29 -
wster for one hour followed by filtra~on and two
washes wlth water ~n the funnel. The wet polymer
was dried in a vacuum oven st 120C.
The polymer had a reduced viscosity of 1.02
8S measured in concentrsted sulfutic ~cid ~t 25C at
1~ concentration.
D-14814
.
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