Note: Descriptions are shown in the official language in which they were submitted.
-- 1 --
PQLYA~YLATES H~VING IMRR~VED
HYD~OLYTIC ~TABIL TY
Brief Su~marY o~ the InvenSion
chnical Field
Thifi inYention rel~te~ in genera1 ~o
~oldable po1yarylates, a1~o k~own as aro~atic
polye~ter6, and ~n particular to ~oldalble
po1yarylate ~o~position~ whi~h ~on~ain repeating
units derived fro~ bi -~3,5-di~ethyl-4-hydroxyphe~yl)
~ulfone (TMBS), optional1y a dihydric phenol ~u~h as
~,2-bi~-(4-hydroxyphe~yl)~ opane (~ispheno1 A) and a
~ix~uce of i~ophthalic acid and terephthalic acid or
deri~atives ~her~of. Such palyarylate~ exhibit
improved hydroly~ic 6tability.
Backqround of the Invention
Po1yarylates are aro~atic polye6ters
derived fro~ a dihydric phenol, particu1arly
2,2~bi~-(4-hydroxyphenyl)propane (Bi~phenol A), and
an aro~atic dicarboxylic acid, particu1ar1y mixtures
of teLephtha1ic and isophthalic acids. Illustrative
polyarylate~ are de~crib~d, for example, i~ V.V.
Korshak and S. V. Vinogrado~a, Po1ye~ters, 1965,
Pergamon P~e66, ~ew Yor~, Chapter I~. Polyary1~tes
are high te~peratu~e, high perfor~ance thermop1a6tic
po1y~ers with a go~d combina~lon of ~herm~1 and
~chanical properties. Polyary1ate6 al60 have good
prQ~e~abili~y ~ch al10ws them to be molded in~o a
variety of artic1e~.
~ owever, ~hen po1yarr1ates are exposed to a
hydrolytic environ~e~t unde~ ~ce~6ive time and/or
,177
.. ,.,,, ~
~2~
-- 2
~emperature conditions, the hydrolytic ~tabili~y of
~he polyarylates i~ ~enerally poor which resul~s in
poor mechanical propertie6. Poor hydroly~ic
stability is reflected by a rapid decrea~e in
reduced viscosity of the polyarylates resulting from
exposure to the hydrolytic environment. T~is
deficiency also reguires careful drying procedures
of the polya~ylates prior to ~elt proces~ing.
U.S. Pa~ent 3,652,499 (Bo~man3 de~crib~s
linear polyester6 having recurring s~ruc~ural units
derived from, for example, a 4,4'-Eulfonyl diph~nol
such as bis-(3,5-dimethyl-4-hydroxyphenyl)sulfone
~TM~53 and an alip~atic polycarboxylic acid halide
selected from substituted and un~ub~ituted malonic,
glutaric and pimelic acid h~lides. The polymers are
characterized as being extremely resistant to
organic solventfi and have substantially t~e 6ame or
better physical properties than polye6te~6 of the
prior art.
Characterized in the Borman patent as
polyesters of the prior art are the aroma~ic
polye~ters of U.S. Paten~ 3,234,167 (Sweeney). The
Sweeney patent de~cribes a~omatic polyesterfi having
recurring structural units derived from a
bi6phenolic ~ompound and an 3romatic dicarboxylic
acid such as terephthalic and isophthalic acids.
From the o~nibu~ formula depicted in column 1, lines
52-60, of the Sweeney paten~, one can incidentally
portray bis-(3,5 dime~hyl-4-oxyphenyl) sulfone
derived f~om T~BS. According to U.S. Patent
3,652,~99 (Borman~, the aromatic polyeG~er~ of U.S.
Patent 3, ~34,167 ~Sweeney) are reporeed ~o be
601uble in organic 601v2n~s.
~-14,~7
36~
-- 3
V.S. Paten~ 4,390,682 (~yo et al.)
de~cribe6 aromatic polye~er~ containing
terephthaloyl ar.d isophthaloyl repeatinq units and
dioxyarylene unit~ derived from aromatic diols such
as Biphenol A. From the omnibu~ formula~ depicted
in column 3, line6 5-34, of the Kyo et ~l. pa~ent,
one can incidentally portray bis-(3,5-dlimethyl-4-
oxyphenyl)~ulfone derived from TMB5. The aromatic
polyester~ are characterized as having high
durabili~y under dry and moi~t heat a6 well a6 high
resi6tance to water crazing. As illustrated in the
working exa~ples hereinbelow, polyarylate~ having
repeating unit~ derived from ~MBS and a dihydric
phenol 6uch as Bi6phenol A exhibit greater
hydrolytic ~tability than polyarylates w~ich contain
repeating units derived only fom bi~phenol
compound6 æuch as ~i~phenol A (no TMBS)as exemplified in
Kyo et al.
It has been ~ound a6 a result of thi~
invention that polyarylate~ which contain repea~ing
unit6 deri~ed from bi6(3,5-dimethyl-~-hydroxyphenyl)
fiulfone (TMBS) exhibit improved hydrolytic
6tability. Such improved hydrolytic ~tability is
a~tributable to the ~olecular configuration of
repeating unit6 derived from TMBS in which t~e ~our
~ethyl group~ att~ched to the aromatic rings of TMBS
~ct to sterically hinder hydrolytic a~tack againæt
the carbonyl-ether oxy~en linkage6 vicinally
po~itioned in the polymer ~hain.
Disclosure of tbe Invention
This invention relate~ t~ moldable
polyarylate~ which have good proces6ability and
~eehanical propertie~ and whieh exhiblt improved
D-14,177
hydrolytic tability. In particular, this inven~ion
relates to a composition compri~ing a polyarylate
containin~ rep9ating units (I) having t~e formula
~3 ~ .
~ ~~CX
in an a~ount 6ufficient to enhance hydrolytic
stabili~y of the polyarylate, and optionally
repeating unit~ (II) haviDg the formula
- ~1~1~ ~
in which repeating unit6 (I) and optionally
repeating unitC t II) are connected by interbonding
unit~ ~III) having the f ormula
O O
-- C - Ar - C - (III)
w~erein Y i~ sel~cted ~ro~ alkyl group~ of 1 to 4
carbon a~om~, chlorine or bror~ine, each z,
independently, has a ~r~lue of from O to 4 inclu~ive,
n ha a value of O or 1, Rl i~ a divalent
6~urated or un~aturated aliphatic hydrocarbon
V-1~,177
,~
radical, particularly an alkylene or alkylidene
rad;cal having from 1 to 6 carbon ato~s; or a
cycloalkylidene or cycloalkylene radicall having up
to and including 9 carbon atoms, O, CO. 52~ S or
a direct bond, with the provi~o that when Rl is
SO2, then repeating unit (II) i~ not the same as
repeating unit ~ r is a subs~i~u~ed or
unsub~tituted mesa- or para-p~enylene group, and
wherein the polyarylate ha~ a reduced viscosity of
dt least abou~ 0.3 dl/g as measured in chloroform at
a concentration of 0.5 gtlOO ml at 25C.
The improved hydrolytic ~tability exhibited
by ~he polyarylates of this invention can be
attributable to ~he incorporation of repeating unit~
(I) above into the polymer chain. The molecular
confiquration of repeating unit6 (I) is important in
this regard. In particular, the four methyl groups
attached to the aromatic rings of repeating unit~
(I) are believed to act to sterically hinder
hydrolytic attack against She carbonyl-ether oxygen
linkages vicinally poitioned in the polymer chain.
In contras~, carbonyl-~ther oxygen linkages in
vi inal posisions to, for example, Bisphenol A have
no sterically hindering methyl groups, and such is
believed to explain w~y such a polymer would be more
su~ceptible to hydrolytic attack. In ~eneral, tho~e
polyarylates containing a higher concentration of
repeating unit6 (I) will have the preferred enhanced
hydrolytic ætability.
Detailed Descri~tion
The polyarylate~ of shi6 invention can be
prepared by a~y of the polyester forming reaction6
known to tho~e skilled in the art. Differe~t
~-14,177
~5~
-- 6
additive equence6 of reactant~ c~n be used. For
example, a diacid which gives interbonlding uni~s
(III) hereinabove and ~he diphenol rea~ant~ which
give repeating unit~ (I) and (II) hereinaboYe are
charged and polymerized 6imul~aneously. In another
~equence, one of the diphenol reactant's which give
either repeating unit~ II) or ~II) hereinabove is
charged with ~he acid reactant which gi~es
interbonding units (III) hereinabove, poly~erization
is initiated, and then the other diphenol reactant
which qive6 either repeating unit~ (I3 or (II)
hereinabove is added and the reaction i~ allowed to
progre~6. Other additive ~equences of reactant6 are
also plau6ible.
Illustrati~e of known polye6ter forming
reactions which can be used to make the polyarylates
of this invention include:
(1) The redction of the acid chlorides of
the isophthalic and terephthalic acid~ which gi~es
interbonding unit6 ( I I I ) hereinabove with the
diphen~l~ which give repeating units ~I) and (II)
hereinabove;
(2~ The reaction of the aromatic diacids
which gives interbonding unit~ ( I I T ) hereinabove
with d ie~t~r derivative~ of the diphenol6 having the
f ormul as
R C - O ~ ~ ~ ~2 ~IV)
CH3 ~H3
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~2~ ii9;~
-- 7
and
gY3 (~)
R2~--t~t~R~o -Dc-P~2 (V)
where Y, z, n and Rl are a~ defined hereinabo~e
and where R2=C1 ~ ~2~ aliphatic skeletons,
hereinaf~er referred to as the Diacetate Proces6 and
(3) The reaction of the diaryl e~ers of
~he aroma~ic diacids having the formula
Arl-o- e ~ C -O-Arl ~VI~
where Arl can ~e a phenyl, o-tolyl, m-tolyl,
p-tolyl, or like re6idues, with the diphenols w~ich
give repeating units (I) and (II~ hereinabove,
hereinafter referred to as the Diphenate Proces~.
TWO procedures can be u~ed for the
preparation of the polyarylates of thi6 invention
via the acid chloride route. One is carried ou~ at
low temperature and the other at high temperature.
In the low temperature technique, polycondensation
of the acid chloride6 derîved from terephthalic and
isophthalic acid which give interbonding unit~ ~III)
hereinabove with t~e dihydric p~enol~ which qive
repeati~g units (I~ and (II) hereinabove is effected
~t ambient temperature6 in an i~ert 601vent, 6uch as
methylene chloride, in the presence of a basic
eataly6t and an acid acceptor. A 6econd immiscible
~olvent, e.g., water, ~ay be present. In the high
te~perature technique, polycondens~tion of acid
chloride6 which give interbo~ding u~its ~III)
14,177
hereinabove wîth ~he dihydric phenols which give
repeating uni~s (I) and ~II) hereinabove i6 effected
in a high boiling ~olvent, ~uch a~
1,2c4-~richlorobenzene, a~ temperatures above about
150C, and preferably at about 200~ to about 220C.
Other suitable inert organic ~olvents
u~eful for low temperature polycondensation include
halogenated aliphatic compound~, such a~,
chloroform, methylene bromide, 1,1,2-trichloroethane
as well a~ methylene chloride mentioned aboYe and
the like; and cy~lic ether~ ~uch as tetrahydrofuran,
dioxane, and t~e like. For the hi~h temperature
polyconden~ation, 6uitable 601vent6 include
halogena~ed aroma~ic compound6 ~uch as,
o-dichlorobenzene, 1,2,4-trichlorobenzene ~r
diphenyl ether, diphenyl 6ulfone, ben~oic acid alkyl
e~ter~ wherein the alkyl group contains 1 to about
12 carbon atoms, phenolic ether6, such a~, ani601e
and the like.
Preferred acid acceptor6 for u6e in the low
temperature polyconden6ation are alkali metal and
alkaline earth metal hydroxides including sodium,
potas6ium, barium, calcium, ~trontium, magnesiu~,
and beryllium hydroxide.
U~eful ba~ic cataly6t~ for u~e in the low
temperature polyconden6ation include ~ertiary amine~
6uch as alkyl amine~, including trimethyla~ine,
triethylamine, tripropylamine, tributylamine, and
th~ 8: where the alkyl group contain~ from 1 ~o
about 10 carbon a~om6; alkaryl amine~ ~uch a~
N,N-dimethylaniline, N,N-aiethyl~nillne,
N,N-di~ethylnaph~hylamine~ benzyl dimethylamine,
D-1~,177
, .
- g
alpha-methylbenzyl dimethylamine, pyridine, cyclic
diazo compounds, such a~, diazobicyclooctane
IDABCo), diazobicyclononene (DBN) and
diazo~icycloundecene (VBU) and the like.
PolymerizatioD~ using the Diacetate Proce~s
can be carried out in ~he melt at between 260GC and
340C, preferably between 275C and 320~C. They can
also be carried out either a~ a solution reac~ion at
those temperatures or a su~pen~ion reac~ion al80 at
those temperatures. The solvent(s) or suspending
agent(s) can be one of any number of organic
compounds boiling between 140C and 3qO~C. They can
be chosen from hydrocarbons, ketones, ethers, or
sulfones which are inert under the reaction
conditions. These polymerizaeion6 may or may not be
run in the presence of a catalyst. Typical solvents
are ~etramethylene ~ulfone, diphenyl ether,
substituted diphenyl ether, and the like. Typical
catalysts include Na, Li, K 6alts (organic and
inorganic), transi~ion metal salts, alkaline earth
metal ~alts, e.g., Mg acetate, and the like. They
may be performed at atmospheric pressure, ~uper
atmo~pheric prefi~ure, or ~ubatmospheric pressure.
Polymerizations using the Diphenate Proce~s
can be carried ou~ in the mel~ at be~ween 250C and
350C. The preferred temperature range i~ about
275~C to 320C. In general, reduced pressure for
th~ inal poreions of the rea~tion is u6ed. The
polymerizations can also be carried out ei~e~ as a
601ution reaction or ~u~pen~ion reaction under those
soDditio~. The 801vent(&~ or su pending agen~
~re the same a~ t~o~e describe~ aboYe. Typical
,177
ca~alyst~ include tin compo~nds and generally tho~e
mentioned above for the Diacetate Proce~s.
Particularly preferred cataly~tfi are Ti and tin
sal~, Mg acetate, and alkali metal ~alt~, alkoxide6
and phenoxides.
If desired. a chain stopper can be u~ed to
control the ~oleculaL weigh~ of the polyarylates
obtained. Suitable chain xtoppers a~en~ include
monohydric phenol~ or their derivatives, 6uch as,
p-phenylphenol, and the like and monofunctional
carboxylic acid or their deriva~i~es, such as
benzoic or naphtholic acids, and ~he like,
The diphenol reactant
bi6 (3,5-dimethyl-~-hydroxyphenyl)sulfone (TMaS)
whi~h give~ repeating UDits ~I) hereinabove can be
prepared according to the process de~cribed in U.S.
Patent ~,383,q21. Die~ter derivatives of TMBS as
describ~d in Formula (IV) hereinabove can also be
prepared accordinq to known proce~es.
Suitable dihydric phenols other ~han
bi~- ( 3, 5-d imethyl-4-hydroxyphenyl)~ulfone (TMBS)
which give repea~ing unit~ (II) hereinabove include
the following: 2,2-bis~4-hydroxyphenyl)propane
(Bi6phenol A); bis-(2-hydroxyphenyl)me~hane
bi (4-hydroxyphenyl)methane;
bi~-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)-
methane;1,1-bi~-(4-hydroxyphen~l)ethane;
1,2-bis-~4-hydroxyphenyl)ethane:
1,1-bi~-~4-hydroxy-2-clhlorophenyl)ethdne;
l,l-bi~ -methyl-4-hydroxyphenyl3ethane:
1,3-bis-(3-methyl-4-hydroxyphenyl)propane;
D-14,177
. .
2,2-bi~-(3-methyl-4~hydroxyphenyl)propane:
2,2-bi~-(3-isopropyl-~-hydroxyphenyl~propane;
2,2-bis-(2-i~opropyl-4-hydroxyphenyl)propane:
2,2-bi~-(4-hydroxyphenyl)pentane;
~,3 bi~-(4-hydroxyphenyl)pentan~:
2,2-bis-(4-hydroxyphenyl)heptane;
1,2-bi~-(4-hydroxyphenyl)1,2-bi~-(phenyl)-propalle:
4,4'-~dihydroxyphenyl)ether:
4,4'-(dihydroxyphenyl)sulfide;
4,4'-(dihydroxyphenyl)sulfoxide: hydroquinone; and
naph~halene diols. Other bisphenol compounds
suitable for u e in this invention 3re d;~clo~ed in
U.S. Patent~ 2,999,8~5, 3,028,365 and 3,339,154.
Preferred dihydric phenols include
2,2-bis-(4-hydroxyphenyl)propane ~Bi6phenol A) and
bi6-(4-hydroxyphenyl)6ulfone (Bi~phenol S). Glycols
and aliphatic dihydroxy compounds other than
bisphenol~ in amount~ typicdlly not greater than
about 10 weight percent of the total weight of
repeating unit6 (I) and (II) in the polyarylate can
also be u~eful in preparing the polyaryla~e~ of ~his
invention. Die~ter derivatives of these dihydric
phenol~ as described in Pormula (V) hereinabove can
also be prepared accordinq to known proce~ses.
Suitable aromatic difunctional acids and
acid halide6 whic~ gi~e interbonding unit6 tTlI~
bereinabove include i~ophthaloyl acid and chloride,
terephthaloyl acid and chloride, mixture6 of
i~ophthaloyl and terephthaloyl acid~ and chloride~,
2,5-dic~loroterephthaloyl acld and chloride,
5-tert-butyl-i~oph~haloyl acid and chloride,
2-chloroi60phthaloyl acid and c~loride,
D-1~,177
g~
- 12 -
4-chloroi60phthaloyl acid and c~loride,
5-chloroi~ophthaloyl acid and chloride, any of the
naphthalene dicarboxylic acid~ and acid halide~ and
the like. The aromatic ring ~ay be sub~ti~uted with
~ub~tituents 5uch a~ al~yl group~ eontaining from 1
to 4 ca~bon atoms, alkoxy group~ containing from 1
to 4 carbon atoms, aryl, halogen and the like.
O~her ~uitable aromatic difunctional acids
and acid halide6 which can be used in preparing the
polyarylate~ o~ this invention include the
6ub6tituted and unsub~ti~uted ~,4'-biphenyl
dicarboxylic acid, ~,4'-diphenyloxide dicarboxylic
acid, halide derivative~ thereof and the like.
~oreover, hydroxyaromatic æcid~ and derivative~
thereof such a6 4-hydroxybenzoic acid and the like
can be used in thi~ invention~ Diaryl e6ters of
these aromatic difunctional acid6 and deriv~tives
theeeof can al60 be u~eful in preparing the
polyarylate6 of this invention.
The preferred aromatic difunctional acids
or derivative~ for u~e in preparing the polyarylate~
of this invention include ieo~hthalic acid,
terephthalic acid and mixture6 of isophthalic and
terephthalic acid.
The reaction for preparing the polyarylates
of thi~ invention proceeds on a ~toichiometric basi6
~uc~ that the desired polyarylate i6 formed.
&toichiometry i6 not critical and the only
requirement i~ that the amount6 employed are
6ufficient to form the polyarylate of the de6ired
~olecular weight having enbanced hydrolytic
~tability. The preferred polyarylate of ~his
inv~ntion h~ ~he following ~tructural formula
D-14,177
_ 13 --
CH3 ~W3
-E ~ C D -~,~ 0~ ; C113 ~:H3 _
wherein the polyarylate has a reduced vi~eosity of
at leas~ about 0.3 dl/g as mea~ured in chloroform at
a concen~ra~ion of 0.5 g/100 ml at 25C. Another
preferred polyarylate of tbi6 invention has the
following structural formula
E_~C~~ ~C~ ~ c~3~
wherein the polyarylate ha~ a reduced vi~cosity of
at least about 0.3 dl/g as mea~ured in chloroform at
a concentration of 0.5 g ~100 ml at 25C.
By varying t~e amounts of reactants, one
can vary the polyarylate polymer ulti~ately produced
and it~ properties. For example, in general, the
polyaryla~e polymer~ of this invention conta;ning
~he greater weight percentages of repea~ing units
(I) will preferably h~ve the better hydrolytic
stability. Thi~ i6 attributable to the molecular
configuration of repeating unit~ (I) in which the
four me~hyl groups attached to the aro~atic rings of
repeati~g uni~ (I) a~t to 6terically ~inder
hydrolytic at~ack aga~6t the carbonyl-ether oxygen
~ a~es vicinally po6itioned in the polymer ~hain.
D-1~,177
. ~ ... . . .. .
6~2
A6 ~ydrolytlc ~tability can be enhancecl by even
minor amoun~s of repeating units (I), 1:he
concentration of repeating uni~ (I) in the
polyarylate6 of thi6 inv0ntion i~ not narrowly
cri~ical and can be varied over a wide range. The
only requirement is that the polyarylat:e~ of t~i~
invention contain a sufficient amount of repeating
unit~ (I) to enhance hydrolytic ~tability t~ereof.
In particular, the polyarylate~ of this
invention can preferably contain from about 5 weight
percent or le~6 to about 95 weight percent or
greater of repea~ing units (I) ~ereinabove, together
with interbonding unit~ ~III) hereinabove, more
prefer~bly from about 25 weight percent to ~bout 75
weight percent, and mo~t preferably from about 40
weig~t percent to about 60 weight percent. The
polyarylates of this invention can preferably
contain from about 95 weight percent or greater to
about S weight percent or le6s of repeating unit~
(II) hereinabove, together with interbonding units
(III) hereinabove, more preferably from about 75
weight percent to about 25 weight percent, and mo~t
preferably from about 60 weight percent to about 40
weigh~ pereent. In general, those polyarylates
con~aining the higher weight percentage~ of
repeating units tI) w~ll preferably have the better
hydrolytic 6tability, and those poly~rylates
containing t~e higher weight percentages of
repeating unitfi (II) ~ill preferably hav~ the better
proce~6ability.
The ~tructure of ~he polyarylate polymers
of th~ invention can be ~odified to ~ome extent by
including in the polymer;zation reaction other
D-14,177
..~. .. .
- 15 -
dihydroxy compounds, typically not mor~ than abo~lt
10 weight percent of t~e total weight of t~e
repea~ing units (I~ and (II) in the po].yarylate.
~or example, one might in~lude along wi.th
Bisphenol-~ and bis-~3~5-di~ethyl-4-hydroxyphenyl)-
6ulfone (TMBS), other dihydroxy compound~ either as
~uch or in the die~ter form, as a partial ~ubstitute
and modifier of the po1ymeric structure, without
adversely affecting the overall propereies of the
polymeric ~tructure of ~his invention. For example,
such dihydroxy compound~ as ethylene glycol,
propylene glycol, 1,4-butylene glycol, and the like
can be included in the polymerization reactions to
~anufacture the polyarylate polymers of this
invention.
Additionally, tbe preparation of the
polyarylate6 of this invention via the Diace~ate
Proce~ or Diphenate Proce~ may be carried out in
the presence of from about 10 to about 60 weight
percent, based on the weight of ~he polyaryla~e
produced, of a processing aid. The preferred
proces~ing aid~ are diphenyl ether compounds, a
cycloaliphatic, sub6tituted aromatic, or
heteroaromatic compound, and a halogena~ed andJor
etherated 6ubstitu~ed aromatic or heteroaromatic
compound, or mixture~ of these. ~uch a proces~ing
a~d ~ay be useful in con~rolling and/or modifying
vi~co~ity, reaction time, color, ~tability and the
like.
Poly~er recovery can be achie~ed by
proce~e~ W~ no~n in ~he art to recover a
~oldable polydrylate ~uch a~ by ~oagulation and
filtra~ion.
D-14,177
. .
- 16 -
In addition. the polyarylate~ of this
invention exhibit excellent compatibili.~y wi~h
polye~hersulfones 6uch a~ ~ho~e which alre de~cribed
in U.S. Patent 3,264,536 and U.S. Pa~sn~ 4,175,175,
as well a~ with poly(aryl@thsr~s,
poly(e~ter-carbonate)s, polye6~er6, po}ycarbonate~,
poly(ether imide)s. 6 tyrenic polymers, vinyl
chloride containing polymer~ and the like. In ~ome
instances, it may be desirable to blend the
polyarylate6 of the inven~ion with other polymers
exhibiting mechanical compatibility with ~he
polyarylate polymer~. Mechanical compatibility
refers to a balance of mechanical properties, e.g.,
~treng~h, toughnes6 and the like, in miscible blend
~ystems which is generally an average of the
mechanical propertie6 of ~he particular blend
constituents. Such moldable and compatible blends
may typically contain feom about 5 weight percent to
about 9S weight parcent of the polyarylates oP thi~
invention and from about 95 weight percent to about
S weight percent of a polymer exhibiting mec~anical
compatibility with the polyarylate. The weight
percent ratio of the polymer~ may vary widely
depending upon the propertie~ ~ought from the molded
products made from ~he blend.
Blending may be done in the u~ual fa~hion,
6ucb a~ by ~i~ple mixing of powder~ of t~ poly~ers,
though u~ually in an extruder mixer. The extruded
product will typically be a ~elt mixture of the
polyarylate and tbe polymer blended therewith. Such
an extruded product ~an be pelleted and u~ed a6 ~uch
in ~aking molded ar~iele~ of co~meree.
D-14,177
_ 17 -
The polyarylates of thi~ invention utili2ed
in manufacturing ~olded article6 may be optionally
used wit~ other ingredlen~ ~uch a~ ~tabilizers,
i.e., ~etal oxides ~uch a6 zinc oxide, an~ioxidant~,
flame retardants, pigment~, and the like. The
polyarylates may be optionally u~ed with reinforcing
fi~ers and/or inorganic fillers. The reinfQrcing
fiber include~ fiberglas~, carbon fiber~, and the
like, and mixture~ thereof. The carbon fibers
include ~ho6e ~aving a high Young's ~odulu~ of
ela6~icity and high ten6ile ~erength. These carbon
fiber~ may be produced rom pitch, as described in
U.S. Pa~ents 3,976,729: 4,005,183 and 4,026,788, for
exa~ple. The particulate inorganic fillers which
~ay be used include wollastonite, calcium oarbonate,
glas~ bead~, ~alc, mica, clay, quartz and the l~ke,
or mixture~ thereof.
The ~iber reinforcement, filler or
combinations thereof, can be utilized in amount6 of
from O to about 50 weight percent, preferably from
about 10 to about 35 weight percent, of the total
weight of ~he molded arti~le.
The polyarylate6 of thi6 invention utilized
in manufacturing molded articles in combination wi~h
one or more other ingredients can be prepared by any
conYentional ~ixing method~. For example, the
polyarylate6 and other optional ingredien~s in
powder or granular fo~ can be blended in an
extruder ~nd tbe mixture can be extruded into
~trand6 and the ~trands can be chopped into
p~ t6. The pellets can then be molded into ~he
desired ar~icle by ~onven~ional techniques ~uch a~
D-14,177
, . ~ .. . .
compre~ion molding, thermoforming, blow molding and
injection molding.
The ~olecular weight of these polyarylate
polymers i~ indicated by reduced vi6co~ity in
indicated ~olvent~. As well understood in the art,
~he vi~cosity of a re~in ~olution bear~ a direct
relation~hip to the weight average molacula~ ~ize of
the polymer chains, and i6 ~ypically the mo6t
important ~ingle property that can be u~ed to
characterize the degree of polymerization. The
reduced vi~co~ity as6igned to the polymeric
~aterial6 of this invention i~ there~ore to be
under6tood as significant in reflecting molecular
6ize rather than consideration concerning the
visco~ity per 6e. Most of these polyarylate
polymer~ have indicated ready solubility in
N-methylpyrrolidinone, chloroform, or
tetrachloroethane or other 6imilar ~olvent.
Reduced vi~cosity (R.V.) as u~ed herein wa~
determined by di6~01ving a 0.2 or 0.5 gram sample of .
polyarylate polymer in the ind;~ated solven~, i.e.,
chloroform, contained in a 100 mill;liter volumetric
fla~k ~o tha~ the re~ultant 601ution ~easured
~xactly 100 milliliter~ at 25C. in a con~tant
tempera~ure b~th. The vi~cosity of 3 millili~ers of
~e ~olution which had been filtered throuqh a
6intered glas6 funnel wa~ ~etermined in an Ostwald
or similar type viscome~er at 25C. Reduced
visco~i~y val~es were obtained from the eguation:
t~ - to
Reduced Visco61ty - _ _
C-to
~-14~177
3~
-- 19 --
w~erein:
~ he ef f lux ti~e of the pure solven~;
t~ i6 ~he e~flux ~i~e of t~e poly~er
solution: and
C i~ t~e concentration of ~e polymer
~olution expre~sed in ~er~ of gram~ of polymer per
lO0 millili~ers of 601ution.
Tbe polyarylates of tbis invention are
characterized as linear ~hermopla~tic structure~
which have a relatively high molecular weight, that
is, a rsduced vi~co~ity determined at a
concentration of 0.5 g/lO0 ml in chloroform at 25C
of at leas~ 0.3 dl/g, preferably at lea6t 0.5 dl~g
and, typically not exceeding about 1. 5 dl/g. T~e~e
polymer6 are exceptionally tough and po6se6s
~uperior hydrolytic 6tability in compari~on with
conventional Bi~phenol A polyarylates of the pr;or
art.
Although thi~ invention has been described
with re~pect to a number of detail~, it i6 not
intended tha~ thi~ invention 6hould be limited
thereby. The example6 which follow are intended
fiolely to illu~trate the embodiment~ of this
invention which to date have be~n determined and are
not intended in any way to limit the ~cope and
intent of t~i6 invention.
Example_l
To a 4-necked 500 ~llliliter fla6k fitted
wi~h a nitrogen inlet pore, ~echanical stirrer,
~flu~ ~onden6er, ~lai~en head. thermometer and a
20~ s~dium hydroxide trap wa~ ~dded 14.27 gra~s
~0.0625 ~ole~) o~ 2,2-bis-~4-hydroxyphenyl)propane
~-14,177
-- ~o --
(Bisphenol A). 19.14 grams (0.0625 mole~) of
bi~(~,5-dimethyl-ql-hydroxyphenyl~sulfone (T~SBS),
12.69 grams (0.0625 mole~) of i~ophthaloyl chloride,
12.69 qrams ~0.0625 moles) of ~ereph~aloyl
chloride, and 175 ~illiliter6 of
1,2,4-trichlorobenzene. The con~ents of the fla6k
were then hea~ed to a temperature of 210C and
maintained at this temperature for a period of 16
hours with con~inuou~ stirring. A sample removed
from the flask after this reaction period had a
reduced visc06ity of 0.157 at 25C in O.S~
chloroform ~olution. An additional 0.507 grams
(0.0025 moles) of terephthaloyl chloride was added
to ~he flask, and the contents in the flask were
reacted for another 16 hour period at a temperature
of 210C with continuous stirring. A sample removed
from the flask after this second 16 ~our reaction
period had a reduced visc06ity of 0.35 at 25C in
0.5% chloroform solution. An additional 0.57 grams
(0.0028 mole6) of terephthaloyl chloride and 0.57
grams (0.0025 ~oles) of
2,2-bis-(4-hydroxyphenyl)propane ~Bisphenol A) were
then added to the fla~ over a period of 24 hours at
a t~mperature of 210C with continuous stirring.
The resulting mixture was ~en coagula~ed in
~ethanol, filtered ana washed with methanol. The
polymer wa6 dried under vacuum at a temperature o~
100C. T~e reduced visc061ty at 25C in 0.5%
chl~roform solution was 0.46.
Co~parative ~xample A
A 6ample of Bi~phe~ol A polyarylate
~ommercially available from Union Carbide
D-14,177
Corporation, Danbury, Connecticut a~ Ardel D-100
prepared from Bisphenol A and a mixture of 50 mole
percent each of terephthaloyl and isopht~aloyl
chlorides by conventional methods) wa~ compres~ion
molded into a plaque in a 4 inch ~ 4 inch ~ 0.020
inch cavity mold at 300C u~ing a South Bend
hydraulic pres6 with heated platens. T~e reduced
viscosity of the polymer co~position of the plaque
was determined and. after placing ~he plaque in
boili~g di6tilled water, t~e reduced viscosi~y of
the polymer composition of the plague was again
detecmined at various period~ of time (boiling
di~tilled water immersion) 2~ 6pecified in Table A
hereinbelow. All reduced viscosity values in Table
A were determined at a tempera~ure of 25C in a 0.
chloroform solution. The re6ults in Table A
indicate the ratio of the reduced visco6ity of the
polymer compo~ition at the 6pecified time to the
initial reduced vi6c06ity of the polymer composition
determined before placing the plaque in boilinq
water.
Exam~le 2
A æample of ehe Bi6phenol A/TMBS
polyarylate prepared in Example 1 wa6 compression
moldsd into a plaque in a ~ inch ~ 4 inch X 0.020
inch cavity mold at 300C using a South Bend
hydraulic pre~s with heated pldtens. The reduced
vi~co~ity of the pvlymer composition of the plaque
~a~ deter~ined and, after placing e~e plaque in
boiling di~tilled water, the r@duced vi6cosity of
the polymer composition of the plaque wa~ again
determined at variou6 psriod~ of time (boilinq
D 1~,177
~t~%
- 22 -
di~tilled water immer~i~n) as ~pecified in Table A.
All reduced vi6c06ity value~ in Table A wer2
de~ermined at a temperature of 25~C in a 0.2%
chloroform solueion. The re6ults in T,able A
indicate the ratio of the reduced visc~ity of the
polymer composition at the ~pecified time to the
initial reduced viscosity of the polymer composition
determined before placing the plaque in boiling
water.
TP.BLE A
Ra~io of Reduced Viscosity at Indicated Ti~e
to Initial Reduced Viscosity a~ a Function of Time
in Boilinq Distilled Water
Plaque Sample ~oiling Di6~illed Water Immersion (Hours)
Identification 0 100 _308_ 316 580
Compara~ive 1 0.89 0.64 - 0.42
Exa~ple A
Example 2 1 0.93 - 0.84
Table A illu6~rates ~hat the reduced
visco~ity of the polymer composition of the plaque
prepared in Comparative Exampl0 A (control Bi~phenol
A polyarylate) decrea~es ~uch more rapidly upon
p~olonged expo~ure in boilin~ distilled water t~an
the reduced vi~co~ity of ~he polymer compo6ition of
the plaque prepared in Example 2 ~Bisphenol A/TMBS
polyarylate) at ~imilar expo~ure time. The polymar
~ompo~ition of the plaque prepared in ~xample 2
~how~ improved hydroly~ic ~tability in compari~on
~ith ~e polymer co~posi$ion of the plaque prepared
~n Comparative ~xample A. A~ reduced visco~ity i6
D-14,177
J
- ~3 -
an indication of polymer ~olecular weig~t, Bi~phenol
~/TM~S polyarylate~ are ~ore hydrolytically ~table
than comparable Bi6phenol A polyarylat,e6 which do
not contain TMBS.
D-1~,177
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