Note: Descriptions are shown in the official language in which they were submitted.
` l
01 -1-
5-KETO-BIS(HYDROXYPHENYL~ANTHRACENE
POLYARYLATE COPOLYMERS AND ALLOYS
05
BACKGROUND OF THE INVENTION
The present invention relates to polyarylate
copolymers and alloys. More particularly, this invention
relates to 5-keto-bis~hydroxyphenyl)anthracene polyarylate
copolymers and alloys having superior thermal properties.
Polyarylates are defined as aromatic polyester
polymers derived ~rom dihydroxy aromatic compo~lnds
~diphenols) and aromatic dicarboxylic acids.
In general, aro~atic polyesters prepared from
bisphenols or functional derivatives thereof and a tere-
phthalic acid-isophthalic acid mixture or a mixture of the
functional derivatives thereof, i.e., bisphenol tere-
phthalate-bisphenol isophthalate polyesters, have
excellent mechanical properties, such as tensile strength,
bsnding strength, bending recovery or impact strength,
~(~
excellent thermal properties, such as deflection tempera-
ture under load or degradation temperature, excellent
electrical properties, such as resistivity, electric
breakdown 0ndurance, arc resistance, dielectric constant
or dielectric loss and low flammability, ~ood dimensional
stability, and the like.
; These aromatic polyesters are thus useflll in
; many ~ields. Aromatic polyesters find special use as
plastics for injection molding, extrusion molding, press
0 molding, and the like, as monofilaments, fibexs, films and
coatings.
U.S. Patent No. 3,216,970 describes polyarylates
which include polymers of bisphenol A and isophthalic acid
or a mixture of isophthalic acid and terephthalic acid.
These polyarylates are prepared by converting the phthalic
acid component to the diacid chloride which is then
reacted with the bisphenol A or its sodium salt.
U.S. Patent No. 3,884,990 describes a blend of
various bisphenol polyarylates and poly(ethylene oxybenzo-
ate), which is useful for producing molded articles having
:a2~
J
~1 2-
improved cracking and crazing resistance. Similarly,U.S. Patent No. 3,946,091 describes a blend of bisphenol
D5 polyarylates and poly(ethylene terephthalate) which pro-
vides molded articles of reduced crazing.
U.S. Patent No. 3,792,118 describes a styrene
resin composition resistant to heat deformation which
comprises a blend of polyarylene esters and various
styrene resins.
SUMMARY OF THE INVENTION
The present invention provides a polyarylate
copolymer derived from
~A) A mixture of a 5-keto-bis~h,ydroxyphenyl)
anthracene compound oE the formula
R~ R3
HO~H
wherein Rl, R2, R3 and R4 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl;
and a bisphenol compound selected from the group consist-
ing of
~_C~<
R6 R8
~0
Ol -3-
wherein R5, R6, R7 and R8 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl;
HO~ ~O
ID ~
rein Rg, Rlo' Rll and R12 are independently hydrogen,
lower alkyl o 1 to 4 carbon atoms or phenyl; and
~
R~ Rl 5
HO~C~OH
21~ R14 ~ R16
wherein R13, R14, R15 and R16 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein
the molar ratio of 5-keto-bis(hydroxyphenyl)anthracene to
bisphenol is from 20:1 to 1:20; and
(B) a mixture of isophthalic and terephthalic acid
in a molar ratio of 9:1 to 1:9, respectively.
The present invention is further concerne~ with
a polyarylate alloy composition comprising
(A) 10 to 90% by weight of a polyarylate of the
formula
~ - C ~
O n
~6~
01 _4_
wherein Rl, R2, R3 and R4 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; n is the
05 degree of polymerization; and wherein
O ..
-C~
is an isophthalic or terephthalic acid moiety present in a
molar ratio of 9:1 to 1:9, respectively; and
(B) 10 to 90% by weight of a polymer resin selected
from the grc~up consisting of polybisphenol A carbonate and
polystyrene.
Also contemplated by the present invention is a
polyarylate alloy composition comprising
(A) 10 to 90~ by weight of a polyarylate copolymer
derived from
(1) a mixture of a 5-keto-bis(hydroxyphenyl)-
anthracene compound of the formula
;~ ()
HO~OH
2 5 R2 R4
Il
o
wherein Rl, R2, R3 and R~ are independently hydrogen,lower alkyl of 1 to 4 carbon atoms or phenyl;
and a bisphenol compound selected from the group consist-
ing Of
HO~)-C~--OH
CH3
R6 R8
wherein R5, R6, R7 and R8 are independently hydrogen,
~ lower alkyl of 1 to 4 carbon atoms or phenyl;
~Zi~4~9~
01 _~_
10~ R12
~-/o
o
n Rg, Rlo, Rll and Rl2 are independently hydrogen,
lower alkyl of l to 4 carbon atoms or phenyl; and
~ ~ RlS
HO~-C~-OH
R14 ~?J R16
rein Rl3, Rl4, Rl5 and Rl6 are independently hydrogen,
lower alkyl of l to 4 carbon atoms or phenyl;
and wherein the molar ratio of 5-keto-bis(hydroxyphenyl)-
anthracene to bisphenol is from 20:1 to 1:20; and
(2) a mixture of isophthalic and terephthalic
acid in a molar ratio of 9:l to l:9, respectively; and
(B) l0 to 90% by weight of a polymer resin selected
from the group consisting of polybisphenol A carbonate and
polystyrene.
Among other factors, the present invention is
based on the discovery that certain polyarylate copoly-
mers, derived from mixtures of 5-keto-bis(hydroxyphenyl)-
anthracene compounds with other bisphenols, have been
found to possess superior thermal properties~ In addi-
tion, it has been found that 5-keto-bis(hydroxy-
phenyl)anthracene polyarylates provide alloy compositionswith polystyrene and polybisphenol A carbonate which also
exhibit excellent thermal properties.
DETAILED DESCRIPTION OF THE INVENTION
For purposes of the present invention, those
polyarylates derived from a single 5-keto-bis(hydroxy-
01 -6-
phenyl)anthracene compound shall be referred to as "homo-
polymers" and those polyarylates derived from a mixture of
05 5-keto-bis(hydroxyphenyl)anthracene and other bisphenol
compounds shall be referred to as "copolymers~. It is, of
course, understood that 5-keto-bis(hydroxyphenyl)anthracene
may be characterized as a type of bisphenol compound.
Furthermore, the term "alloy" as used herein is meant to
define an intimate physical mixture or blend of two or
more polymers.
The 5-keto-bis(hydroxyphenyl)anthracene com-
pounds which are useful for conversion into the instantpolyarylate homopolymers and copolymers may be represented
lS by the ~ollowing formula
R~ R3
HO~ ~OH
R2 ~ R4
o
wherein Rl, R2, R3 and R4 are independently hydrogen,
lower alkyl of l to 4 carbon atoms or phenyl.
Preferred examples of 5-keto-bis(hydroxyphenyl)-
anthracene compounds include the unsubstituted compound
and the tetraalkyl derivative. Particularly pre~erred
compounds are those wherein Rl, R2, R3 and R4 are hydro-
gen; i.e., 5-keto-lO,lO-bis(4'-hydroxyphenyl)anthracene,
and wherein Rl, R2, R3 and R4 are rnethyl, i.e , 5-keto-
lO,lO-bis(31,5'-dimethyl-4'-hydroxyphenyl)anthracene.
The 5-keto-bis(hydroxyphenyl)anthracçne com-
- 35 pounds used in the invention are prepared by reacting an
unsubstituted or ortho-substituted phenol with anthra-
quinone in the presence of a Friedel-Crafts catalyst. A
typical substituted phenol is 2,6-dimethylphenolc Suit-
able Friedel-Crafts catalysts include tin tetrachloride,
aluminum trichloride, and the like.
~1 -7-
The instant polyarylate hoMopolymers and copoly-
mers are prepared from the above-described 5-keto-
05 bis~hydroxyphenyl)anthracenes or from mixtures of thesecompounds and other bisphenols~ The instant polyarylate
homopolymers are prepared from a single 5-keto-bis-
(hydroxyphenyl~anthracene compound or a functional deriva-
tive thereof. Similarlyl the instant polyarylate
copolymers are prepared from a mixture of a 5-keto-
bis~hydroxyphenyl)anthracene compound or functional
derivative thereof and a bisphenol compound, or functional
derivative ~hereof, selected from the group consisting of
~ CH~
CH3
R6 R~
~U wherein R5, R6, R7 and R~ are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl;
R~ Rll
25 HO ~ ~ R12
~/
o
in Rg, Rlo, Rll and R12 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; and
R~ ~ R15
HO~>-C~-OH
R14 1~3 R16
wherein R13~ R14~ R15 and R16 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl.
~0
8~
01 -8-
When R5, R6, R7 and R8 above are all hydrogen,the compound obtained, 2,2-bis(4-hydroxyphenyl)propane, is
05 generally referred to as bisphenol A. When R5, R6, R7 and
R8 are not all hydrogen, the compound obtained will herein
be referred to as a substituted bisphenol A. Preferred
examples of substituted bisphenol A include tetraalkyl
bisphenol A and diphenyl bisphenol A. A particularly
preferred substituted bisphenol A is tetramethyl bis-
phenol A or 2,~-bis(4-hydroxy-3,5-dimethylphenyl)propane.
The various bisphenol A compounds are prepared by reacting
an appropriately substituted phenol, such as 2,6-dimethyl-
phenol, with acetone in the presence of a Friedel-Crafts
catalyst,
Moreover~ when R~, Rlo~ Rll and R12 in the above
formula are all hydrogen, the compound obtained,
1,1-bis(4'-hydroxyphenyl)phthalide, is commonly referred
to as phenolphthalein. When Rg, Rlo, Rll and R12 a
all hydrogen, the compound obtained will herein be
referred to as a substituted phenolphthalein. Preferred
examples of substituted phenolphthalein include the tetra-
alkyl derivatives, that is, wherein Rg, Rlo, Rll and R12
are independently lower alkyl of 1 to 4 carbon atoms. A
5 particularly preferred substituted phenolphthalein is that
n Rg, Rl~, Rll and R12 are methyl, that is, 1,1-
bis(3',5'-dimethyl-4'-hydroxyphenyl)phthalide or,
commonly, tetramethylphenolphthalein. The substituted
phenolphthalein compounds are prepared by reacting an
appropriate ortho-substituted phenol with phthalic
anhydride in the presence of a Friedel-Crafts catalyst,
such as zinc chloride.
Further, when R13, R14~ Rls and R16 above
all hydrogen, the compound obtained, bis(4-hydroxy-
phenyl)diphenylmethane, is conveniently referred to asdihydroxytetraphenylmethane- When R13~ R14~ Rls a~d R16
are not all hydrogen, the compound obtained will herein be
referred to as a substituted dihydroxytetraphenylmethane.
Preferred examples of dihydroxytetraphenylmethane
compounds include the unsubstituted compound and the
~Z6~
o~ g
tetraalkyl derivative. A particularly preferred sub-
stituted dihydroxytetraphenylmethane is that wherein R13,
Rl~, R15 and R16 are methyl, that is, bis(3,5-dimethyl-4-
hydroxyphenyl)diphenylmethane.
The dihydroxytetraphenylmethane compounds are
prepared by reacting an appropriately substituted phenol
with dichlorodiphenylmethane, preferably in the presence
of a Friedel-Crafts catalyst. Typical substituted phe~ols
include 2,6-dimethylphenol and 2-phenylphenol. Suitable
Friedel-Crafts catalysts include aluminum chlorider ferric
chloride, stannic chloride, boron trifluoride, zinc
chloride, hydro~en fluoride, hydrogen chloride, sulfuric
acid, phosphoric acid, and the like.
Typical functional derivatives of the above-
described 5-keto-bis(hydroxyphenyl)anthracenes and bis-
phenols include the metal salts and the diesters with
monocarboxylic acids having 1 to 3 carbon atoms. Pre-
ferred functional derivatives are the sodium salts,
potassium salts and diacetate esters.
For the polyarylate copolymers of the present
invention, the mixture of 5-keto-bis(hydroxyphenyl)-
anthracene and bisphenol will have a molar ratio of 5-
keto-bis(hydroxyphenyl)anthracene to bisphenol of about
20:1 to 1:20. Preferably, the molar ratio of 5-keto-
bis(hydroxyphenyl)anthracene to bisphenol will be about
9:1 to 1:9, more preferably, about ~:1 to 1:4.
The acid component which is reacted with the
5-keto-bis(hydroxyphenyl)anthracene or 5-keto-bis(hydroxy-
phenyl)anthracene-bisphenol mixture to prepare the poly-
arylates of the invention is a mixture of isophthalic and
terephthalic acid or functional derivatives thereof in a
molar ratio of about 9:1 to 1:9, respectively. Prefer-
3~ ably, the molar ratio of isophthalic to terephthalic acidwill be about 3:1 to 1:3, more preferably, about 1:1.
Preferred functional derivatives of isophthalic
or terephthalic acid include acid halides, such as iso-
phthaloyl or terephthaloyl dichloride and isophthaloyl or
~o terephthaloyl dibromide, and diesters, such as dialkyl
~Z~8~.
O 1 -1 O-
esters or diaryl esters, having from 1 to 6 carbon atoms
per ester group. Examples of suitable diesters include
05 diphenyl isophthalate and diphenyl terephthalate.
The polyarylate homopolymers used in the present
invention can be generally represented by the formula
' ~ c~l
o
n
wherein Rl, R2, R3 and R4 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; and n is the
degree of polymerization. Generally, n will be adjusted
to provide a polymer having an average molecular weight
greater than about 15,000.
In the case of the polyarylate copolymers
derived from a 5-keto-bis(hydroxyphenyl)anthracene-bis-
phenol mixture, the 5-keto-bis(hydroxyphenyl)anthracene
and bisphenol moieties will normally occur in random order
throughout the polyarylate.
The polyarylates of this invention can be pre-
pared by several methods. For example, an interfacial
polycondensation process can be used. In this case an
aqueous alkaline solution of a bisphenol or mixture of
bisphenols and a terephthaloyl dihalide-isophthaloyl
dihalide mixture dissolved in an organic solvent which is
immiscible with water are mixed and reacted. Suitable
interfacial polycondensation processes which can be used
are disclosed, for example, in ~O M. Eareckson~ J. Polymer
Sci., XL 399 (1959) and Japanese Patent Publication
No. 1959/65.
8g~L
0 1
The following is a typical polycondensation
process. An aqueous alkali solution of a bisphenol or
05 mixture of bisphenols is added to a terephthaloyl
dihalide-isophthaloyl dihalide mixture, more preferably, a
terephthaloyl dichloride-isophthaloyl dichloride mixture,
dissolved in an organic solvent, or an organic solvent
solution of a terephthaloyl dihalide-isophthaloyl dihalide
mixture is added to an aqueous alkaline solution of a
bisphenol or mixture o~ bisphenols. Alternatively, an
aqueous alkaline solution of a bisphenol or mixture of
bisphenols and an organic solvent solution of a terephtha-
loyl dihalide-isophthaloyl dihalide mixture can be simul-
taneously added to a reaction vessel. Interfacialpolycond~nsation takes place near the interface of the
aqueous phase and the organic phase. However, since the
aqueous phase and the organic phase essentially are not
miscible, it i5 necessary to mutually disperse the phases.
For this purpose an agitator or a mixer such as Homo-mixer
can be used.
The concentration of the terephthaloyl
dihalide-isophthaloyl dihalide mixture dissolved in the
organic solvent is usually from about 2 to 25 weight %,
more preferably, from 3 to 15 weight %. The concentration
of the bisphenol or mixture of bisphenols in the aqueous
alkaline solution i5 also usually from about 2 to
25 weight ~, more preferably, from 3 to 15 weight ~.
The amount of the bisphenol or mixture of bis-
phenols and of the terephthaloyl dihalide-isophthaloyl
dihalide mixture used (molar ratio) is preferably main-
tained equivalent. An excess of the terephthaloyl
dihalide-isophthaloyl dihalide mixture is not desirable in
the preparation of the high molecular weight polyarylate.
Preferred alkalis are sodium hydroxide and
potassium hydroxide. The concentration of the alkali in
the aqueous solution can vary widely depending upon the
reaction conditions, but is usually in the range from
about 0.5 to 10 weight ~. It is advantageous if the
quantity of alkali is nearly equivalent to the hydroxy
~26~1LI~..
01 -12-
groups o the bisphenol or bisphenols used or is presentin a slight excess. The preferred molar ratio of the
05 alkali to the hydroxy group of the bisphenol or bisphenols
is from 1:1 to 2:1, most preferably, from 1:1 to lol l~
As organic solvents which can be used for dis-
solving the terephthaloyl dihalide-isophthaloyl dihalide
mixture, hydrocarbons or halogenated hydrocarbons are
used. For example, methylene dichloride, chloroform,
tetrachloromethane, 1,2-dichloroethane, 1,1,2-trichloro-
ethane, tetrachloroethane, benzene and methylbenzene can
be employed~ Especially preferred are those solvents
which also dissolve the aromatic copolyesters produced.
The most preferred solvent is 1,1,2-trichloroethane.
The reaction temperature is not strictly
limited, and depends on the solvent used. For example, in
the case o~ methylene dichloride, the reaction temperature
is usually preferably below 40C, with from 5 to 30C
being especially preferred.
Interfacial polymerization is usually conducted
at normal pressure and is completed in about 1 to 4 hours.
Antioxidants, dispersing agents, catalysts and
viscosity stabilizers can be added to the aqueous alkaline
solution or to the reaction mixture, if desired. Typical
examples of such agents are as follows. As antioxidants,
sodium hydrosulfite or sodium bisulfite can be used. As
dispersing agents, anionic surface-active agents, such as
sodium lauryl sulfate and octadecyl benzene sulfonate,
cationic surface-active agents, such as cetyl trimethyl
ammonium chloride, and nonionic surface-active agents such
as polytethylene oxide) adducts can be used. As cata-
lysts, quaternary ammonium compounds, such as trimethyl
benzyl ammonium hydroxide, trimethyl benzyl ammonium chlo-
ride and triethyl benzyl ammonium chloride, tertiary sul-
fonium compounds, such as dimethyl-2-hydroxyphenyl
sulfonium chloride, quaternary phosphonium compounds, such
as triphenyl methyl phosphonium iodide and trime~hyl octyl
arsonium iodide can be used. Tertiary ammonium compounds,
such as trimethyl amine, triethyl amine and benzyl
~211~489~
01 -13-
dimethyl amine can also be used as catalysts. As vis-
cosity stabilizers, mono-valent compounds, especially
05 mono-valen~ phenol compounds, such as p-cumyl phenol,
o phenyl phenol, p-phenyl phenol, m-cresol and b-naphthol
can be used, if desired.
Another useful method for forming the poly-
arylates is melt polymerization, as disclosed, for exam-
ple, in A~ Conix, Ind. Eng. Chem., 51 147 (1959), in
Japanese Patent Publication 15,247/63 and in U.S. Patent
No. 3,395,119.
Melt polymerization can be conducted, for exam-
ple, by heating and reacting an aliphatic carboxylic acid
diester of a bisphenol or mixture of bisphenols and a
terephthalic acid-isophthalic acid mixture at reduced
pressure. A preferred diester of a bisphenol is the
diacetate. Melt polymerization can also be conducted by
heating and reacting a bisphenol or mixture of bisphenols
~0 and a mixture of a diaryl ester of terephthalic acid and
isophthalic acid. A typical diaryl ester is the diphenyl
ester. The reaction temperature employed is in the range
of from about 150 to 350~C, more preferably, from 180 to
320C. The reaction pressure is usually varied in the
course of the reaction from atmospheric pressure at the
early part of the reaction to reduced pressure, such as
below about 0.02 mmHg, at the end of the reaction.
In melt polymerization, the molar ratio of the
, bisphenol or mixture of bisphenols and the mixture of
terephthalic acid-isophthalic acid components to prepare a
high molecular ~eight polyarylate must be maintained
exactly equivalent.
A number of catalysts can be used. Catalysts
which are preferably used are titanium compounds, such as
butyl orthotitanate and titanium dioxide. Other cata-
lysts, such as zinc oxide, lead oxide and antimony dioxide
can also be used.
Still another method for forming the poly-
arylates is solution polymerization, in which the poly-
arylates are prepared by reacting a bisphenol or mixture
~1 -14-
of bisphenols with terephthaloyl dihallde and isophthaloyldihalide in an organic solvent solvenl:. Solution poly-
05 merizations which can be used are disclosed, for example,in A. Conix, Ind. Eng. Chem., 51 147 (1959), and in
U.S. Patent No. 3,133,898.
In solution polymerization, the bisphenol or
mixture o~ bisphenols and the mixture of terephthaloyl
dihalide and isophthaloyl dihalide, e.g., terephthaloyl
dichloride and isophthaloyl dichloride, are usually mixed
in equimolar proportions in an organic solvent, and the
mixture is warmed gradually to high temperatures, such as
about 2~0C~ As the organic solvent used, those solvents
which also di~solve the polyarylates produced, such as
dichloroethyl benzene, are preferred. ~sually, the reac-
tion is carrled out in the presence of a base to
neutralize the hydrogen halide, e.g., hydrogen chloride,
formed.
The polyarylate alloy compositions of the
present invention are obtained by mixing the above-
described polyarylate homopolymers and copolymers with a
polymer resin selected from the group consisting of poly-
bisphenol A carbonate and polystyrene. In general, the
alloy composition will contain about 10 to 90% by weight
of polyarylate and about 90 to 20% by weight o~ polybis-
phenol A carbonate or polystyrene. Preferably, the alloy
composition will contain about 20 to 80% by weight of
polyarylate and about 80 to 20% by weight of polybis-
phenol A carbonate or polystyrene. The polystyrene will
normally have an average molecular weight of about 100,000
to 1,000,000, preferably about 300,000. The polybis-
phenol A carbonate will normally have an average molecular
weight of about 20,000 to 50,000, preferably about 30,000.
To add polybisphenol A carbonate or polystyrene
to the polyarylates o~ this invention, any well known
mixing technique can be used. For example, grains or
powders o~ these two components can be mixed and blended
with a V-blender, Henschel mixer, Super mixer or Kneader,
and then the mixture immediately molded. Alternatively,
il9~
01 -15-
the mixture can be formed into pellets after melting with
an extruder, a co-kneader, an intensive mixer, or the
05 like, and then molded. The pelletizing or molding temper-
ature is generally in the range of from about 250 to
350C, more preferably, 260 to 320C.
Another addition method comprises adding the
polybisphenol A carbonate or polystyrene to a solution of
the polyarylate and then evaporating off the solvent. As
the solvent r those which dissolve the polyarylate can be
used, such as methylene dichloride, tetrachloroethane and
chloroform. The preferred solvent is tetrachloroethane.
The solution of polymers in a solvent may be poured into a
nonsolvent to precipitate the polymer and the precipitated
alloy can be removed by filtration. Suitable nonsolvents
are the lower alcohols, such as methanol, ethanol, pro-
panol, butanol and the like. An especially preferred
nonsolvent is ethanol.
The most suitable method for any particular
system can be chosen according to the composition and the
desired shape and properties of the molded articles to be
produced therefrom.
In order to improve the heat resistance, light
~5 stability, weatherability or oxidation resistance of the
composition or articles produced according to this inven-
tion, agents preventing thermal degradation, antioxidants,
ultraviolet absorbants, and the like, can be added there-
to, if desired. For example, benzotriazole, aminophenyl
benzotriazole, benzophenone, trialkyl phosphates, such as
trioctyl phosphate and tributyl phosphate, trialkyl phos-
phites, such as trioctyl phosphite, and triaryl phos-
phites, such as triphenyl phosphite, can be used. These
materials are conveniently added to the polyarylate
copolymers and alloys of this invention at any time prior
to molding. Known plasticizers, such as phthalate esters,
e.g., dioctyl terephthalate, dioctyl orthophthalate and
dioctyl isophthalate, and colorants, such as carbon black
and titanium dioxide, may also be added i~ desired, in
commonly used amounts as are known in this art.
91~89 ~
'~ 01
-16-
The polyarylate polymers and alloys of this
invention can be used to form many useful articles using
generally known molding methods, such as injection molding,
extrusion molding, press molding, and the like. Typical
examples of final products produced therefrom are films,
monofilaments, fibers, injection molded materials, such as
machine parts, automobile parts, electrical parts, vessels
and springs. The polyarylate polymers and alloys of this
invention find special use as engineering plastics for
various uses which require good properties.
The following examples are provided to illustrate
the invention in accordance with the principles of this
invention but are not to be construed as limiting the
invention in any way except as indicated by the appended
claims. In the examples, the term "polycarbonate" refers to
polybisphenol A carbonate.
EXAMPLES
2U Example 1
Preparation of
5-keto-10,10-bis(4'-hydroxyphenyl)anthracene
A 500 ml round bottom, three-necked flask equipped
with mechanical stirrer, water condenser, thermometer and
nitrogen gas inlet tube was connected to a nitrogen supply
line with a needle valve as a regulator. In the flask was
placed 81.0 g (0.39 mole) of anthraquinone, 81.0 9
(0.86 mole) of phenol and 100 g (0.38 mole) of anhydrous
stannic chloride. As the mixture was stirred and heated at
30 100 to 110C by an oil bath, 14.0 g (0.1 mole) of aluminum
chloride was added in small portions. The mixture was then
stirred and maintained at a temperature between 100 to
110~C over a period of 20 hours. The reaction mixture was a
dark brown slurry.
Four hundred ml of hot water was then added to the
flask. The product was filtered and washed with an addi-
tional 2.5 liters of hot water. The crude product was
dissolved in a 10% NaOH solution and filtered. The insol-
uble portion was discarded. The filtrate portion was then
4~ acidified with a 10% HCl solution. A yellowish precipitate
9~
01 -17-
was formed. The solid product was filtered and washed with
distilled water. The residual water was removed by drying
05 the product in a vacuum oven at 100C overnight with nitro-
gen passing through slowly. The product was then recrys-
tallized three times from a mixed solvent of ethanol,
dimethylsulfoxide and water. Each time the crystals were
collected by suction filtration and washed with a minimum
amount of cold ethanol. The solvent was removed by drying in
a vacuum oven at 100C in a nitrogen atmosphere overnight.
The yield was 110 g, 74~ of theory. The product WAS a color-
less powd~r having a meltin~ point of 32~ to 330C. The
product was analyzed for the percent of carbon and hydrogen.
IS Analytical calculated for C26H18O3: C, 82-52~ H, ~.7S.
Found: C, 82.43; H, 4.75. NMR(acetone-d6): ~ 8.2 - 8.0 (m,
2, Ar~), 7.0 - 7.6 (m, 6, ArH), 6.7 (s, 8, ArH), 2.8 (s, 2,
ArOH).
Example 2
Preparation of
5-Keto-10,10-bis(4'-hydroxyphenyl)anthracene
iso/terephthalate Polymer
A 500-ml, three-necked flask equipped with a
mechanical stirrer, thermometer, and nitrogen gas inlet
and outlet was charged with 7.56 grams (0.02 mole) of 5-
keto-10,10-bis(4'-hydroxyphenyl)anthracene, 0.20 gram
(0.0009 mole) of triethylbenzyl ammonium chloride, 0.02
gram sodium bisulfite, 1.7~ grams (0.044 mole) of sodium
hydroxide, 135 ml of water, and 30 ml of 1,1,2-trichloro-
ethane. The reaction mixture was stirred at a motor speed
of 1000 rpm under a nitrogen atmosphere at a temperature
not exceeding 10C maintained by an ice water bath. The
stirrer speed was checked by a photo tachometer. A mixed
solution of terephthaloyl dichloride, 2.03 grams (0.01
mole), and isophthaloyl dichloride, 2.03 grams (0.01
mole), in 49 ml of 1,1,2-trichloroethane was added over a
period of 30 minutes. ~t the same time, the mixture was
vigorously cstirred. The ice water bath was then replaced
with a room temperature water bath and stirring was con-
~0 tinued for an additional four hours. Subsequently, the
upper aqueous layer was decanted and replaced by 100 ml of
~26;~8~
-18-
01
distilled water and 30 ml of 1,1,2-trichloroethane. The
mixture was again stirred for 3~ min~ltes. The resulting
OS aqueous layer was decanted and removed. The organic layer
was poured into 600 ml of 200-proof ethanol. A white
polymer was precipitated which was collected by suction
filtration. The polymer ~as washed four times with 200 ml
ethanol. The yield of polymer was 8.40 grams. It was a
1~ 76.3% yield. The polymer was dissolved in a mixed solvent
of 40/60 phenol and 1,1,2,2-tetrachloroethane by rotating
it overnight. The Gardner viscosity of a 10% solution was
5.50 poises at 25C. The glass transition temperature,
Tg, measured by differential scanning calorimetry (DSC),
was 318C.
~.
Preparation of
5-keto-10,10-bis(4'-hydroxyphenyl)anthracene
_ _b$sphenol A iso/terephthalate copolymer
A 500 ml, three-necked flask equipped with a
mechanical stirrer, thermometer, and nitrogen inlet and
outlet was charged with 2.27 grams (0.006 mole, 20 mole ~)
of 5-keto-10,10-bis(4'-hydroxyphenyl) anthracene, 5.~8
grams (0.024 mole, 80 mole ~) of bisphenol A, 0.20 gram
(0.0009 mole) of triethylbenzyl ammonium chloride, 0.02
gram of sodium bisulfite, 2.84 grams (0.066 mole) of
sodium hydroxide, 135 ml of water, and 30 ml of 1,1,2-
trichloroethane. The reaction mixture was stirred at a
motor speed of 1000 rpm under nitrogen atmosphere at a
temperature not exceeding 10C monitored by an ice water
bath. A mixed solution of terephthaloyl dichloride, 3.05
grams (0.015 mole), and isophtholoyl dichloride, 3.05
- grams (0.015 mole), in 40 ml of 1,1,2-trichloroethane was
added over a period of 30 minutes. At the same time, the
mixture was vigorously stirred. The ice water bath was
then removed and replaced with a room temperature water
bath. Stirring was continued for an additional Eour
hours. Subsequently, the upper layer was decanted and
replaced by 100 ml of distilled water and 30 ml of
1,1,2-trichloroethane. The mixture was again stirred for
30 minutes. The resulting aqueous layer was poured into
I
O 1 -1 9 -
600 ml of 200-proof ethanol. A white polymer was pre-
cipitated which was collected by suction filtration. The
oS polymer was washed four times with 200 ml of ethanol. The
product was placed in a vacuum oven at 100C overnight.
The yield of polymer was 10.7 grams. This was a 77.3%
yield. The polymer was dissolved for Gardner viscosity in
a mixed solvent of 40/60 phenol and 1,1,2,2-tetrachloro-
ethane by rotating it overnight. The Gardner viscosity of
a 10% polymer solution was 3.70 poises at 25C. Reduced
viscosity was measured at 0.25 g/100 ml in 1,1,2,2-tetra-
chloroethane, Reduced viscosity was 0.64 dl/g at 25C.
The glass transition temperature, Tg, measured by di~Eer-
ential scanning calorimetry, was 227C.
Following the above procedure, copolymers wereprepared using other bisphenol monomers in place of bis-
phenol A. The glass transition temperature, Tg, of these
copolymers at various mole ratios of bisphenols is shown
in Table 1.
qO
0l-20- ~6~
TABLE 1
5-Keto-10-,10-bis-~4'-hydroxyphenyl)
05Anthracene Copolyarylates With Various
BisDIlenols and Iso/TereDhthalic Acid 1/1
Mole ~
Comonomer Bisphenol Comonomer Tg, C
Bisphenol A 20 215
~0 238
246
227
2,2-Bis-(4-hydroxy-3,5-dimethylphenyl) 20 298
Propane 40 295
251
215
Bis-(4-hydroxyphenyl) Diphenylmethane 20 317
~0 2~5
243
227
Bis-(3,5-dimethyl-4-hydroxyphenyl) 40 309
Diphenyl~ethane 60 271
~U 80 264
1,1-Di-(3',5'-dimethyl-4'-hydroxyphenyl) 20 311
Phthalide 40 322
311
289
Example 4
Preparation of the Alloy of
5-Keto-10,10-bis-(4'-hydroxyphenyl) Anthracene
Iso/Terephthalate With Polycarbonate
In a 20-ml vial was placed 1.0 gram of 5-keto-
10,10-bis(4'-hydroxyphenyl) anthracene iso/terephthalate,
1.0 gram of polycarbonate (Lexan 141~, and 18.0 grams of
1,1,2,2-tetrachloroethane. The vial was placed on a
rotator and rotated until the mixture was completely dis-
solved. This was now a 1:1 solution of polymers by
weight. Two milliliters of the abo~e polymer solution was
placed on 2.5 in. x 5 in. glass plate. A film was cast
with a 0.02 in. thickness doctor blade. The cast film was
first drîed at room temperature in the hood until most of
the solvent had evaporated. The glass plate with film was
transferred to a forced air oven at 40C for four hours
*Trade Mark
and at 75C for an additional four hoursO The glass with
film was removed from the oven and examined for its com-
patibility. The remainder of the po:Lymer solution was
poured into 150 ml of 200-proof ethanol. A white polymer
was precipiated which was collected by suction filtration.
The polymer was washed four times with 50 ml of ethanol.
The polymer was placed in a vacuum oven at 100C until the
weight was constant.
Following the above procedure, various alloys
were prepared having different weight ratios of polymers.
The glass transition temperature, Tg, for these alloys is
shown in Table 2.
TABLE 2
PoLyarylate, Wt % Polycarbonate, Wt ~ Tg, C
148
15~
269
