Note: Descriptions are shown in the official language in which they were submitted.
3'~7
01 --1--
BIS(HYDROXYPHENYL)FLUORENE POLYARYLATE
POLYMERS AND ALLOYS
~5
BACK~ROUND OF THE INVENTION
The present invention relates to polyarylate
polymers and alloys. More particularly, this invention
relates to bis(hydroxyphenyl)fluorene polyarylate polymers
and alloys having superior thermal properties.
Polyarylates are defined as aromatic polyester
polymers derived from dihydroxy aromatic compounds
(diphenols) and aromatic dicarboxylic acids.
In general, aromatic polyesters prepared from
bisphenols or functional derivatives thereof and a
terephthalic acid-isophthalic acid mixture or a mixture of
the functional derivatives thereof, i.e., bisphenol
terephthalate-bisphenol isophthalate polyesters, have
excellent mechanical properties, such as tensile strength,
bending strength, bending recovery or impact strength,
excellent thermal properties, such as deflection
temperature under load or degradation temperature,
excellent electrical properties, such as resistivity,
electric breakdown endurance, arc resistance, dielectric
constant or dielectric loss and low flammability, good
dimensional stability, and the like.
These aromatic polyesters are thus useful in may
fields. Aromatic polyesters find special use as plastics
for injection molding, extrusion molding, press molding,
and the like, as monofilaments, fibers, 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
lZS~ 7
01 -2-
improved cracking and crazing resistance. Similarly,
U.S. Patent No. 3,946,091 describes a blend of bisphenol
05 polyarylates and poly(ethylene terephthalate) which
provides 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 bisthydroxyphenyl)fluorene
compound of the formula
R~ R3
~ ~ 4
;~() ~
wherein Rl, R2, R3 and R4 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; and a
bisphenol compound of the formula
R5 R7
HO- ~ ~ -OH
30R6 ~ R8
o
wherein R5, R6, R7 and R8 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein
the molar ratio of bis(hydroxyphenyl)fluorene 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.
3~'~
01 _3_
The present invention is further concerned with
a polyarylate alloy composition comprising
05 (A) 10 to 90% by weight of a polyarylate of the
formula
I ~R4
wherein Rl, R2, R3 and R4 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; n is the
degree of polymerization; and wherein
o
;~0 0 "
~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 group 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 bis(hydroxyphenyl)fluorene
compound of the formula
Rl R3
HO~-OH
l;~S~3'-~'7
0 1 ~
wherein Rl, R2, R3 and R4 are independently hydrogen,
05 lower alkyl of 1 to 4 carbon atoms or phenyl; and a
bisphenol compound of the formula
R~5 R7
HO- ~ ~ -OH
R6 ~ R8
wherein R5, R6, R7 and ~8 are independently hydrogen,
lower alkyl of 1 to 4 carbon atoms or phenyl; and wherein
the molar ratio of bis~hydroxyphenyl)fluorene to bisphenol
is from 20:1 to 1:20; and
(2) a mixture of isophthalic and terephthalic
acid 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 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 bis(hydroxyphenyl)fluorene
compounds with other bisphenols, have been found to possess
superior thermal properties. In addition, it has been
found that the above-described bis(hydroxyphenyl)fluorene
polyarylates provide alloy compositions with polystyrene
and polybisphenol A carbonate which also exhibit excellent
thermal properties.
DETAILED DESCRIPTICN OF THE INVENTION
For purposes of the present invention, those
polyarylates derived from a single bis(hydroxyphenyl)-
fluorene compound shall be referred to as "homopolymers"
and those polyarylates derived from a mixture of bis-
(hydroxyphenyl)fluorene and other bisphenol compounds
shall be referred to as ~copolymers". It is, of course,
~0 understood that bis(hydroxyphenyl)fluorene may be
'7
01 _5_
characterized as a type of bisphenol compound.
Furthermore~ the term "alloy" as used herein is meant to
05 define an intimate physical miXture or blend of two or
more polymers.
The bis(hydroxyphenyl)fluorene compounds WhiCh
are useful for conversion into the instant polyarylate
homopolymers and copolymers may be represented by the
following formula
R ~ H
wherein Rl~ R2, R3 and R4 are independently hydrogen~
lower alkyl of 1 to 4 carbon atoms or phenyl. Preferably~
the bis(hydroxyphenyl)fluorene Will have from 2 to 4
substituents in positions ortho to the hydroxy groups.
Preferred examples of bis(hydroxyphenyl)fluorene
compounds include the tetraalkyl derivatives, that is,
wherein Rl, R2, R3 and R4 are independently lower alkyl of
1 to 4 carbon atoms. A particularly preferred compound is
that wherein Rl, R2, R3 and R4 are methyl, that is, 9,9-
bis(3',5'-dimethyl-4'-hydroxyphenyl)fluorene or,
conveniently, tetramethyl bis(hydroxyphenyl) f luorene.
The bis(hydroxyphenyl) f luorene compounds used to
form the polyarylates Of the invention are prepared by
reacting an appropriately substituted phenol With 9~9-
dichlorofluorene in the presence of a Friedel-Crafts
catalyst. A typical ortho-substituted phenol is 2,6-
dimethylphenol. Suitable Friedel-Crafts catalysts include
aluminum chloride, ferric chloride, stannic chloride,
boron trifluoride, hydrogen fluoride, hydrogen chloride,
sulfuric acid, phosphoric acid, and the like.
The instant polyarylate homopolymers and
copolymers are prepared from the above
i~S~'7
01 -6-
bis(hydroxyphenyl)fluorenes or from mixtures of thesecompounds and other bisphenols. The instant polyarylate
05 homopolymers are prepared from a single bis(hydroxy-
phenyl)fluorene compound or a functional derivative
thereof. In a similar fashion, the instant polyarylate
copolymers are prepared from a mixture of a bis(hydroxy-
phenyl)fluorene compound or functional derivative thereof
and a bisphenol compound of the formula
HO~--01:
or functional derivative thereof; wherein R5, R6, ~7 and
R8 are independently hydrogen, lower alkyl of 1 to 4
carbon atoms or phenyl. When R5, R6, R7 and R8 are all
hydrogen, the compound obtained, 5-keto-10,10-bis(4'-
hydroxyphenyl)anthracene, is conveniently referred to as
5-keto-bis(hydroxyphenyl)anthracene. When R5, R6, R7 and
R8 are not all hydrogen, the compound obtained will herein
be referred to as a substituted 5-keto-bis~hydroxyphenyl)-
anthracene.
Preferred examples of 5-keto-bis~hydroxyphenyl)-
anthracene compounds include the unsubstituted compound
and the tetraalkyl derivative. Particularly preferred
compounds are those wherein R5, R6, R7 and R8 are
hydrogen, i.e., 5-keto-10,10-bis(4'-hydroxyphenyl)-
anthracene, and wherein R5, R6, R7 and R8 are methyl,
i.e., 5-keto-10,10-bis(3',5'-dimethyl-4'-hydroxyphenyl)-
anthracene.
The 5-keto-bis(hydroxyphenyl)anthracene
compounds used in the invention are prepared by reacting
an unsubstituted or ortho-substituted phenol with
anthraquinone in the presence of a Friedel-Crafts
catalyst. A typical substituted phenol is
3'~'7
01 _7_
2,6-dimethylphenol. Suitable Friedel-Crafts catalysts
include tin tetrachloride, aluminum trichloride, and the
05 like.
Typical functional derivatives of the above-
described bis(hydroxyphenyl)fluorenes and anthracene
bisphenols 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 bis(hydroxyphenyl)fluorene and
bisphenol will have a molar ratio of bis(hydroxyphenyl)-
fluorene to bisphenol of about 20:1 to 1:20. Preferably,
the molar ratio of bis(hydroxyphenyl)fluorene to bis-
phenol will be about 9:1 to 1:9, more preferably, about
4:1 to 1:4.
The acid component which is reacted with the
~U bis(hydroxyphenyl)fluorene or bis(hydroxyphenyl)fluorene-
bisphenol ~ixture to prepare the polyarylates 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. Preferably, the molar
ratio of isophthalic to terephthalic acid will 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 isoph-
thaloyl or terePhthaloyl dichloride and isophthaloyl or
terephthaloyl dibromide, and diesters, such as dialkyl
esters or diaryl esters, having from 1 to 6 carbon atoms
per ester group. Examples of suitable diesters include
diphenyl isophthalate and diphenyl terephthalate.
The polyarylate homopolymers used in the present
invention can be generally represented by the formula
l~S4;~;
.
01 -8-
L 3 .. ~ ~
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 bis(hydroxyphenyl)fluorene-bisphenol
mixture, the bis(hydroxyphenyl)fluorene and bisphenol
~U moieties will normally occur in random order throughout
the polyarylate.
The polyarylates of this invention can be
prepared 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 W. M. Eareckson,
J. Polymer Sci., XL 399 (1959) and Japanese Patent
Publication No. 1959/65.
The following is a typical polycondensation
process. An aqueous alkali solution of a bisphenol or
3~ 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
`` i~S9~3~'7
01 _9_
bisphenol or mixture of bisphenols. Alternatively, an
aqueous alkaline solution of a bisphenol or mixture of
05 bisphenols and an organic solvent solution of a terephtha-
loyl dihalide-isophthaloyl dihalide mixture can be simul-
taneously added to a reaction vessel. Interfacial poly-
condensation 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 is 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 is also usually from about 2 to
25 weight ~, more preferably, from 3 to 15 weight %.
The amount of the bisphenol or mixture of
bisphenols 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 lO weight %. It is advantageous if the
quantity of alkali is nearly equivalent to the hydroxy
groups of the bisphenol or bisphenols used or is present
in a slight excess. The preferred molar ratio of the
alkali to the hydroxy group of the bisphenol or bisphenols
is from l:l to 2:1, most preferably, from l:l to l.l:l.
As organic solvents which can be used for
dissolving the terephthaloyl dihalide-isophthaloyl
dihalide mixture, hydrocarbons or halogenated
hydrocarbons are used. For example, methylene dichloride,
i;~S~;34'7
01 -10-
chloroform, tetrachloromethane, 1,2-dichloroethane,
1,1,2-trichloroethane, tetrachloroethane, benzene and
05 methylbenzene can be employed. Especially preferred are
those solvents which also dissolve the aromatic copoly-
esters 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 of 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 poly(ethylene oxide) adducts can be used. As
catalysts, quaternary ammonium compounds, such as
trimethyl benzyl ammonium hydroxide, trimethyl benzyl
ammonium chloride and triethyl benzyl ammonium chloride,
tertiary sulfonium compounds, such as dimethyl-2-hydroxy-
phenyl sulfonium chloride, quaternary phosphonium compounds,such as triphenyl methyl phosphonium iodide and trimethyl
octyl arsonium iodide can be used. Tertiary ammonium
compounds, such as trimethyl amine, triethyl amine and
benzyl dimethyl amine can also be used as catalysts. As
viscosity stabilizers, mono-valent compounds, especially
mono-valent 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
~ polyarylates is melt polymerization, as disclosed, for
i ~ S'~3 ~7
Cl -11-
example, in A. Conix, Ind. Enq. Chem., 51 147 (1959), in
Japanese Patent Publication 15,247/63 and in U.S. Patent
05 No. 3,395,119.
Melt polymerization can be conducted, for
example, 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
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 350C, 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
2~ 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 weight 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
polyarylates is solution polymerization, in which the
polyarylates are prepared by reacting a bisphenol or
mixture of bisphenols with terephthaloyl dihalide and
isophthaloyl dihalide in an organic solvent solvent.
Solution polymerizations which can be used are disclosed,
for example, in A. Conix, Ind. Ena. Chem., 51 147 (l9S9),
and in U.S. Patent No. 3,133,898.
In solution polymerization, the bisphenol or
mixture of bisphenols and the mixture of terephthaloyl
'Y
01 -12-
dihalide and isophthaloyl dihalide, e.g., terephthaloyl
dichloride and isophthaloyl dichloride, are usually mixed
05 in equimolar proportions in an organic solvent, and the
mixture is warmed gradually to high temperatures, such as
about 220DC. As the organic solvent used, those solvents
which also dissolve the polyarylates produced, such as
dichloroethyl benzene, are preferred. Usually, the
reaction is carried 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-
lS described polyarylate homopolymers and copolymers with apolymer 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 10% by weight of 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 of this invention, any well known
mixing technique can be used. For example, grains or
powders of 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,
the mixture can be formed into pellets after melting with
an extruder, a co-kneader, an intensive mixer, or the
like, and then molded. The pelletizing or molding
temperature is generally in the range of from about 250
to 350C, more preferably, 260 to 320DC.
Another addition method comprises adding the
polybisphenol A carbonate or polystyrene to a solution of
lZ5~ 7
01 -13-
the polyarylate and then evaporating off the solvent. Asthe solvent, those which dissolve the polyarylate can be
05 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
stability, weatherability or oxidation resistance of the
composition or articles produced according to this
invention, agents preventing thermal degradation,
antioxidants, ultraviolet absorbants, and the like, can be
added thereto, if desired. For example, benzotriazole,
aminophenyl benzotriazole, benzophenone, trialkyl phos-
phates, such as ~rioctyl phosphate and tributyl phosphate,
trialkyl phosphites, such as trioctyl phosphite, and
triaryl phosphites, 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 if desired, in commonly used amounts as are known in
this art.
~he 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,
lZ5~
Ol -14-
such as machine parts, automobile parts, electrical parts,vessels and springs. The polyarylate polymers and alloys
oS 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
Example 1
Preparation of 9,9-bis(3',5'-dimethyl-
4'-hydroxyphenyl)fluorene
A 500-ml four-necked, round-bottom flask
equipped with a mechanical stirrer, air/water condenser
with a drying tube, and a thermometer was charged with
47.0 g t0.20 mole) of 9,9-dichlorofluorene, 98.0 g
(0.80 mole) of 2,6-dimethylphenol and 150 9 of chloro-
benzene. The resulting mixture was heated to 120 to
130C while maintaining stirring. HCl vapors were
released and passed out through the condenser. The course
of the reaction was monitored by gas chromatography.
Heating and stirring were continued for about 24 hours.
The reaction mixture was cooled and filtered to give
67.9 9 of crude product. This material was recrystallized
from 800 ml of absolute ethanol. After drying, there was
30 obtained 41.7 9 of product having a melting point of 279
to 284C. The product was analyzed for the percent of
carbon and hydrogen. Analytical calculated for
C29H26O2: C, 85.68; H, 6.45. Found: C, 85.58;
H, 6.i3. NMR (CDC13): ~ 7.4 (m, 4, ArH), 6.7 ~s, 2,
35 ArH), 4.4 (s, 1, ArOH), 2.1 (s, 6, CH3).
Example 2
Preparation of 9,9-bis(3',5'-dimethyl-
4'-hydroxyphenyl)fluorene
iso/tereDhthalate PolYmer
A 500-ml, three-necked, round-bottom flask
equipped with a mechanical stirrer, thermometer and
1;~5'~ 7
01 -15-
nitrogen gas inlet and outlet was charged with 135 ml of
water, 30 ml of 1,1,2-trichloroethane, 0.14 9 of
05 triethylbenzylammonium chloride, 0.02 9 of sodium
bisulfite, 1.76 9 (0.044 mole) of sodium hydroxide and
8.12 9 (0.02 mole) of 9,9-bis(3',5'-dimethyl-4'-hydroxy-
phenyl)fluorene. 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 tacho-
meter. Then, 2.03 9 (0.01 mole) each of isophthaloyl
chloride and terephthaloyl chloride dissolved in 40 ml of
1,1,2-trichloroethane was added over a one-half hour
period of time. Then the reaction mixture was allowed to
stir at room temperature for four hours. After this time,
the reaction mixture was poured into 600 ml of ethanol.
The solid polymer was precipitated out and collected by
suction filtration. The polymer was washed with ethanol
and dried in a vacuum oven at 100C for 16 hours. The
yield of polymer was 10.7 9, an 87.8~ yield. The polymer
was dissolved in a mixed solvent of 40/60 phenol and
1,1,2,3-tetrachloroethane by rotating it overnight. The
Gardner viscosity of a 10~ solution was 3..70 poises at
25C. Reduced viscosity was measured at 0.25 9/100 ml in
1,1,2,2-tetrachloroethane. Reduced viscosity was 0.71 dl/g
at 25C. The glass transition temperature, measured by
differential scanning calorimetry (DSC), was 327C.
Example 3
Preparation of 9,9-Bis-
(3',5'-dimethyl-4'-hydroxyphenyl)
Fluorene, 5-Keto-10,10-bis
(4'-hydroxyphenyl) Anthracene
Iso/Terephthalate Copolymer
A 500-ml, three-necked flask equipped with
mechanical stirrer, thermometer, and nitrogen inlet and
outlet was charged with 6.09 9 (0.015 mole, 50 mole ~) of
9,9-bis-(3',5'-dimethyl-4'-hydroxyphenyl) fluorene, 5.64 9
(0.015 mole, 50 mole ~) of 5-keto-10,10-bis-(4'-hydroxy-
phenyl) anthracene, 0.20 9 (0.0009 9 mole) of triethyl-
benzyl ammonium chloride, 0.02 9 of sodium bisulfite,
12S~ '7
01 -16-
2.64 9 (0.066 mole) of sodium hydroxide, 135 ml of water,and 30 ml of 1,1,2-trichloroethane. The reaction mixture
05 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. A mixed solution of terephthaloyl
dichloride, 3.05 9 (0.015 mole), and isophthaloyl
dichloride, 3.05 9 (0.015 mole), in 40 ml of 1,1,2-
trichloroethane was added over a period of 30 minutes. Atthe 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 four 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
decanted and removed. The organic layer was poured into
500 ml of 200-proof ethanol. A white polymer was pre-
cipitated, which was collected by suction filtration. The
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 15.2 9. This was a 91% yield.
The polymer was dissolved for Gardner viscosity in a mixed
solvent of 40/60 phenol and 1,1,2-tetrachloroethane by
rotating it overnight. The Gardner viscosity of 10
polymer solution was 2.50 poises at 25C. Reduced
viscosity was measured at 0.25 9/100 ml in 1,1,2-
tetrachloroethane. Reduced viscosity was 0.65 dl/g at
25C. The glass transition temperature, Tg, measured by
differential scanning calorimetry (DSC), was 301C.
Following the above procedure, various
copolymers were prepared having different mole ratios of
bisphenols. The glass transition temperature, Tg, of
3S copolymers having various mole ratios of bisphenols is
shown in Table 1.
~0
i~S~3~'7
01 -17-
Table 1
05Polyarylate Iso/Terephthalate_(l/l) Copolymer
5-Keto-10,10-bis 9,9-Bis-(3',5'-dimethyl-
(4'-hydroxyphenyl) Anthracene 4'-hydroxyphenvl) Fluorene
Mole ~ Mole % Tg
__
315
297
1~ 50 50 301
296
298
Example 4
15Preparation of the Alloy of 9,9-Bis
~3',5'-dimethyl-4'-hydroxyphenyl)
Fluorene Iso/Terephthalate Polymer
With Polvcarbonate
.
In a 20-ml vial was placed 1.6 9 of 9,9-bis-
(3',5'-dimethyl-4'-hydroxyphenyl! fluorene iso/tereph-
2~thalate, 0.4 9 of polycarbonate (Lexan 141), and 18.0 9 of
1,1,2,2-tetrachloroethane. The vial was placed on a
rotator and rotated until the mixture was completely
dissolved. This was about a 1:1 solution of the polymers
by weight. 2 ml of the above polymer solution was placed
on a 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
dried at room temprature 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
and at 75C for an additional four hours. The compat-
ibility of the film was examined after it was removed from
the oven. The remainder of the polymer solution was
poured into 150 ml of ethanol. A white polymer was
precipitated which was collected by suction filtration.
3~ The polymer was washed four times with 50 ml of ethanol.
The product was then placed in a vacuum oven at 100C
until the weight was constant. The glass transition
temperature, Tg, for this alloy, measured by differential
scanning calorimetry, is shown in Table 2.
~0
l;~S~
01 -18-
Table 2
Polyarylate, Wt % Polycarbonate, Wt ~ Tg, C
303
~U
~0
