POLYCARBONATES D'HOLOBISPHENOLETHYLENE A COULEUR STABILISEE

COLOR-STABILIZED HALOBISPHENOLETHYLENE POLYCARBONATES

Abrégé anglais

COLOR-STABILIZED HALOBISPHENOLETHYLENE POLYCARBONATES
ABSTRACT OF THE DISCLOSURE
Thermally stable, color-stabilized halobisphenol-
ethylene polycarbonates comprising halobisphenolethylene
polycarbonates containing an effective amount of a stabiliz-
ing organophosphite are described. The stabilized halo-
bisphenolethylene polycarbonates can be molded or formed
into films, sheets, fibers, laminates or other molded
articles including reinforced articles by conventional
molding techniques.

Revendications

The embodiments of the invention in which an exclu-
sive property or privilege is claimed are defined as follows:
1. A thermally stable, color-stabilized halobisphenol-
ethylene polycarbonate comprising:
(I) (a) about 1-100 parts by weight of halobis-
(phenyl)ethylene carbonate units of formula (A):
(A) <IMG>
where independently each R is hydrogen, chlorine, bromine or a
C1-30 monovalent hydrocarbon or hydrocarbonoxy group, each Y is
hydrogen, chlorine, or bromine subject to the proviso that at
least one Y is chlorine or bromine, and m is an integer of at
least 2, and (b) about 99-0 parts by weight of arene carbonate
units of formula (B):
(B) <IMG>
wherein Rf is an alkylene, alkylidene, cycloalkylene, cyclo-
alkylidene or arylene linkage or a mixture thereof, a linkage
selected from the group consisting of ether, carbonyl, amine,
a sulfur or phosphorus containing linkage, Ar and Ar' are arene
radicals, Y is a substituent selected from the group consisting of
organic, inorganic and organometallic radicals, X is a monovalent
hydrocarbon group selected from the class consisting of alkyl,
aryl and cycloalkyl and mixtures thereof, a halogen, an ether
group of the formula - OE, wherein E is a monovalent hydrocarbon
radical similar to X, a monovalent hydrocarbon group of the type
represented by Rf, d represents a whole number of at least 1 up
to a maximum equivalent to the number of replaceable hydrogens

substituted on the aromatic rings comprising Ar or Ar', e
represents a whole number of from 0 to a maximum controlled by
the number of replaceable hydrogens on Rf, c represents a
whole number equal to at least 0 or more, and a, b and c represent
whole numbers including 0, and when b is not zero neither a nor c
may be zero, otherwise either a or c but not both may be 0, and
when b is zero the aromatic groups can be joined by a direct
carbon bond, and wherein n is an integer of at least 2, and
(II) an effective amount of a stabilizer comprising
a phosphite of the formula:
<IMG>
where R1, R2 and R3 axe independently selected from the group
consisting of hydrogen, alkyl, aryl, cycloalkyl, arylalkyl and
alkaryl and combinations thereof subject to the proviso that
at least one R1, R2 or R3 is other than hydrogen or a group
directly bonded to an oxygen atom by a phenyl ring carbon atom,
subject to the proviso that when R2 and R3 are phenyl, R1 can
be hydrogen.
2. A thermally stable, color-stabilized halobisphenol-
ethylene polycarbonate comprising:
(I) (a) about 1-100 parts by weight of halobis-
(phenyl)ethylene carbonate units of formula (A):
(A)
<IMG>
where independently each R is hydrogen, chlorine, bromine or a
26

C1-30 monovalent hydrocarbon ox hydrocarbonoxy group, each Y
is hydrogen, chlorine or bromine, subject to the proviso that
at least one Y is chlorine or bromine, and m is an integer of
at least 2, and (b) about 99-0 parts by weight of a carbonate
containing units of formula (B):
(B) <IMG> ,
where independently each R is as defined hereinbefore, and
independently Rg and Rh are hydrogen or a C1-30 monovalent
hydrocarbon group, n is an integer of at least 2, and
(II) an effective amount of a stabilizing component
comprising a phosphite of the formula:
<IMG> ,
where R1, R2 and R3 are independently selected from the group
consisting of hydrogen, alkyl, aryl, cycloalkyl, arylalkyl and
alkaryl and combinations thereof subject to the proviso that at
least one R1, R2 or R3 is other than hydrogen or a group directly
bonded to an oxygen atom by a phenyl ring carbon atom, subject
to the proviso that when R2 and R3 are phenyl, R1 can be hydrogen.
3. The claim 2 composition, wherein I(a) the poly-
carbonate units are of the formula:
<IMG>
27

where independently each R is hydrogen, chlorine, bromine,
C1-4 alkyl or phenyl, m is an integer of at least 2, wherein
I(b) the polycarbonate units are of the formula:
<IMG>
where independently each R is as defined hereinbefore, and
independently each Rg and Rh is hydrogen, C1-4 alkyl or phenyl,
n is an integer of at least 2, and wherein II the phosphite is
present in an amount of from 0.025 to 1.0 parts per 100 parts
by weight of halobisphenolethylene polycarbonate.
4. The claim 2 composition, further comprising
(III) an epoxide.
5. The claim 3 composition, further comprising
(III) an epoxide selected from the group consisting of (a)
aliphatic epoxides represented by the formula:
<IMG> ,
wherein Ri and Rj are independently selected from C1-24
alkyl groups and p is an integer of from l to about 10, (b)
cycloaliphatic epoxides containing 1-2 aliphatic rings of 6
carbon atoms each with at least one oxygen bridge being attached
to adjacent carbon atoms in at least one cycloaliphatic ring,
and (c) aromatic epoxides selected from aromatic glycidyl ether
or aromatic diglycidyl ethers containing 1-3 rings, or aromatic
polyglycidyl ethers containing 1-3 aromatic rings.
6. The claim 5 composition, further comprising
(IV) a cadmium, barium or cerium salt of an aliphatic, cyclo-
aliphatic, or aromatic carboxylic acid or a carbonic acid.
28

7. The claim 6 composition, where the salts are
selected from the group consisting of cadmium, barium or cerium
salts of a C2-20 alkanoic acid, a C7-20 benzoic acid or a
carbonic acid.
8. The claim 2 composition, wherein I(a) the
polycarbonate unit R substituents are hydrogen, and I(b)
the polycarbonate unit R substituents are hydrogen, and the
Rg and Rh substituents are methyl.
9. The claim 2 composition, wherein I(a) the
polycarbonate unit R substituents are hydrogen, at least one
Y substituent is chlorine and the other Y substituent is
hydrogen, and I(b) the polycarbonate unit R substituents are
hydrogen, and the Rg and Rh substituents are methyl.
10. The claim 7 composition, wherein the polycarbonate
has an intrinsic viscosity of at least 0.3 dl/g.
11. The claim 7 composition, wherein the polycarbonate
has an intrinsic viscosity of at least 0.5 dl/g.
12. The claim 11 composition, wherein the
polycarbonate comprises about 5-100 parts of the carbonate of
formula (A) and about 95-0 parts of the arene carbonate of
formula (B).
13. The claim 11 composition, wherein the
polycarbonate comprises about 25-100 parts of the carbonate of
formula (A) and about 75-0 parts of the arene carbonate of
formula (B).
14. The claim 13 composition, wherein the amounts
of phosphite, epoxide and salts in parts per 100 parts by
weight of the polycarbonate are within the ranges of 0.05-0.25
0.05-0.25 and 0.05-0.25 respectively.
15. The claim 5 composition, wherein the epoxide
is present in an amount of from 0.025 to 1.0 part per 100 parts
by weight of halobisphenolethylene polycarbonate.
29

16. The claim 7 composition, wherein the epoxide
and the salt are each present in an amount of from 0.025 to 1.0
part per 100 parts by weight of halobisphenolethylene
polycarbonate.
17. The claim 16 composition, wherein the weight of
halobis(phenyl)ethylene carbonate units of formula (A) is at
least about 90 parts.

Description

5~
RD-7842
This invention is related to copending
Canadian Patent application Serial No. ~ 6~
which application is filed concurrently herewith and
which is assigned to the same assignee as the assignee
of this invention.
This invention relates to thermally stable,
color-stabilized polycarbonates comprising halo-
bisphenolethylene polycarbonates containing an ef~ective
amount of a stabilizing organophosphite.
The prior art has made limited observations
regarding the properties of chlorobisphenolethylene
polycarbonates such as the infra-red spectroscopic
data by Z. Wielgosz, Z. Boranowska and K. Janicka,
reported in Plaste und Kautschuk 19 (12) 902 (1972).
Observations regarding attempts to stabilize chloro-
bisphenolethylene polycarbonates are reported
by Z. Gobiczewski, Z Wielgosz, and K. Janicka in Plaste und
Kautschuk 16 (2) 99 (196~) which describe the ineffec~iveness
.
.

RD-7~42
S~
of commercially available hindered phenols, e.g. Parmanox*,
i.e. 2~6-di-t-butyl-4-methylphenol~ Topanol* CA, i.e n 2 ~ 2 / 3~
trist2-methyl-4-hydroxy~5-t-butylphenyl)butane, and Jonox*
330, i.e. 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene
as stabilizers for chlorobisphenolethylene polycarbonates at
elevated temperatures, e.g. from 160 to 260 C. No other
art is known o regarding attempts to stabilize chloro-
bisphenolethylene polycarbonates.
Unexpectedly, it has been found that certain organic
phosphites stabilize halobisphenolethylene polycarbonates
a~ainst deleterious thermal effects -- as evidenced by
reduced color de~radation of organic phosphite stabilized
halobisphenolethylene polycarbonates after havin~ been
subjected to thermal stresses at elevated temperatures.
DESCRIPTION OF THE INVENTION
This invention embodies thermally stable, color-
stabilized halobisphenolethylene polycarbonates comprising
h~lobisphenolethylene polycarbonates containing an eEfective
amount of a stabilizing organophosphite.
As used herein and in the appended claims, the term
"or~anic phosphite" includes any hydrocarbylphosphite oE the
~eneral formula:
/ OR2
(I) R10-P
OR3
*Trade mark

-~~ RD-7842
P5~4
where Rl, R2 and R3 are independently selected from the group
consisting of hydrogen, alkyl, aryl, cycloalkyl, arylalkyl
and alkylaryl and combinations thereof subject to the proviso
that at least one of Rl, R2 or R3 is other than hydroge~ or a
group directly bonded to an oxygen atom by a phenyl ring
carbon atom, subject to the proviso that when R2 and R3 are
phenyl, Rl can be hydrogen. Preferably the radicals have 1
to 20 carbon atoms. The alkyl may be methyl, ethyl, propyl,
isopropyl, the various butyl isomers~ e.g. butyl, sec.-butyl,
tert.-butyl, ~he various amyl isomers, the various hexyl
isomers, the various nonyl isomers, the various eicosyl
isomers, etc.; the cycloalkyl may be cyclobutyl, cyclopentyl,
cyclohexyl, 2-methylcyclohexyl, 4-methylcyclohexyl, 2-ethyl-
cyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, etc.;
the aryl may be phenyl, l-naphthyl, biphenylyl,
terphenylyl, etc.; the aralkyl may be any of the above alkyls
substituted with one or more of the above aryl groups, e.g.,
benzyl, phenylethyl, l-phenylpropyl, etc~; and the alkaryl
may be any of the above aryls substituted with one or more of
the above alkyls, e.g., o-tolyl, xylyl, cumyl, mesityl,
butylphenyl, nonylphenyl, etc. Typical of some of the
phosphites that can be employed in the practice of this
invention are diphenyl dodecyl phosphite, diphenyl phosphite,
di-(t-butylphenyl)octyl phosphite, triethyl phosphite, tris-
(nonylphenyl)phosphite, dipropyl phenyl phosphite, etc. The
~'

RD-7842
5~
preferred phosphites to be employed herein are diaryl phos-
phites, e.g., diphenyl phosphite, etc., and diar~l alkyl
phosphites, e.g., diphenyl decyl phosphite, etc.
As used herein and in the appended claims, the term
"halobisphenolethylene polycarbonate" includes any poly-
carbonate composition containing within the polycarbonate
skeletal backbone "halobis~phenyl)ethylene carbonate units of
the formula:
(II) ~ 0 ~ ) ~ 0 - C ~ ,
where independently each R is hydrogen, chlorine, bromine,
or a Cl 30 monovalent hydrocarbon or hydrocarbonoxy, each Y
is hydrogen, chlorine, or bromine, subject to the proviso
that at least one Y is chlorine or bromine, and m is an
integqr of at least 2~ Presently preferred monovalent hydro-
carbon groups are Cl 4 alkyl or phenyl. More preferred poly-
carbonates cantain units of formula II wherein each R is
hydrogen and each Y is chlorine. Polycarbona~es containing
only recurring moieties of formula II are halobisphenol-
ethylene homopolycarbonates as defined herein the appended
claims. Included within the scope of this invention are
halobisphenolethylene polycarbonates containing both halo-
.~ :

RD-7842
5~!~
bis(phenyl)ethylene carbonate units of formula II as well as
"arene carbonate" units of the formula:
r,)dl r(,)el r(,)dl
(III) - ~ t Ar ~ Rf ~ Ar' ~ O - C - n
wherein Rf is an alkylene, alkylidene, cycloalkylene, cyclo-
alkylidene or arylene linkage or a mixture thereof, a linkage
selected from the group consisting of ether, carbonyl, amine,
a sulfur or phosphorus containing linkage, .~r and ~r' a.re
arene radicals, Y is a substituent selected from the group
consisting of organic, inorganic and organometallic radicals,
X is a monovalent hydrocarbon group selected from the class
consisting of alkyl, aryl and cycloalkyl and mixtures there-
of, a halogen, an ether group of the formula-OE, wherein E
is a monovalent hydrocarbon radical similar to X, a monovalent
hydrocarbon group of the type represented by Rf, d represents
a whole number of at least 1, c represents a whole
number equal to at least O or more, a, b and c represent
whole numbers including O, a or c but not both may be O, and
wherein n is an integer of at least 2.
Preferred copolycarbonates included within the scope
~O o~ this invention are polycarbonates containing both the
halobis(phenyl)ethylene carbonate units of formula II as well
as arene carbonate units of the formula:
,~
,L~ , ~
' ~ ~

RD-7842
.A~
(R)~ (R)4
(IV) t ~ c ~ o c +
wherein independently each R is hydrogen, chlorine, bromine
or a Cl 30 monovalent hydrocarbon group, independently Rg and
~ are hydrogen or a Cl_30 monovalent hydrocarbon
and n is an integer of at least 2. Presently
preferred monovalent hydrocarbon groups are C1 4 alkyl or
phenyl. More preferred copolycarbonates contain bisphenyl
carbonate units of formula IV wherein each R is hydrogen and
Rg and Rh are methyl.
Halobisphenolethylene polycaxbonates can be
prepared by methods known to those skilled in the art such
as those described by S. Porejko e-t al., Polish patent 48,893,
issued December 12, 1964, entitled Process for Synthesizing
Self-Extinguishin~ Thermoplastics and Z. Wielgvsz et al.,
Polimery 17, 76 (1972). In general, the S. Porejko et al. and
Wielgosz et al. methods describe reactions of a chloro-
bisphenolethylene, i.e. l,l-dichloro-2,2-bis(4-hydroxyphenyl)-
ethylene and bisphenol A, i.e. bis(4-hydroxyphenyl)propane-
2,2 mixture with a carbonate precursor, e.g~ phosgene and an
acid acceptor, e.g. caustic soda and a catalyst, e.g.
triethylamine, wherein the reactions are caried out under
conventional phosgenating reaction condi-tions, i.e. reaction
,, - .:
: . ... - . - :

-- ~D-7842
~3~
conditions generally associated with the phosgenation oE
bisphenol-A as described in the Encyclopedia of Polymer
Scierce and Technology 10, entitled Polycarbonates, pages
710-764, Interscience Publishers (1969).
Illustrative of some halobisphenolethylene com-
pounds that can be employed in the preparation of homo- and
co-polycarbonates in accordance with the phosgenating reaction
conditions described by S.Porejko et al., and Wielgosz et al.,
as well as those described in the Encyclopedia of Polymer
Science follow:
1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene;
1,1-dichloro-2,2-bis(5-methyl-4-hydroxyphenyl)ethylene;
1,1-dibromo-2,2-bis(3,6-di-n-butyl-4-hydroxyphenyl)-
ethylene;
1,1-dichloro-2,2-bis(2-chloro-5-ethyl-4-hydroxyphenyl)-
ethylene;
1,1-dibromo-2,2-bis(2,5-dibromo-4-hydroxyphenyl)ethylene;
l-bromo-2,2-bis(4-hydroxyphenyl)ethylene;
l-chloro-2,2-bis(3,5-diisopropyl-4-hydroxyphenyl)-
ethylene;
l-bromo-2,2-bis(2,6-di-t-butyl-4-hydroxyphenyl)ethylene;
l-chloro-2,2-bis(2,6-dichloro-4-hydroxyphenyl)ethylene;
l-bromo-2,2-bis(2,3-dibromo-4-hydroxyphenyl)ethylene;
1,1-dichloro-2,2-bis(3,5-dichloro-4-hydroxyphenyl)-
ethylene;
1,1-dichloro-2,2-bis(3,5-dibromo-4-hydroxyphenyl)-
ethylene;

RD-7842
1,1-di.bromo-2,2-bis(5-chloro-4-hydroxyphenyl)ethylen~;
l-chloro-2,2-bis(3,6-dibromo-4-hydroxyphenyl)ethylene;
l-bromo-2,2-bis(2-chloro-4-hydroxyphenyl)ethylene;
1,1-dichloro-2,2-bis(2,3,5-trichloro-4-hydroxyphenyl)-
ethylene;
1,1-dibromo-2,2-bis(2,3,5,6-tetrabromo-4-hydroxyphellyl)-
ethylene;
l-chloro-2,2-bis(3-phenyl-4-hydroxyphenyl)ethylene;
l-bromo-2,2-bis(3,5-diphenyl-4-hydroxyphenyl)ethylene;
1,1-dichloro-2,2-bis(2,6-diphenyl-4-hydroxyphenyl)-
ethylene;
1,1-dibromo-2,2-bis(3-bromo-5-phenyl-4-hydroxyphenyl)-
ethylene;
l-chloro-2,2-bis(3-methoxy-4-hydroxyphenyl)ethylene;
1-bromo-2,2-bis(3,5-dimethoxy-4-hydroxyphenyl)ethylene;
1,1-dichloro-2,2-bis(2~ethoxy-4-hydroxyphenyl)ethylene;
1,1-dibromo-2,2-bis(2,6-diethoxy-4~hydroxyphenyl)-
ethylene;
l-chloro-2,2-bis(5-phenylether-4-hydroxyphenyl)-
ethylene;
l-bromo-2,2-bis(3,5-diphenylether-4-hydroxyphenyl)-
ethylene;
1,1-dichloro-2,2-bis(3~chloro-5-phenylether-4-
hydroxyphenyl)ethylene;
1,1-dibromo-2,2-bis(2-bromo-5-phenylether-4-
hydroxyphenyl)ethylene; etc., among many others~
Illustrative of some arene dihydroxy compounds that
can be employed in the preparation of halobisphenolethylene
polycarbonates or blends of halobisphenolethylene poly-
- ',

-
RD-7842
carbonates with oth~r polycarbonates which contain phenyl
carbonate units of formulas III and IV in accordance with the
phosgenating reaction conditions described by Wiel~osz et al.
and S.Porejko et al., as well as those described in t.he afore-
said Encyclopedia of Polymer Science publication follow:
resorcinol;
4,4'-dihydroxy-diphenyl;
1,6-dihydroxy-naphthalene;
2,6-dihydroxy-naphthalene;
4,4'-dihydroxy-diphenyl methane;
4,4'-dihydroxy-1,1-ethane;
4,4'-dihydroxy-diphenyl~l,l-butane;
4,4'-dihydroxy-diphenyl-1,1-isobutane;
4,4'-dihydroxy-dipheny:l-1,1-cyclopen~ane;
4,4'-dihydroxy-diphenyl-1,1-cyclohexane;
4,4'-dihydroxy~diphenyl-phenyl methane;
4,4'-dihydroxy-diphenyl-2-chlorophenyl methane;
4,4'-dihydroxy-diphenyl-2,4-dichlorophenyl methane;
4,4' dihydroxy-diphenyl-p-lsopropylphenyl methane;
4,4'-dihydroxy-diphenylnaph~hyl methane;
4,4'-dihydroxy-diphenyl-2,2-propane;
4,4'-dihydroxy-3-methyl-diphenyl-2,2-propane;
4~4'-dihydroxy-3-cyclohexyl-dipllenyl-2,2 propane;
4,4'-dihydroxy-3-methoxy-diphenyl-2,2-propane;
4,4'-dihydroxy-3-isopropyl-diphenyl-2,2-propane;
.X''

- D-7~42
f~
4,4'-dihydroxy-3,3'-dimethyl-diphenyl-2,2-propane;
4,4'-dihydroxy-3,3'~dichloro-diphenyl-2,2~propane;
4,4'-dihydroxy-diphenyl-2,2-butane;
4,4'-dihydroxy-diphenyl-2,2-pentane;
4,4'-dihydroxy-diphenyl-2,2(4-methyl pentane);
4,4'-dihydroxy-diphenyl-2,2-n-hexane;
4,4'-dihydroxy-diphenyl-2,2-nonane;
4/4'-dihydroxy-diphenyl-4,4-heptane;
4,4'-dihydroxy-diphenyl phenylmethyl methane;
4,4'-dihydroxy-diphenyl-4-chlorophenylmethyl methane;
4,4'-dihydroxy-diphenyl-2,5-dichlorophenylmethyl methane;
4,4'-dihydroxy-diphenyl-3,4-dichlorophenylmethyl methane t
4,4'-dihydroxy-diphenyl-4-~luorophenylmethyl methane;
4,4'-dihydroxy-diphenyl-2-naphthylmethyl methane;
lS 4,4'-dihydroxy-tetraphenyl methane;
4,4'-dihydroxy-diphenyl phenylcyano methane;
4,4'-dihydroxy-diphenyl~1,2-ethane;
4,4'-dihydroxy~dipherlyl-1,10-n-decane;
4,4'-dihydroxy-diphenyl-1,6(1,6-dioxo-n-hexane);
4,4'-dihydroxy-diphenyl-1,10(1,10-dioxo-n-decan.e);
bis-p-hydroxy-phenylether-4,4'-diphenyl;
~, CX, d', c~ -tetramethyl- ~,C~'-(di-p-hydroxyphenyl)p-xylylerle;
~,~,C~',C~'-tetramethyl-~,d'-(di-p-hydroxyphenyl)-m-xylylene;
2,2'-dihydroxy-3,3',5,5'-tetramethyldiphenyl methane;
4,4'-dihydroxy-3,31-dimethyl-diphenyl methane;
-- 10 --
.
- : :
.

RD~7842
4,4'-dihydroxy-2,2'-dimethyl-diphenyl methane;
4,4'-dihydroxy-3,3',5,5'-tetramethyl-diphenyl methane;
4,4'-dihydroxy-3,3'-dichloro-diphenyl methane;
4,4'-dihydroxy-3,3'-dimethoxy-diphenyl methane;
4,4'-dihydroxy-2,2',5,5'-tetramethyl-diphenyl methanei
4,4'-dihydroxy-2,2',3,3',5,5',6,6'-octamethyl-diphenyl
methane;
4,4'-dihydroxy-2,2'-dimethyl-5,5'-diisopropyl-diphenyl
methane;
4,4'-dihydroxy-2,2'-dimethyl-5,5'-dipropyl-diphenyl
methane;
4,4'-dihydroxy-2,2'-dimethyl-5,5'-di-tert.-butyl-
diphenyl methane;
4,4'-dihydroxy-diphenyl-5,5-nonane;
4,4'-dihydroxy-diphenyl-6,6-undecane;
4,~'-dihydroxy-diphenyl-3,3-butanone-2;
4, 4'-dihydroxy-3,3'-di.methyl-diphenyl-3,3-butanone-2;
4, 4 ' -dihydroxy-diphenyl-4,4-hexanone-3;
4,4'-dihydroxy-diphenylmethyl-4-methoxy-phenyl methane;
4,4'-dihydroxy-diphenyl ether;
4,4'-dihydroxy-diphenyl sulfide;
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;
4,4'-dihydroxy-diphenyl sulfoxide
4,4'-dihydroxy-diphenyl sulfone;
4, 4'-dihydroxy-3,3'-dichlorodiphenyl sulfone;
4,4'-dihydroxy-3,3',5,5'-tetramethyl-diphenyl methane;
4, 4 ' -dihydroxy-3,3' r 5,5'-tetrachloro-diphenyl-1,1-
cyclohexane;
-- 11 --
X;
'

- RD-78~2
$~
4,4'-dihydroxy-3,3',5,5'~tetrachloro-diphenyl-2,2-
propane;
4,4'-dihydroxy-313',5,5'-tetramethyl-212'16l6'-tetra-
bromo-diphenyl-2/2-propane; and
4,4'-dihydroxy-3,3'l5l5'-tetrabromo-dlphenyl-2l2-
propane, etc.l among many others.
Presently preferred halobisphenolethylene poly-
carbonates e~hibit an intrinsic viscosity of at least 0.3 and
mor~ preferably about 0.5 decilitexs per gram (dl~/g.) as
measured in either methylene chloride or chloroform or
similar solvent systems at 25 C. The upper intrinsic
viscosity number is not criticall however, it will generally
be about 1.5 dl./g. Especially useful halobisphenol-
ethylene polycarbonates generally have an intrinsic viscosity
within the range of from about 0.38 to about 0.7 dl./gO
Preferably, the halobisphenolethylene polycarbonates contain
a sufficient number of repeating units of formulas III or II
and III, or IVI set out hereinbefore/ to give a number average
molecular weight o~ homo- or copolycarbonates -- including
blends thereof with other polycarbonates -- of at least about
5,000 J and more preferably a number average molecular weight
of from about 10lO00 to about 50lO00. Polycarbonates of such
molecular weight characteristics process easily inbetween
about 450 F. and 650 F.
Blends of halobisphenolethylene polycarbonates and
any other polycarbonate containing arenecarbonate units of

RD-7842
5~L
formula III or IV, as described hereinbefore, are included
within the scope of this invention, and can be prepared ~y
any means known to those skilled in the art. Preferred
blends are prepared by heating admixtures of a halobisphenol-
ethylene polycarbonates and any other polycarbonate to a
temperature above their softening point(s). Preferably, the
mixing or blending is carried out ~- when carried out in the
absence of a solvent -- at the aforesaid elevated tempera-
ture, i.e. above their softening point(s), while subjecting
the admixture to mechanical working. Accordingly, blends can
be mixed with such equipment as extruders including mono- and
multiple scr~w types, internal Banbury mixers, roll mills, or
~n~ other mechanical equipment which will subject the ad-
mixture to shear stresses at elevated temperatures.
1~ Especially useful in the practice of this invention
are halobisphenolethylene polycarbonates that contain ~- in
addition to an organic phosphite -- an epoxy compound, i.e.
compounds which possess at least one 1,2-epoxide group of the
formula:
/C
~o (~) --c ~C--
Any saturated or unsaturated epoxy compound can be employed
including aliphatic, cycloaliphatic, aromatic or heterocyclic
epo~ides -- which are defined herein and in the appended
claims as "epoxides". The epoxides may be substituted -- if
~.

~~ RD-78~2
5~L
desired -- with noninterfering subs-tituents, such as halogen
atoms, phosphorus atoms, ether radicals and the
like. The epoxides may also be monomeric or polymeric
and include epoxides derived from both synthetic and natural
sources.
Illustrative of some presently preferred aliphatic
epoxides that may be employed are represented by the formula:
(IV) ~ Ri-C~ C-R ~
wherein Ri and Rj are independently selected from Cl 24
alkyl and p is an integer of from 1 to about 10.
Illustrative of some presently preerred cyclo-
aliphatic epoxides that may be employed are epoxidized cyclo
aliphatic epoxides that may be employed are epoxidized cyclo-
aliphatic compounds containing 1-2 cycloaliphatic rings of 6
carbon atoms each with at least one oxygen bridge being
attached to adjacent carbon atoms in at least one cyclo-
u alîphatic ring.
Illustrative of some presently preferred aromatic
epoxides that may be employed are aroma-tic glycidyl ethers or
~0 aromatic diglycidyl ethers containing 1-3 rings or aromatic
polyglycidyl ethers containing 1-3 aromatic rings.
Illustrative of some specific examples of some of
the members of the above epoxide groups that can be employed
are the following: butadiene diepoxide, epoxidized poly-
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.. . .

RD-7842
butadiene, di~lycidyl ether, bisphenol-A diylycidyl ether,
diglycidyl ester of phthalic acid, diglycidyl ester of
hexahydrophthalic acid, epoxidized soybean oil, -tetraphenyl-
ethylene epo~ide, octyl epoxy tallate, 3,4-~poxycyclohexyl-
S methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methyl-
cyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylate,
2,3-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,
4-(3,4-epoxy-5-methylcyclohexyl)butyl-3,~-epoxycyclohexane
carboxylate, 3,~-epoxycyclohexylethylene oxide, di-3,4-epoxy-
6-methylcyclohexylmethyl adipate, cyclohexylmethyl 3,4-
epoxycyclohexane carboxylate and 3,~-epoxy-6-methylcyclo-
he~ylmethyl 6-methylcyclohexyl carboxylate. Generally
preerred epoxides contain ~rom about 3 to up to about 30
carbon atoms. Presently preferred epoxides are bisphenol-A
diglycidyl ether and 3,4-epoxycyclohexylmethyl-3,4-epoxy
cyclohexane carboxylate.
In addition to the phosphites which can be employed
either alone or in combination with epoxy compounds to impart
th~rmal and color stability to halobisphenolethylene poly-
~0 carbonates, another embodiment of this invention comprises
the use of cadmium, barium, and/or cerium salts of aliphatic,
cycloaliphatic, aromatic carboxylic acids or carbonic acids
-- which are defined herein and in the appended claims as
"metal salts". Preferred cadmium, barium and/or cerium salts
2S of a C2 20 alkanoic, C7_20 benzoic or carbonic acids, and
: : -, . . :

~ RD-78~2
mixtures thereof are employed either alone or in conjunction
with phosphites or phosphite and epoxides as a stabilizer for
halobisphenolethylene polycarbonates. Illustrative of some
of the cadmium, barium and cerium salts of C2 20 alkanoic,
C7_20 benzoic or carbonic acids that can be employed are metal
salts, such as cadmium, barium or cerium acetate, butyrate,
hexanoate, octanoate, dodecanoate, stearate, eicosanoate,
cyclohexane carboxylate, benzoate, phthaloate, isophthaloate,
terephthaloate, toluoate, naphthoate or carbonate, etc.,
among many others. The pre~erred salts employed herein are
cadmium, barium or cerium 2-ethylhexanoate. In general, when
employing the cadmium, barium or cerium salts of the afore-
said organic acids, it is pre~erred that a stabilizing amount
of an organic acid corresponding to the acid types described
hereinbefore be employed in addition to the cadmium, barium or
cerium salts.
Stabilizing organophosphite co~inations, as used
herein and in the appended claims, include combinations of
~1) hydrocarbyl phosphites, (2) a hydrocarbyl phosphite(s)
~0 and an epoxide(s) or (3) a hydrocarbyl phosphite(s), an
epoxide(s) and a cadmium, barium or cesium salt(s)l o~ an
aliphatic, cycloaliphatic, aromatic carboxylic acid(s) or
carbonic acid(s), or a mixture including the components o~
(3) and an organic acid corresponding to those associated
with the cadmium, barium and cesium salts re~erenced herein.
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~ RD-7842
In general, the amount of organophosphite stabilizer or other
stabilizer component employed is any effective amount, i.e.,
any amount which increases the thermal or color stability of
halobisphenolethylene polycarbonates. In general -- as used
herein and in the appended claims -- an effective amount can
be as little as 0.010 or even lower to as much as 5.0 parts
or even higher of stabilizer or stabilizer combination per
100 parts of halobisphenolethylene polycarbonate on a weight
basis. For functional as well as economic considerations,
in general, optimum amounts generally range from about 0.025
to about 1.0 parts of stabilizer or stabilizer combination
per 100 parts of halobisphenolethylene polycarbonate. In a
presently preferred embodiment a stabilizer combination
comprises from about 0.05 to about 0.25 parts of organic
phosphite, from about 0.05 to about 0.25 parts of epoxide and
from about 0.05 to about 0.25 parts of a cadmium, barium or
C2_20 alkanoic C7~20 benzoic or carbonic
acid per 100 parts by weight of halobisphenolethylene poly-
carbonate composition.
The following examples illustrate -- but do not
limit -- the best method of practicing the invention. Unless
otherwise indicated in the examples, the following general
procedures were employed in the preparation and testing of
the stabilizers for the halobisphenolethylene polycarbonates.
Deviations from the general procedure are noted in the
., ,. ~ . . ~ .
. .. .. . . . . .
. . . . ~

- RD--7842
specific e~amples.
GENERAL PROCEDURE
A series of chlorobisphenolethylene polycarbonates
were prepared by the reaction of an aqueous alkaline solution
of 1,1-diehloro-2,2-bis(4 hydroxyphenyl)ethylene with
pllosgene earried out in the presenee of triethylamine and
me~hylene ehloride in the temperature range of from about 0
to about 40 C. to form a high moleeular weight chloro-
bisphenol polycarbonate having an intrinsic viscosity as
measured in methylene ehloride at a temperature of 25.3 C.
o 0.525 dl.~g. Eaeh stabilizer or stabili2er combination
was eombined with the ehlorobisphenol polycarbonate by (1)
eoating a ehlorobisphenolethylene polyearbonate powder with a
solution eontaining a test stabilizer or stabilizer eombi
nation, (2) evaporating the solvent, which in most cases was
a nonsolvent for the ehlorobisphenolethylene polyearbonate,
~3) compressing at room temperature 750 milligrams of the
eoated ehlorobisphenolethylene polycarbonate resin into a
premelt pellet, (4) compressing at 240 C. and 8,000 psi a
~0 pellet into a transparent disc one ineh by 37 mills -thick,
(5) exposing the resulting disc at 300 C. and 8,000 psi for
an additional 5 minutes, and (6) measuring the color o:E the
e~posed dise by measuring the light absorbance at 425 nm in a
1 em. eell of a solution prepared by dissolving 100 milligrams
~5 of the exposed dise in 5 millillters of chloroform. A low
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RD-7842
numerical absorbance value, e.g. 0.022, compared to a high
absorption value, e.g. 0.060, defines a most stable and a
least stable halobisphenolethylene polycarbonate,
respectively.
EXAMPLES 1-5
Summarized in Table I hereafter are the absorption
data associated with a control sample of l,l-dichloro-2,2-
bis(4-hydroxyphenyl)ethylene polycarbonate containing no
stabilizing component, l,l-dichloro-2,2-bis(4-hydroxyphenyl)-
ethylene polycarbonate containing a phosphite, a salt of an
alkanoic acid, and phosphites in combination with a salt of
an alkanoic acid. The ~uantity of each stabilizer component
is also noted.
TABLE I
15 Example Amount Absorbance
No. Stabilizer Component(s) (phr) (425 nm)
1 control none 0.048
2 diphenyl phosphite 0.15 0.022
3 diphenyl phosphite, 0.150
cadmium octanoate (1), 0.087
diphenyldecyl phosphite 0.063
Total 0-300 0.040
4cadmium octanoate (1) 0.15 0.040
5triphenyl phosphite 0.15 0.060
(1) 50% by weight octanoic acid
The above data illustrates that all phosphites are
not effective stabilizers for halobisphenolethylene poly-
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~ RD-7842
carbonates, that "organic phosphites", "metal salts", and
combinations of "organic phosphites" and "metal salts" - as
defined herein are effective stabilizers for "halobisphenol
ethylene carbonates".
EX~MPLES 6-9
Summarized in Table II hereafter is data in a form
analogous to that set out in Table I. In these examples the
samples were given a ~inal exposure at 315 C. and 8,000 psi
for 15 minutes. The color absorption data was measured at a
light waveleng-th of 425 nm in a 1 cm. cell using a solution
prepared by dissolving 52 milligrams of the exposed disc in
1 milliliter of methylene chloride.
TABLE I I
Example Amount Absorbance
No Stabilizer Component(phr) (425 nm)
-
6 control none 0.335
7 (a) diphenyldecyl phosphite 0.036
(b) 3,4-epoxycyclohexylmethyl-3,4-
epoxycyclohexane carboxylate 0.114
Total 0.150 0.245
8 (a) diphenyldecyl phosphite 0.063
(b) cadmium octanoate (1) _087
Total 0.150 0.175
9 3,4-epoxycyclohexylmethyl-3,4-
epoxycyclohexane carboxylate 0.15 0.940
(1) 50% by weight octanoic acid
The above data illustrates that combinations of "or-
ganic phosphite" and "metal salts" and combinatlons of
"organic phosphites" and "epoxides" are effective stabilizers
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RD-7842
for "halobisphenolethylene carbonates".
EXAM~LES 10-11
A polymer blend comprising 90 parts by weight of
the above-mentioned l,l-dichloro-2,2-bis(4-hydroxyphenyl)-
ethylene polycarbonate and 10 parts of a bisphenol-~ poly-
carbonate havlng an intrinsic viscosity of 0.52 as measured
in n~ethylene chloride prepared by the reaction by an aqueous
alkaline solution of bis(4-hydroxyphenyl)propane-2,2 with
phosgene carried out in the presence of triethylamine and
methylene chloride in accordance with standard commercial
reaction conditions was extruded and injection molded to
~rovide a polvmer blend having an intrinsic viscosity of 0.47
as measured in methylene chloride at 25.3 C. The poly-
carbonate blends were injection molded at a temperature of
about 507 F. into a mold with a surface temperature of about
200 F. The resulting injection molded polycarbonate blends
were evaluated for color intensity and color code in
accordance with a General Electric procedure which measures
color intensity (CI) indicative of the lightness or dar~ness
~0 of color and color code (CC~ indicative of the predominant
color (hue~, e.g. violet, blue, green, yellow, orange or red.
The color index and color code of the 1,1-dichloro~2,2-bis-
(4-hydroxyphenyl)ethylene polycarbonate blend was determined
b~ measuring the light absorbance at ~36, 490, 5~6, 570, 620
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RD-7842
and 660nm or millimicrons in the 10 cm cell of a solution
prepared by dissolving 2.5 grams of the injection molded
product in 50 milliliters of methylene chloride.
The numerical values for the color intensity were
calculated according to the following equation:
CI = lO(P + N),
436 490 546 and N A570 + A620 + A660 and the
color code was calculated according to the equation:
CC = 10 (P+N)
wherein P and N are as defined hereinbefore.
A low color index number, e.g. 15.0, identifies a
composition having improved color and improved thermal
stability by contrast with a control which has a higher color
index value, e.g. 23Ø A summary of the results is set out
in Table III:
TABLE III
Example Amount
Not Stabilizer Component ~ C.C. C.I.
9 control none 5.5 23.0
(a) diphenyldecyl phosphite 0~036
(b) 3,4-epoxycyclohexylmethyl-3,4-
epoxycyclohexane carboxylate 0.114
Total 0.150 5.5 15.0
EXAMPLES 11-12
~5 A color evaluation of a blend of a 1,1-dichloro-
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RD-7842
2,2-bis(4-hydroxyphenyl)ethylene polycarbonate and a
bisphenol-A polycarbonate was performed in a manner analogous
to that of Examples 9 and 10 above except that the ratio of
1,1-dichloro~2,2-bis(4-hydroxyphenyl)e~hylene polycarbonate
to bisphenol-A polycarbonate was 96 parts to 4 parts by
weight.
A sun~ary of the results of the evaluation is set
out in Table IV:
TABLE IV
Example Amount
No. Stabilizer Component _ (phr) C.C. C.I.
11 control none 5.4 29.0
12 (a) diphenyldecyl phosphite 0.036
(b) 3,4-epoxycyclohexylmethyl-3,4-
epoxycyclohexane carboxylate 0.114
Total 0.150 5.5 15.0
Although the above illustrative examples describe
the color absorption, color index and color code for specific
1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene polycarbonates
and blends thereof, analogous results are obtained when other
halobisphenolethylene polycarbonates and other blends thereof
are substituted for the polycarbonates employed in the
specific examples.
In general, the halobisphenolethylene polycarbonate
compositions of ~his invention can contain other ingredients
in addition to the stabilizer components describes herein
such as pigments, reinforcing and nonreinforcing fillers,

RD-7842
mold release agents, ultraviolet light stabilizers, anti-
oxidants, drip retarding agents, surfactant agents, etc.
The stabilized halobisphenolethylene polycarbonates
can be molded or ormed into films, sheets, fibers, laminates
or other molded articles including rei.nforced articles by
convent.ional moldin~ techniques.
It will be apparent to those skilled in the art
that other changes and modifications can be made in the
particular embodiments of the invention described herein and
said modifications and embodiments are within the full
intended scope of the invention as defined by the appended
claims.
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