CA1109594A - Color-stabilized halobisphenolethylene polycarbonates - Google Patents
Color-stabilized halobisphenolethylene polycarbonatesInfo
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- CA1109594A CA1109594A CA273,071A CA273071A CA1109594A CA 1109594 A CA1109594 A CA 1109594A CA 273071 A CA273071 A CA 273071A CA 1109594 A CA1109594 A CA 1109594A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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Abstract
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.
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.
Description
5~
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:
(I) R10-P
*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 ~' 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-.~ :
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~ , ~
' ~ ~
.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-
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:
(I) R10-P
*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 ~' 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-.~ :
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~ , ~
' ~ ~
.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;
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-- ', -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;
.
- : :
.
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;
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 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-- ~
- - : . . . - . .
- - . : : .
- . ~ - : :' ': ~
.. . .
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~
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;
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-- ', -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;
.
- : :
.
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;
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 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-- ~
- - : . . . - . .
- - . : : .
- . ~ - : :' ': ~
.. . .
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.
.~1 ' ~ 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 ., ,. ~ . . ~ .
. .. .. . . . . .
. . . . ~
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 ~r ' :' . : ~ .
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.
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-~ 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 '~
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 ~;
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 ~5 A color evaluation of a blend of a 1,1-dichloro-'~
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, 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.
.~1 ' ~ 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 ., ,. ~ . . ~ .
. .. .. . . . . .
. . . . ~
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 ~r ' :' . : ~ .
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.
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-~ 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 '~
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 ~;
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 ~5 A color evaluation of a blend of a 1,1-dichloro-'~
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, 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.
Claims (17)
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) 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) 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:
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.
(I) (a) about 1-100 parts by weight of halobis-(phenyl)ethylene carbonate units of formula (A):
(A) 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) 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:
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) where independently each R is hydrogen, chlorine, bromine or a 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) , 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:
, 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.
(I) (a) about 1-100 parts by weight of halobis-(phenyl)ethylene carbonate units of formula (A):
(A) where independently each R is hydrogen, chlorine, bromine or a 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) , 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:
, 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:
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:
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.
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:
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:
, 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.
, 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.
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.
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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66885776A | 1976-03-22 | 1976-03-22 | |
| US668,857 | 1976-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109594A true CA1109594A (en) | 1981-09-22 |
Family
ID=24684014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA273,071A Expired CA1109594A (en) | 1976-03-22 | 1977-03-03 | Color-stabilized halobisphenolethylene polycarbonates |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS52138543A (en) |
| AU (1) | AU510238B2 (en) |
| BE (1) | BE852747A (en) |
| BR (1) | BR7701779A (en) |
| CA (1) | CA1109594A (en) |
| DD (1) | DD129981A5 (en) |
| DE (1) | DE2709387A1 (en) |
| FR (1) | FR2345488A1 (en) |
| GB (1) | GB1568649A (en) |
| IN (1) | IN146002B (en) |
| MX (1) | MX145114A (en) |
| NL (1) | NL7703064A (en) |
| PL (1) | PL102953B1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3305520A (en) * | 1965-04-06 | 1967-02-21 | Bayer Ag | Polycarbonates stabilized by phosphites |
| FR1488636A (en) * | 1965-08-03 | 1967-07-13 | Gen Electric | Improvements to stable pigmented polymeric compositions based on polycarbonate, and processes for their preparation |
| NO135669C (en) * | 1972-01-03 | 1977-05-11 | Gen Electric |
-
1977
- 1977-02-28 IN IN284/CAL/77A patent/IN146002B/en unknown
- 1977-03-03 CA CA273,071A patent/CA1109594A/en not_active Expired
- 1977-03-04 DE DE19772709387 patent/DE2709387A1/en not_active Withdrawn
- 1977-03-21 NL NL7703064A patent/NL7703064A/en not_active Application Discontinuation
- 1977-03-21 DD DD7700197957A patent/DD129981A5/en unknown
- 1977-03-21 GB GB11792/77A patent/GB1568649A/en not_active Expired
- 1977-03-21 FR FR7708377A patent/FR2345488A1/en not_active Withdrawn
- 1977-03-22 PL PL1977196826A patent/PL102953B1/en unknown
- 1977-03-22 BR BR7701779A patent/BR7701779A/en unknown
- 1977-03-22 BE BE176007A patent/BE852747A/en unknown
- 1977-03-22 AU AU23494/77A patent/AU510238B2/en not_active Expired
- 1977-03-22 MX MX168461A patent/MX145114A/en unknown
- 1977-03-22 JP JP3052577A patent/JPS52138543A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BE852747A (en) | 1977-07-18 |
| PL102953B1 (en) | 1979-05-31 |
| MX145114A (en) | 1982-01-06 |
| JPS52138543A (en) | 1977-11-18 |
| AU2349477A (en) | 1978-09-28 |
| FR2345488A1 (en) | 1977-10-21 |
| AU510238B2 (en) | 1980-06-19 |
| NL7703064A (en) | 1977-09-26 |
| DD129981A5 (en) | 1978-02-22 |
| BR7701779A (en) | 1978-01-17 |
| DE2709387A1 (en) | 1977-09-29 |
| GB1568649A (en) | 1980-06-04 |
| IN146002B (en) | 1979-02-03 |
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