CA1094738A - Polycarbonate having improved critical thickness - Google Patents
Polycarbonate having improved critical thicknessInfo
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- CA1094738A CA1094738A CA277,395A CA277395A CA1094738A CA 1094738 A CA1094738 A CA 1094738A CA 277395 A CA277395 A CA 277395A CA 1094738 A CA1094738 A CA 1094738A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
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Abstract
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TITLE
POLYCARBONATE HAVING IMPROVED
CRITICAL THICKNESS
ABSTRACT OF THE DISCLOSURE
Polycarbonates are provided having improved critical thickness values based on an aromatic diphenol preferably bisphenol A and an aromatic diphenol thioether. By incorporating 2 up to 20 mole percent of the aromatic diphenol thioether based on the total diphenol content into the polymer, the critical thickness of the article molded from the polycarbonate is substantially improved.
TITLE
POLYCARBONATE HAVING IMPROVED
CRITICAL THICKNESS
ABSTRACT OF THE DISCLOSURE
Polycarbonates are provided having improved critical thickness values based on an aromatic diphenol preferably bisphenol A and an aromatic diphenol thioether. By incorporating 2 up to 20 mole percent of the aromatic diphenol thioether based on the total diphenol content into the polymer, the critical thickness of the article molded from the polycarbonate is substantially improved.
Description
10947~ Mo-1607-P-CIP
POLYCARBONATE HAVING IMPROVED
CRITICAL THICKNESS
BACKGROUND OF THE INVENTION
Field of the Invention S This invention relates to polycarbonate copolymers and more particularly to polycarbonate copolymers having improved critical thickness values.
Description of the Prior Art Polycarbonates derived from reactions involving organic dihydroxy compounds and carbonic acid derivatives have found extensive commercial application because of their excellent mechanical and physical properties. These thermoplastic polymers are particularly suited for the manufacture of molded articles where Lmpact strength, rigidity, toughness, thermal and dimensional stability as well as excellent electrical properties are required.
' However, one deficiency of polycarbonate when used in molded articles is the low critical thickness values of the polycarbonate polymer.
It is known that polycarbonate plastics exhibit high notched IzOd (ASTM test D-256~ impact values. This value, however, is dependent upon the thickness of the test specimen.
Typical notched Izod impact values for a 1/8" specimen are about 16 ft.-lbs.per in. These high Izod values result because specimens of 1/8" thickness are thinner than the critical thickness of the polymer and therefore upon impact a hinged or ductile break occurs.
~094738 On the other hand, l/4" specimens exhibit a clean or brittle break and give notched Izod impact values of only about
POLYCARBONATE HAVING IMPROVED
CRITICAL THICKNESS
BACKGROUND OF THE INVENTION
Field of the Invention S This invention relates to polycarbonate copolymers and more particularly to polycarbonate copolymers having improved critical thickness values.
Description of the Prior Art Polycarbonates derived from reactions involving organic dihydroxy compounds and carbonic acid derivatives have found extensive commercial application because of their excellent mechanical and physical properties. These thermoplastic polymers are particularly suited for the manufacture of molded articles where Lmpact strength, rigidity, toughness, thermal and dimensional stability as well as excellent electrical properties are required.
' However, one deficiency of polycarbonate when used in molded articles is the low critical thickness values of the polycarbonate polymer.
It is known that polycarbonate plastics exhibit high notched IzOd (ASTM test D-256~ impact values. This value, however, is dependent upon the thickness of the test specimen.
Typical notched Izod impact values for a 1/8" specimen are about 16 ft.-lbs.per in. These high Izod values result because specimens of 1/8" thickness are thinner than the critical thickness of the polymer and therefore upon impact a hinged or ductile break occurs.
~094738 On the other hand, l/4" specimens exhibit a clean or brittle break and give notched Izod impact values of only about
2.5 ft.-lbs. per in. The l/4" specimens are said to be above the critical thickness of the polymer. "Critical thickness"
has been defined as the thickness at which a discontinuity in Izod impact values occurs. In other words, it is the thic~ness at which a transition from a brittle to a ductile break or vice versa occurs. Thus a standard impact specimen of poly-carbonate polymer thicker than the critical thickness exhibits brittle breaks and those thinner than the critical thickness exhibit hinged or ductile breaks. Further, a polycarbonate based on bisphenol A with a melt flow of 3 to 6 grams/10 minutes at 300 C. (ASTM Dl238) has a critical thickness of 225 mils.
One approach to solving the critical thlckness problem has been to incorporate polyolefin polymers into the polycarbonate which has substantially improved critical thickness (See U.S.
Patent 3,437,631). But along with this improvement has come detrimental effects such as colorant dispersion problems be-cause of the diversity of chemical composition ~f the two component system and also a lack of transparency since the polyolefin and polycarbonate are i~compatible.
PC-009-CIP 2.
`` 10~4738 Thus in accordance with the invention a polycarbonate is provided which has impro~ed critical thickness values and is highly transparent.
BRIEF DESCRIPTION OF THE `INVENTION
A copolycarbonate having a melt flow of 1 to 24 gram/
10 min. at 300C (ASTM 1238) and having improved critical thickness is provided which contains from up to 20 mole percent ; of the repeating structural unit to-c-o /
~1 !~ wherein Rl and R2 are hydrogen or lower alkyl groups having 1 to 4 carbon atoms and n equals 0 to 2, and from 80 to 98 mole percent of the repeating structural unit --I O-C-~- Z
wherein X is ~ydrogen, a Cl to C4 alkyl radical or a halogen, prefera~ly Br or Cl,most preferably wherein X is hydrogen or a Cl-C4 alkyl radical; and nl equals 1 or 2 and Z is a single bond,an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -CO-, -SO- or -SO2-, preferably methylene or isopropylidene.
DETAILED DESCRIPTION OF T~E INVE~ITION
When used herein ~copolycarbonate resin" means the .~
neat resin without additives; "polycarbonate" means the copolycarbonate resin with additives therein.
The copolycarbonate resins of the invention may be prepared by conventional methods for polycarbonate resins, and may have a weight average molecular weight of 10,000 to Z00,000 and preferably a melt flow rate of 1 to 24 gram/10 min at 300C (ASTM 1238~.
Any suitable processes, reactants, catalysts, solvents, and conditions and the like for the production of the polycarbonate resins of this invention which are customarily employed in polycarbonate resin syntheses may be used such as disclosed in German Patent Nos. 1,046 r 311 and 962,274; U.S. Patents 3,028,365r 2,999,846, 3,248,414,
has been defined as the thickness at which a discontinuity in Izod impact values occurs. In other words, it is the thic~ness at which a transition from a brittle to a ductile break or vice versa occurs. Thus a standard impact specimen of poly-carbonate polymer thicker than the critical thickness exhibits brittle breaks and those thinner than the critical thickness exhibit hinged or ductile breaks. Further, a polycarbonate based on bisphenol A with a melt flow of 3 to 6 grams/10 minutes at 300 C. (ASTM Dl238) has a critical thickness of 225 mils.
One approach to solving the critical thlckness problem has been to incorporate polyolefin polymers into the polycarbonate which has substantially improved critical thickness (See U.S.
Patent 3,437,631). But along with this improvement has come detrimental effects such as colorant dispersion problems be-cause of the diversity of chemical composition ~f the two component system and also a lack of transparency since the polyolefin and polycarbonate are i~compatible.
PC-009-CIP 2.
`` 10~4738 Thus in accordance with the invention a polycarbonate is provided which has impro~ed critical thickness values and is highly transparent.
BRIEF DESCRIPTION OF THE `INVENTION
A copolycarbonate having a melt flow of 1 to 24 gram/
10 min. at 300C (ASTM 1238) and having improved critical thickness is provided which contains from up to 20 mole percent ; of the repeating structural unit to-c-o /
~1 !~ wherein Rl and R2 are hydrogen or lower alkyl groups having 1 to 4 carbon atoms and n equals 0 to 2, and from 80 to 98 mole percent of the repeating structural unit --I O-C-~- Z
wherein X is ~ydrogen, a Cl to C4 alkyl radical or a halogen, prefera~ly Br or Cl,most preferably wherein X is hydrogen or a Cl-C4 alkyl radical; and nl equals 1 or 2 and Z is a single bond,an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -CO-, -SO- or -SO2-, preferably methylene or isopropylidene.
DETAILED DESCRIPTION OF T~E INVE~ITION
When used herein ~copolycarbonate resin" means the .~
neat resin without additives; "polycarbonate" means the copolycarbonate resin with additives therein.
The copolycarbonate resins of the invention may be prepared by conventional methods for polycarbonate resins, and may have a weight average molecular weight of 10,000 to Z00,000 and preferably a melt flow rate of 1 to 24 gram/10 min at 300C (ASTM 1238~.
Any suitable processes, reactants, catalysts, solvents, and conditions and the like for the production of the polycarbonate resins of this invention which are customarily employed in polycarbonate resin syntheses may be used such as disclosed in German Patent Nos. 1,046 r 311 and 962,274; U.S. Patents 3,028,365r 2,999,846, 3,248,414,
3,153,0Q8, 3,215,668, 3,187,065, 2,964,974~ 2,970,137, 2~991,273,and2,999~ 835. The preferred process is the interfacial polycondensation process.
According to the interfacial polycondensation process, copolycarbonate resins are obtained by reacting the bisphenols represented by the structural formulae:
(x2nl ( HO ~ Z ~ ~
wherein X is hydrogen, a Cl to C4 al~yl radical, or a halogenj prefexably Br or Cl~ most prefera~ly wherein X
is hydrogen or a Cl-C4 alkyl radical; and n1 equals 1 or PC-009-CIP 4^
`~ `B
10~7~8 2 and wherein Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -0-, -CO-, -SO- or -SO2-, preferably methylene or isopropylidene and (Rl)n (R21n HO ~ S - ~ -OH
wherein Rl and R2 are hydrogen, lowex alkyl groups having ', 1 to 4 carbon atoms, with an alkaline earth metal oxide or PC-009-CIP 5.
hydroxide or àlkali metal hydroxide to form the alkaline earth metal or alkali metal salt of the bisphenols. The salt mixture is present in an aqueous solution or suspension and is reacted with phosgene, carbonyl bromide, or bischloroformic esters of the diphenols.
An organic solvent is provided in the reaction admixture which is a solvent for the polymer but not for the phenolic salts hereinbefore described. Thus, chlorinated aliphatic hydrocarbons or chlorinated aromatic hydrocarbons maybe used as the organic sol~ent which dissolves the condensation product.
In order to limit the molecular weight one may use monofunctional reactants such as monophenols, for example the propyl-, isopropyl- and butyl-phenols, especially p-tert.
-butyl-phenol and phenol itself. In order to accelerate the reaction, catalysts such as tertiary amines, quaternary ammonium, phosphonium or arsonium salts and the like may be used. The reaction temperature should be about -20~ to ~150C., preferably 0C to about 100C.
According to the polycondensation process in a homogeneous phase, the dissolved reaction components are polycondensed in an inert solvent in the presence of an equivalent amount of a tertiary amine base required for absorption of the generated HCl, such as e.g. N,N-dimethylaniline, N,N-dimethyl-cyclo-hexylamine or preferably pyridine and the li~e. In still another process, a diaryl carbonate can be transesterlied wi~h the aromatic dihydroxy compounds to form the polycarbonate r~sin.
PC-009-CIP 6.
10~ ~7~8 It is to be understood that it is possible to combine in the processes described above in a chemically meaningful way both the aromatic dihydroxy compounds, and the monohydroxy compounds in the form of the alkali metal salts and/or bis-haloformic acid esters, and the amount of phosgene or carbonyl bromide then still re~uired in order to obtain high-molecular products. Other methods of synthesis in forming the polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688 may be used.
The two diphenols necessary for synthesizing the repeat~ng structural units (I~ and (II) are thiodiphenol and preferably 4,4'-thiodiphenol and a bisphenol preferably having either methylene or isopropylidine linking the two phenol rings. The most preferred bisphenol is bis-2-(4-hydroxyphenyl)-propane; other bisphenols such as bis-(4-hydroxyphenyl)-methane, bis-2-(-4-hydroxy-3l5-dimeth phenyl) propane and the like may be utilized.
In addition to the 4,4'~thiodiphenol and the bisphenols recited a~ove other di-(monohydroxyaryl)-alkanes may be incorporated in the polymer at low levels (i,e. levels whi~ch do not affect critical thickness values)~ Exemplary dihydroxy compounds are taught by U.S~ Patent 3,028,365, s7~q~
As low as 2 mole percent of the 4,4'-thiodiphenol based on the total diphenol shows improved critical thickness values over a conventional bisphenol A while 10 mole percent of
According to the interfacial polycondensation process, copolycarbonate resins are obtained by reacting the bisphenols represented by the structural formulae:
(x2nl ( HO ~ Z ~ ~
wherein X is hydrogen, a Cl to C4 al~yl radical, or a halogenj prefexably Br or Cl~ most prefera~ly wherein X
is hydrogen or a Cl-C4 alkyl radical; and n1 equals 1 or PC-009-CIP 4^
`~ `B
10~7~8 2 and wherein Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -0-, -CO-, -SO- or -SO2-, preferably methylene or isopropylidene and (Rl)n (R21n HO ~ S - ~ -OH
wherein Rl and R2 are hydrogen, lowex alkyl groups having ', 1 to 4 carbon atoms, with an alkaline earth metal oxide or PC-009-CIP 5.
hydroxide or àlkali metal hydroxide to form the alkaline earth metal or alkali metal salt of the bisphenols. The salt mixture is present in an aqueous solution or suspension and is reacted with phosgene, carbonyl bromide, or bischloroformic esters of the diphenols.
An organic solvent is provided in the reaction admixture which is a solvent for the polymer but not for the phenolic salts hereinbefore described. Thus, chlorinated aliphatic hydrocarbons or chlorinated aromatic hydrocarbons maybe used as the organic sol~ent which dissolves the condensation product.
In order to limit the molecular weight one may use monofunctional reactants such as monophenols, for example the propyl-, isopropyl- and butyl-phenols, especially p-tert.
-butyl-phenol and phenol itself. In order to accelerate the reaction, catalysts such as tertiary amines, quaternary ammonium, phosphonium or arsonium salts and the like may be used. The reaction temperature should be about -20~ to ~150C., preferably 0C to about 100C.
According to the polycondensation process in a homogeneous phase, the dissolved reaction components are polycondensed in an inert solvent in the presence of an equivalent amount of a tertiary amine base required for absorption of the generated HCl, such as e.g. N,N-dimethylaniline, N,N-dimethyl-cyclo-hexylamine or preferably pyridine and the li~e. In still another process, a diaryl carbonate can be transesterlied wi~h the aromatic dihydroxy compounds to form the polycarbonate r~sin.
PC-009-CIP 6.
10~ ~7~8 It is to be understood that it is possible to combine in the processes described above in a chemically meaningful way both the aromatic dihydroxy compounds, and the monohydroxy compounds in the form of the alkali metal salts and/or bis-haloformic acid esters, and the amount of phosgene or carbonyl bromide then still re~uired in order to obtain high-molecular products. Other methods of synthesis in forming the polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688 may be used.
The two diphenols necessary for synthesizing the repeat~ng structural units (I~ and (II) are thiodiphenol and preferably 4,4'-thiodiphenol and a bisphenol preferably having either methylene or isopropylidine linking the two phenol rings. The most preferred bisphenol is bis-2-(4-hydroxyphenyl)-propane; other bisphenols such as bis-(4-hydroxyphenyl)-methane, bis-2-(-4-hydroxy-3l5-dimeth phenyl) propane and the like may be utilized.
In addition to the 4,4'~thiodiphenol and the bisphenols recited a~ove other di-(monohydroxyaryl)-alkanes may be incorporated in the polymer at low levels (i,e. levels whi~ch do not affect critical thickness values)~ Exemplary dihydroxy compounds are taught by U.S~ Patent 3,028,365, s7~q~
As low as 2 mole percent of the 4,4'-thiodiphenol based on the total diphenol shows improved critical thickness values over a conventional bisphenol A while 10 mole percent of
4,4'~iodiphenol raises the critical thickness value of the polycarbonate to levels equivalent to those blends of bisphenol A polycarbonate with a polyolefin polymer. However, the thiodiphenol based polycarbonate maintains transparency, good colorant dispersability and other properties substantially improved over the polycarbonate polyolefin blend.
Although copolymers of bisphenols and thiodiphenols are known, (See U.S. Patent 3,250,744) the contemplated use of these polymers of the prior art were as coatings and moldings having good anchorage. The copolymers of the prior art have from 20 to 100 mole percent of the repeating structural unit tO-C-O-~)S~lL
to obtain good anchorage but the prior art did not recognize the improved critical thickness values obtained with the above structural unit from 2 to up to 20 mole percent in the polymer.
The invention will be further described by illustration in the following examples.
PC-009-CIP 8.
Example I
A copolycarbonate resin was prepared by reacting a mixture of the disodium salts of bis-2-(4-hydroxyphenyl)-propane (bisphenol A) and 4,4'-thiodiphenol with phosgene in accordance with the interfacial polycondensation synthesis hereinbefore
Although copolymers of bisphenols and thiodiphenols are known, (See U.S. Patent 3,250,744) the contemplated use of these polymers of the prior art were as coatings and moldings having good anchorage. The copolymers of the prior art have from 20 to 100 mole percent of the repeating structural unit tO-C-O-~)S~lL
to obtain good anchorage but the prior art did not recognize the improved critical thickness values obtained with the above structural unit from 2 to up to 20 mole percent in the polymer.
The invention will be further described by illustration in the following examples.
PC-009-CIP 8.
Example I
A copolycarbonate resin was prepared by reacting a mixture of the disodium salts of bis-2-(4-hydroxyphenyl)-propane (bisphenol A) and 4,4'-thiodiphenol with phosgene in accordance with the interfacial polycondensation synthesis hereinbefore
5 discussed. The ratio of bisphenol A to 4,4'-thiodiphenol was 9 to 1. The copolycarbonate was tested for physical, mechanical, and optical properties with the test results reported on Table I. The copolycarbonate was found to be highly transparent. Also Table II shows the effect of oven aging at 105C on impact and critical thickness properties.
Example II
Example I was repeated except the mole ratio of 4,4'-thiodiphenol : bisphenol A was 2:98. The copolycarbonate was found to be highly transparent. Test results of Example II
lS and the following Examples are reported on Tables I and II.
Example III
Example II was repeated except the mole ratio of 4,4'-thoidiphenol : bisphenol A was 20:80. The copolycarbonate was found to be highly transparent.
Example IV
Example IV is a bisphenol A polycarbonate resin having no 4,4'-thiodiphenol therein.
PC-009-CIP 9.
109473~
TABLE I
EXAMPLES I II III IV
Mole %
BPAl 90 98 80 100 (Control) 5 Monomers Izod3 (Notched) Impact (Ft. lbs/in) 1/8" 14.89 16.0 14.59 18.44 1/4" 14.96 7.98 14.75 3.20 Critical Thickness 15 mils 255 247 >255 227 Relative Viscosity4 1.340 1.318 1.377 1.355 Melt Index g~10 min 2.9 3~6 2.5 3.1 Heat Distor-tion5 Temp. C 135 - 133 134 %s found (calc.) 1.12(1.32) 0.24(0.30) 2.42~2.63) -Oxygen6 Index% 25.4 - 25.4 25.5 % Brightness 87.49 86.83 87.06 86.30 ~ ~aze7 3.2 _ 1.5 Tensile 30 Strength psi 9000 - 8900 9800 Ultimate Ten-sile Strength psi 940~ - 9Q00 10,100 ~ Elongation 8 - 10 8 ~ Elongation Failure 90 - 95 105 PC-009-CIP 10.
BPA is Bisphenol A
2TDP is 4,4'-thiodiphenol 0.5g. resin/100 ml. methylene chloride at 25C
C under 264 psi load (ASTM-D-648) PC-OO9-CIP 11.
~09473B
TABLE II
EXAMPLES I III IV
Mole % BPA 90 80 100 (Control) 5Monomers TDP 10 20 1/8" Impact (Ft. lbs/in) Unaged 14.8914.59 16.68 24 hr. 14.0514.15 16.35 1048 hr. 14.8214.51 16.35 96 hr. 13.2214.15 16;84 148 hr. 14.3914.76 16.84 288 hr. 14.2013.59 16.30 Critical Thick-ness Values Unaged 255 >255 225 24 hr. 199 227 185 48 hr. 187 219 183 96 hr. 175 205 150 20148 hr. 170- 205 155 288 hr. 170 205 155 PC-005-CIP 12.
109`~738 As is shown in the data presented in Tables I and II
as low as 2 mole% of 4,4'-thiodiphenol based upon the total diphenol content in the polycarbonate resin improves the critical thickness of articles molded there-from while maintaining substantially equivalent physical and mechanical properties of the conventional bisphenol A based on polycarbcnat~ resin.
While it has been known to synthesize polycarbonates from sulfur containing diphenols such as 4,4'-sulfonyl diphenol to incorporate the repeating structural unit t ~~
into the polymer such structural units do not improve the critical thickness values of polycarbonates based partially on 4,4'-sulfonyl-diphenol. Table III shows critical thickness values contrasting 4,4'-sulfonyl-diphenol based polycarbonates with the 4,4'-thiodiphenol based polycarbonates.
!
PC-OOg-CIP 13.
- 10~4738 TABL~ III
Mono~er Compositions Crltical Thickness Melt Flow mole %) _mils(g/10 min.) *BPAl SDP2 t90) (10) 215 6.2 (90) (10) 255 2.9 Random Copolymer BPA
~100) Control 225 3.0 B~sphenol A
24,4'-Sulfonyldiphenol 34, 4'-Thlodiphenol *The BP~(90)-SDP(10) copolycarbonate was found to have the following additional properties:
~eat Distortion Temp at 264 psi, C 147 Imp~ct ft lbs/in (1/8") 14.80 Impact ft lbs/in (1/4") ~.65 Cri~ical Thickness 225 Tensile strength, psi 9300 Ultimate Tensile Strength, psi 9100 Elongation yiel~
Ultimate Elongation ~ 95 PC-009-CIP 14.
Thus copolycarbonates having a minimum of 2 mole per-cent of 4,4'-thiodiphenol based upon the total diphenol content in the polymer exhibit improved critical thickness values over conventional polycarbonates and also copolycar-bonates based on sulfonyl diphenols.
Although the invention has been described with refer-ence to specific materials and testing procedures the inven-tion is only to be limited in so far as is set forth in the accompanying claims.
PC-OO9-CIP ~5
Example II
Example I was repeated except the mole ratio of 4,4'-thiodiphenol : bisphenol A was 2:98. The copolycarbonate was found to be highly transparent. Test results of Example II
lS and the following Examples are reported on Tables I and II.
Example III
Example II was repeated except the mole ratio of 4,4'-thoidiphenol : bisphenol A was 20:80. The copolycarbonate was found to be highly transparent.
Example IV
Example IV is a bisphenol A polycarbonate resin having no 4,4'-thiodiphenol therein.
PC-009-CIP 9.
109473~
TABLE I
EXAMPLES I II III IV
Mole %
BPAl 90 98 80 100 (Control) 5 Monomers Izod3 (Notched) Impact (Ft. lbs/in) 1/8" 14.89 16.0 14.59 18.44 1/4" 14.96 7.98 14.75 3.20 Critical Thickness 15 mils 255 247 >255 227 Relative Viscosity4 1.340 1.318 1.377 1.355 Melt Index g~10 min 2.9 3~6 2.5 3.1 Heat Distor-tion5 Temp. C 135 - 133 134 %s found (calc.) 1.12(1.32) 0.24(0.30) 2.42~2.63) -Oxygen6 Index% 25.4 - 25.4 25.5 % Brightness 87.49 86.83 87.06 86.30 ~ ~aze7 3.2 _ 1.5 Tensile 30 Strength psi 9000 - 8900 9800 Ultimate Ten-sile Strength psi 940~ - 9Q00 10,100 ~ Elongation 8 - 10 8 ~ Elongation Failure 90 - 95 105 PC-009-CIP 10.
BPA is Bisphenol A
2TDP is 4,4'-thiodiphenol 0.5g. resin/100 ml. methylene chloride at 25C
C under 264 psi load (ASTM-D-648) PC-OO9-CIP 11.
~09473B
TABLE II
EXAMPLES I III IV
Mole % BPA 90 80 100 (Control) 5Monomers TDP 10 20 1/8" Impact (Ft. lbs/in) Unaged 14.8914.59 16.68 24 hr. 14.0514.15 16.35 1048 hr. 14.8214.51 16.35 96 hr. 13.2214.15 16;84 148 hr. 14.3914.76 16.84 288 hr. 14.2013.59 16.30 Critical Thick-ness Values Unaged 255 >255 225 24 hr. 199 227 185 48 hr. 187 219 183 96 hr. 175 205 150 20148 hr. 170- 205 155 288 hr. 170 205 155 PC-005-CIP 12.
109`~738 As is shown in the data presented in Tables I and II
as low as 2 mole% of 4,4'-thiodiphenol based upon the total diphenol content in the polycarbonate resin improves the critical thickness of articles molded there-from while maintaining substantially equivalent physical and mechanical properties of the conventional bisphenol A based on polycarbcnat~ resin.
While it has been known to synthesize polycarbonates from sulfur containing diphenols such as 4,4'-sulfonyl diphenol to incorporate the repeating structural unit t ~~
into the polymer such structural units do not improve the critical thickness values of polycarbonates based partially on 4,4'-sulfonyl-diphenol. Table III shows critical thickness values contrasting 4,4'-sulfonyl-diphenol based polycarbonates with the 4,4'-thiodiphenol based polycarbonates.
!
PC-OOg-CIP 13.
- 10~4738 TABL~ III
Mono~er Compositions Crltical Thickness Melt Flow mole %) _mils(g/10 min.) *BPAl SDP2 t90) (10) 215 6.2 (90) (10) 255 2.9 Random Copolymer BPA
~100) Control 225 3.0 B~sphenol A
24,4'-Sulfonyldiphenol 34, 4'-Thlodiphenol *The BP~(90)-SDP(10) copolycarbonate was found to have the following additional properties:
~eat Distortion Temp at 264 psi, C 147 Imp~ct ft lbs/in (1/8") 14.80 Impact ft lbs/in (1/4") ~.65 Cri~ical Thickness 225 Tensile strength, psi 9300 Ultimate Tensile Strength, psi 9100 Elongation yiel~
Ultimate Elongation ~ 95 PC-009-CIP 14.
Thus copolycarbonates having a minimum of 2 mole per-cent of 4,4'-thiodiphenol based upon the total diphenol content in the polymer exhibit improved critical thickness values over conventional polycarbonates and also copolycar-bonates based on sulfonyl diphenols.
Although the invention has been described with refer-ence to specific materials and testing procedures the inven-tion is only to be limited in so far as is set forth in the accompanying claims.
PC-OO9-CIP ~5
Claims (13)
1. A copolycarbonate resin with a melt flow rate of 1-24 gram/10 min. at 300°C (ASTM 1238) consisting essentially of:
2 up to 20 mole percent of the sulfur containing structural unit (I) wherein R1 and R2 are hydrogen or lower alkyl groups having 1 to 4 carbon atoms and n equals 0 to 2, and from 80 to 98 mole percent of the structural unit (II) wherein X is hydrogen, a C1 to C4 alkyl radical or a halogen and n1 equals 1 or 2, and Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -CO-, -SO- or -SO2-.
2 up to 20 mole percent of the sulfur containing structural unit (I) wherein R1 and R2 are hydrogen or lower alkyl groups having 1 to 4 carbon atoms and n equals 0 to 2, and from 80 to 98 mole percent of the structural unit (II) wherein X is hydrogen, a C1 to C4 alkyl radical or a halogen and n1 equals 1 or 2, and Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -CO-, -SO- or -SO2-.
2. The copolycarbonate resin of Claim 1 wherein Z
is selected from the group consisting of methylene and iso-propylidene.
is selected from the group consisting of methylene and iso-propylidene.
3. The copolycarbonate resin of Claim 1 wherein X
is selected from the group consisting of hydrogen, a C1-C4 alkyl radical, Br and Cl.
is selected from the group consisting of hydrogen, a C1-C4 alkyl radical, Br and Cl.
4. The copolycarbonate resin of Claim 3 wherein X
is selected from the group consisting of hydrogen and a C1-C4 alkyl radical.
is selected from the group consisting of hydrogen and a C1-C4 alkyl radical.
5. The copolycarbonate resin of Claim 1 wherein the sulfur containing structural unit is:
6. The copolycarbonate resin of Claim 2 wherein X is hydrogen and Z is isopropylidene.
7. A process for preparing a copolycarbonate comprising, reacting:
a. thiodiphenol; and b. a compound of the structural formula wherein X is hydrogen, a C1 to C4 alkyl group, or a halogen and n1 equals 1 or 2 and Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -CO-, -SO-, or -SO2- with a carbonic acid derivative selected from the group consisting of phosgene, carbonyl bromide, the bischloroformic esters of (a) and/or (b) and diaryl carbonates, under conditions selected to produce a copolycarbonate with a melt flow rate of 1 to 24 gram/10 min. at 300°C (ASTM 1238) wherein (a) is present in the reaction mixture from 2 up to 20 mole percent and (b) is present from 80 to 98 mole percent based on the total moles of both (a) and (b).
a. thiodiphenol; and b. a compound of the structural formula wherein X is hydrogen, a C1 to C4 alkyl group, or a halogen and n1 equals 1 or 2 and Z is a single bond, an alkylene or alkylidene radical with 1 to 7 carbon atoms, a cycloalkylene or cycloalkylidene radical with 5 to 12 carbon atoms, -O-, -CO-, -SO-, or -SO2- with a carbonic acid derivative selected from the group consisting of phosgene, carbonyl bromide, the bischloroformic esters of (a) and/or (b) and diaryl carbonates, under conditions selected to produce a copolycarbonate with a melt flow rate of 1 to 24 gram/10 min. at 300°C (ASTM 1238) wherein (a) is present in the reaction mixture from 2 up to 20 mole percent and (b) is present from 80 to 98 mole percent based on the total moles of both (a) and (b).
8. The process of Claim 7 wherein the thiodiphenol (a) is 4,4'-thiodiphenol.
9. The process of Claim 7 wherein Z is selected from the group consisting of methylene and isopropylidene.
10. The process of Claim 7 wherein (b) is bisphenol A.
11. The copolycarbonate resin of Claim 1 wherein structural unit I is present in an amount from 2 to 19 mole percent and structural unit II is present in an amount from 81 to 98 mole percent.
12. The copolycarbonate resin of Claim 1 wherein structural unit I is present in an amount from 2 to 15 mole percent and structural unit II is present in an amount from 85 to 98 mole percent.
13. The copolycarbonate resin of Claim 1 wherein structural unit I is present in an amount from 2 to 10 mole percent and structural unit II is present in an amount from 90 to 98 mole percent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68749076A | 1976-05-18 | 1976-05-18 | |
| US687,490 | 1976-05-18 | ||
| US76760777A | 1977-02-10 | 1977-02-10 | |
| US767,607 | 1977-02-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1094738A true CA1094738A (en) | 1981-01-27 |
Family
ID=27104015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,395A Expired CA1094738A (en) | 1976-05-18 | 1977-04-28 | Polycarbonate having improved critical thickness |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS52140596A (en) |
| CA (1) | CA1094738A (en) |
| DE (1) | DE2721595A1 (en) |
| FR (1) | FR2352016A1 (en) |
| GB (1) | GB1584743A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174359A (en) * | 1977-09-06 | 1979-11-13 | Mobay Chemical Corporation | Flame retardant polycarbonate polyblends |
| US4605774A (en) * | 1978-09-18 | 1986-08-12 | Mobay Corporation | Preparation of bis(4-hydroxyphenyl thio)benzenes |
| US4430485A (en) | 1980-08-11 | 1984-02-07 | General Electric Company | Flame retardant polycarbonate compositions |
| US4473685A (en) * | 1983-07-28 | 1984-09-25 | General Electric Company | Flame retardant non-dripping polycarbonate compositions exhibiting improved thick section impact |
-
1977
- 1977-04-28 CA CA277,395A patent/CA1094738A/en not_active Expired
- 1977-05-13 DE DE19772721595 patent/DE2721595A1/en active Pending
- 1977-05-16 GB GB2048177A patent/GB1584743A/en not_active Expired
- 1977-05-16 JP JP5553377A patent/JPS52140596A/en active Pending
- 1977-05-18 FR FR7715397A patent/FR2352016A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE2721595A1 (en) | 1977-12-01 |
| FR2352016A1 (en) | 1977-12-16 |
| GB1584743A (en) | 1981-02-18 |
| JPS52140596A (en) | 1977-11-24 |
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| MKEX | Expiry |