WO1980000154A1 - Compositions de polycarbonates de faible viscosite ayant une resistance a l'impact amelioree - Google Patents
Compositions de polycarbonates de faible viscosite ayant une resistance a l'impact amelioree Download PDFInfo
- Publication number
- WO1980000154A1 WO1980000154A1 PCT/US1979/000427 US7900427W WO8000154A1 WO 1980000154 A1 WO1980000154 A1 WO 1980000154A1 US 7900427 W US7900427 W US 7900427W WO 8000154 A1 WO8000154 A1 WO 8000154A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- polycarbonate
- melt viscosity
- weight
- amount
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- This invention relates to flame retardant, aromatic polycarbonate resins having improved impact strength at low melt viscosities.
- Polycarbonate polymers are known as being excellent molding materials since products made therefrom exhibit such properties as high impact strength, toughness, high transparency, wide temperature limits (high impact resistance below -60o C and a UL thermal endurance rating of 115o C with impact), good dimensional stability, good creep resistance, good flame retardance, and the like.
- these properties are generally exhibited in polycarbonate resins having relatively high melt viscosities such as on the order of about 2400 poises. It would be desirable to add to this list of properties that of improved impact strength when the polycarbonates have relatively low melt viscosities such as on the order of about 1500- 2000 poises.
- These low melt viscosity polycarbonate resins having improved impact strength can then be employed to form molded articles requiring long thin wall s ections which are difficult to mold when polycarbonates having high viscosities are employed.
- any of the aromatic polycarbonates can be employed that are prepared by reacting a diphenol with a carbonate precursor.
- Typical of some of the diphenols that can be employed are bisphenol-A (2, 2-bis(4-hydroxyphenyl)propane), bis (4-hydroxyphenyl) methane, 2, 2-bis(4-hydroxy- 3-methylphenyl)propane, 4, 4-bis(4-hydroxyphenyl)heptane, 2, 2- (3, 5, 3',5'-tetrachloro-4, 4'-dihydroxydiphenyl)propane, 2, 2-(3, 5 3', 5'-tetrabromo-4, 4'-dihydroxydiphenyl)propane, (3, 3'-dichloro- 4, 4' -dihydroxyphenyl)methane.
- Other diphenols of the bisphenol type can also be used such as are disclosed in U. S. Patents 2, 999, 835, 3, 028, 365, and 3, 334, 154.
- diphenols can then be employed to obtain the high molecular weight aromatic polycarbonates of the invention which can be linear or branched homopolymers or copolymers as well as mixtures thereof or polymeric blends and which generally have an intrinsic viscosity (IV) of about 0. 40-1, 0 dl/g as measured in methylene chloride at 25o C.
- IV intrinsic viscosity
- the carbonate precursor used can be either a carbonyl halide, a carbonate ester or a haloformate.
- the carbonyl halides can be carbonyl bromide, carbonyl chloride and mixtures thereof.
- the carbonate esters can be diphenyl carbonate, di-(halophenyl) carbonates such as di-(chlorophenyl) carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl)carbonate, di-
- (tribromophenyl) carbonate, etc. di-(alkylphenyl) carbonate such as di(tolyl) carbonate, etc. , di-(naphthyl) carbonate, di- (chloronaphthyl) carbonate, phenyl tolyl carbonate, chloro- phenyl chloronaphthyl carbonate, etc. , or mixtures thereof.
- haloformates examples include bis -haloformates of dihydric phenols (bischloroformates of hydroquinone, etc. ) or glycols (bis haloformates of ethylene glycol, neophenyl glycol, polyethylene glycol, etc. ). While other carbonate precursors will occur to those skilled in the art, carbonyl chloride, also known as phosgene, is preferred.
- polymeric derivatives of a dihydric phenol, a dicarboxylic acid and carbonic acid such as are disclosed in U. S. Patent 3, 169, 121 which is incorporated herein by reference, and which are particularly preferred.
- This class of compounds is generally referred to as copolyestercarbonates.
- Molecular weight regulators, acid acceptors and catalysts can also be used in obtaining the aromatic polycarbonates of this invention.
- the useful molecular weight regulators include monohydric phenols such as phenol, chroman-I, paratertiary- butylphenol, parabromophenol, primary and secondary amines, etc.
- phenol is employed as the molecular weight regulator.
- a suitable acid acceptor can be either an organic or an inorganic acid acceptor.
- a suitable organic acid acceptor is a tertiary amine such as pyridine, triethylamine, dimethylaniline, tributylamine, etc.
- the inorganic acid acceptor can be either a hydroxide, a carbonate, a bicarbonate, or a phosphate of an alkali or alkaline earth metal.
- the catalysts which can be employed are those that typically aid the polymerization of the diphenol with phosgene.
- Suitable catalysts include tertiary amines such as triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammonium compounds such as, for example, tetraethylammonium bromide, cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propyl ammonium bromide, tetramethylammonium chloride, tetramethyl ammonium hydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammonium chloride and quaternary phosphonium compounds such as, for example, n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphonium bromide.
- branched polycarbonates wherein a polyfunctional aromatic compound is reacted with the diphenol and carbonate precursor to provide a thermoplastic randomly branched polycarbonate.
- These polyfunctional aromatic compounds contain at least three functional groups which are carboxyl, carboxylic anhydride, haloformyl, or mixtures thereof.
- polyfunctional aromatic compounds which can be employed include trimellitic anhydride, trimellitic acid, trimellityl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydride, and the like.
- the preferred polyfunctional aromatic compounds are trimellitic anhydride and trimellitic acid or their acid halide derivatives.
- Blends of linear and branched aromatic polycarbonates are also included within the scope of this invention.
- the polycarbonate resins employed are those that exhibit improved flame retardance.
- Typical of the flame retardant polycarbonates that can be used in the practice of this invention are those that are derived from halogenated diphenols such as are disclosed in U. S. Patent 3, 062, 781, German Patent P25 317. 2 and in copending applications Serial Nos. 882, 242; 882, 191; and, 882, 193, all of which were filed on
- the rubbery acrylic-butadiene copolymers that can be employed are those which are commercially available such as those offered by Rohm and Haas Company under their product identifications KM-228, KM-607 and KM-611.
- the rubbery copolymer can be blended with the low melt viscosity polycarbonate in amounts of about 0. 5 to 10%, preferably 1 to 5% and optimumly 2 to 4% based upon the weight of the polycarbonate.
- EXAMPLE I One hundred (100 )parts of an aromatic polycarbonate, prepared by reacting 2, 2-bis(4-hydroxyphenyl)propane and phos gene in the presence of an acid acceptor and a molecular weight regulator and having a melt viscosity of about 1650 poises was mixed with 4. 3 parts of each of two rubbery acrylicbutadiene copolymers by tumbling the ingredients together in a laboratory tumbler. The resulting mixture was then fed through an extruder which was operated at about 265o C and the extruder was comminuted into pellets.
- the pellets were than injection molded about 315°C into test bars of about (5 in.) 12.7 cm by 1/2 in.) 1.27 cm by about (1/16-1/8 in.) 0.16-0.32 cm thick and into test squares of about (2 in. by 2 in.) 5 cm x 5 cm by about (1/8 in.) 0.32 cm thick.
- the test bars (5 for each test listed in the Tables) were subject to the notched Izod impact test in accordance with ASTM D-256 on test bars as molded and after the test bars had been subjected to accelerated heat aging at 125°C for periods set forth in Table 1 below wherein the acrylic-butadiene copolymers are those obtained from Rohm and Haas Company and are shown by their product identifications.
- the unmodified polycarbonate at this low melt viscosity lost its ductile impact strength in less than one hour.
- the formulation containing KM-607 retained its ductile impact strength up to about 8 hours at 125°C whereas the formulation containing KM-611 retained its ductile impact strength after being heat aged at 125°C for over 16 hours.
- Example i The procedure of Example i was repeated except that the polycarbonate obtained had a melt viscosity of 1970 poises. This polycarbonate was also formulated with the acrylic-butadiene copolymers as in Example 1 and subjected to the same tests. The results obtained are set forth in Table II.
- An aromatic polycarbonate was prepared by reacting 2,2-bis (4-hydroxyphenyl) propane and phosgene in the presence of an acid acceptor and a molecular weight regulator to obtain a polycarbonate having a melt viscosity of about 4000 poises.
- a copolycarbonate was also prepared by reacting 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and phosgene the presence of an acid acceptor and a molecular
- V-0 Average flame and/or glowing after removal of the igniting flame shall not exceed 5 seconds and none of the specimens shall drip flaming particles which ignite absorbent cotton.
- V-I Average flaming and/or glowing after removal of the igniting flame shall not exceed 25 seconds and the flowing does not travel vertically for more than ( 1 /8") 0. 32 cm of the specimen after flaming ceases and glowing is incapable of igniting absorbent cotton.
- V-II Average flame and/or glowing after removal of the igniting flame shall not exceed 25 seconds and the specimens drip flaming particles which ignite absorbent cotton.
- a test bar which continues to burn for more than 25 seconds after removal of the igniting flame is classified, not by UL-94, but by the standards of the instant invention as "burns”. 0 The results of these tests are shown in Table III,
- Example 4 The procedure of Example 3 was repeated except that the polycarbonate obtained had a melt viscosity of 1900 poises, the amount of titanium dioxide pigment added was increased to 2.5% and the KM-611 acrylic-butadiene copolymer level was increased to 6%. The same tests were run as in Example 3, the results of which are shown in Table IV.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
On ameliore la resistance aux chocs des resines de polycarbonates aromatiques de poids moleculaire eleve et de faible viscosite en les melangeant avec un copolymere de caoutchouc acrylique-butadiene. La composition de polycarbonates peut eventuellement comporter un additif de resistance aux flammes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US91809478A | 1978-06-22 | 1978-06-22 | |
US918094 | 1978-06-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1980000154A1 true WO1980000154A1 (fr) | 1980-02-07 |
Family
ID=25439794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1979/000427 WO1980000154A1 (fr) | 1978-06-22 | 1979-06-19 | Compositions de polycarbonates de faible viscosite ayant une resistance a l'impact amelioree |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0016111A4 (fr) |
JP (1) | JPS55500393A (fr) |
WO (1) | WO1980000154A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3109904A1 (de) * | 1980-03-20 | 1982-02-04 | General Electric Co., Schenectady, N.Y. | Ternaere polycarbonat-zubereitungen |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3130177A (en) * | 1961-03-24 | 1964-04-21 | Borg Warner | Blends of polycarbonates with polybutadiene, styrene, acrylonitrile graft copolymers |
US3162695A (en) * | 1961-06-26 | 1964-12-22 | Borg Warner | Blends of polycarbonates with butadiene-styrene, methyl methacrylate, styrene graft copolymer |
US3655824A (en) * | 1969-07-31 | 1972-04-11 | Mitsubishi Rayon Co | Rubbery acrylic resin composition containing a resinous 4 4'-dioxy diarylalkane polycarbonate |
US3663471A (en) * | 1969-01-08 | 1972-05-16 | Bayer Ag | Thermoplastic molding compositions and moldings of polycarbonates admixed with a graft copolymer |
US3742088A (en) * | 1971-01-07 | 1973-06-26 | Texaco Inc | Polycarbonate resins blended with elastomers for improved impact strength |
US3813358A (en) * | 1972-01-03 | 1974-05-28 | Gen Electric | Polycarbonate molding composition comprising an aromatic polycarbonate graft copolymer and a modifier |
US3852393A (en) * | 1971-10-06 | 1974-12-03 | Daicel Ltd | Resinous composition comprising a blend of an abs resin and polycarbonate resin |
US3947524A (en) * | 1973-10-25 | 1976-03-30 | Daicel Ltd. | Resin composition having high impact resistance |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1930262A1 (de) * | 1968-06-17 | 1969-12-18 | Mobay Chemical Corp | Thermoplastische Polycarbonatformmassen |
US3801673A (en) * | 1972-01-03 | 1974-04-02 | Gen Electric | Process for preparing polycarbonate alloys |
JPS5430009B2 (fr) * | 1972-03-14 | 1979-09-27 | ||
CA1012282A (en) * | 1972-05-03 | 1977-06-14 | Robert L. Lauchlan | Modified polycarbonate compositions |
DE2329646A1 (de) * | 1973-06-09 | 1975-01-09 | Bayer Ag | Transparente formmassen |
-
1979
- 1979-06-19 WO PCT/US1979/000427 patent/WO1980000154A1/fr unknown
- 1979-06-19 JP JP50103379A patent/JPS55500393A/ja active Pending
-
1980
- 1980-02-01 EP EP19790900810 patent/EP0016111A4/fr not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3130177A (en) * | 1961-03-24 | 1964-04-21 | Borg Warner | Blends of polycarbonates with polybutadiene, styrene, acrylonitrile graft copolymers |
US3162695A (en) * | 1961-06-26 | 1964-12-22 | Borg Warner | Blends of polycarbonates with butadiene-styrene, methyl methacrylate, styrene graft copolymer |
US3663471A (en) * | 1969-01-08 | 1972-05-16 | Bayer Ag | Thermoplastic molding compositions and moldings of polycarbonates admixed with a graft copolymer |
US3655824A (en) * | 1969-07-31 | 1972-04-11 | Mitsubishi Rayon Co | Rubbery acrylic resin composition containing a resinous 4 4'-dioxy diarylalkane polycarbonate |
US3742088A (en) * | 1971-01-07 | 1973-06-26 | Texaco Inc | Polycarbonate resins blended with elastomers for improved impact strength |
US3852393A (en) * | 1971-10-06 | 1974-12-03 | Daicel Ltd | Resinous composition comprising a blend of an abs resin and polycarbonate resin |
US3813358A (en) * | 1972-01-03 | 1974-05-28 | Gen Electric | Polycarbonate molding composition comprising an aromatic polycarbonate graft copolymer and a modifier |
US3947524A (en) * | 1973-10-25 | 1976-03-30 | Daicel Ltd. | Resin composition having high impact resistance |
Non-Patent Citations (1)
Title |
---|
See also references of EP0016111A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3109904A1 (de) * | 1980-03-20 | 1982-02-04 | General Electric Co., Schenectady, N.Y. | Ternaere polycarbonat-zubereitungen |
Also Published As
Publication number | Publication date |
---|---|
EP0016111A1 (fr) | 1980-10-01 |
EP0016111A4 (fr) | 1980-10-09 |
JPS55500393A (fr) | 1980-07-03 |
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