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WO1996029365A1 - Panneaux de carrosserie de voitures prepares a partir de polymeres de diaryle fluorene carbonate - Google Patents

Panneaux de carrosserie de voitures prepares a partir de polymeres de diaryle fluorene carbonate Download PDF

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WO1996029365A1
WO1996029365A1 PCT/US1995/016079 US9516079W WO9629365A1 WO 1996029365 A1 WO1996029365 A1 WO 1996029365A1 US 9516079 W US9516079 W US 9516079W WO 9629365 A1 WO9629365 A1 WO 9629365A1
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carbonate polymer
diaryl fluorene
fluorene
carbonate
polymer composition
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Stephen E. Bales
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Dow Chemical Co
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Dow Chemical Co
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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

Definitions

  • This invention relates to exterior body panels for automobiles or other vehicles which are prepared from diaryl fluorene carbonate polymer compositions. More specifically, the diaryl fluorene carbonate polymers can be directly prepared copolymers or they can be blends of diaryl fluorene carbonate polymers with other carbonate polymers, preferably carbonate polymers based on bisphenol A (BA).
  • BA bisphenol A
  • diaryl fluorene carbonate polymer compositions having molecular weights and concentrations of diaryl fluorene moieties falling in specific critical ranges demonstrate surprisingly good combinations of properties including stability and resistance to melting at high temperatures, solvent resistance, impact resistance and physical strength that make them particularly well suited for use in preparing body panels for automobiles or other similar types of vehicles, particularly when preparing the body panels by an injection molding process.
  • BHPF 9,9-bis(4-hydroxyphenyl) fluorene
  • dihydroxyaryl fluorene can be employed in the preparation of thermoplastic condensation polymers including diaryl fluorene carbonate polymers.
  • BHPF is disclosed to prepare random copolymers with bisphenol A and other bisphenols (U.S. Patent 3,546,165) and to prepare block copolymers with bisphenol A (U.S. Patent 3,128,264) and with diorganosiloxanes (U.S. Patent 3,781,378).
  • a process for preparing BHPF homopolycarbonates is disclosed in JP 63-182,336 (1988) and reported to prepare polymers having high heat resistance, good transparency and a desirable refractive index, which polymers are proposed for use in lenses and automobile body panels.
  • Japanese Patent Publication No. JP 02-304,741 (1990) discloses copolycarbonates of 20 to 90 weight percent BHPF with BA for use in the manufacture of polycarbonates for optical disks.
  • Japanese Patent Publication No. JP 05-155,998 (1993) discloses carbonate polymers containing BHPF and aliphatic units.
  • Japanese Patent Publication No. JP 05-228,350 (1993) discloses gas separation membranes prepared from copolymers of BHPF and BA.
  • JP 06- 25,398 (1994) discloses the use of BHPF/BA (41 to 95 mole percent BHPF) copolymers for lenses.
  • Japanese Patent Publication No. JP 06-25,399 (1994) discloses the use of BHPF/BA (1 to 40 mole percent BHPF) copolymers for laser card substrates.
  • Japanese Patent Publication No. JP 06- 25,401 (1994) discloses the use of BHPF/BA (70 to 95 mole percent BHPF) copolymers for printed circuit applications.
  • the high Tg carbonate polymer used in this blend could be a physical blend of a high Tg carbonate polymer and another carbonate polymer, noting that they may or may not be miscible.
  • these multicomponent blends are suggested for use in automobile body panels.
  • the invention is an exterior body panel for a vehicle consisting essentially of (I) a carbonate polymer composition consisting essentially of (la) a diaryl fluorene carbonate polymer component and optionally (lb) a second, different carbonate polymer component; the carbonate polymer composition (I) having an inherent viscosity as determined at 25°C in methylene chloride at a polymer concentration of 0.5 g/dL in the range of from 0.30 to 0.47 g/dL and comprising from 10 to 50 mole percent, preferably from 35 to 40 mole percent, diaryl fluorene moieties based on the total moles of multihydric diaryl fluorene and additional multihydric compound remnant moieties in the carbonate polymer composition.
  • the diaryl fluorene moieties in the diaryl fluorene carbonate polymer component are represented by the general formula:
  • the present invention is a process for preparing an injection molded, vehicle exterior body panel from a thermoplastic resin characterized in that the thermoplastic resin is the carbonate polymer composition (I) described above.
  • the body panels for automobiles and other vehicles according to this invention are an important development in the efforts to replace metal or thermoset body panels with tough, light weight, high heat, recyclable engineering thermoplastics. These polymers are not only tough and very processable but are also sufficiently stable and heat resistant to withstand
  • Diaryl fluorene carbonate polymers are characterized by containing polymerized therein (in addition to carbonate precursor remnant units) moieties of one or more diaryl fluorene represented by the general formula below:
  • Ri, R 2 , R 3 , and R 4 independently in each occurrence are hydrogen, a C -C , preferably mm C - 6 , linear or cyclic alkyl, alkoxy, aryl or aryloxy radical, such as methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl, xylyl, phenoxy and/or xylynoxy, or a halogen (such as fluorine, chlorine and/or bromine).
  • a C -C preferably mm C - 6
  • linear or cyclic alkyl alkoxy, aryl or aryloxy radical, such as methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl, xylyl, phenoxy and/or
  • Ri, R 2 , R 3 , and R are all hydrogen or Ri and R 2 are phenyl and R 3 and R 4 are hydrogen. mm.
  • the key features of the carbonate polymers suitable for preparing the body panels of the present invention are the content of the diaryl fluorene moieties (monomer remnants) in the carbonate polymer composition together with the molecular weight.
  • the diaryl fluorene carbonate polymers can either consist of (in addition to carbonate precursor remnant moieties) solely multihydric diaryl fluorene monomer moieties or consist of (in addition to carbonate precursor remnant units)
  • the second, different carbonate polymer component (lb) must be employed to provide a diaryl fluorene content in the carbonate polymer composition (I) in the required range.
  • the second, different carbonate polymer component (lb) may optionally be employed to obtain a diaryl fluorene content in the required range.
  • a multihydric diaryl fluorene monomer preferably a dihydroxyaryl fluorene monomer is used to prepare the diaryl fluorene carbonate polymer of the present invention.
  • Dihydroxyaryl fluorene compounds are represented by the general formula below,
  • Ri , R 2 , R 3 , and R independently in each occurrence are hydrogen, a C -C , preferably C ⁇ C., linear or cyclic alkyl, alkoxy, aryl or aryloxy radical, such as methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl, xylyl, phenoxy and/or xylynoxy, or a halogen (such as fluorine, chlorine and/or bromine).
  • a C -C preferably C ⁇ C., linear or cyclic alkyl, alkoxy, aryl or aryloxy radical, such as methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, benzyl, tolyl, xylyl, phenoxy and/or xylynoxy
  • the dihydroxyaryl fluorene is 9,9-bis (4-hydroxyphenyl) fluorene (BHPF).
  • Ri, R 2 , R 3 , and R 4 in the formula are all hydrogen and the dihydroxyaryl fluorene is 9,9-bis (4-hydroxyphenyl) fluorene (BHPF) or Ri and R 2 are phenyl and R 3 and R are hydrogen and the dihydroxyaryl fluorene is 9,9-bis(4- hydroxy-3-phenylphenyl) fluorene.
  • BHPF 9,9-bis (4-hydroxyphenyl) fluorene
  • the diaryl fluorene carbonate polymers may contain moieties or remnants corresponding to the polymerized form of one or more additional multihydric condensation reactive monomers.
  • the diaryl fluorene carbonate polymer contains moieties or remnants of one or more additional, condensation polymerizable dihydroxy compounds, more preferably dihydric phenols.
  • the additional condensation polymerizable multihydric monomer(s) is (are) selected from the following list of suitable dihydric phenols: 2,2-bis(4-hydroxyphenyl) propane, hydroquinone, resorcinol, 2,2-bis-(4-hydroxyphenyl)-pentane, 2,4'-dihydroxy diphenyl methane, bis-(2-hydroxyphenyl)- methane, bis-(4-hydroxyphenyl)-methane, bis(4-hydroxy-5-nitrophenyl)-methane, 1 , 1 -bis-(4- hydroxyphenyl)-ethane, 3,3-bis-(4-hydroxyphenyl)-pentane, 4,4'-dihydroxydiphenyl, 2,6- dihydroxy naphthalene, bis-(4-hydroxyphenyl) sulfide, bis-(4-hydroxyphenyl) sulfone, 2,4'd
  • the diaryl fluorene carbonate polymer in the present invention is a carbonate copolymer of a multihydric diaryl fluorene, preferably a dihydroxyaryl fluorene, and bisphenol A.
  • the desirable carbonate polymers for use in the body panels of the invention may comprise moieties or remnants that correspond in polymerized form to additional, condensation polymerizable multihydric monomers, including preferably dihydroxy compounds, more preferably the above-listed dihydric phenols, in addition to the the diaryl fluorene remnants or moieties.
  • the multihydric diaryl fluorene compound is desirably employed in amounts of at least 10, more preferably at least 20, more preferably at least 30 and most preferably at least 35 mole percent, which mole percentage is based on the total moles of multihydric diaryl fluorene compound and additional multihydric monomer polymerized in the carbonate polymer.
  • the multihydric diaryl fluorene compound is desirably employed in amounts of less than 90 mole percent, preferably less than 70, more preferably less than 50 and most preferably less than 45 mole percent, which mole percentages are based on the total moles of multihydric diaryl fluorene compound and additional multihydric monomer polymerized in the carbonate polymer.
  • the carbonate polymer composition (I) is a blend of (la) diaryl fluorene carbonate polymer component and (lb) a second, different carbonate polymer component
  • such-blend can be prepared across only a limited range of diaryl fluorene carbonate polymer and bisphenol A carbonate polymer weight percentages to obtain the desired content of the diaryl fluorene moieties in the carbonate polymer composition (I) and the desired property balance.
  • the term "weight percentage" as it is used herein with regard to the diaryl fluorene and second, different carbonate polymer components means the weight percentage of the diaryl fluorene or second, different carbonate polymer components based on total weight of those two components and ignoring any amounts of other fillers and additives.
  • diaryl fluorene carbonate polymers including for example, polycarbonates and polyestercarbonates
  • these carbonate polymers are preferably prepared from the multihydric diaryl fluorene, preferably dihydroxyaryl fluorene compounds, and optionally one or more additional multihydric monomers.
  • these carbonate polymers are prepared by reacting the multihydric diaryl fluorene, preferably dihydroxyaryl fluorene, compounds and optionally o other multihydric monomers (or their condensation reactive derivative such as metal phenolate) with a condensation reactive carbonate precursor.
  • multihydric diaryl fluorene monomers dihydroxyaryl fluorene monomers and multihydric monomers include their condensation reactive derivatives such as metal phenolate or the like.
  • Carbonate precursors suitable for use in preparing these carbonate polymers are 5 well known and include carbonic acid derivatives, phosgene, a haloformate, or a carbonate ester such as dimethyl carbonate or diphenyl carbonate.
  • Diaryl fluorene carbonate polymers are prepared from these reactants by an appropriate process selected from one of the known polymerization processes such as the known interfacial, solution or melt processes. General techniques for preparing carbonate polymers are well known and described in the literature.
  • the choice of polymerization process to use to prepare the diaryl fluorene carbonate polymer depends on a number of factors, including particularly the physical properties of the raw materials used. For example, the melt process is not appropriate if the monomers to be used in the polymerization reaction break down or form crosslinks at the higher temperatures at which the melt process is carried out.
  • the diaryl fluorene carbonate 5 polymer of the present invention is preferably prepared with an interfacial process or with a solution process.
  • the multihydric diaryl fluorene component(s), preferably dihydroxyaryl fluorene, and optionally one or more additional multihydric monomers are usually at least partially dissolved and partially deprotonated in an aqueous 0 base solution, and the carbonate precursor is dissolved by an organic solvent.
  • a solution of aqueous base is formed from water and a base which may be selected from those including the alkali metal and alkaline earth metal phosphates, bicarbonates, oxides and hydroxides.
  • a preferred base for preparing such a solution is a caustic soda such as NaOH or OH.
  • Base imparts increased reactivity to multihydric, particularly dihydroxy, compounds by adjusting the 5 pH of the aqueous phase to a level at which the compound is at least partially converted to dimetal salt form.
  • the pH of the aqueous phase is, as a result, adjusted to a level greater than 7.0, often to a pH in the range of 8.5 to 13.5.
  • polycarbonate is prepared from bisphenol-A, which is the monomer most widely used in commercial carbonate polymer production
  • the reaction between bisphenol-A and a carbonate precursor typically occurs at a temperature in the range of 25 to 40°C, and complete dissolution of bisphenol-A in the aqueous phase of the reaction mixture may be easily obtained at that temperature.
  • multihydric diaryl fluorene compounds are not soluble to any significant degree in aqueous base at a temperature in the range which is ordinarily associated with the production of bisphenol-A polycarbonate.
  • a temperature of less than 50°C for example, a mixture of aqueous base and BHPF at a concentration of above 0.05 M has the consistency of a viscous paste.
  • Solution of the multihydric diaryl fluorene compounds in the base may also be improved by adjusting the ratio of moles of base to moles of multihydric diaryl fluorene and other multihydric compounds (if any) in the carbonate polymer-forming reaction mixture.
  • the solubility of BHPF in the aqueous phase of a polycarbonate-forming reaction mixture is enhanced if the ratio of moles of base to moles of BHPF plus all other multihydric compounds present is from 2 to 3.85.
  • the pH of the aqueous phase of the reaction mixture will be in the range of 12.0 to less than 14.0.
  • Reaction of a multihydric diaryl fluorene compound, particularly BHPF, the optional additional multihydric monomer and the carbonate precursor under the conditions described above may be run in the absence of a phase transfer catalyst or using one.
  • Typical phase transfer catalysts are quaternary phosphonium or ammonium salts, such as tetraethyl- ammonium chloride or tributylbenzylammonium chloride, crown ethers and cryptates. These are added to the reaction mixture, or to the aqueous phase thereof, before reaction with a carbonate precursor to enhance solubility of the multihydric diaryl fluorene compound, and to reduce or prevent precipitation of the multihydric diaryl fluorene compound, once it is dissolved, before the reaction occurs.
  • phase transfer catalysts are described in greater detail in Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons (1979), volume 5, pages 62-69; Report AD-777 731 to the Naval Air Systems Command (January 1974), by Kambour and Niznik; U.S. Patent 3,546,165 and Japanese okai Publication 62-12,282 (1987).
  • the carbonate precursor excludes the phosgene dimer trichloromethylchloroformate (C.0 2 CI 4 ).
  • Process steps can be carried out in a single reaction vessel, or may be conducted independently in a series of individual reaction vessels wherein at least a portion of the reaction mixture prepared in a first reaction vessel in a first step is transferred to a second reaction vessel wherein another step is conducted, and so on throughout the process.
  • the contemplated individual reaction vessels may additionally be continuous or batch reactors.
  • the process may be conducted in a continuous reaction system, such as a tubular reactor, wherein the reaction system contains multiple reaction zones.
  • General techniques for preparing carbonate polymers are well known and described in the literature.
  • Carbonate polymers which are suitable for use as optional second carbonate polymer component (lb), include carbonate polymers based on 2,2-bis(4-hydroxyphenyl) propane (“bisphenol A”), including for example, polycarbonates and polyestercarbonates.
  • bisphenol A 2,2-bis(4-hydroxyphenyl) propane
  • these carbonate polymers and process for their preparation are well known in the literature and many are commercially available from a number of sources.
  • Such polymers are typically prepared from one or more known condensation polymerizable multihydric monomers, including preferably dihydroxy compounds, more preferably dihydric phenols.
  • Suitable dihydric phenols include, but are not limited to 2,2-bis(4-hydroxyphenyl) propane, hydroquinone, resorcinol, 2,2-bis-(4-hydroxyphenyl)-pentane, 2,4' -dihydroxy diphenyl methane, bis-(2-hydroxyphenyl)-methane, bis-(4-hydroxyphenyl)-methane, bis(4-hydroxy-5- nitropheny -methane, 1 , 1 -bis-(4-hydroxyphenyl)-ethane, 3,3-bis-(4-hydroxypheny l)-pentane, 4,4'-dihydroxydiphenyl, 2,6-dihydroxy naphthalene, bis-(4-hydroxyphenyl) sulfide, bis-(4- hydroxyphenyl) sulfone, 2,4'dihydroxy-diphenyl sulfone, 5'-chloro-2,4'-dihydroxydiphenyl
  • chain terminating compounds typically monophenols
  • Chain branching agents can also be employed in these polymers to provide branched products and modify the melt viscosities where desired to provide products that may be suitable for blow molding or thermoforming applications.
  • Suitable chain branching agents typically phenols having 3 or more hydroxyls, are known in the art and many are disclosed in U.S. Patents 3,544,514 (Re.27, 682); 4,695,620; 4,888,400; 5,104,964; and 5,367,044.
  • diaryl fluorene carbonate polymers (la) comprising solely carbonate linking moieties and optional additional carbonate polymers (lb) comprising solely carbonate linking moieties
  • a diaryl fluorene polyestercarbonate (la) and/or optional additional polyestercarbonate (lb) can be prepared similarly to the preparation of the polycarbonate except additionally incorporating a glycol, a hydroxy terminated polyester, a dibasic acid, or the like, as a part of the multihydric monomer. Methods of producing polyestercarbonates are known in the prior art.
  • the diaryl carbonate polymer is a diaryl fluorene polyestercarbonate.
  • Such diaryl fluorene polyestercarbonate preferably contains less than 50, more preferably less than 20, more preferably less than 10, and most preferably less than 5 percent of an ester linking group based on the total moles of ester plus carbonate linking groups.
  • the second, different carbonate polymer component (lb) in the carbonate polymer composition (I) it is preferred to select a combination of diaryl fluorene and second, different carbonate polymers such that a miscible blend of the diaryl fluorene and second, different carbonate polymers is prepared.
  • a combination of diaryl fluorene and second, different carbonate polymers such that a miscible blend of the diaryl fluorene and second, different carbonate polymers is prepared.
  • such blends consist essentially of the diaryl fluorene carbonate polymer and a second, bisphenol A carbonate polymer, which second polymer is preferably a homopolycarbonate of bisphenol A (and carbonate precursor).
  • the diaryl fluorene carbonate polymer consists solely of one or more multihydric diaryl fluorene moieties or consists of one or more multihydric diaryl fluorene moieties with moieties of bisphenol A, also including, of course, a carbonate precursor in the carbonate polymers.
  • very desirable miscible blends of the polymers result and provide especially preferred body panels according to the present invention.
  • the carbonate polymer composition (I) whether solely a diaryl fluorene carbonate polymer component (la) or a blend of a diaryl fluorene carbonate polymer component (la) and a second, different carbonate polymer component (lb), must contain from 10 to 50 mole percent multihydric diaryl fluorene moieties which mole percentage is based on the total moles of multihydric diaryl fluorene and additional multihydric monomer remnant moieties in the carbonate polymer(s) in the composition (I).
  • mole percentage as it is used herein with regard to the diaryl fluorene, bisphenol A or other monomeric moieties in the carbonate polymer component(s) means the mole percentage of such moieties in the carbonate polymer(s) based on total weight of those moieties and ignoring the carbonate precursor and any amounts of other polymers, fillers, impact modifiers and additives.
  • the carbonate polymer composition (I) desirably contains the multihydric diaryl fluorene remnant(s) or moieties at levels of at least 15 mole percent, preferably at least 25 mole percent, preferably at least 30, preferably at least 32 mole percent, more preferably at least 35, and most preferably at least 36 mole percent, which mole percentages are based on the total moles of multihydric diaryl fluorene and other multihydric monomer moieties polymerized in the carbonate polymer composition (I).
  • the carbonate polymer composition (I) desirably contains the multihydric diaryl fluorene in amounts of less than or equal to 50 mole percent, preferably less than or equal to 45 mole percent, preferably less than or equal to 40 mole percent, more preferably less than or equal to 30 mole percent, and most preferably less than or equal to 20 mole percent, which mole percentages are based on the total moles of multihydric diaryl fluorene and other multihydric monomer moieties in the carbonate polymer composition (I).
  • the weight average molecular weight of the carbonate polymer compositions (I) suitable for use in the body panels according to the present invention must fall within a relatively narrow molecular weight range to obtain the desired balance of blend properties.
  • the average molecular weight of polymer compositions (I) must result in IV values in the relatively narrow range of from 0.30 to 0.47 deciliters per gram (dL/g) in order to obtain a body panel having sufficient toughness, thermal stability and heat resistance properties.
  • a carbonate polymer composition (I) having an IV value of less than or equal to 0.44 dL/g, preferably less than or equal to 0.43 dL/g, and most preferably less than or equal to 0.42 dL/g.
  • the average molecular weight of the blend composition can also be measured directly by a number of known techniques.
  • the term "molecular weight” as it is used herein means the weight average molecular weight as measured by size exclusion chromatography using a bisphenol A polycarbonate standard.
  • the carbonate polymer composition (I) comprises a blend of components (la) and (lb)
  • the molecular weights of the two components are reasonably close, for example they are within 20 percent of each other, preferably within 10 percent, based on the higher of the two molecular weights.
  • the diaryl fluorene monomeric compound has a relatively high molecular weight per mer unit, resulting in somewhat lower degrees of polymerization in carbonate polymers having the same "molecular weight”.
  • the carbonate polymer composition (I) comprises a blend of components (la) and (lb)
  • the blends can be prepared across a range of weight percentages to obtain the desired balance of blend properties but within the requirements for molecular weight and diaryl fluorene content.
  • weight percentage as it is used herein with regard to the diaryl fluorene or second carbonate polymer components means the weight percentage of that carbonate polymer component based on total weight of those two components and ignoring any amounts of fillers and additives
  • diaryl fluorene carbonate polymer weight percentages of at least 1 , preferably at least 5, more preferably at least 10, more preferably at least 25 and most preferably at least 30 weight percent.
  • diaryl fluorene carbonate polymer weight percentages of less than or equal to 99, preferably less than or equal to 90, more preferably less than or equal to 75, more preferably less than or equal to 50, and most preferably less than or equal to 45 weight percent.
  • additives can be included in the carbonate polymer blends of the present invention such as fillers (including fibrous or particulate materials), pigments, dyes, antioxidants, heat stabilizers, ignition and drip resistant additives, ultraviolet light absorbers, mold release agents and other additives commonly employed in carbonate polymer compositions.
  • the body panels according to the invention can be prepared by any of a variety of known techniques but are preferably prepared by injection molding techniques, which are well known in the art.
  • injection molding techniques which are well known in the art.
  • Pellet samples ranging from 10 to 18 milligrams (mg) were weighed in DSC sample pans on an electronic balance. The samples were placed in a DuPont 912 Dual-Sample differential scanning calorimeter (DSC) purged with nitrogen. The method used involved equilibration at 100°C as a first step followed by scanning at 10°C or 20°C per minute (°C/min), as indicated in reported results, from 100°C to 350. Data analysis was performed on a DuPont Thermal Analyst 2100. Step transition was used to mark the start and end points of the glass transition temperature ranges on the plots followed by computer calculation of the midpoint Tg in °C for each.
  • DSC Dual-Sample differential scanning calorimeter
  • melt flow rate (MFR) values are measured according to ASTM D-1238, conditions of 300°C and 1.2 kilograms mass and are reported in grams per 10 minutes (g/ 10 min).
  • the 1 H-NMR spectra (CDCI3/TMS) of the products were in agreement with the target copolycarbonate composition.
  • BHPF 9,9-bis(4-hydroxyphenyl) fluorene
  • the reaction mixture was worked up by adding methanol (5 mL) and then a solution of 30 mL of concentrated HCI in 90 mL water. After stirring for 15 min at 200 rpm, the mixture was poured into a 2 L separatory funnel and allowed to stand overnight. The chloroform layer containing the dissolved polymer was separated and washed further with a solution of 10 mL concentrated HCI in 200 mL water, followed by 200 mL water, and was then passed through a column of MSC-1-H ion exchange resin (0.5 L bed volume).
  • the polycarbonate product was isolated by adding one volume of the chloroform solution to four volumes of a hexane/acetone (1 /1 v/v) mixture in an explosion resistant Waring blender. The product was filtered, dried in a hood overnight, and then dried for 48 hr. in a vacuum oven at 120°C. The dried product weighed 1 14.6 g and had an IV of 0.405 dL/g (determined in chloroform at 0.5 g/dL and 25°C) and a Tg value of 288°C (midpoint second scan, 20°C/min heating rate).
  • a copolycarbonate of 60 mole percent 9,9-bis(4-hydroxyphenyl) fluorene (BHPF) as the diaryl fluorene and 40 mole percent bisphenol A (B A) as an additional multihydric 5 monomer was prepared as follows. The mole percent of each monomer used in the preparation process for this copolycarbonate was confirmed to be the mole percentage in the final product by NMR of the product.
  • BA 0.13 g, 4.0 mmole
  • BHPF 2.102 g, 6.0 mmole
  • TBP 0.30 mmole
  • aqueous 50 percent NaOH solution 0 2.0 g, 25.0 mmole
  • water 16.14 g.
  • the reactor plug is loosely screwed in and a needle connected to a nitrogen source is then inserted through the injector port septum. Nitrogen gas is blown through the air space of the reactor for 10 minutes, then the plug tightened down.
  • the sealed reactor is placed in a water bath (69-71 c C) and a magnetic stirrer is started. Within 15 minutes the monomer has dissolved.
  • Sample BA PC-X is a 3 melt flow rate polymer based on bisphenol A and phosgene commercially available from The Dow Chemical Company as CALIBRE" 300-3.
  • Sample B A PC-Y is a 10 melt flow rate polymer based on bisphenol A and phosgene commercially available from The Dow Chemical Company as CALIBRE" 300-10.
  • the Haake blend product was removed, chopped, and compression molded using a Tetrahedron press to prepare plaques having dimensions 25.4 mm x 25.4 mm x 3.2 mm (1 in x 1 in x 1 /8 in).
  • Compression molding conditions were as follows: sample dried for 3 hours at 130°C and then placed in press at 320°C and 3.4 megaPascals (MPa) platen pressure (500 pounds per square inch - "psi”) for 2 min, pressure raised to 207 MPa (30,000 psi) for 5 minutes, then cooled at 20°C/minute to room temperature. The mold and sample were sandwiched between thick aluminum foil with external steel backing plates.
  • Additional melt blends were prepared by combining amounts of the BHPF/BA coPC (60/40) with BA PC, incorporating also 1000 parts Phosphite 168 brand thermal stabilizer per million parts resin blend (ppm). Samples were produced containing 0, 4.5, 12.3, 26.5, 41.8, 52 and 60 mole percent BHPF in the final blend product. Extrusion compounding of the samples was performed on a 30 mm Werner-Pfleiderer extruder with the feed zone set at 200°C and the four remaining zones set at 310°C. After drying at 125°C for4 hours in a forced air oven, all samples were molded on a 55 ton Negri-Bossi molding machine. The molding temperature for all samples was set at 350°C.
  • the Izod impact resistance test method was used to evaluate the toughness of samples at ambient temperature using the 10 mil (0.25 mm) notch radius Izod test. Bars were notched using the Testing Machines Incorporated (TMI) notcher. They were subsequently tested on the TMI Izod Machine following ASTM standard D-256. The results are reported in foot-pounds per inch (Ft-lb/in) and Joules per meter (J/m).
  • the samples used were 6 112 inch x 1/2 inch x 1 /8 inch (165.1 mm x 12.7 mm x 3.2 mm) dogbone-shaped bars.
  • the Sintech 2 instrument was used according to ASTM standard D-638 with a 2000 pound (lb) (907.2 kilogram -"kg") load cell and D-638 extensometer at a loading rate of 2 inches per minute (in/min) (50.8 mm/min). Flex properties at ambient temperature were measured in accordance with ASTM standard D790 using a 200 lb (90.7 kg) load cell. The results are reported in pounds per square inch (psi) and megaPascals (MPa).
  • Deflection temperature under load (DTUL) at a load of 66 psi (0.46 MPa) was measured according to ASTM standard D-648 utilizing the Tinius Olsen Heat Distortion Bath for Vicat and DTUL testing and the Tinius Olsen Microprocessor-Controlled Automatic Deflection Temperature Tester.
  • the 5 inch x 1 /2 inch x 1 /8 inch (127 mm x 12.7 mm x 3.2 mm) bars were used -
  • the haze value were measured and reported as "% Haze" for each of the materials by analyzing three disks of each material on the HunterLab Colorquest Sphere
  • Samples tested were 5 inch x 1/2 inch x 1/8 inch (127 mm x 12.7 mm x 3.2 mm) bars (cut in half) of BA PC-Y and BHPF coPC. Three bars of each of the two sample types were tested for crazing at strains of 0.002, 0.004, 0.006, and 0.008. Following this preliminary testing, two more bars were tested for each sample at 0.006 strain and three bars were tested for each at 0.007 strain in an attempt to establish a distinction between the critical strain values at which crazing occurs for each sample. Finally, bars of each of the two samples were annealed for 30 minutes at 20°C below Tg to remove " molded in" stresses.
  • the solvent resistance of the samples was also tested by evaluation of the resistance to crystallization in toluene.
  • a thin sheet was compression molded from pellets (dried under vacuum overnight at 1 10°C) for each of the samples.
  • a Tetrahedron MTP- 14 compression molding machine was used in conjunction with a rectangular 6 1 /8 inch x 6 inch x 1/64 inch (155.6 mm x 152.4 mm x ⁇ .40 mm) mold.
  • the blend samples 5 through 1 1 were further characterized by IV (determined in methylene chloride at 25°C and 0.5 g/dL) and by Dynatup impact resistance. The latter was conducted on a Dynatup Model 8000 drop tower according to ASTM D-3763-86 using a drop height of 12.0 in (304.8 mm) and a drop weight of 138.5 lb (305.3 kg). The specimens were undamped and were tested at 23°C.
  • Tg Range (°C) 9.3 15.3 18.0 28.0 26.7 23.3 18.7
  • Blending the BHPF coPC into the BA PC inhibits such crystallization, indicating improved solvent tolerance.
  • the BHPF coPC is somewhat more brittle than B A PC and tends to
  • Blend 15 reduce the toughness of blends accordingly, but not as much as would be expected based on interpolating the data for the two components separately.
  • Blend 7 is particularly noteworthy because it unexpectedly exhibits improved performance in all Dynatup categories compared to the BA PC reference sample and retains very good Izod impact resistance.
  • the 30/70 blend of BHPF/BA coPC and BA PC prepared in the previous example was fabricated into fender body panels using a 3500 ton Krausse-Maffei injection molding machine equipped with a 1987 Buick T-type fender tool of P-20 steel.
  • the injection molding conditions are shown in the following table.
  • exterior body panels can be injection molded according to the present invention for a range of vehicles including automobiles, trucks, recreational vehicles, and mobile homes, where these combinations of processability, heat resistance, toughness, light weight and recyclability are desired.

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Panneaux de carrosserie pour véhicules constitués essentiellement d'une composition polymère de carbonate comprenant (Ia) un constituant polymère de diaryle fluorène carbonate et éventuellement (Ib) un second constituant polymère de carbonate différent. Ladite composition polymère de carbonate (I) possède une viscosité inhérente, telle que déterminée à 25 °C dans du chlorure de méthylène à une concentration de polymère de 0,5 g/dl, de l'ordre de 0,30 à 0,47 dl/g, et comprend de 10 à 50 moles pour cent de fractions de diaryle fluorène basées sur la totalité des moles des fractions restantes de diaryle fluorène multihydrique et de composé multihydrique supplémentaire. Un procédé de production desdits panneaux de carrosserie de véhicule moulés par injection est également décrit. En particulier, la vitesse d'injection du procédé doit être maintenue inférieure à un certain niveau critique pour fournir une excellent aspect des pièces et éviter les effets de fissure et de décoloration. Des panneaux de carrosserie peuvent être moulés par injection pour toute une série de véhicules, dont les automobiles, les camions, les véhicules à but récréatif et les résidences mobiles, pour lesquels des propriétés d'aptitude au traitement, de résistance à la chaleur, de solidité, de légèreté et de recyclabilité sont souhaitées.
PCT/US1995/016079 1995-03-21 1995-12-13 Panneaux de carrosserie de voitures prepares a partir de polymeres de diaryle fluorene carbonate Ceased WO1996029365A1 (fr)

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US40793595A 1995-03-21 1995-03-21
US08/407,935 1995-03-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8674007B2 (en) 2006-07-12 2014-03-18 Sabic Innovative Plastics Ip B.V. Flame retardant and scratch resistant thermoplastic polycarbonate compositions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288837A (en) * 1991-07-02 1994-02-22 The Dow Chemical Company Preparation of polycarbonate with subsequent addition of chain terminator and base
EP0591962A2 (fr) * 1992-10-09 1994-04-13 Idemitsu Petrochemical Co., Ltd. Copolycarbonate et son procédé de préparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288837A (en) * 1991-07-02 1994-02-22 The Dow Chemical Company Preparation of polycarbonate with subsequent addition of chain terminator and base
EP0591962A2 (fr) * 1992-10-09 1994-04-13 Idemitsu Petrochemical Co., Ltd. Copolycarbonate et son procédé de préparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8674007B2 (en) 2006-07-12 2014-03-18 Sabic Innovative Plastics Ip B.V. Flame retardant and scratch resistant thermoplastic polycarbonate compositions

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