WO2003004561A2 - Composition de melange polyester/polycarbonate - Google Patents

Composition de melange polyester/polycarbonate Download PDF

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Publication number
WO2003004561A2
WO2003004561A2 PCT/US2002/020700 US0220700W WO03004561A2 WO 2003004561 A2 WO2003004561 A2 WO 2003004561A2 US 0220700 W US0220700 W US 0220700W WO 03004561 A2 WO03004561 A2 WO 03004561A2
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group
carbon atoms
inclusive
groups
polyester
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PCT/US2002/020700
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English (en)
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WO2003004561B1 (fr
WO2003004561A3 (fr
Inventor
James T. Rauh
Joseph M. Rauh
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Engineered Plastics Corporation
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Priority to EP02742354A priority Critical patent/EP1409586A4/fr
Priority to AU2002315493A priority patent/AU2002315493A1/en
Publication of WO2003004561A2 publication Critical patent/WO2003004561A2/fr
Publication of WO2003004561A3 publication Critical patent/WO2003004561A3/fr
Publication of WO2003004561B1 publication Critical patent/WO2003004561B1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to polyester / polycarbonate blends useful as either a
  • optical data storage o media such as compact disks.
  • 1 polycarbonate resins have good performance characteristics such as transparency, low 2 water affinity, good processability, good heat resistance and low birefringence.
  • High 3 birefringence is particularly undesirable in high density optical data storage media. 4 Improvements in optical data storage media, including increased data storage s density, are highly desirable, and achievement of such improvements is expected to 6 improve well established and new computer technology such as read only, write once, 7 rewritable, digital versatile and magneto-optical (MO) disks.
  • MO magneto-optical
  • the information to be read is imprinted directly 9 into a moldable, transparent plastic material, such as bisphenol A ("BPA") polycarbonate.
  • BPA bisphenol A
  • the information is stored in the form of shallow pits embossed in a polymer surface.
  • the 1 surface is coated with a reflective metallic film, and the digital information, represented by 2 the position and length of the pits, is read optically with a focused low power (5 mW) laser 3 beam.
  • the user can only extract information (digital data) from the disk without changing 4 or adding any data. Thus, it is possible to "read” but not to "write” or "erase” information.
  • the operating principle in a WORM drive is to use a focused laser beam (20-40 6 mW) to make a permanent mark on a thin film on a disk.
  • the information is then read out 7 as a change in the optical properties of the disk, e.g., reflectivity or absorbance.
  • These 8 changes can take various forms: "hole burning” is the removal of material, typically a thin 9 film of tellurium, by evaporation, melting or spalling (sometimes referred to as laser 0 ablation); bubble or pit formation involves deformation of the surface, usually of a polymer 1 overcoat of a metal reflector.
  • EODs erasable 4 media for optical storage
  • PC phase change
  • MO ⁇ magneto-optic
  • the materials for MO storage are generally amorphous alloys of the
  • Amorphous materials have a distinct advantage in MO storage as they do not suffer ⁇ from "grain noise”, spurious variations in the plane of polarization of reflected light caused
  • thermomagnetic writing 9 by randomness in the orientation of grains in a polycrystalline film. Bits are written by ⁇ o heating above the Curie point, T c , and cooling in the presence of a magnetic field, a ⁇ process known as thermomagnetic writing. In the phase-change technology, information is
  • the film can be melted and quenched to the is amorphous state.
  • the amorphized spot can represent a digital "1 " or a bit of information.
  • the information is read by scanning it with the same laser, set at a lower power, and
  • the recording layer is separated from
  • polymer blend of 3 polymers which comprises: (1 ) polyesters and copolyesters as well as blends thereof; with 4 (2) polycarbonates as well as blends thereof, which exhibit exceptional clarity, stability, s tensile strength, elongation, impact resistance, toughness, ductility, and processability.
  • the formulation of the blends may contain other additives, such as ABS (acrylonitrile- 7 butadiene-styrene), nylons, stabilizers (e.g., phosphates, phosphites, phenols, amines, 8 halogens, phenols, amines, and UV absorbers), process and internal lubricants in all forms 9 (including glycols and fatty acids), colorants in all forms, as well as fillers, and 0 reinforcements (including carbons, talc, clays, oxides, metals, fibers, fabrics, micas, 1 conductives, and other organic and inorganic reinforcements and fillers).
  • ABS acrylonitrile- 7 butadiene-styrene
  • stabilizers e.g., phosphates, phosphites, phenols, amines, 8 halogens, phenols, amines, and UV absorbers
  • process and internal lubricants in all forms 9 including glycols and fatty acids
  • the invention builds in the recognition that blends of polycarbonates and polyesters, as well as specialized copolyesters can produce exceptionally good optical media capable of use in the optical recording industry.
  • the polycarbonate component is completely eliminated.
  • Polycarbonates have been used in the optical recording industry for many years. In general, polycarbonates will have at least the following repeat unit.
  • R is an alkylaryl or arylalkyl group (the nomenclature depending on whether the aryl properties or the alkyl properties of the chemical moiety predominates) of C 15-36 comprising at least one aryl ring.
  • One exemplary specific polycarbonate is a synthetic thermoplastic resin derived from bisphenol A and phosgene, a linear polyester of carbonic acid, e.g.,
  • Polycarbonates can be formed from any dihydroxy compound and any carbonate diester, or by ester interchange. Polymerization may be in aqueous emulsion or in non-aqueous solution.
  • the polymers are transparent (90% light transmission), noncorrosive, weather and ozone-resistant, non-toxic, stain-resistant, low water absorption, high impact strength, heat-resistant, high dielectric strength, and dimensionally stable. It is their link to phosgene that has spurred the search for non-polycarbonate materials with similar properties, or at least to minimize the amount of polycarbonates used in any blend material.
  • new compositions have been developed, which contain novel structures selected from the group consisting of: (a) carbonate structural units corresponding to structure (I)
  • Ri, R2, R 3 , and R are independently selected from the group consisting of
  • Re, R7, R1 0 and Rn are independently selected from the group consisting of
  • R-i 3 , R- I 4 and R ⁇ independently represent H, and C-i - C ⁇ alkyls, R- I5 is H or Ci - C 3 alkyl and n is an integral value from 0 to 2 inclusive, R- I7 is H or Ci - C 5 alkyl; and (2) carbonate structural units corresponding to structure (IV)
  • Ri 8 is independently selected from the group consisting of halogen, hydrogen, monovalent C-i - C ⁇ 0 alkyls, monovalent d - C & alkoxy radicals, aryl groups having from C ⁇ - C-io carbon atoms, aralkyl groups having from C 7 - C 10 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof;
  • Rig is independently selected from the group consisting of halogen, hydrogen, monovalent C-i - C ⁇ 0 alkyls, monovalent d - C ⁇ alkoxy radicals, aryl groups having from C 6 - C 10 carbon atoms, aralkyl groups having from C 7 - do carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof;
  • W is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -C ⁇ hydrocarbon radicals, alkylidene groups having from C2 - C10 carbon atoms, cycloalkylene group having C ⁇ - Cio carbon atoms, cycloalkylidene groups having from C 6 - C10 carbon atoms, alkylene-arylene-alkylene groups having C ⁇ - C15 carbon atoms, -S-, ⁇ S(R 27 ) 2 ⁇ , --S--S--,
  • the polycarbonate will be an aromatic polycarbonate, which is a thermoplastic polycarbonate comprising a carbonic acid ester of an aromatic diol compound as the main recurring unit.
  • This recurring unit is represented by the following formula (IV) and blends thereof
  • R 19 is independently selected from the group consisting of halogen, hydrogen,
  • ⁇ W is selected from the group consisting of a covalent bond, substituted or
  • R 33 and R ⁇ are substituents selected independently from the group consisting of H,
  • R 44 and R 5 are selected from the group consisting of H, d - C 4 alkyls
  • 22 z is an integral value ranging from 4 to 9 inclusive
  • 23 b is 0 or 1 ;
  • each n is independently selected from integers having a value of from 0 to 4.
  • the alkyl group having 1 to 10 carbon atoms may be linear or branched. Examples
  • alkyl group examples include methyl, ethyl, propyl, butyl, octyl, decyl and the like.
  • the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, cumyl, naphthyl and the
  • Examples of the aralkyl group having 7 to 10 carbon atoms include benzyl, 2-
  • Ri ⁇ and R19 are preferably independently
  • the alkylene group having 1 to 10 carbon atoms may be linear or branched.
  • Examples of ⁇ the alkylene group include methylene, 1 ,2-ethylene, 2,2-propylene, 2,2-butylene, 1 ,1 -
  • Examples of the alkylidene group having 2 to 10 carbon atoms o include ethylidene, propylidene, butylidene, hexylidene and the like.
  • Examples of the 1 cycloalkylene group having 6 to 10 carbon atoms include 1 ,4-cyclohexylene, 2-isopropyl- 2 1 ,4-cyclohexylene and the like.
  • Examples of the cycloalkylidene group having 6 to 10 3 carbon atoms include cyclohexylidene, isopropylcyclohexylidene and the like.
  • Examples 4 of the alkylene-arylene-alkylene group having 8 to 15 carbon atoms include m- 5 diisopropylphenylene group and the like.
  • W is preferably a cyclohexylidene group or 2,2- 6 propylidene group, particularly preferably 2,2-propylidene group.
  • the aromatic polycarbonate resin used in the present invention 8 is obtained by melt polymerization in which a dihydric phenol and a carbonate precursor 9 are subjected to ester interchange reaction.
  • hydroquinone hydroquinone, resorcinol, 1 ,6-dihydroxynaphthalene, 1 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, 1 ,1- 2 bis(4-hydroxyphenyl)-1 -phenylmethane, bis ⁇ (4-hydroxy-3,5-dimethyl)phenyl ⁇ methane, 1 ,1- 3 bis(4-hydroxyphenyl)ethane, 1 ,2-bis(4-hydroxyphenyl)ethane, 1 ,1-bis(4-hydroxyphenyl)-1 - 4 phenylethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1 - 5 naphthylmethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as: bisphenol A
  • a homopolymer of bisphenol A is particularly preferable.
  • the carbonate precursor there is used a carbonate ester or a haloformate.
  • Diphenyl carbonate, a dihaloformate of a dihydric phenol, or the like is preferably used, and diphenyl carbonate is more preferably used.
  • These carbonate esters can be used singly or in combination of two or more kinds.
  • the polycarbonate resin may be a
  • ⁇ polycarbonate resin a mixture of two or more polycarbonate resins may be used as the ⁇ polycarbonate resin.
  • fluoroglucine As the aromatic compound having three or more functional groups, there can be o mentioned fluoroglucine; fluoroglucide; trisphenols such as 4,6-dimethyl-2,4,6-tris(4- 1 hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1 ,3,5-tris(4- 2 hydroxyphenyl)benzene, 1 ,1 ,1-tris(4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(3,5-dimethyl-4- 3 hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4- ⁇ 4-[1 ,1-bis(4- 4 hydroxyphenyl)ethyl]benzene ⁇ - ⁇ , ⁇ -dimethylbenzylphenol and the like; tetra(4- 5 hydroxyphenyl)methane; bis(
  • reaction by melt polymerization is an ester interchange reaction between 3 dihydric phenol and carbonate ester, and is conducted by mixing, with heating, a dihydric 4 phenol and a carbonate ester in the presence of an inert gas and distilling the formed 5 alcohol or phenol.
  • the reaction temperature is ordinarily in a range of 120 to 350°C, 6 although it differs depending upon, for example, the boiling point of formed alcohol or 7 phenol.
  • the reaction system is made vacuum about 10 to 8 0.1 Torr (1 ,333 to 13.3 Pa) to make easy the distillation of the formed alcohol or phenol.
  • the reaction time is ordinarily about 1 to 4 hours.
  • a polymerization catalyst may be used for accelerating 1 the polymerization speed.
  • the polymerization catalyst there can be used, for example, 2 a catalyst consisting of (i) an alkali metal compound and/or (ii) a nitrogen-containing basic 3 compound; and condensation is conducted.
  • alkali metal compound used as the catalyst there can be mentioned, for example, hydroxides, hydrogencarbonates, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearates, boron hydrides, benzoates, hydrogenphosphates, bisphenol salts and phenol salts of alkali metals.
  • the alkali metal compound as the catalyst can be used in an amount of 10 "9 to 10 "4 moles, preferably 10 "8 to 10 "5 moles per mole of the dihydric phenol.
  • An amount deviating from the above range is not preferred because it adversely affects the properties of the polycarbonate obtained or the ester interchange does not proceed sufficiently, making impossible the production of a polycarbonate of high molecular weight.
  • ammonium hydroxides having an alkyl group, aryl group, alkylaryl group or the like such as tetramethylammonium hydroxide (Me NOH), tetraethylammonium hydroxide (E NOH), tetrabutylammonium hydroxide (Bu NOH), benzyltrimethylammonium hydroxide ( ⁇ -CH 2 (Me) 3 NOH), hexadecyltrimethylammonium hydroxide and the like; tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, hexadecyldimethylamine and the like; and basic salts such as tetramethylammonium borohydride (Me 4 NBH 4 ), tetrabutylammonium borohydride (Bu NBH 4 ), tetrabutylammonium te
  • Me NOH tetramethylammonium hydroxide
  • tetramethylammonium hydroxide Me NOH
  • E NOH tetraethylammonium hydroxide
  • Bu 4 NOH tetrabutylammonium hydroxide
  • tetramethylammonium hydroxide Me 4 NOH
  • the above nitrogen-containing basic compound is used preferably in such an amount that the ammonium nitrogen atom in nitrogen-containing basic compound comes to be 1 x10 '5 to 1 x10 "3 equivalent per mole of the dihydric phenol.
  • the amount is more preferably 2x10 "5 to 7x10 "4 equivalent on the same basis.
  • the amount is particularly preferably 5x10 '5 to 5x10 "4 equivalent on the same basis.
  • a catalyst generally used in esterification or ester interchange reaction such as alkoxides of alkali metal or alkaline earth metal, organic acid salts of alkali metal or alkaline earth metal, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, or the like.
  • These catalysts may be used singly or in combination of two or more kinds.
  • the use amount of such a polymerization catalyst is selected in a range of preferably 1x10 "9 to 1x10 "5 equivalent, more preferably 1 x10 "8 to 5x10 "6 equivalent per mole of the raw material dihydric phenol.
  • a compound such as phenol, p-tert-butyl phenol, p-tert-butylphenylphenyl carbonate, p-tert-butylphenyl carbonate, p-cumylphenol, p-cumylphenylphenyl carbonate, p-cumylphenyl carbonate, bis(chlorophenyl) carbonate, bis(bromophenyl) carbonate, bis(nitrophenyl) carbonate, bis(phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenyl
  • 2-chlorophenylphenyl carbonate 2- methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate
  • 2-methoxycarbonylphenylphenyl carbonate it is preferred to block the terminals of the aromatic polycarbonate with a terminal-blocking agent. It is also preferred to control the terminal hydroxyl group concentration of the aromatic polycarbonate resin before blocking the terminal with a terminal-blocking agent, to 20 mole % or more, preferably 30 mole % or more, further preferably 40 mole % or more, based on the total terminals.
  • a specified terminal group can be introduced at a high proportion and the aromatic polycarbonate resin can be improved at a high level.
  • a terminal-blocking agent to an aromatic polycarbonate resin whose terminal hydroxyl group concentration is 30 to 95 mole % of the total terminals.
  • the proportion of terminal hydroxyl group in aromatic polycarbonate resin before blocking the terminal with terminal blocking agent can be controlled by the ratio of raw materials fed, i.e. dihydric phenol and diphenyl carbonate.
  • the terminal hydroxyl group concentration (moles) of a determined amount of aromatic polycarbonate resin can be determined by an ordinary method, i.e., 1 H-NMR.
  • the terminal hydroxyl group concentration in the aromatic polycarbonate resin of the present invention is preferably 0 to 40 mole %, more preferably 0 to 18 mole %, further preferably 0 to 9 mole %, most preferably 0 to 7 mole % of the total terminals.
  • “0 mole %” indicates "not detectable” when the measurement was made by 1 H-NMR.
  • the terminal hydroxyl group concentration is in the above range, further improvement in wet heat fatigue and impact resistance of flat can be obtained.
  • it is preferred that the catalytic activity of the aromatic polycarbonate resin is neutralized by using a deactivator.
  • benzenesulfonic acid As specific examples of the deactivator, there can be mentioned benzenesulfonic acid; p-toluenesulfonic acid; sulfonic acid esters such as methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p- toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p- toluenesulfonate, phenyl p-toluenesulfonate and the like; trifluoromethanesulfonic acid; naphthalenesulfonic acid; sulfonated polystyren
  • 4 compounds may be used in combination of two or more kinds.
  • a phosphonium or ammonium salt-based deactivator is
  • the deactivator when added to an
  • Such a deactivator is used in an amount of preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, o particularly preferably 0.01 to 100 ppm relative to the polycarbonate formed after i polymerization. 2
  • Such a deactivator is used in an amount of preferably 0.5 to 50 moles per mole of 3 the polymerization catalyst.
  • the method of adding the 4 deactivator to the aromatic polycarbonate resin after polymerization may be added while the reaction product, i.e. the aromatic polycarbonate 6 resin, is in a molten state; or, the deactivator may be added after the aromatic 7 polycarbonate resin is once pelletized and then remelted.
  • the deactivator is added thereto to form an aromatic 0 polycarbonate resin and then, the resin is passed through an extruder for pelletization; or, 1 the addition of the deactivator and subsequent kneading may be conducted while the 2 aromatic polycarbonate resin after polymerization is passed through an extruder for 3 pelletization, to obtain an aromatic polycarbonate resin.
  • the polymerization 6 catalyst In production of an aromatic polycarbonate resin by melt polymerization, when a 5 polymerization catalyst is used for acceleration of the polymerization, the polymerization 6 catalyst often remains in the aromatic polycarbonate resin after polymerization.
  • the aromatic polycarbonate resin causes 8 trouble such as decomposition or post-reaction owing to the catalytic activity of the 9 residual catalyst. Further, in a composition between such an aromatic polycarbonate resin 0 having a residual catalytic activity and a filler, the adverse effect of the residual catalyst is 1 increased and, moreover, new problem such as reduction in impact resistance of flat and 2 the like may arise. Therefore, it is preferred to control the residual catalytic activity.
  • "Residual catalytic activity index" is used as a yardstick for controlling the residual catalytic activity, and the index is measured as follows.
  • a rotary rheometer which can measure the range of the melt viscosity of a sample resin to be tested; the sample resin is placed in a sufficient nitrogen current so as to prevent the sample resin from being oxidized by external oxygen and is rotated in a given direction at a given angular velocity under the condition of a given temperature at which the sample resin is melted, and the change of the melt viscosity of the sample resin during the rotation is measured.
  • a jig for rheometer used in the measurement, the one having a cone- circular plate shape is used so that the strain of the whole sample becomes constant, that is, the shear speed of the sample becomes constant.
  • the change of melt viscosity per minute is used as residual catalytic activity index.
  • Residual catalytic activity index (%) [(melt viscosity after 30 minutes-melt viscosity after 5 minutes) divided by ((melt viscosity after 5 minutes) x 25)] x 100
  • the residual catalytic activity index is preferably 2% or less, more preferably 1 % or less, further preferably 0.5% or less, most preferably 0.2% or less.
  • a residual catalytic activity index of this range is preferred because the aromatic polycarbonate resin shows little property change with time.
  • the polycarbonate will be a branched polycarbonate.
  • the branched polycarbonate resin can be obtained by the same process for production as conventional processes for production according to a phosgene process except the steps comprising forming a reaction mixture while adding phosgene in bisphenol and trihydric or above phenol and after the completion of addition of phosgene, adding a tetraammonium salt to the reaction mixture to perform polycondensation reaction, then adding both monohydric phenol and a tertiary amine catalyst to the reaction mixture, further preforming polycondensation reaction, thereby obtaining a branched polycarbonate resin wherein number of dichloromethane insoluble gel-like particles with a particle diameter more than 50 ⁇ m is preferably 10 or below per 100 g of the resin.
  • Examples of bisphenols as a raw material to derive the branched polycarbonate resin include 4,4'-biphenyldiol, 1 ,1'-bi-2-naphthol, bis(4-hydroxyphenyl) methane, bis(4- hydroxphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4- hydroxyphenyl)sulf ⁇ de, bis(4-hydroxyphenyl)ketone, 1 ,1 -bis(4-hydroxyphenyl)ethane, 2,2- bis(4-hydroxyphenyl) propane(bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl) butane, 1 ,1 - bis(4-hydroxyphenyl)cyclohexane(bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3,5- dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dich
  • branching agents examples include phloroglucin, 2,4,4'- trihydroxybenzophenone, 2,4,4'-trihydroxydiphenylether, 2,2-bis(2,4-dihydroxyphenyl) propane, 2,2',4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 2,6- dimethyl-2,4,6-tri(4-hydroxyphenyl)-heptene-3, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)- heptane-2, 2,6-bis(2-hydroxy-5-methylbezil)-4-methylphenol, 2,6-bis(2-hydroxy-5- isopropylbenzil)-4-isopropylphenol, tetrakis(4-hydroxyphenyl)methane, ⁇ . ⁇ ', ⁇ "-tris(4- hydroxyphenyl)-1 ,3,5-triisopropylbenzene, 1 ,1-bis(4-hydroxyphen
  • Examples of 1 ,1 ,1 -tris(4-hydroxyaryl)alkanes include 1 ,1 ,1 -tris(4- hydroxyphenyl)methane, 1 ,1 ,1 -tris(4-hydroxyphenyl)ethane, 1 ,1 ,1-tris(4-hydroxyphenyl) propane, 1 ,1 ,1 -tris(2-methyl-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(2-methyl-4- hydroxyphenyl)ethane, 1 ,1 ,1 -tris(3-methyl-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3-methyl- 4-hydroxyphenyl)ethane, 1 ,1 ,1 -tris(3,5-dimethyl-4-hydroxyphenyl)methane, 1 ,1 ,1-tris(3,5- dimethyl-4-hydroxyphenyl)ethane, 1 ,1
  • the amount of branching agent to be used for the branched polycarbonate resin is optionally selected within the range able to maintain characteristics of the branched polycarbonate resin. Considering the range to depress production of solvent insoluble three dimensional polymer and to exhibit good non-Newtonian characteristic, it is preferable that the amount is 0.1 to 3.0 mole % to bisphenol.
  • Examples of monohydric phenols as molecular weight modifier include phenol, alkyl phenols including p-t-butylphenol, cumyl phenol, tribromophenol, p-n-octyl phenol and p-n- stearylphenol, alkylether phenols including p-n-butoxyphenols and p-n-octyloxyphenol and alkyl hydroxybenzoates including n-butyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate and n-stearyl p-hydroxybenzoate.
  • the monohydric phenol to be used as molecular weight modifier is added so as to able to maintain the molecular weight of the branched polycarbonate resin to preferable molecular weight range as molding material.
  • the amount of monohydric phenol to be added is 0.5 to 10 mole % and preferably 1 to 5 mole % to bisphenol.
  • Phosgene is used usually in the range of 100 to 140 mole and preferably 105 to 120 mole per 100 mole of bisphenol.
  • the injection time of phosgene is usually 10 to 120 minutes and preferably 15 to 60 minutes.
  • acid bonding agent such as pyridine, alkali metal hydroxides including sodium hydroxide and potassium hydroxide, etch, is used, among which preferably sodium hydroxide is used. It is preferable that the molar ratio of sodium hydroxides to bisphenol(s) is 2.0/1 to 3.5/1.
  • Sodium hydroxide is used in the state of an aqueous solution. It is preferable that the concentration of sodium hydroxide in the aqueous solution is 6 to 10 (weight/volume) %.
  • Water to be used herein is distilled water, ion exchange water or water recovered in the production of polycarbonate resin.
  • oxidation inhibitor such as sodium sulfite, hydrosulfite, etc.
  • a small amount of oxidation inhibitor such as sodium sulfite, hydrosulfite, etc.
  • oxidation inhibitor such as sodium sulfite, hydrosulfite, etc.
  • tetraammonium salts to be added after the completion of injection of phosgene include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium iodide, etc., among which trimethylbenzylammonium chloride and triethylbenzyl ammonium chloride are preferable.
  • the tetraammonium salt is used usually in 0.0005 to 5 mole % to bisphenol.
  • the tetraammonium salt is added in the state of an aqueous solution so as to be dispersed sufficiently over the whole of the reaction system. It is preferable that the concentration of tetraammonium salt in the aqueous solution is 0.1 to 20 (weight/volume) %.
  • the aqueous solution is added to the reaction mixture, preferably together with sodium hydroxide, after the completion of injection of phosgene.
  • the time at which a viscosity average molecular weight (Mv) of the reaction mixture reaches to 3,000 or above and less than 6,000 after the completion of addition of the tetraammonium salt is 3 to 20 minutes, depending upon the reaction temperature and stirring conditions. All the amount of the acid bonding agent to be used may be initially charged or 70 to 96% of the amount of the acid bonding agent to be used may be initially charged and then 2 to 28% of the acid bonding agent at the time of addition of tetraammonium and 2 to 28% of the acid bonding agent at the time of addition of monohydric phenol may be further added.
  • the polymerization catalysts include tertiary amines such as triethylamine, tertiary phosphine, tetraphosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, and compounds having an amido group(s), among which tertiary amines such as triethylamine are preferable.
  • the amount of the polymerization catalyst to be added is 0.01 to 1 mole % to bisphenol.
  • the organic solvent is an organic compound which is insoluble in water and inert for the reaction and furthermore can dissolve polycarbonate produced by the reaction Examples of the organic solvents include chlorinated aliphatic hydrocarbons including dichloromethane, tetrachloroethane, chloroform, 1 ,2-dichloroethane, trichloroethane and dichloroethane, chlorimated aromatic hydrocarbons including chlorobenzene, dichlorobenzene and chlorotoluene, acetophenone, cyclohexane, anisole, etc, and a mixture thereof, among which dichloromethane is most preferably used.
  • A represents single bond, an alkylene or alkylidene group having from 1 to 20 carbon atoms, a polymethylene group having from 3 to 20 carbon atoms, a cycloakylene or cycloalkylidene group having from 5 to 20 carbon atoms, an arylene or arylalkylene group having from 6 to 20 carbon atoms, -O-, -CO-, -S-, -SO-, or -SO 2 ⁇ ;
  • R 35 represents H, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an arylalkyl group having from 7 to 20 carbon atoms;
  • R 36 represents a halogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an arylalkyl group having from 7 to 20 carbon atoms; and
  • p is an integral value of from 0 to 4 inclusive
  • Still other methods of producing branched polycarbonates include the use of a tri- to hexahydric aliphatic alcohol of the following formula
  • R 37 and R 39 are independently selected from the group consisting of H, a linear Ci - C 30 alkyl, a branched C 3 - C 36 alkyl or R 40 — OH; and wherein
  • R 4 o is selected from the group consisting of linear Ci - C 36 alkylene and branched C 3 - C 36 branched alkylene; and p is an integral value ranging from 2 to 5 inclusive; and R 38 is selected from the group consisting of a single bond, a linear Ci - C 36 alkylene or a branched C 3 - C 36 alkylene. Still yet other methods for producing branched polycarbonates will utilize the branching agent shown below
  • R ⁇ , R 2 , and Rj 3 are independently selected from the group consisting of H,
  • branched polycarbonate resins may be prepared using interfacial polymerization processes wherein, typically, a polyhydric phenol having more than two hydroxy groups in the molecule is reacted with an aromatic dihydroxy compound and carbonic acid derivative in the presence of a chain terminating or molecular weight controlling agent Suitable polyhydric phenols are disclosed in the references cited above and include, for example, 1 ,1 ,1-tris-(4-hydroxyphenyl)-ethane (THPE), 1 ,3,5 tris-(4- hydroxyphenyl)-benzene, 1 ,4 bis-(4', 4"-dihydroxy-triphenylmethyl)-benzene and the like.
  • THPE 1 ,1 ,1-tris-(4-hydroxyphenyl)-ethane
  • THPE 1,3,5 tris-(4- hydroxyphenyl)-benzene
  • branching agents include cyanuric chloride, branched dihydric phenols, 3,3-bis-(4-hydroxyaryl)oxindoles, and aromatic polycarbonates end-capped with branched alkyl acyl halides and/or acids.
  • Another suitable branching agent is trimellitic triacid chloride.
  • the aromatic dihydroxy compounds, carbonate precursors, and chain terminating or molecular weight controlling agents recited previously herein for use in the preparation of linear aromatic polycarbonates are also suitable for preparation of the branched aromatic polycarbonate starting material.
  • Linear aromatic polycarbonate resin to branched chain polycarbonate is effected by contacting the resin with a polyhydric branching agent having more than two hydroxy groups per molecule in the presence of a catalytic amount of a suitable carbonate equilibration catalyst.
  • the branched polycarbonate resins of this invention may also be prepared from the commercially available aromatic branched polycarbonate resins described above by contacting the conventional resin with a polyhydric branching agent having more than two hydroxy groups per molecule in the presence of a catalytic amount of a suitable carbonate equilibration catalyst.
  • reaction is initiated by the formation in-situ of a reactive phenoxide from reaction of the equilibration catalyst with the polyhydric branching agent which can thereafter readily undergo an addition reaction with electrophilic carbonate carbon atoms on the linear polycarbonate backbone causing chain scission to form a lower molecular weight fragment and a branched aromatic polycarbonate. It is further believed that the reaction continues until equilibration is attained and a product having a new molecular weight distribution and which has shorter branched chains than the linear aromatic or branched aromatic polycarbonate substrate is formed.
  • Polyhydric phenols suitable as branching agents in the present invention include any triol or tetrol or higher hydroxy substituted polyhydric phenol, for example, 1 , 1 , 1 -tris- (4- hydroxyphenyl)ethane (or 4,4', 4"-ethylidyne trisphenol or THPE); 1 ,3,5-tris-(2- hydroxyethyl) cyanuric acid ([1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-triazine-2,4,6-(1 H, 3H, 5H)- trione]; 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane-2; 2,2-bis-4,4-(4,4"- dihydroxyphenyl)-cyclohexyl propane; 1 ,3,5-trihydroxybenzene (phloroglucinol)); 1 ,2,3- trihydroxybenzene (pyrogallol); and 1
  • polyhydric phenols useful herein include, for example, 2', 3', 4'-trihydroxyacetophenone; 2,3,4-trihydroxybenzoic acid; 2,3,4- trihydroxybenzophenone; 2,4,4'-trihydroxybenzophenone; 2', 4', 6'-trihydroxy-3-((4- hydroxyphenyl)propiophenone; (phloretin); pentahydroxyflavone; 3,4,5- trihydroxyphenylethylamine (5-hydroxydopanine); 3,4-trihydroxyphenethyl alcohol; 2,4,5- trihydroxypyrimidine (isobarbituric acid); tetrahydroxy-1 , 4-quinone hydrate (tetrahydroxy- 1 ,4'-benzoquinone); 2,2', 4,4'-tetrahydroxybenzophenone; and 1 ,2,5,8- tetrahydroxyanthraquinone (quinalizarin).
  • Suitable carbonate equilibration catalysts include various bases and Lewis acids, and in general, any of those catalysts known for effecting polymerization of cyclic polycarbonate oligomers.
  • bases include lithium 2,2,2- trifluoroethoxide, n-butyllithium, tetramethyl-ammonium hydroxide, and various weakly basic salts such as sodium benzoate and lithium stearate.
  • useful Lewis acids include dioctyltin.
  • triethanolamine titanium isopropoxide triethanolamine titanium isopropoxide
  • tetra(2-ethylhexyl) titanate and polyvalent metal chelates such as aluminum acetylacetonate, bisisopropoxy titanium bisacetylacetonate, and the bisisopropoxy aluminum salt of ethyl acetoacetate.
  • carbonate equilibration catalysts are coordination compounds as employed as polycarbonate formation catalysts.
  • Such a class of basic catalyst compounds is preferred in the practice of the present invention as they are able to generate phenoxides upon contact with the polyhydric phenol branching agents thus providing strong nucleophiles which can readily undergo an addition reaction with the substrate electrophillic carbon atoms.
  • Illustrative examples of such preferred catalysts include tetrabutylammonium tetraphenylborate, tetramethylammonium tetraphenylborate, lithium tetraphenylborate, sodium tetraphenylborate, sodium bis-2,2'-biphenyleneborate, potassium tetraphenylborate, tetramethylphosphonium tetraphenylborate, tetra-n-butylphosphonium tetraphenylborate and tetraphenylphosphonium tetraphenylborate.
  • the choice of any particular catalyst selected is not critical and the use herein of such catalysts described above or similar catalysts may depend upon such factors as their ⁇ thermal stability, the desired rate of reaction and the chemical nature of the particular
  • thermoplastic branched-chain polycarbonate is prepared by melt condensation at a
  • the level of 2 polyhydric branching agent is not critical to the practice of the present invention as varying 3 the level of branching agent will effect the number of branching sites and the average 4 branched polycarbonate chain length. For example, low levels of branching agents will s produce few branching points with relatively long chains, and higher levels will increase 6 the number of branching points, but will decrease the average length of the chains. The 7 amount of branching agent, therefore, will depend upon the various properties of particular s branched polycarbonates desired and end uses contemplated.
  • the polyesters as used in this invention have a dicarboxylic 3 acid component and a glycol component, the dicarboxylic acid component comprising 4 repeat units from at least 90 mole % terephthalic acid and the glycol component 5 comprising repeat units from about 10-95 mole % 1 ,4-cyclohexanedimethanol and from 6 about 90-5 mole % ethylene glycol, the process comprising reacting the dicarboxylic acid 7 component and the glycol component at temperatures sufficient to effect esterification or 8 ester exchange and polycondensing the reaction product under an absolute pressure of 9 less than 10 mm Hg for a time of more than about 2 hours in the presence of a catalyst 0 and inhibitor system consisting essentially of about 0-75 ppm Mn, about 25-
  • the PCTG polymer a poly(1 ,4-cyclohexanedimethylene terephthalate-co-ethylene terephthalate) polymer has a number average molecular weight of about 26,000.
  • PCTG 5445 (CAS No. 25640-14-6) is a poly(cyclohexylenedimethlene terephthalate) modified with 34 mole percent ethylene glycol)
  • PCTG 10179 is a poly(cyclohexylenedimethylene terephthalate) modified with 19 mole percent ethylene glycol.
  • PCTG-like polymer will be of the following formula:
  • R 22 is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent C-i -C ⁇ hydrocarbon radicals, alkylidene groups having from C 2 - C 10 carbon atoms, cycloalkylene group having C 6 - do carbon atoms, cycloalkylidene groups having from C ⁇ - C 10 carbon atoms;
  • R 23 is selected independently from the group consisting of R 22 ;
  • R 24 is selected independently from the group consisting of R 23 ;
  • R 2 sand R2 6 are independently selected from the group consisting of halogen, hydrogen, monovalent C-i - C 10 alkyls, monovalent Ci - C- 6 alkoxy radicals, aryl groups having from C 6 - do carbon atoms, aralkyl groups having from C 7 - C 10 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m an n are integral values ranging from 0 to 4 inclusive; and x and y are as defined previously.
  • PCTA is another example of a polyester suitable for use in this invention. PCTA polymers will have the following formula.
  • PCTA 6761 (CAS No. 36487-02-2) is a poly(cyclohexylenedimethylene terephthalate) modified with 5 mole percent isophthalic acid and wherein v ranges from 0.01 to 0.40 inclusive, preferably 0.03 to 0.30, most preferably
  • a PCTA-like polymer will be of the following formula:
  • R 2 7 is selected from the group consisting of a covalent bond, substituted or unsubstituted divalent Ci -C 8 hydrocarbon radicals, alkylidene groups having from C 2 - C 10 carbon atoms, cycloalkylene group having C ⁇ - do carbon atoms, cycloalkylidene groups having from C 6 - do carbon atoms;
  • R 2 ⁇ is selected independently from the group consisting of R 27 ;
  • R 2 g is selected independently from the group consisting of R 2 ⁇ ;
  • R 3 o is selected independently from the group consisting of R 29 ;
  • R31 and R 32 are independently selected from the group consisting of halogen, hydrogen, monovalent Ci - do alkyls, monovalent d - C 6 alkoxy radicals, aryl groups having from C ⁇ - do carbon atoms, aralkyl groups having from C7 - C10 carbon atoms, nitro, cyano, thioalkyl, and substituted derivatives thereof and combinations thereof; m and n are as previously defined; and v and w are as previously defined. Either dimethyl terephthalate (or other lower dialkyl terephthalate ester) or terephthalic acid can be used in producing the copolyester. These materials are commercially available.
  • the glycols used in the copolyester according to the present invention are CHDM and ethylene glycol. Both of these glycols are commercially available.
  • the copolyesters used in making the articles of this invention have 100 mole % of a dicarboxylic acid portion and 100 mole % of a glycol portion.
  • the dicarboxylic acid portion of the copolyesters comprises repeat units from at least 90 mole % terephthalic acid.
  • Up to about 10 mole % of the dicarboxylic acid repeat units may be from other conventional acids such as those selected from succinic, glutaric, adipic, azelaic, sebacic, fumaric, maleic, itaconic, 1 ,4-cyclohexanedicarboxylic, phthalic, isophthalic, and naphthalene dicarboxylic acid.
  • the glycol component of the copolyesters contains repeat units from about 10-95 mole % 1 ,4-cyclohexanedimethanol and about 90-5 mole % ethylene glycol.
  • the glycol component may include up to about 10 mole % of conventional glycols such as propylene glycol, 1 ,3-propanediol; 2,4-dimethyl-2-ethylhexane-1 ,3-diol, 2,2-dimethyl-l,3-propanediol, 2-ethyl-2-butyl-1 ,3-propanediol, 2-ethyl-2-isobutyl-1 ,3-propanediol, 1 ,3-butanediol, 1 ,4- butanediol, neopentyl glycol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,8-octanediol, 2,2,4- trimethyl-1 ,6-hexanediol, thiodiethanol, 1 ,2-cyclohexanedimethanol, 1
  • the diacid component of the polyester includes aromatic groups and wherein the diol component of the polyester comprises at least a portion of a non-cyclic aliphatic diol.
  • the diacid component will be considered to be aromatic if at least about 50 mole percent of the diacid is aromatic.
  • mixtures of diacids can be used. Useful diacid or diesters result in repeating units represented by the following formulas:
  • a is an integer from 0 to 4 inclusive and each R 20 is independently selected from the group consisting of hydrogen, alkyl groups having from 1 to about 4 carbons and halogens.
  • the second component of the polyester is a diol component which can include cyclic components.
  • Useful diol components result in repeating units which have the following structure:
  • R 21 represents a straight or branched alkylene group of from to about 1 to 10 carbons.
  • R 21 represents a straight or branched alkylene group of from to about 1 to 10 carbons.
  • the copolyesters may be produced using conventional polyesterification procedures described, for example, in U.S. Pat. Nos. 3,305,604 and 2,901 ,460.
  • esters of the acids e.g., dimethyl terephthalate
  • Either the cis or trans isomer of CHDM, or mixture thereof, may be used in accordance with the present invention.
  • a reaction mix of the dicarboxylic acids (or esters as described herein) and glycols is prepared. Mn and/or Zn and Ti are added at the beginning of the process (ester exchange reaction). P and Co (if used) are added after ester exchange. The catalysts and inhibitors can be mixed or added separately. Preferably, P is added after Co. ⁇
  • the ester interchange reaction the preparation of polyesters by means of the ester interchange reaction, the
  • glycol and diester such as dimethyl
  • the second step, or polycondensation step, is continued under higher
  • polyesters are produced by i reacting a free dicarboxylic acid with a glycol at a pressure of from about 1 to about 1000 2 pounds per square inch gauge pressure to produce a low molecular weight linear or 3 branched polyester product having an average degree of polymerization of from about 1.4 4 to about 10. This low molecular weight polymer can then be polymerized by s polycondensation reaction. 6
  • the present process can be advantageously operated as a continuous process.
  • High molecular weight linear or branched polyesters can be produced continuously by s continuously adding free dicarboxylic acid and glycol to molten low molecular weight linear 9 or branched polyester resin and reacting them while continuously withdrawing low 0 molecular weight resin and introducing the resin withdrawn into a polymerization 1 apparatus and continuously polymerizing it to high molecular weight resin and withdrawing 2 high molecular weight linear or branched polyester resin from the polymerization 3 apparatus.
  • manganese is preferably used as a salt.
  • manganese 5 salts are manganous benzoate tetrahydrate, manganese oxide, manganese acetate, 6 manganese acetylacetonate, manganese succinate, manganese glycolate, manganese 7 naphthanate and manganese salicyl salicylate.
  • the zinc portion of the catalyst system is preferably added as a salt.
  • suitable salts include zinc acetate, zinc citrate, zinc lactate, zinc nitrate, zinc glycolate, etc. 0
  • the titanium is preferably added as titanium tetraalkoxide, e.g., titanium 1 tetraisopropoxide, titanium tetraethoxide or titanium tetrabutoxide.
  • the phosphorus is preferably added as trialkyl phosphate, triphenyl phosphate, or 3 phosphoric acid.
  • the blue toner is preferably cobalt, and is preferably added as a salt.
  • suitable cobalt salts are cobaltous acetate tetrahydrate, cobaltous nitrate, cobaltous chloride, cobalt acetylacetonate, cobalt naphthanate and cobalt salicyl salicylate.
  • the levels of the catalysts and inhibitors used with dimethyl terephthalate based copolymers are as follows: Mn, from 0 to 75 ppm, preferably from 20 to 50 ppm, (catalyst); Zn, from 25 to 100 ppm, preferably from 50 to 80 ppm, (catalyst); Ti, from 0.5 to 15 ppm, preferably from 1 to 6 ppm (catalyst); and P, from 5 to 80 ppm, (inhibitor), preferably 10 to 30 ppm.
  • Other mild catalysts, such as Ge can be added but are not necessary.
  • Co from 0 to 60 ppm or an organic blue toning agent at the proper level to control the color.
  • the levels of the catalysts for terephthalic acid based copolymers are as follows: Zn, from 25 to 100 ppm, preferably from 50 to 80 ppm, (catalyst); Ti from 0.5-15 ppm, preferably from 1 to 6 ppm; P, from 5 to 80 ppm, (inhibitor), preferably from 10 to 30 ppm; Co from 0 to 60 ppm or an organic blue toning agent at the proper level to control the color.
  • Other mild catalysts, such as germanium, can be added but are not necessary.
  • Compact discs have been made from alloys of polycarbonate and PCTG clear plastics. Specific ranges in the composition used include 50% PC / 50% PCTG as well as 20% PC / 80% PCTG. These CD's show significant improvements in durability, ductility, impact, chemical resistance, and processability.
  • a 10% polycarbonate (Makrolon 1239) / 90% polyester (PCTG 5445) was molded an extruder with the following physical properties illustrated in Table III.
  • Example #4 The injection molding conditions for molding the specimens were as follows in Table V.
  • a quality control chart from EMI Records is provided for a 20% PC / 80% PCTG 5445 polyester blend as tested as a CD.
  • the test involved a CD-Digital Audio test involving 18 tracks with a total playing time of 74.22 minutes.
  • Discs manufactured have passed current production quality control in all aspects, for the manufacture of CD audio as illustrated in Table VI, a quality control chart from EMI Records for an -80% PCTG / 20% PC alloy.
  • the ability to process at lower temperatures saves energy, slows degradation, reduces optical black specs and enables the incorporation of thermally unstable dyes, inks and other chemicals for new innovation in CDR, CDRW and other inked discs.
  • the improvement in impact and ductility add service life to the optical medial which is significant in storage. It is now possible to sit on a CD made of the blends of this invention and not break the CD.
  • the discs may contain various ratios of PC to PCTG and various melt index or
  • the ratio of polycarbonate e / copolyester will be from ⁇ 100% PCTG / 0% PC to -5% PCTG / 95% PC. It is more
  • Painted/Coated No Yes Yes Yes 3 4 The improved elongation and impact permit these interior parts to be unpainted or 5 coated while becoming safer and more durable with less manufacturing. 6 The same remains true for extruded sheets with respect to clarity, impact ductility, 7 improved chemical resistance and environmental aging. These sheets may be used as 8 glazing, panels, signs, displays, booths, stalls, cubicles, etc. ⁇ In one particular embodiment of the invention, five (5) gallon water bottles
  • heterogeneous blends of partially miscible polymers are regarded as materials of 1 particular importance.
  • Polycarbonate attracts much attention because of its outstanding mechanical 3 properties.
  • the transesterification reaction may generate some block copolymers of polyester and o polycarbonate in the interfaces of the blends and these copolymers may be functioning as i a compatibilizer to improve the interfacial bonding for the phase-separated 2 polyester/polycarbonate blends.
  • the copolyester and/or copolyester/polycarbonate blends are useful in the following 4 applications: 5 Optical media, e.g., CD, DVD, CDR, CDRW, minidisc, VCD, and all other forms of 6 digital optical media; eyewear including glasses, lenses, sunglasses, safety glasses, 7 screens; transportation including interiors, e.g., instrument panels, bolsters, bezels, boxes, 8 covers, holders, knobs, pedals, rests, ducts, lenses, glazing and trim as well as exterior 9 applications, e.g., hubcaps, body parts, bumpers, panels, doors, hoods, fenders, lights, 0 and trim; appliances including housings, panels, displays, bins, trays, covers, boards, 1 bases, bezels, fans, coffee makers, computer housings, etc.; electronics including 2 housings, covers, displays, bezels, boxes, storage, memory, optics, trays, keyboards, 3 mice, conductors, insulators, diodes, capacitor
  • polycarbonate has been used in the manufacture of water receptacles
  • compositions of this invention are equally sized
  • the articles of this invention are characterized by improved physical properties, and ⁇ include in general, automotive, truck, military vehicle, and motorcycle exterior and interior
  • the invention further contemplates additional fabrication operations on said

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Abstract

L'invention concerne des mélanges polymères polyester/polycarbonate présentant une diminution de la teneur en polycarbonate et même souvent une élimination du constituant polycarbonate. Cette invention est particulièrement utile pour une utilisation dans des supports optiques, mais également pour d'autres mises en application pour lesquelles on a déjà utilisé des polymères contenant polycarbonate. Ce mélange polymère comprend : 1) des polyesters et des copolyesters ainsi que leur mélange, associés à 2) des polycarbonates et à leur mélange, et présente des caractéristiques exceptionnelles de transparence, stabilité, résistance à la traction, résistance à l'élongation, résistance à l'impact, robustesse, ductilité et transformabilité, s'adressant en particulier à des disques optiques, des réservoirs à eau et des éléments automobiles, y compris des carénages frontaux.
PCT/US2002/020700 2001-07-05 2002-06-28 Composition de melange polyester/polycarbonate WO2003004561A2 (fr)

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WO2005066277A1 (fr) * 2003-12-31 2005-07-21 General Electric Company Composition de moulage a base de polyester polycarbonate
US7342059B2 (en) * 2003-01-13 2008-03-11 Eastman Chemical Company Polyester-polycarbonate blends useful for extrusion blow-molding
US7345104B2 (en) * 2003-12-16 2008-03-18 Eastman Chemical Company Polyester-polycarbonate blends useful for extrusion blow-molding
WO2008005626A3 (fr) * 2006-07-03 2008-03-27 Gen Electric Mélanges de polycarbonate-polyester transparents à performance améliorée dans des milieux aqueux caustiques
US7411021B2 (en) * 2003-12-18 2008-08-12 Sabic Innovative Plastics Ip B.V. Polycarbonate polyester molding composition
WO2008106868A1 (fr) * 2007-03-08 2008-09-12 Okia Optical Co., Ltd. Lunettes et montures de lunettes comprenant des copolyesters modifiés par un glycol
US7655737B2 (en) 2006-11-16 2010-02-02 Sabic Innovative Plastics Ip B.V. Polycarbonate-polyester blends, methods of manufacture, and methods of use
US8691915B2 (en) 2012-04-23 2014-04-08 Sabic Innovative Plastics Ip B.V. Copolymers and polymer blends having improved refractive indices
CN107987504A (zh) * 2017-12-12 2018-05-04 东莞市优特美工程塑料有限公司 耐高温易成型的pc/pctg材料及其制备方法

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US7342059B2 (en) * 2003-01-13 2008-03-11 Eastman Chemical Company Polyester-polycarbonate blends useful for extrusion blow-molding
US7345104B2 (en) * 2003-12-16 2008-03-18 Eastman Chemical Company Polyester-polycarbonate blends useful for extrusion blow-molding
US7411021B2 (en) * 2003-12-18 2008-08-12 Sabic Innovative Plastics Ip B.V. Polycarbonate polyester molding composition
WO2005066277A1 (fr) * 2003-12-31 2005-07-21 General Electric Company Composition de moulage a base de polyester polycarbonate
US7226973B2 (en) 2003-12-31 2007-06-05 General Electric Company Polycarbonate polyester molding composition
KR101197862B1 (ko) * 2003-12-31 2012-11-05 사빅 이노베이티브 플라스틱스 아이피 비.브이. 폴리카보네이트 폴리에스터 성형 조성물
US8114929B2 (en) 2006-07-03 2012-02-14 Sabic Innovative Plastics Ip B.V. Transparent polycarbonate-polyester blends with improved performance under caustic aqueous environments
WO2008005626A3 (fr) * 2006-07-03 2008-03-27 Gen Electric Mélanges de polycarbonate-polyester transparents à performance améliorée dans des milieux aqueux caustiques
US7655737B2 (en) 2006-11-16 2010-02-02 Sabic Innovative Plastics Ip B.V. Polycarbonate-polyester blends, methods of manufacture, and methods of use
US7753518B2 (en) 2007-03-08 2010-07-13 Okia Optical Co., Ltd Eyeglasses and eyeglass frames comprising glycol modified copolyesters
WO2008106868A1 (fr) * 2007-03-08 2008-09-12 Okia Optical Co., Ltd. Lunettes et montures de lunettes comprenant des copolyesters modifiés par un glycol
US8691915B2 (en) 2012-04-23 2014-04-08 Sabic Innovative Plastics Ip B.V. Copolymers and polymer blends having improved refractive indices
CN107987504A (zh) * 2017-12-12 2018-05-04 东莞市优特美工程塑料有限公司 耐高温易成型的pc/pctg材料及其制备方法

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AU2002315493A1 (en) 2003-01-21

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