WO2001027200A2 - Compositions ameliorees a base de poly(cyclohexylenedimethylene terephtalte) contenant des imides halogenes, des modificateurs de la resistance aux chocs a fonction de caoutchouc et des fibres de renforcement - Google Patents

Compositions ameliorees a base de poly(cyclohexylenedimethylene terephtalte) contenant des imides halogenes, des modificateurs de la resistance aux chocs a fonction de caoutchouc et des fibres de renforcement Download PDF

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WO2001027200A2
WO2001027200A2 PCT/US2000/024522 US0024522W WO0127200A2 WO 2001027200 A2 WO2001027200 A2 WO 2001027200A2 US 0024522 W US0024522 W US 0024522W WO 0127200 A2 WO0127200 A2 WO 0127200A2
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WO2001027200A3 (fr
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Gerald Timothy Keep
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Eastman Chemical Co
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Eastman Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • This invention relates to an improvement in toughness of a fiber reinforced, flame retardant (FR) poly(cyclohexylenedimethylene terephthalate) (PCT) formulation.
  • FR flame retardant
  • PCT poly(cyclohexylenedimethylene terephthalate)
  • HDT heat deflection temperature
  • United States Patent 5,021 ,495 by Minnick discloses high temperature glass fiber reinforced, flame retardant PCT formulations.
  • Minnick patent it is shown that use of functional olefins (not acrylate/methacrylate rubber impact modifiers) can improve flame retardancy without hurting dimensional stability. These materials did not improve the toughness of the PCT formulations.
  • United States Patent 5,428,086 discloses high temperature glass fiber reinforced, flame retardant PCT formulations. This patent discloses that certain additives can compromise the dimensional stability of the PCT formulation.
  • This invention relates to a polymer composition comprised of:
  • glycol component comprising from about 60 to 100 mole % 1 ,4-cyclohexanedimethanol
  • a preferred embodiment of this invention comprises sodium antimonate and or one or more phosphorous based compounds.
  • the polymer composition of this invention has improved dimensional stability, improved toughness, and improved flammability characteristics that are particularly useful in high temperature electronics. Certain embodiments of this invention also have improved melt stability.
  • This invention relates to an improvement in dimensional stability and toughness of a fiber reinforced, flame retardant (FR) poly(cyclohexylenedimethylene terephthalate) (PCT) formulation.
  • FR flame retardant
  • PCT poly(cyclohexylenedimethylene terephthalate)
  • this formulation simultaneously achieves improved dimensional stability (as demonstrated by Heat Deflection Temperature above 260°C) and improved toughness (as demonstrated by tensile elongation as measured by ASTM Method 638).
  • formulations must have acceptable flammability characteristics to be useful.
  • the polyester comprise 90 mole % or more of terephthalic acid based on the mole percentages of the dicarboxylic acid component of the polyester equaling a total of 100 mole %.
  • terephthalic acid suitable synthetic equivalents, such as dimethyl terephthalate, are included.
  • the polyester useful in this invention comprises 0 to 15 mole %, preferably 0 to10 mole %, of dicarboxylic acids other than terephthalic acid, based on the mole percentages of the dicarboxylic acid component of the polyester equaling a total of 100 mole %.
  • the other dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids preferably having 4 to 40 carbon atoms, more preferably, 8 to 14 carbon atoms; aliphatic dicarboxylic acids having, preferably 4 to 40 carbon atoms, more preferably,
  • dicarboxylic acids useful in forming the copolyester of the invention include, but are not limited to, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, 1 ,4-cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylate, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like.
  • isophthaiic acid naphthalenedicarboxy c acid, cyclohexanedicarboxylic acid and naphthalenedicarboxyate are preferred, either singly or in combination
  • trans-, cis-, or cis/trans mixtures may be used
  • naphthalenedicarboxyhc acid isomers Any of the naphthalenedicarboxyhc acid isomers or mixtures of isomers may be used Some preferred naphthalenedicarboxyhc acid isomers include 2,6-, 2,7- 1 ,4- and 1 ,5- isomers
  • dicarboxylic acids includes the corresponding acid anhydrides, esters, and acid chlorides of these acids
  • the mole percentages of the acids of the polyester referred to herein equal a total of 100 mole %
  • the mole percentages of the glycols referred to herein equal a total of 100 mole %
  • the glycol component of the copolyester of the invention contain from about 80 to 100 mole %, preferably 90 to 100 mole %, of one or more isomers of 1 ,4- cyclohexanedimethanol
  • the copolyesters of this invention may be based on trans-, or cis/trans mixtures of 1 ,4-cyclohexa ⁇ ed ⁇ methanoI
  • a trans-, or cis/trans mixtures of 1 ,4-cyclohexa ⁇ ed ⁇ methanoI For example, a
  • the glycol component may comprise up to 20 mole %, and more preferably, up to 10 mole %, of one or more other aliphatic or alicyc c glycols
  • additional diols include cycloaliphatic diols preferably having 6 to 20 carbon atoms or aliphatic diols preferably having 2 to 20 carbon atoms
  • diols are ethylene glycol, diethylene glycol, t ⁇ ethylene glycol, propane-1 ,3-d ⁇ ol, butane-1 ,4-d ⁇ ol, pentane-1 ,5-d ⁇ ol hexane-1 ,6-d ⁇ ol, 3-methylpentaned ⁇ ol-(2,4), 2-methylpentaned ⁇ ol-(1 ,4) 2,2,4-tr ⁇ methylpentane-d ⁇ ol-(1 ,3), 2-ethylhexaned ⁇ ol-(1 ,3), 2,2- diethylpropane-d
  • Copolyesters may be prepared from the above diols in addition to the 1 ,4-cyclohexanedimethanol.
  • the one or more glycols are selected from ethylene glycol, diethylene glycol, triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and tetramethylcyclobutanediol.
  • the copolyester contains ethylene glycol
  • Copolyesters containing substantially only 1 ,4-cyclohexanedimethanol and terephthalic acid or substantially only 1 ,4- cyclohexanedimethanol, isophthalic, and terephthalic acid are preferred.
  • the polyester resins useful in the blend of this invention are well known and are commercially available.
  • copolyesters are also intended. Methods for their preparation are described, for example, in United States Patents 2,465,319 and 3,047,539.
  • the polyesters can be prepared by direct condensation of terephthalic acid or ester interchange using dimethyl terephthalate with the selected glycol.
  • Typical catalysts which may be used to make these copolyesters include titanium alkoxides, dibutyl tin dilaurate, combinations of zinc, manganese, or magnesium acetates or benzoates with antimony oxide or antimony triacetate.
  • the polyesters of the invention preferably have an inherent viscosity of 0.1 to 2.0 dL/g, more preferably 0.3 to 1.5 dL/g, and even more preferably, 0.4 to 1.2 dL/g as measured at a temperature of 25°C for a 0.5 gram sample in 100 ml of a solvent consisting of 60% by weight phenol and 40% by weight tetrachloroethane. It is preferred that the copolyester useful herein have a melting point of greater than 260°C, more preferably greater than 270°C In some embodiments, the copolyester has a melting point of 260°C to 310°C.
  • Melting points for the polyester resins of the invention and for the halogenated imides of the invention are measured by DSC (differential scanning calorimetry) analysis.
  • the invention is meant to incorporate all melt processing methods known in the art.
  • melt processing refers to any processing step commonly used in the art for polyesters or copolyesters which occurs after the polyesters or copolyesters are heated to their melting temperature or melting point. This includes, but is not limited to, injection molding, calendering, extrusion, and rotational molding.
  • the polymer composition of the invention undergoes less than a 50%, preferably 25%, and more preferably 15% loss in number average molecular weight as determined by gel permeation chromatography when melt processed at 25°C above the crystalline melting temperature (Tm) for 10 minutes.
  • the copolyesters useful in the invention may be combined with additives, branching agents, reinforcing agents, and the like either during polymerization or after polymerization to form a copolyester composition.
  • the second component of the composition is an halogenated organic compound containing at least one imide group and having a melting point greater than 240°C.
  • imide-group containing compounds include N,N'-arylenediphthalimides wherein the arylene group includes phenylene, diphenylene, naphthylene and sulfone bridged bisphenyls, tetrabrominated phthalimides, N,N'bis(dibromocyclohexane dicarboxyimides) with various bridging groups, and N,N'- alkylenebis(tetrahalophthalimides).
  • Preferred imide group containing compounds are those corresponding to the following formula
  • n and m may be 1 or 0, X may be halogen, particularly chlorine or bromine, or hydrogen, and R is a Ci to C ⁇ alkyl group, a single bond, a phenylene group, a toluene group, a cyclohexylene group, a bis phenyl methane group, a bis cydohexylmethane group, or a naphthylene group
  • N,N'-alkyleneb ⁇ s(tetrahalophthalimides) suitable in the present invention and a process for their production are described in U S Pat No 4,087,441 , incorporated herein by reference.
  • the preferred N,N'- alkylenebis(tetrahalophthal ⁇ m ⁇ des) are represented by the formula
  • R represents a Ci-C ⁇ alkyl group, preferably a C 2 -C6 alkyl group, and most preferably an ethyl group, and
  • Hal which may be the same or different, represents a halogen atom, preferably Br or CI, and most preferably Br
  • N,N'- alkyleneb ⁇ s(tetrahalophthal ⁇ m ⁇ de) is N,N'-ethylenebis(tetrabromophthalimide) (R is an ethyl group and Hal is a Br atom).
  • R is an ethyl group and Hal is a Br atom.
  • imide group containing compounds include 1 ,4,5,6- tetrabromo-2,3-phthaloimide; N methylol-tetrabromophthalimide; N,N-bis- (1 ,4,5,6-tetrabromo-2,3-phthaloimide); N,N'-p-phenylene-diphthalimide; N,N'-di-phthaiimidodiphenyl; bis-(N phenyl-phthalimido)sulphone; N,N'-p- phenylene-di-tetrachlorophthalimide; 4,4'-di-tetrachlorophthalimidodiphenyl; N-(tetrachlorophthalimido)-tetrachlorophthalimide, N,N'-p-phenylene-di- tetrabromophthalimide; N, N'-di-tetrabromophthalimidodiphenyl; N- (
  • Preferred imides which have a melting point above 240°C, preferably above 300°C, which includes bis-imides made from aromatic or aliphatic diamines, including ethylene diamine, or hydrazine, and tetrabromophthalic anhydride or acid are preferred.
  • the most preferred flame retardant is the imide from reacting tetrabromo phthalic acid (anhydride) with ethylene diamine. This is sold commercially as Saytex BT-93 and BT-93W. This flame retardant has a high bromine content. It is thermally stable to processing temperatures characteristic of PCT, and does not soften below the PCT melting point.
  • This class of phthalimides has an advantage over other high temperature bromine sources like decabromodiphenyl in that they are not singled out as having the same environmental concerns (dioxins/furans). It is preferred that the sum of all flame retardants used in this invention is 5-30%, preferably 10-20%), by weight of the total composition.
  • One or more flame retardants may be used within the context of this invention.
  • Brominated phthalimides are high melting materials, in contrast to other brominated flame retardants, and provide superior HDT.
  • PCT and BPI is especially challenging from a melt stability standpoint.
  • novel molding materials furthermore preferably contain from 0 to
  • rubber impact modifiers impact modifers that have rubbery physical properties are intended. These include, in particular, those capable of making the polymers of the invention tougher. These properties are met by, for example, EP or EPDM rubbers which are grafted or copolymehzed with suitable functional groups. For example, maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate and glycidyl methacrylate are suitable for this purpose.
  • These monomers can be grafted onto the polymer in the melt or in solution, in the presence or absence of a free radical initiator such as cumene hydroperoxide.
  • Suitable rubber impact modifiers are copolymers of alpha - olefins.
  • the alpha -olefins are usually monomers of 2 to 8 carbon atoms, preferably ethylene and propylene.
  • butanol or ethylhexanol and reactive comonomers, such as acrylic acid methacryhc acid, maleic acid maleic anhydride or glycidyl (meth)acrylate and furthermore vinyl esters, in particular vinyl acetate, have proven suitable comonomers
  • Copolymers of ethylene with ethyl or butyl acrylate and acrylic acid and/or maleic anhydride have proven particularly suitable Copolymers of ethylene, methyl acrylate and glycidyl methacrylate are preferred
  • copolymers of ethylene plus methyl acrylate are preferred It is also preferred that the latter two copolymer types be present in the invention as a mixture
  • the copolymers can be prepared in a high pressure process at from
  • the alpha -olefin content of the copolymer is in general from 99 95 to 55% by weight
  • a further group of suitable impact modifiers comprises core-shell graft rubbers These are graft rubbers prepared in emulsion and consisting of at least one hard and one soft component
  • a hard component is usually understood as meaning a polymer having a glass transition temperature of at least 25°C, and a soft component as meaning a polymer having a glass transition temperature of not more than 0°C
  • These products have a structure having a core and at least one shell, the structure being determined by the order of addition of the monomers
  • the soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and, if required, further comonomers.
  • Suitable siloxane polymers can be prepared, for example, starting from cyclic octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane These polymers can be prepared by ring-opening cationic polymerization, for example using gamma -mercaptopropylmethyldimethoxysilane, preferably in the presence of sulfonic acids
  • the siloxanes may also be cross-linked by, for example, carrying out the polymerization reaction in the presence of silanes having hydrolyzable groups, such as halogen or alkoxy, e g tetraethoxysilane, methylt methoxysilane or phenyltrimethoxysilane
  • suitable comonomers are styrene, acrylonitrile and crosslinking or graft-active monomers having more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butan
  • the hard components are derived in general from styrene, alpha -methylstyrene and copolymers thereof, acrylonitrile, methacrylonitrile and methylmethacryiate preferably being used as comonomers.
  • Preferred core-shell graft rubbers contain a soft core and a hard shell or a hard core, a first soft shell and at least one further hard shell.
  • Functional groups such as carbonyl, carboxyl, anhydride, amido, imido, carboxylic ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups.are preferably incorporated here by adding suitable functionaiized monomers in monomers.
  • the soft components are generally derived from butadiene, isopre ⁇ e, alkyl acrylates, alkyl methacrylates or siloxanes and, if required, further comonomers.
  • Suitable siloxane polymers can be prepared, for example, starting from cyclic octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane.
  • These polymers can be prepared by ring-opening cationic polymerization, for example using gamma - mercaptopropylmethyldimethoxysilane, preferably in the presence of sulfonic acids.
  • the siloxanes may also be cross-linked by, for example, carrying out the polymerization reaction in the presence of silanes having hydrolyzable groups, such as halogen or alkoxy, e.g. tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane.
  • Suitable comonomers here are styrene, acrylonitrile and crosslinking or graft-active monomers having more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso)cyanurate.
  • the hard components are derived in general from styrene, alpha -methylstyrene and copolymers thereof, acrylonitrile, methacrylonitrile and methylmethacryiate preferably being used as comonomers.
  • Preferred core-shell graft rubbers contain a soft core and a hard shell or a hard core, a first soft shell and at least one further hard shell
  • Functional groups such as carbonyl, carboxyl, anhydride, amido, imido, carboxy c ester, ammo, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups, are preferably incorporated here by adding suitable functionahzed monomers in the polymerization of the final shell
  • Suitable functiona zed monomers are, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth)acrylate, acrylic acid, glycidyl (meth)acrylate and vinyloxazo ne
  • the amount of monomers having functional groups is in general from 0 1 to 25, preferably from 0 25 to
  • the weight ratio of soft to hard components is in general from 1 9 to 9 1 , preferably from 3 7 to 8 2
  • the polymer compositions of this invention may also contain a flame retardant synergist
  • a flame retardant synergist Any flame retardant synergist known in the art may be used It is preferred that an antimony compound be used but the common choice of Sb 2 O3 performs poorly Sodium antimonate is more preferred Even more preferred is NaSb0 3 that is substantially free of Sb +3 or less than 1 mole % of Sb +3 based on the total mole percentages of antimony in the sodium antimonate Sodium antimonate is normally justified in the art as being a sodium- neutralized version of Sb O 3 but the importance of Sb +3 level and the desire to reduce rather than increase the amount of synergist suggest this different mechanism, reducing catalytic activity of the Sb species
  • the ratio of flame retardant (bisimide) to flame retardant synergist (sodium antimonate) is optimized at a much higher weight ratio (5 1 to 10 1 , preferably 8 1 ) than is commonly practiced
  • melt stability of the composition of the invention can be further improved by addition of a phosphorous-based compound
  • phosphorous-based compounds include, but are not limited to, one or more phosphites or phosphonites wherein at least one of the P-O bonds is attached to an aryl radical Such compounds may be
  • R 1 , R 2 and R 3 is an aryl radical of 6 to 30 carbon atoms and any other(s) of R 1 ( R 2 and R 3 are H or alkyl of 1 to 30 carbon atoms, or
  • R 3 , R 4 and R 5 is an aryl radical of 6 to 30 carbon atoms
  • Phosphites are preferred within the context of this invention Even more preferred are, for example, commonly available symmetrical t ⁇ aryl esters of phosphorous acid which may be used are t ⁇ phenyl phosphite, t ⁇ s(nonylphenyl) phosphite, and t ⁇ s(2,4-d ⁇ -t- butylphenyl) phosphite (Irgafos 168 from Ciba-Geigy Corporation))
  • the most preferred symmetrical ester of phosphorous acid is b ⁇ s(2 4-d ⁇ -t- butylphenyl) pentaeryth ⁇ tol diphosphite (Ultranox 626 - a trademark of
  • phosphorous-based compounds which may be used include, but are not limited to, Ultranox® 633 phosphite, (General Electric Co )
  • the phosphorous compounds may be functioning by inhibiting the metal catalyst system present in the PCT While much is known about use of phosphorous compounds in stabilizing polyester systems, it is not generally recognized as a way to stabilize flame retardants
  • Phenoxy compounds may also be present in the invention which comprise a diepoxide monomer having the structural formula
  • phenoxy compounds include the polyhydroxyether of bisphenol A which is produced from 2,2'-b ⁇ s(4-hydroxy-phenyl) propane and epichlorohyd ⁇ n Preparation of such polymers is described in U S Patent
  • phenoxy compounds are present in the invention that they comprise 1 to 10%, preferably 2 to 5% by weight of the total composition It is also preferred that the phenoxy compound(s) of the invention have an Mn of 10,000 to 20,000 It is understood that other additives such as other stabilizers, other flame retardants (FR), flame retardant synergists, tougheners, epoxy compounds, branching agents, mold release agents, nucleating agents, reinforcing agents such as reinforcing fibers, (such as carbon or glass fibers) fillers, antioxidants and colorants such as carbon black, might also be desirable in such formulations These may be added either during or after polymerization depending on the nature of the additive
  • Such additives are generally present at 0 1 to about 40 weight % total, preferably 0 1 to about 20 weight %, based on the total weight of the copolyester composition It is also preferable that 0 1 to 5 0 weight %, preferably less than 2 0 weight %, of one or more branching agents is included within the context of this invention, including but not limited to, t ⁇ mellitic acid, t ⁇ mellitic anhydride, pyromelhtic anhydride, multifunctional epoxy compounds and multi-functional phenoxy compounds, and the like If the branching agent is a phenoxy compound, 2 0 to 5 0 weight % is preferred
  • reinforcing agents are reinforcing fibers such as glass fibers and carbon fibers, mica, clay, talc, wollastonite, and calcium carbonate
  • a particularly preferred reinforcing agent is glass fiber It is preferable that the glass fibers be present in the polyester composition at from 0 1 to 45%, preferably 10 to 40%, by weight based on the total weight of said polyester composition
  • Glass fibers suitable for use in the polyester compositions of the invention may be in the form of glass filaments, threads, fibers, or whiskers etc , and may vary in length from about 1 /8 inch to about 2 inches Chopped glass strands having a length of about 1/8 inch to about 1 /4 inch are preferred Such glass fibers are well known in the art Of course the size of these glass fibers may be greatly diminished depending on the blending means employed, even to lengths of 300 to 700 microns or lower It is preferred that the glass fibers are coated with polyuretha ⁇ e
  • polyester compositions of the invention may be reinforced with a mixture of glass and other reinforcing agents as described above, such as mica or talc, and/or with other additives
  • copolyester composition of the invention may be blended and/or mixed by any suitable technology known in the art
  • polyester can be mixed dry in any suitable blender or tumbler with the other components and the mixture melt- extruded
  • the extrudate can be chopped If desired the reinforcing material can be omitted initially and added after the first melt extrusion, and the resulting mixture can then be melt extruded
  • the copolyester of this invention may be melt processed and extruded, injection molded, or compression molded into a variety of shapes and forms including fibers, molded parts, bottles, pellets, containers, sheeting, film and the like
  • the product is especially suitable as an injection molding material for producing molded articles
  • Inherent viscosity or "IN.” - refers to inherent viscosity expressed in dL/g measured as described herein;
  • PCT poly(cyclohexylenedimethylene terephthalate);
  • Stabilizer 2 (ST 2) - tetrakis -[methylene -(3,5-di-tert-butyl-4- hydroxyhydro-cynnamate)];
  • Stabilizer 3 - (ST 3) - [bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite; Stabilizer 4 - (ST4) - Phenoxy PKHH;
  • the glass fiber reinforced (GFR) PCT blends of this work were prepared by extrusion compounding using a twin screw extruder at temperatures of 305°C.
  • the resulting pellets were injection molded into tensile and flexural bars for use in mechanical and flammability property testing. Melt stability was determined on these blends by drying a small sample of the compounded pellets. Adequate drying can be obtained by drying in a vacuum oven overnight at 80°C, or by drying for 4 hours at 125°C in a hot air circulating oven.
  • the dried pellets were then loaded into a Tinius Olsen melt indexer or capillary rheometer and held for 10 minutes at 305°C melt temperature, then analyzed by gel permeation chromatography.
  • melt stability of these blends was shown by the retention of number average molecular weight (Mn) and weight average molecular weight (Mw) after 10 minutes at 305°C.
  • Good melt stability is characterized by a loss of less than about 15% of the original Mn and Mw, after exposure for 10 minutes, the original molecular weights being defined as that at zero time.
  • Blends with less than this degree of melt stability may still be useful, but are correspondingly inferior
  • Blends A-D in Table 1 are described as follows
  • Blend A is described as follows: 30 0% GF 1 16 0% FR1
  • Blend B is described as follows:
  • Blend A Same as Blend A except containing 3 5% RIM1 and 3 5% RIM2 Blend C is described as follows:
  • Blend A Same as Blend A except containing 3 5% RIM1 and 2.5% RIM2
  • Blend D is described as follows:
  • Blend A Same as Blend A except containing 2 5% RIM1 and 2 5% RIM2
  • Table 1 shows that the brominated phthalimide FR1 based system can be toughened in this manner while retaining good HDT EXAMPLE 2
  • Blends E-l in Table 2 are described as follows:
  • Blend E is described as follows: 30.0% GF1 16.0% FR1
  • PCT in an amount sufficient for the composition to total 100 weight%.
  • Blend F is described as follows:
  • Blend E Same as Blend E except containing 1.0% RIM1 and 3.0% RIM2.
  • Blend G is described as follows:
  • Blend E Same as Blend E except containing 3.0% RIM1 and 3.0% RIM2.
  • Blend H is described as follows:
  • Blend E Same as Blend E except containing 1.0% RIM1 and 9.0% RIM2.
  • Blend I is described as follows:
  • Blend E Same as Blend E except containing 3.0% RIM1 and 9.0% RIM2.
  • Blends J-N in Table 3 are described as follows Blend J is described as follows:
  • Blend K is described as follows:
  • Blend J Same as Blend J except containing in addition 1.25%> RIM1 and 3.75% RIM2 and with the FR2 adjusted to 13.0% and FRS1 is adjusted to 3.0%.
  • Blend L is described as follows:
  • Blend J Same as Blend J except containing in addition 1.25%> RIM1 and 3.75% RIM2 and with the FR2 adjusted to 15.0% and FRS1 is adjusted to 4.0%.
  • Blend M is described as follows:
  • Blend J Same as Blend J except containing in addition 2.5%> RIM1 and 7.5% RIM2 and with the FR2 adjusted to 13.0% and the FRS1 adjusted to 4.0%.
  • Blend N is described as follows:
  • Blend J Same as Blend J except containing in addition 2.5%> RIM1 and 7.5% RIM2 and with the FR2 is adjusted to 15.0% and the FRS1 adjusted to 3.0%.
  • Table 3 shows that the brominated polystyrene based system cannot be toughened by this method without sacrificing flammability or heat deflection temperature

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition polymère composée (A) d'un polyester contenant (1) de l'acide téréphtalique à raison de 85 à 100 moles % sur la base des pourcentages molaires du constituant acide dicarboxylique équivalent à un total de 100 moles %, (2) un constituant glycol contenant d'environ 60 à 100 moles % de 1,4-cyclohexanediméthanol; (B) un ou plusieurs modificateurs de la résistance aux chocs à fonction de caoutchouc; (C) un ou plusieurs composés organiques halogénés contenant au moins un groupe imide ayant un point de fusion supérieur à 240 °C; et (D) des fibres de renforcement.
PCT/US2000/024522 1999-09-23 2000-09-07 Compositions ameliorees a base de poly(cyclohexylenedimethylene terephtalte) contenant des imides halogenes, des modificateurs de la resistance aux chocs a fonction de caoutchouc et des fibres de renforcement Ceased WO2001027200A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15572199P 1999-09-23 1999-09-23
US60/155,721 1999-09-23
US45055299A 1999-11-30 1999-11-30
US09/450,552 1999-11-30

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WO2001027200A2 true WO2001027200A2 (fr) 2001-04-19
WO2001027200A3 WO2001027200A3 (fr) 2002-01-10

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US9604251B2 (en) 2008-07-16 2017-03-28 Eastman Chemical Company Thermoplastic formulations for enhanced paintability, toughness and melt processability
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9919503B2 (en) 2012-12-06 2018-03-20 Eastman Chemical Company Extrusion coating of elongated substrates
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
EP3286259A4 (fr) * 2015-04-22 2018-10-03 Eastman Chemical Company Composites de bande à base de polyester pour un renforcement du bois
US10576491B2 (en) 2008-07-01 2020-03-03 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US11072685B2 (en) * 2018-01-31 2021-07-27 Exxonmobil Chemical Patents Inc Fiber reinforced terephthalate-CO-4,4′-bibenzoate copolyester

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US10576491B2 (en) 2008-07-01 2020-03-03 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US9604251B2 (en) 2008-07-16 2017-03-28 Eastman Chemical Company Thermoplastic formulations for enhanced paintability, toughness and melt processability
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
US9919503B2 (en) 2012-12-06 2018-03-20 Eastman Chemical Company Extrusion coating of elongated substrates
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
EP3286259A4 (fr) * 2015-04-22 2018-10-03 Eastman Chemical Company Composites de bande à base de polyester pour un renforcement du bois
US10556388B2 (en) 2015-04-22 2020-02-11 Eastman Chemical Company Polyester-based tape composites for wood reinforcement
US11072685B2 (en) * 2018-01-31 2021-07-27 Exxonmobil Chemical Patents Inc Fiber reinforced terephthalate-CO-4,4′-bibenzoate copolyester

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