WO1999032560A1 - Moulding compounds based on polyalkylenterephthalate and thermoplastic polyketone - Google Patents
Moulding compounds based on polyalkylenterephthalate and thermoplastic polyketone Download PDFInfo
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- the invention relates to thermoplastic molding compositions based on polyalkylene terephthalate and thermoplastic polyketones (olefin-carbon monoxide copolymers), their use for the production of moldings and the moldings produced therefrom.
- Polyalkylene terephthalates and their mixture with other thermoplastics are generally known (cf. e.g. EP-A 385 086 and DE-OS 40 16 416).
- thermoplastic polyketones mixed with reinforcing materials and a thermoplastic polyurethane.
- the molding compounds are characterized by improved rigidity and heat resistance.
- Grafted olefin-carbon monoxide copolymers and their mixture with polycarbonate are also known (US Pat. No. 5,189,091, US Pat. No. 5,079,316). Grafted polyketones are described as compatibility agents in the production of mixtures of polycarbonate and styrene-acrylonitrile copolymers and ABS graft polymers (US Pat. No. 5,079,316). Mixtures of polycarbonate, aromatic polyesters and grafted olefin copolymers show improved properties with regard to toughness, impact strength and flow seam strength (US Pat. No. 5,189,091).
- the object of the present invention is now to provide inexpensive materials with good chemical resistance, UV resistance, without impairing processing stability and processing behavior.
- Such active ingredients are particularly suitable for use in the automotive sector.
- the present invention therefore relates to thermoplastic molding compositions comprising polyalkylene terephthalates and linearly alternating polymers Carbon monoxide and at least one ethylenically unsaturated hydrocarbon, which may contain other additives such as fillers and reinforcing materials and flame retardants.
- the invention preferably relates to a thermoplastic molding composition
- Polyalkylene terephthalates in the context of the invention are reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
- Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Carl-Hanser-Verlag, Kunststoff 1973) ).
- Preferred polyalkylene terephthalates contain at least 80, preferably
- the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
- the preferred polyalkylene terephthalates may contain, in addition to ethylene glycol or 1,4-butanediol, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g.
- the polyalkylene terephthalates can be obtained by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, such as those e.g. are described in DE-OS 1 900 270 and US Pat. No. 3,692,744.
- preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
- polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. dialkyl esters) and ethylene glycol and / or 1,4-butanediol (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
- Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the abovementioned acid components and / or of at least two of the abovementioned mentioned alcohol components are produced, particularly preferred copolyesters are poly (ethylene glycol / butanediol-1, 4) terephthalates.
- the polyalkylene terephthalates preferably used as component A generally have an intrinsic viscosity of about 0.5 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1 : 1 part by weight) at 25 ° C.
- the polyketone polymers used as component B have a linear alternating structure and contain essentially 1 molecule of carbon monoxide per molecule of unsaturated hydrocarbon.
- Suitable ethylenically unsaturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic such as ethylene and other ⁇ -olefins, e.g. Propylene, 1-butene, 1-isobutylene, 1-hexene, 1-octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on a carbon atom of the linear chain.
- arylaliphatic monomers examples include styrene, p-methylstyrene, p-ethylstyrene and m-isopropylstyrene.
- Preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, in particular an ⁇ -olefin such as e.g. Propylene.
- Terpolymers of at least 2 monomer units are particularly preferred, one of which is ethylene and the other a second hydrocarbon. About 10 to 100 monomer units of the second hydrocarbon are preferably used.
- the polymer chain of the preferred polyketone polymer is represented by the following formula LC0 (CH 2 CH 2 ) J] ⁇ C0 (G) Jy- (I)
- G is a monomer unit based on an ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, preferably 3 to 10 carbon atoms, which is polymerized on account of the ethylenic double bond and
- the ratio y: x is not more than about 0.5.
- terpolymers are used and the units -CO- (CH2CH 2 ) - and -CO- (G) -unit are statistically distributed over the polymer chain.
- the preferred ratio of y: x is 0.01 to 0.1.
- Polyketone polymers with a number average molecular weight of approximately 1,000 to 200,000, in particular 20,000 to 90,000, determined by gel permeation chromatography are preferred.
- the physical properties of the polyketone polymers depend in part on the molecular weight, e.g. whether the polymer is based on a single or a plurality of ethylenically unsaturated hydrocarbons, the nature and the amount of the ethylenically unsaturated hydrocarbons. Typical
- Melting points of the polymers are in the range between 175 ° C and 300 ° C, preferably between 210 and 270 ° C, determined according to DSC (Differential Scanning Calorimetry), the usual melting point is, for example, 200 to 220 ° C.
- the polymers usually have an intrinsic viscosity of 0.5 dl / g to 10 dl / g, preferably 0.8 to 4 dl / g, in particular 1.2 to 1.8 dl / g, measured in m-cresol at 60 ° C. in a standard capillary viscometer.
- thermoplastic molding composition can also include other components such as Copolymers based on SAN or ABS graft polymers contain, as described for example in EP-A 640 655.
- Glass fibers, glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite, etc. can also be used as fillers and reinforcing materials. can be added, which can also be surface-treated.
- Preferred reinforcing materials are commercially available glass fibers.
- the glass fibers which generally have a fiber diameter between 8 and 14 ⁇ m, can be used as continuous fibers or as cut or ground glass fibers, it being possible for the fibers to be equipped with a suitable sizing system and a silane-based adhesion promoter or adhesion promoter system.
- 10 to 40, in particular 20 to 35 parts by weight of fillers and reinforcing materials are preferably added to the mixture.
- Molding compositions containing fillers and reinforcing materials preferably contain 40 to 89, in particular 40 to 70 parts by weight of polyalkylene terephthalate.
- Halogenated aromatics, halogen-containing molding compounds, phosphorus compounds, mineral flame retardant additives and tetrafluoroethylene polymers can be used as flame retardants.
- the molding compositions according to the invention can contain customary additives, such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, and dyes and pigments.
- customary additives such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, and dyes and pigments.
- the molding compositions according to the invention and optionally other known additives such as stabilizers, dyes, pigments, lubricants and mold release agents, reinforcing materials, nucleating agents and antistatic agents are prepared by mixing the respective constituents in a known manner and at from 230 ° C. to 330 ° C. conventional units such as internal kneaders, extruders, twin-screw extruders melt-compounded or melt-extruded.
- the present invention furthermore relates to a process for the production of thermoplastic molding compositions from components A and B and, if appropriate, further known additives such as copolymers, ABS graft polymers,
- Flame retardants, stabilizers, dyes, pigments, lubricants and mold release agents, reinforcing materials, nucleating agents and antistatic agents which are characterized in that the components and, if appropriate, the additives after mixing at temperatures of 230 ° C. to 330 ° C. in conventional units melt compounded or melt extruded.
- Another object of the invention is the use of the above-mentioned molding compositions for the production of moldings, and the moldings.
- the molding compositions can be used to produce moldings of any kind.
- moldings can be produced by injection molding.
- Examples of moldings that can be produced are: Housings of all types, for example for household appliances, power strips and lamp bases, and parts from the motor vehicle sector.
- Stabilizers, mold release agents and nucleating agents are added as additives in an amount of 0.5% by weight.
- the melt viscosity is measured at 260 ° C with a high pressure capillary viscometer depending on the shear rate.
- the components and additives are mixed on a ZSK 32/1 extruder at 260 ° C.
- the moldings are produced on an Arburg 320-210-500 injection molding machine.
- Blend is obtained. This can be seen from the melt viscosity values.
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Abstract
Description
Formmassen auf Basis Polyalkylenterephthalat und thermoplastischer Poly- ketoneMolding compounds based on polyalkylene terephthalate and thermoplastic polyketones
Die Erfindung betrifft thermoplastische Formmassen auf Basis Polyalkylenterephthalat und thermoplastischer Polyketone, (Olefin-Kohlenmonoxid Copolymere), deren Verwendung zur Herstellung von Formkörpern sowie die daraus hergestellten Formkörper.The invention relates to thermoplastic molding compositions based on polyalkylene terephthalate and thermoplastic polyketones (olefin-carbon monoxide copolymers), their use for the production of moldings and the moldings produced therefrom.
Polyalkylenterephthalate und deren Mischung mit anderen Thermoplasten sind allgemein bekannt (vgl. z.B. EP-A 385 086 und DE-OS 40 16 416).Polyalkylene terephthalates and their mixture with other thermoplastics are generally known (cf. e.g. EP-A 385 086 and DE-OS 40 16 416).
US-P 5,166,252 beschreibt thermoplastische Polyketone in Mischung mit Verstärkungsstoffen und einem thermoplastischen Polyurethan. Die Formmassen zeichnen sich durch verbesserte Steifheit und Hitzebeständigkeit aus.US Pat. No. 5,166,252 describes thermoplastic polyketones mixed with reinforcing materials and a thermoplastic polyurethane. The molding compounds are characterized by improved rigidity and heat resistance.
Gepfropfte Olefin-Kohlenmonoxid-Copolymere und deren Mischung mit Poly- carbonat sind ebenfalls bekannt (US-P 5.189.091, US-P 5.079.316). Gepfropfte Polyketone werden als Verträglichkeitsmittel bei der Herstellung von Mischungen aus Polycarbonat und Styrol-Acrylnitril-Copolymeren und ABS-Pfropfpolymerisaten beschrieben (US-P 5.079.316). Mischungen aus Polycarbonat, aromatischen Poly- estern und gepfropften Olefin-Copolymeren zeigen verbesserte Eigenschaften hinsichtlich Zähigkeit, Schlagzähigkeit, Fließnahtfestigkeit (US-P 5,189,091).Grafted olefin-carbon monoxide copolymers and their mixture with polycarbonate are also known (US Pat. No. 5,189,091, US Pat. No. 5,079,316). Grafted polyketones are described as compatibility agents in the production of mixtures of polycarbonate and styrene-acrylonitrile copolymers and ABS graft polymers (US Pat. No. 5,079,316). Mixtures of polycarbonate, aromatic polyesters and grafted olefin copolymers show improved properties with regard to toughness, impact strength and flow seam strength (US Pat. No. 5,189,091).
Die Aufgabe der vorliegenden Erfindung ist nun die Bereitstellung von preisgünstigen Werkstoffen mit einer guten Chemikalienbeständigkeit, UV-Beständigkeit, ohne daß Verarbeitungsstabilität und Verarbeitungsverhalten beeinträchtigt werden. Solche Wirkstoffe sind insbesondere für den Einsatz im Kfz-Bereich geeignet.The object of the present invention is now to provide inexpensive materials with good chemical resistance, UV resistance, without impairing processing stability and processing behavior. Such active ingredients are particularly suitable for use in the automotive sector.
Der Gegenstand der vorliegenden Erfindung sind daher thermoplastische Formmassen enthaltend Polyalkylenterephthalate und linear alternierende Polymere aus Kohlenmonoxid und wenigstens einem ethylenisch ungesättigten Kohlenwasserstoff, welche weitere Zusatzstoffe wie z.B. Füll- und Verstärkungsstoffe und Flammschutzmittel enthalten können.The present invention therefore relates to thermoplastic molding compositions comprising polyalkylene terephthalates and linearly alternating polymers Carbon monoxide and at least one ethylenically unsaturated hydrocarbon, which may contain other additives such as fillers and reinforcing materials and flame retardants.
Vorzugsweise ist Gegenstand der Erfindung eine thermoplastische Formmasse enthaltendThe invention preferably relates to a thermoplastic molding composition
A) 99 bis 1, besonders bevorzugt 90 bis 10, ganz besonders bevorzugt 80 bis 20, insbesondere 60 bis 40 Gew.-Teile Polyalkylenterephthalat,A) 99 to 1, particularly preferably 90 to 10, very particularly preferably 80 to 20, in particular 60 to 40 parts by weight of polyalkylene terephthalate,
B) 1 bis 99, besonders bevorzugt 10 bis 90, ganz besonders bevorzugt 20 bis 80, insbesondere 60 bis 40 Gew.-Teile linear alternierendes Polymer aus Kohlen- monoxid und wenigstens eines ethylenisch ungesättigten Kohlenwasserstoffs.B) 1 to 99, particularly preferably 10 to 90, very particularly preferably 20 to 80, in particular 60 to 40 parts by weight of linearly alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon.
Polyalkylenterephthalate (Komponente A) im Sinne der Erfindung sind Reaktionsprodukte aus aromatischen Dicarbonsäuren oder ihren reaktionsfähigen Derivaten (z.B. Dimethylestern oder Anhydriden) und aliphatischen, cycloaliphatischen oder araliphatischen Diolen und Mischungen dieser Reaktionsprodukte.Polyalkylene terephthalates (component A) in the context of the invention are reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
Bevorzugte Polyalkylenterephthalate lassen sich aus Terephthalsäure (oder ihren reaktionsfähigen Derivaten) und aliphatischen oder cycloaliphatischen Diolen mit 2 bis 10 C- Atomen nach bekannten Methoden herstellen (Kunststoff-Handbuch, Bd. VIII, S. 695 ff, Carl-Hanser- Verlag, München 1973).Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Carl-Hanser-Verlag, Munich 1973) ).
Bevorzugte Polyalkylenterephthalate enthalten mindestens 80, vorzugsweisePreferred polyalkylene terephthalates contain at least 80, preferably
90 Mol-%, bezogen auf die Dicarbonsäurekomponente, Terephthalsäurereste und mindestens 80, vorzugsweise mindestens 90 Mol-%, bezogen auf die Diolkom- ponente, Ethylenglykol- und/oder butandiol-l,4-reste.90 mol%, based on the dicarboxylic acid component, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, 1,4-ethylene glycol and / or butanediol residues.
Die bevorzugten Polyalkylenterephthalate können neben Terephthalsäureresten bis zu 20 Mol-% Reste anderer aromatischer Dicarbonsäuren mit 8 bis 14 C- Atomen oder aliphatischer Dicarbonsäuren mit 4 bis 12 C- Atomen enthalten, wie Reste von Phthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbon- säure, Bernstein-, Adipin-, Sebacin-, Azelain-, Cyclohexandiessigsäure.In addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
Die bevorzugten Polyalkylenterephthalate können neben Ethylenglykol- bzw. Butan- diol-l,4-Resten bis zu 20 Mol-% anderer aliphatischer Diole mit 3 bis 12 C- Atomen oder cycloaliphatischer Diole mit 6 bis 21 C-Atomen enthalten, z.B. Reste von Pro- pandiol-1,3, 2-Ethylenpropandiol-l,3, Neopentylglykol, Pentandiol-1,5, Hexan- diol-1,6, Cyclohexandimethanol-1,4, 3-Methylpentandiol-2,4, 2-Methyl-pentandiol- 2,4, 2,2,4-Trimethylpentandiol-l,3 und l,6,2-Ethylhexandiol-l,3, 2,2-Diethylpro- pandiol-1,3, Hexandiol-2,5, l,4-Di-(ß-hydroxyethoxy)-benzol, 2,2-bis-(3-ß-hydroxy- ethoxyphenyl)-propan und 2,2-bis-(4-hydroxypropoxyphenyl)-propan (DE-OS 24 07 674, 24 07 776, 27 15 932).The preferred polyalkylene terephthalates may contain, in addition to ethylene glycol or 1,4-butanediol, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. Residues of propanediol-1,3,2-ethylene-propanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol-1,4,3-methylpentanediol-2,4,2- Methyl-pentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and 1,2,2,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di- (β-hydroxyethoxy) benzene, 2,2-bis (3-β-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 24 07 674, 24 07 776, 27 15 932).
Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4- wertiger Alkohole oder 3- oder 4-basischer Carbonsäuren, wie sie z.B. in der DE-OS 1 900 270 und der US-PS 3 692 744 beschrieben sind, verzweigt werden. Beispiele für bevorzugte Verzweigungsmittel sind Trimesinsäure, Trimellitsäure, Trimethylol- ethan und -propan und Pentaerythrit.The polyalkylene terephthalates can be obtained by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, such as those e.g. are described in DE-OS 1 900 270 and US Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
Es ist ratsam, nicht mehr als 1 Mol-% des Verzweigungsmittels, bezogen auf die Säurekompomente, zu verwenden.It is advisable to use no more than 1 mole% of the branching agent, based on the acid components.
Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäsure und deren reaktionsfähigen Derivaten (z.B. Dialkylestern) und Ethylenglykol und/oder Butandiol-1,4 hergestellt worden sind (Polyethylen- und Polybutylen- terephalat), und Mischungen dieser Polyalkylenterephthalate.Particularly preferred are polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. dialkyl esters) and ethylene glycol and / or 1,4-butanediol (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
Bevorzugte Polyalkylenterephthalate sind auch Copolyester, die aus mindestens zwei der obengenannten Säurekomponenten und/oder aus mindestens zwei der obenge- nannten Alkoholkomponenten hergestellt sind, besonders bevorzugte Copolyester sind Poly-(ethylenglykol/butandiol- 1 ,4)-terephthalate.Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the abovementioned acid components and / or of at least two of the abovementioned mentioned alcohol components are produced, particularly preferred copolyesters are poly (ethylene glycol / butanediol-1, 4) terephthalates.
Die als Komponente A vorzugsweise verwendeten Polyalkylenterephthalate besitzen im allgemeinen eine Intrinsic-Viskosität von ca. 0,5 bis 1,5 dl/g, vorzugsweise 0,5 bis 1,3 dl/g, jeweils gemessen in Phenol/o-Dichlorbenzol (1 :1 Gew.-Teile) bei 25°C.The polyalkylene terephthalates preferably used as component A generally have an intrinsic viscosity of about 0.5 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1 : 1 part by weight) at 25 ° C.
Die Polyketonpolymere, welche als Komponente B eingesetzt werden, haben eine lineare alternierende Struktur und enthalten im wesentlichen 1 Molekül Kohlenmon- oxid pro Molekül von ungesättigtem Kohlenwasserstoff. Geeignete ethylenisch ungesättigte Kohlenwasserstoffe als Monomere zum Aufbau des Polyketonpolymeren haben bis zu 20 Kohlenstoffatome, vorzugsweise bis zu 10 Kohlenstoffatome und sind aliphatisch wie beispielsweise Ethylen und andere α-Olefine, z.B. Propylen, 1 -Buten, 1-Isobutylen, 1 -Hexen, 1-Octen und 1-Dodecen, oder sind arylaliphatisch und enthalten einen Arylsubstituenten an einem Kohlenstoffatom der linearen Kette.The polyketone polymers used as component B have a linear alternating structure and contain essentially 1 molecule of carbon monoxide per molecule of unsaturated hydrocarbon. Suitable ethylenically unsaturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic such as ethylene and other α-olefins, e.g. Propylene, 1-butene, 1-isobutylene, 1-hexene, 1-octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on a carbon atom of the linear chain.
Beispielhaft genannt werden für arylaliphatische Monomere Styrol, p-Methylstyrol, p-Ethylstyrol und m-Isopropylstyrol.Examples of arylaliphatic monomers are styrene, p-methylstyrene, p-ethylstyrene and m-isopropylstyrene.
Bevorzugte Polyketonpolymere sind Copolymere aus Kohlenmonoxid und Ethylen oder Terpolymere aus Kohlenmonoxid, Ethylen und einem zweiten ethylenisch ungesättigten Kohlenwasserstoff mit wenigstens 3 Kohlenstoffatomen, insbesondere ein α-Olefin wie z.B. Propylen.Preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, in particular an α-olefin such as e.g. Propylene.
Besonders bevorzugt sind Terpolymere von wenigstens 2 Monomereinheiten, wovon eine Ethylen und die andere ein zweiter Kohlenwasserstoff ist. Vorzugsweise werden von dem zweiten Kohlenwasserstoff ungefähr 10 bis 100 Monomereinheiten eingesetzt.Terpolymers of at least 2 monomer units are particularly preferred, one of which is ethylene and the other a second hydrocarbon. About 10 to 100 monomer units of the second hydrocarbon are preferably used.
Die Polymerkette des bevorzugten Polyketonpolymers wird durch die folgende Formel dargestellt LC0(CH2CH2) J]χ C0(G) Jy- (I)The polymer chain of the preferred polyketone polymer is represented by the following formula LC0 (CH 2 CH 2 ) J] χ C0 (G) Jy- (I)
wobeiin which
G eine Monomereinheit auf Basis eines ethylenisch ungesättigten Kohlenwasserstoffs mit wenigstens 3 Kohlenstoffatomen, vorzugsweise 3 bis 10 C-Atomen, welche aufgrund der ethylenischen Doppelbindung polymerisiert ist undG is a monomer unit based on an ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, preferably 3 to 10 carbon atoms, which is polymerized on account of the ethylenic double bond and
das Verhältnis y:x nicht mehr als ungefähr 0,5 ist.the ratio y: x is not more than about 0.5.
y = 0 für Copolymere aus Kohlenmonoxid und Ethylen.y = 0 for copolymers of carbon monoxide and ethylene.
Falls y von 0 verschieden ist, werden Terpolymere eingesetzt und die Einheit -CO-(CH2CH2)- und -CO-(G)-Einheit sind statistisch über die Polymerkette verteilt.If y is different from 0, terpolymers are used and the units -CO- (CH2CH 2 ) - and -CO- (G) -unit are statistically distributed over the polymer chain.
Das bevorzugte Verhältnis von y:x ist 0,01 bis 0,1.The preferred ratio of y: x is 0.01 to 0.1.
Polyketonpolymere mit einem mittleren Molekulargewicht (Zahlenmittel) von ungefähr 1.000 bis 200.000, insbesondere 20.000 bis 90.000, bestimmt durch Gelpermea- tionschromatographie sind bevorzugt.Polyketone polymers with a number average molecular weight of approximately 1,000 to 200,000, in particular 20,000 to 90,000, determined by gel permeation chromatography are preferred.
Die physikalischen Eigenschaften der Polyketonpolymere hängen teilweise vom Molekulargewicht ab, z.B. davon, ob das Polymer auf einem einzigen oder einer Vielzahl von ethylenisch ungesättigten Kohlenwasserstoffen beruht, von der Natur und der Menge der ethylenisch ungesättigten Kohlenwasserstoffen. TypischeThe physical properties of the polyketone polymers depend in part on the molecular weight, e.g. whether the polymer is based on a single or a plurality of ethylenically unsaturated hydrocarbons, the nature and the amount of the ethylenically unsaturated hydrocarbons. Typical
Schmelzpunkte der Polymere liegen im Bereich zwischen 175°C und 300°C, vorzugsweise zwischen 210 und 270°C, bestimmt nach DSC (Differential Scanning Calorimetry), üblicher Schmelzpunkt ist z.B. 200 bis 220°C. Üblicherweise haben die Polymere eine Grenzviskositätszahl von 0,5 dl/g bis 10 dl/g, vorzugsweise 0,8 bis 4 dl/g, insbesondere 1,2 bis 1,8 dl/g, gemessen in m-Kresol bei 60°C in einem Standard-Kapillarviskosimeter.Melting points of the polymers are in the range between 175 ° C and 300 ° C, preferably between 210 and 270 ° C, determined according to DSC (Differential Scanning Calorimetry), the usual melting point is, for example, 200 to 220 ° C. The polymers usually have an intrinsic viscosity of 0.5 dl / g to 10 dl / g, preferably 0.8 to 4 dl / g, in particular 1.2 to 1.8 dl / g, measured in m-cresol at 60 ° C. in a standard capillary viscometer.
Zur weiteren Charakterisierung und zur Herstellung der Polyketon-Polymere wird auf US-Patent 5 166 252 verwiesen.For further characterization and for the production of the polyketone polymers, reference is made to US Pat. No. 5,166,252.
Die thermoplastische Formmasse kann darüber hinaus noch weitere Komponenten wie z.B. Copolymere auf Basis SAN oder ABS-Pfropfpolymerisate enthalten wie beispielsweise beschrieben in EP-A 640 655.The thermoplastic molding composition can also include other components such as Copolymers based on SAN or ABS graft polymers contain, as described for example in EP-A 640 655.
Als Füllstoffe und Verstärkungsstoffe können weiterhin Glasfasern, Glaskugeln, Glimmer, Silikate, Quarz, Talkum, Titandioxid, Wollastonit, u.a. zugesetzt werden, die auch oberflächenbehandelt sein können. Bevorzugte Verstärkungsstoffe sind handelsübliche Glasfasern. Die Glasfasern, die im allgemeinen einen Faserdurchmesser zwischen 8 und 14 μm haben, können als Endlosfasern oder als geschnittene oder gemahlene Glasfasern eingesetzt werden, wobei die Fasern mit einem geeigneten Schlichtesystem und einem Haftvermittler bzw. Haftvermittlersystem auf Silanbasis ausgerüstet sein können. Vorzugsweise werden der Mischung 10 bis 40, insbesondere 20 bis 35 Gew.-Teile Füll- und Verstärkungsstoffe zugesetzt. Füll- und Verstärkungsstoffe enthaltende Formmassen enthalten vorzugsweise 40 bis 89, insbesondere 40 bis 70 Gew.-Teile Polyalkylenterephthalat.Glass fibers, glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite, etc. can also be used as fillers and reinforcing materials. can be added, which can also be surface-treated. Preferred reinforcing materials are commercially available glass fibers. The glass fibers, which generally have a fiber diameter between 8 and 14 μm, can be used as continuous fibers or as cut or ground glass fibers, it being possible for the fibers to be equipped with a suitable sizing system and a silane-based adhesion promoter or adhesion promoter system. 10 to 40, in particular 20 to 35 parts by weight of fillers and reinforcing materials are preferably added to the mixture. Molding compositions containing fillers and reinforcing materials preferably contain 40 to 89, in particular 40 to 70 parts by weight of polyalkylene terephthalate.
Als Flammschutzmittel können halogenierte Aromaten, halogenhaltige Formmassen, Phosphorverbindungen, mineralische Flammschutzadditive und Tetrafluoroethylen- polymerisate eingesetzt werden.Halogenated aromatics, halogen-containing molding compounds, phosphorus compounds, mineral flame retardant additives and tetrafluoroethylene polymers can be used as flame retardants.
Die erfindungsgemäßen Formmassen können übliche Additive, wie Gleit- und Ent- formungsmittel, Nukleierungsmittel, Antistatika, Stabilisatoren sowie Farbstoffe und Pigmente enthalten. Die erfindungsgemäßen Formmassen und gegebenenfalls weitere bekannte Zusätze wie Stabilisatoren, Farbstoffe, Pigmente, Gleit- und Entformungsmittel, Verstärkungsstoffe, Nukleierungsmittel sowie Antistatika, werden hergestellt, indem man die jeweiligen Bestandteile in bekannter Weise vermischt und bei Temperaturen von 230°C bis 330°C in üblichen Aggregaten wie Innenknetern, Extrudern, Doppelwellenschnecken schmelzcompoundiert oder schmelzextrudiert.The molding compositions according to the invention can contain customary additives, such as lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, and dyes and pigments. The molding compositions according to the invention and optionally other known additives such as stabilizers, dyes, pigments, lubricants and mold release agents, reinforcing materials, nucleating agents and antistatic agents are prepared by mixing the respective constituents in a known manner and at from 230 ° C. to 330 ° C. conventional units such as internal kneaders, extruders, twin-screw extruders melt-compounded or melt-extruded.
Gegenstand der vorliegenden Erfindung ist weiterhin ein Verfahren zur Herstellung von thermoplastischen Formmassen, aus den Komponenten A und B und gegebenen- falls weiteren bekannten Zusätzen wie Copolymere, ABS-Pfropfpolymerisate,The present invention furthermore relates to a process for the production of thermoplastic molding compositions from components A and B and, if appropriate, further known additives such as copolymers, ABS graft polymers,
Flammschutzmittel, Stabilisatoren, Farbstoffen, Pigmenten, Gleit- und Entformungs- mitteln, Verstärkungsstoffen, Nukleierungsmittel sowie Antistatika, das dadurch gekennzeichnet ist, daß man die Komponenten sowie gegebenenfalls die Zusätze nach erfolgter Vermischung bei Temperaturen von 230°C bis 330°C in gebräuchlichen Aggregaten schmelzcompoundiert oder schmelzextrudiert.Flame retardants, stabilizers, dyes, pigments, lubricants and mold release agents, reinforcing materials, nucleating agents and antistatic agents, which are characterized in that the components and, if appropriate, the additives after mixing at temperatures of 230 ° C. to 330 ° C. in conventional units melt compounded or melt extruded.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der obengenannten Formmassen zur Herstellung von Formkörpern, sowie die Formkörper.Another object of the invention is the use of the above-mentioned molding compositions for the production of moldings, and the moldings.
Die Formmassen können zur Herstellung von Formkörpern jeder Art verwendet werden. Insbesondere können Formkörper durch Spritzguß hergestellt werden. Beispiele für herstellbare Formkörper sind: Gehäuse jeder Art, z.B. für Haushaltsgeräte, Steckerleisten und Leuchtensockel sowie Teile aus dem Kraftfahrzeugsektor. The molding compositions can be used to produce moldings of any kind. In particular, moldings can be produced by injection molding. Examples of moldings that can be produced are: Housings of all types, for example for household appliances, power strips and lamp bases, and parts from the motor vehicle sector.
BeispieleExamples
Die folgenden Komponenten werden in den Beispielen verwendet:The following components are used in the examples:
A) Polybutylenterephthalat mit einer Schmelzevolumenrate von 60 cm3/ 10 minA) polybutylene terephthalate having a melt volume rate of 60 cm 3/10 min
(MVR nach ISO 1133; 260°C; 2,16 kg) (POCAN® B 1300, Bayer AG, Leverkusen, Deutschland)(MVR according to ISO 1133; 260 ° C; 2.16 kg) (POCAN® B 1300, Bayer AG, Leverkusen, Germany)
B) linear alternierendes Terpolymer aus Kohlenmonoxid, Ethylen und Propylen (Carilon® DP R 1000, Shell International Chemicals Ltd., London, UK)B) linear alternating terpolymer of carbon monoxide, ethylene and propylene (Carilon® DP R 1000, Shell International Chemicals Ltd., London, UK)
Als Additive werden Stabilisatoren, Entformungsmittel und Nukleierungsmittel in einer Menge von 0,5 Gew.-% zugesetzt.Stabilizers, mold release agents and nucleating agents are added as additives in an amount of 0.5% by weight.
Gemessen wird die Schmelzviskosität bei 260°C mit einem Hochdruckkapillar- viskosimeter in Abhängigkeit von der Scherrate.The melt viscosity is measured at 260 ° C with a high pressure capillary viscometer depending on the shear rate.
Das Mischen der Komponenten und der Additive erfolgt auf einem Extruders des Typs ZSK 32/1 bei 260°C. Die Formkörper werden auf einer Spritzgießmaschine des Typs Arburg 320-210-500 hergestellt.The components and additives are mixed on a ZSK 32/1 extruder at 260 ° C. The moldings are produced on an Arburg 320-210-500 injection molding machine.
Zusammensetzung und Eigenschaften gehen aus der folgenden Tabelle hervor. The following table shows the composition and properties.
Tabelletable
Es zeigt sich, daß in allen erfindungsgemäßen Beispielen ein gut zu verarbeitendesIt can be seen that in all the examples according to the invention, it is easy to process
Blend erhalten wird. Dies erkennt man an den Schmelzeviskositätswerten. Blend is obtained. This can be seen from the melt viscosity values.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU22693/99A AU2269399A (en) | 1997-12-22 | 1998-12-09 | Moulding compounds based on polyalkylenterephthalate and thermoplastic polyketone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997157219 DE19757219A1 (en) | 1997-12-22 | 1997-12-22 | Polyalkylene terephthalate-based thermoplastic molding composition |
| DE19757219.7 | 1997-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999032560A1 true WO1999032560A1 (en) | 1999-07-01 |
Family
ID=7852983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1998/008013 Ceased WO1999032560A1 (en) | 1997-12-22 | 1998-12-09 | Moulding compounds based on polyalkylenterephthalate and thermoplastic polyketone |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2269399A (en) |
| DE (1) | DE19757219A1 (en) |
| WO (1) | WO1999032560A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825042A (en) * | 2019-01-14 | 2019-05-31 | 广东壹豪新材料科技股份有限公司 | A kind of POK/PET/PBT ternary-alloy material and its preparation process |
| CN109880310A (en) * | 2019-01-24 | 2019-06-14 | 广东壹豪新材料科技股份有限公司 | A kind of POK, TLCP, PET trielement composite material and its preparation process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19918729A1 (en) * | 1999-04-24 | 2000-10-26 | Bayer Ag | Thermoplastic molding material, e.g. for molded parts or packaging, contains polyketone and special mixture of emulsion graft copolymer and solution- or bulk-polymerized thermoplastic copolymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818798A (en) * | 1988-06-20 | 1989-04-04 | Shell Oil Company | Polymer blend of carbon monoxide/olefin copolymer and copolyester elastomer |
| US4857605A (en) * | 1988-01-25 | 1989-08-15 | Shell Oil Company | Polymer blend |
| USH1187H (en) * | 1989-08-28 | 1993-05-04 | Shell Oil Company | Polymer blends |
| WO1996018686A1 (en) * | 1994-12-14 | 1996-06-20 | Continental Pet Technologies, Inc. | Transparent package with aliphatic polyketone oxygen-scavenger |
-
1997
- 1997-12-22 DE DE1997157219 patent/DE19757219A1/en not_active Withdrawn
-
1998
- 1998-12-09 WO PCT/EP1998/008013 patent/WO1999032560A1/en not_active Ceased
- 1998-12-09 AU AU22693/99A patent/AU2269399A/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4857605A (en) * | 1988-01-25 | 1989-08-15 | Shell Oil Company | Polymer blend |
| US4818798A (en) * | 1988-06-20 | 1989-04-04 | Shell Oil Company | Polymer blend of carbon monoxide/olefin copolymer and copolyester elastomer |
| USH1187H (en) * | 1989-08-28 | 1993-05-04 | Shell Oil Company | Polymer blends |
| WO1996018686A1 (en) * | 1994-12-14 | 1996-06-20 | Continental Pet Technologies, Inc. | Transparent package with aliphatic polyketone oxygen-scavenger |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825042A (en) * | 2019-01-14 | 2019-05-31 | 广东壹豪新材料科技股份有限公司 | A kind of POK/PET/PBT ternary-alloy material and its preparation process |
| CN109880310A (en) * | 2019-01-24 | 2019-06-14 | 广东壹豪新材料科技股份有限公司 | A kind of POK, TLCP, PET trielement composite material and its preparation process |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2269399A (en) | 1999-07-12 |
| DE19757219A1 (en) | 1999-06-24 |
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