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WO1999032560A1 - Matieres moulables a base de polyalcyleneterephtalate et de polycetones thermoplastiques - Google Patents

Matieres moulables a base de polyalcyleneterephtalate et de polycetones thermoplastiques Download PDF

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Publication number
WO1999032560A1
WO1999032560A1 PCT/EP1998/008013 EP9808013W WO9932560A1 WO 1999032560 A1 WO1999032560 A1 WO 1999032560A1 EP 9808013 W EP9808013 W EP 9808013W WO 9932560 A1 WO9932560 A1 WO 9932560A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
thermoplastic molding
composition according
molding composition
Prior art date
Application number
PCT/EP1998/008013
Other languages
German (de)
English (en)
Inventor
Karsten-Josef Idel
Hans-Jürgen DIETRICH
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU22693/99A priority Critical patent/AU2269399A/en
Publication of WO1999032560A1 publication Critical patent/WO1999032560A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières moulables à base de polyalcylènetéréphtalate et de polycétones thermoplastiques (copolymères oléfine-monoxyde de carbone), leur utilisation pour la production de corps moulés et lesdits corps moulés ainsi obtenus.
PCT/EP1998/008013 1997-12-22 1998-12-09 Matieres moulables a base de polyalcyleneterephtalate et de polycetones thermoplastiques WO1999032560A1 (fr)

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 (de) 1997-12-22 1997-12-22 Formmassen auf Basis Polyalkylenterephthalat und thermoplastischer Polyketone
DE19757219.7 1997-12-22

Publications (1)

Publication Number Publication Date
WO1999032560A1 true WO1999032560A1 (fr) 1999-07-01

Family

ID=7852983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/008013 WO1999032560A1 (fr) 1997-12-22 1998-12-09 Matieres moulables a base de polyalcyleneterephtalate et de polycetones thermoplastiques

Country Status (3)

Country Link
AU (1) AU2269399A (fr)
DE (1) DE19757219A1 (fr)
WO (1) WO1999032560A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109825042A (zh) * 2019-01-14 2019-05-31 广东壹豪新材料科技股份有限公司 一种pok/pet/pbt三元合金材料及其制备工艺
CN109880310A (zh) * 2019-01-24 2019-06-14 广东壹豪新材料科技股份有限公司 一种pok、tlcp、pet三元复合材料及其制备工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19918729A1 (de) * 1999-04-24 2000-10-26 Bayer Ag Thermoplastische Polyketon-Formmassen

Citations (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1994-12-14 1996-06-20 Continental Pet Technologies, Inc. Emballage transparent contenant un agent de suppression d'oxygene de polycetone aliphatique

Patent Citations (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1994-12-14 1996-06-20 Continental Pet Technologies, Inc. Emballage transparent contenant un agent de suppression d'oxygene de polycetone aliphatique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109825042A (zh) * 2019-01-14 2019-05-31 广东壹豪新材料科技股份有限公司 一种pok/pet/pbt三元合金材料及其制备工艺
CN109880310A (zh) * 2019-01-24 2019-06-14 广东壹豪新材料科技股份有限公司 一种pok、tlcp、pet三元复合材料及其制备工艺

Also Published As

Publication number Publication date
AU2269399A (en) 1999-07-12
DE19757219A1 (de) 1999-06-24

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