WO1999064515A1 - Matieres moulables thermoplastiques en polyester presentant une stabilite amelioree - Google Patents

Matieres moulables thermoplastiques en polyester presentant une stabilite amelioree Download PDF

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Publication number
WO1999064515A1
WO1999064515A1 PCT/EP1999/003543 EP9903543W WO9964515A1 WO 1999064515 A1 WO1999064515 A1 WO 1999064515A1 EP 9903543 W EP9903543 W EP 9903543W WO 9964515 A1 WO9964515 A1 WO 9964515A1
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WO
WIPO (PCT)
Prior art keywords
weight
acid
molding compositions
thermoplastic polyester
polybutylene terephthalate
Prior art date
Application number
PCT/EP1999/003543
Other languages
German (de)
English (en)
Inventor
Thomas Heitz
Martin Klatt
Original Assignee
Basf 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 Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU43662/99A priority Critical patent/AU4366299A/en
Publication of WO1999064515A1 publication Critical patent/WO1999064515A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof

Definitions

  • PBT polybutylene terephthalate
  • the invention relates to the use of the aforementioned polyester molding compositions for the production of fibers, films and moldings.
  • Polyesters are characterized by low water absorption and good dimensional stability and solvent resistance.
  • polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester.
  • Such polyesters can be produced, for example, by the process of DE-A 44 01 055.
  • the carboxyl end group content is usually determined by titration methods (e.g. potentiometry).
  • post industrial recyclate this is production waste from polycondensation or processing e.g. Sprues in injection molding processing, approach goods in injection molding processing or extrusion or edge sections of extruded sheets or foils.
  • Z represents an alkylene or cycloalkylene group with up to 8 C atoms, an arylene group with up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in which m is the value Has 0 to 2.
  • the compounds I may carry on the phenylene and Ci-C ⁇ alkyl or alkoxy groups and fluorine, chlorine or bromine.
  • the proportion of fully aromatic polyesters in component A) is generally in the range from 0 to 50, preferably from 10 to 30,% by weight.
  • Polyesters in the sense of the present invention which are different from PBT are also to be understood as meaning polycarbonates which are obtained by polymerizing aromatic dihydroxy compounds, in particular bis - (4-hydroxyphenyl) 2, 2-propane (bisphenol A) or its derivatives, e.g. are available with phosgene. Corresponding products are known per se and described in the literature and for the most part are also commercially available.
  • the amount of the polycarbonates is up to 50% by weight, preferably up to 30% by weight, based on 100% by weight of component (A).
  • stage a) and stage b) of the process being carried out in at least two temperature zones.
  • Stage a) of the process is referred to as the so-called transesterification or esterification reaction.
  • This is carried out in at least two, preferably at least three, temperature zones.
  • the temperature of the following zone should be 1-40, preferably 2-30 and in particular 5-10 ° C higher than the temperature of the previous zone.
  • the temperature range for the entire esterification reaction is generally (depending on the starting material) from 165 to 260, preferably from 170 to 250 and in particular from 180 to 240 ° C, the pressure is generally from 1 to 10, preferably from 1 to 4 and in particular from 1 to 2 bar.
  • Zone temperature from 230 to 270, preferably from 240 to 250 ° C., pressure from 0.6 to 0.9, preferably from 0.7 to 0.9 bar.
  • Residence time from 10 to 30, preferably from 15 to 25, minutes.
  • 4th zone temperature from 250 to 300, preferably from 252 to 285 ° C., pressure from 0.015 to 0.2, preferably from 0.025 to
  • the polyester prepolymer has a viscosity number of 15 to 50, preferably 20 to 30 ml / g, measured as 0.5% by weight solution in phenol / o-dichlorobenzene (1: 1) DIN 53728, part 3 (1985) at 25 ° C.
  • the residence times are usually 30 to 180, preferably 35 to 150, minutes.
  • the surface of the product can preferably be renewed.
  • Surface renewal means that new polymer constantly reaches the surface of the melt, so that the exit of the diol is facilitated.
  • the melt is suspended in the lubricant at elevated temperature.
  • it may be necessary to produce a suspension by heating the mixture of lubricant and nucleating agent in advance to temperatures 10 from 30 to 150, preferably from 60 to 130 ° C. and then adding it to the polymer melt.
  • Examples of this include low molecular weight polyethylene waxes, which are known to be in solid form at room temperature and which have to be heated with the nucleating agent to produce a suspension.
  • the melt can be discharged from the polycondensation reactor using suitable devices, e.g. Dosing
  • the polyethylenes can be produced by the high, medium or low pressure process. It can be both high density polyethylenes (HDPE) (range of 0.94 to 0.97 g / cm 3), preferably Herge ⁇ prepared according to the so-called. Phillips process (medium pressure method), 0 as well as low density polyethylenes (LDPE) ( Range from 0.91 to 0.94 g / cm 3 ), in particular linear low density polyethylenes, preferably produced by the gas phase process, can be used.
  • HDPE high density polyethylenes
  • LDPE low density polyethylenes
  • the carboxylic acids can be 1- or 2-valent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, 30 dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to 40 carbon atoms).
  • the aliphatic alcohols can be 1- to 4-valent, whereby 35 not all OH groups have to be esterified. Examples for
  • Alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, glycerol and pentaerythritol being preferred.
  • nucleating agents are minerals from the group of alkali and / or alkaline earth metal (alumo) silicates, preferably from the group of island silicates or layered silicates.
  • Typical compositions of talc can usually be determined by elemental analysis and contain as essential components Si0 2 , MgO, Al 2 O 3 , Fe 2 ⁇ 3 , CaO (after burning).
  • the molding compositions according to the invention can contain 0 to 40, preferably up to 30% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).
  • these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 C- Atoms in the alcohol component.
  • Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg-Thieme -Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
  • Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
  • the rubbers can also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example esters and anhydrides, and / or monomers containing epoxy groups.
  • Copolymers of are particularly preferred
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate can be copolymerized.
  • R 10 is hydrogen or a C 1 -C 4 -alkyl group
  • the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
  • Some preferred emulsion polymers are listed below.
  • graft polymers with a core and at least one outer shell are to be mentioned, which have the following structure:
  • graft polymers in particular ABS and / or ASA polymers in amounts of up to 40% by weight, are preferably used for impact modification of PBT, optionally in a mixture with up to 40% by weight of polyethylene terephthalate.
  • Corresponding blend products are available under the trademark Ultradur®S (formerly Ultrablend®S from BASF AG).
  • ABS / ASA mixtures with polycarbonates are commercially available under the trademark Terblend® (BASF AG).
  • flame retardants are halogen-containing compounds, as described in the plastic manual 3/1, ed. G.W. Becker, D. Braun, Hanser-Verlag, 1992, Kunststoff, pages 31 to 35, or those based on nitrogen or organic or inorganic phosphorus compounds, for example triphenylphosphine oxide, are suitable.
  • Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.
  • Suitable silane compounds are those of the general formula (X - (CH 2 ) n ) - Si - (0 - C m H 2m + 1 ) 4 - k
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • Kaolin, calcined kaolin, wollastonite, talc and chalk may be mentioned as further fillers.
  • oxidation retarders and heat stabilizers are sterically hindered phenols, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
  • Sodium phenylphosphinate, aluminum oxide, silicon dioxide, nylon 22 and preferably talc can be used as nucleating agents.
  • Lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (e.g. stearic acid or behenic acid), their salts (e.g.
  • the molding compositions according to the invention can also contain 0 to 2% by weight of fluorine-containing ethylene polymers.
  • fluorine-containing ethylene polymers These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.
  • examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers. These are described, for example, by Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494 and by Wall in “Fluorpolymers” (Wiley Interscience, 1972).
  • thermoplastic molding compositions according to the invention can be produced by processes known per se, in which the starting components are mixed in conventional mixing devices, such as screw extruders, Brabender mills or Banbury mills, and then extruded. After the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and the remaining starting materials added individually and / or likewise mixed. The mixed temperatures are usually between 230 and 290 ° C.
  • the molding compositions according to the invention are notable for good mechanical properties, in particular also for excellent elongation at break. Yellowing effects do not occur at all or only to a small extent in the molding compositions according to the invention, even after prolonged intensive exposure or when stored under heat. Molecular degradation reactions of the polymer structure, which are regularly reflected in a change in the viscosity number, are also only observed to a minor extent.
  • the molding compositions according to the invention also have a perfect surface behavior and can be used for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector. These applications are in particular lamp parts such as lamp holders and holders, plugs and power strips, coil formers, housings for capacitors or contactors as well as fuse switches, relay housings and reflectors.
  • the temperature in the first reaction zone was 185 ° C. at a pressure of 1 bar and an average residence time of 182 min.
  • the temperature in the second reaction zone was 205 ° C. at a pressure of 1 bar and an average residence time of 63 min.
  • the temperature in the third reaction zone was 210 ° C. at a pressure of 1 bar and an average residence time of 40 min.
  • the impact strength was measured in the impact bending test according to ISO 179 on the specimen leA at 23 ° C.

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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 thermoplastiques en polyester contenant A) 30 à 100 % en poids de polyesters, constitués de a1) 50à 100 % en poids de téréphtalate de polybutylène avec une teneur en composé métallique inorganique ou organique à acide de Lewis comprise entre 65 et 100 ppm (par rapport au métal) et a2) 0 à 50 % en poids de polyesters différents du téréphtalate de polybutylène ; B) 0 à 40 % en poids de modificateurs de la résistance au choc, C) 0 à 30 % en poids d'agents ignifugeants, D) 0 à 50 % en poids de charges et E) 0 à 20 % en poids d'autres additifs, la somme des pourcentages en poids des constituants A) à E) étant toujours égale à 100.
PCT/EP1999/003543 1998-06-05 1999-05-22 Matieres moulables thermoplastiques en polyester presentant une stabilite amelioree WO1999064515A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43662/99A AU4366299A (en) 1998-06-05 1999-05-22 Thermoplastic polyester molding materials with enhanced stability

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998125350 DE19825350A1 (de) 1998-06-05 1998-06-05 Thermoplastische Polyesterformmasse mit verbesserter Stabilität
DE19825350.8 1998-06-05

Publications (1)

Publication Number Publication Date
WO1999064515A1 true WO1999064515A1 (fr) 1999-12-16

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PCT/EP1999/003543 WO1999064515A1 (fr) 1998-06-05 1999-05-22 Matieres moulables thermoplastiques en polyester presentant une stabilite amelioree

Country Status (3)

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AU (1) AU4366299A (fr)
DE (1) DE19825350A1 (fr)
WO (1) WO1999064515A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7329701B2 (en) 2002-08-23 2008-02-12 Basf Aktiengesellschaft Superabsorbent polymers and method of manufacturing the same
CN100587006C (zh) * 2006-08-25 2010-02-03 中国科学院合肥物质科学研究院 含有路易斯酸的共聚聚酯阻燃材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06234909A (ja) * 1993-02-08 1994-08-23 Kuraray Co Ltd ポリブチレンテレフタレート系樹脂組成物およびその製造法
EP0802225A2 (fr) * 1996-04-16 1997-10-22 Hüls Aktiengesellschaft Compositions à mouler
EP0812818A1 (fr) * 1996-06-11 1997-12-17 Tioxide Specialties Limited Procédé d'estérification

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06234909A (ja) * 1993-02-08 1994-08-23 Kuraray Co Ltd ポリブチレンテレフタレート系樹脂組成物およびその製造法
EP0802225A2 (fr) * 1996-04-16 1997-10-22 Hüls Aktiengesellschaft Compositions à mouler
EP0812818A1 (fr) * 1996-06-11 1997-12-17 Tioxide Specialties Limited Procédé d'estérification

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 018, no. 615 (C - 1277) 24 November 1994 (1994-11-24) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7329701B2 (en) 2002-08-23 2008-02-12 Basf Aktiengesellschaft Superabsorbent polymers and method of manufacturing the same
CN100587006C (zh) * 2006-08-25 2010-02-03 中国科学院合肥物质科学研究院 含有路易斯酸的共聚聚酯阻燃材料及其制备方法

Also Published As

Publication number Publication date
AU4366299A (en) 1999-12-30
DE19825350A1 (de) 1999-12-09

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