EP1232215A1 - Matieres moulables polyesteriques thermostables - Google Patents

Matieres moulables polyesteriques thermostables

Info

Publication number
EP1232215A1
EP1232215A1 EP00974513A EP00974513A EP1232215A1 EP 1232215 A1 EP1232215 A1 EP 1232215A1 EP 00974513 A EP00974513 A EP 00974513A EP 00974513 A EP00974513 A EP 00974513A EP 1232215 A1 EP1232215 A1 EP 1232215A1
Authority
EP
European Patent Office
Prior art keywords
weight
graft
molding compositions
carbon atoms
acid
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00974513A
Other languages
German (de)
English (en)
Inventor
Martin Weber
Walter Heckmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 SE filed Critical BASF SE
Publication of EP1232215A1 publication Critical patent/EP1232215A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • Ci 40 to 80% by weight of a graft base made of a rubber-elastic polymer based on alkyl acrylates with 1 to 8 carbon atoms in the alkyl radical and with a glass transition temperature of below 10 ° C.
  • R represents an alkyl radical having 1 to 8 C atoms or a hydrogen atom and R 1 represents an alkyl radical having 1 to 8 C atoms and n has the value 1, 2 or 3 and
  • the invention relates to the use of the molding compositions according to the invention for the production of moldings of any kind and the moldings obtainable here.
  • Polymer blends are gaining increasing interest in technology because they offer tailor-made combinations of properties. Of particular interest are polymer mixtures made of incompatible polymers that have unusual combinations of properties.
  • Polymer mixtures based on polyesters and polycarbonates have been known for years (US 4,522,797, 4,764,556, 4,897,448, EP-A 180 648, DE-A 3302124).
  • the technically important products also contain impact modifiers to improve toughness, especially at low temperatures, MBS modifiers, acrylate graft rubbers and ethylene copolymers with polar comonomers being preferably used.
  • Blends based on polyesters and styrene copolymers are also known (DE-A 3403 576, EP-A 310 976, EP-A 310 977, EP-A 310 978). Mixtures of polyesters and at least two rubbers of different particle sizes, which are characterized by good toughness, are also known from DE-A 3733 839.
  • the object of the present invention was to provide polyester molding compositions which have improved mechanical properties (in particular toughness) and long-term durability. Accordingly, the molding compositions defined at the outset were found. Preferred embodiments can be found in the subclaims.
  • thermoplastic molding compositions mentioned at the outset which contain epoxy resins as an essential constituent, have an improved property profile with respect to toughness and long-term use resistance compared to the prior art.
  • the molding compositions according to the invention contain 2 to 97.9, preferably 5 to 90.8 and in particular 10 to 81.5% by weight of a thermoplastic polyester as component (A).
  • Polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are generally used.
  • a first group of preferred polyesters are polyalkylene terephthalates, in particular with 2 to 10 carbon atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid.
  • the aromatic ring can also be substituted, for example by halogen such as chlorine and bromine or by C 1 -C 4 alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-3utyl - groups.
  • polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof.
  • Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • aliphatic dihydroxy compounds are diols with 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclo - Hexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.
  • Polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms can be mentioned as particularly preferred polyesters (A).
  • polyesters A
  • polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred in particular.
  • P ⁇ T and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
  • the viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% by weight solution in a phenol / o -dichlorobenzene mixture (% by weight. 1: 1 at 25 ° C) according to ISO 1628).
  • 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).
  • Particularly preferred molding compositions contain, as component A), a mixture of polyesters other than PBT, such as, for example, polyethylene terephthalate (PET).
  • PBT polyethylene terephthalate
  • the proportion e.g. of the polyethylene terephthalate is preferably in the
  • PET recyclates also called scrap PET
  • PBT polyalkylene terephthalates
  • 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.
  • Post consumer recyclate these are plastic items that are collected and processed by the end consumer after use.
  • the most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.
  • Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the tube cyclates are melted and granulated in an extruder after separation and cleaning. This usually facilitates handling, free-flowing properties and meterability for further processing steps.
  • Recyclates, both granulated and in the form of regrind can be used, the maximum edge length being 6 mm, preferably less than 5 mm.
  • the residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%.
  • Aromatic dicarboxylic acids which are suitable are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid are preferred, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids.
  • the aromatic dihydroxy compounds preferably have the general formula
  • 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 represents the value Has 0 to 2.
  • the compounds I can also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • mixtures of polyalkylene terephthalates and fully aromatic polyesters can also be used. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.
  • polyester block copolymers such as copolyether esters can also be used.
  • Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014.
  • Corresponding products are also commercially available, for example Hytrel ® (DuPont).
  • the molding compositions may comprise, as component B), at least one polycarbonate in amounts of 0 to 95.9, preferably 5 to 90.8 and in particular 10 to 81.5% by weight.
  • Halogen-free polycarbonates are preferably used as component B). Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula
  • Q is a single bond, a Ci- to C ⁇ -alkylene, a C 2 - to C -alkylidene, a C 3 - to C ⁇ -cycloalkylidene group, a C 6 - to C 1 2 ⁇ arylene group and -0-, -S - or -S0 2 - means and m is an integer from 0 to 2.
  • the diphenols can also have substituents on the phenylene radicals, such as C] _- to Cg-alkyl or Ci- to C ö -alkoxy.
  • Preferred diphenols of the formula are, for example, kydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1 - bis (4-hydroxyphenyl) cyclohexane.
  • 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, as well as 1,1-bis (4-hydroxyphenyl) -3,3,5- are particularly preferred. trimethylcyclohexane.
  • both homopolycarbonates and copolycarbonates are suitable as component B; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.
  • the diphenols of the general formula are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase interface method or with phosgene by the method in a homogeneous phase (the so-called pyridine method), the molecular weight to be adjusted in each case being achieved in a known manner by a corresponding amount of known chain terminators , (Regarding polydiorganosiloxane-containing polycarbonates, see for example DE-OS 33 34 782).
  • Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or Dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-t-butylphenol, p-t-octylphenol, p-dodecylphenol, 2 - (3, 5-dimethylheptyl) phenol and 4 - (3, 5-dimethylheptyl) phenol.
  • alkylphenols such as 4- (1,3-tetramethylbutyl) phenol, according to DE-OS 28 42 005 or monoalkylphenols or Dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according
  • Halogen-free polycarbonates in the sense of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine resulting, for example, from the production of the polycarbonates with phosgene by the phase interface process. is not to be regarded as containing halogen in the sense of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the sense of the present invention.
  • Amorphous polyester carbonates may be mentioned as further suitable components B), with phosgene being replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during production.
  • Bisphenol A can also be replaced by Bisphenol TMC.
  • Such polycarbonates are available under the trademark APEC HT ® from Bayer.
  • One or a mixture of different graft copolymers are used as component C) in the molding compositions according to the invention in amounts of 1 to 80% by weight, based on the sum of components A to F.
  • Preferred molding compositions according to the invention contain from 2 to 60, particularly preferably from 5 to 50% by weight of at least one graft copolymer C which is different from rubber-elastic polymers F).
  • the graft polymers C are composed of
  • a graft base made of a rubber-elastic polymer based on alkyl acrylates having 1 to 8 carbon atoms in the alkyl radical and having a glass transition temperature of below 0 ° C.
  • c 2 20 to 60% by weight, preferably 30 to 50% by weight, of a graft pad c 2 ⁇ ) 60 to 95 wt .-%, preferably 70 to 85 wt .-% styrene or substituted styrenes of the general formula I.
  • R is a Ci- to Cs-alkyl radical, preferably methyl or ethyl, or hydrogen and R 1 is an O ⁇ - to C ⁇ -alkyl radical, preferably methyl or ethyl, and n has the value 1, 2 or 3 or their mixtures and
  • Polymers whose glass transition temperature is below 10 ° C., preferably below 0 ° C., particularly preferably below -20 ° C., are suitable for the graft base ci. These are elastomers acid on the basis of Ci to C 8 alkyl esters of acrylic, which may contain optionally further comonomers.
  • alkyl acrylate having 1 to 8 carbon atoms in the alkyl radical, preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, in particular n- Butyl acrylate as the sole alkyl acrylate
  • C 12 0 to 30% by weight, in particular 20 to 30% by weight, of a further copolymerizable monoethylenically unsaturated monomer, such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof
  • a further copolymerizable monoethylenically unsaturated monomer such as butadiene, isoprene, styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof
  • Suitable such bi- or polyfunctional crosslinking monomers C 13 are monomers which preferably contain two, optionally also three or more, ethylenic double bonds which are capable of copolymerization and which are not contained in the
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate or triallyl isocyanurate.
  • the acrylic acid ester of tricyclodecenyl alcohol has proven to be a particularly favorable crosslinking monomer (cf. DE-A 12 60 135).
  • graft pads c 2 preference is given to those in which C 21 is styrene or ⁇ -methylstyrene or mixtures thereof and in which c 22 is acrylonitrile or methacrylonitrile. Styrene and acrylonitrile or ⁇ -methylstyrene and acrylonitrile are used as preferred monomer mixtures.
  • the grafting pads can be obtained by copolymerizing components C 21 and C 22 -
  • the graft base Ci of the graft polymers C which is composed of the components cn, optionally C 2 , and c ⁇ 3 , is also referred to as ASA rubber.
  • Their manufacture is known per se and is described, for example, in DE-A 28 26 925, DE-A 31 49 358 and DE-A 3414 118.
  • the graft polymers C can be prepared, for example, by the method described in DE-PS 12 60 135.
  • the graft layer (graft shell) of the graft polymers can be built up in one or two stages.
  • the first stage In the case of a two-stage structure of the graft shell c 2 , the first stage generally makes up 20 to 70% by weight, preferably 25 to 50% by weight, based on C 2 . Only styrene or substituted styrenes or mixtures thereof (C 21 ) are preferably used for their preparation.
  • the second stage of the graft shell generally makes up 30 to 80% by weight, in particular 50 to 75% by weight, based in each case on C 2 .
  • the conditions of the graft polymerization are preferably chosen so that particle sizes of 50 to 700 nm (dso-Wer der integral mass distribution.g) result. Measures for this are known and described, for example, in DE-OS 2826925.
  • a coarse-particle rubber dispersion can be produced directly using the seed latex process.
  • the particles of the rubber are kneaded in a known manner, e.g. by agglomeration, enlarged so that the latex is bimodal (50 to 180 nm and 200 to 700 nm).
  • a mixture of two graft polymers with particle diameters (ds 0 value of the integral mass distribution) of 50 to 180 nm or 200 to 700 nm in a weight ratio of 70:30 to 30:70 is used.
  • the chemical structure of the two graft polymers is preferably the same, although the shell of the coarse-particle graft polymer can in particular also be constructed in two stages.
  • Mixtures of components A and C, the latter having a coarse and fine-particle graft polymer, are e.g. described in DE-OS 36 15 607.
  • Mixtures of components A and C, the latter having a two-stage graft, are known from EP-A 111 260.
  • the molding compositions according to the invention contain 1 to 80% by weight, based on the sum of components A to F, of at least one copolymer based on styrene or substituted styrenes and unsaturated nitriles.
  • Preferred molding compositions according to the invention contain component D in proportions of 2 to 60, in particular 3 to 50,% by weight, based on the sum of components A to F.
  • copolymers D are made according to the invention.
  • copolymers D are resin-like, thermoplastic and rubber-free. Particularly preferred copolymers D are those made from styrene and acrylonitrile, from ⁇ -methylstyrene and acrylonitrile or from styrene, ⁇ -methylstyrene and acrylonitrile. Several of the copolymers described can also be used simultaneously.
  • copolymers D are known per se and can be radicalized
  • Produce polymerization in particular by emulsion, suspension, solution and bulk polymerization. They have viscosity numbers in the range from 40 to 160, this corresponds to average molecular weights M w (weight average) of 40,000 to 2,000,000.
  • the molding compositions according to the invention contain 0.01 to 10, preferably 0.2 to 5 and in particular 0.5 to 3% by weight of an epoxy resin as component E.
  • an epoxy resin as component E.
  • all epoxy resins are suitable, the structure and production of which are described, for example, in B. Ellis, Chemistry and Technology of Epoxy-Resins, Blackie Academic & Professional, 1993.
  • Preferred epoxy resins are those of the general formula II, which are usually obtainable by condensation of 2,2-bis (p-hydroxyphenylpropane) (bisphenol A) and epichlorohydrin:
  • R 1 is a hydrogen radical, an alkyl radical having 1 to 16 carbon atoms, preferably methyl and
  • n 2 to 50, preferably 2 to 13.
  • Epoxy resins usually have an epoxy number according to ISO 3001 of 1.5 to 1.9, preferably 1.68 to 1.75.
  • the softening point according to DIN 51920 is preferably from 75 to 100, in particular 82 to 90 ° C.
  • the melt viscosity according to DIN 53018 Tl at 175 ° C is preferably 250 to 600, in particular 350 to 480 mPas.
  • n has the same meaning as in II and R 2 is an alkyl radical having 1 to 16 carbon atoms.
  • Preferred radicals R 2 are propyl and butyl.
  • Epoxy resins of the general formula IV are also suitable
  • R 3 and n as defined in formula II, wherein R 3 is preferably hydrogen.
  • Cycloaliphatic epoxy resins (formula V) are also suitable:
  • R 4 represents an alkyl radical having 1 to 16 carbon atoms.
  • Condensation products of alcohols, in particular diols and / or bisphenols with triglycidyl isocyanurate, may be mentioned as further preferred resins.
  • Mixtures can of course also be used, the mixing ratio being arbitrary.
  • the molding compositions according to the invention can contain 0 to 15 80, in particular up to 50% by weight, of further additives as component F).
  • the carboxylic acids can be 1- or 2-valent. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to
  • the aliphatic alcohols can be 1- to 4-valent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, 35 glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1- to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, ethylenediamine and hexamethylenediamine being particularly preferred.
  • Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • Additional additives F are, for example, in amounts up to 40, preferably up to 30% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers), which are different from C).
  • 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.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5 -diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cycloocta-dienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethyliden-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3, 8-decadiene or mixtures thereof.
  • conjugated dienes
  • EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives. Examples include acrylic acid, methacrylic acid and their derivatives, for example glycidyl (meth) acrylate, and maleic anhydride.
  • 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, e.g. Contain esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers of the general formulas I or II or III or IV containing dicarboxylic acid or epoxy groups to the monomer mixture
  • R 1 to R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.
  • the radicals R 1 to R 9 are preferably hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, Glyci - dyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior comes close to that of the free acids and is therefore referred to as monomers with latent carboxyl groups 5.
  • the copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or acid anhydride groups - the monomers and the remaining amount of (meth) acrylic acid star ,
  • Copolymers of are particularly preferred
  • n-butyl acrylate 1 to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
  • Fibrous or particulate fillers are carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in quantities of up to 50% by weight. %, in particular 1 to 40%, in particular 20 to 35% by weight, are used.
  • 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.
  • the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.
  • Suitable silane compounds are those of the general formula
  • n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on F) for surface coating.
  • acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character.
  • An example is needle-shaped wollastonite.
  • the mineral preferably has an L / D (length to diameter) ratio of 8: 1 to 35: 1, preferably from 8: 1 to 11: 1.
  • the mineral filler can optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.
  • thermoplastic molding compositions according to the invention can contain customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, flame retardants, nucleating agents, plasticizers, etc.
  • UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition.
  • Inorganic pigments such as ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthrachine-none can also be added as colorants.
  • Sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc can be used as nucleating agents.
  • Further lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain , saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes.
  • long-chain fatty acids eg stearic acid or behenic acid
  • their salts eg Ca or Zn stearate
  • montan waxes mixturetures of straight-chain , saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms
  • low molecular weight polyethylene or polypropylene waxes low molecular weight polyethylene or polypropylene waxes.
  • plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.
  • the molding compositions according to the invention can also contain 0 to 2% by weight of 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.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoropropylene copolymers examples of this are polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (usually up to
  • Another preferred group of lubricants are ethylene oxide / propylene oxide copolymers.
  • the ethylene oxide / propylene oxide copolymers are generally produced by ionic polymerization and have been described by N. Schönfeldt, “interfacially active ethylene oxide adducts”, Horschaff tliehe Verlagsgesellschaft mbh, Stuttgart 1976, p. 53 ff.
  • XYX Copolymers are usually first polymerized into a medium-sized polypropylene oxide block Y, at each end of which a block of ethylene oxide units is attached Usually from 2 to 90% by weight, preferably from 5 to 85% by weight.
  • products with a middle block made of polyethylene glycol (YXY) can also be used. In this case, the proportion of polyethylene glycol is usually from 5 to 80% by weight .-%, preferably from 7.5 to
  • the molecular weights are generally from 1000 to 15000 g / mol.
  • the molecular weights (number average) of these compounds are determined from the OH number in accordance with DIN 53240.
  • Particularly preferred additives F) are inorganic and organic transesterification inhibitors which can be present in the molding compositions according to the invention in amounts of from 0.01 to 5, preferably from 0.05 to 2,% by weight.
  • Suitable organic phosphonites are those of the general formula
  • Y is an oxygen-sulfur - or 1,4-phenylene bridge or a bridge member of the formula -CH (R 2 ) -; all R-0 and R ⁇ O groups independently of one another, the residue of an aliphatic, alicyclic or aromatic alcohol which may contain up to three hydroxyl groups, but the hydroxyl groups are not arranged such that they are part of a ring containing phosphorus can (referred to as monovalent R-O groups), or two RO or R 1 -0- groups bonded to a phosphorus atom, each independently of one another together the remainder of an aliphatic, alicyclic or aromatic alcohol with a total of up to three hydroxyl groups (referred to as divalent RO or R 1 -0 groups),
  • R 2 is hydrogen, -CC 8 alkyl or a group of the formula COOR 3 and
  • R 3 is Ci-g alkyl.
  • Suitable inorganic transesterification stabilizers are described, for example, in US Pat. No. 5,674,928.
  • Acidic salts of phosphoric acid such as monozinc phosphate, calcium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate may be mentioned as particularly suitable.
  • phosphates such as Zn phosphate and copper phosphate can also be used.
  • Other metal phosphates with metals of the first and second subgroups are also suitable.
  • P-containing acids such as phosphoric acid, phosphorous acid, polyphosphorous acid or hypophosphoric acid can also be used.
  • 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 mixing temperatures are usually 230 to 290 ° C.
  • components B) to E) and, if appropriate, customary additives F) can be mixed, made up and granulated with a polyester prepolymer.
  • the granules obtained are then in the solid phase under inert gas continuously or batchwise at a
  • thermoplastic molding compositions according to the invention are notable for a good combination of long-term durability
  • Toughness, flowability and melt stability are suitable for the production of fibers, foils and moldings, in particular for applications in the automotive and electronics sectors, as well as household articles and medical technical devices.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • Polycarbonate based on bisphenol A e.g. Lexan® 161 from General Electric, characterized by a viscosity number of 61 ml / g (measured in 0.5% by weight CH 2 CI 2 solution at 23 ° C).
  • a coarse graft polymer that was prepared as follows:
  • the latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40%.
  • Irgaphos®PEPQ from Ciba Geigy Specialty Chemicals GmbH (tetrakis (-2, 4-di-tert-butylphenyl) -4,4 'diphenylene-diphosphonite)
  • a twin-screw extruder 250 ° C housing temperature was used to mix components A) to F).
  • the melt was passed through a water bath and granulated.
  • the test specimens were produced at a melt temperature of 260 ° C.
  • Example VI V2 V3 components in% by weight
  • HDT B (° C) 210 209 213 211 197 196 an (kJ / m 2 ) 52 55 52 53 64 67

Landscapes

  • 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 thermostables contenant principalement les composantes suivantes : A) 2 à 97,9 % en poids d'au moins un polyester ; B) 0 à 95,9 % en poids d'au moins un polycarbonate ; C) 1 à 80 % en poids d'au moins un polymère greffé constitué de c1) 40 à 80 % d'une base greffage en polymère caoutchouteux à base d'alkyle-acrylates ayant 1 à 8 atomes de carbone dans le reste alkyle et une température de transition vitreuse inférieure à 10 °C ; c2) 20 à 60 % en poids d'une greffe constituée de c21) 60 à 95 % en poids de styrène ou de styrènes substitués de la formule générale (I) où R représente un reste alkyle ayant 1 à 8 atomes de carbone ou un atome d'hydrogène et R1 un reste alkyle ayant 1 à 8 atomes de carbone et n vaut 1, 2 ou 3 et c¿22?) 5 à 40 % en poids d'au moins un nitrile non saturé, D) 1 à 80 % en poids d'un copolymère composé de d 160 à 95 % en poids de styrène ou de styrènes substitués de la formule générale (I) ou de leurs mélanges d2) 5 à 40 % en poids d'au moins un nitrile non saturé ; E) 0,1 à 10 % en poids d'une résine époxy F) 0 à 80 % en poids d'autres adjuvants, la somme des pourcentages en poids des composantes A) à F) étant égale à 100 %.
EP00974513A 1999-11-24 2000-11-10 Matieres moulables polyesteriques thermostables Withdrawn EP1232215A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19956539A DE19956539A1 (de) 1999-11-24 1999-11-24 Thermisch stabile Polyesterformmassen
DE19956539 1999-11-24
PCT/EP2000/011101 WO2001038436A1 (fr) 1999-11-24 2000-11-10 Matieres moulables polyesteriques thermostables

Publications (1)

Publication Number Publication Date
EP1232215A1 true EP1232215A1 (fr) 2002-08-21

Family

ID=7930171

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00974513A Withdrawn EP1232215A1 (fr) 1999-11-24 2000-11-10 Matieres moulables polyesteriques thermostables

Country Status (5)

Country Link
US (1) US6894112B1 (fr)
EP (1) EP1232215A1 (fr)
AU (1) AU1279001A (fr)
DE (1) DE19956539A1 (fr)
WO (1) WO2001038436A1 (fr)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10216071A1 (de) * 2002-04-11 2003-10-23 Basf Ag Polycarbonat-Styrolcopolymer-Blends mit verbesserten Eigenschaften
US20070093583A1 (en) * 2003-10-28 2007-04-26 Asahi Kasei Chemicals Corporation Polytrimethylene terephthalate reinforced resin composition
DE102004005652A1 (de) 2004-02-04 2005-08-25 Basf Ag Fließfähige Polyesterformmassen
DE102004005657A1 (de) * 2004-02-04 2005-08-25 Basf Ag Fließfähige Polyesterformmassen
MY139705A (en) * 2004-07-19 2009-10-30 Basf Ag Mixtures of hyperbranched polyesters with polycarbonates as additive for polyester molding compositions
DE102004035357A1 (de) * 2004-07-21 2006-03-16 Basf Ag Kontinuierliches Verfahren zur Herstellung von Polyalkylenarylaten mit hyperverzweigten Polyestern und/oder Polycarbonaten
DE102004038979A1 (de) 2004-08-10 2006-02-23 Basf Ag Schlagzähmodifizierte Polyester mit hyperverzweigten Polyestern
DE102004059243A1 (de) * 2004-08-10 2006-02-23 Basf Ag Thermoplastische Formmassen mit verbesserten Fließ- und Entformungseigenschaften
DE102004038976A1 (de) * 2004-08-10 2006-02-23 Basf Ag Fließfähige Polyesterformmassen mit ASA/ABS und SAN
DE102004049342A1 (de) * 2004-10-08 2006-04-13 Basf Ag Fließfähige Thermoplaste mit halogenfreiem Flammschutz
DE102004050025A1 (de) * 2004-10-13 2006-04-20 Basf Ag Fließfähige Thermoplaste mit Halogenflammschutz
DE102004051241A1 (de) * 2004-10-20 2006-05-04 Basf Ag Fließfähige Polyamide mit hyperverzweigten Polyestern/Polycarbonaten
DE102005002044A1 (de) * 2005-01-14 2006-07-20 Basf Ag Fließfähige Polyester mit Hydrolyseschutz
DE102005004856A1 (de) * 2005-02-01 2006-08-03 Basf Ag Fliessfähige Polyester mit Carbodilmid-Stabilisatoren
DE102005027549A1 (de) 2005-06-14 2006-12-21 Basf Ag Mehrkomponentenformkörper mit Polyesterschichten
DE102005034980A1 (de) * 2005-07-22 2007-01-25 Basf Ag Fasern und Flüssigkeitsbehälter aus PET
DE102005037329A1 (de) * 2005-08-04 2007-02-08 Basf Ag Thermoplastische Formmassen auf Basis von Polyestern und Styrolcopolymeren
JP5796121B1 (ja) * 2014-12-02 2015-10-21 ユーエムジー・エービーエス株式会社 強化熱可塑性樹脂組成物およびその成形品
CN107429055B (zh) * 2016-02-18 2019-08-23 株式会社Lg化学 聚碳酸酯树脂组合物以及使用该组合物的光学模制品
CN110621733B (zh) * 2017-06-16 2021-11-09 沙特基础工业全球技术有限公司 磺酸在聚碳酸酯中作为稳定剂的用途
CN111116879B (zh) * 2019-12-09 2021-03-09 广东盈骅新材料科技有限公司 不饱和聚酯树脂及其制备方法和应用
DE102020215134A1 (de) 2020-12-01 2022-06-02 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung eines Bauteil-Kunststoff-Verbundes mit einer Übergangsmetall-Phthalocyanin-Schicht
CN114133701A (zh) * 2022-01-06 2022-03-04 天津仁爱学院 高性能环氧高分子材料的制备及应用

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3302124A1 (de) 1983-01-22 1984-07-26 Bayer Ag, 5090 Leverkusen Thermoplastische formmassen
US4522797A (en) 1983-09-08 1985-06-11 Ethyl Corporation Halophosphazene polymers
DE3403576A1 (de) 1984-02-02 1985-08-08 Basf Ag, 6700 Ludwigshafen Elastomere thermoplastische formmassen und deren herstellung
JPS60231757A (ja) 1984-05-01 1985-11-18 Toray Ind Inc ポリエステル組成物
US4629760A (en) * 1985-11-01 1986-12-16 General Electric Company Composition of polycarbonate, polyester, acrylate elastomeric copolymer and a phenoxy resin
DE3617070A1 (de) 1986-05-21 1987-11-26 Basf Ag Thermoplastische formmassen aus polyester und polycarbonat
DE3640875A1 (de) 1986-11-29 1988-06-09 Basf Ag Thermoplastische formmassen auf der basis von polycarbonaten, polyestern und polyamiden
DE3733838A1 (de) 1987-10-07 1989-04-20 Basf Ag Glasfaserverstaerkte thermoplastische formmassen auf der basis von poyestern und pfropfpolymerisaten
EP0310977A3 (fr) 1987-10-07 1990-07-25 BASF Aktiengesellschaft Compositions à mouler thermoplastiques, renforcées par des fibres de verre, à base de polyester et de polymères greffés
DE3733839A1 (de) 1987-10-07 1989-04-20 Basf Ag Glasfaserverstaerkte thermoplastische formmassen auf der basis von polyestern und pfropfpolymerisaten
DE3733857A1 (de) 1987-10-07 1989-04-27 Basf Ag Glasfaserverstaerkte thermoplastische formmassen auf der basis von polyestern und pfropfpolymerisaten
US4897448A (en) 1988-04-01 1990-01-30 Eastman Kodak Company Polyester/polycarbonate blends
US5412028A (en) * 1988-04-13 1995-05-02 Lucky, Ltd. Thermoplastic resin composition
US5187227A (en) * 1990-07-06 1993-02-16 Nippon Zeon Co., Ltd. Polycarbonate resin composition
WO1992014787A1 (fr) * 1991-02-26 1992-09-03 The Dow Chemical Company Melanges de compositons de moulage thermoplastique contenant des resines epoxy

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0138436A1 *

Also Published As

Publication number Publication date
DE19956539A1 (de) 2001-05-31
US6894112B1 (en) 2005-05-17
AU1279001A (en) 2001-06-04
WO2001038436A1 (fr) 2001-05-31

Similar Documents

Publication Publication Date Title
EP1232215A1 (fr) Matieres moulables polyesteriques thermostables
DE10304341A1 (de) Hydrolysebeständige Polyester
EP3004242B1 (fr) Masses de moulage en polyester avec faible émission de toc
DE102004005652A1 (de) Fließfähige Polyesterformmassen
WO2017063841A9 (fr) Mélange de polyesters ignifugé sans halogène
EP1192221B1 (fr) Melanges polyester/polycarbonate
WO2006050872A1 (fr) Melanges polymeriques contenant des polyesters et des polycarbonates oligomeres lineaires
WO2005082994A1 (fr) Composites constitues de thermoplastiques dans lesquels des charges sont reparties de façon monodispersee
WO2008052998A1 (fr) Corps moulés en polyester pauvres en émissions
EP2976385B1 (fr) Polyester pour le moulage par soufflage, l'extrusion de profilés et/ou l'extrusion de tubes
EP3044255B1 (fr) Polyesters ignifuges
WO2004056914A1 (fr) Matiere polyester a mouler electriquement isolante et thermoconductrice
EP2861665A1 (fr) Polyesters ignifugés comprenant des homopolymères polyacrylonitrile
EP1917308B1 (fr) Eléments de phares en polyester
DE10255043A1 (de) Verwendung von Polykondensatmischungen zur Herstellung von Formteilen mit verbesserter Hydrolysebeständigkeit
WO2012163822A1 (fr) Polyester renfermant des copolymères de styrène
WO2012022669A2 (fr) Mélanges de nanocomposites et de polyesters
WO2023088806A1 (fr) Mélanges thermoplastiques
EP3512913B1 (fr) Polyester pour l'extrusion de profilés et/ou l'extrusion de tubes
WO2000041470A2 (fr) Procédé de préparation de mélanges de polymères
WO2000058401A1 (fr) Melanges polyester/polycarbonate a stabilite dimensionnelle
WO2022029260A1 (fr) Mélanges thermoplastiques
WO2009050094A1 (fr) Matières à mouler en polyester thermoplastique contenant des polyétheramines très ramifiées
WO2007088125A1 (fr) Matieres pour moulage a base de polyester comprenant un copolymere d'imide maleique
WO2000046295A1 (fr) Matiere moulable a base de polyester a resistance elevee aux chocs

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020430

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20040427

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20070219