WO2009101026A1 - Polyester à charge minérale - Google Patents

Polyester à charge minérale Download PDF

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Publication number
WO2009101026A1
WO2009101026A1 PCT/EP2009/051320 EP2009051320W WO2009101026A1 WO 2009101026 A1 WO2009101026 A1 WO 2009101026A1 EP 2009051320 W EP2009051320 W EP 2009051320W WO 2009101026 A1 WO2009101026 A1 WO 2009101026A1
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Prior art keywords
molding compositions
weight
thermoplastic molding
compositions according
components
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PCT/EP2009/051320
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German (de)
English (en)
Inventor
Hiroki Fukuhara
Norihiro Sota
Motonori Yamamoto
Jochen Engelmann
Martin Klatt
Chirag Tejuja
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Basf Se
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Publication of WO2009101026A1 publication Critical patent/WO2009101026A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • thermoplastic molding compositions comprising
  • the invention relates to the use of such molding compositions for the production of fiber, films and moldings, in particular lighting elements, as well as the moldings obtainable in this case of any kind.
  • thermoplastic materials In order to reduce the weight and thus the fuel consumption of motor vehicles, many automotive components are made of thermoplastic materials. Thermoplastics also offer the advantage that they can be processed easier and faster than metals to complicated shaped components, for example by injection molding.
  • lighting elements such as lamps, lights, headlamps, position lights, turn signals, etc. have good dimensional stability (low shrinkage) under thermal stress, good processability and surface finish, and balanced mechanical properties Properties required.
  • plastics used must have low fogging. Fogging is the condensation of vaporized volatiles of plastics, textile, leather or other materials to form a cloudy deposit on the inside of glass sheets or other smooth surfaces.
  • the fogging can occur, for example, in the vehicle interior as a coating on the windshield inside, or in vehicle headlamps as a coating on the headlight glass inside or the headlight reflector.
  • the coating on the headlight glass or reflector, the light output and lighting range significantly reduce the orientation of the light beam (glare hazard of oncoming traffic) and lead to electrical short circuits in the headlight.
  • Barium sulfate is suitable for many applications, e.g. for coatings and foils (WO 2007/069353, US 2002/0136879), ceramic surfaces, tablecloths or carpet applications (JP-A 2001/279 069, JP-A 2003/026 908 and JP 2002/332 396).
  • the amounts of filler are substantial, sometimes up to 70% by weight, to achieve sufficient surface gloss. Accordingly, the mechanical properties are disadvantageous.
  • polyester molding compositions for headlamp parts which contain different fillers and lubricants.
  • the object of the present invention was therefore to provide thermoplastic polyesters which have good surface properties (gloss) and processing properties, in particular at elevated temperatures, good dimensional stability, good haze and clarity, and low fogging behavior.
  • the molding compositions according to the invention contain from 10 to 98, preferably from 20 to 88 and in particular from 30 to 82,% by weight of at least one thermoplastic PBT (polybutylene terephthalate).
  • the molding compositions according to the invention contain 1 to 40% by weight, preferably 10 to 30% by weight and in particular 15 to 30% by weight of another polyester B), which is different from A).
  • polyesters B) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.
  • a first group of preferred polyesters are polyalkylene terephthalates, especially those having 2 to 10 C atoms in the alcohol moiety, which are different from A).
  • Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid.
  • the aromatic ring may also be substituted, e.g. by halogen, such as chlorine and bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, isopropyl or n-propyl and n, i and t-butyl groups.
  • polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.
  • 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 having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.
  • polyesters (B) are polyalkylene terephthalates derived from alkanediols having 2 to 6 carbon atoms. Of these, particularly preferred are polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. Preference is furthermore given to PET 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) and B) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5 wt .-% solution in a phenol / o-dichlorobenzene mixture (wt. 1: 1 at 25 ° C) according to ISO 1628.
  • Particularly preferred as component A) is a mixture of PBT different VZ used, wherein the difference VZ (PBT1) - VZ (PBT2) is preferably at least 20-80, preferably at least 22-70.
  • 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 of polyester.
  • Such polyesters can be prepared, 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).
  • PET recyclates also termed scrap PET
  • PBT polyalkylene terephthalates
  • Post Industrial Recyclate these are production waste in polycondensation or in processing, e.g. Sprues in injection molding, starting material in injection molding or extrusion, or edge portions of extruded sheets or foils.
  • Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.
  • the maximum edge length should be 10 mm, preferably less than 8 mm.
  • the residual moisture content after drying is preferably ⁇ 0.2%, in particular ⁇ 0.05%.
  • aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to using mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% of terephthalic acid with 20% of 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 having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 to 2 has.
  • the compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • polyalkylene terephthalates and wholly aromatic polyesters. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and from 2 to 80% by weight of the wholly aromatic polyester.
  • polyester block copolymers such as copolyetheresters may also be used.
  • Such products are known per se and are known in the literature, e.g. in US Pat. No. 3,651,014. Also in the trade, corresponding products are available, e.g. Hytrel® (DuPont).
  • Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula
  • Q is a single bond, a C 1 to C 5 alkylene, a C 2 to C 3 alkylidene, a C 3 to C 6 cycloalkylidene group, a C 6 to C 12 arylene group, and -O-, -S- or -SO 2 - and m is an integer from 0 to 2.
  • the diphenols may also have substituents on the phenylene radicals, such as C 1 to C 6 alkyl or C 1 to C 6 alkoxy.
  • Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1 bis (4-hydroxyphenyl) -cyclohexane.
  • Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane and 1, 1-bis (4-hydroxyphenyl) cyclohexane, and 1, 1-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane.
  • Both homopolycarbonates and copolycarbonates are suitable as component A, and in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 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 relative viscosities ⁇ rei of 1, 10 to 1, 50, in particular from 1, 25 to 1, 40 have. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.
  • 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 boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators.
  • phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process)
  • the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators.
  • Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having 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, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol.
  • alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to
  • Halogen-free polycarbonates in the context 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 subordinate ppm amounts of saponifiable chlorine resulting, for example, from the preparation of the polycarbonates with phosgene Phase interface method, not to be regarded as halogen-containing in the context of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.
  • suitable components B) may be mentioned amorphous polyester carbonates, wherein phosgene against aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units, has been replaced in the preparation.
  • phosgene against aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units
  • bisphenol A can be replaced by bisphenol TMC.
  • polycarbonates are available under the trademark APEC HT® from Bayer.
  • the molding compositions according to the invention contain 0.1 to 10, preferably 1 to 9 and in particular 2 to 8 wt .-% of a mineral filler selected from the group barium sulfate or calcium carbonate or mixtures thereof.
  • barium sulphate occurs in the form of large, translucent or translucent, colorless or yellow, gray to brown colored, glassy to pearly, rhombic crystals which, for their high density, are referred to as barytes (barium sulphate) (density 4.5, Hardness 3 - 3.5).
  • the preparation is in most cases by working up of natural barium sulfate. After washing, it is broken and coarsely ground. Gait is separated by sedimentation. Higher purities than 95% can be achieved by flotation. Great brightness is achieved by chemical acid bleaching and treatment with oxidizing agents or reducing agents. To improve the wettability and dispersibility, special products still receive an organic aftertreatment.
  • Precipitated barium sulphate is obtained from various barium salts and sulphates or sulfuric acid, e.g. according to
  • Preferred BaS ⁇ 4 types have a particle size of 0.1 to 5 ⁇ m, preferably 0.1 to 1 ⁇ m (determined by means of laser diffraction), and a pH preferably of 7.5 to 9 and are commercially available from Sachtleben Micro (Sachtleben) available.
  • natural calcium carbonate (CCN, calcium carbonicum natura-Ns) and precipitated calcium carbonate (CCP, calcium carbonicum praecipitatum) can be distinguished according to the technically significant crystal modifications of calcite and aragonite.
  • Natural caclium carbonate is classified according to the origin and crystallinity in calcite, marble, limestone and chalk.
  • surface-treated (predominantly with stearic acid or calcium stearate) calcium carbonates are surface-treated (predominantly with stearic acid or calcium stearate) calcium carbonates.
  • Chalk (DIN EN ISO 3262-4: 1998-09) with a CaCO 3 content of at least 98 5 belongs to type A, with at least 95% to type B. While the loss on ignition of both types may not exceed 46%, it should be considered Type A the insoluble in hydrochloric acid content not exceeding 2%, with type B not exceeding 5%.
  • Crystalline calcium carbonate, calcite is classified according to DIN EN ISO 3262-5: 1998-09 into types A - D according to a content of CaCO 3 of at least 99, 98, 95 or 90%. The loss on ignition must not exceed 46% in each case, likewise the fraction insoluble in hydrochloric acid in type A 1%, in B and C 2% and in D 8%.
  • Precipitated calcium carbonate (DIN EN ISO 3262-6: 1998-09) preferably has a content of CaCO 3 of at least 98%, a sieve residue (particle diameter> 45 ⁇ m) of max. x 0.1% and a maximum loss on ignition of 46%; the hydrochloric acid insoluble fraction is usually a maximum of 0.2%.
  • Calcite, marble, limestone and chalk are natural calcium carbonates.
  • Synthetic precipitated calcium carbonate usually consists of fine crystals of calcite and / or aragonite having mean sinking speed equivalent diameters of 0.02-0.35 ⁇ m and an upper particle size (grain size) of 4-10 ⁇ m, these predominantly hard agglomerates and grit are.
  • the content of CaCO 3 is preferably (without surface treatment) at 98.5-99%.
  • the precipitation can be done by different methods:
  • Control parameters for setting the mass ratio calcite to aragonite in the precipitation and the average particle diameter are the concentration of the calcium hydroxide suspension and the carbon dioxide in the carrier gas and the temperature. Higher temperatures lead to finer precipitations and higher proportions of aragonite, at lower temperatures first the hexahydrate CaCO 3 • 6H 2 O is formed, which gives the suspension pronounced thixotropy, which irreversibly is lost through good drying.
  • Preferred CaCO 3 products have an average particle size of 1 to 50, preferably 5 to 40 ⁇ m, a pH of 7.5 to 9.5, preferably of 8 to 9.2.
  • the molding compositions according to the invention contain 0.01 to 5, preferably 0.1 to 3 and in particular 0.1 to 1 wt .-% of a lubricant.
  • polyolefin waxes As a first group of preferred lubricants are mentioned polyolefin waxes.
  • Polypropylene waxes are generally understood as meaning polypropylenes of a waxy character, which accordingly have a low molecular weight.
  • the waxes according to the invention have a weight average molecular weight Mw of 2,000 to 60,000 (by GPC and standard polystyrene), preferably from 5,000 to 50,000 and in particular from 10,000 to 45,000.
  • the softening point of the waxes according to the invention is preferably at least 140 ° C., preferably at least 150 ° C., determined in accordance with DIN EN 1427 (ring and ball method).
  • the viscosity of the waxes according to the invention is generally from 10 to 5000 mPas, preferably from 100 to 3000 mPas at 170 ° C according to DIN 53018.
  • the density of the waxes according to the invention is usually from 0.87 to 0.92 g / cm 3 , preferably from 0.88 to 0.91 g / cm 3 according to DIN 53479.
  • Preferred PP waxes have the form of so-called micropowders whose d 50 value is from 1 to 50 ⁇ m, preferably from 5 to 30 ⁇ m.
  • the preparation of the PP waxes according to the invention can be carried out in stirred high-pressure autoclaves or in high-pressure tubular reactors using regulators. Production in stirred high pressure autoclave is preferred.
  • the A description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York , Tokyo, 1996. In them, the ratio length / diameter predominantly behaves at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1.
  • the likewise applicable high-pressure tube reactors can likewise be found in Ullmann's Encyclopedia of Industrial Chemistry, 5 Edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996.
  • the commercially available PP waxes are translucent, colorless to white powder products which give clear melts and are soluble in nonpolar solvents.
  • Licowax® PP especially Licowax PP 230 and Licowax VP PP grades (Firmal Clariant GmbH) and Ceridust® VP 6071 as well as the LC 525 N, LC 502 N, LC 502 NC, LC 503 N, LC 503 NC grades Hana Corporation, Korea.
  • Polyethylene waxes are obtainable by free-radical polymerization in the high-pressure process or in the presence of organometallic catalysts in a low-pressure process produced hydrocarbon waxes having an average molecular weight of 2000 - 20,000 (weight average).
  • low molecular weight waxy products can be obtained by thermal degradation from high molecular weight polyethylene.
  • polyethylene waxes are classified not by the manufacturing process but rather by density in HDPE (High Density Polyethylene) and LDPE (Low Density Polyethylene), where the high pressure process gives HDPE, and the low pressure process LDPE grades.
  • HDPE High Density Polyethylene
  • LDPE Low Density Polyethylene
  • thermally degraded PE waxes are similar to those of high pressure products.
  • branched types of low density (LDPE) are available.
  • PE waxes polyethylene wax oxidates
  • Suitable starting materials for such oxidation processes are all customary polyolefin waxes, ie, for example, by Ziegler or Phillips catalysis or polyolefin waxes produced by high-pressure processes.
  • the underlying structural elements for such oxidation processes are all customary polyolefin waxes, ie, for example, by Ziegler or Phillips catalysis or polyolefin waxes produced by high-pressure processes.
  • Waxes can be taken directly from a polymerization process or obtained by thermal cleavage of higher molecular weight olefin polymers.
  • Suitable waxes are derived, for example, from ethylene and / or C 3 -C 10 -alk-1-enes, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
  • the polyolefin waxes used are preferably homo- or copolymers of ethylene or propylene, particularly preferably those of ethylene.
  • the monomers may be homopolymerized or copolymerized with each other in any proportion.
  • Preferred polyolefins on which the oxidized waxes are based are ethylene homopolymers having a density in the range from 0.89 to 0.98 g / cm 3 , preferably in the range from 0.90 to 0.96 g / cm 3 and an M w , determined by the method of GPC in 1, 2,4-trichlorobenzene at 135 ° C with polyethylene or polypropylene standard, in the range of 1000 to 40 000 g / mol, preferably in the range of 2000 to 20,000 g / mol.
  • ethylene / C 3 -C 10 -alk-1-ene copolymers having a total content of structural units in the copolymer based on the alk-1-ene or the alk-1-enes in the range from 0.1 to 15 mol -%, preferably in the range of 1 to 10 mol%, based on the copolymer.
  • Preferred ethylene / alk-1-ene copolymers are ethylene / propylene copolymers having a content of structural units derived from propylene in the copolymer in the range from 0.1 to 10 mol%, preferably in the range from 1 to 5 mol%, based on the copolymer.
  • the copolymers generally have an M w , determined by the method of GPC as described above, in the range from 1000 to 40 000 g / mol, preferably in the range from 2000 to 20 000 g / mol.
  • polyolefins which may underlie the oxidized waxes are isotactic propylene homopolymers having a pentad content (content of isotactic pentads), determined by the 13 C-NMR spectroscopy method, in US Pat Range of 90 to 98% and a M w , determined by the method of GPC as described above, in the range of 1000 to 40,000 g / mol, preferably in the range of 2000 to 20,000 g / mol.
  • copolymers of propylene with ethylene and / or C 4 - to Cio-alk-1-enes are also suitable as base polyolefins.
  • These propylene copolymers usually have a total content of structural units in the copolymer in the range of 0.1 to 15 mol%, preferably in the range of 1, based on the ethylene and / or the C 4 to C 10 alk-1-enes to 10 mol%, based on the copolymer.
  • Preferred propylene copolymers are propylene / ethylene copolymers having a content of structural units derived from the ethylene in the copolymer in the range from 0.1 to 10 mol%, preferably in the range from 1 to 5 mol%, based on the copolymer.
  • the propylene copolymers generally have an M w , determined by the method of GPC as described above, in the range from 1000 to 40 000 g / mol, preferably in the range from 1000 to 20 000 g / mol.
  • the acid number of the preferred oxidized waxes is preferably from 1 to 100, preferably from 12 to 55 and in particular from 12 to 30 [mg KOH / g].
  • the saponification number is preferably from 1 to 100, preferably from 10 to 50 and in particular from 20 to 30 [mg KOH / g] (according to DIN EN D-1387).
  • Further preferred components D) are esters or amides of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 carbon atoms with aliphatic saturated alcohols or amines containing 2 to 40, preferably 2 to 6 carbon atoms.
  • the carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are 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 having 30 to 40 carbon atoms).
  • 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, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • Preferred esters or amides are accordingly glyceryl distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • 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
  • Ca or Na. montanate eg. stearic acid or behenic acid
  • the molding compositions of the invention may contain from 0 to 70, in particular up to 40% by weight of further additives and processing aids.
  • Customary additives are, for example, in amounts of up to 40, preferably up to 15 wt .-% 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 esters with 1 to 18 C Atoms in the alcohol component.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have virtually no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers for example, 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-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes, and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- butylidene-2-norbornene, 2-Methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
  • EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called 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 may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. 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 containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture
  • R 1 to R 9 are 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 preferably denote 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 IJI and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.
  • the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
  • 0.1 to 40 in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and
  • 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 methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.
  • Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization".
  • the emulsifiers and catalysts which can be used are known per se.
  • homogeneously constructed elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
  • acrylates such as n-butyl acrylate and 2-ethylhexyl, corresponding Methacrylates, butadiene and isoprene and their mixtures called.
  • monomers for the preparation of the rubber part of the elastomers acrylates such as n-butyl acrylate and 2-ethylhexyl, corresponding Methacrylates, butadiene and isoprene and their mixtures called.
  • monomers can be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate.
  • the soft or rubber phase (with a glass transition temperature below 0 ° C.) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two-shelled construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
  • one or more hard components on the structure of the elastomer, so these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, Acrylklareestern and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
  • methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
  • smaller proportions of other comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups, and functional groups obtained by concomitant use of monomers of the general formula
  • R 10 is hydrogen or a C 1 to C 4 alkyl group
  • R 11 is hydrogen, a C 1 - to C 5 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or -OR 13
  • R 13 is a C 1 - to C 5 -alkyl or C 6 - to C 12 -aryl group which may optionally be substituted by O- or N-containing groups,
  • X is a chemical bond, a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group or
  • Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-) Diethylamino) ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.
  • graft-linking monomers can also be used, i. Monomers having two or more polymerizable double bonds, which react at different rates in the polymerization. Preferably, those compounds are used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerized much slower (polymerize).
  • the different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie. the grafted phase is at least partially linked via chemical bonds to the graft base.
  • graft-crosslinking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • graftlinking monomer for further details, reference is made here, for example, to US Pat. No. 4,148,846.
  • 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.
  • graft polymers with a core and at least one outer shell are listed.
  • graft polymers with a core and at least one outer shell are to be named here, 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 the impact modification of PBT, if appropriate 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).
  • graft polymers having a multi-shell structure it is also possible to use homogeneous, ie single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or copolymers thereof. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.
  • Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred.
  • Fibrous or particulate fillers which may be mentioned 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 may be used in amounts of up to 20% by weight. -%, in particular up to 10 wt .-% are used.
  • Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.
  • Suitable silane compounds are those of the general formula
  • X is NH 2 -, CH 2 -CH-, HO-,
  • 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 wt .-% (based on E) for surface coating.
  • acicular mineral fillers are also suitable.
  • the term "needle-shaped mineral fillers” is understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
  • the mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not essential.
  • Kaolin, calcined kaolin, wollastonite, talc and chalk are mentioned as further fillers.
  • thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • processing aids such as stabilizers, antioxidants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called.
  • UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition, of various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants.
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones
  • nucleating agents sodium phenylphosphinate, alumina, silica and preferably talc may be used.
  • plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually 230 to 320 0 C.
  • the components B) and optionally C) can be mixed with a prepolymer, formulated and granulated.
  • the resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.
  • thermoplastic molding compositions according to the invention are distinguished by good dimensional stability and surface properties as well as good processability / flowability and thermal stability. In particular, the fogging behavior is improved, in particular for applications as lighting elements.
  • PBT Polybutylene terephthalate
  • Polypropylene terephthalate PTT with a VZ of 115 ml / g (Corterra® C 200, Shell AG) (VZ according to ISO 1628-1, 5)
  • the components A) to D) were homogenized according to the compositions listed in the table on a twin-screw extruder ZSK 30 from. Werner & Pfleiderer at 260 ° C, the mixture extruded into a water bath, granulated and dried. Were injection molded on an injection molding machine at 260 0 C and 80 0 C zetemperatur-melting, mold surface temperature circular disks, rods or shoulder standard small rods and then checked from the granules.
  • the gloss values of the surface were measured at 60 and 20 ° angles according to DIN 67530 on plates 60 x 60 x 2 mm.
  • the demolding force was determined on an Arburg Allrounder 750 KN with a screw diameter of 30 mm.
  • the mold had an inside diameter of 82 mm and a height of 60 mm (cylinder).
  • the demolding pressure sensor is located on the plate. Melting temperature 260 ° C, mold temperature 80 ° C. The mean value of 20 injection molding cycles is given.
  • the haze is the diffuse transmission, measurable as large-angle scattering with over 2.5 ° deviation from the incident light beam, and the image clarity (clarity) the diffuse transmission, measurable as small-angle scattering in an angular range less than 2.5 °.
  • Plates (60 x 60 x 2 mm) were stored at 160 ° C. for 24 h in air. The surface was visually and finger-tested and the tactile blooming of the additives was rated +, o and -.
  • the plates and round disks were metallized on META 1 103 from VTD VAKUUMTECHNIK DRESDEN GmbH.
  • the aluminum layer of about 100 nm was evaporated in 15 s. Then again turbidity, clarity and surface gloss were measured at 20 0 C before and after heat aging.

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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 à mouler thermoplastiques, contenant A) 10 à 98 % en poids d'au moins un polybutylène téréphtalate (PBT), B) 1 à 40 % en poids d'un polyester, différent de A), C) 0,1 à 10 % en poids d'une charge minérale, choisie dans le groupe comprenant le sulfate de baryum ou le carbonate de calcium ou leur mélange, D) 0,01 à 5 % en poids d'un lubrifiant, E) 0 à 70 % en poids d'autres additifs, la somme des pourcentages en poids des composants A) à E) étant de 100 %.
PCT/EP2009/051320 2008-02-12 2009-02-05 Polyester à charge minérale WO2009101026A1 (fr)

Applications Claiming Priority (2)

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EP08101522.4 2008-02-12
EP08101522 2008-02-12

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104088033A (zh) * 2014-06-17 2014-10-08 福建百宏聚纤科技实业有限公司 一种异形有光细旦涤纶低弹纤维的制备方法
CN111718563A (zh) * 2020-06-28 2020-09-29 黎明职业大学 一种灯具用强韧与高导热的pbt复合材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1657279A1 (fr) * 2003-08-19 2006-05-17 Oiles Corporation Composition de resine pour element glissant et element glissant associe
US20070254150A1 (en) * 2004-08-11 2007-11-01 Koichi Seino Polyester Resin Composition for Light-Reflecting Article
WO2008015934A1 (fr) * 2006-07-31 2008-02-07 Mitsubishi Engineering-Plastics Corporation Composition de résine polyester et réflecteur de lumière

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1657279A1 (fr) * 2003-08-19 2006-05-17 Oiles Corporation Composition de resine pour element glissant et element glissant associe
US20070254150A1 (en) * 2004-08-11 2007-11-01 Koichi Seino Polyester Resin Composition for Light-Reflecting Article
WO2008015934A1 (fr) * 2006-07-31 2008-02-07 Mitsubishi Engineering-Plastics Corporation Composition de résine polyester et réflecteur de lumière
EP2048199A1 (fr) * 2006-07-31 2009-04-15 Mitsubishi Engineering-Plastics Corporation Composition de resine polyester et reflecteur de lumiere

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104088033A (zh) * 2014-06-17 2014-10-08 福建百宏聚纤科技实业有限公司 一种异形有光细旦涤纶低弹纤维的制备方法
CN104088033B (zh) * 2014-06-17 2015-06-03 福建百宏聚纤科技实业有限公司 一种异形有光细旦涤纶低弹纤维的制备方法
CN111718563A (zh) * 2020-06-28 2020-09-29 黎明职业大学 一种灯具用强韧与高导热的pbt复合材料及其制备方法

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