WO2011000816A1 - Mélanges nanocomposites contenant des polyamides et des polyoléfines - Google Patents

Mélanges nanocomposites contenant des polyamides et des polyoléfines Download PDF

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WO2011000816A1
WO2011000816A1 PCT/EP2010/059172 EP2010059172W WO2011000816A1 WO 2011000816 A1 WO2011000816 A1 WO 2011000816A1 EP 2010059172 W EP2010059172 W EP 2010059172W WO 2011000816 A1 WO2011000816 A1 WO 2011000816A1
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component
thermoplastic molding
molding compositions
compositions according
weight
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PCT/EP2010/059172
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German (de)
English (en)
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Sachin Jain
Matthias Müller
Christian Schmidt
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Basf Se
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • Nanocomposite blends containing polyamides and polyolefins Description The invention relates to thermoplastic molding compositions containing
  • thermoplastic polyamide A) at least one thermoplastic polyamide,
  • the invention relates to the use of the thermoplastic molding compositions for the production of fibers, films and moldings as well as fibers, films and moldings, which are obtainable from the thermoplastic molding compositions according to the invention.
  • WO2006 / 071833 A1 discloses blends of a polyolefin nanocomposite and a polyamide nanocomposite, wherein the polyolefin preferably forms the continuous phase.
  • the nanoparticles are so-called nanoclays (nanoparticulate phyllosilicates, which are preferably present in exfoliated form).
  • the application aims at improved thermal properties, in particular improved heat resistance.
  • G. Filippone et al., Polymer 49 (2008), 1312-1322 describe the influence of so-called organoclay (organically modified nanoclays) on the co-continuous morphology of blends of HDPE and PA-6. In it, HDPE forms the surplus component.
  • the filler forms during melt processing exclusively within the more hydrophilic polyamide phase, with a co-continuous morphology upon re-melting of an extruded sample.
  • Zelikman Evgeni et al., Polymer Composites (2006), 425-430 disclose ternary composites of polypropylene and a nylon 6/6,6 copolymer in a weight ratio of 70 to 30 containing nanoparticulate alumina.
  • the alumina used has an affinity for the hydrophobic polyamide.
  • polyamide-affine Al 2 O 3 of particle size 13 nm an increase in the melt viscosity occurred.
  • melt viscosity of blends of polyamide and polyolefin is in relation to the mechanical properties not sufficient for all applications and for all polyamide types and molecular weights.
  • toughening modifiers are usually used to optimize the mechanical properties.
  • impact modifiers, rubbers or modified polyolefins which carry polar groups is often undesirable and economically unfavorable, for example by restricting the flexibility with regard to the order of addition of the components in the extruder.
  • Polyamide molding compositions in particular filled polyamide molding compositions, should be made available which, with comparable flowability in the melt, have better mechanical properties compared to the prior art and, in particular, improved impact strength at low temperatures or with comparable impact strength at low temperatures having the melt.
  • impact modifiers and associated drawbacks such as insufficient flowability and / or insufficient modulus of elasticity should be avoided.
  • thermoplastic molding compositions according to the invention are described in the description and the subclaims. Combinations of preferred embodiments do not depart from the scope of the present invention.
  • thermoplastic molding compositions contain the following components:
  • thermoplastic polyamide A) at least one thermoplastic polyamide,
  • thermoplastic molding compositions comprising the following components as separate phases:
  • thermoplastic polyamide A) at least one thermoplastic polyamide,
  • component C) and component B) form a first phase and component A) a separate second phase.
  • the separate second phase is preferably continuous. If the phase formed by components C) and B) is also continuous, this is referred to as a co-continuous structure, which is likewise preferred.
  • thermoplastic molding compositions can vary over a wide range, provided that it is ensured that component A), i. the above separate second phase is continuous. It is known to the person skilled in the art that mixtures of polyamides and polyolefins are immiscible and that the polyamides form a continuous phase, provided that the polyamide is present in a sufficient amount.
  • novel thermoplastic molding compositions preferably comprise from 36 to 99.9% by weight of component A), from 0.05 to 60% by weight of component B) and from 0.05 to 4% by weight of component C). in which the sum of the percentages by weight of components A) to C) based on the total weight of components A) to C) is 100% by weight.
  • novel thermoplastic molding compositions particularly preferably comprise from 46 to 98.9% by weight of component A), from 1 to 50% by weight of component B) and from 0.1 to 4% by weight of component C), wherein the sum of theandsprozen- te of components A) to C) based on the total weight of components A) to C) 100 wt .-% results.
  • the novel thermoplastic molding compositions contain from 66 to 99.9% by weight of component A), from 0.05 to 30% by weight of component B) and from 0.05 to 4% by weight.
  • component C) the sum of the percentages by weight of components A) to C) based on the total weight of components A) to C) being 100% by weight.
  • novel thermoplastic molding compositions may moreover contain optional particulate or fibrous fillers, in particular glass fibers, as component D) and further additives and auxiliaries as component E).
  • thermoplastic molding compositions preferably contain components B) and C) in a weight ratio B to C of 60: 1 to 4: 1, particularly preferably 20: 1 to 4: 1, very particularly preferably 15: 1 to 6: 1, especially from 10 to 1 to 7 to 1.
  • the thermoplastic molding compositions comprise as component A) at least one thermoplastic polyamide.
  • the novel thermoplastic molding compositions preferably comprise from 36 to 99.9% by weight of component A), based on the total amount of components A), B) and C).
  • the thermoplastic molding compositions according to the invention particularly preferably contain from 56 to 97.9% by weight of component A), in particular from 60 to 95% by weight, based on the total amount of components A), B) and C).
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 70 to 350, preferably 70 to 200 ml / g, determined in 96% strength by weight sulfuric acid at 25 ° C according to ISO 307.
  • Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000 e.g. U.S. Patent Nos. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred.
  • polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.
  • Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids, in particular adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid.
  • Suitable diamines are, in particular, alkanediamines having 6 to 12, in particular 6 to
  • polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also copolyamides 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.
  • polyamides are obtainable from ⁇ -aminoalkyl nitriles such as, in particular, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and US Pat EP 922065.
  • PA 6 aminocapronitrile
  • PA 66 adiponitrile with hexamethylenediamine
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary.
  • partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, in particular those whose triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444 ).
  • the preparation of the preferred partially aromatic copolyamides having a low triamine content can be carried out by the processes described in EP-A 129,195 and 129,196.
  • the preferred partly aromatic copolyamides A) contain as component a-i) from 40 to 90% by weight of units derived from terephthalic acid and hexamethylenediamine, based on component A).
  • a small proportion of the terephthalic acid preferably not more than 10% by weight of the total aromatic dicarboxylic acids used, can be replaced by isophthalic acid or other aromatic dicarboxylic acids, preferably those in which the carboxyl groups are in the para position.
  • the partly aromatic copolyamides contain units derived from ⁇ -caprolactam (a2) and / or units derived from adipic acid and hexamethylenediamine (a3).
  • wt .-% preferably from 20 to 50 wt .-%, in particular from 25 to 40 wt .-%, while the proportion of units derived from adipic acid and hexamethylenediamine, up to 60 wt .-%, preferably from 30 to 60 wt .-% and in particular from 35 to 55 wt .-%, in each case based on component A).
  • the copolyamides may also contain both units of ⁇ -caprolactam and units of adipic acid and hexamethylenediamine; In this case, care must be taken that the proportion of units which are free of aromatic groups is at least 10% by weight, preferably at least 20% by weight, based on component A).
  • the ratio of the units derived from ⁇ -caprolactam and from adipic acid and hexamethylenediamine is subject to no particular restriction.
  • the partly aromatic copolyamides A) according to the invention may also contain minor amounts, preferably not more than 15% by weight, in particular not more than 10% by weight, of further polyamide units (a 4 ) as known from other polyamides.
  • These building blocks can be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms and from aminocarboxylic acids or corresponding lactams having 7 to 12 carbon atoms.
  • Suitable monomers of these types are here only suberic acid, azelaic acid, sebacic acid or isophthalic acid as representatives of the dicarboxylic acids, 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2- ( 4,4'-diaminodicyclohexyl) propane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane as representatives of the diamines and capryllactam, enanthlactam, omega-aminoundecanoic acid and laurolactam as representatives of lactams or aminocarboxylic acids.
  • the melting points of partly aromatic copolyamides A) are in the range of 260 to 300 0 C, this high melting point greater than 75, especially more than 85 ° C is also associated with a high glass transition temperature of usually.
  • Binary copolyamides based on terephthalic acid, hexamethylenediamine and ⁇ -caprolactam have, at levels of about 70 wt .-% of units derived from terephthalic acid and hexamethylenediamine, melting points in the range of 300 0 C and a glass transition temperature of more than 1 10 0th C on.
  • Binary copolyamides based on terephthalic acid, adipic acid and hexamethylenediamine (HMD) reach melting points of 300 ° C.
  • the glass transition temperature being not quite as high as in binary Copolyamides containing ⁇ -caprolactam instead of adipic acid or adipic acid / HMD.
  • PA 7 ethanolactam
  • PA 8 capryllactam
  • PA 1 1 1 1-aminoundecanoic acid
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedicarboxylic acid
  • PA 613 hexamethylenediamine, undecanedicarboxylic acid
  • PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
  • PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA MXD6 m-xylylenediamine, adipic acid
  • PA 6I hexamethylenediamine, isophthalic acid
  • PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
  • PA 6 / 6T (see PA 6 and PA 6T)
  • PA 6/66 (see PA 6 and PA 66)
  • PA 6/12 see PA 6 and PA 12
  • PA 66/6/610 see PA 66, PA 6 and PA 610)
  • PA 6I / 6T see PA 6I and PA 6T
  • PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
  • PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane
  • PA 12 / MACMI laurolactam dimethyldiaminodicyclohexylmethane
  • PA 12 / MACMT laurolactam dimethyldiaminodicyclohexylmethane
  • PA PDA-T phenylenediamine, terephthalic acid
  • the thermoplastic molding compositions comprise as component B) at least one polyolefin composed of repeating units selected from ethylene and propylene, polar functional groups being excluded.
  • the novel thermoplastic molding compositions preferably comprise from 0.05 to 60% by weight of component B), based on the total amount of components A), B) and C).
  • the novel thermoplastic molding compositions particularly preferably comprise from 1 to 50% by weight of component B), in particular from 0.05 to 30% by weight, based on the total amount of components A), B) and C).
  • the proportion of component B) in the total amount of components A), B) and C) is at least 2, in particular at least 5 wt .-%.
  • Polar functional groups are understood as meaning all functional groups in incorporated monomer units which contain atoms other than carbon and hydrogen.
  • the polyolefins according to the invention are composed of the monomer units ethylene and propylene, wherein comonomers and / or functional groups containing atoms other than C and H are likewise excluded, as are unsaturated groups.
  • component B) is composed of saturated aliphatic repeating units consisting of carbon and hydrogen.
  • the polyolefins according to component B) may contain customary branching sites and, to a small extent, in particular up to 2% by weight, further monomer units which are composed of C and H.
  • the polyolefins of component B) can thus small amounts of other monomer units, for.
  • those derived from 1-butene, 1-pentene, 1-hexene, 1-heptene or 1-octene or 4-methylpentene-1 contain.
  • the polyolefin is not modified by functional groups.
  • the polyolefin does not contain any functional monomer building blocks which carry acid groups or other hydrophilic groups.
  • thermoplastic molding compositions contain as component B) at least one linear or branched polyolefin consisting essentially of repeating units which are selected from ethylene and propylene.
  • the polyolefins used according to the invention are obtainable by polymerization of at least one of the monomers ethylene and propylene.
  • component B in particular polyolefins selected from the group of low density polyethylene (LDPE), very low density polyethylene (VLDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), isotactic polypropylene, atactic polypropylene and syndiotactic Polypropylene into consideration.
  • component B) is a polyethylene homopolymer. If polyethylene is mentioned in the context of the present invention, then it is understood to mean a homopolymer of ethylene which may have branching, in particular linear branching; the same applies to polypropylene.
  • low-density polyethylene (LDPE) is understood to mean those having a density of 0.91-0.94 g / cm 3 .
  • High density polyethylenes (HDPE) generally have a density of 0.94-0.965 g / cm 3 .
  • Very low density polyethylene has densities less than 0.918 g / cm 3 .
  • LDPE is preferably obtained by radical polymerization of ethylene.
  • the polymerization of ethylene can be carried out, for example, by free-radical polymerization in high-pressure reactors at pressures of about 150 to 200 MPa and average temperatures of about 200 ° C. or more. Due to chain transfer mechanisms, this form of reaction generation produces the so-called "low density polyethylene” (LDPE) with a molecular weight of about 50,000 to
  • High-pressure processes can also produce "Linear Low Density Polyethylene” (LLDPE) and "Very Low Density Polyethylene” (VLDPE). These materials are typically translucent, white, flexible solids that may be transparent even slightly milky cloudy films can be processed.
  • high density polyethylenes can be produced in low pressure reactors using transition metal catalysts. These include, for example, the Phillips catalysts, such as chromium trioxide-impregnated quartz particles, or conceptually similar compounds such as bis (triphenylsilyl) chromate or Chromacen (Dicyclopentadienylchrom).
  • the group of transition-metal catalysts also includes the Ziegler catalysts, which usually contain titanium alkoxylates and long-chain aluminum alkyls. With both catalyst groups can be unbranched polyethylenes with high tendency to crystallize and thus produce high density.
  • the materials thus available are usually opaque, white materials with low flexibility.
  • the residual content of catalyst material is usually about 20 ppm.
  • component B) is an LDPE.
  • LDPE low density polyethylene
  • this has preferably a density (23 0 C) 0.910 to 0.925, preferably 0.915 to
  • LDPE has a molecular weight Mw of 50,000 to 150,000 g / mol, in particular 60,000 to 130,000 g / mol.
  • component C) is at least one nanoparticulate oxide and / or hydrated oxide of at least one metal or semimetal having a number-weighted one average diameter of the primary particles of 0.5 to 50 nm and a hydrophobic particle surface.
  • the novel thermoplastic molding compositions preferably comprise from 0.05 to 4% by weight of component C), based on the total amount of components A), B) and C).
  • the thermoplastic molding compositions according to the invention particularly preferably contain from 0.1 to 4% by weight of component C), in particular from 0.1 to 3% by weight, very particularly preferably from 0.3 to 2% by weight, in each case on the total amount of components A), B) and C).
  • Component C) can be characterized in particular by at least one of the following features a) and / or b): a) Component C) is at least one nanoparticulate oxide and / or hydrated oxide of at least one metal or semimetal having a number-weighted mean diameter of the primary particles from 0.5 to 50 nm, wherein, according to transmission electron microscopy, the oxide and / or hydrated oxide is present exclusively in component B or at the interface of component B) with component A).
  • component C) and component (B) form a first phase and component (A) a separate second phase.
  • Methods for the determination of phases in polymer blends and the determination of nanoparticulate constituents in polymer blends are known to the person skilled in the art. In the context of the present invention, the phases and their constituents are determined by means of transmission electron microscopy.
  • Component C) has a methanol wettability of at least 50%.
  • the methanol wettability is a measure of how hydrophobic an oxide and / or oxide hydrate of at least one metal or semi-metal is.
  • oxides and / or hydrated oxides are wetted using a methanol / water mixture.
  • the proportion of methanol in the mixture is a measure of the water repellency of the metal oxide. The higher the proportion of methanol, the more hydrophobic the substance is.
  • the degree of hydrophobicity is determined by titration. For this purpose, 0.2 g of the sample are weighed in a 250 ml separating funnel and 50 ml ultrapure water added. The oxide or hydrated oxide with hydrophobic surface remains on the surface of the water. sers. It is now added ml-wise methanol from a burette. In doing so, the separating funnel is shaken with a circular hand movement so that no swirls are created in the liquid. In this way, methanol is added until the powder is wetted. This can be seen from the decrease in the total powder from the water surface. The consumption of methanol is converted into wt .-% methanol and indicated as a value for the methanol wettability.
  • the number-weighted average diameter of the primary particles is determined in the thermoplastic molding composition by transmission electron microscopy and subsequent image analysis analysis on the basis of a statistically significant number of samples. Corresponding methods are known to the person skilled in the art.
  • the diameter of the primary particles in the context of the present invention is the largest diameter through the geometric center of the particle.
  • Oxides with a hydrophobic particle surface generally have a BET surface area according to DIN 66131 of at most 300 m 2 / g.
  • Component C) preferably has a BET specific surface area to DIN 66131 of 50 to 300 m 2 / g, in particular from 100 to 250 m 2 / g.
  • the metal and / or semimetal according to component C) is silicon.
  • the thermoplastic molding compositions according to the invention preferably contain as component C) a nanoparticulate oxide and / or hydrated oxide of silicon having a number-average average diameter of the primary particles of 0.5 to 50 nm, in particular 1 to 20 nm.
  • Component C) is particularly preferably flame-pyrolytically produced nanoparticulate silicon dioxide whose surface is hydrophobically modified.
  • Component C) particularly preferably has a number-weighted mean diameter of the primary particles of from 1 to 20 nm, preferably from 1 to 15 nm.
  • component C) is hydrophobically modified by a surface modifier, preferably an organosilane.
  • a surface modifier preferably an organosilane.
  • the surface modification can be carried out by contacting the nanoparticles, preferably as a suspension or as such, with a surface modifier, for example by spraying.
  • the nanoparticles with water and then with the surface modifier.
  • the spraying can also be done in reverse order.
  • the water used may be acidified with an acid, for example hydrochloric acid, to a pH of 7 to 1. If several Surface modifiers are used, they can be applied as a mixture or separately, simultaneously or sequentially.
  • the surface modifier (s) may be dissolved in suitable solvents. After the spraying is finished, mixing can be continued for 5 to 30 minutes. Preferably, the mixture is then thermally treated at a temperature of 20 to 400 0 C over a period of 0.1 to 6 h.
  • the thermal treatment can be carried out under protective gas, such as nitrogen.
  • An alternative method of surface modification of the nanoparticles may be accomplished by treating the nanoparticles with the surface modifier in vapor form and then thermally treating the mixture at a temperature of 50 to 800 ° C. for a period of 0.1 to 6 hours.
  • the thermal treatment can be carried out under protective gas, such as nitrogen.
  • the temperature treatment can also be carried out in several stages at different temperatures.
  • the application of the surface modifier (s) can be carried out with single-component, double-material or ultrasound nozzles.
  • the surface modification can be carried out continuously or batchwise in heatable mixers and dryers with sprayers.
  • Suitable devices may be, for example: plowshare mixers, plate, fluidized bed or fluid bed dryers.
  • silanes Preferably can be used as surface modifiers following silanes: octyltrimethoxysilane, octyltriethoxysilane, hexamethyldisilazane, 3-methacryl oxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, silane Hexadecyltrimethoxy-, hexadecyltriethoxysilane, dimethylpolysiloxane, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, Nonafluorohexyltrimethoxysilan, trimethoxysilane Tridecaflourooctyl-, Tridecaflourooctyltriethoxysilan, aminopropyl triethoxysilane, hexamethyldisilazane ,
  • Hexamethyldisilazane, hexadecyltrimethoxysilane, dimethylpolysiloxane, octyltrimethoxysilane and octyltriethoxysilane are particularly preferably used.
  • hexamethyldisilazane, octyltrimethoxysilane and hexadecyltrimethoxysilane are used, most preferably hexamethyldisilazane.
  • thermoplastic molding compositions may contain particulate or fibrous fillers, in particular glass fibers.
  • Component D) is preferably from 0 to 60 wt .-% based on the total amount by weight of components A), B), C) and D).
  • thermoplastic molding compositions according to the invention preferably contain glass fibers as component D).
  • thermoplastic molding compositions contain from 1 to 70 parts by weight of component D), based on 100 parts by weight of the thermoplastic molding composition.
  • thermoplastic molding compositions may be present in the thermoplastic molding compositions according to the invention.
  • These glass fibers can be prepared by methods known to the person skilled in the art and, if appropriate, surface-treated.
  • the glass fibers may be provided with a size for better compatibility with the matrix material, e.g. in DE 10117715.
  • glass fibers having a diameter of from 5 to 15 ⁇ m, preferably from 7 to 13 ⁇ m, particularly preferably from 9 to 11 ⁇ m are used.
  • the incorporation of the glass fibers can take place both in the form of chopped glass fibers and in the form of endless strands (rovings).
  • the length of the usable glass fibers is usually before incorporation as chopped glass fibers into the thermoplastic molding compositions 4 to 5 mm.
  • the glass fibers are usually present in an average length of 100 to 400 .mu.m, preferably 200 to 350 .mu.m.
  • thermoplastic molding compositions according to the invention may contain, as component E), further additives which are different from A) to D).
  • the molding compositions of the invention may contain a total of 0 to 70, in particular up to 50 wt .-% of other additives and processing aids, based on the total amount of components A) to E).
  • thermoplastic molding compositions advantageously contain a lubricant.
  • the molding compositions of the invention may be from 0 to 3, preferably from 0.05 to 3, preferably from 0.1 to 1, 5 and in particular from 0.1 to 1 wt .-% of a lubricant based on the total amount of components A) to E).
  • the metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.
  • Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate. It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.
  • 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.
  • esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • thermoplastic molding compositions according to the invention may moreover contain conventional processing aids such as stabilizers, oxidation retardants, further agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc. contain.
  • antioxidants and heat stabilizers include phosphites and further amines (eg TAD), hydroquinones, 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.
  • TAD phosphites and further amines
  • hydroquinones 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.
  • 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. It is possible to add inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite, furthermore organic pigments, such as phthalocyanines, quinacridones, perylenes and also dyes, such as nigrosine and anthraquinones, as colorants.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes, such as nigrosine and anthraquinones, as colorants.
  • sodium phenylphosphinate, alumina, silica and preferably talc may be used as nucleating agents.
  • flame retardants red phosphorus, P- and N-containing flame retardants and halogenated flame retardant systems and their synergists may be mentioned.
  • the novel thermoplastic molding compositions may contain from 0.01 to 2% by weight, preferably from 0.05 to 1.5% by weight, more preferably from 0.1 to 1.5% by weight. contain at least one heat stabilizer, each based on the total weight of components A) to E).
  • the heat stabilizers are selected from the group consisting of
  • Hydrohalic acids the hydrocyanic acids or the copper salts of aliphatic carboxylic acids.
  • Particularly preferred are the monovalent copper compounds CuCl, CuBr, CuI, CuCN and CU2O, and the divalent copper compounds CuCb, CuSO 4 , CuO, copper (II) acetate or copper (II) stearate. If a copper compound is used, preferably the amount of
  • the copper compounds are commercially available or their preparation is known in the art.
  • the copper compound can be used as such or in the form of concentrates. Concentrate here is to be understood as meaning a polymer, preferably of the same chemical nature as component (A), which contains the copper salt in high concentration.
  • the use of concentrates is a common procedure and is especially often used when very small
  • the copper compounds are used in combination with other metal halides, in particular alkali halides such as NaI, Kl, NaBr, KBr, where the molar ratio of metal halide to copper is 0.5 to 20, preferably 1 to 10 and particularly preferably 2 to 5;
  • stabilizers based on secondary aromatic amines these stabilizers preferably being present in an amount of 0.2 to 2, preferably 0.5 to 1.5,% by weight, based in each case on the total weight of the thermoplastic molding composition;
  • Stabilizers based on secondary aromatic amines are known per se to a person skilled in the art and can be used advantageously in the context of the present invention.
  • Stabilizers based on secondary aromatic amines are preferably present in an amount of from 0.2 to 2% by weight, in particular from 0.5 to 1.5% by weight, based on the total weight of the thermoplastic molding composition.
  • Particularly preferred stabilizers based on secondary aromatic amines are described in US Pat
  • Stabilizers based on sterically hindered phenols are also known to the person skilled in the art. Stabilizers based on sterically hindered phenols are preferably present in an amount of 0.05 to 1, 5 wt .-%, in particular 0.1 to 1 wt .-% based on the total weight of the thermoplastic molding composition. Particularly preferred stabilizers based on sterically hindered phenols are described in WO2008 / 022910 on page 10, line 3 to page 11, before line 10.
  • novel thermoplastic molding compositions within the scope of component E) may comprise plasticizers, preferably from 0 to 15% by weight, based on the total weight of the thermoplastic molding composition.
  • Plasticizers are substances which are added to thermoplastic molding compositions to make them more supple and elastic in use or as part of further processing.
  • Softeners may, for example, be low-volatile esters, in particular esters of phthalic acid, or oils. Suitable plasticizers are known per se to the person skilled in the art.
  • thermoplastic molding compositions according to the invention contain plasticizers in the context of component E), these are preferably from 1 to 12% by weight, in particular from 2 to 10 wt .-%, each based on the total weight of the thermoplastic molding composition.
  • Suitable plasticizers are in particular branched phthalates, adipates, trimellitates and linear phthalates.
  • Preferred plasticizers are in particular phthalic acid dioctyl ester, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils and N- (n-butyl) benzenesulfonamide.
  • plasticizers for example, p-hydroxybenzoic acid, benzenesulfonamide, benzenesulfonic N-alkylamides, wherein the alkyl radicals carry a total of 1 to 20 carbon atoms, such as.
  • toluenesulfonic acid N-ethylamide are used.
  • the novel thermoplastic molding compositions can be prepared by processes known per se, in which the starting components are mixed in customary mixing devices, such as screw extruders, Brabender mills or Banbury mills, and then extruded. After extrusion, the extrudate can be cooled and comminuted. Basically, the individual components can be added in any order. In particular, individual components can be premixed and then the remaining starting materials are added individually and / or also mixed. The mixing temperatures are generally from 230 to 320 ° C. In a preferred embodiment, components B) and C) are first premixed and then mixed with component A). The premix can also be done via the aforementioned methods (compounding). Subsequently, the compounded premix can be mixed by conventional methods with component A).
  • the premix ensures that component C) is part of the phase formed by component B) as described above. As a result, good mechanical properties and processing properties can be achieved.
  • the addition of components A), B) and C) takes place simultaneously.
  • the components are each introduced in the cold-feed mode in the mixing device. Due to the simultaneous introduction, ensures that component C) is part of the phase formed by component B).
  • thermoplastic molding compositions according to the invention are distinguished by good mechanical properties combined with good processability / flowability.
  • thermoplastic molding compositions according to the invention themselves are suitable for the production of fibers, films and moldings of any kind.
  • Examples of this are household articles, electronic components, medical devices, automotive components, housings of electrical appliances, housings of electronic components in the motor vehicle, fenders, door planking, tailgates, spoilers, intake pipes, water tanks, housings of power tools.
  • Another subject of the invention are the said fibers, films or moldings which are obtainable from the thermoplastic molding compositions according to the invention.
  • Component A-1 Polyamide-6 having a viscosity number VN according to ISO 307 before extrusion of 140 ml / g.
  • Component A-2 Polyamide-6 having a viscosity number VN to ISO 307 before extrusion of 100 ml / g ..
  • Component B-1 Lupolen ® A2420F, an unmodified LDPE with a diche (ISO 1 183) of 0.923 g / cm 3, a Shore D hardness (ISO 868) of 48 and a melt flow rate MFR (ISO 1 133) of 0.75 g / 10 min (190 ° C, 2.16 kg).
  • Component B-2V (Comparative Experiment): Lucalen® A2920 M, one with butyl acrylate
  • modified density LDPE (> 10% by weight) modified density LDPE (ISO 1183) of 0.927 g / cm 3 , MFI according to
  • Component B-4 Lupolen 1800S, an unmodified LDPE of one density
  • Component C-1 Aerosil® R8200, a hydrophobically modified flame-pyrolysis produced SiO 2 of medium particle size (transmission electron microscopy) of 15 nm with a hydrophobicized with hexamethyldisilazane particle surface, a specific surface BET of about 160 m 2 / g and a pH at 4% dispersion of at least 5.
  • Component C-2V comparative experiment: Aerosil ® 380, an unmodified Flux-pyroxylic produced SiO 2 of average particle size (transmission electron microscopy) of 7 nm with hydrophilic particle surface and BET surface area of about 380 m 2 / g and a pH at 4% dispersion of 3.7 to 4.7.
  • Component D-1 Glass fibers with a mean diameter of 10 to 20 microns and a mean length of 200 to 250 microns (Ownes Corning Fiberglass OFC 11 10).
  • Component E-1 calcium stearate
  • Component E-2 Antioxidant (Irganox 1098)
  • Component E-3 Ultrabatch 112 (a color batch based on soot)
  • Component E-4 Heat Stabilizer
  • the molding compositions were prepared as follows:
  • the specimens used to determine the properties were determined by injection molding (injection temperature 280 0 C, mold temperature 80 ° C) according to DIN EN ISO 294- 1: receive 1996th
  • the injection rate of the polymer into the mold was 6 mm / s, the screw speed 100 rpm and the cycle time 60 s.
  • the injection pressure (melt pressure) was determined according to DIN EN ISO 294-1: 1996.
  • the Charpy impact strength was determined unnotched at -30 0 C according to ISO 179-2 / 1 eil.
  • the viscosity number of the polyamides was measured according to DIN 53 727 on 0.5% strength by weight solutions in 96% by weight sulfuric acid.
  • the spiral length was determined using a flow spiral of diameter 1, 5 mm at a temperature of 280 ° C.
  • the modulus of elasticity was determined according to ISO 527-2: 1993.
  • the properties of various comparative experiments and examples according to the invention and the corresponding compositions of the molding compositions are shown in Tables 1 and 2.
  • the novel thermoplastic molding compositions are distinguished by improved mechanical properties, in particular improved impact strength at low temperatures and by an increased modulus of elasticity and by improved flowability. All components except glass fibers could be added to both cold-feed and hot-feed without adversely affecting the properties.

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention porte sur des masses à mouler thermoplastiques, contenant A) au moins un polyamide thermoplastique, B) au moins une polyoléfine constituée d'éthylène et/ou de propylène, à l'exclusion de groupes fonctionnels polaires, et C) au moins un oxyde et/ou un hydrate d'oxyde nanoparticulaire d'au moins un métal ou d'un semi-métal ayant un diamètre moyen pondéré en nombre des particules primaires de 0,5 à 50 nm et une surface particulaire hydrophobe. L'invention porte en outre sur l'utilisation des masses à mouler thermoplastiques pour la fabrication de fibres, de feuilles et d'objets moulés, ainsi que des fibres, des feuilles et des objets moulés pouvant être obtenus à partir des masses à mouler thermoplastiques selon l'invention.
PCT/EP2010/059172 2009-07-03 2010-06-29 Mélanges nanocomposites contenant des polyamides et des polyoléfines WO2011000816A1 (fr)

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US8658724B2 (en) 2009-06-19 2014-02-25 Basf Se Copolyamides
US8759458B2 (en) 2009-06-08 2014-06-24 Basf Se Method for producing poly(arylene ether) block copolymers
US8796365B2 (en) 2007-06-28 2014-08-05 Basf Se Thermoplastic molding materials comprising organic black pigments
US8906992B2 (en) 2007-06-22 2014-12-09 Basf Se Molding compositions comprising polyaryl ether with improved surface quality
US9051432B2 (en) 2009-04-03 2015-06-09 Basf Se Method for producing low-chlorine polybiphenyl sulfone polymers
US9056961B2 (en) 2009-11-20 2015-06-16 Basf Se Melamine-resin foams comprising hollow microbeads
US9296896B2 (en) 2010-11-23 2016-03-29 Basf Se Polyamides with nanoparticles on the surface
US9315626B2 (en) 2009-12-08 2016-04-19 Basf Se Process for preparing polyamides
US9962889B2 (en) 2009-07-08 2018-05-08 Basf Se Method for producing fiber-reinforced composite materials from polyamide 6 and copolyamides made of polyamide 6 and polyamide 12
CN109679221A (zh) * 2018-12-29 2019-04-26 重庆普利特新材料有限公司 一种高韧性高断裂伸长率长玻纤增强热塑性材料及其制备方法

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
US8906992B2 (en) 2007-06-22 2014-12-09 Basf Se Molding compositions comprising polyaryl ether with improved surface quality
US8796365B2 (en) 2007-06-28 2014-08-05 Basf Se Thermoplastic molding materials comprising organic black pigments
US9051432B2 (en) 2009-04-03 2015-06-09 Basf Se Method for producing low-chlorine polybiphenyl sulfone polymers
US9365680B2 (en) 2009-04-03 2016-06-14 Basf Se Method for producing low-chlorine polybiphenyl sulfone polymers
US8759458B2 (en) 2009-06-08 2014-06-24 Basf Se Method for producing poly(arylene ether) block copolymers
US8658724B2 (en) 2009-06-19 2014-02-25 Basf Se Copolyamides
US9962889B2 (en) 2009-07-08 2018-05-08 Basf Se Method for producing fiber-reinforced composite materials from polyamide 6 and copolyamides made of polyamide 6 and polyamide 12
US9056961B2 (en) 2009-11-20 2015-06-16 Basf Se Melamine-resin foams comprising hollow microbeads
US9315626B2 (en) 2009-12-08 2016-04-19 Basf Se Process for preparing polyamides
US9296896B2 (en) 2010-11-23 2016-03-29 Basf Se Polyamides with nanoparticles on the surface
CN109679221A (zh) * 2018-12-29 2019-04-26 重庆普利特新材料有限公司 一种高韧性高断裂伸长率长玻纤增强热塑性材料及其制备方法

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