Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/06—Polysulfones; Polyethersulfones
• • 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
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

• Molding compositions comprising polyaryl ethers with improved surface quality
• Polymers made of polyarylether or with a polyarylether component have been known for years and belong to the group of high-performance thermoplastics. They are used in highly stressed applications because of their high heat resistance and chemical resistance (see, for example, Blinne et al., Kunststoffe 75, 219 (1985); EM Koch, Kunststoffe 80, 1146 (1990), E. Döring, Kunststoffe 80, 1149 (1990)). Due to the high glass transition temperature and the associated dimensional stability of the molded parts polyaryl ethers are also used for the production of headlamp reflectors, for example in the automotive industry.
• the present invention relates to improved molding compositions containing polyaryl ethers and characterized by high toughness, improved flowability, good melt stability and high surface quality.
• Molding compounds of various polyarylethers are known from the literature.
• DE-A 2 917 903 discloses compositions for producing semipermeable membranes which are obtained by mixing two pulverulent polyarylene ether sulfones, one consisting essentially of the structural units (I) and the other essentially consisting of structural units (II).
• EP-A 127 852 is a cookware made of a mixture of polyarylene ether sulfones with the following, repeating units (III)
• EP-A 663 426 discloses blends based on a copolyaryl ether A consisting of 91 to 97 mol% of structural units (I) and 3 to 9% by weight of structural units (II) having a disperse phase consisting of a copolyaryl ether B, which has 91 to 97 mol% of structural units (II) and 3 to 9 mol% of structural units (I). These blends are characterized by improved flowability, reduced bleed tendency and improved chemical resistance.
• An object of the present invention is to provide low cost molding compositions having improved flowability and good toughness.
• This object is achieved by the provision of a molding composition containing the components A, B and C, and optionally the other components D and E, the sum of which gives a total of 100 wt .-%, wherein the molding composition contains:
• the molding composition may also contain 0.1 to 2.5 wt .-% of stearic acid or stearic acid derivatives.
• the invention also relates to a molding composition which contains:
• the invention further relates to a molding composition which contains:
• component A just 40 to 97.9 wt .-% of at least one polyethersulfone having a glass transition temperature of greater than 200 ° C.
• This component is preferably composed of recurring units of the formula (I)
• t and q are independently 0, 1, 2 or 3,
• Ar and Ar 1 each other arylene 8 independently each a C 6 -C, said d-Ci 2 -alkyl, C 6 -C 8 -ArVl-, Ci-Ci2 alkoxy groups or halogen atoms may be substituted.
• the invention also relates to a molding composition which contains:
• component A just 42.5 to 89.85% by weight of at least one polyether ether composed of repeating units of the formula (I) in which t and q are each independently 0, 1 or 2,
• Q, T, Z are each independently a chemical bond or a group selected from -O- and -SO 2 -, with the proviso that at least one of the groups T, Q and Z represents - SO 2 and when t and q is 0, Z is -SO 2 , and
• Ar and Ar 1 are each independently for one stand.
• the invention also relates to a molding composition, characterized in that it contains as component B just 2 to 59.9 wt .-% of at least one polysulfone, composed of recurring units of the formula (II)
• R 1 is H, C 1 -C 6 -alkyl, or - (CH 2 ) n -COOH, n is an integer from 0 to 6,
• Ar 2 and Ar 3 are independently each a C 6 -C 8 arylene group, said one or more d-Ci 2 alkyl, C ⁇ -C-is-
• Aryl, Ci-Ci 2- Alkoxy phenomenon or halogen atoms can be substituted, and
• the invention also relates to a molding composition which contains:
• component B just 10 to 57.35 wt .-% of at least one polysulfone, composed of recurring units of the formula (II) wherein R 1 is H or C r C 4 alkyl, n is an integer from 0 to 4 stands,
• Ar 2 and Ar 3 are each independently for one stand, and
• Component B often contains just 10 to 57.35 wt .-% of at least one polysulfone, which has a glass transition temperature of 170 to 195 ° C, in particular 175 to 190 0 C.
• This polymer is z. B. composed of bisphenol A and dichlorodiphenyl sulfone.
• the invention also relates to a molding composition which contains:
• component C just 0.1 to 1, 75 wt.% Of stearic acid, stearic acid derivatives and / or stearates, wherein as stearates the usual salts of stearic acid, eg. B. with metals such as Na, Ca, Mg, Al are preferred.
• the salts are preferred.
• the molding composition as component C preferably contains just 0.1 to 0.9% by weight of stearic acid and / or stearates. Also, a combination of small amounts of stearic acid with small amounts of stearates, especially of aluminum, are suitable. As component C, it is preferable to use just 0.1 to 0.7% by weight of stearic acid and / or aluminum tristearate. Preference is also given to using pure stearic acid.
• the invention also relates to a molding composition which contains:
• component D just 1 to 40 wt .-% of other additives from the group of fillers, reinforcing agents and impact-modified rubbers.
• the invention also relates to a molding composition which contains:
• the invention also relates to a molding composition which contains:
• component E contains as component E just 0.1 to 20 wt .-% of one or more auxiliaries from the group of processing aids, pigments, stabilizers and flame retardants.
• the invention also provides a process for the preparation of thermoplastic molding compositions by mixing components A to C and optionally components D and E.
• molding compositions for the production of fibers, films and moldings is the subject of the invention, wherein the use of molding compositions z.
• the molding compositions are particularly suitable for the production of headlamps for motor vehicles.
• the invention also relates to a shaped body, fibers and films of a molding compound, for example a housing for a headlight (eg for a vehicle).
• the molding compositions according to the invention have improved flowability, better notched impact strength and, surprisingly, also an improved surface quality. Furthermore, the molding compositions according to the invention show good processing stability.
• the molding compositions preferably contain at least two polymeric phases and are o-paque mixtures.
• the molding compositions according to the invention contain at least one polyethersulfone. Preference is given to a polyethersulfone corresponding to structural formula (I), in particular with a glass transition temperature of more than 210 ° C, z. B. used by 225 0 C.
• the novel molding materials comprise component A in amounts of from 40 to 97.9, in particular from 42.5 to 89.85% by weight and more preferably from 45 to 84.8% by weight, based on the total weight of components A. to E.
• component A a polyethersulfone is used according to the invention. It is also possible to use mixtures of two or more different poly (arylene) ether sulfones as component A.
• the arylene groups of the polyarylene ether sulfones A can be identical or different and independently of one another denote an aromatic radical having 6 to 18 C atoms.
• suitable arylene radicals are phenylene, bisphenylene, terphenylene, 1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene or 2,6-anthrylene. Of these, 1, 4-phenylene and 4,4'-biphenylene are preferred.
• these aromatic radicals are not substituted. However, they can carry one or more substituents.
• Suitable substituents are, for example, alkyl, arylalkyl, aryl, nitro, cyano or alkoxy groups and heteroaromatics, such as pyridine and halogen atoms.
• substituents include alkyl radicals having up to 10 carbon atoms, such as methyl, ethyl, iso-propyl, n-hexyl iso-hexyl, Cr to Cio-alkoxy, such as methoxy, ethoxy, n-propoxy, n-butoxy, aryl radicals with bis to 20 carbon atoms, such as phenyl or naphthyl, as well as fluorine and chlorine.
• various units of the formula (I) can also be present randomly or in blocks distributed in the polyarylene ether sulfone.
• polyethersulfones A usable according to the invention can be carried out, for example, on the basis of GB 1 152 035 and US Pat. No. 4,870,153.
• Suitable process conditions for the synthesis of polyarylene ether sulfones are described, for example, in EP-A 0 113 1 12 and EP-A 0 135 130.
• Particularly suitable is the reaction of the monomers in aprotic polar solvents in the presence of anhydrous alkali metal carbonate.
• a particularly preferred combination is N-methylpyrrolidone as solvent and potassium carbonate as catalyst.
• the reaction in the melt is also possible.
• suitable polyarylene ether sulfones A are those having at least one of the following recurring structural units (I 1 ) to (I 13 ):
• the polyarylene ether sulfones may have different groups. These groups may be attached to atoms of the polymer chain or may be present as end groups of the polymer chain.
• the groups are those which are inert to the other components of the thermoplastic composition and those which can react with the components.
• the inert groups include halogen, in particular chloro, alkoxy, especially methoxy or ethoxy, aryloxy, preferably phenoxy or benzyloxy groups.
• the polyarylene ether sulfones have average molecular weights M n (number average) in the range from 5000 to 60000 g / mol and relative viscosities from 0.20 to 0.95 dl / g.
• M n number average
• the relative viscosities depending on the solubility of the polyarylene ether sulfones either in 1 wt .-% sodium N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% sulfuric acid measured at each of 20 0 C and 25 0 C.
• the molding compositions according to the invention contain a polyarylene sulfone. Preference is given to using a polyarylene sulfone corresponding to structural formula (II):
• R 1 is H, d-Ce-alkyl, or - (CH 2 ) n -COOH, n is an integer of 0 to 6,
• Ar 2 and Ar 3 are each independently a C ⁇ -C-is-arylene group which may be substituted by one or more C 1 -C 12 -alkyl, C 6 -C -aryl, C 1 -C 12 -alkoxy or halogen atoms, and
• the polyarylene sulfone has a glass transition temperature of 180 0 C to 190 0 C, in particular 187 0 C, and is derived from bisphenol A and Dihalogendiphenylsulfon.
• the molding compositions according to the invention comprise component B in amounts of from 2 to 59.9, preferably from 10 to 57, 35 and particularly preferably from 15 to 54.8% by weight, based on the total weight of components A to E.
• the polyarylene ether sulfones have average molecular weights M n (number average) in the range from 5000 to 60,000 g / mol and relative viscosities of from 0.20 to 0.95 dl / g.
• M n number average
• the relative viscosities are dependent on the solubility of the polyarylene Nethersulfone either in 1 wt .-% N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% sulfuric acid at 20 0 C or 25 0 C measured.
• the molding compositions according to the invention contain 0.1 to 2, preferably 0.1 to 1, 75, more preferably 0.1 to 1, 5 wt .-% and in particular 0.1 to 0.9 wt .-% (relative on the entire molding composition) of stearic acid and / or stearates.
• stearic acid preferably 0.1 to 1, 75, more preferably 0.1 to 1, 5 wt .-% and in particular 0.1 to 0.9 wt .-% (relative on the entire molding composition) of stearic acid and / or stearates.
• other stearic acid derivatives such as esters of stearic acid can be used.
• Stearic acid is preferably produced by hydrolysis of fats.
• the products thus obtained are usually mixtures of stearic acid and palmitic acid. Therefore, such products have a wide softening range, for example from 50 to 70 ° C., depending on the composition of the product. Preference is given to using products having a stearic acid content of more than 20, particularly preferably more than 25,% by weight. Pure stearic acid (> 98%) can also be used.
• stearates can also be used as component C.
• Stearates can be prepared either by reaction of corresponding sodium salts with metal salt solutions (for example CaCl 2 , MgCl 2 , aluminum salts%) Or by direct reaction of the fatty acid with metal hydroxide (see, for example, Baerlocher Additives, 2005).
• metal salt solutions for example CaCl 2 , MgCl 2 , aluminum salts
• metal hydroxide see, for example, Baerlocher Additives, 2005.
• aluminum tristearate is used.
• thermoplastic molding compositions according to the invention contain from 0 to 50, preferably from 0 to 45, and in particular from 0 to 40,% by weight of additives, such as rubbers and reinforcing materials or impact-modified rubbers.
• the molding compositions may also contain auxiliaries, such as processing aids, pigments, stabilizers or mixtures of various additives.
• the molding compositions preferably contain from 0 to 45, in particular from 0 to 40,% by weight of fibrous or particulate fillers or reinforcing substances or mixtures thereof.
• the quantities are in each case based on the total mass of components A to E.
• Preferred fibrous fillers or reinforcing materials are carbon fibers, potassium tartanate whiskers, aramid fibers and particularly preferably glass fibers.
• glass fibers can be provided with a size, preferably a polyurethane size, and a primer for better compatibility with the matrix material.
• the carbon and glass fibers used have a diameter in the range of 6 to 20 microns.
• the incorporation of the glass fibers can take place both in the form of short glass fibers and in the form of endless strands (rovings).
• the average length of the glass fibers is preferably in the range of 0.08 to 0.5 mm.
• Carbon or glass fibers can also be used in the form of woven fabrics, mats or glass silk rovings.
• Suitable particulate fillers are amorphous silicic acid, carbonates, such as magnesium carbonate (chalk), powdered quartz, mica, various silicates, such as clays, muscovite, biotite, suzoite, cinnamon, talc, chlorite, phlogopite, feldspar, calcium silicates, such as wollastonite or Aluminum silicates, such as kaolin, especially calcined kaolin.
• carbonates such as magnesium carbonate (chalk)
• chalk magnesium carbonate
• various silicates such as clays, muscovite, biotite, suzoite, cinnamon, talc, chlorite, phlogopite, feldspar
• calcium silicates such as wollastonite
• Aluminum silicates such as kaolin, especially calcined kaolin.
• particulate fillers are used, of which at least 95% by weight, preferably at least 98% by weight, of the particles have a diameter (largest dimension) determined on the finished product of less than 45 ⁇ m, preferably less than 40 ⁇ m, and whose so-called aspect ratio is in the range from 1 to 25, preferably in the range from 2 to 20, determined on the finished product.
• the particle diameters can be determined, for example, by recording electron micrographs of thin sections of the polymer mixture and using at least 25, preferably at least 50 filler particles for the evaluation. Likewise, the determination of the particle diameter can be carried out by means of sedimentation analysis, according to Transactions of ASAE, page 491 (1983).
• the weight fraction of the fillers which is less than 40 ⁇ m, can also be measured by sieve analysis.
• the aspect ratio is the ratio of particle diameter to thickness (largest dimension to smallest dimension).
• Particularly preferred particulate fillers are talc, kaolin, such as calcined kaolin or wollastonite, or mixtures of two or all of these fillers.
• talc with a proportion of at least 95 wt .-% of particles having a diameter of less than 40 microns and an aspect ratio of 1, 5 to 25, each determined on the finished product, particularly preferred.
• Kaolin preferably has a proportion of at least 95% by weight of particles with a diameter of less than 20 ⁇ m and an aspect ratio of 1.2 to 20, in each case determined on the finished product.
• the molding compositions according to the invention may also contain, as further component E, auxiliaries, such as processing aids, pigments, stabilizers, flame retardants or mixtures of different additives.
• auxiliaries such as processing aids, pigments, stabilizers, flame retardants or mixtures of different additives.
• Common additives include, for example, oxida- Retarder, means against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, dyes and plasticizers.
• Their proportion is according to the invention from 0 to 30, preferably from 0 to 20 wt .-%, in particular 0 to 15 wt .-%, based on the total weight of the components A to E.
• the proportion of these stabilizers is usually up to 2 wt .-%, preferably 0.01 to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the total weight of A to E ,
• Pigments and dyes are generally present in amounts of up to 6, preferably 0.05 to 5 and especially 0.1 to 3 wt .-%, based on the sum of A to E, included.
• the pigments for coloring thermoplastics are well known, see, for example, R. Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pages 494 to 510.
• white pigments may be mentioned, such as zinc oxide, Zinc sulfide, lead white [2 PbCO 3 -Pb (OH) 2 ], lithithopones, antimony white and titanium dioxide.
• rutile and anatase type of the titanium dioxide, in particular the rutile form is used for whitening the molding compositions according to the invention.
• Black color pigments which can be used according to the invention are iron oxide black (Fe 3 O 4 ), spinel black [Cu (Cr, Fe) 2 O 4 ], manganese black (mixture of manganese dioxide, silica and iron oxide), cobalt black and antimony black, and are particularly preferred Carbon black, which is usually used in the form of furanite or gas black [see G. Benzing, Pigments for paints, Expert-Verlag (1988), pages 78 ff.].
• inorganic colored pigments such as chromium oxide green or organic colored pigments, such as azo pigments or phthalocyanines, can be used according to the invention.
• organic colored pigments such as azo pigments or phthalocyanines.
• Such pigments are generally commercially available.
• Oxidation inhibitors and thermal stabilizers which can be added to the thermoplastic compositions according to the invention are, for example, halides of metals of Group I of the Periodic Table, for example sodium, potassium, lithium halides, for example chlorides, bromides or iodides.
• zinc fluoride and zinc chloride can be used.
• sterically hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in conjunction with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations up to 1 wt .-%, by weight the mixture A to F can be used.
• UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benophenones, which are generally used in amounts of up to 2% by weight.
• Lubricants and mold release agents which are generally added in amounts of up to 1% by weight of the thermoplastic composition, are stearyl alcohol, stearic acid alkyl esters and amides, and esters of pentaerythritol with long-chain fatty acids. It is also possible to use dialkyl ketones, for example distearyl ketone.
• nucleating agents such as talc
• the molding compositions according to the invention can be prepared by processes known per se, for example by means of extrusion.
• the molding compositions can be prepared, for example, by mixing the starting components A, B and C, and optionally D and E in conventional mixing devices, such as screw extruders, preferably twin-screw extruders, Brabender mills or Banbury mills and kneaders and then extruded.
• screw extruders preferably twin-screw extruders, Brabender mills or Banbury mills and kneaders
• the extrudate is cooled and comminuted after extrusion.
• the molding compositions according to the invention can preferably also be prepared by precipitating the components from a solution containing the components A and B in a solvent (L) (such as N-methylpyrrolidone) and then extracting them, if necessary, and then adding the catalyst Component C and, if appropriate, mixed D and E in conventional mixing devices and then extruded.
• a solvent such as N-methylpyrrolidone
• the order of mixing of the components can be varied, so two or possibly three components can be premixed, but it can also be mixed all components together.
• Components A and B can also be premixed in the solution.
• the molding compositions according to the invention are characterized by good flowability, improved toughness, in particular elongation at break and notched impact strength and by an improved Surface quality.
• the molding compositions according to the invention are therefore suitable for the production of moldings for household articles, electrical or electronic components and moldings for the vehicle sector.
• the viscosity number of the polyarylethersulfones is determined in 1% solution of N-methylpyrrolidone at 25 0 C.
• the heat resistance of the samples was determined according to ISO 306 (Vicat B) (loading 50 N, temperature increase of 50 K per hour, on ISO rods).
• the notched impact strength of the products was determined in accordance with ISO 179 1 eB.
• the elongation at break of the materials was determined according to ISO 527.
• the flowability of the products was determined by measurement in a capillary rheometer at 370 0 C.
• the surface quality was determined visually on plates of size 60 to 60 to 2 mm and classified according to the school grading system between 1 (very good) and 6 (insufficient).
• the melt stability of the products was determined by measuring the melt viscosity in a capillary rheometer at 400 ° C. The change in the viscosity determined at 55 Hz over a period of 60 minutes is considered.
• ⁇ ⁇ 60- - ⁇ 5 - ⁇ 5 -
• Ultrason ® E in 2010 (BASF Aktiengesellschaft, characterized by a glass transition temperature of 225 0 C and a viscosity number of 55 ml / g) were used.
• Ultrason ® S 2010 (BASF Aktiengesellschaft, characterized by a glass transition temperature of 187 0 C and a viscosity number of 63 ml / g) were used.
• component C1 is commercially available stearic acid, characterized by a softening range of 55 to 60 0 C and an acid number of 200 to 212 mg KOH / g used.
• a finely divided talc is used as component D.
• the components A1, B1 and C were mixed in a twin-screw extruder (ZSK 30 of the company. Cerperion) at a housing temperature of 350 0 C and granulated. The granules were used to produce test specimens for mechanical testing by injection molding. When melt temperature was 350 0 C is used, the mold surface temperature was 140 0 C.

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