WO1999010432A1 - Matieres moulables a base d'ethers de polyarylene et de polyamides - Google Patents

Matieres moulables a base d'ethers de polyarylene et de polyamides Download PDF

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Publication number
WO1999010432A1
WO1999010432A1 PCT/EP1998/003283 EP9803283W WO9910432A1 WO 1999010432 A1 WO1999010432 A1 WO 1999010432A1 EP 9803283 W EP9803283 W EP 9803283W WO 9910432 A1 WO9910432 A1 WO 9910432A1
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groups
weight
units
polyarylene ether
molding compositions
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PCT/EP1998/003283
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German (de)
English (en)
Inventor
Martin Weber
Karin Elbl-Weiser
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Basf Aktiengesellschaft
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Priority to AU86242/98A priority Critical patent/AU8624298A/en
Publication of WO1999010432A1 publication Critical patent/WO1999010432A1/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
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether 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

Definitions

  • the present invention relates to molding compositions which
  • x stands for 0.5 or 1
  • t and q independently of one another stand for 0, 1, 2 or 3
  • n stands for an integer from 0 to 6
  • Q, T, Y and Z each independently represent a chemical bond or a group selected from -0-, -S-, -S0 2 -, and -CR c R d -, where R a and R are each independently a water -
  • Substance atom or a C ⁇ -C -alkyl group and R c and R d independently of one another each represent a hydrogen atom or a -C-C ⁇ -alkyl-, -C-C ⁇ -alkoxy or c 6 - (_ i 8 aryl group, where R c and R d can be substituted independently of one another with fluorine and / or chlorine atoms or together with the carbon atom to which they are attached can form a C 3 -C 2 cycloalkyl group, which if desired with one or more C 1 -C 6 alkyl groups is substituted, with the proviso that at least one of the groups T, Q and
  • R 1 is H, -CC 6 alkyl, or - (CH 2 ) n -COOH;
  • the present invention relates to the use of these molding compositions for the production of moldings, films or fibers and the moldings, films or fibers per se.
  • Fo ⁇ timassen based on polyarylene ethers and polyamides are known.
  • the properties of these blends can be influenced by the weight distribution of the two components. Mixtures with more than 50% by weight of polyamide have the same properties as the pure polyamides, but have better impact strengths.
  • Tough materials are obtained when the proportion of polyether sulfone predominates. Tougher objects can be produced by adding elastomers (DE-A 21 22 735). However, the toughness of the molding compositions mentioned in DE-A 21 22 735 is not sufficient for many applications, since the mixing partners are not compatible with one another.
  • Alkyl radicals which can be used according to the invention comprise straight-chain or branched, saturated carbon chains having up to 12 carbon atoms.
  • the following radicals can be mentioned: Ci-C ö alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, 2- or 3-methyl-pentyl; and longer chain residues such as unbranched heptyl, octyl, nonyi, decyl, undecyl, lauryl and the one or more branched analogues thereof.
  • alkyl part of alkoxy groups which can be used according to the invention is defined as indicated above.
  • Cvcloalkyl residues which can be used according to the invention include, in particular, C -C cycloalkyl residues, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylylbutyl, butyl, butyl Cyclohexylmethyl, dimethyl or trimethyl.
  • C -C cycloalkyl residues such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobut
  • C ⁇ -cis-arylene groups which can be used according to the invention are phenylene groups such as 1,2-, 1,3- or 1,4-phenylene, naphthylene groups, e.g. 1,6-, 1,7-, 2,6- or 2,7-naphthylene, as well as the bridging groups derived from anthracene, phenanthrene or naphthacene.
  • polyarylene ethers which comprise the structural elements I and II and have carboxyl groups are generally in proportions of 0.1 to 50, preferably 0.5 to 30, in particular 1.5 to 20% by weight, based on the total weight of the molding compositions, contained in the molding compositions according to the invention.
  • polyarylene ethers A modified according to the invention are obtainable on the basis of EP-A-0 185 237 and according to those of IW Parsons et al., In Polymer, 34, 2836 (1993) and T. Koch, H. Ritter, in Macromol. Phys. 195, 1709 (1994).
  • the polyarylene ethers A are accordingly obtainable, for example, by polycondensation of compounds of the general formula III
  • R 1 and n have the abovementioned meanings least another with little ⁇ , for example chloro-functionalized aromatic compound, such as bis (4-chlorophenyl) sulfone, and optionally, other hydroxy compounds such as bisphenol A and / or bisphenol S.
  • Suitable reactants are generally known to the person skilled in the art.
  • the manufacture can be based on GB 1 152 035 and US 4,870,153, to which express reference is hereby made.
  • Suitable process conditions for the synthesis of polyarylene ethers are described, for example, in EP-A-0 113 112 and
  • EP-A-0 135 130 The reaction of the monomers in aprotic polar solvents in the presence of anhydrous alkali carbonate is particularly suitable.
  • a particularly preferred combination is N-methylpyrrolidone as solvent and potassium carbonate as catalyst.
  • Particularly preferred units of the formula I are units of the formulas I and I which can be present individually or in a mixture.
  • n is an integer from 0 to 4.
  • the polyarylene ethers C containing acid groups used according to the invention generally have viscosity numbers of 15 to 80 ml / g (determined in 1% strength NMP solution at 25 ° C.).
  • the proportion of free acid groups in component C is generally from 0.05 to 25, preferably 0.1 to 20 and in particular 0.1 to 15 mol%, the determination of the proportion of acid groups, such as in IW Parsons et al., Polymer, 34, 2836 (1993), by i H-MR.
  • the polyarylene ethers A contain chlorine and / or alkoxy end groups, in particular methoxy or ethoxy, aryloxy, preferably phenoxy or benzyloxy end groups.
  • the molding compositions can contain at least one polyarylene ether with anhydride end groups (bi).
  • the molding compositions according to the invention optionally contain at least one polyarylene ether with epoxy end groups (b).
  • the molding compositions according to the invention can also contain a mixture of bi and b 2 as component B.
  • the molding compositions generally contain from 0 to 90% by weight of component B.
  • Preferred molding compositions contain from 0.5 to 88.5% by weight, in particular from 1 to 25% by weight, of the polyarylene ethers B.
  • polyarylene ethers bi can, for example, be composed of different or the same arylene ether groups.
  • the arylene groups are preferably not substituted. However, you can use one or more
  • Suitable substituents are, for example, alkyl, arylalkyl, aryl, nitro, cyano or alkoxy groups.
  • the preferred substituents include alkyl groups.
  • the arylene groups can be linked to one another, an alkylene radical or a chemical bond.
  • the arylene groups can also be linked to one another via different bridge groups.
  • Preferred polyarylene ethers bi are composed of recurring structural elements of the formula I '
  • the polyarylene ethers bi can also be copolymers or block copolymers in which polyarylene ether segments and segments of other thermoplastic polymers such as polyamides, polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides are present.
  • Such copolymers or block copolymers each contain at least one outer polyarylene ether segment with an anhydride end group.
  • the molecular weights (number average) of the block or graft arms in the copolymers are generally in the range from 1,000 to 30,000 g / mol.
  • the blocks of different structures can be arranged alternately or statistically.
  • the proportion by weight of the polyarylene ethers in the copolymers or block copolymers is generally at least 10% by weight.
  • the proportion by weight of the polyarylene ethers can be up to 97% by weight.
  • Co or block copolymers with a weight fraction of polyarylene ether of up to 90% by weight are preferred.
  • Co or block copolymers with 20 to 80% by weight polyarylene ether are particularly preferred.
  • the polyarylene ethers have average molecular weights M n (number average) in the range from 5,000 to 60,000 g / mol and relative viscosities from 0.20 to 0.9.5 dl / g.
  • M n number average
  • relative viscosities are measured either in 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% strength sulfuric acid at 20 ° C. or 25 ° C. in each case.
  • polyarylene ethers bi are e.g. from polyarylene ethers which contain hydroxy end groups (polyarylene ether B ').
  • Polyarylene ethers B ' which have 0.02 to 2% by weight of hydroxyl end groups are preferably used. Those which have 0.1 to 1.5% by weight of hydroxyl end groups are particularly preferred.
  • the polyarylene ethers B 'can for example, be reacted with phthalic anhydrides such as 3-fluorophthalic anhydride or 3-chlorophthalic anhydride to give the polyarylene ethers.
  • phthalic anhydrides such as 3-fluorophthalic anhydride or 3-chlorophthalic anhydride
  • the reaction of the hydroxy-terminated polyarylene ethers B 'with the phthalic anhydrides to give the polyarylene ethers bi preferably takes place at temperatures in the range from 100 to 250 ° C.
  • a solvent for example an aliphatic or aromatic sulfoxide or sulfone such as dimethyl sulfoxide, dimethyl sulfone, 1, 1-dioxothiolane or diphenyl sulfone, of which dimethyl sulfoxide and diphenyl sulfone are preferred.
  • a solvent for example an aliphatic or aromatic sulfoxide or sulfone such as dimethyl sulfoxide, dimethyl sulfone, 1, 1-dioxothiolane or diphenyl sulfone, of which dimethyl sulfoxide and diphenyl sulfone are preferred.
  • N-cyclohexylpyrrolidone, N, N-dimethylacetamide, dimethylformamide and N-methylpyrrolidone are also suitable.
  • N-Methylpyrrolidone is particularly preferably used.
  • reaction is carried out in the presence of approximately stoichiometric amounts of potassium fluoride, and the potassium fluoride is generally used in stoichiometric amounts to give phthalic anhydride.
  • reaction can also be carried out in the presence of potassium carbonate.
  • polyarylene ethers b 2 are composed of recurring structural elements of the formula I "
  • the polyarylene ethers b 2 can also be prepared from polyarylene ethers B '.
  • the polyarylene ethers B ' can be reacted, for example, with suitable compounds which have propylene oxide groups or from which propylene oxide groups are accessible, preferably epichlorohydrin.
  • the reaction of the hydroxy-terminated polyarylene ethers B 'with epichlorohydrin preferably takes place at temperatures in the range from 30 to 200 ° C. in a solvent. Suitable solvents are those mentioned under bi. As a rule, the reac- tion in a weakly basic environment in order to prevent ring opening of the epoxy groups as far as possible.
  • the preferred molding compositions contain the polyarylene ethers C in a proportion of 1 to 98.4, preferably 5 to 93, in particular 7 to 89% by weight, based on the total weight of the molding compositions.
  • polyarylene ethers C are known per se or can be obtained by processes known per se as have already been described above.
  • a wide variety of polyarylene ethers can be used as polyarylene ether C.
  • the polyarylene ethers C contain no recurring structural units of the formula II and their end groups differ from those of the polyarylene ether B.
  • Preferred polyarylene ethers C are composed of recurring structural elements of the formula I '' '
  • polyarylene ethers C can also contain halogen, in particular chlorine and / or alkoxy, especially methoxy or ethoxy, aryloxy, preferably phenoxy or benzyloxy groups as end groups.
  • the molding compositions according to the invention can contain polyarylene ethers A to C, the units I, I ', I “and I"''of which are different from one another. However, it is also possible to use polyarylene ethers A to C, the structural elements I, I', I "and I ''' are the same. According to a particularly preferred embodiment, the molding compositions according to the invention contain polyarylene ethers A, B and C, with structural elements I, I ', I "and I”"which are among the units of the formulas
  • Component D in the preferred molding compositions contains from 1 to 25 98.4, preferably from 5 to 93, in particular from 7 to 89% by weight, based on the total weight of the molding compositions, of at least one polyamide.
  • the polyamides contained as component D in the compositions comprise 30 partially crystalline and amorphous resins with a molecular weight (weight average) of at least 5000, which are usually referred to as nylon.
  • Such polyamides are e.g. in U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,322,966, 2,512,606 and 3,393,210. 35
  • the polyamides D are known per se or can be obtained by methods known per se. You can e.g. by condensation of equimolar amounts of a saturated or an aromatic dicarboxylic acid with 4 to 12 carbon atoms, with a saturated 40th or aromatic diamine which has up to 14 carbon atoms or by condensation of ⁇ -aminocarboxylic acids or polyaddition of corresponding lactams.
  • polyamides examples include polyhexamethylene adipic acid amide (nylon 66), polyhexamethylene azelaic acid amide (nylon 69), polyhexamethylene sebacic acid amide (nylon 610), polyhexamethylene dodecanoic acid amide (nylon 612), which are formed by ring opening of lactams polyamides obtained such as polycaprolactam, polylauric acid lactam, also poly-11-aminoundecanoic acid and a polyamide of di (p-amino-cyclohexyl) methane and dodecanedioic acid.
  • polyamides made by copolycondensation of two or more of the above-mentioned polymers or their components, e.g. Copolymers of adipic acid, isoph necked acid or terephthalic acid and hexamethylene diamine or copolymers of caprolactam, terephthalic acid and hexamethylene diamine.
  • Such partially aromatic copolyamides contain e.g. di) 20 to 90 wt .-% units derived from terephthalic acid and hexamethylenediamine.
  • These partially aromatic copolyamides preferably contain from 50 to 80, in particular from 60 to 75,% by weight of units di.
  • 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 partially aromatic copolyamides contain units which are derived from ⁇ -caprolactam and / or units which are derived from adipic acid and hexamethylenediamine.
  • the proportion of units in the partially aromatic polyamides derived from ⁇ -caprolactam is, for example, d) from 10 to 80% by weight, preferably 20 to 50% by weight, in particular 25 to 40% by weight, while the proportion of units derived from adipic acid and hexamethylenediamine, for example d 3 ), is from 0 to 70% by weight, preferably 0 to 30% by weight and in particular 0 to 15% by weight.
  • the weight percentages of components di to d 3 together add up to 100%.
  • the copolyamides can also contain units of ⁇ -caprolactam as well as units of adipic acid and hexamethylenediamine; in this case care must be taken to ensure that the proportion of units which are free from aromatic groups is at least 10% by weight, preferably at least 20% by weight.
  • the ratio of the units derived from ⁇ -caproiactam and from adipic acid and hexamethylenediamine is not subject to any particular restriction.
  • R 2 is hydrogen or a C 1 -C 4 alkyl group
  • R 3 is a C 1 -C 4 alkyl group or hydrogen
  • R 4 represents a C 1 -C 4 alkyl group or hydrogen.
  • Particularly preferred diamines III are bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl methane, bis (4-aminocyclohexyl) -2, 2-propane or bis (4-amino-3-methylcyclohexyl) -2, 2 - propane.
  • 1,3- or 1,4-cyclohexanediamine or isophoronediamine may be mentioned as further diamines III.
  • partially aromatic copolyamides can be used as component D which consist essentially of
  • the diamine units d ⁇ ) and d) are preferably reacted approximately aquimolar with the dicarboxylic acid units d 4 ) and d 5 ).
  • Suitable monomers d) are preferably the diamines III.
  • Aromatic diacarboxylic acids with generally 8 to 16 carbon atoms are suitable as monomers da).
  • Suitable aromatic dicarboxylic acids are, for example, substituted terephthalic and isophthalic acids such as 3-t-butylisophthalic acid, polynuclear dicarboxylic acids, e.g. B. 4,4'- and 3, 3'-diphenyldicarboxylic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'-diphenylsulfondicarboxylic acid, 1,4- or 2, 6-naphthalenedicarboxylic acid and phenoxyterephthalic acid.
  • substituted terephthalic and isophthalic acids such as 3-t-butylisophthalic acid
  • polynuclear dicarboxylic acids e.g. B. 4,4'- and 3, 3'-diphenyldicarboxylic acid, 4,4'- and 3,3
  • polyamide-forming monomers ds can e.g. derived from dicarboxylic acids with 4 to 16 carbon atoms and aliphatic diamines with 4 to 16 carbon atoms and from aminocarboxylic acids or corresponding lactams with 7 to 12 carbon atoms. Suitable monomers of these types are only here
  • Suberic acid, azelaic acid or sebacic acid as representatives of the aliphatic dicarboxylic acids, 1, 4-butanediamine, 1, 5-pentanediamine or piperazine, as representatives of the diamines and caprolactam, capryllactam, onanthlactam, laurolactam and ⁇ -aminoundecanoic acid as representatives of lactams or aminocarboxylic acids.
  • the melting points of the copolyamides B are generally in the range from 290 to 340 ° C., preferably from 292 to 330 ° C., this melting point having a high glass transition temperature of generally more than 120 ° C., in particular more than 130 ° C. ( in the dry state).
  • copolyamides B preference is given to those which have a degree of crystallinity> 30%, preferably> 35%, and in particular> 40%.
  • the degree of crystallinity is a measure of the proportion of crystalline fragments in the copolyamide and is determined by X-ray diffraction or indirectly by measuring ⁇ H kr i . ⁇ . certainly.
  • the partially aromatic copolyamides can be prepared, for example, by the process described in EP-A-129 195 and EP 129 196.
  • Preferred partially aromatic polyamides are those which have a content of triamine units, in particular units of dihexamethylene triamine, of less than 0.5% by weight. Such partially aromatic polyamides with triamine contents of 0.3% by weight or less are particularly preferred.
  • Linear polyamides with a melting point above 200 ° C. are preferred.
  • Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam as well as polyamide 6 / 6T and polyamide 66 / 6T as well as polyamides which contain cyclic diamines as comonomers.
  • the polyamides generally have a relative viscosity of 2.0 to 5, determined on a 1% strength by weight solution in 96% strength sulfuric acid at 23 ° C., which corresponds to a molecular weight (number average) of about 15,000 to 45,000 .
  • Polyamides with a relative viscosity of 2.4 to 3.5, in particular 2.5 to 3.4, are preferably used.
  • Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
  • the preferred molding compositions according to the invention contain from 0.5 to 50, preferably from 1 to 40, in particular from 1.5 to 30,% by weight of at least one impact-modifying rubber E.
  • the rubbers egg have functional groups which can react with carboxyl groups.
  • Preferred functionalized rubbers & ⁇ are made up of the following components:
  • ⁇ ) 0 to 50% by weight of a diene; ⁇ 3 ) 0 to 45% by weight of a C 1 -C 2 alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters;
  • Suitable ⁇ -olefins ⁇ i) include ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3- Ethyl-1-butylene can be mentioned, with ethylene and propylene being preferred.
  • Suitable diene monomers ⁇ ) include, for example, conjugated dienes with 4 to 8 C atoms, such as isoprene and butadiene, non-conjugated dienes with 5 to 25 C atoms, such as penta-1,4-diene, hexa-1,4 -diene, hexa-1, 5-diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes, such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene, and also alkenylnorborene, 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.
  • Hexa-1,5-diene, 5-ethylidene-norbornene and dicyclopentadiene are preferred.
  • the diene content is preferably 0.5 to 50, in particular 2 to 20 and particularly preferably 3 to 15% by weight, based on the total weight of the olefin polymer.
  • esters ⁇ 3 are methyl, ethyl, propyl, n-butyl, i-butyl and 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid.
  • methyl, ethyl, propyl, n-butyl and 2-ethylhexyl acrylate or methacrylate are particularly preferred.
  • the olefin polymers may also contain acid-functional and / or latently acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids ⁇ 4 ).
  • monomers ⁇ 4 ) are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular t-butyl acrylate and dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids and their monoesters.
  • Latent acid-functional monomers are to be understood as those compounds which form free acid groups under the polymerization conditions or when the olefin polymers are incorporated into the molding compositions.
  • Examples of these are anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular maleic anhydride and tertiary C 1 -C 4 -alkyl esters of the abovementioned acids, in particular t-butyl acrylate and t-butyl methacrylate.
  • Ethylenically unsaturated dicarboxylic acids and anhydrides ⁇ 4 can be represented by the following general formulas IV and V:
  • R 5 , R 6 , R 7 and R 8 independently of one another are H or -CC 6 alkyl.
  • Monomers 8 5 ) bearing epoxy groups can be represented by the following general formulas VI and VII
  • R 9 , R 10 , R 11 and R 12 are independently H or Ci-Cg-alkyl, m is an integer from 0 to 20 and p is an integer from 0 to 10.
  • R 5 to R 12 are preferably hydrogen, m is 0 or 1 and p is 1.
  • Preferred compounds ⁇ 4 ) and ⁇ s) are maleic acid, fumaric acid and maleic anhydride or alkenyl glycidyl ether and vinyl glycidyl ether.
  • Particularly preferred compounds of the formulas IV and V or VI and VII are maleic acid and maleic anhydride or epoxy group-containing esters of acrylic acid and / or methacrylic acid, in particular glycidyl acrylate and glycidyl methacrylate.
  • Olefin polymers of are particularly preferred
  • Particularly suitable functionalized rubbers B are ethylene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl acrylate and ethylene-methyl methacrylate-glycidyl acrylate polymers.
  • monomers ⁇ 6 are, for example, vinyl esters and vinyl ethers.
  • Rubbers are preferred which are functionalized with oxazine groups.
  • Rubbers E of this type can be obtained from polymers which contain units which are derived from acrylonitrile or alkylacrylonitrile. They are particularly preferably accessible from polymers which contain from 0.7 to 70% by weight, based on the total weight of all units, of units (e 7 ) which are derived from acrylonitrile or methacrylonitrile.
  • the preferred polymers from which the rubbers E can be produced contain from 20 to 99.5, preferably from 30 to 99.3% by weight, based on the total weight of all units, units ( ⁇ s) are derived from vinyl aromatic compounds, vinyl esters, acrylic acid esters or other copolymerizable monomers. These polymers can also contain mixtures of different units.
  • the preferred vinylaromatic compounds include styrene, nuclear-alkylated styrenes or ⁇ -alkylstyrenes such as ⁇ -methylstyrene, in particular styrene.
  • As preferred Vinylester are vinyl C 2 - to C ⁇ o _ alkyl esters, especially vinyl acetate mentioned.
  • acrylic acid esters are acrylic acid esters with 2 to 10 carbon atoms in the alcohol component such as acrylic acid ethyl, propyl, butyl, hexyl, -2-ethylhexyl ester, preferably butyl acrylate.
  • other copolymerizable monomers which do not react with oxazine groups can also be used.
  • N-phenyl maleiimide is an example of such copolymerizable monomers.
  • These starting polymers for the rubbers ei can be random copolymers or block copolymers.
  • the starting polymers can also be graft copolymers, for example with a rubber-elastic graft base and one or more graft pads.
  • Natural rubber, synthetic rubber or polymers based on conjugated dienes, as well as elastomers based on Ci to Cio alkyl esters of acrylic acid or cross-linked siloxanes can e.g. serve as a graft base.
  • Graft copolymers such as so-called acrylonitrile / butadiene / styrene (ABS), acrylic acid ester / styrene / acrylonitrile (ASA) or acrylonitrile / ethylene / styrene (AES) rubbers as well as hydrogenated or non-hydrogenated nitrile rubbers based on acrylic esters, vinyl esters, dienes and acrylonitrile , as described in DE-A 33 02 124, are among the preferred starting polymers for the rubbers.
  • ABS acrylonitrile / butadiene / styrene
  • ASA acrylic acid ester / styrene / acrylonitrile
  • AES acrylonitrile / ethylene / styrene
  • the rubbers egg can be made from the starting polymers e.g. by reacting with a monoamino alcohol.
  • Monoamino alcohols of the general formula VIII are preferred:
  • radicals R 13 to R 16 independently represent a hydrogen atom, C ⁇ ⁇ C ⁇ o to ⁇ alkyl, C ⁇ to C ⁇ 0 - can mean to Cia-aryl - alkylaryl or C ⁇ .
  • the variable n can be an integer from 1 to 5, in particular 1 or 2.
  • the alkyl radicals are either linear or branched. Examples of suitable alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl, preferably methyl.
  • the preferred alkylaryl radical is methylphenyl. Phenyl is to be mentioned as the preferred aryl radical.
  • the radicals R 13 to R 16 are very particularly preferably hydrogen.
  • a monoamino alcohol is also understood to mean mixtures of different monoamino alcohols.
  • the reaction takes place in the presence of a catalyst.
  • a catalyst Compounds which form complexes with the nitrile groups to be reacted, the monoamino alcohol or both reactants are catalytically active.
  • Metal salts in particular salts of zinc or cadmium, are particularly suitable as catalysts. These can both contain water of hydration and be free of water of hydration.
  • Zinc stearate or cadmium acetate are particularly preferred.
  • Mixtures of different complex-forming compounds can also be used as catalysts.
  • the starting polymer is first melted, preferably in a kneader or an extruder. Both catalyst and monoamino alcohol are added to the melt. Generally from 0.005 to 0.2 moles of catalyst are used per mole of nitrile group. The monoamino alcohol is generally used in amounts of 0.05 to 10 moles per mole of nitrile group.
  • rubbers can be used which contain carboxylic acid, carboxylic anhydride, carboxylic acid ester, carboximide, amino, hydroxyl or urethane groups.
  • Such rubbers can e.g. by grafting rubbers such as EP or EPDM rubbers with suitable grafting reagents such as maleic anhydride, itaconic acid, acrylic acid, glycidyl acrylate or glycidyl methacrylate.
  • suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, t-butyl (meth) acrylate, acrylic acid or glycidyl (meth) acrylate.
  • Rubbers of this type are known per se and are described, for example, in EP-A 208 187.
  • polyester elastomers are understood to mean segmented copolyether esters, the long-chain segments that usually differ from
  • Contain poly (alkylene) ether glycols and short chain segments derived from low molecular weight diols and dicarboxylic acids are known per se and are described in the literature, for example in US Pat. No. 3,651,014. Corresponding products are also commercially available under the names Hytrel® (Du Pont), Arnitel® (Akzo) and Pelprene® (Toyobo Co. Ltd.).
  • component E can also be a mixture of the rubbers ei with toughening rubbers which have no functional groups which can react with carboxyl groups (e 2 ).
  • Suitable rubbers e 2 are, for example, rubbers as described above as starting polymers for the rubbers ei.
  • the mixtures preferably contain at least 25% by weight, based on the weight of component E, of rubbers e.
  • the proportion of the rubbers egg in the mixtures is particularly preferably at least 50% by weight, based on the weight of component E.
  • the moldings according to the invention can also contain reinforcing agents or fillers.
  • the molding compositions according to the invention can e.g. from 0 to 60, preferably from 0 to 45, preferably 0 to 35% by weight of fibrous or particulate fillers or reinforcing materials or mixtures thereof.
  • Preferred fibrous fillers or reinforcing materials are carbon fibers, potassium titanate whiskers, aramid fibers and particularly preferably glass fibers. If glass fibers are used, they can be equipped with a size and an adhesion promoter for better compatibility with the matrix material. In general, the carbon and glass fibers used have a diameter in the range from 6 to 20 ⁇ m.
  • the glass fibers can be incorporated 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 from 0.08 to 0.5 mm.
  • Carbon or glass fibers can also be used in the form of fabrics, mats or glass silk rovings.
  • particulate fillers are amorphous silica, magnesium carbonate (chalk), powdered quartz, mica, talc, feldspar, glass spheres and in particular calcium silicates such as wollastoni and aluminum silicates such as kaolin (especially calcined kaolin).
  • Preferred combinations of fillers are, for example, 20% by weight of glass fibers with 15% by weight of wollastonite and 15% by weight of glass fibers with 15% by weight of wollastonite.
  • the molding compositions may also contain additives as component G.
  • Common additives are, for example, stabilizers and oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, flame retardants, lubricants and mold release agents, dyes and pigments and plasticizers.
  • Pigments and dyes are generally present in amounts of up to 6, preferably 0 to 5 and in particular 0 to 3% by weight.
  • the pigments for coloring thermoplastics are generally known, see, for example, R. Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, pp. 494 to 510.
  • the first preferred group of pigments are white pigments such as zinc oxide and zinc sulfide , Lead white (2 PbC0 3 -Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • white pigments such as zinc oxide and zinc sulfide , Lead white (2 PbC0 3 -Pb (OH) 2 ), lithopone, antimony white and titanium dioxide.
  • the rutile form is used in particular for the white coloring of the molding compositions according to the invention.
  • Black color pigments which can be used according to the invention are iron oxide black (Fe 3 0 4 ), spinel black (Cu (Cr, Fe) 2 0 4 ), manganese black (mixture of manganese dioxide, silicon dioxide and iron oxide), cobalt black and antimony black and particularly preferably carbon black, which is mostly used in the form of furnace or gas black (see G. Benzing, Pigments for Paints, Expert Verlag (1988), p. 78ff).
  • inorganic colored pigments such as chrome oxide green or organic colored pigments such as azo pigments and phthalocyanines can be used according to the invention to adjust certain shades. Pigments of this type are generally commercially available.
  • Oxidation retarders and heat 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 system, for example sodium, potassium, lithium halides, if appropriate in combination with copper (I) Halides, for example chlorides, bromides or iodides.
  • the halides, especially copper can also contain electron-rich ⁇ ligands.
  • Cu halide complexes with, for example, triphenylphosphine may be mentioned as examples of such copper complexes.
  • Zinc fluoride and zinc chloride can also be used.
  • Sterically hindered phenols hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally in combination with phosphorus-containing acids or their salts, and mixtures of these compounds, preferably in concentrations of up to 1% by weight, based on the weight of the mixture, applicable.
  • phosphorus-containing compounds can be used as flame retardants in amounts of up to 20% by weight, preferably up to 10% by weight.
  • Examples are phosphorus ⁇ klareester, phosphinic acid, phosphine oxides, phosphorus or organic phosphates.
  • the phosphorus-containing compounds can also be used in a mixture with a triazine derivative or polytetrafluoroethylene. Triarylphosphine oxides or triarylphosphates are preferably used.
  • UV stabilizers are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, 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 stearic acid, stearyl alcohol, alkyl stearates and amides, and esters of pentaerythritol with long-chain fatty acids. Salts of calcium, zinc or aluminum of stearic acid and dialkyl ketones, e.g. Distearyl ketone can be used.
  • the molding compositions according to the invention can be produced by processes known per se, for example extrusion. They are thermoplastic and can e.g. are produced by mixing the starting components in conventional mixing devices such as screw extruders, preferably twin-screw extruders, Brabender mills or Banbury mills and kneaders, and then extruding them. The extrudate is usually cooled and comminuted after the extrusion.
  • the order of mixing the components can be varied, so two or possibly three components can be premixed, but all components can also be mixed together.
  • intensive mixing is advantageous. Average mixing times of 0.2 to 30 minutes are generally involved. Temperatures of 280 to 380 ° C are required.
  • the molding compositions according to the invention have very good notched impact strengths and an improved toughness / stiffness ratio. They are therefore suitable, for example, for the production of molded parts that are exposed to high mechanical loads or chemical influences.
  • the viscosity number of the products was determined in 1% strength by weight solution in N-methylpyrrolidone at 25 ° C.
  • the proportion of units with acid groups in the copolyaryl ethers C) was as in IW Paronsons et. al., Polymer 34, 2836 (1993), was determined by i H-NMR spectroscopy.
  • the heat resistance of the samples was determined using the Vicat softening temperature.
  • the Vicat softening temperature was determined according to DIN 53 460, with a force of 49.05 N and a temperature increase of 50 K per hour, on standard small bars.
  • the impact strength of the products was measured on ISO bars according to ISO 179 leA.
  • the stiffness (modulus of elasticity) was determined according to DIN 53 457, the tensile strength and elongation at break according to DIN 53 455.
  • the damage work of the products was measured according to DIN 53 443 on round disks.
  • the toughness-stiffness ratio shown in Table 1 is defined as the quotient of notched impact strength and modulus of elasticity. The. Chemical resistance was tested in that
  • reaction mixture was stirred at a pressure of 300 mbar with continuous distillation of the reaction water and N-Methylpyrro ⁇ lidon initially heated 1 h at 180 ° C and then further reacted for 6 hours at 190 ° C.
  • the proportion of units with acid groups was determined by 1 H-NMR to be 1.2 mol%, the viscosity number of the product was 38.1 ml / g.
  • the proportion of units with acid groups was determined by means of 1 H-NMR to be 3.0 mol%, the viscosity number of the product was 40.2 ml / g.
  • the reaction mixture was first heated to 180 ° C. at a pressure of 300 mbar while continuously distilling off the water of reaction and N-methylpyrrolidone and then reacted further at 190 ° C. for 6 hours.
  • a white material was obtained.
  • the content of phthalic anhydride end groups was 0.83% by weight and the viscosity number of the polyarylene ether was 49.7 ml / g.
  • This product is further characterized by a glass step at 110 ° C and a melting peak at 289 ° C.
  • MMA Ethylene methyl methacrylate
  • GMA glydidyl methacrylate
  • the components were mixed in a twin-screw extruder at a melt temperature of 300 to 350 ° C.
  • the melt was passed through a water bath and granulated.
  • the molding compositions containing polysulfone Cl were processed at a melt temperature of 310 ° C., while the molding compositions containing polyethersulfone C2 were processed at 350 ° C.
  • the mold temperature was 100 ° C in each case.
  • thermoplastic molding compositions according to the invention have very good notched impact strengths and significantly improved toughness / stiffness ratios.

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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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne des matières moulables contenant: A) au moins un polyarylènéther modifié présentant des groupes carboxyle et ayant des motifs récurrents des formules (I) et (II) où x vaut 0,5 ou 1, t et q valent, indépendamment l'un de l'autre, 0, 1, 2 ou 3, n vaut un entier compris entre 0 et 6, Q, T, Y et Z représentent, indépendamment les uns des autres, respectivement une liaison chimique ou un groupe, choisi parmi -O-, -S-, -SO2-, S=O, C=O, -N=N-, -RaC=CRb- et -CRcRd- sachant que Ra et Rb représentent, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe alkyle C¿1?-C12 et R?c et Rd¿ repésentent, indépendamment l'un de l'autre, respectivement un atome d'hydrogène ou un groupe alkyle C¿1?-C12, alcoxy C1-C12 ou aryle C6-C18, R?c et Rd¿ pouvant être substitués, indépendamment l'un de l'autre, par des atomes de fluor et/ou de chlore ou ensemble par l'atome de carbone auquel ils sont liés, pouvant ainsi former un groupe cycloalkyle C¿3?-C12 qui peut être substitué par au moins un groupe alkyle C1-C6, à condition qu'au moins un des groupes T, Q et Z représente -SO2- ou C=O et que, si t et q valent O, z représente -SO2- ou C=O, Ar, Ar1, Ar?2 et Ar3¿ représentent, indépendamment les uns des autres, des groupes arylène C¿6?-C18, ces derniers étant, si on le souhaite, substitués par des groupes alkyle C1-C12, aryle C6-C18, alcoxy C1-C12 ou des atomes d'halogène; R?1¿ représente H, alkyle C¿1?-C6 ou bien -(CH2)n-COOH, le rapport molaire des unités de formule (I) aux unités de formule (II) se trouvant dans la plage allant de 0,05:99,95 à 99,95:0,05; B) si on le souhaite, au moins un éther de polyarylène avec des groupes anhydride (b1) ou un éther de polyarylène avec des groupes époxy (b2), ou bien avec un mélange de b1 et b2; C) au moins un éther de polyarylène avec des groupes terminaux qui se différencient de ceux des éthers de polyarylène B; D) au moins un polyamide; et E) au moins un caoutchouc modifiant la ténacité, avec des groupes pouvant réagir par rapport aux groupes carboxyle (e1), ou bien un mélange de e1 et d'au moins un caoutchouc modifiant la ténacité, qui ne contient aucun groupe pouvant réagir par rapport aux groupes carboxyle (e2).
PCT/EP1998/003283 1997-08-25 1998-06-02 Matieres moulables a base d'ethers de polyarylene et de polyamides WO1999010432A1 (fr)

Priority Applications (1)

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AU86242/98A AU8624298A (en) 1997-08-25 1998-06-02 Moulding material on the basis of polyarylene ethers and polyamides

Applications Claiming Priority (2)

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DE19736973A DE19736973A1 (de) 1997-08-25 1997-08-25 Formmassen auf der Basis von Polyarylenethern und Polyamiden
DE19736973.1 1997-08-25

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DE (1) DE19736973A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU783088B2 (en) * 1999-08-12 2005-09-22 Ortho-Mcneil Pharmaceutical, Inc. Antibacterial heterobicyclic substituted phenyl oxazolidinones
US7329711B2 (en) * 2001-11-12 2008-02-12 Basf Aktiengesellschaft Modified epoxy resins

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723389A (en) * 1971-10-27 1973-03-27 Allied Chem Thermoplastic aromatic poly(ether-sulfones)
EP0185237A1 (fr) * 1984-12-05 1986-06-25 BASF Aktiengesellschaft Masses à mouler thermoplastiques
EP0590392A2 (fr) * 1992-09-23 1994-04-06 BASF Aktiengesellschaft Masses à mouler à base de polyaryléthers et de copolyamides partiellement aromatiques modifiés résistants aux chocs
US5457169A (en) * 1993-03-04 1995-10-10 Basf Aktiengesellschaft Molding materials based on polyarylene ethers having terminal anhydride groups
US5612425A (en) * 1991-03-30 1997-03-18 Basf Aktiengesellschaft Molding compositions based on modified polyaryl ethers
EP0855428A1 (fr) * 1997-01-24 1998-07-29 Basf Aktiengesellschaft Masses à mouler thermoplastiques ayant une absorption d'eau réduite

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723389A (en) * 1971-10-27 1973-03-27 Allied Chem Thermoplastic aromatic poly(ether-sulfones)
EP0185237A1 (fr) * 1984-12-05 1986-06-25 BASF Aktiengesellschaft Masses à mouler thermoplastiques
US5612425A (en) * 1991-03-30 1997-03-18 Basf Aktiengesellschaft Molding compositions based on modified polyaryl ethers
EP0590392A2 (fr) * 1992-09-23 1994-04-06 BASF Aktiengesellschaft Masses à mouler à base de polyaryléthers et de copolyamides partiellement aromatiques modifiés résistants aux chocs
US5457169A (en) * 1993-03-04 1995-10-10 Basf Aktiengesellschaft Molding materials based on polyarylene ethers having terminal anhydride groups
EP0855428A1 (fr) * 1997-01-24 1998-07-29 Basf Aktiengesellschaft Masses à mouler thermoplastiques ayant une absorption d'eau réduite

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU783088B2 (en) * 1999-08-12 2005-09-22 Ortho-Mcneil Pharmaceutical, Inc. Antibacterial heterobicyclic substituted phenyl oxazolidinones
US7329711B2 (en) * 2001-11-12 2008-02-12 Basf Aktiengesellschaft Modified epoxy resins

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DE19736973A1 (de) 1999-03-04
AR016863A1 (es) 2001-08-01
AU8624298A (en) 1999-03-16
TW376403B (en) 1999-12-11

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