WO2011069942A1 - Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine - Google Patents

Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine Download PDF

Info

Publication number
WO2011069942A1
WO2011069942A1 PCT/EP2010/068930 EP2010068930W WO2011069942A1 WO 2011069942 A1 WO2011069942 A1 WO 2011069942A1 EP 2010068930 W EP2010068930 W EP 2010068930W WO 2011069942 A1 WO2011069942 A1 WO 2011069942A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
copolyamide
molding compositions
units
compositions according
Prior art date
Application number
PCT/EP2010/068930
Other languages
German (de)
English (en)
Inventor
Christian Schmidt
Philippe Desbois
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2011069942A1 publication Critical patent/WO2011069942A1/fr

Links

Classifications

    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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

Definitions

  • the invention relates to partially aromatic copolyamide molding compositions containing
  • the invention relates to the use of the copolyamides according to the invention for the production of fibers, films and moldings of any kind, as well as the moldings obtainable in this case.
  • High-temperature-resistant polyamides usually build up on the units 6T (hexamethylenediamine, terephthalic acid).
  • 6T hexamethylenediamine, terephthalic acid
  • pure 6T has a very high melting temperature and can not be processed without decomposition. Accordingly, copolymer systems have been developed to avoid this: e.g.
  • EP-A 299 444 (PA6 / 6T, PA66 / 6T), EP-A 19 94 075 (PA6T / 6I / MXD6), EP-A 667 367 (6T / 6l / cycloaliphatic diamine) and US Pat. No. 3,843,611 (PA8T / 88).
  • HTPA's which have the highest possible glass transition temperature and a high melting temperature (without decomposition), are particularly desired for problem-free processing for many applications.
  • the tendency to water absorption, which impairs many properties, should be minimized. It is an object of the present invention to provide partially aromatic, partially crystalline copolyamides which have a high T g and a high T m (without decomposition) and a low water absorption. Accordingly, the Copolyamidformmassen defined above were found. Preferred embodiments are given in the dependent claims.
  • the copolyamide molding compositions of the invention comprise from 35 to 100, preferably from 35 to 95,% by weight of a copolyamide synthesized from a-i) from 60 to 95 mol% of units derived from 1,8-octamethylenediamine and terephthalic acid,
  • Preferred partially aromatic partially crystalline copolyamides A) are composed of: a-i) from 70 to 95 mol%, in particular from 80 to 95 mol%, of units a-1) and
  • terephthalic acid units 5 to 30 mol%, in particular 5 to 20 mol% units 32).
  • a small proportion of up to 30 mol%, preferably up to 20 mol%, of the terephthalic acid units can be replaced by other aromatic carboxylic acids.
  • Suitable aromatic dicarboxylic acids are, for example, isophthalic acid, substituted terephthalic and isophthalic acids such as 3-t-butyl isophthalic acid, 3-sulfoisophthalic acid, 3-aminoisophthalic acid, polynuclear dicarboxylic acids, e.g. 4,4'- and 3,3'-diphenyldicarboxylic acid, phthalic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'-diphenylsulfonedicarboxylic acid, 1, 4 or 2, 6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, with isophthalic acid being particularly preferred.
  • Preferred aliphatic dicarboxylic acids are those having linear or branched alkyl radicals having 2 to 20 C atoms, preferably having 4 to 16 C atoms, very particularly preferably having 6 to 14 C atoms.
  • dicarboxylic acids there can be used those which have two carboxylic acid groups (carboxy groups) or derivatives thereof.
  • derivatives in particular C 1 -C 10 -alkyl, preferably methyl, ethyl, n-propyl or isopropyl mono- or diesters of the abovementioned dicarboxylic acids, the corresponding dicarboxylic acid halides, in particular the dicarboxylic acid dichlorides and the corresponding dicarboxylic anhydrides use.
  • Examples of such compounds are ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (brassylic acid), C32-dimer fatty acid (commercial product from.
  • oxalic acid propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic
  • Methylester for example Ethandiklaredimethylester, -propanedioic acid dimethyl ester, Butandiklaredimethylester, Pentandiklaredimethylester, Hexandiklaredimethylester, Heptandiklaredimethylester, Octandiklaredimethylester, Nonandiklaredimethylester, Decandiklaredimethylester, Undecandiklaredimethylester Dimethyl dodecanedioate, tridecanedioic acid diester, C32 dimer fatty acid dimethyl ester, their dichlorides, for example ethanedioic dichloride, propanedioic dichloride, butanedioic dichloride, pentanedioic dichloro idand, hexanedioic acid dichloride, heptanedioic dichloride, octanedioic acid
  • Further possible units a2) are derived from aromatic or aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms and from aminocarboxylic acids.
  • Suitable monomers of these types are 1, 4-butanediamine, 1, 5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,3- (4,4'-diaminodicyclohexyl) propane or 3,3'-dimethyl-4 , 4'-diaminodicyclohexylmethane, hexamethylenediamine, 1,8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 12-diaminododecane, 1, 13-diaminotridecane, 2,2,4- or 2,4,4 Trimethylhexamethylenediamine, xylylenediamines, methylpentamethylenediamine and alkyl-substituted xylylenediamines.
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid (particularly preferred)
  • 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 61 and PA 6T
  • PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
  • PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane
  • PA PDA-T phenylenediamine, terephthalic acid
  • Preferred units a2) are combinations of aromatic dicarboxylic acids having 8 to 16 C atoms with aliphatic or cycloaliphatic diamines having 4 to 16 C atoms or of aliphatic diamines having 4 to 16 C atoms with aliphatic dicarboxylic acids having 2 to 20 C atoms. atoms.
  • PA6I Hexamethylenediamine with isophthalic acid
  • PA66 Hexamethylenediamine with adipic acid
  • the polyamides A) can be prepared by methods known per se (for example EP 129 195, US 3,948,862). It is likewise possible to use the process described in WO 2007/23108, in which the corresponding dinitriles of the diacids are used as acid equivalents or so-called direct polymerization in the presence of water, for example in DE-A 10313681, EP-A 1 198491 and EP 922065 described.
  • the preparation of the polyamides of the invention is preferably carried out in a discontinuous or continuous hydrolytic polycondensation reaction between the corresponding diamines and free dicarboxylic acids from aqueous solution or from an aqueous solution of a water-soluble hypophosphite salt (0.05 to 0.5% by weight).
  • the prepolymer thus formed having a viscosity number (CV) of 40 to 120 ml / g (in concentrated sulfuric acid, 0.5% by weight, ISO 307) is subjected to a postcondensation either in solid phase or in the molten state in an extruder. until a VZ of at least 80 ml / g is reached, preferably from 90 to 160 ml / g.
  • the copolyamide according to the invention can be produced from a polyamide having units a-1 and a polyamide having units 32) by melting and transamidation in the melt, in particular in an extruder.
  • the respective polyamides are supplied separately and, if appropriate, catalytically active additives and / or accelerators (for example hypophosphite compounds, organophosphites, organophosphonates) are added.
  • the copolyamide thus produced has only a uniform glass transition temperature after transamidation and copolyamide formation.
  • the copolyamides A) preferably have a glass transition temperature TG of greater than 104 ° C, especially greater than 1 10 ° C and in particular from 120 to 140 ° C.
  • the melting temperature T m is preferably less than 330 ° C, in particular from 280 to 315 ° C. These parameters are usually measured by means of DSC (Diffusive Scanning Calorimetry) according to ISO 1 1357-2, 3 and 7 (20 K / min, 2nd heating curve).
  • molding compositions of the invention may contain up to 65, preferably up to 50 wt .-% of other additives.
  • fibrous or particulate fillers are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts of 1 to 50 wt .-%, in particular 5 to 40, preferably 10 to 40 wt .-% are used.
  • Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.
  • Suitable silane compounds are those of the general formula
  • n is an integer from 2 to 10, preferably 3 to 4
  • n is an integer from 1 to 5, preferably 1 to 2
  • k is an integer from 1 to 3, preferably 1.
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of from 0.01 to 2, preferably from 0.025 to 1, 0 and in particular from 0.05 to 0.5% by weight (based on B)) of the surface coating.
  • acicular mineral fillers are also suitable.
  • needle-shaped mineral fillers are understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1.
  • the mineral filler may optionally be pretreated with the silane compounds mentioned above; however, pretreatment is not absolutely necessary.
  • fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called as well as platelet or needle-shaped nanofillers preferably in amounts between 0.1 and 10%.
  • Boehmite, bentonite, montmorillonite, vermicullite, hectorite and laponite are preferably used for this purpose.
  • the platelet-shaped nanofillers according to the prior art are organically modified.
  • the addition of the platelet- or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical strength.
  • the molding compositions according to the invention may contain 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.
  • a lubricant Preference is given to Al, alkali metal, alkaline earth metal salts or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably having 12 to 44 carbon atoms.
  • 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.
  • 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.
  • alcohols examples include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • the molding compositions of the invention 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a Cu stabilizer, preferably a Cu (l) halide, in particular in a mixture with an alkali metal halide, preferably KJ, in particular in the ratio 1: 4, or of a sterically hindered phenol or mixtures thereof.
  • a Cu stabilizer preferably a Cu (l) halide, in particular in a mixture with an alkali metal halide, preferably KJ, in particular in the ratio 1: 4, or of a sterically hindered phenol or mixtures thereof.
  • Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. These are contained in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide.
  • the advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide.
  • This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution.
  • a typical con- For example, concentrate consists of 79 to 95 wt .-% polyamide and 21 to 5 wt .-% of a mixture of copper iodide or bromide and potassium iodide.
  • the concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 1 1, 5, preferably between 1 and 5.
  • Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular polyamide 6 and polyamide 6.6.
  • R 1 and R 2 are an alkyl group, a substituted alkyl group or a substituted triazole group, where R 1 and R 2 may be identical or different and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.
  • Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).
  • Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.
  • Particularly preferred compounds of this class are compounds of the formula
  • R 4 , R 5 , R 7 and R 8 independently of one another are C 1 -C 8 -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding full group) and R 6 is a divalent aliphatic radical having 1 to 10 carbon atoms, which may also have CO bonds in the main chain.
  • antioxidants B which can be used individually or as mixtures, are in an amount of 0.05 to 3 wt .-%, preferably from 0.1 to 1, 5 wt .-%, in particular 0.1 to 1 Wt .-%, based on the total weight of the molding compositions A) to B).
  • sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time.
  • the molding compositions of the invention may contain 0.05 to 5, preferably 0.1 to 2 and in particular 0.25 to 1, 5 wt .-% of a nigrosine.
  • Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, gas-soluble) which are useful in wool dyeing and printing, in the black dyeing of silks, for dyeing leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscope dyes.
  • azine dyes in various embodiments (water-soluble, fat-soluble, gas-soluble) which are useful in wool dyeing and printing, in the black dyeing of silks, for dyeing leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscope dyes.
  • Component B) can be used as free base or else as salt (for example hydrochloride).
  • nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".
  • customary additives B) are, for example, in amounts of up to 25, preferably up to 20 wt .-% rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).
  • these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic esters with 1 to 18 C Atoms in the alcohol component.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1, 5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes, and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
  • EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.
  • Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
  • the rubbers may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture
  • R 1 to R 9 are hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.
  • the radicals R 1 to R 9 preferably denote hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.
  • the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to
  • copolymers of from 50 to 98, in particular from 55 to 95,% by weight of ethylene,
  • 0.1 to 40 in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.
  • Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization".
  • the usable emulsifiers and catalysts are known per se.
  • homogeneously constructed elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
  • acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called.
  • monomers for the preparation of the rubber portion of the elastomers acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called.
  • monomers can be reacted with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
  • the soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers may be the core, the outer shell, or a middle shell (for elastomers having more than two shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
  • one or more hard components are involved in the construction of the elastomer, these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene , Acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers. In addition, smaller proportions of other comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula can be introduced, wherein the substituents may have the following meaning:
  • R 11 is hydrogen, a C 1 - to C 5 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or -OR 13
  • R 13 is a C 1 - to C 6 -alkyl or C 6 - to C 12 -aryl group which may optionally be substituted by O- or N-containing groups,
  • X is a chemical bond, a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group or
  • Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-) Diethylamino) ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.
  • graft-linking monomers ie monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preference is given to using those compounds in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups), for example, polymerizes (polymerizes) much more slowly.
  • graft-crosslinking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • graft-linking monomers there are a variety of other suitable graft-linking monomers; for further details, reference is made here, for example, to US Pat. No. 4,148,846.
  • the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
  • graft polymers having a core and at least one outer shell, which have the following structure:
  • III such as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1, 3-diene, isoprene, ethylhexyl acrylate
  • graft polymers having a multi-shell structure instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1, 3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by co-use of crosslinking monomers or monomers having reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.
  • Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred. Of course, it is also possible to use mixtures of the rubber types listed above.
  • thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, Oxidationsverzogerer, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • processing aids such as stabilizers, Oxidationsverzogerer, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation promoters and heat stabilizers are sterically hindered phenols and / or phosphites and amines (eg TAD), hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight called on the weight of the thermoplastic molding compositions.
  • TAD sterically hindered phenols and / or phosphites and amines
  • hydroquinones such as diphenylamines
  • aromatic secondary amines such as diphenylamines
  • various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight called on the weight of the thermoplastic molding compositions.
  • UV stabilizers which are generally used in amounts of up to 2 wt .-%, based on the molding composition, 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, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.
  • sodium phenylphosphinate, alumina, silica and preferably talc may be used as nucleating agents.
  • 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. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually 230 to 320 ° C.
  • the components B) can be mixed with a prepolymer, formulated and granulated.
  • the resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.
  • thermoplastic molding compositions according to the invention are distinguished by a good processability coupled with good mechanical properties, as well as by a high T g coupled with a high T m , but without decomposition of the polymer during processing.
  • the water absorption of the polyamides has been further reduced.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • motorcycle covers intake pipes, intercooler caps, connectors, gears, fan wheels, cooling water boxes.
  • dashboards Inside the car, there is use for dashboards, steering column switches, seat parts, headrests, center consoles, gear components and door modules, in the car exterior for door handles, exterior mirror components, windscreen wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds (In particular intake manifold), windscreen wipers and body exterior parts possible.
  • Further applications include electronic components (lead-free soldering) and applications in the field of electronics, fuel supply and cooling systems under the bonnet (metal set), lamp sockets (also LED sockets), bobbins, power strips, chain tensioners, intercoolers, ignition coil plugs, components for lead-free soldering (eg SIM card holders, circuit boards, plugs, printed conductors, CPU sockets), water meter housings (also for hot water), housings of sensors in contact with water, fuel and / or oils.
  • bonnet metal set
  • lamp sockets also LED sockets
  • bobbins power strips
  • chain tensioners e.g. SIM card holders, circuit boards, plugs, printed conductors, CPU sockets
  • water meter housings also for hot water
  • housings of sensors in contact with water, fuel and / or oils e.g SIM card holders, circuit boards, plugs, printed conductors, CPU sockets
  • Octamethylenediamine, terephthalic acid and other comonomers (a dicarboxylic acid and optionally another diamine) were weighed in a test tube together with an aqueous solution of sodium hypophosphite monohydrate ("NHP", 0.1% by weight)
  • the reaction mixture was then introduced into an autoclave reactor and purged 3 times with 10 bar nitrogen each
  • the autoclave was heated to 350 ° C outside temperature and maintained a pressure of 16 bar for a total of 2 hours Minutes, the autoclave was depressurized to ambient pressure and the postcondensation was carried out under nitrogen flow for 120 minutes at the same temperature After cooling under a nitrogen atmosphere, the removed, dry product was comminuted (for exact sample weights and data, see the following tables).
  • the initial weight was about 8.5 mg - the heating and cooling rate 20 K / min (2nd heating curve).
  • the samples were measured on the basis of ISO 1 1357 - 2, 3, u. 7 Measurement in the 2nd heating run (after cooling the sample from 380 ° C with 20 K min)
  • Tgi glass transition temperature in delivery condition
  • Tmi melting point in delivery condition
  • Tg2 glass transition temperature of a sample cooled from the melt at 20 ° C./min
  • Trri2 melting point of a sample cooled from the melt at 20 ° C./min.
  • ⁇ 2 heat of fusion of a sample cooled from the melt at 20 ° C./min
  • compositions and the results of the measurements are shown in the tables.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières à mouler constituées de copolyamide partiellement aromatique, contenant A) 35 à 100 % en poids d'un copolyamide partiellement aromatique, partiellement cristallin, constitué de a1) 60 à 95 % en moles de motifs qui sont dérivés de la 1,8-octaméthylène diamine et de l'acide téréphtalique, a2) 5 à 40 % en moles de motifs qui sont dérivés d'autres monomères constitutifs du polyamide, différents de a1) la combinaison d'octaméthylène diamine et d'acide subérique étant exclue dans les motifs a2), B) 0 à 65 % en poids d'autres additifs, la somme des pourcentages en poids de A) et de B) étant égale à 100 %.
PCT/EP2010/068930 2009-12-08 2010-12-06 Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine WO2011069942A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09178361 2009-12-08
EP09178361.3 2009-12-08

Publications (1)

Publication Number Publication Date
WO2011069942A1 true WO2011069942A1 (fr) 2011-06-16

Family

ID=43466440

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/068930 WO2011069942A1 (fr) 2009-12-08 2010-12-06 Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine

Country Status (1)

Country Link
WO (1) WO2011069942A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8957180B2 (en) 2011-08-23 2015-02-17 Basf Se Process for producing moldings
WO2015197124A1 (fr) * 2014-06-26 2015-12-30 Dsm Ip Assets B.V. Procédé de préparation d'un polyamide semi-aromatique semi-cristallin
US9315626B2 (en) 2009-12-08 2016-04-19 Basf Se Process for preparing polyamides
TWI651369B (zh) * 2014-06-26 2019-02-21 Ｄｓｍ智慧財產有限公司 用於製備半晶質半芳香聚醯胺之方法

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843611A (en) 1972-05-22 1974-10-22 Phillips Petroleum Co Copolyamide from terephthalic acid,dodecanedioic acid and dodecane diamine
US3948862A (en) 1974-05-06 1976-04-06 E. I. Du Pont De Nemours And Company Continuous process for preparing aliphatic polycarbonamides
DE2702661A1 (de) 1976-02-05 1977-08-11 Ciba Geigy Ag Stabilisatorsysteme aus triarylphosphiten und phenolen
US4148846A (en) 1970-09-10 1979-04-10 Rohm And Haas Company Acrylic modifiers for polycarbonamides
EP0050265A1 (fr) 1980-10-16 1982-04-28 Bayer Ag Compositions de polyesters thermoplastiques
EP0129195A2 (fr) 1983-06-15 1984-12-27 BASF Aktiengesellschaft Procédé pour la production continue de polyamides
US4607073A (en) * 1984-01-27 1986-08-19 Mitsui Petrochemical Industries, Ltd. Molding polyamide composition
EP0208187A2 (fr) 1985-07-06 1987-01-14 Bayer Ag Polymères greffés et leurs mélanges avec des polyamides
EP0235690A2 (fr) 1986-03-04 1987-09-09 Bayer Ag Polymères greffés sur des polymères caoutchouteux à structure séquencée
EP0299444A2 (fr) 1987-07-17 1989-01-18 BASF Aktiengesellschaft Copolyamides partiellement aromatiques avec un taux de triamine abaissé
DE3725576A1 (de) 1987-08-01 1989-02-09 Bayer Ag Formmassen aus aromatischem polyester und gepfropftem silikonkautschuk
EP0319290A2 (fr) 1987-12-04 1989-06-07 Polyplastics Co. Ltd. Composition de résines
DE3800603A1 (de) 1988-01-12 1989-07-20 Bayer Ag Formmassen aus aromatischen polyestern, vinyl-copolymerisaten und gepfropftem siliconkautschuk
JPH0453870A (ja) * 1990-06-20 1992-02-21 Toray Ind Inc 自動車用アンダーフード部品
JPH07126381A (ja) * 1993-11-02 1995-05-16 Toray Ind Inc ポリアミドの製造方法
EP0922065A2 (fr) 1996-08-30 1999-06-16 Basf Aktiengesellschaft Procede pour la preparation de polyamides a partir d'aminonitriles
EP1198491A1 (fr) 1999-07-30 2002-04-24 Basf Aktiengesellschaft Procede de production de polyamides a partir de dinitriles et de diamines
DE10313681A1 (de) 2003-03-26 2004-10-07 Basf Ag Verfahren zur Herstellung von Polyamiden
CN1537881A (zh) * 2003-04-18 2004-10-20 上海杰事杰新材料股份有限公司 高韧性半芳香族尼龙及其制备方法
WO2007023108A1 (fr) 2005-08-26 2007-03-01 Basf Aktiengesellschaft Procede pour preparer des polyamides
EP1994075A2 (fr) 2006-03-08 2008-11-26 Basf Se Copolyamides partiellement aromatiques à haute cristallinité

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4148846A (en) 1970-09-10 1979-04-10 Rohm And Haas Company Acrylic modifiers for polycarbonamides
US3843611A (en) 1972-05-22 1974-10-22 Phillips Petroleum Co Copolyamide from terephthalic acid,dodecanedioic acid and dodecane diamine
US3948862A (en) 1974-05-06 1976-04-06 E. I. Du Pont De Nemours And Company Continuous process for preparing aliphatic polycarbonamides
DE2702661A1 (de) 1976-02-05 1977-08-11 Ciba Geigy Ag Stabilisatorsysteme aus triarylphosphiten und phenolen
US4360617A (en) 1976-02-05 1982-11-23 Ciba-Geigy Corporation Stabilizer systems of triarylphosphites and phenols
EP0050265A1 (fr) 1980-10-16 1982-04-28 Bayer Ag Compositions de polyesters thermoplastiques
EP0129195A2 (fr) 1983-06-15 1984-12-27 BASF Aktiengesellschaft Procédé pour la production continue de polyamides
US4607073A (en) * 1984-01-27 1986-08-19 Mitsui Petrochemical Industries, Ltd. Molding polyamide composition
EP0208187A2 (fr) 1985-07-06 1987-01-14 Bayer Ag Polymères greffés et leurs mélanges avec des polyamides
EP0235690A2 (fr) 1986-03-04 1987-09-09 Bayer Ag Polymères greffés sur des polymères caoutchouteux à structure séquencée
EP0299444A2 (fr) 1987-07-17 1989-01-18 BASF Aktiengesellschaft Copolyamides partiellement aromatiques avec un taux de triamine abaissé
DE3725576A1 (de) 1987-08-01 1989-02-09 Bayer Ag Formmassen aus aromatischem polyester und gepfropftem silikonkautschuk
EP0319290A2 (fr) 1987-12-04 1989-06-07 Polyplastics Co. Ltd. Composition de résines
DE3800603A1 (de) 1988-01-12 1989-07-20 Bayer Ag Formmassen aus aromatischen polyestern, vinyl-copolymerisaten und gepfropftem siliconkautschuk
JPH0453870A (ja) * 1990-06-20 1992-02-21 Toray Ind Inc 自動車用アンダーフード部品
JPH07126381A (ja) * 1993-11-02 1995-05-16 Toray Ind Inc ポリアミドの製造方法
EP0922065A2 (fr) 1996-08-30 1999-06-16 Basf Aktiengesellschaft Procede pour la preparation de polyamides a partir d'aminonitriles
EP1198491A1 (fr) 1999-07-30 2002-04-24 Basf Aktiengesellschaft Procede de production de polyamides a partir de dinitriles et de diamines
DE10313681A1 (de) 2003-03-26 2004-10-07 Basf Ag Verfahren zur Herstellung von Polyamiden
CN1537881A (zh) * 2003-04-18 2004-10-20 上海杰事杰新材料股份有限公司 高韧性半芳香族尼龙及其制备方法
WO2007023108A1 (fr) 2005-08-26 2007-03-01 Basf Aktiengesellschaft Procede pour preparer des polyamides
EP1994075A2 (fr) 2006-03-08 2008-11-26 Basf Se Copolyamides partiellement aromatiques à haute cristallinité

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
AJROLDI, G.; STEA, A.; MATTIUSSI, F., J. APPL. POLY. SEI., vol. 17, 1973, pages 3187 - 3197
C.B. BUCKNALL: "Toughened Plastics", 1977, APPLIED SCIENCE PUBLISHERS
DATABASE EPODOC [online] EUROPEAN PATENT OFFICE, THE HAGUE, NL; 2004, SHANGHAI JIESHIJIE NEW MATERIAL CO LTD [CN], XP002630803, Database accession no. CN-03116483-A *
GAYMANS ET AL., J. POLYM. SEI. A, CHEM., vol. 27, 1989, pages 423 - 430
H. LUDEWIG, FASERFORSCHUNG UND TEXTILCHEMIE, vol. 7, 27 June 1955 (1955-06-27)
HOUBEN-WEYL: "Methoden der organischen Chemie", 1961, GEORG-THIEME-VERLAG, pages: 392 - 406

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9315626B2 (en) 2009-12-08 2016-04-19 Basf Se Process for preparing polyamides
US8957180B2 (en) 2011-08-23 2015-02-17 Basf Se Process for producing moldings
WO2015197124A1 (fr) * 2014-06-26 2015-12-30 Dsm Ip Assets B.V. Procédé de préparation d'un polyamide semi-aromatique semi-cristallin
TWI651369B (zh) * 2014-06-26 2019-02-21 Ｄｓｍ智慧財產有限公司 用於製備半晶質半芳香聚醯胺之方法
US10577500B2 (en) 2014-06-26 2020-03-03 Dsm Ip Assets B.V. Process for the preparation of a semi-crystalline semi-aromatic polyamide

Similar Documents

Publication Publication Date Title
EP2510056B1 (fr) Copolyamide semi-aromatique, semi-cristallin
EP1851265B1 (fr) Polyamides resistants au vieillissement thermique
EP2001951B1 (fr) Polyamides thermoconducteurs
EP2379644B1 (fr) Polyamides résistants au vieillissement thermique
EP2356174B1 (fr) Polyamide stabilisé
EP2652032B1 (fr) Polyamides résistants au fil incandescent
EP2493968A1 (fr) Polyamides résistant au vieillissement thermique
WO2009156342A1 (fr) Polyamide thermoconducteur avec terre de diatomées
WO2011069942A1 (fr) Matières à mouler constituées de copolyamide partiellement aromatique à base d'octaméthylène diamine
WO2006010543A1 (fr) Polyamides thermostabilises
EP2861666A1 (fr) Polyamides ignifugés comprenant des homopolymères polyacrylonitrile
EP2665777B1 (fr) Polyamides stables à l'hydrolyse
EP3322753A1 (fr) Compositions de polyamide présentant des propriétés optiques améliorées
WO2013139827A1 (fr) Polyamides ignifuges de couleur claire
EP2817363B1 (fr) Mélanges cuo/zno servant de stabilisants pour des polyamides ignifugés
EP3283562B1 (fr) Polyamide présentant des caractéristiques optiques améliorées
EP2756033B1 (fr) Mélanges d'argent et d'oxyde de zinc en tant que stabilisant pour des polyamides ignifugés contenant du phosphore rouge
EP2702102A1 (fr) Matières à mouler ignifugées
DE102015215118A1 (de) Polyamide mit 2,6-BAMP-Derivaten
EP2415827A1 (fr) Polyamides ignifuges dotés de silicate en couche
WO2012062594A1 (fr) Polyamides résistant au vieillissement thermique
DE102008058246A1 (de) Hochmolekulare Polyamide
WO2013083508A1 (fr) Polyamides ignifugés comprenant des polyesters à cristaux liquides

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10793193

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10793193

Country of ref document: EP

Kind code of ref document: A1