EP3322753A1 - Compositions de polyamide présentant des propriétés optiques améliorées - Google Patents

Compositions de polyamide présentant des propriétés optiques améliorées

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Publication number
EP3322753A1
EP3322753A1 EP16741585.0A EP16741585A EP3322753A1 EP 3322753 A1 EP3322753 A1 EP 3322753A1 EP 16741585 A EP16741585 A EP 16741585A EP 3322753 A1 EP3322753 A1 EP 3322753A1
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EP
European Patent Office
Prior art keywords
radicals
substituted
measured
acid
unsubstituted
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Legal status (The legal status 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 status listed.)
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EP16741585.0A
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German (de)
English (en)
Inventor
Florian Richter
Rainer Xalter
Hye Jin Park
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/21—Urea; Derivatives thereof, e.g. biuret
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Definitions

  • the invention relates to the use of thermoplastic molding compositions containing
  • thermoplastic polyamide from 30 to 99.99% by weight of a thermoplastic polyamide
  • Z is linear or branched C1 to C14-alkylene radicals, unsubstituted or substituted cycloalkylene radicals having 3 to 17 C atoms, substituted or unsubstituted aromatic radicals having 6 to 20 C atoms,
  • R 1 to R 10 independently of one another are linear C 1 -C 14 -alkyl radicals, branched C 3 to C 12 -alkyl radicals, unsubstituted or substituted C 3 -C 14 -cycloalkyl radicals, unsubstituted or substituted aromatic radicals having 6 to 20 C atoms or acetyl radicals, R 1 and R 2 and R 3 and R 4 are independently taken together with the nitrogen as
  • the invention relates to the thermoplastic molding compositions and the use for the production of moldings of any kind with reduced turbidity or improved clarity, in particular by laser transmission welding and the use of such moldings in different fields of application.
  • Polyamides are used in a wide variety of applications, e.g. for motor vehicles, electrical, electronic components and as packaging material for food.
  • Sheets, films, containers, headlights and similar components require greater transparency (especially laser transparency) and reduced haze for certain applications.
  • urea derivatives as additives for improving the optical properties of polyamides.
  • Substituted ureas to use as an activator for the anionic polymerization of caprolactam is u.a. from WO2013 / 4645. The improvement of optical properties is not mentioned.
  • the object of the present invention was therefore to improve the optical properties of clarity and / or haze and / or transparency (in particular laser transparency) in the case of polyamides. Surprisingly, this object is achieved by adding the compounds of the formula I according to the invention to give polyamides.
  • the molding compositions according to the invention contain 30 to 99, preferably 30 to 98 and in particular 30 to 90 wt .-% of at least one polyamide.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 1 10 to 240 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to Semi-crystalline or amorphous resins having a weight-average molecular weight of at least 5,000, as described, for example, in US Pat. Nos.
  • 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512 606 and 3,393,210 are preferred.
  • Examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.
  • Suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, in particular 6 to 10, carbon atoms and aromatic dicarboxylic acids.
  • adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned as acids.
  • Suitable diamines are particularly alkanediamines having 6 to 12, especially 6 to 8 carbon atoms and m-xylylenediamine are suitable (for example Ultramid ® X17 from BASF SE, a 1: 1 molar proportionality nis of MXDA with adipic acid), di- (4-aminophenyl) methane, di- (4-amino-cyclohexyl) -methane, 2,2-di- (4-aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1,5-diamino-2- methylpentane.
  • Ultramid ® X17 from BASF SE, a 1: 1 molar proportionality nis of MXDA with adipic acid
  • di- (4-aminophenyl) methane di- (4-amino-cyclohexyl) -methane
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacin Text- acid amide and polycaprolactam and copolyamides 6/66, in particular with a proportion of 5 to 95 wt .-% of caprolactam units (for example Ultramid ® C31 BASF SE).
  • polystyrene resin Suitable polyamides are obtainable from ⁇ -aminoalkyl nitriles such as aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP 922065.
  • PA 6 aminocapronitrile
  • PA 66 adiponitrile with hexamethylenediamine
  • polyamides which are e.g. are obtainable by condensation of 1, 4-diaminobutane with adipic acid at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 described.
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary. Particular preference is given to mixtures of polyamide 66 with other polyamides, in particular copolyamides 6/66. Furthermore, such partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444). Further high-temperature-resistant polyamides are known from EP-A 19 94 075 (PA 6T / 6I / MXD6).
  • the production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedicarboxylic acid
  • PA 613 hexamethylenediamine, undecanedicarboxylic acid
  • PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
  • PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA 9T 1, 9-nonanediamine, 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 12 / MACMI laurolactam dimethyldiaminodicyclohexylmethane, isophthalic acid
  • PA 12 / MACMT laurolactam dimethyl-diaminodicyclohexylmethane, terephthalic acid
  • the molding compositions which can be used according to the invention comprise from 0.01 to 10, preferably from 0.05 to 5, and in particular from 0.5 to 2,% by weight of a compound of the formula I.
  • Z is linear or branched C1 to C14-alkylene radicals, unsubstituted or substituted cycloalkylene radicals having 3 to 17 C atoms, substituted or unsubstituted aromatic radicals having 6 to 20 C atoms,
  • R 1 to R 10 independently of one another are linear C 1 -C 14 -alkyl radicals, branched C 3 to C 12 -alkyl radicals, unsubstituted or substituted C 3 to C 14 -cycloalkyl radicals, unsubstituted or substituted aromatic radicals having 6 to 20 C atoms or acetyl radicals,
  • R 1 and R 2 and R 3 and R 4 independently of one another together with the nitrogen as a link form a heteroalkylene radical which can carry one or two keto groups as substituent.
  • Linear alkyl radicals R 1 to R 6 are understood to mean unbranched alkyl chains having 1 to 14, preferably 1 to 10, carbon atoms. Examples which may be mentioned are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.
  • the acetyl radicals are preferred combinations with
  • Branched alkyl radicals are understood to mean alkyl chains having branches which have 3 to 12, preferably 3 to 10, carbon atoms, in particular 1 to 4 carbon atoms.
  • cycloalkyl radicals having 3 to 14 carbon atoms, preferably 3 to 10 carbon atoms are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • Substituted cycloalkyl radicals are to be understood as meaning in particular those radicals which have a heteroatom, preferably N or O, in the ring or may carry substituents such as one or more alkyl radicals having 1 to 4 C atoms.
  • heterocycles for example pyrrolidine may be mentioned.
  • Substituted aromatic radicals having 6 to 20, preferably 6 to 17 carbon atoms are to be understood as meaning aromatic ring systems such as phenyl, naphthyl, anthracenyl or phenanthryl.
  • Such aromatic radicals may carry one or more substituents such as alkyl radicals (linear or branched, see the above definition) having 1 to 10, preferably 1 to 4 carbon atoms or halogen, preferably bromine or chlorine.
  • aromatic radicals can be connected via Alkylenmaschinen having 1 to 4 carbon atoms with another aromatic radical.
  • R 1 to R 4 are those in which R 1 and R 2 and R 3 and R 4, independently of one another, together with the nitrogen as the connecting link, form a heteroalkylene radical with 3 to 14 carbon atoms, preferably 5 to 12 carbon atoms, which may carry as substituent one or two keto groups. This is in particular in the direct vicinity of the nitrogen atom, ie the nitrogen forms a lactam ring with the carbon atoms.
  • examples of such radicals having a keto group are butyrolactam, laurolactam and very particularly preferably ⁇ -caprolactam.
  • Preferred radicals R 7 to R 10 are independently of one another aromatic radicals having 6 to 12, preferably 6 to 10, carbon atoms, the compounds
  • the preparation can be carried out, for example, according to E. Delebecq et al., Chemical Reviews 2013, 1 13, 80-1 18. It is further apparent from this article that all of the substituents A or B are so-called protecting groups for the nucleus Z, i. the mode of action depends on the core Z.
  • Preferred radicals R 1 to R 6 are those in which the radicals R 1 to R 6 independently of one another are methyl, ethyl, n-propyl, phenyl or cyclohexyl, or in which the radicals R 1 and R 2 and also R 3 and R 4 as well as R 5 and R 6 are the same.
  • Preferred radicals Z are linear or branched C1 to C14-alkylene radicals, unsubstituted or substituted cycloalkylene radicals having 3 to 17 C atoms, substituted or unsubstituted aromatic radicals having 6 to 20 C atoms.
  • Preferred alkylene radicals (also called alkanediyl radicals) have 1 to 10 carbon atoms.
  • methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene and heptamethylene may be mentioned.
  • branched alkylene chains are radicals defined above which can carry one or more alkyl radicals having 1 to 4 C atoms.
  • Unsubstituted cycloalkylene radicals preferably have 3 to 14 carbon atoms and correspond to the above definition for cycloalkyl radicals, but another hydrogen atom is replaced by a bond and thus forms a bivalent unit (bivalent radical).
  • cyclohexylene, cyclopentylene may be mentioned.
  • Substituted cycloalkylene radicals can have heteroatoms such as N or O in the ring or carry one or more alkyl radicals having 1 to 4 C atoms. Furthermore, such radicals can be connected via Alkylenmaschinen having 1 to 4 carbon atoms with another cycloalkylene radical.
  • substituted or unsubstituted aromatic radicals having preferably 6 to 17 C atoms, o.g. Understood ring systems in which another H atom has been replaced by a chemical bond and thus forms a divalent unit (also called bivalent radical).
  • Z is particularly preferably a 1,4-trans-cyclohexylene radical.
  • the compounds of formula (I) may be prepared by standard methods known in the literature or as described in the experimental part of this application.
  • a diamine component of the formula (II) reacts with two equivalents of carbamoyl chloride (III) to give the compound of the formula (I) in good yields.
  • the reaction is usually carried out in an organic solvent with the addition of a base such as triethylamine.
  • Suitable solvents are polar aprotic solvents such as e.g. Tetrahydrofuran.
  • the bisurea of formula (I) can also be prepared by reacting a diisocyanate of formula (IV) with two equivalents of an amine of formula (V). The reaction is usually carried out in an organic solvent. Suitable solvents are polar aprotic solvents such as tetrahydrofuran.
  • a diamine component of the formula (VI) reacts with two equivalents of chloroformate (VII) to give the compound of the formula (I) in good yields.
  • the reaction is usually carried out in an organic solvent with the addition of a base such as triethylamine.
  • Suitable solvents are polar aprotic solvents such as e.g. Tetrahydrofuran.
  • the bisurea of formula (I) can also be prepared by reacting a diisocyanate of formula (VIII) with two equivalents of an alcohol of formula (IX). The reaction is usually carried out in an organic solvent. Suitable solvents are polar aprotic solvents such as e.g. Tetrahydrofuran.
  • the molding compositions of the invention may contain 0 to 60, preferably 0 to 50 wt .-% of other additives.
  • the molding compositions in amounts 0 to 40, preferably 1 to 30, in particular 2 to 20 wt .-% of elastomeric 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 acid esters having 1 to 18 carbon 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 also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclo
  • 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 skimmers may also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably by Addition of dicarboxylic acid or epoxy groups containing monomers of the general formulas I or II or III or IV to the monomer mixture incorporated into the rubber
  • R 1 to R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 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 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 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
  • 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 emulators and catalysts are known per se. Basically, 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.
  • 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.
  • These monomers may 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.
  • 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 several shells to consist of one 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 esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate are prepared 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 e.g. Epoxy, carboxy, latent carboxyl, amino or amide groups and functional groups, which by using monomers of the general formula
  • R 10 is hydrogen or a C 1 - to C 4 -alkyl group
  • R 11 is hydrogen, a C 1 - to C 5 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or -OR 13
  • R 13 is a C 1 - to C 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
  • 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 called.
  • 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.
  • the different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie the grafted-on phase is at least partially linked to the grafting base via chemical bonds.
  • graft-crosslinking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • 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:
  • 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 their copolymers are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers,
  • Graft polymers having an inner core of n-butyl acrylate or butadiene-based and a outer shell of the aforementioned 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.
  • Particularly preferred rubbers C) are ethylene copolymers, as described above, which contain functional monomers, the functional monomers being selected from the group of the carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxylic acid amide, carboxylic acid imide, amino, hydroxyl, Epoxy, urethane or oxazoline groups or mixtures thereof.
  • the proportion of the functional groups is 0.1 to 20, preferably 0.2 to 10 and in particular 0.3 to 7 wt .-%, based on 100 wt .-% C).
  • Particularly preferred monomers are built up from an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid.
  • esters of acrylic acid or methacrylic acid are suitable, but esters having 1 to 12 C atoms, in particular 2 to 10 C atoms, are preferred.
  • esters examples thereof are methyl, ethyl, propyl, n-, i-butyl and t-butyl, 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid.
  • n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids or monomers containing epoxy groups may also be present in the olefin polymers.
  • Acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters may be mentioned as further examples of monomers.
  • Suitable latent acid-functional monomers are those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions. Examples which may be mentioned are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride and tertiary C 1 -C 12 -alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.
  • the acid-functional or latent acid-functional monomers and the epoxy group-containing monomers are preferably incorporated into the olefin polymers by addition of compounds of the general formulas I-IV to the monomer mixture.
  • the melt index of the ethylene copolymers is generally in the range of 1 to
  • the molecular weight of these ethylene- ⁇ -olefin copolymers is between 10,000 and
  • ethylene- ⁇ -olefin copolymers prepared by so-called “single site catalysts" are used Further details can be found in US 5,272,236 In this case, the ethylene- ⁇ -olefin copolymers have a molecular weight distribution narrow for polyolefins 4, preferably less than 3.5.
  • molding compositions of the invention may contain up to 60, preferably up to 50 wt .-% of other additives.
  • fibrous or particulate fillers C there may be mentioned carbon fibers, glass fibers, glass spheres, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, in amounts of from 1 to 50% by weight, 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 thermoplastics 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 0.01 to 2, preferably 0.025 to 1, 0 and in particular 0.05 to 0.5 wt .-% (based on C)) for surface coating.
  • acicular mineral fillers are also suitable.
  • the term "needle-shaped mineral fillers” is understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is random-shaped 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, the pretreatment However, it is not absolutely necessary to use further fillers such as kaolin, calcined kaolin, wollastonite, talc and chalk, as well as platelet-shaped or needle-shaped nano-fillers, preferably in quantities between 0.1 and 10%, boehmite, bentonite, montmorillonite, vermicullite and In order to obtain a good compatibility of the platelet-shaped nanofillers with the organic binder, the platelet-shaped nanofillers according to the prior art are organically modified The addition of the platelet-shaped or needle-shaped nanofillers to the nanocompos
  • 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.
  • the metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.
  • Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate. It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.
  • the carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 C 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. Accordingly, preferred esters or amides are glycerin distearate, glycerol tristearate, ethylenediamine distearate, glycerin monopalmitate, glycerol trilaurate, glycerin monobehenate and pentaerythritol tetrastearate. It is also possible to use mixtures of different esters or amides or esters with amides in combination, the mixing ratio being arbitrary.
  • Suitable hindered phenols C) are in principle all compounds having a phenolic structure which have at least one sterically demanding group on the phenolic ring.
  • R 1 and R 2 are an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R 1 and R 2 may be the same 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 where 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 group) and R 6 is a bivalent aliphatic radical having 1 to 10 C atoms means that may also have CO bonds in the main chain.
  • the antioxidants C 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 C).
  • 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) used in wool dyeing and printing, in black dyeing of silks, for dyeing of leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscopy dyes.
  • Component C) 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".
  • the molding compositions of the invention may contain 0 to 20, preferably 1 to 15 and in particular 5 to 15 wt .-% red phosphorus and / or a nitrogen-containing flame retardant, preferably a melamine compound.
  • Suitable compounds are melamine sulfate, melamine, melamine borate, oxalate, phosphate prim., Phosphate sec. And pyrophosphate sec, neopentylglycolboronic acid melamine and polymeric melamine phosphate (CAS No. 56386-64 -2 or
  • thermoplastic molding compositions of the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • antioxidants 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 up to 1 wt .-%, based on the Weight of the thermoplastic molding materials called.
  • TAD sterically hindered phenols and / or phosphites and amines
  • hydroquinones such as diphenylamines
  • aromatic secondary amines such as diphenylamines
  • UV stabilizers which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, Benzotria- zole and benzophenones may be mentioned.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.
  • nucleating agents Natnumphenylphosphinat, alumina, silica and preferably talc can be used.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se by mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruding. 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) and optionally C) can be mixed with a prepolymer, formulated and granulated.
  • the resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.
  • the molding compositions which can be used according to the invention are suitable for the production of molded articles of any type which have improved (laser) transparency and / or reduced haze. These molding compounds have at least one of the following advantages:
  • the haze value is at least 10% lower compared to a reference polymer composition without the component B), measured according to ASTM D1003 (with a sample body thickness of 1.3 mm);
  • the Clarity value is at least 10% higher compared to a reference polymer composition without component B), measured according to ASTM D1003 (with a sample body thickness of 1.3 mm);
  • the laser transparency is at least 1% higher compared to a reference polymer composition without the component B) measured at 1064 nm (with a sample body thickness of 1.3 mm).
  • haze as used herein is defined as the percentage of transmitted light which differs by more than 2.5 ° from the incident light when traversing a specimen (plate) .
  • the haze is determined according to ASTM D1003 Haze which is at least 10% lower, more preferably 15% lower and in particular 20% lower compared to a reference polymer composition without component B), measured at a sample body thickness (plate) of 1.3 mm.
  • the Clarity is determined according to ASTM D1003.
  • the molding compositions which can be used according to the invention have a clarity which is at least 10% higher, more preferably 15% higher and in particular 20% higher compared to a reference polymer composition without component B), measured at a sample body thickness (plate) of 1.3 mm.
  • the molding compositions which can be used according to the invention have a laser transparency which is at least 1% higher, preferably 3% higher, more preferably 5% higher and in particular 10% higher, compared to a reference polymer composition without component B), measured at a sample body thickness (plate) of 1 , 3 mm.
  • the determination of the laser transparency at a wavelength of 1064 nm was carried out by means of a thermoelectric power measurement.
  • the measuring geometry was as follows:
  • a laser beam (diode-pumped Nd-Y AG laser with a wavelength of 1064 nm, FOBA DP50) with a total power of 2 watts was by means of a beam splitter (type SQ2 non-polarizing beam splitter from. Laser Optics GmbH) a reference beam at an angle of 90 ° with 1 Watt power divided. This met the reference sensor. The portion of the original beam passing the beam splitter also represented the measuring beam with 1 watt of power. This was focused by a mode diaphragm (5.0) behind the beam splitter to a focus with a diameter of 0.18 ⁇ m. At a distance of 80 mm below the focus, the laser transparency (LT) measurement sensor was positioned.
  • a mode diaphragm 5.0
  • the test plate was positioned 2 mm above the LT measuring sensor.
  • the entire measurement duration was 30 s, whereby the measurement result was determined in the last 5 s.
  • the signals from the reference and measuring sensors were recorded at the same time. The start of the measurement was carried out simultaneously with the insertion of the sample.
  • LT (signal (measuring sensor) / signal (reference sensor)) x 100%.
  • Such laser-transparent moldings are used according to the invention for the production of moldings by means of laser transmission welding.
  • a laser-absorbent molding generally shaped body of all laser-absorbing materials can be used. These may be, for example, composite materials, thermosets or preferred moldings of their own thermoplastic molding compositions. Suitable thermoplastic molding compositions are molding compositions which have sufficient laser absorption in the wavelength range used. Suitable thermoplastic molding compositions may be, for example, thermoplastics which are laser-absorbent by the addition of inorganic pigments such as carbon black and / or by the addition of organic pigments or other additives. Suitable organic pigments for achieving laser absorption are, for example, preferably IR-absorbing organic compounds, as described, for example, in DE 199 16 104 A1.
  • the invention furthermore relates to shaped bodies and / or molded part combinations to which molded parts according to the invention have been joined by laser transmission welding.
  • Moldings according to the invention are outstandingly suitable for permanently and stably attaching to laser-absorbent molded parts by the laser transmission welding method. They are therefore particularly suitable for materials for covers, housings, attachments, sensors, for example, for automotive, electronics, telecommunications, information technology, computer, household, sports, medical or entertainment applications.
  • Component A Component A
  • 4,4 'diaminodicyclohexylmethane 147.3 g, 700 mmol were dissolved in 1200 ml water at 80 ° C and brought to a pH of 6 with 30% hydrochloric acid. It was then cooled to room temperature and slowly added with stirring potassium cyanate (1 16 g, 1430 mmol). The mixture was heated to 90 ° C and stirred for 2 hours at this temperature. After cooling to room temperature, the white precipitate was filtered off and washed with water. The resulting white solid was dried in vacuo at 80 ° C.
  • N, N "- [1,3-cyclohexanediylbis (methylene)] bis-urea (component B2 / V) 1 .3-Bis (aminomethyl) cyclohexane (99.54 g, 700 mmol) were dissolved in 1000 ml of water at 80 ° C and brought to a pH of 6 with 30% hydrochloric acid. It was then cooled to room temperature and slowly added with stirring potassium cyanate (1 16 g, 1430 mmol). The mixture was heated to 90 ° C and stirred for 2 hours at this temperature. After cooling to 5 ° C within 12 h, a white precipitate, which was filtered off. The resulting white solid was dried in vacuo at 80 ° C.
  • 1,4-Transcyclohexyl diisocyanate (10 g, 60 mmol) is dissolved in dry THF (300 mL). Subsequently, caprolactam (14.7 g, 130 mmol) is slowly added with stirring. The resulting mixture is heated to reflux and stirred for 24 h. The precipitate is filtered off and washed with THF. The resulting white solid is dried in vacuo at 80 ° C.
  • the crystallization behavior of the polymer mixtures is determined by means of differential scanning calorimetry (DSC) in a manner known per se (ISO 1 1357-2: 2013). The determination is carried out under nitrogen in open aluminum crucibles at a heating rate and cooling rate of 20 K / min. After the first heating, the sample is melted for 5 minutes to quench the thermal history of the polymer. The DSC measurement is expediently repeated once or twice on one and the same sample in order to ensure a defined thermal history of the respective polyamide.
  • the crystallization temperature Tk was determined according to DIN EN ISO 1 1357-3. The crystallization temperature Tk is the exothermic peak minimum of the DSC curve at the first cooling at 20 K / min according to a defined thermal history.
  • Haze, Clarity and Transmission were measured with a haze-guard plus measuring instrument (BYK, Gardner®, Illumination CIE-E) at room temperature. The measurement was carried out according to ASTM D-1003. Haze and Clarity values were measured 24 to 48 hours after injection molding. Table 1 :

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne l'utilisation de masses de moulage thermoplastiques, contenant A) 30 à 99,99 % en poids d'un polyamide thermoplastique, B) 0,01 à 10 % en poids d'un composé de formule I, les substituants A) représentant un radical (cf. II) ou un radical –O-R5 ou un radical (cf. III), B) représentant un radical (cf. IV) ou un radical –O-R6 ou un radical (cf. V) et Z représentant des radicaux C1-C14-alkylène linéaires ou ramifiés, des radicaux cycloalkylène non substitués ou substitués comprenant 3 à 17 atomes de carbone, des radicaux aromatiques substitués ou non substitués comprenant 6 à 20 atomes de carbone, R1 à R10 représentant, indépendamment les uns des autres, des radicaux C1-C14-alkyle linéaires, des radicaux C3-C12-alkyle ramifiés, des radicaux C3-C14-cycloalkyle non substitués ou substitués, des radicaux aromatiques non substitués ou substitués comprenant 6 à 20 atomes de carbone ou des radicaux acétyle, R1 et R2 ainsi que R3 et R4 formant, indépendamment les uns des autres, ensemble avec l'atome d'azote comme chaînon de liaison, un radical hétéroalkylène, qui peut porter un ou deux groupes céto comme substituant, C) 0 à 60 % en poids d'autres additifs, la somme des pourcentages en poids des composants A) à C) valant 100 %, pour la préparation de masses de moulage de tous types présentant des propriétés optiques améliorées.
EP16741585.0A 2015-07-15 2016-07-13 Compositions de polyamide présentant des propriétés optiques améliorées Withdrawn EP3322753A1 (fr)

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CN111205453B (zh) * 2020-03-02 2021-04-30 吉林大学 一种含有1,3-二甲基-1,3-二苯基脲结构的聚酰胺及其制备方法

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EP3118247A1 (fr) 2017-01-18
CN108026325A (zh) 2018-05-11
JP2018524452A (ja) 2018-08-30
CN108026325B (zh) 2021-03-02
US10633516B2 (en) 2020-04-28
US20180201758A1 (en) 2018-07-19
WO2017009357A1 (fr) 2017-01-19
BR112018000725A2 (pt) 2018-09-04
BR112018000725B1 (pt) 2022-03-29

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