EP3655479A1 - Compositions contenant du carbodiimide polymère, de l'époxyde et des polymères à base de polyester, leur préparation et leur utilisation - Google Patents

Compositions contenant du carbodiimide polymère, de l'époxyde et des polymères à base de polyester, leur préparation et leur utilisation

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Publication number
EP3655479A1
EP3655479A1 EP18737647.0A EP18737647A EP3655479A1 EP 3655479 A1 EP3655479 A1 EP 3655479A1 EP 18737647 A EP18737647 A EP 18737647A EP 3655479 A1 EP3655479 A1 EP 3655479A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
epoxide
composition according
weight
radical
Prior art date
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.)
Withdrawn
Application number
EP18737647.0A
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German (de)
English (en)
Inventor
Wilhelm Laufer
Boris NEUWALD
Matthias Bienmüller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP3655479A1 publication Critical patent/EP3655479A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • 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
    • C08G2120/00—Compositions for reaction injection moulding processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • compositions comprising polymeric carbodiimide, epoxy and Polvester based polymers, their preparation and use
  • the present invention relates to compositions containing polymeric carbodiimide, epoxy and polyester-based polymers, in particular polybutylene terephthalate-based compositions and products thereof, their preparation and use for hydrolysis protection.
  • Epoxides are cheaper to manufacture, but have the disadvantage that they do not reach the hydrolysis stabilizing effect of carbodiimides even in very high concentrations. They only act as acid scavengers and lead insufficiently to a long-term stabilization at higher temperatures. Especially in very demanding applications under conditions such as high humidity and temperature, these fail in their effect as a hydrolysis, since usually the ester-based plastics are processed at temperatures above 200 ° C.
  • DE 10 349 168 A1 describes a hydrolysis protection agent of epoxidized fatty acid esters and glycerides, and a mixture of these with a monomeric carbodiimide.
  • the stabilizers described herein act as acid scavengers in oils. However, these show under the conditions mentioned above in the processing of ester-based thermoplastics no or only an insufficient effect in the long-term stability against hydrolysis. Furthermore, the use of monomeric carbodiimides leads to an increased emission of toxic gases.
  • the object of the present invention was therefore to provide new cost-effective compositions which are resistant to hydrolysis, can be produced inexpensively and show reduced emission.
  • the object of the present invention was to provide in particular hydrolysis-stabilized polybutylene terephthalate compositions for products, which are also characterized by particular melt stability in their processing, especially in injection molding, the polybutylene terephthalate used neither as a copolymer nor as a block polymer and without additional components requiring the presence of halogen.
  • melt stability describes the change in melt viscosity at elevated temperatures over time.
  • melt viscosity decreases over time.
  • chain-extending additives such as e.g.
  • molecules containing two or more carbodiimide or epoxide groups may also increase melt viscosity. This is unfavorable because the fluidity of the melt decreases which, among other things, can lead to lower processing speeds.
  • an increase in the melt viscosity can lead to specks in the product to be manufactured, to a solidification of the injection-molding compound in the nozzle to be used during injection molding, or to obstructions or closures in the gate system (hot runner).
  • the present invention therefore relates to compositions containing (a) at least one polymeric aromatic carbodiimide of the formula (I)
  • alkylene bridged arylene atoms in total 7 to 30 carbon
  • - R 2 represents Ci-Ci 2 alkyl substituted arylenes, C 7 -C 8 alkyl-aryl-substituted arylene and optionally for CrCl 2 -alkyl-substituted on CrC 8 and arylene, preferably
  • R 6 , R 7 and R 8 are each independently methyl or ethyl, each benzene ring having only one methyl group and n being an integer in the range of 1 to 10, and R 1 being a radical of the series.
  • R 3 and R 4 are identical or different and are a CRCI 2 alkyl, C 6 -C 2 - cycloalkyl, C 7 -C 8 represent aralkyl or aryl radical and R 5 represents a radical from the series Ci-C 22 - alkyl, C 6 -C 2 cycloalkyl, C 6 -C 8 -aryl or C 7 -C 8 aralkyl, as well as an unsaturated alkyl radical having 2 - 22 carbon atoms or a
  • thermoplastic polyester-based polymer At least one thermoplastic polyester-based polymer.
  • the invention preferably relates to compositions containing (a) at least one halogen-free polymeric aromatic carbodiimide of the formula (I)
  • alkylene bridged arylene atoms in total 7 to 30 carbon
  • - R 2 represents Ci-Ci 2 alkyl substituted arylenes, C 7 -C 8 alkyl-aryl-substituted arylene and optionally for CrCl 2 -alkyl-substituted on CrC 8 and arylene, preferably
  • R 6 , R 7 and R 8 are each independently methyl or ethyl, each benzene ring having only one methyl group and n is an integer in the range of 1 to 10, and
  • R 1 is a radical of the series -NCO, -NCNR 3 -NHCONHR 3 , -NHCONR 3 R 4 or -NHCOOR 5 , wherein R 3 and R 4 are the same or different and each independently is a radical of the series dC ⁇ alkyl -, C 6 -C 2 cycloalkyl, C 7 -C 8 are aralkyl or aryl radical and R 5 represents a radical from the group Ci-C 22 alkyl, C 6 -C 2 cycloalkyl, C 6 - Ci is 8 -aryl or C 7 -C 18 -aralkyl-, as well as an unsaturated alkyl radical having 2-22 carbon atoms or an alkoxypolyoxyalkylene radical,
  • arylene includes in particular phenylene, naphthylene, anthrylene and / or phenanthrylene radicals, preferably phenylene radicals.
  • halogen-free polymeric aromatic carbodiimides of component (a) are preferably compounds of the formula (II)
  • R 1 is selected from the group -NCO, -NHCONHR 3 , -NHCONR 3 R 4 or
  • R 3 and R 4 are identical or different and are a CRCI 2 alkyl, C 6 -C 2 cycloalkyl, C 7 -C 8 represent -Aralkylrest- or aryl radical,
  • R 5 is a dC 2 2-alkyl, C 6 -C 2 -cycloalkyl, C 6 -C 8 -aryl or C 7 -C 8 -aralkyl radical, and also an unsaturated alkyl radical having 2-22 carbon atoms, preferably 12-20 Carbon atoms, more preferably 16-18 carbon atoms, or an alkoxypolyoxyalkylene radical, and
  • the carbodiimide content (NCN content, measured by titration with oxalic acid) of the halogen-free carbodiimides of the formula (II) to be used according to the invention as component (a) is preferably from 2 to 14% by weight, preferably from 4 to 13% by weight. , Particularly preferably at 6 - 12 wt .-%, based on 100 wt .-% of the respective as component (a) to be used carbodiimide.
  • the halogen-free carbodiimides of the formula (II) to be used according to the invention as component (a) preferably have an average molecular weight (Mw) to be determined by GPC viscometry in the range from 1000 to 5000 g / mol, particularly preferably in the range from 1500 to 4000 g / mol, most preferably in the range of 2000 to 3000 g / mol.
  • Mw average molecular weight
  • Physical, mechanical and rheological properties are often determined by the polymolecularity (the ratio of weight average to number average). This ratio is also called polydispersity and is a measure of the width of a molecular weight distribution (MMV).
  • the halogen-free carbodiimides to be used according to the invention as component (a) are preferably commercially available compounds, in particular polymeric carbodiimides which are sold under the name Stabaxol® by Lanxess GmbH. However, they can also be prepared by the processes described in EP 3 018 124 A1.
  • the halogen-free component (b) has a total of at least two epoxide groups per molecule, wherein preferably at least one epoxide group is terminal.
  • halogen-free epoxidized compounds are polyglycidyl or poly (beta-methylglycidyl) ethers, preferably obtainable by reacting a compound having at least two free alcoholic or phenolic hydroxyl groups and / or by reacting phenolic hydroxy groups with a substituted epichlorohydrin.
  • Preferred polyglycidyl or poly (beta-methylglycidyl) ethers are derived from acyclic alcohols, in particular ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1, 2-diol or poly (oxypropylene) glycols, Propane-1,3-diol, butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, Glycerol, 1, 1, 1 trimethylolpropane, Bistrimethylolpropan, pentaerythritol, sorbitol and polyepichlorohydrins.
  • acyclic alcohols in particular ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1, 2-diol or poly (oxypropylene)
  • polyglycidyl or poly (beta-methylglycidyl) ethers are derived from cycloaliphatic alcohols, in particular 1, 3 or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis ( 4-hydroxycyclohexyl) -propane or 1, 1-bis (hydroxy- methyl) -cyclohex-3-ene, or they have aromatic nuclei based on N, N-bis-8,2-hydroxyethyl) -aniline or p, p'-bis (2-hydroxyethyl-amino) -diphenylmethane.
  • Preferred epoxidized compounds are also based on mononuclear phenols or polynuclear phenols.
  • Preferred mononuclear phenols are resorcinol or hydroquinone.
  • Preferred polynuclear phenols are bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane or 4, 4'-dihydroxydiphenylsulfone.
  • Preferred condensation products of phenols with formaldehyde are phenolic novolacs.
  • Preferred aromatic epoxide compounds have 2 terminal epoxide functions.
  • halogen-free aromatic epoxy compound having 2 terminal epoxide functions is an oligomeric reaction product of bisphenol A with epichlorohydrin with an according to EN ISO 10927 to be determined average molecular weight in the range of 900 to 1200 g / mol and one after ISO 3001 epoxy index ranging from 450 to 600 grams per equivalent.
  • component (b) a halogen-free oligomeric reaction product of the formula (III) from the reaction of bisphenol A with epichlorohydrin,
  • a is an integer in the range of 0 to 10, preferably wherein a is an integer in the range of 1 to 8, more preferably wherein a is an integer in the range of 1 to 6, most preferably wherein a is an integer in the range of 2 to 3, where a is the average number.
  • halogen-free epoxides to be used as component (b) are preferably prepared by a process according to US2002 / 0128428 A1 and then have an average molecular weight in the range from 900 to 1200 g / mol according to EN ISO 10927, which in the formula (III) corresponds to an a in the range of 2 to 3 with an epoxy index to be determined according to ISO 3001 in the range of 450 to 600 grams per equivalent.
  • An epoxide compound to be used according to the invention as component (b) preferably has a softening point to be determined according to DIN 51920 in the range from 0 to 150.degree. C., more preferably in the range from 50.degree. C. to 120.degree. C., most preferably in the range from 60 ° C to 1 10 ° C and especially in the range of 75 ° C to 95 ° C.
  • the Mettler softening point is the temperature at which the sample flows out of a cylindrical nipple with a 6.35 mm diameter orifice, breaking a 19 mm lower photocell. For this purpose, the sample is heated in air under constant conditions
  • Epoxy compounds preferably to be used as component (b) have an average epoxide equivalent weight (EEW) to be determined by means of titration in accordance with DIN 16945, grams of resin containing one mole of epoxide-bonded oxygen in the range from 160 to 2000 g / eq, preferably Range of 250 to 1200 g / eq, more preferably in the range of 350 to 1000 g / eq and particularly preferably in the range of 450 to 800 g / eq.
  • EW average epoxide equivalent weight
  • component (b) a poly (bisphenol A-co-epichlorohydrin) [CAS No. 25068-38-6], preferably with a MALDI-TOF mass spectrometry by matrix-assisted laser desorption / ionization time of flight Mass spectrometry according to EN ISO 10927 to determine number average molecular weight (M n ) in the range of 600 to 1800 g / mol, for example, available as Epilox® from Leuna Harze GmbH, Leuna.
  • M n number average molecular weight
  • epoxide compounds having at least 2 epoxide functions are compounds from the series of epoxides, commercially available under the name Joncryl® from BASF AG, in particular Joncryl® 4368, which contain the following units in any desired combination
  • R 9 , R 10 are each independently H or C 1 -C 8 -alkyl
  • R 11 is C 1 -C 8 -alkyl
  • x and y are each independently an integer in the range of 1 to 20
  • z stands for an integer in the range of 2 to 20.
  • the chain termination form end groups R * which independently of one another represent H or C 1 -C 8 -alkyl.
  • a halogen-free epoxide of the formula (IV) to be used as component (b) preferably corresponds to
  • R 9 , R 10 are each independently of one another H or C 1 -C 8 -alkyl
  • R 11 is C 1 -C 8 -alkyl
  • x and y, independently of one another are an integer in the range from I to 20
  • z is a integer in the range of 2 to 20, wherein the end groups R * independently of one another are H or C 1 -C 8 -alkyl.
  • epoxidized fatty acid esters of glycerol in particular epoxidized vegetable oils, are used as component (b). These are obtained by epoxidizing the reactive olefin groups of triglycerides of unsaturated fatty acids.
  • epoxidized fatty acid esters of glycerol can be carried out starting from unsaturated fatty acid esters of glycerol, preferably vegetable oils and organic peroxycarboxylic acids (Prileschajew reaction). Methods of making epoxidized vegetable oils are described, for example, in Smith, March, March's Advanced Organic Chemistry, 5th Ed., Wiley-Interscience, New York, 2001. Preferred epoxidized fatty acid esters of glycerol are vegetable oils.
  • Epoxidized fatty acid ester of glycerol which is particularly preferred for use as component (b) according to the invention is epoxidized soybean oil [CAS No. 8013-07-8].
  • component (b) used is epoxy-functional comonomers based on glycidyl methacrylate-modified styrene-acrylate polymers obtainable by polymerization of styrene, glycidyl methacrylate and acrylic acid and / or methacrylic acid according to DE 10 316 615 A1.
  • thermoplastic polyester-based polymers c) are on the one hand poly-CrC 8 -alkylene terephthalates, more preferably polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and also copolyesters, thermoplastic polyester elastomers (TPE E), ethylene vinyl acetate (EVA) , Polylactic acid (PLA) and / or PLA derivatives, polybutylene succinates (PBS), polyhydroxyalkanoates (PHA), as well as various blends thereof. Preference is given to polylactides (PLA).
  • the composition according to the invention contains a) from 0.2 to 2% by weight, preferably from 0.4 to 1.5% by weight, particularly preferably from 0.5 to 1.0% by weight; b) 0.05 to 4 wt .-%, preferably 0.1 to 2 wt .-%, particularly preferably 0.5 to 1, 5 wt .-%; c) 94 to 99.75 wt .-%, preferably 96.5 to 99.5 wt .-%, particularly preferably 97.5 to 99.0 wt .-%.
  • PBT polybutylene terephthalate
  • the PBT to be used as component (c) preferably has an intrinsic viscosity in the range from 30 to 150 cm 3 / g, more preferably in the range from 40 to 130 cm 3 / g, very particularly preferably in the range from 50 to 100 cm 3 / g each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • the intrinsic viscosity IV also referred to as the Staudinger index or intrinsic viscosity, is proportional to the average molecular mass according to the Mark-Houwink equation and is the extrapolation of the viscosity number VN in the case of vanishing polymer concentrations.
  • the VN [ml / g] is obtained from the measurement of the solution viscosity in the capillary viscometer, preferably Ubbelohde viscometer.
  • the solution viscosity is a measure of the average molecular weight of a plastic.
  • the determination is carried out on dissolved polymer, wherein different solvents, preferably formic acid, m-cresol, tetrachloroethane, phenol, 1, 2-dichlorobenzene, and concentrations are used.
  • the viscosity number VN makes it possible to control the processing and service properties of plastics.
  • Components (a), (b) and (c) are preferably used in such a manner that 0.1 to 5 parts by mass of component (a) and 0.1 to 10 parts by mass are added to 100 parts by mass of the PBT to be used as component (c) of component (b) are used.
  • compositions according to the invention and products to be produced therefrom contain, in addition to components (a), (b) and (c), at least one component (d), an additive other than (a), (b) and (c).
  • the component (d) is preferably used in amounts ranging from 0.1 to 30 parts by mass based on 100 parts by mass of the component (c), the PBT.
  • Preferred additives of component (d) are lubricants and mold release agents, UV stabilizers, colorants, chain-extending additives, plasticizers, flow aids, heat stabilizers, antioxidants, gamma ray stabilizers, hydrolysis stabilizers, elastomer modifiers, antistatic agents, emulsifiers, nucleating agents, processing aids, anti-drip agents, flameproofing agents and II and reinforcing materials.
  • the additives of component (d) can be used alone or in admixture or in the form of masterbatches.
  • halogen-free additives are used for the reasons mentioned above.
  • At least one of the series of long-chain fatty acids, the salts of long-chain fatty acids, the ester derivatives of long-chain fatty acids and montan waxes is selected as the lubricant and release agent.
  • Preferred long-chain fatty acids are stearic acid or behenic acid.
  • Preferred salts of the long-chain fatty acids are Ca or Zn stearate.
  • Preferred ester derivatives of long-chain fatty acids are those based on pentaerythritol, in particular C 16 -C 18 fatty acid esters of pentaerythritol [CAS No. 68604-44-4] or [CAS No. 851 16-93-4].
  • Montan waxes for the purposes of the present invention are mixtures of straight-chain, saturated carboxylic acids having chain lengths of 28 to 32 C atoms.
  • Lubricants and / or mold release agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated alcohols having 2 to 40 carbon atoms and metal salts of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 C are particularly preferred according to the invention Pentaerythritol tetrastearate, calcium stearate [CAS No. 1592-23-0] and / or ethylene glycol dimontanate, here in particular Licowax® E [CAS no.
  • Substituted resorcinols, salicylates, benzotriazoles, triazine derivatives or benzophenones are preferably used as UV stabilizers.
  • the colorants used are preferably organic pigments, preferably phthalocyanines, quinacridones, perylenes and dyes, preferably nigrosine or anthraquinones, furthermore inorganic pigments, in particular titanium dioxide (if not already used as filler), ultramarine blue, iron oxide, zinc sulfide or carbon black.
  • Titanium dioxide pigments which may be prepared by the sulfate (SP) or chloride (CP) process and which have the anatase and / or rutile structure, preferably rutile structure, are suitable for the titanium dioxide which is preferably used as pigment according to the invention.
  • the main body need not be stabilized, but a special stabilization is preferred: in the case of the CP base body by an Al doping of 0.3-3.0 Wt .-% (calculated as Al 2 0 3 ) and an excess of oxygen in the gas phase in the oxidation of titanium tetrachloride to titanium dioxide of at least 2%; in the SP base body by doping z. B. with Al, Sb, Nb or Zn.
  • Titanium dioxide As a white pigment in paints and varnishes, plastics, etc., it is known that unwanted photocatalytic reactions produced by UV absorption lead to the decomposition of the pigmented material. Titanium dioxide pigments absorb light in the near ultraviolet range, creating electron-hole pairs that generate highly reactive radicals on the titanium dioxide surface. The radicals formed in organic media result in a binder degradation. According to the invention, to lower the photoactivity of the titanium dioxide, it is preferably after-treated inorganic, more preferably with oxides of Si and / or Al and / or Zr and / or by the use of Sn compounds.
  • the surface of pigmentary titanium dioxide is preferably covered with amorphous precipitates of oxide hydrates of the compounds SiO 2 and / or Al 2 O 3 and / or zirconium oxide.
  • the Al 2 O 3 sheath facilitates pigment dispersion in the polymer matrix, the Si0 2 sheath impedes the charge exchange on the pigment surface and thus prevents polymer degradation.
  • the titanium dioxide is preferably provided with hydrophilic and / or hydrophobic organic coatings, in particular with siloxanes or polyalcohols.
  • Titanium dioxide [CAS No. 13463-67-7] preferably used as the colorant of component (d) preferably has an average particle size d50 in the range from 90 to 2000 nm, particularly preferably in the range from 200 to 800 nm.
  • the mean particle size d50 is the value determined from the particle size distribution at which 50% by weight of the particles have an equivalent spherical diameter smaller than this d50 value.
  • the underlying standard is ISO 13317-3.
  • the details of the particle size distribution or the average particle size in the case of titanium dioxide relate to so-called surface-based particle sizes, in each case before incorporation into the thermoplastic molding composition.
  • the particle size determination is carried out according to the invention by laser diffractometry, see CM. Keck, Modern Pharmaceutical Technology 2009, Freie (2015) Berlin, Chapter 3.1. or QUANTACHROME PARTICULAR WORLD NO 6, June 2007, pages 1 to 16.
  • titanium dioxide Commercially available titanium dioxide are, for example, Kronos® 2230, Kronos® 2233, Kronos® 2225 and Kronos® vlp7000 from Kronos, Dallas, USA.
  • the titanium dioxide to be used as the pigment is used in amounts ranging from 0.1 to 60 parts by mass, more preferably in amounts ranging from 1 to 35 parts by mass, most preferably in amounts ranging from 2 to 20 parts by mass, each based on 100 parts by mass Component (c) used.
  • Softeners to be preferably used as component (d) are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.
  • Preferred flow agents used as component (d) are copolymers containing at least one ⁇ -olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol. Particular preference is given to copolymerates of at least one ⁇ -olefin with at least one methacrylic acid ester or acrylic ester of an aliphatic alcohol. Very particular preference is given to copolymerates of an ⁇ -olefin and an acrylic ester of an aliphatic alcohol.
  • copolymers in which the ⁇ -olefin is synthesized from ethene and / or propene and the methacrylic acid ester or acrylic acid ester contains linear or branched alkyl groups having 6 to 20 C atoms as the alcohol component.
  • a copolymer of ethene and 2-ethylhexyl acrylate is particularly preferred.
  • Copolymers which are suitable according to the invention as flow aids are notable, apart from the composition, also for their low molecular weight. Accordingly, preference is given above all to copolymers which have an MFI value measured at 190 ° C.
  • the MFI Melt Flow Index
  • ISO 1 133 or ASTM D 1238 The MFI or all information on the MFI in the context of the present invention relate or have become uniform ISO 1 133 measured at 190 ° C and a test weight of 2.16 kg.
  • Elastomeric modifiers to be preferably used as component (d) include i.a. one or more graft polymers of D.1 5 to 95 wt .-%, preferably 30 to 90 wt .-%, of at least one vinyl monomer on
  • D.2 95 to 5 wt .-%, preferably 70 to 10 wt .-% of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, more preferably ⁇ -20 ° C.
  • the percentages by weight in this case relate to 100% by weight of the elastomer modifier to be used as component (d).
  • the graft base D.2 generally has an average particle size (d50 value) in the range from 0.05 to 10 ⁇ m, preferably in the range from 0.1 to 5 ⁇ m, particularly preferably in the range from 0.2 to 1 ⁇ m.
  • Monomers D.1 are preferably mixtures of
  • Preferred monomers D.1.1 are selected from at least one of the monomers styrene, oc-methylstyrene and methyl methacrylate
  • preferred monomers D.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, glycidyl methacrylate and methyl methacrylate.
  • Particularly preferred monomers are D.1.1 styrene and D.1.2 acrylonitrile.
  • Suitable graft bases D.2 for the graft polymers to be used in the elastomer modifiers are, for example, diene rubbers, EPDM rubbers, ie those based on ethylene / propylene and optionally diene, furthermore acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • EPDM stands for ethylene-propylene-diene rubber.
  • Preferred grafting principles D.2 are diene rubbers, in particular based on butadiene, isoprene, etc., or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers, in particular according to D.1.1 and D.1.2, with the proviso that the glass transition temperature of component D.2 is ⁇ 10 ° C., preferably ⁇ 0 ° C., more preferably ⁇ -10 ° C.
  • Particularly preferred graft bases D.2 are ABS polymers (emulsion, bulk and suspension ABS) where ABS stands for acrylonitrile-butadiene-styrene, as described, for example, in US Pat.
  • the elastomer modifiers or graft polymers are prepared by free-radical polymerization, preferably by emulsion, suspension, solution or bulk polymerization, in particular by emulsion or bulk polymerization.
  • Particularly suitable graft rubbers are also ABS polymers which are prepared by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • graft polymers according to the invention are also understood as those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during the workup.
  • suitable acrylate rubbers are based on graft bases D.2 which are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on H.2 of other polymerizable, ethylenically unsaturated monomers.
  • Preferred polymerizable acrylic acid esters include C 1-8 alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen-C 1 -C 8 -alkyl esters, preferably chloroethyl acrylate, glycidyl esters and mixtures of these monomers.
  • graft polymers with butyl acrylate as core and methyl methacrylates as shell in particular Paraloid® EXL2300, Dow Coming Corporation, Midland Michigan, USA, are particularly preferred.
  • Suitable grafting bases according to D.2 are silicone rubbers with graft-active sites, as described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631 539.
  • Preferred graft polymers having a silicone moiety are those which comprise methyl methacrylate or styrene-acrylonitrile as shell and a silicone / acrylate graft as core.
  • styrene-acrylonitrile shell may, for. Metablen ® SRK200.
  • methyl methacrylate shell may, for. B.
  • Metablen S2001 Metablen S2030 ® and / or Metablen SX-005 ® be used. Especially preferred Metablen ® S2001 is used.
  • the products with the trade name Metablen® ® are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.
  • crosslinking monomers having more than one polymerizable double bond can be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate ; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of crosslinked monomers is preferably 0.02 to 5 wt .-%, in particular 0.05 to 2 wt .-%, based on 100 wt .-% of the graft D.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used to prepare the graft base D.2 in addition to the acrylic acid esters are acrylonitrile, styrene, oc-methylstyrene, acrylamides, vinylCrC 6 -alkyl ethers, methyl methacrylate, glycidyl methacrylate, butadiene.
  • Preferred acrylate rubbers as grafting base D.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft polymer-based elastomer modifiers which have glass transition temperatures ⁇ 10 ° C., preferably ⁇ 0 ° C., particularly preferably ⁇ -20 ° C., can likewise be used.
  • Flame retardants to be preferably used as component (d) are halogen-free.
  • the other phosphorus-containing flame retardants preferably used as component (d) include, for example, phosphorus-containing compounds from the group of inorganic metal phosphinates, in particular aluminum phosphinate and zinc phosphinate, the mono- and oligomeric phosphoric and phosphonic acid esters, in particular triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate ) (RDP), bisphenol A bis-diphenyl phosphate (BDP) including oligomers, polyphosphonates, in particular bisphenol A-diphenyl methyl phosphonate copolymers such.
  • TPP triphenyl phosphate
  • RDP resorcinol bis
  • BDP bisphenol A bis-diphenyl phosphate
  • ring-shaped phenoxyphosphazenes such as 2,2,4,4,6,6-hexahydro-2, 2,4,4,6,6-hexaphenoxytriazatriphosphorine [CAS No. 1 184-10-7] and / or those as they are z.
  • Rabitle® FP1 10 From Fushimi Pharmaceutical Co. Ltd., Kagawa, Japan, under the name Rabitle® FP1 10 [CAS No. 1203646-63-2].
  • nitrogen-containing flame retardants can be used individually or in admixture as flame retardants of component (d).
  • guanidine salts in particular guanidine carbonate, guanidine cyanurate prim., Guanidine phosphate prim., Guanidine phosphate sec, guanidine sulfate prim., Guanidine sulfate sec, pentaerythritol borane, neopentylglycolboronic acid, urea phosphate and urea cyanurate.
  • reaction products of Meiern, melam, melon with condensed phosphoric acids can be used.
  • nitrogen-containing components are allantoin compounds, and their salts with phosphoric acid, boric acid or pyrophosphoric acid and glycolurils or their salts in question.
  • Further preferred nitrogen-containing flame retardants are the reaction products of trichlorotriazine, piperazine and morpholine according to CAS No. 1078142-02-5, in particular MCA PPM triazine HF from the company MCA Technologies GmbH, Biel-Benken, Switzerland.
  • flame retardants or flame retardant synergists not specifically mentioned here can also be used as component (d).
  • component (d) include purely inorganic phosphorus compounds, in particular red phosphorus or Borphosphathydrat.
  • Suitable flame retardant additives to be used as component (d) are carbon formers, particularly preferably poly (2,6-diphenyl-1,4-phenyl) ether, in particular poly (2,6-dimethyl-1,4-phenylene) ether [ CAS No. 25134-01 -4], phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyethersulfones or polyether ketones, as well as anti-dripping agents, in particular tetrafluoroethylene polymerates.
  • carbon formers particularly preferably poly (2,6-diphenyl-1,4-phenyl) ether, in particular poly (2,6-dimethyl-1,4-phenylene) ether [ CAS No. 25134-01 -4]
  • phenol-formaldehyde resins polycarbonates, polyimides, polysulfones, polyethersulfones or polyether ketones, as well as anti-dripping agents, in particular tetrafluor
  • the Tetrafluorethylenpolymensate can be used in pure form or in combination with other resins, preferably styrene acrylonitrile (SAN), or acrylates, preferably methyl methacrylate or butyl acrylate.
  • SAN styrene acrylonitrile
  • a particularly preferably suitable example of tetrafluoroethylene-styrene-acrylonitrile resins is z.
  • B. cycolac ® INP 449 [CAS No 1427364-85-9.] Of the company Sabic Corp., Riyadh, Saudi Arabia.
  • a particularly preferably suitable example of tetrafluoroethylene-acrylate resins is z. Metablen A3800 [CAS No.
  • component (d) preferably in amounts ranging from 0.01 to 5 parts by mass, more preferably in the range of 0.05 to 2 parts by mass, based in each case on 100 parts by mass of component (c).
  • halogen-containing flame retardants can also be used as component (d) in one embodiment of the present invention.
  • These include commercially available organic halogen compounds with or without synergists.
  • Preferred halogenated, in particular brominated and chlorinated compounds are ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol A epoxyoligomer, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, polypentabromobenzyl acrylate, brominated polystyrene and brominated polyphenylene ethers.
  • the flame retardants which can additionally be used as component (d) can be added to the polyalkylene terephthalate or polycycloalkylene terephthalate in pure form and via masterbatches or compactates.
  • Thermostabilizers which are preferably used as component (d) are selected from the group of sulfur-containing stabilizers, in particular sulfides, dialkylthiocarbamates or thiodipropionic acids, and those selected from the group consisting of iron salts and copper salts, in particular copper (I) iodide, which are preferably in Combined with potassium iodide and / or sodium hypophosphite NaH 2 P0 2 are used, further sterically hindered amines, in particular Tetrametyhlpiperidin derivatives, aromatic secondary amines, in particular diphenylamines, hydroquinones, substituted resorcinols, salicylates, benzotriazoles and benzophenones, further hindered phenols and aliphatically or aromatically substituted phosphites and various substituted representatives of these groups.
  • sulfur-containing stabilizers in particular sulfides, dialkylthiocarbamates or thiodipropi
  • sterically hindered phenols preference is given to using those having at least one 3-tert-butyl-4-hydroxy-5-methylphenyl and / or at least one 3,5-di- (tert-butyl-4-hydroxyphenyl) building block , wherein 1, 6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [CAS No. 35074-77-2] (Irganox® 259 Fa. BASF SE , Ludwigshafen, Germany), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [CAS No.
  • ADK Stab® AO 80 is particularly preferred.
  • ADK Stab® AO 80 is a commercial product of Adeka-Palmerole SAS, Mulhouse, France.
  • aliphatically or aromatically substituted phosphites is preferably bis (2,4-dicumylphenyl) -pentaerythritol-diphosphite [CAS No. 154862-43-8], z. From Dover Chemical Corp., Dover, USA, under the trade name Doverphos® S9228, and tetrakis (2,4-di-tert-butylphenyl) -1, 1-biphenyl-4,4'-diylbisphosphonite [CAS No. 38613-77-3] used, the z. B. as Hostanox® P-EPQ from Clariant International Ltd., Muttenz, Switzerland can be obtained.
  • the composition in addition to the components (a), (b) and (c) as component (d), contains at least one filler or reinforcing agent, preferably a filler or reinforcing material in the form of fibers, in particular glass fibers.
  • a filler or reinforcing material in the form of fibers, in particular glass fibers.
  • Preference according to the invention is preferably used as component (d) cut long glass fibers having an initial length in the range of 1 to 50mm, more preferably in the range of 1 to 10mm, most preferably used in the range of 2 to 7mm.
  • the initial length denotes the average length of the glass fibers as present before compounding of the composition (s) according to the invention to a molding composition according to the invention.
  • the fibers to be used as component (d), preferably glass fibers, may have a smaller d97 or d50 value than the fibers originally used or due to the processing, in particular compounding, to the molding composition or to the product in the molding composition or in the product. glass fibers.
  • the arithmetic mean of the fiber length or glass fiber length after processing is often only in the range of 150 ⁇ and 300 ⁇ .
  • the determination of the fiber length and fiber length distribution or glass fiber length and glass fiber length distribution is carried out in the context of the present invention in the case of processed fibers or glass fibers according to ISO 22314, which initially provides an ashing of the samples at 625 ° C. Subsequently, the ash is placed on a covered with demineralized water slide in a suitable crystallizing and the ashes distributed without effect of mechanical forces in the ultrasonic bath. The next step involves drying in an oven at 130 ° C and then using optical micrographs to determine the fiber length. For this purpose, at least 100 glass fibers are measured from three images, so that a total of 300 glass fibers are used to determine the length.
  • / c and ⁇ are special characteristics of the normal distribution; l c is the mean value and ⁇ is the standard deviation (see: M. Schossig, damage mechanisms in fiber-reinforced plastics, 1, 2011, Vieweg and Teubner Verlag, page 35, ISBN 978-3-8348-1483-8).
  • glass fibers not bound into a plastic matrix are analyzed for their lengths according to the above methods without the treatment by ashing and separation from the ashes.
  • the glass fibers [CAS No. 65997-17-3)] preferably to be used according to the invention as filler of component (d) preferably have a fiber diameter in the range from 7 to 18 ⁇ m, particularly preferably in the range from 9 to 15 ⁇ m, which can be obtained by at least one skilled in the art Available option is to determine, in particular to be determined by ⁇ -X-ray computed tomography in analogy to "Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts by means of ⁇ -X-ray computed tomography", J. KASTNER, et al DGZfP Annual Meeting 2007 - Lecture 47.
  • the preferably used as component (d) glass fibers are preferably added as cut or ground glass fibers.
  • the fillers and / or reinforcing materials, in particular glass fibers, to be used as component (d) are preferably provided with a suitable sizing system and a bonding agent or adhesion promoter system, particularly preferably silane-based.
  • compositions in addition to components a), b) and c) contain no further components, in which case the sum of the proportions of (a), (b) and (c) 100 wt .% is.
  • the present invention also provides a process for the preparation of the composition, according to which the components a) and b) and optionally at least one component (d) are mixed in PBT with the proviso that the PBT is present neither as a block nor as a copolymer.
  • Extruders or kneaders, more preferably extruders, are preferred here. These are commercially available stirring and mixing units.
  • the incorporation of components (a), (b) and optionally at least one component (d) into the PBT takes place at temperatures in the range from 150 to 300 ° C.
  • the present invention further relates to a process for the preparation of hydrolysis-stable products by adding compositions comprising components (a), (b), optionally with at least one component (d), and (c) in at least one mixing aggregate, preferably a compounder Processed molding compounds and subjecting them to further processing, preferably an injection molding process or an extrusion for the production of products.
  • Processes according to the invention for the production of products by extrusion or injection molding are particularly advantageous at melt temperatures in the range from 160 to 330 ° C., preferably in the range from 190 to 300 ° C. and optionally additionally at pressures of not more than 2500 bar, preferably at pressures of not more than 2000 bar preferably at pressures of not more than 1500 bar and very particularly preferably at pressures of not more than 750 bar.
  • the PBT based compositions according to the invention are characterized by particular melt stability, the expert understands melt stability in the context of the present invention, that even after residence times> 5 min significantly above the melting point of the molding compound of> 260 ° C no structure according to ISO 1 133 (1997) to be determined melt viscosity.
  • Extrusion is preferably distinguished by profile extrusion and sequential coextrusion.
  • sequential coextrusion two different materials are ejected in succession in succession.
  • a preform with sections of different material composition in the extrusion direction Certain article sections can be equipped with specific required properties by appropriate selection of materials, for example for articles with soft ends and hard middle part or integrated soft bellows areas (Thielen, Hartwig, Gust, "Blow molding of hollow plastic bodies", Carl Hanser Verlag, Kunststoff 2006 , Pages 127-129).
  • the method of injection molding is characterized in that the raw material, preferably in granular form, is melted (plasticized) in a heated cylindrical cavity. and injected as a spray mass under pressure in a temperature-controlled cavity.
  • the raw materials used are compositions according to the invention, which have preferably already been processed to a molding compound by compounding, and these in turn preferably into a granulate. After cooling (solidification) of injected into the tempered cavity molding compound, the injection molded part is removed from the mold.
  • an endlessly shaped plastic strand in this case of a molding composition according to the invention, is used in the extruder during extrusion, the extruder being a machine for producing thermoplastic molded articles / products.
  • Applicable are single-screw extruders and twin-screw extruders, as well as the respective subgroups
  • Extrusion plants preferably consist of extruder, tool, downstream device, extrusion blow molding.
  • Extrusion systems for producing profiles preferably consist of: extruder, profile tool, calibration, cooling section, caterpillar and roller removal, separating device and tilting channel.
  • Extrusion lines for the production of films consist of: extruder, cooling section, stretch and roller take-off.
  • Products obtainable according to the invention are preferably materials which are exposed to aqueous media, atmospheric moisture or sprayed water.
  • compositions according to the invention for the preparation of hydrolysis-stable films z. B. for packaging or solar cells.
  • the present invention furthermore relates to the use of the compositions according to the invention for the production of products by extrusion, preferably for packaging or solar cells.
  • the scope of the invention covers all of the above-mentioned general or preferred radical definitions, indices, parameters and explanations with one another, ie also between the respective ranges and preferred ranges in any desired combination.
  • the following examples serve to illustrate the invention without being limiting.
  • additives such as nucleating agents, flow improvers, mold release agents or stabilizers.
  • component (a) and (b) to be used were dispersed in component (c) at about 260 ° C. using a ZSK 25 laboratory twin-screw extruder from Werner & Pfleiderer prior to the measurement described below in PBT. From the granules obtained, the F3 standard specimens used for measuring the tensile strength were then produced on an injection molding machine of the type Arburg Allrounder 320 S 150-500.
  • results of the hydrolysis protection tests show the required hydrolytic stability of the PBT-based compositions according to the invention or of the products to be produced therefrom, the compositions being characterized by high melt stability during processing.

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Abstract

La présente invention concerne des compositions contenant du carbodiimide polymère exempt d'halogène, de l'époxyde exempt d'halogène et des polymères à base de polyester, en particulier des compositions et des produits à base de polybutylène térephtalate, leur préparation et leur utilisation.
EP18737647.0A 2017-07-17 2018-07-16 Compositions contenant du carbodiimide polymère, de l'époxyde et des polymères à base de polyester, leur préparation et leur utilisation Withdrawn EP3655479A1 (fr)

Applications Claiming Priority (2)

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EP17181680.4A EP3431538A1 (fr) 2017-07-17 2017-07-17 Compositions contenant un polymère carbodiimide, un époxyde et des polymères à base de polyester, leur fabrication et utilisation
PCT/EP2018/069279 WO2019016143A1 (fr) 2017-07-17 2018-07-16 Compositions contenant du carbodiimide polymère, de l'époxyde et des polymères à base de polyester, leur préparation et leur utilisation

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EP17181680.4A Withdrawn EP3431538A1 (fr) 2017-07-17 2017-07-17 Compositions contenant un polymère carbodiimide, un époxyde et des polymères à base de polyester, leur fabrication et utilisation
EP18178041.2A Pending EP3431539A1 (fr) 2017-07-17 2018-06-15 Compositions contenant un polymère carbodiimide, un époxyde et des polymères à base de polyester, leurs fabrication et utilisation
EP18737647.0A Withdrawn EP3655479A1 (fr) 2017-07-17 2018-07-16 Compositions contenant du carbodiimide polymère, de l'époxyde et des polymères à base de polyester, leur préparation et leur utilisation

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EP17181680.4A Withdrawn EP3431538A1 (fr) 2017-07-17 2017-07-17 Compositions contenant un polymère carbodiimide, un époxyde et des polymères à base de polyester, leur fabrication et utilisation
EP18178041.2A Pending EP3431539A1 (fr) 2017-07-17 2018-06-15 Compositions contenant un polymère carbodiimide, un époxyde et des polymères à base de polyester, leurs fabrication et utilisation

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US (2) US20190016853A1 (fr)
EP (3) EP3431538A1 (fr)
JP (2) JP6708703B2 (fr)
KR (2) KR20200030057A (fr)
CN (2) CN110809601A (fr)
BR (1) BR102018014532B1 (fr)
CA (1) CA3011457A1 (fr)
DE (1) DE202018006716U1 (fr)
MX (1) MX2018008776A (fr)
PH (1) PH12018000199A1 (fr)
SG (1) SG10201806051XA (fr)
TW (1) TWI780177B (fr)
UA (1) UA125434C2 (fr)
WO (1) WO2019016143A1 (fr)
ZA (1) ZA201804729B (fr)

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EP3431538A1 (fr) * 2017-07-17 2019-01-23 LANXESS Deutschland GmbH Compositions contenant un polymère carbodiimide, un époxyde et des polymères à base de polyester, leur fabrication et utilisation
CN116134042A (zh) 2020-06-17 2023-05-16 朗盛公司 用于与热塑性塑料一起使用的组合的阻燃剂和稳定剂

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CA3011457A1 (fr) 2019-01-17
JP6708703B2 (ja) 2020-06-10
ZA201804729B (en) 2019-06-26
EP3431539A1 (fr) 2019-01-23
EP3431538A1 (fr) 2019-01-23
PH12018000199B1 (en) 2019-03-18
TWI780177B (zh) 2022-10-11
BR102018014532A2 (pt) 2019-03-12
WO2019016143A1 (fr) 2019-01-24
KR20200030057A (ko) 2020-03-19
CN110809601A (zh) 2020-02-18
SG10201806051XA (en) 2019-02-27
PH12018000199A1 (en) 2019-03-18
RU2018126055A (ru) 2020-01-20
TW201920481A (zh) 2019-06-01
US20200165442A1 (en) 2020-05-28
KR20190008816A (ko) 2019-01-25
DE202018006716U1 (de) 2022-05-05
BR102018014532B1 (pt) 2023-04-11
CN109265994A (zh) 2019-01-25
US20190016853A1 (en) 2019-01-17
BR102018014532A8 (pt) 2023-01-03
JP2020528092A (ja) 2020-09-17
KR102624356B1 (ko) 2024-01-11
UA125434C2 (uk) 2022-03-09
JP2019019323A (ja) 2019-02-07
CN109265994B (zh) 2021-11-02
RU2018126055A3 (fr) 2021-09-17
MX2018008776A (es) 2019-02-08

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