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BR-112022005585-B1 - Thermoplastic molding composition, method of producing fibers, sheets and molds, and fiber, sheet or mold.

BR112022005585B1BR 112022005585 B1BR112022005585 B1BR 112022005585B1BR-112022005585-B1

Abstract

THERMOPLASTIC MOLDING COMPOSITION, METHOD FOR PRODUCING FIBERS, SHEETS AND MOLDS AND FIBER, SHEET OR MOLD. The present invention relates to a thermoplastic molding composition comprising a thermoplastic polyester, a metallic salt of formula (I), a halogen-containing flame retardant and an anti-drip agent; a method for producing fibers, sheets and molds comprising the use of the thermoplastic molding composition; and a fiber, sheet or mold obtained from the thermoplastic molding composition.

Inventors

  • Michael Roth
  • Manfred Doering
  • Daniela Goedderz

Assignees

  • BASF SE

Dates

Publication Date
20260310
Application Date
20201125
Priority Date
20191126

Claims (15)

  1. 1. THERMOPLASTIC MOLDING COMPOSITION, characterized by comprising: 10 to 98% by weight of a thermoplastic polyester; 0.5 to 20% by weight of a metallic salt of the following formula (I): wherein: R1, R2, R3, R4, R5 and R6 are each independently hydrogen or C1-C4 alkyl; x is 1, 2, 3 or 4; Met is a metal, respectively, a metalloid of the 1st, 2nd, 13th, 14th or 15th group of the Periodic Table of Elements (IUPAC), a transition metal of the 3rd to 12th group of the Periodic Table of Elements (IUPAC), a lanthanide metal or an oxy derivative of one of the metals, metalloids or transition metals mentioned; C) from 1.5 to 30% by weight of the flame retardant combination prepared with: C1) a flame retardant containing halogen; and C2) an anti-drip agent; D) from 0 to 50% by weight of other additives; wherein the total of the percentages by weight of components A) to D) is 100%.
  2. 2. COMPOSITION, according to claim 1, characterized by being free of diantimony trioxide (Sb2O3).
  3. 3. COMPOSITION, according to any one of claims 1 to 2, characterized by Met in the metallic salt B) being a metal, respectively, a metalloid of the 13th, 14th or 15th group of the Periodic Table of Elements (IUPAC), a transition metal of the 3rd to 12th group of the Periodic Table of Elements (IUPAC), a lanthanide metal or an oxy derivative of one of the metals, metalloids or transition metals mentioned.
  4. 4. COMPOSITION, according to any one of claims 1 to 3, characterized in that Met is selected from the group consisting of Al, Ge, Sn, Bi, Ti, V, Cr, Mn, Fe, La, Ce, OTi, OV, OCr, OSn and OBi; preferably, Met is Al and x is 3.
  5. 5. COMPOSITION, according to any one of claims 1 to 4, characterized in that R1, R2, R3, R4, R5 and R6 are hydrogen.
  6. 6. COMPOSITION, according to any one of claims 1 to 5, characterized by the thermoplastic polyester A) being a semicrystalline or amorphous polyester, based on dicarboxylic acids and diols, with a viscosity number of 50 to 180 ml/g, more preferably 80 to 150 ml/g, determined in a 0.5% by weight solution in phenol/o-dichlorobenzene (1:1) at 25 °C according to DIN 53728/ISO 307.
  7. 7. COMPOSITION, according to claim 6, characterized in that the dicarboxylic acids are aliphatic or aromatic dicarboxylic acids containing 4 to 18 carbon atoms, preferably selected from the group consisting of phthalic acid, terephthalic acid, dimethyl terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4’-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid, and mixtures thereof, more preferably selected from terephthalic acid and naphthalene dicarboxylic acid or a mixture thereof.
  8. 8. COMPOSITION, according to any one of claims 6 to 7, characterized in that the diols are selected from the group consisting of cycloaliphatic diols with 6 to 20 carbon atoms, and aliphatic diols with 2 to 20 carbon atoms, preferably selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol, propane-1,3-diol, propane-1,2-diol, butane-1,2-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, 3-methylpentane-2,4-diol, 2-methylpentane-1,4-diol, 2,2,4-trimethylpentane-1,3-diol, hexane-1,3-diol, hexane-1,4-diol, 2,2-bis(4-hydroxycyclohexyl)propane, and 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane isosorbide, poly(alkylene oxide) glycols containing a total of 3 to 12 carbon atoms, including up to 3 or 4 oxygen atoms, wherein the remaining atoms are hydrocarbon atoms, preferably poly(oxyethylene)diol, poly(oxypropylene)diol or poly(oxytetramethylene)diol, and mixtures thereof, more preferably ethylene glycol, butane-1,4-diol or propane-1,3-diol, poly(oxyethylene)diol, poly(oxypropylene)diol, or poly(oxytetramethylene)diol, and mixtures thereof.
  9. 9. COMPOSITION, according to any one of claims 1 to 8, characterized by component C) comprising: 95 to 99.95% by weight of C1); and 0.05 to 5% by weight of C2).
  10. 10. COMPOSITION, according to any one of claims 1 to 9, characterized in that the anti-drip agent (C2) is a compound selected from the group consisting of fluorine-containing polymers, siloxane-based anti-drip agents, and mixtures thereof; preferably, the anti-drip agent is or comprises a fluorine-containing polymer or a siloxane.
  11. 11. COMPOSITION, according to claim 10, characterized in that the fluorine-containing polymers are selected from the group consisting of poly(tetrafluoroethylene), tetrafluoroethylene/hexafluoropropylene copolymers, tetrafluoroethylene/ethylene copolymers, poly(vinylidene fluoride), poly(chlorotrifluoroethylene) and mixtures thereof, preferably poly(tetrafluoroethylene), and the siloxane-based anti-drip agent comprises polydimethylsiloxane.
  12. 12. COMPOSITION, according to any one of claims 1 to 11, characterized in that component C1) is a flame retardant containing bromine or chlorine, preferably a flame retardant containing bromine.
  13. 13. COMPOSITION, according to claim 12, characterized in that the flame retardant containing bromine is selected from the group consisting of brominated diphenyl ether, brominated trimethylphenylindane, tetrabromobisphenol A, hexabromocyclododecane, brominated oligocarbonates, preferably brominated tetrabromobisphenol A oligocarbonates having the following formula, where n is greater than 2: polypentabromobenzyl acrylate of the following formula, where n is greater than 4: Oligomeric reaction products of tetrabromobisphenol A with epoxides of the following formula, where n is greater than 3: Brominated oligostyrenes, preferably with an average degree of polymerization (numerical mean) between 3 and 90, preferably between 5 and 60, as measured by toluene vapor pressure osmometry, and brominated polystyrenes; wherein it is also possible to use mixtures of brominated oligomeric styrenes and brominated polystyrenes, in any mixing ratio; a suitable chlorine-containing flame retardant is DecloranePlus, of the following formula:
  14. 14. METHOD FOR PRODUCING FIBERS, SHEETS AND MOLDS, characterized by comprising the use of a thermoplastic molding composition, as defined in any one of claims 1 to 13.
  15. 15. FIBER, SHEET OR MOLD, preferably an injection-molded electronic component, characterized by being obtained from a thermoplastic molding composition, as defined in any one of claims 1 to 13.

Description

[001] The present invention relates to a thermoplastic molding composition comprising a thermoplastic polyester, a method for producing fibers, sheets and molds, comprising the use of the thermoplastic molding composition and fibers, sheets or molds obtained from the thermoplastic molding composition. [002] Reinforced or unreinforced thermoplastic polyesters are used for the production of electronic parts, such as connectors, structures, moving parts, transformers, micromotors, and others. In most of these applications, flame-retardant properties are required, which are normally provided by flame-retardant systems based on a combination of brominated flame retardants with diantimony trioxide as a synergist. This type of flame-retardant system, however, has a limitation, as diantimony trioxide, which is a very efficient synergist, tends to significantly increase smoke production, hindering visibility and creating problems for the evacuation of people in case of fire. In addition, diantimony trioxide has a very high bulk density, which increases the specific gravity of molded parts and has a negative impact on electrical properties, such as the tracking index (CTI). This is especially undesirable in transportation and aviation. Furthermore, some environmental labels require the elimination of diantimony trioxide from thermoplastic parts. [003] Although there is a clear need for flame-retardant plastics with low or no antimony trioxide content, they typically require significant increases in the load of brominated flame retardants. [004] WO 2012/088080 refers to a diantimony trioxide-free flame-retardant thermoplastic composition comprising: (a) at least one thermoplastic polyester or polyamide; (b) at least one brominated flame retardant; and (c) at least one metal phosphonate or metal phosphinate. Suitable metal phosphonates or metal phosphinates have the following formula: where Me is a metal, R1 and R2 are identical or different linear, branched or cyclic C1 to C6 alkyl groups or benzyl groups, n is a metallic valence that can be 1, 2, 3 or 4, x is 1 for metal phosphonates and ex is 0 for metal paraphosphinates. [005] WO 2018/073813 refers to a composition comprising a polyester and a flame retardant mixture having at least the following two components: calcium hypophosphite and a bromine-containing polymer. The composition is substantially free of diantimony trioxide, meaning that the concentration of diantimony trioxide in the composition is well below the acceptable amount used in plastic compounds, in conjunction with halogenated additives, such as not more than 1.0% by weight, more preferably up to 0.5% by weight, for example 0.0 to 0.3% by weight (based on the total weight of the composition). More preferably, the composition is completely free of diantimony trioxide. [006] WO 2018/073819 refers to a composition comprising a polyester and a flame retardant mixture having at least the following two components: aluminum hypophosphite and a bromine-containing polymer. The composition is substantially free of diantimony trioxide, wherein “substantially free” is defined as in WO 2018/073818. [007] EP 1,657,972 A1 refers to phosphinate complexes of formula (I): where M is a metal from group 2, 3, 12, or 13 of the Periodic Table of Elements; x is 2 or 3; en > 10. [008] In addition, EP 1,657,972 A1 refers to phosphinate complexes of formula (II): where M is a metal from group 2, 3, 12, or 13 of the Periodic Table of Elements; x is 2 or 3; R is a hydrogen atom or 2-hydroxyphenyl residue; B is a Lewis base; y is 1 or 2; and en is 1 to 100. [009] EP 1,657,972 A1 also refers to flame retardants or polymers comprising the phosphinate complexes mentioned above, as well as to the use of said phosphinate complexes as flame retardants, especially for polyester, polyamides, epoxy resins and prepared products, such as fibers and base material for conductor boards. [0010] US 4,317,769 refers to a flame retardant comprising alkali metal and/or alkaline earth metal salts of a cyclic phosphorus compound represented by formula I: where each of X1 to X8 indicates hydrogen, halogen, cyano, acyl, alkyl, halogen-substituted alkyl, aryl, halogen-substituted aryl, or aralkyl. [0011] JP 2001 139 586 A refers to a method for producing a monohydroxy organic cyclic phosphorus compound and its metallic salt, which has high purity and high quality, capable of being used as a stabilizer, flame retardant, etc. of an organic polymer, especially electronic or optical material in a sintered process, safely and with high yield. The monohydroxy organic cyclic phosphorus compound has the following general formula (1): wherein X1, X2 and X3 are independently H, a halogen atom, alkyl group, cycloalkyl group, aryl group or aralkyl group. [0012] In view of the state of the art mentioned above, the object of the present invention is to provide flame-retardant thermoplastic molding compositions free of diantimony trioxide based on thermoplastic