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CN-121991484-A - Polyketone molding composition having improved properties, molded article produced therefrom, and method for producing same

CN121991484ACN 121991484 ACN121991484 ACN 121991484ACN-121991484-A

Abstract

The present invention relates to a polyketone molding composition comprising (A) 30 to 79.8 wt.% of an aliphatic semi-crystalline polyketone consisting of a terpolymer, and (A1) 0 to 15 wt.% of an optional second thermoplastic, different from polyketone (A), comprising a polyolefin and/or a polyamide, and (B) 20 to 60 wt.% of long glass fibers or long carbon fibers, and (C) 0.1 to 2 wt.% of an antioxidant, and (D) 0.1 to 2 wt.% of a phosphate compound, and (E) 0 to 3 wt.% of an optional colorant, and (F) 0 to 3 wt.% of an optional organic phosphinate, wherein the total amount of components (A) to (F) is 100 wt.%, a molded article produced therefrom, and a process for producing the same.

Inventors

  • HARDER PHILLIPP

Assignees

  • 艾曼斯（苏州）工程塑料有限公司

Dates

Publication Date
20260508
Application Date
20260121
Priority Date
20250710

Claims (18)

  1. 1. A polyketone molding composition comprising or consisting of: (A) An aliphatic semi-crystalline polyketone in an amount of from 30% to 79.8% by weight, said aliphatic semi-crystalline polyketone consisting of a terpolymer of ethylene, carbon monoxide and a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, and (A1) Optionally a second thermoplastic, different from the aliphatic semicrystalline polyketone, in an amount of from 0% to 15% by weight, the second thermoplastic comprising a polyolefin and/or a polyamide, and (B) Long glass fiber or long carbon fiber in an amount of 20 to 60% by weight, and (C) An antioxidant in an amount of 0.1 to 2% by weight, and (D) A phosphate compound in an amount of 0.1 to 2% by weight, and (E) An optional colorant in an amount of 0 to 3% by weight, and (F) Optionally an organic phosphinate in an amount of from 0 wt% to 3 wt%; wherein the total amount of components (A) to (F) is 100% by weight.
  2. 2. The polyketone molding composition according to claim 1, wherein the aliphatic semi-crystalline polyketone has a melting temperature of 200 ℃ to 240 ℃, wherein the melting temperature is measured by differential scanning calorimetry at a heating rate of 20 ℃ per minute according to ISO 11357-1:2023, and/or the aliphatic semi-crystalline polyketone has a melt mass flow rate in the range of 10 g/10 minutes to 200 g/10 minutes, the melt mass flow rate being determined at 240 ℃ at a load of 2.16 kg according to ISO 1133-2:2022.
  3. 3. The polyketone molding composition according to claim 2, wherein the aliphatic semi-crystalline polyketone has a melt mass flow rate in the range of 80 g/10 min to 200 g/10 min.
  4. 4. The polyketone molding composition according to claim 1, wherein the aliphatic semi-crystalline polyketone has a relative viscosity of 1.3 to 1.8, said relative viscosity being measured according to ISO 307:2007 using a capillary viscometer on a solution of 0.5 g polyketone dissolved in 100 ml m-cresol at 20 ℃, and/or the aliphatic semi-crystalline polyketone having a number average molecular weight in the range of 20,000 g/mol to 100,000 g/mol, said number average molecular weight being determined by gel permeation chromatography in hexafluoroisopropanol relative to polymethyl methacrylate standard.
  5. 5. The polyketone molding composition according to claim 1, wherein said aliphatic semi-crystalline polyketone is a terpolymer of the general formula: wherein Q is a divalent group derived from an ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, x and y are each the number of repeating units, and the molar ratio y: x is less than or equal to 0.5.
  6. 6. The polyketone molding composition according to claim 1, wherein the long glass fibers have a diameter in the range of 10 to 20 μιη and/or are selected from E-glass fibers, ECR-glass fibers, D-glass fibers, L-glass fibers, S-glass fibers, R-glass fibers, or mixtures thereof.
  7. 7. The polyketone molding composition of claim 1 wherein the long glass fibers are derived from long glass fiber rovings having a weight of 0.5kg to 2.4 kg per kilometer.
  8. 8. The polyketone molding composition of claim 1, wherein the long glass fibers are surface modified with an amino-or epoxy-functional alkoxysilane, chlorosilane, pentaerythritol, dipentaerythritol, resorcinol, or mixtures thereof.
  9. 9. The polyketone molding composition according to claim 1, wherein the long carbon fibers have a diameter of 4 to 10 μm.
  10. 10. The polyketone molding composition of claim 1, wherein the antioxidant is a sterically hindered phenol, an aromatic amine, a phosphite or phosphonite, a benzotriazole, or a mixture thereof.
  11. 11. The polyketone molding composition of claim 10 wherein the sterically hindered phenol is selected from pentaerythritol tetrakis [3- (3 ',5' -di-tert-butyl-4 '-hydroxyphenyl) propionate ], ethylene bis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate), octadecyl- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2', 3-bis [ [3- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionyl ] ] propionyl hydrazine, or mixtures thereof.
  12. 12. The polyketone molding composition of claim 1, wherein the phosphate compound is calcium phosphate, potassium phosphate, magnesium phosphate, sodium phosphate, ammonium phosphate, aluminum phosphate, or mixtures thereof.
  13. 13. The polyketone molding composition of claim 1, wherein the phosphate compound is hydroxyapatite and/or tetrakis (2, 4-di-tert-butylphenyl) -4,4' -biphenylene diphosphonite.
  14. 14. The polyketone molding composition of claim 1, wherein the colorant is carbon black, an organic dye, a pigment, or a mixture thereof.
  15. 15. The polyketone molding composition of claim 1, wherein the organic phosphinate is a halogen-free organic phosphinate.
  16. 16. A molded article made from the polyketone molding composition of any one of claims 1 to 15.
  17. 17. The molded article of claim 16, comprising the form of a housing, a functional component for a pump, a gearbox, a valve, a water meter, a throttle valve, a cylinder, a piston, a headlamp housing, a reflector, a cornering lamp, a gear, an engine and gearbox bearing, a connector, a profile, a film or layer of a multilayer film, a fiber, an electronic component, a housing for an electronic component, a battery housing, a connector, a mobile phone housing, a component for an LED housing, a housing or housing part for a personal computer, a tool, a composite, a fluid delivery container, a sleeve, a fitting for connecting hoses, layers in a multilayer container, or a brake fluid reservoir.
  18. 18. A process for producing a molded article according to claim 16 or 17 by injection molding, extrusion or blow molding.

Description

Polyketone molding composition having improved properties, molded article produced therefrom, and method for producing same Technical Field The present invention relates to polyketone molding compositions based on semicrystalline aliphatic polyketones. In particular, the present invention relates to halogen-free and long fiber reinforced molding compositions based on semi-crystalline aliphatic polyketones. Furthermore, the invention relates to molded articles produced from the polyketone molding compositions. Furthermore, the invention relates to a process for the production of the polyketone molding composition. The molding composition exhibits good mechanical properties and can be easily produced by a pultrusion process. These molding compositions are particularly suitable for producing thin-walled moldings for the electrical and electronics industry, for example housings, housing components or connectors, and for the electric automobile industry, in particular for housing parts of automobile batteries. Background Aliphatic polyketones have been known for many years, and the advantages of aliphatic polyketones include almost constant mechanical properties between 10 ℃ and 100 ℃, very good resistance to hydrolysis, high resistance to thermal deformation, good abrasion resistance and good fuel barrier properties. On the other hand, while aliphatic polyketones are thermoplastic polymers with consistently good properties, they have the disadvantage of having a relatively high melting point, which is close to the temperature at which they undergo chemical degradation, in particular intermolecular aldol condensation reactions and intramolecular aldol condensation reactions. That is, when an attempt is made to melt aliphatic polyketones, chemical degradation may occur, particularly intermolecular aldol condensation reaction and intramolecular aldol condensation reaction. This is problematic in terms of processing of aliphatic polyketones, since, on the one hand, polyketone molding compositions are difficult to process using conventional processing techniques (for example in the form of a melt), and, on the other hand, the properties of such molding compositions may be adversely affected by degradation and crosslinking reactions caused during processing. EP 322959 describes fiber-reinforced polyketone molding compositions, in particular glass fiber-reinforced molding compositions, and a process for producing such molding compositions from polyketone solutions. The aim is to increase the strength and the modulus of elasticity of the molding composition. KR 2019088230A describes a process for producing polyketone long fiber particles comprising long fibers and a thermoplastic resin, and polyketone long fiber particles produced thereby. The long fibers as the reinforcing material are impregnated in the thermoplastic resin used as the matrix, can be easily produced in the form of particles due to good cutting characteristics, and are suitable for materials of various electronic and industrial parts due to their excellent mechanical characteristics. KR 2019094827A describes a process for producing reinforcing fiber pellets by granulating the mixture after feeding the continuous reinforcing fibers directly into a twin screw extruder in the form of rovings and mixing with a matrix comprising a polyketone resin. The method enables continuous production in a twin screw extruder without gelling the polyketone resin. Pultrusion does not work properly due to gelation, and only up to two hours of operation is possible. US 10047215 B2 describes glass fiber reinforced polyketones comprising a process stabilizer and further fluorine stabilizers and a colorant which is a black pigment masterbatch comprising carbon black, polyethylene wax and polyethylene resin. One aspect of the disclosure is to provide a polyketone composite resin composition produced by a pultrusion process including impregnating a glass fiber filler with a melt of a thermoplastic resin as a long fiber reinforcement process, the thermoplastic resin being a polyketone resin composition, and an injection molding material using the composition. The cited patent does not describe the pultrusion process in detail. Polyketones have good mechanical properties, low water absorption, chemical resistance and high hydrolytic stability. Polyketones do not contain harmful substances such as heavy metals, formaldehyde, perfluoroalkyl substances, and polyfluoroalkyl substances (PFAS), etc., and are also distinguished from other polymers by a lower CO 2 footprint. Polyketones also have very high barrier properties against fuel and oxygen, short cycle times, high elongation at break, good tribological properties with low wear and good sliding properties. In view of the above-mentioned advantages of polyketones, in particular aliphatic polyketones, and the problems associated with their processing, there is a need to develop a polyketone-based molding composition which can be re