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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

• TITLE COMPOSITIONS BASED ON POLYAMIDES AND GLASS FIBERS AND THEIR USE IN THE FIELD OF SANITARY AND WATER [Technical field]
• the present invention relates to molding compositions based on polyamides and glass fibers and their use in the field of sanitation, transport or distribution of water, in particular drinking water, at a temperature less than or equal to 60°C.
• Brass is a material widely used in the field of sanitary, but this material is expensive. Its use can also involve the release of heavy metals into the water and in particular drinking water. For these reasons, brass is replaced by plastic materials (such as PPSU, PVDF, PA).
• polyamide compositions reinforced with glass fibers for use in the field of drinking water, said polyamide being a mixture of semi-crystalline aliphatic polyamide and amorphous transparent polyamide, in particular based cycloaliphatic diamines such as 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane (called BMACM, MACM or B), p-bis(aminocyclohexyl)-methane commonly (called PACM or P) and l isophorone-diamine (referred to as IPD).
• BMACM 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane
• PACM p-bis(aminocyclohexyl)-methane commonly
• IPD l isophorone-diamine
• polyamide compositions reinforced with glass fibers for use in the field of drinking water, said polyamide being a mixture of semi-crystalline aliphatic polyamide and amorphous transparent polyamide chosen from B9-36, B9- 36/P9-36, 12/BI and 12/BT.
• compositions comprising a polyamide and a condensation product of a phenol and a carbonyl compound.
• the present invention therefore relates to a molding composition, comprising by weight: a) 20 to 60%, in particular from 20 to 50%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atom per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution of less than or equal to 1.3, in particular less than or equal to 1.25, as determined according to standard ISO 307: 2007 at a temperature of 20°C.
• the inventors have therefore found that the selection of at least one long-chain aliphatic polyamide having a particular inherent viscosity in solution with a particular range of glass fibers makes it possible to form a composition which, after injection, has improved mechanical properties at lower temperatures. or equal to 60° C., in particular in terms of creep resistance or breaking stresses before or after immersion in drinking water.
• the inherent viscosity in solution (iv) is determined according to ISO 307:2007 modified in that the solvent is m-cresol rather than sulfuric acid, and that the concentration is 0.5% by weight and in that the temperature is 20°C.
• a molding composition according to the invention is a composition transformed for example by injection, injection blow molding, expansion molding and rotational molding.
• the molding composition comprises from 20 to 60%, in particular from 20 to 50%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a higher number of carbon atoms per nitrogen atom or equal to 9, in particular greater than or equal to 10.
• the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
• said polyamide is a semi-crystalline polyamide or copolyamide.
• melt-crystalline within the meaning of the invention, denotes a (co)polyamide which has a melting point (Tm) in DSC according to standard ISO 11357-3:2013, and an enthalpy of crystallization during the cooling step at a speed of 20 K/min in DSC measured according to standard ISO 11357-3 of 2013 greater than 20 J/g, preferably greater than 30 J/g.
• Said polyamide is derived from a repeating unit obtained by polycondensation: of at least one amino acid in Cg to Cis, preferentially in Cio to Cis, more preferentially in Cio to C, or at least one Cg to Cis, preferably Cio to Cis, more preferably Cio to C 12 lactam, or at least one C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12, with at least one Cb C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12 dicarboxylic acid, or a mixture thereof, provided that the number of carbon atoms per nitrogen atom of the repeating unit is greater than or equal to 9, in particular greater than or equal to 10.
• the long-chain aliphatic polyamide is obtained by polycondensation: of at least one Cg to Cis amino acid, preferentially Cio to Cis, in particular Cio to C 12 , or of at least one Cg to Cis lactam, preferentially in Cio to Cis, in particular in Cio to C 12 .
• a Cg to Cis amino acid is in particular 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular acid N-heptyl-ll-aminoundecanoic acid.
• a Cg to Cis lactam is in particular lauryllactam.
• Said at least one C4-C36 diamine Ca can be chosen in particular from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylediamine, 1,8-octamethylediamine, 1,9-nonamethyldiamine, 1,10-decamethyldiamine, 1,11-undecamethyldiamine, 1,12-dodecamethyldiamine, 1,13-tridecamethyldiamine, 1,14-tetradecamethyldiamine, 1,16-hexadecamethyldiamine and 1, 18-octadecamethylediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.
• said at least one Ca diamine is C 6 -Cis and chosen from 1,6-hexamethylenediamine, 1,7-heptamethylediamine, 1,8-octamethylediamine, 1,9-nonamethylediamine, 1,10- decamethyldiamine, 1,11-undecamethyldiamine, 1,12-dodecamethyldiamine, 1,13-tridecamethyldiamine, 1,14-tetradecamethyldiamine, 1,16-hexadecamethyldiamine and 1,18-octadecamethyldiamine.
• Said at least one Cb C 4 to C 36 dicarboxylic acid can be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid , dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecanediamine, eicosanediamine, docosanediamine and diamines obtained from acids bold.
• said at least one Cb dicarboxylic acid is C 6 to Cis and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
• the long-chain aliphatic polyamide is chosen from: polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), polyamide 11 (PAU), polyamide 12 (PA12), or a mixture thereof or a copolyamide thereof.
• the polyamide is in particular PAU and PA12.
• said long chain aliphatic polyamide is a mixture of two polyamides in a range of proportion by weight of 5/95 to 95/5.
• said mixture is a mixture of two identical polyamides having the same number of carbon atoms per nitrogen atom but with an inherent viscosity in solution of one of the two polyamides greater than 1.3 but on the condition that the mixture meets the condition of having an inherent viscosity in solution of less than or equal to 1.3, in particular less than or equal to 1.25.
• the glass fibers are present from 40% to 75%, in particular from 50 to 75%, in particular from 60 to 70% by weight relative to the total weight of the composition.
• the glass fibers can be solid and/or hollow, advantageously they are solid.
• the glass fibers are advantageously short.
• the short glass fibers preferably have a length of between 2 and 13 mm, preferably of 3 to 8 mm before the compositions are implemented.
• the short glass fibers have a fiber length of 120 to 350 ⁇ m.
• This fiber length of 120 to 350 ⁇ m is measured on the compound.
• the short glass fibers can be circular or non-circular in section.
• a fiber with a circular section is defined as a fiber having at any point of its circumference a distance equal to the center of the fiber and therefore represents a perfect or almost perfect circle.
• Any fiberglass that does not have this perfect or near-perfect circle is therefore defined as a fiber with a non-circular section.
• non-circular fibers having for example an elliptical, oval or cocoon shape, star fibers, flake fibers, fibers plates, cruciforms, a polygon and a ring.
• Fiberglass can be: - either with a circular cross-section with a diameter of between 4 ⁇ m and 25 ⁇ m, preferably from 4 to 15 ⁇ m.
• L and D can be measured by scanning electron microscopy (SEM).
• the glass fibers are circular.
• the at least one additive is optionally present from 0 to 5% by weight, in particular from 0.1 to 5%, relative to the total weight of the composition.
• the additive is selected from fillers, colorants, stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes, additives for laser marking , and mixtures thereof.
• the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of that of irganox ® 1010 from the company Ciba- BASF).
• a phenol-type antioxidant for example of the type of that of irganox ® 1010 from the company Ciba- BASF.
• the fillers can be chosen from carbon black, talc, pigments, metal oxides (titanium oxide).
• the molding composition comprises by weight: a) 20 to 60%, in particular from 20 to 50%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atoms per atom of nitrogen greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to 1.3, in particular less than or equal to 1.25, as determined according to the ISO 307: 2007 standard at a temperature of 20°C.
• An amorphous polyamide within the meaning of the invention denotes an amorphous transparent polyamide having only a glass transition temperature (no melting temperature (Tm)), or a very slightly crystalline polyamide having a glass transition temperature and a melting point such as the enthalpy of crystallization during the cooling step at a rate of 20 K/min in differential calorimetric analysis ("Differential Scanning Calorimetry" DSC in English) measured according to ISO 11357-3:2013 is less than 20 J/g.
• the glass transition temperature (Tg) measured by DSC at a heating rate of 20 K/min according to standard ISO 11357-2:2013 for these polyamides is greater than 75°C.
• a microcrystalline polyamide within the meaning of the invention has an enthalpy of crystallization during the cooling step at a rate of 20 K/min in differential scanning calorimetry (“Differential Scanning Calorimetry” DSC) measured according to the ISO 11357-3 standard. :2013 is less than 20 J/g.
• a microcrystalline polyamide is therefore excluded from said molding composition.
• An amorphous polyamide is for example a polyamide based on at least one cycloaliphatic diamine such as MACM, PACM, and IPD.
• An amorphous polyamide is therefore excluded from said molding composition.
• a microcrystalline polyamide and an amorphous polyamide as a mixture are therefore excluded from said molding composition.
• a polyamide other than an aliphatic polyamide, in particular a semi-crystalline one, is excluded from the composition.
• a condensation product of a phenol and a carbonyl compound is excluded from the composition.
• the molding composition consists of (by weight): a) 20 to 60%, in particular from 20 to 50%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atoms per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to 1.3, in particular less than or equal to 1.25, as determined according to ISO 307: 2007 at a temperature of 20°C.
• the molding composition comprises by weight: a) 20 to 50%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atoms per atom of nitrogen greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to
• the molding composition comprises by weight: a) 20 to 49.9%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atom per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to
• the composition consists of: a) 20 to 50%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atoms per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to
• the composition consists of: a) 20 to 49.9%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atom per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to
• the molding composition comprises by weight: a) 25 to 40%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atoms per atom of nitrogen greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to
• the molding composition comprises by weight: a) 25 to 39.9% of at least one long-chain aliphatic polyamide having a higher number of carbon atoms per nitrogen atom or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to
• the molding composition consists of: a) 25 to 40%, in particular 25 to 39.9% of at least one long-chain aliphatic polyamide having an atomic number of carbon per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution less than or equal to 1.3, in particular less than or equal to 1.25, as determined according to ISO 307: 2007 at a temperature of 20°C. b) 60 to 70% of glass fibres, and c) 0 to 5% by weight, preferably 0.1 to 5% by weight of at least one additive, the sum of the proportions of each constituent of the said composition being equal 100%.
• the molding composition consists of: a) 25 to 39.9% of at least one long-chain aliphatic polyamide having a number of carbon atoms per nitrogen atom greater than or equal to 9, in particular greater than or equal to 10, said at least one polyamide having an inherent viscosity in solution of less than or equal to 1.3, in particular less than or equal to 1.25, as determined according to the ISO standard 307:2007 at a temperature of 20°C. b) 60 to 70% of glass fibers, and c) 0.1 to 5% by weight of at least one additive, the sum of the proportions of each constituent of said composition being equal to 100%.
• the present invention relates to the use of a composition as defined above, for the manufacture of an article for the field of sanitary, transport or water distribution, in particular of drinking water, at a temperature below 60°C.
• article for the sanitary sector, water transport or distribution designates, for example, all articles used in the rooms of water, in particular the bathroom, the kitchen, the laundry room, the toilets. ..
• This article designates a valve element, an element of pipes, supplies, evacuations and connections.
• This article can be a container, a pipe, a fitting, a connector, a quick connector, a screw, a valve, a valve element, a valve, a filter element and a structural part.
• the transport or distribution of water in the present invention relates to water, whether potable or not, at a temperature less than or equal to 60°C.
• the article is selected from a container, a conduit, a fitting, a connector, a quick connector, a screw, a valve, a valve element, a valve and filter element and a structure.
• the article has improved mechanical properties compared to an article whose inherent viscosity in solution is greater than 1.3, determined at 23° C. according to standard ISO 527: 2012 on a type IA specimen.
• the article has improved mechanical properties compared to an article whose inherent viscosity in solution is greater than 1.3, determined at 60° C. according to standard ISO 527: 2012 on a type IA specimen.
• the article has improved creep resistance compared to an article whose inherent viscosity in solution is greater than 1.3, as determined according to ISO 899-1:2017 on a type IA specimen.
• the article has improved mechanical properties compared to an article whose inherent viscosity in solution is greater than 1.3, determined at 23° C. and at 60° C., according to standard ISO 527: 2012 on a test specimen. type IA.
• the article has improved mechanical properties compared to an article whose inherent viscosity in solution is greater than 1.3, determined at 23° C. and at 60° C., according to standard ISO 527: 2012 on a type IA specimen and improved creep resistance compared to an article whose inherent viscosity in solution is greater than 1.3, as determined according to ISO 899-1:2017 on a type IA specimen.
• the article is made by injection molding.
• the present invention relates to an article obtained by injection molding with a composition as defined above.
• compositions of Table 1 were prepared by mixing in the molten state the polyamide granules, with the glass fibers and optionally the additives.
• compositions based on PAU and PA12 were implemented by compounding on a co-rotating twin-screw extruder with a diameter of 40 mm with a temperature profile (T°) flat at 250°C.
• the screw speed is 300 rpm and the throughput 100 kg/h.
• the semi-crystalline aliphatic polyamide and possibly the additives are added in the main hopper.
• the compositions were then molded on an injection molding machine (Engel brand) at a set temperature of 260° C. and a mold temperature of 70° C. in the form of dumbbells in order to study the properties of the compositions according to the ci standards. -below.
• the tensile modulus was measured at 23°C and 60°C according to the ISO 527-1: 2012 standard on type IA dumbbells.
• the breaking stress was also measured at 23°C and 60°C according to this same ISO 527-1: 2012 standard.
• the machine used is of the INSTRON 5966 type.
• the crosshead speed was set at 1 mm/min for modulus measurement and 5mm/min for strain measurement.
• Creep resistance was tested on type A specimens, at 60°C under constant stress according to standard IS0899-1:2017.
• the samples were tested either dry or after immersion in drinking water at 90°C.
• CE composition according to the invention
• CE counter-example The FoodContactTM 295-10 fiberglass (with a circular section of diameter 10 miti) is marketed by the company Owens Corning.
• the CSG3PA820 glass fiber (with a non-circular cross-section of 7 ⁇ 28 ⁇ m cross-section) is marketed by the company Nitto Boseki.
• the PAU and PA12 are produced by the applicant.
• Calcium stearate is marketed by the company Greven.
• the licowax ® E is marketed by the company Clariant.
• Irganox ® 1010 is marketed by BASF.
• Composition E6 according to the invention exhibits very clearly improved mechanical properties compared with CE2, determined at 23 and 60°C in the dry state and after immersion in drinking water at 90°C.
• the creep resistance at 60°C is also significantly improved compared to a formulation composed of a polyamide matrix having an inherent viscosity > 1.3

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• 2021
  • 2021-05-05 FR FR2104728A patent/FR3122659A1/fr active Pending
• 2022
  • 2022-04-29 CN CN202280032669.1A patent/CN117255826A/zh active Pending
  • 2022-04-29 KR KR1020237040977A patent/KR20240004688A/ko unknown
  • 2022-04-29 JP JP2023567239A patent/JP2024517226A/ja active Pending
  • 2022-04-29 WO PCT/FR2022/050827 patent/WO2022234222A1/fr active Application Filing
  • 2022-04-29 EP EP22726787.9A patent/EP4334387A1/fr active Pending

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