Classifications

• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/014—Stabilisers against oxidation, heat, light or ozone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/14—Lactams
  • C08G69/16—Preparatory processes
  • C08G69/18—Anionic polymerisation
  • C08G69/20—Anionic polymerisation characterised by the catalysts used
• • 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
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/16—Halogen-containing compounds
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/435—Sulfonamides
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • 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
  • 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
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/546—Flexural strength; Flexion stiffness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes

Definitions

• the present invention relates to the use of at least one catalyst, at least one copper thermal stabilizer and at least one oligo- or polycarbodiimide with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, for constitute a viscous and stable composition for processing, in particular extrusion.
• the present invention also relates to the viscous and stable composition as defined above.
• the invention also relates to the use of the above composition for the constitution of a structure, such as:
• a flexible hose for the automobile in particular for the transportation of fuel (gasoline, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, for pipes made in particular by extrusion blow molding for the supply of air,
• fuel gasoline, diesel, biodiesel or ethanol
• refrigeration for air conditioning
• pipes made in particular by extrusion blow molding for the supply of air
• the invention also relates to the structures obtained from said compositions.
• Such pipes must in particular withstand hot oil, gas, water and mixtures of at least two of these products for periods of up to 20 years.
• these pipes comprise an unsealed metal inner layer formed by a helically wound profiled metal strip such as a stapled strip.
• This metal inner layer which gives shape to the pipe, is coated, generally by extrusion, with a polymer layer intended to provide sealing.
• Other protective and / or reinforcing layers such as metal fiber webs, thermoplastics and rubbers may also be arranged around the sealed polymer layer.
• the polymer is HDPE (high density polyethylene) crosslinked or not.
• HDPE high density polyethylene
• polyamide is used and for temperatures above 90 ° C is used PVDF (polyvinylidene fluoride).
• polystyrene resin such as PA1 1 and PA12, well known for their good thermal resistance, their chemical resistance, especially to solvents, their resistance to weather and radiation, their impermeability to gases and liquids and their quality of electrical insulators.
• the document US 2003/0220449 proposes a composition comprising a mixture of PA, plasticizer and a chosen elastomer.
• NBR nitrile butadiene rubber
• H-NBR hydrogenated nitrile butadiene rubber
• H-NBR elastomers or hydrogenated NBRs
• H-NBR elastomers have a high cost and require, like their non-hydrogenated NBR counterparts, moreover, to implement a preliminary milling step, adding a further cost to that already generated by the NBR raw material. or H-NBR.
• the Applicant describes in WO 08/122743 the use of a composition comprising at least one semi-crystalline polyamide, a functionalized polyolefin and a plasticizer for the manufacture of flexible tubes used in particular for the production of plastics. exploitation of oil or gas deposits.
• compositions having high melt viscosities but also a stability to the transformation (the residence time of the product during its extrusion is at least 5 min or 300 seconds), as well as resistance to thermo-oxidation.
• phosphoric catalysis allows, under certain conditions (rate of catalysis, vacuum, humidity), to arrive there but the product can continue to evolve in the transformation.
• this post reactivity is sensitive to the residual moisture of the granules.
• the current polyamide compositions generally allow only a pipe operating temperature of 60 ° C. to 70 ° C. dependent the pH or total acid number (TAN) of the transported fluid and the acceptance criterion used.
• TAN total acid number
• a first object of the invention is therefore the use of at least one catalyst, at least one copper thermal stabilizer and at least one oligo- or poly-carbodiimide with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, to constitute a viscous and stable composition for processing, in particular extrusion.
• a second subject of the invention is the provision of a composition defined above and its use for the constitution of a structure, such as: a flexible pipe intended for the transport of gas, for the exploitation of the oil deposits under the sea,
• a flexible hose for the automobile in particular for the transportation of fuel (gasoline, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, for pipes made in particular by extrusion blow molding for the supply of air,
• fuel gasoline, diesel, biodiesel or ethanol
• refrigeration for air conditioning
• pipes made in particular by extrusion blow molding for the supply of air
• Another object of the invention is the provision of flexible pipes defined above.
• the present invention relates to the use of at least one catalyst, at least one copper thermal stabilizer and at least one oligo- or polycarbodiimide with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, for constitute a composition having a good viscosity in the molten state and stable to the transformation.
• thermoplastic polymer in particular a polyamide
• the melt viscosity is determined by oscillatory rheology at 270 ° C. at 10 rad / sec under a nitrogen sweep with 5% deformation and a shear of 10 sec -1 on a Physica MCR301 apparatus between two parallel planes of 25 mm diameter.
• the inherent viscosity is determined according to ISO 307-2007 but in m-cresol instead of sulfuric acid, the temperature being 20 ° C.
• melt viscosity does not change by more than 70% over time, and specifically between 1 minute (time to melt the product) and at least 30 minutes especially between 1 minute and 30 minutes.
• melt viscosity of said composition is substantially constant between 1 minute and at least 5 minutes, in particular between 1 minute and 5 minutes.
• melt viscosity does not evolve by more than 20% between 1 minute and at least 5 minutes, especially between 1 minute and 5 minutes.
• the time of 5 minutes represents the residence time of the material, especially in the extruder during the implementation.
• said composition also has a resistance to thermo-oxidation.
• thermo-oxidation is characterized by the half-life (in hours) of materials. It corresponds to the time at which the ISO 527-2 1 BA test pieces, aged in air at 140 ° C, lost half of their initial elongation at break measured according to ISO 527-2 (2012).
• the resistance to thermoxidation is at least 80 days, in particular 100 days.
• said composition has a melt viscosity of about 13000 to about 23000 Pa.s, as determined by oscillatory rheology at 270 ° C as defined above.
• the key factor for the transformation of the composition of the invention is its rheology and not the inherent viscosity. Indeed, at constant inherent viscosity, it can be seen that only the compositions comprising the copper thermal stabilizer-catalyst system and the oligo- or poly-carbodiimide make it possible to obtain a composition having an adequate rheology, ie a melt viscosity of from about 13000 to about 23000 Pa.s, said viscosity also being substantially constant and stable to the transformation as defined above.
• the catalyst is a mixture of:
• catalyst refers to a polycondensation catalyst such as a mineral or organic acid.
• the proportion by weight of catalyst is from about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to the total weight of the composition.
• the catalyst is chosen from phosphoric acid (H 3 PO 4 ), phosphorous acid (H 3 PO 3 ), hypophosphorous acid (H 3 PO 2), or a mixture thereof.
• the present invention therefore relates to the use defined above of at least one catalyst, in proportion by weight of catalyst of from about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to the total weight of the composition, at least one copper thermal stabilizer and at least one oligo- or poly-carbodiimide, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said catalyst being chosen from phosphoric acid (HsPO 4 ), phosphorous acid (H 3 PO 3 ), hypophosphorous acid (H 3 PO 2), or a mixture thereof.
• the catalyst is chosen from phosphoric acid (H 3 PO 4 ) and phosphorous acid (H 3 PO 3) in a proportion of from about 100 to about 3000 ppm.
• a well-known example is the mixture of Cul and Kl, where the ratio Cul: KI is typically between 1: 2 to 1:15.
• An example of such a stabilizer is PolyAdd P201 from Polyad Services.
• the copper-based stabilizer is chosen from copper halides, copper acetate, copper halides or copper acetate mixed with at least one alkali metal halide, and mixtures thereof, preferably mixtures of copper iodide and potassium iodide (Cul / KI).
• the copper stabilizer may also be a Bruggolen® H3386.
• the copper thermal stabilizer used to constitute the composition defined above is in a proportion of about 0.05% to about 1%, in particular about 0.05% to about 0.3% by weight relative to to the total weight of the composition.
• the copper thermal stabilizer is a mixture of potassium iodide and copper iodide (KI / CaI).
• the mixture of potassium iodide and copper iodide useful according to the present invention is in a ratio of 90/10 to 70/30.
• the present invention therefore relates to the above-defined use of at least one catalyst, at least one copper thermal stabilizer in a proportion of about 0.05% to about 1%, in particular about 0%. , 05% to about 0.3% by weight relative to the total weight of the composition, and at least one oligo- or poly-carbodiimide, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said thermal stabilizer the copper being a mixture of potassium iodide and copper iodide (Kl / Cul), preferably in a ratio of 90/10 to 70/30.
• Kl / Cul potassium iodide and copper iodide
• the present invention relates to the above-defined use of at least one catalyst, in a proportion by weight of catalyst of from about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm with respect to total weight of the composition, of at least one copper thermal stabilizer in a proportion of from about 0.05% to about 1%, in particular from about 0.05% to about 0.3% by weight based on weight total of the composition, and of at least one oligo- or poly-carbodiimide, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said catalyst being chosen from phosphoric acid (HsPO 4 ), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof and said copper thermal stabilizer being a mixture of potassium iodide and copper iodide (KI / CaI), preferably in a ratio of from 90/10 to 70/30.
• HsPO 4 phosphoric acid
• H3PO3 phosphorous acid
• the catalyst is chosen from phosphoric acid (H 3 PO 4 ) and phosphorous acid (H 3 PO 3) in a proportion of from about 100 to about 3000 ppm.
• the carbodiimide represents a conventionally known oligomer and carbodiimide polymer and can be prepared by polymerization of diisocyanates. This reaction can be accelerated by catalysts and products with removal of carbon dioxide (J. Org Chem 28, 2069 (1963) J. Am Chem Chem 84, 3673 (1962) Chem Rev. 81, 589 (1981), Angel Chem., 93, 855 (1981)).
• the NCO end-group reagents may comprise a reactive compound CH, NH or OH, for example esters of malonic acid, caprolactam, alcohols or phenols.
• mixtures of mono- and diisocyanates may be polymerized to obtain oligo- or polycarbodiimides containing essentially unreactive end groups.
• the carbodiimide used is an oligo or polycarbodiimide of general formula:
• R2 represents an alkylene group having 2 to 20 carbon atoms, cycloalkylene having 5 to 20 carbon atoms, arylene having 6 to 20 carbon atoms or aralkylene having 7 to 20 carbon atoms;
• n 1 to 100, preferably 2 to 80 and preferably 3 to 70.
• the oligo- or polycarbodiimide may be a homopolymer or a copolymer, for example a copolymer of 2,4-diisocyanato-1,3,5-triisopropylbenzene and 1,3-diisocyanato-3,4-diisopropylbenzene.
• the oligo- or polycarbodiimide may also be selected from those described in US 5,360,888.
• the oligo- or polycarbodiimide can also be cyclic, in particular TCC (cyclic Teijin carbodiimide marketed by the company).
• Suitable oligo and polycarbodiimides can be obtained from commercially available sources such as Rhein Chemie, Raschig, Ziko or Teijin.
• the proportion by weight of oligo- or poly-carbodiimide used is from about 0.1 to about 3%, in particular from 0.5 to 2%, in particular about 1% relative to the total weight of the product. composition.
• the oligo- or poly-carbodiimide is selected from Stabilize, especially Stabilizer ® 9000, a Stabaxol ®, including a Stabaxol ® P, particularly Stabaxol ® P100 or P400 Stabaxol ®, or a mixture thereof -this.
• the present invention therefore relates to the use defined above of at least one catalyst, at least one copper thermal stabilizer, and at least one oligo- or poly-carbodiimide in a proportion of about 0, 1 to about 3%, in particular from 0.5 to 2%, in particular about 1% by weight relative to the total weight of the composition, with a matrix comprising at least one thermoplastic polymer, especially a polyamide, said oligo- or poly-carbodiimide is selected from Stabilize, especially Stabilizer ® 9000, a Stabaxol ®, including a Stabaxol ® P, particularly Stabaxol ® P100 or Stabaxol ® P400, or a mixture thereof.
• the present invention relates to the above-defined use of at least one catalyst, in a proportion by weight of catalyst of from about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm with respect to total weight of the composition, at least one copper thermal stabilizer, and at least one oligo- or poly-carbodiimide in a proportion of from about 0.1 to about 3%, in particular from 0.5 to 2% , in particular approximately equal to 1% by weight relative to the total weight of the composition, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said catalyst being chosen from phosphoric acid (HsPO 4 ), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof and said oligo- or poly-carbodiimide being selected from Stabilizer, in particular Stabilizer ® 9000, Stabaxol ® , especially Stabaxol ® P, especially Stabaxol ® P100 or Staba
• H 3 PO 4 phosphorous acid
• H 3 PO 3 phosphorous acid
• the present invention relates to the above defined use of at least one catalyst, at least one copper thermal stabilizer in a proportion of about 0.05% to about 1%, in particular about 0, From about 5% to about 0.3% by weight based on the total weight of the composition, and from at least one oligo- or poly-carbodiimide in a proportion of about 0.1 to about 3%, in particular about 0.5%.
• a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said copper thermal stabilizer being a mixture of potassium iodide and copper iodide (Kl / Cul), preferably in a ratio of 90/10 to 70/30 and said oligo- or poly- carbodiimide being selected from a Stabilizer, in particular Stabilizer ® 9000, a Stabaxol ® , in particular stabaxol ® P, in particular Stabaxol ® P100 or Stabaxol ® P400, or a mixture thereof.
• the present invention therefore relates to the use defined above of at least one catalyst, in proportion by weight of catalyst of from about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to to the total weight of the composition, at least one copper thermal stabilizer in a proportion of from about 0.05% to about 1%, in particular from about 0.05% to about 0.3% by weight, based on total weight of the composition, and at least one oligo- or poly-carbodiimide and at least one oligo- or poly-carbodiimide in a proportion of from about 0.1 to about 3%, in particular from 0.5 to 2%, in particular approximately equal to 1% by weight relative to the total weight of the composition, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said catalyst being chosen from phosphoric acid (HsPO 4 ), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof, said stabilized wherein the copper thermal is a
• the catalyst is chosen from phosphoric acid (H 3 PO 4 ) and phosphorous acid (H 3 PO 3) in a proportion of from about 100 to about 3000 ppm.
• thermoplastic polymer The thermoplastic polymer
• thermoplastic polymer it may be chosen from polyamides or polyamide mixtures.
• the polyamide according to the present invention may have a homopolyamide or copolyamide structure.
• homopolyamide within the meaning of the present invention, is meant a polyamide, which consists only of the repetition of a single unit.
• copolyamide means a polyamide which consists of the repetition of at least two units of different chemical structure. This copolyamide may have a random, alternating or block structure.
• the polyamide according to the present invention may comprise one or more structural units chosen from amino acids, lactams and (diamine) units. (Diacid).
• the polyamide has an amino acid in its structure
• the polyamide comprises a lactam
• the polyamide comprises is a unit corresponding to the formula (diamine Ca).
• (Cb diacid) Ca and Cb denoting the number of carbon atoms respectively in the diamine and the diacid the unit (diamine Ca) is selected from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines.
• the diamine When the diamine is aliphatic and branched, it may have one or more methyl or ethyl substituents on the main chain.
• the monomer (diamine in Ca) may advantageously be chosen from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3 diaminopentane, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine.
• bis (3,5-dialkyl-4-aminocyclohexyl) methane bis (3,5-dialkyl-4-a
• the monomer (Ca diamine) is alkylaromatic, it is selected from 1,3-xylylene diamine and 1,4-xylylenediamine.
• the (Cb diacid) unit is chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids.
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
• the diacid when it is cycloaliphatic, it may comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane.
• the diacid is aromatic, it is selected from terephthalic acid (noted T), isophthalic acid (noted I) and naphthalenic diacids.
• thermoplastic polymer is a polyamide chosen from an aliphatic polyamide, a cycloaliphatic polyamide, an aromatic polyamide or a mixture thereof.
• the polyamide has a Tf of 160 ° C to 290 ° C determined according to the standard ISO 1,1357-3 (2013).
• the proportion of polyamide is from about 95.5 to about 99.845%.
• the useful polyamide according to the invention is chosen from PA 6, PA 1 1, PA 12, PA 6.10, PA 6.6, PA 6.12, PA 10.10, PA 10.12, PA 1 1 / 10.T, PA 1 1/6 .T, 12 / 10.T, 6.10 / 10.T, 6.12 / 10.T, 10.10 / 10.T, 10.12 / 10.T, 1 1 /6.T/10.T, 12.12 / 10.T, 12 / 6.10 / 10.T, 12 / 6.12 / 10.T, 12 / 10.10 / 10.T, 12 / 10.10 / 10.T, 12 / 10.12 / 10.T and 12 / 12.12 / 10.T.
• the polyamide is chosen from: PA1 1, PA12, PA 1 1 / 10.T, PA 10.10, PA 10.12 and copolyamides 1 1/12 having more than 90% of units 1 1 or more 90% of units 12, preferably among PA 1 1, PA 12, PA 1 1 / 10.T, PA 10.10 and PA 10.12.
• thermoplastic polymer in particular the polyamide, may contain at least one polyolefin.
• the polyolefin may be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one nonfunctionalized.
• functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below.
• the functionalized polyolefin (B1) can be chosen from
• PE polystyrene
• PP polystyrene
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
• EPR abbreviation of ethylene-propylene-rubber
• EPDM ethylene / propylene / diene
• SEBS Styrene / ethylene-butene / styrene block copolymers
• SBS styrene / butadiene / styrene
• SIS styrene / isoprene / styrene
• SEPS styrene / ethylene-propylene / styrene
• EVA ethylene-vinyl acetate copolymers
• ethylene and vinyl acetate (EVA) and alkyl (meth) acrylate copolymers containing up to 40% by weight of comonomers EVA
• alkyl (meth) acrylate copolymers containing up to 40% by weight of comonomers.
• maleated polyolefins such as TAFMER® MH5020, TAFMER® 610MP, TAFMER® MD715, Orevac® IM800, Exxelor® VA 1801 and 1803 and Fusabond.
• TAFMER® are marketed by Mitsui Chemicals, Orevac® by the Applicant, Exxelor by Exxon Mobil Chemicals.
• the functionalized polyolefin (B1) may also be a copolymer or copolymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth) acrylic acid.
• alkyl (meth) acrylate in (B1) or (B2) refers to C1-C12 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate and the like. , n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
• copolymers mentioned above, (B1) and (B2) can be copolymerized randomly or sequentially and have a linear or branched structure.
• MFI molecular weight
• density may also vary to a large extent, which the skilled person will appreciate.
• MFI abbreviation of Melt Flow Index, is the melt flow index. It is measured according to ASTM 1238-13.
• the non-functionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of an alpha-olefinic type comonomer such as propylene, butene or hexene, octene or 4-methyl-1-pentene.
• PP high density PE
• medium density PE linear low density PE
• low density PE very low density PE.
• These polyethylenes are known to those skilled in the art as being produced according to a "radical” process, according to a “Ziegler” type of catalysis or, more recently, according to a so-called "metallocene” catalysis.
• the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units carrying polar reactive functional groups, such as the carboxylic acid or carboxylic acid anhydride functions.
• polymers include polymers of ethylene and alkyl acrylate such as Lucalen®, ter polymers of ethylene, alkyl acrylate and maleic anhydride such as the Lotader ® of the Applicant or polyolefins grafted with maleic anhydride such as Orevac ® of the Applicant, or ter ter polymers of ethylene, octene and maleic anhydride named Fusabond® 493 Dupont, as well as ter polymers of ethylene, alkyl acrylate and (meth) acrylic acid.
• thermoplastic polymer in particular the polyamide, may contain at least one usual additive such as heat stabilizers, glass fibers, carbon fibers, a flame retardant, talc, a nucleating agent, a plasticizer, a dye, a fluorinated agent, lubricant, a stearate such as zinc stearate or calcium stearate or magnesium stearate, and another polyamide, catalyzed or otherwise, different from that used above.
• heat stabilizers glass fibers, carbon fibers, a flame retardant, talc, a nucleating agent, a plasticizer, a dye, a fluorinated agent, lubricant, a stearate such as zinc stearate or calcium stearate or magnesium stearate, and another polyamide, catalyzed or otherwise, different from that used above.
• thermal stabilizer is different from the copper thermal stabilizer described above and therefore does not contain copper.
• the heat stabilizer may be an organic stabilizer or more generally a combination of organic stabilizers, such a primary antioxidant of phenol type (for example of the type of Irganox ® 245 or 1098 or 1010 of BASF), a secondary antioxidant phosphite type and or optionally other stabilizers such as HALS, which means hindered amine light stabilizer or stabilizing hindered amine light (e.g., Tinuvin ® 770 from BASF), a UV stabilizer (e.g., Tinuvin ® 312 from BASF), a phenolic or phosphorus stabilizer.
• a primary antioxidant of phenol type for example of the type of Irganox ® 245 or 1098 or 1010 of BASF
• secondary antioxidant phosphite type such as HALS, which means hindered amine light stabilizer or stabilizing hindered amine light (e.g., Tinuvin ® 770 from BASF), a UV stabilizer (e.g., Tinuvin ® 3
• Amino-type antioxidants can also be used such as Naugard® 445 (4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylannine) from Crompton, Flexamine® from Addivant or polyfunctional stabilizers such as Nylostab® S-EED from Clariant.
• the present invention relates to one of the uses defined above in which at least one polyolefin and / or at least one additive are optionally present, in particular up to 30% each by weight relative to the total weight of the composition. .
• the present invention relates to one of the uses defined above wherein a polyolefin is also present, in particular from about 1 to about 15% by weight relative to the total weight of the composition.
• the polyolefin is chosen from a maleated EPR, in particular EXXELOR® VA 1801 and EXXELOR® VA1803 sold by ExxonMobil, a Fusabond®, in particular Fusabond® 493 from DuPont, and TAFMER® MH5020. , TAFMER® 610MP and TAFMER® MD715 from MitsuiChemicals.
• the present invention relates to one of the uses defined above in which at least one additive is optionally present, in particular up to 30%.
• the present invention relates to one of the uses defined above in which an additive is also present, in particular from about 0.1 to about 1% by weight relative to the total weight of the composition.
• the additive is a thermal stabilizer.
• the present invention relates to one of the uses defined above wherein a polyolefin is present, in particular from about 1 to about 15% by weight relative to the total weight of the composition and at least one additive is also present. in particular from about 0.1 to about 30%, in particular from about 0.1 to about 20%, especially from about 0.1 to about 10% by weight based on the total weight of the composition.
• the present invention relates to one of the above-defined uses in which a polyolefin is present, in particular from about 1 to about 15% by weight relative to the total weight of the composition and an additive is also present in particular from about 0.1 to about 1% by weight relative to the total weight of the composition.
• the polyolefin is chosen from a maleated EPR, in particular EPR 1801 and a Fusabond ® , in particular Fusabond ® 493 and the additive is a thermal stabilizer.
• plasticizer it is chosen from benzene sulphonamide derivatives, such as n-butyl benzene sulphonamide (BBSA) or N- (2-hydroxypropyl) benzene sulphonamide (HP-BSA) from Proviron, ethyl toluene.
• BBSA n-butyl benzene sulphonamide
• HP-BSA N- (2-hydroxypropyl) benzene sulphonamide
• esters of hydroxy-benzoic acids such as 2-ethylhexyl parahydroxybenzoate (EHPD) from the company Ueno Fine Chemicals and 2-decyl parahydroxybenzoate (HD-PB) from the company KAO
• esters or ethers of tetrahydrofurfuryl alcohol such as oligoethyleneoxytetrahydrofurfurylalcohol
• esters of citric acid or hydroxy-malonic acid such as oligoethyleneoxy malonate.
• a particularly preferred plasticizer is n-butyl benzene sulfonamide (BBSA). It would not be outside the scope of the invention using a mixture of plasticizers.
• the plasticizer can be introduced into the polyamide during the polycondensation or later.
• the proportion of plasticizer can be from 0 to 15% by weight.
• the plasticizer used is a benzene sulphonamide derivative, such as n-butyl benzene sulphonamide (BBSA).
• BBSA n-butyl benzene sulphonamide
• the present invention relates to one of the above-defined uses in which a plasticizer is also present, in particular from about 1 to about 10% by weight relative to the total weight of the composition.
• the present invention relates to one of the uses defined above wherein a polyolefin is present, in particular from about 1 to about 15% by weight relative to the total weight of the composition, at least one additive is also present in particular from about 1 to about 10% by weight relative to the total weight of the composition and a plasticizer in particular from about 1 to about 10% by weight based on the total weight of the composition.
• the present invention relates to one of the uses defined above wherein a polyolefin is present, in particular from about 1 to about 15% by weight relative to the total weight of the composition, an additive is also present in particular from about 0.1 to about 1% by weight relative to the total weight of the composition and a plasticizer in particular from about 1 to about 10% by weight relative to the total weight of the composition.
• the polyolefin is chosen from a maleated EPR, in particular EPR® 1801 and a Fusabond®, in particular Fusabond® 493 and the additive is a thermal stabilizer, and the plasticizer is a benzene sulphonamide derivative, such as n-butyl benzene sulfonamide (BBSA).
• EPR® 1801 a maleated EPR
• Fusabond® in particular Fusabond® 493
• the additive is a thermal stabilizer
• the plasticizer is a benzene sulphonamide derivative, such as n-butyl benzene sulfonamide (BBSA).
• the present invention relates to a viscous composition which is stable to transformation as defined above, characterized in that it comprises, relative to the total weight of the composition:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 0 to 15% of at least one plasticizer;
• the catalyst, the copper thermal stabilizer, the oligo- or polycarbodiimide, the plasticizer, the polyolefin and the additive are as defined above for use, and the various combinations and variants thereof.
• the proportions of these different constituents therefore apply to these compositions as such.
• Said composition has all the properties defined above, namely having a good melt viscosity and stable to transformation, in particular to extrusion, between 1 minute and at least 30 minutes, in particular between 1 minute and 30 minutes, and in particular said melt viscosity of said composition is substantially constant between 1 minute and at least 5 minutes, in particular between 1 minute and 5 minutes.
• Said composition also has a resistance to thermo-oxidation. It has in particular a melt viscosity of about 13000 to about 23000 Pa.s, as determined by oscillatory rheology at 270 ° C (plane), especially for at least 30 minutes, especially for 30 minutes.
• said composition has a resistance to hydrolysis.
• the term "resistance to hydrolysis” means that the half-life of the tubes (in hours) corresponds to the time after which the tubes tested after exposure to hot water or a mixture of water and ethylene glycol at 140 ° C. break, with elongation test at break according to ISO 527-2 (2012), is at least 40 days. In other words, it is the time to have 50% absolute elongation at break of the pipes.
• said composition exhibits resistance to thermoxidation and resistance to hydrolysis.
• the composition of the invention whether or not it comprises polyolefins and / or plasticizers and / or additives, has a melt viscosity of about 13000 to about 23000 Pa.s for at least 30 minutes. and regardless of the inherent viscosity of the composition free of said polyolefins, plasticizers and additives.
• compositions of the invention facilitate the extrusion of large tubes, especially for pipe gas or oil exploitation under the sea.
• the compositions of the invention are particularly stable in heat resistance and hydrolysis.
• the polyamide is chosen from PA1 1, PA12, PA 1 1 / 10.T, PA 10.10, PA 10.12 and copolyamides 1 1/12 having either more than 90% of units 1 1 or more than 90% of units 12, in particular among PA1 1, PA12, PA 1 1 / 10.T, PA 10.10 and PA 10.12
• the catalyst is chosen from phosphoric acid (HsPO 4 ), the acid phosphorus (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof
• the copper thermal stabilizer is a mixture of potassium iodide and copper iodide
• the oligo- or poly-carbodiimide is selected from a Stabilizer, in particular Stabilizer ® 9000, a Stabaxol ® , in particular a Stabaxol ® P, in particular Stabaxol ® P100 or Stabaxol ® P400, or a mixture of these.
• composition comprises:
• composition comprises or consists of:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. from 1 to 10% by weight of at least one additive.
• the additives of said composition a., B., C, d., And e. above defined are a mixture of a dye in the form of a masterbatch, a UV stabilizer, a nucleating agent and thermal stabilizers.
• composition can be in the form of granules or powder and is suitable for many applications.
• the composition comprises or consists of: a. 80.5 to 98.845% by weight of at least one polyamide as defined above;
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 1 to 15% of at least one plasticizer.
• composition comprises or consists of:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 1 to 15% of at least one plasticizer.
• the additives of said composition a., B., C, d., E. and F. above defined are a mixture of a dye in the form of a masterbatch, a UV stabilizer, a nucleating agent and thermal stabilizers.
• This composition may be in the form of granules or powders and is particularly suitable for molding parts, especially for sports.
• composition consists of:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 1 to 30% of at least one polyolefin;
• the additives of said composition a., B., A, d, e. and F. above defined are a mixture of a dye in the form of a masterbatch, a UV stabilizer, a nucleating agent and thermal stabilizers.
• composition consists of:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 1 to 30% of at least one polyolefin;
• compositions may be in the form of granules or of powder and are more particularly adapted to the extrusion of pipe gas.
• composition consists of:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 1 to 15% of at least one plasticizer;
• the additives of said composition a., B., C, d., E., F. and g. above defined are a mixture of a dye in the form of a masterbatch, a UV stabilizer, a nucleating agent and thermal stabilizers.
• composition consists of:
• vs. 0.05 to 1% by weight of at least one copper thermal stabilizer d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 1 to 15% of at least one plasticizer;
• compositions may be in the form of granules or of powder and are more particularly adapted to the extrusion of pipes for the exploitation of oil deposits under the sea or of pipe for use under a bonnet or the molding of a particular part. for Sport.
• the polyamide of the compositions of the invention is chosen from an aliphatic polyamide, a cycloaliphatic polyamide, an aromatic polyamide or a mixture thereof.
• the present invention relates to the use of a composition as defined above, for the constitution of a structure, such that:
• a flexible hose for the automobile in particular for the transportation of fuel (gasoline, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, for pipes made in particular by extrusion blow molding for the supply of air,
• fuel gasoline, diesel, biodiesel or ethanol
• refrigeration for air conditioning
• pipes made in particular by extrusion blow molding for the supply of air
• the catalyst, the copper thermal stabilizer, the oligo- or polycarbodiimide, the plasticizer, the polyolefin and the additive are as defined above for the use or the composition, and the different combinations and variants relating to the proportions of these various constituents defined above therefore apply to the use of these compositions for the constitution of said structure.
• the flexible pipe intended for the transport of gas, for the exploitation of oil deposits under the sea has a good resistance to thermo-oxidation and a resistance to hydrolysis and especially a service temperature of at least 70 ° C for 20 years.
• compositions used for the constitution of a structure which is a flexible pipe intended for the exploitation of oil deposits under the sea can also be used for the constitution of a structure which is a flexible hose for the automobile, especially for the transport of fuel (gasoline, diesel, biodiesel or ethanol), for refrigeration, for air conditioning or for pipes made in particular by extrusion blow molding for air supply.
• fuel gasoline, diesel, biodiesel or ethanol
• the present invention relates to a flexible pipe for the transport of gas or the exploitation of oil deposits under the sea, or for the automobile, in particular for the transport of fuel (gasoline, diesel, biodiesel or ethanol). ), for refrigeration, for air conditioning, for the air supply as defined above, comprising at least one layer of a composition as defined above.
• the catalyst, the copper thermal stabilizer, the oligo- or polycarbodiimide, the plasticizer, the polyolefin and the additive are as defined above for the use or the composition, and the different combinations and variants relating to the proportions of these different constituents defined above therefore apply to the pipes as such.
• the hose defined above is characterized in that said layer is the layer in contact with the fluid and the composition is as defined above for the constitution of a structure which is a flexible hose intended for the transportation of the fluid. gas.
• said pipe for transporting the gas is a single-layer pipe.
• said flexible pipe for the transport of gas is characterized in that it may further comprise at least one other layer, in particular thermoplastic.
• Said pipe may further comprise a reinforcement, in particular a reinforcement selected from a metal reinforcement, fiberglass, carbon fiber and aramid fiber.
• the flexible pipe of the invention defined above is characterized in that said layer is the inner layer of a flexible pipe intended for the exploitation of oil deposits under the sea, the composition being as defined herein. above, for the constitution of a structure that is a flexible pipe for the exploitation of oil deposits under the sea.
• Said inner layer corresponds in this case to the pipe layer 3 of the international application WO 2013/128097, that is to say the pressure sheath or sealing sheath.
• the hose defined above is characterized in that said layer is the outer layer of a flexible pipe for the exploitation of oil deposits under the sea, the composition being as defined above, for the constitution of a structure that is a flexible pipe for the exploitation of oil deposits under the sea.
• Said outer layer corresponds in this case to the layer (8) of the pipe of the international application WO 2013/128097.
• the flexible hose of the invention intended for the exploitation of oil deposits under the sea comprises an inner layer (3) defined above and an outer layer (8) defined above, said inner and outer layers being consisting of the same composition of the invention or each of a different composition of the invention.
• one of the layers (3) or (8) consisted of a thermoplastic different from that of the invention as described in WO 2013/128097, in particular another polyamide.
• the flexible pipe of the invention intended for the exploitation of oil deposits under the sea consists of layers 2/3/4/6/7/8 described in WO 2013/1 28097, the layers 3 and 8 being as defined above, and the layer 2 corresponding to the internal carcass in contact with the oil, the layer 4 corresponding to an intermediate sheath made of polyethylene or polypropylene, the layers 6 and 7 corresponding to layers of tensile armor.
• the flexible pipe of the invention intended for the exploitation of oil deposits under the sea consists of layers 2/3/4/5/6/7/8 described in WO 2013/128097, layers 2 to 4 and 6 to 8 being as defined above and the layer (5) corresponding to the pressure vault.
• the flexible pipe of the invention intended for the exploitation of oil deposits under the sea consists of the layers 30/40/50/80/90 described in application US 2009/0308478.
• Said above-defined inner layer consisting of compositions of the invention may correspond to the inner layer 30.
• Said outer layer defined above consisting of compositions of the invention may correspond to the outer layer 90 of said application US 2009/0308478.
• the flexible pipe as defined above for the automobile in particular for the transport of gasoline, for refrigeration, for air conditioning, for pipes made in particular by extrusion blow molding for the air supply, is characterized in that it comprises at least one layer consisting of a composition as defined for the constitution of a structure which is a flexible pipe for the exploitation of oil deposits under the sea.
• the pipe for the air conditioning is particularly suitable for the transport of refrigerant and in particular gas R-1234yf or 1234-ze cis or trans), used in particular in the field of automotive air conditioning or stationary air conditioning.
• R-1234yf or 1234-ze cis or trans used in particular in the field of automotive air conditioning or stationary air conditioning.
• Figure 1 shows the oscillatory rheology at 270 ° C (frequency: 10 rad / s, 5% deformation, shear 10s -1 ) from 0 to 30 minutes.
• the graph has on the abscissa the analysis time in seconds and on the ordinate the viscosity in Pa.s.
• Catalytic PA 1 1 600 ppm H 3 PO.
• Catalytic PA 1 1 600 ppm H 3 PO + 1% stabilize 9000.
• PA 12 non-catalyzed + 1% stabilize 9000 + 0.25% iodine 201.
• PA 1 1 uncatalysed + 1% stabilize 9000.
• Catalytic PA 1 1 (600 ppm H 3 PO) + 0.25% iodine 201.
• PA 1 1 uncatalyzed.
• PA1 1 BESNO marketed by Arkema
• PA12 AESNO marketed by Arkema
• PA10.10 marketed by Arkema: Hiprolon 200
• PA10.12 sold by Arkema: Hiprolon 400
• the copper-based thermal stabilizer is PolyAdd P201 from Polyad Services (iodine 201).
• the carbodiimide used is Stabiliser® 9000 (Poly- (1,3,5-triisopropylphenylene-2,4-carbodiimide) marketed by Raschig or TCC marketed by Teijin.
• the catalyst used is H 3 PO 3 or H 3 PO 4 .
• ANOX®NDB TL89 organic stabilizer phenol phosphite type marketed by Chemtura.
• BBSA n-butylbenzenesulfonamide marketed by PROVIRON EPR 1801: polyolefin (ethylene functional copolymer maleic anhydride) marketed by Exxon.
• Fusabond® 493 polyolefin (anhydride functionalized ethylene copolymer) marketed by DuPont.
• Example 1 Determination of the melt viscosity of polyamides of the inventions with or without a catalyst in the presence or absence of a copper stabilizer and / or a carbodiimide
• the flat temperature profile at 270 ° C is programmed.
• the various mixtures are made with a screw speed of 100 rpm and a recirculation time of 25 minutes, to which must be added the machine feeding time is between 30 and 2 '.
• the tests are carried out under a nitrogen sweep (0.5 bar).
• the normal force is measured in N. It represents the evolution of the viscosity in the molten state.
• the viscosity at T0 and its evolution at T + 30 minutes are determined by oscillatory rheology in plane plane.
• Atmosphere Nitrogen sweep.
• Example 1.1 PA 11, PA 12 and PA 10.10 without catalyst: with or without copper and / or carbodiimide-based thermal stabilizer
• the melt viscosity is determined at T0 and after 30 minutes.
• the inherent viscosity is determined in m-cresol according to ISO 307- 2007.
• a PA1 1, without catalyst, of relatively high inherent viscosity (1.45, extrusion grade) is not viscous enough either with copper stabilizer alone or with copper stabilizer and carbodiimide.
• a PA12 (AESNO from ARKEMA company without chain limiter), without catalyst, of high inherent viscosity (1, 6) is not viscous enough even with addition of copper stabilizer and carbodiimide.
• carbodiimide provides a rise in melt viscosity which, however, is not sufficient for product conversion.
• An average inherent viscosity PA10.10 (1, 35) is too fluid whether with a copper stabilizer supplemented or not with carbodiimide.
• Example 1.2 PA 11, PA 10.10 and PA 10.12 with catalyst: with or without copper and / or carbodiimide-based thermal stabilizer
• a PA1 1 of relatively high inherent viscosity (1.45, extrusion grade) is sufficiently viscous in the molten state at T0 (ie melt viscosity greater than or equal to about 13000 Pa.s) but too evolutionary since the melt viscosity is well above 23,000 Pa.s).
• Carbodiimide - - 1% stabilize 9000 plan plan 270 ° c
• a PA10.10 of inherent viscosity of 1.45 comprising only one catalyst is not sufficiently viscous in the molten state at T0 (ie, a melt viscosity of less than 13000 Pa.s).
• thermo stabilizer does not achieve a sufficient melt viscosity.
• thermo stabilizer and carbodiimide makes it possible not only to obtain a melt viscosity greater than or equal to about 13,000 Pa.s but also to be stable for at least 30 minutes.
• melt viscosity at TO is too low (less than 13000 Pa.s).
• thermo stabilizer does not achieve a sufficient melt viscosity.
• the polyamide used for all the tests of this example is PA 1 1 of inherent viscosity 1, 45 as above.
• Example 2.2 The polyamide used for all the tests of this example is PA 1 1.
• Example 3 Evaluation of the compositions of the invention further comprising polyolefins and / or plasticizers and / or additives: Thermal resistance at 140 ° C.
• the proportions indicated are percentages by weight relative to the total weight of the composition.
• PA base is dried ( ⁇ 0.1% moisture)
• the half life measured on the elongation at break increases from 30 days for the comparative composition 1 (PA 11 + 600 ppm of catalyst), which does not include no thermal stabilizer and carbodiimide at 90 days for a composition of the invention comprising both a catalyst (same proportion as Comparative 1), a copper stabilizer and a carbodiimide.

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• 2014
  • 2014-11-05 FR FR1460666A patent/FR3027907B1/fr active Active
• 2015
  • 2015-11-05 EP EP15808709.8A patent/EP3215562B1/fr active Active
  • 2015-11-05 JP JP2017542349A patent/JP2018502206A/ja active Pending
  • 2015-11-05 WO PCT/FR2015/052987 patent/WO2016071638A1/fr not_active Ceased
  • 2015-11-05 US US15/522,805 patent/US11377536B2/en active Active
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