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    • 专利摘要:
    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, to constitute a composition having a good melt viscosity and stable to processing, in particular to extrusion.
    公开号:FR3027907A1
    申请号:FR1460666
    申请日:2014-11-05
    公开日:2016-05-06
    发明作者:Philippe Blondel；Patrick Dang；Francois Fernagut；Jean-Jacques Flat；Fabrice Glasson
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the use of at least one catalyst, at least one copper thermal stabilizer and at least one oligo- or at least one oligo- or at least one oligo- or at least one oligo- or at least one oligosilicon. polycarbodiimide with a matrix comprising at least one thermoplastic polymer, especially a polyamide, to form a viscous composition which is stable to processing, in particular to 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 hose for transporting gas, the exploitation of oil deposits under the sea, a flexible hose for the automobile, in particular for the transport of fuel (petrol, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, for pipes made in particular by extrusion blow molding for air supply, a hollow body, a molding or sports article. The invention also relates to the structures obtained from said compositions.
    [0002] The exploitation of oil deposits located at sea subjects extreme conditions to the materials used, and in particular the pipes connecting the various underwater devices of the platform and conveying the extracted hydrocarbons, which are generally transported at high temperature and high pressure (eg 700 bar).
    [0003] During the operation of the installations, there therefore arise acute problems of mechanical, thermal and chemical resistance of the materials used. 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. In conventional manner, 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 layer of polymer for sealing. Other protective and / or reinforcing layers such as metal fiber webs, thermoplastics and rubbers may also be arranged around the sealed polymer layer. For operating temperatures below 40 ° C, the polymer is HDPE (crosslinked high density polyethylene) or not. For temperatures above 40 ° C., polyamide is used and, for temperatures above 90 ° C., PVDF (polyvinylidene fluoride) is used. Given the high cost of PVDF, and despite the involvement of higher temperatures than those recommended, the choice of the polymer was focused on polyamides, such as PA11 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. These polyamides are already commonly used for the manufacture of pipes intended to convey hydrocarbons extracted from oil deposits located under the sea (offshore) or not (on-shore) but have the disadvantage of aging too quickly. To overcome this disadvantage and thus improve the aging resistance of these polyamide-based pipes, the document US 2003/0220449, in the name of the Applicant, proposes a composition comprising a mixture of PA, plasticizer and an elastomer. selected from nitrile butadiene rubber (NBR) and hydrogenated nitrile butadiene rubber (H-NBR). The use of an elastomer of the NBR or H-NBR type in the compositions described in US 2003/0220449 has several advantages over prior compositions based solely on polyamide and plasticizer.
    [0004] In particular, the introduction of one or other of these elastomers makes it possible to significantly increase the resistance to aging of the flexible pipes comprising such a layer, in particular by limiting the weight content of plasticizer.
    [0005] However, the H-NBR elastomers (or hydrogenated NBRs) have a high cost and require, like their non-hydrogenated NBR counterparts, moreover, to carry out a preliminary milling step, adding a further cost to that already generated by the NBR raw material. or H-NBR. To overcome the above disadvantages, the Applicant 10 describes in WO 08/122743 the use of a composition comprising at least one semicrystalline polyamide, a functionalized polyolefin and a plasticizer for the manufacture of flexible tubes used especially for the exploitation of oil or gas deposits. On the other hand, the extrusion of large diameter pipes for these applications requires compositions having high melt viscosities but also a processing stability (the residence time of the product during its extrusion is at least 5 min or 300 seconds), as well as resistance to thermo-oxidation. To obtain this type of viscosity, phosphoric catalysis makes it possible, under certain conditions (catalytic rate, vacuum, humidity), to arrive there, but the product can continue to evolve during processing. In addition, this post reactivity is sensitive to the residual moisture of the granules. To remedy this, the application US 2013/0171388 describes PA materials with chain extenders (Bruggolen® and / or Stabaxo1,0). Nevertheless, these compositions also have high polymolecularity indices and therefore a large number of branches, which results in obtaining high viscosities in solution. However, the higher the viscosity in solution, the higher the pressures and torques on the extruders, but also the lower the viscosity in the melt. Thus the viscosity in solution is not representative of the melt viscosity due to the potential connections in the polyamide.
    [0006] Furthermore, the current polyamide compositions generally allow only a pipe operating temperature of 60 ° C. to 70 ° C. depending on the pH or the total acid number (TAN) of the fluid transported and on the criterion of acceptance used.
    [0007] There is therefore a need to find a compromise between these different parameters and to increase the operating temperature of the pipes. 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 transport of fuel (petrol, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, for pipes made in particular by extrusion blow molding for the supply of fuel. Another object of the invention is the provision of hoses above defined. 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, to constitute a composition having a good viscosity in the molten state and stable to the transformation. The inventors have found quite unexpectedly that the combination of three elements, namely a catalyst, a copper thermal stabilizer and an oligo- or poly-carbodiimide, in combination with a thermoplastic polymer, in particular a polyamide, allowed to obtain compositions which have good viscosities, that is to say melt viscosities that are high enough to be able to be transformed, in particular by extrusion, without increasing the viscosity in solution, in other words the inherent viscosity, said melt viscosity being otherwise sufficiently stable during processing, especially for extrusion. The melt viscosity is determined by oscillatory rheology at 270 ° C at 10 rad / sec under nitrogen sweep with 5% deformation and 10 sec-1 shear on a Physica MCR301 between two parallel planes of 25 mm diameter.
    [0008] The inherent viscosity is determined according to ISO 307-2007 but in m-cresol instead of sulfuric acid, the temperature being 20 ° C. The term "process stable" means that the 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. Advantageously, the melt viscosity of said composition is substantially constant between 1 minute and at least 5 minutes, in particular between 1 minute and 5 minutes.
    [0009] By "substantially constant" is meant that the 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.
    [0010] Advantageously, said composition also has a resistance to thermo-oxidation. The term "resistance to thermo-oxidation" is characterized by the half-life (in hours) of materials. It corresponds to the time at which the ISO 527-2 1BA test pieces, aged in air at 140 ° C, lost half of their initial elongation at break measured according to ISO 527-2 (2012).
    [0011] Advantageously, the resistance to thermoxidation is at least 80 days, in particular 100 days. Advantageously, 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. Advantageously, 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 inventors have therefore found quite unexpectedly that 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. Catalyst: The term "catalyst" refers to a polycondensation catalyst such as an inorganic or organic acid. Advantageously, 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. Advantageously, 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. Advantageously, the present invention therefore 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 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 (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof. Advantageously, 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. Copper stabilizer: A well-known example is the mixture of Cul and KI, 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. Further details on copper stabilizers can be found in US Patent 2,705,227. Advantageously, 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 / K1). Advantageously, 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. Preferably, the copper thermal stabilizer is a mixture of potassium iodide and copper iodide (KI / Cul). Preferably, the mixture of potassium iodide and copper iodide useful according to the present invention is in a ratio of 90/10 to 70/30. Further details on copper stabilizers can be found in US Patent 2,705,227. Advantageously, 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 (KI / Cul), preferably in a ratio of 90/10 to 70/30. Advantageously, 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 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 (H3PO4), 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 / Cul), preferably in a ratio of 90/10 to 70/30. Advantageously, 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.
    [0012] Carbodiimide: Carbodiimide represents a classically known carbodiimide oligomer and 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.
    [0013] Chem. Soc. 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. Alternatively, 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 5: R 1 -N = C = N (-R 2 -N = C = N -) - R 3 in which R 1 and R 3 represent C 1 -C 20 alkyls, cycloalkyls C5 to C20, aryls having 6 to 20 carbon atoms or aralkyls having 7 to 20 carbon atoms, each optionally substituted with an isocyanate group optionally comprising CH, NH or an OH reactive compound; 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 2,4-1,3,5-diisocyanato 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 may also be cyclic. Suitable oligo and polycarbodiimides can be obtained from commercially available sources such as Rhein Chem, Raschig, Ziko or Teijin. Advantageously, 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% by weight relative to total weight of the composition. Advantageously, the oligo- or poly-carbodiimide is chosen from a Stabilizer, in particular Stabilizee 9000, a Bruggolere, a Stabaxor, in particular a Stabaxol® P, in particular Stabaxol P100 or Stabaxol® P400, or a mixture of these.
    [0014] Advantageously, the present invention therefore relates to the above-defined use 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, in particular a polyamide, said oligo or polycarbodiimide being chosen from a Stabilizer, in particular Stabilizee 9000, a Bruggolere, a Stabaxor, in particular a Stabaxol® P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture thereof. Advantageously, the present invention relates to the above-defined use of at least one catalyst, in the proportion by weight of catalyst of from about 50 ppm to about 5000 ppm, particularly 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 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, in particular a polyamide, said catalyst being chosen from phosphoric acid (H 3 PO 4), phosphorous acid (H 3 PO 3), hypophosphorous acid (H 3 PO 2), or a mixture thereof and said oligo- or poly-carbodiimide being selected from a stabilizer, in particular Stabilizee 9000, a Bruggolere, a Stabaxor, in particular a Stabaxol ° P, in particular Stabaxol ° P100 or Stabax ol ° P400, or a mixture thereof. Advantageously, the catalyst is chosen from phosphoric acid (H 3 PO 4) and phosphorous acid (H 3 PO 3) in an amount of from about 100 to about 3000 ppm. Advantageously, 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%, particularly 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 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, in particular a polyamide, said copper thermal stabilizer being a mixture of iodide of potassium and copper iodide (KI / Cul), preferably in a ratio of 90/10 to 70/30 and said oligo- or polycarbodiimide being selected from a Stabilizer, in particular the Stabilizer 9000, a Bruggolere, a Stabaxol , especially Stabaxol® P, in particular Stabaxol P100 or Stabaxol P400, or a mixture thereof i.
    [0015] Advantageously, the present invention therefore 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 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 about 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 (H 3 PO 4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof, said stabilizer wherein the copper thermal is a mixture of potassium iodide and copper iodide (KI / Cul), preferably in a ratio of 90/10 to 70/30, said oligo- or poly-carbodiimide being selected from among a stabilizer, especially Stabilizee 9000, a Bruggolere, a Stabaxol, in particular stabaxol ° P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture thereof.
    [0016] Advantageously, 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.
    [0017] The thermoplastic polymer As regards the thermoplastic polymer, it may be chosen from polyamides and polyamide mixtures. The nomenclature used to define polyamides is described in ISO 1874-1: 1992 "Plastics - Polyamides (PA) for molding and extrusion - Part 1: Designation", particularly on page 3 (Tables 1 and 2) and is well known to those skilled in the art. The polyamide according to the present invention may have a homopolyamide or copolyamide structure. By homopolyamide, within the meaning of the present invention, is meant a polyamide, which consists only of the repetition of a single unit. For the purposes of the present invention, the term "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 selected from amino acids, lactams and (diamine) units (diacid). When the polyamide has an amino acid in its structure, it may be selected from 9-aminononanoic acid (A = 9), 10-aminodecandic acid (A = 10), 10-aminoundecanoic acid (A = 11 ), 12-aminododecanoic acid (A = 12) and 11-aminoundecanoic acid (A = 11) and its derivatives, especially N-heptyl-11-aminoundecanoic acid, where A denotes the number of carbon in the pattern. When the polyamide comprises a lactam, it may be selected from pyrrolidinone, 2-piperidinone, caprolactam, enantholactam, caprylolactam, pelargolactam, decanolactam, undecanolactam, and lauryllactam (A = 12). When the polyamide comprises a unit corresponding to the formula (diamine in Ca), (diacid in Cb) Ca and Cb denoting the number of carbon atoms in the diamine and the diacid respectively, the unit (diamine in Ca) is selected from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines. When the diamine is aliphatic and linear, of formula 1-12N- (CI-12), - NI-12, the monomer (diamine Ca) is preferably selected from butanediamine (a = 4), pentanediamine (a = 5 ), hexanediamine (a = 6), heptanediamine (a = 7), octanediamine (a = 8), nonanediamine (a = 9), decanediamine (a = 10), undecanediamine (a) = 11), dodecanediamine (a = 12), tridecanediamine (a = 13), tetradecanediamine (a = 14), hexadecanediamine (a = 16), octadecanediamine (a = 18), octadecenediamine ( a = 18), eicosanediamine (a = 20), docosanediamine (a = 22) and diamines obtained from fatty acids. When the diamine is aliphatic and branched, it may have one or more methyl or ethyl substituents on the main chain. For example, the monomer (Ca-diamine) may advantageously be selected from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3-trimethyl-1,6-hexanediamine, diaminopentane, 2-methyl-1,5-pentanediamine, 2-methy1-1,8-octanediamine. When the monomer (diamine in Ca) is cycloaliphatic, it is chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3 5-dialkyl-4-aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis- (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM), p-bis (aminocyclohexyl) methane (PACM) and isopropylidenedi (cyclohexylamine) (PACP), isophoronediamine (a = 10), piperazine (a = 4), amino-ethylpiperazine. It may also comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane. A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405).
    [0018] When the monomer (Ca diamine) is alkylaromatic, it is chosen from 1,3-xylylene diamine and 1,4-xylylenediamine.
    [0019] The (Cb diacid) unit is chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids. When the monomer (Cb diacid) is aliphatic and linear, it is chosen from succinic acid (b = 4), pentanedioic acid (b = 5), adipic acid (b = 6), and heptanedioic acid (b = 7), octanedioic acid (b = 8), azelaic acid (b = 9), sebacic acid (b = 10), undecanedioic acid (b = 11), dodecanedioic acid (b = 12), brassylic acid (b = 13), tetradecanedioic acid (b = 14), hexadecanedioic acid (b = 16), octadecanedioic acid (b = 18), octadecenedioic acid (b = 18), eicosanedioic acid (b = 20), docosanedioic acid (b = 22) and fatty acid dimers containing 36 carbons. The fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of long chain unsaturated hydrocarbon-based monobasic fatty acids (such as linoleic acid and oleic acid), as described in particular in US Pat. EP 0 471 566. When the diacid is cycloaliphatic, it may comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane. When the diacid is aromatic, it is selected from terephthalic acid (noted T), isophthalic acid (noted I) and naphthalenic diacids. Advantageously, the thermoplastic polymer is a polyamide selected from an aliphatic polyamide, a cycloaliphatic polyamide, an aromatic polyamide or a mixture thereof. Advantageously, the polyamide has a Tf of 160 ° C to 290 ° C determined according to ISO 11357-3 (2013). Advantageously, the proportion of polyamide is from about 95.5 to about 99.845%. Preferably, the useful polyamide according to the invention is chosen from PA 6, PA 11, PA 12, PA 6.10, PA 6.6, PA 6.12, PA 10.10, PA 10.12, PA 11 / 10.T, PA 11 / 6.T , 12 / 10.T, 6.10 / 10.T, 6.12 / 10.T, 10.10 / 10.T, 10.12 / 10.T, 11 / 6.T / 10.T, 12.12 / 10.T, 12 / 6.10 /10.T, 12 / 6.12 / 10.T, 12 / 10.10 / 10.T, 12 / 10.12 / 10.T and 12 / 12.12 / 10.T.
    [0020] Advantageously, the polyamide is chosen from: PA11, PA12, PA 11 / 10.T, PA 10.10, PA 10.12 and copolyamides 11/12 having either more than 90% of units 11 or more than 90% of patterns 12, preferably among PA 11, PA 12, PA 11 / 10.T, PA 10.10 and PA 10.12.
    [0021] The polyolefin Advantageously, the 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 non-functionalized. For simplicity, functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below. The functionalized polyolefin (B1) may be chosen from the following (co) polymers, grafted with maleic anhydride, in which the degree of grafting is, for example, from 0.01 to 5% by weight: PE, PP, copolymers of ethylene with propylene, butene, hexene or octene containing, for example, from 35 to 80% by weight of ethylene; ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM). Styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS). ethylene-vinyl acetate copolymers (EVA), containing up to 40% by weight of vinyl acetate; Ethylene and alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate; ethylene and vinyl acetate (EVA) and alkyl (meth) acrylate copolymers containing up to 40% by weight of comonomers. maleated polyolefins such as TAFMEle MH5020, TAFMEle 610MP and TAFMEle MD715. 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. By way of example of functionalized polyolefins of the latter type, mention may be made of the following copolymers, in which ethylene is preferably at least 60% by weight and in which the monomer ter (the function) represents, for example, from 0.1 to 10% by weight of the copolymer: ethylene / alkyl (meth) acrylate / (meth) acrylic acid or maleic anhydride copolymers; ethylene / vinyl acetate / maleic anhydride copolymers; ethylene / vinyl acetate copolymers or alkyl (meth) acrylate / (meth) acrylic acid or maleic anhydride copolymers. The term "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, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate. The copolymers mentioned above, (B1) and (B2), can be copolymerized randomly or sequentially and have a linear or branched structure.
    [0022] The molecular weight, the MFI index and the density of these polyolefins 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. Advantageously, 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. We can cite, for example, 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 "metallocene" catalysis.
    [0023] Advantageously, 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. Examples of such 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 the Orevacede of the Applicant and ter polymers of ethylene, alkyl acrylate and (meth) acrylic acid. The additives The 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 dye, a fluorinated agent and a lubricant. , a stearate such as zinc stearate or calcium stearate or magnesium stearate, and another polyamide, catalyzed or otherwise, different from that used above. It should be noted that said thermal stabilizer is different from the copper thermal stabilizer described above and therefore does not contain copper. The thermal stabilizer may be an organic stabilizer or, more generally, a combination of organic stabilizers, such as a phenol-type primary antioxidant (for example of the type of Irganox 245 or 1098 or 1010 from BASF), a secondary antioxidant of phosphite type and possibly other stabilizers such as HALS, which means Hindered Amine Light Stabilizer or hindered amine light stabilizer (eg Tinuvin 770 from BASF), an anti-UV (eg Tinuvire 312 from BASF), a phenolic or phosphorus stabilizer. It is also possible to use amine antioxidants such as Naugare 445 (4,4'-Bis (α, α-dimethylbenzyl) diphenylamine) from Crompton, Flexamine from Addivant or polyfunctional stabilizers such as Nylostab S. -EED of the company Clariant.
    [0024] Advantageously, 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. . Advantageously, 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. Advantageously, the polyolefin is chosen from a maleated EPR, in particular EXXELOe VA 1801 and EXXELOe VA1803 sold by ExxonMobil, a Fusabond, in particular Fusabond 493 from DuPont, and TAFMEe MH5020, TAFMEe 610MP and the MD715 TAFMEe from MitsuiChemicals. Advantageously, 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%. Advantageously, the present invention relates to one of the above-defined uses in which an additive is also present, in particular from about 0.1 to about 1% by weight based on the total weight of the composition. Advantageously, the additive is a thermal stabilizer. Advantageously, 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 25 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 relative to the total weight of the composition. Advantageously, 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 based on the total weight of the composition and an additive is also present in particularly from about 0.1 to about 1% by weight based on the total weight of the composition.
    [0025] Advantageously, 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. Plasticizers As regards the plasticizer, it is chosen from benzene sulphonamide derivatives, such as n-butyl benzene sulphonamide (BBSA) or N- (2-hydroxypropyl) benzenesulfonamide (HP-BSA) from Proviron, ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide from Sigma-Aldrich; esters of hydroxybenzoic acids, such as ethyl-2-hexyl parahydroxybenzoate (EHPD) from Ueno Fine Chemicals and decyl-2-hexyl parahydroxybenzoate (HD-PB) from Kao; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxytetrahydrofurfurylalcohol; and 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. Advantageously, the plasticizer used is a benzene sulphonamide derivative, such as n-butyl benzene sulphonamide (BBSA). Advantageously, 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.
    [0026] Advantageously, 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 relative to the total weight of the composition.
    [0027] Advantageously, 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. Advantageously, the polyolefin is chosen from a maleated EPR, in particular EPFe 1801 and a Fusabond, in particular Fusabond 493 and the additive is a thermal stabilizer, and the plasticizer is a benzene sulfonamide derivative, such as n-butyl benzene sulfonamide (BBSA). COMPOSITIONS According to another aspect, the present invention relates to a viscous composition which is stable to transformation as defined above, characterized in that it comprises, with respect to the total weight of the composition: a. 20.5 to 99.845% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 0 to 30% of at least one polyolefin; boy Wut. 0 to 30% of at least one additive.
    [0028] In this aspect, apart from the proportion of polyamide present in the composition which is limited from 20.5 to 99.845% by weight relative to the total weight of the composition, the catalyst, the copper thermal stabilizer, the polyol carbodiimide, the plasticizer, the polyolefin and the additive are as defined above for use, and the various combinations and variants relating to the proportions of these different constituents therefore apply to these compositions as such.
    [0029] 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. Advantageously, 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. Advantageously, said composition exhibits resistance to thermoxidation and resistance to hydrolysis.
    [0030] Thus, 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. The compositions of the invention make it possible to facilitate the extrusion of large tubes, in particular for pipe gas or the exploitation of oil under the sea. In addition, the compositions of the invention are particularly stable in heat resistance and in 'hydrolysis.
    [0031] Advantageously, the polyamide is chosen from PA11, PA12, PA 11 / 10.T, PA 10.10, PA 10.12 and copolyamides 11/12 having either more than 90% of units 11 or more than 90% of units. 12, in particular from PA1 1, PA12, PA 11 / 10.T, PA 10.10 and PA 10.12, the catalyst is chosen from phosphoric acid (H 3 PO 4), phosphorous acid (H 3 PO 3), 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 among a stabilizer, particularly Stabilizee 9000, a Bruggolere, a Stabaxor, in particular Stabaxol® P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture thereof. Advantageously, the composition comprises: a. 95.5 to 99.845% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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. More preferably, said composition comprises or consists of: a. 85.5 to 98.845% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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. Advantageously, 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. This composition can be in the form of granules or powder and is suitable for many applications.
    [0032] Advantageously, the composition comprises or consists of: a. 80.5 to 98.845% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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.
    [0033] More preferably, said composition comprises or consists of: a. 70.5 to 97.845% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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. f. 1 to 10% by weight of at least one additive.
    [0034] Advantageously, 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.
    [0035] Advantageously, the composition consists of: a. 55.5 to 98.745% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 0.1 to 10% of at least one additive. Advantageously, 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.
    [0036] Advantageously, the composition consists of: a. From 64.5 to 98.745% by weight of at least one polyamide as defined above; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 0.1 to 1% of at least one additive. These last two compositions may be in the form of granules or of powder and are more particularly adapted to the extrusion of pipe gas. Advantageously, the composition consists of: a. 40.50 to 97.745% by weight of at least one polyamide as defined in claim 12 to 14; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 1 to 30% of at least one polyolefin; boy Wut. 0.1 to 10% of at least one additive. Advantageously, 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. Advantageously, the composition consists of: a. 49.50 to 97.745% by weight of at least one polyamide as defined in claim 12 to 14; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 1 to 30% of at least one polyolefin; boy Wut. 0.1 to 1% of at least one additive.
    [0037] These latter two 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.
    [0038] Advantageously, the polyamide of the compositions of the invention is chosen from an aliphatic polyamide, a cycloaliphatic polyamide, an aromatic polyamide or a mixture thereof. According to another aspect, the present invention relates to the use of a composition as defined above, for the constitution of a structure, such as: a hose for transporting the gas, to the exploitation of oil deposits under the sea, a flexible hose for the automobile, in particular for the transport of fuel (petrol, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, for pipes carried out in particular in extrusion blowing for air supply, a hollow body, a molding or a sporting article.
    [0039] According to this aspect, as 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 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 resistance to hydrolysis and in particular an operating temperature of at least 70 ° C. for 20 years.
    [0040] Advantageously, the 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. STRUCTURE In another aspect, 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.
    [0041] According to this aspect, as 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.
    [0042] Advantageously, 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. Advantageously, said pipe for transporting the gas is a monolayer pipe. Advantageously, 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 furthermore comprise a reinforcement, in particular a reinforcement chosen from a metal reinforcement, made of fiberglass, carbon fiber and aramid fiber. Advantageously, the hose of the invention defined above is characterized in that said layer is the inner layer of a flexible pipe for the exploitation of oil deposits under the sea, the composition being as defined herein. above, for the constitution of a structure which is a flexible pipe for the exploitation of oil deposits under the sea.
    [0043] The structure of pipes intended for the exploitation of oil deposits under the sea is described in particular in International Application WO 201 3/1 28097 and corresponds in particular to the pipe comprising layers 2 to 8 of FIG. 1 of said international application WO 2013/128097.
    [0044] 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. Advantageously, 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.
    [0045] Advantageously, the flexible pipe 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.
    [0046] It would not be departing from the scope of the invention if 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. Advantageously, the flexible pipe of the invention intended for the exploitation of oil deposits under the sea consists of the 2/3/4/6/7/8 layers described in WO 2013/128097, the layers 3 and 8 being such 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 of polyethylene or polypropylene, the layers 6 and 7 corresponding to layers of tensile armor.
    [0047] Advantageously, 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. Advantageously, 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 5 described in the application US 2009/0308478. Said inner layer defined above 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 the said application US 10 2009 / 0308478. The other layers are as defined in the application US 2009/0308478. Advantageously, the flexible hose 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 supply of air, 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 the 20 oil deposits under the sea. 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. The description will now be illustrated with the aid of the following examples which are not however limiting of the invention. DESCRIPTION OF THE FIGURES FIG. 1 shows the oscillatory rheology at 270 ° C (frequency: 10 rad / s, 5% deformation, shear 10s-1) from 0 to 30 minutes.
    [0048] The graph has on the abscissa the analysis time in seconds and on the ordinate the viscosity in Pa.s. At 1800 seconds, from top to bottom: catalyzed PA 11 (600 ppm H 3 PO 4).
    [0049] Catalyzed PA 11 (600 ppm H 3 PO 4) + 1) stabilize 9000. PA 11 catalyzed (600 ppm H 3 PO 4) + 1) stabilize 9000 + 0.25% iodine 201: curve of the invention, the only one having a ciscosity of between 13000 and 23000 Pa.s. PA 12 non-catalyzed + 1% stabilize 9000 + 0.25% iodine 201.
    [0050] PA 11 non-catalyzed + 1`) / 0 stabilize 9000. PA 11 catalyzed (600 ppm H3PO4) + 0.25% iodine 201. PA 11 uncatalyzed. Examples Products used The polyamides used are PA11 (BESNO marketed by Arkema), PA12 (AESNO marketed by Arkema), PA10.10 (marketed by Arkema: Hiprolon 200) and PA10.12 (marketed by the company). Arkema: Hiprolon 400) The copper-based thermal stabilizer is PolyAdd P201 from Polyad Services (iodine 201). The carbodiimide used is Stabilizer 9000 (Poly- (1,3,5-triisopropylphenylene-2,4-carbodiimide) marketed by Raschig The catalyst used is H3PO3 or H3PO4.
    [0051] 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.
    [0052] 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 tests (mixing of PA with or without a catalyst to which a copper stabilizer and / or a carbodiimide are added or not) are made on Xplore MC15 micro-compounder equipped with screws 111 and 123 (screw profile 2). 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 feed time is between 1'30 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 TO and its evolution at T + 30 minutes are determined by oscillatory rheology in plane plane. Plan: 30 min at 270 ° c 10 rad / sec 5% deformation according to the following operating conditions Device: PHYSICA MCR301 Geometry: parallel planes of 25mm diameter 20 Temperature: 270 ° C Frequency: 10rad.s-1 Duration: 30 minutes Atmosphere: Nitrogen sweep. Shear of 10s Example 1.1: PA 11, PA 12 and PA 10.10 without catalyst: with or without copper and / or carbodiimide thermal stabilizer Percentages are by weight. The melt viscosity is determined at TO and after 30 minutes. The inherent viscosity is determined in m-cresol according to ISO 307- 2007.
    [0053] The method is well known to those skilled in the art. ISO 3072007 is followed but the solvent is changed (use of m-cresol in place of sulfuric acid and the temperature is 20 ° C). PA11 PA11 PA11 Inherent viscosity 1.45 1.45 1.45 Catalyst - - - Thermal stabilizer - 0.25% iodine 201 0.25% iodine 201 with Copper Carbodiimide - - 1`) / 0 stabilize 9000 plan plane 270 ° c Pa. s Pa.s Pa.s 10radisec (melt viscosity) TO 384 No REV 5350 After 30 min 807 No REV 5278 Note Too fluid Too fluid Too fluid "No REV" means there is no fluid. no rise in viscosity. A PA11, 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.
    [0054] The addition of 0.25% iodine 201 does not increase the viscosity. The addition of carbodiimide provides a rise in melt viscosity which, however, is not sufficient for product conversion. PA12 PA12 Inherent viscosity 1.60 1.60 catalyst - - Thermal stabilizer - 0.25% iodine 201 to copper Carbodiimide - 1`) / 0 stabilize 9000 plan plane 270 ° c Pa.s Pa.s 10radisec (viscosity in the molten state ) TO 7152 9000 After 30 min 7800 10000 Note Too fluid Too fluid A PA12 (AESNO from ARKEMA without chain limiter), without catalyst, with high inherent viscosity (1.6) is not viscous enough even with addition of copper stabilizer and carbodiimide. The addition of carbodiimide provides a rise in melt viscosity which, however, is not sufficient for product conversion. PA10.10 PA10.10 PA10.10 Inherent viscosity 1.35 1.35 1.35 catalyst - - - Stabilizer - 0.25% iodine 0.25% copper thermal iodine 201 201 Carbodiimide - - 1% stabilize 9000 plan plane 270 ° c Pa .s Pa.s Pa.s 10radisec (melt viscosity) TO 1650 REV 7685 After 30 min 2648 REV 9635 Note Too much fluid Too fluid Too fluid An average inherent viscosity PA10.10 (1.35 ) is too fluid whether with copper stabilizer supplemented or not with carbodiimide.
    [0055] Therefore, the problem of melt viscosity can not be solved by increasing the inherent inherent viscosity. Example 1.2: PA 11, PA 10.10 and PA 10.12 with catalyst: with or without copper and / or carbodiimide thermal stabilizer The percentages are given by weight. PA11 PA11 catalyzed PA11 catalysed Inner viscosity 1.45 1.45 1.45 catalyst 600 ppm H3PO4 600 ppm H3PO4 600 ppm H3PO4 Thermal stabilizer - 0.25% iodine 201 0.25% iodine 201 to copper Carbodiimide - - 1% stabilize 9000 plane 270 ° plane c Paid Pa.s Pa.s 10radisec (melt viscosity) 302 790 7 33 TO 13500 1550 19000 After 30 minutes 30000 7300 23000 Remarks Evolution after 400 sec Evolution after 30 mn Too evolutive Too fluid Invention 21000 ie 5 % ± 55% 148% 22% A PA11 of relatively high inherent viscosity (1.45; extrusion grade) is sufficiently viscous in the molten state at TO (ie, a melt viscosity greater than or equal to about 13000 Pa). . $) but too evolutionary since the viscosity in the molten state is very clearly greater than 23000 Pa. $). The addition of a thermal stabilizer to catalyzed PA11 does not improve the viscosity, on the contrary since it drops drastically, stopping even the revolution. On the other hand, the addition of a thermal stabilizer and carbodiimide not only makes it possible to obtain a melt viscosity greater than or equal to about 13,000 Pa.s but also stable for at least 30 minutes. PA10.10 PA10.10 PA10.10 Inherent viscosity 1.45 1.45 1.45 catalyst 2000 ppm H3PO4 2000 ppm H3PO4 2000 ppm H3PO4 Thermal stabilizer - 0.2% iodine 201 0.2% iodine 201 to copper Carbodiimide - - 1`) / 0 stabilize 9000 plan plane 270 ° c Pa.Pa. Pa. 10radisec (melt viscosity) TO 9369 10200 13357 After 30 min 12805 16400 20313 Note Evolution after 30 mn Too fluid Too fluid invention 52% 15 Un PA10.10 of inherent viscosity of 1.45 comprising only one catalyst is sufficiently viscous in the molten state at TO (ie a melt viscosity less than 13000 Pa. $).
    [0056] The addition of a thermal stabilizer does not achieve a sufficient melt viscosity. On the other hand, the addition of a thermal 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. PA10.12 PA10.12 PA10.12 Inner viscosity 1.4 1.4 1.4 catalyst 100 ppm H3PO3 100 ppm H3PO3 100 ppm H3PO3 Stabilizer - 0.2% iodine 201 0.2% iodine 201 thermal copper Carbodiimide - - 1% stabilize 9000 plan plane 270 ° c Pa.Pa.Pa.s 10radisec (melt viscosity) TO 6156 9000 17653 After 30 minutes 27558 17000 19772 Note Evolution after 30 mn Too much fluid and Too much fluid and Invention evolutive too evolutive 347% 89% 12% In the same way, with a PA10.12 of inherent viscosity of 1.4 comprising only a catalyst, the melt viscosity at TO is too low (less than 13000 Pa. ). The addition of a thermal stabilizer does not achieve a sufficient melt viscosity.
    [0057] On the other hand, the addition of a thermal 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. Example 2: Influence of the presence of catalyst and the proportion of a copper stabilizer and / or carbodiimide on the rheological properties of the polyamides of the invention.
    [0058] Example 2.1 Percentages are by weight. The polyamide used for all the tests of this example is PA 11 with an inherent viscosity of 1.45 as above.
    [0059] Catalyst Stabilizer Carbodiimide Rheology Stability viscosity (ppm) thermal% by weight copper (lodine 201)% by weight 0 0 0 - ++ 0 0 1 - ++ 0 0 1,5 + + 0 0 2 + + 600 0 0 + - 600 0 1 - - 600 0.25 0 - + 600 0.25 1 ++ ++ The 100% complement is in each case the percentage by weight of PA 11. "-" means that the value obtained is insufficient for the "+" transformation means that the value is limited for the transformation "++" means that the value obtained is good for the transformation This example shows that the most important aspect for the transformation is not the value of inherent viscosity but the value of the melt viscosity with the combination catalyst-thermal stabilizer cuivrecarbodiim ide. EXAMPLE 2.2 The polyamide used for all the tests of this example is PA 11. The percentages given are by weight. Inherent viscosity Plan plan at tO PA 11 + 600 ppm H3PO4 1.77 15000 PA11 non-catalyzed + 1% stabilizer® 9000 1.80 6600 PA11 non-catalyzed + 1.5% stabilizer® 9000 2.25 12130 PA 11 + 600 ppm H3PO4 + 1% stabilizer® 9000 + 0.25% iodine 201 2.30 20000 There is no correlation between solution viscosity (inherent viscosity in metacresol) and melt viscosity. This can be explained by the representative polydispersity index of the branches. EXAMPLE 3 Evaluation of the Compositions of the Invention Comprising Further 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. Bi screw test at 280 ° C - 300 rpm under vacuum - 600 mm / hg (werner 40) at 60 kg / h. The PA base is dried (<0.1% moisture) comparative comparative comparative comparative invention 1 2 3 4 ANOX NDB TL89 1.2 BBSA 6 6 10 6 6 PA 11 + 600 ppm 82.8 83.8 82, 8 H3PO4 Inner viscosity 1.45 EPR 1801 10 10 FUSABOND 493 10 6 iodine 201 0.2 0.2 0.2 0.2 PA11 viscosity 82.5 inherent 82.5 1.45 STABILIZE 9000 0 1.3 1, 3 0 1 Head pressure (bars). 23 35 33 16.5 40 Couple. 71 68 63 63 86 RCG at 260 ° c 5 mn to 100 sec-1: in Pa s 2819 2209 1936 3830 plan plan to 13000 10300 9800 1200 14000 lOrad / sec: to 270 ° c in Pa.s plan plan to 10 31800 5140 2770 8000 21000 rad / sec: after 30 minutes at 270 ° c in Pa s ISO 527-2 1BA test pieces 1/2 life at 140 ° c 720h> 2000h> 2000h Inherent viscosity 1.72 2.22 2.49 1.50 2.31 corrected 1 The lifetime measured on the elongation at break increases from 30 days for comparative composition 1 (PA 11 + 600 ppm catalyst), which does not include a thermal stabilizer and carbodiimide, to 90 days for a composition of the invention comprising both a catalyst (same proportion as Comparative 1), a copper stabilizer and a carbodiimide.
    [0060] The composition according to the invention is more viscous than Comparative 4, the only difference being the presence of carbodiimide in the formulation according to the invention (at t0 and t = 30m in). Moreover, Comparative 1 has a melt viscosity which a priori seems good (t0 = 13000) but which evolves much too much up to t = 30 min thus making difficult its transformation contrary to the composition according to the invention . On the other hand, Comparatives 2 and 3 which do not comprise a catalyst but comprise a carbodiimide in a proportion greater than that of the composition of the invention (1.3% instead of 1%) not only have viscosities at the same time. melted state at t = 0 which do not reach the value of 13000 Pa.s required but still are completely devoid of stability since the viscosity at t = 30 min decreases sharply.
    [0061] EXAMPLE 4 Hydrolysis Resistance of a Formulation of the Invention (Example 3) Compared to that of a BESNOP4OTL BESNOP4OTL Example 3 of the Invention Thermal Stability at 140 ° C. 1/2 Life 700h 2000h Maintenance at hydrolysis 140 ° C Volvic water pH4 Time to have 50% absolute 280h 950h elongation at break Viscosity plane plane at 270 ° C 10 rad / sec, 5% deformation TO 9000 14000 T = 30 min 32000 21000 The product BESNOP4OTL is a Arkema PA11 + H3PO4 Offshore reference + plasticizer + thermal stabilizer. This table shows that the compounds of the invention exhibit stability to hydrolysis whatever the time (t = 0 or t = 30 min).
    权利要求:
    Claims (35)
    [0001]
    REVENDICATIONS1. 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 composition having good viscosity in the molten state and stable to processing, in particular to extrusion.
    [0002]
    2. Use according to claim 1, characterized in that 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.
    [0003]
    3. Use according to claim 1 or 2, characterized in that said composition further has a resistance to thermo-oxidation.
    [0004]
    4. Use according to one of claims 1 to 3, characterized in that said composition has a melt viscosity of about 13000 to about 23000 Pa.s, as determined by oscillatory rheology at 270 ° C.
    [0005]
    5. Use according to claim 4, characterized in that said melt viscosity is from about 13000 to about 23000 Pa.s for at least 30 minutes.
    [0006]
    6. Use according to one of claims 1 to 5, characterized in that 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.
    [0007]
    7. Use according to one of claims 1 to 6, characterized in that the catalyst is selected from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture of them.
    [0008]
    8. Use according to one of claims 1 to 7, characterized in that the proportion by weight of copper thermal stabilizer is from about 0.05% to about 1%, in particular from about 0.05% to about 0.3% relative to the total weight of the composition.
    [0009]
    9. Use according to claim 8, characterized in that the copper thermal stabilizer is a mixture of potassium iodide and copper iodide.
    [0010]
    10. Use according to one of claims 1 to 9, characterized in that the proportion by weight of oligo- or poly-carbodiimide is from about 0.1 to about 3%, in particular from 0.5 to 2 %, in particular approximately equal to 1 ') / 0 relative to the total weight of the composition.
    [0011]
    11. Use according to claim 10, characterized in that the oligo- or poly-carbodiimide is chosen from a stabilizer, in particular Stabilizer® 9000, a Bruggolen®, a StabaxoI0, in particular a Stabaxol® P, in particular Stabaxol® P100. or Stabaxol® P400, or a mixture thereof.
    [0012]
    12. Use according to one of claims 1 to 11, characterized in that the thermoplastic polymer is a polyamide selected from an aliphatic polyamide, a cycloaliphatic polyamide, an aromatic polyamide or a mixture thereof.
    [0013]
    13. Use according to claim 12, characterized in that the polyamide has a Tf of 160 ° C to 290 ° C determined according to ISO 11357-3 (2013).
    [0014]
    14. Use according to claim 12 or 13, characterized in that the polyamide is chosen from the polyamide is chosen from: PA11, PA12, 11 / 10.T, PA 10.10, PA 10.12 and copolyamides 11 / 12 having more than 90% of reasons 11 or more than 90% of reasons 12.
    [0015]
    15. Viscous and stable composition for processing as defined in claim 1, characterized in that it comprises, with respect to the total weight of the composition: a. 20.5 to 99.845% by weight of at least one polyamide as defined in one of claims 12 to 14; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 0 to 30% of at least one polyolefin; boy Wut. 0 to 30% of at least one additive.
    [0016]
    16. Composition according to claim 15, characterized in that it consists of: a. 64.5 to 98.745% by weight of at least one polyamide as defined in one of claims 12 to 14; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 0.1 to 1% of at least one additive
    [0017]
    17. Composition according to claim 15, characterized in that it consists of: a. 49.50 to 97.745% by weight of at least one polyamide as defined in one of claims 12 to 14; b. 0.005 to 0.5% by weight of at least one catalyst; 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; f. 1 to 30% of at least one polyolefin; boy Wut. 0.1 to 1% of at least one additive;
    [0018]
    18. Composition according to one of claims 15 to 17, characterized in that the polyamide is chosen from an aliphatic polyamide, a cycloaliphatic polyamide, an aromatic polyamide or a mixture thereof.
    [0019]
    19. Composition according to one of claims 15 to 18, characterized in that the polyamide has a Tf of 160 ° C to 290 ° C determined according to ISO 11357-3 (2013).
    [0020]
    20. Composition according to one of claims 15 to 19, characterized in that the polyamide is chosen from: PA11, PA12, 11 / 10.T, PA 10.10, PA 10.12 and copolyamides 11/12 having more than 90% of patterns 11 or more than 90% of patterns 12.
    [0021]
    21. Composition according to one of claims 15 to 20, characterized in that the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture of them. 25 30
    [0022]
    22. Composition according to one of claims 15 to 21, characterized in that the copper thermal stabilizer is a mixture of potassium iodide and copper iodide.
    [0023]
    23. Composition according to one of claims 15 to 22, characterized in that the oligo- or poly-carbodiimide is chosen from a Stabiliser, in particular Stabilizer® 9000, a Bruggolen®, a Stabaxol®, in particular a Stabaxol ° P, especially Stabaxol® P100 or Stabaxol® P400, or a mixture thereof.
    [0024]
    24. Use of a composition as defined in one of claims 15 to 23, for the constitution of a structure, such as: a flexible pipe for the transport of gas or the exploitation of oil deposits under the sea, a flexible hose for the automobile, in particular for the transport of fuel (petrol, diesel, biodiesel or ethanol), for refrigeration, for air conditioning, or for pipes carried out in particular in extrusion blow molding for the supply of fuel. air, a hollow body, a molding or a sporting article.
    [0025]
    25. Use according to claim 24, characterized in that a flexible pipe for the transport of gas or the exploitation of oil deposits under the sea, has a good resistance to thermo-oxidation and resistance to hydrolysis .
    [0026]
    26. Use according to claim 24 or 25, characterized in that the pipe has a service temperature of at least 70 ° C for 20 years.
    [0027]
    27. Use according to one of claims 24 to 26, characterized in that the composition is as defined in one of claims 16 and 18 to 23 and the structure is a pipe is intended for the transport of gas.
    [0028]
    28. Use according to one of claims 24 to 27, characterized in that the composition is as defined in one of claims 17 to 23 and the structure is a flexible pipe for the exploitation of oil deposits under the sea.
    [0029]
    29. Use according to one of claims 24 to 27, characterized in that the composition is as defined in one of claims 17 to 23 and the structure is a flexible hose for the automobile, in particular 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.
    [0030]
    30. Hose for the transportation of gas or the exploitation of oil deposits under the sea, or for the automobile, in particular for the transportation of fuel (gasoline, diesel, biodiesel or ethanol), for refrigeration, for transportation air conditioning unit for the air supply as defined in claim 24 comprising at least one layer of a composition as defined in one of claims 15 to 23.
    [0031]
    31. A flexible hose according to claim 30, characterized in that said layer is the layer in contact with the fluid and the composition is as defined in one of claims 16 and 18 to 23, for the transport of gas.
    [0032]
    32. Flexible pipe according to claim 31, characterized in that it may further comprise at least a second layer, in particular thermoplastic.
    [0033]
    33. A hose according to claim 30, characterized in that said layer is the inner layer of a flexible pipe for the exploitation of oil deposits under the sea and the composition is as defined in one of claims 17. at 23.
    [0034]
    34. Pipe according to claim 30, characterized in that said layer is the outer layer of a flexible pipe for the exploitation of oil deposits under the sea and the composition is as defined in one of claims 17. at 23.
    [0035]
    35. Pipe according to claim 30, characterized in that it comprises an inner layer and an outer layer consisting of a composition as defined in one of claims 17 to 23, said inner and outer layers being constituted of the same composition of the invention or each of a different composition of the invention.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5360888A|1992-04-30|1994-11-01|Rhein Chemie Rheinau Gmbh|Hydrolysis-stable polyamides|
    US20060074158A1|2004-10-05|2006-04-06|Philippe Blondel|Flexible semicrystalline polyamides|
    US20080314471A1|2005-03-14|2008-12-25|Graeme Bulmer|Pipe Fitting|
    WO2008122743A2|2007-03-07|2008-10-16|Arkema France|Use of a polyamide based composition for flexible pipes for conveying crude oil or gas and flexible pipe using such composition|WO2019097184A1|2017-11-17|2019-05-23|Arkema France|Block-copolymer-based stretchable, flexible, waterproof and breathable film|
    WO2019097185A1|2017-11-17|2019-05-23|Arkema France|Stretchable and anti-pilling, flexible textile material based on block copolymer|
    WO2019097179A1|2017-11-17|2019-05-23|Arkema France|Block copolymer exhibiting improved abrasion resistance and improved tear resistance|
    WO2019097178A1|2017-11-17|2019-05-23|Arkema France|Block copolymer foam|KR100558024B1|1998-03-30|2006-03-07|닛신보세키 가부시키 가이샤|Polyamide resin composition and member made from the same|
    EP1652887B1|2002-03-04|2012-10-31|Arkema France|Polyamide-based composition for the making of flexible hoses containing oil or gas|
    FR2876109B1|2004-10-05|2006-11-24|Arkema Sa|SOFT SEMI-CRYSTALLINE POLYAMIDES|
    DE502008000140D1|2007-05-03|2009-11-26|Ems Patent Ag|Partially aromatic polyamide molding compounds and their uses|
    CA2799554A1|2010-07-08|2012-01-12|Mitsubishi Gas Chemical Company, Inc.|Polyamide resin compositions|
    JP5853446B2|2010-07-08|2016-02-09|三菱瓦斯化学株式会社|Polyamide resin composition|
    JP5729189B2|2010-07-23|2015-06-03|三菱瓦斯化学株式会社|Polyamide resin composition|
    ES2614407T3|2011-08-25|2017-05-31|Lanxess Deutschland Gmbh|Thermoplastic molding masses with increased hydrolysis resistance|
    DE102011090092A1|2011-12-29|2013-07-04|Evonik Degussa Gmbh|Process for the production of a molding from a polyamide molding compound with improved hydrolysis resistance|
    WO2014050303A1|2012-09-25|2014-04-03|三菱瓦斯化学株式会社|Fiber-reinforced polyamide resin material|FR3049953B1|2016-04-08|2020-04-24|Arkema France|COPPER-BASED THERMOPLASTIC AND STABILIZING POLYMER COMPOSITION, ITS PREPARATION AND USES|
    WO2021251192A1|2020-06-09|2021-12-16|株式会社クレハ|Polyamide resin composition, molded polyamide resin article, and production method therefor|
    法律状态:
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    2016-05-06| PLSC| Publication of the preliminary search report|Effective date: 20160506 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1460666|2014-11-05|
    FR1460666A|FR3027907B1|2014-11-05|2014-11-05|COMPOSITION BASED ON VISCOUS THERMOPLASTIC POLYMER AND STABLE FOR TRANSFORMATION, PREPARATION AND USES THEREOF|FR1460666A| FR3027907B1|2014-11-05|2014-11-05|COMPOSITION BASED ON VISCOUS THERMOPLASTIC POLYMER AND STABLE FOR TRANSFORMATION, PREPARATION AND USES THEREOF|
    JP2017542349A| JP2018502206A|2014-11-05|2015-11-05|Deformation-stable composition comprising viscous polyamide, its production process and its use|
    US15/522,805| US20170313843A1|2014-11-05|2015-11-05|Transformation-stable composition comprising viscous polyamide, production thereof and use of same|
    PCT/FR2015/052987| WO2016071638A1|2014-11-05|2015-11-05|Transformation-stable composition comprising viscous polyamide, production thereof and use of same|
    EP15808709.8A| EP3215562B1|2014-11-05|2015-11-05|Transformation-stable composition comprising viscous polyamide, production thereof and use of same|
    CN201580060022.XA| CN107075247B|2014-11-05|2015-11-05|Transition-stable compositions comprising viscous polyamides, their manufacture and their use|
    KR1020177014611A| KR102331111B1|2014-11-05|2015-11-05|Transformation-stable composition comprising viscous polyamide, production thereof and use of same|
    BR112017008483-0A| BR112017008483B1|2014-11-05|2015-11-05|USE OF AT LEAST ONE CATALYST TO FORM A COMPOSITION, COMPOSITION COMPRISING POLYAMIDE, USE OF COMPOSITION AND FLEXIBLE TUBE COMPRISING LAYER OF SUCH COMPOSITION|
    JP2020136674A| JP2020204032A|2014-11-05|2020-08-13|Transformation-stable composition comprising viscous polyamide, production method thereof, and use thereof|
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