EP2920246A1 - Zusammensetzung mit einem halbaromatischen copolyamid, einem polyolefin und einem kupferwärmestabilisator, herstellung davon und anwendungen davon - Google Patents

Zusammensetzung mit einem halbaromatischen copolyamid, einem polyolefin und einem kupferwärmestabilisator, herstellung davon und anwendungen davon

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Publication number
EP2920246A1
EP2920246A1 EP13795207.3A EP13795207A EP2920246A1 EP 2920246 A1 EP2920246 A1 EP 2920246A1 EP 13795207 A EP13795207 A EP 13795207A EP 2920246 A1 EP2920246 A1 EP 2920246A1
Authority
EP
European Patent Office
Prior art keywords
composition
ethylene
acid
polyolefin
semi
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13795207.3A
Other languages
English (en)
French (fr)
Inventor
Philippe Blondel
Thierry Briffaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2920246A1 publication Critical patent/EP2920246A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0884—Epoxide containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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
    • 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
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • composition based on a semi - aromatic copolyamide, a polyolefin and a copper thermal stabilizer, its preparation and uses
  • the object of the present invention is a composition comprising at least one semi-aromatic copolyamide, at least one polyolefin and at least one copper thermal stabilizer, its preparation process, and its uses, in particular in the manufacture of various objects. as consumer goods, such as electrical, electronic or automotive equipment, surgical equipment, packaging or sporting goods.
  • the invention essentially relates to the use of said composition for the manufacture of tubes for under hood applications.
  • compositions based on one or more semi-aromatic polyamides are increasingly used, because of the remarkable thermomechanical properties they confer on parts made from such compositions.
  • the temperature of the air surrounding the engine is rising for reasons of efficiency and noise. This is particularly the case for diesel engines with direct injection with common rail.
  • the outer face is in contact with the hot air and the inner face in contact with the aggressive liquids.
  • the higher external temperature will tend to increase the temperature of the liquid, making this the latter even more aggressive with respect to the thermoplastic material of the tube.
  • the resistance to aging against liquids, such as the coolant must be improved.
  • These liquids, under the effect of higher temperatures, are particularly sensitive to oxidation and degradation. This typically results in the formation of peroxides, which decompose into free radicals, which themselves attack the polymeric material of the automotive part in contact with said liquid.
  • these structures are generally made from compositions comprising a polymer, typically a polyamide, various additives such as a plasticizer, impact modifier and a stabilizer.
  • US 2008/0038499 discloses a composition comprising a particular semi-aromatic copolyamide and a polyolefin for the manufacture of water tubes for automobiles.
  • compositions used today lead to lifetimes of about 400 hours. As a result, these parts need to be changed regularly.
  • multilayer tubes formed of an in-house fluid barrier layer, generally based on fluoropolymers, and a thermally resistant layer externally. These structures have a much longer service life, but the use of fluorinated material is extremely expensive and these are difficult to process materials.
  • an improved resistance to high temperature such as for example between 130 to 175 ° C and inside an improved resistance to liquids. aggressive, especially at high temperatures, such as 80 to 130 ° C, while maintaining a reasonable cost of production.
  • the copper thermal stabilizer being a mixture of potassium iodide and copper iodide, and
  • A is selected from
  • b represents the number of carbon atoms of the diacid between 6 and 32
  • XT denotes a unit obtained from the polycondensation of a Cx diamine denoted X and terephthalic acid denoted T, where x represents the number of carbon atoms of the diamine in Cx, x being between 9 and 36, advantageously between 10 and 18,
  • dumbbells made in said composition lead to improved aging in an aggressive medium at 130 ° C.
  • the invention also relates to a process for preparing the composition and to its uses, in particular as a layer constituting a structure that can be monolayer or multilayer.
  • the invention also relates to a part formed wholly or partly from a composition according to the invention as well as the uses of such a part.
  • the invention finally relates to the use of 0.05 to 0.50% by weight relative to the total weight of the copper thermal stabilizer composition in a composition comprising predominantly at least one polyamide of A / XT structure. as defined above and 10 to 36% by weight of polyolefin for the manufacture of aging resistant parts, especially in aggressive hot liquids, particularly cooling liquids.
  • composition according to the invention comprises at least one predominant semi-aromatic copolyamide comprising at least two distinct units corresponding to the following general formula: A / XT
  • A is selected from
  • b represents the number of carbon atoms of the diacid between 6 and 32
  • XT denotes a unit obtained from the polycondensation of a Cx diamine denoted X and terephthalic acid denoted T, where x represents the number of carbon atoms of the diamine in Cx, x being between 9 and 36, advantageously between 10 and 18.
  • A represents an amino acid
  • it can be chosen from the acid
  • the copolyamides formed would then comprise three, four, ... or more, patterns, respectively.
  • A represents a lactam
  • A denotes a unit obtained from a monomer chosen from 10-aminoundecanoic acid (denoted 1 1), 11-aminoundecanoic acid (denoted 1 1), 12-aminododecanoic acid (denoted 12). ) and lauryllactam (noted 12).
  • the unit A is a unit corresponding to the formula (diamine in Ca). (Cb diacid), the (diamine Ca) unit is selected from aliphatic diamines, linear or branched.
  • 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 (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-methyl-1,8-octanediamine.
  • the diamine in Ca of unit A has a number of carbon atoms a of between 7 and 18.
  • the unit (Cb diacid) is chosen from linear or branched aliphatic diacids and aromatic diacids.
  • the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of acids unsaturated monobasic fatty oils with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in document EP 0471 566.
  • the diacid is aromatic, it is selected from terephthalic acid (noted T), isophthalic acid (noted I) and naphthalenic diacids.
  • unit A designates 10-aminoundecanoic acid (denoted 11).
  • the unit X denotes a unit obtained from a diamine comprising a number of carbon atoms, denoted x ranging from 9 to 36, preferably from 10 to 18 and more preferably equal to 10.
  • This diamine can be aliphatic, linear or branched.
  • the diamine When the diamine is aliphatic and branched, it may have one or more methyl or ethyl substituents on the main chain. For example, it may advantageously be selected from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine and 2-methyl-1,8-octanediamine.
  • copolyamides are of particular interest: it is copolyamides corresponding to one of the formulas chosen from 11 / 10.T, 12/10. T, 6.10 / 10. T, 6.12 / 10. T, 10.10 / 10. T, 10.12 / 10. T and 12.12 / 10. T.
  • the copolyamides correspond to one of the formulas chosen from PA11 / 10.T, PA12 / 10.T, PA10.10 / 10. T, PA10.12 / 10. T, PA12.12 / 10.T.
  • the molar proportions of diamine denoted X and terephthalic acid denoted T are preferably stoichiometric.
  • the copolyamide is a copolymer containing only two distinct units, namely a unit A and the unit X.T, preferably 10%.
  • the copolyamide comprises at least three distinct units and corresponds to the following formula:
  • Z is selected from a unit obtained from an amino acid, a unit obtained from a lactam and a unit having the formula (Cd diamine). (diacid in Ce), with d representing the number of carbon atoms of the diamine and e representing the number of carbon atoms of the diacid, d and e being each between 4 and 36, advantageously between 9 and 18.
  • Z represents a unit obtained from an amino acid
  • the copolyamides formed would then comprise four, five, ... or more, patterns, respectively.
  • Z represents a unit obtained from a lactam
  • a lactam a mixture of two, three, ... or more lactams or a mixture of one or more amino acids and one or more lactams could also be contemplated.
  • the copolyamides formed would then comprise four, five, ... or more, patterns, respectively.
  • copolyamides are of particular interest: they are copolyamides corresponding to one of the formulas chosen from 1 1/1 0. T / 12, 1 1 / 10.T / 6 and 12 / 10.176.
  • the Z motif when it is a motif obtained from a lactam or an amino acid is strictly identical to the pattern A. Indeed, in this particular hypothesis, it is in the presence of copolyamide already envisaged according to the first aspect of the invention.
  • the (Cd diamine) unit is chosen 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 (Cd 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-methyl-1,8-octanediamine.
  • the monomer (Cd diamine) is cycloaliphatic, it is chosen from bis (3,5-dialkyl-4-amino cyclohexyl) 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 risopropylidene di (cyclohexylamine) (PACP).
  • bis (3,5-dialkyl-4-amino cyclohexyl) methane bis (3,5-dialkyl-4-aminocyclohexyl) ethane
  • the monomer (Cd diamine) is alkylaromatic, it is chosen from 1, 3 -xylylenediamine and 1,4-xylylenediamine.
  • the (Ce 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 long-chain hydrocarbon-based monobasic fatty acids (such as linoleic acid and oleic acid), as described especially in the 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 chosen from terephthalic acid (noted T), isophthalic acid (denoted I) and naphthalenic diacids.
  • (Cd diamine) unit is excluded.
  • (Ce diacid) is strictly identical to the pattern 10.T or to the pattern A, when A has the following meaning: (diamine in Ca). (diacid in Cb). Indeed, in these particular cases, it is also in the presence of the copolyamide already envisaged according to the second aspect of the invention.
  • a / 10.T / Z wherein Z is a (Cd diamine) unit. (Ce diacid), copolyamides corresponding to one of the formulas chosen from 1 1 / 10.T / 10.I, 12 / 10.T / 10.I, 10. 10 / 10.T / 10.I, 10.6 / 10.T / 10.I and 10. 14 / 10. T / 1 0.I.
  • the molar ratio of the sum of the units A and Z on the unit (s) 10. T (ie (A + Z) / 10.T) in the terpolymer is between 0, 1 and 1, and preferably between 0.2 and 0.7.
  • the copolyamide according to the invention may comprise monomers derived from resources derived from renewable raw materials, that is to say containing organic carbon derived from biomass and determined according to the ASTM D6866 standard. These monomers derived from renewable raw materials may be 1, 10-decanediamine or, when present, in particular 11-aminoundecanoic acid, aliphatic diamines and diacids and linear as defined above.
  • amino acids, diamines, diacids are effectively linear, nothing forbids to consider that they can in all or part be branched, such as 2-methyl-1, 5-diaminopentane, and / or partially unsaturated.
  • the C 18 dicarboxylic acid diacid may be octadecanedioic acid, which is saturated, or octadecenedioic acid, which has an unsaturation.
  • the term "major copolyamide” means that the copolyamide is the component whose content is greater than that of the other components of the composition.
  • the copolyamide thus constitutes the matrix of the composition.
  • the copolyamide is in a content greater than 40%, preferably greater than 50% by weight relative to the total weight of the composition.
  • the semi-aromatic polyamide has a melting point greater than 230 ° C., advantageously between 240 ° C. and 280 ° C., and more particularly between 250 ° C. and 270 ° C.
  • the semi-aromatic copolyamide according to the invention is a copolyamide of structure 1 1 / 10.T, and more preferably a copolyamide of structure 1 1 / 10.T resulting from the polycondensation the amino-1 1 -undecanoic acid , 1,10-decanediamine and terephthalic acid.
  • the molar ratio between the unit 11 and the unit 10 T is between 0.5 / 1.1 (meaning 0.5 mole of unit derived from 11-amino-undecanoic acid per 1 mole of pattern from 1, 10-decanediamine and 1 mole of unit derived from terephthalic acid) and 1 / 1.1.
  • the molar ratio between the unit 11 and the unit 10.sub.T is 0.5 / 1.1.
  • the copolyamide according to the invention has a melting temperature of 255-260 ° C., with a molar ratio of 0.7 / 1.1.
  • the copolyamide according to the invention has a melting point of 270 ° C., with a molar ratio of 0.5 / 1.1.
  • the amine chain end content of the copolyamide useful according to the invention is between 0.020 and 0.058 meq / g.
  • the end-of-amine content is measured in a conventional manner and known to those skilled in the art, by NMR (Nuclear Magnetic Resonance).
  • the composition according to the invention comprises from 10 to 36% by weight relative to the total weight of the composition of at least one polyolefin.
  • the polyolefin according to the invention may be chosen from a crosslinked polyolefin, a functionalized polyolefin, and their mixture, and optionally an unfunctionalized polyolefin.
  • the crosslinked polyolefin may be a dispersed phase in the matrix formed by the polyamide (s).
  • This cross-linked polyolefin is derived from the reaction of two or at least two products having reactive groups with one another.
  • the crosslinked polyolefin is obtained from at least one product (A) comprising an unsaturated epoxide and at least one product (B) comprising an unsaturated carboxylic acid anhydride.
  • the product (A) is advantageously a polymer comprising an unsaturated epoxide, this unsaturated epoxide being introduced into said polymer, either by grafting or by copolymerization.
  • the unsaturated epoxide may especially be chosen from the following epoxides:
  • aliphatic glycidyl esters and ethers such as rallyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, glycidyl acrylate and methacrylate, and
  • alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate, and endo-cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
  • the product (A) is a polyolefin grafted with an unsaturated epoxide.
  • polyolefin is meant a homopolymer or copolymer comprising one or more olefin units such as ethylene, propylene, butene-1 or any other alpha-olefin units.
  • olefin units such as ethylene, propylene, butene-1 or any other alpha-olefin units.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • polypropylene ethylene / propylene copolymers
  • elastomeric polyolefins such as ethylene-propylene (EPR or EPM) or ethylene-propylene-diene monomer (EPDM); or the metallocene polyethylenes obtained by monosite catalysis;
  • SEB S styrene / ethylene-butene / styrene block copolymers
  • SB S styrene / butadiene / styrene block copolymers
  • SIS styrene / isoprene / styrene block copolymers
  • SIS styrene / ethylene-propylene / styrene blo cs copolymers
  • the polyolefin may in particular be a copolymer of ethylene and alkyl (meth) acrylate or a copolymer of ethylene and vinyl acetate.
  • the product (A) is a copolymer of alpha-olefin and an unsaturated epoxide and, advantageously, a copolymer of ethylene and an unsaturated epoxide.
  • the amount of unsaturated epoxide may represent up to 15% by weight of the copolymer (A), the amount of ethylene representing in turn at least 50% by weight of the copolymer (A).
  • the alkyl of the (meth) acrylate comprises from 2 to 10 carbon atoms.
  • alkyl acrylates or methacrylates which may be used include methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and acrylate. 2-ethylhexyl.
  • the product (A) is a copolymer of ethylene, methyl acrylate and glycidyl methacrylate or a copolymer of ethylene, n-butyl acrylate and glycidyl methacrylate.
  • Use may in particular the product marketed by Arkema under the name LOTADER® ® AX8900.
  • the product (A) is a product having two epoxide functional groups, such as, for example, the diglycidyl ether of bisphenol A (DGEBA).
  • DGEBA diglycidyl ether of bisphenol A
  • the product (B) is advantageously a polymer comprising an unsaturated carboxylic acid anhydride, this unsaturated carboxylic acid anhydride being introduced into said polymer, either by grafting or by copolymerization.
  • the product (B) is a polyolefin grafted with an unsaturated carboxylic acid anhydride.
  • a polyolefin is a homopolymer or copolymer comprising one or more olefin units such as ethylene, propylene, butene-1 or any other alpha-olefin units.
  • This polyolefin may in particular be chosen from the examples of polyolefins listed above for the product (A), when the latter is a polyolefin grafted with an unsaturated epoxide.
  • the product (B) is a copolymer of alpha-olefin and an unsaturated carboxylic acid anhydride and, advantageously, a copolymer of ethylene and an unsaturated carboxylic acid anhydride.
  • the amount of unsaturated carboxylic acid anhydride may represent up to 15% by weight of the copolymer (B), the amount of ethylene representing in turn at least 50% by weight of the copolymer (B).
  • alkyl and an unsaturated carboxylic acid anhydride Preferably, the alkyl of the (meth) acrylate comprises from 2 to 10 carbon atoms.
  • the acrylate or the alkyl methacrylate may be chosen from those mentioned above for the product (A).
  • the product (B) is a copolymer of ethylene, an alkyl (meth) acrylate and an unsaturated carboxylic anhydride.
  • the product (B) is a copolymer of ethylene, ethyl acrylate and maleic anhydride or a copolymer of ethylene, butyl acrylate and maleic anhydride.
  • Use may in particular products sold by Arkema under the names LOTADER® 4700 ® and 3410 ® LOTADER®.
  • the weight contents of product (A) and product (B), which are respectively noted [A] and [B] may be such that the ratio [B] / [A] is from 3 to 14 and advantageously from 4 to 9.
  • the crosslinked polyolefin can also be obtained from the products (A), (B) as described above and from at least one product (C), this product (C) comprising an unsaturated carboxylic acid or an alpha-omega-amino carboxylic acid.
  • the product (C) is advantageously a polymer comprising an unsaturated carboxylic acid or an alpha-omega-aminocarboxylic acid, one or the other of these acids being introduced into said polymer by copolymerization.
  • unsaturated carboxylic acids which may be used as constituents of the product (C) are, in particular, acrylic acid, methacrylic acid, the carboxylic acid anhydrides mentioned above as constituents of the product (B), these anhydrides being completely hydrolysed.
  • alpha-omega-aminocarboxylic acids which can be used as constituents of the product (C) are in particular 6-aminohexanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
  • the product (C) can be a copolymer of alpha-olefin and an unsaturated carboxylic acid and, advantageously, a copolymer of ethylene and an unsaturated carboxylic acid.
  • the fully hydrolysed copolymers of the product (B) may be mentioned.
  • the product (C) is a copolymer of ethylene and (meth) acrylic acid or a copolymer of ethylene, an alkyl (meth) acrylate and (meth) acrylic acid.
  • the amount of (meth) acrylic acid may be up to 10% by weight and preferably from 0.5 to 5% by weight of the copolymer (C).
  • the amount of alkyl (meth) acrylate is generally between 5 and 40% by weight of the copolymer (C).
  • the product (C) is a copolymer of ethylene, butyl acrylate and acrylic acid. Use may in particular the product marketed by BASF under the name LUCALENE ® 3 1 1 0.
  • the weight contents of product (A), product (B), product (C) which are respectively noted [A], [B] and [C] can be such that the ratio [B] / ([A] + [C]) is between 1, 5 and 8, the weight contents of products (A) and (B) being such that [C] ⁇ [A].
  • the ratio [B] / ([A] + [C]) can be between 2 and 7.
  • the dispersed phase of crosslinked polyolefin can of course come from the reaction of one or more products (A) with one or more products (B) and, where appropriate, with one or more products (C).
  • Catalysts can be used to accelerate the reaction between the reactive functions of the products (A) and (B).
  • the polyolefin according to the invention is a crosslinked polyolefin, it is present in the composition in a content of between 13 and 30% by weight relative to the total weight of the composition.
  • composition according to the invention may comprise at least one functionalized polyolefin (D).
  • functionalized polyolefin is understood to mean
  • the functionalized polyolefin (D) may be an alpha-olefin polymer having reactive moieties: functionalities.
  • Reactive units are the carboxylic acid, anhydride or epoxy functions.
  • polyolefins of homopolymers or copolymers of alpha olefins or of diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene, and more particularly:
  • LDPE low density polyethylene
  • HDPE linear low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metalloethylene po lyethylene ethylene
  • ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (English abbreviation: ethylene-propylene-rubber or ethylene-propylene rubber) and EPDM (abbreviation: ethylene / propylene / diene monomer or terpolymer based on ethylene / propylene / diene),
  • SEB S styrene / ethylene-butene / styrene block copolymers
  • SB S styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • unsaturated carboxylic acid salts or esters such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids Saturated such as vinyl acetate (EVA), the proportion of comonomer up to 40% by weight.
  • polyolefins described above may be grafted, copolymerized or ter polymerized by reactive units (functionalities), such as carboxylic acid, anhydride or epoxy functional groups.
  • these polyolefins are grafted or co-polymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the it can be totally or partially neutralized with metals such as Zn, etc.) or with anhydrides of carboxylic acids such as maleic anhydride.
  • unsaturated epoxides such as glycidyl (meth) acrylate
  • carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the it can be totally or partially neutralized with metals such as Zn, etc.) or with anhydrides of carboxylic acids such as maleic anhydride.
  • the functionalized polyolefin (D) may be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is, for example, from 0.01 to 5% by weight:
  • PE polyethylene
  • PP polypropylene
  • ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM),
  • SEB S styrene / ethylene-butene / styrene block copolymers
  • SB S styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • EVA ethylene-vinyl acetate copolymers
  • copolymers of ethylene and vinyl acetate (EVA) and alkyl (meth) acrylate containing up to 40% by weight of comonomers.
  • a functionalized polyolefin is, for example, a PE / EPR mixture, the weight ratio of which may vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride. according to a degree of grafting, for example from 0.0 to 5% by weight.
  • the functionalized polyolefin (D) may also be chosen from ethylene / propylene copolymers of predominantly propylene grafted with maleic anhydride and then condensed with monoamino polyamide (or polyamide oligomer) (products described in EP-A). -0342066).
  • the functionalized polyolefin (D) may also be a co-polymer or at least one of the following:
  • anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
  • the (meth) acrylic acid may be salified with Zn or Li.
  • alkyl (meth) acrylate in (D) refers to C 1 to C 8 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate, dimethyl acrylate and the like. n-butyl acrylate, iso-butyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
  • the above-mentioned polyolefins (D) can also be crosslinked by any suitable method or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the above-mentioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with them or mixtures of at least two functionalized polyolefins which can react with one another.
  • the copolymers mentioned above (D) can be copolymerized randomly or sequentially and have a linear or branched structure.
  • the molecular weight, the MFI index, the density of these polyolefins may also vary to a large extent, which the skilled person will appreciate.
  • the MFI Index, short for Melt Flow Index, is the Melt Flow Index. It is measured according to ASTM 1238.
  • the functionalized polyolefins (D) are chosen from any polymer comprising alpha olefinic units and units carrying polar reactive functional groups such as the epoxy, carboxylic acid or carboxylic acid anhydride functions.
  • examples of such polymers include terpolymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as Lotader® of the Applicant or polyolefins grafted with maleic anhydride such as the Orevac® of the Applicant as well as terpolymers of ethylene, alkyl acrylate and (meth) acrylic acid.
  • the functionalized polyolefins (D) are:
  • copolymers of ethylene and octene grafted with maleic anhydride and their mixture.
  • the polyolefin according to the invention is a functionalized polyolefin (D)
  • it is present in a content of between 10 and 30% by weight, preferably between 15 and 25% by weight relative to the total weight. of the composition.
  • composition according to the invention may comprise, in addition to a crosslinked and / or functionalized polyolefin, at least one nonfunctionalized polyolefin (E).
  • a nonfunctionalized polyolefin (E) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • LDPE linear low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metallocene polyethylene metallocene polyethylene
  • ethylene / alpha-olefin copolymers such as ethylene
  • EPR abbreviation for ethylene-propylene-rubber
  • EPDM ethylene-propylene-diene
  • SEB S styrene / ethylene-butene / styrene block copolymers
  • SB S styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • unsaturated carboxylic acid salts or esters such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids saturated, such as vinyl acetate (EVA)
  • copolymers (E) can be copolymerized randomly or sequentially and have a linear or branched structure.
  • the non-functionalized polyolefins (E) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type such as butene or hexene. octene or 4-methyl-1-pentene.
  • PP PolyPropylene
  • high density polyethylenes medium density polyethylenes
  • linear low density polyethylenes low density polyethylenes
  • low density polyethylenes very low density polyethylenes.
  • po lyethylenes 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 so-called metallocene catalysis.
  • composition according to the invention comprises a nonfunctionalized polyolefin, then this is preferably present in a content of between 5 and 25% by weight, preferably between 10 and 20% by weight relative to the total weight of the composition.
  • the composition according to the invention comprises from 0.05 to 0.30% by weight relative to the total weight of the composition of at least one copper thermal stabilizer.
  • the copper thermal stabilizer is a mixture of potassium iodide and copper iodide (KI / CuI).
  • 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 composition according to the invention comprises from 0.1 to 0.25% by weight of copper thermal stabilizer.
  • composition according to the invention may consist solely of these three families of compounds, namely at least one polyolefin, at least one copper thermal stabilizer as defined above and at least one copolyamide. semi-aromatic majority.
  • composition may also include other compounds besides those just mentioned.
  • the composition according to the invention may in particular comprise at least one additive and / or at least one additional polymer.
  • composition according to the invention may also comprise at least one additive.
  • This additive can in particular be chosen from processing aid additives (or processing aids), fillers, thermal stabilizers other than the one defined above, such as phosphite-based organic thermal stabilizers, coloring agents, bleaching agents and the like. demolding agents, flame retardants, surfactants, optical brighteners, antioxidants, such as those based on phenol or the product sold under the name Naugard 445® sold by the company CHEMTURA, the anti-oxidants, UV such as HALS and their mixtures.
  • the dyes are present in a proportion of 0 to 1.5%, especially 0.5 to 1% by weight relative to the total weight of the composition.
  • the thermal stabilizers are present in a proportion of 0 to 2%, especially 0.5 to 1% by weight relative to the total weight of the composition and the antioxidants are present in a proportion of 0 to 2%, especially 0.5 to 1% by weight relative to the total weight of the composition.
  • the adjuvants aiding processing or processing aids include stearates, such as calcium or zinc stearates, natural waxes, polymers including tetrafluoroethylene (TFE).
  • the weight ratio of processing aids is conventionally between 0.01 and 0.3% by weight, advantageously between 0.02 and 0.1% by weight, relative to the total weight of the composition.
  • fillers mention may be made of silica, graphite, expanded graphite, carbon black, glass beads, kaolin, magnesia, slag, talc, nanofillers (carbon nanotubes), pigments, metal oxides (titanium oxide), metals, fibers (aramids, glass, carbon).
  • the amount of these can be up to 30% by weight, the total weight of the composition.
  • a composition according to the invention may further comprise one or more additional polymers, and in particular at least one third polymer, such a polymer being distinct from the semi-aromatic copolyamide (s) and the (or) polyolefin (s) mentioned above.
  • this additional polymer may in particular be chosen from a polyamide other than that defined above, a polyamide-blo c-ether, a polyetheramide, a polyesteramide, a phenylene polysulfide (PPS), a polyphenylene oxide (PPO), a polymer fluorinated, and mixtures thereof.
  • the additional polymer may also be selected from starch, which may be modified and / or formulated, cellulose or its derivatives such as cellulose acetate or cellulosic ethers, poly lactic acid, glycolic acid. and polyhydroxyalkanoates.
  • the additional polymer is chosen from aliphatic polyamides and polyamides-blo-ethers.
  • aliphatic polyamides there may be mentioned polyamides with long chain such as PA U, PA 12, PA6. 1 0, PA6. 12, PA6. 14, PA 10. 10, PA 10. 12 and PA 12. 12.
  • the composition may thus contain up to 20% by weight, based on the total weight of the composition, of at least one additional polymer.
  • the invention also relates to a method for preparing a composition as defined above.
  • the composition may be prepared by any method which makes it possible to obtain a homogeneous mixture such as melt extrusion, compacting or roller mill.
  • the composition according to the invention may be prepared by melt blending the semi-aromatic copolyamide (s), the copper heat stabilizer (s), and the (Of) polyolefin (s) during compounding of the composition.
  • the polyolefin used is a crosslinked polyolefin
  • the products (A), (B) and optionally (C) as defined above are introduced into the aforementioned mixture in the molten state.
  • the copper thermal stabilizer (s) is (are) added to the monomers of the copolyamide during its polycondensation.
  • the composition according to the invention may be prepared by melt blending of the semi-aromatic copolyamide (s) already containing the copper thermal stabilizer (s) and the polyolefin (s). Other additives or a supplement of copper stabilizer may be added during compounding.
  • the optional additional additives and / or polymers may, in turn, be introduced, at the same time as the semi-aromatic copolyamide (s), the copper and polyolefin thermal stabilizer (s). (s) and, where appropriate, at a later stage.
  • the composition can be obtained in the form of granules by compounding, in particular by means of an extruder bi-screw, a co-kneader or an internal mixer.
  • These granules of the composition according to the invention obtained by the method of preparation described above can then be transformed using tools known to those skilled in the art (such as an injection molding machine or a extruder) in the form of filaments, tubes, films and / or molded objects.
  • the process for preparing the composition according to the invention may also use a twin-screw extruder feeding, without intermediate granulation, an injection molding machine or an extruder for producing filaments, tubes, films and / or and molded.
  • the invention thus also relates to a material or article obtained from a composition as defined above by a known transformation process such as injection, extrusion, extrusion-blowing, co-molding, extrusion or multi-injection.
  • the invention also relates to the use of a composition as described above to form a structure.
  • This structure may be monolayer, when it is formed only of the composition according to the invention.
  • This structure may also be multilayer, when it comprises at least two layers and at least one of these different layers consists of the composition according to the invention.
  • this multilayer structure can be reinforced and comprise at least one layer constituted by a braid or by fibers.
  • the invention also relates to a part formed wholly or partly from the composition according to the invention.
  • This piece may comprise the monolayer or multilayer structure which has just been mentioned.
  • Such a piece may in particular be an injected part and, more particularly, an extruded part, coextruded or extruded-blown. It may especially be in the form of a tube, a pipe, a reservoir, fibers, a film, a sheet or a plate.
  • the invention finally relates to the use of such a piece for storing or conveying a fluid.
  • Such a fluid may in particular be chosen from a fuel (such as a gasoline, alcoholic or not, a diesel or a bio-diesel), a refrigerant (such as those used in air conditioning circuits), a coolant (such as a solution based on alcohol and / or water which can be used in the engine cooling circuit), a brake fluid, an oil, a lubricant, a hydraulic fluid, a liquid-based urea solution, a chemical, water or a gas (such as air, alkanes, hydrogen or carbon dioxide) or fumes of gases or vapors (from, for example engine), this gas can be in pressure or depression.
  • a fuel such as a gasoline, alcoholic or not, a diesel or a bio-diesel
  • a refrigerant such as those used in air conditioning circuits
  • a coolant such as a solution based on alcohol and / or water which can be used in the engine cooling circuit
  • a brake fluid such as a solution based on alcohol and /
  • the part formed wholly or partly from the composition according to the invention may in particular be used for the production of all or part of surgical equipment, packaging or sports or leisure items.
  • This part can also be used for the realization of all or part of items of electrical and electronic equipment such as solar panels, encapsulated soenoids, rolling cages, pumps, multimedia systems, cables and wires.
  • the cables and wires may be covered by a layer formed of the composition according to the invention thus constituting a thermal protection sheath.
  • This part comprising the composition according to the invention may advantageously be used for the production of all or part of industrial equipment elements for the storage, transport or transfer of fluids such as those listed above, in particular fluids hot air, oil, lubricants, hydraulic fluids or oil and its compounds.
  • Such equipment may be intended for use in the field of industry in general (for example, for pneumatic or hydraulic lines) as well as in the field of exploitation of oil and gas deposits under the sea (field Off Shore).
  • This part comprising the composition according to the invention can very advantageously be used for the realization of all or part of automotive or truck equipment items.
  • Such elements may in particular be tubes, tube connectors, pumps or parts injected under the engine hood.
  • these items of automotive or truck equipment especially when they have the shape of tubes and / or connectors, can in particular be used:
  • a gas circulation device under pressure or under vacuum, such as an air intake or engine gas ventilation device or a braking assistance device,
  • an oil or lubricant circulation device such as an oil cooling device, a hydraulic device or a braking device
  • an aqueous circulation device whether aqueous or not, such as an engine cooling device or a selective catalytic reduction device,
  • a refrigerant circulation device such as an air conditioning circuit
  • Such elements can of course be rendered antistatic or conductive, by prior addition of suitable amounts of conductive fillers (such as carbon black, carbon fibers, carbon nanotubes, etc.) in the composition according to the invention.
  • conductive fillers such as carbon black, carbon fibers, carbon nanotubes, etc.
  • the invention finally relates to the use of 0.05 to 0.50% by weight relative to the total weight of the copper thermal stabilizer composition as defined above in a composition comprising predominantly at least one semi-aromatic copolyamide structure A / XT as defined above and 10 to 36%> polyolefin as defined above for the manufacture of aging-resistant parts, especially in aggressive hot liquids, in particular the coolants.
  • a composition comprising predominantly at least one semi-aromatic copolyamide structure A / XT as defined above and 10 to 36%> polyolefin as defined above for the manufacture of aging-resistant parts, especially in aggressive hot liquids, in particular the coolants.
  • compositions tested were prepared from the following products:
  • Ta semi-aromatic copolyamide, of molar ratio
  • 1 1 / 10.T equal to 0.7, obtained by polycondensation of 11-aminocarboxylic acid, 1,10-decanediamine and terephthalic acid, having a glass transition temperature Tg of 88 ° C., a melting temperature Tf of 260 ° C, an inherent viscosity of 1.22 (measured according to ISO 307), a melting enthalpy of 47 J / g measured by DSC and an amine end-chain content of 0.035 meq / g.
  • the sample is placed at ambient temperature in dichloromethane-d 2 with the addition of trifluoroacetic anhydride for 16 hours, in order to lubilize the polymer.
  • the concentration is of the order of 20 mg / ml.
  • a proton NMR spectrum is produced at a frequency of
  • Lotader AX8900 copolymer of ethylene, methyl acrylate and glycidyl methacrylate (Et / MA / GMA - 68/24/8 by weight), corresponds to product (A)
  • Lotader 4700 copolymer of ethylene, ethyl acrylate and maleic anhydride (Et / EA / MAH - 69/30/1 by weight), corresponds to the product (B)
  • Iodine 201 thermal stabilizer containing by weight 80% KI,
  • Organic thermal stabilizers such as Irgafos 12, antioxidants and dyes are added in some of the compositions tested.
  • compositions 1 to 6 were all prepared on a twin-screw extruder, according to the formulations detailed in Table 1 below.
  • compositions 1 to 4 are compositions according to the invention, while compositions 5 and 6 are comparative compositions.
  • compositions 1 to 6 were injected in the form of dumbbells ISOR 527 1 BA according to ISO 179.
  • the tensile mechanical properties that is, the percentage elongation at break of a sample chemically aged at 130 ° C in a 50/50 water / glysantin mixture (the glysantin is ethylene glycol) are evaluated. These samples were evaluated after a residence time in the autoclave of Oh, 50h, 350h, 500h, 660h, 1220h, 1660h and 1850h.
  • compositions 1 and 2 according to the invention were confirmed by extruding tubes 8 mm in diameter and 1 mm thick (8> ⁇ 1 mm).
  • the water / glysantin mixture (50/50) at 130 ° C passes inside the tube, while the outside air temperature is 130 ° C. After 1500 hours, the tube does not break at DIN shock at 23 ° C.

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EP13795207.3A 2012-11-19 2013-11-18 Zusammensetzung mit einem halbaromatischen copolyamid, einem polyolefin und einem kupferwärmestabilisator, herstellung davon und anwendungen davon Withdrawn EP2920246A1 (de)

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FR1260965A FR2998299B1 (fr) 2012-11-19 2012-11-19 Composition a base d'un copolyamide semi-aromatique, d'une polyolefine et d'un stabilisant thermique au cuivre, sa preparation et ses utilisations
PCT/EP2013/074082 WO2014076281A1 (fr) 2012-11-19 2013-11-18 Composition à base d'un copolyamide semi-aromatique, d'une polyoléfine et d'un stabilisant thermique au cuivre, sa préparation et ses utilisations

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US9890247B2 (en) * 2010-04-29 2018-02-13 Dsm Ip Assets B.V. Semi-aromatic polyamide
KR20170069067A (ko) 2015-12-10 2017-06-20 현대자동차주식회사 자동차 터보용 인테이크 호스 소재의 수지 조성물
EP3526281A1 (de) * 2016-10-17 2019-08-21 L. Brüggemann GmbH & Co. KG Verfahren zur herstellung von polyamid-werkstoffen mit verbesserten langzeitgebrauchseigenschaften
EA202092603A1 (ru) * 2018-05-23 2021-04-28 Бореалис Аг Сшиваемая полиолефиновая композиция, содержащая первый и второй олефиновые полимеры
FR3089147B1 (fr) * 2018-12-04 2020-11-06 Arkema France Structure tubulaire multicouche destinee au transport d’un fluide de climatisation
FR3094010B1 (fr) * 2019-03-21 2021-10-08 Arkema France Compositions de copolyamides comprenant des fibres de renforts et presentant une stabilité de module élevée et leurs utilisations
FR3109389B1 (fr) * 2020-04-16 2024-09-20 Arkema France Structure multicouche pour le transport ou le stockage de l’hydrogene
CN112724662B (zh) * 2020-12-08 2022-12-06 金发科技股份有限公司 一种增韧耐磨聚酰胺组合物及其制备方法和应用
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CN105121549A (zh) 2015-12-02
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FR2998299A1 (fr) 2014-05-23
FR2998299B1 (fr) 2015-04-03
US20150291794A1 (en) 2015-10-15
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