• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a structure comprising at least one layer (1) comprising a BACT / XT copolyamide in which: BACT is an amide unit having a molar ratio ranging from 20 to 70%, preferably from 25 to 60% %, more preferably from 35 to 55%, wherein BAC is selected from 1,3-bis (aminomethyl) cyclohexyl (1,3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1,4 BAC) and a mixture thereof, and T is terephthalic acid, - XT is a majority amide unit unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65% where X is a linear aliphatic diamine of C9 to C18, preferably C9, C10, C11 and C12, and wherein T is terephthalic acid, preferably C10, C11 and C12.
    公开号:FR3053694A1
    申请号:FR1656623
    申请日:2016-07-11
    公开日:2018-01-12
    发明作者:Mathieu Capelot；Nicolas Dufaure；Thierry Briffaud
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    Field of the invention
    The present invention relates to a barrier structure based on copolyamide BACT / XT of high Tg without reinforcing fibers. This structure can either be made of a single layer of this polyphthalamide or comprise a layer of polyphthalamide BACT / XT and at least one layer of another material.
    This barrier structure is useful for objects intended for the storage and / or transport of fluids, such as bottles, tanks, containers, pipes and containers of all kinds. This structure can also be in the form of films with which, for example, packaging is made which requires barrier properties to fluids such as gases. All of these objects have good barrier properties, that is to say very little permeability to fluids, in particular automobiles, in particular to fuels.
    The invention also relates to the use of a high Tg BACT / XT copolyamide for the manufacture of a structure, in particular a multilayer structure, comprising at least one barrier layer comprising said BACT / XT copolyamide.
    The invention also relates to the use of these structures and these objects.
    The prior art and the technical problem
    Whatever the fluid transported or stored in objects such as bottles, tanks, containers, pipes and receptacles of any kind, the material in direct contact with the fluid must not be permeable to it, whether acts of a liquid or a gas.
    Thus, in the automotive sector, and in transport in general, the composition of fuels is constantly changing, especially for ecological reasons, which is reflected in the gradual arrival of bio-fuels on the market. These fuels are more aggressive. Consequently, it is essential to improve the quality of the thermoplastic parts in contact with these new fuels such as petrol transport pipes.
    For safety and environmental reasons, automobile manufacturers impose on these pipes both mechanical characteristics such as burst strength and flexibility with good resistance to cold shock (-40 ° C ) as well as at high temperature (125 ° C), and also very low permeability to hydrocarbons and their additives, in particular alcohols such as methanol and ethanol. These tubes must also have good resistance to motor fuels and lubricating oils.
    Application WO 2014/064375 relates to a composition of or for a thermoplastic composite material with a semi-crystalline polyamide (PA) matrix with a glass transition temperature Tg of at least 90 ° C and a melting temperature Tf less than or equal to 280 ° C as well as mechanical or structural parts based on said material, the use of the composition of the invention for parts of composite material for applications in the fields of: automotive, rail, marine, road transport , wind, sport, aeronautics and space, building, panels and leisure.
    This composition can be used for the manufacture of mechanical parts relating to applications in the automotive field, but there is no mention in this application for a structure comprising a barrier layer to a fluid, in particular a fuel. Furthermore, this composition always comprises reinforcing fibers.
    EP 1988113 describes molding compositions based on a 10T / 6T copolyamide with:
    at 95% mol of 10T 5 to 40% of 6T.
    EP 1988 113 is silent on the barrier properties of structures made up of a layer of these compositions.
    EP 1741553 describes a multilayer structure comprising two or more layers comprising at least one layer (a) comprising (A) an aliphatic polyamide and a layer (b) comprising a semi-aromatic polyamide comprising at least 60 mol% of aliphatic diamine having 9 to 13 carbon atoms and at least 50 mol% of terephthalic acid, the layer (b) being the inner layer.
    EP 1741553 is completely silent on the barrier properties of such a structure.
    EP1860134 describes a semi-aromatic polyamide resin comprising dicarboxylic acid units in which from 50 to 100 mol% of the dicarboxylic acid units are aromatic dicarboxylic acid units, and diamine units in which from 60 to 100% of the diamine units are aliphatic diamine units having from 9 to 13 carbon atoms, said semi-aromatic polyamide having a ratio of ends of amine chains / ends of acid chains greater than or equal to 6.
    EP 1860134 in particular exemplifies 9T / 9’T (or 8MT / 9T) compounds and shows that the resistance to alcohol is reduced when said ratio is less than 6 and in particular by 4 or less.
    International application WO 10/015786 relates to a copolyamide of formula A / 10.T, in which:
    A is chosen from a unit obtained from an aminocarboxylic acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca). ((Cyclo) aliphatic diacid in Cb), with a representing the number of carbon atoms in the diamine and b representing the number of carbon atoms in the diacid, a and b each being between 4 and 36;
    characterized in that it has a polymolecularity index, noted Ip less than or equal to 3.5, measured by gel permeation chromatography (in English: Gel Perméation Chromatography).
    WO 10/015786 is completely silent on the barrier properties of such a structure.
    Furthermore, these polyamides still need to be improved, in particular in terms of crystallinity, kinetics of crystallization with a view to improving the temperature resistance of the copolyamide, of processability or even improving their impact resistance properties as well as their barrier properties. .
    Thus, there is a real need to find polyphthalamides having improved properties, in particular in terms of barrier properties.
    Brief description of the invention
    Surprisingly, it has been found that these needs are met with a structure comprising at least one layer comprising a BACT / XT copolyamide, in which:
    BACT is an amide unit present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is chosen from 1,3-bis (aminomethyl) cyclohexyl (1.3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1.4 BAC) and a mixture thereof, and T is terephthalic acid,
    - XT is a unit with a majority amide motif present at a molar ratio ranging from 30 to
    80%, preferably 40 to 75%, more preferably 45 to 65%, where X is a linear aliphatic diamine in C9 to C18, preferably in C9, C10, C11 and C12, and where T is terephthalic acid , preferably in C10, C11 and C12. in the BACT and / or XT units, independently of one another, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, relative to the total amount of dicarboxylic acids, terephthalic acid can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and in BACT and / or XT units, independently from each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, of the BAC and / or as the case may be X, relative to the amount total of the diamines, can be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular 6 to 12 carbon atoms, and in the copolyamide, not more than 30 mol%, preferably not more than 10% in mole, relative to the total amount of monomers, can be formed by lactams or aminocarboxylic acids, and provided that the sum e of the monomers which replace terephthalic acid, BAC and X do not exceed a concentration of 30% by mole, preferably 10% by mole, relative to the total amount of the monomers used in the copolyamide, and provided that BACT and XT units are always present in said copolyamide, said layer being devoid of reinforcing fibers.
    It was therefore found that these products, originally developed for composite applications because of their compromise high rigidity (high Tg), including hot, good processability (relatively low Tf), also had a crystal structure above expectations and could be used as a barrier layer, that is to say very little permeable to fluids, in particular automotive, in particular to fuels, in a structure, in particular multilayer, for the transport of fluid, although the ratio of fine amine chain / ends of acid chains is in particular less than 5.
    The structure of the invention can either be made up of a single layer of this polyamide or comprise a layer comprising the polyamide BACT / XT and at least one layer of another material.
    In the structure of the invention, the layer comprising the polyamide BACT / XT can also comprise other polymers. By way of example of these other polymers, mention may be made of polyamides, EVOH, PPS, PPO, polycarbonate, ABS.
    The invention also relates to the use of a high Tg BACT / XT copolyamide for the manufacture of a structure, in particular a multilayer structure, comprising at least one barrier layer comprising said BACT / XT copolyamide.
    The invention also relates to bottles, tanks, containers, pipes and containers of all kinds made with the above structure. This structure can also be in the form of films with which packaging is made, for example. All of these objects have good barrier properties.
    The invention also relates to these objects and the use of these structures and these objects.
    Detailed description of the invention
    Other characteristics, aspects, objects and advantages of the present invention will appear even more clearly on reading the description and the examples which follow.
    According to a first aspect of the invention, the invention relates to a structure comprising at least one layer comprising a BACT / XT copolyamide, in which:
    BACT is an amide unit present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is chosen from 1,3-bis (aminomethyl) cyclohexyl (1.3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1.4 BAC) and a mixture thereof, and T is terephthalic acid,
    XT is a unit with a majority amide unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear aliphatic diamine from C9 to C18, preferably in C9, C10, C11 and C12, and where T is terephthalic acid, preferably in C10, C11 and C12.
    in the BACT and / or XT units, independently of one another, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, relative to the total amount of dicarboxylic acids, terephthalic acid can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and in BACT and / or XT units, independently from each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, of the BAC and / or as the case may be X, relative to the amount total of the diamines, can be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular 6 to 12 carbon atoms, and in the copolyamide, not more than 30 mol%, preferably not more than 10% in mole, relative to the total amount of monomers, may be formed by lactams or aminocarboxylic acids, and provided that the sum e of the monomers which replace terephthalic acid, BAC and X do not exceed a concentration of 30% by mole, preferably 10% by mole, relative to the total amount of the monomers used in the copolyamide, and provided that BACT and XT units are always present in said copolyamide, said layer being devoid of reinforcing fibers.
    Advantageously, said copolyamide has a ratio: quantity of amine chain end groups / quantity of acid chain end groups <5, said quantities of amine chain end groups and quantity of acid chain end groups being determined by potentiometry .
    1,3-BAC (or 1,3 bis (aminomethyl) cyclohexane, CAS No: 2579-20-6) is a cycloaliphatic diamine monomer obtained in particular by hydrogenation of metaxylene diamine (MXDA). 1,3-BAC exists in the form of two isomers, cis and trans, CAS No: 2579-20-6 corresponding to a mixture of isomers.
    1,4-BAC (or 1,4 bis (aminomethyl) cyclohexane, CAS No: 2549-07-9) is a cycloaliphatic diamine monomer obtained in particular by hydrogenation of paraxylene diamine (PXDA). 1,4-BAC exists in the form of two isomers, cis and trans, CAS No. 2549-07-9 corresponding to a mixture of isomers.
    Advantageously, the 1.3 BAC or the 1.4 BAC used in the BACT unit is a mixture of cis and trans isomers in respective proportions from 0/100 to 100/0, in particular from 75/25 to 25/75.
    Advantageously, the proportion of cis isomer in 1.3 BAC is greater than 60%, preferably greater than 70%, in particular greater than 80%, in particular greater than 90%.
    Advantageously, the proportion of trans isomer in 1.4 BAC is greater than 60%, preferably greater than 70%, in particular greater than 80%, in particular greater than 90%.
    BAC and / or X can be replaced, independently of one another, up to 30 mol% by other diamines defined above, in particular by an aliphatic diamine, linear or branched, a cycloaliphatic diamine or a arylaromatic diamine such as meta-xylene diamine (MXDA).
    For example, the linear or branched aliphatic diamine is chosen from 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine (MPMD), 1,6 hexanediamine, 1,8-octanediamine (OMDA), 1,9-nonanediamine (NMDA), Ia2-methyl1,8-octane-diamine (MODA), 2,2,4-trimethylhexamethylenediamine (TMHMD), 2,4,4trimethylhexamethylenediamine (TMHMD), 5-methyl-1,9-nonanediamine, 1,11undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1 , 14-tetradecanediamine, 1,16-hexadecanediamine and 1,18octadecanediamine.
    The cycloaliphatic diamine can be chosen from isophoronediamine, norbornanedimethylamine, 4,4'-diaminodicyclohexylmethane (PACM), 2,2- (4,4'diamino-dicyclohexyl) propane (PACP), and 3,3 ' -dimethyl-4,4'-diaminodicyclohexylethane (MACM).
    T can be replaced up to 30 mol% by other dicarboxylic acids above defined, in particular by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids.
    The aromatic dicarboxylic acids can be chosen from naphthalenedicarboxylic acid (NDA) and isophthalic acid (IPS).
    The aliphatic dicarboxylic acids can be chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid and dimerized fatty acids.
    The cycloaliphatic dicarboxylic acids can be chosen from cisand / or trans-cyclohexane-1,4-dicarboxylic acid and / or cis- and / or trans-cyclohexane-1,3dicarboxylic acid (CHDA).
    BAC and / or X and / or T can be replaced, independently of one another, up to 30 mol% by lactams or aminocarboxylic acids.
    The lactams and aminocarboxylic acids can be chosen from caprolactam (CL), a, ω-aminocaproic acid, a, ω-aminononanoic acid, α, ωaminoundecanoic acid (AUA), lauryllactam (LL) and l 'α, ω-aminododecanoic acid (ADA).
    30 mole maximum, relative to the total sum of the BAC, X and T monomers, replacement whether by another diamine, another diacid, a lactam or an aminocarboxylic acid or any mixture of these is possible .
    Advantageously, 20% by mole maximum, relative to the total sum of the monomers BAC, X and T, of replacement whether it be by another diamine, another diacid, a lactam or an aminocarboxylic acid or any mixture of these. is possible.
    Advantageously, 10% by mole maximum, relative to the total sum of the monomers BAC, X and T, of replacement whether it be by another diamine, another diacid, a lactam or an aminocarboxylic acid or any mixture of these. is possible.
    The expression “reinforcing fibers” or “fibrous reinforcement” designates an assembly of fibers, short or long. The fibers can be continuous, in the form of unidirectional reinforcement (UD) or multidirectional (2D, 3D), in the form of fabrics, tablecloths, strips or braids and can also be cut for example in the form of nonwovens (mats) or in the form of felts.
    The expression “reinforcing fibers” designates in particular:
    - mineral fibers, in particular carbon fibers, which includes fibers of carbon nanotubes or nanotubes (NTC), carbon nanofibers or graphenes; silica fibers such as glass fibers, in particular of type E, R or S2; boron fibers; ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers; fibers or filaments based on metals and / or their alloys; the fibers of metal oxides, in particular of alumina (AI2O3); metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the abovementioned fibers.
    - polymeric or polymer fibers, in particular:
    • fibers of thermosetting polymers and more particularly chosen from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as bis-maleimide resins, aminoplasts resulting from the reaction of an amine such as melamine with an aldehyde such as glyoxal or formaldehyde • fibers of thermoplastic polymers and more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), • polyamide fibers , • aramid fibers (such as Kevlar®) and aromatic polyamides such as those corresponding to one of the formulas: PPDT, MPD.I, PAA and PPA, with PPD and MPD being respectively p- and m-phenylene diamine, PAA being polyarylamides and PPA being polyphthalamides • fibers of polyamide block copolymers such as polyamide / polyether, fibers of polyarylether ketones (PAEK) such as poly ether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether ketone ketone (PEKEKK).
    - or mixtures of the fibers mentioned above.
    Consequently, all the reinforcing fibers and in particular those defined above are excluded from the scope of the invention.
    In an advantageous embodiment, the present invention relates to a structure No. 1 to 3 defined below comprising at least one layer (1) comprising a BACT / XT copolyamide in the proportions defined in Table I below:
    Structure No. BACT% molar XT% molar 1 20-70 30-80 2 25-60 40-75 3 35-55 45-65
    Table I
    Advantageously, in the structures defined above, X is a diamine in C9, C10, C11 and C12, in particular in G10, C11 and C12.
    In an advantageous embodiment, the present invention relates to a s as defined above, in which said copolyamide has a melting temperature Tf <290 ° C, preferably <285 ° C, more preferably <280 ° C, such as determined in accordance with ISO 11357-3 (2013).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said copolyamide has a glass transition temperature Tg> 120 ° C, preferably> 130 ° C, more preferably> 140 ° C, determined according to ISO 11357-2: 2013.
    Advantageously, the Tg is between 125 and 165 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said copolyamide exhibits a difference between the melting temperature and the crystallization temperature Tf-Tc <40 ° G, preferably <30 ° C , determined according to ISO 11357-3: 2013.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that the crystallization enthalpy of copoiyamide, measured in Differential Scanning Calorimetry (DSC) according to Standard ISO 11357-3: 2013 , is greater than 40 J / g, preferably greater than 45 J / g, and even more preferentially 50J / g.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <290 ° C and a Tg> 120 ° C.
    In an advantageous embodiment, the present invention relates to a structure 10 as defined above, characterized in that said copolyamide has a melting temperature: Tf <290 ° C and a Tg> 130 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <290 ° C and a Tg> 140 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <285 ° C and a Tg> 120 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <285 ° C and a Tg> 130 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <285 ° C and a Tg> 140 ° C.
    In an advantageous embodiment, the present invention relates to a tefle structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <280 ° C and a Tg> 120 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <280 ° C and a Tg> 130 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copolyamide has a melting temperature: Tf <280 ° C and a Tg> 140 ° C.
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that said copoiyamide has the following characteristics (Table II):
    Structure No. Initial structures Tf (° C) Tg (° C) Tf-Tc (° C) Delta Hc(J / g) 4 Structures 1 to 3 <290 > 120 ° C 5 Structures 1 to 3 <290 > 130'C 6 Structures 1 to 3 <290 > 140 ° C 7 Structures 1 to 3 <285 > 120 ° C 8 Structures 1 to 3 <285 > 130 ° C 9 Structures 1 to 3 <285 > 140 ° C 10 Structures 1 to 3 <280 > 120 ° C 11 Structures 1 to 3 <280 > 130 ° C 12 Structures 1 to 3 <280 > 14Q ° C 13 Structures 1 to 3 <290 > 120 ° C <40 14 Structures 1 to 3 <290 > 130 ° C <40 15 Structures 1 to 3 <290 > 140 ° C <40 16 Structures 1 to 3 <285 > 120 ° C <40 17 Structures 1 to 3 <285 > 130 ° C <40 18 Structures 1 to 3 <285 > 140 ° C <40 19 Structures 1 to 3 <280 > 120 ° C <40 20 Structures 1 to 3 <280 > 130 ° C <40 21 Structures 1 to 3 <280 > 140 ° C <40 22 Structures 1 to 3 <290 > 120 ° C <30 23 Structures 1 to 3 <290 > 130 ° C <30 24 Structures 1 to 3 <290 > 140 ° C <30 25 Structures 1 to 3 <285 > 120 ° C <30 26 Structures 1 to 3 <285 > 130 ° C <30 27 Structures 1 to 3 <285 > 140 ° C <30 28 Structures 1 to 3 <280 > 120 ° C <30 29 Structures 1 to 3 <280 > 130 ° C <30 30 Structures 1 to 3 <280 > 140 ° C <30 31 Structures 1 to 3 <290 > 120 ° C <40 > 40 32 Structures 1 to 3 <290 > 130 ° C <40 > 40 33 Structures 1 to 3 <290 > 140 ° C <40 > 40 34 Structures 1 to 3 <285 > 120 ° C <40 > 40 35 Structures 1 to 3 <285 > 130 ° C <40 > 40
    36 Structures 1 to 3 <285 > 140 ° C <40 > 40 37 Structures 1 to 3 <280 > 120 ° C <40 > 40 38 Structures 1 to 3 <280 > 130 ° C <40 > 40 39 Structures 1 to 3 <280 > 140 ° C <40 > 40 40 Structures 1 to 3 <290 > 120 ° C <30 > 40 41 Structures 1 to 3 <290 > 130 ° C <30 > 40 42 Structures 1 to 3 <290 > 140 ° C <30 > 40 43 Structures 1 to 3 <285 > 120 ° C <30 > 40 44 Structures 1 to 3 <285 > 130 ° C <30 > 40 45 Structures 1 to 3 <285 > 140 ° C <30 > 40 46 Structures 1 to 3 <280 > 120 ° C <30 > 40 47 Structures 1 to 3 <280 > 130 ° C <30 > 40 48 Structures 1 to 3 <280 > 140 ° C <30 > 40 49 Structures 1 to 3 <290 > 120 ° C <40 > 45 50 Structures 1 to 3 <290 > 130 ° C <40 > 45 51 Structures 1 to 3 <290 > 140 ° C <40 > 45 52 Structures 1 to 3 <285 > 120 ° C <40 > 45 53 Structures 1 to 3 <285 > 130 ° C <40 > 45 54 Structures 1 to 3 <285 > 140 ° C <40 > 45 55 Structures 1 to 3 <280 > 120 ° C <40 > 45 56 Structures 1 to 3 <280 > 130 ° C <40 > 45 57 Structures 1 to 3 <280 > 140 ° C <40 > 45 58 Structures 1 to 3 <290 > 120 ° C <30 > 45 59 Structures 1 to 3 <290 > 130 ° C <30 > 45 60 Structures 1 to 3 <290 > 140 ° C <30 > 45 61 Structures 1 to 3 <285 > 120 ° C <30 > 45 62 Structures 1 to 3 <285 > 130 ° C <30 > 45 63 Structures 1 to 3 <285 > 140 ° C <30 > 45 64 Structures 1 to 3 <280 > 120 ° C <30 > 45 65 Structures 1 to 3 <280 > 130 ° C <30 > 45 66 Structures 1 to 3 <280 > 140 ° C <30 > 45 67 Structures 1 to 3 <290 > 120 ° C <40 > 50 68 Structures 1 to 3 <290 > 130 ° C <40 > 50 69 Structures 1 to 3 <290 > 140 b C <40 > 50
    70 Structures 1 to 3 <285 > 120 ° C <40 > 50 71 Structures 1 to 3 <285 > 130 ° C <40 > 50 72 Structures 1 to 3 <285 > 140 ° C <40 > 50 73 Structures 1 to 3 <280 > 120 ° C <40 > 50 74 Structures 1 to 3 <280 > 130 ° C <40 > 50 75 Structures 1 to 3 <280 > 140 ° C <40 > 50 76 Structures 1 to 3 <290 > 120 ° C <30 > 50 77 Structures 1 to 3 <290 > 130 ° C <30 > 50 78 Structures 1 to 3 <290 > 140 ° C <30 > 50 79 Structures 1 to 3 <285 > 120 ° C <30 > 50 80 Structures 1 to 3 <285 > 130 ° C <30 > 50 81 Structures 1 to 3 <285 > 140 ° C <30 > 50 82 Structures 1 to 3 <280 > 120 ° C <30 > 50 83 Structures 1 to 3 <280 > 130 ° C <30 > 50 84 Structures 1 to 3 <280 > 140 ° C <30 > 50
    TABLE II
    In an advantageous embodiment, the present invention relates to a structure as defined above, characterized in that the BAC is 1,3 BAC.
    Advantageously, fa 1,3 BAC is a mixture of cis and trans isomers in respective proportions from 0/100 to 100/0, in particular from 75/25 to 25/75.
    Advantageously, the proportion of cts isomer in 1.3 BAC is greater than 60%, preferably greater than 70%, in particular greater than 80%, in particular greater than 90%.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which the BAC is 1.3 BAC and XT is chosen from 9T, 10T, 11T and 12T, more preferably 10T, 11T and 12T .
    Advantageously, XT is 10T, 10 corresponding to 1.10 decanediamine.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which the sum of the monomers which replace terephthalic acid, BAC and X is equal to 9. In this latter embodiment, it there is therefore no longer any possible substitution of the monomers in structures 1 to 84 as defined above.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said layer (1) comprises an impact modifier and / or a core-shell type modifier.
    The expression “impact modifier” means a polyolefin-based polymer having a flexural modulus of less than 100 MPa measured according to ISO standard 178: 2010 and of Tg less than 0 ° C (measured according to standard 11357-2 : 2013 at the inflection point of the DSC thermogram), in particular a polyolefin, coupled or not with a PEBA (polyether-block-amide) having a flexural modulus <200 MPa.
    In this advantageous embodiment, this polyolefin-based polymer is therefore present in the copolyamide constituting the layer (1).
    The impact modifier polyolefin can be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized.
    In particular, some or all of the polyolefins carry a function chosen from the carboxylic acid, carboxylic anhydride and epoxide functions, and is in particular chosen from an ethylene-propylene copolymer of elastomeric character (EPR), an ethylene-propylene copolymer -diene with an elastomeric character (EPDM) and an ethylene / (meth) alkyl acrylate copolymer, an ethylene-higher alkene copolymer, in particular an ethylene-octene copolymer, an ethylene-alkyl acrylate-maleic anhydride terpolymer.
    Advantageously, the impact modifier is chosen from the Fusabond F493, a Lotader®, in particular the Lotader 5500 or the Lotader 7500, the Escor VA1801 or VA1803, the Excelsior E1040, the Amplify GR216, the Tafmer MH5020 or the Orevac IM800, or a mixture of these, in this case they are in a ratio ranging from 0.1 / 99.9 to 99.9 / 0.1, preferably 1/2 to 2/1 when they are mixed of two.
    By way of example, the impact modifier is chosen from the following mixtures: F493 / Lotader®, in particular F493 / Lotader® 5500 or F493 / Lotader® 7500.
    The expression “core-shell modifier” is also known as “core-shell modifier” or “core-shell copolymer”.
    The “core-shell type modifier” is in the form of fine particles having an elastomer core and at least one thermoplastic shell, the particle size is generally less than a μm and advantageously between 150 and 500 nm.
    The "core-shell type modifier" has an acrylic or butadiene base, unlike the impact modifier which has a polyolefin base.
    Examples of cores that may be mentioned are homopolymers of isoprene or butadiene, copolymers of isoprene with at most 30 mol% of a vinyl monomer and copolymers of butadiene with at most 30 mol% of a vinyl monomer. The vinyl monomer can be styrene, an alkylstyrene, acrylonitrile or an alkyl (meth) acrylate. Another core family consists of homopolymers of an alkyl (meth) acrylate and copolymers of an alkyl (meth) acrylate with at most 30 mol% of a vinyl monomer. The alkyl (meth) acrylate is advantageously butyl acrylate. The vinyl monomer can be styrene, an alkylstyrene, acrylonitrile, butadiene or isoprene. The core of the copolymer (A) can be crosslinked in whole or in part. It suffices to add at least difunctional monomers during the preparation of the core, these monomers can be chosen from poly (meth) acrylic esters of polyols such as butylene di (meth) acrylate and trimethylol propane trimethacrylate. Other difunctional monomers are for example divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate. The heart can also be crosslinked by introducing therein, by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as anhydrides of unsaturated carboxylic acids, unsaturated carboxylic acids and unsaturated epoxides. By way of example, mention may be made of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
    The bark or barks are homopolymers of styrene, of an alkylstyrene or of methyl methacrylate or of copolymers comprising at least 70 mol% of one of these preceding monomers and at least one comonomer chosen from the other preceding monomers , vinyl acetate and acrylonitrile. The bark can be functionalized by introducing, by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as anhydrides of unsaturated carboxylic acids, unsaturated carboxylic acids and unsaturated epoxides. By way of example, mention may be made of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate. By way of example, mention may be made of core-shell copolymers (A) having a polystyrene shell and core-shell copolymers (A) having a PMMA shell. There are also core-shell copolymers (A) having two shells, one made of polystyrene and the other outside of PMMA. Examples of copolymer (A) and their preparation process are described in the following patents: US 4,180,494, US 3,808,180, US 4,096,202, US 4,260,693, US 3,287,443, US 3,657,391, US 4,299,928, US 3,985,704.
    The “core-shell modifier is therefore different from the polyolefin of the impact modifier and in particular in that the impact modifier reacts with the polyamide matrix while the core-shell does not react with it because the core of the latter does not 'is likely to react only with the bark of it.
    Advantageously, the impact modifier and / or the core-shell modifier is present from 5 to 35% by weight relative to the weight of all the constituents of the copolyamide of layer (1), in particular from 5 to 25%, and more particularly from 5 to 15%.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in proportion from 5 to 35% by weight relative to the weight of all the constituents of the copolyamide, in particular from 5 to 25%, and more particularly from 5 to 15%.
    Advantageously, in structures comprising a shock modifier and / or a core-shell type modifier, X is 1,10-decanediamine.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said structure consists of a single layer (1).
    The invention therefore relates here to a monolayer pipe and in this embodiment, no other layer is present.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said layer (1) comprises a stabilizer chosen from an organic stabilizer, an inorganic stabilizer, in particular a stabilizer based on copper, and a mixture of these.
    The expression “organic stabilizer” or more generally a “combination of organic stabilizers” designates a primary antioxidant of phenol type, a secondary antioxidant of phosphite type and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or light stabilizer of the hindered amine type (for example Tinuvin® 770 from the company Ciba), an anti-UV (for example Tinuvin® 312 from the company Ciba), a phenolic stabilizer or based on phosphorus. Amine-type antioxidants can also be used, such as Naugard® 445 from the company Crompton, or polyfunctional stabilizers, such as Nylostab® S-EED from the company Clariant.
    The organic stabilizer present in the layer (1) can be chosen, without this list being restrictive, from:
    - phenolic antioxidants, for example irganox® 245, Irganox® 1010, Irganox® 1098 from the company Ciba, irganox® MD1024 from the company Ciba, Lowinox® 44B25 from the company Great Lakes , ADK® Stab AO-80 from Adeka Palmarole,
    stabilizers based on phosphorus, such as phosphites, for example the frgafos® 168 from the company Ciba,
    - a UV absorber, such as Tinuvin © 312 from Ciba,
    - a HALS, as previously mentioned,
    - an amine stabilizer, such as Naugard® 445 from the company Crompton, or also a hindered amine type such as Tinuvin® 770 from the company Ciba,
    - a polyfunctional stabilizer such as Nylostab® S-EED from the company Clariant.
    It is obviously possible to envisage a mixture of two or more of these organic stabilizers.
    Preferably, the organic stabilizer is present in the copolyamide of the layer (1) of the structure in a content of between 0.3 and 3% by weight relative to the total weight of the constituents of the copoiyamide.
    The term "mineral stabilizer" means a copper-based stabilizer. By way of example of such mineral stabilizers, mention may be made of halides and copper acetates. Incidentally, we can possibly consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, in particular potassium.
    These mineral stabilizers are more particularly used, when the structures must have an improved long-term thermal resistance in hot air, in particular for temperatures greater than or equal to 100-120 ° C., because they tend to prevent polymer chain cuts. .
    More particularly, by copper-based stabilizer is meant a compound comprising at least one copper atom, in particular in ionic, ionizable form, for example in the form of complex.
    The copper-based stabilizer present in the layer (1) can be chosen from cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous acetate and cupric acetate. Mention may be made of halides, acetates of other metals such as silver in combination with the copper-based stabilizer. These copper-based compounds are typically associated with alkali metal halides. A well-known example is the mixture of Cul and Kl, where the Cul: KI ratio is typically between 1: 5 to 1:15. An example of such a stabilizer is Polyadd P201 from the company Ciba.
    More details on copper-based stabilizers can be found in US Patent 2,705,227. More recently, copper-based stabilizers have appeared, such as complexed copper such as the Bruggolen H3336, H3337, H3373 from the company Brüggemann.
    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 the mixtures of copper iodide and potassium iodide (Cul / KI).
    Preferably, the copper-based stabilizer is present in the layer (1) of the structure in a content of between 0.05 and 1.5% by weight relative to the total weight of the constituents of the copolyamide.
    Preferably, the layer (1) also does not comprise any other transition metal.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in proportion from 5 to 35% by weight relative to the weight of all the constituents of the copolyamide and an organic stabilizer.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in proportion from 5 to 35% by weight relative to the weight of all the constituents of the copolyamide and a mineral stabilizer, in particular a stabilizer based on copper.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in proportion from 5 to 35% by weight relative to the weight of all the constituents of the copolyamide and a mixture of organic stabilizer and mineral stabilizer, in particular a stabilizer based on copper.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in proportion from 5 to 25% by weight relative to the weight of all the constituents of the copolyamide and an organic stabilizer.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in a proportion of 5 to 25% by weight relative to the weight of all the constituents of the copolyamide and a mineral stabilizer, in particular a stabilizer based on copper.
    Advantageously, the invention therefore relates to a structure as defined above comprising at least one layer (1) comprising a BACT / XT copolyamide as defined above and comprising an impact modifier and / or a core-type modifier shell in a proportion of 5 to 25% by weight relative to the weight of all the constituents of the copolyamide and a mixture of organic stabilizer and mineral stabilizer, in particular a stabilizer based on copper.
    Advantageously, in structures comprising a shock modifier and / or a core-shell type modifier, and a stabilizer X is 1,10-decanediamine.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said layer (1) comprises an antistatic filler chosen from carbon black, graphite, carbon fibers, carbon nanotubes , in particular carbon black and carbon nanotubes.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which said layer (1) can comprise at least one additive chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a nucleating agent, a plasticizer and a colorant.
    The reinforcing fibers are excluded from the additives and in particular the term "inorganic filler" excludes the reinforcing fibers.
    Advantageously, the additive (s) are present in the layer (1) in proportion by weight from 1 to 20%, in particular from 5 to 15%, relative to the total weight of the constituents of the layer (1).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, the layers (1) and (2) being capable of adhering to one 'other.
    The expression "being capable of adhering to each other" means that if the structure is made up of two layers, layers (1) and (2) adhere to each other, at least partially.
    If the structure comprises at least a third layer, said third layer can be placed between layer (1) and layer (2), in which case layers (1) and (2) do not adhere to each other but on the other hand layers (1) and (3) adhere to each other as well as layers (3) and (2).
    Advantageously, the structure consists of two layers (1) and (2) adhering to each other.
    Advantageously, said layer (2) comprises at least one polyamide chosen from an aliphatic polyamide and an aromatic polyamide, in particular an aliphatic polyamide.
    Advantageously, said aliphatic polyamide is derived from the polycondensation of at least one lactam or at least one aminocarboxylic acid, or of a diamine and of a dicarboxylic acid or of a mixture of these, the diamine being chosen among an aliphatic diamine, a cycloaliphatic diamine and the dicarboxylic acid being chosen from an aliphatic diacid and a cycloaliphatic diacid, or a mixture of these.
    The aminocarboxylic acid can be chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular N-heptyl-11- acid aminoundecanoic acid, advantageously 12-aminododecanoic acid and 11-aminoundecanoic acid.
    The lactam can be chosen from pyrrolidinone, piperidinone, caprolactam, enantholactam, caprylolactam, pelargolactam, decanolactam, undecanolactam, and laurolactam, advantageously undecanolactam, and laurolactam.
    When the diamine is aliphatic and linear, it has the formula H2N- (CH2) a-NH2. The diacid can be aliphatic (in particular linear aliphatic), cycloaliphatic or aromatic.
    Preferably, when the diamine is linear and aliphatic, it is chosen from butanediamine (a = 4), pentanediamine (a = 5), hexanediamine (a = 6), heptanediamine (a = 7), l '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), octadecanediamine (a = 18), eicosanediamine (a = 20), docosanediamine (a = 22) and diamines obtained from dimerized fatty acids.
    When the diamine is cycloaliphatic, it is preferably chosen from those comprising two cycles. They respond in particular to the following general formula:
    in which :
    R1, R2, R3 and R4 independently represent a group chosen from a hydrogen atom or an alkyl of 1 to 6 carbon atoms and
    - X represents either a single bond, or a divalent group consisting of:
    - a linear or branched aliphatic chain comprising from 1 to 10 carbon atoms, optionally substituted by cycloaliphatic or aromatic groups of 6 to 8 carbon atoms,
    - a cycloaliphatic group of 6 to 12 carbon atoms.
    More preferably, the cycloaliphatic diamine Ca of the polyamide is chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3,5-dialkyl -4-aminocyclo-hexyl) propane, bis (3,5-dialkyl-4-amino cyclohexyl) butane, bis- (3-methyl-4-amino cyclohexyl) -methane (noted BMACM, MACM or B), p- bis (aminocyclohexyl) -methane (PACM) and isopropylidenedi (cyclohexylamine) (PACP).
    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).
    The aliphatic and linear dicarboxylic acid is chosen from succinic acid (b = 4), pentanedioic acid (b = 5), adipic acid (b = 6), heptanedioic acid (b = 7), l octanedioic acid (b = 8), azelaic acid (b = 9), sebacic acid (b = 10), undecanedioic acid (b = 11), dodecanedioic acid (b = 12), l 'brassylic acid (b = 13), tetradecanedioic acid (b = 14), hexadecanedioic acid (b = 16), octadecanoic acid (b = 18), octadecenedioic acid (b = 18), l eicosanedioic acid (b = 20), docosanedioic acid (b = 22) and dimers of fatty acids containing 36 carbons.
    The fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with a long hydrocarbon chain (such as linoleic acid and oleic acid), as described in particular in the document EP 0 471 566.
    When the diacid is cycloaliphatic, it can comprise the following carbon skeletons norbornylmethane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) propane.
    The polyamide of the layer (2) can be a homopolyamide or a copolyamide.
    The nomenclature used to define polyamides is described in ISO standard 16396-1: 2015 "Plastics - Polyamide materials (PA) for molding and extrusion - Part 1: Designation system, product marking and specification basis".
    Advantageously, the polyamide of the layer (2) is chosen from PA11, PA12, PA1010, PA1012, PA610 and PA612.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which another polyamide, different from that of the layer (2) may be present in the layer (2).
    Said other polyamide is as defined above in layer (2) provided that it is different from that of layer (2).
    Advantageously, a plasticizer is present in the layer (2).
    Advantageously, the plasticizer of the layer (2) is present from 1 to 20%, in particular from 5 to 15% by weight relative to the weight of all the constituents of the copolyamide of the layer (2).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which an impact modifier and / or a modifier of the coreshell type is present in the layer (2).
    The shock modifier and / or the core-shell modifier are as defined above.
    Advantageously, the impact modifier and / or the core-shell modifier is present from 5 to 35% by weight relative to the weight of all the constituents of the copolyamide of layer (2), in particular from 5 to 25%, and more particularly from 5 to 15%.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, the layers (1) and (2) adhering to each other, the layer (1) being one of those defined above, and layer (2) comprising another polyamide or not, layer (2) comprising a plasticizer of 1 to 20% by weight and an impact modifier and / or a core-shell type modifier in proportion of 5 to 35% by weight relative to the weight of all the constituents of the copolyamide of the layer (2).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, the layers (1) and (2) adhering to each other, the layer (1) being one of those defined above, and layer (2) comprising another polyamide or not, layer (2) comprising a plasticizer of 1 to 20% by weight and an impact modifier and / or a core-shell type modifier in proportion of 5 to 25% by weight relative to the weight of all the constituents of the copolyamide of the layer (2).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, the layers (1) and (2) adhering to each other, the layer (1) being one of those defined above, and layer (2) comprising another polyamide or not, layer (2) comprising a plasticizer of 5 to 15% by weight and an impact modifier and / or a core-shell type modifier in proportion of 5 to 35% by weight relative to the weight of all the constituents of the copolyamide of the layer (2).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, the layers (1) and (2) adhering to each other, the layer (1) being one of those defined above, and layer (2) comprising another polyamide or not, layer (2) comprising a plasticizer of 5 to 15% by weight and an impact modifier and / or a core-shell type modifier in proportion of 5 to 25% by weight relative to the weight of all the constituents of the copolyamide of the layer (2).
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, in which said layer (2) comprises a stabilizer chosen from an organic stabilizer, an inorganic stabilizer , in particular a copper-based stabilizer, and a mixture thereof.
    The stabilizers are as defined above.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, in which the layer (1) comprises an organic stabilizer and the layer (2) comprises a mineral stabilizer, in particular a copper-based stabilizer.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, in which the layer (1) comprises an inorganic stabilizer, in particular a stabilizer based on copper and the layer (2) comprises an organic stabilizer.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, in which said layer (2) comprises an antistatic filler chosen from carbon black, graphite, carbon fibers, carbon nanotubes, in particular carbon black and carbon nanotubes.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which a second layer (2) is present, in which said layer (2) can comprise at least one additive chosen from an antioxidant, a heat stabilizer, UV absorber, light stabilizer, lubricant, inorganic filler, flame retardant, nucleating agent and colorant.
    In an advantageous embodiment, the present invention relates to a structure as defined above, in which the layer (1) is a barrier layer, in particular to a fluid, said fluid being chosen from a fuel, said fuel being a gasoline , in particular a bio gasoline (mixture of gasoline and alcohol, in particular methanol or ethanol), or diesel in particular bio-diesel, an oil, a brake fluid, solutions of urea, a glycol-based coolant, a gas, in particular compressed air, said barrier layer (1) is in contact with the fluid.
    The structure defined in this embodiment therefore comprises at least one layer (1) and can therefore be monolayer or bilayer (1) and (2) but it would not go beyond the scope of the invention if the structure included other layers .
    Advantageously, the structure consists of two layers (1) and (2) and the layer (1) is the barrier layer.
    Therefore, in the case where the structure comprises two layers, it comprises from outside to inside the following layers: (2) // (1).
    In the case where the structure comprises at least one other layer, the latter cannot be in contact with the fluid.
    In an advantageous embodiment, the present invention relates to a structure comprising at least one layer (1) as defined above, and a second layer (2) as defined above, the layers (1) and (2 ) being capable of adhering to each other, further comprising a layer (3), the layer (3) being identical to or different from the layer (1).
    In this embodiment, the structure comprises or consists of the following layers, from the outside to the inside:
    (3) // (2) // (1) or (2) // (3) // (1).
    Advantageously, the layer (3) is different from the layer (1) and is a tie layer and the structure comprises from outside to inside the following layers: (2) // (3) // (1) , the layer (1) being in contact with the fluid.
    Advantageously, in the structure (2) // (3) // (1), the layer (1) has a thickness of 100 to 300pm, in particular from 200 to 300pm, in particular 250pm, the layer (3) has a thickness from 50 to 100pm or from 100 to 200pm, in particular 150pm and the layer (2) has a thickness of 50 to 800pm, in particular from 50 to 200pm or from 500 to 700pm.
    The bonding layer may be a mixture of at least one polyamide having an average number of carbon atoms per nitrogen atom noted between 4 and 8.5, advantageously between 4 and 7; at least one polyamide having a melting point greater than or equal to 180 ° C. and an average number of carbon atoms per nitrogen atom of between 7 and 10, advantageously between 7.5 and 9.5 and at least one polyamide having an average number of carbon atoms per nitrogen atom of between 9 and 18, advantageously between 10 and 18, in particular as defined in document WO 09/122060.
    In an advantageous embodiment, the present invention relates to a structure comprising at least one layer (1) as defined above, a second layer (2) as defined above, the layers (1) and (2) being capable of adhering to each other and a layer (3), the layer (3) being identical to or different from the layer (1), said structure further comprising at least one other layer (4), the layer (1) being in contact with the fluid.
    Advantageously, the layer (4) is a layer of EVOH.
    In an advantageous embodiment, the present invention relates to a structure comprising at least one layer (1) as defined above, and a second layer (2) as defined above, the layers (1) and (2 ) being capable of adhering to each other and a layer (3), the layer (3) being identical to or different from the layer (1) and at least one other layer (4), the layer (1 ) being in contact with the fluid, said structure comprising from outside to inside the following layers: (2) // (4) // (3) // (1), the layer (1) being in contact with the fluid.
    Advantageously, in the structure (2) // (4) // (3) // (1), the layer (3) is a layer of binder as defined above.
    Advantageously, in the structure (2) // (4) // (3) // (1), the layer (4) is a layer of EVOH as defined above.
    Advantageously, in the structure (2) // (4) // (3) // (1), the layer (3) is a layer of binder as defined above and the layer (4) is a layer of 'EVOH as defined above.
    Advantageously, the structure consists of layers (2) // (4) // (3) // (1) as defined above.
    In an advantageous embodiment, the present invention relates to a structure comprising at least one layer (1) as defined above, a second layer (2) as defined above, the layers (1) and (2) being capable of adhering to each other, a layer (3), the layer (3) being identical to or different from the layer (1), at least one other layer (4), the layer (1) being in contact with the fluid, and comprising from outside to inside the following layers: (2) // (4) // (3) // (1), the layer (1) being in contact with the fluid,
    Said structure further comprising a tie layer (3 ’), identical to or different from the tie layer (3) is present.
    The layer (3 ’) is therefore a binder of the same type as that defined above for the layer (3) but of identical or different composition.
    Advantageously, said structure further comprising a bonding layer (3 '), comprises from the outside to the inside the following layers: (2) // (3') // (4) // (3) // (1), the layer (1) being in contact with the fluid.
    Advantageously, the layer (1) has a thickness of 100 to 200pm, in particular 150pm, the layer (2) has a thickness of 100 to 200pm, in particular 150pm, the layer (3) has a thickness of 200 to 400pm, in especially 300pm, the layer (3 ') has a thickness of 200 to 400pm, in particular 300pm and the layer (4) of 50pm to 150pm, in particular 100 pm.
    According to another aspect, the present invention relates to bottles, reservoirs, containers, pipes and containers made with one of the structures as defined above.
    According to another aspect, the present invention relates to packages made of films made with one of the structures as defined above.
    According to another aspect, the present invention relates to the use of a BACT / XT dcopolyamide in which:
    BACT is an amide unit present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is chosen from 1,3-bis (aminomethyl) cyclohexyl (1.3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1.4 BAC) and a mixture thereof, and T is terephthalic acid,
    - XT is a unit with a majority amide unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear C 9 to C 18 aliphatic diamine, preferably in C9, C10, C11 and C12, and where T is terephthalic acid, preferably in C10, C11 and C12. in the BACT and / or XT units, independently of one another, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, relative to the total amount of dicarboxylic acids, terephthalic acid can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and in BACT and / or XT units, independently from each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, of the BAC and / or as the case may be X, relative to the amount total of the diamines, can be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular 6 to 12 carbon atoms, and in the copolyamide, not more than 30 mol%, preferably not more than 10% in mole, relative to the total amount of monomers, can be formed by lactams or aminocarboxylic acids, and provided that the sum e of the monomers which replace terephthalic acid, BAC and X do not exceed a concentration of 30% by mole, preferably 10% by mole, relative to the total amount of the monomers used in the copolyamide, and provided that BACT and XT units are always present in said polyamide polymer, for the manufacture of a structure, in particular multilayer, comprising at least one barrier layer (1) comprising said BACT / XT copolyamide, said structure being devoid of reinforcing fibers.
    Examples:
    1) Preparation of a BACT / 10T and comparative polyamides
    The following procedure is an example of a preparation process, and is not limiting. It is representative of all the compositions according to the invention and comparative:
    5 kg of the following raw materials are introduced into an autoclave reactor of 14 liters
    500 g of water, the diamines, the amino acid (optionally), the terepthalic acid and optionally one or other diacids, the monofunctional chain regulator: benzoic acid in an amount suitable for the
    Mn targeted and variant (benzoic acid) from 50 to 100 g, g of sodium hypophosphite in solution,
    0.1 g of WACKER AK1000 defoamer (company Wacker Silicones).
    The nature and molar ratios of the units and molecular structures of the polyamides (by referenced test) are given in Table III below.
    The 1.3 BAC used has a cis / trans ratio of 75/25 mol%.
    The closed reactor is purged of its residual oxygen and then heated to a temperature of 230 ° C. relative to the material introduced. After 30 minutes of stirring under these conditions, the pressurized vapor which has formed in the reactor is gradually expanded in 60 minutes, while gradually increasing the material temperature so that it becomes established at Tf + 10 ° C at atmospheric pressure.
    The polymerization is then continued under a nitrogen flush of 20 l / h until the target mass Mn indicated in the table of characteristics is obtained.
    The polymer is then drained by the bottom valve and then cooled in a water tank and then put in the form of granules.
    The products are then injected in the form of a 100 mm × 100 mm × 1 mm plate using an injection press using an injection temperature equal to Tf + 20 ° C. and a mold heated to 100 ° C. The plates which are not entirely crystallized (presence of recrystallization on DSC heating according to ISO 11357-2: 2013) are annealed for 2 hours under vacuum at Tg + 30 ° C.
    - The measurement of intrinsic or inherent viscosity is carried out in m-cresol. The method is well known to those skilled in the art. We follow the ISO 307: 2007 standard but by changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
    - The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC), after a second heating pass, according to ISO 113572: 2013. The heating and cooling rate is 20 ° C / min.
    - The melting temperature Tf and the crystallization temperature Tc are measured by DSC, according to standard ISO 11357-3: 2013. The heating and cooling rate is 20 ° C / min.
    - The enthalpy of crystallization of said matrix polymer is measured in Differential Scanning Calorimetry (DSC), after a second heating pass, according to ISO standard 11357-3: 2013.
    - The determination of the rate of end of amine and acid chains is determined by potentiometry.
    - The gasoline permeability measurements are determined at 60 ° C according to a gravimetric method with CE10: isooctane / toluene / ethanol = 45/45/10 vol. And CE85: isooctane / toluene / ethanol = 7.5 / 7 , 5/85 vol.% On the plates prepared above. The instant permeability is zero during the induction period, then it gradually increases until an equilibrium value which corresponds to the permeability value in steady state. This value obtained in steady state is considered to be the permeability of the material.
    The results are presented in Table III below.
    Ref. Molecular structure / (Compositionmolar) Tf (° C) / Tg (° C) Te (° C) / Tf-Tc (° C) ΔΗο Viscosiyouinherent (mresol) CE10 permeability g.mm/m 2 .24 h CE85 permeability g.mm/m 2 .24h nh 2 pkg / g co 2 h pkg / g 11 BACT / 10T(50/50) 282/153 248/33 53.5 1.05 0.3 1.7 5467 C1 MXDT / 10T(41/59) 269/131 - - 1.01 0.3 2 38134 C2 8MT / 9T(48/52) 265/125 - - 1.25 0.5 3.2 C3 (10I / 10T33.3 / 66.6) 283/107 205/78 32 1.11 0.4 7 C4 10T / 6T / 11(42.5 / 42.5 / 15) 269/114 - - 1.25 0.8 5 C5 10T / 6T / 11(61 / 24.5 / 14.5) 269/111 220/49 39 1.25 0.35 6 C6 10T / 101/11 (64 / 20.5 / 15.5) 265/100 - - 1.15 2.75 20 C7 11 / 6T (35/65) 312/100 - - 1.21 0.65 6.7 C8 11 / 6T (50/50) 273/79 - - 1.05 20 76 C9 11 / 10T (33.3 / 66.6) 269/84 232/37 50 1.18 3.1 13
    : Invention C: comparative
    TABLE III
    The structures of the invention show a permeability to species lower than that of the comparative structures, that is to say barrier properties to the species higher than that of the comparative structures.
    权利要求:
    Claims (37)
    [1" id="c-fr-0001]
    Claims
    1. Structure comprising at least one layer (1) comprising a BACT / XT copolyamide in which:
    - BACT is a unit with amide motif present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is chosen from 1,3-bis (aminomethyl) cyclohexyl (1.3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1.4 BAC) and a mixture thereof, and T is terephthalic acid,
    - XT is a unit with a majority amide unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear C9 to C18 aliphatic diamine, preferably in C9, C10, C11 and C12, and where T is terephthalic acid, preferably in C10, C11 and C12.
    - in BACT and / or XT units, independently of each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, relative to the total amount dicarboxylic acids, terephthalic acid can be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and in the BACT and / or XT units, independently of each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, of the BAC and / or as the case of X, relative to the total quantity of diamines, can be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular 6 to 12 carbon atoms, and
    in the copolyamide, not more than 30 mol%, preferably not more than 10 mol%, relative to the total amount of the monomers, can be formed by lactams or amino carboxylic acids, and
    - provided that the sum of the monomers which replace terephthalic acid, BAC and X does not exceed a concentration of 30% by mole, preferably 10% by mole, relative to the total amount of monomers used in the copolyamide, and
    - provided that BACT and XT units are always present in said polyamide polymer, said structure being devoid of reinforcing fibers.
    [2" id="c-fr-0002]
    2. Structure according to claim 1, wherein said copolyamide has a melting temperature Tf <290 ° C, preferably <285 ° C, more preferably <280 ° C, as determined according to ISO 11357-3 (2013) .
    [3" id="c-fr-0003]
    3. Structure according to claim 1 or 2, wherein said copolyamide has a glass transition temperature Tg> 120 o C, preferably> 130 ° C, more preferably> 140 ° C, determined according to ISO 11357-2: 2013 .
    [4" id="c-fr-0004]
    4. Structure according to one of claims 1 to 3, wherein said copolyamide has a difference between the melting temperature and the crystallization temperature Tf -Te <40 ° C, preferably <30 ° C, determined according to ISO standard 11357 -3: 2013.
    [5" id="c-fr-0005]
    5. Structure according to one of claims 1 to 4, characterized in thatTenthalpy of crystallization of the copolyamide, measured in Differential Scanning Calorimetry (DSC) according to Standard ISO 11357-3: 2013, is greater than 40 J / g, of preferably greater than 45 J / g, more preferably greater than 50 J / g.
    [6" id="c-fr-0006]
    6. Structure according to one of claims 1 to 5, wherein the BAC is 1.3 BAC.
    [7" id="c-fr-0007]
    7. Structure according to one of claims 1 to 6, in which the BAC is 1.3 BAC andXT is chosen from 9T, 10T, 11T and 12T.
    [8" id="c-fr-0008]
    8. Structure according to one of claims 1 to 7, in which XT is 10T, 10 corresponding to 1.10 decanediamine.
    [9" id="c-fr-0009]
    9. Structure according to one of claims 1 to 8, in which the sum of the monomers which replace terephthalic acid, BAC and X is equal to 0.
    [10" id="c-fr-0010]
    10. Structure according to one of claims 1 to 9, wherein said layer (1) comprises an impact modifier and / or modifier of the core-shell type.
    [11" id="c-fr-0011]
    11. Structure according to one of claims 1 to 10, wherein said structure consists of a single layer (1).
    [12" id="c-fr-0012]
    12. Structure according to one of claims 1 to 11, wherein said layer (1) comprises a stabilizer chosen from an organic stabilizer, an inorganic stabilizer, in particular a stabilizer based on copper, and a mixture thereof.
    [13" id="c-fr-0013]
    13. Structure according to one of claims 1 to 12, wherein said layer (1) comprises an antistatic filler chosen from carbon black, graphite, carbon fibers, carbon nanotubes, in particular carbon black and carbon nanotubes.
    [14" id="c-fr-0014]
    14. Structure according to one of claims 1 to 13, wherein said layer (1) may comprise at least one additive chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, inorganic filler, flame retardant, nucleating agent, plasticizer and colorant.
    [15" id="c-fr-0015]
    15. Structure according to one of claims 1 to 10 and 12 to 14, wherein a second layer (2) is present, the layers (1) and (2) being capable of adhering to each other.
    [16" id="c-fr-0016]
    16. Structure according to claim 15, in which said layer (2) comprises at least one polyamide chosen from an aliphatic polyamide and an aromatic polyamide, in particular an aliphatic polyamide.
    [17" id="c-fr-0017]
    17. Structure according to claim 16, in which said aliphatic polyamide is derived from the polycondensation of at least one lactam, an aminocarboxylic acid, or of a diamine and of a dicarboxylic acid, the diamine being chosen from an aliphatic diamine, an aromatic diamine and a cycloaliphatic diamine and the dicarboxylic acid being chosen from an aliphatic diacid, an aromatic diacid and a cycloaliphatic diacid, or a mixture thereof.
    [18" id="c-fr-0018]
    18. Structure according to one of claims 16 to 17, wherein said aliphatic polyamide of the layer (2) is chosen from PA11, PA12, PA1010, PA1012, PA610 and PÀ612.
    [19" id="c-fr-0019]
    19. Structure according to one of claims 16 to 18, in which another polyamide, different from that of the layer (2) may be present in the layer (2).
    [20" id="c-fr-0020]
    20. Structure according to one of claims 15 to 19, in which a plasticizer is present in the layer (2).
    [21" id="c-fr-0021]
    21. Structure according to one of claims 15 to 20, in which an impact modifier is present in the layer (2).
    [22" id="c-fr-0022]
    22. Structure according to one of claims 15 to 21, in which said layer (2) comprises a stabilizer chosen from an organic stabilizer, an inorganic stabilizer, in particular a stabilizer based on copper, and a mixture thereof.
    [23" id="c-fr-0023]
    23. Structure according to one of claims 15 to 22, wherein the layer (1) comprises an organic stabilizer and the layer (2) comprises an inorganic stabilizer, in particular a stabilizer based on copper.
    [24" id="c-fr-0024]
    24. Structure according to one of claims 15 to 22, wherein the layer (1) comprises an inorganic stabilizer, in particular a copper-based stabilizer and the layer (2) comprises an organic stabilizer.
    [25" id="c-fr-0025]
    25. Structure according to one of claims 15 to 24, wherein said layer (2) comprises an antistatic filler selected from carbon black, graphite, carbon fibers, carbon nanotubes, in particular carbon black and carbon nanotubes.
    [26" id="c-fr-0026]
    26. Structure according to one of claims 15 to 25, wherein said layer (2) may comprise at least one additive chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, inorganic filler, flame retardant, nucleating agent and colorant.
    [27" id="c-fr-0027]
    27. Structure according to one of claims 1 to 26, in which the layer (1) is a barrier layer, in particular against a fluid, said fluid being chosen from a fuel, said fuel being a gasoline, in particular a bio gasoline ( mixture of petrol and alcohol (in particular methanol or ethanol), or diesel in particular bio-diesel, an oil, a brake fluid, urea solutions, a glycol-based coolant , a gas, in particular compressed air, said barrier layer (1) being in contact with the fluid.
    [28" id="c-fr-0028]
    28. Structure according to one of claims 15 to 27, further comprising a layer (3), the layer (3) being identical to or different from the layer (1).
    [29" id="c-fr-0029]
    29. Structure according to claim 28, in which the layer (3) is different from the layer (1) and is a tie layer and the structure comprises from outside to inside the following layers: (2) // (3) // (1), the layer (1) being in contact with the fluid.
    [30" id="c-fr-0030]
    30. Structure according to one of claims 28 to 29, in which at least one other layer (4) is present, your layer (1) being in contact with the fluid.
    [31" id="c-fr-0031]
    31. Structure according to claim 30, in which the layer (4) is a layer of EVOH.
    [32" id="c-fr-0032]
    32. Structure according to one of claims 30 to 31, in which the structure comprises from outside to inside the following layers: (2) // (4) // (3) // (1), the layer (1) being in contact with the fluid.
    [33" id="c-fr-0033]
    33. Structure according to claim 28 to 31, in which a tie layer (3 ’), identical to or different from the tie layer (3) is present.
    [34" id="c-fr-0034]
    34. Structure according to claim 33, in which the structure comprises from the outside to the inside the following layers: (2) // (3 ') // (4) // (3) // (1), the layer (1) being in contact with the fluid.
    [35" id="c-fr-0035]
    35. Bottles, tanks, containers, pipes and containers made with the structure according to any one of the preceding claims.
    [36" id="c-fr-0036]
    36. Packages made of films made with the structure according to any one of the preceding claims.
    [37" id="c-fr-0037]
    37. Use of a BACT / XT copoiyamide in which:
    - BACT is a unit with amide motif present at a molar level ranging from 20 to 70%, preferably from 25 to 60%, more preferably from 35 to 55%, where BAC is chosen from 1,3-bis (aminomethyl) cyclohexyl (1.3 BAC), 1,4-bis (aminomethyl) cyclohexyl (1.4 BAC) and a mixture thereof, and T is terephthalic acid,
    - XT is a unit with a majority amide unit present at a molar level ranging from 30 to 80%, preferably from 40 to 75%, more preferably from 45 to 65%, where X is a linear C9 to C18 aliphatic diamine, preferably in C9, C10, C11 and C12, and where T is terephthalic acid, preferably in C10, C11 and C12.
    - in BACT and / or XT units, independently of each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, relative to the total amount dicarboxylic acids, terephthalic acid may be replaced by other aromatic, aliphatic or cycloaliphatic dicarboxylic acids comprising 6 to 36 carbon atoms, in particular 6 to 14 carbon atoms, and in BACT and / or XT units, independently of each other, up to 30% by mole, preferably 20% by mole, in particular up to 10% by mole, of the BAC and / or as the case of X, relative to the total quantity of diamines, can be replaced by other diamines comprising from 4 to 36 carbon atoms, in particular 6 to 12 carbon atoms, and
    in the copolyamide, not more than 30 mol%, preferably not more than 10 mol%, relative to the total amount of the monomers, can be formed by lactams or aminocarboxylic acids, and
    - provided that the sum of the monomers which replace terephthalic acid, BAC and X does not exceed a concentration of 30% by mole, preferably 10% by mole, relative to the total amount of monomers used in the copolyamide, and
    - provided that BACT and XT units are always present in said polyamide polymer, for the manufacture of a structure, in particular a multilayer structure, comprising at least one barrier layer (1) comprising said BACT / XT copolyamide, said structure being devoid of fibers reinforcement.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3481890B1|2020-01-29|Barrier structure made from bact/xt copolyamide with a high glass transition temperature
    EP3443022B1|2020-08-26|Semi-crystalline polyamide composition having a high glass transition temperature and a high melting temperature for a thermoplastic material, production method thereof and uses of same
    EP2576658B1|2018-07-11|Sulfonate-modified polyamide having improved barrier properties
    WO2018011494A1|2018-01-18|Semi-crystalline polyamide composition having a high glass transition temperature for a thermoplastic material, production method thereof and uses of same
    FR2973731A1|2012-10-12|PROCESS FOR MANUFACTURING RESERVOIRS WITH HIGH BARRIER PROPERTIES TO FLUIDS
    EP3390493A1|2018-10-24|Barrier structure based on mpmdt/xt copolyamide with a high tg
    WO2017103504A1|2017-06-22|Barrier structure made from mxdt/xt copolyamide with a high tg
    EP3907247A1|2021-11-10|Glass transition high-temperature semi-crystalline polyamide composition made of near-field diamine for thermoplastic material, method for manufacturing same and uses thereof
    EP3466681B1|2019-08-07|Multilayer material with resistance to ageing and hot burst, for high temperature automotive applications
    EP3941969A1|2022-01-26|Copolyamide compositions comprising reinforcing fibers with high modulus stability and uses thereof
    WO2020188203A1|2020-09-24|Copolyamide compositions comprising reinforcing fibers and having high modulus stability and uses thereof
    WO2021209729A2|2021-10-21|Hot melt adhesive withstanding motor vehicle fluids
    同族专利:
    公开号 | 公开日
    US20190232628A1|2019-08-01|
    KR20190031257A|2019-03-25|
    EP3481890B1|2020-01-29|
    KR102330137B1|2021-11-23|
    WO2018011493A1|2018-01-18|
    CN109476839B|2021-11-02|
    EP3481890A1|2019-05-15|
    JP2019520464A|2019-07-18|
    FR3053694B1|2018-07-06|
    CN109476839A|2019-03-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2117978A1|1970-12-10|1972-07-28|Hoechst Ag|
    FR2189448A1|1972-05-27|1974-01-25|Hoechst Ag|
    DE2256214A1|1972-11-16|1974-05-22|Hoechst Ag|Transparent polyamides for mouldings - obtd. from 1,3-and 1,4-bis cyclohexane, linear aliphatic diamine and aromatic dicarboxy-lic acid|
    EP1860134A1|2005-03-18|2007-11-28|Kuraray Co., Ltd.|Semi-aromatic polyamide resin|
    US2705227A|1954-03-15|1955-03-29|Du Pont|Heat stabilization of polyamides|
    DE1470866B2|1962-12-24|1971-01-21|Kanegafuchi Chemical Industry Co, Ltd, Osaka |Thermoplastic molding compounds|
    US3657391A|1969-03-12|1972-04-18|Borg Warner|Graft copolymers of styrene acrylonitrile and methyl acrylate onto diene polymers and blends thereof with vinyl chloride resins|
    US3808180A|1970-04-13|1974-04-30|Rohm & Haas|Composite interpolymer and low haze impact resistant thermoplastic compositions thereof|
    US3985704A|1975-06-19|1976-10-12|Rohm And Haas Company|Methacrylate-butadiene-styrene graft polymers and process for their production|
    US4096202B1|1976-06-09|1983-08-09|
    US4180494A|1977-08-15|1979-12-25|Rohm And Haas Company|Thermoplastic polyesters|
    US4260693A|1979-08-27|1981-04-07|General Electric Company|Polycarbonate compositions|
    US4299928A|1980-03-14|1981-11-10|Mobay Chemical Corporation|Impact modified polycarbonates|
    GB9018144D0|1990-08-17|1990-10-03|Unilever Plc|Polymerisation process|
    EP1449885B1|2003-02-18|2013-10-02|Arkema France|Use of carbon nanotubes in compositions based on polyamides and polyolefins|
    BRPI0510314B1|2004-04-27|2016-10-18|Kuraray Co|multilayer structure|
    DE502008000140D1|2007-05-03|2009-11-26|Ems Patent Ag|Partially aromatic polyamide molding compounds and their uses|
    FR2928649A1|2008-03-12|2009-09-18|Ceca Sa Sa|LUBRICANT FOR TRANSPORTING CHAIN OF CONTAINERS|
    FR2934865B1|2008-08-08|2010-08-27|Arkema France|SEMI-AROMATIC COPOLYAMIDE AND PROCESS FOR PREPARING THE SAME|
    JP2010285553A|2009-06-12|2010-12-24|Mitsubishi Gas Chemical Co Inc|Heat-resistant polyamide resin|
    ES2437440T3|2009-08-06|2014-01-10|Arkema France|Composition comprising a copolyamide and a crosslinked polyolefin|
    MX340557B|2010-12-27|2016-07-14|Mitsubishi Gas Chemical Co|Polyamide composition.|
    FR2997089B1|2012-10-23|2015-11-13|Arkema France|THERMOPLASTIC COMPOSITE MATERIAL BASED ON SEMI-CRYSTALLINE POLYAMIDE AND PROCESS FOR PRODUCING THE SAME|
    EP2727951A1|2012-11-06|2014-05-07|Solvay Specialty Polymers USA, LLC.|Mobile electronic devices made of amorphous polyamides|
    EP2767555A1|2013-02-15|2014-08-20|Solvay Specialty Polymers USA, LLC.|Mobile electronic devices made of amorphous polyamides|
    DE102013218957A1|2013-09-20|2015-03-26|Evonik Industries Ag|Molding composition based on a partly aromatic copolyamide|
    WO2016058991A1|2014-10-16|2016-04-21|Solvay Specialty Polymers Usa, Llc|Polymers featuring enhanced flow|FR3064271B1|2017-03-24|2021-04-30|Arkema France|COMPOSITION OF SEMI-CRYSTALLINE POLYAMIDE OF HIGH GLASS TRANSITION TEMPERATURE AND HIGH MELTING TEMPERATURE FOR THERMOPLASTIC MATERIAL, ITS MANUFACTURING PROCESS AND ITS USES|
    FR3090450B1|2018-12-20|2022-01-21|Arkema France|FIBROUS MATERIAL IMPREGNATED WITH THERMOPLASTIC POLYMER OF OPTIMUM MOLECULAR WEIGHT AND VISCOSITY AND METHOD FOR PREPARING IT|
    CN110951248A|2019-11-04|2020-04-03|江门市德众泰工程塑胶科技有限公司|Black LED support material and preparation method thereof|
    WO2021224337A1|2020-05-07|2021-11-11|Solvay Specialty Polymers Usa, Llc|Polymer compositions including a polyamide and a poly and corresponding articles|
    法律状态:
    2017-06-13| PLFP| Fee payment|Year of fee payment: 2 |
    2018-01-12| PLSC| Publication of the preliminary search report|Effective date: 20180112 |
    2018-06-12| PLFP| Fee payment|Year of fee payment: 3 |
    2020-06-12| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1656623A|FR3053694B1|2016-07-11|2016-07-11|BARRIER STRUCTURE BASED ON HIGH B TG / XT COPOLYAMIDE|
    FR1656623|2016-07-11|FR1656623A| FR3053694B1|2016-07-11|2016-07-11|BARRIER STRUCTURE BASED ON HIGH B TG / XT COPOLYAMIDE|
    JP2019500835A| JP2019520464A|2016-07-11|2017-07-10|Barrier structure manufactured from BACT / XT copolyamide with high Tg|
    KR1020197003568A| KR102330137B1|2016-07-11|2017-07-10|Barrier construct made from BACT/XT copolyamide with high Tg|
    US16/316,361| US20190232628A1|2016-07-11|2017-07-10|Barrier structure made from bact/xt copolyamide with a high tg|
    CN201780043211.5A| CN109476839B|2016-07-11|2017-07-10|Barrier structures made from BACT/XT copolyamides with high TG|
    EP17745844.5A| EP3481890B1|2016-07-11|2017-07-10|Barrier structure made from bact/xt copolyamide with a high glass transition temperature|
    PCT/FR2017/051871| WO2018011493A1|2016-07-11|2017-07-10|Barrier structure made from bact/xt copolyamide with a high tg|
    [返回顶部]