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    • 专利摘要:
    The invention relates to a rigid polyamide block copolymer PA and flexible blocks, characterized in that it comprises at least one carboxylic acid end chain blocked by a polycarbodiimide, said copolymer according to the invention being in non-crosslinked linear form. The invention also relates to the use of a polycarbodiimide in a process for the manufacture of rigid polyamide PA block copolymers and flexible blocks comprising at least one end of the carboxylic acid chain, to improve the extrudability of the copolymer, the stretching capacity of the copolymer, the abrasion resistance, the tear resistance and the durability of the copolymer, without increasing its dispersity.
    公开号:FR3073848A1
    申请号:FR1760880
    申请日:2017-11-17
    公开日:2019-05-24
    发明作者:Quentin Pineau；Philippe Blondel；Jean-Jacques Flat
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    BLOCK COPOLYMER HAVING IMPROVED ABRASION AND TEAR RESISTANCE
    FIELD OF THE INVENTION
    The present invention relates to a new copolymer with rigid polyamide PA blocks and flexible blocks, such as polyether PE or polyester PES, allowing the manufacture of materials which are both abrasion and tear resistant, more durable thanks to a limitation of the residual deformation, while being easily recyclable.
    The present invention also relates to a method of manufacturing such a composition and its use in particular in the sports industry, in particular footwear, in particular for the manufacture of soles and very particularly of sports shoe soles.
    TECHNICAL BACKGROUND
    During the last decade, copolymers with polyamide PA blocks and polyether PE blocks (abbreviated PEBA copolymer in the present description), in particular those marketed by the company Arkema under the brand Pebax®, have gradually established themselves in the field of high-end footwear. , in particular sports, thanks to their mechanical properties and in particular their exceptional elastic return property. Indeed, PEBA can be advantageously used in sports shoes as a semi-rigid sole (football, baseball, ...) or flexible (jogging) allowing the internal sole to be produced directly (cushioning ) and / or the outsole (resistance to abrasion-rigidity).
    Unfortunately, the abrasion resistance, expressed by the loss of mass in mg (according to ISO 9352: 2012) and the tear resistance, expressed in kN / m (according to ISO 34-1: 2015), PEBA-based substrates from prior art systems are far from optimal. Thus, with some of the PEBA substrates with a hardness of 25 to 55 Shore D on average (for example Pebax® 2533), a tear resistance of 41 kN / m, measured according to ISO 34-1: 2015, is obtained at best. However, shoe manufacturers require for certain applications a tear strength of at least 45 kN / m, preferably at least 50 kN / m, or even at least 60 kN / m. For other PEBA substrates with a hardness of 25 to 55 Shore D on average, for example Pebax® 35R53, the abrasion is such that the loss of mass measured according to ISO 9352: 2012 is greater than 55 mg.
    The present invention therefore aims to provide a block copolymer with improved properties of abrasion resistance and tear resistance.
    The present invention also aims to provide a copolymer with a lower residual tensile deformation according to ISO standard 5271A: 2012, that is to say a lower percentage of residual deformation, to allow better durability of the copolymer material.
    The present invention also aims to provide materials that are both durable and recyclable, two generally contradictory requirements in the field of elastomeric thermoplastic materials.
    The Applicant has now developed a new type of block copolymer, which has improved abrasion resistance, tear resistance, and durability, while retaining excellent recyclability properties.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION
    In the present description, it is specified that when reference is made to intervals, the expressions of the type "going from ... to" or "comprising / comprising from ... to" include the limits of the interval. Conversely, expressions of the type "between ... and ..." exclude the limits of the interval.
    Unless otherwise stated, the percentages expressed are mass percentages. Unless otherwise stated, the parameters to which reference is made are measured at atmospheric pressure and ambient temperature (20-25 ° C, generally 23 ° C).
    The invention is now described in detail and without limitation in the description which follows.
    The subject of the invention is therefore a copolymer with rigid polyamide PA blocks and flexible blocks, characterized in that it comprises at least one end of the carboxylic acid chain blocked by a polycarbodiimide.
    The polyamide PA rigid block copolymer and flexible blocks thus defined according to the invention is one of the elastomeric thermoplastic polymers. The term “thermoplastic elastomeric polymer”, abbreviated “TPE”, designates a polymer which constitutes a multiphase material having at least two transitions, namely a first transition at a temperature T1 (in general it is the glass transition temperature) and a second transition at a temperature T2 higher than T1 (in general it is the melting point). At a temperature below T1, the material is rigid, between T1 and T2 it has an elastic behavior, and above T2 it is melted. Such a polymer combines the elastic behavior of rubber-like materials with the processability of thermoplastics.
    A thermoplastic elastomer based on polyamide (TPE-A) within the meaning of the invention, such as a PEBA, is a block copolymer comprising a block of blocks, alternately rigid or hard (BD) and flexible or soft (BM), according to the following general formula:
    - [BD-BM] net in which:
    BD or Hard Block or rigid block: represents a block comprising polyamide (homopolyamide or copolyamide) or a mixture of blocks comprising polyamide (homopolyamide or copolyamide), hereinafter abbreviated independently PA or BD block;
    BM or Soft Block or flexible block: represents a block based on polyether (PE block), polyester (PES block), polydimethylsiloxane (PDMS block), polyolefin (PO block), polycarbonate (PC block) and / or any other polymer with a low glass transition temperature, or mixtures thereof in the form of alternating, random or block copolymers. Preferably, BM is a polyether-based block comprising alkylene oxide units, in whole or in part.
    n represents the number of repeating units of the -BD-BMdudit copolymer motif, n is in the range from 1 to 60, preferably from 5 to 30, or better still from 6 to 20.
    By low glass transition temperature for a polymer entering into the composition of a BM within the meaning of the invention, is meant a glass transition temperature Tg of less than 15 ° C, preferably less than 0 ° C, preferably less than -15 ° C, more preferably less than -30 ° C. By way of example, said soft block can be based on PEG of molar mass in number equal to 1500 g / mol and of Tg of the order of 35 ° C. Said glass transition temperature Tg can also be less than -50 ° C., in particular in the case where said soft block is based on PTMG.
    The copolyether block amides, also called copolymers with polyether blocks and polyamide blocks, or in short “PEBA”, result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
    1) polyamide blocks with chain ends diamines with polyoxyalkylene blocks with ends of dicarboxylic chains;
    2) polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends, obtained by cyanoethylation and hydrogenation of polyoxyalkylene alpha-omega dihydroxylated aliphatic blocks called polyetherdiols;
    3) polyamide blocks with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.
    The polyamide blocks with dicarboxylic chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid. The polyamide blocks with diamine chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain limiting diamine.
    The number-average molar mass Mn of the polyamide blocks is between 400 and 20,000 g / mol and preferably between 500 and 10,000 g / mol.
    The polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly.
    Three types of polyamide blocks can advantageously be used.
    According to a first type, the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms and from an aliphatic or aromatic diamine, in particular those having from 2 to 20 carbon atoms, preferably those having from 6 to 14 carbon atoms.
    As examples of dicarboxylic acids, mention may be made of 1,4cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acid and terephthalic and isophthalic acids, but also dimerized fatty acids.
    As examples of diamines, mention may be made of tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylene diamine, isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis - (3-methyl-4aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4aminocyclohexyl) -propane (BMACP), and para-amino-di-cyclo-hexyl-methane (PACM), and isophoronediamine (IPDA), 2,6-bis- (aminomethyl) -norbomane (BAMN) and piperazine (Pip).
    Regarding the rigid polyamide block, standard NF EN ISO 1874-1: 2011 defines a classification of polyamides. The term "monomer" in the present description should be taken in the sense of "repeating unit". The case where a repeating unit of the polyamide consists of the association of a diacid with a diamine is particular. It is considered that it is the combination of a diamine and a diacid, that is to say the pair "diaminediacide", also called "XY", in equimolar amount which corresponds to the monomer. This is explained by the fact that individually, the diacid or the diamine is only one structural unit, which by itself is not sufficient to polymerize.
    We have for example blocks PA412, PA414, PA418, PA610, PA612, PA614, PA618, PA912, PA1010, PA1012, PA1014 and PA1018.
    According to a second type, the polyamide blocks result from the condensation of one or more alpha omega aminocarboxylic acids and / or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine. Examples of lactams include caprolactam, enantholactam and lauryllactam. As examples of alpha omega amino carboxylic acid, mention may be made of aminocaproic, amino7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
    Advantageously, the polyamide blocks of the second type are made of polyamide 11, of polyamide 12 or of polyamide 6.
    According to a third type, the polyamide blocks result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
    In this case, the polyamide PA blocks are prepared by polycondensation:
    - linear or aromatic aliphatic diamine (s) having X carbon atoms;
    - Carboxylic acid (s) having Y carbon atoms; and
    - the comonomer (s) {Z}, chosen from lactams and alpha-omega aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X1 carbon atoms and at least one dicarboxylic acid having Y1 carbon atoms, (X1, Y1) being different from (X, Y);
    - Said comonomer (s) {Z} being introduced in a proportion by weight of up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all of the polyamide precursor monomers;
    - In the presence of a chain limiter chosen from dicarboxylic acids.
    Advantageously, the chain limiter is used the dicarboxylic acid having Y carbon atoms, which is introduced in excess relative to the stoichiometry of the diamine (s).
    According to a variant of this third type, the polyamide blocks result from the condensation of at least two alpha omega aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or from a lactam and an aminocarboxylic acid n 'not having the same number of carbon atoms in the possible presence of a chain limiter. By way of example of alpha omega amino aliphatic carboxylic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids. By way of example of lactam, mention may be made of caprolactam, oenantholactam and lauryllactam. Examples of aliphatic diamines that may be mentioned include hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylene diamine. By way of example of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid. By way of example of aliphatic diacids, mention may be made of butane-dioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, dimerized fatty acids (these dimerized fatty acids preferably have a dimer content of at least 98% ; preferably they are hydrogenated; they are marketed under the brand Pripol® by the company Unichema, or under the brand Empol® by the company Henkel) and polyoxyalkylenes - α, ω diacids. By way of example of aromatic diacids, mention may be made of terephthalic (T) and isophthalic (I) acids. By way of example of cycloaliphatic diamines, mention may be made of the isomers of bis- (4-aminocyclohexyl) methane (BACM), bis- (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-
    2-bis- (3-methyl-4-aminocyclohexyl) -propane (BMACP), and para-amino-dicyclo-hexyl-methane (PACM). Other commonly used diamines can be isophoronediamine (IPDA), 2,6-bis- (aminomethyl) norbornane (BAMN) and piperazine.
    In the case where the PA blocks of the PEBA according to the invention comprise at least two different monomers, called “co-monomers”, that is to say at least one monomer and at least one co-monomer (monomer different from the first monomer) , they comprise a copolymer such as an abbreviated copolyamide CoPA.
    As examples of polyamide blocks of the third type, the following may be cited:
    - 66/6 in which 66 denotes hexamethylenediamine units condensed with adipic acid. 6 designates units resulting from the condensation of caprolactam.
    - 66/610/11/12 in which 66 denotes hexamethylenediamine condensed with adipic acid. 610 denotes hexamethylenediamine condensed with sebacic acid. 11 denotes units resulting from the condensation of aminoundecanoic acid. 12 designates patterns resulting from the condensation of lauryllactam.
    The mass Mn of the flexible blocks is between 100 and 6000 g / mol and preferably between 200 and 3000 g / mol.
    Preferably, the polymer comprises from 1 to 80% by mass of flexible blocks and from 20 to 99% by mass of polyamide blocks, preferably from 4 to 80% by mass of flexible blocks and 20 to 96% by mass of polyamide blocks . According to a preferred embodiment, the rigid polyamide block, in the copolymer with rigid blocks PA and flexible blocks according to the invention, comprises at least one of the following polyamide units: 11, 12, 6, 610, 612, 1010, 1012 , and their mixtures or copolyamides.
    PE polyether blocks consist of alkylene oxide units. These units can for example be ethylene oxide units, propylene oxide or tetrahydrofuran units (which leads to polytetramethylene glycol sequences). PEG (polyethylene glycol) blocks are used, that is to say those made up of ethylene oxide units, PPG blocks (propylene glycol), that is to say those made up of propylene oxide units, PO3G blocks (polytrimethylene glycol ) that is to say those made up of polytrimethylene ether glycol units (such copolymers with polytrimethylene ether blocks are described in document US6590065), and PTMG blocks that is to say those made up of tetramethylene glycol units also called polytetrahydrofuran. PEBA copolymers can comprise in their chain several types of polyethers, the copolyethers possibly being block or random.
    It is also possible to use blocks obtained by oxyethylation of bisphenols, such as for example bisphenol A. These latter products are described in patent EP613919.
    The polyether blocks can also consist of ethoxylated primary amines. By way of example of ethoxylated primary amines, mention may be made of the products of formula:
    H - (OCH 2 CH 2 ) m —N - (CH 2 CH 2 O) n —H (CH 2 ) x ch 3 in which m and n are between 1 and 20 and x between 8 and 18. These products are commercially available under the Noramox® brand from CECA and under the Genamin® brand from Clariant.
    The flexible polyether blocks can comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being able to be obtained by cyanoacetylation of polyoxyalkylene alpha-omega dihydroxylated aliphatic blocks called polyetherdiols. More particularly, Jeffamines can be used (For example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of the company Huntsman, also described in patent documents JP2004346274, JP2004352794 and EP1482011).
    The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends. The general method for the preparation in two stages of PEBA copolymers having ester bonds between the PA blocks and the PE blocks is known and is described, for example, in French patent FR2846332. The general method for preparing the PEBA copolymers of the invention having amide bonds between the PA blocks and the PE blocks is known and described, for example in European patent EP1482011. The polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to make polymers containing polyamide blocks and polyether blocks having randomly distributed units (one-step process).
    Of course, the designation PEBA in the present description of the invention relates as well to Pebax® marketed by Arkema, to Vestamid® marketed by Evonik®, to Grilamid® marketed by EMS, as to Kellaflex® marketed by DSM or any other PEBA from other suppliers.
    Advantageously, the PEBA copolymers have PA blocks in PA 6, in PA 11, in PA 12, PA 612, in PA 66/6, in PA 1010 and / or in PA 614, preferably PA 11 and / or PA blocks 12; and PE blocks in PTMG, PPG and / or PO3G. PEBAs based on PE blocks mainly consisting of PEG are to be included in the range of hydrophilic PEBAs. PEBAs based on PE blocks mainly consisting of PTMG should be included in the range of hydrophobic PEBAs.
    Advantageously, said PEBA used in the composition according to the invention is obtained at least partially from bio-resourced raw materials.
    By raw materials of renewable origin or bio-resourced raw materials is meant materials which include bioresourced carbon or carbon of renewable origin. Unlike materials from fossil materials, materials made from renewable raw materials contain 14 C. The “carbon content of renewable origin” or “bio-resourced carbon content” is determined in accordance with standards ASTM D 6866 (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04). For example, the PEBAs based on polyamide 11 come at least in part from bioresourced raw materials and have a bio-resourced carbon content of at least 1%, which corresponds to an isotopic ratio of 12 C / 14 C at least 1.2 x
    10 '14 . Preferably, the PEBAs according to the invention comprise at least 50% by mass of bio-resourced carbon over the total mass of carbon, which corresponds to an isotopic ratio 12 C / 14 C of at least 0.6.10 -12 . This content is advantageously higher, in particular up to 100%, which corresponds to an isotopic ratio 12 C / 14 C of 1.2 x 10 -12 , in the case for example of PEBA with PA blocks 11 and PE blocks comprising PO3G, PTMG and / or PPG from raw materials of renewable origin.
    PES polyester blocks are usually made by polycondensation between a dicarboxylic acid and a diol. Suitable carboxylic acids include those mentioned above used to form the polyamide blocks with the exception of terephthalic and isophthalic acids. Suitable diols include linear aliphatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, branched diols such as neopentyl glycol,
    3-methylpentane glycol, 1,2-propylene glycol, and cyclic diols such as 1,4-bis (hydroxymethyl) cyclohexane and 1,4-cyclohexane-dimethanol.
    Polyesters are also understood to mean poly (caprolactone) and PES based on fatty acid dimers, in particular the products of the PRIPLAST® range from the company Croda or Uniqema.
    One can also envisage a PES block of the “copolyester” type, alternating, statistical or block, containing a chain of at least two types of PES mentioned above.
    The term “polysiloxane block” (hereinafter abbreviated as PSi) within the meaning of the invention means any organized or polymerized oligomer or oligomer with a linear or cyclic, branched or crosslinked structure obtained by polymerization of functionalized silanes and essentially consisting of a repetition of units main atoms in which silicon atoms are linked to each other by oxygen atoms (Si-O-Si siloxane bond), optionally substituted hydrocarbon radicals being directly linked via a carbon atom on said silicon atoms . The most common hydrocarbon radicals are alkyl radicals, in particular in CICI 0 and in particular methyl, fluoroalkyl radicals, aryl radicals and in particular phenyl, and alkenyl radicals and in particular vinyl; other types of radicals capable of being linked either directly or through a hydrocarbon radical to the siloxane chain are in particular hydrogen, halogens and in particular chlorine, bromine or fluorine, thiols, alkoxy radicals, polyoxyalkylene (or polyether) radicals and in particular polyoxyethylene and / or polyoxypropylene, hydroxyl or hydroxyalkyl radicals, substituted or unsubstituted amine groups, amide groups, acyloxy or acyloxyalkyl radicals, hydroxyalkylamino or aminoalkyl radicals , quaternary ammonium groups, amphoteric or betainic groups, anionic groups such as carboxylates, thioglycolates, sulfosuccinates, thiosulfates, phosphates and sulfates, and their mixtures, this list being of course in no way limiting (so-called organomodified silicones).
    Preferably, said polysiloxane blocks comprise polydimethylsiloxane (hereinafter abbreviated as PDMS blocks), polymethylphenylsiloxane, and / or polyvinylsiloxane.
    By polyolefin block (hereinafter abbreviated as PO block) within the meaning of the invention means any polymer comprising as monomer an alpha-olefin, that is to say the homopolymers of an olefin or the copolymers of at least an alpha-olefin and at least one other copolymerizable monomer, the alpha-olefin advantageously having from 2 to 30 carbon atoms.
    By way of example of an alpha-olefin, mention may be made of ethylene, propylene,
    1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1 -tetradecene, 1hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1 -tetracocene, 1hexacocene, 1 -octacocene, and 1 -triacontene. These alpha-olefins can be used alone or as a mixture of two or more than two.
    As examples, we can cite:
    homopolymers and copolymers of ethylene, in particular low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), polyethylene obtained by catalysis metallocene;
    homopolymers and copolymers of propylene, essentially amorphous or attactic polyalphaolefins (AP AO), ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene-propylene-rubber), and EPDM (ethylene-propylene-) elastomers diene), and blends of polyethylene with an EPR or EPDM, styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), and styrene / ethylene-propylene / styrene (SEPS), the copolymers of ethylene with at least one product chosen from salts or esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyl possibly having up to 24 carbon atoms, vinyl esters of saturated carboxylic acids such as for example vinyl acetate or propionate, and dienes such as for example 1,4-hexadiene or polybutadiene.
    According to an advantageous embodiment of the invention, said at least one polyolefin block comprises polyisobutylene and / or polybutadiene.
    According to a particularly advantageous embodiment, the block copolymer according to the invention comprises at least one flexible polyolefin block (PO block) and at least one hydrophilic hard block (hereinafter abbreviated BDh) comprising both polyamide and polyether, such as a polyetheramide block, a polyetheresteramide block, and / or a polyetheramideimide block, etc. The said PO block preferably comprises a polyolefin comprising terminal acid, alcohol or amine groups. Preferably, the PO block is obtained by thermal degradation of high molecular weight polyolefins to form polyolefins of lower mass and functionalized (reference method: Japanese Kokai Publication Hei-03-62804). As regards the BDh block, it can also comprise at least one polymer chosen from: cationic polymers, of quaternary amine type and / or phosphorus derivatives; and / or anionic polymers, of modified diacid type, comprising a sulfonate group and capable of reacting with a polyol. The addition of organic salt can then be envisaged in the preparation of the BDh block or during the reaction between the PO block and the BDh block. The document US Pat. No. 6,552,131 describes the synthesis and the different possible structures for the copolymer with PO blocks and with BDh blocks, these being of course possible in the process according to the invention.
    By polycarbonate block (hereinafter abbreviated as PC block) within the meaning of the invention, more particularly means any aliphatic polycarbonate. Aliphatic polycarbonates are described for example in documents DE2546534 and JP1009225. Such homopolymer or copolymer polycarbonates are also described in the document.
    US471203. Applications WO92 / 22600 and WO95 / 12629 describe copolymers comprising polycarbonate blocks as well as their methods of synthesis. The blocks (and their synthesis) described in these documents are perfectly conceivable for the synthesis of a PC block copolymer according to the invention. Preferably, the polycarbonate blocks of the copolymer according to the invention have the formula:
    1¾ in which a is an integer from 2 to 300; R1 and R2, which may be identical or different, represent a straight or branched chain, aliphatic or alicyclic having from 2 to 18 carbon atoms, or else represent a polyoxyalkylene group or else represent a polyester group.
    The polycarbonates in which R1 and R2 are chosen from hexylene, decylene, dodecylene, 1,4-cyclohexylene, 2,2-dimethyll, 3-propylene, 2,5-dimethyl-2,5-hexylene or polyoxyethylene groups are preferred.
    If the block copolymers described above generally comprise at least one rigid polyamide block and at least one flexible block, it is obvious that the present invention in fact covers all the copolymers comprising two, three, four (or even more) different blocks chosen among those described in the present description, as soon as at least one of these blocks is a polyamide block.
    Advantageously, the copolymer according to the invention comprises a segmented block copolymer comprising three different types of blocks (called "triblock" in the present description of the invention), which result from the condensation of several of the blocks described above. Said triblock is preferably chosen from copolyetheresteramides, copolyetheramideurethanes, in which one (s):
    - the weight percentage in rigid polyamide block is greater than 10%;
    - the mass percentage in flexible blocks is greater than 20%; on the total mass of triblock.
    According to a preferred embodiment, the flexible block in the copolymer with rigid blocks PA and flexible blocks according to the invention comprises (and preferably is) a polyether block PE, preferably chosen from PTMG, PPG, PO3G and / or PEG .
    According to another advantageous embodiment, the flexible block in the copolymer with rigid blocks PA and flexible blocks according to the invention comprises (and preferably is) a polyester block PES, chosen from polyester diols, poly (caprolactone) and polyesters based on fatty acid dimers. Advantageously, in the copolymer according to the invention, the weight ratio of the PA blocks to the flexible blocks is in the range from 0.3 to 10, preferably from 0.3 to 6, preferably from 0.3 to 3 , preferably 0.3 to 2.
    Polycarbodiimides suitable for the present invention are represented by the following general formula:
    R - [- N = C = N-R '] where R is monovalent, R' is divalent, n is from 2 to 50, preferably from 2 to 45, preferably from 2 to 20, and preferably from 5 to 20.
    R may be, for example, a C1-C20 alkyl or C3-C10 cycloalkyl or a C1-C20 alkenyl, and may be cyclic or branched, or may contain a C8-C16 aromatic ring, and may be substituted by groups functional.
    R ’can be a divalent group corresponding to all of the above, for example a C1-C20 alkylene, a C3-C10 cycloalkylene, etc. Examples of functional groups include, but are not limited to, cyanato and isocyanato, halo, amido, carboxamido, amino, imido, imino, silyl, etc. These lists are intended only for purposes of illustration and not by way of limitation of the scope of the present invention.
    As examples of polycarbodiimides which can be used according to the present invention, mention may be made of repeating units of N, N'-dicyclohexylcarbodiimide, N, N'-diisopropylcarbodiimide, Ν, Ν'-diphenylcarbodiimide, N, N'-di-2, 6diisopropylphenylcarbodiimide, 4,4'-dicyclohexylmethanecarbodiimide, tetramethylxylyleneecarbodiimide (aromatic carbodiimide), N, Ndimethylphenylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiim
    2,2 ', 6,6'-tetraisopropyl diphenyl carbodiimide (aromatic carbodiimide), aromatic homopolymer of 1,3,5-triisopropyl-2,4-diisocyanatobenzene, aromatic heteropolymer of 1,3,5-triisopropyl-2,4- diisocyanatobenzene and
    2,6-diisopropylphenylisocyanate, or combinations thereof.
    Specific examples of R 'include, but are not limited to, divalent radicals derived from 2,6-diisopropylbenzene, naphthalene, 3,5diethyltoluene, 4,4'-methylene-bis (2,6-diethylenephenyl), 4,4'-methylenebis (2-ethyl-6-methylphenyl), 4,4'-methylene-bis (2,6-diisopropylphenyl), 4,4'methylene-bis (2-ethyl-5-methylcyclohexyl), 2 , 4,6-triisopropylphenyl, nhexane, cyclohexane, dicyclohexylmethane and methylcyclohexane, and the like.
    Patent documents US5130360, US5859166, US368493, US7456137 US2007 / 0278452, US2009 / 0176938, and in particular US5360888 also describe other examples of polycarbodiimides.
    Suitable polycarbodiimides can be obtained from commercially available sources such as the Stabaxol P series from Rhein Chemie, the Stabilizer series from Raschig, and others from Ziko or Teijin for example.
    Advantageously, the polycarbodiimide is chosen from a Stabilizer, in particular the Stabilizer® 9000 corresponding to Poly- (1,3,5-triisopropylphenylene-2,4-carbodiimide), a Stabaxol®, in particular a stabaxol® P, in particular Stabaxol ® P100 or Stabaxol® P400, or a mixture of these.
    Preferably, the polycarbodiimide has a weight-average molecular mass greater than 10,000 g / mol.
    Advantageously, the weight average molecular weight of the polycarbodiimide is in the range of 10,000 to 40,000 g / mol, preferably from 15,000 to 30,000 g / mol.
    The content by weight of the polycarbodiimide advantageously represents from 0.5 to 10% by weight, preferably from 0.5 to 7% by weight, preferably from 0.5 to 3% by weight, preferably from 0.5 to 2 0.5%, preferably 0.5 to 2% by weight, based on the total weight of the copolymer according to the invention.
    According to an advantageous embodiment of the invention, said carboxylic acid of the copolymer according to the invention forms a urea bond by reaction with a carbodiimide of the polycarbodiimide.
    One of the advantages of the block copolymer at the end of a blocked acid chain according to the invention is that it remains in non-crosslinked linear form, the dispersity Mw / Mn of the copolymer being less than 3. This is surprising in that, in the 'prior art, carbodiimides are rather used to viscosify polyamides (see for example patent document FR3027907), in particular by crosslinking them, and to improve their resistance to hydrolysis as described in US5360888.
    A subject of the present invention is also the use, in a method of manufacturing a copolymer with rigid PA polyamide blocks and with flexible blocks, said copolymer comprising at least one end of the carboxylic acid chain, of a polycarbodiimide to improve the extrudability of the copolymer, the stretching capacity of the copolymer, the abrasion resistance, the tear resistance and the durability of said copolymer, without increasing its dispersity,
    Preferably, for the use according to the invention, the polycarbodiimide is of average molecular mass by weight greater than 10,000 g / mol, preferably included in the range of 10,000 to 40,000 g / mol, preferably from 15,000 to 30,000 g / mol.
    Advantageously, at least one end of the carboxylic acid chain of the copolymer is blocked by a urea function formed by reaction with the polycarbodiimide.
    The present invention also relates to a composition based on copolymer according to the invention, characterized in that it comprises:
    - from 51% to 99.9% by weight of said copolymer,
    - from 0.1 to 49% by weight of at least one other component chosen from polyamides, functional polyolefins, copolyetheresters, thermoplastic polyurethanes (TPU), copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylate, and copolymers of ethylene and alkyl (meth) acrylate, and / or
    - from 0.1 to 10% by weight of additives chosen from nucleating agents, fillers, in particular mineral fillers, such as talc, reinforcing fibers, in particular glass or carbon, dyes, UV absorbers , antioxidants, in particular phenolic, or based on phosphorus or based on sulfur, light stabilizers of the hindered amine type or HALS, and their mixtures, on the total weight of the composition.
    The present invention also relates to a method of manufacturing a copolymer according to the invention, comprising the mixture of block copolymer as defined according to the invention and of polycarbodiimide as defined above so that at least one end of chain carboxylic acid of the block copolymer reacts with the carbodiimide function of the polycarbodiimide, to advantageously form a urea function.
    According to an advantageous embodiment of the process of the invention, the mixing is carried out by means of a single-screw or twin-screw extruder in order to produce an intimate mixture of the copolymer and of the polycarbodiimide in the molten route, and allow the reaction between the acid function of the copolymer and the carbodiimide function of the polycarbodiimide. The components can also be mixed by adding the polycarbodiimide during the synthesis of the block copolymer. The copolymer according to the invention can also be manufactured by using a masterbatch comprising the block copolymer and the polycarbodiimide produced in the manner described above, then dilution of the masterbatch in the block copolymer during the implementation step. of the finished object.
    A subject of the present invention is also a shaped article, such as fiber, fabric, film, sheet, rod, tube, injected and / or extruded part, comprising a copolymer or a composition according to the invention.
    Preferably, said article constitutes at least part of one of the following articles: sports article, shoe element, sport shoe element, shoe sole, in particular crampon, ski element, in particular ski boot or shell skis, sports utensils such as ice skates, ski bindings, snowshoes, sports bats, boards, horseshoes, protective gaiters, fins, golf balls, hobby, DIY, road tools or equipment , protective equipment or article, such as helmet visors, glasses, sunglasses temples, automobile part, car element such as dashboard, airbag, headlight protectors, rear view mirror, small part of all terrain cars, tank, in particular of scooter , moped, motorcycles, industrial part, industrial additive, electrical part, electronics, computers, tablet, telephone, computer, security accessory, sign, light strip, sign board aletics and advertising, display, engraving, furniture, store fixtures, decoration, contact ball, medical device, dental prosthesis, implant, ophthalmology item, hemodialyzer membrane, optical fiber, art object, sculpture, contact lenses cameras, disposable camera lenses, printing medium, in particular direct printing medium with UV inks, for photo boards, glass, panoramic roof, transmission belt, anti-static additive, waterproof or breathable product or film, active molecules, coloring agent, soldering agent, decoration element, and / or additive for polyamide, sole for rail, part for stroller, wheel, handle, seat element, car seat part for children, construction part, audio, sound and / or thermal insulation equipment, part intended to absorb shocks and / or vibrations, such as those generated by a means of transport, wheels, soft rolling such as a tire, textile, woven or nonwoven, packaging, peristaltic belt, conveyor belt strip, skin and / or synthetic leather, and any article comprising a mixture of these articles.
    EXAMPLES
    The following examples illustrate the invention without limiting it. The standards used in the examples also correspond to those used more generally to characterize the invention in the description or the claims.
    Used materials :
    In the following examples:
    PEBA 1: PA 12-PTMG (Mn: 600-2000)
    PEBA 1 is a copolymer with PA 12 blocks and PTMG blocks with respective number average molecular weights (Mn) 600 - 2000.
    Copo 1: 98.5% PEBA 1 + 1.5% PCDI
    PEBA 2: PA 12-PTMG (Mn: 850-2000)
    PEBA 2 is a copolymer according to the invention, with PA 12 blocks and PTMG blocks with respective number average molecular weights (Mn) 850 - 2000. Copo 2: 98% PEBA 2 + 2% PCDI
    PEBA 3: PA 12-PTMG (Mn: 2000-1000)
    PEBA 3 is a copolymer according to the invention, with PA 12 blocks and PTMG blocks with respective number average molecular weights (Mn) 2000 -1000. Copo 3: 98.5% PEBA 3 + 1.5% PCDI
    PEBA 4: PA11-PTMG (600-1000)
    ΡΕΒΑ 4 is a copolymer with PA11 blocks and PTMG blocks of respective number average molecular weights (Mn) 600 - 1000.
    Copo 4: 98% PEBA 4 + 2% PCDI
    PCDI: Polycarbodiimide used in the examples: Poly- (1,3,5-triisopropylphenylene-2,4-carbodiimide)
    Example 1: Measurement of the Extrudability of PEBAs and Copos Materials
    The following table 1 gives the measurement results of viscosity in the molten state eta * (in Pa.s) at 220 ° C., as a function of the angular frequency (rad / s) according to standard ISO 6721-10: 2015.
    Table 1
    Angular frequency eta * PEBA 1 Eta * -Copo 1 eta * PEBA 3 eta * Copo 3 eta * PEBA 4 eta * Copo 4 [1 / s] [Not] [Not] [Not] [Not] [Not] [Not] 628 206 363 312 404 182 361 292 258 508 415 575 237 518 135 302 659 516 767 288 705 62.8 334 802 606 967 337 943 29.2 353 923 676 1160 382 1190 13.5 363 1010 726 1340 418 1490 6.28 368 1080 761 1510 444 1820 2.92 372 1120 785 1660 461 2170 1.35 375 1150 805 1810 470 2520 0.628 379 1170 825 1980 476 2830 0.292 381 1170 849 2260 472 3080 0,135 396 1190 930 2910 477 3380 0.0628 442 1210 1190 4200 498 3750
    It is observed that the Copos materials according to the invention have a greater viscosity in the molten state than the comparative PEBAs.
    The Copos materials according to the invention are therefore more easily extrudable than the comparative PEBAs materials.
    Example 2: Measurement of the stretching capacity of PEBAs and Copos using a Rheotens
    Description of the elongational rheology test:
    Principle: A rod is extruded through a die of a capillary rheometer; this is gripped, in the molten state, by 2 pairs of wheels driven by a variable speed motor. A first pair of wheels and the motor are mounted at the free, deviable end of a support directly connected to a sensor, representing the restoring force.
    The second pair of wheels (coupled to the first) helps guide and limit the winding of the rod around the upper wheels. Small pads soaked in surfactant liquid (water, ethanol, and surfactant mixture) are also applied to the wheels to cool them and thus limit the sticking effect.
    The melt strenqht curves of Figures 1 and 2 represent the elongation stress on the ordinate as a function of the elongation factor on the abscissa.
    f
    Elongation stress: ** F = -
    Elongation factor:
    With v : Speed with which the rod is stretched: speed of the wheels
    F: Force applied by the rod: Area of the rod when it leaves the die v °: Extrusion speed of the rod at the end of the die
    Operating conditions:
    - Capillary rheometer:
    Device: GOTTFERT RHEOTESTER 2000 CAPILLARY RHEOMETER.
    Die: 30 mm X 1 mm L / d = 30/1
    Sensor: 0-1400 bar (reference 131055)
    Warm-up time: 300 s (5 min)
    Test temperatures: 150 ° C or 180 ° C depending on the grade
    Shear gradient: 50 s -1
    - Rheotens:
    Wheels: Grooved stainless steel
    Pulling height: 105 mm
    Air gap: approx. 0.6 mm
    Vo (initial speed) "6 mm / s
    Accelerations: a * t, a = 2.4 mm / s 2
    Lubrication: water + surfactant mixture
    Piston diameter: 12 mm
    Piston speed: 0.043 mm / s
    FIG. 1 represents the measurement result of elongational rheology of PEBA 3 (bottom curve) and Copo 3 (top curve) at 180 ° C.
    FIG. 2 represents the result of elongational rheology measurement of PEBA 4 (bottom curve) and Copo 4 (top curve) at 150 ° C.
    The Copo 3 and Copo 4 copolymers according to the invention have an improved stretchability compared to that of the respective controls PEBA 3 and PEBA 4.
    Block copolymers comprising at least one end of the carboxylic acid chain blocked by a polycarbodiimide have improved stretchability compared to the same respective unblocked copolymers.
    Example 3 - Comparison of the residual tensile deformation of PEBA 1 and Copo 1
    Figure 3 shows the results of traction curves according to ISO 527-1A: 2012 at 23 ° C for PEBA 1 (bottom curve) and Copo 1 (top curve).
    For the same tensile stress (on the ordinate), the percentage of residual deformation (abscissa) is lower in the case of the Copo 1 according to the invention (top curve) than for the PEBA 1 (bottom curve), which indicates better durability of the material shaped from Copol.
    Example 4 Comparison of the Abrasion Resistance and the Adhesion of Different PEBAs and COPOs
    The results of these tests are given in Table 1 below.
    Table 2
    standards TESTS units PEBA1 Copo1 PEBA2 Copo2 PEBA3 Copo3 PEBA4 Copo4 ISO Abrasion resistancen = 4 n = 4 n = 4 n = 4 n = 4 n = 4 n = 4 n = 4 9352: 2012 A loss of mass mg 36.7 26.3 41.9 33.9 17.0 13.1 55.4 41.9AND7.3 6.0 4.4 3.3 3.9 2.4 2.8 2.9Tear resistancen = 5 n = 5 Median SI kN / m 41 48 ISO min37 45 34-1: 2015 max45 49 Median N / A kN / m 29 33 min27 31 max35 35
    The loss of mass is lower in the case of copolymers according to the invention, therefore the copolymers according to the invention exhibit better abrasion resistance than the respective control PEBAs.
    Likewise, the copolymers according to the invention have better tear resistance than the respective control PEBAs.
    Example 5 - Measurement of the dispersity of the various PEBAs and Copos
    The weight-average and number-average molecular weights Mw and Mn measured increase respectively when passing from a PEBA to the corresponding Copo according to the invention, which indicates that the reaction has occurred between the carbodiimide function of the polycarbodiimide and the function PEBA acid, to form the block copolymer at the end of the blocked acid chain according to the invention.
    The dispersity Mw / Mn is moreover preserved in each Copo according to the invention with respect to the corresponding initial PEBA, and it is measured less than 3, in all the copolymers, which proves that the copolymers according to the invention have remained in the form uncrosslinked linear. They are therefore perfectly recyclable.
    The dispersity is determined to be equal to the ratio between molecular weight by weight and number Mw / Mn. The accuracy of the measurement is given to the nearest 5%.
    The number average molecular (or molar) mass is fixed by the content of chain limiter. It can be calculated according to the relation:
    Mn = (n monomer / niimitor) * M repeating motif + Rimonomer miimitor = number of moles of niimiting monomer = number of moles of excess diacid M repeating motif = Molar mass of the repeating motif
    Miimitor = Molar mass of excess diacid
    Ultimately, the polycarbodiimide thus used according to the present invention makes it possible to improve the extrudability, stretchability, durability of the copolymer, abrasion resistance, and tear resistance, while maintaining its dispersity and therefore its recyclability.
    These advantageous properties could not be observed with monomeric carbodiimides, their volatility having not allowed the latter to react or effectively block said carboxylic acid of the block copolymer of the invention.
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1. Block copolymer comprising at least one rigid polyamide PA block and at least one flexible block, characterized in that it comprises at least one end of the carboxylic acid chain blocked by a polycarbodiimide.
    [2" id="c-fr-0002]
    2. Copolymer according to claim 1, in which the weight-average molecular weight of the polycarbodiimide is greater than 10,000 g / mol, preferably included in the range of 10,000 to 40,000 g / mol, preferably from 15,000 to 30,000 g / mol.
    [3" id="c-fr-0003]
    3. Copolymer according to any one of claims 1 or 2, in which the content by weight of the polycarbodiimide represents from 0.5 to 10% by weight, preferably from 0.5 to 7% by weight, preferably from 0, 5 to 3% by weight, preferably 0.5 to 2.5%, preferably 0.5 to 2% by weight, based on the total weight of the copolymer.
    [4" id="c-fr-0004]
    4. Copolymer according to any one of claims 1 to 3, in which said carboxylic acid forms a urea bond by reaction with the carbodiimide of the polycarbodiimide.
    [5" id="c-fr-0005]
    5. Copolymer according to any one of claims 1 to 4, characterized in that it is in non-crosslinked linear form, its dispersity Mw / Mn being less than 3.
    [6" id="c-fr-0006]
    6. Copolymer according to any one of claims 1 to 5, in which said flexible block comprises at least one block chosen from: polyether, polyester, polydimethylsiloxane, polyolefin, polycarbonate, and mixtures or copolymers thereof.
    [7" id="c-fr-0007]
    7. Copolymer according to any one of claims 1 to 6, in which said flexible block comprises at least one polyether PE, preferably chosen from PTMG, PPG, PO3G and / or PEG.
    [8" id="c-fr-0008]
    8. Copolymer according to any one of claims 1 to 7, wherein said flexible block comprises at least one polyester PES, preferably chosen from polyester diols, poly (caprolactone) and polyesters based on fatty acid dimers .
    [9" id="c-fr-0009]
    9. Copolymer according to any one of claims 1 to 8, in which said polyamide PA block comprises at least one of the following polyamide units: 11, 12, 6, 610, 612, 1010, 1012, and their mixtures or copolyamides.
    [10" id="c-fr-0010]
    10. Copolymer according to any one of claims 1 to 9, in which the weight ratio of the PA blocks to the flexible blocks is in the range from 0.3 to 10, preferably from 0.3 to 6, preferably from 0.3 to 3, preferably from 0.3 to 2.
    [11" id="c-fr-0011]
    11. Use of a polycarbodiimide in a process for manufacturing a copolymer with polyamide blocks and flexible blocks comprising at least one end of the carboxylic acid chain, to improve the extrudability of the copolymer, the stretching capacity of the copolymer, the resistance to l abrasion, tear resistance and durability of the copolymer, without increasing its dispersity, in which at least one end of the carboxylic acid chain of the copolymer is blocked by a carbodiimide function of the polycarbodiimide.
    [12" id="c-fr-0012]
    12. Use according to claim 11, in which the polycarbodiimide has a weight-average molecular mass greater than 10,000 g / mol, preferably comprised in the range from 10,000 to 40,000 g / mol, preferably from 15,000 to 30,000 g / mol.
    [13" id="c-fr-0013]
    13. Composition based on copolymer according to any one of claims 1 to 10, characterized in that it comprises:
    - from 51% to 99.9% by weight of said copolymer,
    - from 0.1 to 49% by weight of at least one other component chosen from polyamides, functional polyolefins, copolyetheresters, thermoplastic polyurethanes (TPU), copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylate, and copolymers of ethylene and alkyl (meth) acrylate, and / or
    - from 0.1 to 10% by weight of additives chosen from nucleating agents, fillers, in particular mineral fillers, such as talc, reinforcing fibers, in particular glass or carbon, dyes, UV absorbers , antioxidants, in particular phenolic, or based on phosphorus or based on sulfur, light stabilizers of the hindered amine type or HALS, and their mixtures, on the total weight of the composition.
    [14" id="c-fr-0014]
    14. A method of manufacturing a copolymer according to any one of claims 1 to 10, comprising the mixture of block copolymer and polycarbodiimide so that at least one end of the carboxylic acid chain of the block copolymer reacts with a carbodiimide function of the polycarbodiimide.
    [15" id="c-fr-0015]
    15. Method according to claim 14, characterized in that the mixing is carried out by means of a single-screw or twin-screw extruder or by addition of the polycarbodiimide during the synthesis of the block copolymer.
    [16" id="c-fr-0016]
    16. Shaped article, such as fiber, fabric, film, sheet, rod, tube, injected and / or extruded part, comprising a copolymer as defined in any one of claims 1 to 10, or a composition according to claim 13 .
    [17" id="c-fr-0017]
    17. Shaped article according to claim 16, characterized in that it constitutes at least part of one of the following articles: sporting article, shoe element, sport shoe element, shoe sole, in particular crampon, element of ski, in particular ski boot or ski boot, sports utensil such as ice skates, ski bindings, snowshoes, sports bats, boards, horseshoes, protective gaiter, fins, golf balls, hobbies, DIY, road tool or equipment, protective equipment or article, such as helmet visors, glasses, branches of glasses, automobile part, car element such as dashboard, airbag, headlight protectors, rear view mirror, small all-terrain car part, tank, in particular scooter, moped, motorbikes, industrial part, industrial additive, electrical part, electronics, computers, tablet, telephone, computer, electrical accessory curity, sign, light strip, sign and advertising panel, display, engraving, furniture, store layout, decoration, contact ball, medical device, dental prosthesis, implant, ophthalmology item, membrane for hemodialyzer, optical fibers, object of , sculpture, camera lenses, disposable camera lenses, print media, including direct print media with UV inks, for photo boards, glass, panoramic roof, drive belt, anti-static additive, product or waterproof-breathable film, support for active molecules, coloring agent, welding agent, decoration element, and / or additive for polyamide, sole for rail, piece for stroller, wheel, handle, seat element, piece of car seat for children, construction part, piece of audio equipment, sound and / or thermal insulation, part intended to absorb shocks and / or vibrations, such as those generated by a n means of transport, wheels, soft rolling like a tire, textile, woven or nonwoven, packaging, peristaltic belt, conveyor belt band, skin and / or synthetic leather, and any article comprising a mixture of these articles.
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    同族专利:
    公开号 | 公开日
    FR3073848B1|2020-11-13|
    US20200385574A1|2020-12-10|
    JP2021503526A|2021-02-12|
    WO2019097179A1|2019-05-23|
    CN111356718A|2020-06-30|
    EP3710511A1|2020-09-23|
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    法律状态:
    2019-05-24| PLSC| Publication of the preliminary search report|Effective date: 20190524 |
    2019-10-14| PLFP| Fee payment|Year of fee payment: 3 |
    2020-10-13| PLFP| Fee payment|Year of fee payment: 4 |
    2021-10-18| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1760880|2017-11-17|
    FR1760880A|FR3073848B1|2017-11-17|2017-11-17|BLOCK COPOLYMER WITH IMPROVED RESISTANCE TO ABRASION AND TEARING|FR1760880A| FR3073848B1|2017-11-17|2017-11-17|BLOCK COPOLYMER WITH IMPROVED RESISTANCE TO ABRASION AND TEARING|
    US16/763,567| US20200385574A1|2017-11-17|2018-11-16|Block copolymer exhibiting improved abrasion resistance and improved tear resistance|
    JP2020527017A| JP2021503526A|2017-11-17|2018-11-16|Block copolymer with improved wear resistance and improved tear resistance|
    CN201880074614.0A| CN111356718A|2017-11-17|2018-11-16|Block copolymers exhibiting improved abrasion resistance and improved tear resistance|
    EP18827158.9A| EP3710511A1|2017-11-17|2018-11-16|Block copolymer exhibiting improved abrasion resistance and improved tear resistance|
    PCT/FR2018/052870| WO2019097179A1|2017-11-17|2018-11-16|Block copolymer exhibiting improved abrasion resistance and improved tear resistance|
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