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    • 专利摘要:
    The present invention relates to a composition comprising: from 45 to 94.95% by weight of a matrix consisting of at least one polyamide; from 0.05% to 20% by weight of at least one prepolymer, the proportion by weight of polyamide matrix and that of prepolymer being respectively 60 to 99.9% and 40 to 0.1%, relative to polyamide-prepolymer sum; from 5 to 45% by weight of at least one impact modifier; from 0 to 20% of an additive, said composition having greater melt flowability than the same composition without prepolymer.
    公开号:FR3019553A1
    申请号:FR1452901
    申请日:2014-04-02
    公开日:2015-10-09
    发明作者:Benoit Brule；Jean-Jacques Flat；Mathieu Sabard
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] A new shock modified thermoplastic composition with greater melt flowability.
    [0002] The present invention relates to shock-modified polyamide thermoplastic compositions comprising at least one prepolymer having a greater melt flowability than a prepolymer-free composition, while maintaining the same modulus and impact properties. It also relates to its use for extrusion, injection, in particular for the manufacture of articles obtained by extrusion, injection, in particular for the manufacture of sports shoes, especially ski or running shoes, or molding by compression.
    [0003] The invention also relates to the use of prepolymers with impact modified polyamide thermoplastic dies to increase melt flowability. The invention also relates to a method of manufacturing said sports articles and the articles obtained by said method.
    [0004] Thermoplastic compositions based on polyamide are raw materials that can be processed by extrusion, molding or injection, in particular by injection molding to manufacture plastic parts. There are several major properties that are desired for these polyamide-based compositions, especially when used in these transformation processes. One of these properties lies in the fact that these thermoplastic compositions used must be characterized, in the molten state, by a fluidity or a rheological behavior compatible with the shaping processes of interest, such as molding. by injection. Indeed, these thermoplastic compositions must be sufficiently fluid when they are molten, to be transported and handled easily and quickly in certain shaping devices, such as for example injection molding.
    [0005] As a rule, functionalized polyolefins, added or not with ungrafted polyolefins, are used to improve the impact properties of the polyamides. Nevertheless, the addition of these polyolefins is most often to the detriment of the melt flow, generally because of the reaction between the maleic anhydride of the functional polyolefin and the ends of amine chains of the polyamide. Too much viscosity can make it difficult to use the product, especially by injection molding. In extrusion too high viscosity limits the line speed and productivity It is then necessary to use other polyamides more fluid.
    [0006] EP 1568487 discloses molded articles comprising: - a resin member which comprises a resin of the polyamide series which may be a resin composition containing a resin of the polyamide series and a compound having an amino group comprising at least one polyamide oligomer, and - a resin member comprising a resin of the polyurethane series. This document is silent on the fluidity of the compositions obtained. Surprisingly, it has been found by the Applicant that the addition of prepolymers to a composition comprising functionalized polyolefins, with or without addition of ungrafted polyolefins, said composition having a high viscosity, makes it possible to improve the fluidity of the latter and thus obtain a fluidity or a rheological behavior compatible with the shaping processes of interest, such as injection molding.
    [0007] The present invention relates to a composition comprising: from 45 to 94.95% by weight of a matrix consisting of at least one polyamide; from 0.05% to 20% by weight of at least one prepolymer, the proportion by weight of polyamide matrix and that of prepolymer being respectively 60 to 99.9% and 40 to 0.1%, relative to polyamide-prepolymer sum; from 5 to 45% by weight of at least one impact modifier; from 0 to 20% of an additive, said composition having greater melt flowability than the same composition without prepolymer. Regarding polyamide The term polyamide should be understood in the broad sense of the term and containing amide functions resulting from a polycondensation reaction between the carboxylic acid and amine functions. The nomenclature used to define polyamides is described in ISO 1874-1: 2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", especially on page 3 (Tables 1 and 2) and is well known to those skilled in the art. According to the present application, the term "polyamide", also denoted PA, refers to: homopolymers, copolymers, or copolyamides, based on different amide units, such as, for example, copolyamide 6/12 with amide units derived from lactam- 6 and lactam-12. The symbol "I" serves to delimit the patterns of a copolymer. Advantageously, the polyamide of the matrix present in the above composition is chosen from linear or branched aliphatic polyamides, cycloaliphatic polyamides, semi-aromatic polyamides, aromatic polyamides and Peba. Linear or branched aliphatic polyamides, cycloaliphatic polyamides, semi-aromatic polyamides, aromatic polyamides: The polyamides are obtained from an aminocarboxylic acid (also called amino acid), a lactam or a motif. having the formula XY, X being a diamine of Ca and Y being a diacid in Cb, also called (diamine in Ca). (diacid in Cb), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b being each ranging from 4 to 36. When the polyamide is obtained from a unit derived from an amino acid, it may be chosen from 9-aminononanoic acid , 10-aminodecanoic acid, 10-aminoundecandic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid and its derivatives, especially N-heptyl-11-aminoundecanoic acid. When the polyamide is obtained from a unit derived from a lactam, it may be selected from pyrrolidinone, 2-piperidinone, caprolactam, enantholactam, caprylolactam, pelargolactam, decanolactam, undecanolactam , and the lauryllactam. When the polyamide is obtained from a unit derived from a unit having the formula (C-diamine) (Cb diacid), the (C-diamine) unit is selected from aliphatic, linear or branched diamines cycloaliphatic diamines and alkylaromatic diamines. When the diamine is aliphatic and linear, of formula H2N- (CH2) a-NH2, the monomer (diamine Ca) is preferably chosen from butanediamine (a = 4), pentanediamine (a = 5), hexanediamine (a = 6), heptanediamine (a = 7), octanediamine (a = 8), nonanediamine (a = 9), decanediamine (a = 10), undecanediamine (a = 11), dodecanediamine (a = 12), tridecanediamine (a = 13), tetradecanediamine (a = 14), hexadecanediamine (a = 16), octadecanediamine (a = 18), octadecenediamine (a = 18), eicosanediamine (a = 20), docosanediamine (a = 22) and diamines obtained from fatty acids. When the diamine is aliphatic and branched, it may have one or more methyl or ethyl substituents on the main chain. For example, the monomer (Ca-diamine) may conveniently be selected from 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,3-trimethyl-1,6-hexanediamine, Diaminopentane, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine. When the monomer (Ca-diamine) is cycloaliphatic, it is preferably chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3 5-dialkyl-4-aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis- (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM ), p-bis (aminocyclohexyl) methane (PACM) and isopropylidene di (cyclohexylamine) (PACP). It may also comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane. A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405). When the monomer (diamine Ca) is alkylaromatic, it is preferably selected from 1,3-xylylenediamine and 1,4-xylylenediamine.
    [0008] When the unit C is a unit corresponding to the formula (diamine in Ca) (diacid in Cb), the unit (diacid in Cb) is chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids. When the monomer (diacid Cb) is aliphatic and linear, it is preferably selected from succinic acid (b = 4), pentanedioic acid (b = 5), adipic acid (b = 6), heptanedioic acid (b = 7), octanedioic acid (b = 8), azelaic acid (b = 9), sebacic acid (b = 10), undecanedioic acid (b = 11), dodecanedioic acid (b = 12), brassylic acid (b = 13), tetradecanedioic acid (b = 14), hexadecanedioic acid (b = 16), octadecanedioic acid (b = 18), octadecenedioic acid (b = 18), eicosanedioic acid (b = 20), docosanedioic acid (b = 22) and fatty acid dimers containing 36 carbons. The fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of 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 may comprise the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane. When the diacid is aromatic, it is preferably selected from terephthalic acid (noted T), isophthalic acid (noted I) and naphthalenic diacids.
    [0009] More preferably, the polyamide is obtained from a single aminocarboxylic acid, a single lactam or a single X.Y. However, it is quite possible to use, to obtain this polyamide, a mixture of two or more aminocarboxylic acids, a mixture of two or more lactams, but also a mixture of one, two and or more aminocarboxylic acids with one, two or more lactams. Advantageously, the second lactam or amino acid represents up to 30% by weight of the sum of the two lactams or amino acid.
    [0010] Also, each monomer of the XY unit may be substituted by another monomer X 'and / or Y', different from X or Y. Advantageously, the second monomer X 'and / or Y' represents up to 30% by weight of the sum X + X 'and / or Y + Y'. Peba: Peba are copolymers (A) with amide units (Aa1) and polyether units (Aa2) which result from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia: 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends. 2) Polyamide sequences having dicarboxylic chain ends with polyoxyalkylene sequences having diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic alpha-omega dihydroxylated polyoxyalkylene sequences known as polyalkylene ether diols (polyetherdiols). 3) Polyamide sequences with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides. The copolymers of the invention are advantageously of this type. The polyamide blocks having dicarboxylic chain ends are derived, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
    [0011] The polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine. Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks. For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain. It is also possible to react polyetherdiamine, polyamide precursors and a chain-limiting diacid. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain. Amide motif (Aal)): The amide unit (Aal) corresponds to an aliphatic repeating unit as defined above for the polyamide. Advantageously, (Aal)) represents 11-aminoundecanoic acid or undecanolactam. Polyether motif (Aa2): The polyether units are especially derived from at least one polyalkylene ether polyol The number-average molecular mass of the polyether blocks is advantageously from 200 to 4000 g / mol, preferably from 250 to 2500 g / mol, in particular 300 and 1100 g / mole. The copolymer (A) can be prepared by the process according to which: in a first step, the polyamide blocks (Bal) are prepared by polycondensation of the diamine or diamines; o dicarboxylic acid (s); and where appropriate, the comonomer or comonomers selected from lactams and alpha-omega aminocarboxylic acids; o in the presence of a chain limiter chosen from dicarboxylic acids; then in a second step, the resulting polyamide blocks (Aa1) are reacted with polyether blocks (Aa2) in the presence of a catalyst. The general method for the two-step preparation of the copolymers of the invention is known and is described, for example, in French patent FR 2,846,332 and in European patent EP 1,482,011. The formation reaction of the block (Aa1 ) is usually between 180 and 300 ° C, preferably 200 to 290 ° C, the pressure in the reactor is between 5 and 30 bar, and is maintained for about 2 to 3 hours. The pressure is slowly reduced by putting the reactor at atmospheric pressure, and the excess water is distilled for example for one to two hours. The carboxylic acid terminated polyamide having been prepared, the polyether and a catalyst are then added. The polyether can be added in one or more times, as can the catalyst. According to an advantageous form, the polyether is first added, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with formation of ester bonds and elimination of water. As much water as possible is removed from the reaction medium by distillation, and then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks. This second step is carried out with stirring, preferably under a vacuum of at least 15 mmHg (2000 Pa) at a temperature such that the reagents and copolymers obtained are in the molten state. For example, this temperature can be between 100 and 400 ° C and most often 200 and 300 ° C. The reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the target torque or power.
    [0012] It is also possible to add during the synthesis, at the moment deemed most appropriate, one or more molecules used as an antioxidant, for example Irganox® 1010 or Irganox® 245. It is also possible to consider the process for the preparation of copolyamide ( A) such that all the monomers are added at the beginning, or in a single step, to effect the polycondensation: of the diamine (s); dicarboxylic acid (s); and where appropriate, of the other one or more polyamide comonomers; in the presence of a chain limiter chosen from dicarboxylic acids; in the presence of blocks (Aa2) (polyether); in the presence of a catalyst for the reaction between the soft blocks (Aa2) and the blocks (Aa1).
    [0013] Advantageously, said dicarboxylic acid is used as chain limiter, which is introduced in excess relative to the stoichiometry of the diamine or diamines. Advantageously, the catalyst used is a derivative of a metal selected from the group consisting of titanium, zirconium and hafnium or a strong acid such as phosphoric acid, hypophosphorous acid or boric acid. The polycondensation can be conducted at a temperature of 240 to 280 ° C. In general, the copolymers with known ether and amide units consist of linear and semi-crystalline aliphatic polyamide sequences (for example "Pebax®" from Arkema).
    [0014] Regarding the prepolymer The term "prepolymer" refers to oligomers of polyamides necessarily of lower molecular weight than the polyamides used in the matrix, in particular said prepolymer with a mass of from 1000 to 10000 g / mol.
    [0015] The prepolymer may be chosen from oligomers of linear or branched aliphatic polyamides, oligomers of cycloaliphatic polyamides, oligomers of semi-aromatic polyamides, oligomers of aromatic polyamides, linear or branched aliphatic polyamides, cycloaliphatic and semi-aromatic polyamides. aromatics having the same definition as above. The prepolymer may also be a copolyamide oligomer or a mixture of oligomers of polyamides and copolyamide. With regard to the impact modifier The impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to ISO 178 and Tg of less than 0 ° C. (measured according to standard 11357-2 at the level of point of inflection of the DSC thermogram), in particular a polyolefin, coupled or not with a Peba having a flexural modulus <200 MPa. The impact modifier polyolefin may be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized. For simplicity, the polyolefin has been designated by (B) and functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below. A non-functionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. By way of example, mention may be made of: Homopolymers and copolymers of polyethylene, in particular LDPE, HDPE, linear low density polyethylene (LLDPE), VLDPE (very low density polyethylene, or very low polyethylene) density) and metallocene polyethylene. homopolymers or copolymers of propylene. ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM). - Styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS). copolymers of ethylene with at least one product chosen from unsaturated carboxylic acid salts or esters, such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids Saturated such as vinyl acetate (EVA), the proportion of comonomer up to 40% by weight. The functionalized polyolefin (B1) may be a polymer of alpha olefins having reactive units (functionalities); such reactive units are acid, anhydride or epoxy functions. By way of example, mention may be made of the preceding polyolefins (B2) grafted or copolymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (which may be totally or partially neutralized by metals such as Zn, etc.) or by anhydrides of carboxylic acids such as maleic anhydride. A functionalized polyolefin is for example a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a grafting rate of, for example, 0.01 to 5% by weight. The functionalized polyolefin (B1) may be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is, for example, from 0.01 to 5% by weight of: - PE, PP, copolymers of ethylene with propylene, butene, hexene or octene containing, for example, 35 to 80% by weight of ethylene; ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM). - Styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS). ethylene-vinyl acetate copolymers (EVA), containing up to 40% by weight of vinyl acetate; ethylene and alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate; ethylene and vinyl acetate (EVA) and alkyl (meth) acrylate copolymers containing up to 40% by weight of comonomers.
    [0016] The functionalized polyolefin (BI) may also be chosen from ethylene / propylene predominantly propylene copolymers grafted with maleic anhydride and then condensed with monoamino polyamide (or a polyamide oligomer) (products described in EP-A-0342066). . The functionalized polyolefin (BI) may also be a copolymer or copolymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate. By way of example of functionalized polyolefins of the latter type, mention may be made of the following copolymers, in which ethylene is preferably at least 60% by weight and in which the monomer ter (the function) represents, for example, from 0.1 to 10% by weight of the copolymer: ethylene / alkyl (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers; ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers; ethylene / vinyl acetate or alkyl (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers. In the foregoing copolymers, the (meth) acrylic acid may be salified with Zn or Li.
    [0017] The term "alkyl (meth) acrylate" in (BI) or (B2) refers to C1-C8 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate and the like. , n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
    [0018] Moreover, the aforementioned polyolefins (BI) may also be crosslinked by any suitable method or agent (diepoxy, diacid, peroxide, etc.); the term "functionalized polyolefin" also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with them or mixtures of at least two functionalized polyolefins that can react with one another. The copolymers mentioned above, (B1) and (B2), can be copolymerized randomly or sequentially and have a linear or branched structure. The molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which the skilled person will appreciate. MFI, abbreviation of Melt Flow Index, is the melt flow index. It is measured according to the ASTM 1238 standard. Advantageously, the non-functionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of an alpha-olefinic comonomer. such as butene, hexene, octene or 4-methyl-1-pentene. We can cite, for example, PP, high density PE, medium density PE, linear low density PE, low density PE, very low density PE. These polyethylenes are known to those skilled in the art as being produced according to a "radical" process, according to a "Ziegler" type of catalysis or, more recently, according to a "metallocene" catalysis. Advantageously, the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units carrying polar reactive functional groups such as the epoxy, carboxylic acid or carboxylic acid anhydride functions. Examples of such polymers include ter polymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as Lotader® of the Applicant or polyolefins grafted with maleic anhydride such as the Orevac® of the Applicant as well as ter ter polymers of ethylene, alkyl acrylate and (meth) acrylic acid. Homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or monoamino oligomers of polyamide can also be mentioned.
    [0019] The MFI of the polyamide, the MFI of (B1) and (B2) can be chosen from a wide range; however, it is recommended to facilitate the dispersion of (B) that the MFI of the polyamide is greater than that of (B). As regards the additives The composition may also comprise up to 20% by weight, relative to the total weight of the composition, of an additive chosen from antistatic fillers, nucleants, lubricants, dyes, pigments, brighteners, anti-oxidants, fibers, in particular aramid fibers, glass fibers, carbon fibers, advantageously glass fibers, fillers, in particular, silica, graphite, expanded graphite, black carbon, glass beads, kaolin, magnesia, slag, talc, wollastonite, nanofillers (carbon nanotubes) and stabilizers. The usual stabilizers used with polymers are phenols, phosphites, UV absorbers, stabilizers of HALS (Hindered Amine Light Stabilizer) type, metal iodides, etc. Examples include Irganox 1010, 245, 1098, Irgafos 168, Tinuvin 312, Iodide P201 from Ciba. The Applicant has therefore surprisingly found that the introduction of a prepolymer into a PA / impact modifier composition thus leads to a more fluid melt composition than the same prepolymer free composition. Another advantage of the invention, besides the greater fluidity of the compositions, is that the impact properties and flexural rigidity are not impaired in comparison with the properties of the same compositions without prepolymer.
    [0020] Advantageously, the composition of the invention is devoid of thermoplastic polyurethanes. The polyamide of the matrix is predominant with respect to the total of the polyamides present in the composition. Advantageously, the polyamide of the matrix present in the composition is an aliphatic polyamide, in particular a long-chain polyamide, such as PA11, PA12, or an XY polyamide, in particular PA10.10, PA10.12 or PA12. .12, or a short chain polyamide such as PA6, 6.6 or 6.10, in particular the polyamide is selected from PA6 and PA11. Homopolyamides and copolyamides are distinguished by their number of carbon atoms per nitrogen atom, knowing that there are as many nitrogen atoms as amide groups (-CO-NH-). In the case of a PAX.Y type homopolyamide, the number of carbon atoms per nitrogen atom is the average of the X unit and the Y unit. By long-chain polyamide, it is necessary to understand a polyamide whose number carbon per nitrogen atom is greater than 9.
    [0021] Short-chain polyamide should be understood to mean a polyamide whose carbon number per nitrogen atom is less than or equal to 9. Advantageously, said prepolymer corresponds to a polyamide, in particular an aliphatic one, in particular chosen from PA6, PA11, PA12 and PA6 / 12 or a mixture thereof.
    [0022] Advantageously, a single prepolymer is used in the composition. Said prepolymer may have a mass of from 1000 to 10,000 g / mol, especially from 1000 to 9000 g / mol, especially from 1000 to 8000 g / mol, especially from 1000 to 7000 g / mol, in particular from 1000 to 6000 g / mol in particular from 1000 to 5000 g / mol, in particular from 2000 to 5000 g / mol, in particular from 2000 to 4000 g / mol, in particular from 2000 to 3000 g / mol, preferably 2500 g / mol. Advantageously, the proportion by weight of prepolymer is from 0.1 to 20%, especially from 1 to 20%, especially from 3 to 20%, especially from 3 to 15%, relative to the total of the composition. Advantageously, the proportion by weight of prepolymer is from 1 to 30%, especially from 3 to 25% relative to the weight of prepolymer-polyamide. Advantageously, the proportion by weight of prepolymer is from 0.1% to 6% by weight relative to the weight of prepolymer-polyamide.
    [0023] Advantageously, the ratio: viscosity at a shear rate of 100 s -1 of a composition without prepolymer / viscosity of a prepolymer composition is at least 1.6, in particular at least 1.6 to approximately 5, as determined by capillary rheometry on Rheo_tester 2000 Gottfert at 260 ° C). This ratio is determined at comparable concentration of the various constituents of the composition, that is to say impact modifiers, where appropriate with additives, the same, the proportion of polyamide of the matrix being corrected according to the proportion of prepolymer introduced. . Therefore, the compositions of the invention have a fluidity dependent on the prepolymer concentration introduced and greater than that of a prepolymer-free composition.
    [0024] Advantageously, the ratio: flexural modulus at 23 ° C. of a composition without prepolymer / flexural modulus at 23 ° C. of a composition with a prepolymer is approximately 1, as determined according to ISO 178. Advantageously, the ratio: Notched impact at -30 ° C of a composition without prepolymer / impact notched at -30 ° C of a composition with prepolymer is about 1, as determined according to ISO 179 eA. Advantageously, the compositions of the invention have a viscosity ratio of at least 1.6, in particular from at least 1.6 to about 5, and a flexural modulus ratio of about 1 and a ratio of notched shock of about 1, these three ratios being as defined above.
    [0025] The prepolymer present does not affect the properties, especially of modulus and shock, of the polyamide with which it is introduced into the composition. The prepolymer may comprise a carbon number per nitrogen atom different from that of the polyamide, or identical to that of the polyamide or close to that of the polyamide.
    [0026] The polyamide and the prepolymer can therefore both be long chain or both short chain or the polyamide is long chain and the short chain prepolymer, or the polyamide is short chain and the prepolymer is long chain . Advantageously, in the composition of the invention, the prepolymer is chosen from short-chain polyamides and is compatible with the polyamide of the matrix, in particular the polyamide of the matrix is chosen from short-chain polyamides. The short-chain prepolymer and the polyamide of the short-chain matrix may be chosen from the following: 6, 4.6, 6.6, 6.T, 6.1, 6.10, 6.12, 9.T, 9'T, 9 denoting the 2- methy1-1,8-octanediamine, i.e. the isomer of diamine-9 or 1,9-nonanediamine, 6 / 6.6, 6.T / 6.6, 6.T / 61 / 6.6. By way of example, in the composition of the invention, the prepolymer consists of PA6 and the polyamide is a short chain PA, in particular a PA6, PA6.Y, Y representing a C4 to C12 diacid, especially a PA6.10 or PA6.12. According to another example, the prepolymer consists of a PA6 / 12 copolymer and the polyamide is a short chain PA, in particular PA6 or PA6.12.
    [0027] It is obvious that the ratio of monomers in copolyamide PA6 / PA12 can be from 0.1 / 99.9 to 99.9 / 0.1 by weight. Advantageously, in the composition of the invention, the prepolymer is chosen from long-chain polyamides and is compatible with the polyamide of the matrix, in particular the polyamide of the matrix is chosen from long-chain polyamides, in particular aliphatic polyamides, semi-aromatic or cycloaliphatic. The long-chain prepolymer and the polyamide of the long-chain matrix may be selected from the following: 12, 11, 10.10, 10.12, 6.18, 10.T, 12.T, 12 / 10.T, 12.12, 10.10 / 10.12 and 10.10 / 10.TA as an example, the prepolymer consists of PA11 and the polyamide is selected from PA11, PA12, PA10.10 and PA10.12. Advantageously, the impact modifier used in the composition is chosen from a polyolefin or a mixture of several polyolefins or a non-reactive Peba.
    [0028] In particular, some or all of the polyolefins carry a functional group chosen from carboxylic acid, carboxylic anhydride and epoxide functions, and is in particular chosen from an ethylene-propylene copolymer with an elastomeric nature (EPR), an ethylene-propylene copolymer with an elastomeric nature (EPDM) and an ethylene / alkyl (meth) acrylate copolymer, a higher ethylene-alkene copolymer, in particular an ethylene-octene copolymer, an ethylene-alkyl acrylate-maleic anhydride terpolymer. Advantageously, the impact modifier is chosen from F493, a Lotader®, in particular Lotader 5500 or Lotader 7500, VA1803, or a mixture of these, in this case they are in a ratio of 0.1 / 99.9 to 99.9 / 0.1, preferably 1/2 to 2/1 when in a mixture 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.
    [0029] Advantageously, the impact modifier in the composition of the invention is present in a proportion of 5 to 45% by weight, in particular of 10 to 30% by weight, in particular of 15 to 30% by weight relative to the total weight of the composition. . Advantageously, the additives of the composition are chosen from stabilizers, dyes, plasticizers, fibers, fillers and impact modifiers other than polyolefins. According to another aspect, the invention relates to the use of a composition as defined above, for the manufacture of articles obtained by extrusion, injection or molding. The articles obtained by extrusion may be tubes or pipes for dispensing fluids, in particular gasoline, compressed air or refrigerant fluids. The articles obtained by injection are for example sports articles, especially sports shoes and especially ski boots or running shoes.
    [0030] The articles obtained by molding can be tanks, in particular fuel tanks or gas. According to another aspect, the present invention relates to a process for the preparation of articles as defined above, comprising a step of extruding, injecting or molding the composition defined above.
    [0031] According to another aspect, the present invention relates to articles as obtained by the method defined above. The polyamide composition used in the invention can be prepared by compounding the polyamide of the matrix, the prepolymer and the impact modifier, optionally the mold release agent as well as any other components. The composition is usually recovered in the form of pellets or granules.
    [0032] According to another aspect, the invention relates to the use of a prepolymer with a matrix consisting of at least one polyamide, a shock modifier and optionally an additive, to constitute a composition having a greater fluidity in the molten state than the same composition without prepolymer, said polyamide being present in a proportion of 55 to 94.95% by weight; said prepolymer being present in a proportion of from 0.05% to 20% by weight, the proportion by weight of polyamide matrix and that of prepolymer being respectively from 60 to 99.9% and from 40 to 0.1%, relative to the sum polyamide-prepolymer; said impact modifier being present in a proportion of 5 to 45% by weight; and said additive being in proportion by weight of 0 to 20%, the sum of the polyamide, the prepolymer of the impact modifier and optionally additives being equal to 100%.
    [0033] The polyamide, the prepolymer, the impact modifier and the additive being as defined above. Advantageously, said composition is devoid of resin of the series of polyurethanes.
    [0034] DESCRIPTION OF THE FIGURES FIG. 1 shows the capillary rheometry on Rhéo_tester 2000 Gottfert at 260 ° C. of compositions of the invention consisting of variable amounts of PA6 (proportions of 60 to 70% by weight) and impact modifier (Lotader 7500: 10 % by weight and Fusabond F493: 20% by weight) in the presence of variable amounts of PA6 prepolymer (from 0 to 10% by weight). Abscissa: Corrected shear gradient Rabinowitsch (s-1) Ordinate: Rabinowitsch corrected viscosity (Pa. $) Square: 0% PA6 prepolymer and 70% PA6 (matrix) Triangle: 5% PA6 prepolymer and 65% PA6 ( matrix) Circle: 10% of PA6 prepolymer and 60% of PA6 (matrix) FIG. 2 shows the capillary rheometry on Rhéo_tester 2000 Gottfert at 260 ° C. of compositions of the invention constituted by PA6 (proportions of 55 to 70% by weight). weight) and impact modifiers (Lotader 5500: 10% by weight and Fusabond F493: 20% by weight) in the presence of variable amounts of PA6 prepolymer. Abscissa: Corrected shear gradient Rabinowitsch (s-1) Ordinate: Rabinowitsch corrected viscosity (Pa. $) Square: 0% PA6 prepolymer and 70% PA6 (matrix) Triangle: 10% PA6 prepolymer and 60% PA6 ( matrix) Circle: 15% PA6 prepolymer and 55% PA6 (matrix) FIG. 3 shows the capillary rheometry on Rheo_tester 2000 Gottfert at 260 ° C. of compositions of the invention (PA11 and 20% impact modifier: fusabond F493) in the presence or absence of 3% by weight of prepolymer PA11) Abscisse: Corrected shear gradient Rabinowitsch (s-1) Ordinate: Rabinowitsch corrected viscosity (Pa. $) Circle: 0% prepolymer PA11 and 80% PA11 (matrix) Square: 3% of prepolymer PA11 and 77% of PA11 (matrix) FIG. 4 shows the capillary rheometry on Rhéo_tester 2000 Gottfert at 260 ° C. of compositions of the invention (PA11 and 15% impact modifier: fusabond F493 in the presence or absence of not of 3% by weight of prepolymer PA11) Abscisse: Gradient Rabinowitsch corrected shear (s-1) Ordinate: Rabinowitsch corrected viscosity (Pa. $) Circle: 0% prepolymer PA11 and 85% PA11 (matrix) Square: 3% prepolymer PA11 and 82% PA11 (matrix) EXAMPLES Products used: * Fusabond 493: maleic anhydride grafted ethylene-octene copolymer (MAH) marketed by Dupont. * Lotader 7500 and 5500: ethylene / alkyl acrylate / maleic anhydride terpolymer marketed by the Applicant. * Exxelor TM VA 1803: copolymer of ethylene and propylene grafted maleic anhydride marketed by Exxon Mobil Chemical. * Domamid 24: polyamide 6 marketed by Domo Chemicals (iv = 1.15 dl / g measured in metacresol). * PA11 KNO (iv = 1.42) produced by the applicant. * Prepolymers: polyamide 6 and polyamide 11 mono NH2 of Mn 2500 g / mol (produced by the applicant). The following compositions are exemplified: Compositions of the invention based on PA11 - A polyamide 11 (KNO, matrix) - An ethylene-octene copolymer grafted with maleic anhydride, reference Fusabond 493 sold by the company Dupont. - A mono-functional NH 2 prepolymer of mass 2500 g / mol. Example 1: 80% PA11 (KNO) + 20% F493 77% PA11 (KNO) + 20% F493 + 3% prepolymer PA11 (mass ratio matrix PA 11 / prepolymer PA 11 96.25 / 3.75) Example 2: 85% PA11 (KNO, template) + 15% F493 82% PA11 (KNO, template) + 15% F493 + 3% PA11 prepolymer (matrix mass ratio PA 11 / prepolymer PA 11 of 96.5 / 3.5) Example 3: 85% PA11 ( KNO, Matrix) + 15% VA1803 82% PA11 (KNO, template) + 15% VA1803 + 3% prepolymer PA11 (mass ratio PA11 matrix / PA11 prepolymer 96.5 / 3.5) Compositions of the invention based on PA6 - One polyamide 6 (Domamid reference 24) - An ethylene-octene graft copolymer maleic anhydride, reference Fusabond 493 sold by the company Dupont. - An ethylene / acrylate / maleic anhydride terpolymer (Lotader range). - A mono-functional NH 2 polyamide 6 prepolymer of mass 2500 g / mol.
    [0035] Example 4: 70% PA6 + 20% F493 + 10% Lotader5500 65% PA6 + 5% prepolymer PA6 + 20% F493 + 10% Lotader5500 mass ratio PA6 / PA6 prepolymer of 92.9 / 7.1 60% PA6 + 10% prepolymer PA6 + 20% F493 + 10% Lotader5500 mass ratio PA6 / prepolymer PA6 85.7 / 14.3 55% PA6 + 15% prepolymer PA6 + 20% F493 + 10% Lotader5500 (mass ratio PA6 HM / PA6 prepolymer 78.6 / 21.4) Example 5: 70% PA6 + 20% F493 + 10% Lotader7500 65% PA6 + 5% prepolymer PA6 + 20% F493 + 10% Lotader7500 (mass ratio PA6 HM / prepolymer PA6 of 92.8 / 7.1 60% PA6 + 10% prepolymer PA6 + 20% F493 + 10% Lotader7500 (mass ratio PA6 HM / PA6 prepolymer 85.7 / 14.3) Compounding: Formulation base PA11: Twin-screw extruder type Thermo Haake PTW 16 / 25D Machine temperature: 270 ° C Screw speed: 300 rpm Extruder output: 3.5 kg / h Base formulation PA6: Clextral Evolum 32 twin-screw extruder Machine temperature: 240 ° C. Screw speed: 300 rpm.
    [0036] Extruder output flow: 40 kg / h.
    [0037] Transformation: Bars 80x10x4 mm3 were made by injection molding. The following process parameters were used: Base formulation PA1 1: - Injection temperature (supply / nozzle): 250/270 ° C - Mold temperature: 40 ° C - Hold time: 15 seconds - Hold pressure material: 500 bars. - Cooling time: 20 seconds 10 Base formulation PA6 - Injection temperature (feed / nozzle): 240/260 ° C - Mold temperature: 40 ° C - Hold time: 15 seconds - Material holding pressure: 340 bars. Cooling Time: 25 seconds The results of the viscosities of the compositions, flexural moduli and notched impact, of the bars obtained, are presented in the following Table I. TABLE I Notched Choc Module -30 ° C. (kJ / m2) 1 (100s-1 (1000s-1) in Pa.s flexion 1) in Pa.s (ambient temperature) MPa PA6 modified shock 70% PA6 + 0% prepolymer PA6 580 19 645 170 + 20% F493 + 10% Lotader5500 65% PA6 + 5% prepolymer PA6 585 19 370 145 + 20% F493 + 10% Lotader5500 60% PA6 + 10% prepolymer PA6 590 19 210 100 + 20% F493 + 10% Lotader5500 55% PA6 + 15% prepolymer 560 18 140 70 PA6 + 20% F493 + 10% Lotader5500 70% PA6 + 0% prepolymer PA6 + 20% F493 + 10% Lotader7500 630 16 635 170 65% PA6 + 5% oligo PA6 + 20% 640 16 360 135 F493 + 10% Lotader7500 60% PA6 + 10% oligo PA6 + 20% 595 17 240 100 F493 + 10% Lotader7500 PAH modified shock 85% PAll + 15% VA1803 800 34 1000 230 82% PAll + 15% VA1803 + 3% 820 35 560 195 prepolymer PAl 1 80% PAll + 20% F493 705 62 1375 280 77% PAll + 20% F493 + 3% 715 60 730 220 prepolymer PAl 1 85% PA11 + 15% F493 805 29 1095 280 82% PAll + 15% F493 + 3% 830 26 670 220 prepolymer PAl 1 The examples described above show that the impact modified compositions of the invention which comprise a prepolymer exhibit greater melt flowability than the same prepolymer-free compositions while the impact properties and flexural stiffness are not impaired.
    权利要求:
    Claims (18)
    [0001]
    REVENDICATIONS1. A composition comprising: - from 45 to 94.95% by weight of a matrix consisting of at least one polyamide; from 0.05% to 20% by weight of at least one prepolymer, the proportion by weight of polyamide matrix and that of prepolymer being respectively 60 to 99.9% and 40 to 0.1%, relative to polyamide-prepolymer sum; from 5 to 45% by weight of at least one impact modifier; from 0 to 20% of an additive, said composition having greater melt flowability than the same composition without prepolymer.
    [0002]
    2. Composition according to claim 1, wherein the polyamide of the matrix is chosen from: linear or branched aliphatic polyamides, cycloaliphatic polyamides, semiaromatic polyamides, aromatic polyamides, Peba.
    [0003]
    3. Composition according to claim 2, wherein the polyamide is an aliphatic polyamide, in particular chosen from PA6, PA11.
    [0004]
    4. Composition according to one of claims 1 to 3, wherein the prepolymer corresponds to a polyamide, in particular aliphatic, in particular selected from PA-6, PA11, PA12 and PA6 / 12 or a mixture thereof.
    [0005]
    5. Composition according to one of claims 1 to 4, wherein said prepolymer has a mass of from 1000 to 10000 g / mol, in particular from 1000 to 5000 g / mol, preferably 2500 g / mol.
    [0006]
    6. Composition according to one of claims 1 to 5, wherein the proportion by weight of prepolymer is 0.1 to 20%, especially 1 to 20%, especially 3 to 20%, especially 3 to 15%. , relative to the total of the composition.
    [0007]
    7. Composition according to one of claims 1 to 6, wherein the proportion by weight of prepolymer is 1 to 30%, especially 3 to 25% relative to the weight of prepolymer-polyamide
    [0008]
    8. Composition according to one of claims 1 to 7, wherein the prepolymer is compatible with the polyamide.
    [0009]
    9. Composition according to one of claims 1 to 8, wherein the prepolymer consists of PA6 and the polyamide is a short chain PA, in particular a PA6.Y, Y representing a C4 to C12 diacid, in particular a PA6 .10 or PA6.12.
    [0010]
    10. Composition according to one of claims 1 to 9, wherein the prepolymer consists of PA11 and the polyamide is selected from PA11 PA12, PA10.10 and PA10.12.
    [0011]
    11. Composition according to one of claims 1 to 10, wherein the prepolymer consists of PA6 / 12 and the polyamide is selected from PA6 and PA6.12.
    [0012]
    12. Composition according to one of claims 1 to 11, wherein the impact modifier is selected from a polyolefin or a mixture of several polyolefins or a non-reactive Peba.
    [0013]
    13. Composition according to claim 12, in which some or all of the polyolefins carry a functional group chosen from carboxylic acid, carboxylic anhydride and epoxide functions, and is in particular chosen from a copolymer of ethylene and propylene with an elastomeric character ( EPR), an ethylene-propylene-diene copolymer with elastomeric character (EPDM) and an ethylene / alkyl (meth) acrylate copolymer.
    [0014]
    14.Composition according to one of claims 12 or 13, wherein the impact modifier is present in a proportion of 5 to 45% by weight, in particular 10 to 30% by weight, relative to the total weight of the composition.
    [0015]
    15.Cornposition according to one of claims 1 to 14, wherein the additives are selected from stabilizers, dyes, plasticizers, fibers, fillers and impact modifiers other than polyolefins.
    [0016]
    16. Use of a composition as defined in one of claims I to 15, for the manufacture of articles obtained by extrusion, injection or molding. 20
    [0017]
    17.Use of a composition according to claim 16, for the manufacture of articles obtained by injection, in particular for the manufacture of sports shoes, especially ski boots or running shoes. 25
    [0018]
    18. Use of a composition according to claim 16 for the manufacture of articles obtained by molding, in particular tanks. 10 15
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    同族专利:
    公开号 | 公开日
    EP3126448A1|2017-02-08|
    KR20160140645A|2016-12-07|
    CN106133061B|2021-04-13|
    WO2015150687A1|2015-10-08|
    KR102277345B1|2021-07-13|
    US20170022363A1|2017-01-26|
    CN106133061A|2016-11-16|
    US10800918B2|2020-10-13|
    JP2020007563A|2020-01-16|
    JP2017509763A|2017-04-06|
    FR3019553B1|2020-07-31|
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    法律状态:
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    2017-03-13| PLFP| Fee payment|Year of fee payment: 4 |
    2018-03-15| PLFP| Fee payment|Year of fee payment: 5 |
    2020-03-12| PLFP| Fee payment|Year of fee payment: 7 |
    2021-03-10| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1452901A|FR3019553B1|2014-04-02|2014-04-02|NEW IMPACT MODIFIED THERMOPLASTIC COMPOSITION WITH GREATER MELT FLUIDITY|FR1452901A| FR3019553B1|2014-04-02|2014-04-02|NEW IMPACT MODIFIED THERMOPLASTIC COMPOSITION WITH GREATER MELT FLUIDITY|
    KR1020167026433A| KR102277345B1|2014-04-02|2015-03-31|Novel impact-modified thermoplastic composition having a higher level of fluidity in the melted state|
    CN201580017644.4A| CN106133061B|2014-04-02|2015-03-31|Novel impact modified thermoplastic compositions having a higher level of flowability in the molten state|
    JP2016559646A| JP2017509763A|2014-04-02|2015-03-31|A novel impact-modified thermoplastic composition with a high level of fluidity in the molten state|
    US15/301,251| US10800918B2|2014-04-02|2015-03-31|Impact-modified thermoplastic composition having a higher level of fluidity in the melted state|
    EP15717047.3A| EP3126448A1|2014-04-02|2015-03-31|Novel impact-modified thermoplastic composition having a higher level of fluidity in the melted state|
    PCT/FR2015/050825| WO2015150687A1|2014-04-02|2015-03-31|Novel impact-modified thermoplastic composition having a higher level of fluidity in the melted state|
    JP2019165874A| JP2020007563A|2014-04-02|2019-09-12|Novel impact resistance modified thermoplastic composition having high level flowability at molten state|
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