Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
  • B32B5/022—Non-woven fabric
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/02—Synthetic macromolecular fibres
  • B32B2262/0253—Polyolefin fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to waterproof breathable films based on block copolymers, which are permeable to water vapor and impermeable to water. These films can be used especially in the food field, packaging, sports equipment, or in the building, especially as insulation material under the roof of homes and for the insulation of walls.
• films that are both flexible, stretchable, solid, that is to say, tear-resistant, abrasion-resistant, recyclable and having sufficient water vapor permeability. .
• the permeability to water vapor is evaluated using the MVTR (Moisture Vapor Transmission Rate) parameter.
• MVTR Magnetic Vapor Transmission Rate
• ASTM E96 Measured Vapor Transmission Rate
• the present invention aims to improve the flexibility, the stretchability, the strength of these films and their resistance to abrasion, without modifying their permeability to water vapor.
• Flexibility is evaluated using the modules: tensile modulus according to ISO 527 1 A: 2012, and flexural modulus at 23 ° C according to ISO 178: 2010. A decrease of these modules goes in the direction of a better flexibility of the films.
• the stretchability is evaluated using the elongational rheology test, as defined hereinafter in the examples of the present application.
• the abrasion resistance is evaluated by the mass loss according to ISO 527-1 A: 2012: the lower the mass loss of the material, the better the abrasion resistance of the films made of this material.
• PEBA polyamide block and polyether block copolymers
• These PEBAs belong to the particular class of polyetheresteramides when they result from the copolycondensation of polyamide sequences with reactive carboxyl ends with polyether sequences with reactive ends, which are polyether polyols (polyetherdiols), the bonds between the polyamide blocks and the polyether flexible blocks. being ester bonds.
• PEBAs are known for their physical properties such as their flexibility, their impact resistance, and their ease of use by injection.
• these copolymers are difficult to transform into film form by extrusion, in particular because of a low melt viscosity and a low melt strength resulting therefrom.
• melt viscosity by lengthening the polymer chains, for example by prolonging the polymerization.
• This approach has been disappointing because of the degradation of the PEG blocks, which further causes a coloration (yellowing) of the material, without being able to reach the desired levels of melt viscosity, of at least 300 Pa.s, measured according to ISO 1621-10: 2015.
• the object of the invention is therefore also to provide an improved process for producing breathable, stretchy and flexible films based on block copolymers, in which extrusion is facilitated and maximum attainable extrusion speeds are increased.
• the Applicant has now found that the use, under certain conditions, of a polycarbodiimide in a process for the production of polyamid block and flexible block copolymer-based film comprising at least one end of a carboxylic acid chain, makes it possible to improve significant ability of stretching said copolymer film form and / or increase the extrusion rate of said copolymer, while improving the stretchability of the film thus obtained, the flexibility of the film, its resistance to abrasion, and its tear resistance, without sacrificing the water vapor permeability of the obtained film, nor its recyclability.
• the percentages expressed are percentages by mass. Unless otherwise stated, the parameters referred to are measured at atmospheric pressure, and ambient temperature (20-25 ° C, usually 23 ° C).
• the subject of the invention is therefore a flexible, breathable and waterproof breathable film based on a block copolymer comprising at least one rigid polyamide block PA and at least one flexible block, characterized in that the said copolymer comprises at least one end of the chain.
• carboxylic acid blocked by a polycarbodiimide it is specified that the film "copolymer-based" means that the film comprises at least 51% by weight of copolymer on the total weight of the film.
• the film according to the invention comprises at least 60% by weight of said copolymer as defined by the invention.
• it contains at least 70% by weight, preferably at least 80%, or even at least 90%, or better still at least 95%, by weight of copolymer as defined hereinafter by the invention, on the total weight of the film.
• thermoplastic elastomer polymer refers to a polymer which constitutes a multiphase material having at least two transitions, namely a first transition at a temperature T1 (generally it is the glass transition temperature) and a second transition at a temperature T2 greater than T1 (usually this 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.
• TPE thermoplastic elastomer polymer
• thermoplastic elastomer based on polyamide (TPE-A) within the meaning of the invention, such as a PEBA, is a block copolymer comprising a series of blocks, alternately rigid or hard (BD) and soft or soft (BM), according to the following general formula:
• 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 soft 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 their mixtures in the form of alternating, random or block copolymers.
• PE block polyether
• PET block polyester
• PDMS block polydimethylsiloxane
• PO block polyolefin
• PC block polycarbonate
• BM is a polyether block having alkylene oxide units, in whole or in part.
• n represents the number of repeating units of the -BD-BM- unit of said copolymer n is in the range of 1 to 60, preferably 5 to 30, more preferably 6 to 20.
• low glass transition temperature for a polymer used in 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 0 ° C. -15 ° C, more preferably below -30 ° C.
• said rrou block may be based on PEG molar mass in a number equal to 1500g / mol and Tg of the order of - 35 ° C.
• Said glass transition temperature Tg may also be less than -50 ° C., especially in the case where said soft block is based on PTMG.
• Amide block copolymers also called polyether block copolymers and polyamide blocks, abbreviated as "PEBA" result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
• polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends obtained by cyanoethylation and hydrogenation of polyoxyalkylene aliphatic alpha-omega dihydroxylated blocks called polyetherdiols;
• the polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
• the polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
• the molar mass in number Mn of the polyamide blocks is between 400 and 20000 g / mol and preferably between 500 and 10000 g / mol.
• Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. Three types of polyamide blocks can advantageously be used.
• 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 an aliphatic or aromatic diamine, in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• dicarboxylic acids examples include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. .
• diamines examples include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, 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-di-cyclohexyl-methane ( PACM), and isophoronediamine (IPDA), 2,6-bis- (aminomethyl) -norbornane (BAMN) and piperazine (Pip).
• BCM bis (4-aminocyclohexyl) methane
• BMACM bis - (3-methyl-4-aminocyclohexyl) methane
• BMACP 2-2-
• the standard NF EN ISO 1874-1: 201 1 defines a nomenclature of polyamides.
• the term "monomer” in the present description should be understood as “repetitive unit”.
• the case where a repeating unit of the polyamide consists of the combination 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 “diaminediacid” pair, also called “XY”, in equimolar quantity which corresponds to the monomer. This is explained by the fact that, individually, the diacid or the diamine is only a structural unit, which is not enough on its own to polymerize.
• the polyamide blocks result from the condensation of one or more alpha omega-aminocarboxylic acids and / or 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.
• lactams mention may be made of caprolactam, oenantholactam and lauryllactam.
• alpha omega amino carboxylic acid there may be mentioned aminocaproic acid, amino-7-heptanoic acid, amino-1 1-undecanoic acid and amino-12-dodecanoic acid.
• the polyamide blocks of the second type are made of polyamide 11, polyamide 12 or polyamide 6.
• 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.
• polyamide PA blocks are prepared by polycondensation:
• comonomer (s) ⁇ Z ⁇ chosen from lactams and alpha-omega aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X 1 carbon atoms and at least one dicarboxylic acid having Y 1 carbon atoms, (X1, Y1) being different from (X, Y);
• said one or more comonomers ⁇ 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 the polyamide precursor monomers;
• the dicarboxylic acid having Y carbon atoms which is introduced in excess with respect to the stoichiometry of the diamine or diamines, is used as chain limiter.
• the polyamide blocks result from the condensation of at least two alpha omega aminocarboxylic acids or at least two lactams having from 6 to 12 carbon atoms or a lactam and an aminocarboxylic acid. not having the same number of carbon atoms in the possible presence of a chain limiter.
• alpha omega amino carboxylic acid mention may be made of aminocaproic acid, amino-7-heptanoic acid, amino-1 1 -undecanoic acid and amino-12-dodecanoic acid.
• lactam mention may be made of caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines there may be mentioned hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids By way of example of aliphatic diacids, mention may be made of butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid or dimerized fatty acid (these dimerized fatty acids preferably have a dimer content of at least 98% preferably they are hydrogenated, they are marketed under the trade name Pripol® by the company Unichema, or under the brand Empol® by Henkel) and the polyoxyalkylenes-a, w diacids.
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• cycloaliphatic diamines 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-di-cyclohexyl methane (PACM).
• BMACP bis (4-aminocyclohexyl) methane
• BMACP 2- (2-bis) - (3-methyl-4-aminocyclohexyl) propane
• PAM para-amino-di-cyclohexyl methane
• IPDA isophoronediamine
• BAMN 2,6-bis (aminomethyl) norbornane
• PA blocks of 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 comonomer (monomer different from the first monomer) they comprise a copolymer such as an abbreviated copolyamide CoPA.
• co-monomers that is to say at least one monomer and at least one comonomer (monomer different from the first monomer) they comprise a copolymer such as an abbreviated copolyamide CoPA.
• polyamide blocks of the third type As examples of polyamide blocks of the third type, the following can be cited:
• 66/6 wherein 66 denotes hexamethylenediamine units condensed with adipic acid. 6 denotes patterns resulting from the condensation of caprolactam.
• 66/610/11/12 wherein 66 denotes hexamethylenediamine condensed with adipic acid. 610 denotes hexamethylenediamine condensed with sebacic acid. 1 1 denotes patterns resulting from the condensation of aminoundecanoic acid. 12 denotes patterns resulting from the condensation of lauryllactam.
• the mass Mn of the soft blocks is between 100 and 6000 g / mol and preferably between 200 and 3000 g / mol.
• the polymer comprises from 1 to 80% by weight of flexible blocks and from 20 to 99% by weight of polyamide blocks, preferably from 4 to 80% by weight of flexible blocks and from 20 to 96% by weight of polyamide blocks.
• the rigid polyamide block in the rigid block copolymer PA and flexible blocks according to the invention comprises at least one of the following polyamide units: 1 1, 12, 6, 610, 612, 1010, 1012, and mixtures or copolyamides thereof.
• the polyether PE blocks consist of alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide or tetrahydrofuran units (which leads to polytetramethylene glycol linkages).
• PEG (polyethylene glycol) blocks are used, ie those consisting of ethylene oxide units, PPG (propylene glycol) blocks, ie those consisting of propylene oxide units, P03G (polytrimethylene glycol) blocks. ) that is to say those consisting of glycol polytrimethylene ether units (such copolymers with polytrimethylene ether blocks are described in US6590065), and PTMG blocks, ie those consisting of tetramethylene glycol units also called polytetrahydrofuran.
• the PEBA copolymers may comprise in their chain several types of polyethers, the copolyethers may be block or statistical.
• the polyether blocks may also consist of ethoxylated primary amines.
• ethoxylated primary amines mention may be made of the products of formula:
• the flexible polyether blocks may comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic polyoxyalkylene aliphatic alpha-omega dihydroxy blocks known as polyether diols. More particularly, Jeffamines (e.g. Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, also described in JP2004346274, JP2004352794 and EP1482011) can be used.
• Jeffamines e.g. Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, also described in JP2004346274, JP2004352794 and EP1482011
• the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends.
• the general two-step preparation method for PEBA copolymers having ester bonds between PA blocks and 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 linkages between PA blocks and 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 the polyamide block and polyether block polymers having statistically distributed units (one-step process).
• PEBA designation in the present description of the invention relates as well to Pebax® marketed by Arkema, Vestamid® marketed by Evonik®, Grilamid® marketed by EMS, Kellaflex® marketed by DSM or to any other PEBA from other suppliers.
• the PEBA copolymers have PA blocks PA 6, PA 11, PA 12, PA 612, PA 66/6, PA 1010 and / or PA 614, preferably PA 11 blocks and / or PA 12; and PE blocks made of PTMG, PPG and / or P03G.
• PEBAs based on PE blocks consisting mainly of PEG are to be included in the range of PEBA hydrophilic.
• PEBAs based on PE blocks consisting mainly of PTMG are to be included in the range of hydrophobic PEBA.
• said PEBA used in the composition according to the invention is obtained at least partially from bio-resourced raw materials.
• Raw materials of renewable origin or bio-resourced raw materials are materials that include biofouled carbon or carbon of renewable origin.
• materials made from renewable raw materials contain 14 C.
• the "carbon content of renewable origin” or “bio-resourced carbon content” is determined according to the standards ASTM D 6866 (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
• PEBAs based on polyamide 1 1 come at least partly from bioprocessed raw materials and have a bio-resourced carbon content of at least 1%, which corresponds to an isotopic ratio of 12%.
• the PEBAs according to the invention comprise at least 50% by mass of bio-resourced carbon on the total mass of carbon, which corresponds to a 12 C / 14 C isotope ratio of at least 0.6 ⁇ 10 12 .
• This content is advantageously higher, especially up to 100%, which corresponds to a 12 C / 14 C isotopic ratio of 1.2 ⁇ 10 12 , in the case, for example, of PEBA with PA 1 1 blocks and PE blocks comprising P03G, PTMG and / or PPG from raw materials of renewable origin.
• PES polyester blocks are usually manufactured 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 products from the PRIPLAST® range from Croda or Uniqema.
• PSi polysiloxane block
• PSi polysiloxane block
• hydrocarbon-based radicals are alkyl radicals, especially of C 1 -C 0 and in particular methyl, fluoroalkyl radicals, aryl radicals and in particular phenyl radicals, and alkenyl radicals and in particular vinyl radicals; other types of radicals that can be bonded either directly or via a hydrocarbon radical to the siloxane chain include hydrogen, halogens and in particular chlorine, bromine or fluorine, thiols, alkoxy radicals, polyoxyalkylene (or polyether) radicals and in particular polyoxyethylene and / or polyoxypropylene radicals, hydroxyl or hydroxyalkyl radicals, substituted or unsubstituted amine groups, amide groups, acyloxy or acyloxyalkyl radicals, hydroxyalkylamino or aminoalkyl radicals quaternary ammonium groups, amphoteric or betaine groups, anionic groups such as carboxylates, thioglycolates, sulphos,
• said polysiloxane blocks comprise polydimethylsiloxane (hereinafter abbreviated PDMS blocks), polymethylphenylsiloxane, and / or polyvinylsiloxane.
• PDMS blocks polydimethylsiloxane
• polymethylphenylsiloxane polymethylphenylsiloxane
• polyvinylsiloxane polyvinylsiloxane
• Polyolefin block within the meaning of the invention means any polymer comprising as monomer an alpha-olefin, that is to say homopolymers of an olefin or copolymers of at least an alpha-olefin and at least one other copolymerizable monomer, the alpha-olefin preferably having from 2 to 30 carbon atoms.
• alpha-olefin By way of example of alpha-olefin, mention may be made of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 - methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1 -ococene, 1-tetracocene, 1-hexacocene, 1-octacocene , and 1-triacontene. These alpha-olefins can be used alone or as a mixture of two or more.
• LDPE low density polyethylene
• HDPE high density polyethylene
• LLDPE linear low density polyethylene
• VLDPE very low density polyethylene
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR elastomers (ethylene-propylene rubber), and EPDM (ethylene-propylene-diene), and polyethylene blends with EPR or EPDM,
• SEBS styrene / ethylene-butene / styrene block copolymers
• SBS styrene / butadiene / styrene
• SIS styrene / isoprene / styrene
• SEPS styrene / ethylene-propylene / styrene
• unsaturated carboxylic acid salts or esters such as, for example, alkyl (meth) acrylates, alkyl 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.
• said at least one polyolefin block comprises polyisobutylene and / or polybutadiene.
• 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 polyetheramideamide block, etc.
• Said PO block preferably comprises a polyolefin comprising acidic terminal groups, alcohols or amines.
• 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).
• the BDh block may further 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 group sulfonate 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 block PO and the block BDh.
• Document US Pat. No. 5,552,131 describes the synthesis and the various possible structures for the PO block and BDh block copolymer, these being of course conceivable in the process according to the invention.
• PC block polvcarbonate block
• the aliphatic polycarbonates are described for example in DE2546534 and JP1009225. Such homopolymeric or copolymeric polycarbonates are also described in US471203.
• Applications WO92 / 22600 and WO95 / 12629 disclose copolymers comprising polycarbonate blocks and 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.
• the polycarbonate blocks of the copolymer according to the invention have the formula:
• R1 and R2 which may be the same or different, represent a straight or branched chain, aliphatic or alicyclic having 2 to 18 carbon atoms, or represent a polyoxyalkylene group or represent a polyester group.
• R 1 and R 2 are selected from hexylene, decylene, dodecylene, 1,4-cyclohexylene, 2,2-dimethyl, 3-propylene, 2,5-dimethyl-2,5-hexylene or polyoxyethylene are preferred.
• block copolymers described above generally comprise at least one polyamide rigid block and at least one flexible block
• present invention in fact covers all copolymers comprising two, three, four (or more) different blocks selected among those described in the present description, as long as at least one of these blocks is a polyamide block.
• 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:
• the polyamide rigid block mass percentage is greater than 10%
• the mass percentage of flexible blocks is greater than 20%
• the flexible block in the rigid block copolymer-based film PA and flexible blocks according to the invention comprises (and preferably is) a polyether PE block, preferably chosen from PTMG, PPG, P03G and / or PEG.
• the flexible block in the rigid block copolymer PA and soft blocks of the film according to the invention comprises (and preferably is) a polyester block PES, chosen from polyesters diols, poly (caprolactone). ) and polyesters based on fatty acid dimers.
• the ratio by weight of the PA blocks on the soft blocks is in the range of 0.3 to 10, preferably of 0.3 to 6, preferably of 0.3 to 3. preferably from 0.3 to 2.
• said copolymer at the base of the film according to the invention comprises from 45 to 75% by weight of polyethylene glycol (PEG) flexible blocks, preferably from 50 to 70% by weight of PEG blocks, relative to the total weight of copolymer .
• PEG polyethylene glycol
• said polyamide block PA of the copolymer used in the film of the invention comprises at least one of the following polyamide units: 6, 66, 610, 612, PA1010, PA1012, PA1 1, PA12, PA6 / 12, PA6 / 66, and mixtures or copolyamides thereof.
• the copolymer comprises a rigid block copolymer polyamide and polyether soft blocks (PEBA), preferably chosen from the following PEBAs: PA6-PEG, PA1010-PEG, PA1012-PEG, PA1 1 -PEG, PA12-PEG, PA6 / 12-PEG, PA66-PEG, PA6 / 66-PEG, and mixtures thereof.
• PEBAs preferably chosen from the following PEBAs: PA6-PEG, PA1010-PEG, PA1012-PEG, PA1 1 -PEG, PA12-PEG, PA6 / 12-PEG, PA66-PEG, PA6 / 66-PEG, and mixtures thereof.
• PEBA polyether soft blocks
• 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, C 1 -C 20 alkyl or C 3 -C 10 cycloalkyl or C 1 -C 20 alkenyl, and may be cyclic or branched, or may contain a C 8 -C 16 aromatic ring, and may be substituted by functional groups.
• R ' may be a divalent group corresponding to all the foregoing, for example C1-C20 alkylene, C3-C10 cycloalkylene, etc.
• functional groups include, but are not limited to, cyanato and isocyanato, halo, amido, carboxamido, amino, imido, imino, silyl, etc.
• R ' include, but are not limited to, divalent radicals derived from 2,6-diisopropylbenzene, naphthalene, 3,5-diethyltoluene, 4,4'-methylenebis (2,6-diethylenephenyl) ), 4,4'-methylenebis (2-ethyl-6-methylphenyl), 4,4'-methylenebis (2,6-diisopropylphenyl), 4,4'-methylenebis (2-ethyl-5) methylcyclohexyl), 2,4,6-triisopropylphenyl, n-hexane, cyclohexane, dicyclohexylmethane and methylcyclohexane, and the like.
• Patent documents US5130360, US5859166, US368493, US7456137 US2007 / 0278452, US2009 / 0176938, and in particular US5360888 still disclose 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.
• the polycarbodiimide is chosen from a stabilizer, in particular 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 thereof.
• a stabilizer in particular Stabilizer® 9000 corresponding to Poly- (1,3,5-triisopropylphenylene-2,4-carbodiimide
• Stabaxol® in particular a stabaxol® P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture thereof.
• the polycarbodiimide has a weight average molecular weight greater than 10,000 g / mol.
• the weight average molecular weight of the polycarbodiimide is in the range of 10,000 to 40,000 g / mol, preferably 15,000 to 30,000 g / mol.
• the weight content of the polycarbodiimide is advantageously 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% by weight. , 5%, preferably from 0.5 to 2% by weight, relative to the total weight of copolymer according to the invention.
• said carboxylic acid of the copolymer in the film 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 an acid chain blocked at the base of the film according to the invention is that it remains in non-crosslinked linear form, the Mw / Mn dispersity of the copolymer being less than 3. This is surprising in the as in the prior art, carbodiimides are rather used to viscosify polyamides (see for example the patent document FR3027907), in particular by crosslinking, and for improving their resistance to hydrolysis as described in US5360888.
• the subject of the present invention is also the use of a polycarbodiimide in a process for manufacturing a film based on polyamide block copolymers and flexible blocks comprising at least one end of a carboxylic acid chain, in order to improve the extrudability and / or the stretching (or stretching) of the film copolymer and / or improving the extrusion rate of said copolymer, wherein at least one end of the carboxylic acid chain of the copolymer is blocked by a carbodiimide function of the polycarbodiimide.
• Another subject of the present invention is the use of a polycarbodiimide in a film based on a copolymer of polyamide blocks and flexible blocks comprising at least one end of the carboxylic acid chain, in order to improve the stretchability of the film, the flexibility of the film, its abrasion resistance, and its tear resistance, wherein at least one end of the carboxylic acid chain of the copolymer is blocked by a carbodiimide function of the polycarbodiimide.
• the polycarbodiimide has a weight average molecular mass greater than 10,000 g / mol, preferably in the range of 10,000 to 40,000 g / mol, preferably 15,000 to 30,000 g / mol. mol.
• the weight average molecular weight of the polycarbodiimide used in the present invention is measured by gel permeation chromatography (G PC) in tetrahydrofuran (THF).
• 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 copolymer-based film composition according to the invention, characterized in that it comprises:
• polyamides 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,
• TPU thermoplastic polyurethanes
• additives chosen from nucleating agents, fillers, in particular mineral fillers, such as talc, reinforcing fibers, in particular glass or carbon fibers, dyes, UV absorbers , antioxidants, in particular phenolics, or phosphorus-based or based on sulfur, hindered amine light stabilizers or HALS, and mixtures thereof,
• the film according to the invention comprises a functional polyolefin comprising a grafting with a monomer chosen from the group comprising unsaturated carboxylic acids, unsaturated carboxylic anhydrides, vinyl monomers, acrylic monomers, and mixtures thereof.
• the functional polyolefin is selected from the group consisting of ethylene-acrylic ester copolymers, ethylene-acrylic ester-maleic anhydride copolymers, ethylene-acrylic ester-glycidyl methacrylate copolymers.
• the film according to the invention has a thickness less than or equal to 100 mih, preferably less than or equal to 50 mih, preferably less than or equal to 30 ⁇ m, preferably less than or equal to 25 ⁇ m, preferably comprised in range from 5 to 25 pm.
• Another subject of the present invention is a process for manufacturing the film according to the invention, comprising the steps of:
• the process of the invention comprises, prior to step a), the mixture of block copolymer comprising at least one polyamide rigid block PA and at least one flexible block 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.
• the mixture is produced by means of a single-screw or twin-screw extruder or by addition of the polycarbodiimide during the synthesis of the block copolymer.
• the stretching step c) is carried out by extrusion blow molding, extrusion-inflating, extrusion-drawing, extrusion-sheathing, extrusion-calendering, extrusion in a flat die, extrusion-coating, lamination, and / or coextrusion.
• step b) is carried out at a temperature in the range of 80 to 350 ° C, preferably 100 to 300 ° C, preferably 150 to 250 ° C.
• the present invention also relates to a laminate product comprising at least one textile material and at least one film according to the invention, said film adhering to at least one surface of the textile material with a peel force in the range of 0.5. at 50 N, preferably from 0.5 to 10 N, measured according to the standard ISO 1339.
• said at least one textile material is in the form of a porous membrane, a woven fabric or a nonwoven fabric.
• said at least one textile material comprises synthetic fibers, in particular synthetic fibers obtained from bio-resourced raw materials, natural fibers, artificial fibers made from natural raw materials, mineral fibers, and / or metal fibers.
• said at least one textile material constitutes a felt, a filter, a film, a gauze, a cloth, a bandage, a diaper, a fabric, a knit, an article of clothing, a garment, an article of bedding, an article of furniture, a curtain, a cockpit liner, a functional technical textile, a geotextile, and / or an agrotextile.
• the present invention further relates to the use of a film according to the invention in the medical field, hygiene, luggage, clothing, clothing, household equipment or home, furniture, carpets, automobiles, industry, especially industrial filtration, agriculture and / or building.
• Said film according to the invention advantageously constitutes a packaging component, especially a food-processing component, a food packaging film, a packaging film for cooking and / or smoking, in particular sausage, a waterproof-breathable film, especially used in the building, a textile component, sports equipment, shoe, sports shoe, shoe sole, decoration, luggage, glasses, furniture, equipment audio-visual, computer, automotive or aeronautical equipment and / or a component of medical equipment.
• a packaging component especially a food-processing component, a food packaging film, a packaging film for cooking and / or smoking, in particular sausage, a waterproof-breathable film, especially used in the building, a textile component, sports equipment, shoe, sports shoe, shoe sole, decoration, luggage, glasses, furniture, equipment audio-visual, computer, automotive or aeronautical equipment and / or a component of medical equipment.
• PEBA 1 PA 12-PTMG (Mn: 600-2000)
• PEBA 1 is a PA 12 block copolymer and PTMG blocks of number average molecular weights (Mn) 600 - 2000 respectively.
• PEBA 2 PA 12-PTMG (Mn: 850-2000)
• PEBA 2 is a copolymer according to the invention, with PA 12 blocks and PTMG blocks of number-average molecular masses (Mn) 850 - 2000 respectively.
• 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 of number-average molecular masses (Mn) respectively 2000 - 1000. Copo 3: 98.5% PEBA 3 + 1.5% PCDI
• PEBA 4 PA1 1 -PTMG (600-1000)
• PEBA 4 is a block copolymer PA1 1 and PTMG blocks of number average molecular weights (Mn) 600 - 1000 respectively.
• PCDI Polycarbodiimide used in the examples: Poly- (1,3,5-triisopropylphenylene-2,4-carbodiimide)
• Breathable waterproof films have been prepared from the above materials.
• the waterproof breathability (or MVTR) of the various films of the abovementioned materials (PEBAs and Copos) is measured.
• the MVTR of the PEBA film and that of the corresponding Copo film are substantially identical: the breathability (MVTR) is measured greater than 100 g / m2 per 24 hours at 23 ° C for a relative humidity level 50% and a sample thickness of 30 miti, measured according to ASTM E96B.
• the adhesion of the films is directly related to the peel fcrces values.
• Peeling tests are preferably carried out within 2 hours to 48 hours after the manufacture of a laminate comprising PEBA film having 25 cc adhesive, by extrusion, on a nonwoven fabric of pelyprepylene.
• the laminates of each of the tests were subjected to a peel test (SEQ ID NO: 1339) on a 15 mm strip of laminate which was ground and then pulled at a speed of 200 mm / min.
• the following table 1 shows the results of viscesity measurement in the split state eta * (in Pa.s) at 220 ° C, in fenctien of the frequenceuneangulaire (rad / s) selen the seed ISO 6721 -10: 2015.
• Copos materials according to the invention have a higher melt viscosity than the comparative PEBAs.
• a rod is extruded through a die of a capillary rheometer; it is entered in the molten state by two pairs of wheels driven by a variable speed motor.
• a first pair of wheels and the motor are mounted at the free end, deviable, a support connected directly to a sensor, representing the restoring force.
• the second pair of wheels (coupled to the first pair) makes it possible to guide and limit the winding of the ring around the upper wheels.
• Small buffers soaked with surfactant liquid water, ethanol, and surfactant mixture are also applied to the wheels to cool them and thus limit the bonding effect.
• the melt strenght curves of FIGS. 1 and 2 represent the elongation constraint on the ordinate as a function of the elongation factor on the abscissa.
• Test temperatures 150 ° C or 180 ° C depending on the graies
• Diameter of the piston 12 mm
• Figure 1 shows the elongational measurement result of PEBA 3 (bottom curve) and Copo 3 (top curve) at 180 ° C.
• Figure 2 shows the elongational flow rheology measurement result of PEBA 4 (bottom curve) and Copo 4 (top curve) at 150 ° C.
• copolymers Copo 3 and Copo 4 used in the films according to the invention have an improved stretching ability compared to that of the respective controls PEBA 3 and PEBA 4.
• the films according to the invention based on block copolymers comprising at least one carboxylic acid end chain blocked by a polycarbodiimide exhibit improved stretchability compared to films based on the same respective unblocked copolymers.
• Copo copolymers 1 to 4 used in the textile materials according to the invention have lower tensile and flexural moduli than those of the respective controls PEBA 1 to 4.
• the films according to the invention based on block copolymers comprising at least one carboxylic acid end chain blocked by a polycarbodiimide have an improved flexibility compared to the films based on the same respective unblocked copolymers.
• Example 4 Comparison of Abrasion and Tear Resistance of Different PEBAs and COPOs
• the loss of mass is lower in the case of copolymers according to the invention, so the films based on the copolymers according to the invention have a better abrasion resistance than the films based on the respective control PEBAs.
• the films based on the copolymers according to the invention have a better tear resistance than the films based on the respective control PEBAs.
• Example 5 Measurement of the Dispersibility of the Different PEBAs and Copos
• the average molecular weights in weight and in number Mw and Mn measured increase respectively when passing from a PEBA to the corresponding Copo used in the films according to the invention, which indicates that the reaction has occurred between the carbodiimide function of the polycarbodiimide and the acid function of PEBA to form the end-blocked acid end Copo used according to the invention.
• the dispersity is determined to be equal to the ratio between molecular weight and number Mw / Mn.
• the accuracy of the measurement is given to within 5%.
• the number average molecular (or molar) mass is set by the chain limiter content. It can be calculated according to the relation:
• Mn (nmonomer / niimiter) * M repetition pattern + Mlimitor
• niimiter number of moles of excess diacid
• Repeat pattern Molecular weight of the pattern of repetition
• the Mw / Mn dispersity is also 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 remained in the form of linear non-crosslinked.
• the films based on these copolymers therefore remain perfectly recyclable.
• the polycarbodiimide thus used in the film according to the present invention makes it possible to improve the properties of extrudability, stretchability, flexibility, abrasion resistance, and tear resistance of the film, while maintaining its breathability, adhesion and recyclability. These advantageous properties could not be observed with monomeric carbodiimides, their volatility having not allowed them to react or actually block said carboxylic acid block copolymer used in the film of the present invention.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Textile Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)
• Laminated Bodies (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)
• Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=61750237

Family Applications (1)

Country Status (6)

Cited By (6)

Families Citing this family (6)

Citations (23)

Family Cites Families (12)

• 2017
  • 2017-11-17 FR FR1760883A patent/FR3073851B1/fr active Active
• 2018
  • 2018-11-16 JP JP2020526528A patent/JP7851685B2/ja active Active
  • 2018-11-16 EP EP18827164.7A patent/EP3710518B1/fr active Active
  • 2018-11-16 CN CN201880074582.4A patent/CN111356725B/zh active Active
  • 2018-11-16 US US16/763,566 patent/US12312444B2/en active Active
  • 2018-11-16 WO PCT/FR2018/052877 patent/WO2019097184A1/fr not_active Ceased
• 2023
  • 2023-10-02 JP JP2023171039A patent/JP2024012291A/ja active Pending

Patent Citations (23)

Also Published As

Similar Documents

Legal Events