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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
  • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
  • C08G65/3332—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group
  • C08G65/33327—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group cyclic
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  • 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
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  • 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
  • C08G69/44—Polyester-amides
• • C—CHEMISTRY; METALLURGY
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
  • C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/017—Antistatic agents
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0075—Antistatics
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/12—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/017—Additives being an antistatic agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/04—Antistatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/06—Properties of polyethylene
  • C08L2207/066—LDPE (radical process)

Definitions

• the present invention relates to thermoplastic elastomeric polymers (TPE), including high value - added technical polymers used in various sectors, such as electronics, automotive or sports.
• TPE thermoplastic elastomeric polymers
• the present invention relates more particularly to copolymers with polyether blocks and polyamide blocks, abbreviated "PEBA", having good antistatic properties.
• PEBA polyether blocks and polyamide blocks
• the invention relates to a copolymer containing at least one polyamide block (PA), at least one polyethylene glycol block (PEG) and at least one more hydrophobic block than the PEG block.
• PA polyamide block
• PEG polyethylene glycol block
• the invention also relates to a process for the synthesis of such thermoplastic elastomers having good antistatic properties and their use in any type of thermoplastic polymer matrix in order to provide antistatic properties to this matrix.
• Antistatic agents such as ethoxylated amine or sulfonate ionic surfactants
• ethoxylated amine or sulfonate ionic surfactants are known as additives for polymeric matrices.
• the antistatic properties of the polymers incorporating these surfactants depend on the ambient humidity and are therefore not permanent. Indeed, these surfactants tend to migrate to the surface of the polymers and then disappear.
• Polyamide block copolymers and hydrophilic polyether blocks are also used as antistatic agents which have the advantage of not migrating. Their antistatic properties are permanent and independent of the ambient humidity. It may be mentioned in particular the documents JP 60 023 435 A, EP 242 158, WO2001 / 01095 1, EP 1 046 675 and EP 829 520, which describe polymer substrates made antistatic by adding a block copolymer po lyether and blocks po lyamide.
• TPE such as the materials marketed by the ARKEMA Group under the Pebax® brand, have progressively become established in the field of electronic components, thanks to their mechanical properties and in particular their exceptional springback properties.
• TPE is meant a block copolymer comprising, alternately, so-called hard or rigid blocks or segments (with rather thermoplastic behavior) and so-called flexible or flexible blocks or segments (with rather elastomeric behavior).
• Pebax ® grades have good antistatic properties and excellent mechanical properties. Nevertheless, when they are used as an antistatic additive within a thermoplastic polymer matrix, said matrix has a surface of mediocre quality.
• the object of the present invention is to provide a copolymer which improves the antistatic properties of the polymer matrices which incorporate it and which does not have the drawbacks of the prior art.
• the present invention therefore has obj and a copolymer comprising: from 5 to 50% by weight, relative to the total weight of the copolymer, of at least one polyamide (PA) block,
• PA polyamide
• the copolymer from 1 to 45% by weight, relative to the total weight of the copolymer, of at least one block which is more hydrophobic than the polyethylene glycol block (PEG), the said block being more hydrophobic than the block PEG being chosen from a block polyether (PE) other than PEG, a polyester block (PES) and a polyolefin block (PO).
• PEG polyethylene glycol block
• the present invention also relates to a method for synthesizing the copolymer, as well as to its uses.
• the subject of the present invention is a composition comprising such a copolymer.
• FIG. 1 is a histogram comparing the surface resistances of different materials obtained by an injection method.
• FIG. 2 is a graph comparing the surface resistances of different materials, comprising copolymers incorporated in a polyolefin matrix at various mass ratios, obtained by an extrusion process.
• FIG. 4 is a graph comparing the surface resistances of various materials comprising copolymers, doped with an ionic liquid, incorporated into a polyolefin matrix at various mass ratios.
• polymeric segment of the same chemical nature, namely for example polyamide or polyether.
• This polymeric block consists of a homopolymer, that is to say consisting of the repetition of the same pattern.
• the present invention therefore has obj and a copolymer comprising:
• blo c from 1 to 45% by weight, relative to the total weight of the copolymer, of at least one block which is more hydrophobic than polyethylene glycol (PEG) blo c, said blo c more hydrophobic than blo c PEG being chosen from a block polyether (PE) other than PEG, a blo c polyester (PES) and a polyolefin block (PO).
• PE block polyether
• PES blo c polyester
• PO polyolefin block
• the block or blocks PA contained in the copolymer according to the invention may be chosen from:
• the amino acid units that may constitute a PA block are chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid and its derivatives. including N-heptyl-1-aminoundecanoic acid.
• the lactam units that may constitute an AP block are chosen from pyrrolidinone, 2-piperidinone, enantholactam, caprylolactam, pelargolactam, decanolactam, undecano lactam, and lauryllactam.
• the unit (diamine in Ca) is chosen from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines .
• the diamine When the diamine is aliphatic and branched, it may include one or more substituents (s) methyl or ethyl on the main chain.
• 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- diaminopentane, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine.
• the cycloaliphatic (diamine Ca) monomer is advantageously chosen from bis (3,5-dialkyl-4-aminocyclohexyl) methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane and bis (3,5-dialkyl) 4-aminocyclohexyl) propane, bis (3,5-dialkyl-4-aminocyclohexyl) butane, bis (3-methyl-4-aminocyclohexyl) methane (BMACM or MACM), bis (aminocyclohexyl) methane (PACM) and risopropylidenedi (cyclohexylamine) (PACP).
• bis (3,5-dialkyl-4-aminocyclohexyl) methane bis (3,5-dialkyl-4-aminocyclohexyl) ethane and bis (3,5-dialkyl) 4-aminocyclohexyl)
• the monomer (diamine Ca) alkylaromatic is preferably selected from 1, 3-xylylenediamine and 1,4-xylylenediamine.
• the (Cb diacid) unit is chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids.
• the fatty acid dimers mentioned above are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated long-chain hydrocarbon-based monobasic fatty acids (such as linoleic acid and oleic acid), as described especially in EP 0 471 566.
• the monomer (di (Cb) cycloaliphatic diacid may include the following carbon skeletons: norbornyl methane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl), di (methylcyclohexyl) propane.
• the monomer (diacid Cb) aromatic is preferably selected from terephthalic acid (noted T), isophthalic (noted I) and naphthalenic diacids.
• the PA blocks are chosen from blocks PA6, PAU, PA12 and PA blocks 4.6, PA 4.12, PA 4.14, PA 4.18, PA 6.6, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.6, PA 9.12. , PA 10.10, PA 10.12, PA 10.14 and PA 10.18.
• the molar mass in Mn number of PA blocks is between 400 and 20000 g / mol and preferably between 500 and 10000 g / mol.
• 80 ml of benzyl alcohol are poured into a container comprising 1 g of polymer.
• the solution is heated with stirring for 45 minutes at 155 ° C or for 90 minutes at 130 ° C.
• the solution is then cooled to 80 ° C. and then titrated with the previously calibrated tetra-n-butylammonium hydroxide.
• the PA block ends either with amine functions or with acid functions.
• the PA block is acid chain terminated. This is called diacid PA block.
• the PA block is amine chain termination. This is called PA diamine block.
• the copolymer according to the invention may comprise several PA blocks of different chemical nature.
• the PA block is a random, alternating or block copolyamide.
• the copolymer according to the invention comprises from 5 to 50% by weight, relative to the total weight of the copolymer, preferably from 30 to 47% by weight, relative to the total weight of the copolymer, of the PA block or blocks.
• the blo c polyethylene glycol (PEG) included in the copolymer according to the invention is a block comprising a molar mass of 100 to 20000 g / mol, preferably 600 to 1500 g / mol.
• the PEG block is a homopolymer obtained by the reaction of ethylene glycol units.
• the PEG block is preferably terminated with an alcohol or amine chain.
• the terminal functions of the PEG block are not modified when the PEG block is terminated with an alcohol chain.
• the terminal functions of the PEG block are modified when the PEG block is amine chain terminated.
• the PEG block with amino chain ends can be obtained by cyanoacetylation of the PEG sequences.
• the copolymer according to the invention comprises from 20 to 94% by weight, relative to the total weight of the copolymer, preferably from 20 to 60% by weight, more preferably from 20 to 45% by weight, relative to the total weight of the copolymer. copolymer, said PEG block.
• hydrophobic block is meant that the PEG block, a block whose ratio of the number of carbon atoms to the number of oxygen atoms, in a monomeric unit, is greater than or equal to 2.
• the PE blocks comprise alkylene oxide units. These units can usually be propylene oxide or tetrahydrofuran units (which leads to polytetramethylene glyco l chain linkages).
• said PE block included in the copolymer according to the invention is chosen from glyco polypropylene (PPG), ie consisting of propylene oxide units, polytetramethylene glyco (PTMG), it is it is composed of tetramethylene glycol units, but also polyhexamethylene ether glycol, polytrimethylene ether glycol (PO 3 G), poly (3-alkyl tetrahydrofuran), in particular poly (3-methyltetrahydrofuran (poly (3 MeTHF)) and their block copolymers or statistics.
• the copolymer according to the invention may comprise a copolyether PE blister containing a sequence of at least two PE blocks mentioned above.
• the ratio of the number of carbon atoms to the number of oxygen atoms can be calculated in the propylene glyco l unit, which is 3.
• the PPG block is a more hydrophobic block than the PEG block within the meaning of the invention.
• the polyether blocks may also consist of ethoxylated primary amines.
• ethoxylated primary amines mention may be made of the products of formula:
• the mass Mn of the polyether blocks is between 100 and 6
• the PE block is terminated with an alcohol or amine chain.
• the terminal functions of the PE block are not modified when the PE block is at alcohol chain termination.
• the terminal functions of the PEG block are modified when the PE block is amine chain terminated.
• the polyether (PE) blocks may comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic polyoxyalkylene aliphatic alpha-omega dihydroxy blocks.
• Jeffamines e.g. Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, also described in JP2004346274, JP2004352794 and EP 148201 1).
• Polyester blocks (PES) that can be used as more hydrophobic blocks than PEG blocks are the polyesters usually produced by polycondensation between a dicarboxylic acid and a diol and whose repeating unit comprises at least nine carbon atoms.
• Suitable carboxylic acids include those mentioned above used to form the polyamide blocks with the exception of aromatic acids, such as terephthalic and isophthalic acid.
• 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-cyclohexanedimethanol.
• An example of a polyester used is the polyadipate family.
• the ratio of the number of carbon atoms to the number of oxygen atoms in the repeating unit can be calculated as an example for the block prepared from heptanedioic acid and ethylene glycol. namely a pattern comprising a diacid unit and a dio unit 1, which is 2.25.
• the block prepared from heptanedioic acid and ethylene glycol is a more hydrophobic block than the PEG block within the meaning of the invention.
• Polyesters are also understood to mean poly (caprolactone) and PES based on fatty acid dimers, in particular the products of the PRIPLAST® range from Uniqema.
• the PES block is chain-terminated alcohols or acid.
• the polyolefin (PO) block that can be used as a more hydrophobic block than the PEG block is a polymer comprising as monomer an alpha-olefin, that is to say the homopolymers of an olefin or the copolymers of at least one alpha-olefin. olefin and at least one other copolymerizable monomer, the alpha-olefin having advantageously from 2 to 30 carbon atoms.
• the blo c PO responds well to the definition of the more hydrophobic block than the PEG block, mentioned above, when in the absence of an oxygen atom, the calculation of the ratio gives an infinite result.
• 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-dococene, 1-tetracocene, 1-hexacocene, 1- octacocene, and 1-triacontene.
• alpha-o-olefins can be used alone or in a mixture of two or more.
• LDPE low density polyethylene
• HDPE high density polyethylene
• LLDPE linear low density polyethylene
• VLDPE very low density polyethylene
• APAO essentially amorphous or attachable polyalphaolefins
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene-propylene-rubber) and EPDM (ethylene-propylene-diene) elastomers, and polyethylene mixtures with an EPR or an EPDM,
• styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS) and styrene / ethylene-propylene / styrene (SEPS) copolymers copolymers of ethylene with at least one product chosen from 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.
• unsaturated carboxylic acid salts or esters such as, for example, alkyl (meth) acrylates, alkyl having up to 24 carbon atoms, vinyl esters
• the repeating unit of the block PO contains one or more oxygen atom (s).
• the block PO must meet the definition of hydrophobic block p lobroblo PEG for the purposes of the present invention, that is to say that the monomer unit of said block PO has a ratio of the number of carbon atoms to the number of oxygen atoms greater than 2.
• the PO block that can be used as a more hydrophobic block than the PEG block is a polyolefin block functionalized either by a maleic anhydride function or by an epoxy function.
• said polyolefin block comprises polyisobutylene and / or hydrogenated or non-hydrogenated polybutadiene.
• the more hydrophobic block than the PEG block is the PTMG block.
• the PA block is the block PA6, PA1 1 or
• the PES block is a polyadipate block.
• the copolymer according to the invention comprises from 1 to 45% by weight, relative to the total weight of the copolymer, preferably from 15 to 35% by weight, relative to the total weight of the copolymer, of at least one more hydrophobic block than the PEG block.
• the polyamide blo c is bound to a more hydrophobic blo c than the PEG block and to a PEG block.
• the arrangement of the copolymer is such that the PA block is in a central position in the sequence of the blocks. Nevertheless, this arrangement is not the only one possible.
• the terminal acid functions of the polyester block can react, for example, with the terminal amine functions of the PEG block (or with the terminal acid functions of the PEG block) on the one hand and with the amine functions of the PA block on the other hand.
• the arrangement of the copolymer is then PA-PES-PEG.
• the copolymer according to the invention comprises at least one acid chain terminated or amine terminated polyamide block.
• the terminal acid functions of polyamide blo c can react:
• the bond between the polyamide block and the polyether block (s) is an ester or amide bond.
• the bond between the PA block and the PES block (s) and / or the PO block (s) is an ester bond.
• the terminal alcohol functions of the polyester blocks can not react with each other, or
• the terminal amino functions of the polyamide may react with the acid functional groups of the PES block (s) or with the maleic anhydride functions of the PO block (s).
• PES is an amide bond.
• the bond between the polyamide block and the polyolefin block (s) is also an amide bond.
• the copolymer according to the invention has the following structure: PEG-PA6-PTMG, PEG-PA 1 1 -PTMG, PEG-PA12- PTMG, PEG-PA10. 10-PTMG, PEG-PA 10. 12-PTMG and mixtures thereof, and preferably comprises PEG-PA12-PTMG.
• the copolymer according to the invention may comprise only three blocks, namely a PA block, a PEG block and a block that is more hydrophobic than the PEG as defined above.
• the copolymer may comprise four, five or more identical or different blocks selected from the aforementioned blocks.
• blocks may be derived from renewable materials and / or materials of fossil origin.
• said blocks are derived at least partially from renewable materials.
• the polyamide blocks and / or the polyether blocks and / or the polyester blocks and / or the polyolefin blocks are entirely derived from renewable materials.
• the present invention also relates to a process for synthesizing the copolymer according to the invention comprising the following steps:
• the method according to the invention comprises the following steps:
• the invention also relates to a composition comprising a copolymer according to the invention.
• the composition comprising the copolymer according to the invention, thanks to the permanent antistatic properties of the latter, namely a surface (or surface) resistivity of less than 10 12 ohm / square, does not require and therefore does not contain an organic salt. .
• the composition according to the invention further comprises from 0.1 to 10%, preferably from 0.1 to 5%, by weight of at least one organic salt in the molten state relative to the total weight of the composition.
• Organic salts are salts consisting of organic cations associated with inorganic or organic anions.
• the organic salt is added in the molten state, that is when the organic salt is at a temperature above its melting point.
• said organic salt has a melting point of less than 300 ° C., preferably less than 200 ° C., preferably less than 100 ° C., and advantageously constitutes an ionic liquid, preferably less than 30 ° C.
• Ionic liquids in particular have the main properties of being non-volatile (no diffusion in the atmosphere of volatile organic compounds), non-flammable (therefore easy to handle and store), stable at high temperature (up to 400 ° C. for some), very good conductors, and very stable vis-à-vis water and oxygen.
• the organic salt comprises at least one cation chosen from ammonium, sulphonium, pyridinium, pyrrolidinium, imidazolium, imidazolinium, phosphonium, lithium, guanidinium, piperidinium, thiazolium, triazolium, oxazolium, pyrazolium, and mixtures thereof.
• the organic salt comprises at least one anion chosen from imides, in particular bis (trifluoromethanesulfonyl) imide (abbreviated as NTf 2 " ), borates, especially tetrafluoroborate (abbreviated as BF4 " ), phosphates, in particular hexafluorophosphate (abbreviated as PF 6 ⁇ ), phosphinates and phosphonates, in particular alkyl-phosphonates, amides, in particular dicyanamide (abbreviated as DCA “ ), aluminates, especially tetrachloroaluminate (AlCU), halides (such as anions bromide, chloride, iodide, etc.) , cyanates, acetates (CH 3 COO), in particular trifluoroacetate, sulphonates, in particular methanesulphonate (CH 3 SO 3 - ), trifluoromethanesulphonate, sulphates
• organic salt is understood to mean, more particularly, any organic salt which is stable at the temperatures used during the synthesis of the block copolymer according to the invention.
• Those skilled in the art can refer to the technical sheets of organic salts, which indicate the limit decomposition temperature of each organic salt.
• organic salts based on ammonium cation combine, for example:
• organic salts based on imidazole such as imidazo disubstituted, imidazo monosubstituted, trisubstituted imidazoles, in particular those based on imidazolium cation or imidazolinium cation.
• organic salts based on pyridinium cation such as: N-Butyl-3-methylpyridinium bromide, N-Butyl-methyl-4-pyridinium chloride, N-Butyl-methyl-4-pyridinium tetrafluoroborate N-Butyl-3-methylpyridinium chloride, N-Butyl-3-methylpyridinium dicyanamide, N-Butyl-3-methylpyridinium methylsulfate, 1-Butyl-3-methylpyridinium tetrafluoroborate, N-Butylpyridinium chloride, N-Butylpyridinium tetrafluoroborate, N-Butylpyridinium trifluoromethylsulfonate, 1-ethyl-3-hydroxymethylpyridiniumethylsulfate, N-hexylpyridinium bis (trifluoromethylsulfonyl) imide, N-hexyl
• pyrrolidinium cation such as: Butyl-1-methyl-1-pyrrolidinium chloride, butyl-1-methyl-pyrrolidinium dicyanamide, butyl-1-methyl-1 pyrrolidinium trifluoromethanesulfonate, butyl-1-methyl-1-pyrrolidinium tris (pentafluoroethyl), 1-butyl-1-methylpyrrolidinium bis [oxalato (2 -)] borate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide, 1-butyl 1-Methylpyrrolidinium dicyanamide, 1-Butyl-1-methylpyrrolidinium trifluoroacetate, 1-Butyl-1-methylpyrrolidinium trifluoromethanesulfonate, Butyl-1-methyl-1-pyrrolidinium tris (pentaflufluoroethyl), 1-butyl-1-methylpyrrolidinium bis
• guanidine trifluoromethylsulfonate guanidine tris (pentafluoroethyl) trifluoro phosphate
• hexamethylguanidine tris pentafluoroethyl trifluorophosphate
• organic salts based on a phosphonium cation such as trihexyl (tetradecyl) phosphonium bis [oxalate (2-)] borate, trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide, trihexyl (tetradecyl) phosphonium tris (pentafluoroethyl) trifluorophosphate.
• a phosphonium cation such as trihexyl (tetradecyl) phosphonium bis [oxalate (2-)] borate, trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide, trihexyl (tetradecyl) phosphonium tris (pentafluoroethyl) trifluorophosphate.
• the composition according to the invention further comprises at least one inorganic salt, that is to say an alkali metal salt or alkaline earth metal salt, among which mention may be made of alkali metals, such as lithium, sodium, potassium, etc. and those of alkaline earth, such as magnesium, calcium, etc. with organic acids (mono- or di-carboxylic acids containing 1 to 12 carbon atoms, for example formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.
• an alkali metal salt or alkaline earth metal salt among which mention may be made of alkali metals, such as lithium, sodium, potassium, etc. and those of alkaline earth, such as magnesium, calcium, etc.
• organic acids mono- or di-carboxylic acids containing 1 to 12 carbon atoms, for example formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.
• sulphonic acids containing 1 to 20 carbons for example methanesulphonic acid, p-toluenesulphonic acid, thiocyanic acid, etc.
• mineral acids hydrohalic acids, for example hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, phosphoric acid, etc.
• halides are preferred, preferably lithium chloride, sodium chloride, potassium chloride, potassium acetates and potassium perchlorates.
• the amount of inorganic salt is generally in the range of 0.001 to 3%, preferably 0.01 to 2%, based on the total weight of the composition.
• composition according to the invention may further comprise at least one agent improving the surface conductivity chosen from: hygroscopic agents, fatty acids, lubricants, metals, metal films, metal powders, metal nanopowders, aluminosilicates, amines, such as quaternary amines, esters, fibers, carbon fibers, carbon nanotubes, intrinsically conductive polymers, such as derivatives of polyaniline, polythiophene, polypyrrole and mixtures thereof.
• agent improving the surface conductivity chosen from: hygroscopic agents, fatty acids, lubricants, metals, metal films, metal powders, metal nanopowders, aluminosilicates, amines, such as quaternary amines, esters, fibers, carbon fibers, carbon nanotubes, intrinsically conductive polymers, such as derivatives of polyaniline, polythiophene, polypyrrole and mixtures thereof.
• composition according to the invention may also comprise at least one additive and / or adjuvant chosen from organic or inorganic fillers, reinforcements, plasticizers, stabilizers, anti-oxidants, anti-UV agents, flame retardants, carbon black, inorganic or organic dyes, pigments, dyes, release agents, foaming agents, anti-shock agents, anti-shrink agents, flame retardants, nucleating agents, and mixtures thereof.
• additives chosen from organic or inorganic fillers, reinforcements, plasticizers, stabilizers, anti-oxidants, anti-UV agents, flame retardants, carbon black, inorganic or organic dyes, pigments, dyes, release agents, foaming agents, anti-shock agents, anti-shrink agents, flame retardants, nucleating agents, and mixtures thereof.
• composition according to the invention may be a mixture of antistatic agents comprising the copolymer according to the invention.
• the present invention also relates to the use of such a copolymer according to the invention or of such a composition, as an anti-static additive, to improve the antistatic properties of a polymer matrix to which it is added.
• the present invention also relates to a composition comprising the polymer matrix and the copolymer according to the invention.
• said polymer matrix comprises at least one thermoplastic polymer, homopolymer or copolymer, selected among: polyolefins, polyamides, fluoropolymers, saturated polyesters, polycarbonate, styrenic resins, PMMA, thermoplastic polyurethanes (TPU), copolymers of ethylene and vinyl acetate (EVA), polyamide and polyether block copolymers, polyester and polyether block copolymers, polyamide block, polyether block and polyester block copolymers, copolymers of ethylene and a (meth) acrylate, alkyl, copolymers of ethylene and vinyl alcohol (EVOH), ABS, SAN, ASA, polyacetal, polyketones, and mixtures thereof.
• PC / ABS and PC / ASA resins can be mentioned in particular.
• thermoplastic polymer matrix any thermoplastic polymer material capable of incorporating a copolymer according to the invention.
• Thermoplastic polymers are well known to those skilled in the art and include polyolefins (polyethylene, polypropylene %), polyvinyl chloride, polyethylene terephthalate, polystyrene, polyamides, acrylics.
• the present invention also relates to the use of the composition comprising the polymer matrix and the composition comprising the copolymer according to the invention for the manufacture of at least some of the following objects: industrial part, automobile part, accessory of security, signboard, banner, sign and advertising signage, display, engraving, furnishing, store layout, decoration, contact ball, dental prosthesis, ophthalmology implant, membrane for hemodialysis, fiber optics, optical and art, decoration , sculpture, lenses, especially camera lenses, camera lenses, print media, including direct print media with UV inks for photo boards, window panes, panoramic roofs, vehicle headlights, etc.
• compositions of the copolymers according to the invention (Copo 1, Copo 2 and Copo 3) and of the comparative copolymer (Copo 4) are shown in Table 2 below. The values are expressed as weight percentage.
• PEG (600) alcohol chain terminated polyethylene glycol having a molar mass (Mn) of 600 g / mol.
• PEG (1500) alcohol chain terminated polyethylene glycol having a molar mass (Mn) of 1500 g / mol.
• PTMG (1000) alcohol terminated PTMG homopolymer having a molar mass (Mn) of 1000 g / mol.
• Copo2 and Copo3 consist of three blocks, a PA block, a PEG block and a PTMG block.
• Copol contains 113.4g PA, 82g PEG and 21.9g of
• Copo2 comprises 109.8g PA, 52.6g PEG and 87.6g
• Copo3 comprises 83.5g of PA, 99.9g of PEG, 66.6g of
• the three blocks are charged and a heating phase is started with a set temperature of 250 ° C.
• rods were made by extrusion on ⁇ dSM machine.
• the antistatic property of a polymer is mainly characterized by its surface resistivity which is expressed in ohm / square and measured according to ASTM D257. 2) Evaluation of the copolymers and results a) Measurement of surface resistance
• the copo3 is incorporated, at various mass levels, into a polyolefin LDPE matrix (low density polyethylene), grade 1022 FN
• the copo4 is incorporated, at various mass ratios, into the polyolefin matrix LDPE (low density polyethylene), grade 1022 FN
• the material When the materials are obtained by an injection method, the material is in the form of a plate. When the materials are obtained by an extrusion process, the material is in the form of a film.
• composition of the different materials are reported in Table 4 below. Values are expressed as a percentage by mass:
• Material A is a material in which the mass ratio of copo3 is 10% relative to the weight of material A.
• Material B is a material in which the mass ratio of copo3 is 15% relative to the weight of material B.
• Material C is a material in which the mass ratio of copo3 is 20% relative to the weight of material C.
• Material D is a material in which the mass ratio of copo4 is 10% relative to the weight of material D.
• the material E is a material in which the mass ratio of copo4 is 15% relative to the weight of the material E.
• Material F is a material in which the mass ratio of copo4 is 20% relative to the weight of material F.
• These materials A to F are materials in the form of a film.
• the LDPE polyolefin matrix alone represents the material G in the form of a plate.
• the material C 1 has the same composition as the material C but it is in the form of a plate.
• the material F 1 has the same composition as the material F but it is in the form of a plate
• copo3 and copo4 are called additives when incorporated into the polyolefin matrix.
• FIG. 1 represents a histogram comparing the surface resistance of materials C 1, F 1 and G obtained by an injection method.
• FIG. 1 shows that the surface resistance of the materials C 1 and F 1 is significantly lower than that of the material G. Furthermore, it is also observed that the surface resistance of the material C 1 is lower than that of the material F 1.
• FIG. 2 represents a graph comparing the surface resistance of materials A to F obtained by an extrusion process.
• the results indicate that the copolymer according to the invention makes it possible to improve the antistatic properties of the polymer matrix which incorporates it.
• This observation is valid for low mass levels of additives (between 10 and 20% by weight). This represents an advantage because a low level of additive in a polymer matrix has only a slight impact on the mechanical properties of said matrix.
• Figure 3 shows two surface scanning electron microscope (SEM) images of materials C ( Figure 3B) and F ( Figure 3A).
• Figure 3B shows that the network formed by Copo3 within the polyolefin matrix is finer than the network formed by Copo4 within the polyolefin matrix as Figure 3A shows.
• Copo3 and 1.5% by weight of an ionic liquid (LU), 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide, based on the total weight of the copo3 and the ionic liquid, are incorporated in the LDPE polyolefin matrix at various mass ratios. Materials in film form are obtained.
• the ionic liquid is introduced into the copo3 during the step of steaming said copo3 in a mixer which is rotated under vacuum at 60 ° C for 8 hours.
• copo4 and 1.5% by weight of LU are incorporated in the polyolefin LDPE matrix at various mass levels. Materials in film form are obtained. The composition of the different materials are reported in Table 5 below. Values are expressed as a percentage by mass:
• Material H is a material in which the mass ratio of copo3 and LI 1 is 10% relative to the weight of material H.
• Material I is a material in which the mass ratio of copo3 and LU is 15% relative to the weight of material I.
• Material I is a material in which the mass ratio of copo3 and LU is 20% relative to the weight of material J.
• the material K is a material in which the mass ratio of copo4 and LI 1 is 10% relative to the weight of the material K.
• the material L is a material in which the mass ratio of copo4 and LI 1 is 15% relative to the weight of the material L.
• the material M is a material in which the mass ratio of copo4 and LI 1 is 20% relative to the weight of the material M.
• copo3 and LU sets represented by copo3 and LU, and copo4 and LU, are called additives when incorporated into the polyolefin matrix.
• FIG. 4 represents a graph comparing the surface resistance of materials H to M.

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