EP3233969A1

EP3233969A1 - Copolymer comprising at least three blocks: polyamide blocks, peg blocks and other blocks

Info

Publication number: EP3233969A1
Application number: EP15821058.3A
Authority: EP
Inventors: Alejandra REYNA-VALENCIA; Frédéric MALET; Quentin Pineau
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2014-12-19
Filing date: 2015-12-18
Publication date: 2017-10-25
Also published as: FR3030535A1; JP2020090672A; US20200283581A1; US20180037701A1; JP2017538832A; JP6698659B2; CN107001643A; FR3030535B1; WO2016097342A1; KR20170099956A

Abstract

One subject of the present invention is a copolymer comprising: - from 5 to 50% by weight, relative to the total weight of the copolymer, of at least one polyamide (PA) block, - from 20 to 94% by weight, relative to the total weight of the copolymer, of at least one polyethylene glycol (PEG) block, - from 1 to 45% by weight, relative to the total weight of the copolymer, of at least one block more hydrophobic than the PEG block, said block more hydrophobic than the PEG block being selected from a polyether (PE) block different from the PEG, a polyester (PES) block and a polyolefin (PO) block. Another subject of the present invention is a process for synthesizing said copolymer.

Description

COPOLYMER COMPRISING AT LEAST THREE SELF-BLOCK BLOCKS, PEG BLOCKS AND OTHER BLOCKS

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. The present invention relates more particularly to copolymers with polyether blocks and polyamide blocks, abbreviated "PEBA", having good antistatic properties. Even more particularly, 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. 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.

The formation and retention of static charges on the surface of most plastics are known. For example, the presence of static electricity on thermoplastic films causes these films to coel each other making their separation difficult. The presence of static electricity on packaging films can cause the accumulation of dust on the objects to be packaged and thus hinder their use. Static electricity can also damage microprocessors or electronic circuit components. Static electricity can further cause the combustion or explosion of flammable materials such as, for example, expandable polystyrene beads which contain pentane.

Antistatic agents, such as ethoxylated amine or sulfonate ionic surfactants, are known as additives for polymeric matrices. However, 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.

During the last decade, the TPEs, 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. By 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).

For this type of application, the parts must be able to withstand both high pressure and high temperature to avoid damage, deterioration, deformation and mechanical properties. 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,

from 20 to 94% by weight, relative to the total weight of the copolymer, of at least one polyethylene glycol (PEG) 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 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).

The present invention also relates to a method for synthesizing the copolymer, as well as to its uses.

Finally, the subject of the present invention is a composition comprising such a copolymer.

Other advantages and features of the invention will appear more clearly on examination of the detailed description and the attached drawings in which:

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.

- Figure 3 shows two SEM images representing the surface of two materials.

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.

The nomenclature used to define polyamides is described in ISO standard 1 874-1: 1992 "Plastics - Polyamides (PA) 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. It is furthermore specified that the expressions "between ... and ..." and "from ... to ..." used in the present description must be understood as including each of the mentioned terminals.

By block is meant in the sense of the present invention a 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:

from 5 to 50% by weight, relative to the total weight of the copolymer, of at least one polyamide block (denoted PA),

from 20 to 94% by weight, relative to the total weight of the copolymer, of at least one polyethylene glycol block (denoted PEG),

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).

Polyamide block

Three types of PA blocks can be advantageously used. The block or blocks PA contained in the copolymer according to the invention may be chosen from:

a block obtained by the polycondensation of amino acid units;

a block obtained by the polycondensation of lactam units;

a block obtained by the polycondensation of units corresponding to the formula (diamine in Ca). (diamine in Cb).

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.

As regards the units corresponding to the formula (diamine in Ca) (diamine in Cb) which can constitute a block PA, the unit (diamine in Ca) is chosen from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines .

The monomer (diamine in Ca) aliphatic and linear, of formula H ₂ N- (CH ₂ ) _a -NH ₂ , is preferentially 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 = 1 6), 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 include one or more substituents (s) methyl or ethyl 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- 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). It can also have 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).

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 monomer (diacid Cb) aliphatic and linear is advantageously 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 = 1 8), acid 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 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. Advantageously, 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. The molar mass is determined from the potentiometric assay of carboxylic acid functions -COOH in benzyl alcohol with tetra-n-butylammonium hydroxide by the following relationship: Mn = 2 / [COOH], where Mn is expressed in g / mol and [COOH], expressed in mol / g, represents the amount of material of the carboxylic acid functions per gram of polymer.

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.

Chain termination

The PA block ends either with amine functions or with acid functions.

Preferably, the PA block is acid chain terminated. This is called diacid PA block.

Advantageously, 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.

According to a particular embodiment of the invention, 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. PEG block

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.

It is possible to modify the terminal functions of the blo

PEG.

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. Thus, 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

By more 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.

PE block

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). Advantageously, 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.

By way of example, for the PPG block, 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. Thus, the PPG block is a more hydrophobic block than the PEG block within the meaning of the invention.

It is also possible to use blocks obtained by oxyethylation of bisphenols, such as, for example, bisphenol A. These latter products are described in patent EP613919.

The polyether blocks may also consist of ethoxylated primary amines. By way of example of ethoxylated primary amines, mention may be made of the products of formula:

H (OCH ₂ CH ₂ ) _m - N (CH ₂ CH ₂ 0) n - H

(CH ₂ ) _X

C ^H 3

in which m and n are between 1 and 20 and x between 8 and

8. These products are commercially available under the NORAMOX® brand from CECA and under the GENAMIN® brand from CLARIANT.

The mass Mn of the polyether blocks is between 100 and 6

000 g / mol and preferably between 200 and 3000 g / mol.

Preferably, 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.

Thus, 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. More particularly, Jeffamines (e.g. Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, also described in JP2004346274, JP2004352794 and EP 148201 1).

PES block

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. Thus, 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.

Preferably, the PES block is chain-terminated alcohols or acid.

It is also possible to envisage an alternating block of "copolyester" type, statistical or block, containing a sequence of at least two types of PES mentioned above. PO block

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.

It should be noted that 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.

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. These alpha-o-olefins can be used alone or in a mixture of two or more.

By way of examples, mention may be made of:

homopolymers and copolymers of ethylene, in particular low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), polyethylene obtained by metallocene catalysis,

homopolymers and copolymers of propylene,

essentially amorphous or attachable polyalphaolefins (APAO),

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,

the 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.

It is therefore conceivable that the repeating unit of the block PO contains one or more oxygen atom (s). Of course, if this is the case, 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.

Advantageously, 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.

According to an advantageous embodiment of the invention, said polyolefin block comprises polyisobutylene and / or hydrogenated or non-hydrogenated polybutadiene.

Preferably, the more hydrophobic block than the PEG block is the PTMG block.

Preferably, the PA block is the block PA6, PA1 1 or

PA12.

Advantageously, 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.

Copolymer arrangement

Generally, 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. In fact, 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.

Acid functions of the PA block

The terminal acid functions of polyamide blo c can react:

with the alcohol or terminal amine functions of the other two blocks, namely the PEG block and the PE block,

with the alcoo l functions of the PES block

- with the epoxy functions of the PO block.

Thus, 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.

As a result, there will be for example:

a sequence PE-PA-PEG, the alcohol endings of the polyether blocks being unable to react with each other,

a sequence PES-PA-PEG, the terminal alcohol functions of the polyester blocks can not react with each other, or

a PO-PA-PEG sequence, the epoxy terminal functions of the polyolefin blocks being unable to react with each other.

Amino functions of the PA block

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).

Thus, the connection between the polyamide block and the block (s)

PES is an amide bond. The bond between the polyamide block and the polyolefin block (s) is also an amide bond.

Advantageously, 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. However, the copolymer may comprise four, five or more identical or different blocks selected from the aforementioned blocks.

Advantageously, blocks may be derived from renewable materials and / or materials of fossil origin. Advantageously, said blocks are derived at least partially from renewable materials. According to a particularly advantageous embodiment of the present invention, the polyamide blocks and / or the polyether blocks and / or the polyester blocks and / or the polyolefin blocks are entirely derived from renewable materials.

Process

The present invention also relates to a process for synthesizing the copolymer according to the invention comprising the following steps:

mixing and reacting at least one blo c PA with at least one PEG block and at least one block that is more hydrophobic than the blo c PEG,

recovering said copolymer.

In a preferred embodiment, the method according to the invention comprises the following steps:

loading a reactor with a mixture comprising at least one PA block, at least one PEG block and at least one block that is more hydrophobic than the PEG block,

heating at a set temperature in the range from 1 80 to 340 ° C, preferably from 200 to 300 ° C, preferably from 220 to 270 ° C,

- stirring and sweeping under an inert gas,

evacuation at a pressure of less than 100 mbar, preferably less than 50 mbar, preferably less than 10 mbar,

- addition of a catalyst, stopping when a pair at least equal to 5 N.cm, preferably at least 10 N.cm, preferably at least 20 N cm, is reached.

Composition

The invention also relates to a composition comprising a copolymer according to the invention.

Advantageously, 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. .

Nevertheless, it is possible to incorporate an organic salt or an ionic liquid in the composition according to the invention, to further improve its antistatic performance.

Advantageously, 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. Preferably, 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.

Advantageously, 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.

Preferably, 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, especially in particular ethyl sulphate, hydrogen sulphate, and mixtures thereof.

In the sense of the invention, 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.

By way of examples of organic salts which can be used in the synthesis process according to the invention, mention may in particular be made of organic salts based on ammonium cation, based on imidazo lium cation or imidazo linium cation, based on pyridinium cation, based on dihydropyridinium cation, based on tetrahydropyridinium cation, based on a pyrrolidinium cation, based on a guanidine cation, based on phosphonium cation.

The organic salts based on ammonium cation combine, for example:

an N-trimethyl-N-propylammonium cation with a bis (trifluoromethanesulfonyl) imide anion

an N-trimethyl-N-butylammonium or N-trimethyl-N-hexylammonium cation with an anion chosen from bromide, tetrafluoroborate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide

an N-tributyl-N-methylammonium cation with an iodide, bis (trifluoromethanesulfonyl) imide or dicyanamide anion

a tetraethylammonium cation with an tetrafluoroborate anion

a cation (2-hydroxyethyl) trimethylammonium with a dimethylphosphate anion

a di (2-hydroxyethyl) ammonium cation with a trifluoroacetate anion

an N, N-di (2-methoxy) ethylammonium cation with a sulfamate anion

an N, N-dimethyl (2-hydroxyethyl) ammonium cation with an anion 2-hydroxyacetate or trifluoroacetate

an N-ethyl-N, N-dimethyl-2-methoxyethyl ammonium cation with a bis (trifluoromethylsulfonyl) imide anion

an ethyl-dimethylpropylammonium cation and a bis (trifluoromethylsulfonyl) imide anion

a methyltrioctylammonium cation and a bis (trifluormethylsulfonyl) imide anion

a methyltrio-alkylammonium cation and an trifluoroacetate or trifluoromethylsulfonate anion

a tetrabutylammonium cation and a bis (trifluoromethylsulfonyl) imide anion

a tetramethylammonium cation and a bis (oxalato (2 -)) - borate or tris (pentafluoroethyl) trifluorophosphate anion

Mention may also be made of organic salts based on imidazole, such as imidazo disubstituted, imidazo monosubstituted, trisubstituted imidazoles, in particular those based on imidazolium cation or imidazolinium cation.

Mention may be made of organic salts based on imidazo lium cation combining, for example:

an H-methylimidazolium cation with a chloride anion a 1-ethyl-3-methylimidazolium cation with anion chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide, tetrachloroaluminate, ethylphosphonate or methylphosphonate, methanesulphonate, ethylsulphate, ethylsulfonate

a 1-butyl-3-methylimidazolium cation with anion chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide, tetrachloroaluminate, acetate, hydrogen sulphate, trifluoroacetate, methanesulphonate

a 1,3-dimethylimidazolium cation with a methylphosphonate anion

a 1-propyl-2,3-dimethylimidazolium cation with a bis (trifluoromethanesulfonyl) imide anion

a 1-butyl-2,3-dimethylimidazolium cation with an anion tetrafluoroborate bis (trifluoromethanesulfonyl) imide

a 1-hexyl-3-methylimidazolium cation with an anion tetrafluoroborate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide

a 1-octyl-3-methylimidazolium cation with a bis (trifluoromethanesulfonyl) imide anion

a 1-ethanol-3-methylimidazolium cation with anion chloride, bromide, tetrafluoroborate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide, dicyanamide.

Mention may also be made, by way of examples, of 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-hexylpyridinium trifluoromethanesulfonate, N- (3-hydroxypropyl) pyridinium bis (trifluoromethylsulfonyl) imide, N-butyl-3-methylpyridinium trifluoromethanesulfonate, N-butyl-3-methylpyridinium hexafluorophosphate.

Mention may also be made, by way of example, of organic salts based on a 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 (pentafluoroethyl) trifluorophosphate, 1,1-dimethylpyrrolidinium iodide, 1 - (2 -Ethoxyethyl) -1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide, 1-hexyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide, 1- (2-methoxyethyl) -1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide, methyl-1-octyl- 1 pyrrolidinium chloride, 1-butyl-1-methylpyrrolidinium bromide.

In addition, mention may be made of organic salts combining:

a 1-ethyl-1-methylpyrrolidinium cation with an anion bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate

a 1-butyl-1-methylpyrrolidinium cation with anion chloride, bromide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imide, dicyanamide, acetate or hydrogen sulfate

an N-propyl-N-methylpyrrolidinium cation with a bis (trifluoromethanesulfonyl) imide anion

a 1-methyl-1-propylpiperidinium cation with a bis (trifluoromethanesulfonyl) imide anion

Mention may also be made, by way of examples, of organic salts based on a guanidine cation, such as: guanidine trifluoromethylsulfonate, guanidine tris (pentafluoroethyl) trifluoro phosphate, hexamethylguanidine tris (pentafluoroethyl) trifluorophosphate.

Mention may be made of 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.

The list of organic salts and anions and cations mentioned above that can be used in the composition according to the invention is given for illustrative purposes only, it is not exhaustive or limiting. Therefore, the addition of any other organic salt is of course conceivable in the composition of the invention, as soon as the decomposition temperature of the organic salt is higher than the temperatures of the steps of the process for preparing the composition according to the invention. in which the organic salt is present.

In one embodiment, 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. sulphonic acids containing 1 to 20 carbons, for example methanesulphonic acid, p-toluenesulphonic acid, thiocyanic acid, etc.) or mineral acids (hydrohalic acids, for example hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, phosphoric acid, etc.). There may be mentioned potassium acetate, lithium acetate, lithium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium, bromide, perchlorate lithium perchlorate sodium, or potassium, potassium sulphate, potassium phosphate, thiocyanate, and the like.

Of these, the 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.

The 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.

The 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.

Thus, the 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.

Advantageously, 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.

By thermoplastic polymer matrix is meant 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.

The examples below illustrate the present invention without limiting its scope. EXAMPLES

1) Manufacture of the copolymers a) Synthesis of the prepolymers

Water, lactam 12 and adipic acid are introduced into a 14L autoclave and then inerted under nitrogen. The reaction medium is stirred and heated to 290 ° C for 3 hours. The autogenous pressure generated is of the order of 30 bars. The reactor is then expanded to atmospheric pressure and then flushed with nitrogen for 1 hour. The prepolymer thus obtained is drained into water and then dried at 80 ° C. under vacuum for 12 hours.

3 prepolymers, respectively PA 12 (600), PA12 (1000) and PA12 (1500) having a number-average molecular weight (Mn) of respectively 600, 1000 and 1500 g / mol are thus prepared. These prepolymers are homopolyamides with acid chain termination. The compounds used, as well as their weights, for the synthesis are shown in Table 1 below:

Table 1 (b) Copolymer formulation

The 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.

Table 2

(1) PEG (600): alcohol chain terminated polyethylene glycol having a molar mass (Mn) of 600 g / mol.

(2) PEG (1500): alcohol chain terminated polyethylene glycol having a molar mass (Mn) of 1500 g / mol.

(3) PTMG (1000): alcohol terminated PTMG homopolymer having a molar mass (Mn) of 1000 g / mol.

Thus, each of the three copolymers according to the invention (Copol,

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

PTMG.

Copo2 comprises 109.8g PA, 52.6g PEG and 87.6g

PTMG.

Copo3 comprises 83.5g of PA, 99.9g of PEG, 66.6g of

PTMG c) Synthesis of copolymers

In a glass reactor, the three blocks are charged and a heating phase is started with a set temperature of 250 ° C.

Once the medium is melted, the mixture is stirred and then a first nitrogen sweeping phase is carried out for one hour. The evacuation (<10 mbar) is then carried out before the introduction of the catalyst (0.3% by weight of Zr (OBu) ₄ ). The rise in couple is followed and the test is stopped when a torque of 20 N cm at 60 rpm is reached.

After grinding said products, rods were made by extrusion on μdSM machine.

The rushes have been tested. Resistivity was evaluated.

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 tests were carried out on the M 1500P Megohmmeter equipped with electrodes, with the following conditions:

- potential difference: 40V

distance between electrodes: 10mm

charging time before reading: 20s

conditioning: 2 weeks in conditioned room

The results are shown in Table 3 below

Table 3 These results indicate that the surface resistance of the comparative copo4 is similar to that of the copolymers according to the invention despite the fact that they contain a lower weight ratio in terms of PEG. The copolymer according to the invention therefore represents an alternative with high added value in terms of mechanical properties and cost. b) Use of copolymers in a thermoplastic matrix i) Figures 1 and 2

The copo3 is incorporated, at various mass levels, into a polyolefin LDPE matrix (low density polyethylene), grade 1022 FN

24, and materials are obtained.

The copo4 is incorporated, at various mass ratios, into the polyolefin matrix LDPE (low density polyethylene), grade 1022 FN

24, and materials are obtained.

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.

The composition of the different materials are reported in Table 4 below. Values are expressed as a percentage by mass:

Table 4

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.

It should also be noted that the material C 1 has the same composition as the material C but it is in the form of a plate.

Similarly, the material F 1 has the same composition as the material F but it is in the form of a plate

It should be noted that 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.

It is observed that the surface resistance of the material C is lower than that of the material F.

Furthermore, it is observed that for the same mass content of additive, the surface resistance of the material comprising Copo3 is significantly lower than that of the material comprising Copo4.

Thus, 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.

ii) Figure 3

Figure 3 shows two surface scanning electron microscope (SEM) images of materials C (Figure 3B) and F (Figure 3A).

On these plates, phosphotungstic acid labeling was carried out. The additive appears in white and the matrix in black.

Different morphologies are observed for both materials. Indeed, 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.

A better connectivity of the additive network in the case of the copolymer according to the invention is assumed due to the modification of the interfacial tension in the polyolefin matrix. Indeed, the surface of the material C seems of better quality than that of the material F.

iii) Figure 4

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.

The copo4 and 1.5% by weight of LU, based on the total weight of the copo4 and the ionic liquid, 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:

Table 5

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.

It should be noted that the 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.

It is observed that for the same mass content of additive, the surface resistance of the material comprising Copo3, doped with LI 1, is much lower than that of the material comprising Copo4 doped with LI 1.

These results prove a better connectivity of the network formed by the copolymer according to the invention incorporated into the polyolefin matrix. Thus, 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.

Claims

1. Copolymer comprising:

from 5 to 50% by weight, relative to the total weight of the copolymer, of at least one polyamide block (PA),

from 20 to 94% by weight, relative to the total weight of the copolymer, of at least one polyethylene glycol (PEG) block,

from 1 to 45% by weight, relative to the total weight of the copolymer, of at least one block that is more hydrophobic than the PEG block, the said block being more hydrophobic than the PEG block being chosen from a polyether block (PE) other than the PEG block; , a blo c polyester (PES) and a blo c polyolefin (PO).

2. Copolymer according to claim 1, characterized in that the more hydrophobic block than the PEG block is chosen from:

the PE block chosen from polypropylene glycol (PPG), polytetramethylene glyco (PTMG), polyhexamethylene ether glycol, polytrimethylene ether glycol (PO 3 G), poly (3-alkyl tetrahydrofuran), in particular poly (3 methyltetrahydrofuran (poly (3 MeTHF)) and their copolymers,

the PES block, preferably a polyadipate,

the PO block chosen from homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, block copolymers of styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), and styrene / ethylene-propylene / styrene (SEP S) copolymers of ethylene with at least one product selected from unsaturated carboxylic acid salts or esters, vinyl esters of saturated carboxylic acids and the dienes.

3. Copolymer according to claim 1 or 2, characterized in that said block more hydrophobic than the PEG block is the PTMG block.

4. Copolymer according to any one of the preceding claims, characterized in that said PA block is chosen from PA6, PA U, PA12 blocks 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 1 0.12, PA 10.14 and PA 10 18.

5. Copolymer according to any one of the preceding claims, characterized in that the arrangement of said copolymer is such that the PA block, bound to a more hydrophobic block than the PEG block and to a PEG block, is in a central position in the sequence of blocks.

6. Copolymer according to any one of the preceding claims, characterized in that it has the following structure: PEG-PA6-PTMG, PEG-PA 1 1 -PTMG, PEG-PA12-PTMG, PEG-PA 10. PTMG, PEG-PA10. 12-PTMG and mixtures thereof, and preferably PEG-PA12-PTMG.

7. Synthesis process of the copolymer as defined in any one of claims 1 to 6, comprising the following steps:

mixing and reacting said PA block with said PEG block and said more hydrophobic block than the PEG block, said block more hydrophobic than the PEG block being selected from a polyether block (PE) other than the PEG, a polyester block (PES ) and a polyolefin block (PO).

recovering said copolymer.

8. Composition comprising a copolymer as defined in any one of Claims 1 to 6.

9. Composition according to claim 8, comprising at least one organic salt.

10. Composition according to claim 8 or 9, characterized in that it comprises at least one agent improving the surface conductivity chosen from: hygroscopic agents, ionic liquids, 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 polyaniline, polythiophene derivatives; , polypyrrole and mixtures thereof.

1 1. Composition according to any one of Claims 8 to 10, characterized in that it comprises at least one additive and / or adjuvant selected from organic or inorganic fillers, reinforcements, plasticizers, stabilizers, antioxidants, anti-UV, flame retardants, carbon black, inorganic or organic colorants, pigments, coloring agents , release agents, foaming agents, anti-shock agents, anti-shrink agents, flame retardants, nucleating agents, and mixtures thereof.

12. Composition according to any one of claims 8 to 11 comprising a thermoplastic polymer matrix.

13. Use of a copolymer according to any one of claims 1 to 6 or a composition according to any one of claims 8 to 12 in a thermoplastic polymer matrix for improving the antistatic properties.

14. Use according to claim 13 wherein said polymer matrix comprises at least one thermoplastic polymer, homopolymer or copolymer chosen from: polyolefins, polyamides, fluoropolymers, saturated polyesters, polycarbonate, styrenic resins, PMMA, thermoplastic polyurethanes (TPU), copolymers of ethylene and vinyl acetate (EVA), copolymers with polyamide blocks and polyether blocks, copolymers with polyester blocks and polyether blocks, copolymers with polyamide blocks, with polyether blocks and polyester blocks, copolymers of ethylene and an alkyl (meth) acrylate, copolymers of ethylene and vinyl alcohol (EVOH), ABS, SAN, ASA, polyacetal, polyketones, and mixtures thereof.

15. Use of a composition as defined in any one of claims 8 to 12 for the manufacture of at least a portion of the following objects: industrial part, automobile part, safety accessory, signboard, light strip, signboard and advertising, display rack, engraving, furnishing, store layout, decoration, contact ball, dental prosthesis, ophthalmic implant, diaphragm for hemodialysis, fiber optics, obj and art, decoration, sculpture, lenses, in particular lenses cameras, camera lenses, support printing, including direct printing support with UV inks for photo boards, windows, panoramic roofs, vehicle headlights.