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WO2024002457A1 - Polyamides functionalized with chains containing thiol functions - Google Patents

Polyamides functionalized with chains containing thiol functions Download PDF

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Publication number
WO2024002457A1
WO2024002457A1 PCT/EP2022/067520 EP2022067520W WO2024002457A1 WO 2024002457 A1 WO2024002457 A1 WO 2024002457A1 EP 2022067520 W EP2022067520 W EP 2022067520W WO 2024002457 A1 WO2024002457 A1 WO 2024002457A1
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WIPO (PCT)
Prior art keywords
polyamide
chain
formula
preparation
polymer
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PCT/EP2022/067520
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French (fr)
Inventor
Laurent Bouteiller
Samir Zard
Brigitte ROUSSEAU
Khaled BELAL
Pierpaolo MASI
Valentin DOROKHOV
Original Assignee
Centre National De La Recherche Scientifique
Sorbonne Universite
Ecole Polytechnique
Ecole Nationale Superieure De Techniques Avancees
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Application filed by Centre National De La Recherche Scientifique, Sorbonne Universite, Ecole Polytechnique, Ecole Nationale Superieure De Techniques Avancees filed Critical Centre National De La Recherche Scientifique
Priority to PCT/EP2022/067520 priority Critical patent/WO2024002457A1/en
Publication of WO2024002457A1 publication Critical patent/WO2024002457A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention is in the field of polymer synthesis, and more particularly concerns the preparation of polyamides comprising thiol functions, with no or a minimum of chemical transformations after the polymerization, such as melting, cross-liking and/or curing.
  • the field of the present invention belongs to polymers used to form coatings on surfaces, adhesives and various materials.
  • Polyamides is a class of polymers widely used in the industry for different applications, and they are a prime candidate for surface coating, for example metal coating or elastomer bonding. These interfacial interactions are sometimes essential to preserve the integrity of the part being treated, for example a metal surface against corrosion, an elastomer composite against delamination or protection of electronic devices such as printed circuit masking. Unfortunately, the adhesion of polyamides is often insufficient with respect to the specifications of the industry.
  • the purpose of the present invention is to develop processes implementing starting material to control the length of side chains incorporating a thiol function at their end, the number, and the distribution of these side chains in the material resulting from the synthesis.
  • substituted refers to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent.
  • substituents contained in formulae of this invention refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent.
  • the substituent may be either the same or different at every position.
  • substituted is contemplated to include all permissible substituents of organic compounds.
  • aliphatic includes both saturated and unsaturated, straight chain (i.e., unbranched) or branched aliphatic hydrocarbons, which are optionally substituted with one or more functional groups.
  • aliphatic is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl moieties.
  • alkyl refers to straight and branched alkyl groups. An analogous convention applies to other generic terms such as “alkenyl”, “alkynyl” and the like. As used herein, “lower alkyl” is used to indicate those alkyl groups (substituted, unsubstituted, branched or unbranched) having about 1-6 carbon atoms.
  • Illustrative alkyl groups include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl, moieties and the like, which again, may bear one or more substituents.
  • Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl- 2-buten-l-yl, and the like.
  • Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl and the like.
  • alicyclic refers to compounds which combine the properties of aliphatic and cyclic compounds and include but are not limited to cyclic, or polycyclic aliphatic hydrocarbons and bridged cycloalkyl compounds, which are optionally substituted with one or more functional groups.
  • alicyclic is intended herein to include, but is not limited to, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties, which are optionally substituted with one or more functional groups.
  • Illustrative alicyclic groups thus include, but are not limited to, for example, cyclopropyl, -CH2-cyclopropyl, cyclobutyl, -CH2-cyclobutyl, cyclopentyl, -CH2- cyclopentyl-n, cyclohexyl, -CH2-cyclohexyl, cyclohexenylethyl, cyclohexanylethyl, norbornyl moieties and the like, which again, may bear one or more substituents.
  • heteroaliphatic refers to aliphatic moieties in which one or more carbon atoms in the main chain have been substituted with a heteroatom.
  • a heteroaliphatic group refers to an aliphatic chain which contains one or more oxygen, sulfur, nitrogen, phosphorus or silicon atoms, i.e., in place of carbon atoms.
  • Heteroaliphatic moieties may be branched or linear unbranched. An analogous convention applies to other generic terms such as “heteroalkyl”, “heteroalkenyl”, “heteroalkynyl” and the like.
  • heterocyclic refers to compounds which combine the properties of heteroaliphatic and cyclic compounds and include but are not limited to saturated and unsaturated mono- or polycyclic heterocycles such as morpholino, pyrrolidinyl, furanyl, thiofuranyl, pyrrolyl etc., which are optionally substituted with one or more functional groups, as defined herein.
  • heterocyclic refers to a non-aromatic 5-, 6- or 7- membered ring or a polycyclic group, including, but not limited to a bi- or tri-cyclic group comprising fused six-membered rings having between one and three heteroatoms independently selected from oxygen, sulfur and nitrogen, wherein (i) each 5-membered ring has 0 to 2 double bonds and each 6- membered ring has 0 to 2 double bonds, (ii) the nitrogen and sulfur heteroatoms may optionally be oxidized, (iii) the nitrogen heteroatom may optionally be quaternized, and (iv) any of the above heterocyclic rings may be fused to an aryl or heteroaryl ring.
  • heterocycles include, but are not limited to, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, and tetra hydrofuryl.
  • aromatic refers to stable substituted or unsubstituted unsaturated mono- or polycyclic hydrocarbon moieties having preferably 3-14 carbon atoms, comprising at least one ring satisfying Huckel’s rule for aromaticity.
  • aromatic moieties include, but are not limited to, phenyl, indanyl, indenyl, naphthyl, phenanthryl and anthracyl.
  • heteroaryl refers to unsaturated mono-heterocyclic or polyheterocyclic moieties having preferably 3-14 carbon atoms and at least one ring atom selected from S, O and N, comprising at least one ring satisfying the Huckel’s rule for aromaticity.
  • heteroaryl refers to a cyclic unsaturated radical having from about five to about ten ring atoms of which one ring atom is selected from S, O and N; zero, one or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like.
  • heteroaryl moieties include, but are not limited to, pyridyl, quinolinyl, dihydroquinolinyl, isoquinolinyl, quinazolinyl, dihydroquinazolyl, and tetrahydroquinazolyl.
  • C x -C y preferably C x i-C y i, alkylaryl, aralkyl or aryl
  • x, y, x1 and y1 represent integers denoting the number of carbon atoms in the chemical moiety to which it refers (e.g., “alkylaryl”, “aralkyl”, “aryl”)
  • C x -C y alkylaryl, aralkyl or aryl means “C x -C y alkylaryl, C x - C y aralkyl or C x -C y aryl”.
  • halogen refers to an atom selected from fluorine, chlorine, bromine and iodine.
  • amine refers to a group having the structure -N(R)2 wherein each occurrence of R is independently hydrogen, or an aliphatic, heteroaliphatic, aryl or heteroaryl moiety, or the R groups, taken together with the nitrogen atom to which they are attached, may form a heterocyclic moiety.
  • hydroxy refers to the -OH group.
  • hydroxyalkyl refers to an alkyl as defined above in which a carbon atom carries a -OH group.
  • alkyoxy refers to an -O-Alkyl group, in which the alkyl group is as defined above, as an example, without being limiting, the methoxy group -O-CH3 or the ethoxy group -O-CH2-CH3.
  • cyano refers to the -ON group.
  • nitro refers to the -NO2 group.
  • thioalkyl refers to an alkyl as defined above in which a carbon atom carries a -SH group.
  • alkylthio refers to a -S-Alkyl group, in which the alkyl group is as defined above, as an example, without being limiting, the -S-CH3 group or the S-CH2-CH3 group.
  • carboxylate refers to a -O-CO-NR- group, in which R is an aliphatic group as defined above.
  • thiocarbamate refers to a -S-CO-NR- group, in which R is a hydrogen or an aliphatic group as defined above.
  • urea or “carbamide” refers to a -RN-CO-NR’- group, in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
  • carbonate refers to a -RO-CO-OR’- group, in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
  • phosphate refers to a -O-PO(OR)(OR’) group, in which -OR and -OR’ are both directly linked to the P atom, and in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
  • phosphonate refers to a -PO(OR)(OR’) group, in which -OR and -OR’ are both directly linked to the P atom, and in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
  • sulfone refers to a -SO2R group, in which R is a hydrogen or an aliphatic group as defined above.
  • peroxide refers to a R-O-O-R’ group, or to a compound comprising this group, in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
  • lactone refers to any heterocyclic compound having an oxygen heteroatom that is directly bonded to the carbon atom of a carbonyl group.
  • thiolactone refers to any heterocyclic compound having a sulfur heteroatom that is directly bonded to the carbon atom of a carbonyl group.
  • the term “independently” refers to the fact that the substituents, atoms, or moieties to which these terms refer, are selected from the list of variables independently from each other (i.e. , they may be identical or the same).
  • number average molecular weight also referred to as "Mn”
  • Mn the average of the molecular weights weighted by the number of chains of each length, and corresponds to the molecular weight of a chain of average length (Mn is also known to be the ratio of the total weight of the chains constituting the said polymer measured on a given sample, W, to the number of polymer chains N in the said sample).
  • monomer unit means the constituent unit of the structure of a macromolecule formed from a single monomer molecule.
  • monomer units -A- they are called homopolymers (a), according to the following scheme:
  • copolymers are produced from more than one type of single monomer, and a distinction is made on how the different type of monomers are arranged in the resulting copolymer chains: (b) ‘alternating’, (c) ‘statistic’, (c) ‘block’ and (e) ‘multiblock’.
  • the scheme below illustrated the structures of different copolymers arranged according to
  • An object of the present invention is a polyamide comprising at least one monomer unit containing at least one elementary unit according to formula (I) : wherein R1 is a linear alkyl containing 1 to 6 carbon atoms; and wherein R2 is an aliphatic chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the following: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano
  • the polyamide according to the invention is a homopolymer according to formula (Ibis), the homopolymer may optionally comprise terminal groups selected among -NH2, -COOH and thiolactone, preferably 50% of these terminal groups being - NH2 and 50% of these terminal groups being -COOH and/or thiolactone: i being an integer, preferably greater than 10, and less than 50.
  • the polyamide according to the invention has the formula (II) : wherein the polyamide according to formula (II) is a copolymer selected among a statistical copolymer and a multiblock copolymer, Ri and R2 being as previously defined for the present invention ;
  • n is from 2 to 500 ;
  • - xi ranges between 0 and 1 , and represents the molar ratio of a first monomer units in the copolymer
  • - yi ranges between 0 and 1 , and represents the molar ratio of a second monomer units in the copolymer
  • R3 is independently of R2, selected among a polymer chain and a chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone ; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the followings: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
  • the polymer comprises -CO2H and -NH2 terminal groups and is configured according to the following formula (Ilbis):
  • the polymer chain is preferably selected among any amino-functionalized polymer, preferably selected among: a polyamide, a polylysine, chitosan, poly(ethyleneimine), a polyether, a polyester, a poly(vinylamine), a poly(allylamine), a polystyrene, a poly(meth)acrylate, a poly(meth)acrylonitrile, a polyalkene, a polydiene, a polysiloxane, and preferably the Mn of the polymer chain is in between 5 and 500 kg/mol.
  • the polymer may optionally comprise terminal groups selected among -NH2, -COOH and thiolactone, preferably 50% of these terminal groups being - NH2 and 50% of these terminal groups being -COOH and/or thiolactone, and is configured according to the following formula (liter) :
  • the polyamide according to the invention has the formula (III) : m
  • R3 is independently of R2, selected among a polymer chain and a chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the followings: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
  • the polymer comprises -NH2 and thiolactone terminal groups and is configured according to the following formula (lllbis):
  • the polymer can eventually include -NH2, -COOH and thiolactone terminal groups, and is configured according to the following formula (inter) :
  • the polymer chain is preferably selected among any amino-terminated polymer, preferably selected among: a polyamide, a polyether, a polyester, a polystyrene, a poly(meth)acrylate, a poly(meth)acrylonitrile, a polyalkene, a polydiene and a polysiloxane, and preferably the Mn of the polymer chain is in between 5 and 500 kg/mol.
  • Ri comprises 2 to 4 carbon atoms. The inventors have determined that it is more efficient to use compounds as starting material having a thiolactone comprising 2 to 4 carbon atoms in the cycle.
  • R2 represents a linear alkyl chain containing more than 6 carbon atoms, and preferably more than 7 carbon atoms.
  • the inventors have demonstrated that the length of the aliphatic chain R2 is an important parameter; and that R2 contains advantageously more than 6, and even 7, atoms to avoid intramolecular reaction of the starting material containing the R2 chain, instead of the desired polymerization reaction.
  • R3 represents a linear alkyl chain.
  • the polyamide is preferably a cross-linked polyamide by formation of intermolecular -S-S- bonds in between at least two -SH functional groups of two chains having the formula selected among one of the followings: formula (II), (I Ibis), (III) and (I I Ibis).
  • the cross-linked polyamide is advantageously a polyamide according to previously presented formula (liter) or (inter).
  • the cross-linked polyamide is obtained by oxidizing the polyamide with a peroxide, above 120°C.
  • the peroxide is preferably hydrogen peroxide and/or the reaction solvent is preferably dimethylacetamide.
  • the present invention also concerns a preparation method of a polyamide (PA) comprising thioalkylated group branched on the main chain of the PA, said preparation method resulting preferably of the reaction between amine groups with thiolactone groups, to provide thioalkylated group according to the formula (I): wherein Ri is a linear alkyl containing 1 to 6 carbon atoms; and wherein R2 is a aliphatic chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl
  • Said preparation method results preferably of the reaction between amine groups with thiolactone of the same monomer, said monomer being as defined in the following: wherein the R1, R2 groups are as defined previously for the invention ; and wherein the G, G’ groups are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (Boc), or are forming together with the N atom a protecting group, preferably a phthalimide.
  • an amino protecting group preferably a tert-butoxycarbonyl group (Boc)
  • n' being from 1 to 80, and preferably 10 to 50.
  • this preparation method is advantageously performed by using as starting material a mixture of the following compounds: wherein the Ri, R2 and R3 groups are as defined previously for the invention ; and wherein the G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (Boc), or are forming together with the N atom a protecting group, preferably a phthalimide; and wherein the molar ratio of (I lb)/(l la + lib) is preferably from 0,5% to 15%.
  • X2, y2, n being defined according to:
  • n is from 2 to 500 ;
  • - X2 ranges between 0 and 1 , and represents the molar ratio of a first monomer units in the copolymer
  • TAPA 1 can also be represented otherwise according to the next formula, without taking only accounts of the monomer units, but also of other repetitive units, wherein :
  • TAPA 1 x, y, n being defined according to:
  • n is from 2 to 500 ;
  • - x ranges between 0 and 1 , and represents the molar ratio of a first repetitive units in the copolymer
  • - y ranges between 0 and 1 , and represents the molar ratio of a second repetitive units in the copolymer
  • the present invention concerns a preparation method for the synthesis of a polyamide according to the invention, and in particular for the synthesis of a polymer according to formula (III) or formula (111 bis) with the number of m and Ri, R2 and R3 groups being as defined above in relation with these formulas; using as starting material a mixture of the following compounds: wherein the R1, R2 and R3 groups are as defined previously ; wherein the molar ratio of (111 b)/(l I la + 111 b) is preferably from 0.3 to 0.7.
  • the compound of formula (Illa) is selected among :
  • the compound of formula (I lib) is selected among at least one of the following : H 2 N-(CH 2 )2-NH 2 ; H 2 N-(CH 2 ) 4 -NH 2 ; H 2 N-(CH 2 ) 6 -NH 2 ; H 2 N-(CH 2 )I 2 -NH 2 ;
  • the present invention concerns a preparation method for the synthesis of the polyamide according to the invention, said preparation method resulting preferably of the reaction between amine groups with thiolactone groups of two polymers and/or copolymers, using as starting material a mixture of the following polymers: wherein the Ri, R2 and R3 groups are as defined previously; and
  • the polymer according to the formula (IVa) is prepared from the polycondensation of the previously presented compound: wherein the Ri and R2 groups are as defined previously; and wherein the G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (BOC), or are forming together with the N atom a protecting group, preferably a phthalimide.
  • the Ri and R2 groups are as defined previously; and wherein the G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (BOC), or are forming together with the N atom a protecting group, preferably a phthalimide.
  • the compound of formula (lib) is selected among :
  • the polymer according to the formula (IVb) is prepared from the polycondensation of the previously presented compound: wherein the R3 group is as defined above.
  • the compound of formula (Ila) is :
  • the Preparation method according to the invention is performed using a reactive extrusion method and preferably an extrusion molding method.
  • the present invention also concerns the use of the polyamide according to the invention as an adhesive; and preferably the polyamide has a strength lap shear above 20 MPa (megapascals), the substrate to which the polyamide adheres being preferably selected between a metal surface and an elastomer surface.
  • the present invention also concerns the use of the polyamide according to the invention as a meltable organic polymer.
  • the present invention also concerns a y-thiolactone for the preparation of a polyamide according to the invention, the y-thiolactone being selected among compounds according of formula (V) :
  • the y-thiolactone is selected among the following compounds :
  • the y-thiolactone is prepared according to the following, and comprise 10 the steps according to the following synthetic pathway : and eventually a deprotection step of the Boc group.
  • Flash column chromatography was carried out on silica gel 60 (40-63 pm).
  • Preparative TLC was performed on glass plates coated with silica gel (Merck PLC silica gel, 60 F254). Petroleum ether refers to the fraction of petroleum boiling between 40°C and 60°C.
  • FT-Raman analyses were performed using a near infrared excitation at 1064 nm provided by an Nd-YAG laser diode coupled to a Bruker RFS 100/S spectrometer based on a Michelson-type interferometer and equipped with a liquid nitrogen-cooled Ge detector.
  • the studied samples were analysed using a macroscopic interface equipped with a 90° collecting mirror allowing the objects to be placed on a horizontal surface.
  • the laser nominal power was of 490 mW (400 mW at the sample) and the spot size about 100 pm.
  • Spectra were recorded between 3500 and 50 cm -1 with a 4 cm -1 resolution, and with 500 to 1500 scans to optimize the signal-to-noise ratio.
  • Size Exclusion Chromatography analyses were performed on a two columns set (PSS SDV, linear M, 8 mm x 300 mm, bead diameter: 5 pm) at 40°C connected to a Viscotek VE 5200 automatic injector and a refractometer (LDC analytical Refracto Monitor IV) using THF as eluent (1 mL.min' 1 ).
  • the chromatograms were processed using the Viscotek OmniSEC software. Poly(methyl methacrylate) standards (Polymer Laboratories) were used for the calibration.
  • DSC Differential scanning calorimetry
  • Thermogravimetric analysis (TGA) analysis was conducted with a Q50 (TA Instrument) device on 10-20 mg samples under nitrogen atmosphere from 30°C to 600°C at a heating rate of 10°C/min.
  • Tensile tests were performed at room temperature with an lnstron-6985 device, equipped with a 1 kN load cell.
  • the flat dumbbell-type specimens, with an effective gauge length of 40 mm, a width of 4 mm, and a thickness of 2 mm were prepared using an injection press Haake Minijet II at 130°C to 220°C according to the material and under 700 bar.
  • the tensile tests were run at a rate of 20 mm/min. Reported values are averages from three specimens measured for each sample.
  • DMA analysis was performed with DMA850 - TA Instruments. Samples in strap shape with length of 60 mm, width of 10 mm and a thickness of 1 mm were prepared using an injection press Haake Minijet II at 150°C to 260°C according to the material and under 700bar. Samples were tested under a heating ramp at 10 °C/min from 20°C to 200 °C and a mechanical stress at 1 Hz and with 100 pm amplitude.
  • Adhesion tests were carried out on an lnstron-6985 tensile machine.
  • the single-lap shear specimens were prepared by the insertion of a flat sample ( ⁇ 5x5 mm, 1mm thickness) between the ends of two steel plates oriented in opposite direction.
  • An aluminium foil of 0.25 mm is used as spacer and the devices were completed with steel plates at both sides, wrapped with aluminium foil and cured at 220°C under 100 bars for 5 min using a hot press.
  • Tensile tests were performed at 1 mm/min deformation rate.
  • Protocols - Polyamides synthesis The TL-62 monomer bearing one thiolactone function is synthesized in 5 steps from conventional reagents according to the synthetic pathway provided in detail on the scheme 1 that is represented on the figure 1 .
  • TAPA 1 a thioalkylated polyamide copolymer
  • PA12-di(NH2) society Arkema®
  • Mn number average molecular weight
  • PA12-di(NH2) reacts with the monomer DTL53 (named DLT in figure 2 or 3) bearing two thiolactone functions to provide copolymers as represented on scheme 3 (see figure 3).
  • DLT monomer bearing two thiolactone functions
  • This reaction is performed under reactive extrusion conditions at 190°C, during 30 min.
  • the name of the resulting thioalkylated polyamide copolymer is TAPA 2. Details concerning this synthetic route are provided below:
  • DTL53 (0.8 g, 2.54 mmol) and PA12-di(NH 2 ) oligomer (Arkema) (4.07 g, 1.6 kg/mol, 2.42 mmol) were charged in a test tube and mixed by magnetic stirring for 5min at 160°C, under an argon flow in order to obtain an homogeneous mixture. After cooling, the solid was grinded and introduced in the twin-screw extruder (Haake Mini-Lab, commercialized by Thermoscientific). The reaction was conducted in re-circulation mode for 30min at 190°C. The product was flushed out and recovered as a white to slightly yellowish hard solid.
  • TAPA 1 and TAPA 2 are polyamides with an adjustable amount of thiol functions that improve:
  • PA12-diNH2 (10.68 g, 6.35 mmol)
  • 15 mL DMAc 15 mL
  • a solution of DTL53 (2 g, 6.35 mmol) in DMAc (6mL) was added and the mixture was left at 140°C under atmospheric pressure.
  • 1 .5 mL of H2O2 (30%wt in water) was added drop by drop and the reaction mixture was maintained for 1h at 140°C.
  • the resulting soft yellowish gel was cut in small pieces, washed by stirring in 400 mL of acetone for 12h, filtered and dried under vacuum for 8 hours.
  • TL-62 2g of TL-62 were charged in a glass reactor equipped with a central mechanical stirrer, an argon inlet and an outlet and heated under argon at 280°C with a 1 salt bath for 5 min to remove the BOC protecting group. The polymerization was then conducted at 110°C in an oil bath for 1 h. Polyamide PM021 (also named Poly TL62) was recovered after cooling as a sticky yellow product. M n and dispersity (D) values of the sample, 3000 g/mol and 2.7 respectively, were estimated by SEC analysis.
  • the two copolymers PM021 and PM023 are copolymerized together to obtain a multiblock polymer according to scheme 7 represented on figure 8; this multiblock polymer is named PM024.
  • This synthetic pathway falls also within the scope of the present invention, as the preparation method results of the reaction between amine groups with thiolactone groups of two copolymers, to provide thioalkylated groups.
  • T g and T m are respectively glass transition and melting temperatures determined from the heating DSC curves.
  • T c is the crystallization temperature determined from the cooling DSC curves.
  • Td (2%) the temperature of decomposition corresponding to the loss of 2% weight, is determined by TGA measurement.

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Abstract

A polyamide comprising monomer units containing at least one elementary unit according to formula (I), wherein R1 is a linear alkyl containing 1 to 6 carbon atoms; and wherein R2 is an aliphatic chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO- N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the following: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.

Description

POLYAMIDES FUNCTIONALIZED WITH CHAINS CONTAINING THIOL FUNCTIONS
FIELD OF THE INVENTION
The present invention is in the field of polymer synthesis, and more particularly concerns the preparation of polyamides comprising thiol functions, with no or a minimum of chemical transformations after the polymerization, such as melting, cross-liking and/or curing. The field of the present invention belongs to polymers used to form coatings on surfaces, adhesives and various materials.
BACKGROUND OF THE INVENTION
Polyamides is a class of polymers widely used in the industry for different applications, and they are a prime candidate for surface coating, for example metal coating or elastomer bonding. These interfacial interactions are sometimes essential to preserve the integrity of the part being treated, for example a metal surface against corrosion, an elastomer composite against delamination or protection of electronic devices such as printed circuit masking. Unfortunately, the adhesion of polyamides is often insufficient with respect to the specifications of the industry.
It is known from WO2016020297 the synthesis of polyamides comprising thiol functions on the main chain. Thiols are used to reinforce adhesion properties, however the polymers described in this document are limited to thiol functions directly linked to the main chain of the polymer.
The purpose of the present invention is to develop processes implementing starting material to control the length of side chains incorporating a thiol function at their end, the number, and the distribution of these side chains in the material resulting from the synthesis.
DEFINITIONS
To facilitate an understanding of the present invention, a number of terms and phrases are defined below:
In general, the term “substituted” whether preceded by the term “optionally” or not, and substituents contained in formulae of this invention, refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds.
The term “aliphatic”, as used herein, includes both saturated and unsaturated, straight chain (i.e., unbranched) or branched aliphatic hydrocarbons, which are optionally substituted with one or more functional groups. As will be appreciated by one of ordinary skill in the art, “aliphatic” is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl moieties.
As used herein, the term “alkyl”, refers to straight and branched alkyl groups. An analogous convention applies to other generic terms such as “alkenyl”, “alkynyl” and the like. As used herein, “lower alkyl” is used to indicate those alkyl groups (substituted, unsubstituted, branched or unbranched) having about 1-6 carbon atoms. Illustrative alkyl groups include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl, moieties and the like, which again, may bear one or more substituents. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl- 2-buten-l-yl, and the like. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl and the like.
The term “alicyclic”, as used herein, refers to compounds which combine the properties of aliphatic and cyclic compounds and include but are not limited to cyclic, or polycyclic aliphatic hydrocarbons and bridged cycloalkyl compounds, which are optionally substituted with one or more functional groups. As will be appreciated by one of ordinary skill in the art, “alicyclic” is intended herein to include, but is not limited to, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties, which are optionally substituted with one or more functional groups. Illustrative alicyclic groups thus include, but are not limited to, for example, cyclopropyl, -CH2-cyclopropyl, cyclobutyl, -CH2-cyclobutyl, cyclopentyl, -CH2- cyclopentyl-n, cyclohexyl, -CH2-cyclohexyl, cyclohexenylethyl, cyclohexanylethyl, norbornyl moieties and the like, which again, may bear one or more substituents.
The term “heteroaliphatic”, as used herein, refers to aliphatic moieties in which one or more carbon atoms in the main chain have been substituted with a heteroatom. Thus, a heteroaliphatic group refers to an aliphatic chain which contains one or more oxygen, sulfur, nitrogen, phosphorus or silicon atoms, i.e., in place of carbon atoms. Heteroaliphatic moieties may be branched or linear unbranched. An analogous convention applies to other generic terms such as “heteroalkyl”, “heteroalkenyl”, “heteroalkynyl” and the like.
The term “heterocyclic” or “heterocycle”, as used herein, refers to compounds which combine the properties of heteroaliphatic and cyclic compounds and include but are not limited to saturated and unsaturated mono- or polycyclic heterocycles such as morpholino, pyrrolidinyl, furanyl, thiofuranyl, pyrrolyl etc., which are optionally substituted with one or more functional groups, as defined herein. In certain embodiments, the term “heterocyclic” refers to a non-aromatic 5-, 6- or 7- membered ring or a polycyclic group, including, but not limited to a bi- or tri-cyclic group comprising fused six-membered rings having between one and three heteroatoms independently selected from oxygen, sulfur and nitrogen, wherein (i) each 5-membered ring has 0 to 2 double bonds and each 6- membered ring has 0 to 2 double bonds, (ii) the nitrogen and sulfur heteroatoms may optionally be oxidized, (iii) the nitrogen heteroatom may optionally be quaternized, and (iv) any of the above heterocyclic rings may be fused to an aryl or heteroaryl ring. Representative heterocycles include, but are not limited to, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, and tetra hydrofuryl.
In general, the term “aromatic” or “aryl”, as used herein, refers to stable substituted or unsubstituted unsaturated mono- or polycyclic hydrocarbon moieties having preferably 3-14 carbon atoms, comprising at least one ring satisfying Huckel’s rule for aromaticity. Examples of aromatic moieties include, but are not limited to, phenyl, indanyl, indenyl, naphthyl, phenanthryl and anthracyl.
As used herein, the term “heteroaryl” refers to unsaturated mono-heterocyclic or polyheterocyclic moieties having preferably 3-14 carbon atoms and at least one ring atom selected from S, O and N, comprising at least one ring satisfying the Huckel’s rule for aromaticity. The term “heteroaryl” refers to a cyclic unsaturated radical having from about five to about ten ring atoms of which one ring atom is selected from S, O and N; zero, one or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like. Examples of heteroaryl moieties include, but are not limited to, pyridyl, quinolinyl, dihydroquinolinyl, isoquinolinyl, quinazolinyl, dihydroquinazolyl, and tetrahydroquinazolyl.
As used herein, the expression “Cx-Cy, preferably Cxi-Cyi, alkylaryl, aralkyl or aryl”, where x, y, x1 and y1 represent integers denoting the number of carbon atoms in the chemical moiety to which it refers (e.g., “alkylaryl”, “aralkyl”, “aryl”)), means “Cx-Cyalkylaryl, Cx- Cyaralkyl or Cx-Cyaryl, preferably Cxi-Cyi alkyl aryl, Cxi-Cyi aralkyl or Cxi-Cyiaryl”. Likewise, the expression “Cx-Cy alkylaryl, aralkyl or aryl”, means “Cx-Cyalkylaryl, Cx- Cyaralkyl or Cx-Cyaryl”. The term “halogen” as used herein refers to an atom selected from fluorine, chlorine, bromine and iodine.
The term “amine” refers to a group having the structure -N(R)2 wherein each occurrence of R is independently hydrogen, or an aliphatic, heteroaliphatic, aryl or heteroaryl moiety, or the R groups, taken together with the nitrogen atom to which they are attached, may form a heterocyclic moiety.
The term “hydroxy” refers to the -OH group.
The term “hydroxyalkyl” refers to an alkyl as defined above in which a carbon atom carries a -OH group.
The term “alkyoxy” refers to an -O-Alkyl group, in which the alkyl group is as defined above, as an example, without being limiting, the methoxy group -O-CH3 or the ethoxy group -O-CH2-CH3.
The term “cyano” refers to the -ON group.
The term “nitro” refers to the -NO2 group.
The term “thioalkyl” ” refers to an alkyl as defined above in which a carbon atom carries a -SH group.
The term “alkylthio” refers to a -S-Alkyl group, in which the alkyl group is as defined above, as an example, without being limiting, the -S-CH3 group or the S-CH2-CH3 group. The term “carbamate” refers to a -O-CO-NR- group, in which R is an aliphatic group as defined above.
The term “thiocarbamate” refers to a -S-CO-NR- group, in which R is a hydrogen or an aliphatic group as defined above.
The term “urea” or “carbamide” refers to a -RN-CO-NR’- group, in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
The term “carbonate” refers to a -RO-CO-OR’- group, in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
The term “phosphate” refers to a -O-PO(OR)(OR’) group, in which -OR and -OR’ are both directly linked to the P atom, and in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
The term “phosphonate” refers to a -PO(OR)(OR’) group, in which -OR and -OR’ are both directly linked to the P atom, and in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
The term “sulfoxide” refers to a -S(=O)R group, in which R is a hydrogen or an aliphatic group as defined above.
The term “sulfone” refers to a -SO2R group, in which R is a hydrogen or an aliphatic group as defined above. The term “peroxide” refers to a R-O-O-R’ group, or to a compound comprising this group, in which R and R’ are both independently a hydrogen or an aliphatic group as defined above.
The term “lactone” refers to any heterocyclic compound having an oxygen heteroatom that is directly bonded to the carbon atom of a carbonyl group.
The term “thiolactone” refers to any heterocyclic compound having a sulfur heteroatom that is directly bonded to the carbon atom of a carbonyl group.
As used herein, the term “independently” refers to the fact that the substituents, atoms, or moieties to which these terms refer, are selected from the list of variables independently from each other (i.e. , they may be identical or the same).
The term "number average molecular weight", also referred to as "Mn", defines the average of the molecular weights weighted by the number of chains of each length, and corresponds to the molecular weight of a chain of average length (Mn is also known to be the ratio of the total weight of the chains constituting the said polymer measured on a given sample, W, to the number of polymer chains N in the said sample).
The term “monomer unit” means the constituent unit of the structure of a macromolecule formed from a single monomer molecule. When produced from one single type of monomer, giving rise to monomer units -A-, they are called homopolymers (a), according to the following scheme:
(a) -A-A-A-A-A-A-A-A-A-A-A-
Besides, copolymers are produced from more than one type of single monomer, and a distinction is made on how the different type of monomers are arranged in the resulting copolymer chains: (b) ‘alternating’, (c) ‘statistic’, (c) ‘block’ and (e) ‘multiblock’. The scheme below illustrated the structures of different copolymers arranged according to
(b)-(e), and made from two monomer units -A- and -B-:
(b) -A-B-A-B-A-B-A-B-A-B-A-B-
(c) -A-B-A-A-B-B-A-A-B-B-B-A-
(d) -A-A-A-A-A-A-A-B-B-B-B-B-B-
(e) -(A)n(B)m-(A)n(B)m-(A)n(B)m-
PRESENT INVENTION An object of the present invention is a polyamide comprising at least one monomer unit containing at least one elementary unit according to formula (I) :
Figure imgf000008_0001
wherein R1 is a linear alkyl containing 1 to 6 carbon atoms; and wherein R2 is an aliphatic chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the following: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
The inventors have demonstrated that these thioalkyl functions -R1-SH allow to improve the mechanical properties at high temperature, the adhesion on metals, the bonding on elastomers and the functionalization of the polyamide surface.
Advantageously, the polyamide according to the invention is a homopolymer according to formula (Ibis), the homopolymer may optionally comprise terminal groups selected among -NH2, -COOH and thiolactone, preferably 50% of these terminal groups being - NH2 and 50% of these terminal groups being -COOH and/or thiolactone:
Figure imgf000009_0001
i being an integer, preferably greater than 10, and less than 50.
Advantageously, the polyamide according to the invention has the formula (II) :
Figure imgf000009_0002
wherein the polyamide according to formula (II) is a copolymer selected among a statistical copolymer and a multiblock copolymer, Ri and R2 being as previously defined for the present invention ;
- the number of repetitive unit n is from 2 to 500 ;
- xi ranges between 0 and 1 , and represents the molar ratio of a first monomer units in the copolymer;
- yi ranges between 0 and 1 , and represents the molar ratio of a second monomer units in the copolymer;
Wherein xi + yi =1 and the xi and yi repeat monomer units are distributed (statistic, block, etc) in the copolymer;
- R3 is independently of R2, selected among a polymer chain and a chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone ; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the followings: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
Preferably, the polymer comprises -CO2H and -NH2 terminal groups and is configured according to the following formula (Ilbis):
Figure imgf000010_0001
(Ilbis) xi, yi, n being as defined precedingly for the compound of formula (II).
For compounds of formula (II) and (Ilbis) the polymer chain is preferably selected among any amino-functionalized polymer, preferably selected among: a polyamide, a polylysine, chitosan, poly(ethyleneimine), a polyether, a polyester, a poly(vinylamine), a poly(allylamine), a polystyrene, a poly(meth)acrylate, a poly(meth)acrylonitrile, a polyalkene, a polydiene, a polysiloxane, and preferably the Mn of the polymer chain is in between 5 and 500 kg/mol.
Preferably, in combination or alternately with the preceding paragraph in the context of the present invention, the polymer may optionally comprise terminal groups selected among -NH2, -COOH and thiolactone, preferably 50% of these terminal groups being - NH2 and 50% of these terminal groups being -COOH and/or thiolactone, and is configured according to the following formula (liter) :
Figure imgf000011_0001
(liter) xi, yi, n being as defined precedingly for the compound of formula (II).
Advantageously, the polyamide according to the invention has the formula (III) :
Figure imgf000011_0002
m
(HI) wherein the number of monomer units m is from 1 to 500, Ri and R2 being as previously defined for the present invention ; and
- R3 is independently of R2, selected among a polymer chain and a chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the followings: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
Preferably, the polymer comprises -NH2 and thiolactone terminal groups and is configured according to the following formula (lllbis):
Figure imgf000012_0001
- R1, R2 and R3; and m being as defined above for the formula (III).
Preferably, in combination or alternately with the preceding paragraph in the context of the present invention, the polymer can eventually include -NH2, -COOH and thiolactone terminal groups, and is configured according to the following formula (inter) :
Figure imgf000012_0002
(inter)
- Ri, R2 and R3; m being as defined above for the formula (III). For compounds of formula (III), (lllbis) and (inter) the polymer chain is preferably selected among any amino-terminated polymer, preferably selected among: a polyamide, a polyether, a polyester, a polystyrene, a poly(meth)acrylate, a poly(meth)acrylonitrile, a polyalkene, a polydiene and a polysiloxane, and preferably the Mn of the polymer chain is in between 5 and 500 kg/mol. Preferably, Ri comprises 2 to 4 carbon atoms. The inventors have determined that it is more efficient to use compounds as starting material having a thiolactone comprising 2 to 4 carbon atoms in the cycle.
Preferably, R2 represents a linear alkyl chain containing more than 6 carbon atoms, and preferably more than 7 carbon atoms. The inventors have demonstrated that the length of the aliphatic chain R2 is an important parameter; and that R2 contains advantageously more than 6, and even 7, atoms to avoid intramolecular reaction of the starting material containing the R2 chain, instead of the desired polymerization reaction.
Preferably, R3 represents a linear alkyl chain.
The polyamide is preferably a cross-linked polyamide by formation of intermolecular -S-S- bonds in between at least two -SH functional groups of two chains having the formula selected among one of the followings: formula (II), (I Ibis), (III) and (I I Ibis). The cross-linked polyamide is advantageously a polyamide according to previously presented formula (liter) or (inter). Advantageously, the cross-linked polyamide is obtained by oxidizing the polyamide with a peroxide, above 120°C. The peroxide is preferably hydrogen peroxide and/or the reaction solvent is preferably dimethylacetamide.
The present invention also concerns a preparation method of a polyamide (PA) comprising thioalkylated group branched on the main chain of the PA, said preparation method resulting preferably of the reaction between amine groups with thiolactone groups, to provide thioalkylated group according to the formula (I):
Figure imgf000013_0001
wherein Ri is a linear alkyl containing 1 to 6 carbon atoms; and wherein R2 is a aliphatic chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the following: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
Said preparation method results preferably of the reaction between amine groups with thiolactone of the same monomer, said monomer being as defined in the following:
Figure imgf000014_0001
wherein the R1, R2 groups are as defined previously for the invention ; and wherein the G, G’ groups are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (Boc), or are forming together with the N atom a protecting group, preferably a phthalimide.
This preparation method for the synthesis of a thioalkylated polyamide directly from a single monomer is more particularly exemplified in scheme 5 for the synthesis of PM021. It will be appreciated, however, that this example does not limit the invention.
Figure imgf000015_0001
n' being from 1 to 80, and preferably 10 to 50.
This synthetic pathway is described in more general terms below for the preparation of the polymer (IVa) directly from monomers (lib):
Figure imgf000015_0002
p' being from 1 to 80, and preferably 10 to 50.
Alternately or in combination with the preceding paragraphs in the context of the preparation method according to the present invention, and in particular for the synthesis of a polymer according to the formula (II) and (I I bis) with the number of x, y and n, and R1, R2 and R3 groups being as defined above in relation with these formulas; this preparation method is advantageously performed by using as starting material a mixture of the following compounds:
Figure imgf000015_0003
wherein the Ri, R2 and R3 groups are as defined previously for the invention ; and wherein the G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (Boc), or are forming together with the N atom a protecting group, preferably a phthalimide; and wherein the molar ratio of (I lb)/(l la + lib) is preferably from 0,5% to 15%.
This preparation method preferably for the synthesis of a polymer according to the formula (II) and (I Ibis), is more particularly exemplified in scheme 2 (see figure 2) for the synthesis of TAPA 1. It will be appreciated, however, that this example does not limit the invention:
Figure imgf000016_0001
X2, y2, n being defined according to:
- the number of monomer units n is from 2 to 500 ;
- X2 ranges between 0 and 1 , and represents the molar ratio of a first monomer units in the copolymer;
- y2 ranges between 0 and 1 , and represents the molar ratio of a second monomer units in the copolymer; wherein X2 + y2 =1 and the X2 and y2 repeat monomer units are distributed (statistic, block, etc) in the copolymer.
TAPA 1 can also be represented otherwise according to the next formula, without taking only accounts of the monomer units, but also of other repetitive units, wherein :
Figure imgf000017_0001
TAPA 1 x, y, n being defined according to:
- the number of repetitive unit n is from 2 to 500 ;
- x ranges between 0 and 1 , and represents the molar ratio of a first repetitive units in the copolymer;
- y ranges between 0 and 1 , and represents the molar ratio of a second repetitive units in the copolymer;
Wherein x + y =1 and the x and y repetitive units are distributed (statistic, block, etc) in the copolymer.
Alternatively, and/or in combination with the above, the present invention concerns a preparation method for the synthesis of a polyamide according to the invention, and in particular for the synthesis of a polymer according to formula (III) or formula (111 bis) with the number of m and Ri, R2 and R3 groups being as defined above in relation with these formulas; using as starting material a mixture of the following compounds:
Figure imgf000017_0002
wherein the R1, R2 and R3 groups are as defined previously ; wherein the molar ratio of (111 b)/(l I la + 111 b) is preferably from 0.3 to 0.7.
Preferably, the compound of formula (Illa) is selected among :
Figure imgf000018_0001
and/or advantageously, the compound of formula (I lib) is selected among at least one of the following : H2N-(CH2)2-NH2 ; H2N-(CH2)4-NH2 ; H2N-(CH2)6-NH2 ; H2N-(CH2)I2-NH2 ;
H2N-(CH2- CH2-O)2-CH2-CH2-NH2 ; H2N-CH2- CH2-NH-CH2-CH2-NH2 ; H2N-(CH2- CH2-NH)2-CH2-CH2-NH2 and melamine.
This preparation method preferably for the synthesis of a polymer according to the formula (III) and (lllbis) is more particularly exemplified in scheme 3 for the synthesis of TAPA 2. It will be appreciated, however, that this example does not limit the invention.
Figure imgf000019_0001
TAPA 2 m being as defined precedingly for the compound of formula (III). Alternatively, and/or in combination with the above, the present invention concerns a preparation method for the synthesis of the polyamide according to the invention, said preparation method resulting preferably of the reaction between amine groups with thiolactone groups of two polymers and/or copolymers, using as starting material a mixture of the following polymers:
Figure imgf000019_0002
wherein the Ri, R2 and R3 groups are as defined previously; and
- p is from 1 to 100, preferably 1 to 20 ; - q is from 1 to 100, preferably 1 to 20 ; wherein the molar ratio of (IVa)/(IVa + IVb) is preferably from 0.5 to 50%.
Preferably, the polymer according to the formula (IVa) is prepared from the polycondensation of the previously presented compound:
Figure imgf000020_0001
wherein the Ri and R2 groups are as defined previously; and wherein the G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (BOC), or are forming together with the N atom a protecting group, preferably a phthalimide.
Preferably, the compound of formula (lib) is selected among :
Figure imgf000020_0002
Preferably, the polymer according to the formula (IVb) is prepared from the polycondensation of the previously presented compound:
Figure imgf000020_0003
wherein the R3 group is as defined above. Preferably, the compound of formula (Ila) is :
Figure imgf000021_0001
Preferably, the Preparation method according to the invention, is performed using a reactive extrusion method and preferably an extrusion molding method.
This preparation method for the synthesis of a polymer resulting of the reaction between amine groups with thiolactone groups of two polymers is more particularly exemplified in scheme 7 for the synthesis of PM024. It will be appreciated, however, that this example does not limit the invention.
Figure imgf000021_0002
PM024
The present invention also concerns the use of the polyamide according to the invention as an adhesive; and preferably the polyamide has a strength lap shear above 20 MPa (megapascals), the substrate to which the polyamide adheres being preferably selected between a metal surface and an elastomer surface.
The present invention also concerns the use of the polyamide according to the invention as a meltable organic polymer.
The present invention also concerns a y-thiolactone for the preparation of a polyamide according to the invention, the y-thiolactone being selected among compounds according of formula (V) :
Figure imgf000022_0001
R2 is as defined previously; wherein n is 1 or 2: when n=1 , n -1; and when n=2, n’=0; and with the exclusion of the following compounds :
Figure imgf000022_0002
Figure imgf000023_0001
Preferably, the y-thiolactone is selected among the following compounds :
Figure imgf000023_0002
Most preferably the y-thiolactone is prepared according to the following, and comprise 10 the steps according to the following synthetic pathway :
Figure imgf000024_0001
and eventually a deprotection step of the Boc group.
EXPERIMENTAL SECTION AND PROTOCOLS
The following examples contain important additional information, exemplification and guidance that can be adapted to the practice of this invention in its various embodiments and the equivalents thereof. The polymer materials and compositions of this invention and their preparation can be understood further by the examples that illustrate some of the processes by which these polymer materials and compositions are prepared or used. It will be appreciated, however, that these examples do not limit the invention. Variations of the invention, now known or further developed, are considered to fall within the scope of the present invention as described herein and as hereinafter claimed.
GENERAL EXPERIMENTAL METHODS
Monomer synthesis and analysis
Reactions sensitive to air and/or moisture were performed under nitrogen atmosphere. For the reactions that require heating, an oil bath or a DrySyn heating block was used as the heat source.
Flash column chromatography was carried out on silica gel 60 (40-63 pm). Thin layer chromatography (TLC) was performed on alumina plates precoated with silica gel (Merck silica gel, 60 F254). Products spots were visualized by exposure to the UV light (Amax = 254 nm) and/or by staining with vanillin in acidic ethanol solution and/or basic aqueous KMnC , followed by heating. Preparative TLC was performed on glass plates coated with silica gel (Merck PLC silica gel, 60 F254). Petroleum ether refers to the fraction of petroleum boiling between 40°C and 60°C.
Nuclear magnetic resonance spectra were recorded at ambient temperature on a Bruker Avance DPX 400 instrument. Proton magnetic resonance spectra (1H NMR) were recorded at 400 MHz and coupling constants (J) are reported to ± 0.5 Hz. The following abbreviations were utilized to describe peak patterns when appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet and m = multiplet. Carbon magnetic resonance spectra (13C NMR) were recorded at 101 MHz. Chemical shifts (H, C) are quoted in parts per million (ppm) and are referenced to the residual solvent peak (CDCh: bH = 7.26 and bC = 77.2; DMSO: bH = 2.50 and bC = 39.5; Acetone: bH = 2.05 and bC = 29.8).
High resolution mass spectrometry experiments were performed on a tims-TOF mass spectrometer (Bruker, France). Electrospray source has been used in positive mode. The quoted masses are accurate to ± 5 ppm. Infrared spectra were recorded on a Perkin- Elmer Spectrum Two apparatus. Absorption maxima (umax) are reported in wavenumbers (cm-1). Melting points were recorded in degrees Celsius (°C), using a Stuart SMP40 Automatic Melting Point apparatus.
Polyamides analysis
Nuclear magnetic resonance spectra of linear polyamides were recorded on a Bruker Avance DPX 400 instrument at 400 MHz (1H-NMR). Polyamides were cryo-grinded to a fine powder before analysis. 20 mg of sample were dissolved in 0.7 mL of solvent (CDCh, CDCh I formic acid (6:1) or CDCh/trifluoro acetic anhydride (6:1) according to the sample). Chemical shifts were referenced to residual CHCh peak at 7.26 ppm (1H-NMR). 1H-NMR spectra of partially cross-linked polymers were recorded on a Bruker 500 Avance III instrument at 500MHz using a high resolution magic-angle spinning DUAL sensor (4 mm 1 H/13C z gradient) and an accumulation of 512 scans. The samples were swelled in the solvent mixture (CDCh I formic acid 10:1) for 24 h before analysis.
FT-Raman analyses were performed using a near infrared excitation at 1064 nm provided by an Nd-YAG laser diode coupled to a Bruker RFS 100/S spectrometer based on a Michelson-type interferometer and equipped with a liquid nitrogen-cooled Ge detector. The studied samples (bulk) were analysed using a macroscopic interface equipped with a 90° collecting mirror allowing the objects to be placed on a horizontal surface. The laser nominal power was of 490 mW (400 mW at the sample) and the spot size about 100 pm. Spectra were recorded between 3500 and 50 cm-1 with a 4 cm-1 resolution, and with 500 to 1500 scans to optimize the signal-to-noise ratio. Size Exclusion Chromatography analyses were performed on a two columns set (PSS SDV, linear M, 8 mm x 300 mm, bead diameter: 5 pm) at 40°C connected to a Viscotek VE 5200 automatic injector and a refractometer (LDC analytical Refracto Monitor IV) using THF as eluent (1 mL.min'1). The chromatograms were processed using the Viscotek OmniSEC software. Poly(methyl methacrylate) standards (Polymer Laboratories) were used for the calibration.
Differential scanning calorimetry (DSC) analysis was performed with a Q2000 (TA Instrument) device coupled with RCS90 cooling system under nitrogen atmosphere. IQ- 15 mg of samples were introduced in hermetic aluminum pan. Two cycles of heating (from -80°C to 200°C) and cooling (from 200°C to -80°C) ramps were performed at a heating/cooling rate of 10°C/min.
Thermogravimetric analysis (TGA) analysis was conducted with a Q50 (TA Instrument) device on 10-20 mg samples under nitrogen atmosphere from 30°C to 600°C at a heating rate of 10°C/min.
Tensile tests were performed at room temperature with an lnstron-6985 device, equipped with a 1 kN load cell. The flat dumbbell-type specimens, with an effective gauge length of 40 mm, a width of 4 mm, and a thickness of 2 mm were prepared using an injection press Haake Minijet II at 130°C to 220°C according to the material and under 700 bar. The tensile tests were run at a rate of 20 mm/min. Reported values are averages from three specimens measured for each sample.
DMA analysis was performed with DMA850 - TA Instruments. Samples in strap shape with length of 60 mm, width of 10 mm and a thickness of 1 mm were prepared using an injection press Haake Minijet II at 150°C to 260°C according to the material and under 700bar. Samples were tested under a heating ramp at 10 °C/min from 20°C to 200 °C and a mechanical stress at 1 Hz and with 100 pm amplitude.
Adhesion tests were carried out on an lnstron-6985 tensile machine. The single-lap shear specimens were prepared by the insertion of a flat sample (~ 5x5 mm, 1mm thickness) between the ends of two steel plates oriented in opposite direction. An aluminium foil of 0.25 mm is used as spacer and the devices were completed with steel plates at both sides, wrapped with aluminium foil and cured at 220°C under 100 bars for 5 min using a hot press. Tensile tests were performed at 1 mm/min deformation rate.
Protocols - Polyamides synthesis The TL-62 monomer bearing one thiolactone function is synthesized in 5 steps from conventional reagents according to the synthetic pathway provided in detail on the scheme 1 that is represented on the figure 1 .
The TL-62 monomer is copolymerized with another monomer, 12-aminododecanoic acid (12-ADDA), bearing an amine function and an acid function, according to scheme 2 represented on the figure 2, to obtain a thioalkylated polyamide copolymer named TAPA 1 , TAPA 1 is a statistic copolymer. Details concerning this synthetic route are provided below:
TAPA1 preparation:
12-ADDA (17.38 g, 80.7 mmol) and TL62 (3 g, 8.1 mmol) were copolymerized in the bulk. The reagents were charged in a three-necked glass reactor equipped with an argon inlet, a central mechanical stirrer, a distillation head connected to a condenser and a receiver flask. The reaction was conducted by heating at 240°C with a salt bath for 2h under an argon stream and 1h under reduced pressure (10-2 mbar). The polyamide TAPA1 was recovered after cooling and is cryo-grinded to a fine powder before analysis. FT-Raman (A = 1064 nm, 400mW), v (cm’1): 3300; 2893-2857; 2700; 2596; 1642; 1445; 1375; 1296; 1114-1069; 942; 690-626.
Another route has been investigated starting from the commercially available polymer PA12-di(NH2) (society Arkema®) with a number average molecular weight, Mn, of 1.6 kg/mol. PA12-di(NH2) reacts with the monomer DTL53 (named DLT in figure 2 or 3) bearing two thiolactone functions to provide copolymers as represented on scheme 3 (see figure 3). This reaction is performed under reactive extrusion conditions at 190°C, during 30 min. The name of the resulting thioalkylated polyamide copolymer is TAPA 2. Details concerning this synthetic route are provided below:
TAPA2 preparation:
DTL53 (0.8 g, 2.54 mmol) and PA12-di(NH2) oligomer (Arkema) (4.07 g, 1.6 kg/mol, 2.42 mmol) were charged in a test tube and mixed by magnetic stirring for 5min at 160°C, under an argon flow in order to obtain an homogeneous mixture. After cooling, the solid was grinded and introduced in the twin-screw extruder (Haake Mini-Lab, commercialized by Thermoscientific). The reaction was conducted in re-circulation mode for 30min at 190°C. The product was flushed out and recovered as a white to slightly yellowish hard solid. FT-Raman (A = 1064 nm, 400mW), v (cm’1): 3300; 2893-2857; 2724; 2596; 1642; 1445; 1372; 1296; 1114-1069; 942; 690-626.
The resulting polymers, TAPA 1 and TAPA 2 are polyamides with an adjustable amount of thiol functions that improve:
1) mechanical properties at high temperatures,
2) adhesion on metals,
3) bonding to elastomers,
4) surface treatments of the polyamide.
The same route as this one represented on scheme 3 has been performed under oxidizing conditions, at 140°C in DMAc with hydrogen peroxide (H2O2) as represented on scheme 4 (see figure 4). The resulting polymer is a copolymer named DAPA 2 (disulfuralkylated polyamide analogue of TAPA 2). The solid copolymer is thus grinded, washed with acetone and dried to produce a yellow pale powder. Details concerning this synthetic route are provided below:
DAPA2 preparation:
PA12-diNH2 (10.68 g, 6.35 mmol)) and 15 mL DMAc were charged in glass vial and heated at 140°C with an oil bath under magnetic stirring until complete dissolution. A solution of DTL53 (2 g, 6.35 mmol) in DMAc (6mL) was added and the mixture was left at 140°C under atmospheric pressure. After 10min, 1 .5 mL of H2O2 (30%wt in water) was added drop by drop and the reaction mixture was maintained for 1h at 140°C. After cooling, the resulting soft yellowish gel was cut in small pieces, washed by stirring in 400 mL of acetone for 12h, filtered and dried under vacuum for 8 hours.
FT-Raman (A = 1064 nm, 400mW), v (cm’1): 3300; 2893-2857; 2724; 2596; 1642; 1445; 1372; 1296; 1114-1069; 942; 690-626.
The reaction of TL-62 monomer and 12-ADDA monomer independently of each other have also been investigated:
-The polymerization of monomer TL-62 is performed by simple heating according to the scheme 5 represented on figure 5 to provide a polymer named PM021.
Protocol: 2g of TL-62 were charged in a glass reactor equipped with a central mechanical stirrer, an argon inlet and an outlet and heated under argon at 280°C with a 1 salt bath for 5 min to remove the BOC protecting group. The polymerization was then conducted at 110°C in an oil bath for 1 h. Polyamide PM021 (also named Poly TL62) was recovered after cooling as a sticky yellow product. Mn and dispersity (D) values of the sample, 3000 g/mol and 2.7 respectively, were estimated by SEC analysis. 1H NMR spectrum is presented in figure 6; FT-Raman (A = 1064 nm, 400mW), v (cm-1): 2893- 2857; 2724; 2575; 1700; 1642; 1445; 1372; 1168-1078; 730-626.
-The polymerization of monomer 12-ADDA is performed by simple heating according to the scheme 6 represented on figure 7 to provide a polymer named PM023. PM023, also named PA12: this polymer has the same repetitive unit than the previously presented Arkema® polymer PA12-di(NH2); but without the NH-(CH2)i2-NH2 terminal group.
Protocol: 60 g of 12-ADDA were charged in a three-necked glass reactor equipped with an argon inlet, a central mechanical stirrer, a distillation head connected to a condenser and a receiver flask. The polymerization was conducted under an argon flow by heating with a salt bath at 220°C for 2 hours. Polyamide PM023 was recovered after cooling. The Mn value of the sample, 5000 g/mol, was obtained by 1H-NMR-400MHz in CDCI3 / Trifluoro acetic anhydride 6:1 as solvent according to the chains ends peak.
The two copolymers PM021 and PM023 are copolymerized together to obtain a multiblock polymer according to scheme 7 represented on figure 8; this multiblock polymer is named PM024. This synthetic pathway falls also within the scope of the present invention, as the preparation method results of the reaction between amine groups with thiolactone groups of two copolymers, to provide thioalkylated groups.
Protocol: PM021 (0.83 g) and PM023 (15 g) were charged in a glass reactor equipped with a central mechanical stirrer, an argon inlet and an outlet. The reaction was conducted in the bulk by heating at 200°C with a salt bath for 2h under an argon flow. The pressure was reduced to 10'2 mbar and the reaction was maintained at 200°C for 1 h. Polyamide PM024 was recovered after cooling.
FT-Raman (A = 1064 nm, 400m W), v (cm’1): 2893-2857; 2724; 2575 (S-H str, m); 1642; 1445; 1372; 1300; 1111-1062; 744-696.
Thermal and tensile stress analyses
The results of thermal and tensile stress analyses of the polyamides are described in Table 1 and 2 respectively. The DMA analysis curves are presented in figure 10 (PM023=PA12, TAPA1 , PM024) and figure 11 (PMA023=PA12, TAPA2, DAPA2). The results of lap Shear Adhesion test are presented in figure 12 (PMA023=PA12) and Table 3.
Tablel : Thermal Properties of Polyamides. Tg and Tm are respectively glass transition and melting temperatures determined from the heating DSC curves. Tc is the crystallization temperature determined from the cooling DSC curves. Td (2%), the temperature of decomposition corresponding to the loss of 2% weight, is determined by TGA measurement.
Sample Tg Tm Tc Td (2%)
(°C) (°C) (°C) (°C)
TAPA1 34 174 133 379
TAPA2 30 157 103 302
DAPA2 27 149 100 300
PM021 -3 - - 228
PM023 46 180 152 380
PM024 29 175 135 380 Table 2: Mechanical properties of polyamides measured by tensile tests at room temperature
.. Tensile
Elastic . . . Elongation
. i yield . . a . modulus ? ., at break strength
(MPa) (MPa) (%)
PM023 1100 35,5 130
TAPA1 2300 52 40
TAPA2 1320 38,2 18
DAPA2 1600 53,7 80
PM024 1900 51 32
Table 3: Lap-Shear strength values (MPa) = F/Amax
Figure imgf000030_0001

Claims

1. A polyamide comprising at least one monomer unit units containing at least one elementary unit according to formula (I) :
Figure imgf000031_0001
wherein Ri is a linear alkyl containing 1 to 6 carbon atoms; and wherein R2 is an aliphatic chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; - CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the following: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
2. A polyamide according to claim 1, having the formula (II) :
Figure imgf000031_0002
wherein the polyamide according to formula (II) is a copolymer selected among a statistical copolymer and a multiblock copolymer ;
- the number of monomer units n is from 2 to 500 ;
- xi ranges between 0 and 1, and represents the molar ratio of a first monomer units in the copolymer;
- yi ranges between 0 and 1, and represents the molar ratio of a second monomer units in the copolymer; wherein xi + yi =1 and the xi and yi repeat monomer units are distributed in the copolymer randomly or not; and
- R3 is independently of R2, selected among a polymer chain and a chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone ; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the followings: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
3. A polyamide according to claim 1, having the formula (III) :
Figure imgf000032_0001
wherein the number of monomer units m is from 1 to 500 ; and
- R3 is independently of R2, selected among a polymer chain and a chain containing 1 to 30 carbon atoms selected among one of the followings: an alkyl chain, an alkenyl chain, an alkynyl chain, eventually containing at least one of the following atoms or groups: O; N; S; -CO-; -CO-O-; -CO-N-; -CO-S-; carbonate; carbamate; urea; phosphate; phosphonate; sulfoxide; sulfone; cycloalkyl; aryl and heteroaryl; the cycloalkyl, aryl and heteroaryl being eventually substituted by one of the followings: alkyl; hydroxy; hydroxyalkyl; alkyloxy; halogen; cyano; -SH; nitro; thioalkyl and alkylthio.
4. A polyamide according to claim 2, wherein the polymer chain is selected among any amino-functionalized polymer, preferably selected among: a polyamide, a polylysine, chitosan, poly(ethyleneimine), a polyether, a polyester, a poly(vinylamine), a poly(allylamine), a polystyrene, a poly(meth)acrylate, a poly(meth)acrylonitrile, a polyalkene, a polydiene, a polysiloxane, and preferably the Mn of the polymer chain is in between 5 and 500 kg/mol.
5. A polyamide according to claim 3, wherein the polymer chain is selected among any amino-terminated linear polymer, preferably selected among: a polyamide, a polyether, a polyester, a polystyrene, a poly(meth)acrylate, a poly(meth)acrylonitrile, a polyalkene, a polydiene and a polysiloxane, and preferably the Mn of the polymer chain is in between 5 and 500 kg/mol.
6. A polyamide according to any of claim 1 to 5, wherein Ri comprises 2 to 4 carbon atoms.
7. A polyamide according to any of claim 1 to 6, wherein R2 represents a linear alkyl chain containing more than 6 carbon atoms, and preferably more than 7 carbon atoms.
8. A polyamide according to any of claim 1 to 7, wherein R3 represents a linear alkyl chain.
9. A polyamide according to anyone of claims 2 to 8, wherein the polyamide is a cross-linked polyamide by formation of intermolecular -S-S- bonds in between at least two -SH functional groups of two chains having the formula selected among one of the followings: formula (II) and formula (III).
10. A polyamide according to claim 9, wherein the cross-linked polyamide is obtained by oxidizing the polyamide with a peroxide, above 120°C.
11. Preparation method for the synthesis of the polyamide according to claim 1 and 2, and preferably to any of claims 4 and 6 to 10 combined with claim 2, using as starting material a mixture of the following compounds:
Figure imgf000034_0001
wherein the Ri, R2 and R3 groups are as defined in claims 1 to 2, and preferably to any of claims 4 to 6 combined with claim 2 ; wherein the G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (BOC), or are forming together with the N atom a protecting group, preferably a phthalimide; and wherein the molar ratio of (I lb)/(lla + lib) is preferably from 0,5% to 15%.
12. Preparation method for the synthesis of the polyamide according to claim 1 and 3, and preferably to any of claims 5 to 10 combined with claim 3, using as starting material a mixture of the following compounds:
Figure imgf000034_0002
wherein the R1, R2 and R3 groups are as defined in claims 1 and 3, and preferably to any of claims 4 to 6 combined with claim 3 ; wherein the molar ratio of (I llb)/(l I la + II lb) is preferably from 0.3 to 0.7.
13. Preparation method for the synthesis of the polyamide according to claim 1 and 2, and preferably to any of claims 4 and 6 to 10 combined with claim 2, using as starting material a mixture of the following polymers:
Figure imgf000035_0001
wherein the Ri, R2 and R3 groups are as defined in claims 1 and 4, and preferably to any of claims 5 to 7 combined with claim 4 ; and
- p is from 1 to 100, preferably 1 to 20 ;
- q is from 1 to 100, preferably 1 to 20 ; wherein the molar ratio of (IVa)/(IVa + IVb) is preferably from 0.5 to 50%.
14. Preparation method according to claim 13, wherein polymer according to the formula (IVa) is prepared from the polycondensation of:
Figure imgf000035_0002
wherein the R1 and R2 groups are as defined in claims 11 ; and wherein the
G, G’ group are independently selected in the following: an H, and an amino protecting group, preferably a tert-butoxycarbonyl group (BOC), or are forming together with the N atom a protecting group, preferably a phthalimide.
15. Preparation method according to claim 13 or 14, wherein the polymer according to the formula (IVb) is prepared from the polycondensation of:
Figure imgf000036_0001
wherein the R3 group is as defined in claims 11.
16. Preparation method according to claims 11 or 14 to 15, wherein the compound of formula (lib) is selected among :
Figure imgf000036_0002
17. Preparation method according to any of claims 11 or 14 to 16, wherein the compound of formula (Ila) is :
Figure imgf000036_0003
18. Preparation method according to claim 12, wherein the compound of formula (Illa) is selected among :
Figure imgf000037_0001
19. Preparation method according to claims 12, wherein the compound of formula (I lib) is selected among at least one of the following : H2N-(CH2)2-NH2 ; H2N-(CH2)4-NH2 ; H2N-(CH2)6-NH2 ; H2N-(CH2)I2-NH2 ; H2N- (CH2- CH2-O)2-CH2-CH2-NH2 ; H2N-CH2- CH2-NH-CH2-CH2-NH2 ; H2N-(CH2- CH2-NH)2-CH2-CH2-NH2 and melamine.
20. Preparation method according to any of claims 11 to 19, using a reactive extrusion method and preferably an extrusion molding method.
21. Use of at least one polyamide according to any of claim 1 to 10, as an adhesive.
22. Use according to claim 21, wherein the polyamide has a strength lap shear above 20 MPa (megapascals), the substrate to which the polyamide adheres being preferably selected between a metal surface and an elastomer surface.
23. Use of at least one polyamide according to any one of claims 1 to 10, as a meltable organic polymer.
24. y-thiolactone for the preparation of a polyamide according to any of claims 1 to 10, wherein the y-thiolactone is selected among compounds according of formula (V) :
Figure imgf000038_0001
R2 is as defined in preceding claims 1 to 9; wherein n is 1 or 2: when n=1 , n’=1 ; and when n=2, n’=0; and with the exclusion of the following compounds :
Figure imgf000038_0002
Figure imgf000039_0001
25. v-thiolactone according to claim 24, wherein the y-thiolactone is selected among the following compounds :
Figure imgf000039_0002
Figure imgf000040_0001
26. Preparation method of a y-thiolactone according to claim 25 comprising the steps according to the following synthetic pathway, and eventually a deprotection step of the Boc group :
Figure imgf000040_0002
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Citations (2)

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WO1996040746A1 (en) * 1995-06-07 1996-12-19 Trustees Of Boston University Lysyloxidase inhibitors
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WO1996040746A1 (en) * 1995-06-07 1996-12-19 Trustees Of Boston University Lysyloxidase inhibitors
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