WO2020002556A1 - Composition thermoplastique comprenant un polysiloxane portant des fractions de diaminotriazine - Google Patents

Composition thermoplastique comprenant un polysiloxane portant des fractions de diaminotriazine Download PDF

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WO2020002556A1
WO2020002556A1 PCT/EP2019/067251 EP2019067251W WO2020002556A1 WO 2020002556 A1 WO2020002556 A1 WO 2020002556A1 EP 2019067251 W EP2019067251 W EP 2019067251W WO 2020002556 A1 WO2020002556 A1 WO 2020002556A1
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group
polymer
thermoplastic composition
composition according
formula
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PCT/EP2019/067251
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Soumyadeb Ghosh
Grégory LANDELLE
Rabih AL RAHAL AL ORABI
Caroll Vergelati
Franck Touraud
Hemang DARJI
Rakesh Banerjee
Bala N.S THOTA
Gururajan Padmanaban
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Rhodia Operations
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Priority claimed from EP18306147.2A external-priority patent/EP3617251A1/fr
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Publication of WO2020002556A1 publication Critical patent/WO2020002556A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups

Definitions

  • Thermoplastic composition comprising a polysiloxane bearing
  • the present invention relates to a thermoplastic composition
  • a thermoplastic composition comprising at least one polysiloxane (Pl) bearing diaminotriazine moieties and at least one polymer (P2) having a glass transition temperature, measured by differential scanning calorimetry, lower than 0 °C, functionalized with at least two isocyanuric or barbituric acid moieties.
  • H-bond donor and H-bond acceptor moieties onto polymer backbone may result in hydrogen bondings between the polymer chains that may confer new properties to the so formed supramolecular assembly.
  • US8575291 discloses polydimethylsiloxane (PDMS) bearing functional group having atomic groups capable of forming hydrogen bonding such as thymine group. According to the authors thymine is responsible, through self-association, for hydrogen bondings between the polysiloxane chains leading to the formation of a supramolecular network finally resulting in a thermoplastic silicone resin.
  • the supramolecular assembly is solid at 25°C and becomes liquid at relatively low temperatures of 55°C-65°C. The authors noticed that heating of such supramolecular assembly is often accompanied with a yellowing which is characteristic of thermal degradation detrimental to a reuse of the product.
  • US7622131 discloses PDMS containing self-complementary quadruple hydrogen bonding groups, namely pyrimidine group having an urea link. These polymers are, depending on the nature of the substituent and on the nature of the backbone (telechelic polymer or comblike copolymers), clear sticky, clear elastic, clear glassy or white gummy materials resulting from the reversible association of the polysiloxane chains via hydrogen bondings. None is said about the thermal stability of the urea and of the pyrimidine group.
  • thermoset polydimethylsiloxane obtained by the cyclotrimerization of a cyanate group to a cyanurate structure. Accordingly, the rubbery material is an irreversibly crosslinked material, having a glass transition ranging from -43°C to l5°C, which can be reuse after melting.
  • US3892643 relates to a thermally curable composition comprising an
  • thermosetting resin composition including a diglycidyl isocyanuryl modified polysiloxane that may be crosslinked using an acid anhydride -based curing agent. Crosslinking is not reversible and the material is thermoset not thermoplastic.
  • US4855378 relates to an organopolysiloxane composition which may be crosslinked via an addition of Si-bonded hydrogen with Si-C bonded vinyl groups which can be an alkenylisocyanurate moiety to give elastomeric material. Hydro silylation reaction is not reversible and the material is thus not
  • thermoplastic thermoplastic
  • DAT diaminotriazine
  • US4113947 discloses a product obtained by addition of N-allylaminotriazine onto organopolysiloxane.
  • the resulting polsiloxane which bears pendant diaminotriazine group is used in a process for treating fibrous materials.
  • US5712391 discloses telechelic polyorganosiloxanes bearing 4,6- bis(ethylamino)-s-triazine on both ends obtained by the reaction between“a, co- diaminosilicone” and 2-chloro-4,6-bis(ethylamino)-s-triazine.
  • the resulting compound is highly viscous and paste-like. An increase in viscosity is observed when the telechelic polyorganosiloxanes are mixed with“dimethylpolysiloxane”.
  • JP2005194378 describes an amino resin obtained from the reaction between (4, 6-diamino- 1, 3, 5-triazin-2yl)-benzoic acid and a silicone compound having at least one epoxy group.
  • the authors further disclose a composition comprising the amino resin, which can be cured to improve scratch resistance when used for coating application. The curing process is not reversible and the resulting material is thermoset and not thermoplastic.
  • thermoplastic composition comprising a polysiloxane backbone comprising Id- bond donor and H-bond acceptor groups not capable of self-association and another polymer bearing complementary H-bond donor and H-bond acceptor groups capable of giving supramolecular association when mixed with said polysiloxane.
  • thermoplastic composition comprising a polysiloxane backbone comprising H-bond donor and H-bond acceptor groups capable of giving reversible hydrogen bonding when mixed with a polymer backbone bearing complementary H-bond donor and H-bond acceptor groups to give a thermoplastic material having a large range of temperature of use.
  • thermoplastic composition comprising a polysiloxane backbone comprising H-bond donor and H-bond acceptor groups and another polymer bearing complementary H-bond donor and H-bond acceptor groups which gives a thermoplastic material having a range of temperature of use that can be tune easily.There is a need for such material having high thermal stability. There is a need for such material that is inherently self-healing material.
  • thermoplastic composition a thermoplastic composition
  • polysiloxane (Pl) chosen from polysiloxanes corresponding to formula (A) and polysiloxanes corresponding to formula (B), with formulae (A) and (B) as represented hereinafter :
  • n is an integer ranging from 5 to 2000 and
  • n/m is ranging from 500 to 2
  • polymer (P2) being a polymer functionalized with at least two isocyanuric or barbituric acid moieties corresponding to formula (D):
  • R is H or a -Cg alkyl group
  • Each Ri is independently selected from Ci-C 2 o hydrocarbyl groups.
  • each Ri is independently selected from Ci-C 2 o hydrocarbyl groups optionally substituted by a perfluoroalkyl group.
  • hydrocarbyl group is meant univalent group comprising only carbon and hydrogen atoms formed by removing a hydrogen atom from a hydrocarbon.
  • the hydrocarbyl group can be saturated or unsaturated, linear, branched or cyclic. When the hydrocarbyl group is cyclic it may be an aryl group formed by removing a hydrogen atom from an aromatic hydrocarbon i.e.
  • perfluoroalkyl group any alkyl group in which each H atom is replaced by F atom.
  • Hydrocarbyl group Ri is advantageously an alkyl or an aryl group.
  • suitable alkyl group may be chosen among the list consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, cyclohexyl, heptyl, n-octyl, dodecyl, tetradecyl, hexadecyl and octadecyl groups.
  • Suitable aryl groups may be optionally substituted phenyl group. Good results were obtained with Ri being phenyl group.
  • Ri is an alkyl group and more preferably a methyl group.
  • Si is generally nil or a C 1 -C 40 hydrocarbylene group optionally interrupted by one or more heteroatoms or heteroatom-containing groups.
  • hydrocarbylene group is meant divalent group comprising only carbon and hydrogen atoms formed by removing two hydrogen atoms from a hydrocarbon, the free valencies of which are not involved in a double bond.
  • the hydrocarbylene group can be saturated or unsaturated, linear, branched or cyclic. When the hydrocarbylene group is cyclic it may be an aryl group formed by removing two hydrogen atoms from an aromatic ring i.e.
  • aromatic ring encompasses also polycyclic aromatic compounds.
  • the rings can be fused or they can be linked by C-C linkage or by a spiro linkage.
  • 5 1 is preferably nil or a C1-C40 hydrocarbylene group, more preferably Si is nil or -(CH 2 ) q - with q ranging from 1 to 12, even more preferably Si is nil or -(CH 2 ) - and most preferably S 3 is -(CH 2 ) 3 -.
  • 5 2 is preferably nil or -(CH 2 ) q - with q ranging from 1 to 12, more preferably S 2 is nil or -(CH 2 ) - and even more preferably S 2 is nil.
  • R 2 is preferably H or a Ci-C 2 o hydrocarbyl group.
  • R 2 is preferably an acetyl moiety -CO-CH 3 . Good results were obtained with R 2 equal to H.
  • R 2 is H, W is -NH-, Si is -(CH 2 ) 3 - and S 2 is nil while Ri is as previously defined. In some still preferred embodiments, R 2 is H, W is -NH-, Si is -(CH 2 ) 3 - and S 2 is nil while Ri is -CH 3 .
  • polysiloxane (Pl) may be the polysiloxane (Pl)
  • PDMS polydimethylsiloxane
  • the polysiloxane (Pl) according to the invention is a telechelic PDMS corresponding to formula (Ai) the synthesis of which is described later in the experimental part.
  • n represents an average number of repeating units that can be determined by NMR spectroscopy by a method well known by the skilled person and that will be described in the experimental part.
  • n is an integer at least equal to 5, preferably at least equal to 7, more preferably at least equal to 10 and even more preferably at least equal to 12.
  • n is an integer at most equal to 4000, preferably at most equal to 2000, more preferably at most equal to 1000 and even more preferably at most equal to 200.
  • n is ranging from 5 to 4000.
  • n is ranging from 7 to 2000, more preferably from 10 to 1000 and even more preferably from 12 to 200.
  • m represents an average number of repeating units that can be determined by NMR spectroscopy.
  • n/m is ranging from 500 to 2, preferably from 100 to 4 and more preferably from 50 to 6.
  • the polysiloxane (Pl) bearing diaminotriazine moieties is capable of giving supramolecular association via H-bond interactions when mixed with polymer (P2) bearing complementary cyanuric or barbituric acid.
  • the composition comprising such polymers generally results in a thermally reversible supramolecular network and in a material exhibiting thermoplastic behavior in a temperature range generally reaching temperature well above room temperature. Accordingly, the composition generally gives a solid material at room temperature that can be soften by heating and even liquefied when the temperature reached is enough to break all the intermolecular H-bonds responsible for supramolecular association.
  • Functionalized polysiloxane (Pl) also exhibit a high thermal stability and do not degrade up to 220°C.
  • the polymer (P2) has a glass transition temperature, measured by differential scanning calorimetry, which is generally lower than 0°C. In some embodiments, the glass transition of polymer (P2) is lower than -50 °C. In some other embodiments the glass transition of polymer (P2) is lower than -100 °C.
  • the polymer (P2) functionalized with at least two isocyanuric or barbituric acid moieties is generally selected from the list of functionalized polymers consisting of functionalized Poly(vinylidene chloride) (PVDC), Poly(vinylidene fluoride) (PVDF), Polychloroprene (Neoprene®), Poly(2-ethylhexyl acrylate), Poly(2,2,3,3-tetrafluoropropyl acrylate), Poly(4- cyanobutyl acrylate), Poly(butyl acrylate), Poly(dodecyl acrylate), Poly(ethyl acrylate), Poly(hexyl acrylate), Poly(isobutylyl acrylate), Poly(isopropyl acrylate), Poly(nonyl acrylate), Poly(propyl acrylate), Poly(sec -butyl acrylate), Poly(dodecyl acrylate), Poly(l
  • Polymer (P2) is a polymer functionalized with at least two isocyanuric or barbituric acid moieties corresponding to formula (D):
  • R is H or a Ci-C 8 alkyl group
  • R is preferably H or a Ci-C 2 o
  • R is advantageously an alkyl group.
  • suitable alkyl group may be chosen among the list consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, cyclohexyl, heptyl, n-octyl. Good results were obtained with R equals to H.
  • the polymer (P2) is chosen from polysiloxanes corresponding to formula (E) and polysiloxanes corresponding to formula (F), with formulae (E) and (F) as represented hereinafter :
  • each R 4 is independently selected from Ci-C 2 o hydrocarbyl groups optionally substituted by a perfluoroalkyl group, and
  • S 3 and S 4 which may be the same or different are nil or a C1-C40 hydrocarbylene groups optionally interrupted by one or more heteroatoms or heteroatom-containing groups chosen from the list consisting of -O-, -S-, -
  • Y is a divalent group selected from the list consisting of -CH 2 -CH 2 -, -
  • n’ is an integer ranging from 5 to 4000
  • n’/m’ is ranging from 500 to 2
  • Q 2 is an isocyanuric or a barbituric acid moiety corresponding to formula (D): wherein
  • Each R 4 is independently selected from Ci-C 2 o hydrocarbyl groups. In some embodiments, each R 4 is independently selected from Ci-C 2 o hydrocarbyl groups optionally substituted by a perfluoroalkyl group.
  • hydrocarbyl group is meant univalent group comprising only carbon and hydrogen atoms formed by removing a hydrogen atom from a hydrocarbon.
  • the hydrocarbyl group can be saturated or unsaturated, linear, branched or cyclic. When the hydrocarbyl group is cyclic it may be an aryl group formed by removing a hydrogen atom from an aromatic hydrocarbon i.e. from a cyclic conjugated unsaturated hydrocarbon ring having a number of delocalized p electrons following the Huckel rule.
  • perfluoroalkyl group any alkyl group in which each H atom is replaced by F atom.
  • Hydrocarbyl group R 4 is advantageously an alkyl or an aryl group. Without being exhaustive suitable alkyl group may be chosen among the list consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, cyclohexyl, heptyl, n-octyl, dodecyl, tetradecyl, hexadecyl and octadecyl groups. Suitable aryl groups may be optionally substituted phenyl group. Good results were obtained with R 4 being phenyl group.
  • R 4 is an alkyl group and more preferably a methyl group.
  • R 3 is preferably H or a C1-C20
  • R 3 is preferably an acetyl moiety -CO-CH 3 .
  • R 3 is advantageously an alkyl group.
  • suitable alkyl group may be chosen among the list consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, hexyl, cyclohexyl, heptyl, n-octyl. Good results were obtained with R 3 equals to H.
  • 5 3 is preferably a C1-C40 hydrocarbylene group, more preferably S3 is -(CH 2 ) q - with q ranging from 1 to 12 and even more preferably S3 is -(CH 2 ) 3 -. In some other preferred embodiments S3 is nil.
  • S4 is preferably a C1-C40 hydrocarbylene group, more preferably S4 is -(CH 2 )q- with q ranging from 1 to 12 and even more preferably S4 is -(CH 2 )-.
  • S3 is nil and S4 is -CH 2 -.
  • S3 is -(CH 2 ) 3 - and S4 is -CH 2 -.
  • R 3 is H
  • Y is -CH 2 -CH 2 -
  • S3 is nil
  • S4 is -CH 2 - while R 4 is as previously defined.
  • R 3 is H
  • Y is -CH 2 -CH 2 -
  • S3 is nil
  • S4 is -CH 2 - while R 4 is -CH 3
  • R 3 is H
  • Y is - S-CH 2 -CH 2 -
  • S 3 is -(CH 2 ) -
  • S 4 is -CH 2 - while R 4 is as previously defined.
  • R is H
  • Y is - S-CH 2 -CH 2 -
  • S 3 is -(CH 2 ) -
  • S 4 is -CH 2 - while R 4 is -CH .
  • R 3 is H
  • S 3 is -(CH 2 ) 3 -
  • S 4 is -CH 2 - while R 4 is as previously defined.
  • R is H
  • S 3 is -(CH 2 ) 3 -
  • S 4 is -CH 2 - while R 4 is -CH .
  • R is H
  • Y is -CH 2 -CH 2 -
  • S 3 is nil
  • S 4 is - C 6 H 4 - while R 4 is -CH
  • R 3 is H
  • Y is -*S-CH 2 -CH 2 -
  • S 3 is -(CH 2 ) -
  • S 4 is -C 6 H 4 - while R 4 is -CH .
  • R 3 is H
  • S 3 is -(CH 2 ) 3 -
  • S 4 is -C 6 H 4 - while R 4 is -CH 3 .
  • the polysiloxane (P2) suitable for the composition according to the invention is a telechelic PDMS corresponding to formula (Ei), (E’i), (E”i), (E 2 ), (E’ 2 ), (E” 2 ), (E 3 ), (E’ 3 ) or (E” 3 ). More preferably, the polysiloxane (P2) suitable for the composition according to the invention is a telechelic PDMS corresponding to formula (Ei), (E’i), (E”i), (E 2 ), (E’ 2 ), (E” 2 ), (E 3 ), (E’ 3 ) or (E” 3 ). More preferably, the polysiloxane (P2) suitable for the composition according to the invention is a telechelic PDMS
  • the polysiloxane (P2) suitable for the composition according to the invention is a telechelic PDMS corresponding to formula (E 3 ).
  • n represents an average number of repeating units that can be determined by NMR spectroscopy by a method well known by the skilled person and that will be described in the experimental part.
  • n’ is an integer at least equal to 5, preferably at least equal to 7, more preferably at least equal to 10 and even more preferably at least equal to 12.
  • n’ is an integer at most equal to 4000, preferably at most equal to 2000, more preferably at most equal to 1000 and even more preferably at most equal to 200.
  • n’ is ranging from 5 to 4000.
  • n is ranging from 7 to 2000, more preferably from 10 to 1000 and even more preferably from 12 to 200.
  • the polysiloxanes (Ei), (E’ I ), (E”i), (Fi) and (F’i) can be obtained by hydro silylation reaction involving Si-H groups, carbon-carbon double bond and for example platinum based catalyst as represented below for the synthesis of (Ei):
  • the polysiloxanes (E 2 ), (E’ 2 ), (E” 2 ), (F 2 ) and (F’ 2 ) can be obtained by thiol-ene addition involving a free radical initiator as represented below for the synthesis
  • the polysiloxanes (E 3 ), (E’ 3 ), (E”), (F ) and (F’ ) can be obtained by condensation reaction of amine with carboxylic acid involving for example carbonyldiimidazole (CDI) as activating agent as represented below for the synthesis of (E ): O
  • the polymer (P2) is chosen from polyalkylene oxide-based polymers functionalized at both ends with an isocyanuric acid moiety and/or a barbituric acid moiety.
  • the functionalized polyalkylene oxide -based polymers have generally a number- average molecular weight (Mn) from 100 to 35000 g/mol, more preferably from 300 to 25000 g/mol.
  • polyalkylene oxide -based polymer for the composition according to the invention may, for instance, include a polymer having a main chain including a repeating unit represented by a general formula : -(M’-0) n’ - wherein M’ represents an alkylene group having 1 to 14 carbon atoms, and n’ is the number of repeating units and is a positive integer n' may be comprised for instance between 2 and 800, preferably from 4 to 600, more preferably from 6 to 400.
  • the main chain backbone of the polyalkylene oxide-based polymer may be composed of only one type of repeating unit or two or more types of repeating units.
  • polyethylene oxide “PEO”,“EO”,“polyethylene glycol” and“PEG” are used interchangeably and refer to synthetic polymers of ethylene oxide
  • polypropylene oxide “PPO”, “PO”, “polypropylene glycol” and “PPG” are used interchangeably and refer to synthetic polymers of propylene oxide.
  • Examples of the main chain backbone of the polyalkylene oxide -basded polymer include polyethylene oxides, polypropylene oxides, polytetramethylene oxides (i.e polybutylene oxides), polyethylene oxide -polypropylene oxide copolymers, and polypropylene oxide-polybutylene oxide copolymers, or block copolymers of such units. Of these, polypropylene oxides are preferred.
  • the polyalkylene oxide polymer preferably a polymer of polyethylene oxide and/or polypropylene oxide, may refer to a polymer of varying molecular weights, and of various types, ranging from linear multi-block copolymers, side- chain grafted block copolymers, and hyper-branched block copolymers to star shaped block copolymers. Said polymers may also comprise end-modified and chain-extended polymers of various types.
  • Polyalkylene oxide -based polymers suitable for the invention may represent a homopolymer or a copolymer which can be obtained by polymerization of one or more linear, cyclic and/or branched, monounsaturated or polyunsaturated monomers.
  • Polymer may represent a homopolymer or a copolymer which can be obtained by ring-opening polymerization of epoxides, lactones or lactams.
  • the polyalkylene oxide -based polymer capable of forming all or part of the polymer backbone suitable for the composition according to the invention, is of formula PO, in which PO represents a homopolymer or a copolymer which can be obtained by polymerization of one or more linear, cyclic and/or branched, polyunsaturated (preferably diunsaturated), C 2 -Cio, preferably C 2 -C 4 alkylene oxides.
  • PO preferably represents a homopolymer or a copolymer which can be obtained by polymerization of one or more diunsaturated, linear or branched C 2 - C 4 alkylene oxides. More preferably, PO represents a polymer chosen from a polyethylene oxides, a polypropylene oxides, polytetramethylene oxides
  • polybutylene oxides polyethylene oxide -polypropylene oxide copolymers, and polypropylene oxide -polybutylene oxide copolymers. Of these, polypropylene oxides are preferred.
  • Polyalkylene oxide -based polymers suitable for the invention may comprise for instance the units as follows:
  • x is from 1 to 500
  • y is from 0 to 800
  • z is from 1 to 500
  • the x, y and z values represent the average value of each respective repeat unit.
  • the values of x, y, and z are typically determined based on molecular weight. Examples of such polymers are for instance copolymers supplied by Solvay under trade name Antarox ® (such as Antarox ® L61, Antarox ® 17R2, etc.), by BASF under trade name Pluronic ® (such as Pluronic ® 25R4), by DOW under trade name Tergitol ® (such Tergitol ® L81), etc.
  • the polyalkylene oxide-based polymer suitable for the composition according to the invention may have an average molecular weight (M n ) from 100 to 35000 g/mol, more preferably from 300 to 25000 g/mol; measured by NMR
  • the isocyanuric acid moiety and/or a barbituric acid moiety may be attached to the polyalkylene oxide -based polymer directly with a single bond or via a linker, such as for instance a linear or branched C i -C 6 alkylene group, C 6 -Ci2 aryl, C 7 - C 12 alkaryl and C 7 -C 12 alkylaryl groups, ether function, carbonyl function, ester function, carboxyl function, amine function, amide function, an urea or carbamate functional group, and/or a combination thereof.
  • a linker such as for instance a linear or branched C i -C 6 alkylene group, C 6 -Ci2 aryl, C 7 - C 12 alkaryl and C 7 -C 12 alkylaryl groups, ether function, carbonyl function, ester function, carboxyl function, amine function, amide function, an urea or carbamate functional group, and/or a
  • the isocyanuric acid moiety may be preferably chosen in the group consisting of
  • a substituted or unsubstituted trioxotriazine -based group such as isocyanuric acid; notably the isocyanuric acid moiety as follows:
  • the barbituric acid moiety may be preferably chosen in the group consisting of (it being understood that all the tautomeric forms are included) a substituted or unsubstituted trioxypyrimidine group, such as barbituric acid (or malonylurea or 6-hydroxyuracil), notably the barbituric acid moiety as follows:
  • polyalkylene oxide polymer (P2) suitable for the composition according to the invention is a polypropylene oxide polymer functionalized at both ends with isocyanuric acid (ICA), such as ICA-PPO-ICA.
  • ICA isocyanuric acid
  • Polyalkylene oxide polymer (P2) suitable for the composition according to the invention may also be a polypropylene oxide -based polymer functionalized at both ends with barbituric acid (BA), such as BA-PPO-BA.
  • BA barbituric acid
  • the rate of chain-end functionalization of the functionalized polyalkylene oxide-based polymer (P2) of the invention ranges from 70 to 100%, more preferably from 85 to 100% and even more preferably from 95 to 100%; as calculated by 1H NMR comparison of signal corresponding to functionalized end-groups with the isocyanuric acid moiety and/or the barbituric acid moiety, and signal corresponding to non-functionnalized end-groups.
  • the functionalized polyalkylene oxide -based polymer (P2) suitable for the composition according to the invention may correspond to formula (G) as represented hereinafter:
  • A is an alkanediyl group, O is oxygen;
  • Z is a divalent group selected from the list consisting of - CH 2 -NH-,
  • triphenylmethyl or a benzylidene group
  • Q2 is an isocyanuric acid moiety or a barbituric acid moiety; and n’ is an integer ranging from 2 and 800, preferably from 4 to 600, more preferably from 6 to 400.
  • alkanediyl is meant divalent group obtained by removal of 2 hydrogen atoms to aliphatic hydrocarbon.
  • A is -CH 2 -CH 2 - group.
  • A is -CH 2 -CH(CH 3 )- group.
  • the functionalized polyalkylene oxide -based polymer (P2) suitable for the composition according to the invention is a polymer of formula (H) as follows:
  • n’ is comprised between 2 and 800, preferably from 4 to 600, more preferably from 6 to 400, m’ is comprised between 0 and 20, preferably from 1 to 12, X is an oxygen or a nitrogen atom.
  • the functionalized polyalkylene oxide -based polymer (P2) suitable for the composition according to the invention mays also be a polymer of formula (I) as follows:
  • n’ is comprised between 2 and 800, preferably from 4 to 600, more preferably from 6 to 400, m’ is comprised between 0 and 20, preferably from 1 to 12, G is comprised between 1 and 5, X is an oxygen or a nitrogen atom.
  • the functionalized polyalkylene oxide -based polymer (P2) suitable for the composition according to the invention mays also be a polymer of formula (J) as follows:
  • n’ is comprised between 2 and 800, preferably from 4 to 600, more preferably from 6 to 400.
  • the polyalkylene oxide-based polymer suitable for the composition according to the invention may be prepared by any process normally employed by a person skilled in the art, such as for instance by polymerization or reaction between a polyalkylene oxide-based polymer intermediate and a compound comprising an isocyanuric acid moiety and/or a barbituric acid moiety.
  • the polymer suitable for the composition according to the invention can be polymerized in a one-step process in the presence of a suitable catalyst in order to achieve the desired product.
  • the polyalkylene oxide-based polymer may be first polymerized or prepolymerized and subsequently co reacted with a compound comprising an isocyanuric acid moiety and/or a barbituric acid moiety, to obtain such product.
  • a polymer can be
  • the compound comprising an isocyanuric acid moiety and/or a barbituric acid moiety may comprise a suitable leaving group such as for example halogen or a reactive functionality like ester function, amide function, acyl chloride function or isocyanate function.
  • Compounds comprising an isocyanuric acid moiety and/or a barbituric acid moiety is preferably chosen in the group consisting of: benzyl 2-(2,4,6-trioxo- 1 ,3,5-triazinan- 1 -yl)acetate, benzyl 2-(2,4,6-trioxohexahydropyrimidin-5- yl)acetate, methyl 2-(2,4,6-trioxo-l,3,5-triazinan-l-yl)acetate, methyl 2-(2,4,6- trioxohexahydropyrimidin-5-yl)acetate, 1 -(2-chloroethyl)- 1 ,3,5-triazinane-2,4,6- trione, 5-(2-chloroethyl)pyrimidine-2,4,6(lH,3H,5H)-trione.
  • the molar ratio between the polyalkylene oxide-based polymer and the compound comprising an isocyanuric acid moiety and/or a barbituric acid moiety may be comprised between 1:1 and 1:4, preferably between 1:1.5 and 1:2.5.
  • Reaction between the polyalkylene oxide-based polymer and the compound comprising an isocyanuric acid moiety and/or a barbituric acid moiety may occur at a temperature from 20°C to 300°C, preferably from a temperature from 50°C to 230°C. Said reaction may be made in bulk conditions or also in presence of solvents, such as polar solvents, for instance tetrahydrofuran,
  • the reaction may be carried out with or without catalyst for instance.
  • the catalyst for the said reaction can be an acid catalyst, a base catalyst, a Lewis Acid catalyst, a titanium-based catalyst, an organotin catalyst or a catalyst commonly used for ester or amide synthesis.
  • the functionalized polymer (P2) of formula (G) as represented hereinafter:
  • A is an alkanediyl group
  • O is oxygen
  • - Y is a reactive group and capable of reacting with X so as to obtain a bridge Z between S5 and A;
  • Q 2 is an isocyanuric acid moiety or a barbituric acid moiety
  • n’ is an integer ranging from 2 and 800, preferably from 4 to 600, more preferably from 6 to 400;
  • Functionalized polyalkylene oxide -based polymers (P2) suitable for the composition according to the invention also have the faculty of forming three- dimensional networks with other functionalized polymer, notably with polysiloxanes (Pl) functionalized with diaminotriazine moieties.
  • Those three- dimensional networks may have anchoring points that are free to aggregate in the form of clusters, thus reinforcing the molecular cohesion of the constituted associations. The organization persists well beyond ambient temperature.
  • Functionalized polyalkylene oxide -based polymers also exhibit a high thermal stability and do not degrade up to 220°C.
  • the molar ratio between the at least one polysiloxane (Pl) and the at least one polymer (P2) is generally adjusted in such a way that the molar ratio between the diaminotriazine moieties and the cyanuric or barbituric acid moieties ranges from 0.25 to 4.0.
  • the molar ratio preferably ranges from 0.5 to 2.0, more preferably from 0.75 to 1.5, even more preferably from 0.9 to 1.1.
  • the molar ratio between the diaminotriazine moieties and the cyanuric or barbituric acid moieties is substantially equal to 1.
  • composition according to the invention comprises, as sole polymers, at least one polymer (Pl) and at least one polymer (P2).
  • composition according to the invention consists of at least one polymer (Pl) and at least one polymer (P2).
  • the composition according to the invention consists of at least one polysiloxane (Pl) corresponding to formula (A) and of at least one polymer (P2) corresponding to formula (E).
  • the composition consists of telechelic polysiloxane (Pl) corresponding to formula (Ai) and of telechelic polysiloxane (P2) corresponding to formula (Ei) as represented hereinafter :
  • composition according to the invention consists of at least one polysiloxane (Pl) corresponding to formula (A) and of at least one polyalkylene oxide polymer (P2) corresponding to formulae (H), (I) or
  • composition consists of telechelic polysiloxane (Pl) corresponding to formula (A and of telechelic polyalkylene oxide (P2) corresponding to formula (J) as represented hereinafter :
  • thermoplastic composition according to the invention is generally substantially free of any liquid i.e. generally comprises an amount of liquid not exceeding 0.5 wt. % based on the total weight of the composition, or is even totally free of any liquid.
  • thermoplastic composition according to the invention may comprise at least one other ingredient; for example, it may comprise a stabilizer, a filler, a plasticizer or a processing aid.
  • a thermoplastic composition composed essentially of, i.e. comprising an amount of other ingredient not exceeding 0.5 wt. % based on the total weight of the composition , or even composed of the polysiloxane (Pl) and of the polymer (P2).
  • compositions according to the invention may be assessed with regard to their rheological properties as will be described in experimental part.
  • the polysiloxane (Pl) bearing diaminotriazine moieties is capable of giving supramolecular association via H-bond interactions when mixed with polymer (P2) bearing complementary cyanuric or barbituric acid.
  • the composition comprising such polymers generally results in a thermally reversible supramolecular network and in a material exhibiting thermoplastic behavior in a temperature range generally reaching temperature well above room temperature. Accordingly, the composition generally gives a solid material at room temperature that can be soften by heating and even liquefied when the temperature reached is enough to break all the intermolecular H-bonds responsible for supramolecular association.
  • the different physical states of the compositions can be characterized by rheological measurements.
  • the dissociation temperature of the supramolecular network can generally be associated to the temperature of the cross-over point (T C- o) between the curve representing the storage modulus G’ vs temperature and the curve representing the loss modulus G’’ vs temperature.
  • the cross-over point may be determined by rheological measurement, using a RDA III instrument with TA orchestrator software, equipped with a parallel plates geometry (diameter 8 mm or 25 mm).
  • the linear domain can be firstly determined, and a temperature sweep at 10 rad/s between Tmin and Tmax at 2°C/min can be acquired.
  • Cross-Over point can be measured on the Tsweep curve at the temperature where moduli G’ and G” cross.
  • the temperature of the cross-over point (T C- o) can surprisingly be tuned by changing the nature of the polymer bearing the isocyanuric or barbituric acid moieties. This is advantageous when compared to a method which would consist in replacing isocyanuric or barbituric acid moieties (instead of replacing the polymer) by other H bond donor/acceptor moieties which are generally very expensive functional groups.
  • the crosslink density of the supramolecular network is generally related to the ratio of the number of diaminotriazine containing repetitive units with the number of siloxane repetitive units or to the ratio of diaminotriazine containing end groups with the number of siloxane repetitive units.
  • the material may have different mechanical and rheological properties.
  • the material may be a soft elastomeric network when crosslink density is low or a hard and brittle network when crosslink density is high.
  • the broadness of rubbery plateau is very large and can surprisingly be tuned by changing the nature of the polymer bearing the isocyanuric or barbituric acid moieties.
  • thermoplastic composition according to the invention generally comprising the steps of:
  • Li and L 2 which may be the same or different are liquids selected from the list consisting of water, methanol, ethanol, n-propanol, isopropanol, butanol, acetone, methylethylketone, carbon tetrachloride, chloroform, methylene chloride, ethylacetate, diethylether, tetrahydrofuran, benzene, toluene, xylene and of mixtures thereof.
  • Li and L 2 are mixtures of liquids consisting of at least one liquid, selected from the list consisting of acetone,
  • methylethylketone carbon tetrachloride, chloroform, methylene chloride, ethylacetate, diethylether, tetrahydrofuran, benzene, toluene and xylene and at least one liquid selected from the list consisting of water, methanol, ethanol, n- propanol, isopropanol and butanol.
  • Li and L 2 are mixtures of liquids consisting of at least one liquid selected from the list consisting of methylethylketone, chloroform, methylene chloride, ethylacetate, diethylether, tetrahydrofuran and toluene and at least one liquid selected from the list consisting of water, methanol and ethanol.
  • Li and L 2 are mixtures of liquids consisting of at least one liquid selected from the list consisting of chloroform, methylene chloride and tetrahydrofuran and at least one liquid selected from the list consisting of water, methanol and ethanol.
  • the mixtures of liquids Li and L 2 consisting of chloroform and methanol suitable for preparing the thermoplastic composition according to the invention generally comprise at least 1 wt.%, preferably at least 5 wt.% and more preferably at least 8 wt.% of methanol. Besides, the mixtures generally comprise at most 30 wt.%, preferably at most 20 wt.% and more preferably at most 15 wt.% of methanol.
  • the mixtures Li and L 2 suitable for preparing the thermoplastic composition according to the invention generally comprise at least 70 wt.%, preferably at least 80 wt.% and more preferably at least 85 wt.% of chloroform. Besides, the mixtures generally comprise at most 99 wt.%, preferably at most 95 wt.% and more preferably at most 90 wt.% of chloroform.
  • Li and L 2 are liquids consisting of one liquid, selected from the list consisting of acetone, methylethylketone, carbon tetrachloride, chloroform, methylene chloride, ethylacetate, diethylether, tetrahydrofuran, benzene, toluene and xylene.
  • the mixture (Ml) generally comprises at least 5 g.l 1 of polysiloxane (Pl), preferably at least 10 g.l 1 and more preferably at least 50 g.l 1 .
  • the mixture (Ml) generally comprises at most 600 g.l 1 of polysiloxane (Pl), preferably at most 400 g.l 1 , more preferably at most 300 g.l 1 and even more preferably at most 260 g.l 1 .
  • the polysiloxane (Pl) is partially soluble in the liquid Li of the mixture (Ml).
  • the polysiloxane (Pl) is completely soluble in the liquid Li.
  • the mixture (Ml) according to the invention may comprise at least one other ingredient; for example, it may comprise a stabilizer, a filler, a plasticizer or a processing aid. Good results can be obtained with mixture (Ml) composed essentially of (i.e. comprising an amount of other ingredient not exceeding 0.5 wt. % based on the total weight of the mixture), or even composed of the polysiloxane (Pl) and of the liquid Li.
  • the mixture (M2) generally comprises at least 5 g.l 1 of polymer (P2), preferably at least 10 g.l 1 and more preferably at least 50 g.l 1 .
  • the mixture (M2) generally comprises at most 600 g.l 1 of polymer (P2), preferably at most 400 g.l 1 , more preferably at most 300 g.l 1 and even more preferably at most 260 g.l 1 .
  • the polymer (P2) is partially soluble in the liquid L 2 of the mixture (M2).
  • the polymer (P2) is completely soluble in the liquid L 2 .
  • the mixture (M2) according to the invention may comprise at least one other ingredient; for example, it may comprise a stabilizer, a filler, a plasticizer or a processing aid.
  • Good results can be obtained with mixture (M2) composed essentially of (i.e. comprising an amount of other ingredient not exceeding 0.5 wt. % based on the total weight of the mixture), or even composed of the polymer (P2) and of the liquid L 2 .
  • the mixture (M3) is obtained by stirring mixture (Ml) with mixture (M2) at a temperature generally of at least 10 °C, preferably of at least 15 °C and more preferably of at least 20 °C.
  • the mixture (M3) is obtained by stirring mixture (Ml) with mixture (M2) at a temperature generally of at most 50 °C, preferably of at most 40 °C and more preferably of at most 30 °C.
  • Stirring of (Ml) with (M2) is performed for a duration generally of at least 0.5 minute, preferably of at least 1 minutes, more preferably of at least 2 minutes and even more preferably of at least 5 minutes.
  • stirring of (Ml) with (M2) is performed for a duration generally of at most 120 minutes, preferably of at most 60 minutes, more preferably of at most 45 minutes and even more preferably of at most 30 minutes. Good results were obtained when stirring (Ml) with (M2) during 30 minutes.
  • the mixture (M3) can be obtained by stirring of mixture (Ml) with mixture (M2) in a vessel equipped with mechanical stirring equipment.
  • this mechanical stirring is accompanied by further sonication.
  • the polysiloxane (Pl) and the polymer (P2) are partially soluble in the liquid comprising Li and L 2 of the mixture (M3).
  • the polysiloxane (Pl) and the polymer (P2) are completely soluble in the liquid comprising Li and L 2 of the mixture (M3).
  • Removing the liquids Li and L 2 from the mixture (M3) is generally obtained by distillation. Generally Li and L 2 are removed by heating the mixture (M3), preferably under reduced pressure.
  • thermoplastic composition according to the invention generally comprising the steps of:
  • thermoplastic composition as a solid
  • T is ranging from (T C- o - 50°C) to (T C- o + 50°C) with T C- o the temperature of the cross-over point of the composition determined by rheological measurements and Tgl is the glass transition temperature of the polysiloxane (Pl) measured by differential scanning calorimetry (DSC).
  • the mixture (M) can be obtained in any vessel or apparatus equipped with mechanical stirring and heating functionalities.
  • the mixture (M) can be obtained in a twin screw extruder and the desired composition can be recovered in solid form after cooling and, optionally, after being granulated by a process well known by the skilled person.
  • Tgl is the glass transition temperature of the polysiloxane (Pl) measured by differential scanning calorimetry (DSC) by a procedure well-known by the skilled person.
  • thermoplastic composition as previously described and as previously prepared.
  • thermoplastic composition as previously described and as previously prepared in sealing, in gaskets or in damping elements.
  • thermoplastic composition as previously described for preventing or reducing ice formation on the coating according to the present invention.
  • thermoplastic composition as previously described for causing self-healing of the coating according to the invention after the coating has been damaged.
  • Telechelic amino-terminated polydimethylsiloxanes were supplied by Gelest (references DMS A-12 and DMS A-15). According to the provider, the molecular weight of DMS A- 15 was 3000 g.mol 1 and the molecular weight of DMS A- 12 was 1000 g.mol 1 .
  • the other reagents were purchased from Sigma- Aldrich, Acros or Alfa-Aesar. All chemicals were used as received without any further purification.
  • the NMR spectra were recorded on a Briiker AV 400 MHz at 300 K.
  • the solvents used were CDCl 3 or DMSO-d 6 .
  • the chemical shifts (d) are expressed in ppm, using the signal of residual solvent as an intern reference.
  • the signals multiplicity is indicated as follows: s (singulet), bs (broad singulet), d (doublet), m (multiplet).
  • TGA Thermal Gravimetric Analysis
  • TGA experiments were performed under nitrogen on a Perkin Elmer TGA 4000 instrument to determine the thermal stability of the materials. 20-30 mg of product were analyzed in a ceramic crucible from 40°C to 800°C at l0°C/min. This first thermal analysis allows to determine the maximum temperature (T max ) for the rheological experiments (working temperature is selected 10 °C below the temperature at which the sample exhibits a weight loss of 1 wt. %).
  • DSC experiments were performed under nitrogen on a Perkin Elmer DSC 8000 instrument in order to determine the melting/crystallization temperatures (Tm, Tc) and the glass transition temperature (Tg) of the materials. 5-8 mg of product were analyzed in an aluminum crucible. Three heating/cooling cycles were performed between -60°C and Tmax (determined by TGA). The first cycle at l0°C/min allows erasing the thermal history of the sample. The second and third cycles were performed at l0°C/min and 40°C/min, respectively.
  • the rheological properties were investigated on ARES G2 instrument, equipped with parallel plates geometry (diameter 25 mm or 50 mm). The linear domain was firstly determined, and a temperature sweep at 10 rad/s between 25 °C and T max at 2°C/min was acquired.
  • Thymine- 1- acetic acid was prepared according to the reaction scheme below:
  • the polymer was extracted with 3 x 150 ml of dichloromethane and the combined organic phase was washed with 5 % aqueous LiCl solution, and finally with water. The organic phase was dried over anhydrous sodium sulfate before being filtered and concentrated under vacuum. Finally, the resulting solid compound was dried under high vacuum to give the desired material in 85 % yield.
  • DAT diaminopyrazine moiety
  • the supramolecular materials were prepared by solution casting using a methanol/chloroform mixture as the solvent.
  • a blend comprising DAT-PDMS3000-DAT and THY -PDMS3000-THY in 1/1 molar ratio was prepared in a similar way.
  • a blend comprising DAT-PDMS3000-DAT and ICA-PP02000-ICA in 1/1 molar ratio was prepared as follows:
  • non supramolecular reference high molecular weight PDMS (140000 g/mol) from Wacker (AK 1000000 silicon oil). Rheology data taken from: Kokuti et al. Inter. J. Eng. 2011, 2, 177.
  • the cross-over point (°C) was determined on the temperature sweep curve at the temperature where the curve representing modulus G’ and the curve representing modulus G” cross. It denotes the temperature at which the physical crosslinkers (which assume the cohesion of the system) dissociate.
  • °C Broadeness of Rubbery Plateau
  • the composition of DAT-PDMS-DAT with ICA- PDMS-ICA of example 1 demonstrates a high cohesive reinforcement due to hydrogen bonding up to temperatures surprisingly as high as 195 °C.
  • the reversible nature of the hydrogen bondings responsible for these performances makes these materials advantageously reprocesssable like thermoplastic materials.
  • composition of DAT-PDMS-DAT with ICA-PPO-ICA of example 2 demonstrates also a high cohesive reinforcement due to hydrogen bonding but up to a temperature surprisingly of 80 °C which is still higher than for comparative example 2.
  • the inventors have demonstrated thereby that the range of temperature of use, illustrated by the cross over temperature, of a composition comprising DAT-PDMS-DAT and at least one polymer having a glass transition temperature below 0 °C and comprising at least 2 cyanuric acid moieties can surprisingly be tune by changing the nature of said polymer without severly altering mechanical properties.

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Abstract

La présente invention concerne une composition thermoplastique comprenant au moins un polysiloxane (Pl) portant des fractions de diaminotriazine et au moins un polymère (P2) ayant une température de transition vitreuse, mesurée par calorimétrie différentielle à balayage, inférieure à 0 °C, fonctionnalisée avec au moins deux fractions d'acide isocyanurique ou barbiturique.
PCT/EP2019/067251 2018-06-29 2019-06-27 Composition thermoplastique comprenant un polysiloxane portant des fractions de diaminotriazine WO2020002556A1 (fr)

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