WO2019243621A1 - Composition comprenant un polymère à base d'oxyde de polyalkylène - Google Patents

Composition comprenant un polymère à base d'oxyde de polyalkylène Download PDF

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WO2019243621A1
WO2019243621A1 PCT/EP2019/066558 EP2019066558W WO2019243621A1 WO 2019243621 A1 WO2019243621 A1 WO 2019243621A1 EP 2019066558 W EP2019066558 W EP 2019066558W WO 2019243621 A1 WO2019243621 A1 WO 2019243621A1
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polyalkylene oxide
based polymer
group
acid moiety
polymer
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PCT/EP2019/066558
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English (en)
Inventor
Grégory LANDELLE
Rabih AL RAHAL AL ORABI
Franck Touraud
Caroll Vergelati
Soumyadeb Ghosh
Hemang DARJI
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Rhodia Operations
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Priority claimed from EP18306120.9A external-priority patent/EP3611213A1/fr
Application filed by Rhodia Operations filed Critical Rhodia Operations
Publication of WO2019243621A1 publication Critical patent/WO2019243621A1/fr

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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • composition comprising a polvalkylene oxide-based polymer
  • the present invention concerns a polyalkylene oxide-based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing 3 carbonyl functions.
  • the invention also concerns processes for producing said polymer and articles obtained thereof.
  • Supramolecular materials are formed by small chain-length polymers or molecules bonded together by physical bonds such as, for example, hydrogen bonds, ionic bonds, hydrophobic bonds, and more particularly hydrogen bonds also known as“H bridges” or“H bonds”.
  • An advantage of these supramolecular polymers is that these physical bonds are reversible, that is to say that they may easily break leading to the partial or complete depolymerization of said polymers under the influence of various factors such as temperature.
  • polymers of low glass-transition temperature (T g ) are used to obtain the molecular mobility required for formation of the supramolecular bond, as well as for effective contact between the surfaces to be joined for the healing process.
  • Supramolecular materials since made from flexible low-T g polymers, have very low stiffness and dimensional stability. Further, due to supramolecular bonds, which are intrinsically weaker than typical covalent bonds, the supramolecular materials are also mechanically weak.
  • Cortese et al., ./. Am. Chem. Soc., 2012, 134, 3671-3674 reports telechelic supramolecular polymers based on polypropylene oxide) (PPO), thymine (Thy) and diaminotriazine (DAT) having complementary interactions that can suppress mesoscopic order and thus lead to a counterintuitive change in material properties. It discloses supramolecular polymer with weakly self-complementary stickers (DAT), DAT-PPO-2000-DAT, which is a liquid.
  • the present invention thus concerns a polyalkylene oxide -based polymer functionalized at one or both ends with an isocyanuric acid moiety and/or a barbituric acid moiety, and having a number- average molecular weight (Mn) from 100 to 35000 g/mol, more preferably from 300 to 25000 g/mol.
  • Mn number- average molecular weight
  • the invention also concerns a composition
  • a composition comprising the functionalized polyalkylene oxide-based polymer of the invention and a polyalkylene oxide -based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine.
  • Functionalized polyalkylene oxide -based polymers of the invention also have the faculty of forming three-dimensional networks with other functionalized polyalkylene oxide-based polymer, notably with polyalkylene oxide-based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine.
  • 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 specific to the functionalized polyalkylene oxide-based polymers of the invention persist well beyond ambient temperature, since most dissociation temperatures of the physical crosslinking nodes that maintain their structure are evaluated between 35°C and 50°C. Even more remarkable, for some of the compositions studied, a three-dimensional order remains perennial up to l30°C.
  • Functionalized polyalkylene oxide-based polymers of the invention also exhibit a high thermal stability and do not degrade up to 220°C.
  • the invention also concerns compositions comprising at least the functionalized polyalkylene oxide -based polymer of the invention, and a phenol-carbonyl condensation product.
  • Such a composition notably exhibits a good level of mechanical properties, such as stiffness and tensile strength, and can be self-healed, recovering about the same level of mechanical properties; and even higher mechanical properties, such as modulus, when the healing process is performed at higher temperatures.
  • composition comprising at least:
  • a polyalkylene oxide-based polymer functionalized at one or both ends with an isocyanuric acid moiety and/or a barbituric acid moiety, and having a number-average molecular weight (Mn) from 100 to 35000 g/mol, more preferably from 300 to 25000 g/mol;
  • a polyalkylene oxide -based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine;
  • Such a composition notably exhibits a good level of mechanical properties, such as stiffness and tensile strength, and an inherent self-healing property. Healing occurs permitting to recover about the same level of mechanical properties, when the healing process is performed at higher temperatures.
  • the articles“a”,“an” and“the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
  • a temperature range of about l20°C to about l50°C should be interpreted to include not only the explicitly recited limits of about l20°C to about l50°C, but also to include sub-ranges, such as l25°C to l45°C, l30°C to l50°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 122.2°C, 140.6°C, and 141.3°C, for example.
  • hydrocarbon group refers to a group mainly consisting of carbon atoms and hydrogen atoms, which group may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic.
  • hydrocarbyl used in the description and the claims describes radicals which are based on hydrocarbons with the stated number of carbon atoms and which may be pure hydrocarbon radicals but may also have substituents.
  • Hydrocarbon groups of the present invention may be alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkylaryl groups, aryalkyl groups, heterocyclic groups, and/or alkylheterocyclic groups.
  • Hydrocarbon groups of the present invention may be alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkylaryl groups, aryalkyl groups, heterocyclic groups, and/or alkylheterocyclic groups.
  • Alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight- chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or “alicyclic” or “carbocyclic” groups), such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched-chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkyl- substituted alkyl groups, such as alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups.
  • straight- chain alkyl groups such as methyl,
  • aliphatic group includes organic moieties characterized by straight or branched-chains, typically having between 1 and 22 carbon atoms. In complex structures, the chains may be branched, bridged, or cross- linked. Aliphatic groups include alkyl groups, alkenyl groups, and alkynyl groups.
  • alkenyl or“alkenyl group” refers to an aliphatic hydrocarbon radical which can be straight or branched, containing at least one carbon-carbon double bond.
  • alkenyl groups include, but are not limited to, ethenyl, propenyl, n- butenyl, i-butenyl, 3-methylbut-2-enyl, n-pentenyl, heptenyl, octenyl, decenyl, and the like.
  • alkynyl refers to straight or branched chain hydrocarbon groups having at least one triple carbon to carbon bond, such as ethynyl.
  • aryl group includes unsaturated and aromatic cyclic hydrocarbons as well as unsaturated and aromatic heterocycles containing one or more rings.
  • Aryl groups may also be fused or bridged with alicyclic or heterocyclic rings that are not aromatic so as to form a polycycle, such as tetralin.
  • An "arylene” group is a divalent analog of an aryl group.
  • heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated. Additionally, heterocyclic groups, such as pyrrolyl, pyridyl, isoquinolyl, quinolyl, purinyl, and furyl, may have aromatic character, in which case they may be referred to as “heteroaryl” or “heteroaromatic” 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.
  • the hydrocarbylene group is cyclic it may be an aryl group formed by removing two hydrogen atoms from an aromatic hydrocarbon i.e. from a cyclic conjugated unsaturated hydrocarbon ring having a number of delocalized p electrons following the Huckel rule.
  • hydrocarbylene group When the hydrocarbylene group is interrupted by one or more heteroatoms or heteroatoms containing groups it can be interrupted by one or more ether linkage -0-, one or more thioether linkage -S-, one or more amide linkage -CO-NH- or one or more urea linkage -NH-CO-NH-.
  • 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.
  • the functionalized polyalkylene oxide -based polymer of the invention at one or both ends may, for instance, include a polymer having a main chain including a repeating unit represented by a general formula: -(R-0) n - ; wherein R 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.
  • polyalkylene oxide-based polymer examples 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 -based 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 of 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 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.
  • 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 of the invention may comprise for instance the units as follows: -EO x PO y EO z -, wherein x is from 1 to 500, y is from 0 to 800, z is from 1 to 500; -PO x EO y PO z -, wherein x is from 1 to 500, y is from 0 to 800, z is from 1 to 500; or
  • 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.
  • polymers examples include 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.
  • Antarox ® such as Antarox ® L61, Antarox ® 17R2, etc.
  • Pluronic ® such as Pluronic ® 25R4
  • Tergitol ® such Tergitol ® L81
  • the polyalkylene oxide-based polymer of 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 spectroscopy or by gel permeation chromatography.
  • M n average molecular weight
  • 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 Ci-C 6 alkylene group, C 6 -Ci2 aryl, C7-C12 alkaryl and C7-C12 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 Ci-C 6 alkylene group, C 6 -Ci2 aryl, C7-C12 alkaryl and C7-C12 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.
  • the isocyanuric 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 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-based polymer of the invention is a polypropylene oxide polymer functionalized at one or both ends with isocyanuric acid (ICA), such as ICA-PPO or ICA-PPO-ICA.
  • ICA isocyanuric acid
  • Polyalkylene oxide-based polymer of the invention may also be a polypropylene oxide polymer functionalized at one or both ends with barbituric acid (BA), such as BA-PPO or BA-PPO-BA.
  • BA barbituric acid
  • the rate of chain-end functionalization of the functionalized polyalkylene oxide-based polymer of the invention ranges from 70 to 100%, more preferably from 85 to 99%; 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 polymer of the invention may correspond to formula (A) as represented hereinafter:
  • A is an alkanediyl group, O is oxygen;
  • Qi 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.
  • the functionalized polyalkylene oxide-based polymer of the invention is a polymer of formula (B) 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 of the invention mays also be a polymer of formula (C) 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, 1 is comprised between 1 and 5, X is an oxygen or a nitrogen atom.
  • the functionalized polyalkylene oxide-based polymer of the invention mays also be a polymer of formula (D) 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 of 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 of 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 synthesized by either a solution or a bulk reaction process.
  • 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, 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-l,3,5-triazinan-l- yl)acetate, benzyl 2-(2,4,6-trioxohexahydropyrimidin-5-yl)acetate, methyl 2-(2,4,6- trioxo- 1 ,3,5-triazinan- 1 -yl)acetate, methyl 2-(2,4,6-trioxohexahydropyrimidin-5- yl)acetate, l-(2-chloroethyl)-l,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, dimethylformamide or dimethylsulfoxide.
  • Said 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.
  • 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 W between Si and A;
  • Qi 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;
  • the invention also concerns a composition comprising at least a functionalized polyalkylene oxide -based polymer of the invention.
  • Composition of the present invention may also comprise another polymer or a resin.
  • One or more additives may be added to said composition. They may be, for example, at least: an antioxidant, a plasticizer, a mineral filler, an organic filler, a pigment and/or a dye.
  • the fillers may be chosen in the group constituted by talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate; glass fibers, carbon fibers, synthetic polymeric fiber, aramid fiber, aluminium fiber, titanium fiber, magnesium fiber, boron carbide fibers, rock wool fiber, steel fiber, wollastonite and mixtures thereof.
  • additives can additionally be added during the processing to produce the composition of this invention.
  • Such additives may be for instance chosen in the group consisting of: diols, such as linear or branched Ci-C 2 o alkylene diols, diamines, such as linear or branched Ci-C 2 o alkylene diamines, diisocyanates, such as linear, branched or cyclic Ci-C 2 o alkylene diisocyanates, Ci-C 2 o amino alcohols, Ci-C 2 o triols, Ci-C 2 o triamines, Ci-C 2 o tri-isocyanates or Ci-C 2 o polyalcohols.
  • diols such as linear or branched Ci-C 2 o alkylene diols
  • diamines such as linear or branched Ci-C 2 o alkylene diamines
  • diisocyanates such as linear, branched or cyclic Ci-C 2 o alkylene diisocyanates,
  • composition may also comprises a polyalkylene oxide -based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine.
  • the nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine, 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 Ci-C 6 alkylene group, ether function, ester function, carboxylic function, amine function, amide function, an urea or carbamate functional group.
  • a linker such as for instance a linear or branched Ci-C 6 alkylene group, ether function, ester function, carboxylic function, amine function, amide function, an urea or carbamate functional group.
  • the nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine, may be preferably chosen in the group consisting of (it being understood that all the tautomeric forms are included):
  • a substituted or unsubstituted triazine-based group such as diaminotriazine and melamine
  • a substituted or unsubstituted pyrazine -based group such as aminopyrazine
  • a substituted or unsubstituted imidazolidine-based group such as imidazolidone, imidazolidine 2,4-dione (hydantoin);
  • a substituted or unsubstituted isocytosine-based group such as alkylisocytosine, and substituted ureido pyrimidinone.
  • the nitrogen-containing heterocyclic group is preferably a heteroaryl group, such as pyridine, diazine, triazine, tetrazine, imidazole, and pirazole.
  • the nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine, may have the general structure of formula (E) as follows:
  • the ring is a 6-membered aromatic ring wherein Ai, A 2 , A 3 , A 4 and A 5 are each independently carbon or nitrogen, with the proviso that at least 3 of A l A 2 , A 3 , A 4 and A 5 are carbon atoms, n is from 1 to 4, notably from 1 to 3, notably 1, 2 or 3, each Ri is independently alkyl, alkenyl, carboxyl, carboxyl ester, amino, hydroxyl, halo, haloalkyl, or heteroaryl, with the proviso that said nitrogen-containing heterocyclic group bears at least a primary amine and/or a secondary amine.
  • Polyalkylene oxide -based polymer may notably be connected to nitrogen-containing heterocyclic group by a carbon atom of said heterocyclic group, by an oxygen atom of said heterocyclic group or by a nitrogen atom of said heterocyclic group, via a linker or a single bond as previously expressed.
  • the nitrogen-containing heterocyclic group may bear at least one primary amine function wherein“primary amine” denotes a -NH 2 group.
  • the nitrogen-containing heterocyclic group may bear at least one secondary amine function wherein“secondary amine” denotes a -NHR group, wherein R is selected from the group consisting of Ci-C 6 alkyl, C 6 -Ci2 aryl, C7-C12 alkaryl and C7-C12 alkylaryl groups, wherein the alkyl groups may be linear, branched or cyclic.
  • nitrogen-containing heterocyclic group is substituted or unsubstituted triazine -based heterocyclic group. More preferably, nitrogen-containing heterocyclic group of the invention is derived from a 4,6-diaminotriazine (DAT).
  • DAT 4,6-diaminotriazine
  • the substituted or unsubstituted nitrogen-containing heterocyclic group of the invention may be H-bonding and may comprise at least two sites capable of H-donor capability and at least one site capable of H-acceptor capability (where these two sites are not be fully reacted).
  • the H-donor site may be a H-donor group well known by those skilled in the art. Such an H-donor group may comprise -NH2, -NH-, -OH or - SH groups.
  • the H-acceptor site may be a H-acceptor site well known by those skilled in the art. Such an H-acceptor site may comprise atoms like O, N or S.
  • functionalized polyalkylene oxide -based polymer is DAT-PPO or DATPPO-DAT.
  • the functionalized polyalkylene oxide based polymers may have a number- average molecular weight (M n ) of between 100 and 80000 g/mol, more preferably between 300 and 35000 g/mol, notably between 400 and 25000 g/mol.
  • M n number-average molecular weight
  • the number-average molecular weight (M n ) may be measured by NMR spectroscopy or by Gel Permeation Chromatography.
  • the functionalized polyalkylene oxide-based polymer may be a polymer of formula (F) as follows:
  • the functionalized polyalkylene oxide -based polymer may be a polymer of formula (G) as follows:
  • n is comprised between 2 and 1500, preferably from 4 to 625.
  • the functionalized polyalkylene oxide -based polymer may be a polymer of formula (H) as follows:
  • n is comprised between 2 and 1500, preferably from 4 to 625, m is comprised between 1 and 5, X is an oxygen or a nitrogen atom.
  • Composition of the invention may also comprise a phenol-carbonyl condensation product.
  • Phenol-carbonyl condensation products of the invention are preferably chosen from the group consisting of phenol-aldehyde condensation product and phenol-ketone condensation product.
  • Phenol-aldehyde or phenol-ketone condensation products are condensation products of phenolic compounds with aldehydes or ketones; in particular a condensation product of at least one phenolic compound with at least one aldehyde and/or one ketone. These condensation reactions are generally catalysed with an acid or a base.
  • the phenolic compounds may be chosen, alone or as a mixture, from phenol, cresol, xylenol, naphthol, alkylphenols, such as butylphenol, tert-butylphenol, isooctylphenol, nitrophenol, phenylphenol, resorcinol or bisphenol A; or any other substituted phenol.
  • aldehyde used most frequently is formaldehyde. However, others may be used, such as acetaldehyde, para-formaldehyde (polyoxymethylene), butyraldehyde, crotonaldehyde, glycoxal and furfural.
  • ketone it is possible to use acetone, methyl ethyl ketone or acetophenone.
  • the phenol-aldehyde condensation product is a condensation product of phenol and formaldehyde.
  • the phenol-carbonyl condensation product is a novolac resin or a resole resin.
  • the composition according to the invention may comprise one or more different types of novolac resin.
  • Novolacs are phenol-formaldehyde resins with a formaldehyde to phenol molar ratio of less than one.
  • the polymerization is brought to completion using acid-catalysis such as oxalic acid, hydrochloric acid or sulfonate acids.
  • the phenol units are mainly linked by methylene and/or ether groups.
  • Resole are base-catalysed phenol-formaldehyde resins made with a formaldehyde to phenol ratio of greater than one (usually around 1.5). Phenol, formaldehyde, water and catalyst are usually mixed in the desired amount, depending on the resin to be formed, and are then heated. The first part of the reaction, at around 70°C, forms a thick reddish-brown tacky material, which is rich in hydroxymethyl and benzylic ether groups.
  • Phenol-carbonyl condensation products are generally have a degree of condensation between 2 and 15.
  • the novolac resins preferably have a degree of condensation between 2 and 15.
  • Phenol-carbonyl condensation products may have an average molecular weight comprised between 500 and 10000 g/mol, preferably between 500 and 3000 g/mol. It may be measured by gel permeation chromatography (GPC) or by other techniques commonly used by person skilled in the art, as it is well described in Determination of Molecular Weight Distributions of Novolac Resins by Gel Permeation Chromatography, T.R. Dargaville et a , 1996.
  • the novolac resins used advantageously have an average molecular weight comprised between 500 and 3000 g/mol, preferably between 800 and 2000 g/mol.
  • Composition of the invention may notably comprise at least:
  • Composition of the invention may notably comprise at least:
  • a polyalkylene oxide- based polymer functionalized at one or both ends with an isocyanuric acid moiety and/or a barbituric acid moiety, and having a number- average molecular weight (Mn) from 100 to 35000 g/mol, more preferably from 300 to 25000 g/mol; and
  • Composition of the invention may notably comprise at least:
  • the molar ratio between the polyalkylene oxide-based polymer functionalized at one or both ends with an isocyanuric acid moiety and/or a barbituric acid moiety, and having a number- average molecular weight (Mn) from 100 to 35000 g/mol, more preferably from 300 to 25000 g/mol and the polyalkylene oxide- based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine may range from 1:0.25 to 1:4, preferably 1:1 to 1:2.
  • a composition according to the present invention may be obtained for instance by blending, notably with a mechanical blender followed by an extrusion process. It is also possible to blend the polymer of the invention with other polymers and/or additives in a solvent media via a solvent-casting technique, such as for instance in ethyl acetate, acetone, chloroform or dichloromethane.
  • a solvent-casting technique such as for instance in ethyl acetate, acetone, chloroform or dichloromethane.
  • the invention also relates to a process for preparing the composition of the invention comprising at least the steps of
  • the invention also relates to a process for preparing the composition of the invention comprising at least the steps of: - preparing under stirring and heating up to a temperature of 10 to 200°C a mixture comprising at least the polymer of the invention and at least an other polymer, such as polyalkylene oxide-based polymer functionalized at one or both ends with a nitrogen- containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine, and optionally at least an other additive such a phenol-carbonyl condensation product;
  • compositions of the present invention may have a glass transition temperature from -80 to -20°C, preferably from -60°C to -20°C, more preferably from -60°C to -30°C, notably from -50°C to -40°C.
  • the invention also concerns then a composition
  • a composition comprising at least 2 polyalkylene oxide-based polymers and having a glass transition temperature from -60 to -20°C.
  • Composition of the present invention may also have a Cross-Over point from 10 to 200°C, preferably from 20 to l50°C.
  • Cross-Over point denotes the temperature at which the physical crosslinkers (which assume the cohesion of the system) dissociate.
  • Cross-Over point may notably by rheological measurement, such as with a RDA III instrument with TA orchestrator software, equipped with a parallel plates geometry (diameter 8 mm or 25 mm). The linear domain was firstly determined, and a temperature sweep at 10 rad/s between Tmin and Tmax at 2°C/min was acquired. Finally, angular frequency sweep at different temperatures are performed allowing the construction of Time-Temperature-Superposition (TTS) mastercurves.
  • TTS Time-Temperature-Superposition
  • Compositions of the present invention may have an elongation at break from 0.5% to 700%. Elongation at break may be measured for instance by using mechanical UTM instrument, which determines the value as strain on the material at break from the change in position of the cross-head, during measurement of the stress-strain characteristics of the material.
  • the present invention also relates to an article or a part of an article comprising the functionalized polymer of the invention or a composition comprising at least the functionalized polymer of the invention.
  • Articles may be for instance, used as additives, coatings, adhesive compositions, sealing compositions, thickeners, composites, gelling agents and binders.
  • these articles are produced from a composition as described above by injection molding, by extrusion or by blow molding.
  • composition according to the invention may be for instance used for the following applications:
  • additives in the processing of thermoplastics to effect reversible crosslinking affecting as processing aid, toughening agent and/or for self-healing properties; additives in the formulation of rubber;
  • anti-corrosion additives in particular in protective coatings
  • additives for impact modification in polymers in particular in polyamides; as adhesive or as additive to adhesive formulations; and
  • composition according to the present invention is very useful in coating applications such as decorative, protective, thermos-reversible and self-healing coatings, adhesive compositions, sealing compositions, as thickener, gelling agents or binder, and in imaging or biomedical applications.
  • 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 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 are 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 l0°C below the temperature at which the sample exhibits a weight loss of l%wt)
  • DSC Differential scanning calorimetry
  • 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 are analyzed in an aluminium crucible. Three heating/cooling cycles are performed between -60°C and T max (determined by TGA). The first cycle at lO°C/min allows erasing the thermal history of the sample. The second and third cycles are performed at lO°C/min and 40°C/min, respectively.
  • the rheological properties were investigated on a RDA III instrument with TA orchestrator software, equipped with a parallel plates geometry (diameter 8 mm or 25 mm). The linear domain was firstly determined, and a temperature sweep at 10 rad/s between T mm and T max at 2°C/min was acquired. Finally, angular frequency sweep at different temperatures are performed allowing the construction of Time-Temperature- Superposition (TTS) mastercurves.
  • TTS Time-Temperature- Superposition
  • Thymine- 1 -acetic acid (110 mmol) was dissolved in DMF (250 mL).
  • NH 2 -PP02000- NH 2 (Jeffamine® D-2000, 50 mmol)
  • TBTU (0-(Benzotriazol-l-yl)-/V,/V,/V’,/V’- tetramethyluronium tetrafluoroborate, 125 mmol
  • triethylamine 400 mmol
  • the reaction was stirred at room temperature for 16 h and subsequently quenched with water (250 mL).
  • the reaction mixture was extracted with toluene (2 x 500 mL).
  • the combined organic extracts were washed with water (2 x 500 mL), concentrated under reduced pressure, and dried at 100 °C under vacuum leading to THY -PP02000-THY in 86% yield.
  • the blends of supramolecular materials were prepared following a solvent-casting procedure in chloroform or acetone.
  • preparation of Suprapolymer blend made of DAT-PP02000-DAT /ICA-PP02000-ICA in 1/1 molar ratio has been made as follows: to a 250 mL flask with a magnetic stirrer were added 5.0 g of DAT-PP02000- DAT (2.3 mmol) and 40 mL of chloroform (or acetone). The mixture was stirred at 25°C for 0.5 h. To this colorless mixture was added a solution of 5.28 g of ICA- PP02000-ICA (2.3 mmol) in 50 mL of chloroform (or acetone).
  • Modulus G°N (Pa) is measured on the TTS master curve. It corresponds to the value of G’ at the minimum of tand
  • Modulus G is also reported for the compositions at -20°C, 20°C and 80°C in Table 2 to denote the thermal stability of functionalized polyalkylene oxide-based polymers of the invention
  • composition A Experiment has been performed with Novolac of type Nowolak S (LERG S.A., Poland).
  • the Novolac resin powder (1 gm) was taken in an aluminium sheet and equal amount of ICA-PPO-ICA (1 gm) was added.
  • the components were mixed well at 25°C, using a spatula for 4 min forming a thick paste.
  • the mixture was then heated at l00°C with stirring and till the viscosity of the material reduces forming a flowable mass.
  • the yellow to brown coloured viscous liquid was poured into a mould and casted into a small bar of dimension about 40 mm x 10.0 mm x 2.5 mm.
  • Composition B Experiment has been performed with Novolac of type Nowolak S (LERG S.A., Tru). Equal amounts of D AT-PPO-D AT and ICA-PPO-ICA were mixed together at 25 °C using a spatula. The Novolac resin powder (1 gm) was taken in an aluminium sheet and an equal amount of the D AT-PPO-D AT - ICA-PPO-ICA mixture (total 1 gm) was added. The mixture was then heated to l40°C with stirring and till the viscosity of the material reduces forming a flowable mass.
  • the yellow to brown coloured viscous liquid was poured into small mould and casted into a small bar of dimension about 40 mm x 10.0 mm x 2.5 mm.
  • Tensile properties of the test samples were measured using UTM (Zwick Roell, UTM-030), by application of strain at the rate of 1 mm/min. During tensile test measurement, failure of some of the samples occurred from the centre or grip. This is specifically observed for the samples which either have no ductility or were healed at 20°C.
  • the samples which have ductility i.e to say DAT-PPO-DAT and 50% Novolac, DAT-PPO-DAT and 50% Novolac-After healing at 50°C, DAT-PPO-DAT and ICA-PPO-ICA and 50% Novolac, DAT-PPO-DAT and ICA-PPO-ICA and 50% Novolac-After healing at 60°C, the tensile test was performed at least up to 15% elongation point.
  • Ductile material elongation of at least 15%.
  • Tensile Strength the maximum value of the tensile stress
  • composition according to the invention with a sufficient level of stiffness and strength, such as described above, can be self-healed, regaining about 75% of the original strength, after two broken parts of the material are joined together and kept for about half an hour at room temperature. If the self-healing process is performed at higher temperatures, almost full recovery of strength and also the ductility of the material is achieved.

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Abstract

La présente invention concerne un polymère à base d'oxyde de polyalkylène fonctionnalisé à une extrémité ou aux deux extrémités avec un groupe hétérocyclique contenant de l'azote porteur de 3 fonctions carbonyle. L'invention concerne également des procédés de production dudit polymère et des articles obtenus à partir de celui-ci.
PCT/EP2019/066558 2018-06-22 2019-06-21 Composition comprenant un polymère à base d'oxyde de polyalkylène WO2019243621A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5912189A (en) * 1998-05-12 1999-06-15 The Lubrizol Corporation Compositions containing reaction product of a cyclic compound containing both a nitrogen atom and a carbonyl group, an aldehyde or ketone, and an etheramine
WO2014185779A1 (fr) * 2013-05-14 2014-11-20 Suprapolix B.V. Polymère supramoléculaire biodégradable
PL218533B1 (pl) * 2010-10-19 2014-12-31 Politechnika Rzeszowska Sposób otrzymywania polieteroli z pierścieniami azacyklicznymi

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5912189A (en) * 1998-05-12 1999-06-15 The Lubrizol Corporation Compositions containing reaction product of a cyclic compound containing both a nitrogen atom and a carbonyl group, an aldehyde or ketone, and an etheramine
PL218533B1 (pl) * 2010-10-19 2014-12-31 Politechnika Rzeszowska Sposób otrzymywania polieteroli z pierścieniami azacyklicznymi
WO2014185779A1 (fr) * 2013-05-14 2014-11-20 Suprapolix B.V. Polymère supramoléculaire biodégradable

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
BRAS ET AL., MACROMOLECULES, vol. 46, 2013, pages 9446 - 9454
CORTESE ET AL., J. AM. CHEM. SOC., vol. 134, 2012, pages 3671 - 3674
JESSALYN CORTESE ET AL: "Suppression of Mesoscopic Order by Complementary Interactions in Supramolecular Polymers", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY|, vol. 134, no. 8, 29 February 2012 (2012-02-29), pages 3671 - 3674, XP009171151, ISSN: 0002-7863, [retrieved on 20120209], DOI: 10.1021/JA2119496 *
L. LEIBLER ET AL., J. AM. CHEM. SOC., vol. 49, 2011, pages 19672
R. P. SIJBESMA ET AL., MACROMOLECULES, vol. 23, 2007, pages 8464
ROXANNE E. KIELTYKA ET AL: "Mesoscale Modulation of Supramolecular Ureidopyrimidinone-Based Poly(ethylene glycol) Transient Networks in Water", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 135, no. 30, 31 July 2013 (2013-07-31), pages 11159 - 11164, XP055161854, ISSN: 0002-7863, DOI: 10.1021/ja403745w *
T.R. DARGAVILLE ET AL., DETERMINATION OF MOLECULAR WEIGHT DISTRIBUTIONS OF NOVOLAC RESINS BY GEL PERMEATION CHROMATOGRAPHY, 1996

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