WO2019243620A1 - 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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WO2019243620A1
WO2019243620A1 PCT/EP2019/066555 EP2019066555W WO2019243620A1 WO 2019243620 A1 WO2019243620 A1 WO 2019243620A1 EP 2019066555 W EP2019066555 W EP 2019066555W WO 2019243620 A1 WO2019243620 A1 WO 2019243620A1
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Prior art keywords
group
composition according
polymer
nitrogen
polyalkylene oxide
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PCT/EP2019/066555
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English (en)
Inventor
Soumyadeb Ghosh
Hemang DARJI
Rabih AL RAHAL AL ORABI
Grégory LANDELLE
Franck Touraud
Caroll Vergelati
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Rhodia Operations
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Priority claimed from EP18306119.1A external-priority patent/EP3611212A1/fr
Application filed by Rhodia Operations filed Critical Rhodia Operations
Publication of WO2019243620A1 publication Critical patent/WO2019243620A1/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
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
    • 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

Definitions

  • composition comprising a polvalkylene oxide-based polymer
  • the present invention concerns a composition
  • a composition comprising at least 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, and a phenol-carbonyl condensation product.
  • the invention also concerns processes to produce such a composition 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.
  • the present invention thus concerns a composition
  • a composition comprising at least
  • 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 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.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • 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 l22.2°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 should be construed under the ordinary meaning.
  • 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,
  • 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.
  • 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 polyalkylene oxide -based polymer of the invention 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, 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 20000, preferably from 2 to 2000, more preferably from 4 to 1400, notably from 4 to 800, and specifically from 4 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. 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:
  • x is from 1 to 1000
  • y is from 0 to 1000
  • z is from 1 to 1000
  • 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 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 of the invention may have an average molecular weight (M n ) comprised between 100 and 80000 g/mol, preferably from 400 to 20000 g/mol measured by NMR spectroscopy or by gel permeation chromatography.
  • the polyalkylene oxide-based polymer is 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 functionalization is preferably carried out at the chain ends.
  • the term telechelic polymer is then used.
  • 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, amine 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, ether function, ester function, amine function, an urea or carbamate functional group, and/or a combination thereof.
  • 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 pyrimidine-based group such as cytosine, and thymine
  • 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 derived from a heteroaryl group, such as pyridine, diazine, triazine, tetrazine, imidazole, and pirazole.
  • 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 provided below:
  • the ring is a 6-membered aromatic ring wherein Ai, A 2 , A3, A 4 , and A5, are each independently carbon or nitrogen, with the proviso that at least 3 of Ai, A 2 , A 3 , A 4 , and A5 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 of the invention 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) moiety.
  • 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 -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.
  • Polyalkylene oxide -based polymer of the invention is preferably a polypropylene oxide polymer functionalized at one or both ends with a substituted or unsubstituted triazine-based heterocyclic group.
  • polyalkylene oxide-based polymer is a polypropylene oxide polymer functionalized at one or both ends with a 4,6-diaminotriazine (DAT) moiety.
  • DAT 4,6-diaminotriazine
  • the functionalized polyalkylene oxide-based polymer capable of forming all or part of the polymer backbone according to the invention, is of formula X-PO or X-PO-X, 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 oxide, a polypropylene oxides, polytetramethylene oxides (polybutylene oxides), polyethylene oxide-polypropylene oxide copolymers, and polypropylene oxide -polybutylene oxide copolymers. Of these, polypropylene oxides are preferred.
  • X represents a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of a primary amine and secondary amine.
  • X preferably represents a substituted or unsubstituted triazine-based heterocyclic group. More preferably X is a 4,6-diaminotriazine (DAT) moiety.
  • DAT 4,6-diaminotriazine
  • functionalized polyalkylene oxide -based polymer is DAT-PPO or DAT- PPO-DAT.
  • the functionalized polyalkylene oxide based polymers of the invention may have a number- average molecular weight (M n ) of between 100 and 80000 g/mol, more preferably between 400 and 20000 g/mol.
  • the number- average molecular weight (M n ) may be measured by NMR spectroscopy or by Gel Permeation Chromatography.
  • the functionalized polyalkylene oxide-based, ie. polymer a), of the invention is a polymer as follows:
  • n is comprised between 2 and 2000, preferably between 2 and 1400, more preferably from 4 to 800, more preferably from 4 to 400.
  • n is comprised between 2 and 2000, preferably between 2 and 1400, more preferably from 4 to 800, more preferably from 4 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 a nitrogen-containing heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine.
  • the polymer a) 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 a nitrogen-containing heterocyclic group bearing at least a primary amine or secondary amine, to obtain such product.
  • a polymer can be synthesized by either a solution or a bulk reaction process.
  • the compound comprising a nitrogen-containing heterocyclic group bearing at least a primary amine or secondary amine may comprise a suitable leaving group such as for example halogen.
  • a suitable leaving group such as for example halogen.
  • the polyalkylene oxide -based polymer may be for instance a polyalkylene oxide-based polymer or a polyalkylene oxide-based polymer functionalized at one or both ends with a primary amine or hydroxyl groups.
  • Reaction between the polyalkylene oxide-based polymer and the compound comprising a nitrogen-containing heterocyclic group bearing at least a primary amine or secondary amine may occur at a temperature from 50°C to l50°C, preferably from a temperature from 80°C to l20°C.
  • Said reaction may be made in presence of solvents, such as mixture of alcohol and water, for instance isopropanol and water. Said reaction may be carried out without catalyst for instance.
  • 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.
  • 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.
  • GPC gel permeation chromatography
  • 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 comprises at least 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, and a phenol- carbonyl condensation product, may be for instance obtained by blending.
  • Blending of at least one 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, with at least one phenol-carbonyl condensation products may be carried out according to several methods such as for instance:
  • Blending of at least one 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, with at least one phenol-carbonyl condensation products may be carried out at a temperature comprised of 10 to 200°C.
  • the composition of the invention comprises at least a polypropylene 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 a phenol-carbonyl condensation product. More preferably, composition of the invention comprises at least a polypropylene oxide-based polymer functionalized at one or both ends with a substituted triazine-based heterocyclic group bearing at least a function chosen in the group consisting of primary amine and secondary amine, and a phenol-carbonyl condensation product.
  • composition of the invention comprises at least a polypropylene oxide -based polymer functionalized at one or both ends with a 4,6-diaminotriazine moiety, and a phenol- carbonyl condensation product.
  • composition of the invention comprises at least a polypropylene oxide- based polymer functionalized at one or both ends with a 4,6-diaminotriazine moiety, and a novolac. That is to say, composition comprises DAT-PPO and novolac or DAT-PPO-DAT and novolac.
  • composition according to the invention may comprise one or more different types of novolac resin.
  • the composition of the invention may comprise from 5% to 95% by weight, preferably from 10% to 80% by weight, notably from 20% to 60% by weight, of the phenol-carbonyl condensation product relative to the total weight of the polymer a) and the phenol-carbonyl condensation product.
  • the composition may comprise from 5% to 95% by weight, preferably from 20% to 80% by weight, of the polypropylene oxide -based functionalized polymer, relative to the total weight of said polymer a) and the phenol-carbonyl condensation product.
  • the weight ratio between the phenol-carbonyl condensation product and the polymer a) may range from 10:1 to 1:5.
  • 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.
  • compositions of the present invention may have a glass transition temperature from -80 °C to l00°C, preferably from -20°C to l00°C, notably from 20°C to 75°C.
  • Compositions of the present invention may have an elongation at break from 0.5% to 100%, preferably from 1% to 5%. 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.
  • 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, Ci
  • composition of the invention may also comprise a polyalkylene oxide -based polymer functionalized at one or both ends with a nitrogen-containing heterocyclic group bearing at least 2 carbonyl functions, notably a polyalkylene oxide-based polymer functionalized at one or both ends with an isocyanuric acid moiety and/or a barbituric acid moiety.
  • the polyalkylene oxide -based polymer functionalized at one or both ends with a nitrogen- containing heterocyclic group bearing at least 2 carbonyl functions may have an average molecular weight (M n ) comprised between 100 and 80000 g/mol, preferably from 100 to 35000 g/mol measured by NMR spectroscopy or by gel permeation chromatography.
  • 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 -Ci 2 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 Ci-C 6 alkylene group, C 6 -Ci 2 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.
  • 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
  • BA polypropylene oxide polymer functionalized at one or both ends with barbituric acid
  • the functionalized polyalkylene oxide-based polymer of the invention is a polymer of formula (III) 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 (IV) 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 (V) as follows: wherein n is comprised between 2 and 800, preferably from 4 to 600, more preferably from 6 to
  • Such a functionalized polyalkylene oxide-based polymer 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.
  • This polymer 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.
  • Such 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-l,3,5-triazinan-l- yl)acetate, methyl 2-(2,4,6-trioxohexahydropyrimidin-5-yl)acetate, and l-(2-chloroethyl)-l,3,5- triazinane-2,4,6-trione, 5-(2-chloroethyl)pyrimidine-2,4,6(lH,3H,5H)-trione.
  • the present invention also relates to an article or a part of an article comprising the composition of at least one polypropylene oxide -based polymer functionalized at one or both ends with 3,5-a diaminotriazine (DAT) moiety, and at least one novolac.
  • 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:
  • thermoplastics to effect reversible crosslinking; affecting as processing aid, toughening agent and/or for self-healing properties;
  • anti-corrosion additives in particular in protective coatings
  • additives for impact modification in polymers in particular in polyamides
  • 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.
  • DAT-PPO-DAT telechelic polypropylene oxide end-capped with diamino-triazine
  • PPO polypropylene oxide
  • the oligomer was reacted with 2-chloro-4, 6-diamino- 1, 3, 5-triazine at 90°C in dioxane to obtained PPO terminated with 4,6-diamino triazine units, which act as supramolecular moieties with hydrogen -bonding functionalities.
  • the oligomer produced, PPO-DAT was purified by dissolving in toluene and repeated by washing with water. The material was subsequently dried at 70°C under vacuum, forming a clear colourless liquid.
  • the polymer was characterized by 1H- NMR using CDCl 3 as solvent confirming the attachment of the hydrogen bonding moiety, diamino-triazine, to the polymer chain and the bifunctionality of the oligomer was confirmed by the absence of the alkyl amine at the chain-end, evident by the potentiometric titration with isopropanol as a solvent.
  • DAT-PPO-DAT bifunctionality of the oligomer (DAT-PPO-DAT) was confirmed by the absence of the alkyl amine at the chain-end, evident by the potentiometric titration (Metrohm Autotitrator- 905 Titrando & Electrode- I Ecotrode Plus) with isopropanol as a solvent and 0.05N HC1 (aqueous solution) as titrant at 25 °C.
  • Novolac resin of two grades were obtained from Plenco, USA and as Nowolak S, from LERG S.A., Tru
  • the compressive strength of the samples was measured using UTM (Zwick Roell, UTM-030), measured according to the following details: For the measurement, samples were moulded in the form of cylindrical shape of diameter l6.lmm and height of 4.55mm and stress on the sample with respect to the strain applied at the rate of 50mm/min was measured. A modulus of about 2 GPa and a strength of 30 MPa were obtained.
  • a sample for a bar prepared as described above, with dimension of 40mm x 10.36mm x 2.45mm was broken into two pieces and reattached by hand pressure for 2 minutes and left it for 15 minutes at 25°C. A weight of 200 gm was then hanged on the healed sample that did not lead to any breakage for a period of at least 3 minutes, demonstrating hence the strength of the healing process for the material.
  • Coatings of sample A and B were made on a glass slide. Each of the coatings, measured about lOmm x lOmm, were of a thickness approximately 0.8 to 0.9 mm. Surfaces of the sample A and B were then scratched of length lOmm and of substantial depth with respect to the film thickness (>50% of the film thickness) with a sharp blade at a temperature of 25°C. After heating at 70°C for 10 minutes, scratch on sample B was visually observed to be healed while the one on sample A had remained unaffected.
  • 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.
  • ND* Sample broke during start of measurement (not measured as the sample brittle as broke on clamping)
  • Ductile material elongation of at least 15%.
  • Tensile Strength The maximum value of the tensile stress
  • Novolac “Novolak S” grade in all cases It appears then that a 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 une composition comprenant au moins un polymère à base d'oxyde de polyalkylène fonctionnalisé à une extrémité ou aux deux extrémités avec un groupe hétérocyclique contenant de l'azote portant au moins une fonction choisie dans le groupe constitué par une amine primaire et une amine secondaire; et un produit de condensation phénol-carbonyle. L'invention concerne également des procédés de production d'une telle composition et des articles obtenus à partir de celle-ci.
PCT/EP2019/066555 2018-06-22 2019-06-21 Composition comprenant un polymère à base d'oxyde de polyalkylène WO2019243620A1 (fr)

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IN201821023464 2018-06-22
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EP18306119.1A EP3611212A1 (fr) 2018-08-14 2018-08-14 Composition comprenant un polymère à base d'oxyde de polyalkylène

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5210195A (en) * 1991-11-08 1993-05-11 Texaco Chemical Co. Bis(2,2',6,6'-tetramethyl-4-aminoethyleneamidopiperidyl) polyoxyalkylene
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
US6001905A (en) * 1997-04-23 1999-12-14 Ciba Specialty Chemicals Corporation Polyalkylene glycol group-containing hindered amines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5210195A (en) * 1991-11-08 1993-05-11 Texaco Chemical Co. Bis(2,2',6,6'-tetramethyl-4-aminoethyleneamidopiperidyl) polyoxyalkylene
US6001905A (en) * 1997-04-23 1999-12-14 Ciba Specialty Chemicals Corporation Polyalkylene glycol group-containing hindered amines
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

Non-Patent Citations (5)

* 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
CORTESE ET AL.: "Suppresion of Mesoscopic Order by Complementary Interactions in Supramolecular Polymers", J. AM. CHERN. SOC.,, vol. 134, 2012, pages 3671 - 3674, XP002788832 *
CORTESE J. ET AL: "Binding and supramolecular organisation of homoand heterotelechelic oligomers in solutions", POLYMER CHEMISTRY, vol. 5, 2014, pages 116 - 125, XP002788833 *
T.R. DARGAVILLE ET AL., DETERMINATION OF MOLECULAR WEIGHT DISTRIBUTIONS OF NOVOLAC RESINS BY GEL PERMEATION CHROMATOGRAPHY, 1996

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