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WO2019002273A1 - Polymères aromatiques pouvant être obtenus par réaction de cycloaddition - Google Patents

Polymères aromatiques pouvant être obtenus par réaction de cycloaddition Download PDF

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Publication number
WO2019002273A1
WO2019002273A1 PCT/EP2018/067080 EP2018067080W WO2019002273A1 WO 2019002273 A1 WO2019002273 A1 WO 2019002273A1 EP 2018067080 W EP2018067080 W EP 2018067080W WO 2019002273 A1 WO2019002273 A1 WO 2019002273A1
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Prior art keywords
optionally
group
monomer
moeity
optionally substituted
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PCT/EP2018/067080
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English (en)
Inventor
John Scott Flanagan
Kermit S. Kwan
Stéphane JEOL
Joel POLLINO
David KERCHER
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Solvay Specialty Polymers Usa, Llc
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Publication of WO2019002273A1 publication Critical patent/WO2019002273A1/fr

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    • 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
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/60—Polymerisation by the diene synthesis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/46—Diels-Alder reactions
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/73—Depolymerisation
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking

Definitions

  • Aromatic polymers obtainable by cycloaddition reaction
  • the present invention relates to polymers obtainable by cycloaddition
  • Cyclizations can be promoted by heating (thermal cyclizations) or by UV light (photocyclizations).
  • DA Diels-Alder
  • reaction i.e. is a [4+2] cycloaddition reaction between a conjugated diene and a substituted alkene (referred to as “dienophile"), to provide a cyclohexene system.
  • dienophile a conjugated diene and a substituted alkene
  • the synthetic value of this reaction lies mainly in the fact that, through appropriate selection of the diene and dienophile, it allows control of the regio-/stereochemistry of the final product.
  • DA reactions involving at least one heteroatom of either the diene or the dienophile (referred to as “hetero DA”) are a useful synthesis tool to obtain heterocycles. [0004]
  • the DA reaction is reversible; this reaction is called “retro DA”.
  • US 2009/0148717 (Washington University, OF), published on June 1 1 , 2009, relates to a cross-linkable polymer useful for making cross-linked films having electro-optic activity and to cross-linked polymers and films obtained therefrom.
  • the cross-linkable polymer consists essentially of:
  • the cross-linkable polymer comprises two or more anthracene moieties.
  • the cross-linked polymer consists essentially of:
  • crosslinking agents include bismaleimides and trismaleimides.
  • the crosslinkable compounds comply with formula (I): wherein D is a ⁇ -electron donor group; A is a ⁇ -electron acceptor group; Di is a dendron moiety functionalized with one or more crosslinkable groups; D2 is a dendron moiety functionalized with one or more crosslinkable groups; n is 0, 1 , or 2; m is 0, 1 , or 2; and m+n is ⁇ 1 ; wherein the crosslinkable groups are independently selected from the group consisting of an anthracenyl group and an acrylate group.
  • Di and D2 are selected from dendritic groups comprising at least two anthracene or acrylate moieties (par. [0013] and [0014]). It also stems from par. [0015] to [0018], [0021] and [0097] that the cross-linked polymer (and films or composites) can be obtained by Diels-Alder reaction of a compound (I) wherein both Di and D2 comprise anthracene moieties with another compound (I) wherein both Di and D2 comprise acrylate moieties or by reaction of a compound (I) wherein either Di or D2 is anthracene and the other one is acrylate. [0013] Therefore, the sole cross-linkable groups disclosed in this document that react together through DA reaction are anthracenyl and acrylate groups.
  • US 2010/0108996 A1 (Electronics and Communications Research Institute, Gwangju Institute of Science and Technology), published on May 6, 2016, relates to a composition for organic thin film transistor and film formed from the composition.
  • the composition comprises a polymer (for example a polymethylmethacrylate polymer) having pendant groups comprising anthracenyl moieties [formulae (I) and (II) on page 1] and a cross-linker comprising two or three maleimide groups [see formulae (III) - (VI) on page 1].
  • the film can be manufactured by means of a process which comprises heat treatment (par. [0017]); in some embodiments, the heat treatment makes a DA reaction occur between the polymer and cross-linker.
  • JP 2010185049 A2 (NK RES KK), published on August 26, 2010, relates to a method for obtaining a biodegradable poly-L-lactic acid (PLLA) block copolymer by reaction of anthracenyl-terminated PLLA and maleimide- terminated PLLA.
  • PLLA poly-L-lactic acid
  • JP 2011236325 A2 MUSASHINO CHEMICAL LABORATORY LTD;
  • Thomas, lain, P., et al, Chem. Commun., 1999, 1507-1508 discloses the DA reaction of polystyrene resin beads carrying respectively maleimide and anthracene groups attached to extended side-chains.
  • Additive manufacturing may also make use of molten aromatic polymers, but the high viscosity of molten aromatic polymers and their high T g in general present difficulties for conventional three-dimensional (3D) printers.
  • Thermoplastic composites are usually prepared by impregnation of carbon fibers or glass fiber fabrics with high performance thermoplastics like aromatic polymers; however, due to the high polymer viscosity in the molten state, the fabrics or fibers are not sufficiently impregnated and holes form in the composite that negatively affect mechanical properties. Viscosity in the molten state can be reduced by reducing the molecular weight of the thermoplastic polymer; this solves the impregnation issue, but leads to poor mechanical properties of the resulting thermoplastic composite. There is an outstanding need to recycle thermoplastic composites in order to recover the carbon of glass fibers.
  • the present invention relates to a polymer (P) comprising recurring units obtainable by cycloaddition reaction of:
  • At least one monomer (A) comprising at least two optionally substituted anthracenyl rings (AnR):
  • - W is selected from the group consisting of:
  • an aromatic, aliphatic of cycloaliphatic moeity said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising at least one atom or a moiety selected from the group consisting of - 0-, -C(O)-, -NH-, -S-, -SO2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - and said moeity optionally comprising one or several groups R;
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 -C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 18, preferably 0;
  • the optionally substituted anthracenyl rings of monomer (A) can be equal to or different from each other.
  • the present invention relates to a formulation
  • polymer (P) in admixture with additional components, for example for use for 3D printing.
  • the present invention relates to methods for the manufacture of films, coatings or shaped articles from polymer (P) or from composition (C).
  • the present invention relates to a method of recycling said films, coatings or shaped articles by submitting said films, coatings or shaped articles to retro-cycloaddition reaction.
  • a cycloaddition reaction is a reaction in which two or more unsaturated molecules (or parts of the same molecule) combine with the formation of a cyclic adduct in which there is a net reduction of the bond multiplicity, as defined in International Union of Pure and Applied Chemistry, Compendium of Chemical Terminology, Gold Book, Version 2.3.3 February 24, 2014, page 367);
  • DA reaction is a [4+2] cycloaddition reaction between a conjugated diene and a substituted alkene (referred to as "dienophile"), to provide a cyclohexene system.
  • dienophile a substituted alkene
  • the expression "DA reaction” includes also hetero DA reactions, i.e. those DA reactions involving at least one heteroatom of either the diene or the dienophile;
  • photocycloaddition reaction is a reaction in which two unsaturated molecules connect via four atoms from each molecule to form an eight membered ring;
  • halogen includes fluorine, chlorine, bromine and iodine, unless indicated otherwise;
  • parentheses ( )" before and after names of compounds, symbols or letters identifying formulae, e.g. "polymer (P)", “monomer (A)”, “monomer (B)”, “film (F)”, etc ., has the mere purpose of better distinguishing that name, symbol or letter from the rest of the text; thus, said parentheses could also be omitted;
  • aromatic denotes any mono- or polynuclear cyclic group (or moiety) having a number of ⁇ electrons equal to 4n+2, wherein n is 0 or any positive integer; an aromatic group can be an aryl or an arylene group (or moiety); an aromatic group may also include in any of its cyclic group one or more heteroatoms, preferably selected from N, O or S and may also be substituted with optionally halogenated straight or branched alkyl groups, optionally comprising one or more heteroatoms selected from N, O or S or functional groups comprising such heteroatoms;
  • an "aryl group” is a hydrocarbon monovalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings either linked together via a C-C bond between one carbon atom of one ring and one carbon atom of an adjacent ring or fused together by sharing two or more neighboring ring carbon atoms, and of one end.
  • the end of an aryl group is a free electron of a carbon atom contained in a (or the) benzenic ring of the aryl group, wherein a hydrogen atom linked to said carbon atom has been removed.
  • the end of an aryl group is capable of forming a linkage with another chemical group;
  • an "arylene group” is a hydrocarbon divalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings either linked together via a C-C bond between one carbon atom of one ring and one carbon atom of an adjacent ring or fused together by sharing two or more neighboring ring carbon atoms, and of two ends.
  • An end of an arylene group is a free electron of a carbon atom contained in a (or the) benzenic ring of the arylene group, wherein an hydrogen atom linked to said carbon atom has been removed.
  • Each end of an arylene group is capable of forming a linkage with another chemical group.
  • monomer (A) comprises at least two
  • - W is selected from the group consisting of:
  • an aromatic, aliphatic or cycloaliphatic moeity said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising at least one atom or moiety selected from the group consisting of - 0-, -C(O)-, -NH-, -S-, -SO2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - (preferably at least one divalent -O- or at least one divalent -S-) and said moeity optionally comprising one or several groups R;
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 -C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 18, preferably 0;
  • monomer (A) is according to formula (A-l):
  • the polymer (P) is such that W in formula is an aromatic, aliphatic or cycloaliphatic moeity, said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising at least one a divalent oxygen or sulphur, preferably two divalent oxygens or sulphurs, more preferably two divalent oxygens.
  • W may for example be composed of at least one benzene moiety, for example two, three or four benzene moieties.
  • the at least two optionally substituted anthracenyl rings (AnR) are preferably linked to the benzene moeity(ies) by one(several) divalent oxygen(s) or sulphur(s).
  • the polymer (P) is such that W in formula (A) is selected from the group consisting of:
  • - X is a divalent oxygen or sulphur, preferably divalent oxygen
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 - C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 8, preferably 0.
  • Preferred monomers (A) are 2,2'-((sulfonylbis(4,1 - phenylene))bis(oxy))dianthracene (BANDS), 2,4,6-tris(4-(anthracen-2- yloxy)phenyl)-1 ,3,5-triazine (TANTA), or oxybis(4,1 -phenylene))bis((2- (anthracen-1 -yloxy)-6-(anthracen-2-yloxy)phenyl)methanone (BDABPE).
  • monomer (B) comprises at least two moieties being able to react in a cycloaddition reaction with the optionally substituted anthracenyl ring (AnR) of monomer (A).
  • monomer (B) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • - Z is selected from the group consisting of:
  • an aromatic, aliphatic of cycloaliphatic moeity said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising one atom or moiety selected from the group consisting of -0-, -C(O)-, -NH-, -S-, -SO2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - and said moeity optionnally comprising one or several groups R;
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 -C18 alkyl group optionally substituted with one or several halogen atoms, and - Di , D2, D3, D 4 , independently from each other, is a moiety able to react in a cycloaddition reaction with the optionally substituted anthracenyl ring (AnR) of monomer (A).
  • Z in formula (B-1 ), (B-2) or (B-3) above is selected from the group consisting of:
  • - X is a bond, a divalent oxygen or a divalent sulphur
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 - C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 8, preferably 0.
  • Preferred monomer (B) is 4,4'-bismaleimido-diphenylmethane (BMI).
  • polymers (P) according to the present invention can be obtained by cycloaddition reaction of at least one monomer (A) and, optionally, at least one monomer (B) as defined above.
  • the cycloaddition reaction is a [4+2] cycloaddition reaction (DA reaction); in another embodiment the cycloaddition reaction is a [4+4] photocycloaddition reaction.
  • At least one means that each of monomer (A) and, optionally, monomer (B) can be equal to or different from one another.
  • polymers (P) can be obtained by cycloaddition reaction of at least one monomer (A) comprising only optionally substituted
  • polymers (P) can be obtained by cycloaddition
  • the at least one monomer (A) comprises at least one substituted anthracenyl ring and at least another moiety able to react in a cycloaddition reaction with said optionally substituted anthracenyl ring, without the use of any monomer (B).
  • the at least one monomer (A) comprises at least one substituted anthracenyl ring and at least another moiety able to react as dienophile in a [4+2] cycloaddition reaction with said at least one optionally substituted anthracenyl.
  • polymers (P) can be obtained by cycloaddition
  • Preferred polymers (P) are those that can be obtained by DA reaction of monomers (A) and monomers (B) substituted with maleimide moiety. Even more preferred are polymers obtained by DA reaction of 2,2'-((sulfonylbis(4,1 - phenylene))bis(oxy))dianthracene (BANDS), 2,4,6-tris(4-(anthracen-2- yloxy)phenyl)-1 ,3,5-triazine (TANTA) or oxybis(4,1 -phenylene))bis((2- (anthracen-1 -yloxy)-6-(anthracen-2-yloxy)phenyl)methanone (BDABPE) with 4,4'-bismaleimido-diphenylmethane (BMI).
  • BANDS 2,2'-((sulfonylbis(4,1 - phenylene))bis(oxy))dianthracene
  • TANTA 2,4,6-tris
  • monomers (A), optionally monomers (B), is advantageously carried out by exposure to light of wavelength from 300 to 600 nm, preferably from 340 to 450 nm or from 350 to 400 nm, more preferably at a wavelength of 365 nm.
  • the reaction can be carried out in a solvent or in the melt.
  • the reaction of monomers (A) and monomers (B) is advantageously carried out by heating at temperatures ranging from 50 to 300°C, preferably from 60 to 250 °C, more preferably from 50 to 200 °C.
  • the reaction can be carried out in a solvent or in the melt.
  • UV radiation sources of different type may be used. Further, a source emitting a monochromatic radiation or a source emitting a wider range of wavelength may be used.
  • the polymerization reaction proceeds via a cycloaddition reaction between monomers (A) and, optionally monomers (B).
  • the polymer (P) of the present invention may have a number average
  • Mn molecular weight of less than 15,000 g/mol, as determined by Gel Permeation Chromatography (GPC) in methylene chloride, preferably less than 10,000 g/mol or less than 7,500 g/mol.
  • the number average molecular weight Mn (e.g. obtained by multiplying the number average degree of polymerization by the molecular weight of the monomer unit) can be controlled by choosing the number/concentration of reactive groups, so-called optionally substituted anthracenyl rings (AnR), and it will depend on the extent of the reaction that is controlled mainly bychoosing the time and intensity of exposure to heat and/or UV light, or by a stoichiometric imbalance of A and B monomers.
  • the desired number average degree of polymerization can be calculated according to Carothers' equation.
  • polymers (P) can then be isolated from the reaction mixture by known methods, preferably by precipitation with a polar protic organic solvent, typically methanol, and drying.
  • a polar protic organic solvent typically methanol
  • the cycloaddition reaction does not involve the formation of by-products that would need to be removed from the polymer and can also be directly carried out in an extruder, in a compression mold or in a 3D printer, while
  • the present invention relates to a method for coating a surface, comprising: a) applying to the surface:
  • At least one monomer (A) comprising at least two optionally substituted anthracenyl rings (AnR):
  • - W is selected from the group consisting of:
  • an aromatic, aliphatic of cycloaliphatic moeity said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising at least one atom or moiety selected from the group consisting of - 0-, -C(O)-, -NH-, -S-, -SO2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - and said moeity optionally comprising one or several groups R;
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 -C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 18, preferably 0;
  • the present invention also relates to a method for coating a surface, comprising:
  • At least one monomer (A) comprising at least two optionally substituted anthracenyl rings (AnR):
  • - W is selected from the group consisting of:
  • an aromatic, aliphatic of cycloaliphatic moeity said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising at least one atom or moiety selected from the group consisting of - 0-, -C(O)-, -NH-, -S-, -SO2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - and said moeity optionally comprising one or several groups R;
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 -C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 18, preferably 0;
  • At least one monomer (B) comprising at least two moieties being able to react in a cycloaddition reaction with the optionally substituted anthracenyl ring (AnR) of monomer (A),
  • Monomers (A) and optionally monomers (B) in these methods may be in the form of a powder or a solution in a solvent.
  • the methods described above may also comprise at least one step consisting of:
  • the present invention also relates to a polymer formulation (F) comprising:
  • At least one monomer (A) comprising at least two optionally substituted anthracenyl rings (AnR):
  • - W is selected from the group consisting of:
  • an aromatic, aliphatic of cycloaliphatic moeity said moeity optionally comprising one or several optionally substituted anthracenyl rings (AnR), said moeity optionally comprising at least one atom or moiety selected from the group consisting of - 0-, -C(0)-, -NH-, -S-, -SO2-, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 - and said moeity optionnally comprising one or several groups R;
  • - R is a halogen atom or an alkyl group, optionally branched, preferably an C1 -C18 alkyl group optionally substituted with one or several halogen atoms, and
  • - a is 0 or an integer from 1 to 18, preferably 0;
  • At least one additive selected from the group consisting of excitation transfer reagents, upconverters, complex formers and Lewis acids.
  • Excitation transfer reagents are molecules that absorb photons to reach an excited state, that then transfer the excited state to anthracene moieties. The excited anthracene moiety can then react to form dimers without ever having absorbed a photon.
  • Upconverters are excitation transfer reagents that can absorb photons at wavelengths ineffective for anthracene dimerization, but are still able to transfer the excited state to anthracene moieties.
  • Complex formers are molecules, such as gamma-cyclodextrin, that can form complexes with two anthracene moieties to geometrically constrain them into close proximity that favors dimerization.
  • Diels Alder reactions with electron poor dienophiles e.g. maleimide
  • dienophiles e.g. maleimide
  • the present invention also relates to a method for manufacturing a three- dimensional (3D) article, comprising:
  • the polymer formulation (F) is heated to a
  • the step of printing comprises irradiating the polymer formulation (F), for example a layer of such formulation (F) deposited onto the printing surface, with UV light.
  • the layer preferably presents a size in the range of 10 pm to 300 pm, for example 50 pm to 150 pm.
  • the UV light can for example be laser light.
  • the irradiation is preferably of sufficient intensity to cause substantial curing of the polymer formulation (F), for example the layer of such formulation (F). Also, the irradiation is preferably of sufficient intensity to cause adhesion of the layers of polymer formulation (F).
  • the present invention also relates to a method for recycling a coating or a formed article, comprising the polymer (P) of claim 7, wherein the method comprises submitting the coating or formed article to UV irradiation at a wavelengths lower than 300 nm.
  • the present invention also relates to a method for recycling a coating or a formed article, comprising the polymer (P) of claim 8, wherein the method comprises submitting the coating or formed article to heating at a temperature ranging from 100°C to 500°C.
  • the present invention also relates to a recycled material obtainable by these recycling methods.
  • the present invention also relates to films, coatings or shaped articles obtained from the polymer (P) as above-desribed.
  • molecular weight was determined using gel permeation chromatography (GPC) analysis with ⁇ , V-dimethylformamide (DMF) as the eluent and referenced to polystyrene standards of known molecular weight.
  • GPC analysis was performed with a Waters 2695 separations module with a Waters 2487 Dual Wavelength UV detector (Milford, MA, USA).
  • the mixture was allowed to stir at room temperature for 24 hours resulting in a light brown solution.
  • the mixture was acidified by the drop wise addition of concentrated hydrochloric acid (Fisher Scientific) until the pH was about 5.
  • the resulting precipitate was collected by vacuum filtration, washed with deionized water, and dried in a vacuum oven (80 °C @ 30 mmHg) overnight to obtain a greenish brown solid (17.949 g).
  • the product was sublimed by heating under vacuum (200 °C @ 2-5 mmHg) and condensed on a glass finger cooled with ice water.
  • the apparatus was taken apart and rinsed with acetone (Acros) to wash the collected yellow solid off of the cold finger.
  • the collected acetone solution was evaporated to yield a yellow solid (3.563 g).
  • the reaction mixture was allowed to cool down to room temperature and then the product was precipitated by pouring reaction solution into 400 mL of deionized water.
  • the crude product was collected by vacuum filtration and was again washed by suspending in 400 mL of deionized water.
  • the crude product was again collected by vacuum filtration and placed in vacuum oven (60 °C @ 30 mmHg) for 18 hours to dry. After drying, 4.189 g of crude solid was obtained (102.9% yield).
  • the final product was obtained by recrystallization from /7-butoxyethanol (Alfa Aesar) to provide 1.782 g (43.8% yield) of black solid.
  • Example 2A A 20ml_ scintillation vial was charged with 60 mg of 2,2'- ((sulfonylbis(4,1 -phenylene))bis(oxy))dianthracene (abbreviated as BANDS), magnetic stir bar, and 10 ml_ of N-Methyl-2-pyrrolidone (NMP). The suspension was capped and the sample was irradiated under 100W, 365nm light for 48h with agitation while heated at 55°C. After the 48h, the vial was removed from the light source and allowed to stand to cool to room temperature.
  • BANDS 2,2'- ((sulfonylbis(4,1 -phenylene))bis(oxy))dianthracene
  • NMP N-Methyl-2-pyrrolidone
  • Example 2B- A 20ml_ scintillation vial was charged with 60 mg of 2,2'- ((sulfonylbis(4,1 -phenylene))bis(oxy))dianthracene (BANDS), magnetic stir bar, and 10 mL of 1 ,4-Dioxane. The suspension was capped and the sample was under 100W, 365nm light source for 48h with agitation while heated at 55°C. After the 48h, the vial was removed from the light source and allowed to stand to cool to room temperature.
  • BANDS 2,2'- ((sulfonylbis(4,1 -phenylene))bis(oxy))dianthracene
  • the mixture was heated to 165 °C and allowed to stir for 2 hours under a flow of nitrogen.
  • the crude product was precipitated by the addition of 20 mL of hexane and 30 mL of diethyl ether and collected by vacuum filtration.
  • the crude product was washed with three 100 mL portions of deionized water and three 100 mL portions of methanol.
  • the resulting product was collected by vacuum filtration and placed under vacuum at 30 mmHg and 80 °C for 24 hours to obtain 0.5266 g of product 2,4,6-tris(4-anthracen-2-yloxy)phenyl)-1 ,3,5-triazine (TANTA).
  • a 20ml_ scintillation vial 0.090 g of TANTA from step 1 and 10.0 mL of N- methyl-2-pyrrolidone (NMP) were combined.
  • the vial was capped and the sample was irradiated under 100W, 365 nm light for 72h with magnetic stirring while heated at 55°C. After the 72 hours, the vial was removed from the light source, allowed to stand and cool to room temperature.
  • NMP N- methyl-2-pyrrolidone
  • a 2mL sample from Example 5 was placed in a well plate and irradiated using a 14W, 254 nm light source for 4h at room temperature.
  • a 2ml_ sample from Example 5 was placed in a three-neck round bottomed flask.
  • the flask was then equipped with a magnetic stir bar, dean-stark trap with condenser above, and a gas inlet/outlet and charged with 3.5g of diphenyl ether.
  • the reaction flask was then heated in an oil bath at 215°C, to remove via distillation, 2+ mL of N-methyl-2-pyrrolidone, distilled over 2 mL of A-methyl-2-pyrrolidone, and the resulting mixture allowed to stir for 4 hours under a flow of nitrogen. After 4 hours of reacting at 215 °C, the mixture was allowed to cool to room temperature.
  • the product was precipitated by the addition of 20 mL of methanol and collected by vacuum filtration.
  • the crude product was washed with three 100 mL portions of methanol.
  • the resulting product was collected by vacuum filtration and placed under vacuum at 30 mmHg and 50 °C for 24 hours to obtain 1 .1806 g of a white solid.
  • a sample of 0.062 g of TANTA-co-BM I was washed with three 50 mL portions of dichloromethane and the insoluble fraction was collected by vacuum filtration, indicative of the formation of a crosslinked polymer, polymer.
  • BDABPE oxybis(4,1-phenylene))bis((2-(anthracen-1-yloxy)-6-(anthracen- 2- loxy)phenyl)methanone
  • a 250 ml amber two neck round-bottomed flask equipped with a Dean-Stark trap was charged with 45ml_ of anhydrous toluene, 50ml_ anhydrous NMP, and a magnetic stir bar, and the mixture was agitated under a flow of N2.
  • the flask was then charged with 4.85 g of 2-anthrol, 1 .2 g of potassium hydroxide, and 0.7 g of potassium carbonate and then heated to 140°C for 2h to azeotrope all water out of the flask.
  • the mixture was then heated to 160 °C to remove the toluene via distillation. After the removal of toluene, the reaction mixture was then allowed to cool to 60°C.
  • a 100ml_ three-neck RBF equipped with a thermocouple, a reflux condenser, a gas inlet/outlet, and a mechanical stirrer was charged with 580 mg of BDABPE, 159 mg of BMI, 125 mg of butylated hydroxyl toluene (BHT), and 10 mL of chlorobenzene.
  • the suspension was then placed on an oil bath and heated under a flow of inert gas (nitrogen) at 130°C for 20h. After heating, the reaction was allowed to stand for 1 h to cool to room temperature.
  • the reaction mixture was then poured into 100mL of methanol, and the precipitate was collected by vacuum filtration and washed with 200 mL methanol.
  • the resulting powder, BDABPE-co-BMI was then dried under vacuum at 50°C, and 30inHg for 72h.

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Abstract

L'invention concerne des polymères pouvant être obtenus par réaction de cycloaddition de composés non polymères. Lesdits polymères sont utiles pour diverses utilisations industrielles, telles que la fabrication de films, de revêtements ou d'articles façonnés.
PCT/EP2018/067080 2017-06-26 2018-06-26 Polymères aromatiques pouvant être obtenus par réaction de cycloaddition WO2019002273A1 (fr)

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