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Benzoxazine Derivatives Vitrimers

20240034720 ยท 2024-02-01

    Inventors

    Cpc classification

    International classification

    Abstract

    A process for producing a benzoxazine containing free aliphatic hydroxyl groups and monoester comprising the steps of: a) a reaction of a phenolic acid derivative with a monofunctional oligomer or molecule at a temperature of from 80 C. to 200 C., during 12 h-48 h, in a presence of a Bronsted type acid catalyst, resulting in a monophenol terminated oligomer or molecule and b) reaction of the monophenol terminated oligomer or molecule of step a) with a mixture of an amino-alcohol, a primary amine derivative and paraformaldehyde at a temperature range of from 80 C. to 100 C., from 1 h to 48 h, under stirring.

    Claims

    1.-14. (canceled)

    15. An ester containing benzoxazine monomer of formula (I) ##STR00017## wherein R.sub.1 is ##STR00018## and R.sub.p is selected from the group consisting of H, a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group and ##STR00019## R.sub.1 and R.sub.2 of formula (I) are different; x.sub.1, x.sub.2 and x.sub.p, independently, are of from 0 to 1 and are not together 0; y.sub.1=1-x.sub.1; y.sub.2=1-x.sub.2 and y.sub.p=1-x.sub.p; p is 1-100; wherein x 1 = n aminoalcohol ( R 1 ) n amines ( R 1 ) total x 2 = n aminoalcohol ( R 2 ) n amines ( R 2 ) total x p = n aminoalcohol ( Rp ) n amines ( Rp ) total y 1 = n amines ( R 1 ) n amines ( R 1 ) total y 2 = n amines ( R 2 ) n amines ( R 2 ) total y p = n amines ( Rp ) n amines ( Rp ) total wherein n.sub.amine(R1).sup.total=n.sub.amines(R1)+n.sub.aminoalcohol(R1), and n.sub.aminoalcohol(R1) being the number of aminoalcohol per R.sub.1 group, n.sub.amines(R1) represent the number of amines (excepting the number of aminoalcohol) per group R.sub.1 and n.sub.amine(R1).sup.total=n.sub.amines(R1)+n.sub.aminoalcohol(R1) is the total number of amino groups per group R.sub.1; wherein n.sub.amine(R2).sup.total=n.sub.amines(R2)+n.sub.aminoalcohol(R2), and n.sub.aminoalcohol(R1) being the number of aminoalcohol per R.sub.2 group, n.sub.amines(R2) represents the number of amines (excepting the number of aminoalcohol) per group R.sub.2 and n.sub.amine(R2).sup.total=n.sub.amines(R2)+n.sub.aminoalcohol(R2) is the total number of amino groups per group R.sub.2; wherein n.sub.amine(Rp).sup.total=n.sub.amines(Rp)+n.sub.aminoalcohol(Rp), and n.sub.aminoalcohol(Rp) being the number of aminoalcohol per R.sub.p group, n.sub.amines(Rp) represents the number of amines (excepting the number of aminoalcohol) per group R.sub.p and n.sub.amine(Rp).sup.total=n.sub.amines(Rp)+n.sub.aminoalcohol(Rp) is the total number of amino groups per group R.sub.p, R.sub.1, R.sub.2, and R.sub.p, independently, are selected from the group consisting of a C-linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a C-linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a C-substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, and a C-linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group; R.sub.p is selected from the group consisting of a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group and a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group; R* is selected from the group consisting of a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a cyclo(C.sub.3-C.sub.6alkyl) group, a heteocyclo(C.sub.3-C.sub.6alkyl) group, wherein the hetero atom is selected from N, S, and O, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group, a (CH.sub.2).sub.n3-phenyl group and a (CH.sub.2).sub.n3O(CH.sub.2).sub.n4 group, wherein n3 and n4, independently, are an integer from 1 to 10; R** is the same as R* and further includes a member selected from the group consisting of a O, N or S(CH.sub.2).sub.n3CH(CH.sub.3).sub.2 group, a O, N or S(CH.sub.2).sub.n3(CHZ).sub.n4(CH.sub.3).sub.2 group, a O, N or S(CH.sub.2).sub.n3(CHZ).sub.n4(CH.sub.2).sub.n3CH.sub.3 group, a O, N or S(CHZ).sub.n4(CH.sub.2).sub.n3CH.sub.3 group, a O, N or S(CHZ).sub.n4[(CH.sub.2).sub.n3CH.sub.3].sub.2 group, a O-substituted or unsubstituted C.sub.2-C.sub.6 linear or branched alkynyl group, a (CH.sub.2).sub.n3CN group and a polycyclic aromatic or a heteroaromatic hydrocarbon, such as naphthalene, anthracene, fluorene, phenanthrene, optionally substituted by a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a cyclo(C.sub.3-C.sub.6alkyl) group, a heterocyclo(C.sub.3-C.sub.6alkyl) group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, or by a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, wherein n3 and n4, independently, are an integer from 1 to 10, Z being selected from the group consisting of a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group and a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group, and at least one O atom is present or not between two adjacent C, R*** is selected from the group consisting of H, OH and a O-linear or branched C.sub.1-C.sub.6 alkyl group, and further includes a linear or branched C.sub.1-C.sub.15 alkyl group or a C.sub.2-C.sub.15 alkenyl group or ##STR00020##

    16. The ester containing benzoxazine monomer according to claim 15, wherein R* is selected from the group consisting of a linear or branched C.sub.1-C.sub.4 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.4 alkenyl or alkylenoxy group, an unsubstituted linear or branched C.sub.2-C.sub.4 alkynyl group, an unsubstituted phenyl group and a (CH.sub.2).sub.n3-phenyl group, a (CH.sub.2).sub.n3O(CH.sub.2).sub.n4 group, wherein n3 and n4, independently, are an integer from 1 to 6; R** is the same as R* and may further include a member selected from a O, N or S(CH.sub.2).sub.n3CH(CH.sub.3).sub.2 group, a O, N or S(CH.sub.2).sub.n3(CHZ).sub.n4(CH.sub.3).sub.2 group, a O, N or S(CH.sub.2).sub.n3(CHZ).sub.n4(CH.sub.2).sub.n3CH.sub.3 group, a O, N or S(CHZ).sub.n4(CH.sub.2).sub.n3CH.sub.3 group, a O, N or S(CHZ).sub.n4[(CH.sub.2).sub.n3CH.sub.3].sub.2 group, a O-substituted or unsubstituted C.sub.2-C.sub.4 linear or branched alkynyl group, a (CH.sub.2).sub.n3CN group and a polycyclic aromatic or a heteroaromatic hydrocarbon, wherein the hetero atom is selected from N, S, and O, such as naphthalene, anthracene, fluorene, furane, which is optionally substituted by a linear or branched C.sub.1-C.sub.4 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.4 alkenyl or alkylenoxy group, a cyclo(C.sub.3-C.sub.4alkyl) group, a heteocyclo(C.sub.3-C.sub.4 alkyl) group, or by a substituted or unsubstituted linear or branched C.sub.2-C.sub.4 alkynyl group, wherein n3 and n4, independently, are an integer from 1 to 6, Z being as defined in claim 1; R*** is selected from the group consisting of H, OH and a O-linear or branched C.sub.1-C.sub.4 alkyl group, and further including a linear or branched C.sub.1-C.sub.1 alkyl group or C.sub.2-C.sub.10 alkenyl group or ##STR00021##

    17. The ester containing benzoxazine monomer according to claim 15, wherein R* is selected from the group consisting of groups CH.sub.3, (CH.sub.2).sub.n3CH.sub.3, (CH.sub.2).sub.n3CH[(CH.sub.2).sub.n4CH.sub.3].sub.2, C(CH.sub.3).sub.3, (CH.sub.2).sub.n3(C.sub.6H.sub.5), (CH.sub.2).sub.n3CHCH.sub.2, (CH.sub.2).sub.n3CCH, (CH.sub.2).sub.n3O(CH.sub.2).sub.n4 wherein n3 and n4 independently are integer from 1 to 4, phenyl, and (CH.sub.2).sub.3-phenyl; R** is the group R*, or is selected from the group consisting of groups CH.sub.3, (CH.sub.2).sub.n3CH.sub.3, (CH.sub.2).sub.n3CH[(CH.sub.2).sub.n4CH.sub.3].sub.2, C(CH.sub.3).sub.3, (CH.sub.2).sub.n3(C.sub.6H.sub.5), (CH.sub.2).sub.n3CHCH.sub.2, (CH.sub.2).sub.n3CCH, O(CH.sub.2).sub.n3CCH, O(CH.sub.2).sub.n3CN, (CH.sub.2).sub.n3CN, and (CH.sub.2).sub.n3-substituted or unsubstituted furan, phenyl, and wherein n3 and n4, independently, are integer from 1 to 4; R*** is selected from the group consisting of H, OH and a O-linear or branched C.sub.1-C.sub.3 alkyl group, and further includes a linear or branched C.sub.1-C.sub.6 alkyl group or C.sub.2-C.sub.6 alkenyl group or ##STR00022##

    18. A process for synthesizing an ester-containing benzoxazine monomer of formula (I) ##STR00023## comprising the following steps consisting of: a) reacting a phenolic acid derivative of formula (II), comprising at least one R*** group on the phenolic ring: ##STR00024## wherein x is of from 0 to 1, and y=1-x, with a polyfunctional molecule or oligomer of formula (III) ##STR00025## at a temperature of from 25 C. to 200 C., during 1 h-72 h, in the presence of a catalyst of Bronsted acid type, resulting in a phenol terminated oligomer or molecule (IV), and b) reacting the compound (IV) with a mixture of: an amino-alcohol of formula (V): ##STR00026## a primary amine derivative of formula (VI),
    R**NH.sub.2(VI), and paraformaldehyde of formula (VII) ##STR00027## at a temperature range of from 80 C. to 100 C., from 1 h to 10 h, under stirring, for obtaining the compound of formula (I); wherein R.sub.1, R.sub.2, R.sub.p, R*, R**, R***, x.sub.1, x.sub.2, x.sub.p, y.sub.1, y.sub.2, y.sub.p, and p are, independently, as defined in claim 16, R.sub.n being R.sub.1 or R.sub.2, R.sub.1 being different of R.sub.2, with the proviso that when at least one R*** of the phenolic acid derivative is in ortho position with regard to OH group, then R*** is H.

    19. The process according to claim 18, wherein the phenolic acid derivative (formula (II)) is selected from the group consisting of mono-, di-, tri-hydroxybenzoic acid derivatives, anacardic acid derivatives, hydroxycinnamic acid derivatives, aliphatic X-hydroxyphenyl acid derivatives, wherein X is 2-4 and aliphatic diphenolic acid derivatives, or mixtures thereof.

    20. The process according to claim 18, wherein the respective stoichiometry of starting reactants on step a), phenolic acid derivative:polyfonctional molecule or oligomer is 1.0-3.0 eq.:1.0 eq, resulting in an 1.0 eq. of phenol terminated oligomer or molecule.

    21. The process according to claim 18, wherein the primary amine derivatives are selected from the group consisting in allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, cyclohexylamine, stearylamine, 2-aminofluorene, aminophenyl acetylene, propargyl ether aniline, 4-aminobenzonitrile, furfurylamine and aniline, or mixtures thereof.

    22. The process according to claim 18, wherein the temperature range of step b) is of from 80 C. to 95 C.

    23. The process according to claim 18, wherein the step b) is performed from 1 h to 8 h, for the highest yield of at least 75%.

    24. The process according to claim 18, wherein the respective stoichiometry of starting reactants on step b), phenol terminated oligomer or molecule:amino-alcohol:primary amine derivative:paraformaldehyde is 1.0 eq.:x.sub.1 (1.0 eq-18.0 eq):y.sub.1 (1.0 eq-18.0 eq):2.0-36.0 eq; or 1.0 eq.:x.sub.2 (1.0 eq-18.0 eq): y.sub.2 (1.0 eq-18.0 eq):2.0-36.0 eq; or 1.0 eq.:x.sub.p (1.0 eq-18.0 eq): y.sub.p (1.0 eq-18.0 eq):2.0-36.0 eq resulting in an 1.0 eq. of the ester-containing benzoxazine monomer, wherein x.sub.1, x.sub.2 and x.sub.p, independently, =0-1, and y.sub.1=1-x.sub.1, y.sub.2=1-x.sub.2 and y.sub.p=1-x.sub.p.

    25. The process according to claim 18, wherein the relative molar % of amino-alcohol vs the relative molar % of primary amine derivative is 10 molar % vs 90 molar % respectively.

    26. A process for preparing a polybenzoxazine derivative vitrimer comprising the step of polymerization of an ester-containing benzoxazine monomer of formula (I) ##STR00028## wherein R.sub.1 is ##STR00029## and R.sub.p is selected from the group consisting of H, a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group and ##STR00030## R.sub.1 and R.sub.2 of formula (I) are different; x.sub.1, x.sub.2 and x.sub.p, independently, are of from 0 to 1 and are not together 0; y.sub.1=1-x.sub.1; y.sub.2=1-x.sub.2 and y.sub.p=1-x.sub.p; p is 1-100; wherein x 1 = n aminoalcohol ( R 1 ) n amines ( R 1 ) total x 2 = n aminoalcohol ( R 2 ) n amines ( R 2 ) total x p = n aminoalcohol ( Rp ) n amines ( Rp ) total y 1 = n amines ( R 1 ) n amines ( R 1 ) total y 2 = n amines ( R 2 ) n amines ( R 2 ) total y p = n amines ( Rp ) n amines ( Rp ) total wherein n.sub.amine(R1).sup.total=n.sub.amines(R1)+n.sub.aminoalcohol(R1), and n.sub.aminoalcohol(R1) being the number of aminoalcohol per R.sub.1 group, n.sub.amines(R1) represent the number of amines (excepting the number of aminoalcohol) per group R.sub.1 and n.sub.amine(R1).sup.total=n.sub.amines(R1)+n.sub.aminoalcohol(R1) is the total number of amino groups per group R.sub.1; wherein n.sub.amine(R2).sup.total=n.sub.amines(R2)+n.sub.aminoalcohol(R2), and n.sub.aminoalcohol(R2) being the number of aminoalcohol per R.sub.2 group, n.sub.amines(R2) represents the number of amines (excepting the number of aminoalcohol) per group R.sub.2 and n.sub.amine(R2).sup.total=n.sub.amines(R2)+n.sub.aminoalcohol(R2) is the total number of amino groups per group R.sub.2; wherein n.sub.amine(Rp).sup.total=n.sub.amines(Rp)+n.sub.aminoalcohol(Rp), and n.sub.aminoalcohol(Rp) being the number of aminoalcohol per R.sub.p group, n.sub.amines(Rp) represents the number of amines (excepting the number of aminoalcohol) per group R.sub.p and n.sub.amine(Rp).sup.total=n.sub.amines(Rp)+n.sub.aminoalcohol(Rp) is the total number of amino groups per group R.sub.p, R.sub.1, R.sub.2, and R.sub.p, independently, are selected from the group consisting of a C-linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a C-linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a C-substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, and a C-linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group; R.sub.p is selected from the group consisting of a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group and a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group; R* is selected from the group consisting of a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a cyclo(C.sub.3-C.sub.6alkyl) group, a heteocyclo(C.sub.3-C.sub.6alkyl) group, wherein the hetero atom is selected from N, S, and O, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group, a (CH.sub.2).sub.n3-phenyl group and a (CH.sub.2).sub.n3O(CH.sub.2).sub.n4 group, wherein n3 and n4, independently, are an integer from 1 to 10; R** is the same as R* and further includes a member selected from the group consisting of a O, N or S(CH.sub.2).sub.n3CH(CH.sub.3).sub.2 group, a O, N or S(CH.sub.2).sub.n3(CHZ).sub.n4(CH.sub.3).sub.2 group, a O, N or S(CH.sub.2).sub.n3(CHZ).sub.n4(CH.sub.2).sub.n3CH.sub.3 group, a O, N or S(CHZ).sub.n4(CH.sub.2).sub.n3CH.sub.3 group, a O, N or S(CHZ).sub.n4[(CH.sub.2).sub.n3CH.sub.3].sub.2 group, a O-substituted or unsubstituted C.sub.2-C.sub.6 linear or branched alkynyl group, a (CH.sub.2).sub.n3CN group and a polycyclic aromatic or a heteroaromatic hydrocarbon, such as naphthalene, anthracene, fluorene, phenanthrene, optionally substituted by a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a cyclo(C.sub.3-C.sub.6alkyl) group, a heterocyclo(C.sub.3-C.sub.6alkyl) group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group, or by a substituted or unsubstituted linear or branched C.sub.2-C.sub.6 alkynyl group, wherein n3 and n4, independently, are an integer from 1 to 10, Z being selected from the group consisting of a linear or branched C.sub.1-C.sub.6 alkyl or alkoxy group, a linear or branched C.sub.2-C.sub.6 alkenyl or alkylenoxy group and a linear or branched C.sub.1-C.sub.6 alkyl or C.sub.2-C.sub.6 alkenyl substituted or unsubstituted phenyl group, and at least one O atom is present or not between two adjacent C, R*** is selected from the group consisting of H, OH and a O-linear or branched C.sub.1-C.sub.6 alkyl group, and further includes a linear or branched C.sub.1-C.sub.15 alkyl group or a C.sub.2-C.sub.15 alkenyl group or ##STR00031## at temperatures within the range of from 100 C. to 250 C. for 1 h to 24 h, for obtaining polybenzoxazine derivatives vitrimers.

    Description

    DRAWINGS

    [0125] Other features and advantages of the present invention will be readily understood from the following detailed description and drawings among them.

    [0126] FIG. 1 exemplarily shows a schematic synthesis reaction for obtaining ester-containing benzoxazine monomer of PEG-DPA/PA-mea/fa type, wherein R1 and R2 is CH2-CH2- if either x1 or y1=0 and if either x2 or y2=0, and R1 and R2 is CH2-C(CH3)- if either x1 and y10 and x2 and y20, and 0<x10.75, 0<y10.25 and 0<x20.75, 0<y20.25.

    [0127] FIG. 2a) exemplarily displays the NMR spectrum of PEG-DPA/PA-mea/fa ester-containing benzoxazine monomer; FIG. 2b) exemplarily presents the DSC curve of PEG-DPA/PA-mea/fa.

    [0128] FIG. 3 exemplarily shows the Stress relaxation curve of PEG-DPA-mea/fa vitrimer at 150 C.

    [0129] FIG. 4 exemplarily shows a schematic synthesis reaction for obtaining the ester-containing benzoxazine monomer of PEG-DPA/PA-mea/a type, wherein R1 and R2 is CH2-CH2- if either x1 or y1=0 and if either x2 or y2=0, and R1 and R2 is CH2-C(CH3)- if either x1 and y10 and x2 and y20, and 0<x10.75, 0<y10.25 and 0<x20.75, 0<y20.25.

    [0130] FIG. 5 exemplarily shows the Stress relaxation curve of PEG-DPA-mea/a vitrimer at 150 C.

    [0131] FIG. 6 exemplarily shows a schematic synthesis reaction for ester-containing benzoxazine monomer named PEG-DPA/PA-aee/fa, wherein R1 and R2 is CH2-CH2- if either x1 or y1=0 and if either x2 or y2=0, and R1 and R2 is CH2-C(CH3)- if either x1 and y10 and x2 and y20, and 0<x10.75, 0<y10.25 and 0<x20.75, 0<y20.25.

    [0132] FIG. 7 exemplarily represents the stress relaxation curve of PEG-DPA/PA-aee/fa vitrimer at 150 C.

    [0133] FIG. 8 exemplarily shows a schematic synthesis reaction for obtaining the ester containing benzoxazine monomer of EG-DPA/PA-mea/ste type, wherein R1 and R2 is CH2-CH2- if either x1 or y1=0 and if either x2 or y2=0, and R1 and R2 is CH2-C(CH3)- if either x1 and y10 and x2 and y20, and 0<x11.0, 0<y11.0 and 0<x21.0, 0<y21.0.

    [0134] FIG. 9 exemplarily shows the stress relaxation curve of poly(EG-DPA-mea/ste) vitrimer at 150 C.

    [0135] FIG. 10 exemplarily shows a schematic synthesis reaction for obtaining the ester containing benzoxazine monomer of GLY-PHBA/PA-na/mipa/aee type, wherein R1 and R2 is (phenyl) and 0<x11.0, 0<y11.0, 0<y11.0; 0<x21.0, 0<y21.0, 0<y21.0; and 0<xp1.0, 0<yp1.0, 0<yp1.0.

    [0136] FIG. 11 exemplarily shows the stress relaxation curve of poly(GLY-PHBA-na/mipa/aee) vitrimer at 150 C.

    [0137] FIG. 12 exemplarily shows a schematic synthesis reaction for obtaining the ester containing benzoxazine monomer of PEG-DPA-mea/fa type, wherein R1 and R2 is CH2-CH2-C(CH3)- and 0<x11.0, 0<y11.0 and 0<x21.0, 0<y21.0.

    [0138] FIGS. 13a), 13b) and 13c) exemplarily show the NMR spectrum of PEG-DPA-mea/fa ester-containing benzoxazine monomers.

    [0139] FIG. 14a) exemplarily shows the DSC and Figure b) the isothermal rheology monitoring curves of PEG-DPA-mea/fa ester-containing benzoxazine monomers.

    [0140] FIG. 15 shows the stress relaxation curves of poly(PEG-DPA-mea/fa) vitrimers at 150 C.

    DETAILED DESCRIPTION

    [0141] All chemicals are commercially available and starting compounds, when applies, used as purchased.

    Example 1: Synthesis of an Ester-Containing Benzoxazine Monomer from 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) and 3-(4-Hydroxyphenyl)propanoic acid (PA) as Phenolic Acid Derivatives and Furfurylamine (fa) and Ethanolamine (mea) as Primary Amine with Aliphatic OH

    [0142] The first step, step a), corresponds to a Fischer esterification between polyethylene glycol (PEG) (M.sub.n=400 g.Math.mol.sup.1, p=8-9, 1 eq, 2.8 g), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) (0.85 eq, 1.73 g) and 3-(4-Hydroxyphenyl)propanoic acid (PA) (0.15 eq, 1.35 g) in presence of p-toluene sulfonic acid (pTSA) introduced in catalytic amount (1 wt %). PEG, DPA, PA and pTSA were reacted together in melt at 130 C. and agitated by mechanical stirring for 24 hours, to provide 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic acid ester terminated polyethylene glycol (PEG-DPA/PA).

    [0143] The second step, step b), corresponds to a Mannich condensation between 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic acid ester terminated polyethylene glycol (PEG-DPA/PA) (1 eq, 5.4 g), furfurylamine (1.25 eq, 0.51 g) ethanolamine (mea) (1.75 eq, 0.97 g) and paraformaldehyde (PFA) (8.5 eq, 2 g). All these reactants were reacted together in melt at 85 C. and agitated by mechanical stirring for 8 hours to provide the ester-containing benzoxazine monomer named PEG-DPA/PA-mea/fa (see FIG. 1).

    [0144] The FIG. 2a) displays the NMR spectrum (AVANCE III HD Bruker spectrometer) of PEG-DPA/PA-mea/fa ester-containing benzoxazine monomer in CDCl.sub.3.

    [0145] The DSC curve (Netzsch DSC 204 F1 Phoenix apparatus) shows an exothermic peak starting at a temperature of 125 C., with a maximum located at 180 C. (FIG. 2b)). This peak corresponds to the ring opening of the benzoxazine rings upon heating. The second peak corresponds to the thermal decomposition of the ester linkage confirmed by TGA experiment.

    Example 2: Vitrimer Synthesis from PEG-DPA/PA-mea/fa Benzoxazine Monomer

    [0146] The PEG-DPA/PA-mea/fa benzoxazine monomer was cured 1 h at 170 C., allowing the benzoxazine rings to open and to react on themselves to form a 3D network vitrimer in a disk shape. The vitrimer behaviour of this sample was demonstrated through several rheology experiment.

    [0147] Viscoelastic properties of PEG-DPA-mea/fa vitrimer were studied by stress relaxation experiments recorded on Anton Paar Physica MCR 302 rheometer in plate-plate mode at 1% shear strain (FIG. 3). The relaxation time of the polymer was clearly noticeable and was recorded at 39.6 min at 150 C.

    Example 3: Synthesis of an Ester-Containing Benzoxazine Monomer from 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) and 3-(4-Hydroxyphenyl)propanoic acid (PA) as a Phenolic Acid Derivatives and Aniline (a) and Ethanolamine (mea) as Primary Amine with Aliphatic OH

    [0148] Ester-containing benzoxazine monomer was synthesized in two stages.

    [0149] The first step, step a), corresponds to a Fischer esterification between polyethylene glycol (PEG) (M.sub.n=400 g.Math.mol.sup.1, p=8-9, 1 eq, 2.8 g), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) (0.85 eq, 1.73 g) and 3-(4-Hydroxyphenyl)propanoic acid (PA) (0.15 eq, 1.35 g) in presence of p-toluene sulfonic acid (pTSA) introduced in catalytic amount (1 wt %). PEG, DPA, PA and pTSA were reacted together in melt at 130 C. and agitated by mechanical stirring for 24 hours, to provide 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic acid ester terminated polyethylene glycol (PEG-DPA/PA).

    [0150] The second step, step b), corresponds to a Mannich condensation between 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic acid ester terminated polyethylene glycol (PEG-DPA/PA) (1 eq, 5.4 g), aniline (1.25 eq, 0.79 g) ethanolamine (mea) (1.75 eq, 0.97 g) and paraformaldehyde (PFA) (8.5 eq, 2 g). All these reactants were reacted together in melt at 85 C. and agitated by mechanical stirring for 8 hours to provide the ester-containing benzoxazine monomer named PEG-DPA/PA-mea/a (see FIG. 4).

    Example 4: Vitrimer Synthesis from PEG-DPA/PA-mea/a Benzoxazine Monomer

    [0151] The PEG-DPA/PA-mea/a benzoxazine monomer was cured 1 h at 170 C., allowing the benzoxazine rings to open and to react on themselves to form a 3D network vitrimer in a disk shape. The vitrimer behaviour of this sample was demonstrated through several rheology experiment.

    [0152] Viscoelastic properties of PEG-DPA/PA-mea/a vitrimer were studied by stress relaxation experiments recorded on Anton Paar Physica MCR 302 rheometer in plate-plate mode at 1% shear strain (FIG. 5). The relaxation time of the polymer was clearly noticeable and was recorded at 41.5 min at 150 C.

    Example 5: Synthesis of an Ester-Containing Benzoxazine Monomer from 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) and 3-(4-Hydroxyphenyl)propanoic acid (PA) as a Phenolic Acid Derivatives and Furfurylamine (a) and 2-(2-Aminoethoxy)ethanol (aee) as Primary Amine with Aliphatic OH

    [0153] The first step, step a), corresponds to a Fischer esterification between polyethylene glycol (PEG) (M.sub.n=400 g.Math.mol.sup.1, p=8-9, 1 eq, 2.8 g), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) (0.85 eq, 1.73 g) and 3-(4-Hydroxyphenyl)propanoic acid (PA) (0.15 eq, 1.35 g) in presence of p-toluene sulfonic acid (pTSA) introduced in catalytic amount (1 wt %). PEG, DPA, PA and pTSA were reacted together in melt at 130 C. and agitated by mechanical stirring for 24 hours, to provide 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic acid ester terminated polyethylene glycol (PEG-DPA/PA).

    [0154] The second step, step b), corresponds to a Mannich condensation between 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic acid ester terminated polyethylene glycol (PEG-DPA/PA) (1 eq, 5.4 g), furfurylamine (1.25 eq, 0.51 g), 2-(2-Aminoethoxy)ethanol (aee) (1.75 eq, 1.53 g) and paraformaldehyde (PFA) (8.5 eq, 2 g). All these reactants were reacted together in melt at 85 C. and agitated by mechanical stirring for 8 hours to provide the ester-containing benzoxazine monomer named PEG-DPA/PA-aee/fa (FIG. 6).

    Example 6: Vitrimer Synthesis from PEG-DPA/PA-aee/fa Benzoxazine Monomer

    [0155] The PEG-DPA/PA-aee/fa benzoxazine monomer was cured 1 h at 170 C., allowing the benzoxazine rings to open and to react on themselves to form a 3D network vitrimer in a disk shape. The vitrimer behaviour of this sample was demonstrated through several rheology experiment.

    [0156] Viscoelastic properties of PEG-DPA/PA-aee/fa vitrimer were studied by stress relaxation experiments recorded on Anton Paar Physica MCR 302 rheometer in plate-plate mode at 1% shear strain (FIG. 7). The relaxation time of the polymer was clearly noticeable and was recorded at 75.6 min at 150 C.

    Example 7: Synthesis of an Ester-Containing Benzoxazine Monomer from Ethylene Glycol (EG), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) and 3-(4-hydroxyphenyl)propanoic acid (PA) as Phenolic Acid Derivatives and Stearylamine (ste) and Mono-Ethanolamine (mea) as Primary Amine with Aliphatic OH

    [0157] The first step, step a), corresponds to a Fischer esterification between ethylene glycol (EG) (1 eq, 5.00 g), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) (1 eq, 23.07 g) and 3-(4-Hydroxyphenyl)propanoic acid (PA) (1 eq, 13.39 g) in presence of p-toluene sulfonic acid (pTSA) introduced in catalytic amount (1 wt %). EG, DPA, PA and pTSA were reacted together in melt at 130 C. and agitated by mechanical stirring for 24 hours, to provide 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-hydroxyphenyl) propanoic ester terminated ethylene glycol (EG-DPA/PA).

    [0158] The second step, step b), corresponds to a Mannich condensation between 4,4-Bis(4-hydroxyphenyl)valeric and 3-(4-Hydroxyphenyl)propanoic ester terminated ethylene glycol (EG-DPA/PA) (1 eq, 5.00 g), stearylamine (ste) (1 eq, 2.82 g), mono-ethanolamine (mea) (1 eq, 0.64 g) and paraformaldehyde (PFA) (4 eq, 1.25 g). All these reactants were reacted together in melt at 85 C. and agitated by mechanical stirring for 8 hours to provide the ester-containing benzoxazine monomer named EG-DPA/PA-mea/ste (FIG. 8).

    Example 8: Vitrimer Synthesis from EG-DPA/PA-mea/ste Benzoxazine Monomer

    [0159] The EG-DPA/PA-mea/ste benzoxazine monomer was cured 1 h at 170 C., allowing the benzoxazine rings to open and to react on themselves to form a 3D network vitrimer in a disk shape. The vitrimer behaviour of this sample was demonstrated through several rheology experiment. Viscoelastic properties of poly(EG-DPA/PA-mea/ste) vitrimer were studied by stress relaxation experiments recorded on Anton Paar Physica MCR 302 rheometer in plate-plate mode at 1% shear strain (FIG. 9). The relaxation time of the polymer was clearly noticeable and was recorded at 49.4 min at 150 C.

    Example 9: Synthesis of an Ester-Containing Benzoxazine Monomer from Glycerol (GLY), 4-hydroxybenzoic acid (PHBA) as a Phenolic Acid Derivative and Nitroaniline (Na) and Mono-Isopropylamine (mipa) and 2-(2-Aminoethoxy)ethanol (aee) as Primary Amine with Aliphatic OH

    [0160] The first step, step a), corresponds to a Fischer esterification between glycerol (GLY) (1 eq, 5.00 g), 4-hydroxybenzoic acid (PHBA) (3 eq, 22.50 g) in presence of p-toluene sulfonic acid (pTSA) introduced in catalytic amount (1 wt %). GLY, PHBA, and pTSA were reacted together in melt at 130 C. and agitated by mechanical stirring for 24 hours, to provide 4-hydroxybenzoic ester terminated glycerol (GLY-PHBA).

    [0161] The second step, step b), corresponds to a Mannich condensation between 4-hydroxybenzoic ester terminated glycerol (GLY-PHBA) (1 eq, 5.00 g), nitroaniline (na) (1 eq, 1.53 g), mono-isopropylamine (mipa) (1 eq, 0.65 g), 2-(2-Aminoethoxy)ethanol (aee) (1 eq, 1.16 g), and paraformaldehyde (PFA) (6 eq, 1.99 g). All these reactants were reacted together in melt at 85 C. and agitated by mechanical stirring for 8 hours to provide the ester-containing benzoxazine monomer named GLY-PHBA-na/mipa/aee (FIG. 10).

    Example 10: Vitrimer Synthesis from GLY-PHBA-na/mipa/aee Benzoxazine Monomer

    [0162] The GLY-PHBA-na/mipa/aee benzoxazine monomer was cured 1 h at 170 C., allowing the benzoxazine rings to open and to react on themselves to form a 3D network vitrimer in a disk shape. The vitrimer behaviour of this sample was demonstrated through several rheology experiment. Viscoelastic properties of poly(GLY-PHBA-na/mipa/aee) vitrimer were studied by stress relaxation experiments recorded on Anton Paar Physica MCR 302 rheometer in plate-plate mode at 1% shear strain (FIG. 11). The relaxation time of the polymer was clearly noticeable and was recorded at 88.1 min at 150 C.

    Example 11: Synthesis of an Ester-Containing Benzoxazine Monomer from Polyethylene Glycol (PEG), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) as Phenolic Acid Derivative and Furfurylamine (fa) and Mono-Ethanolamine (mea) as Primary Amine with Aliphatic OH

    [0163] The first step, step a), corresponds to a Fischer esterification between polyethylene glycol (PEG) (M.sub.n=400 g.Math.mol.sup.1, p=8-9, 1 eq, 5.00 g), 4,4-Bis(4-hydroxyphenyl)valeric acid (DPA) (2 eq, 7.16 g) in presence of p-toluene sulfonic acid (pTSA) introduced in catalytic amount (1 wt %). PEG, DPA, and pTSA were reacted together in melt at 130 C. and agitated by mechanical stirring for 24 hours, to provide 4,4-Bis(4-hydroxyphenyl)valeric ester terminated polyethylene glycol (PEG-DPA).

    [0164] The second step, step b), corresponds to a Mannich condensation between 4,4-Bis(4-hydroxyphenyl)valeric ester terminated polyethylene glycol (PEG-DPA) (1 eq, 5.00 g), furfurylamine (fa) (1.0-2.0-3.0 eq, 0.52-1.04-1.56 g), mono-ethanolamine (mea) (3.0-2.0-1.0 eq, 0.98-0.65-0.33 g) and paraformaldehyde (PFA) (8 eq, 1.28 g). All these reactants were reacted together in melt at 70 C. and agitated by mechanical stirring for 24 hours to provide ester-containing benzoxazine monomers named respectively PEG-DPA-mea75/fa25 (1.0 eq fa, 3.0 eq. mea), PEG-DPA-mea50/fa50 (2.0 eq fa, 2.0 eq. mea), and PEG-DPA-mea25/fa75 (3.0 eq fa, 1.0 eq. mea) (FIG. 12).

    [0165] The FIG. 13 is displaying the .sup.1H NMR spectrum (AVANCE III HD Bruker spectrometer) of NMR spectrum of a) PEG-DPA-mea75/fa25, b) PEG-DPA-mea50/fa50, and c) PEG-DPA-mea25/fa75 ester-containing benzoxazine monomers.

    [0166] DSC curves in FIG. 14.a show an exothermic peak starting at a temperature of 123, 127 and 135 C. for PEG-DPA-mea75/fa25, PEG-DPA-mea50/fa50, and PEG-DPA-mea25/fa75, respectively. This peak corresponds to the ring opening of the benzoxazine rings upon heating. The second peak corresponds to the thermal decomposition of the ester linkage.

    [0167] The curing of the PEG-DPA-mea/fa ester-containing benzoxazine monomers was monitored by rheological measurement in FIG. 14.b. The rheogram is performed under the following conditions: 1 Hz, with linear amplitude from 1 to 0.1%; 25 mm plates. The test is performed following a heating ramp from 80 C. to 140 C. at 15 C..Math.min.sup.1 followed by an isothermal measurement at 140 C. The storage and loss modulus are recorded as a function of time. The term gelation time is defined as the time when the storage and the loss modulus of the soften monomer increases abruptly to transform into a gel. The gelation is defined by the crossover point between the storage and the loss modulus. At 140 C., the gelation time is reached after 2012, 3172 and 3410 s, respectively for PEG-DPA-mea75/fa25, PEG-DPA-mea50/fa50, and PEG-DPA-mea25/fa75.

    Example 12: Vitrimer Synthesis from PEG-DPA-mea/fa Benzoxazine Monomers

    [0168] The PEG-DPA-mea/fa benzoxazine monomer from Example 11 was cured 1 h at 150 C. and 0.5 h at 170 C., allowing the benzoxazine rings to open and to react on themselves to form a 3D network vitrimer in a disk shape. The vitrimer behaviour of this sample was demonstrated through several rheology experiment. Viscoelastic properties of PEG-DPA-mea/fa vitrimers were studied by stress relaxation experiments recorded on Anton Paar Physica MCR 302 rheometer in plate-plate mode at 1% shear strain (FIG. 15). The relaxation time of the polymer was clearly noticeable and was recorded at 33.5, 52.9, and 56.8 min at 150 C. for poly(PEG-DPA-mea75/fa25), poly(PEG-DPA-mea50/fa50), and poly(PEG-DPA-mea25/fa75), respectively.