US 2024/0034720 A1 · Benzoxazine Derivatives Vitrimers

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.

Claims13

Dependent claims

-14. (canceled)

An ester containing benzoxazine monomer of formula (I)

wherein
R1 is
and
Rp is selected from the group consisting of H, a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group and
R1 and R2 of formula (I) are different;
x1, x2 and xp, independently, are of from 0 to 1 and are not together 0;
y1=1-x1;
y2=1-x2 and yp=1-xp;
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 namine(R1)total=namines(R1)+naminoalcohol(R1), and naminoalcohol(R1) being the number of aminoalcohol per R1 group, namines(R1) represent the number of amines (excepting the number of aminoalcohol) per group R1 and namine(R1)total=namines(R1)+naminoalcohol(R1) is the total number of amino groups per group R1;
wherein namine(R2)total=namines(R2)+naminoalcohol(R2), and naminoalcohol(R1) being the number of aminoalcohol per R2 group, namines(R2) represents the number of amines (excepting the number of aminoalcohol) per group R2 and namine(R2)total=namines(R2)+naminoalcohol(R2) is the total number of amino groups per group R2;
wherein namine(Rp)total=namines(Rp)+naminoalcohol(Rp), and naminoalcohol(Rp) being the number of aminoalcohol per Rp group, namines(Rp) represents the number of amines (excepting the number of aminoalcohol) per group Rp and namine(Rp)total=namines(Rp)+naminoalcohol(Rp) is the total number of amino groups per group Rp,
R1′, R2′, and Rp′, independently, are selected from the group consisting of a —C-linear or branched C1-C6 alkyl or alkoxy group, a —C-linear or branched C2-C6 alkenyl or alkylenoxy group, a —C-substituted or unsubstituted linear or branched C2-C6 alkynyl group, and a —C-linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
Rp″ is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group and a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
R* is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heteocyclo(C3-C6alkyl) group, wherein the hetero atom is selected from N, S, and O, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group, a (CH2)n3-phenyl group and a —(CH2)n3—O—(CH2)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—(CH2)n3—CH—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—[(CH2)n3—CH3]2 group, a O-substituted or unsubstituted C2-C6 linear or branched alkynyl group, a —(CH2)n3—C≡N group and a polycyclic aromatic or a heteroaromatic hydrocarbon, such as naphthalene, anthracene, fluorene, phenanthrene, optionally substituted by a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heterocyclo(C3-C6alkyl) group, a linear or branched C2-C6 alkenyl or alkylenoxy group, or by a substituted or unsubstituted linear or branched C2-C6 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 C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group and a linear or branched C1-C6 alkyl or C2-C6 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 C1-C6 alkyl group, and further includes a linear or branched C1-C15 alkyl group or a C2-C15 alkenyl group or

132 more elements

A process for preparing a polybenzoxazine derivative vitrimer comprising the step of polymerization of an ester-containing benzoxazine monomer of formula (I)

wherein
R1 is
and
Rp is selected from the group consisting of H, a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group and
R1 and R2 of formula (I) are different;
x1, x2 and xp, independently, are of from 0 to 1 and are not together 0;
y1=1-x1;
y2=1-x2 and yp=1-xp;
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 namine(R1)total=namines(R1)+naminoalcohol(R1), and naminoalcohol(R1) being the number of aminoalcohol per R1 group, namines(R1) represent the number of amines (excepting the number of aminoalcohol) per group R1 and namine(R1)total=namines(R1)+naminoalcohol(R1) is the total number of amino groups per group R1;
wherein namine(R2)total=namines(R2)+naminoalcohol(R2), and naminoalcohol(R2) being the number of aminoalcohol per R2 group, namines(R2) represents the number of amines (excepting the number of aminoalcohol) per group R2 and namine(R2)total=namines(R2)+naminoalcohol(R2) is the total number of amino groups per group R2;
wherein namine(Rp)total=namines(Rp)+naminoalcohol(Rp), and naminoalcohol(Rp) being the number of aminoalcohol per Rp group, namines(Rp) represents the number of amines (excepting the number of aminoalcohol) per group Rp and namine(Rp)total=namines(Rp)+naminoalcohol(Rp) is the total number of amino groups per group Rp,
R1′, R2′, and Rp′, independently, are selected from the group consisting of a —C-linear or branched C1-C6 alkyl or alkoxy group, a —C-linear or branched C2-C6 alkenyl or alkylenoxy group, a —C-substituted or unsubstituted linear or branched C2-C6 alkynyl group, and a —C-linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
Rp″ is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group and a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
R* is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heteocyclo(C3-C6alkyl) group, wherein the hetero atom is selected from N, S, and O, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group, a (CH2)n3-phenyl group and a —(CH2)n3—O—(CH2)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—(CH2)n3—CH—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—[(CH2)n3—CH3]2 group, a O-substituted or unsubstituted C2-C6 linear or branched alkynyl group, a —(CH2)n3—C≡N group and a polycyclic aromatic or a heteroaromatic hydrocarbon, such as naphthalene, anthracene, fluorene, phenanthrene, optionally substituted by a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heterocyclo(C3-C6alkyl) group, a linear or branched C2-C6 alkenyl or alkylenoxy group, or by a substituted or unsubstituted linear or branched C2-C6 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 C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group and a linear or branched C1-C6 alkyl or C2-C6 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 C1-C6 alkyl group, and further includes a linear or branched C1-C15 alkyl group or a C2-C15 alkenyl group or
at temperatures within the range of from 100° C. to 250° C. for 1 h to 24 h, for obtaining polybenzoxazine derivatives vitrimers.

133 more elements

Dependencies are inferred from the claim text.

Facts

Application

18/256,785Filed 7 Dec 2021

Priority

LU 1023189 Dec 2020

Published

1 Feb 2024

Term ends

Not estimatedThe source records don’t support an estimate.

Classification12 codes

C07D 265/16
Condensed with one six-membered ring: with only hydrogen or carbon atoms directly attached in positions 2 and 4
C07D 413/12
Containing two hetero rings: linked by a chain containing hetero atoms as chain links
C07D 413/14
Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms:…
C08G 65/34
Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule: from hydroxy compounds or their…

Abstract

Claims13

Dependent claims

-14. (canceled)

An ester containing benzoxazine monomer of formula (I)

wherein
R1 is
and
Rp is selected from the group consisting of H, a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group and
R1 and R2 of formula (I) are different;
x1, x2 and xp, independently, are of from 0 to 1 and are not together 0;
y1=1-x1;
y2=1-x2 and yp=1-xp;
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 namine(R1)total=namines(R1)+naminoalcohol(R1), and naminoalcohol(R1) being the number of aminoalcohol per R1 group, namines(R1) represent the number of amines (excepting the number of aminoalcohol) per group R1 and namine(R1)total=namines(R1)+naminoalcohol(R1) is the total number of amino groups per group R1;
wherein namine(R2)total=namines(R2)+naminoalcohol(R2), and naminoalcohol(R1) being the number of aminoalcohol per R2 group, namines(R2) represents the number of amines (excepting the number of aminoalcohol) per group R2 and namine(R2)total=namines(R2)+naminoalcohol(R2) is the total number of amino groups per group R2;
wherein namine(Rp)total=namines(Rp)+naminoalcohol(Rp), and naminoalcohol(Rp) being the number of aminoalcohol per Rp group, namines(Rp) represents the number of amines (excepting the number of aminoalcohol) per group Rp and namine(Rp)total=namines(Rp)+naminoalcohol(Rp) is the total number of amino groups per group Rp,
R1′, R2′, and Rp′, independently, are selected from the group consisting of a —C-linear or branched C1-C6 alkyl or alkoxy group, a —C-linear or branched C2-C6 alkenyl or alkylenoxy group, a —C-substituted or unsubstituted linear or branched C2-C6 alkynyl group, and a —C-linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
Rp″ is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group and a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
R* is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heteocyclo(C3-C6alkyl) group, wherein the hetero atom is selected from N, S, and O, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group, a (CH2)n3-phenyl group and a —(CH2)n3—O—(CH2)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—(CH2)n3—CH—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—[(CH2)n3—CH3]2 group, a O-substituted or unsubstituted C2-C6 linear or branched alkynyl group, a —(CH2)n3—C≡N group and a polycyclic aromatic or a heteroaromatic hydrocarbon, such as naphthalene, anthracene, fluorene, phenanthrene, optionally substituted by a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heterocyclo(C3-C6alkyl) group, a linear or branched C2-C6 alkenyl or alkylenoxy group, or by a substituted or unsubstituted linear or branched C2-C6 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 C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group and a linear or branched C1-C6 alkyl or C2-C6 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 C1-C6 alkyl group, and further includes a linear or branched C1-C15 alkyl group or a C2-C15 alkenyl group or

132 more elements

A process for preparing a polybenzoxazine derivative vitrimer comprising the step of polymerization of an ester-containing benzoxazine monomer of formula (I)

wherein
R1 is
and
Rp is selected from the group consisting of H, a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group and
R1 and R2 of formula (I) are different;
x1, x2 and xp, independently, are of from 0 to 1 and are not together 0;
y1=1-x1;
y2=1-x2 and yp=1-xp;
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 namine(R1)total=namines(R1)+naminoalcohol(R1), and naminoalcohol(R1) being the number of aminoalcohol per R1 group, namines(R1) represent the number of amines (excepting the number of aminoalcohol) per group R1 and namine(R1)total=namines(R1)+naminoalcohol(R1) is the total number of amino groups per group R1;
wherein namine(R2)total=namines(R2)+naminoalcohol(R2), and naminoalcohol(R2) being the number of aminoalcohol per R2 group, namines(R2) represents the number of amines (excepting the number of aminoalcohol) per group R2 and namine(R2)total=namines(R2)+naminoalcohol(R2) is the total number of amino groups per group R2;
wherein namine(Rp)total=namines(Rp)+naminoalcohol(Rp), and naminoalcohol(Rp) being the number of aminoalcohol per Rp group, namines(Rp) represents the number of amines (excepting the number of aminoalcohol) per group Rp and namine(Rp)total=namines(Rp)+naminoalcohol(Rp) is the total number of amino groups per group Rp,
R1′, R2′, and Rp′, independently, are selected from the group consisting of a —C-linear or branched C1-C6 alkyl or alkoxy group, a —C-linear or branched C2-C6 alkenyl or alkylenoxy group, a —C-substituted or unsubstituted linear or branched C2-C6 alkynyl group, and a —C-linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
Rp″ is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group and a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group;
R* is selected from the group consisting of a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heteocyclo(C3-C6alkyl) group, wherein the hetero atom is selected from N, S, and O, a linear or branched C2-C6 alkenyl or alkylenoxy group, a substituted or unsubstituted linear or branched C2-C6 alkynyl group, a linear or branched C1-C6 alkyl or C2-C6 alkenyl substituted or unsubstituted phenyl group, a (CH2)n3-phenyl group and a —(CH2)n3—O—(CH2)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—(CH2)n3—CH—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH3)2 group, a O—, N— or S—(CH2)n3—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—(CH2)n3—CH3 group, a O—, N— or S—(CHZ)n4—[(CH2)n3—CH3]2 group, a O-substituted or unsubstituted C2-C6 linear or branched alkynyl group, a —(CH2)n3—C≡N group and a polycyclic aromatic or a heteroaromatic hydrocarbon, such as naphthalene, anthracene, fluorene, phenanthrene, optionally substituted by a linear or branched C1-C6 alkyl or alkoxy group, a cyclo(C3-C6alkyl) group, a heterocyclo(C3-C6alkyl) group, a linear or branched C2-C6 alkenyl or alkylenoxy group, or by a substituted or unsubstituted linear or branched C2-C6 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 C1-C6 alkyl or alkoxy group, a linear or branched C2-C6 alkenyl or alkylenoxy group and a linear or branched C1-C6 alkyl or C2-C6 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 C1-C6 alkyl group, and further includes a linear or branched C1-C15 alkyl group or a C2-C15 alkenyl group or
at temperatures within the range of from 100° C. to 250° C. for 1 h to 24 h, for obtaining polybenzoxazine derivatives vitrimers.

133 more elements

Dependencies are inferred from the claim text.

Benzoxazine Derivatives Vitrimers

Life of this patent

Abstract

Claims13

Benzoxazine Derivatives Vitrimers

Life of this patent

Abstract

Claims13