Epoxy-derived covalent adaptable networks and methods of their production
The invention relates to a composition comprising an epoxy-derived covalent adaptable network, preferably an epoxy vitrimer comprising at least one unit of formula (I) The invention further relates to a method for preparing a composition comprising an epoxy-derived covalent adaptable network by contacting at least one amine comprising primary, at least one vinylogous precursor comprising vinylogous precursor groups and at least one epoxide comprising epoxide groups whereby the number of amine groups, the number of vinylogous precursor groups and the number of epoxide groups is controlled.
1 . A composition comprising an epoxy-derived covalent adaptable network, said epoxy-derived covalent adaptable network comprising at least one unit of formula (I)
wherein
R 1 , R 2 , R 1′ , R 2′ , R 1″ , R 2″ and each occurrence of R 3 , each occurrence of R 3′ and each occurrence of R 3″ are individually selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, arylalkyl and polymeric groups, wherein one or wherein one or more of the carbon atoms in the backbone of said alkyl, alkenyl, alkynyl, aryl or cycloalkyl may be replaced by a heteroatom independently selected from O, S, N and Si and/or wherein said alkyl, alkenyl, alkynyl, aryl or cycloalkyl may be substituted;
R 4 , R 7 and each occurrence of R 9 are individually selected from H or methyl;
R 5 , R 6 and each occurrence of R 8 are individually selected from H or methyl;
X 1 , X 2 and each occurrence of X 3 are individually selected from O, CR 10 R 11 and NR 12 ;
R 10 , R 11 and R 12 are individually selected from H or methyl;
Y 1 and Y 2 are individually selected from O and N;
Z 1 , Z 2 , Z 6 and Z 7 represent the remainder of the epoxy-derived covalent adaptable network;
Z 3 , Z 4 , and Z 5 represent H or the remainder of the epoxy-derived covalent adaptable network;
A represents an epoxide linking moiety;
B represents an amine linking moiety;
C represents a vinylogous precursor linking moiety;
a, b, and c individually represent an integer higher than or equal to 0;
a+b+c is greater than or equal to 1;
the epoxide linking moiety A, the amine linking moiety B and the vinylogous precursor linking moiety C each comprising or consisting of a group independently selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, cycloalkyls and aryl alkyls, wherein one or more of the carbon atoms in the backbone of said alkyls, alkenyls, alkynyls, aryls, cycloalkyls and aryls alkyls may be replaced by a heteroatom independently selected from O, S, N and Si and/or wherein said alkyl, alkenyl, alkynyl aryl, cycloalkyl or arylalkyl may be unsubstituted or further substituted; and
wherein the composition further comprises primary amine groups.
2 . A method for preparing a composition comprising an epoxy-derived covalent adaptable network, comprising the following steps:
a) providing at least one amine of formula (II) comprising primary amine groups, at least one vinylogous precursor of formula (III) comprising vinylogous precursor groups, and at least one epoxide comprising (2+a) epoxide groups
wherein
X 1 , X 2 and each occurrence of X 3 are individually selected from O, CR 10 R 11 and NR 12 ;
R 10 , R 11 and R 12 are individually selected from H or methyl;
W 1 , W 2 and each occurrence of W 3 each represent a functional groups so that —X 1 —C(═O)—W 1 , —X 2 —C(═O)—W 2 and —X 3 —C(═O)—We constitute a vinylogous precursor group;
B represents an amine linking moiety;
C represents a vinylogous precursor linking moiety;
wherein the amine linking moiety B and the vinylogous precursor linking moiety C each comprising or consisting of a group independently selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, cycloalkyls and aryl alkyls, wherein one or more of the carbon atoms in the backbone of said alkyls, alkenyls, alkynyls, aryls, cycloalkyls and aryls alkyls may be replaced by a heteroatom independently selected from O, S, N and Si and/or wherein said alkyl, alkenyl, alkynyl aryl, cycloalkyl or arylalkyl may be unsubstituted or further substituted;
a, b, and c individually represent an integer higher than or equal to 0;
and
b) contacting the compounds provided in step (a) thereby obtaining an epoxy-derived covalent adaptable network;
wherein a vinylogous precursor group consists of or comprises a functional group which is capable of forming a vinylogous urethane, vinylogous amide or vinylogous urea upon reacting with a primary amine;
wherein the average functionality F, determined before the compounds are contacted and determined over all compounds provided in step (a), is at least 2.01, the average functionality F being defined as
F
=
∑
n
i
(
2
+
a
i
)
+
∑
n
j
(
2
+
b
j
)
+
∑
n
k
(
2
+
c
k
)
∑
n
i
+
∑
n
j
+
∑
n
k
wherein n i is the number of moles of epoxide with functionality (2+a i ); n j is the number of moles of amine of formula (II) with functionality (2+b j ) and n k is the number of moles of vinylogous precursor of formula (III) with functionality (2+C k ); and
wherein the ratio P, determined before the compounds are contacted and determined over all compounds provided in step (a), is more than 1, the ratio P being defined as
P
=
∑
n
j
(
2
+
b
j
)
∑
n
i
(
2
+
a
i
)
+
∑
n
k
(
2
+
c
k
)
.
3 . The method according to claim 2 wherein the epoxide comprising (2+a) epoxide groups provided in step (a) is
an epoxidized terpene or a co-polymer thereof;
an epoxidized polydiene or a co-polymer thereof;
an epoxidized vegetable oil or a co-polymer thereof; or
a compound of formula (VII)
wherein
R 1 , R 2 and each occurrence of R 3 are individually selected from H or methyl;
R 1′ , R 2′ and each occurrence of R 3′ are individually selected from H or methyl;
R 1″ , R 2″ and each occurrence of R 3″ are individually selected from H or methyl;
a represents an integer higher than or equal to 0, ; and A represents an epoxide linking moiety, wherein the epoxide linking moiety A comprises or consists of a group selected from the group consisting of alkyls, alkenyls, alkynyls, aryls, cycloalkyls and aryl alkyls, wherein one or more of the carbon atoms in the backbone of said alkyls, alkenyls, alkynyls, aryls, cycloalkyls and aryls alkyls may be replaced by a heteroatom selected from O, S, N and Si and/or wherein said alkyl, alkenyl, alkynyl aryl, cycloalkyl or arylalkyl may be unsubstituted or further substituted.
4 . The method according to claim 2 wherein step (b) comprises contacting the compounds provided in step (a) such that the ratio P is more than 1.005.
5 . The method according to claim 2 wherein step (b) comprises contacting the compounds provided in step (a) such that the average functionality F is more than 2.02 and/or less than 4.
6 . The method to claim 2 , wherein step (b) comprises contacting the compounds provided in step (a) such that the ratio of the number of vinylogous precursor groups to the sum of the number of epoxide groups and the number of vinylogous precursor groups, determined before the compounds are contacted and determined over all compounds provided in step (a) is in the range of 0.1-0.8, preferably in the range of 0.2-0.6, more preferably in the range of 0.3-0.5, most preferably in the range of 0.35-0.45.
7 . The method according to claim 2 wherein the vinylogous precursor of formula (III) is 1,3 dicarbonyl of formula (IV), an alkynon of formula (V), or an alkenon of formula (VI)
wherein
R 4 , R 7 and each occurrence of R 9 are individually selected from H, methyl or phenyl;
R 5 , R 6 and each occurrence of R 8 are individually selected from H or methyl;
X 1 , X 2 and each occurrence of X 3 have the same meaning as defined herein before;
C represents a vinylogous precursor linking moiety; and
L 1 , L 2 and each occurrence of L 3 represent a leaving group which can be displaced upon reaction with a primary amine.
8 . The method according to claim 2 , wherein step (b) comprises the following steps
b1) contacting at least part of the amine of formula (II) with at least part of the vinylogous precursor of formula (III) to obtain a composition comprising a vinylogous curing agent;
b3) contacting the composition comprising the vinylogous curing agent of step (b1) or (b2) with the epoxide comprising at least (2+a) epoxide groups and optional remaining reagents provided in step (a), thereby obtaining an epoxy-derived CAN.
9 . The method to claim 2 wherein step (a) comprises providing an amine according to formula (II) in the form of a primary amine precursor.
10 . The method according to claim 3 wherein the epoxide comprising (2+a) epoxide groups provided in step (a) is a compound selected from the group consisting of diglycidyl ethers, triglycidyl ethers, diglycidyl amines, triglycidyl amines, diglycidyl isocyanurates and triglycidyl isocyanurates.
11 . The method according to claim 2 wherein the compound of formula (II) provided in step (a) is a compound selected from the group consisting of Diethylenetriamine (DTA); triethylenetetramine; 2,2-Dimethyl-1,3-propanediamine; 4,4′-Methylenebis(2-methylcyclohexylamine); Menthane diamine; Isophoronediamine; 4-4′-Diaminocyclohexylmethane; 1,2-Diaminocyclohexane; 1,3-Bis(Aminomethyl) cyclohexane; m-xylenediamine; Diaminodiphenylmethane; 2-2′-(Ethylenedioxy) bis(ethylamine); Poly(propylene glycol) bis(2-aminopropyl ether); and Tris(2-aminomethyl) amine.
12 . The method according to claim 2 wherein the compounds of formula (III) is a 1,3 dicarbonyl of formula (IV), alkynon of formula (V), or alkenon of formula (VI) obtainable from converting the alcohol groups in a compound selected from the group consisting of 1,4-Benzenedimethanol; 1,4-Cyclohexanedimethanol; 1,2-Ethanediol; 1,10-Decanediol; Trimethylolpropane; 2,2′-Biphenyl dimetanol; 2,4-Dimethyl-2,4-pentanediol; 1,2-Cyclohexanediol; Isosorbide; Di(trimethylolpropane); Dipentaerythritol; and 2,2-Dimethyl-1,3-propanediol into 1,3 dicarbonyls, alkynons or alkenons.
13 . A composition comprising an epoxy-derived covalent adaptable network obtainable by the method according to claim 2 .
14 . A composite comprising the composition according to claim 1 and at least one fiber material.
15 . The composite of claim 14 wherein the at least one fiber material is selected from the group consisting of glass fibers, carbon fibers or combinations thereof.
16 . The method according to claim 2 , wherein step (b) comprises the following steps:
b1) contacting at least part of the amine of formula (II) with at least part of the vinylogous precursor of formula (III) to obtain a composition comprising a vinylogous curing agent;
b2) reducing the water content of the composition comprising the vinylogous curing agent of step (b1); and
b3) contacting the composition comprising the vinylogous curing agent of step (b1) or (b2) with the epoxide comprising at least (2+a) epoxide groups and optional remaining reagents provided in step (a), thereby obtaining an epoxy-derived CAN.
17 . The method according to claim 10 wherein the epoxide comprising (2+a) epoxide groups provided in step (a) is a compound selected from the group consisting of Tris(4-hydroxyphenyl) methane, Trimethylolpropane triglycidyl ether; Bisphenol A diglycidyl ether; Bisphenol F diglycidyl ether; Bisphenol C diglycidyl ether; Bisphenol E diglycidyl ether; Bisphenol BP diglycidyl ether; Bisphenol FC diglycidyl ether; Bisphenol Z diglycidyl ether; 1,6-Hexanediol diglycidyl ether; 1,4-Butanediol diglycidyl ether; Triglycidylisocyanuraat; Hydrogenated Bisphenol A diglycidyl ether; Hydrogenated Bisphenol F diglycidyl ether; Hydrogenated Bisphenol C diglycidyl ether; Hydrogenated Bisphenol E diglycidyl ether; Hydrogenated Bisphenol BP diglycidyl ether; Hydrogenated Bisphenol FC diglycidyl ether; Hydrogenated Bisphenol Z diglycidyl ether; 1,6-Naphthalenediol diglycidyl ether; Neopentyl glycol diglycidyl ether; Poly(propylene glycol) diglycidyl ether; 4,4′-Methylenebis(N,N-diglycidylaniline); and N,N-diglycidyl-4-glycidyloxyaniline.