Self-healing oligomers and the use thereof
Disclosed herein are self-healing oligomers according to the structure [UPy-(D m -U-D m )( 2+q )]-[A(G)( n−1 )-D m ] k -Z; wherein UPy, D, m, U, q, A, G, n, k, and Z are defined and described further herein, and wherein the oligomer possesses at least 3 urethane linking groups and comprises a backbone derived from a polyether polyol, a polyester polyol, a poly(dimethylsiloxane), a disulfide polyol, or combinations thereof. Also described and claimed are various compositions containing such oligomers as part of a self-healing component, wherein such compositions also include an optional reactive monomer and/or oligomer component and a photoinitiator component. Yet further described and claimed are articles cured from the compositions elsewhere described using the oligomers elsewhere described.
1 . A self-healing oligomer according to the following structure (VII):
[UPy-(D m -U-D m ) (2+q) ]-[A(G) (n−1) -D m ] k -Z (VII);
wherein
UPy represents a UPy group, wherein the UPy group is a 2-ureido-4-pyrimidinone;
U represents —NHC(O)E- or -EC(O)NH—, wherein E is O, NH, N(alkyl), or S;
q is a number greater than or equal to 0 and less than or equal to 10;
k is a number from 0 to 20;
A is selected from carbon and nitrogen;
n is 2 or 3, wherein when A is an sp3 carbon, n=3, and when A is an sp2 carbon or a nitrogen, n=2;
m is an integer from 0 to 500;
D is, for each occurrence of m, a divalent spacer independently chosen from —O—,
—C(O)—, -Aryl-, —C≡C—, —N═N—, —S—, —S(O)—,
—S(O)(O)—,
—(CT 2 ) i -, —N(T)-, —Si(T) 2 (CH 2 ) i —, —(Si(T) 2 O) i —, —C(T)=C(T)-, —C(T)=N—, —C(T)=, —N═, or combinations thereof;
wherein
for each instance in D of a single bond, a single bond is connected thereto, and for each instance in D of a double bond, a double bond is connected thereto;
wherein
each T is selected for each occurrence from single valent units including hydrogen, F, Cl, Br, I, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, substituted amino, or substituted aryl;
wherein each T can also be selected from divalent D m and connects to another divalent T that is also selected from D m and form a ring structure;
and i is an integer from 1-40;
Z is chosen from a hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimido group; and
G is, for each occurrence of n, independently selected from hydrogen, -D m -Z, or a self-healing moiety according to the following structure (VII-b):
(Z-D m ) j X-D m - (VII-b);
wherein
X is a multi-hydrogen bonding group, a disulfide group, or a urea group;
j=1 when X is divalent, and j=0 when X is monovalent;
wherein the self-healing oligomer possesses at least 3 occurrences of U;
and wherein the oligomer comprises a backbone derived from a polyether polyol, a polyester polyol, a poly(dimethylsiloxane), a disulfide polyol, or mixtures thereof.
2 . The self-healing oligomer of claim 1 , wherein the oligomer possesses from 0.025 to 0.4 equivalents of UPy groups per 100 grams of the oligomer.
3 . The self-healing oligomer of claim 1 , wherein Z is an isocyanato or protected isocyanato.
4 . The self-healing oligomer according to claim 1 , wherein q is greater than or equal to 1 and less than or equal to 4.
5 . The self-healing oligomer according to claim 1 , wherein 2+q is a number larger than or equal to 2 and less than or equal to 4.
6 . The self-healing oligomer according to claim 1 , wherein 2+q is a number larger than 4 and less than or equal to 10.
7 . The self-healing oligomer according to claim 1 , wherein the theoretical molecular weight (MW theo ) (in g/mol) of the self-healing oligomer is between 500 and 8000.
8 . The self-healing oligomer according to claim 1 , wherein UPy is represented by the following structure (VIII-a):
wherein R is the remaining portion of structure VII; and wherein
m is an integer from 0 to 500;
D is, for each occurrence of m, a divalent spacer independently chosen from —O—,
—C(O)—, -Aryl-, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—_,
—(CT 2 ) i -, —N(T)-, —Si(T) 2 (CH 2 ) i —, —(Si(T) 2 O) i —, —C(T)=C(T)-, —C(T)=N—, —C(T)=, —N═, or combinations thereof;
wherein
for each instance in D of a single bond, a single bond is connected thereto, and for each instance in D of a double bond, a double bond is connected thereto;
wherein
each T is selected for each occurrence from single valent units including hydrogen, F, Cl, Br, I, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, substituted amino, or substituted aryl;
wherein each T can also be selected from divalent D m and connects to another divalent T that is also selected from D m and form a ring structure; and
and i is an integer from 1-40; and
Z is chosen from a hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate acid, hydrogen, F, Cl, Br, I, or maleimido group.
9 . The self-healing oligomer according to claim 1 , wherein UPy is represented by the following structure (VIII-b):
wherein R is the remaining portion of structure (VII).
10 . The self-healing oligomer according to claim 1 , wherein X is a multi-hydrogen bonding group or a disulfide group.
11 . The self-healing oligomer according to claim 1 , wherein the multi-hydrogen bonding group comprises UPy groups.
12 . The self-healing oligomer according to claim 1 , wherein the self-healing oligomer according to structure (VII) possesses from 3 to 6 urethane linking groups.
13 . The self-healing oligomer according to claim 12 , wherein if the self-healing oligomer according to structure (VII) possesses from 3 to 4 urethane linking groups, the oligomer possesses a MW theo from 500 to 4505 g/mol.
14 . The self-healing oligomer according to claim 12 , wherein if the self-healing according to structure (VII) possesses from 4 to 5 urethane linking groups, the oligomer possesses a MW theo from 500 to 8000 g/mol.
15 . The self-healing oligomer according to claim 1 , wherein the self-healing oligomer is according to any one of the following structures (XI), (XII), (XIII), (XVIII), (XXI), or (XXXIV):
or mixtures thereof;
wherein n is greater than 0 and may be any number provided that the MW theo of the oligomer is maintained to less than 5000 g/mol.
16 . The self-healing oligomer according to claim 1 , wherein the self-healing oligomer is according to any one of the following structures (IX), (X), (XIV)-(XVII), (XXII), (XXIII), (XXV)-(XXVII), (XXIX), (XXX), (XXXII), (XXXIII), (XXXV)-(XXXVII), or (XL):
or mixtures thereof;
wherein n and m are greater than 0 and may be independently any number provided that the MW theo of the oligomer is maintained to less than 5000 g/mol;
wherein, for each occurrence of an acrylate group above, a methacrylate group alternatively may be substituted therefor, and for each occurrence of a methacrylate group above, an acrylate group alternatively may be substituted therefor.
17 . The self-healing oligomer according to claim 1 , wherein the self-healing oligomer is according to the following structure (XXXI):
wherein, for each occurrence of an acrylate group above, a methacrylate group alternatively may be substituted therefor, and for each occurrence of a methacrylate group above, an acrylate group alternatively may be substituted therefor.
18 . The self-healing oligomer according to claim 1 , wherein the oligomer according to structure (VII) possess a MW theo from 500 to 4500 per every instance of a UPy moiety.