Self-healing optical fibers and the compositions used to create the same
Disclosed herein are compositions for coating an optical fiber containing an optional reactive monomer and/or oligomer, a self-healing component with self-healing moieties, an initiator component, and optionally an additive component. The self-healing component preferably includes polymerizable moieties. Such compositions contain greater than 30% by weight of the self-healing component, and/or greater than 0.015 equivalents of self-healing moieties per 100 g of the composition. Also disclosed herein are coated optical fibers having a glass fiber, at least one coating layer and an optional ink layer, which are configured to possess self-healing properties and/or stress relaxation behavior. Further disclosed are methods for coating self-healing optical fibers, and optical fiber cables comprising a one or more self-healing coated optical fibers.
1 . A composition for coating an optical fiber comprising:
optionally, a reactive monomer and/or oligomer component;
a self-healing component consisting of molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties, wherein the one or more self-healing moieties comprise 2-ureido-4-pyrimidinone (UPy) groups, and wherein
(a) the self-healing component is present, relative to the weight of the entire composition, in an amount greater than 30 wt. %; or
(b) the composition possesses greater than 0.02 equivalents of the one or more self-healing moieties per 100 g of the composition;
an initiator component; and
optionally, an additive component,
wherein the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties have a theoretical molecular weight (MWtheo) of between 500 and 2000 g/mol and comprise 0.9 to less than 1.5 units of a constitutional unit derived from a polyether, a polyester, a polycarbonate, a polycaprolactone, and/or an acrylic compound having two hydroxyl groups.
2 . The composition according to claim 1 , wherein the self-healing component is present, relative to the weight of the entire composition, in an amount of greater than 30 wt. % and up to 80 wt. %; and the composition possesses greater than 0.02 equivalents and up to 0.10 equivalents of the one or more self-healing moieties per 100 g of the composition.
3 . The composition according to claim 1 , wherein the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties have a backbone derived from a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone, an acrylic polyol, a poly(dimethylsiloxane), a disulfide polyol, or combinations thereof.
4 . The composition according to claim 1 , wherein the composition contains one or more of the following:
(1) an adhesion promoter compound as part of the additive component;
(2) an adhesion promoter functional group as part of the oligomer component, the monomer component, or the self-healing component; and/or
(3) an antioxidant as part of the additive component.
5 . The composition according to claim 1 , wherein the reactive monomer component, the reactive oligomer component, and the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties each comprise one or more polymerizable moieties, wherein the polymerizable moieties comprise:
(i) radiation curable moieties;
(ii) thermally curable moieties; or
(iii) both radiation curable moieties and thermally curable moieties.
6 . The composition according to claim 5 , wherein the polymerizable moieties of the reactive monomer component, the reactive oligomer component, and/or the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable groups comprise (meth)acrylate groups;
wherein the composition possesses from 0.1 to 0.4 equivalents of (meth)acrylate groups per 100 g of the composition; and/or
wherein a ratio of equivalents of (meth)acrylate groups to equivalents of UPy groups in the composition is less than 14.
7 . The composition according to claim 6 , wherein a ratio of equivalents of (meth)acrylate groups to equivalents of UPy groups in the composition is from 3 to 10.
8 . The composition according to claim 1 , wherein at least 50% of the equivalents of the one or more self-healing moieties in the composition consist of UPy groups.
9 . The composition according to claim 1 , wherein the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties comprise a first molecule possessing a first self-healing moiety; and a second molecule possessing a second self-healing moiety;
wherein the first self-healing moiety of the first molecule is configured to bond to the second self-healing moiety of the second molecule.
10 . The composition according to claim 9 , wherein a bond dissociation energy between the first self-healing moiety and the second self-healing moiety is between 9-100 kcal/mol, or between 30-60 kcal/mol.
11 . The composition according to claim 9 , wherein the first self-healing moiety and the second self-healing moiety are configured to form a dimer, wherein the dimer possesses 3 or 4 hydrogen bonds, wherein the dimer comprises a first linear chain linked to each of the 3 or 4 hydrogen bonds on a side of the first self-healing moiety, and a second linear chain linked to each of the 3 or 4 hydrogen bonds on a side of the second self-healing moiety, wherein each of the first linear chain and the second linear chain comprise less than 7 covalent bonds.
12 . The composition according to claim 11 , wherein the dimer is according to one of the following structures (I)-(V):
wherein R is selected from organic substituents that optionally have reactive groups attached to the substituents;
wherein the reactive groups comprise acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, aziridino, silyl, siloxy, silylhydride, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimido groups.
13 . The composition according to claim 1 , wherein the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties comprise a plurality of molecules comprising at least one UPy group and at least three urethane linking groups.
14 . The composition according to claim 13 , wherein the composition possesses greater than 0.015 equivalents of UPy groups per 100 g of the composition.
15 . The composition according to claim 1 ,
wherein the reactive monomer component is present and comprises methyl acrylate, ethyl acrylate, butyl acrylate, 2-phenoxy ethyl acrylate, 2-ethylhexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, lauryl-acrylate, ethoxylated nonyl-phenol acrylate, or diethylene-glycol-ethyl-hexyl acylate; and
wherein the initiator component comprises one or more photoinitiators, wherein the one or more photoinitiators comprise acylphosphine oxide photoinitiators, α-hydroxy ketone photoinitiators, and/or Norrish Type II photoinitiators.
16 . The composition according to claim 1 , wherein the self-healing component possesses a glass transition temperature (Tg) that is from −30 to 20° C.
17 . The composition according to claim 1 , wherein the composition possesses a segment modulus from 0.1 to 5 MPa; and/or
a viscosity, as measured at a shear rate of 50 s −1 and a temperature of 25° C., of less than 15 Pascal Seconds (Pas).
18 . The composition according to claim 1 , wherein, relative to the weight of the entire composition,
the reactive monomer and/or oligomer component is present from 10 wt. % to 65 wt. %;
the self-healing component is present from greater than 30 wt. % to 80 wt. %;
the initiator component is present from 0.01 wt. % to 10 wt. %;
and the additive component is present from 0 wt. % to 59.99 wt. %;
wherein each of the components adds up to 100 wt. %.
19 . The composition according to claim 1 , wherein the composition contains less than 5 wt. % of solvent.
20 . The composition according to claim 1 , wherein the composition contains less than 1 wt. % of solvent, wherein the determination of solvent content excludes any (meth)acrylate functional compounds.
21 . The composition according to claim 1 , wherein the composition contains less than 0.1 wt. % of solvent, wherein the determination of solvent content excludes any (meth)acrylate functional compounds.
22 . The composition according to claim 1 , wherein at least 75% of the equivalents of all the one or more self-healing moieties in the composition consist of UPy groups.
23 . The composition according to claim 1 , wherein at least 99% of the equivalents of all the one or more self-healing moieties in the composition consist of UPy groups.
24 . The composition according to claim 1 , wherein the one or more self-healing moieties consist of 2-ureido-4-pyrimidinone (UPy) groups.
25 . The composition according to claim 1 , wherein the composition possesses from 0.022 to 0.05 equivalents of UPy groups per 100 g of the composition and a viscosity, as measured at a shear rate of 50 s −1 and a temperature of 25° C., from 1 Pa's to 15 Pa·s.
26 . The composition according to claim 25 , wherein the composition possesses a viscosity, as measured at a shear rate of 50 s −1 and a temperature of 25° C., from 0.05 Pa's to 5 Pa·s.
27 . The composition according to claim 1 , wherein the composition possesses from 0.022 to 0.1 equivalents of the one or more self-healing moieties per 100 g of the composition.
28 . The composition according to claim 1 , wherein the molecules possessing one or more self-healing moieties, urethane linking groups, and optionally one or more polymerizable moieties comprise a first molecule possessing a first self-healing moiety; and a second molecule possessing a second self-healing moiety, wherein the first self-healing moiety and the second self-healing moiety are independently multi-hydrogen bonding groups.