AZIDO-CONTAINING MONOMERS, POLYMERS, AND ARTICLES
An azido-containing monomer, a polymer containing monomeric units derived from the azido-containing monomer, and various articles containing a substrate and a coating layer of the polymer positioned on the substrate are provided. The azido groups, which are pendant groups of the polymer, can undergo a click chemistry reaction with an unsaturated compound such as those having a terminal —C≡CH group, a dibenzocyclooctyne-containing group, an unsaturated bicyclic olefinic group, or an amido group. The click chemistry reaction can be used to covalently attach a fluorescent or bioactive compound to the polymer.
1 . A monomer of Formula (I)
wherein
R 1 is hydrogen or methyl;
X 1 is —NH— or —O—;
n is equal to 0 or 1;
R 2 is an alkylene or a heteroalkylene having at least one oxygen heteroatom (i.e., ether or polyether group);
Q 1 is —(C═O)—X 2 — or —NH—(C═O)—X 2 —;
X 2 is —NH— or —O—; and
R 3 is either
(a) an ether or polyether group terminated with an azido group; or
(b) a branched hetero-hydrocarbon group terminated with two or more azido groups, the hetero-hydrocarbon group having a branching location and comprising (i) an ether or polyether group before the branching location and (ii) an ether or polyether group in each branch after the branching location.
2 . The monomer of claim 1 , where in the monomer of Formula (I) is of Formula (I-A)
wherein
R 1 is hydrogen or methyl;
X 1 is —O—;
n is equal to 1;
R 2 is a heteroalkylene having at least one oxygen heteroatom (i.e., an ether or polyether group);
Q 1 is —NH—(C═O)—X 2 ;
X 2 is —NH— or —O—; and
R 3 is either
(a) an ether or polyether group terminated with an azido group; or
(b) a branched hetero-hydrocarbon group terminated with two or more azido groups, the hetero-hydrocarbon group having a branching location and comprising (i) an ether or polyether group before the branching location and (ii) an ether or polyether group in each branch after the branching location.
3 . The monomer of claim 1 , where in the monomer of Formula (I) is of Formula (I-B)
wherein
R 1 is hydrogen or methyl;
X 1 is —NH—;
n is equal to 1;
R 2 is an alkylene (typically —C(CH 3 ) 2 —)
Q 1 is —(C═O)—X 2 ;
X 2 is —NH— or —O—; and
R 3 is either
(a) an ether or polyether group terminated with an azido group; or
(b) a branched hetero-hydrocarbon group terminated with two or more azido groups, the hetero-hydrocarbon group having a branching location and comprising (i) an ether or polyether group before the branching location and (ii) an ether or polyether group in each branch after the branching location.
4 . A monomer of claim 1 , where in the monomer of Formula (I) is of Formula (I-C)
wherein
R 1 is hydrogen or methyl;
X 1 is —NH— or —O—;
n is equal to 0; and
R 3 is either
(a) an ether or polyether group terminated with an azido group; or
(b) a branched hetero-hydrocarbon group terminated with two or more azido groups, the hetero-hydrocarbon group having a branching location and comprising (i) an ether or polyether group before the branching location and (ii) an ether or polyether group in each branch after the branching location.
5 . The monomer of claim 1 , wherein R 3 is of formula —R 4 —(O—R 4 ) m —R 4 —N 3 ,
wherein each R 4 is independently an alkylene and m is an integer in a range of 0 to 40.
6 . The monomer of claim 1 , wherein R 3 is of formula
—R 5 —O—(R 5 —O) p —R 5 —N[—R 5 —O—(R 5 —O) q —R 5 —N 3 ] 2 where each R 5 is independently an alkylene, p is an integer in a range of 0 to 30 and q is an integer in a range of 0 to 10.
7 . The monomer of claim 1 , wherein R 3 is of formula
—R 6 —O—(R 6 —O) x —R 6 —(C═O)—NH—CH[—R 6 —O—R 6 —(C═O)—NH—R 6 —O—(R 6 —O) y —R 6 —N 3 ] 2 where each R 6 is independently an alkylene, x is in integer in a range of 0 to 30 and y is an integer in a range of 0 to 10.
8 . A polymer comprising a first monomeric unit derived from a monomer of Formula (I)
wherein
R 1 is hydrogen or methyl;
X 1 is —NH— or —O—;
n is equal to 0 or 1;
R 2 is an alkylene or a heteroalkylene having at least one oxygen heteroatom (i.e., ether or polyether group);
Q 1 is —(C═O)—X 2 — or —NH—(C═O)—X 2 —;
X 2 is —NH— or —O—; and
R 3 is either
(a) an ether or polyether group terminated with an azido group; or
(b) a branched hetero-hydrocarbon group terminated with two or more azido groups, the hetero-hydrocarbon group having a branching location and comprising (i) an ether or polyether group before the branching location and (ii) an ether or polyether group in each branch after the branching location.
9 . The polymer of claim 8 , wherein the first monomeric unit of Formula (I) is derived from the monomers of claim 2 .
10 . The polymer of claim 8 , further comprising a second monomeric unit comprising an acidic group or a salt thereof.
11 . The polymer of claim 10 , wherein the acidic group is a carboxylic acid group (—COOH), a phosphoric acid group (—O—PO 3 H 2 ), a phosphoric acid ester group (—O—PO 3 RH where R is hydrogen or alkyl), a phosphonic acid group (—OPO 3 H 2 ), a phosphonic acid ester group (—O—PO 3 RH where R is hydrogen or alkyl), sulfonic acid group (—SO 3 H), or a salt thereof.
12 . The polymer of claim 8 , further comprising a second monomeric unit having primary amino group, secondary amino group, tertiary amino group, quaternary amino group, or a salt thereof.
13 . The polymer of claim 8 , further comprising a second monomeric unit comprising a hydrogen bond acceptor group or a hydrogen bond donor group.
14 . The polymer of claim 8 , wherein the polymer comprises 0.1 to 50 mole percent first monomeric unit based on a total weight of monomeric units in the polymer.
15 . A first article comprising a substrate and a coating positioned on the substrate, wherein the coating comprises one or more layers of different polymers and wherein at least one layer comprises a first polymer comprising a first monomeric unit derived form an azido-containing monomer of Formula (I)
wherein
R 1 is hydrogen or methyl;
X 1 is —NH— or —O—;
n is equal to 0 or 1;
R 2 is an alkylene or a heteroalkylene having at least one oxygen heteroatom (i.e., ether or polyether group);
Q 1 is —(C═O)—X 2 — or —NH—(C═O)—X 2 —;
X 2 is —NH— or —O—; and
R 3 is either
(a) an ether or polyether group terminated with an azido group; or
(b) a branched hetero-hydrocarbon group terminated with two or more azido groups, the hetero-hydrocarbon group having a branching location and comprising (i) an ether or polyether group before the branching location and (ii) an ether or polyether group in each branch after the branching location.
16 . The first article of claim 15 , wherein the coating comprises one or more bilayers comprising a first layer and a second layer adjacent to the first layer, wherein
a) the first layer comprises the first polymer comprising first monomeric units derived from the azido-containing monomer of Formula (I); and
b) the second layer comprises a second polymer having a monomeric unit that interacts with the first polymer electrostatically or through hydrogen bonding; and
wherein either the first layer or the second layer is adjacent to the substrate.
17 . The first article of claim 16 , wherein the second polymer further comprises first monomeric units derived from the azido-containing monomer of Formula (I).
18 . A second article comprising a click chemistry reaction product of the first article of claim 15 with an unsaturated compound capable of undergoing a click chemistry reaction with an azido group of the first monomeric unit in the first polymer, wherein the unsaturated compound is covalently linked to the first polymer.
19 . The second article of claim 18 , wherein the unsaturated compound is a fluorescent-compound or a bioactive compound.
20 . The second article of claim 18 , or wherein the unsaturated compound has a terminal
—C≡CH group, a dibenzocyclooctyne-containing group, an unsaturated bicyclic olefinic group, or an amido group.