Preparation of conjugated aromatic/heteroaromatic oligomer-containing dielectric polymers and their applications
A π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer is generally provided, which can include a polymerizable group, a linker group, and a π-conjugated aromatic/heteroaromatic side chain. The π-conjugated aromatic/heteroaromatic side chain includes a first cyclopentadiene ring covalently attached to the linder group, a set of second cyclopentadiene rings covalently attached to the first cyclopentadiene ring, and a third cyclopentadiene ring positioned at a terminal end of the π-conjugated aromatic/heteroaromatic side chain such that the set of second cyclopentadiene rings is positioned between the first cyclopentadiene ring and the third cyclopentadiene ring. Methods are also provided for forming a polymer via polymerizing the π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer, and for grafting a π-conjugated aromatic/heteroaromatic oligomer-containing polymer onto a surface of a nanomaterial.
1. A method grafting a π-conjugated aromatic/heteroaromatic oligomer-containing polymer onto a surface of a nanomaterial, the method comprising:
polymerizing a π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer via a free radical polymerization or a controlled/living radical polymerization method in the presence of an anchored nanomaterial, wherein the anchored nanomaterial comprises an anchoring group attached the surface of the nanomaterial, wherein the π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer comprises:
a polymerizable group, a linker group, and a π-conjugated aromatic/heteroaromatic side chain, and wherein the polymerizable group comprises a vinyl group, and further wherein the a π-conjugated aromatic/heteroaromatic side chain comprises:
a first cyclopentadiene ring covalently attached to the linker group and having substituted or unsubstituted first hetero-atom substituted therein;
one or more second cyclopentadiene ring(s) covalently attached to the first cyclopentadiene rings(s), wherein the second cyclopentadiene ring comprises a number (n) of repeating second cyclopentadiene rings(s) covalently bonded together in a chain, with n being an integer of 1 to about 25, and wherein each of the second cyclopentadiene rings has a substituted or unsubstituted second hetero-atom substituted therein; and
a third cyclopentadiene ring positioned at a terminal end of the a π-conjugated aromatic/heteroaromatic side chain such that the second cyclopentadiene ring(s) is positioned between the first cyclopentadiene ring and the third cyclopentadiene ring, wherein the third cyclopentadiene ring has a substituted or unsubstituted third hetero-atom substituted therein.
2. The method as in claim 1 , wherein the polymerizable group comprises an acrylic group or a methacrylic group, and wherein the controlled/living radical polymerization method is a RAFT polymerization method where the a π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer is polymerized in the presence of a RAFT agent.
3. The method as in claim 1 , wherein the a π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer is polymerized without any other monomer present such that a homopolymer is formed.
4. The method as in claim 1 , wherein the a π-conjugated aromatic/heteroaromatic oligomer-containing vinyl monomer is polymerized with another co-monomer present such that a copolymer is formed.
5. The method as in claim 4 , wherein the copolymer is a random copolymer or a block copolymer.
6. The method as in claim 1
wherein polymerization is performed via a controlled/living polymerization method.
7. The method as in claim 1 , wherein the one or more second cyclopentadiene ring(s) comprises the second cyclopentadiene rings covalently attached to the first cyclopentadiene ring, wherein the second cyclopentadiene ring(s) comprises a number (n) of repeating second cyclopentadiene rings covalently bonded together in a chain, with n being an integer of 2 to about 10, and wherein each of the second cyclopentadiene rings has a substituted or unsubstituted second hetero-atom substituted therein.