Short, Amy L.
(2016)
Sequenced copolymers with controlled molecular weights prepared via entropy-driven ring-opening metathesis polymerization.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
This is the latest version of this item.
Abstract
A segmer-based approach towards monomer synthesis was successfully carried out to produce a series of linear α,ω-diolefinic species with varying linker lengths. Ring-closing metathesis (RCM) using a cis-selective ruthenium catalyst yielded a large strainless macrocycle that then underwent entropy-driven ring-opening metathesis polymerization (ED-ROMP). When compared to the same polymerization carried out with the complementary trans-monomer, the ED-ROMP of cis-monomer demonstrated a significantly higher degree of molecular weight control. The narrow dispersity exhibited by this process suggests that a new regime of selectivity enhanced ED-ROMP (SEED-ROMP) has been achieved. Reaction kinetics for this process were probed and the process was compared to alternative polymerization methods. Finally, the high degree of control was exemplified in a series of chain extension and block copolymerization experiments. Ultimately, SEED-ROMP represents a novel method to obtain well-defined copolymers of precise molecular weights.
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
3 October 2016 |
| Date Type: |
Publication |
| Defense Date: |
27 May 2016 |
| Approval Date: |
3 October 2016 |
| Submission Date: |
1 July 2016 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Number of Pages: |
222 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
Sequenced copolymer, entropy-driven ring-opening metathesis polymerization (ED-ROMP), thermodynamic and kinetic enhancement, molecular weight control, controlled polymerization, cis-selective ring closing metathesis (RCM), poly-(lactic-co-glycolic) acid (PLGA), well-defined block copolymer formation, chain extension polymerization, selectivity-enhanced entropy-driven ring-opening metathesis polymerization (SEED-ROMP), deactivation entropy-driven ring-opening metathesis polymerization (DED-ROMP) |
| Date Deposited: |
03 Oct 2016 16:07 |
| Last Modified: |
15 Nov 2016 14:35 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/29287 |
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Sequenced copolymers with controlled molecular weights prepared via entropy-driven ring-opening metathesis polymerization. (deposited 03 Oct 2016 16:07)
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