Polymers containing calix[4]arenes and triptycenes : new syntheses, properties and applications

This thesis details the development of new synthetic methods for making polymers with complex molecular structures. Calix[4]arenes and triptycenes are the two major molecular building blocks for constructing the functional polymers. Unusual properties, with the emphasis on mechanical and sensory properties, are demonstrated. In Chapter 2, early investigations on the synthesis of main-chain calix[4]arene polymers are introduced. High molecular-weight main-chain calixarene homopolymers via linkages on lower rims are synthesized by the polymerization based on acetylenic coupling reaction. The conformation of calixarene monomers dictates the ability to produce the new polymers: the calix[4]arene monomers with a partial cone conformation produce high molecular-weight polymers while the calix[4]arene monomers with a cone conformation only afford oligomers. Other polymerization methods, including Sonogashira coupling and Cu(I)catalyzed Huisgen 1,3-dipolar cycloaddition, are also investigated but found to be inferior to the acetylenic coupling polymerization. In Chapter 3, main-chain calix[4]arene elastomers are achieved by metathesis reactions. Alkene-bridged calix[4]arene monomers are synthesized by ring-closing metathesis (RCM). All the three possible conformers (cone, partial cone, and 1,3-alternate) are used as comonomers with cyclooctene and norbornene in ring-opening metathesis polymerization (ROMP). The resultant polymers are high molecular-weight, transparent and stretchable materials with high calixarene incorporation (up to 25 mol% or 70 wt%) and low glass transition temperatures. The conformational properties of the calixarene moieties play a crucial role in determining the mechanical properties of the polymers.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2008

Author dc:creator

• Yang, Yong, Ph. D. Massachusetts Institute of Technology

Advisor dc:contributor.advisor

• Timothy M. Swager.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/43768

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/43768