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Lecture 1:

General Introduction to Polymers

Karen L. Wooley

Departments of Chemistry & Chemical Engineering

Texas A&M University

¾Synthetic vs. retrosynthetic analyses

¾Polymers and polymerizations

¾Covalent vs. supramolecular polymers

¾Controlled properties via controlled macromolecular architectures

¾-to-

Sophisticated Plastics

1

1 Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

The Uniqueness and Importance of Polymers

2

Monomers

Reagents

Polymerizations

Transformations

Functional Polymers of

Controlled Architectures

For development of macroscopic to nanoscopic devicesmotivated by applications but driven by fundamentals:

¾ Develop synthetic strategies

¾ Incorporate functions (pollutant clean-up, diagnostics, therapeutics, anti-fouling, etc.) ¾ Conduct rigorous characterization and test performance

Mechanical

Function

Barrier

Function

Signaling

Function

www.oled-display.net www.bernos.org www.homepage.mac.com Sophisticated Plastics Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

Synthetic Analysis

of Increasingly Complex Macromolecular Structures 3

Synthetic Approach:

¾Develop chemistries to make polymers

¾Characterize their properties (provides important structure-property information)

¾Determine practical applications

Functional Polymers of

Controlled Architectures

Initiator

n

Monomer

Sequential Controlled Polymerizations

n

Monomer

Block Copolymer

Initiator

Chain End Chemical

Transformation

Controlled Polymerization ( and chain end control)

Chain-Chain Grafting-Onto

(alternate schemes could be easily designed for grafting-from or grafting-through strategies) n

Monomer

Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

Retrosynthetic Analysis

of Increasingly Complex Macromolecular Structures 4

Retrosynthetic Approach:

¾Identify desired physical, chemical and mechanical properties ¾Design macromolecules that are expected to possess those properties (knowledge of structure-property relationships is critical) ¾Design retrosynthetic strategies by which to produce those macromolecules

Initiator

Sequential

Controlled

Polymerizations

www.oled-display.net

Functional Polymers of

Controlled Architectures

Initiator and terminator

(provides the and chain ends) n

Monomer

n

Monomer

Grafting-through Polymerization

n

Monomer

Growth of a Diblock Copolymer

from a Graft Block Copolymer Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014 Direct Synthetic vs. Retrosynthetic Approaches to the Preparation of Increasingly Complex Macromolecular Structures 5

Direct Synthetic Approach:

¾Develop chemistries to make polymers

¾Characterize their properties (provides important structure-property information)

¾Determine practical applications

Retrosynthetic Approach:

¾Identify desired physical, chemical and mechanical properties ¾Design macromolecules that are expected to possess those properties (knowledge of structure-property relationships is critical) ¾Design retro-synthetic strategies by which to produce those macromolecules Both strategies are important to polymer / materials chemistry Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

Polymers and Polymerizations

6

¾mers

(many repeat units)

¾Monomers are often small

molecules (otherwise macromonomer

¾Polymerization links together

many copies of monomers

¾For covalent polymers,

polymerization involves a transition from weak intermolecular interactions to strong intramolecular bonding

Polymerization

Linear

Homopolymers

Monomers

Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

Polymers and Polymerizations

7

¾Growth of polymer chains

results in changes in physical properties

¾Demo: Beads in flasks

¾Example: Increasing

oligomeric to polymeric styrene chain lengths (increasing n)

Mp = 580 Da = peak molecular weight

DPn ~ 6 = number-average degree of polymerization

(by size exclusion chromatography, e.g.)

Viscous oil

Mp = 7000 Da

DPn ~ 70

Glassy material/powder

Mp

970 Da

Mp

1340 Da

Mp

1680 Da

Mp

2050 Da

Mp

5050 Da

Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

Polymers and Polymerizations

8

¾Copolymers can also be

formed

¾Statistical (random) copolymers

¾Alternating copolymers

¾Block copolymers

¾Gradient copolymers

¾The properties can be quite

different for each type

¾Monomer compositions

¾Intramolecular characteristics

¾Intermolecular interactions

Linear

Block

Copolymer

Linear

Alternating

Copolymer

Polymer Chemistry, Chem 466, Spring 2014, January 14, 2014

Covalent vs. SupramolecularStaudinger

9

Hermann Staudinger (1881-1965)

1953, Nobel Prize in Chemistry,

confirmation of their existence as covalent chain molecules vs. colloidal systems or aggregates of smaller molecules

H. Ringsdorfquotesdbs_dbs17.pdfusesText_23