Fundamentals of Polymer Science

Monday 10:30 12:00 pm Nicholas A Peppas

Center for Biomaterials, Drug Delivery, Bionanotechnology and Molecular Recognition Departments of Chemical Engineering, Biomedical Engineering and College of Pharmacy University of Texas, Austin, TX, 78712, USA

CONTROLLED RELEASE: Art or Science?

dMt dt

CONTROLLED RELEASE FORMULATION

dMt dt t t

CHEMICALLY-ACTIVATED DIFFUSION-CONTROLLED Matrix Systems Membrane Reservoirs Biodegradable Polymers Pendant Chain Chemistry

CONTROLLED RELEASE
PULSATILE SOLVENT-ACTIVATED Swellable Gels S ll bl G l Osmotic Systems pH- or Temperature- Sensitive Electric or Ultrasonic Multi-Compartmental

Introduction
Macromolecules Synthetic Natural (Collagen, cellulose, lignin) Basic unit: repeating unit

Some Typical Polymers of Commercial Interest

Chain Polymerization

Typical Chain Polymers

Free Radical Polymerization Mechanism

Free Radical Initiation

Azo Compounds

Other Initiators

Photochemical Initiation UV or Visible Light

Photoinitiation

Radical Propagation

Termination

Chain Transfer

Step Polymerization

Typical Step Polymers

Step Polymerization Reaction Scheme

Comparison of Step and Addition Polymerizations

Molecular Structure Linear

Branched B h d

Crosslinked

Homopolymers versus Copolymers

Random

Block

Graft

Stereochemical Configuration Tacticity Atactic

Isotactic

Syndiotactic S di t ti

Importance on Properties

Copolymerizations p y

Kinetics

Reactivity Ratios

Copolymerization Equations

Experimental Techniques

Gel Permeation Chromatography (GPC)

Polymer Physics
From the physical structure point of view, polymers may be amorphous or crystalline Amorphous: Random chains, no order Crystalline phase: Order of structure y p

In the amorphous phase there are two possibilities Rubbery state (mobile chains) Glassy state (immobile chains)

Two characteristic temperatures: Melting point Glass transition temperature

The Crystalline Phase

Most polymers are semicrystalline Crystallinity can be achieved only when chemical structure allows it Crystallizability Examples

Single Crystals

Fringed micelles

Folded chains

DEGREE OF CRYSTALLINITY X(t) %

Experimental Techniques of Determination By Density Measurements

Differential Scanning Calorimetry

Dynamic Mechanical Behavior y Storage and Loss Moduli Viscoelasticity

Models of Viscoelastic Behavior

Simple tension

Maxwell Model

Maxwell Model under Constant Rate of Strain

Stress Relaxation of a Maxwell Model

Creep Behavior of a Maxwell Model

Maxwell Model under Harmonic Motion

Complex Dynamic Modulus

Stress Relaxation of Voigt Model

Comparison of Maxwell and Voigt Models