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BENG 186A: Principles of Biomaterials Design

Lecture 4: Polymers

Molecular Weight

Very important to know the MW of your polymer Same monomer doesn t mean same properties

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Molecular Weight Effects

Degree of Polymerization and MW

O O O

OH

1 +

1 +

1 +

Degree of Polymerization = 4

If synthesis was exact for polymers then could easily calculate the molecular weight with this way But, you always have a distribution of chains with different length

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Molecular Weight

2 Methods Number average MW = Mn

Treats all polymer chains equally

Weight average MW = Mw

Larger chains make a larger contribution

Number average MW
Mn = total weight of the polymer total # of chains in the polymer

Wi =NiMi
Wi = weight of chains with molecular weight Mi Ni = # of chains of with molecular weight Mi Mi = molecular weight of species i

Mn =NiMi Ni

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Weight average MW
Mw = WiMi Wi = NiMi2 NiMi

Wi =NiMi

Wi = weight of chains with molecular weight Mi Ni = # of chains of with molecular weight Mi Mi = molecular weight of species i

Polydispersity Index

PI or PDI PDI = Mw/Mn Tells you the breadth of distribution PDI = 1 : Monodisperse

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MW Distribution
Just knowing Mn or Mw can be misleading Important to know the MW distribution

MW Distribution

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Gel Permeation Chromatography (GPC)

Size exclusion Flow dilute polymer over column of porous beads High MW species can t fit in pores - dilute first Low MW species pass through the pores - longer elution time Compare to standards with known MW

GPC Trace

Which polymer has the lowest Mn? Which polymer has largest PDI?

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How can you make a polymer?

Polymerization Addition Polymerization (chain reaction)

Poly(ethylene), Poly(propylene), poly(styrene)

Condensation Polymerization (stepwise growth)

Nylons, poly(carbonates), natural polymers

Addition Polymerization
Free radical polymerization Initiation - activation of a monomer through reaction with a radical species

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Propagation

Growing polymer chains

Termination

Coupling

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Disproportionation

Condensation Polymerization

Often involves more than one monomer species Part of monomer is kicked out when added to the polymer Product does not have same chemical formula as either mer

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Polymerization

There are others

Ring-opening Controlled Polymerizations

Polymer Characterization

Nuclear Magnetic Resonance (NMR)

Structure and composition Often used to assure quality and purity

Infrared Spectroscopy

Structure and composition

Mass Spectrometry

Measure mass

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Structure of Polymers

Single macromolecules can assume a variety of shapes (unlike metals and ceramics) Rotation of carbon atoms in the backbone

Many conformations!

Polymer Conformation

Affected by what impairs rotation around the bonds in the backbone Bulky side groups

Double bonds

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Polymer Configurations

To change the configuration would have to break and reform a bond Isotactic Syndiotactic Atactic

Polymer Structures

Linear
Homopolymer Copolymer
Random Alternating Block Graft

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Polymer Structures

Crosslinked

Networked

Crystallinity and Polymers

Can be amorphous (random organization) or semicrystalline Purely crystalline is extremely rare Dependent on chemical structure of repeat units Anything that prevents chain alignment or discourages secondary bonding between chains will reduce crystallinity

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What Affects Crystallinity

1. Mer side groups

Large bulky groups prevent chains from coming close together

2. Chain branching

Increased branching decreases chances of chains coming close together

What Affects Crystallinity

3. Tacticity

Arrangement of side chains around backbone Atactic - more difficult to crystallize

4. Regularity of mer placement

Which would be the least crystalline?

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Defects in Polymers

Linear

Dislocation in crystalline regions of polymer Covalent bonds within chain are stronger than secondary forces between the chains - slip takes place along the axis of the polymer chains Dislocations don t play large role in the deformation of polymers - they deform by viscous flow

Defects in Polymers

Planar

External (surface) Boundary between spherulites

Volume

Can add solids or gases to create pores during processing

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Thermal Properties

Amorphous and crystalline materials behave differently Crystalline material (metals and crystalline ceramics) melting point (Tm)

> Tm Behaves like a liquid and deforms via viscous flow < Tm Highly ordered solid

Amorphous ceramics (glasses)

Don t solidify below certain temperature (no distinct Tm) Become more and more viscous until like a solid Working Point: easily deformed, but maintains solid properties Glass Transition Temp. (Tg): < Tg material is considered a glass (solid)

Thermal Properties

Polymers can behave like a liquid, rubbery solid, or a glass depending on temperature and molecular structure Polymers with crystallinity have a Tm

< Tm highly ordered (semicrystalline) >Tm random ordering Properties that prevent crystal formation also lower Tm Branching, random copolymers, etc. Tm increases with increasing MW Few chain ends

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Thermal Properties

Polymers that are amorphous have Tg < Tg glassy and brittle > Tg rubbery, elastic material High enough energy to cause molecular motion around the polymer backbone Increased chain flexibility leads to lower Tg

C-O bonds rotate more easily than C-C Polar side groups which promote chain interaction Lack of bulky side groups

Increased Tg with increased MW

Tg Demo

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Thermal Properties
Semicrystalline polymers can have both Tm and Tg Tm may be undetectable in amorphous polymers or

those with low % crystallinity

Also can have crystallization temperature (Tc)

Temperature at which there is sufficient energy to move into a highly ordered state
Exothermic process Can be annealed by raising up to Tc to organize into a crystal and then slowly cooled If you go above Tc to Tm, crystal will be disrupted

Determining Crystallinity

X-ray Diffraction (metals, ceramics, polymers)

Size of unit cell and geometry Arrangement of atoms Compound identification

Differential Scanning Calorimetry (DSC)

Typically used for polymers Sample and reference cell are supplied with energy at varying rates to maintain equal temperatures Amount of this energy over a certain temperature range is recorded

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DSC

arranges into crystalline state

Tg : energy is absorbed with chain rearrangement Tc : exothermic peak, energy is released when polymer Tm : additional energy is require to disrupt crystal structure
Can use area under the curve to determine % crystallinity

Processing of Polymers

Need to know Tg and Tm Thermoplastic Thermosetting

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Thermoplastic Polymers

Soften/liquify when heated Reduction in secondary bonding between chains at high temperatures If temperature goes too high, covalent bonds in backbone can break Hardens when cooled Can go through many heat/cool cycles Most linear polymers

Thermosets

Become permanently hard when heated to a high temperature Covalent crosslinks between chains are created Macromolecules can t slide past each other and deform Excessive heat can cause degradation Vulcanized rubbers, epoxies, resins

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Thermoplastic vs. Thermoset

Both can form complex shapes Thermosets

Casting

(molding)

Compression, Injection, Blow

Mold

can be removed at high temperatures

Thermoplastics
Molding Pressure

must be maintained until cooled below Tg before removing mold Forming

Extrusion, Fiber Spinning

Can

bubble gases through to form porous foams

Special Classes of Polymers

Hydrogels Natural or bio-derived

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Hydrogels
Water-swollen, crosslinked, insoluble polymer structures Can be swollen up to thousands of times their dry weight

Ionically Crosslinked Gels

Heise et al. Reproductive Biology and endocrinology, 2005.

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Hydrophobic Interactions

Hydrogel Applications
Soft contact lenses Pills/capsules Bioadhesive carriers Implant coatings Transdermal drug delivery Electrophoresis gels Wound healing Tissue engineering scaffolds

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Advantages of Hydrogels

Environment can protect cells and other substances (i.e. drugs, proteins, and peptides) Timed release of growth factors and other nutrients to ensure proper tissue growth Good transport properties Biocompatible Can be injected Easy to modify

Disadvantages of Hydrogels

Low mechanical strength Hard to handle Difficult to load Sterilization

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Hydrogel Classification

Based on method of fabrication

Homopolymer

One hydrophilic monomer monomer

Copolymer

Two monomers - one must be hydrophilic

Multipolymer

Three or more monomers - one must be hydrophilic

Interpenetrating network (IPN)

1st network is swollen in a monomer - latter reacts to form a second intermeshing network

Based on Ionic Charges

Neutral Anionic Cationic Ampholytic

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Based on Physical Structures

Amorphous - chains arranged randomly Semicrystalline - dense regions of ordered chains Hydrogen-bonded or complexation structures

Hydrogel Structure

Usually not perfect Multi-functional junctions Physical molecular entanglements (semipermanent junctions) Unreacted functionality Chain loops

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Synthesis

Crosslinking through radiation reactions (electron beams, gamma-rays, X-rays, or UV light) Chemical crosslinking

small molecular weight crosslinking agent that links two chains together through its di- or multifunctional groups copolymerization-crosslinking: reaction between 1 or more abundant monomers and one mult-functional monomer that is present in small quantities combination of above with monomer and linear chains that are crosslinked with an interlinking agent

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