Lecture 1


Course Introduction 

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Polymer Chemistry
 Professor Appel (pronounced like apple)
• Research primarily in designing new materials that
mimic biology for biomedical applications

• Prof. Appel
– Raised in Long Beach, CA
– Cal Poly SLO (BS, MS), Cambridge (PhD), MIT (Postdoc)
– Research advisor for PhD students from 4 departments
– Want to learn more about my laboratory’s research?
(www.supramolecularbiomaterials.com)
 MATSCI 190/210
• Our goal: Structure - Properties - Applications
• Main take-away is to understand how and why polymers act the way they do
under different conditions. (Pro tip: When doing math, if you get an answer that
doesn’t make sense, write that why you think it doesn’t make sense.)
• Introduction to fundamental concepts:
– Polymer physics
• Phase transitions
• Entropic elasticity
• Thermodynamics of solubility

– Polymer chemistry
• Synthesis
• Polymerization kinetics
• Statistics of chain sizes

– Polymer engineering
• Phase microstructure (crystallization, self-assembly, gelation)
• Polymer mechanics and viscoelasticity

– Special topics
• DNA/RNA, proteins, amphiphiles, colloids,
• Organic electronics
• Drug delivery
 MATSCI 190/210
• Required reading
– None
– No single textbook covers all of the material in a comprehensive
manner suitable for this diverse audience
– All lecture slides and lecture notes will be available on Canvas

• Supplemental reading
– Suggested text: Young and Lovell, Introduction to Polymers
– On reserve at the library
– Available through numerous online sites for purchase
– Last page of syllabus: Descriptions of books on the reading list
 MATSCI 190/210
Introduction to Polymers
Young and Lovell
($53 paperback on Amazon)
 MATSCI 190/210
• Grading: HW 33% - Quizzes 33% - Final 33%

• Office hours
– Prof. Appel, Friday, 11:00-12:00, Durand 135
– CA’s: Doreen Chan, Junzhe (Robin) Lou
– Mondays, TBA
 Class Schedule
• Homework: 5 assignments total
– Assigned every other week and due two weeks later
– Similar to past homework that may be floating around
– For extensions email CAs
– Late homework penalized 10% per day
– Homework sets will require external resources
– Group work is okay, each person must turn in individual write up

• Quizzes
– Comprising multiple-choice, true/false and short answer.
– 20 min

• Final Exam
– In class, closed book, based on lecture material
– An equation sheet will be provided
– Final will cover all material is covered in class
– Mixture of questions similar to quizzes and HWs
 Introduction to Polymers
• What distinguishes soft/organic materials?
– Chemistry
– Length scales
– Ordering
– Intermolecular forces

• Supplemental Reading
– Young & Lovell, 1.1-1.2, 6.1-6.2, 10.3
– Painter & Coleman, Chapter 1, Sections A-B
– Grosberg & Khokhlov, Chapter 2
– Hamley, Sections 1.1-1.3, 2.1, 2.3.3, 2.3.4
 Polymers
“poly” - many
“mer” - unit
 How Important are Polymers in Our Life?

Professor Mark Foster and Family with all their polymer belongings!
(National Geographic Magazine June 2004)
 Polymer History
“Dear Colleague, Leave the concept of large
molecules well alone; organic molecules with a
molecular weight higher than 5000 do not exist.”
- Advice given to Hermann Staudinger

“We are shocked like zoologists would be if they

were told somewhere in Africa an elephant was
found who was 1500 feet long and 300 feet
high.”
- German chemist after a 1926 public debate on
macromolecules
Hermann Staudinger
(Nobel Prize in Chemistry, 1953)

• Polymers are the third largest manufacturing industry in the U.S.

• The U.S. Polymer industry alone produces more than $380B/year
• “I am inclined to think that the development of polymerization is, perhaps,
the biggest thing that chemistry has done, where it has had the biggest
effect on everyday life.” – Lord Todd (President of the Royal Society, 1980)
 Molecular Weight

from “Principles of Polymer Science” by Paul J. Flory, Professor of Chemistry,

Stanford University… 1974 Nobel Laureate “for his fundamental achievements,
both theoretical and experimental, in the physical chemistry of macromolecules"
 Why are polymers interesting?
• Inherently nanoscale
• Inexpensive, low density, resilient
• Biology of life
• Amazing structural transitions
– Amount of DNA in one cell is ~ 2 meters
– Size of cell is ~ 10 µm x 50 µm
• Incredible range of tunable material properties
• Often dynamic and/or switchable

Hartl and Jones

1998

Salleo and Melosh Group cover articles

 How are polymers different?
• Chemistry - generally limited to C, H, O, N, S, F

• Length scales (polymers can be cm in length)

– Very large molecules
– Depends on environmental conditions
– Can be dynamic

• Ordering (Packing)
– In practice, polymers do not fully crystallize

• Intermolecular forces
– Due to chemistry
– Due to large size
 Chemistry Review
• Organic Chemistry Terminology
– alkanes: CnH2n+2 "saturated" - all 4 C bonds linked
– alkenes: CnH2n one C=C bond
– alkynes: CnH2n-2 one triple bond
– cycloalkanes: CnH2n all single C-C bonds, cyclic
– aromatic: ring structures, alternating single and double bonds

• Functional groups
– Groups of atoms that do something
– Can be thought of as "decorating groups"
 Isomers
• Structural
– Same chemical formula, different bonds

• Geometrical
– Same bonds, different interatomic spacing

• Stereoisomers
– Non-superimposable mirror images
 Classification Systems: Source
• Natural

• Synthetic
Classification Systems: Formation Mechanism
• Step-growth

• Chain-growth
 Classification Systems: Chemistry
• Homopolymer (e.g., polystyrene)

• Heterpolymer (or “copolymer”; e.g. protein)

 Classification Systems: Chemical Structure
• Isotactic/Syndiotactic/Atactic (or Heterotactic)

• Homopolymer/Heteropolymer (or Copolymer)

• Block copolymer
• Graft copolymer
Classification Systems: Mesoscopic Structure
• Linear

• Branched

• Networked
- In networked polymers, the individual polymer chains are
connected (i.e., linked together) by “crosslinks”
- Examples of polymer networks include gels (i.e. solvent-
swollen polymer networks), thermosets, and elastomers

crosslink
Natural gel: aloe Synthetic gels
 Example: Polyethylene (PE)
• High density polyethylene, HDPE
– Linear molecular structure
– Molecules can pack tightly together
– Stronger, more rigid material
– More temperature resistant

• Low density polyethylene, LDPE

– Branched molecular structure
– Molecules cannot pack as tightly together
– More flexible material
– Sensitive to changes in temperature
 PE as a Biomaterial
• Ultra high density polyethylene
(UHDPE) is often used in knee
joint replacements
 PE in Body Armor
• Ultra high molecular weight
polyethylene (UHMWPE) is often
used in high strength ropes or
body armor

Body armor is 2x lighter than 7x lighter than steel at

kevlar, and can stop knives the same strength
 Classification Systems: Thermal Properties
• Thermoplastics (flows when heated; soluble)

• Thermosets (doesn’t flow when heated; insoluble)

Thermoplastic Thermoset
 Classification Systems: Mech. Properties
• Elastomers (rubber)

• Flexible plastic (bags)

• Rigid polymers (fibers)

 What does structure predict?
• Density, i.e. molecular packing
– Predicted by molecular structure

• Intermolecular forces
– Predicted by chain and side-chain chemistry
 Predicting Density
• How well do the chains fit together?
– Type of side chains
– Location of side chains
– Example: poly-L-lactide (PLLA)

• How flexible are the chains?

– Single bonds vs. double bonds vs. aliphatic rings vs. aromatic rings
• How easily can the chains move around?
– Chain length and branching (polyethylene example)
– Type of side chains
• Processing conditions?
 What does structure predict?
• Density, i.e. molecular packing
– Predicted by molecular structure

• Intermolecular forces
– Predicted by chain and side-chain chemistry

• Phase transitions, e.g. melting temperature

• Degradation rate

• Mechanical properties, e.g. elastic modulus

• Thermal properties, e.g. thermal expansion

 What does structure predict?
• Density, i.e. molecular packing
– Predicted by molecular structure

• Intermolecular forces
– Predicted by chain and side-chain chemistry

• Phase transitions, e.g. melting temperature

• Degradation rate

• Mechanical properties, e.g. elastic modulus

• Thermal properties, e.g. thermal expansion

Application: Anterior Cruciate Ligament Repair
If you tear your ACL, how is
it repaired?

Patellar tendon autograft

fixed with bone screws

LactoSorb® copolymer maintains

almost all its mechanical strength
throughout the healing process with
complete mass loss in 9–15 months.
 Intermolecular Interactions
• Van der Waal’s forces
• Dipole-induced dipole
• Dipole-dipole
• Hydrogen bonding

• Electrostatics
 What does structure predict?
• Density, i.e. molecular packing
– Predicted by molecular structure

• Intermolecular forces
– Predicted by chain and side-chain chemistry

• Phase transitions, e.g. melting temperature

• Degradation rate

• Mechanical properties, e.g. elastic modulus

• Thermal properties, e.g. thermal expansion

 What does structure predict?
• Density, i.e. molecular packing
– Predicted by molecular structure

• Intermolecular forces
– Predicted by chain and side-chain chemistry

• Phase transitions, e.g. melting temperature

• Degradation rate

• Mechanical properties, e.g. elastic modulus

• Thermal properties, e.g. thermal expansion

 Example: Kevlar
• Poly-paraphenylene terephthalamide
• Invented by Stephanie Kwolek at DuPont
• Very high intermolecular forces
• Tensile strength ~ 3.6 GPa
• Density ~ 1.44 g/cm3
• Strength/Weight ratio is ~5X steel
 Summary
chemical structure

density, packing of chains intermolecular bonding

Material Properties:
phase transitions degradation mechanics thermal properties

Applications:
absorbable bullet-proof circuit board
bone screws vests glue

Next lecture: Polymer physics… big chains

do crazy stuff!