Introduction and Nomenclature
Concepts
Know the basic morphologies of a polymer: linear, branched, crosslinked, dendritic.
Know the basic morphologies of a polymer: random, alternating, block, graft, interspersed
Recognize the relationships between carbonates, ureas and urethanes
Know how to name nylon with the Nylon-
α
,
β
designation
Understand the difference between common names, source names, IUPAC names and trade names for polymers
Understand the difference between a constitutional repeat unit and a structural repeat unit
Know how to prioritize subunits to find the correct structural repeat unit for a polymer
Know how to name a polymer from the subunits in its structural repeat unit
Terms and Definitions
Oligomer
Monomer
Homopolymer
Copolymer
Dendrimer
Ethylene
Vinyl monomer
Vinylidene monomer
Substances
Stryene
Acrylic acid
Acrylate
Cinnamic acid
Oxalic acid
Malonic acid
Succinic acid
Lactam
Lactone
Carbonate
Urea
Urethane
Siloxane
Sulfone
Sulfoxide
Glutaric acid
Adipic acid
Sebacic acid
Maleic acid
Terephthalic acid
Isophthalic acid
Phthalic acid
1

Polymer Structure and Morphology
Concepts
Be able to recognize or draw a polymer for a given tacticity
Understand the Ziegler-Natta catalysts are used to synthesize a polymer with a desired tacticity
Understand the difference between the full contour length, the end-to-end length and the radius of gyration for a polymer
Understand how secondary polymer structure arises from intermolecular forces
Understand the distinction between amorphous regions and crystalline regions in a polymer
Understand the difference between thermoplastic and thermoset polymers
Understand how crystalline polymers result from the creation of lamellae and subsequently spherulites and axialites
Understand how crystallization rates can be characterized using the specific volumes and the
Avrami equation
Understand how secondary structure affects crystallinity
Know the difference between axial stress/strain and shear stress/strain
Recognize the features in a typical stress/strain diagram
Know the difference between a Newtonian fluid and a non-Newtonian fluid
Know the importance of the glass transition temperature as a characteristic of a polymer
Know how the glass transition temperature is different from the melting point for a polymer
Know the difference between differential thermal analysis and differential scanning calorimetry
Know what endothermic changes create troughs and what exothermic changes create peaks in a thermogram
Know how entropy and enthalpy are used with the Flory-Huggins solubility theory describing the interaction between polymer and solvent within a polymer solution
Know solubility parameters are used to find compatibility between polymer and solvent
Understand how the Hansen solubility parameters are an improvement on the Hildebrand solubility parameters
Understand the relationship between a theta solvent and a polymer’s random walk configuration
Understand the relationship between solubility and theta temperature
Understand how polymer structure affects properties such as crystallinity, glass transition temperature and solubility
2

Terms and Definitions
Head-to-head
Head-to-tail
Atactic
Isotactic
Syndiotactic
Eutactic
Erythrodiisotactic
Threodiisotactic
Disyndiotactic
Ziegler-Natta catalyst
Full contour length
End-to-end length
Radius of gyration
Amorphous polymer
Crystalline polymer
Crosslink density
Thermoset
Thermoplastic
Lamella
Tie regions
Spherulite
Axialite
Degree of crystallinity
Avrami equation
Specific volume
Cold drawing
Key Equations
First-tier
σ =
F
A
Second-tier
ε =
Δ l
0 l
=
V t
−
V f
V
0
−
V f
= e
−
Kt n l
− l
0 l
0
τ = μ d dt
γ
= μγ
Axial stress
Shear stress
Axial strain
Shear strain
Elasticity
Plasticity
Yield point
Necking
Ultimate strength
Young’s modulus
Viscosity
Viscoelastic
Non-newtonian
Glass transition temperature
Plasticizer
Elastomer
Differential thermal analysis
Differential scanning calorimetry
Thermogram
Cohesive energy density
Flory-Huggins solubility theory
Hildebrand solubility parameter
Hansen solubility parameter
Theta solvent
Theta temperature
3

4
Molecular Weights
Concepts
Know why different definitions of molecular weight for a polymer are necessary
Know the different definitions of molecular weight and how they relate to each other.
Know the primary measurement methods for each definition of molecular weight
Know how the Mark-Houwink equation is used to find viscosity-average molecular weight
Know what polydispersity is
Know what consequences of polydispersity are for the properties of polymer
Know where the different molecular weights are on a molecular weight distribution
Know how a molecular weight distribution can be found fractionation or GPC
Understand how osmometry can be used to measure the number-average molecular weight
Understand the concentration limiting process that allows for the determination of numberaverage molecular weight using osmometry
Understand how end point analysis can determine the number-average molecular weight
Know why ebulliometry, cryoscopy and vapor pressure lowering are rarely used method for molecular weight determinations
Qualitatively understand the microscopic basis for light scattering
Be able to give an outline of the light scattering process used to find the weight-average molecular weight
Know the difference between absorptivity and turbidity (i. e. the difference between Beer’s law and Lambert’s law
Qualitatively understand the double-extrapolation process on a Zimm plot
Qualitatively understand the difference between static light scattering and dynamic light scattering
Know how viscosity-average molecular weight is determined via the Mark-Houwink equation
Know the trail of viscosity definitions that leads to the intrinsic viscosity definition
Know that the Flory equation relates intrinsic viscosity to molecular weight and end-to-end distance
Quantitatively understand the balance of forces in sedimentation
Be able to physically interpret what the sedimentation constant means
Know that the sedimentation constant has units of time
Compare and contrast sedimentation and centrifugation
Understand the quasi-equilibrium that exist between the particle flux due to centrifugation and the particle flux due to diffusion
Know the two different plots that are used in conjunction with centrifugation to determine the z-average molecular weight and the conditions under which is used
Know the basic physical processes behind the matrix-assisted laser deposition/ionization mass spectroscopy (MALDI-MS)

Terms and Definitions
Number-average molecular weight
Weight-average molecular weight
Viscosity-average molecular weight
Z-average molecular weight
Polydispersity index
Fractionation
Nonsolvent
Gel permeation chromatography
Size-exclusion chromatography
Osmometry van’t Hoff equation
Ebulliometry
Cryoscopy
Refractometry
Light scattering
Optical constant
Rayleigh ratio
Lambert’s law
Key Equations
First-tier
M n
=
W
=
N
∑
∑
N M i i
N i
M w
=
∑
M W i i
W
Turbidity
Double-extrapolation plot
Zimm plot
Dynamic light scattering
Relative viscosity
Specific viscosity
Reduced viscosity
Intrinsic viscosity
Mark-Houwink equation
Ultracentrifugation
Sedimentation
Buoyancy
Sedimentation constant
Svedberg
Centrifugation
Centrifugal force
MALDI-MS
=
∑
∑
N M i i
2
N M i i
M z
=
∑
∑
N M i i
3
N M i i
2
M v
=
∑
∑
N M i
N M i i
[ ]
KM a v
π = cRT
M n
+
Bc
2 +
PDI
=
M w
M n
η
η
0
η−η
0
η
0
η = red
η sp c lim c
→
0
⎛
⎝
η c sp
⎞
⎠
= lim c
→
0
η red
F g
= mg F b
= mv g
2
ρ
F
= fu f s
= u ter g
5

Second-tier
R
Hc
( )
=
1
RT
⎛
⎝
∂π
∂ c
⎞
⎠ lim c
→
0
⎡
⎣ R
Hc
( )
⎦
R i
( ) r
2
0
( − θ )
1
M w
⎢
⎢
⎡
1
⎣
+
1
3
⎛
4
λ
π
′
1
⎞ 2
2
R sin
2
θ
2
+
φ
M
3
2
α
M z
=
RTs
)
R
⎤
⎥
( )
Hc
( )
=
1
M P w lim
θ→
0 s
=
1
ω 2 d ln x b dt
⎡
⎣ R
Hc
( )
⎤ =
⎦
M z
1
M w
+
2Bc
+
+
2Bc
+
= d ln c
( ) (
RT
1 v
)
2
6

7
Step Polymerization
Concepts
Know step polymerizations need two difunctional monomers to form a single repeat unit
Know that a step polymer grows at both ends of the polymer chain
Know that the monomers in a step polymerization are rapidly consumed
Know that high molecular weight polymer can be difficult to achieve in a step polymerization
Know that uncatalyzed step polymerizations have third-order kinetics and that the diacid acts as a catalyst
Know that the monomers in a step polymerization must be stoichiometically balanced to achieve high molecular weights
Know that catalyzed step polymerizations follow second-order kinetics
Know that the ideal polydispersity index for a step polymerization is 2
Understand how the monomer ratio affects the degree of polymerization
Understand how the functionality factor affects the degree of polymerization
Know that polyamides are formed from diamines reacting with diacids
Know that polyamide synthesis from diamines and diacids occurs via a salt intermediate
Know the resonance forms of an isocyanate
Know that polyamides are formed from diisocyanates and diacids
Know that polyamides are formed from diamines and diacid chlorides
Know that polyamides are formed dicyanides and diols
Know that polyesters are formed from diols and diacids
Know that polyesters are formed from diols and diacid chlorides
Know that polyesters are formed from diesters and diols
Know that polyesters are formed from dianhydrides and diols
Know that polycarbonates are formed from diols and phosgene
Know that polycarbonates are formed from diols and bischloroformates
Know that polycarbonates are formed from diols, dichlorides and carbon dioxide
Know that polyurethanes are formed from diols and diisocyanates
Know that crosslinking in a polyurethanes may occur through the formation of allophanates
Know that polyurethanes are formed from diamines and bischloroformates
Know that polyureas are formed diisocyanates and diamines
Know that polyureas are formed from diamines and phosgene
Know that polyureas are formed from diamines and carbonates
Know that polysulfides are formed from dichlorides and sodium polysulfide
Know that polysulfides are formed from dihalides and dithiols
Know that polyethers are formed from the dehydration of diols
Know that polyethers are formed from the diols and methylene chloride (w/ base catalyst)
Know that polyethers are formed from diols reacting with dibromides (w/ phase transfer catalyst)
Know that polysulfones are formed from bischloroalkyl(aryl)sulfones and diols
Know that polysulfones are formed from sulfonyl chlorides via a Friedel-Crafts reaction
Know that polyimides are formed from diamines and dianhydrides
Know that polyimides are formed from diisocyanates and dianhydrides
Know the three basic phenolic resins
Know the resonance forms of the phenolate ion
Understand the basic mechanism behind the formation of the (mono-, di-, tri-) methylolphenolate ion in the synthesis of phenol-formaldehyde resins

8
Understand the difference in the synthesis of resole resin and a novolac resin
Know how the molar ratio of phenol and formaldehyde affects the synthesis of a phenolformaldehyde resin
Know that cyanamine trimerizes to form melamine
Know how formaldehyde reacts with melamine to form methylolmelamines
Know that urea and formaldehyde react to form the cyclic intermediate, triazine, on way to forming urea-formaldehyde resins
Know that polyamides have good tensile strength, good elasticity, absorb water, high T g
and low coefficient of friction
Know that polyamides are used in clothing, bulletproof vests, tire cord, carpeting, rope, gears, wheels and foams
Know that polyesters have high tensile strengths at elevated temperatures, high impact strength, high fatigue resistance, good solvent and moisture resistance
Know that polyesters are used in clothing, beverage bottles, fiberglass, tarps, canoes and paints
Know that the recycling code for polyethylene terephthalate is 1
Know that polycarbonates have high impact strength, high moisture resistance, good high temperature mechanical stability and high indices of refraction
Know that polycarbonates are used for optical lenses, drinking glasses and bulletproof glass
Know that polyurethanes have high elasticity, solvent resistance, abrasion resistance, high impact strength and low coefficients of friction
Know that polyurethanes are used in foams (mattresses, insulation), bowling pins, Spandex and floor coatings
Know that polyureas have high thermal properties, solvent resistance, high mechanical strength, and resistance to puncture
Know that polyureas are used in automotive parts, chemical waste containers and truck bed liners
Know that polysulfides have high solvent/grease resistance, good thermal stability and heat resistance
Know that polysulfides are used in structural plastics, heat resistance coatings, sealants and gaskets
Know that polyethers can be water-soluble and non-toxic
Know that polyethers are used as surfactants and thickeners
Know that epoxy resins used in adhesives and coatings are polyethers
Know that polyphenylene oxide is a polyether used as an engineering polymer
Know that PPO is blended with polystyrene to reduce crystallinity
Know that polyetheretherketone is a polyether with high electrical resistance, excellent oxidative stability and excellent solvent/acid resistance
Know that PEEK is used as an engineering polymer and in nuclear waste containers
Know that polysulfones have solvent resistance, thermal stability and are autoclavable
Know that polysulfones are used in medical devices, filter membranes, high dryers and cookware
Know that polyimides have excellent thermal stability, but are brittle
Know that polyimides are used in heat resistant coatings and adhesives
Know that phenol-formaldehyde resins have high tensile strengths, moisture resistance, but are oxidatively unstable
Know that phenol-formaldehyde resins are used for Bakelite, plywood laminate and cheap consumer goods
Know that melamine-formaldehyde resins have high tensile strengths, moisture/solvent resistance, high heat resistance
Know that urea-formaldehyde resins have high tensile strength and moisture resistance

Know that urea-formaldehyde resins are used in plywood laminate, coatings and adhesives and architectural insulation
Know that phenolic resins are brittle
Terms and Definitions
Extent of reaction
Degree of polymerization
Carothers equation
Monomer ratio
Functionality factor
Alkyd resin
Glyptal resin
Crosslinker
Phase transfer catalyst
Resole
A-stage resole
C-stage resole
Novolac
Blowing agent
Reaction injection molding
Surfactant
Thickener
Coating
Adhesive
Epoxy
Substances
Isocyanate
Phosgene
Bisphenol-A
Bischloroformate
Allophanate
Sodium polysulfide
Bischloroalkyl(aryl)sulfone
Pyromellitic anhydride
Methylol
Methylolphenol
Paraformaldehyde
Hexamethylenetetramine
Melamine
Cyanamine
Triazine
Polyethylene glycol (PEG)
Polyphenylsulfide (PPS)
Polyphenylene oxide (PPO)
Polyetheretherketone (PEEK)
Key Equations
First-tier
DP
N
M w
M n
=
[ ]
A
0
=
1
[ ] ( ) t
( ) ⇒ p
=
1;
M w
M n
=
2
Second-tier
2kt
=
1 1
[ ] [ ]
2
0
M n
= mN
0
N
= m
( ) M w
=
( )
( )
= n
( + )
9

10
Ionic Polymerization
Concepts
Understand how the basic mechanism of ionic polymerization contrasts with step polymerizations
Know why ionic polymerizations are sometimes called living polymerizations
Understand the role of the gegenion in a living polymerization
Know that the initiation step in ionic polymerizations is first-order in initiator and first-order in monomer
Know the common cationic initiators and the mechanism behind how they work
Know that the propagation step in cationic polymerization is first-order in monomer and first-order in carbocation
Know the role of carbocation stabilization in the propagation step of cationic polymerization
Be able to make a relative assessment of the stability of various carbocations (including styrene)
Know the resonance forms of the styrene carbocation
Know how a solvent can help to stabilize a carbocation
Know the mechanism for chain transfer and how it affects molecular weight
Know how proton traps reduce chain transfer
Know that termination is first-order in carbocation
Know how to calculate the degree of polymerization in cationic polymerization
Know the common anionic initiators and the mechanism behind how they work
Know that the propagation step in anionic polymerization is first-order in monomer and firstorder in carbanion
Know the role of carbanion stabilization in the propagation step of anionic polymerization
Be able to make a relative assessment of the stability of various carbanions (including styrene)
Know how a solvent can help to stabilize a carbanion
Understand how termination in anionic polymerization is different from termination in cationic polymerization
Know how to calculate the degree of polymerization in cationic polymerization
Be able to predict whether a vinyl polymer is suitable for cationic or anionic polymerization
Know that polyisobutylene is elastomeric and impervious to air
Know that polyisobutylene is used for gaskets and sealants, a fuel additive and roofing
Know that polyisoprene has natural and synthetic sources
Know that hevea rubber is also known as natural rubber
Know that hevea rubber is poly(cis-1,4-isoprene)
Know that gutta percha and gutta balatá is poly(trans-1,4-isoprene)
Know that polyisoprene is hyperelastic with a low T g
and solvent susceptible
Know that gutta percha is more crystalline than hevea rubber and therefore more brittle
Know that polyisoprene is used for tires, rubber bands, latex gloves, rubber cement, chewing gum and erasers
Know that the recycling code for polystyrene is 6
Know that polystyrene has high tensile strength, is waterproof, is solvent susceptible, is not biodegradeable and is flammable
Know that polystyrene is used as a foam is food packaging, “Stryofoam”, pipe insulation and beverage coolers

11
Know that bulk polystyrene is used for CD cases, license plate frames, disposable test tubes and disposable cutlery
Know that polymethylmethacrylate has high impact strength, low crystallinity (transparent) and a lower cost than polycarbonate
Know that polymethylmethacrylate is used for “Plexiglas”, hockey glass, bone cement and dentures
Know that polyvinylacetate is synthesized with a head-to-head connectivity
Know that polyvinylacetate is water soluble and susceptible to degradation from bases
Know that polyvinylacetate is used to synthesize polyvinylalcohol via the hydrolysis of PVAc
Know that polyvinylacetate is used is white glue, bookbinder’s glue and coatings
Know that polyacrylamide is water-soluble, nontoxic and highly water absorbent
Know that polyacrylamide is used for diapers, electrophoresis gels, flocculents, thickening agents and soil conditioners
Know that polyacrylonitrile is solvent resistant, has high impact resistance and is often part of a copolymer system
Know that polyacrylonitrile is used to make “acrylic” fiber and Orlon fabric
Know that polyacrylonitrile is used to make tents, sails, awnings, fiber reinforcement for concrete and as a matrix for carbon fiber composite
Know that an alternative name for polycaprolactam is Nylon 6
Know that polycaprolactam and polycaprolactone are synthesized in a ring-opening polymerization via nucleophilic attack
Know that polycaprolactam has high tensile strength, abrasion resistance, acid and alkali resistance and slightly water absorbent
Know that polycaprolactam is used for toothbrush bristles, surgical sutures, fibers, ropes and panty hose
Know that polycaprolactone is solvent and water resistant, will hydrolyze over time, has high tensile strength and has a low melting point
Know that the trade name for polycaprolactone is Shapelock
Know that polycaprolactone is used in dental fillings, as a tissue support, as a tissue glue and in drug capsules
Terms and Definitions
Ionic polymerization
Cationic polymerization
Anionic polymerization
Living polymerization
Gegenion
Initiation
Propagation
Chain transfer
Substances
Olefin
Triphenylmethyl halide
Tropylium halide
Proton trap
Termination
Latex
Hevea rubber
Gutta percha
Ebonite
Flocculent
Ring-opening polymerization
Glyme
Isobutylene
Isoprene

Key Equations
First-tier
ν = i k I M i
[ ][ ] k t
ν = p
ν = ν i t
DP
=
ν p
ν t
Second-tier k k I M p i
[ ][ ]
2 k p
[ ] ⎡
M
+ ⎤
DP
=
DP
=
ν p
ν tr
[ ] [ ]
0
[ ]
0
M
ν =
Tr k
Tr
[ ] ⎡
M
+ ⎤
[
3
]
⎣ M
−
⎦
ν = t k t
⎡
M
+ ⎤
12

13
Free-Radical Polymerization (part 1)
Concepts
Know that free-radical polymerization is a type of chain polymerization
Know that initiation begins with the thermal or photolytic decomposition of an initiator
Know that the rate law for decomposition is first-order in initiator
Know initiators are characterized with decomposition temperature or half-life
Know that the half-life of an initiator is very temperature sensitive
Know that the rate law for the initiation step is first-order in initiator and first-order in monomer
Know that initiator efficiency can be affected by recombination, combination with polymer radical, hydrogen abstraction and reaction with solvent
Know peroxides can decompose to form free radicals
Know how azo compounds can decompose to form free radicals
Know how redox initiators can react to form free radicals
Know how photoinitiators interact with light to form free radicals
Know that the propagation step in free-radical polymerization is first-order in monomer and first-order in radical
Know that during the propagation step a steady-state is assumed in equating the initiation rate and the termination rate
Know that inhibitors and retarders are used to remove or slow unwanted free radicals in a polymerization
Know that inhibitors are necessary for the storage of many vinyl monomers
Know that termination occurs via a mixture of combination and disproportionation
Know that both termination steps in a free-radical polymerization are second-order in radical
Understand how dilatometry how for the real-time measurement of polymerization rate
Know the three substances that contribute to the overall volume of a reaction mixture in dilatometry
Understand that in the analysis of dilatometric data, the weight of polymer is assumed to be the weight of consumed monomer
Understand how dilatometric data is used to find the real-time polymerization rate
Understand the difference between the degree of polymerization and kinetic chain length in free-radical polymerizations and why a distinction between the two is necessary
Know that the initiation, propagation and termination steps in free-radical polymerization follow Arrhenius kinetics
Understand how enthalpic and entropic effects determine the depolymerization temperature of a vinyl polymer
Understand how the degree of polymerization can be limited by the increasing viscosity of a reaction mixture

14
Terms and Definitions
Decomposition temperature
Half-life
Initiator efficiency
Solvent cage
Recombination
Hydrogen abstraction
Inhibitor
Substances
Benzoyl peroxide
Diacetyl peroxide
Di t-butyl peroxide
Cumyl peroxide
2-2
′
-azobisisobutylnitrile (AIBN)
Phenylazotriphenylmethane
Key Equations
First-tier
ν = d k d
[ ] ν = i i
[ ][ ] ν = p k M M p
Retarders
Combination
Disproportionation
Dilatometry
Kinetic chain length
Depolymerization
Persulfate ion
Benzoin
Benzil
Benzophenone
X n k t
= k tc
+ k td
Second-tier
ν = p w m
= w
[ ][ ]
0 m
1
2
V
−
V
∞
V
0
−
V
∞
=
1
η
⎛
1
+
1
η
⎞
⎠
− n
⎛
⎜
⎝
ν = t k f I d
[ ]
ν poly
=
Y
[ ]
0 t
η
⎜
⎝
⎛
+
+
2
⎛
⎝ k k td tc
⎞
⎠
⎞
⎟
⎠
⎛
⎝ k k td tc
⎞
⎠
⎞
⎟
⎠
DP
=
ν
ν p = t
=
Δ ( )
( ) k p
[ ]
0 t
[ ] 1
2
DP
=
2
η ( k tc
+ k
( k tc
+
2k td td
)
)
0
−
1
+
C
I
V
= w v m m
+ w v p p
+ w v s s
[ ]
[ ]
+
C
S
[ ]
[ ]
+
C
Y
[ ]
[ ]
+
C polymer
[ ]
[ ]

15
Free-Radical Polymerization (part 2)
Concepts
Be able to compare and contrast bulk, solution, suspension and emulsion polymerizations
Understand the different synthetic routes that are available for a conjugated diene
Understand how isolated dienes can form crosslinks or five- and six-membered rings
Know the recycling code for low-density polyethylene
Understand the differences in morphology between low-density and high-density polyethylene
Know that LDPE is resistant to acids, alcohols, bases and esters
Know that LDPE is susceptible to hydrocarbons and halogenated hydrocarbons
Know that LDPE is used for plastic trash bags, food packaging and laminate on milk cartons
Know the recycling code for high-density polyethylene
Know the Ziegler-Natta catalysts are used to control back-biting in the synthesis of HDPE
Know why HDPE is more chemically resistant than LDPE
Know that HDPE is used for milk jugs, outdoor furniture, industrial drums, piping and in the fabric, Tyvek
Know the recycling code for polypropylene
Know that most industrial polypropylene is isotactic
Know that the tacticity of polypropylene is controlled by Ziegler-Natta catalysts
Know that polypropylene is fatigue resistant and autoclavable
Know that polypropylene is used for medical equipment, food containers and moisturewicking clothing
Know that Teflon is the trade name for polytetrafluoroethylene
Know that PTFE is an excellent electrical conductor, is very resistant to strong alkali, acid and solvent, has a low coefficient of friction, good impact resistance, poor abrasion resistance, is difficult to machine, is difficult to adhere to a surface, decomposes at a relatively low temperature and is often made with emulsion polymerization with perfluorooctanoic acid
Know that PTFE is used for gaskets, bearings, non-stick cookware, electrical insulation, plumber’s pipe dope and in Gore-Tex fabric
Know the recycling code for polyvinyl chloride
Know that most industrial polyvinyl chloride is syndiotactic
Know that PVC is easily extruded above its glass transition temperature
Know that plasticizer must be added to PVC to make less crystalline and less brittle
Know that PVC is relatively unstable to heat and light and has low electrical conductivity
Know that PVC is used for water piping, gutters, siding, power line insulation
Know that PVC is used with polyacrylonitrile to make Orlon
Know that PVC is used with polyvinylidene chloride to make food wrap
Know that polyvinylpyrollidone is water-soluble, non-toxic and forms aqueous solutions with Newtonian viscosity
Know that PVP is used in blood plasma substitute, as a pharmaceutical binder, as a binder for ink-jet printer ink and a thickerer in cosmetic formulations

Terms and Definitions
Bulk polymerization
Popcorn polymerization
Solution polymerization
Suspension polymerization
Emulsion polymerization
Emulsifying agent
Soap
Substances
Chloroprene
Perfluorooctanoic acid
Detergent
Micelle
Critical micelle concentration
Isolated diene
Back-biting
Laminate
Tyvek
Tri-2-ethylhexyl trimellitate
N-vinyl-2-pyrrolidone
16

17
Copolymerization
Concepts
Know the basic morphologies of a copolymer: random, alternating, block, graft, interspersed, blended
Understand the basic kinetic scheme for the propagation of a copolymer
Understand how the reactivity ratios are related to reaction rates of each monomer to a given monomer
Know that reactivity ratios must be measured for a pair of monomers used in a copolymerization
Understand the difference between the feed mole fraction and the polymer mole fraction
Understand how copolymer mole fractions can be related to the ratio of monomer disappearance rates
Understand how the reactivity ratios affect the composition of the copolymer (especially the five cases considered in class
Know the conditions for an ideal polymerization
Know what is the meant by azeotropic conditions for a copolymer
Be able to draw of sketch of the effect of reactivity ratios on copolymer composition on a copolymer mole fraction vs. feed mole fraction
Know that reactivity ratios can be estimated the “Q – e” scheme
Know that “Q” in the Q-e scheme is a measure of resonance stabilization of the monomer radical
Know that “e” in the Q-e scheme is a measure of polarity of the monomer
Know the difference between Buna rubber, SAN rubber and ABS rubber
Know that polybutadiene in a copolymer adds elasticity and impact resistance
Know that polystyrene in a copolymer adds strength, abrasion resistance and heat resistance
Know that polyacrylonitrile adds strength (toughness) and solvent resistance
Know that Buna rubber is used for tires and shoe soles
Know that SAN rubber is used for optical disks
Know that ABS rubber is used for automotive parts, athletic helmets and Legos
Know that adding polyvinyl acetate to polyethylene increases the wettability of the polymer
Know that the copolymer of ethylene and vinyl acetate is used to make boots, Crocs and synthetic corks
Know that the copolymer of ethylene and tetrafluoroethylene has a low coefficient of friction and is puncture resistant
Know that the copolymer of ethylene and tetrafluoroethylene is used for electrical insulation and protective gloves
Know that the copolymer of polyurethane (polyurea) and polyethylene glycol is known by the tradenames of Spandex and Lycra
Know that the polyethylene glycol adds significant elasticity to the copolymer of polyurethane (polyurea) and polyethylene glycol
Know that the polyurethane adds strength to the copolymer of polyurethane (polyurea) and polyethylene glycol
Know that the copolymer of polyurethane (polyurea) and polyethylene glycol is used for athletic garments and other high-fashion apparel
☺
Know that the maleic anhydride adds solubility and impact resistance to the styrene/maleic anhydride copolymer

18
Second-tier f
1
=
M
1
[ ]
[ ] [ ]
Know that the styrene/maleic anhydride copolymer is blended with ABS or PVC to increase heat stability
Know that the styrene/maleic anhydride copolymer is used as a compatibilizer to blend nylon with ABS
Terms and Definitions reactivity ratio copolymer equation monomer feed azeotrope ideal polymerization
Substances
Alfrey-Price “Q-e” scheme crazing terpolymer wettability
ABS rubber maleic anhydride
Buna rubber
SAN rubber
Key Equations
First-tier r
1
= k k
11
12 r
2
= k k
22
21
[ ]
[ ]
=
[ ]
[ ]
⋅
(
(
1
[ ] [ ]
[ ] [ ] )
)
1
⋅ =
1
[ ]
[ ]
=
[ ]
[ ]
F
1
= r f
1 1
2 + f f
1 2 r f
1 1
2 +
2f f
1 2
+ r f
2 2
2 r
1
=
Q
1
Q
2 e
− (
1
− e
2
) r r
1 2
= e
− ( e
1
− e
2
) 2

19
Polymer Characterization and Testing
Concepts
Know that difference between bulk spectroscopies and surface spectroscopies
Know how infrared spectroscopy can be used to characterize copolymers and polymer blends
Know that Raman spectroscopy can be used to examine conformations and crosslink densities
Know that NMR spectroscopy can be used to examine stereochemistry, tacticity and monomer sequences
Be able to compare and contrast NMR and electron spin resonance spectroscopies
Know that ESR spectroscopy can be used to examine different modes of polymer degradation
Know how UV-vis spectroscopy can be used to characterize the relative amount of monomer and polymer during a polymerization
Understand the mechanism behind x-ray photoelectron spectroscopy
Know that XPS is used to characterize the chemical composition of a surface
Know why XPS is useful for polymer characterization
Understand the mechanism behind Auger spectroscopy
Understand the similar utility of Auger spectroscopy with XPS
Understand the mechanism behind attenuated total reflectance
Be to compare and contrast bulk infrared spectroscopy with ATR
Understand the mechanism behind secondary-ion mass spectroscopy
Understand why SIMS is useful characterization technique for polymers
Understand the mechanism behind scanning electron microscopy
Understand the mechanism behind scanning tunneling microscopy
Understand the mechanism behind atomic force microscopy
Know the difference in resolution between the SEM and STM/AFM
Be able to compare and contrast x-ray, neutron and electron diffraction
Be able to compare and contrast differential thermal analysis with differential scanning calorimetry
Know the different physical and chemical processes that correspond to peaks and troughs in a thermogram
Understand the nature of the physical measurements taken in a thermal gravimetric analysis
Know the types of processes examined in TGA
Know the different zones of combustion
Understand the basic mechanism behind the flash point test
Understand the difference between the closed-cup and open-cup flash point test
Know the difference between the flash point of a substance and its auto-ignition temperature
Understand how the limiting oxygen index test is done
Understand how the degree of sustainable combustion test is done
Compare and contrast natural, accelerated and artificial weathering
Know the ways that weathering can be induced artificially in a polymer sample
Know the difference classes of reagents that are commonly used to test a polymer for its chemical compatibility
Have a general idea how the structure of a material affects its dielectric constant
Know how a material’s dielectric constant is related to its insulation properties
Know why it can be important to test a material’s dielectric constant for a large range of electrical frequencies
Know the difference between an object’s resistance and a material’s resistivity

Know why measuring a material’s dissipation factor is important
Know why measuring a material’s dielectric breakdown is important
Know how a material’s refractive index is related to its dielectric constant
Know how a material’s refractive index affects its optical properties
Know the mechanism behind measuring the optical clarity of a substance
Terms and Definitions
ESR
XPS
ESCA
Auger spectroscopy
ATR
SIMS sputtering ablation
SEM
STM volatilization char flash point auto-ignition temperature limiting oxygen index degree of sustainable combustion weathering dielectric constant resistivity dissipation factor dielectric breakdown refractive index refractometer optical clarity
AFM
DTA
DSC
TGA preheating
Key Equations
First-tier
R
= κ
A l n
= εμ
Second-tier
ε =
C I
C
0
I
0
= e
−
Ad
20

21
Mechanical Properties and Rheology
Concepts
Know that a material is elastic when its strain is linearly proportional to its stress
Know the difference between axial and shear stress/strain
Know that Poisson’s ratio is equal to 0.5 for incompressible materials
Know that a spring is used to model the elasticity of a material
Know the difference between Newtonian and non-Newtonian fluids
Know that the dashpot is used to model the fluid properties of a materialMa
Know that the Maxwell model of viscoelasticity employs a spring and dashpot in series with each other to model that shear strains are additive
Know that the Voigt – Kelvin model of viscoelasticity employs a spring and dashpot in parallel with each other to model that shear stress are additive
Know the viscoelasticity of a material can be modeled with combinations of springs and dashpot in series and parallel with each other
Know the definitions and give an example for each of the following non-Newtonian rheological properties: Bingham plasticity, dilantancy, pseudoplasticity, thixotropicity, rheopecticity
Understand the different material response of a thermoplastic with changing temperature on the molecular level
Know the different classes of elastic material response
Be able to distinguish between the following words when considering elastic material response: soft, weak, hard, brittle, tough, strong
Be able to draw stress-strain curves for the different elastic material responses
Be able to draw stress-strain curves for the Maxwell and Voigt – Kelvin models
Know how the mechanical properties of a material are measured
Know the difference between engineering stress/strain and true stress/strain
Know the difference between stiffness and Young’s modulus
Know that absolute viscosity measurements are made with cone-and-plate and parallel plate viscometers
Know relative viscometric measurements are made with the following viscometers:
Ubbelohde, falling-ball, Brookfield, Ford cup, bubble and vibrational
Know that creep is modeled with the four-element model
Know that a perfectly elastic material exhibits no creep or fatigue
Know that fatigue measures are probabilistic
Know that fatigue is often modeled with an “S – n” curve
Be able to compare and contrast the Izod and Charpy methods for impact testing
Be able to compare and contrast the Brinell and Rockwell hardness tests
Be able to compare and contrast the rotary abrasion, linear abrasion and falling sand tests for abrasion resistance

22
Terms and Definitions
Hooke’s law shear modulus
Poisson’s ratio dashpot viscoelasticity
Maxwell model
Voigt – Kelvin model rheology relative viscosity specific viscosity reduced viscosity intrinsic viscosity
Bingham plastic dilantancy pseudoplacticity thixotropicity rheopecticity tensiometer engineering stress engineering strain true stress true strain cone-and-plate viscometer parallel plate viscometer
Ubbelohde viscometer falling-ball viscometer
Brookfield viscometer
Ford cup bubble viscometer vibrational viscometer creep four-element model fatigue thermal expansivity
Izod method
Charpy method
Brinell hardness
Rockwell hardness
Key Equations
First-tier
E
=
σ
ε
G
η
η
0 k
Second-tier
F F
δ −
0
=
τ
γ
ν = −
ε trans
ε axial
η−η
η
0
0
ε thermal
= αΔ
T
τ = τ
0 e
−
Gt
η γ =
τ
G
⎛
⎜
−
Gt
η
⎞
⎟
τ = ηγ = η d
γ dt
η = red
η sp c
σ = true
F
A
σ = lim c
→
0 eng
ε = true dl l
⎛
⎝
η c sp
⎞
⎠
F
A
0
= lim c
→
0
η red k
=
ε eng
= l
Δ
0 l
= l
− l
0 l
0
L
A
E

23
Polymer Reactions
Concepts
Understand how polyvinyl acetate is hydrolyzed to polyvinyl alcohol
Understand how polyacrylamide is hydrolyzed to polyacrylic acid
Understand how polyethylene can be chlorinated
Know the application of chlorinated polyethylene
Understand how polyethylene can be chlorosulfonated
Know the application of chlorosulfonated polyethylene
Understand how polystyrene is chloromethylated
Understand how chloromethylated polystyrene can be further modified to form ion-exchange resins
Understand how polystyrene can be lithiated
Understand that lithiopolystyrene can be further modified to form carboxylate, thiol or benzophenone derivative
Understand how polyvinylamine is made from polyacrylamide
Know the application of polyvinylamine
Know how head-to-head polyvinyl bromide is synthesized
Know how the epoxidation of polyisoprene is done
Know why polyisoprene undergoes epoxidation
Know that polyvinyl chloride can be converted to polyvinyl cyclopentadienyl
Know how polyvinyl cyclopentadienyl can be used as a moldable and recyclable thermoset
Know that polyvinylacetate and polyvinylchloride can be pyrolyzed to form polyacetylene
Know an application for polyacetylene
Terms and Definitions hydrolysis chlorination chlorosulfonation
Substances chlorosulfonyl group chloromethyl group had little lamb a little lamb
Key Equations
First-tier
Second-tier

Section Title
Concepts
Mary had a little lamb
Terms and Definitions
Mary had a
Substances
Mary had a
Key Equations
First-tier
Second-tier little lamb little lamb
24