Académique Documents
Professionnel Documents
Culture Documents
Polymer Microstructure
Polymer = many mers
mer H H H H H H C C C C C C H H H H H H
Polyethylene (PE)
mer H H H H H H C C C C C C H Cl H Cl H Cl
Polyvinyl chloride (PVC)
mer H H H H H H C C C C C C H CH 3 H CH 3 H CH 3
Polypropylene (PP)
Adapted from Fig. 14.2, Callister 6e.
Polymer Microstructure
More rigid
Linear
Branched
Cross-Linked
Network
Common Examples
- Textile
- IC packaging materials. - Resists for photolithography/microfabrication. - Plastic bottles (polyethylene plastics). - Adhesives and epoxy. - High-strength/light-weight fibers: polyamides, polyurethanes, Kevlar - Biopolymers: DNA, proteins, cellulose
Common Classification
Thermoplastics: polymers that flow more easily when squeezed, pushed, stretched, etc. by a load (usually at elevated T). Can be reheated to change shape. Thermosets: polymers that flow and can be molded initially but their shape becomes set upon curing. Reheating will result in irreversible change or decomposition. Other ways to classify polymers. By chemical functionality (e.g. polyacrylates, polyamides, polyethers, polyeurethanes). Vinyl vs. non-vinyl polymers. By polymerization methods (radical, anionic, cationic). Etc
H
H C C
=
C H H
trans
cis
H C C H
Ethers
Dimethyl Ether
Acids
Acetic acid
Aldehydes
Formaldehyde
Aromatic hydrocarbons
Phenol
Polyacrylonitrile (PAN)
C H
Nomenclature
Monomer-based naming: poly________
Monomer name goes here
e.g. ethylene -> polyethylene if monomer name contains more than one word: poly(_____ ____)
Monomer name in parentheses
C C C C H H H H
C C C C H H H H
polyethylene
polymethylene
Polymerization Methods
A. Free Radical Polymerization 1. Initiation
R
H C C H H H
H R C H
H C H
Radical transferred
monomer
sp2 carbons
Polymerization Methods
A. Free Radical Polymerization 2. Propagation
H R C H H C H
H H C C H H
H C C H H H
H R C H
H C H
H C H
H C H
H R C H
H C H
H C H
H C H
H C H
H C H
H C R H C
H C H H C H
Polymerization Methods
A. Free Radical Polymerization 3. Termination
H R C H H C H
H H C R H
C H
H R C H
H C H
H C H
R
H C H
H C H
H C H
H C H R
C H
Polymerization Methods
B. Stepwise polymerization
O
O
O H2N R C OH
H2N
OH
H2N
N H
C O
OH
H N
O R C
+ (n-1)
n
Various R groups
n
Molecular Weights
Not only are there different structures (molecular arrangements) but there can also be a distribution of molecular weights (i.e. number of monomers per polymer molecule).
20 mers
16 mers
10 mers
N j M j
Mn =
j
mo N j j =
j
N j
j
N j
j
j
Note:
N j M j = Total weight
j
N j =
W j M j
Mw =
j
N j M 2 j
=
j
W j
j
N j M j
j
Wj = N jM j
In general:
+1 N j M j
M=
N j M j
j
If = 0 then Mn
If = 1 then Mw
N j M j
Mn =
j
Mn = x i Mi
i
Ni xi = N j
j
N j
j
2 N M j j
wi =
N i Mi N j M j
j
Mw =
N jM
j
Mw = w i Mi
i
Molecular Weights
Why do we care about weight average MW? -some properties are dependent on MW (larger MW polymer chains can contribute to overall properties more than smaller ones).
Examples Light scattering: larger molecules scatter more light than smaller ones. Infrared absorption properties: larger molecules have more side groups and light absorption (due to vibrational modes of side groups) varies linearly with number of side groups.
Mw 1 Mn
Mn nn = mo
Mw nw = mo
Example 1
Compute the number-average degree of polymerization for polypropylene, given that the number-average molecular weight is 1,000,000 g/mol. C3H6
M m nn = n = 0 mo m0 =
jN N
j j
jN = N
j j
M 1 nw = w = mo mo
( jm ) N j N = N ( jm ) jN
2 2 j o j j j j o j
5 *10 2 + 25 *100 2 + 50 * 500 2 + 30 *1000 2 + 10 * 5000 2 + 5 * 50000 2 = = 35,800 5 *10 + 25 *100 + 50 * 500 + 30 *1000 + 10 * 5000 + 5 * 50000
Example 2 (cont.)
B. If the polymer is PMMA, calculate number and weight average molecular weights. Mw if monomer is methylmethacrylate (5C, 2O, and 8H) So m0= 5(12)+2(16)+8(1)= 100 g/mol
CH3 | -CH2-C| CO2CH3
Example 2 (cont.)
C. If we add polymer chains with avg # of monomers = 10 such that their relative abundance changes from 5 to 10, what are the new number and weight average degrees of polymerization and polydispersity?
M nn = n = mo =
jN N
j j
2 Mw j j N j nw = = = 35,800 mo j jN j
Note: significant change in number average (3.8 %) but no change in weight average! M w 3, 580, 000 = ~ 13 Mn 275000
Polydispersity:
Polymerize
Stereoisomerism: (the situation in which atoms are linked together in the same order (head-to-tail) but differ in their spatial arrangement.) Syndiotactic Alternating sides Atactic Randomly placed
- Conversion from one stereoisomerism to another is not possible by simple rotation about single chain bond; bonds must be severed first, then reformed!
cis-structure
trans-structure
Cis-polyisoprene
trans-polyisoprene
-Conversion from one isomerism to another is not possible by simple rotation about chain bond because double-bond is too rigid! -Refer Callister for taxonomy of polymer structures
CH3 C C H CH2
H2C
trans-isoprene
trans-1,4-polyisoprene
trans-1,2-polyisoprene
3,4-polyisoprene
CH3 C H2 C C H
H2 C
n
H2 C C H3C H2C
n
H2 C H C C H2C
CH
CH3
Polymer Microstructure
Covalent chain configurations and strength:
Van der Waals, H
secondary bonding
More rigid
Linear
Branched
Cross-Linked
Network
Short branching
Long branching
Star branching
Dendrimers
CoPolymers
Random, Alternating, Blocked, and Grafted
Molecular Structure
How do crosslinking and branching occur in polymerization?
1. Start with or add in monomers that have more than 2 sites that bond with other monomers, e.g. crosslinking polystyrene with divinyl benzene
stryene
polystyrene
crosslinked polystyrene
Molecular Structure
Branching in polyethylene (back-biting)
H2 C H2 C H2 C C H
H2C CH2
C H2
C H2
Same as
H H C H C CH2 CH2
H H H C C CH2 C H H 2 CH2
C H H2
Process is difficult to avoid and leads to (highly branched) low-density PE . When there is small degree of branching you get high-density PE.
Example 3
Nitrile rubber copolymer, co-poly(acrylonitrile-butadiene), has
Mn = 106,740 g / mol
n n = 2000
mo =
m o = f 1m 1 + f 2m 2 = f 1(m 1 m 2 ) + m 2
m m 2 53.37 54.09 f1 = 0 = = 0.7 m 1 m 2 53.06 54.09
f 2 = 1 f 1 = 0.3
Vulcanization
Crosslinking in elastomers is called vulcanization, and is achieved by irreversible chemical reaction, usually requiring high temperatures.
Sulfur compounds are added to form chains that bond adjacent polymer backbone chains and crosslinks them. Unvulcnaized rubber is soft and tacky and poorly resistant to wear. e.g., cis-isoprene
Single bonds
Stress-strain curves
Double bonds
+ (m+n) S
(S)m (S)n
smaller M w
Tensile strength (TS): --often increases with Mw. --Why? Longer chains are entangled (anchored) better. % Crystallinity: % of material --TS and E often increase with % crystallinity. --Annealing causes crystalline regions to grow. % crystallinity increases.
that is crystalline.
crystalline region amorphous region
Polymer Crystallinity
polyethylene Some are amorphous. Some are partially crystalline (semi-crystalline). Why is it difficult to have a 100% crystalline polymer?
%crystallinity =
c ( s a ) 100% s ( c a )
s = density of specimen in question a = density of totally amorphous polymer c = density of totally crystalline polymer
%cr ystallinity =
Mc rystalline Mtotal
c f c 100 % s
sV s = cVc + aV a s = c
V fc = c Vs
V fa = a Vs
Vc V + a a = c f c + a f a = c f c + a (1 f c ) = f c ( c a ) + a Vs Vs s a fc = c a
c ( s a ) %crystallinity = 100% s ( c a )
Polymer Crystallinity
Degree of crystallinity depends on processing conditions (e.g. cooling rate) and chain configuration. Cooling rate: during crystallization upon cooling through MP, polymers become highly viscous. Requires sufficient time for random & entangled chains to become ordered in viscous liquid. Chemical groups and chain configuration:
More Crystalline Smaller/simper side groups Linear Less Crystalline Larger/complex side groups Highly branched Crosslinked, network Isotactic or syndiotactic Random
Semi-Crystalline Polymers
Fringed micelle model: crystalline region embedded in amorphous region. A single chain of polymer may pass through several crystalline regions as well as intervening amorphous regions.
s a fc = c a
Crystalline volume fractions Important
Semi-Crystalline Polymers
Chain-folded model: regularly shaped platelets (~10 20 nm thick) sometimes forming multilayers. Average chain length >> platelet thickness.
Semi-Crystalline Polymers
Spherulites: Spherical shape composed of aggregates of chain-folded crystallites.
Natural rubber
Thermoplastics vs Thermosets
Thermoplastics:
T
mobile liquid viscous liquid Callister, rubber Fig. 16.9 tough plastic
--little cross linking --ductile --soften w/heating --polyethylene (#2) polypropylene (#5) polycarbonate polystyrene (#6)
Thermosets:
Tm Tg
crystalline solid
--large cross linking (10 to 50% of mers) --hard and brittle --do NOT soften w/heating --vulcanized rubber, epoxies, polyester resin, phenolic resin
Molecular weight
Adapted from Fig. 15.18, Callister 6e.
Tm: melting over wide range of T depends upon history of sample consequence of lamellar structure thicker lamellae, higher Tm. Tg: from rubbery to rigid as T lowers
Packing of Polymers
Packing of spherical atoms as in ionic and metallic crystals led to crystalline structures. How polymers pack depend on many factors: long or short, e.g. long (-CH2-)n. stiff or flexible, e.g. bendy C-C sp3. smooth or lumpy, e.g., HDPE. regular or random single or branched slippery or sticky, e.g. C-H covalent (nonpolar) joined via vdW.
Candle wax more crystalline than PE, even though same chemical nature.
Summary
Polymers are part crystalline and part amorphous.
The more lumpy and branched the polymer, the less dense and less crystalline. The more crosslinking the stiffer the polymer. And, networked polymers are like heavily crosslinked ones. Many long-chained polymers crystallize with a Spherulite microstructure - radial crystallites separated by amorphous regions. Optical properties: crystalline -> scatter light (Bragg) amorphous -> transparent.
Most covalent molecules absorb light outside visible spectrum, e.g. PMMA (lucite) is a high clarity tranparent materials.