Polymer Structures

TEM of spherulite structure in natural rubber(x30,000).

Chain-folded lamellar crystallites (white lines) ~10nm thick extend radially.

Chapter 4- Polymer Structures

ISSUES TO ADDRESS...
What are the basic Classification? Monomers and chemical groups? Nomenclature? Polymerization methods? Molecular Weight and Degree of Polymerization? Molecular Structures? Crystallinity? Microstructural features?

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.

Polyethylene perspective of molecule

A zig-zag backbone structure with covalent bonds

Polymer Microstructure

Covalent chain configurations and strength:

Van der Waals, H
secondary bonding

More rigid

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

Common Examples
- Textile

fibers: polyester, nylon

- 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

Common Chemical Functional Groups

H H C C H
H

Ethylene (ethene) Propylene (propene) 1-butene 2-butene

H
H C C

=
C H H

trans

cis

Acetylene (ethyne) Saturated hydrocarbons (loose H to add atoms)

H C C H

Unsaturated hydrocarbons (double and triple bonds)

Common Hydrocarbon Monomers

Alcohols Methyl alcohols

Ethers

Dimethyl Ether

Acids

Acetic acid

Aldehydes

Formaldehyde

Aromatic hydrocarbons

Phenol

Some Common Polymers

Common backbone with substitutions
H H C C N

Polyacrylonitrile (PAN)

C H

Vinyl polymers (one or more Hs of ethylene can be substituted)

H C C H X H
H C H H C X

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

e.g. acrylic acid -> poly(acrylic acid)

Note: this may lead to polymers with different names but same structure.
H H H H H H H H

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

Free radical initiator (unpaired electron)

monomer

R H H C H bonds bond C H H H sp3 carbon C C H H

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 Both carbon atoms will change from sp2 to sp3.

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

Intentional or unintentional molecules/impurities can also terminate.

Polymerization Methods
B. Stepwise polymerization
O
O

Loses water (condensation)

O H2N R C OH

H2N

OH

H2N

N H

C O

OH

Proteins (polypeptides have similar composition)

H N H C C R O

H N

O R C

+ (n-1)
n

Various R groups
n

C. Other methods Anionic polymerization, cationic polymerization, coordination polymerization

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

Average molecular weight =

20 + 16 + 10 M monomer = 15.3M monomer 3

This is what is called number average molecular weight.

Number average molecular weight:

N j M j
Mn =
j

mo N j j =
j

Nj = # of polymer chains with length j

Mj = jmo mass of polymer chain with length j (mo = monomer molecular weight).

N j
j

N j
j
j

Note:

N j M j = Total weight
j

N j =

Total # of polymer chains

Weight average molecular weight:

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

Molecular Weight: Different Notations

In Lecture Notes In Callister Textbook

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).

Distribution of polymer weights

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.

Polydispersity and Degree of Polymerization

Polydispersity:

Mw 1 Mn

When polydispersity = 1, system is monodisperse. Degree of Polymerization:

Number avg degree of polymerization

Mn nn = mo
Mw nw = mo

Weight avg degree of polymerization

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

What is mer of PP?

Mer molecular weight of PP is

mo=3AC+6AH =3(12.01 g/mol)+6(1.008 g/mol) = 42.08 g/mol

Number avg degree of polymerization

Mn 106 g / mol nn = = = 23,700 mo 42.08 g / mol

Example 2 (a, b, and c)

A. Calculate the number and weight average degrees of polymerization and polydispersity for a polymer sample with the following distribution.
Avg # of monomers/chain 10 100 500 1000 5000 50,000 Relative abundance 5 25 50 30 10 5

M m nn = n = 0 mo m0 =

jN N
j j

jN = N
j j

5 *10 + 25 *100 + 50 * 500 + 30 *1000 + 10 * 5000 + 5 * 50000 = 2860.4 5 + 25 + 50 + 30 + 10 + 5

M 1 nw = w = mo mo

( jm ) N j N = N ( jm ) jN
2 2 j o j j j j o j

Note: m0 cancels in all these!

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

Mn = n n mo = 2860.4(100g / mol ) = 286,040g / mol Mw = nw mo = 35,800(100 g / mol ) = 3,580,000g / mol

Polydispersity:

Mw 3,580,000 = ~ 12.52 286,040 Mn

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

Add 5 more monomers of length 10 .

10 * 10 + 25 * 100 + 50 * 500 + 30 * 1000 + 10 * 5000 + 5 * 50000 = 2750 10 + 25 + 50 + 30 + 10 + 5

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:

Polymer Molecular Configurations

Regularity and symmetry of side groups affect properties

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

Isotactic On one side

- Conversion from one stereoisomerism to another is not possible by simple rotation about single chain bond; bonds must be severed first, then reformed!

Polymer Geometrical Isomerism

Regularity and symmetry of side groups affect properties

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

Polymer Structural Isomerism

Some polymers contain monomers with more than 1 reactive site e.g. isoprene 1 2

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

Note: there are also cis-1,4- and cis-1,2-polyisoprene

Polymer Microstructure
Covalent chain configurations and strength:
Van der Waals, H
secondary bonding

More rigid

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

Short branching

Long branching

Star branching

Dendrimers

CoPolymers
Random, Alternating, Blocked, and Grafted

Synthetic rubbers are often copolymers. e.g., automobile tires (SBR)

Styrene-Butadiene Rubber random polymer

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

Control degree of + crosslinking by styrene-divinyl styrene benzene ratio divinyl benzene

crosslinked polystyrene

Monomers with trifunctional groups lead to network polymers.

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

Radical moves to a different carbon (H transfer)

R

C H H2

Polymerization continues from this carbon

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

Calculate the ratio of (# of acrylonitrile) to (# of butadiene).

3 C = 3 x 12.01 g/mol 3 H = 3 x 1.008 g/mol 1 N = 1 x 14.007 g/mol m0= 53.06 g/mol
1,4-addition product

4 C = 4 x 12.01 g/mol 6 H = 6 x 1.008 g/mol m0= 54.09 g/mol

We need to use an avg. monomer MW:

mo =

Mn 106,740 = = 53.57 g / mol nn 2000

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

f / 2 0.7 = 7 : 3(4.96 / 5.04) f1 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

Molecular Weight and Crystallinity

Molecular weight, Mw:

Mass of a mole of chains.

larger M w

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

Adapted from Fig. 14.11, Callister 6e.

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

Volume fraction of crystalline component.

%cr ystallinity =

Mc rystalline Mtotal

V 100 % = c c 100 % = sVs

c f c 100 % s

M total = M crystallin e + M amorphous Ms = Mc + Ma

Using definition of volume fractions:

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

Substituting in fc into the original definition:

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

Cross-polarized light through spherulite structure of PE.

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

partially 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.