Chain Microstructure

TOPICS COVERED :

Linear chains,branching

Cross - linking and network formation

Sequence isomerism Stereoisomerism in vinyl polymers Diene polymers (structural isomerism) Copolymers and blends

Philosophical Approach
There is a direct connection between structure and properties. Consider crystallinity in polymers.

RANDOM COIL

CRYSTALLINE

Like cooked spaghetti

Like "uncooked spaghetti

Effect ofCrystallinity on the Properties Crystallinity affects

Strength Stiffness Toughness Barrier Properties Solubility Transparency Thermal Properties Etc

Property
Strength Stiffness Toughness

Change with Increasing Degree of Crystallinity

Generally increases with degree of crystallinity Generally increases with degree of crystallinity Generally decreases with degree of crystallinity Generally decreases with increasing degree of crystallinity. Semi-crystalline polymers usually appear opaque because of the difference in refractive index of the amorphous and crystalline domains, which leads to scattering. Will depend upon crystallite size. Small molecules usually cannot penetrate or diffuse through the crystalline domains, hence barrier properties, which make a polymer useful for things like food wrap, increase with degree of crystallinity Similarly, solvent molecules cannot penetrate the crystalline domains, which must be melted before the polymer will dissolve. Solvent resistance increases with degree of crystallinity

Optical Clarity

Barrier Properties

Solubility

Whats covered, whats next . . .

Linear chains, branching Networks Cross-linking Sequence isomers Stereo-isomers, tacticity Structural isomers Copolymers, terpolymers Degree of polymerization Molecular weights Number average and weight average MWs MW distributions

Copolymers and Terpolymers

Copolymers- two different polymers in the chain. Mer variations composition (relative amounts), structure (distribution) and architecture. These variations affect the properties of the copolymer. Terpolymer three monomers, same mer considerations, more complicated.

Copolymers
-A-B-B-B-A-A-B-A-B-A-A-A-B-A-B-B-A-B-B-A-A-A-BRandom

-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-BAlternating
-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-B-A-A-A-A-A-ABlock A-A-A-A-A-A-A-A-

-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-B-BA-A-A-A-A-A-A-A-A-AA-A-A-A-A-AGraft

Copolymers: Adjusting Properties

How would you design a polymer to adjust the following . . . . . . Disrupt the packing order? Improve the compatibility with water? How would the properties of a copolymer change with mer Composition? Structure? a

Molecular Weight
MW directly impacts the properties of the polymer
Tensile Strength

Melt Viscosity

Mol. Wt.

Mol. Wt.

Molecular Weight
CH4 -----------------------------------------------------------------------Gases 16 30 44 58

CH3CH3

CH3CH2CH3

------------------------

CH3CH2CH2CH3 CH3(CH2)6CH3

Incr. MW

--------------Liquids

--------------"Semi-solid"

114

CH3(CH2)30CH3

--------------Solids

450

CH3(CH2)30000CH3

----------

420030

Increasing Molecular Weight

Molecular Weight of Polymers

Degree of Polymerization (DP) Number of mers in the polymer MWpolymer / MWmonomer

Polymers MWs are averages (weight, number) have distributions breadth or skewness (polydispersity)

Molecular Weight Distributions

Synthetic polymers have a distribution of chain lengths.
The distributions can have -different widths. -several distributions. So, there will be a -distribution of chain MWs, -an average MW, and -a width to the MW distributions.

Defining an Average
200 monomers form 10 chains. The average chain length is 20

Molecular Weight Number Average and Weight Average

200/20 provides the number average MW.

Mn =

N M N
x x

Number Average Molecular Weight (Mn)

4 Mosquitos (weighing 1 lb ea.)

Mn =

Nx Mx Nx

= [1 10 ,000] + [4 1] ~ 2,000 4 +1
Number average favors the number of chains.

10,000 lb Elephant

Weight Average Molecular Weight (Mw)

4 Mosquitos (weighing 1 lb ea.)

Mw = Wx Mx W x [10, 000 10, 000] + [ 4 1] = 10, 000 + 4 ~ 10, 000

Weight average favors the wt of the chains.

10,000 lb Elephant

Number Average Molecular Weight

Consider a sample with 5 (moles) chains of length 100 (DP of 100 mers/chain) 5 (moles) chains of length 150 5 (moles) chains of length 200. Ave. DP. = 150 (Mn). If the MW of each mer were 100, the Mn = 15,000. (DP x M)
5 chains DP 200 5 chains DP 100

5 chains DP 150

Mn =

Nx Mx Nx

Number Average Molecular Weight

Heres how the equation works;

Mn =

Nx Mx Nx

= [5 10, 000] + [5 15, 000 ] + [5 20, 000] 5+5+5

= 50 ,000 + 75 ,000 + 100 ,000 = 15,000 15

What about weight average MW?

Weight Average Molecular Weight

Definition of weight average;

The total wt of species x is the MW of each chain of type, x , multiplied by the number of chains of this type.
5 chains, each of wt. 10,000, means that wx is 50,000.

Mw = Wx Mx W x

W x = NxM x

Substituting into the top equation gives a different form of the equation for weight average;

Mw =

WxMx

Nx M Nx Mx

2 x

Weight Average Molecular Weight

Mw =

W M W
x x

N M N M
x
x

2 x x
2 2 2

= 5 10 ,000 + 5 15 , 000 + 5 20 , 000 5 10,000 + 5 15,000 + 5 20,000

Polydispersity (PD) = Mw / Mn Always greater than 1.
Polydispersity = Mw

= 16 ,111

Mn

Molecular Weight of Polymers What Average ?

Number Average Molecular Weight

Weight Average Molecular Weight

Mn

Nx M x = Nx

Mw =

Nx Mx

Nx Mx

Go from Mn to Mw average by multiplying each of the terms inside the summations by Mx. Higher order averages are constructed in the same way. For example, the z-average,

Nx M x Mz = 2 N M x x

The ratios of these averages relates to the moments of the distribution and reveal the breadth and skewdness

Mole (Number) and Weight Distributions

12 _ Mn = 100 ,0 00 10

Moles

A narrow MW distribution plotted according to number (left) and weight (below).

12 000 00
0 10 000 0 20 000 0

Molecular Weight
10 000 00

_ Mw = 104,50 0

80 000 0

Weight

60 000 0

40 000 0

20 000 0

10 000 0

20 000 0

Molecular Weight

Molecular Weight Distributions

12 10 8 6 Fraction of Chains 4 2 0 Mn @ 1 0 8 , 5 0 0 Mw @ 1 1 8 , 2 0 0 Moles

0.06

0.05

0.04

Number Fraction

0.03

100000 200000 Molecular Weight

300000

0.02

Weight Fraction

0.01

0.00

100

200

300

Degree of Polymerization

MW Distributions
Unimodal, bimodal, trimodal Strongly affect properties Produced in synthesis; Subsequent blending Minor population Lower MW Higher MW

Moles, Numbers, Fractions, Etc. in Calculations of Averages

Deg. polymerization (x) and MW MWp = (x)(MWmer) [MW of mer] Chain count: Number = moles x NA MN = (ni)(MWi)/(ni) can be written as NA(molesi)(MWi)/NA(molesi) Weight ratio = weight fraction ratio (wi)(MWi)/(wi) can be written as ((w1/wi)(MWi)/(wi/wi) = ((1/wi)/(1/wi)) ( (wi)(MWi)/(wi))

Average Degree of Polymerization (Xn)

Deg. polymerization (x) and MW
MWi = (xi)(MWmer) MN = (XN) (MWmer) MN = (ni)(MWi)/(ni) (XN)(MWmer) = (ni)(xi)(MWmer)/(ni) (XN) = (ni)(Xi)/(ni) [MW of mer]