Chapter 4-Polymer Structures Chapter 4 - Polymer Structures: Polymer Microstructure Polymer Microstructure

Chapter 4- Polymer Structures 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?
TEM of spherulite structure in natural rubber(x30,000).
Chain-folded lamellar crystallites (white lines) ~10nm thick extend radially.
MatSE 280: Introduction to Engineering Materials D.D. Johnson 2004, 2006, 2007-08 MatSE 280: Introduction to Engineering Materials D.D. Johnson 2004, 2006, 2007-08
Polymer Microstructure Polymer Microstructure

Polymer = many mers
Covalent chain configurations and strength:

More rigid
Van der Waals, H
Adapted from Fig. 14.2, Callister 6e.
Polyethylene perspective of molecule
Direction of increasing strength

A zig-zag backbone structure with covalent bonds
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Common Examples Common Classification
- Textile fibers: polyester, nylon Thermoplastics: polymers that flow more easily when
squeezed, pushed, stretched, etc. by a load (usually at
- IC packaging materials. elevated T).
Can be reheated to change shape.
- Resists for photolithography/microfabrication.
Thermosets: polymers that flow and can be molded
initially but their shape becomes set upon curing.
- Plastic bottles (polyethylene plastics). Reheating will result in irreversible change or decomposition.
- Adhesives and epoxy. Other ways to classify polymers.

By chemical functionality (e.g. polyacrylates, polyamides,
polyethers, polyeurethanes).
- High-strength/light-weight fibers: polyamides, Vinyl vs. non-vinyl polymers.
polyurethanes, Kevlar By polymerization methods (radical, anionic, cationic).
Etc
- Biopolymers: DNA, proteins, cellulose
Common Chemical Functional Groups Common Hydrocarbon Monomers

H H
Alcohols Methyl alcohols
Ethylene C C
H H
(ethene)
H H
Propylene C C = Ethers Dimethyl Ether
H C H
(propene) H
H
1-butene
Acids Acetic acid
2-butene
trans cis
Aldehydes Formaldehyde
Acetylene H C C H
(ethyne)
Saturated hydrocarbons Unsaturated hydrocarbons Aromatic Phenol

(loose H to add atoms) (double and triple bonds) hydrocarbons
2
Some Common Polymers Nomenclature
Monomer-based naming:
Common backbone with substitutions poly________
H H
C C Monomer name goes here
Polyacrylonitrile (PAN) C
H
e.g. ethylene -> polyethylene
N
Vinyl polymers (one or more Hs of ethylene can be substituted) if monomer name contains more than one word:
H H H H poly(_____ ____)
C C C C Monomer name in parentheses
H X H X
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 C C C C
H H H H H H H H
polyethylene polymethylene
Polymerization Methods Polymerization Methods

A. Free Radical Polymerization
H H
A. Free Radical Polymerization 2. Propagation C C
H H
1. Initiation H Radical H H H H H H H H H H H H H H
H
H H
R R C C
transferred R C C C C R C C C C R C C C C C C
C C
H H H H H H H H H H H H
H H H H H
Free radical initiator H
(unpaired electron) monomer
H H
R C C
R
H H
R
H H H
C C C C Both carbon atoms will
sp2 carbons H
change from sp 2 to sp 3.
H H H H C C
H
bonds H H
sp3 carbon H
bond
3
Polymerization Methods Polymerization Methods
Loses water
B. Stepwise polymerization
(condensation)
A. Free Radical Polymerization
3. Termination O O O
H2N C
+ H2N C H2N C R OH + O
R OH R OH R N C H H
H
H H H O
H
R C C + R R C C R
H H H H
Proteins (polypeptides have similar composition) O

H
H
O
N C + (n-1) H
O
H
N H C R
H H H H H H H H C Various R groups n
R C C + R C C R C C C C R R n
H H H H H H H H
C. Other methods
Anionic polymerization, cationic
Intentional or unintentional molecules/impurities can also terminate. polymerization, coordination
polymerization
Molecular Weights Number average molecular weight:

N j M j mo N j j Nj = # of polymer chains with length j
Not only are there different structures (molecular arrangements) j j
Mn = = Mj = jmo mass of polymer chain with length j
but there can also be a distribution of molecular weights N j N j (mo = monomer molecular weight).
(i.e. number of monomers per polymer molecule). j
j
Note: N j M j = Total weight N j = Total # of polymer chains
j j

Weight average
molecular weight:
20 mers 16 mers
W j M j N j M2j
j j W j = N jM j
Mw = =
10 mers W j N j M j
j j
20 + 16 + 10
Average molecular weight = M monomer = 15.3M monomer N j M j
+1
3 In general: j If = 1 then Mw
M= If = 0 then Mn
N j M j
This is what is called number average molecular weight.
j
MatSE 280: Introduction to Engineering Materials D.D. Johnson 2004, 2006, 2007-08 MatSE 280: Introduction to Engineering Materials
D.D. Johnson 2004, 2006, 2007-08

4
Molecular Weight: Different Notations Molecular Weights
Why do we care about weight average MW?
-some properties are dependent on MW (larger MW polymer chains can
In Lecture Notes In Callister Textbook contribute to overall properties more than smaller ones).
N j M j Mn = x i Mi
j i
Mn = Distribution of
N j polymer weights
Ni Ni M i
j xi = wi =
N j N j M j
j j

N j M 2j
j
Mw = Mw = w i Mi Examples
Light scattering: larger molecules scatter more light than smaller ones.
N j M j
i
j 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 Example 1

Mw
Polydispersity: 1 Compute the number-average degree of polymerization for polypropylene,
Mn given that the number-average molecular weight is 1,000,000 g/mol.
When polydispersity = 1, system is monodisperse. What is mer of PP? C3H6

Degree of Polymerization: Mer molecular weight of PP is mo=3AC+6AH
=3(12.01 g/mol)+6(1.008 g/mol)
Mn = 42.08 g/mol
Number avg degree of polymerization nn =
mo
Number avg degree of polymerization
M
Weight avg degree of polymerization nw = w Mn 106 g / mol
mo nn = = = 23,700
mo 42.08g / mol
5
Example 2 (a, b, and c) Example 2 (cont.)
A. Calculate the number and weight average degrees of polymerization
and polydispersity for a polymer sample with the following distribution. B. If the polymer is PMMA, calculate number and weight average
molecular weights.
Avg # of monomers/chain Relative abundance
10 5 CH3
100 25 |
500 50 Mw if monomer is methylmethacrylate (5C, 2O, and 8H)
-CH2-C-
1000 30 So m 0= 5(12)+2(16)+8(1)= 100 g/mol
|
5000 10
50,000 5 CO2CH3
M n m0 jN j j jN j j
nn = =
mo m0 N
=
N Mn = nnmo = 2860.4(100g / mol ) = 286,040g / mol
j j j j
5 *10 + 25 *100 + 50 * 500 + 30 *1000 + 10 * 5000 + 5 * 50000 Mw = nw mo = 35,800(100g / mol ) = 3,580,000g / mol
= = 2860.4
5 + 25 + 50 + 30 + 10 + 5 Mw 3,580,000
Polydispersity: = ~ 12.52
2 2 Mn 286,040
Mw 1 ( jm ) N j N
j o j j j
Note: m 0 cancels in all these!
nw = = =
mo mo N ( jm ) jN j o j

j 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.) Sequence isomerism

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
For an asymmetric monomer T H T H
and weight average degrees of polymerization and polydispersity?
Mn jN j T H + T H T H H T
nn = =
j
Add 5 more monomers of length 10 .
mo N j j
H T T H
10 * 10 + 25 * 100 + 50 * 500 + 30 * 1000 + 10 * 5000 + 5 * 50000
= = 2750
10 + 25 + 50 + 30 + 10 + 5
e.g. poly(vinyl fluoride): e.g. PMMA
2
Mw j j N j H3C H3C H3C
nw = = = 35,800 H3C
mo j jN j H F H H F H H H O O O O O O O O
C C C C C C C C H C H C H C H C
Note: significant change in number average (3.8 %)
H H H F H H H F C C C C C C C C
but no change in weight average!
H to T T to T H CH3 H CH3H CH3 H CH3
H to H
M w 3, 580, 000 H to T H to T
Polydispersity: = ~ 13 H to T
Random arrangement
Mn 275000 Exclusive H to T arrangement (Why?)
6
Polymer Molecular Configurations Polymer Geometrical Isomerism
Regularity and symmetry of side groups affect properties
Regularity and symmetry of side groups affect properties
Can it crystallize?
Polymerize Melting T?
H H
cis-structure trans-structure
Stereoisomerism: (can add geometric isomerism too)
Syndiotactic
Alternating sides
with R= CH3 to form rubber
Cis-polyisoprene trans-polyisoprene
Isotactic Atactic -Conversion from one isomerism to another is not possible by simple
On one side Randomly placed rotation about chain bond because double-bond is too rigid!
- Conversion from one stereoisomerism to another is not possible by simple -See Figure 4.8 for taxonomy of polymer structures
rotation about single chain bond; bonds must be severed first, then reformed!
Polymer Structural Isomerism Polymer Microstructure

Some polymers contain monomers with more than 1 reactive site
e.g. isoprene 2 4
Covalent chain configurations and strength:
CH3 More rigid
Van der Waals, H
1 C CH2
H2C C
H 3
trans-isoprene
Direction of increasing strength

trans-1,4-polyisoprene trans-1,2-polyisoprene 3,4-polyisoprene
CH3 H2 H2
H2
C C C Short branching
n C H
C C C
H2 H C n
H3C CH
n C
H2C H2C CH3
Long branching
Note: there are also cis-1,4- and cis-1,2-polyisoprene Star branching Dendrimers
7
CoPolymers Molecular Structure
Random, Alternating, Blocked, and Grafted How do crosslinking and branching occur in polymerization?
Synthetic rubbers are often copolymers. 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
e.g., automobile tires (SBR)
stryene polystyrene
Styrene-Butadiene Rubber random polymer

Control degree of +
crosslinking by
styrene-divinyl styrene
benzene ratio
divinyl benzene crosslinked polystyrene
Monomers with trifunctional groups lead to network polymers.
Molecular Structure Example 3

Branching in polyethylene (back-biting)
Nitrile rubber copolymer, co-poly(acrylonitrile-butadiene), has
H2 H2 H2 Mn = 106,740g / mol nn = 2000

C C C
H2C CH2 R C C C H
H2 H2
H Calculate the ratio of (# of acrylonitrile) to (# of butadiene).
Same as
H 3 C = 3 x 12.01 g/mol
H 4 C = 4 x 12.01 g/mol
H H 3 H = 3 x 1.008 g/mol
6 H = 6 x 1.008 g/mol
C H
C 1 N = 1 x 14.007 g/mol
CH2
H CH2 Radical moves to a different carbon m 0= 54.09 g/mol
m 0= 53.06 g/mol
CH2 C CH2
C (H transfer) 1,4-addition product
R C R C
H H2 H H2
We need to use an Mn 106,740

mo = = = 53.57g / mol
Polymerization continues from this carbon avg. monomer MW: nn 2000
mo = f1m 1 + f2m 2 = f1(m 1 m 2 ) + m 2
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. f2 0.7
m 0 m 2 53.37 54.09 7 :3
f1 = = = 0.7 f2 = 1 f1 = 0.3 =
54.09
m 1 m 2 53.06 f1 0.3
8
Vulcanization See also sect. in Chpt. 8 Molecular Weight and Crystallinity
Crosslinking in elastomers is called vulcanization, and is achieved by
irreversible chemical reaction, usually requiring high temperatures. Molecular weight, Mw: Mass of a mole of chains.
Sulfur compounds are added to form chains that bond adjacent

polymer backbone chains and crosslinks them.
Unvulcnaized rubber is soft and tacky an poorly resistant to wear. Tensile strength (TS):
--often increases with M w.
e.g., cis-isoprene Single bonds Stress-strain curves --Why? Longer chains are entangled (anchored) better.
% Crystallinity: % of material that is crystalline.

--TS and E often increase
with % crystallinity.
(S)m crystalline
--Annealing causes
Double bonds + (m+n) S region
(S)n crystalline regions to grow.
% crystallinity increases. amorphous
region
Polymer Crystallinity Volume fraction of crystalline component.
polyethylene Some are amorphous. Mcrystalline V

%crystallinity = 100% = c c 100% = c fc 100%
Some are partially crystalline (semi-crystalline). Mtotal sVs s
Why is it difficult to have a 100% crystalline polymer?
c ( s a ) Mtotal = Mcrystalline + Mamophous Using definition of volume fractions:

%crystallinity = 100%
s ( c a ) Ms = Mc + Ma V V
fc = c fa = a
sVs = cVc + aVa Vs Vs
V V
s = c c + a a = c fc + a fa = c fc + a (1 fc ) = fc ( c a ) + a
Vs Vs
s = density of specimen in question a
a = density of totally amorphous polymer fc = s
c = density of totally crystalline polymer c a

( a )
Substituting in f c into the original definition: %crystallinity = c s 100%
s ( c a )

9
Polymer Crystallinity Semi-Crystalline Polymers
Degree of crystallinity depends on processing conditions (e.g. Fringed micelle model: crystalline region embedded in amorphous region.
cooling rate) and chain configuration. A single chain of polymer may pass through several crystalline regions as
well as intervening amorphous regions.
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:

a
More Crystalline Less Crystalline fc = s
c a
Smaller/simper side groups Larger/complex side groups
Linear Highly branched Crystalline volume fractions Important
Crosslinked, network
Isotactic or syndiotactic Random
Semi-Crystalline Polymers Semi-Crystalline Polymers

Spherulites: Spherical shape composed of aggregates of chain-folded crystallites.
Chain-folded model: regularly shaped platelets (~10 20 nm thick)
sometimes forming multilayers.
Average chain length >> platelet thickness.
Natural rubber
Cross-polarized light through

spherulite structure of PE.
10
Diblock copolymers
Thermoplastics vs Thermosets
T
Thermoplastics: Callister,
viscous rubber
--little cross linking Fig. 16.9
mobile liquid Tm
--ductile tough
liquid
--soften w/heating plastic
--polyethylene (#2)
Tg
polypropylene (#5)
partially
polycarbonate crystalline
polystyrene (#6) crystalline
solid
solid
Representative polymer-polymer
phase behavior with different Thermosets: Molecular weight
architectures:
A) Phase separation with mixed --large cross linking (10 to 50% of mers) Adapted from Fig. 15.18, Callister 6e.
LINEAR homopolymers. --hard and brittle
B) Mixed LINEAR homopolymers and Tm: melting over wide range of T
DIBLOCK copolymer gives
--do NOT soften w/heating depends upon history of sample
surfactant-like stabilized state. --vulcanized rubber, epoxies, consequence of lamellar structure
C) Covalent bond between blocks in polyester resin, phenolic resin thicker lamellae, higher T m.
DIBLOCK copolymer give
F. Bates, Science 1991. Tg: from rubbery to rigid as T lowers
microphase segregation.
Packing of Polymers What Are Expected Properties?

Packing of spherical atoms as in ionic and metallic crystals led to Would you expect melting of nylon 6,6 to be lower than PE ?
crystalline structures. H O H O
H H
nylon 6,6
|
|| |

|| polyethylene
How polymers pack depend on many factors: N C N C C N C
C C

long or short, e.g. long (-CH 2-)n. | | | | | H H
stiff or flexible, e.g. bendy C-C sp 3. H H 6 H H H
4
+ +
smooth or lumpy, e.g., HDPE. + + + bonds
+ Waals
Van der
regular or random +
Hydrogen bonds
+ + +

single or branched + +
H H
slippery or sticky, e.g. C-H covalent (nonpolar) joined via vdW. H O H O
|| | || C C
|

Analogy: Consider dried (uncooked) spaghetti (crystalline) vs. N C N C C N C H H
cooked and buttered spaghetti (amorphous).
| | |

| |
pile of long stiff spaghetti forms a random arrangement. H H 6 H H H
4
cut into short pieces and they align easily. cohesion in Nylon vs PE?
a) What is the source of intermolecular
b) How does the source of linking affect temperature?
Candle wax more crystalline than PE, even though same
chemical nature. With H-bonds vs vdW bonds, nylon is expected to have (and does) higher melting T.
11
What Are Expected Properties? What Are Expected Properties?
Which polymer more likely to crystallize? Can it be decided? Which polymer more likely to crystallize? Can it be decided?
Networked Linear and highly crosslink
Linear syndiotactic polyvinyl chloride Linear isotactic polystyrene
Phenol-Formaldehyde cis-isoprene
(Bakelite)
+ H
+ H 20
For linear polymers, crystallization is more easily accomplished as Networked and highly crosslinked structures are near impossible
chain alignment is not prevented. to reorient to favorable alignment.
Crystallization is not favored for polymers that are composed of
chemically complex mer structures, e.g. polyisoprene .
Linear and syndiotactic polyvinyl chloride is more likely to crystallize.

The phenyl side-group for PS is bulkier than the Cl side-group for PVC. Not possible to decide which might crystallize. Both not likely to do so.
Generally, syndiotactic and isotactic isomers are equally likely to crystallize.
What Are Expected Properties? Detergents

Which polymer more likely to crystallize? Can it be decided? Soap is a detergent based on animal or vegetable product,
some contain petrochemicals
random water
alternating
Poly(Polystyrene-Ethylene) poly(vinyl chloride-tetra-fluoroethylne)
Copolymer copolymer detergent
grease
What properties of soap molecules do you need to remove grease?

green end must be hydrophilic. Why?
Opposite end must be hydrocarbon. Why?
Water must be like oxygen (hoard

Alternating co-polymer more likely to crystallize than random ones, as they electrons and promote H-bonding)
are always more easily crystallized as the chains can align more easily.
e.g., oxy-clean grease
12
Simple polymer: Elmers glue + Borax SLIME! Simple polymer: Elmers glue + Borax SLIME!
Chemistry Elmers glue is similar to poly (vinyl alcohol) with formula: Hydrolyzed molecule acts in a condensation reaction with PVA,
OH OH OH OH OH OH OH OH OH OH OH OH OH OH OH
crosslinking it.
this is a SHORT, n=15 chain of poly(vinyl alcohol)
B(OH) 3 + 2H 2O B(OH) 4- + H 3O+ pH=9.2
Borax is sodium tetraborate decahydrate (B4Na 2O7 10 H 2O).
The borax actually dissolves to form boric acid, B(OH) 3. Crosslinked

This boric acid-borate solution is a buffer with a pH of about 9 (basic).
Boric acid will accept a hydroxide OH- from water.
B(OH) 3 + 2H 2O B(OH) 4- + H 3O+ pH=9.2
Hydrolyzed molecule acts in a condensation reaction Crosslinking ties chains via weak non-covalent
with PVA, crosslinking it. (hydrogen) bonds, so it flows slowly.
Range of Bonding and Elastic Properties Summary

Polymers are part crystalline and part amorphous.
Is slime a thermoset or thermoplastic, or neither?
The more lumpy and branched the polymer, the less
dense and less crystalline.
Thermoset Slime? Thermoplastic The more crosslinking the stiffer the polymer. And,
bonding bonding networked polymers are like heavily crosslinked ones.
Covalent bonds Induced dipolar bonds
form crosslinks form crosslinks Many long-chained polymers crystallize with a Spherulite
H-bonds form
crosslinks microstructure - radial crystallites separated by
amorphous regions.
Optical properties: crystalline -> scatter light (Bragg)

Stiffness increases amorphous -> transparent.
Most covalent molecules absorb light outside visible spectrum ,
Where is nylon? e.g. PMMA (lucite) is a high clarity tranparent materials.
13

Chapter 4-Polymer Structures Chapter 4 - Polymer Structures: Polymer Microstructure Polymer Microstructure

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Chapter 4- Polymer Structures Chapter 4- Polymer Structures

What are the basic

Polymer Microstructure Polymer Microstructure

Covalent chain configurations and strength:

Adapted from Fig. 14.2, Callister 6e.

Polyethylene perspective of molecule

Direction of increasing strength

A zig-zag backbone structure with covalent bonds

- Adhesives and epoxy. Other ways to classify polymers.

Common Chemical Functional Groups Common Hydrocarbon Monomers

Saturated hydrocarbons Unsaturated hydrocarbons Aromatic Phenol

Polymerization Methods Polymerization Methods

Proteins (polypeptides have similar composition) O

Molecular Weights Number average molecular weight:

Polydispersity and Degree of Polymerization Example 1

When polydispersity = 1, system is monodisperse. What is mer of PP? C3H6

5 *10 2 + 25 *100 2 + 50 * 500 2 + 30 *1000 2 + 10 * 5000 2 + 5 * 50000 2

Example 2 (cont.) Sequence isomerism

Polymer Structural Isomerism Polymer Microstructure

Direction of increasing strength

Styrene-Butadiene Rubber random polymer

Molecular Structure Example 3

H2 H2 H2 Mn = 106,740g / mol nn = 2000

We need to use an Mn 106,740

Sulfur compounds are added to form chains that bond adjacent

% Crystallinity: % of material that is crystalline.

Adapted from Fig. 14.11, Callister 6e.

Polymer Crystallinity Volume fraction of crystalline component.

polyethylene Some are amorphous. Mcrystalline V

c ( s a ) Mtotal = Mcrystalline + Mamophous Using definition of volume fractions:

Chemical groups and chain configuration:

Semi-Crystalline Polymers Semi-Crystalline Polymers

Cross-polarized light through

Packing of Polymers What Are Expected Properties?

Linear and syndiotactic polyvinyl chloride is more likely to crystallize.

What Are Expected Properties? Detergents

What properties of soap molecules do you need to remove grease?

Water must be like oxygen (hoard

Borax is sodium tetraborate decahydrate (B4Na 2O7 10 H 2O).

The borax actually dissolves to form boric acid, B(OH) 3. Crosslinked

B(OH) 3 + 2H 2O B(OH) 4- + H 3O+ pH=9.2

Range of Bonding and Elastic Properties Summary

Optical properties: crystalline -> scatter light (Bragg)

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5 10 2 + 25 100 2 + 50 * 500 2 + 30 1000 2 + 10 5000 2 + 5 * 50000 2