Chapter 3.

Chemical Structure and Polymer Morphology

3.1 Introduction

3.2 Molecular weight and intermolecular forces

3.3. The Amorphous State - Rheology

3.4 Glass Transition Temperature

3.5 Stereochemistry

3.6 Crystallinity

3.7 Liquid Crystallinity

3.8 Chemical Crosslinking

3.9 Physical Crosslinking.

3.10 Polymer Blends

3.1 Introduction

A. The polymer properties for applications

a. Plastic : toughness, durability, transparency, weather resistance,
heat and flame resistance.

b. Fiber : tensile strength, spinnability, dyeability.

c. Rubber : resilience.
3.1 Introduction

B. Main subject of polymer chemistry :

The effect of chemical structure on polymer properties

C. Type of polymer properties

a. Mechanical properties

b. Thermal properties

c. Chemical properties

d. Other physical properties

POLYMER CHEMISTRY
D. Polymer morphology : structure, arrangement, and physical form

a. Amorphous : lack of order among the molecules

b. Crystalline or semicrystalline : regular orientation in the crystal lattice

(not 100% of crystal for polymer)

* intermolecular and intramolecular forces

* stereochemistry,
* chemical composition

c. Network : crosslinked polymer chain

d. Polymer blend : mixing polymers

e. Others : liquid crystallinity.

POLYMER CHEMISTRY
 3.2 Molecular weight and intermolecular forces

A. Factors influencing mechanical property

a. Molecular weight

b. Chemical composition

c. Intermolecular forces

B. Intermolecular forces

a. Hydrogen bond (eg., polyamide) : strong interaction

b. Dipole-dipole interaction (eg., polyester) : strong interaction

POLYMER CHEMISTRY
FIGURE 3.1. Intermolecular forces in polar polymers : (a) dipole-dipole in a polyester;
(b) hydrogen bonding in a polyamide; and (c) ionic in a carboxyl-containing polymer.

H H2
C
N
δ+ O δ+ CH
C R C R
CO 2-
δ- O δ- O
O M2+
δ+ H
δ+ C R
CO 2-
O N
δ- R
δ- C CH
C
O H2

(a) (b) (c)

 3.2 Molecular weight and intermolecular forces
C. Example: Interaction depends on molecular weight

a. Polyethylene (Mw=10,000) : Waxy solid, poor mechanical property

b. Polyester and Nylon (Mw=1000-2000) : hard and brittle,

good mechanical property

D. Distance between molecules influences intermolecular forces

and mechanical property

a. Unstretched rubber band (long distance between molecules) :

amorphous state, lower molecules, susceptible to attack by organic solvent

b. Stretched rubber band (short distance between molecules) :

crystalline state, higher modulus (2000 times), solvent resistance
3.3. The Amorphous State - Rheology
A. Amorphous state: Characteristic of the solid state, but no crystallinity

Solid amorphous:
molecular motion (very
short range vibration
rotation

Liquid amorphous:
Segmental motion
(conformational
Freedom)
A. Amorphous state: Characteristic of the solid state, but no crystallinity

a. Molecular scale of amorphous state :

* for solid amorphous state, a bowl of cooked spaghetti

(short range restricted vibrational and rotational motion)

* for liquid amorphous state, can of worms

(wriggling, jumping and rotational segmental motion)

b. Rheology : Science of deformation and flow

to be of more interest to engineer or physicist
to be useful for designing processing machine
cf) Chemist designs polymer molecular structure to be processed.
B. Viscoelastic property of polymer

a. Die swelling of molten polymer

Die
swell

PRESSURE

Die

Molten polymer

FIGURE 3.2. Schematic representation of polymer flow through a die orifice.

b. Time dependent bouncing and flowing of Silly Putty.

 C. Shear

a. Shear stress (τ) :

F
t= (tangential stress) (F: force, A: area)
A
b. Shear strain (g) = X :
Y
amount of deformation
x

A
c. Shear modulus G=τ/γ :
F the ratio of shear stress
to shear strain
y
d. Shear rate
.( ) = dr :
g
dt

the rate at which the planes

FIGURE 3.3 Representation of shear (tangential stress) (or molecules)
flow relative to one another
POLYMER CHEMISTRY
3.4 Glass Transition Temperature

A. Definition of Glass Transition Temperature.

a. The temperature at which the glassy state is changed into the rubbery state.

b. the glassy state: short-range vibrational and rotational motion of atoms

→ hard, rigid and brittle.

c. the rubbery state: long-range rotational motion of segments (20-50 atoms)

→ soft and flexible.

3.4 Glass Transition Temperature

B. Change of physical properties at Tg.

a. Specific volume : increase free volume above Tg.

b. Enthalpy(ΔH) change : kinetic energy of segmental motion.

c. Refractive index : change of density.

d. Modulus : glass → rubber

e. Heat conductivity : free volume.

3.4 Glass Transition Temperature

C. Factors influencing Tg.

a. Molecular weight

for polystyrene Mn =3,000 Tg=40℃, Mn =300,000 Tg=100℃.

b. Free volume : space for segmental motion.

plasticizer, flexible side chain.

c. Degree of freedom of internal rotation.

d. Chemical structure
 Chemical Structure
1) Intermolecular forces
( Hydrogen bond, dipole-dipole interaction).
to restrict segmental motion.
CH2CH
Poly(vinyl alcohol) Tg : 85℃ (hydrogen bond)
OH

CH2CH
Polystyrene Tg: 100℃

Poly(4-vinylpyridine) CH2CH Tg : 142℃ (dipole-dipole interaction

of pyridine ring)

POLYMER CHEMISTRY
2) Substituent or pendent group : to restrict rotation

Polyethylene CH2CH Tg : -20℃

H

Polypropylene CH2CH Tg : 5℃
CH3

CH2CH
Polystyrene Tg : 100℃

CH2CH

Poly(2-vinylnaphthalene) Tg : 151℃

POLYMER CHEMISTRY
 3) Chain stiffness of backbone.

O
Aliphatic polyester O OO Tg : -63℃
C(CH2)4CO(CH2)2O

O O
PET Tg : 80℃
C CO(CH2)2O

N NH

Polybenzimidazole Tg : 429℃
NH N
4) Side chains of linear long alkyl group.

: increase side chain length, decreased Tg

TABLE 3.1. Glass Transition Temperature (Tg) of Representative Vinyl Polymersa
Polymer
Number CH2CH R Tg(oC)
R

4 Polyethylene H -20
5 Polypropylene CH3 5
6 Poly(1-butene) CH3CH2 -24
7 Poly(1-pentene) n-C3H7 -40
8 Poly(1-hexene) n-C4H9 -50
9 Poly(1-heptene) n-C5H11 -31
10 Poly(1-decene) n-C8H17 -41
11 Poly(1-dodecene) n-C10H21 -6
12 Poly(3-methyl-1-butene) CH(CH3)2 50
13 Poly(4-methyl-1-pentene) CH2CH(CH3)2 29
14 Poly(3,3-dimethyl-1-butene) C(CH3)3 64
15 Poly(5-methyl-1-hexene) CH2CH2CH(CH3)2 -14
POLYMER CHEMISTRY
TABLE 3.1. Glass Transition Temperature (Tg) of Representative Vinyl Polymersa

Polymer
Number CH2CH
R Tg(oC)
R

16 Poly(4,4-dimethyl-1-pentene) CH2C(CH3)3 59
17 Poly(vinyl n-butyl ether) O-C4H9-n -55
18 Poly(vinyl t-butyl ether) O-C4H9-t 88
19 Poly(vinyl chloride) Cl 81
20 Poly(vinyl alcohol) OH 85
21 Polystyrene C6H5 100

22 Poly(2-vinylnaphthalene) 151

142
23 Poly(4-vinylpyridine)

N
5) Cis-trans isomer of diene polymer : no generalization

TABLE 3.3. Glass Transition Temperature (Tg) of Diene Polymers

Tg(oC)
Polymer
Cis trans

1,4-Polybutadienea -102 -58

1,4-Polyisopreneb -67 -70
1,4-Polychloroprenea -20 -40

aData from Peyser14a

bData from Burfield and Lim.15
3.5 Stereochemistry
A. Tacticity

a. Isotactic

b. Syndiotactic

c. Atactic (heterotactic: no stereoregularity).

H R H RH R
RH RH
C C C C C Isotactic
H2C
CH2 CH2 CH2 CH2

H H H HH R
RR RR
C C C C C
H2C
CH2 CH2 CH2 CH2
Syndiotactic

FIGURE 3.10. Stereoregular polymers derived from monomer CH2=CHR.

 POLYMER CHEMISTRY
no tacticity CH2=CR2.

CH2 CHR (3.1)

R R R
(3.2)
CH2 CH CH2 CH CH2 CH

B. Erythro and threo form.

a. Disubstituted vinyl monomer (RCH=CHR').
H RH RH RH RH R
C C C C C
C C C C C
H
R' H
Threo-diisotactic
R H
'
R H
' '
R
H
R'

H RH RH RH RH R
C C C C C
C C
R'
C C C Erythro-diisotactic
H R' H R' H R' R'
H H

H RH RH RH RH R
C C C C C
C C C C C Disyndiotactic
H ' R'
R H H R' R' H
H
R'

FIGURE 3.12. Stereoregular polymers derived from monomer RCH=CHR'.

b. Cyclobutene monomer.

Erythro-diisotactic

Erythro-disyndiotactic

Threo-diisotactic

Threo-disyndiotactic

FIGURE 3.13. Stereoregular polymers derived from cyclobutene.

 c. Disubstituted diene monomer.
RCH=CH-CH=CHR'

1) Depend on monomer form(cis or trans), initiator, temperature and solvent polarity.

2) To exist cis-trans isomers.

H H H
R' R' R'
H H H
C C
C C
C C C C Trans-erythro-diisotactic
C C C C
R H H H
H R R
H H

H H R H
H H R' H
C C C C C C Cis-threo-disyndiotactic
C C C C C C
H R H R' H H H R H R'

FIGURE 3.14. Two stereoregular 1,4-polymers derived from monomer RCH=CH CH=CHR’.
 3.5 Stereochemistry

C. Hemitactic
a. Hemiisotactic

b. Hemisyndiotactic

D. Stereoregularity
a. To lead crystallinity.

b. To influence Tg.

1) Tg of syndiotactic is higher than Tg of isotactic.

2) Tg of atactic is similar to Tg of syndiotactic.

3) It's hard to determine Tg for high crystalline polymers.

 TABLE 3.4. Glass Transition Temperature (Tg) of Polymers of Varying Tacticitya

Tg(oC)

Polymer
Syndiotactic Atactic Isotactic

Poly(methyl methacrylate) 105 105 38

Poly(ethyl methacrylate) 65 65 12

Poly(t-butyl methacrylate) 114 118 7

Polypropyleneb -4 -6 -18

Polystyrene 100c 99c

aData from Peyser14a unless otherwise noted.

bData from Burfield and Doi.23
cData from lshihara, Kuramoto, and Uoi, Macromolecules, 21, 3356 (1988).
3.6 Crystallinity

A. Requirements for crystallization.

a. Regularity of molecular structure.

b. Intermolecular forces.
B. Inducing crystallinity.

a. Cooling.

b. Annealing : heating at a specified temperature, inert atmosphere.

c. Stretching : orientation.
 C. Models of crystallinity

a. Fringed micelle model for low crystallinity.

FIGURE 3.15. Schematic representation of a polymer matrix showing

crystalline regions (fringed micelle model).

Crystallnity imbedded in amorphous matrix.

b. Folded-chain lamella model for high crystallinity.

Single crystal : lamella form.

Thickness of lamella : 100Å.

Chain folded perpendicularly.

FIGURE 3.16. Folded-chain lamella model : (a) regular adjacent folds;

(b) irregular adjacent folds; and (c) nonadjacent switchback.
 C. Models of crystallinity
c. Extended-chain crystals.
No micelle and no folded chain.
Needle form, low molecular weight by slow crystallization.
Molecular regularity : not necessary.

d. Spherulites
Aggregation of small hairlike strands.
Clusters in an essentially radical pattern.
Nucleation : homogeneous nucleation, heterogeneous nucleation(silica).

e. Epitaxial crystallinity
One crystalline growth on another.
Shish Kebab type.

(a) (b) (c)

FIGURE 3.17. Some crystalline morphologies: (a) spherulitic; (b) drawn fibrillar; and (c) epitaxial (shish kebab).
D. Properties of crystalline polymers

a. Tougher.

b. Stiffer.

c. Opaque : light scattering.

d. Resistant to solvents.

e. Higher density.
 E. Relationship between structure and crystallinity

a. crystalline structure.
Cl
OO O
O

CH2 C OCH2CH2CH2OC C

Cl

52
50
Crystalline (melting point 220oC)

CN
CH3 O
O O

OCH2CCH2OC C CH2 C

CH3 CN

54
51
Crystalline(melting point 140oC)
E. Relationship between structure and crystallinity

b. Amorphous structure.

CH3 OO O

OCH2CHCH2OC C

53 Noncrystalline
3.7 Liquid Crystallinity

A. Definition of liquid crystallinity

a. Liquids which exhibits anisotropic behavior.

b. Molecules are ordered in liquid.

c. The ordered regions in the liquid are called mesophases.

B. Two types of liquid crystal molecules.

a. Low molecular weight liquid crystals which have been studied since 1960.

b. Polymeric liquid crystals which have been studied since 1970s.

3.7 Liquid Crystallinity

C. Classifications of liquid crystals.

a. Lyotropic liquid crystals : to form under the influence of solvent.

b. Thermotropic liquid crystals : to form in the melt.

D. Orientation of molecules in the mesophase.

a. Nematic

b. Smetic

c. Cholesteric

d. Discotic, etc.
 FIGURE 3.18 Effect of p-hydroxybenzoic acid concentration on melt viscosity
of a terephthslic acid/p-gydroxybenzoic acid/ethylene glycol copolyester.
[From Jackson and Kuhfuss,37 copyright 1976. Reprinted by permission
of John Wiley & Sons, Inc.]

Melt viscosity Shear rate, s-1

105
(275oC)
poise 15
104
100

1600
103
54,000
102

0 20 40 60 80 100
P-Hydroxybenzoic acid, mol-%
FIGURE 3.19. Representations of mesogenic groups (box) and flexible spacers ( )
in (a) the backbone and (b) the side chain of liquid crystalline polymers.

(a)

(b)
E. Commercial liquid crystal polymer
a. Copolyester ( thermotropic liquid crystal ) :

HO2C CO2H HOCH2CH2OH HO CO2H

55 56 57
Trade name : Vectra ( 55 + 56 + 57 )

b. Aromatic polyamide ( lyotropic liquid crystal ):

O O

C C NH NH 58

Trade name : Kevlar

F. Advantage and disadvantage of liquid crystal polymer.
a. Advantage : low viscosity.
high tensile strength.

b. Disadvantage : high melting transition.

poor solubility.

c. Circumventing these difficulties :

in cooperation spacer onto rigid backbone.
spacer
CH3

CH2CH2O SiO
CH2 n
CH3
n

59 60 61
 3.8 Chemical Crosslinking

A. Definition and physical property change.

a. Linking the polymer chains together through covalent or ionic bonds

to form a network.

b. Not to be soluble but swelling by any solvent.

c. Not to be melted but decompose at any temperature.

d. For ionic crosslinking, to be melted at high temperature.

B. The method of chemical crosslinking.

a. Simultaneously crosslinking during polymerization,

using polyfunctional monomer.

b. Stepwise crosslinking.

First step : to make free polymer (linear or branched polymer).

Second step : curing step to be made network from free polymer.

C. Gel

a. Swollen crosslinked polymer.

b. Microgel: small particles of gel(300～1000㎛)

c. Packed microgel can be suspended in solvents.

d. Microgel can be used in solid-phase synthesis

(techniques for immobilizing catalysts).
 3.8 Chemical Crosslinking

D. Crosslink Density(Γ)
a. The number of crosslinked monomer units per main chain.
(Mn)o
b. Γ=
(Mn)c

(Mn)o : the number average molecular weight of uncrosslinked polymer

(Mn)c : the number average molecular weight between crosslinks.

c. High crosslink density: hard and embrittlement.

Low crosslink density: Elastomer
(about one crosslink per 100monomer units).

E. Telechelic Elastomer:

Reactive chain ends that become incorporated

into the network on crosslinking.
3.9 Physical Crosslinking.

A. Definition
a. Not covalent crosslink but strong secondary force attraction between
polymer chains.

b. Physical crosslinked polymer can be recycled.

B. Examples of physical crosslinking.

a. Crystalline polymer : To act like crosslinked amorphous polymer.

b. Hydrogen bond : Gelatin, an animal-derived protein.
c. Block copolymer : A-B-A type.
A : styrene, short-hard segment, microdomain.
B : butadiene, long-soft segment, matrix.
d. TPE : Thermoplastic elastomer.
FIGURE 3.20 Representation of aggregation in an ABA block thermoplastic elastomer
( represents end blocks, circle represents microdomains).
 TABLE 3.6. Commercially Important Thermoplastic Elastomers

Type End Blocks Middle Block

Styrenic Polystyrene Polybutadiene or polyisoprene

Polyolefina Isotactic polypropylene Ethylene-propylene copolymer

Polyurethane Rigid polyurethane Flexible polyester or polyether

Copolyester Rigid polyesterb Flexible polyester

Polyamide Rigid polyamidec Flexible polyether

a Also manufactured by mechanical blinding of isotactic polypropylene and ethylene-propylene-diene copolymer.

b Principally poly(ethylene terephthalate).
c Nylons 6, 66, 11, 12, and 612.
 3.10 Polymer Blends

A. Definition of polymer blends.

a. Physical mixture of two or more different polymer or copolymer.

b. No covalent bonds among the polymers.

c. Polymer alloys : like metal alloys.

d. Blending is much easier than developing new polymers.

B. Technology of polymer blendings.

 TABLE 3.7. Types of Polyblends

Type Description

Mechanical blends Polymers are mixed at temperatures above Tg or Tm for

Mechanochemical blends
Solution-cast blends
Latex blends
Chemical blends
Interpenetrating polymer
networks (IPN)
amorphous and semicrystalline polymers, resectively
Polymers are mixed at shear rates high enough to cause
degradation. Resultant free radicals combine to form
complex mixtures including block and graft components
Polymers are dissolved in common solvent and solvent is
removed
Fine dispersions of polymers in water (latexes) are mixed, and
the mixed polymers are coagulated
Crosslinked polymer is swollen with different monomer,
then monomer is polymerized and crosslinked

Semi-interpenetrating polymer Polyfunctional monomer is mixed with thermoplastic

networks (semi-IPN) polymer, then monomer is polymerized to network polymer
(also called pseudo-IPN)
Semultaneous interpenetrating Different monomers are mixed, them homopolymerized and
polymer networks (SIN) crosslinked simultaneously, but by noninteracting mechacisms

Interpenetrating elastomeric Latex polyblend is crosslinked after coagulation

networks (IEN)
 C. Miscible polymer blends.
a. Homogeneous one phase blends like solution.

b. To show single Tg.

c. Semiempirical relationship of properties for homogeneous binary system.

P = P1Φ1 + P2Φ2 + IΦ1Φ2

P : Properties of blends.
Φ : The volume fraction.
P1,P2 : Properties of polymer components 1,2
I : Interaction term.
( I = 0 : strictly additive, I > 0 : synergistic, I < 0 : nonsynergistic. )

d. Glass transition temperature of miscible blends.

Tg = w1Tg1 + w2Tg2 ( w : weight fraction, Tg : kelvins )

 C. Miscible polymer blends.
e. Commercial examples of miscible blends.

1) Noryl (GE) : polystyrene + PPO.

CH3

poly(oxy-2,6-dimethyl-1,4-phenylene) O

CH3
Tensile strength : synergic.

2) LDPE + EPDM(ethylene-propylene-diene monomer rubber).

Tensile strength : synergic.

f. Stereochemistry is important for miscibility.

syndiotactic poly(methylmethacrylate) + poly(vinyl chloride) : miscible.

isotactic poly(methylmethacrylate) + poly(vinyl chloride) : immiscible.
 D. Immiscible polymer blends.
a. Because of immiscibility, to appear phase separation and to show
poor mechanical property.
b. Methods of mixing effectively for immiscible blends.
1) IPN techniques.
2) Using compatibilizer like A-B block copolymer or graft copolymer.
A A A
A
A A
A A A
FIGURE 3.33. Representation of the use of
A A Poly (A) A A
A
A A A
an AB block copolymer to improve interfacial B
adhesion in an immiscible polyblend.
B
B Poly (B) B B
B
B
B B B
B
B
B B

3) Example of this methodology.

: ABS (acrylonitrile-butadiene-styrene) plastics.
amorphous styrene-butadiene copolymer
+ graft copolymer
styrene monomer (chain-transfer)
+ copolymerization +
acrylonitrile monomer ABS