Class PPT Upto 20 Aug PDF

Department of Chemical Engineering
IIT Madras
CH 3160 Polymeric Materials
R. Vinu
IIT Madras
IIT Madras
Classification of polymers based on application

1. Elastomers
2. Plastics
Commodity plastics
Engineering plastics
3. Fibers
4. Coatings and Adhesives
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Application
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Homo- vs copolymers
Copolymers are not alloys of
homopolymers!
Synthesized by step or chain
growth polymerization
E.g. Poly(acrylamide-ranacrylic acid)

Poly(styrene-alt-maleic
anhydride)
Polystyrene-block-polymethyl
methacrylate
Polystyrene-graft-polymethyl
methacrylate
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Polymer Blends
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Topology linear vs branched
E.g. HDPE
(High density)
LLDPE
(Linear low density)
LDPE
(Low density)
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Special Polymer Topologies / Architectures
Semi-ladder Polymer
Star polymer
Comb Polymer
Ladder Polymer
Polyrotaxene
Dendrimer
Polycatenane
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Dendrimers
Hyperbranched polymers
with controlled structure
1st - generation polyphenylene dendrimer
Globular in shape
Special applications drug
delivery, separations,
nanoparticles, sensors, etc.
Degree of branching
DB =
D+T
(D + T + L)
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Interrelation of states of bulk polymers

MELT
RUBBER or
FLEXIBLE
PLASTIC
Temperature
High
THERMOSET
ENGINEERING
PLASTIC
GLASS
CRYSTALLINE
PLASTIC
FIBER
Low
Low
Intermolecular forces
High
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Forces of interaction in polymers

Dispersion / van der Waals forces
Nonpolar
6
Short range, varies as (-1/r )
Energy ~ 0.2 0.5 kcal/mol
Polyethylene, polystyrene, other hydrocarbon polymers
Dipole/dipole interactions
Short range, varies as (-1/r6)
Energy ~ 0.5 2 kcal/mol
Polyacrylonitrile, PVC
Strongly polar interactions / hydrogen bonds
Short range
Energy ~ 1 10 kcal/mol
Polyamide (nylon), polyurethanes
Coulombic interactions (Ionomers)
Long range, varies as 1/r
Energy ~ 10 20 kcal/mol
Surlyn
Highly polar
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Hydrogen bonding in Nylon

Paulings description:
under certain circumstances , an
atom of hydrogen is attracted by
rather strong forces to two atoms
instead of only one, so that it may
be considered to be acting as a
bond between them. This is called
a hydrogen bond.
The chains stack so as to allow all
the amide groups to hydrogen bond
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Polymer Molecular Weight
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What is the mean (or) average mass?

5 milligrams
5 tons
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Average Molecular Weights

Number average molecular weight, Mn
Weight average molecular weight, Mw
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Average Molecular Weights

Generalized expression
k = 0, Mn
k = 1, Mw
k = 2, Mz
k = 3, Mz+1
Viscosity average molecular weight, Mv
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Typical Molecular Weight Distribution (MWD)
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Mechanical properties depend on molecular weight
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Simple Problem
Consider a mixture containing 95 wt.% of PS of
molecular weight 10,000, and 5 wt.% of plasticizer of

molecular weight 100. Determine Mn and Mw.
Mn = (0.95/10000 + 0.05/100)-1 = 1680.67 g/mol
Mw = (0.95*10000 + 0.05*100) = 9505 g/mol
PDI = 9505/1680.67 = 5.655
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Mn measured using methods involving colligative

property measurement
Vapor pressure lowering
Elevation in boiling pt.
Depression of freezing point
Osmotic pressure
Mw measured using light scattering

Mv determined using solution viscosity
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Modeling MWDs
Log-normal distribution
Gamma distribution
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Poisson distribution
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Lorentzian distribution
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Classification of Polymerization
1.
2.
3.
4.
Step growth polymerization

Chain growth polymerization
Coordination polymerization
Ring opening polymerization
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Step growth - Condensation polymerization

Polyester
Polycarbonate
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Step growth - Condensation polymerization

Polyamide Nylon 6,6
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Step growth non-condensation polymerization

(or) Polyaddition
Polyurethane
Diol
Diisocyanate
Other examples: Epoxy resins, chlorinated polyether, crosslinked

polyurethane
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Few other examples

Condensation Polymers
Polyamide
Polycarbonate
Polyester
Polyimide
Polysulfone
Dicarboxylic acid
Bisphenol-A
Dicarboxylic acid
Tetracarboxylic acid
Bisphenol-A
+
+
+
+
+
Diamine
Phosgene
Diol or polyol
Diamine
Dichlorophenyl
sulfone
Noncondensation or Addition polymers

Polyurethane
Diisocyanate
Poly(phenylene oxide) 2,6-disubstituted phenol
+ Diol or polyol
+ Oxygen
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1. Free radical
2. Ionic (cationic, anionic)
e.g. PE, PP, PS, PMMA, PA,
Key steps
Initiation
Propagation
Termination
Chain transfer
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Ziegler-Natta catalysts
(organometallic compound + transition metal salt)
e.g. Al (C2H5)3 + TiCl4 , Li(C4H9) + TiCl4
Homogeneous or heterogeneous catalyst

Used for producing isotactic/stereoregular polymers
Follows insertion mechanism
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Polymer tacticity
Isotactic
Syndiotactic
Atactic
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Example
Ziegler-Natta
catalysts
HDPE
(Essentially
linear)
Ethylene
High pressure
free radical
polymerization
LDPE
(significantly
branched)
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Ring Opening Polymerization

533 K, N2
n
-Caprolactam
Ethylene oxide
Nylon-6
Polyethylene oxide
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Condensation polymerization
Thermosets / duroplastics
Phenol resin
Urea, thiourea resin
Melamine resin
Alkyd resin
Allyl resin
Silicon resin
Polyimide
Unsaturated polyester resin
Polybenzimidazole
Thermoplastics
Polyamides
Polycarbonates
Polyester
Polyphenylene oxide
Polysulfone
Polyvinyl acetate
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Thermoplastics
Polyethylene (PE)
Polypropylene (PP)
Polybutylene
Poly-4-methyl-1-pentene
Polyvinyl chloride (PVC)
Polyvinylidene chloride
Polymethyl methacrylate (PMMA)
Polyacrylonitrile (PAN)
Polystyrene (PS)
Polyacetal
Polyvinyl acetate
Fluorine based plastics
Poly-p-xylene
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Polymerization techniques
Bulk polymerization (monomer + initiator + )
Solution polymerization
(monomer + solvent + initiator + )
Monomer and polymer soluble in solvent
Precipitation polymerization
(monomer + solvent + initiator + )
Monomer soluble in solvent, but polymer is not
Suspension polymerization
Emulsion polymerization
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Variation of conversion in free radical polymerization
Monomer conc. in solvent
Diffusion free regime

Autoacceleration
Reaction diffusion
Autodeceleration
Benzoyl peroxide-initiated polymerization of methyl methacrylate

in benzene at 50 oC
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Suspension polymerization
Suitable for
water insoluble
polymers
Polymerization medium water

Droplets of monomer + initiator + chain transfer agent
Controlling parameters:
monomer:water ratio
stirring speed
surfactant / colloid concentration
E.g. PVC, butyl rubber, PVDF, 100-5000 m polymer beads
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Emulsion polymerization
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Water is the medium
Initiator is water soluble
Monomer and polymer water

insoluble
Surfactant / emulsifiers
Excellent heat transfer
Very high monomer conversions
Very low PDI, particle size (0.1 m)
E.g. chloroprene, vinyl acetate,

vinyl chloride
Recipe for emulsion co-polymerization
of styrene-butadiene (World war II)
Butadiene
Styrene
Water
Soap
Lorol mercaptan
K2S2O8
75 (parts by wt.)
25
180
5
0.5
0.3
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Typical PDI of Polymers

Free radical polymerization
1.5 2
(solution, suspension, emulsion)

Free radical polymerization (bulk)
2-5
Free radical polymerization (without
8 10
temperature control)
Cationic/anionic (homogeneous)
< 1.5
Cationic/anionic (heterogeneous)
> 10
Step growth polymerization
23
> 10
Polymerization with branches
> 20
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Ceiling Temperature
Odian, Chap. 3-9c
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Ceiling Temperature
At equilibrium,
G G0 RT ln Keq
G0 H 0 Tc S 0 RT ln Keq
Keq
[ M n 1 ]
1
[ M n ][ M ] c [ M ]c
H 0
Tc
S 0 R ln[ M ]c
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Ionic polymerization
Cationic polymers polyisobutylene, polybutylene,
isobutylene-isoprene copolymer, poly(vinyl ether)s
Electrophilic addition to monomers
Carbocation initiators mineral acids (H2SO4, H3PO4), Aprotonic
acids (Lewis acids, Friedel-Crafts halides) like AlCl3, BF3, TiCl4,
SnCl4, Protonic (Brnsted) acids
Anionic polymers 1,4-polybutadiene, 1,4-polyisoprene,
styrene-butadiene rubber
Carbanion initiators organometallic compounds of alkali
metals (butyl lithium), Grignard reagents
Nucleophilic addition to monomers
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Free radical vs Ionic/Co-ordination polymerization
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Cationic polymerization
Protonation by mineral acids
HSO4-
Termination by the counterion
HSO4-
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Initiation
Catalyst Co-catalyst
Stable carbocation
Propagation
Reaction rate is high at low temperatures (e.g. -80 oC in chlorinated

solvents like CH3Cl
Head-to-tail addition is energetically favored
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Effect of solvent polarity on rate of cationic

polymerization of -methyl styrene
Solvent
Cyclohexane
Dielectric
constant
1.9
Polymerization rate
mol/min
1.25
Dichloroethane
10
3.30
Nitroethane
28
20.40
Nitrobenzene
36
150.00
Solvent polarity also affects the degree and type of stereoregularity

(isotactic or syndiotactic)
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Effect of temperature on Mv of
polyisobutylene
Temperature, oC
Viscosity average
molecular weight, Mv
-10
10,000
-25
13,000
-45
25,000
-80
74,000
-90
1,20,000
Higher stereoregularity is achieved at lower temperatures
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Kinetics of cationic polymerization

Typical reactions
Formation of catalystco-catalyst complex
Initiation
Propagation
Termination
Chain transfer
A RH H AR
ki
H AR M
HM AR
HM x AR M
HM
ki
x 1
AR
HM x AR
M x H AR
kt
HM x AR M
M x HM AR
kt
Billmeyer, page 87
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Kinetics of cationic polymerization

Same analysis as free radical polymerization, except
for the termination step
Chain transfer steps to monomer, polymer and solvent
are possible
Rp = Kkpki[A][RH][M]2 / kt
Kinetic chain length, DP = kp[M]/kt
<only termination>
Kinetic chain length, DP = kp/ktr
<only chain transfer>

Billmeyer, page 87
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Anionic (Living) Polymerization

Initiation
Propagation
Solvents aliphatic and aromatic hydrocarbons, ethers

Anionic polymerization not too much temperature sensitive as
cationic polymerization
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Kinetics
Initiation:
KNH2 K+ + NH2
NH2 + M H2N-M
Ri = ki[NH2][M]
Propagation: H2N-(M)n-M + M H2N-(M)n+1-M

Rp = kp[M][M]
Chain transfer: H2N-(M)n-M + NH3 H2N-(M)n-MH + NH2
Rtr = ktr[M][NH3]
Kinetic chain length, DP = kp[M]/ktr[NH3]
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When there is no termination by chain transfer

DP = Rp/Ri
DP = no. of monomer molecules / no. of chains initiated
DP = ([M]0 [M])/[I]0 = [M]0/[I]0 for X = 1 & high rates of
initiation
Vary narrow MWD can be obtained
Effect of ion-pair association and solvent polarity affect

kp
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Effect of solvent on kp for polystyrene

Solvent
Counter ion
Tetrahydrofuran
Na+
kp,
L/mol-s
80*
1,2-Dimethoxy ethane
Na+
3600*
Tetrahydrofuran
Li+
160*
Benzene
Li+
0.001 0.1 #
Cyclohexane
Li+
(5 100)10-5 #
* - at 25 oC, # - variable temperature
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Effect of solvent and counter ion on polymer structure
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Geometric isomerism in polyisoprene
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Cis- and Trans- 1,4-isoprene polymers
Trans-
Cis-
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Ziegler-Natta / Coordination polymerization

Nobel prize contribution Ziegler (1964) and Natta (1965)
Polymers with unusual stereospecific structures
Usually carried out in industry in fluidized bed reactors with
supported solid catalyst in the form of slurry
Components Organometallic compound + transition-metal salt
Organometallic compound
Transition metal salt
Triethyl aluminium
Titanium tetrachloride
Diethyl aluminium chloride
Vanadium trichloride / triacetyl acetone

vanadium / triacetyl acetone vanadium /
Co-chloride-pyridine complex
Butyl lithium
Titanium tetrachloride
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Crystal structure of -TiCl3
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Ti
Vacancy
Cl
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Mechanism of Ziegler-Natta polymerization

Catalyst activation / adsorption
Ethyl aluminium
dichloride
Dicyclopentadienyl
ethyl titanium
chloride
First monomer addition
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Formation of a new Ti-C bond
Polyinsertion
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Chain transfer to monomer or alkyl alumina
-Elimination at high temp. to form transition metal hydrides
Termination by addition of H2
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Variation of polypropylene isotacticity with catalyst

Catalyst
AlEt3 + TiCl4
AlEt3 + -TiCl3
AlEt3 + -TiCl3
AlEt3 + ZrCl4
AlEt3 + VCl3
AlEt3 + TiCl4 + P, As or Sb
AlEt2X + TiCl3
AlEtX2 + -TiCl3 + amine
Stereoregularity (%)
35
45
85
55
73
35
90-99
99
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Monomer type
Ethylene
Propylene
Isobutylene
Dienes
Styrene
Vinyl chloride
Acrylonitrile
Tetrafluoroethylene
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Radical
Cationic
Anionic
Coordination
+
+
+
+
+
+
+
+
+
-
+
+
+
-
+
+
+
+
+
+
+
+
+ denotes formation of long chain polymers

- Denotes formation of oligomers or no polymerization at all
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Specific References
Billmeyer, Textbook of polymer science
Chapters 1-5, Chapter 13,14,15,16 self study

Odian, Principles of polymerization
Chapters 1, 2 (upto page 53, 69-92), 3 (upto page 214, 236-246, 279-287), 6
(464-481, 487-502)
Pg. 92-101, 300-313 (specific commercial polymers) - Self study
Pg. 264-271 (determination of rate constants) Self study
Gowariker et al. Polymer science
Chapters 1, 2, 3, 4, 8
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Potential paper topics

Gradient copolymerization kinetics
Penultimate effect in copolymerization

Sequence length distribution in copolymers
Kinetics of emulsion polymerization
Kinetics of branching, crosslinking and gelation
Kinetics of Ziegler-Natta / Alfin polymerization
Other polymerization techniques

CRP Controlled Radical Polymerization
RAFT Radical Addition Fragmentation Termination
ATRP Atom Transfer Radical Polymerization

NMP Nitroxide Mediated Polymerization
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www.scopus.com
Potential journals
Polymer
Progress in Polymer Science

European Polymer Journal (Elsevier)
Journal of Physical Chemistry
Macromolecules (ACS)
Journal of Polymer Science
Macromolecular Chemistry and Physics
Macromolecular Reaction Engineering (Wiley)
66

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Department of Chemical Engineering

CH 3160 Polymeric Materials

Department of Chemical Engineering

Department of Chemical Engineering

Classification of polymers based on application

Department of Chemical Engineering

Department of Chemical Engineering

E.g. Poly(acrylamide-ranacrylic acid)

Department of Chemical Engineering

Department of Chemical Engineering

Topology linear vs branched

Department of Chemical Engineering

Special Polymer Topologies / Architectures

Department of Chemical Engineering

1st - generation polyphenylene dendrimer

Department of Chemical Engineering

Interrelation of states of bulk polymers

Department of Chemical Engineering

Forces of interaction in polymers

Department of Chemical Engineering

Hydrogen bonding in Nylon

Department of Chemical Engineering

Polymer Molecular Weight

Department of Chemical Engineering

What is the mean (or) average mass?

Department of Chemical Engineering

Average Molecular Weights

Weight average molecular weight, Mw

Department of Chemical Engineering

Average Molecular Weights

Department of Chemical Engineering

Typical Molecular Weight Distribution (MWD)

Department of Chemical Engineering

Mechanical properties depend on molecular weight

Department of Chemical Engineering

molecular weight 10,000, and 5 wt.% of plasticizer of

Department of Chemical Engineering

Mn measured using methods involving colligative

Mw measured using light scattering

Department of Chemical Engineering

Department of Chemical Engineering

Department of Chemical Engineering

Step growth polymerization

Department of Chemical Engineering

Step growth - Condensation polymerization

Department of Chemical Engineering

Step growth - Condensation polymerization

Department of Chemical Engineering

Step growth non-condensation polymerization

Other examples: Epoxy resins, chlorinated polyether, crosslinked

Department of Chemical Engineering

Few other examples

Noncondensation or Addition polymers

Department of Chemical Engineering

Chain growth polymerization

Department of Chemical Engineering

Homogeneous or heterogeneous catalyst

Department of Chemical Engineering

Department of Chemical Engineering

Department of Chemical Engineering

Ring Opening Polymerization

Department of Chemical Engineering

Chain growth polymerization