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Department of Chemical Engineering

IIT Madras

CH 3160 Polymeric Materials

R. Vinu

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Department of Chemical Engineering

IIT Madras

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Department of Chemical Engineering

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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Department of Chemical Engineering IIT Madras Application 4 .

g.vs copolymers Copolymers are not alloys of homopolymers! Synthesized by step or chain growth polymerization E.Department of Chemical Engineering IIT Madras Homo. Poly(acrylamide-ranacrylic acid) Poly(styrene-alt-maleic anhydride) Polystyrene-block-polymethyl methacrylate Polystyrene-graft-polymethyl methacrylate 5 .

Department of Chemical Engineering IIT Madras Polymer Blends 6 .

g. HDPE (High density) LLDPE (Linear low density) LDPE (Low density) 7 .Department of Chemical Engineering IIT Madras Topology – linear vs branched E.

Department of Chemical Engineering IIT Madras Special Polymer Topologies / Architectures Semi-ladder Polymer Star polymer Comb Polymer Ladder Polymer Polyrotaxene Dendrimer Polycatenane 8 .

separations. sensors. Degree of branching DB = D+T (D + T + L) 9 . nanoparticles.Department of Chemical Engineering IIT Madras Dendrimers Hyperbranched polymers with controlled structure 1st .generation polyphenylene dendrimer Globular in shape Special applications – drug delivery. etc.

Department of Chemical Engineering IIT Madras 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 10 .

polystyrene. other hydrocarbon polymers Dipole/dipole interactions Short range. varies as (-1/r6) Energy ~ 0. polyurethanes Coulombic interactions (Ionomers) Long range. varies as 1/r Energy ~ 10 – 20 kcal/mol Surlyn Highly polar 11 .5 kcal/mol Polyethylene.5 – 2 kcal/mol Polyacrylonitrile.2 – 0. PVC Strongly polar interactions / hydrogen bonds Short range Energy ~ 1 – 10 kcal/mol Polyamide (nylon). varies as (-1/r ) Energy ~ 0.Department of Chemical Engineering IIT Madras Forces of interaction in polymers Dispersion / van der Waals forces Nonpolar 6 Short range.

so that it may be considered to be acting as a bond between them. The chains stack so as to allow all the amide groups to hydrogen bond 12 .Department of Chemical Engineering IIT Madras Hydrogen bonding in Nylon Pauling’s description: … under certain circumstances . an atom of hydrogen is attracted by rather strong forces to two atoms instead of only one. This is called a hydrogen bond.

Department of Chemical Engineering IIT Madras Polymer Molecular Weight 13 .

Department of Chemical Engineering IIT Madras What is the mean (or) average mass? 5 milligrams 5 tons 14 .

Department of Chemical Engineering IIT Madras Average Molecular Weights Number average molecular weight. Mw 15 . Mn Weight average molecular weight.

Mv 16 . Mw k = 2. Mn k = 1.Department of Chemical Engineering IIT Madras Average Molecular Weights Generalized expression k = 0. Mz+1 Viscosity average molecular weight. Mz k = 3.

Department of Chemical Engineering IIT Madras Typical Molecular Weight Distribution (MWD) 17 .

Department of Chemical Engineering IIT Madras Mechanical properties depend on molecular weight 18 .

67 g/mol Mw = (0.% of PS of molecular weight 10. Determine Mn and Mw.000. and 5 wt.05/100)-1 = 1680.Department of Chemical Engineering IIT Madras Simple Problem Consider a mixture containing 95 wt. Mn = (0.95*10000 + 0.67 = 5.95/10000 + 0.% of plasticizer of molecular weight 100.05*100) = 9505 g/mol PDI = 9505/1680.655 19 .

Department of Chemical Engineering IIT Madras 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 20 .

Department of Chemical Engineering IIT Madras Modeling MWDs Log-normal distribution Gamma distribution 21 .

Department of Chemical Engineering Poisson distribution IIT Madras Lorentzian distribution 22 .

Department of Chemical Engineering IIT Madras Classification of Polymerization 1. Step growth polymerization Chain growth polymerization Coordination polymerization Ring opening polymerization 23 . 3. 2. 4.

Department of Chemical Engineering

IIT Madras

Step growth - Condensation polymerization
Polyester

Polycarbonate

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Department of Chemical Engineering

IIT Madras

Step growth - Condensation polymerization
Polyamide – Nylon 6,6

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Department of Chemical Engineering

IIT Madras

Step growth non-condensation polymerization
(or) Polyaddition
Polyurethane

Diol
Diisocyanate

Other examples: Epoxy resins, chlorinated polyether, crosslinked
polyurethane
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6-disubstituted phenol + Diol or polyol + Oxygen 27 .Department of Chemical Engineering IIT Madras 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.

PP. PA.Department of Chemical Engineering IIT Madras Chain growth polymerization 1. Free radical 2. PMMA. anionic) e. Ionic (cationic.g. PS. PE. …… Key steps Initiation Propagation Termination Chain transfer 28 .

Department of Chemical Engineering IIT Madras Coordination polymerization Ziegler-Natta catalysts (organometallic compound + transition metal salt) e.g. Li(C4H9) + TiCl4 Homogeneous or heterogeneous catalyst Used for producing isotactic/stereoregular polymers Follows insertion mechanism 29 . Al (C2H5)3 + TiCl4 .

Department of Chemical Engineering IIT Madras Polymer tacticity Isotactic Syndiotactic Atactic 30 .

Department of Chemical Engineering IIT Madras Example Ziegler-Natta catalysts HDPE (Essentially linear) Ethylene High pressure free radical polymerization LDPE (significantly branched) 31 .

Department of Chemical Engineering IIT Madras Ring Opening Polymerization 533 K. N2 n ω-Caprolactam Ethylene oxide Nylon-6 Polyethylene oxide 32 .

Department of Chemical Engineering 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 IIT Madras Chain growth polymerization 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 33 .

Department of Chemical Engineering IIT Madras Polymerization techniques Bulk polymerization (monomer + initiator + Δ) Solution polymerization (monomer + solvent + initiator + Δ) Monomer and polymer soluble in solvent Precipitation polymerization (monomer + solvent + initiator + Δ) Monomer soluble in solvent. but polymer is not Suspension polymerization Emulsion polymerization 34 .

Department of Chemical Engineering IIT Madras 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 35 .

PVC. butyl rubber. 100-5000 μm polymer beads 36 . PVDF.Department of Chemical Engineering IIT Madras 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.

1 μm) E. chloroprene.3 37 .5 0.) 25 180 5 0. 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. particle size (0.Department of Chemical Engineering Emulsion polymerization IIT Madras 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.g.

suspension.Department of Chemical Engineering IIT Madras Typical PDI of Polymers Free radical polymerization 1. emulsion) Free radical polymerization (bulk) 2-5 Free radical polymerization (without 8 – 10 temperature control) Cationic/anionic (homogeneous) < 1.5 – 2 (solution.5 Cationic/anionic (heterogeneous) > 10 Step growth polymerization 2–3 Coordination polymerization > 10 Polymerization with branches > 20 38 .

Department of Chemical Engineering IIT Madras 39 .

Chap. 3-9c 40 .Department of Chemical Engineering IIT Madras Ceiling Temperature Odian.

Department of Chemical Engineering IIT Madras Ceiling Temperature 0 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 41 .

4-polyisoprene. polybutylene. Aprotonic acids (Lewis acids. Friedel-Crafts halides) like AlCl3. Protonic (Brönsted) acids Anionic polymers – 1. poly(vinyl ether)s Electrophilic addition to monomers Carbocation initiators – mineral acids (H2SO4. H3PO4). isobutylene-isoprene copolymer. TiCl4. BF3.4-polybutadiene. Grignard reagents Nucleophilic addition to monomers 42 . 1.Department of Chemical Engineering IIT Madras Ionic polymerization Cationic polymers – polyisobutylene. SnCl4. styrene-butadiene rubber Carbanion initiators – organometallic compounds of alkali metals (butyl lithium).

Department of Chemical Engineering IIT Madras Free radical vs Ionic/Co-ordination polymerization 43 .

Department of Chemical Engineering IIT Madras Cationic polymerization Protonation by mineral acids HSO4- Termination by the counterion HSO4- 44 .

g.Department of Chemical Engineering IIT Madras Initiation Catalyst Co-catalyst Stable carbocation Propagation Reaction rate is high at low temperatures (e. -80 oC in chlorinated solvents like CH3Cl Head-to-tail addition is energetically favored 45 .

30 Nitroethane 28 20.Department of Chemical Engineering IIT Madras Effect of solvent polarity on rate of cationic polymerization of α-methyl styrene Solvent Cyclohexane Dielectric constant 1.25 Dichloroethane 10 3.40 Nitrobenzene 36 150.00 Solvent polarity also affects the degree and type of stereoregularity (isotactic or syndiotactic) 46 .9 Polymerization rate mol/min 1.

000 -80 74.000 -25 13.000 Higher stereoregularity is achieved at lower temperatures 47 .000 -45 25.Department of Chemical Engineering IIT Madras Effect of temperature on Mv of polyisobutylene Temperature. oC Viscosity average molecular weight.20.000 -90 1. Mv -10 10.

page 87 48 .Department of Chemical Engineering IIT Madras Kinetics of cationic polymerization Typical reactions Formation of catalystco-catalyst complex Initiation Propagation Termination Chain transfer K    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.

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.Department of Chemical Engineering IIT Madras Kinetics of cationic polymerization Same analysis as free radical polymerization. page 87 49 .

ethers Anionic polymerization – not too much temperature sensitive as cationic polymerization 50 .Department of Chemical Engineering IIT Madras Anionic (“Living”) Polymerization Initiation Propagation Solvents – aliphatic and aromatic hydrocarbons.

Department of Chemical Engineering IIT Madras 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] 51 .

Department of Chemical Engineering IIT Madras When there is no termination by chain transfer… DP = Rp/Ri DP = 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 52 . of monomer molecules / no.

at 25 oC.2-Dimethoxy ethane Na+ 3600* Tetrahydrofuran Li+ 160* Benzene Li+ 0.Department of Chemical Engineering IIT Madras Effect of solvent on kp for polystyrene Solvent Counter ion Tetrahydrofuran Na+ kp.1 # Cyclohexane Li+ (5 – 100)×10-5 # * .variable temperature 53 . L/mol-s 80* 1. # .001 – 0.

Department of Chemical Engineering IIT Madras Effect of solvent and counter ion on polymer structure 54 .

Department of Chemical Engineering IIT Madras Geometric isomerism in polyisoprene 55 .

4-isoprene polymers Trans- Cis- 56 .and Trans.Department of Chemical Engineering IIT Madras Cis.1.

Department of Chemical Engineering IIT Madras 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 57 .

Department of Chemical Engineering Crystal structure of α-TiCl3 IIT Madras Ti Vacancy Cl 58 .

Department of Chemical Engineering IIT Madras Mechanism of Ziegler-Natta polymerization Catalyst activation / adsorption Ethyl aluminium dichloride Dicyclopentadienyl ethyl titanium chloride First monomer addition 59 .

Department of Chemical Engineering IIT Madras Formation of a new Ti-C bond Polyinsertion 60 .

Department of Chemical Engineering IIT Madras Chain transfer to monomer or alkyl alumina β-Elimination at high temp. to form transition metal hydrides Termination by addition of H2 61 .

As or Sb AlEt2X + TiCl3 AlEtX2 + γ-TiCl3 + amine Stereoregularity (%) 35 45 85 55 73 35 90-99 99 62 .Department of Chemical Engineering IIT Madras Variation of polypropylene isotacticity with catalyst Catalyst AlEt3 + TiCl4 AlEt3 + β-TiCl3 AlEt3 + α-TiCl3 AlEt3 + ZrCl4 AlEt3 + VCl3 AlEt3 + TiCl4 + P.

Department of Chemical Engineering Monomer type Ethylene Propylene Isobutylene Dienes Styrene Vinyl chloride Acrylonitrile Tetrafluoroethylene IIT Madras Radical Cationic Anionic Coordination + + + + + + + + + - + + + - + + + + + + + + + denotes formation of long chain polymers .Denotes formation of oligomers or no polymerization at all 63 .

16 – self study Odian. 2. 3 (upto page 214. 3. Principles of polymerization Chapters 1.14. 92-101. 4. 264-271 (determination of rate constants) – Self study Gowariker et al.15. 6 (464-481. Textbook of polymer science Chapters 1-5. 2 (upto page 53. Polymer science Chapters 1.Department of Chemical Engineering IIT Madras Specific References Billmeyer. 279-287).Self study Pg. 69-92). 487-502) Pg. 236-246. Chapter 13. 300-313 (specific commercial polymers) . 8 64 .

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 65 .Department of Chemical Engineering IIT Madras Potential paper topics Gradient copolymerization kinetics Penultimate effect in copolymerization Sequence length distribution in copolymers Kinetics of emulsion polymerization Kinetics of branching.

Department of Chemical Engineering IIT Madras 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 .