Tell me and I forget

Teach me and I remember

Involve me and I learn
- Benjamin Franklin

SYBTech
Polymer Chemistry (PO221 Trimester-I)

Introduction to Polymer Science :

Classification of Polymers

Prof. (Dr.) Hemant V. Joshi

School of Polymer Engineering
MIT-World Peace University, Pune
hemant.joshipoly@mitwpu.edu.in
hemant.joshi@mitpune.edu.in
(Off.) 020-3027 3110; (Mob.) 0 98818 34968
 Objective

• Provide building blocks of Polymer

1 Science

• Impart fundamental knowledge of

2 Polymer Science

• Provide in-depth knowledge of

3 polymerization mechanisms and kinetic

• Impart basic knowledge of polymer

4 modification reactions

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 Topic I : Introduction to polymer science

 Basic concepts such as monomer, polymer, oligomer, initiator,

functionality, molecular weight, polydispersity, viscosity, etc.

 Classification of polymers, nomenclature of polymers,

 Generalized mechanisms of step and chain polymerization,

 Various average molecular weights (Mn, Mw, Mv and Mz) and

molecular weight distribution (MWD), molecular weight
determination techniques

 Polymerization techniques such as bulk, solution, suspension

and emulsion

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 Classification of Polymers

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 Classification

Factors for classification

Response to thermal energy
Polymerization reactions
Molecular weight
Number/type of monomers
Molecular architecture
Market consumption and properties

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 Classification Molecular architecture
 Response to thermal energy  Linear
 Thermoplastics  Branched
 Thermosets  Cross-linked
 Polymerization reactions  Star and dendrimers
 Condensation or step polymers  Cyclolinear
 Addition or chain polymers  Ladder
 Ring opening polymers  Cyclomatrix
 Copolymers
 Molecular weight
 Terpolymers
 Low, high, ultra-high
 Telechelic
 Number/type of monomers
 Market consumption and
 Homopolymers
 Copolymers properties
 Terpolymers  Commodity polymers
 Engineering polymers
 Specialty polymers

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 Response to Thermal Energy :
Thermoplastics

 Any material that softens on heating

 Material passing through definite
sequence of property changes with
increase in temperature
 Ease of reforming, hence, recycling - +
 Amorphous, crystalline
 PE, PP, PET, PBT, Nylon

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 Response to Thermal Energy :Thermosets
 Range of systems
Polymerized systems as liquids
Heating
Undergo chemical reaction
 Solid, highly cross-linked network - +
structure
 Reheating
 Charring due to degradation/
decomposition
 Difficult to reform, hence, recycle
 Prepolymers
 Partly polymerized systems
capable of liquid flow +
 Epoxy, Phenolics, PUR, UPR,
Amino resins

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 Polymerization Reactions :
Condensation (Step) & Addition (Chain) Polymers

  2 monomer molecules  Addition reactions of monomers

 Reactive functional groups with unsaturated bonds
 Condensation by-product  Synthesis of
 Polyolefins (PE, PP, PS)
(small molecules)
 PTEF
 H2O, NH3, CH3OH
 POM from HCHO
 Synthesis of  NR
 Polyamides (N66)  Neoprene rubber
 Polyesters (PET)  PAN
 Phenolic resins (PF)  Acrylics
 Amino resins (UF, MF)
 Epoxy

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 Polymerization Reactions :
Condensation (Step) Polymers

Polyamides (N66)

Polyesters (PET)

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 Polymerization Reactions :
Condensation (Step) Polymers

Phenolic resins (PF)

Epoxy

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 Polymerization Reactions :
Addition (Chain) Polymers

PP PTFE

PVC PMMA

PS

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 Polymerization Reactions :
Ring Opening Polymers

Cyclic compounds
Opening or cleavage of
ring in presence of
catalysts
Synthesis of
POM from trioxane
N6 from caprolactum
Polyethers from epoxides
PDMS

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 Molecular Weight

Low MW
Medium MW
High MW
Very High MW
Ultra High MW

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 Number/Type of Monomer(s)

Homopolymer
Copolymer PE PVC

Terpolymers

 Homopolymers PET
 Same repeating unit
 PE, PVC, PET, N66

N66

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 Number/Type of Monomer(s)
 Homopolymer
 Copolymer
 Terpolymers
SBR SAN
 Copolymers
  2 different repeating
units
 Sequence of repeating
units vary according to
EVA
method and mechanism
of synthesis
 Random, alternating,
block, graft
 SBR, SAN, EVA, SMA,
SMMA SMA
SMMA

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 Copolymers
Homopolymer

Random

Block

Graft Alternate

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 Number/Type of Monomer(s)
 Homopolymer
 Copolymer
 Terpolymers

 Terpolymers
ABS
 3-different repeating units
 Random or block
 ABS, TFE-HFP-VDF

TFE-HFP-VDF
(tetrafluoroethylene-co-hexafluoropropylene-co-vinylidene fluoride) 
drug eluting coating on medical devices

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 Molecular Architecture :
Linear Polymers

 Long chain of skeletal atoms

with side groups
 Usually soluble in some
solvent
 At room temperature, in
solid state – elastomers, Linear,
flexible polymers, glass-like unbranched

materials
 PE, PVC, PMMA, PAN,
Nylon66

Linear, branched

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 Molecular Architecture :
Branched Polymers
 Linear polymers with branches of
same basic structure as the main
chain
 Soluble in same solvent as that of
corresponding linear polymer
Linear, unbranched
 Resemble linear polymer in many
of properties
 Difference w.r.t. linear polymers
 Lower tendency to crystallize
 Differ in solution viscosity
 Differ in light scattering behaviour
 Heavily branched – incomplete crosslinked, branched
dissolution; swelling in solvents
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 Molecular Architecture :
Cross-linked or Network Polymers

 Presence of chemical
linkages between chains
 Do not dissolve
 Swelling in solvents
 Swelling extent  cross-link
density
 Light cross-linking
 Rubbery, elastomeric material
 High cross-linking crosslinked, unbranched
 Rigid, high melting, non-
swellable material

crosslinked, branched

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 Molecular Architecture :
Star Polymers

 Number of arms radiating

from common core
 Number of arms  4 to 6
 Synthesis
 Polymerization from
multifunctional core 
growing arms
 Linking preformed polymer
molecules to core via reactive
groups on polymer
 Theoretically, no limit to arm
length

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 Molecular Architecture :
Dendritic Polymers (Dendrimers)

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 Molecular Architecture :
Dendritic Polymers (Dendrimers)
 3-D structure with overall spherical outer shape
 Synthesis
 Core first method –
 Reactions of multifunctional core with  3 functional monomer
 Molecular growth in successive layers (generations) moving
further away from core
 Each generation doubling number of functional sites on
outside of molecule
 With increasing number of branch points, reaction zone
moves further away core
 Less space availability for further reactions
 Molecules reach size and spherical shape in 3-4 generations
 Prevention of further growth

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 Molecular Architecture :
Dendritic Polymers (Dendrimers)
 Synthesis
 Arm first method –
 Each highly branched arm synthesis
 Several arms linking to core in final step
 Star and Dendrimers
 Significant difference in solution of solid-state
properties compared to linear polymers of
same MW
 Spherical shape of dendrimers
 Restriction on molecular entanglement
 Lower viscosities

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 Molecular Architecture :
Cyclolinear Polymers

 Special type of linear polymer

 Linkage through ring systems
 Usually aromatic (benzene)
ring
 Heterocyclic and inorganic
rings can be used
 Properties similar to linear
polymers
 Solubility lower than linear
polymers
Cyclolinear polyphosphazene
 Higher tendency of
crystallization

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 Molecular Architecture :
Ladder Polymers
 Linear molecules
 2-skeletal strands/chains linked
in regular sequence by cross-
linking units
 Usually aromatic rings as
linking units
 Ladder type silicone polymers
– Si-O units as linking units
 Compared to linear polymers Silicone ladder polymer

 More rigid molecular structure

 Very less solubility
 Excellent thermal stability

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 Molecular Architecture :
Cyclomatrix Polymers
 Ring systems linked together
forming 3-D matrix of
connecting units
 Organic and inorganic rings
 Silicone resins
 Silicate minerals Cyclomatrix silicone resins
 Graphite
 Highly insoluble, rigid, very
high melting, stability at
elevated temperatures
 Typically thermosetting resins
 Heat-resistant wire coatings Cyclomatrix polyphosphazene

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 Molecular Architecture :
Telechelic Polymers
 Reactive functional groups
at one or both end of chain
 Synthesized by living Monotelechelic polymer

polymerization
 Usually used to synthesize
Di-telechelic polymer
 Block copolymers
 Star polymers
Active functional group
 Dendrimers
 Network structures by end-
linking

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