2.

Polymer Synthesis

Dr. Wang, Mingfeng

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Polymer Synthesis
 Content

Ø Radical polymerization
Ø Anionic polymerization
Ø Cationic polymerization
Ø Ring-opening polymerization (ROP)
Ø Ring-opening metathesis polymerization (ROMP)
Ø Condensation polymerization
Ø Supramolecular polymerization

• We will survey addition, ring-opening, and polycondensation routes including

recent developments.

• The ability to synthesize polymers in increasingly creative ways with

increasing control of macromolecular architecture has revolutionalized everyday
life and will play a key role in future scientific developments.

CHE4250 Polymers for Nanotech

Polymer Synthesis 2
 Classification of Synthetic Routes

Ø Chain Growth Polymerization

e.g. addition polymerization or ring-opening polymerization

• Polymerization is a chain reaction.

• Species with a highly reactive center exist where polymerization takes place
e.g. a radical, a cationic, an anionic center etc

• Initiation, propagation, and usually chain transfer and chain termination steps
exist

• High molecular weight polymer is formed even at low conversion of monomer

e.g. 95 % monomer and 5 % polymer (except for living polymerizations or
enzyme syntheses where molecular weight increases linearly with conversion)

http://www.youtube.com/watch?v=Els5JNYfHQE

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Polymer Synthesis
 Classification of Synthetic Routes (contd)

Ø Step Growth Polymerization

e.g. polycondensations

• All species (monomer, dimer, trimer etc) are approx. equally reactive and
all react with each other.

• No highly reactive species relative to the others

• High molecular weight polymer is formed only at very high conversion of

monomer ( > 99 %).

n x-A-x + n y-B-y A-B + 2n x-y

n

T. Yokozawa et al. Adv Polym Sci (2008) 217: 1–77

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Polymer Synthesis
 Evolution of molecular weight vs. conversion:
Comparison between different polymerization methods

Chain Growth Step Growth Living chain Growth

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Polymer Synthesis
 Radical polymerization

Ø Probably the most important method of addition polymerization.

Used for an enormous variety of monomers.

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Polymer Synthesis
Radical polymerization

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Polymer Synthesis
Radical polymerization

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Polymer Synthesis
 Radical polymerization

§ X is usually H or a halogen atom and X-A could be monomer (M), initiator (I),
solvent (S), or polymer (P) (in which case chain transfer can be intramolecular or
intermolecular).

§ Chain transfer can lead to lower molecular weights and/or branching.

§ Chain transfer agents with large Ktr, e.g. CBr4, RSH, allow molecular weight control.

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Polymer Synthesis
Radical Polymerization of Ethylene and other a-Olefins

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Polymer Synthesis
Radical Polymerization of Ethylene and other a-Olefins

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Polymer Synthesis
 Coordination Polymerization
• 1950's Ziegler and Natta (Nobel Prize in Chemistry in 1963)
- developed coordination polymerization (accidently) and stereoregular polymerization

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Polymer Synthesis
Coordination Polymerization

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Polymer Synthesis
Coordination Polymerization
Cossee-Arlman Mechanism

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Polymer Synthesis
Cationic polymerization

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Polymer Synthesis
 Cationic polymerization

• Small amounts of isoprene, CH2=C(Me)-CH=CH2, are incorporated to allow

crosslinking and hinder crystallization

• Initiation system is AlCl3 in MeCl (the true initiator could be a MeCl•AlCl3

complex that acts as a source of Me+ or H+[AlCl3OH]- derived from trace
amounts of moisture)

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Polymer Synthesis
An example: Cationic polymerization of styrene

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Polymer Synthesis
An example: Cationic polymerization of styrene

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Polymer Synthesis
Anionic polymerization

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Polymer Synthesis
 Anionic polymerization

• The absence of termination and chain transfer leads to this type of

polymerization being described as a LIVING POLYMERIZATION

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Polymer Synthesis
 Living anionic polymerization

Synthetic utility:
i) molecular weight control - depends on monomer / initiator ratio (linear plot vs Mn)
ii) end-group functionalization, surface functionalization, and block copolymer synthesis
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Polymer Synthesis
 Living Anionic Polymerizations : Practical Considerations

§ Practically living anionic polymerization requires extremely low levels of reactive

impurities (e.g. O2, CO2, H2O) as the concentration of propagating centers is very
low. Solvents and reagents must be carefully purified.

§ The counterions that give ion-pairs with the propagating anionic centers can
influence the polymerization

Only works with large counterion at low T - prevents reaction with C=O group

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Polymer Synthesis
 Ring-Opening Polymerization (ROP)

• ROP is important commercially.

• ROP of cyclic ethers (e.g. ethylene oxide, propylene oxide, THF) are used to
produce polyether diols (telechelic polyethers with OH end groups) which are
used in condensation polymerizations to form polyurethane and polyester-
based thermoplastic elastomers.

• High molecular weight poly(ethylene oxide) (PEO) and its copolymers are
used (with dissolved salts) as polymeric electrolytes in rechargeable batteries.

• Cationic ROP of trioxane is an important route to poly(methylene oxide)

(POM), an important engineering plastic.

• Nylon 6 (from caprolactam), certain polycarbonates and polyesters,

polysiloxanes, and polyphosphazenes are also formed by ROP.

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Polymer Synthesis
 ROP: Scope and mechanisms
ROP can involve thermal, anionic, cationic, radical, transition metal-catalyzed
or radiationinduced processes.

Examples with main methods of polymerization:

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Polymer Synthesis
ROP: Scope and mechanisms

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Polymer Synthesis
ROP: Scope and mechanisms

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Polymer Synthesis
 Anionic ROP of ethylene oxide

• Living polymerization can be formed with care (no protic

impurities e.g. H2O !).

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Polymer Synthesis
ROP of Strained Silicon-Bridged [1]Ferrocenophanes

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Polymer Synthesis
Properties of polyferrocenylsilanes (PFSs)

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Polymer Synthesis
 Ring-Opening Metathesis Polymerization (ROMP)

Olefin metathesis

§ ROMP catalysts: 1950 s Metal halide + alkylating/reducing agent e.g. WCl6/SnEt4

§ ROMP catalysts: 1970's-1980's well-defined metal alkylidenes transition metal catalysts -

some permit living ROMP

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Polymer Synthesis
 R. H. Grubbs
R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760 – 3765 (Nobel Prize in Chemistry, 2005)

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Polymer Synthesis
 Examples of polymers synthesized through ROMP

Several polymers are produced via ROMP commercially:

• Polynorbornene (trade name: Norsorex) - a heavily platicized speciality elastomer.

• Poly(endo-dicyclopentadiene) is a commercially important plastic (snowmobile

bodies).

• Polycyclooctene is also used in blends.

• Living ROMP can be used to make monodisperse polymers and also block copolymers.

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Polymer Synthesis
CHE4250 Polymers for Nanotech 33
Polymer Synthesis
 Polycondensations

• Occur via a step growth process

- no reactive intermediate and molecular weight builds up gradually with conversion

• The successful synthesis of a high polymer requires:

- in the case of 1, exact stoichiometries (better than 0.99 : 1.00 ratios of pure
difunctional monomers)
- in both cases, very high conversions (> 99 %) (favourable DG and no side reactions)

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Polymer Synthesis
The Carothers Equation - The Influence of Stoichiometry and
Conversion on Molecular Weight

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Polymer Synthesis
The Carothers Equation - The Influence of Stoichiometry and
Conversion on Molecular Weight

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Polymer Synthesis
 Example
• To obtain a polymer with useful mechanical properties DPn > ca. 100 is needed
This corresponds to Mn > ca. 10,000 for a monomer of molecular weight 100
What values of r and p will allow this to be achieved ?

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Polymer Synthesis
 Molecular Weight Distribution in Polycondensations

Polydispersity:
A simple statistical analysis involving the most probable (Shultz-Flory) Distribution)
based on the random nature of step growth polymerization gives:

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Polymer Synthesis
Important Examples of Polycondensations

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Polymer Synthesis
Ultrathin, highly flexible and stretchable polymer light-emitting
diodes (PLEDs)

M. S. White et al. Nature Photon 2013, DOI: 10.1038/NPHOTON.2013.188

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Polymer Synthesis
Important Examples of Polycondensations

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Polymer Synthesis
 Important Examples of Polycondensations

§ Remain stable in a wide range of temperatures,

from −273 to +400 C

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Polymer Synthesis
Important Examples of Polycondensations

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Polymer Synthesis
Important Examples of Polycondensations

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Polymer Synthesis
Important Examples of Polycondensations

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Polymer Synthesis
Supramolecular polymers are defined as polymeric
arrays of monomeric units that are brought together
by reversible and highly directional secondary
interactions, resulting in polymeric properties in dilute
and concentrated solutions, as well as in the bulk.

Chem. Rev. 2001, 101, 4071-4097

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Supramolecular Polymers
 Supramolecular Chemistry

1987 Nobel Prize for Chemistry

While traditional chemistry focuses on the covalent bond, supramolecular chemistry examines the
weaker and reversible noncovalent interactions between molecules. These forces include hydrogen
bonding, metal coordination, hydrophobic forces, van der Waals forces, pi-pi interactions and
electrostatic effects.
http://en.wikipedia.org/wiki/Supramolecular_chemistry
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Supramolecular Polymers 47
 Self-assembly in Nature: Viral capsids

Biological systems are often the inspiration for supramolecular research.

http://www.youtube.com/watch?v=7iVm1uEIyP0

Source: htt p://tfy.tkk.fi/kurssit/Tfy-3.363/lectures/

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Supramolecular Polymers
CHE4250 Polymers for Nanotech 49
Supramolecular Polymers
CHE4250 Polymers for Nanotech 50
Supramolecular Polymers
Supramolecular polymers: Stimuli-responsive properties

Illustration of the phase changes in a rubbery material based on Kraton®, (poly(ethylene-co-

butylene), modified with UPy, exemplifying the diversity in phase behavior because of the
supramolecular interactions. Mater. Today, 2004, 7, 34
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Supramolecular Polymers
 Additional Reading Lists

1. George G. Odian, Principles of Polymerization, Wiley-Interscience (QD281.P7D24 2004, 2

reserve copies available at Lee Wee Nam Library)

2. R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760 – 3765. Olefin-Metathesis Catalysts
for the Preparation of Molecules and Materials (Nobel Lecture)

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Polymer Synthesis