Seminar on Polymer Science

1. Polymer Synthesis (Ring opening)
Graded Seminar
Submitted By-
Tejas Chandrakant Jagtap
M.Pharm (Pharamceutics)
1st Sem
Guided by-
Dr.(Mrs.) Shilpa Chaudhari
Dr. D. Y. Patil College of Pharmacy, Akurdi, Pune-44

2.  Introduction to Polymer Synthesis
 Classification of Polymer
 Ring Opening Polymerization
I. Radical ROP
II. Cationic ROP
III. Anionic ROP
 History
 Mechanism of ROP
 References
Ring Opening Polymerization

3. Polymers are extremely large molecules that are essential to our every
existence. They are main constituents of food (starch, protein, etc.), clothes
(polyester, nylons, etc.), houses (wood cellulose, alkyl, paints, etc.), and bodies
(poly(nucleic acids), proteins, etc.).
Polymer Synthesis
There are two major types of polymerization methods used to convert
small molecules (monomers) into polymers.
These methods were originally referred to as addition and condensation
polymerization.
Depending on the author,
Addition polymerization is called as chain, chain-growth, or chain
reaction polymerization.
Condensation polymerization is now referred to as step-growth or step-
reaction polymerization.
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Ring Opening Polymerization

4. Based on
Origin
• Natural
• Eg. Cellulose,
natural rubber,
nucleic Acid
• Synthetic
• Eg. fibers,
elastomers, plastics,
adhesives, etc.
Based on
Structure
• Linear, Branched or
Cross-linked, Ladder
vs. Functionality
• Amorphous or
Crystalline
• Homopolymer or
Copolymer
• Random
• Alternating
• Block
• Graft
• Fibers, Plastics, or
Elastomers
Based on
POLYMERIZATION
MECHANISM
• Condensation
• Addition
• Ring Opening
Based on
Thermal Behavior
• Thermo Plastic
• Thermosetting Plastic
Based on
Mechanical Behavior
• Soluble polymers
• Hydrogels
• Nano- and micro
particles
• Foams for tissue
engineering
• Fibers
• Lenses
• Adhesive
• Surface modifications
• Polymer brushes
• Interpenetrating
networks
• Shape memory
materials
• Composites/additives
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Ring Opening Polymerization

5. Ring-opening polymerization (ROP) is a form of chain-growth polymerization,
in which the terminal end of a polymer chain acts as a reactive center where further cyclic
monomers can react by opening its ring system and form a longer polymer chain. (Fig.1)
A Polymerization in which a cyclic monomer yields a monomeric unit which
is acyclic or contains fewer cycles than the monomer.
If the monomer is polycyclic, the opening of a single ring is sufficient to classify
the reaction as ring-opening polymerization.
The propagating center can be radical, anionic or cationic.
ROP continues to be the most versatile method of synthesis of major groups
of biopolymers, particularly when they are required in quantity.
Polymer
Fig.1 Ring opening polymerization
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Ring Opening Polymerization

6. Cyclic monomers that are polymerized using ROP encompass a variety of
structures, such as: alkanes, alkenes, etc.
Compounds containing heteroatoms in the ring:
Oxygen: ethers, acetals, esters (lactones, lactides, and carbonates)
and anhydrides.
Sulfur : polysulfur, sulfides and polysulfide.
Nitrogen : amines, amides (lactames), imides, N-carboxyanhydride and 1,3-
oxaza derivatives.
Phosphorus : Phosphates, phosphonates, phosphites, phosphines and
phosphazenes.
Silicon: siloxanes, silathers, carbosilanes and silanes.
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Ring Opening Polymerization

7. Ring-opening polymerization (ROP) has been used since the beginning of the
1900s in order to synthesize polymers. Synthesis of polypeptides which has the
oldest history of ROP, dates back to the work in 1906 by Leuchs.
Many years later came the method of the ROP of anhydro sugars,
providing polysaccharides, including synthetic dextran, Xanthan gum, welan
gum, gellan gum, diutan gum, and pullulan.
Mechanisms and thermodynamics of ring-opening polymerization was further
established in the 1950s.
The first high-molecular weight polymers (Mn up to 105) with a repeating unit were
prepared by ROP as early as in 1976.
Nowadays, ROP plays an important role in industry such as production of nylon-6.
ROP can introduce functional groups such as ether, ester, amide, and carbonate into
the polymer main chain, which cannot be achieved by vinyl polymerization affording
polymers only with C-C main chain.
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Ring Opening Polymerization

8.  Polymers obtained by ROP can be also prepared by polycondensation in most cases,
but following controlled radical polymerization is possible in ROP, which is
difficult in polycondensation.
 Recently, development of novel monomers and catalysts has enabled polymer
chemists to control molecular weights, structure, and configuration of the polymers
precisely.
 Cyclic carbonates undergo both cationic polymerization and anionic
polymerization to afford the corresponding polycarbonates, which are expected as
biocompatible and biodegradable polymers.
 Recently, ultra high molecular weight bisphenol A polycarbonate (> 2,000 kDa) has
been synthesized by ROP of a large-membered bisphenol A-based cyclic carbonate.
 The resulted polymer can be used as engineering plastics due to its thermal stability
and high impact resistance. When the reactive center of the propagating chain is a
carbocation, the polymerization is called cationic ring-opening polymerization.
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Ring Opening Polymerization

9.  Ring-opening polymerization can proceed via
1. Radical Polymerization
2. Anionic Polymerization
3. Cationic Polymerization
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Ring Opening Polymerization

10.  With radical ring-opening polymerization, it is possible to produce polymers of the same or lower
density than the monomers. This is important for applications that require constant volume after
polymerization, such as tooth fillings, coatings, and the molding of electrical and electronic
components.
 Mechanism
In free radical ROP, the cyclic structure will undergo homolytic dissociation rather than
undergoing heterolytic dissociation (as is the case for any ionic ROP). There are two typical
mechanistic schemes in radical ROP.
Scheme1: The terminal vinyl group accepts a radical. The radical will be transformed into
a carbon radical stabilized by functional groups (i.e. halogen, aromatic, or ester groups). This
will lead to the generation of an internal olefin.
Fig.2 Radical ROP of Vinyl cyclopropane 8
Ring Opening Polymerization

11. Scheme 2: In this case, the exo-methylene group is the radical acceptor. The ring-opening reaction will
form an ester bond, and the radical produced is stabilized by a phenyl group.
Fig.3 Radical ROP of Ketene Acetal
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Ring Opening Polymerization

12. Anionic ring-opening polymerizations (AROP) are ring-opening polymerizations that
involve nucleophilic reagents as initiators.
Monomers with a three-member ring structure - such as epoxide, aziridine, and episulfide - are able to
undergo anionic ROP due to the ring-distortion, despite having a less electrophilic functional group
(e.g. ether, amine, and thioether).
These cyclic monomers are important for many practical applications. The polarized functional
group in cyclic monomers is characterized by one atom (usually a carbon) that is electron-deficient due
to an adjacent atom that is highly electron-withdrawing (e.g. oxygen, nitrogen, sulfur etc.)
Ring-opening will be triggered by the nucleophilic attack of the initiator to the carbon, forming a new
species that will act as a nucleophile. The sequence will repeat until the polymer is formed.
Fig.4 General Mechanism of Anionic Ring opening ROP 10
Ring Opening Polymerization

13. 11
 A typical example of anionic ROP is that of ε-caprolactone, initiated by an alkoxide functional group.
Fig.5 The anionic ring-opening polymerization of ε - caprolactone, initiated by alkoxide function.
Ring Opening Polymerization

14. 12
I. Initiation
Common nucleophilic reagents used for the initiation of AROP usually will include
organometals (e.g. alkyl lithium, alkyl magnesium bromide, alkyl aluminum, etc.), metal amides,
alkoxides, phosphines, amines, alcohols and water.
The monomers that undergo AROP will contain polarized bonds
(ester carbonate, amide, urethane, and phosphate) which respectively leads to the production of the
corresponding polyester, polycarbonate, polyamide, polyurethane and polyphosphate. Monomer
rings that are asymmetrically substituted will open with nucleophilic attack on the least substituted
carbon atom.
II. Propagation
The general mechanism of propagation for anionic ROP relies on the nucleophilic attack of a
propagating chain end to a monomer. Another possible mechanism for propagation is
the nucleophilic attack of an activated monomer to the growing chain end. ε-caprolactam and N-
carboxy-anhydride undergo this kind of mechanism.
III. Transfer and termination
Termination in AROP can be described as chain transfer reactions to monomer that is
available. The active centers of AROP monomers are nucleophilic and also act as bases to
abstract protons from the monomer, initiating new chains.
Thus, AROP often results in low molecular-weight polymers.
Ring Opening Polymerization

15. 13
 Cationic ring-opening polymerization (CROP) is characterized by having a cationic initiator and
intermediate. Examples of cyclic monomers that polymerize through this mechanism
include lactones, lactams, amines and ethers.
 CROP proceeds through an SN1 or SN2 propagation, chain-growth process. The predominance of one
mechanism over the other depends on the stability of the resulting cationic species.
 For example, if the atom bearing the positive charge is stabilized by electron-donating groups,
polymerization will proceed by the SN1 mechanism.
 The cationic species is an heteroatom and the chain grows by the addition of cyclic monomers thereby
opening the ring system.
Fig.6 SN1 and SN2 mechanisms of CROP.
Ring Opening Polymerization

16. 14
Fig.7 Typical Example of CROP.
Ring Opening Polymerization
Cationic polymerization is used in the production of polyisobutylene (used in inner tubes)
and poly(N-vinylcarbazole) (PVK).

17. 15
I. Initiation
The monomers can be activated by Bronsted acids, carbenium ions, onium ions, photo -
initiators, and covalent initiators.
II. Propagation
The cationic species is an heteroatom and the chain grows by the addition of cyclic
monomers thereby opening the ring system. In CROP, three mechanisms are distinguished by the
propagating species.
When the cationic species is a secondary ion, polymerization proceeds by ring expansion. This
mechanism is observed when the monomer is in low concentration. When it is a tertiary ion,
polymerization proceeds by linear growth.
The monomer can likewise be activated (i.e. cationic) and the propagation step will proceed
via electrophilic addition of the activated monomer to the growing chain.
III. Termination
CROP can be considered as a living polymerization and can be terminated by intentionally
adding termination reagents such as phenoxy anions, phosphines or polyanions. When the amount of
monomers becomes depleted, termination can occur intra or intermolecular.
The active end can "backbite" the chain, forming a macrocycle. Alkyl chain transfer is also
possible, where the active end is quenched by transferring an alkyl chain to another polymer.
Ring Opening Polymerization

18. 16
1. IUPAC, "Ring-opening polymerization“, Compendium of Chemical Terminology, 2nd ed. (the "Gold
Book") (1997). Online corrected version: (2006).
2. Jenkins, A. D.; Kratochvíl, P.; Stepto, R. F. T.; Suter, U. W., "Glossary of basic terms in polymer
science (IUPAC Recommendations 1996)". Pure and Applied Chemistry. Pg. no. 68(12): 2287–2311.
3. Dainton, F. S.; Devlin, T. R. E.; Small, P. A, "The thermodynamics of polymerization of cyclic
compounds by ring opening“, (1955), Transactions of the Faraday Society, Pg. no. 51: 1710.
4. Conix, André; Smets, G., "Ring opening in lactam polymers". Journal of Polymer Science, (January
1955), Science Direct, Pg. no. 15: 221–229.
5. www.wikipedia.com, The Free Encyclopedia.
Ring Opening Polymerization

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