Polymer Synthesis

Dr. P.R. Shukla DDU

Polymer Synthesis
Preparation of Polymers from monomers can be by: 1. Addition Polymerization
Free radical polymerization Cationic polymerization Anionic polymerization Coordination polymerization Ring Opening polymerization

2. Condensation Polymerization

Addition Polymerization
Addition or chain reactive polymerization involves chain reactions in which the chain carrier may be a reactive substance with one unpaired electron called a free radical, or may be a cation, an anion, or a coordination complex. The free radical or ion is capable of reacting to open the double bond and add to it, with an electron or an ion remaining unpaired. In a very short time, many more monomers add to the growing chain.

Addition Polymerization
Under correct conditions of temperature and pressure, and with the aid of catalysts and promotors, the monomers simply add onto themselves like links in a chain. Examples polyethylene, polypropylene

Addition Polymerization
Three Steps:
1. Initiation 2. Propagation 3. Termination

Free Radical PolymerizationInitiation

The initiator generates free radicals as the active species through its homolytic thermal decomposition. A typical redox system is that of ferrous ion and hydrogen peroxide. Another widely used redox system is of persulfate with thiosulfate or biosulfite as reducing agents.

Termination terminology
Chain growth stops by bimolecular reaction of two growing radicals: termination A terminator: another free radical Forms a stable molecule with n mer units Recombination: the termination step Combination: *Mi + *Mj Mi+j Disproportionation: *Mi + *Mj Mi + Mj Obtaining a monomer like double bond Hydrogen Abstraction: obtaining a hydrogen atom with unpaired electron

The Chain Transfer

Often the growing chain terminates before it fully grows by interaction with a small molecule, say RH, in such a way that a portion of the small molecule terminates the active chain and at the same time produces a new radical R. The chain transfer reaction can be shown as follows: ----M* + RH ----MH + R*

The Chain Transfer

The chain transfer can be done by the monomer itself, through solvent, from initiation, from initiator, or from polymer. It can also be intentionally done by adding substances called chain transfer agents or chain modifiers. The chain transfer during the polymerization leads to low molecular weight polymers (sometimes desirable, at other times undesirable)

Cationic Polymerization - Initiation

Cationic polymerization involves initiators which produce a cationic species that interacts with the monomer. Initiators used include Lewis acids such as BF3, AlCl3, etc. Protonic acids like sulfuric acid, perchloric acid, phosphoric acid also act as initiators.

Anionic Polymerization - Initiation

Anionic polymerization uses initiators which produce anionic species. Organoalkali compounds like butyl lithium, electron transfer reagents like disodiumnaphthalene complex, and NaNH2 are common initiators for anionic polymerization.

Coordination Polymerization
The reactive species in a coordination polymerization is a coordination complex. Ziegler-Natta polymerization is a particular case. These catalysts involve a variety of transition metal complexes. These complexes are usually based on Ti, V, or Cr type metals and organometallic compounds like triethyl aluminium.

Propagation
The newly generated active species adds to another monomer, in the same manner as the initiation step. Monomers simply add onto themselves like links in a chain

Termination
The termination step is one where the growing chain with active species reacts with other growing chain or by spontaneous decomposition of the active site. In free radical polymerization, termination follows either coupling or disproportionation mechanism.

Termination
In cationic polymerization, termination occurs by anion attachment or by proton abstraction. In anionic polymerization, termination does not take place by itself and the living chains are made to terminate, e.g. by adding ammonia. In coordination polymerization, termination is by an active hydrogen compound; by transfer with monomers; and by spontaneous internal transfer.

Ring Opening Polymerization

Some polymers can be prepared by reactions involving ring opening. Few typical examples of monomers for ring-scission polymerization are cyclic ethers, cyclic anhydrides. The polymerization of ethylene oxide leading to a high molecular weight polyethylene oxide (PEO) can be accomplished by ring opening polymerization. The monomer is added to form a chain (chain polymerization), the polymer growth is through step wise addition, and thus molecular weight of the polymer increases during the course of reaction (polycondensation).

Autoacceleration
Trommsdorff effect In radical polymerization we speak about: 1) low conversion, i.e. polymer chains are in dilute solution (no contact among chains) 2) intermediate conversion, i.e. the area in between low and high conversion 3) high conversion, i.e. chains are getting highly entangled; kp decreases. Somewhere in the intermediate conversion regime: * polymer chains loose mobility. * Termination rate decreases * Radical concentration increases * Rate of polymerization increases * Molar mass increases This effect is called: gel effect, Trommsdorff effect,or auto-acceleration

In the polymerization of MMA this occurs at relatively low conversion.

Techniques of Polymerization
Bulk polymerization Solution polymerization Precipitation polymerization Suspension (or pearl) polymerization Emulsion polymerization

Polymerization techniques
Sometimes for one monomer several techniques of polymerizing are available. Choice of a specific technique depends on a number of factors: Kinetic / mechanistic factors related to chain length, chain composition Technological factors e.g. heat removal, reaction rate, viscosity of the reaction mixture, morphology of the product Economic factors; production costs, environmental aspects, purification steps etc.

Polymerization techniques
Homogeneous systems Bulk polymerization Solution polymerization Heterogeneous systems Suspension polymerization Emulsion polymerization Precipitation polymerization Polymerization in solid state Polymerization in the gas phase

Bulk Polymerization
The polymerization reaction is carried out within the monomer itself. The reaction is catalyzed by additives or under the influence of heat or light. Polymer is obtained as a powdery porous solid. The polymer formed is usually pure Examples vinyl chloride, vinyl acetate, and acrylic esters

Bulk polymerization
Polymerization of the undiluted monomer. Viscosity increases dramatically during conversion. Heat removal and hot spots Advantages * Pure products * Simple equipment * No organic solvents Disadvantages * heat control * dangerous * molecular weights very disperse

Applications Polymers through step reactions (nylon 6) PMMA-plates

Solution Polymerization
When both the monomer and the polymer produced are soluble in a suitable solvent, the polymerization reaction is carried out with the monomer in solution. Solution polymerization is mainly applied when solutions of polymers are required (for ready made use) for technical applications, e.g. as lacquers, paints, adhesives.

Solution polymerization
Monomer dissolved in solvent, formed polymer stays dissolved. Depending on concentration of monomer the solution does not increase in viscosity. Advantages * Product sometimes directly usable * Controlled heat release Disadvantages * Contamination with solvent * Chain transfer to solvent * Recycling solvent

Applications Acrylic coating, fibrespinning, film casting

Precipitation Polymerization
In such a polymerization reaction, the monomer is soluble in the solvent, and the polymer precipitates out as a result of polymerization (polymer being insoluble in solvent). The so precipitated polymer can be separated in the form of a gel or powder by centrifugation or simple filtration. Polyethylene, polyvinyl esters, polyacrylic esters are obtained commercially with hydrocarbons as solvents. Polyacryonitrile is prepared using water as solvent.

Suspension Polymerization
The monomer containing initiator, modifier etc. is dispersed in a solvent (generally water) by vigorous stirring. For a stable suspension of monomer in the solvent, some stabilizers are added. The polymerization takes place within the dispersed (or suspended) monomer particles and the agglomeration of which is prevented by stabilizer. After the reaction is completed, the polymer is separated by centrifugation or filtration, washed, and dried.

Suspension polymerization
Water insoluble monomers are dispersed in water. Initiator dissolved in monomer. Stabilization of droplets/polymer particles with nonmicelle forming emulsifiers like polyvinylalcohol or Nacarboxymethylcellulose. Equivalent to bulk polymerization, small droplets dispersed in water. Product can easily be separated, particles 0.01-1mm. Pore sizes can be controlled by adding a combination of solvent (swelling agent) and non-solvent. Viscosity does not change much.

Suspension Polymerization
Advantages Disadvantages * Heat control simple * Contamination with * Product directly stabilizing agent usable * Coagulation possible * Easy handling

Applications Ion-exchange resins, polystyrene foam, PVC

Emulsion Polymerization
The liquid monomer is dispersed in an insoluble liquid, which in turn gives an emulsion (usually in water). So the monomer in water emulsion, containing catalyst and stabilized by emulsifying agents (e.g. by surface active agents), is then used as the polymerizing mixture.

Emulsion Polymerization
Polymerization takes place within the surfactant micelles (size about 10 nm) which grow in size at the expense of the dispersed monomer droplets (size about 1000 nm). In the end, a latex (or a polymer colloid) with dispersed polymer (size about 100 nm) is left. The polymer is then isolated by evaporation of water in spray dryer, or by coagulation of the polymer latex, filtration and drying.

Emulsion Polymerization
A micelle forming emulsifier is used. Initiator is water soluble. The formed latex particles are much smaller than suspension particles (0.05-2 m). Kinetics differ considerable from other techniques. Polymer is formed within the micelles and not in the monomer droplets.

Emulsion Polymerization
Advantages Disadvantages * Low viscosity even * Contamination of at high solid contents products with additives * Independent control * More complicated of rate and in case of water molecular-weight soluble monomers

* Direct application of complete reactor contents

Condensation Polymerization
In condensation, or step-reaction polymerization, two reactive monomers join together with the release (i.e. condensation) of a molecule of water. Examples:
Polyester PET (polyethylene terephthalate) Terephthalic acid + ethylene glycol PET Polyamide Nylon Adipic acid + hexamethylene diamine PA

Phase Techniques in Polycondensation

The polycondensation involves the reactions of the functional groups and therefore the reactants need to be in the fluid phase. This can be achieved either by melting the reacting monomers (melt polycondensation) or by dissolving them in a suitable inert common solvent (solution polymerization).

Phase Techniques in Polycondensation

A third technique is called interfacial polycondensation. This technique uses the solutions of the two monomers prepared separately in two solvents immiscible with each other. When these two solutions are brought in contact, the polycondensation reaction begins at the interface separating the liquids.

Kinetics of Polycondensation
A simple relation, called the Carouthers equation, exists between the average degree of polymerization DP of the polycondensation polymer at time t, and the extent of reaction p. DP = 1/ (1-p)

Kinetics of Polycondensation
Question: What is the molecular weight of a polymer prepared by the self polycondensation of OH--COOH if 99.50 of the functional groups react?

Kinetics of Polycondensation
Answer: Repeat unit (O--CO)n p=0.995; DP = 1/(1-p) = 200 Molecular weight of repeat unit is O--CO = O + C6H4 + C =16 + 72+ 4+ 12+ 16 = 120 Molecular weight of polymer = 120 x DP =120 x 200 = 24,000 gmol-1