A. Different Polymerization processes: 1. Step growth polymerization 2. Chain growth polymerization a. Free radical polymerization b. Ionic polymerization c.

Coordination polymerization Step-growth polymerization is a polymerization process that involves a chemical reaction between multifunctional monomers molecules. In a step-growth reaction, the growing chains may react with each other to form even longer chains.

PPO is a heterochain homopolymer, which is created by a free-radical, step-growth, oxidative-coupling polymerization of 2,6-dimethylphenol and oxygen.

Chain growth polymerization is a polymerization technique where unsaturated monomer molecules add on to a growing polymer chain one at a time. It is basically a three-stage process, involving initiation of active molecules, their propagation and termination of the active chain ends.

Thiophene polymerization using an external initiator

o Free radical polymerization is a method of polymerization by which a polymer is formed from the successive addition of free radical building blocks.

o Ionic polymerization is a polymerization in which the propagating species is a long chain cation or anion. Reactions are typically carried out in solvents of low or moderated polarity and generally proceed much faster than radical polymerization.

Anionic polymerization

Cationic polymerization

o Coordination polymerization is a form of addition polymerization in which monomer adds to a growing macromolecule through an organometallic active center.

B. Characteristics of Step-growth and Chain growth polymerization a. Differences:

Step-growth polymerization o It uses multiple and very different reaction mechanism Reactions at carbonyls Aromatic Nucleophilic Substitution; Aromatic Electrophilic Substitution Michael type additions Oxidative coupling reactions, etc. o Products from step usually have heteroatoms (O,N,S) in main chain o Component reaction Initiation, Propagation, Termination identical in rate and mechanism o Polymer growth Coupling can occur between any 2 species (monomer, oligomer, or polymer) all reactive. Slow, random growth of MW, very high conversion required before ANY polymer chains are formed. All species reactive throughout polymerization o Monomer concentration Compared with chain final Xn~small ; Mn~40-60k o Heat of polymerization Not very exothermic; some endothermic, most are heated o Reaction mixture At any time t, all molecular species present in calculable distribution. Chain growth polymerization o Component reaction Initiation, Propagation, Termination are distinct steps with different rates and mechanisms

o Polymer growth Occurs by random addition of M to a very small number of active chains. Rapid increase In MW, high polymer forms immediately. Only very few chains grow at any point in time. Mostly monomer and inactive chains. o Monomer concentration Xn, Mn very high Mn~105 106 common o Heat of polymerization Very exothermic o Reaction mixture Only M and high polymer, and ~ 10-8 mol/L growing chains. b. Similarities: All chains reactive throughout polymerization (both chain ends) Functional group reactivity does not change with MW Slow increase in MW HMW only after p > 99% Most step polymerizations proceed with production of volatile by-products Both have initiation, propagation, and termination c. Advantages and Disadvantages: i. Step-growth polymerization Advantages There is not heat generated during step growth polymerization so heat transfer is not a problem. High Molecular Weight Excellent Optical Clarity and color Catalyst is not necessary Not necessarily need an initiator Disadvantages By-product is produced Synthetic solvent is used ii. Chain-growth polymerization Advantages Organic solvent is used No by-products Disadvantages Catalyst is necessary Is very exothermic so energy for heat control is high

 Initiator is necessary Low molecular weights compared to step-growth 1. Free radical polymerization a. ADVANTAGES i. Relatively insensitive to trace impurities ii. Reactions can occur in aqueous media iii. Can use chain transfer to solvent to modify polymerization process b. DISADVANTAGES i. Structural irregularities are introduced during initiation and termination steps ii. Chain transfer reactions lead to reduced molecular weight and branching iii. Limited control of tacticity iv. High pressure often required 2. Anionic Polymerization a. ADVANTAGES i. Narrow molecular weight distribution ii. Limited chain transfer reactions iii. Predictable molecular weight average iv. Possibility of forming living polymers v. End groups can be tailored for further reactivity b. DISADVANTAGES i. Solvent-sensitive due to possibility of chain transfer to the solvent ii. Can be slow iii. Sensitive to trace impurities iv. Narrow molecular weight distribution 3. Cationic polymerization a. ADVANTAGES i. Large number of reactive monomers ii. High reactivity of active site, therefore quick reaction times iii. Reactions proceed rapidly even at low temperatures b. DISADVATAGES i. High reactivity leads to undesirable side reactions ii. Requires a very high purity reaction medium iii. Chain transfer leading to low molecular weight and high branching iv. Kinetic mechanisms are poorly understood

v. Reaction often does not go to completion 4. Coordination polymerization a. ADVANTAGES i. Can engineer polymers with specific tacticities based on the catalyst system ii. Can limit branching reactions iii. Polymerization can occur at low pressure and modest temperatures iv. Otherwise non-polymerizable monomers(e.g., propylene) can be polymerized b. DISADVANTAGES i. Mainly applicable to olefinic monomers