PMMA

Presented By:-
Anshul Gautampurkar
M.Tech. (Polymer Engineering and Technology)
 Introduction

 Poly- means “many”

 Mer- means “unit”
 Definition- “A large molecule built up by repeating units joined by the
covalent bonds”.
 Polymers; not macromolecules.
 Monomer- “A molecule which can bind chemically with other molecules to
form a polymer”.
 Some examples of Polymer : Monomer systems.
 Degree of Polymerization
Functionality

 Definition
 Examples:
 Ethane CH2=CH2

 Ethylene OH
 Acetylene
 Phenol
 1,3 Butadiene
CH2=CH-CH=CH2
 Ethylene Glycol
 Glycerol
Importance of Functionality

 Relation of Functionality and Polymerization in homo-polymers.

 Concept of average functionality in co-polymers.
 Equal reactivity of functional groups.
 Reaction between pthallic anhydride and glycerol if the molar ratio of the
two reactants is 3:2.
 Carothers Equation :-
p= 2/f(1-1/Xn)
Classification of Polymers:

 Polymers can be classified on the basis of:

 Source
 End-use Application
 Response towards heat and pressure cycles
 Line Structure
 Techniques of Polymerization
 Type of repeating units
 Tacticity
Crystallinity

 Packing of the polymer chains.

 It also depends on the physical conditions, rate of cooling and chemical
nature of the polymers.
 Depends upon the molecular symmetry and structural regularity or
irregularity.
 Polymers are not completely crystalline though and polymers having high
crystallinity (>60%) are termed as crystalline polymers.
 The polymer molecules can also be oriented by inducing stress (cold
drawing from melt)
Molecular Weight and Molecular
Weight Distribution

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Simple Molecules Long Chain Molecules
Mono-dispersed Poly-dispersed
Structure-Property Relationship

 Factors on which the properties of the polymer depend are:-

 Molecular Weight
 Linearity and Non-linearity of polymer chains
 Molar Cohesion, Polarity and Crystallinity
 Temperature
 Nature of Intermolecular forces (Cohesive Energy Density)
Polymerization Techniques

 Condensation Polymerization
 Also known as step-growth polymerization
 Nylon 6,6, Polycarbonate, Polyurethane are condensation polymers.
 Calculation of gel point for bi-functional systems using Carothers
Equation.
 Step growth polymerization should be carried out till very high
conversion, ie, 98%, since degree of polymerization>50 is required for a
polymer to be widely used.
Polymerization Techniques

 Addition Polymerization
 Also known as Chain Growth Polymerization.
 Unsaturated monomers are converted into polymers.
 Is a fast reaction.
 Three steps are involved in the process:- Initiation, Propagation and
Termination.
 Initiator Efficiency
 Trommsdorff effect
Polymerization Techniques

 Ionic Polymerization
 Anionic Polymerization- Used for polymerization of monomers having
electron withdrawing substituents.
 Amides, alkoxides, alkyls and aryls of alkali metals and different
Grignard reagents have been used as catalysts for anionic polymerization

 Cationic Polymerization- Used for polymerization of monomers having

electron releasing substituents.
 Protonic acids such as H2SO4 and HClO4 or Lewis acids such as BF3,
SnCl4, AlCl3, Al,Br3, TiCL4, etc. become effective along with a co-
catalyst(water, alcohol, organic acids etc.) and act as proton donors.
Coordination Polymerization
Methods of Free Radical Polymerization

 There are four commonly used methods for free radical

polymerization
 1. Bulk polymerization
 2. Solution polymerization
 3. Suspension polymerization
 4. Emulsion polymerization
 BULK POLYMERIZATION

 The simplest method of polymerization where the reaction mixture contains

only the monomer and a monomer soluble initiator.
 Example
 PMMA
 ADVANTAGE

 Advantage of the high concentration of monomer result in

 1. High rates of polymerization
 2. High degree of polymerization
 3. High purity of product
 4. High molar mass polymer are produce
 DISADVANTAGE

 Increase in the reaction viscosity with conversion.

 *difficulty in removing heat.
 *autoacceleration
 *if the polymer formed is insoluble in the monomer (such as acrylonitrile,
vinyl chloride) ==> precipitating of the polymer and we can not apply the
kinetics.
 SOLUTION POLYMERIZATION
 This method is used to solve the problems associated with the bulk
polymerization because the solvent is employed to lower the viscosity of the
reaction, thus help in the heat transfer and reduce autoacceleration.
 BUT
 The disadvantage of solvent presence is
 1. Reduce monomer concentration which results in decreasing the rate of
the reaction and the degree of polymerization.
 2. Solvent may cause chain transfer.
 3. Clean up the product with a non solvent or evaporation of solvent.
SUSPENSION POLYMERIZATION
 This method is used also to solve the problem of heat transfer.

 It is similar to bulk polymerization where the reaction mixture is

suspended as droplets in an inert medium.

 Monomer, initiator and polymer must be insoluble in the

suspension media such as water.
EMULSION POLYMERIZATION
 This is similar to suspension polymerization except that the initiation is soluble
in suspension media and insoluble in the monomer.

 The reaction product is colloidally stable dispersion known as latex.

 The polymer particles have diameter in the range of (0.05 - 1  m) smaller

than suspension.