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Essentials of Polymer Engineering

(Introduction to Polymers)
ChE 197
Copolymerization

What we have covered so far
• Introduction – basic concepts and definitions; classification of polymers
• Polymerization mechanisms – chain-reaction; ionic and coordination
polymerization; step-growth and ring-opening polymerization
• Chemical bonding and polymer structure – primary, secondary, and
tertiary structures
• Thermal transition in polymers – Tg and Tm
• Polymer modification – copolymerization; postpolymerization reactions;
functional polymers
• Condensation (Step-Reaction) polymerization – mechanism; kinetics;
stoichiometry; molecular weight control and distribution
• Chain-Reaction (Addition) Polymerization
• Copolymerization

Review on types of copolymers
Alternating copolymer

Block copolymer

Graft copolymer

propagation steps in copolymerization of two monomers involves four reactions) • Number of radicals to be considered equals the number of monomers • Two radicals in the copolymerization of two monomers • Composition and structure of the resulting copolymer are determined by the relative rates of the different chain propagation reactions .g.Relevant observations of copolymerization kinetics • Number of reactions involved in copolymerization of two or more monomers increases geometrically w/ the number of monomers (e.

second subscript designates the monomer .first subscript in the rate constant refers to the reacting radical .The copolymer equation Four propagation steps for copolymerization of two monomers .homopropagation or self-propagation (reactions with k11 and k22) .crosspropagation or crossover reaction Rate of disappearance of monomers M1 and M2: .

The copolymer equation M1* .a steady-state concentration is assumed for each of the reactive species M1* and M2* separately.for the concentrations of M1* and M2* to remain constant. their rates of interconversion must be equal rates of generation and consumption of these radicals are equal Dividing the top and bottom of the right side by copolymer equation Mayo-Lewis equation . .

The copolymer equation f1 and f2 are the mole fractions of monomers M1 and M2 in the feed Copolymer equation in terms of mole fractions F1 and F2 are the mole fractions of monomers M1 and M2 in the copolymer .

Types of copolymerization behavior: Ideal two types of propagating species M1* and M2* show the same preference for adding one or the other of the two monomers relative rates of incorporation of the two monomers into the copolymer are independent of the identity of the unit at the end of the propagating species Copolymer equations sequence of monomer units in an ideal copolymer is random .copolymer will contain a greater proportion of the more reactive monomer in the random sequence of monomer units -growing radicals cannot distinguish between the two monomers -composition of the copolymer is the same as that of the feed -monomers are arranged randomly along the chain .one of the monomers is more reactive than the other toward the propagating species .

Types of copolymerization behavior: Alternating -each radical reacts exclusively with the other monomer -neither radical can regenerate itself -monomer units are arranged alternately along the chain irrespective of the feed composition Copolymer equations Extreme or perfect alternation Moderate alternating behavior .

addition of the same type of monomer would continue successively until there is a chance addition of the other type of monomer .Types of copolymerization behavior: Block each radical would prefer adding its own monomer .sequence of this monomer is added repeatedly Extreme case: Both monomers undergo simultaneous and independent homopolymerization .

Reactivity Ratios of Some Monomers There are no established cases where r1r2 > 1 Product r1r2 is almost always less than unity .

a chemist decided to carry out the copolymerization reaction with a feed composed of 80% vinyl chloride.Example 1 • The reactivity ratios for the copolymerization of methyl methacrylate (1) and vinyl chloride (2) at 68°C are r1 = 10 and r2 = 0. Will the chemist achieve his objective? . To ensure that the copolymer contains an appreciable quantity (>40% in this case) of the vinyl chloride.1.

.Example 1 Solution Copolymer equation If the difference in the reactivities of the two monomers is large. it is impossible to increase the proportion of the less-reactive monomer in the copolymer simply by increasing its composition in the feed.

range of feed composition that gives copolymers containing appreciable amounts of both monomers is small except the monomers have very similar reactivities Analogy of curves with vapor– liquid equilibria in ideal liquid mixtures .Polymer Composition Variation with Feed Composition: Ideal Variation of instantaneous composition of copolymer (mole fraction. F1) with feed composition (mole fraction f1 for ideal copolymerization with the values of r1 = 1/r2 indicated).

the F1/f1 plots cross the line representing F1 = f1 crossover points = the copolymer and feed compositions are the same and copolymerization occurs without a change in the feed composition. Azeotropic copolymerizations .Polymer Composition Variation with Feed Composition: Nonideal Instantaneous composition of copolymer F1 as a function of monomer composition f1 for the values of the reactivity ratios r1/r2 indicated When r1 and r2 both less than unity.

there will be no critical feed composition Special nonideal copolymerization: both types of propagating species preferentially add monomer M1 (consecutive homopolymerization) .Polymer Composition Variation with Feed Composition: Nonideal Azeotropic copolymerization Simplification of copolymer equation Critical feed composition -If both r1 and r2 are greater than unity or if both are less than unity. critical composition lies within the acceptable range 0 < f1 < 1 -If r1 > 1 and r2 < 1 or vice versa.

the polymer will contain F1dM moles of monomer 1 and the feed will contain (M .e.Polymer Composition Variation with Conversion Consider a system initially containing a total of M moles of the two monomers and in which the copolymer formed is richer in monomer M1 that is the feed (i. F1 > f1) When dM moles of monomers have been copolymerized.dM)(f1 – df1) moles of monomer 1 material balance for monomer 1 requires that the moles of M1 copolymerized equal the difference in the moles of M1 in the feed before and after reaction Assume df1dM to be very small: Degree of conversion Use copolymer equation to solve F1 as function of f1.. and r2  Numerical or graphical integration to solve conversion . r1.

56 .53.20. r1 = 0.Polymer Composition Variation with Conversion (Analytical Solution) Analytical solution to obtain the conversion Variations in feed and copolymer compositions with conversion for styrene (M1)-methyl methacrylate (M2) with (f1)0 = 0. (f2)0 = 0.80. r2 = 0.

Dependence of Polymer Composition with Feed Composition and Conversion Dependence of the instantaneous copolymer composition F1 on the initial comonomer feed composition f1 and the percent conversion for styrene (M1)–2vinylthiophene (M2) with r1 = 0:35 and r2 = 3:10. .

the polymer formed first will be richer in butadiene while the polymer formed at the later stages of the reaction will be richer in styrene .rate of consumption of butadiene by either radical is greater than the rate of addition of styrene.Example 2 • What is the composition of the copolymer formed by the polymerization of an equimolar mixture of butadiene (1) and styrene (2) at 66°C? Which will contain more styrene — the polymer formed first or that formed later in the reaction? . .

Critical feed composition .Example 3 Estimate the feed and copolymer compositions for the azeotropic copolymerization of acrylonitrile and styrene at 60°C.

II. r1 = 0. r1 = 55. Vinyl acetate (1). III. r2 = 0. r2 = 0. 75°C. Styrene (1).01. Vinyl chloride (1). vinyl acetate (2). maleic anhydride (2). r2 = 10 .1. r1 = 0.Example 4 Plot graphs showing the variation of the instantaneous copolymer composition F1 with monomer composition for the following systems I.003.055. 60°C. methyl methacrylate (2) 68°C.

copolymers with comparable quantities of both monomers are obtainable. .Example 4 Solution -Range of feed composition that gives copolymers with appreciable quantities of both monomers is small for Cases II and III where the differences in reactivity ratios are large -Case I where the reactivity ratios are comparable.

Effect of Reaction Conditions: Monomer Reactivity inverse of the reactivity ratio is the ratio of the rate of reaction of the given radical w/ another monomer to its rate of reaction with its own monomer If k11 = 1. k12 values give the relative reactivities of monomers with respect to the reference radical .

Effect of Reaction Conditions: Monomer Reactivity Effect of substituents in enhancing monomer reactivity The effect of a second 1-substituent is generally additive - order of monomer reactivities corresponds to the order of increased resonance stabilization of the resulting radical by the particular substituent substituents with unsaturation = most effective in conferring resonance stabilization on radicals substituents that have only nonbonding electrons for interaction with the radical = weak .

Effect of Reaction Conditions: Radical Reactivity Order of enhancement of radical reactivity due to substituents is the reverse of that for the monomers .

to 20-fold .Effect of Reaction Conditions: Steric Effects Vinyldene chloride Vinyl chloride Cis-1.or α-position increases monomer reactivity .2.2dichloroethylene .addition of a second substituent to the 1. 1.disubstitution).same substituent is in the 2. the reactivity of the monomer decreases 2.or β-position (i..e.

Second substituent in 1-position increases monomer reactivity .Increasing stabilization of resulting radical .Example 5 Arrange the following monomers in the possible order of decreasing reactivity with an acrylonitrile radical. Methyl methacrylate > Methacrylate > Vinyl acetate > Vinyl methylether .

Effect of Reaction Conditions: Alternation-Polar Effects Monomer reactivity is a function of radical reactivity and vice versa As the quantity r1r2 deviates from unity (ideal behavior) and approaches zero. the tendency for alternation increases Alternation tendency increases if the substituents on both monomers exhibit different electrondonating or electron-attracting characteristics Alternation tendency is enhanced by an increased difference in the polarity of monomer pairs .

89. styrene (2).78 b. 60°C. r2 = 0. r1 = 0. 60°C. Vinyl acetate (1).002. .01. Maleic anhydride (1). Butadiene (1). 60°C. r2 = 55 c.032. r1 = 0. Monomer pair (c) has the highest alternating tendency. r1 = 1.Example 6 Which of the following pairs of monomers will most probably form an alternating copolymer? a. Styrene (2). isopropenyl acetate (2). r2 = 0.

Q2 .degrees of polarity of the radical and monomer.reactivity of radical M1*.reactivity of monomer M2 e1 and e2 .The Q-e scheme The Q-e scheme is an attempt to express free radical copolymerization data on a quantitative basis by separating reactivity ratio data for monomer pairs into parameters characteristic of each monomer P1 . respectively Monomer and its radical have the same e value Negative values of e indicate electron-rich monomers Positive e values indicate electron-poor monomers .

The Q-e scheme Criticisms on the Q-e scheme 1. No justification for assuming the same e values for the monomer and the radical derived from it 2. they vary with the monomer to which the monomer is paired . Q and e values for a particular monomer are not unique.