Block copolymerization of Styrene and MMA (Anionic Polymerization) Prepared By: Muhammad Farooq Matriculation # 764316

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INTRODUCTION Polymerization reaction can be classified into two major categories that further have their sub categories. Two major categories are as follows: Step Growth Polymerization Chain Growth Polymerization

In this experiment, our focus is on chain growth polymerization and more specifically on anionic polymerization, which is further class of Chain growth polymerization. If we compare the anionic polymerization with its very closely resembling reaction technique, which is free radical polymerization we will be able to distingue both of them as they have some dissimilarities. More preciously, an Anionic polymerization involves an attack of nucleophile (negatively charged specie) on the electron withdrawing monomer sites. Another difference between the free radical polymerization and anionic polymerization is that in free radical polymerization the active centers depend only on the nature of the monomer and are generally independent of the reaction medium. Where as in ionic polymerizations reactions involves the successive insertions of monomers between a macromolecular ion and an attached counterion, Successful ionic polymerizations must be carried out at controlled, inert conditions than normal free-radical syntheses. If we compare the rate of polymerization, ionic polymerizations are largely much faster than the free-radical polymerization and this is mainly because termination by combination of active centers will not occur in anionic polymerization as it occurs in free-radical systems. Macro ions with the same charge will repel each other and concentrations of active centers can be much higher in ionic than in free-radical polymerization systems. Here are the few prominent characteristics of anionic polymerization that makes it different from free radical polymerization Table. 1 Comparison of Anionic Polymerization with Free Radical Polymerization Reaction Feature Initiation Propagation Termination Initiator Choice Reaction Medium Anionic Polymerization Rapid Slow Absent Major Effect Major Effect Free radical Polymerization Slow Fast Yes No Effect Less Effect

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REACTION MECHANISM Initiations used in anionic polymerization are all electron donors of varying base strengths. The initiator type required for a particular polymerization depends on the ease with which an anion can be formed from the monomer, which acts as an electron acceptor in anionic polymerizations. In our experiment we used n-Butyllithium, 1.6M solution in hexanes as initiator, which forms its ions.

Nucleophilic attack is essentially addition of a negatively charged entity to the monomer and involves mainly alkali metal alkyls, metal alkoxides, metal amides, and Grignard reagents. Initiation

H3C H3C

H3C

H3C

H3C

Reaction Scheme 1.

Initiator attacks the double bond in styrene monomer, due to resonance electron delocalization

Propagation

Reaction Scheme 2.

Propagation of polystyrene growing chain

Upper reaction scheme 2. is valid for homo polymerization of Styrene but for Block copolymerization of PS with MMA, we need to add our second monomer but if we directly add the MMA then the electron present at polystyrene will attack the MMA carbonyl group.

Reaction Scheme 3.

Methyl Methacrylate Monomer undergoing undesired propagation

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1,1-diphenylethylene (DPE) To avoid this self-propagation 1, 1-diphenylethylene (DPE) which reacts with the polystyrene growing chain and forms a new active center. Diphenyl ethylene will initiate MMA segments and block copolymerization will occur.

Reaction Scheme 4. 1,1-diphenylethylene (DPE) reacting with styrene growing chain forming new active center

Bu

C C O

Bu

C C O

OCH3
Propagation

OCH3

Cl

Si Bu
n

Si

C m C

C O

Bu

C m C

C O

O C

OCH3

OCH3

Termination/ Quenching

O C

OCH3

OCH3

Reaction Scheme 5. Propagation and quenching of growing polymer chain of MMA block

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EXPERIMENT Following values of monomers, initiator, capping agent and quenching agent were consumed. Table 2 Sr. No 1 2 3 4 5 PROCEDURE 1. Two 25ml schlenk flasks loaded with magnetic stirrer were filled with 10 mL of dry toluene 2. Separate schlenk flash was used to dissolve 0.45 grams of 1,1-diphenyl ethylene in 5 ml toluene 3. Earlier prepared flasks with dry toluene where placed in ice bath and temperature was maintained at -78 C using dry ice. 4. Flasks were given nos 1 & 2 5. In flask 1 we injected our styrene monomer of 1mL 6. In flask 2 we injected our styrene monomer of 2 mL 7. 0.175mL of BuLi and 4mL od DME (dry) was added in both the flasks 1 & 2 8. After 30 minutes, 1.45 ml of 1,1-diphenyl ethylene was added to flask 1for capping the polymer 9. After 10 minutes 0.95 ml MMA was added in flask 1 for block copolymerization 10. Solution in flask 1 changed to yellow color 11. Water was used to quench the reaction in both flask 1 and flask 2. We did not used Trimethylesilyl chloride. Polymer residual was precipitated in 150 ml methanol, filtration, washing with methanol and then dried in vacuum at 50 C Table 3. Polymer Yield Polymer Block Copolymer Polystyrene Amount After Drying 1.56 G 0.7 G Mass In Flask 1.79 G 1.82 G. Regent & material Styrene Methyl methacrylate (MMA) Dimethoxyethane (DME) 1,1-Diphenyl ethylene n-BuLi (1.6M in hexane) Molar Mass (g/ mol) 104.15 100.121 g/mol 90.12 g/mol 180.25 g/mol 64.06 Block Copolymer 1ml 0.95 ml 4 ml 1.45 ml 0.175 ml Homo Polymer 2ml 0 4 ml 0 0.175 ml

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Answer.1 The degree of polymerization for anionic polymerization is defined as the concentration of monomer consumed divided by the total concentration of initiator.

at 100% conversion

In order to calculate the degree of polymerization in homo polymerization we will take the monomer concentration of 2ml and 5mole % of initiator was consumed. In copolymerization we used styrene monomer and methacrylate monomer of I ml and 0.95 ml which ultimately gives us the same value of monomer as a whole as used in homo polymerization so we will end up having same degree of polymerization which is ///////////

Answer.2 The reason behind calculating the degree of polymerization from Monomer Initiator ratio is because anionic polymerization will carry on until all the monomer is consumed, and we can still grow the chain by adding more monomer at any stage of the reaction. Hence we need one initiator to propagating a one growing chain so this is one is to one ratio. Since we have this knowledge we can calculate the degree of polymerization at any instant in anionic polymerization. Thus a plot of Mn vs. % Conversion is linear for a living polymerization Mn = Dpnx Mo Mo = Mass of the Repeat Unit Answer.3

Differential scanning calorimetry is a characterization technique, which is very useful to proof a block copolymer or a polymer blend. In case of a copolymer DSC plot will give us two peaks for glass transition temperatures, which will indicate that two blocks are presents in a polymeric structure. Whereas Polymer blends for example based of polystyrene (Tg = 100C) and poly (dimethylphenylene oxide) (Tg = 210C) are miscible in all proportions. DSC thermal profiles of this blend compositions show only a single glass transition temperature, located somewhere between 100C and 210C. Therefore, it is clear from the fact that blends have one Glass transition temperature in DSC plot whereas Copolymers have two Tgs.

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Answer.4 1, 1-diphenylethylene is used as capping agent in order to avoid the following self-propagation reaction.

1, 1-diphenylethylene (DPE) reacts with the polystyrene growing chain and forms a new active center. Diphenyl ethylene will initiate MMA segments and block copolymerization will take place.

References

George Odian, Principles Of Polymerization, Fourth Edition, pp 372,412-417

Alfred Rudin, The Elements Of Polymer Science And Engineering Second Edition, pp 303-13

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