Polymerization of Methyl Methacrylate

Experiment has many facets:

a. introduction to polymers and polymerization

b. use of inert atmosphere methods
c. characterization of polymers

Polymers and Polymerization

monomers - dimers - trimers - oligomers (n = 5-20; low mol. wt.) - polymers

trimers and tetramers often cyclic

H
O H H H H H
H2CO H C C
H C C
O O O O
C
n
H H

polymers - high molecular weight

linear polymers polyethylene (PE)

R
R R R R

branched polymers - PE (low density) cross-linked - greater rigidity and stability

e.g., PS + 1-3% DVB

ladder polymers

more regular than cross linking

copolymers -

random -A-B-B-B-A-B-A-A-B-

regular alternating - -A-B-A-B-A-B-A-B-

block copolymers - -A-A-A-A-A-B-B-B-B-

(also tri-blocks)

Example of alternating copolymer from CO + C2H4

O O
polyketone
n
O

thermoplastic - substance that is rigid

glass at low T and rubbery elastomer at high T

transition occurs at Tg, glass transition temperature

Types of polymerizations and types of polymers

a. condensation (linking of units comes with extrusion of small

(step growth) molecule like H2O)

b. addition (monomers add on to the ends of growing chains)

(chain growth)

c. ring opening (cyclic structure cleaved and each end binds with
other units)

In step growth, any molecule (monomer, dimer, trimer, etc) can react with any other
molecule

In chain growth - sequential growth onto ends of initiated chains.

Variations in polymer weight at different stages in polymerization characteristic of each

type of growth.

Condensation Polymers

polyesters, polyamides, polycarbonates

Examples
O O
HO-R-OH + HOOC=R'-COOH → O R O C R' C
n
 COOH
O
OH C C
+ HO O
O
O
COOH n
p-terephthalic acid
film base; soda bottles

H2N COOH
NH2 + HOOC

hexamethylene diamine adipic acid

H O
N C
N C Nylon 66

H O n

ladder polymers also

O O H 2N NH2 N N
+
O O H 2N NH2
N N
n

Many examples: see Contemporary Polymer Chemistry by Allcock and Lampe

High MW polymers need high purity and equal concentrations of both components.

Ring formation always a competing reaction

A A B B BA AB BA AB

A A
B B or "dimer"

Addition Polymers - chain growth

R
n
R R R

differences in R; differences in mechanism of growth; differences in stereoregularity

R = H, CN, Cl, Ph, COOR, etc.
In all cases, an initiator is needed
 propagating chain radical

cationic

anionic

Stereoregularity of polymers is an important feature that affects polymer properties and is

determined by the mechanism of polymerization.
atactic
(random)
R R R R R

syndiotactic
(alternating)
R R R R

isotactic
R R R R

The question of stereoregularity is central to the experiment to be conducted. We will

probe this question by NMR.

Addition polymers formed by radical mechanism

R" R" R"
polystyrene (R = Ph, R" = H)
polyvinyl chloride (R = Cl, R" = H)
poly methyl methacrylate (PMMA; R = R R R n
COOMe, R" = Me)
O

radical initiators C
peroxides
Ph O
2
N N
C C
AlBN N N

redox agents

MMA + AlBN PMMA

40˚
200 : 1 24 h

Addition polymers formed by anionic mechanism

polystyrene
PMMA
polyacrylonitrile

Anionic polymerization is good for polymers with electron withdrawing groups (EWG).
 Initiation by the addition of an anion to monomer.
EWG
R'
MR' + M+
EWG
H H

In our experiment we use Li+ _

Since the propagating species has charge, the behavior of the polymerization should be
sensitive to solvent and how well the propagating charge is stabilized.

Addition polymers formed by cationic mechanism

OR poly vinyl ethers

CH3 substituents need to

poly(isobutylene)
stabilize propagating
CH3 charge

poly(butadiene)

polystyrene derivatives

R'

Possible initiators: strong acids - H2SO4, HCl

R
Lewis acids - BF3, BF3⋅OEt2,
TiCl4 from In +
In R
Another mechanism of chain growth polymerization involves catalysis by a metal center

Ziegler-Natta TiCl4 + R3Al in hydrocarbon solvent

C2H4 → linear PE (HDPE) room temperature and atmospheric pressure

Handle under N2. Many formulations of catalyst, e.g.

Cl
Cp2TiCl2 + Et3Al → Cp2Ti Al
Cl

The mechanism of reaction: condensation/insertion

R+ R+ +
M + M M R
Current efforts focus on:

1. single component catalysts (cationic) with non-coordinating anions

For example, CF3

+ _
Me
Zr B

vacant site CF3

4

other metals also: Ni and Fe

2. stereoregularity - important for polypropylene

Cl
Zr + >99.5% isotactic PP
MAO
Cl

partially
hydrated
Me3 Al

Cl
+ atactic PP
Zr MAO
Cl

partially
hydrated
Me 3Al

Cl
Zr + syndiotactic PP
Cl MAO

partially
hydrated
Me3Al
 3. MW distribution and linearity of polymer.

A key consideration in all chain growth mechanisms concerns termination and chain
transfer.

R
M
R M
M R

β-elimination
H
M +
R

chain transfer
H
M
M

Living polymerization - chain growth termination does not occur and chain growth
continues as long as monomer is present.

In a radical polymerization chain transfer occurs by H atom abstraction - 2˚ radicals are

more stable than 1˚.
 2 P CH2 P H2C CH2 P
termination

P P CH3 + P CH P
P CH2 + P CH2

branched polymer

Ring Opening Polymerizations

O H+
O
n

O
O
C
N
N
N H n
caprolactam Nylon 6

Ru + Mo catalysts Grubbs; Schock

R'

R
Cl P P
P
R Cl
Cl R Ru C
NBE
Cl R' Ru
Ru C
C R' P Cl
l P
P

Molecular Weight Distributions

Monodisperse - narrow range of n; similar MW's

Polydisperse - wide range of n

Measurement of MW's

Osmometry - number average MW Mn

Mn = 1
N Σi
Ni Mi

# of chains with mass M i

total # chains

Light scattering - weight average MW Mw

Mw = 1
M Σi
mi Mi

total mass of molecules with mass M i

total mass

Σ
i
N i M 2i
Mw =
Σ
i
Ni Mi

A concern to us in this experiment is the stereoregularity of the polymer.

For anionic polymerization

Me
Me
In- + COOMe In COOMe

MMA

Me
Me
COOMe
In
COOMe

Stereoregularity and tacticity are determined by NMR

toluene - isotactic
THF - syndiotactic

NMR is very useful in revealing the local geometry about each tertiary C atom. This is
because the 13C chemical shifts depend on the local environment.
 Analyze each α-Me carbon in terms of its local environment by looking at triads, pentads
and heptads. (E = COOMe)

Me Me Me
mm
E E E

Me E Me
triads rr
E Me E

Me Me E
mr
E E Me

13C chemical shift of α-Me in CDCl3

Me Me E E E
pentad example
E E Me Me Me

mrmm

E E E Me E Me E
heptad example
Me Me Me E Me E Me

mmrrrr

See Ferguson, R. C.; Ovenall, D. W.; "High Resolution NMR Analysis of the Stereochemistry of
Poly(methyl methacrylate)," Macromolecules 1987, 20, 1245-1248.