Mechanisms of polyemerization

(Note: Polyethylene falls under the category of chain-growth polymerization)

POLYMERIZATION REACTIONS

Types of Polymerization

Polymerization can proceed according to two different mechanisms, referred

to as chain-growth and step-growth polymerization. In chain-growth

polymerization (also called addition polymerization) reaction occurs by

successive addition of monomer molecules to the reactive end (e.g. a radical

end) of a growing polymer chain.

The most important group of chain-growth polymerizations is

polymerization of vinyl monomers such as ethene, propene, styrene, and vinyl

chloride:

nCH2= CHX → - (-CH2-CHX)n –

in which X = H, CH3, C5H6, or Cl, respectively.

An initiator or a catalyst is usually required to start the chain-growth reaction.

Step-growth polymerization involves the reaction between the

functional groups (HO-, HOOC-, etc.) of any two molecules (either monomers

or polymers). By repeated reaction long chains are gradually produced. Most

commonly, the reactions are condensation reactions resulting in the

elimination of a small molecule like water or methanol. Examples are the

production of poly (ethene terephthalate) by reaction of ethene glycol with

either terephthalic cid or dimethyl terephthalate (see Scheme 1).

Scheme 2 shows the principle reactions taking place when two

different functional groups are present on the same molecule (indicated as

AB. e.g. in the production of caprolactam), and when two different molecules
each contain two identical functional groups (indicated as AA and BB, e.g. in

production of PET).

O O
|| ||
n HO-C-- ___ C-OH + n HO-CH2-CH2-OH →

terephthalic acid ethene glycol

O O
|| ||
-O-CH2-CH2-O-C- -C- + 2n-1 H2O

poly-ethene terephthalate

O O
|| ||
n H3C-O-C - ___ C-O-CH3 + n HO-CH2-CH2-OH →

dimethyl terephthalic ethene glycol

O O
|| ||
-O-CH2-CH2-O-C- -C- + 2n-1 CH3OH

poly-ethene terephthalate

Scheme 1 Reactions for the production of polyethene terephthalate (PET)

In chain-growth polymerization, a high molecular weight product is

produced right from the start, while the monomer quantity deceases slowly

with time. In contrast, in step-growth polymerization there is a slow increase in

average molecular weight of the product. The molecular weight is usually not

as high as in chain-growth polymerization, and relatively small amounts of

unreacted monomer are present after the start of the reaction.

 Chain-growth polymerization generally is fast, irreversible, and

moderately to highly exothermic. On the other hand, step-growth

polymerization is usually slow, equilibrium-limited, and isothermal to slightly

exothermic.

Polymerization of bifunctional monomer (A,B: two different functional groups):

AB + AB → ABAB (or AB)2 )

AB + (AB)2 → (AB)3

AB + (AB)3 → (AB)4

(AB)2 + AB)2 → (AB)4

(AB)r + (AB)s → (AB)r+s

Polymerization of two monomers with different functional groups:

AA + BB → AABB

AABB + AA → AABBAA

AABBAA + BB → AABBAABB

AABB + AABB → AABBAABB

Scheme 2 Reactions in step-broth polymerization.

Mechanisms of Chain-Growth Polymerization

Chain-growth polymerization can be classified (in order of commercial

importance) as radical, coordination, anionic, or cationic polymerization,

depending on the type of initiation. The next two sections will briefly discuss

radical and coordination polymerization respectively.

Radical polymerization

Scheme 3 outlines a typical reaction scheme for radical polymerization. Most

radical polymerizations need an initiator to produce the first radical and thus

start the chain of addition reactions. The most common initiation reaction is

the thermal decomposition of molecules containing weak bonds, e.g.

peroxides (-O-O-) or azo compounds (-N=N-). The formed radicals then react

with the monomers. Once initiated, a chain will grow by repeated additions of

monomer molecules with simultaneous creation of a new radical site. This

propagation is very fast, so very long polymer chains will form already in the

earliest stage of the reaction.

Termination can occur by disproportionation or recombination.

Initiation: R-R → R• ki ≈ 10-4 – 10-6 s-1 (300-350 K)

R• + M →RM1•

Propagation: RM1• + M → RM2• kp ≈ 102 – 104 m3 kmol-1 s-1(300 -

350 K)

RM2• + M → RM3•

Etc.

RMn-1• + M → RMn•

Termination

by disproportionation: RMn• + RMn• → RMm= + RMn

Termination

by recombination: RMm• + RMn• → RMm-MnR

Transfer to solvent: RMn• + S → RMn + S•

Transfer to monomer: RMn• + M → RMn + RM•

Scheme 3 Steps in radical polymerization; M1, Mn, number of monomers in

chain.
 H H H CH2 – CH2
| | |
C–CH2–CH2–CH2–CH2- C • C H CH2
|
H H C CH2
|
H

H H
| |
CH = CH
C –CH2–CH2–CH2–CH2-CH3 ⎯⎯⎯
2
⎯⎯
2
→ C-CH2-CH2-CH2-CH2-CH3
•
|
CH2
|
H–C–H
C
•

Figure 1 Backbiting in the synthesis of LDPE by radical polymerization.

In the first case, the final polymers on an average have the same length as

the growing chains. Termination occurs by transfer of a hydrogen atom from

one of the radicals to the other, leading to unsaturation at one chain end.

Recombination results in polymers with on average double the length of the

growing chains.

Chain transfer is common in many radical polymerization processes. It

involves the transfer of the radical end of a growing polymer chain to another

species, for instance a monomer or a solvent. Chan transfer reduces the

average polymer size and molecular weight. It is possible to add a special

agent, a modifier, in order to control the average degree of polymerization.

 In the production of low-density polyethene (LDPE), side chains are

generated by internal chain transfer, in which the end of the chain abstracts a

hydrogen atom from an internal –CH2- group, a process termed backbiting.

Figure 1 illustrates this process. A branch starts to grow from the internal

carbon radical. In this branch, backbiting is also possible resulting in widely

branched chains. Backbiting has a significant influence on the structure, and

hence, the properties of the final polymer.

Coordination polymerization

In coordination polymerization, usually transition-metal catalysts are involved.

Figure 2 indicates the main features of chain propagation in the coordination

polymerization of ethene. A growing polymer chain is coordinatively bound to

a metal atom that has another coordinative vacancy (partially empty d-

orbitals). A new ethene molecule is inserted by the creation of bonds between

one of its carbon atoms and the metal and between the other carbon atom

and the innermost carbon atom of the existing chain. Branching will not occur

through this mechanism since no radicals are involved; the active site of the

growing chain is the carbon atom directly bonded to the metal. High density

polyethene (HDPE) is produced by this type of polymerization.

 When higher 1-alkenes are added, the resultant polymer chain will

have a few short branches. These are all of the same length since they are

simply the rest of the 1-alkene molecule. Figure 3 shows the incorporation of

1-butene in a growing polyethene chain The ethene copolymer known as

linear-low-density polyethene (LLDPE) is produced by coordination

polymerization of ethene and 1-butene or 1-hexane.

 The most important catalysts for coordination polymerization are so-

called Ziegler-Natta or Ziegler catalysts, and ‘Phillips’ catalysts, both

discovered to be effective for alkene polymerization in the 1950s. Ziegler

catalysts combine transition-metal compounds such as titanium and vanadium

with organometallic compounds. An important property of these catalysts is

that they yield stereoregular polymers when higher alkenes are polymerized,

e.g. polymerization of propene produces isotactic polypropene with high

selectivity. On Ziegler catalysts, the polymer chains grow to a very long

length. Therefore, a chain-transfer agent is added to the system. Most

commonly H2 is used, which donates a hydrogen atom to terminate and

detach the chain from the metal atom.

In catalyst systems developed at Phillips Petroleum Co., chromium

oxide supported on silica is the most important constituent. Phillips catalysts

are less active than Ziegler catalysts, and therefore are limited to the

production of polyethene. They produce a polymer with a large molecular-

weight distribution, with chains varying in molecular weight from 103 to 106

g/mol.

It is not surprising that polymerization catalysis draws a lot of attention,

and many new systems have been discovered. Even plastic materials that

only melt at temperatures of over 770 K (!) can be produced.