Polymer Synthesis

"I am inclined to think that the development of polymerization is perhaps the biggest thing that chemistry has done, where it has had the biggest effect on everyday life
Lord Todd, 1980

Ethylene
CH = CH
2 2
Magic ?

Polyethylene
[C H C H ]n 2 2

Polymer Types
Carothers: ..most polymers could be classified according to the mechanism of polymerization,

Condensation Addition

. or the kinetics of the reactions.

Step-growth Chain

Condensation reactions, Nylon (1938)

.based on Synthesis.

Types of Reactions
O O

Condensation

H2N(CH2)6NH2 + HOC(CH2)4COH

Nylon 6,6

Addition

CH2

CH2

Polyethylene

Ring opening

C N

O
Nylon 6

Condensation Reactions
(Small molecules)
O CH3COH + CH3CH2OH
Acetic Acid Ethyl Alcohol Reversible Reaction!

Ester linkage

CH3COCH2CH3 + H2O
Ethyl Acetate

Reactants with a functional group Mono-functional Step-wise reaction. H2O by-product.

....produce a more stable state.

Acetic Acid

CH3COH

Reaction intermediate

HOCH2CH3
Ethyl Alcohol or Ethanol

Carboxylic acids react with alcohols to form esters

O CH3COH + CH3CH2OH
Acetic Acid Ethyl Alcohol Reversible Reaction!

Ester linkage

CH3COCH2CH3 + H2O
Ethyl Acetate

Reaction: cat. by acid and higher temps. Heating to just over 100C, -gets the reaction going, drives off water, Step-wise reaction 1st step: addition reaction (rev.) 2nd step: product formed; water eliminated (rev.). Why doesnt it form a polymer?

Producing a Polymer
Mono-functional molecules: undergo only one step; produce small molecules

+
Bi-functional molecules: each product can react again; produce linear chains;

The reaction proceeds step-wise!

First step towards a Polyester

Monomers
O O HOC(CH2)nCOH + HO(CH2)mOH
O O

HOC(CH2)CO(CH2)mOH + H2O

Dimer?
Bi-functionality is retained through-out the polymerization; This is the first repeat unit (AB). Is it a copolymer?

Step-Growth Reaction
O O + O O HOC(CH2)nCO(CH2)mOH
H2O

HOC(CH2)nCOH
O O

HOC(CH2)nCO(CH2)mOC(CH2)nCOH
M1 + M 1 M2

Trimer

This is the ABA, or half-way to the AB dimer.

M2 + M1
M2 + M 2 M3 + M 1 M4 + M 1 M3 + M 2 M5 + M 1 Etc.

M3
M4 M4 M5 M5 M6

Step-Growth Polymerization; Summary

Polyesters Oligomers and Carothers

First polyesters had low MWs, low MPs. (<100C) and dissolved in common solvents. Oligomers! (Reversibility; more stable amide bond) Carothers shifted to polyamides discovered nylon.
What is the difference between a polyester and a polyamide?

Nylons (Polyamides)
O H2N(CH2)6NH2
Hexamethylene Diamine

+ HOC(CH2)4COH
Adipic Acid

O + H2O

H2N(CH2)6NC(CH2)4COH
Amide Group

AB with asymmetric reactive ends.

Condensation reaction: proceeds step-wise, rev. steps, elim. water. Reactants: carboxylic acid plus amide.

Nylon 6,6
Amide Group

O
Error: N not O

N(CH2)6NC(CH2)4CO
6

-Several

nylons. -Structures vary by the number of (CH2) groups between the amide linkages; 6,6; 4,6; etc. - Basic repeat unit has two different mers.

Ad. from N.Y. Herald Tribune, Oct. 30 1938

I am making the announcement of a brand new chemical textile fiber --derivable from coal, air and water -- and characterized by extreme toughness and strength -- Charles Stine V.P. for research, Du Pont, 1938
Biggest initial impact on products for the military and stockings.

Post WWII stocking sale, San Francisco.

Find Waldo.

Stoichiometry Issue
The reaction requires equal molar amts of the monomers. . . . not an easy on an industrial scale. Trick with nylon: pre-prep the acid:amine salt, precipitates as a 1:1 complex .

OOC(CH2)4COO NH3(CH2)6NH3 +
Nylon Salt

Nylons (Polyamides) From Diacyl Halides

Is a water molecule always eliminated?
O H2N(CH2)6NH2 O

+ ClC(CH2)4CCl
Adipoyl Chloride

Hexamethylene Diamine

O + HCl

Amide Group

HCl is driven off, drives the reaction, makes it irrev.

H2N(CH2)6NC(CH2)4COH

The Nylon Rope Trick

Nylon "skin" carefully drawn off to form fiber or rope Hexamethylene diamine in water

Adipoyl chloride in chloroform

Forms amide bond; HCl byproduct

Nylon 6,6 formed at the interface

What about the stoichiometry in the reactor?

Polyurethanes
-Bi-functional monomers -Addition reaction -No small molecule eliminated.
O C N(CH2)6N C O + HO(CH2)2OH
Ethylene Glycol

Hexamethylene Diisocyanate

Urethane Linkage

R-N=C=O from the dehydration of R-NH-COOH.

N(CH2)6NCO(CH2)2OH

Polyesters From Diesters

O CH3OC O COCH3 + 2(HO(CH 2)2OH)

Dimethyl Terephthalate

Ethylene Glycol

O HOCH2CH2OC

O COCH2CH2OH
+ 2CH3OH

COOH was converted (activated) to an ester group. Ester monomer produces ester polymer Methanol by product

Polyesters from Trans-esterification

O HOCH 2CH2OC O COCH2CH2OH
O HOCH 2CH2OC O COCH2CH2OH

Transesterification
O HOCH 2CH2OC O O O COCH2CH2OH

CO CH2CH2OC

+ HOCH2CH2OH

And so on

Summary of Polymerization Reactions

Addition
Chain reaction Initiator Double bond present in monomer Single monomer No by-products Few long chains; no double bonds Branching possible

Condensation*
Step-wise reaction H+ Initiator Bifunctional monomers 2 different monomers 2 mer repeat unit By-products Oligomers Branching is unlikely