elements of step-growth polymerization branching network ...manias/matse259/lecture3.pdf · topics...
TRANSCRIPT
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Topics to be Covered
•Elements of Step-Growth Polymerization
•Branching Network Formation
Chapters 1 & 2 in CD (Polymer Science and Engineering)
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Dawn of Understanding
"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 PolyethyleneCH2=CH2 [-CH2-CH2-]nMagic ?
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Staudinger“My dear chap, give up your ideas on big molecules. There are no organic molecules with a molecular weight of more than 5000. Just clean up your products and they will crystallize and reveal themselves as low-molecular-weight compounds”.
CH2 CH CH2 CHCH2 CH CH2 CH CH2 CHCH2 CHCH2 CH
CHCH2
CH2CH C
CH2
CH2
CCH3
CH3
A cyclic isoprene dimer
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Timeline
1920 – STAUDINGER; The macromolecular hypothesis.
1926 – CHARLES STINE; Initiates a program of fundamentalresearch at du Pont.
LATE 1920's – CAROTHERS; Set out to prove the existence ofmacromolecules by systematicallybuilding them from small moleculesusing well known chemistry.
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Condensation Reactions
Acetic Acid Ethyl Alcoholor Ethanol
ReversibleReaction!
Ethyl AcetateIf you don’tknow what this is you should be castigated unmercifully
Ester linkage
CH3 - C - OH + CH3 - CH2 - OH CH3 - C - O - CH2 - CH3 + H2O
O O
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Why do Molecules React ?
CH3 - C - OH
O
HO - CH2 - CH3
Acetic Acid
kersplat!
Ethyl Alcoholor Ethanol
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Why do Molecules React ?
H:O - CH2 - CH3CH3 - C:OH
O
HO. + .H HO:H ~ H2O
CH3 - C. + .O - CH2 - CH3 CH3 - C:O - CH2 - CH3
OO O
This isn’t what really happens, but shows you how the valency electrons get rearranged
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Making a Polymer
Acetic Acid Ethyl Alcoholor Ethanol
ReversibleReaction!
Ethyl Acetate
Ester linkage
CH3 - C - OH + CH3 - CH2 - OH CH3 - C - O - CH2 - CH3 + H2O
O O
If we heat acetic acid and ethanol up to just over 1000C, to get the reaction going and drive off water, why don’t we form polymer?
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Making a PolymerThe molecules are monofunctional;
To make linear chains we need bifunctional molecules;
Except the reaction doesn’t happen all in one go, like this, but in a step- growth fashion.
+
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O O
HO - C - (CH2)n - C - O - (CH2)m - OH + H2O
O O
Making a Polyester
HO - C - (CH2)n - C - OH + HO - (CH2)m - OH
Dimer
Monomers
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Making a Polyester
HO - C - (CH2)n - C - OH
O O
HO - C - (CH2)n - C - O - (CH2)m - OH +
O O
HO - C - (CH2)n - C - O - (CH2)m - O - C - (CH2)n - C - OH
O OO O- H2O Trimer
M1 + M1 M2
M2 + M1 M3
M2 + M2 M4
M3 + M1 M4
M4 + M1 M5
M3 + M2 M5
M5 + M1 M6
Etc.
Note, reacting a diacid and a dialcohol will give you a polyester!
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The Invention of Nylon
1927 - Stine offers Carothersa job.
1929 - Carothers and hisgroup succeed inmaking low molecularweight aliphaticpolyesters
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The molecular still and the shift to polyamides
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Nylons
H2N - (CH2)6 - NH2 + HO - C - (CH2)4 - C - OH
O
H2N - (CH2)6 - N - C - (CH2)4 - C - OH + H2O
OO
O
Adipic AcidHexamethylene Diamine
Amide Group
H
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Nylon 6,6
- N - (CH2)6 - N - C - (CH2)4 - C -
O O
n6 6
H H
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Julian Hill reenacting the discovery of Nylon
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Ad. from N.Y. Herald Tribune, Oct. 30 1938
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
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Demonstration of knitting nylon stockings at the N.Y. World’s Fair, 1939
Stockings!
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Marie Wilson’s Leg, 2 ton 35 ft cast, N.Y. World’s Fair1939
DuPont did a masterly job in two areas;– Advertising– Technical Service
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Golden Gate Exposition, 1939
As skirts got shorter after the end of WWI, shocking expanses of leg were being revealed and the appearance and "feel" of stockings became a pressing fashion concern. And, there was money to be made! At that time nothing could compare with silk for sheerness. Wool was thick and scratchy; cotton was, well, cotton, not very exciting; rayon also was not sheer enough and tended to droop and bag at the ankles. But, silk was expensive and not very durable (silk stockings would "run" at the slightest provocation). Nevertheless, about 1.6 million pairs of silk stockings were being a day in the U.S. alone!
Why Stockings?
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Wilmington gets the first nylon stockings,
1939
May 15 1940 - “Nylon Day” . Four Million pairs go on sale throughout the U.S. Supply
exhausted in 4 days.
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Nylon Parachute WWII
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Betty Grable auctions her stockings for the war effort.
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Post WWII stocking sale, NYC.
She couldn’t wait!
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Post WWII stocking sale, San Francisco.
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Sold Out!
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A Tragic End
Carothers in happier times.
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Polymer Synthesis - Classification
Carothers suggested that most polymers could be classified into two broad categories according to the mechanism of polymerization;
• Condensation• Addition
As you will see, a better classification may be;
• Step-growth• Chain
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Types of Reactions
Condensation
Addition
Ring opening
CH2 = CH2
N
CO
H
H2N - (CH2)6 - NH2 + HO - C - (CH2)4 - C - OH
OO
Nylon 6,6
Polyethylene
Nylon 6
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Nylon 6,6
- N - (CH2)6 - N - C - (CH2)4 - C -
O O
n6 6
H H
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Nylon 6,10
- N - (CH2)6 - N - C - (CH2)10 - C -
O O
n
What would nylon 6,10 look like?
A
- N - (CH2)10 - N - C - (CH2)6 - C -
O O
n
- N - (CH2)6 - N - C - (CH2)8 - C -
O O
n
B
C
H H
H H
H H
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More on Nylons
ApplicationsCarpet FibersClothesGear wheelsEtc.
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Back to Condensation
O
H2N - (CH2)6 - N - C - (CH2)4 - C - OH + HCl
OO
O
Adipoyl ChlorideHexamethylene Diamine
Amide Group
Is a molecule of water always split out?
H2N - (CH2)6 - NH2 + Cl - C - (CH2)4 - C - Cl
H
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Hexamethylene diamine in water
Adipoyl chloride in chloroform
Nylon 6,6 formed at the interface
Nylon "skin" carefully drawn off to form fiber or rope
The Nylon Rope Trick
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The Nylon Rope Trick
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Polyurethanes
A reaction that does not involve the splitting out of a small molecule;
O = C = N - (CH2)6 - N = C = O + HO - (CH2)2 - OH
O = C = N - (CH2)6 - N - C - O - (CH2)2 - OH
O
Hexamethylene Diisocyanate Ethylene Glycol
Urethane Linkage
H
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Network Formation
How would you make chains that branch and then perhaps interconnect to form networks?
A. Use a mixture of bifunctional and monofunctionalunits
B. Get a tube of Molecular Super Glue and stick a bunchof chains together
C. Use multifunctional (f>2) monomers
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Network Formation
OH
CH2 OH
OHCH2
OH
CH2
CH2
OH
CH2
OH
OHOH
CH2
CH2
OH
+ CH2O*
*
**
The hydrogens in the ortho and para positions to the OH group, which by convention are not usually shown but here are indicated by a ,can react with fomaldehyde to form (initially) oligomers.
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OH
H
H
H
H H
OH
H
H
H
H H
H
H
O
H H
O
OH
H
H
H
H H
Another Condensation Reaction
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OH
CH2O
H2C
CH2
HO
OH
CH2
CH2
OH
CH2
HOCH2
OH
CH2
CH2
O
OH
CH2
CH2
OH
O
CH2
HO
CH2
CH2
OH
CH2CH2
OH
HO
CH2HO
CH2CH2
H2C
HO
Network Formation
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Step-Growth Polymerization ; Summary
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x n = 1(1− p)
Conversion and Molecular Weightin Step-Growth Polymerizations
1.00.80.60.40.20.00
100
200
Conversion, p
1
(1 - p)
Note; you only get high molecular weight polymer at high degrees of conversion.
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Some Important Step Growth Polymers
NylonsPolyestersPolyurethanesPolycarbonateEpoxiesPhenolics