historical perspective on the use of polymers

7/21/2019 Historical Perspective on the Use of Polymers

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Historical Perspective on the

Use of Polymers

CHE 653



Polymer Use Ancient Civilizations

• Polymers havebeen utilizedthroughout ancienthistory

• Most ancient

civilizations utilizedpolymers in one wayor another

– Egyptian

– Hindu

– Mesoamerican



Polymers fit for the Pharaoh

• Polymers and resinsfound many uses in

ancient Egypt• Mummification wasperformed using eitherresin or bitumen

– Resin is from trees

(pistacio) – Bitumen petroleumbased

• The term Mummy isderived from the Persian

word for pitch• Resins were also usedin the manufacture ofperfumes



Shellac Ancient Hindu Resin

• Shellac is a naturalresin that comes

from Laccifer Lacca• Lac is the resinoussubstance secretedto form the cocoon

• This sticklac is theraw material forshellac

•

Originally prized forit’s red color (LacDye) ~250AD

•First use as a

coating in ~1590



Mesoamerican uses for Rubber

• Sap from certaintrees could be mixedwith other plants toproduce a solidmaterial.

–

Water proof – Elastic

• Use dates from~1600BC

– Olmecs

– Aztecs

– Maya



Making the Ball

• Starting latex camefrom Castilla Elastica

– cis 1,4-polyisoprene

– Water

– Emulsifiers

– Proteins

• Mixed with juicefrom a Morning Glory

• Turns into a solid“rubber” mass in ~10minutes

• Must be shapedquickly



Rediscovery of Rubber

• This feat wouldn’tbe repeated until

1839• Charles Goodyeardiscovers thevulcanization of

rubber with sulfur• Doesn’t patent ituntil 1844

• Simplest definitionis heating of naturalrubber with sulfurunder pressure



Commercialized Rubber

• Castilla Elastica notviable for commercialrubber production

• Modern naturalrubber derives from

Hevea Brasiliensis• While derived fromBrasil, most naturalrubber comes from

SE Asia

• Latex contains cis-1,4-polyisoprene



Gutta Percha: the Other Natural Rubber

• Another version ofnatural rubber isderived fromPalaqu ium gu t ta

• Not elastic like the

Mesoamerica latex• Could be heatcycled

• Softens around100°C

• trans-1,4-polyisoprene



Review: 3 BC to 1844

• Polymer use hasbeen tied to humanhistory

• Resins were used inPharaonic Egypt

– Continued usethrough history

• Elastomers used inAncient Mesoamerica

– First example ofPolymer Processing

– Techniques lostuntil 1839



The Arrival of Celluloid

• In 1846, ChristianSchonberg creates Gun

Cotton, the firstnitrocellulose

• Georges Audemarsdevelops cellulose nitrate

fibers (rayon) in 1855• Parkesine is developed byAlexander Parkes in ~1862

• John Wesley Hyatt refines

the process and moves it toan industrial scale to createCelluloid in 1863

– Required the use of a goodsolvent (Camphor)



The Arrival Injection Molding

• John Wesley Hyatt is alsocredited with creating the firstInjection Molding System in

1868 (patent in 1872)• Operates as a simpleplunger system

• First used as a replacementfor ivory to create billiard

balls as part of a contest• Doesn’t change until 1946when James Hendry buildsthe first screw injectionmolding machine

• Used in Photographic Film(1888) and later in MotionPicture Film



Bakelite and the Rise of Art Deco

• Leo Baekelanddiscovers the phenolformaldehyde resinbased polymers in1907

• Becomes very

popular after WWI foruse in the home

• Rise of Art Deco,

with rounded edgesand streamlining,help bakelite become

a material of choice



Discovery of Macromolecules

• Hermann Staudinger proposes thatrubber and polymers are long chains of

short repeating molecular units (1920)• Prevailing thought at the time is that the

high measured molecular weights ofthese molecules was due to an

aggregation phenomenon• Experimental evidence comes in the

1930s

– membrane osmometry

–

viscosity – x-ray diffraction

• Receives the 1953 Nobel Prize inChemistry for “his discoveries in the field

of macromolecular chemistry.”



Introduction of Condensation Polymers

• Wallace Carothersdevelops the first

synthetic Rubber(Neoprene) in 1929

• Sets the stage forthe concept of

condensation vs.addition polymers

• Goes on to developmany of DuPont’s

namesake brandsincluding the nylonseries (1934)

• Died in 1937



Other significant Milestones

• 1926 Plastisizing and Moulding ofPVC by Waldo Semon (BF Goodrich)

– Discovered twice in the 1800’s • 1838 Henri Victor Regnault• 1872 by Eugen Baumann

– Seen as white flake in vinyl chloride gasthat was left in the sun – Patented in 1913 by Friedrich HeinrichAugust Klatte

• Originally investigated as a replacement fornatural rubber• First used in shock absorber seals andfabric coatings• Success came when used to insulate

wiring on military ships in WW2• First used as a piping material in the 1950’swhich now accounts for the half the PVCmanufactured today.




• 1938 TEFLON by Roy Plunkett – First synthesized by freezing andcompressing Freon gases – Initially formed a white, waxy solid using theiron from the container as a catalyst

• Patented in 1941• Teflon trademarked in 1945• Used early on to coat valves and sealsfor uranium processing at Oak RidgeNational Lab for the Manhattan Project• First applied to a pan in 1954 by MarcGrégoire and sold under the brand nameTefal (he originally used it to coat fishing

line)• Used in NASA space suits starting withthe Apollo missions




• 1943 Silly Putty by James Wright(General Electric)

– Combined Boric acid with Silicone oil – Looking for synthetic rubber – Earl Warwick and Rob Roy McGregor(DowCorning) also claim credit

• 1949 Ruth Fallgatter and Peter Hodgson – Block Shop toy store – Sell Bouncing Putty for $2

• Hodgson comes up with the name SillyPutty in 1950• Responsible for the first TV adstargeted at children in 1957• Marks the beginning of silicone basedrubbers and sealants




• 1953/1954 Polyethylene/polypropyleneKarl Ziegler & Giulio Natta (Nobel Prize1963)

– First synthesized in 1898 by Hans vonPechmann

• Reacted diazomethane under heat and pressure• Results in a white, waxy material

– First synthesized commercially in 1933 by EricFawcett and Reginald Gibson (ICI)

• Reacted ethylene with benzaldehyde and trace amountsof oxygen under heat and pressure• Again results in a white, waxy material

– Developed a catalyst that could operate at lowertemperatures and pressures and providestereoselectivity

•

Titanium Halides• Organometallic aluminum (triethyaluminum)

• Off spec material originally used in thehula hoop (1957)• Used as a replacement for glass in baby

bottles (1959)




• Polymer Related Nobel Prizes – 1953 Hermann Staudinger: “for his discoveries in the fieldof macromolecular chemistry”

– 1963 Karl Ziegler and Giulio Natta: “for their discoveries inthe field of the chemistry and technology of high polymers” –1974 Paul J. Flory: "for his fundamental achievements,both theoretical and experimental, in the physical chemistryof the macromolecules“ – 1991 Pierre-Gilles de Gennes:"for discovering thatmethods developed for studying order phenomena insimple systems can be generalized to more complex formsof matter, in particular to liquid crystals and polymers" – 2000 Alan J. Heeger, Alan G. Macdiarmid, HidekiShirakawa: "for the discovery and development ofconductive polymers"

historical perspective on the use of polymers

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