THE BIG BANG

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THE BIG BANG

• THE ICI ACCIDENT - 1933
• FAWCETT AND GIBSON SCOUTING NEW USES FOR ETHYLENE
  GAS
• HIGH PRESSURE - 2000 ATMOSPHERES
• HIGH TEMPERATURE - gt 200oC
• SOMETIMES SAW A WHITE POWDER
• FREQUENTLY BLEW UP THE PRESSURE VESSEL
• IGNORED ORDER TO CEASE EXPERIMENTATION
• IDENTIFIED THE KEY INGREDIENT - AIR
• DISCOVERED LOW DENSITY POLYETHYLENE
• COMMERCIALIZED 1939

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THE BIG BANG

• GREAT TIMING !
• LDPE FOUND TO BE THE PERFECT ELECTRICAL
  INSULATOR FOR COMPONENTS ESSENTIAL FOR THE
  EMERGING RADAR TECHNOLOGY IN WW ll

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THE BIG BANG NUMBER 2

• THE DUPONT ACCIDENT - 1938
• ROY PLUNKET SEEKING AN ALTERNATIVE TO AMMONIA AS
  A REFRIGERANT GAS
• CHLOROFLUOROCARBONS AVAILABLE INCLUDING
  TETRAFLUOROETHYLENE GAS
• EMPTY CYLINDER WHICH APPEARED TO HAVE LOST
  WEIGHT OVER THE WEEKEND
• TECHNICIAN CUT IT OPEN TO REVEAL A WHITE, TOTALLY
  INERT, POLYMERIC POWDER
• DISCOVERED TEFLONR
• COMMERCIALIZED 1940

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THE BIG BANG NUMBER 2

• GREAT TIMING
• USED FOR GASKETS AND SEALS IN EQUIPMENT HANDLING
  CORROSIVE CHEMICALS (UF6) IN THE URANIUM
  ENRICHMENT AND REFINING PROCESS (MANHATTAN
  PROJECT, WW2)
• NASTY SURPRISE
• 1944 EXPLOSION KILLED TWO IN NEW JERSEY
  POLYTETRAFLUOROETHYLENE PILOT PLANT
• PURE TETRAFLUOROETHYLENE FOUND TO BE HIGHLY
  EXPLOSIVE (LOVES TO FORM CF4 AND CARBON)

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THE MISS AND HIT APPROACH- POLYMER ALLOYS

• THE GE MISS - 1960s
• INVENTING THE HIGH Tg AMORPHOUS POLYPHENYLENE
  OXIDE - A MARKETING DISASTER THE POLYMER THAT
  WAS IMPOSSIBLE TO PROCESS.
• THE GE HIT - 1966
• DISCOVERED THAT HIGH IMPACT POLYSTYRENE IS
  MISCIBLE WITH POLYPHENYLENE OXIDE IN ALL
  PROPORTIONS
• NORYLR PRODUCT FAMILY CREATED
• NORYLR 731 IS A 60/40 PPO/HIPS ALLOY, WITH ONE
  Tg 150oC

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THE MISS AND HIT APPROACH- POLYMER ALLOYS

• THE UNIROYAL MISS - PRE 1985
• DECLARED THAT A HOMOGENEOUS BLEND OF
  POLYPROPYLENE AND 100 CROSSLINKED EPDM RUBBER
  COULD NOT BE PROCESSED
• THE MONSANTO HIT - 1986
• BY SHOWING THAT POLYPROPYLENE INTIMATELY MIXED
  WITH FINELY DISPERSED, SMALL PARTICLE SIZE (lt0.1
  MICRON), 100 CROSSLINKED EPDM WAS A MELT
  PROCESSABLE THERMOPLASTIC ELASTOMER
• THE RESULT ..
• AESS SANTOPRENER TPE BECOMES A HIGHLY
  PROFITABLE, PATENT- PROTECTED, PRODUCT

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THE MISS AND HIT APPROACH

• THE DUPONT MISS - CARROTHERS 1930s
• INVENTED AND PATENTED LINEAR POLYAMIDES (NYLON
  66) IN LATE 1930s .. BUT
• DID NOT EXPLORE AROMATIC POLYESTERS (PET) BASED
  ON TEREPHTHALIC ACID
• THE CALICO PRINTERS HIT - WINFIELD AND DIXON
  1940s
• PATENTED AROMATIC POLYESTER (PET) IN 1946
• LICENSED ICI TO MAKE TERYLENER FIBRE (1950)
• ICI ASSIGNED RIGHTS TO DUPONT MAKE DACRONR FIBRE
  (1953) AND MYLARR FILM

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THE MISS AND HIT APPROACH - NYLON

• GREAT TIMING
• NYLON 66 FIBRE REPLACED SILK FOR PARACHUTES IN
  WW2
• BIG HIT FOR LADIESSTOCKINGS, POSTWAR
• ANSWER TO A FISHERMANS PRAYER - STRENR
• OFFERED THE FIRST HIGH TEMPERATURE ENGINEERING
  POLYMER AS AN ALTERNATIVE TO ALUMINIUM

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POLYMERS BY DESIGN - NEW CATALYSTS

• THE ALTERNATIVE TO THE BRUTE FORCE AND HIGH
  INVESTMENT OF HIGH PRESSURE POLYMERIZATION -
  ORGANOMETALLIC CATALYST CHEMISTRY.
• CATALYST RESEARCH
• 1940 BANKS/HOGAN (PHILLIPS
  PETROLEUM, USA)
• 1943 ZIEGLER (INST.
  COAL RESEARCH, GERMANY)
• 1954 NATTA
  (MONTECATINI, ITALY)
• 1975 KAMINSKI
  (UNIVERSITY OF HAMBURG)
• COMMERCIALIZATION
• HDPE 1954 PHILLIPS
  PETROLEUM
• 1955
  HOECHST (ZIEGLER CATALYST)
• POLYPROPYLENE 1957 MONTECATINI (NATTA
  CATALYST) METALLOCENE PE 1991
  EXXON (BUTENE)
• 
  1993 DOW (OCTENE)

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POLYMERS BY DESIGN - NEW CATALYSTS
METALLOCENE - BASED POLYMERS

• THE DOW DESIGN 1990s
• SEMICRYSTALLINE POLYSTYRENE (SYNDIOTACTIC)
  QUESTRAR MELTING POINT 277oC, GLASS TRANSITION
  TEMPERATURE 100oC
• ETHYLENE / STYRENE COPOLYMERS - FAMILIES OF
  SEMICRYSTALLINE AND ELASTOMERIC MATERIALS
• THE TICONA DESIGN 1998
• ETHYLENE / NORBORNENE AMORPHOUS COCs (CYCLIC
  OLEFIN COPOLYMER) FAMILY (TOPASR) Tg 180
  -380oC
• THE DUPONT / DOW DESIGN 2004
• NEW ELASTOMERS (EPDM)
• THE BASF / HOECHST TARGOR) DESIGN
• NEW POLYPROPYLENES

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POLYMERS - BY ACCIDENT OR DESIGN

• POLYMERIZATION TECHNOLOGY HAS PROGRESSED FROM THE
  UNEXPECTED TO THE PREDICTABLE
• POLYMER MANUFACTURE HAS MOVED FROM HIGH ENERGY TO
  LOW ENERGY PROCESSES
• WHATS NEXT?
• NEW CATALYST TECHNOLOGY HAS CREATED THE
  OPPORTUNITY TO MAKE NEW POLYMERS FROM OLD (LOW
  COST) MONOMERS
• TODAYS POLYMERS ARE DESIGNED TO MEET THE
  SPECIFIC NEEDS OF NEW APPLICATIONS AND END-USES
• OPPORTUNITY FOR NEW POLYMER ALLOYS THROUGH
  REACTIVE COMPOUNDING

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ACKNOWLEDGMENTS
PROFESSOR EMERITUS MIKE COLEMAN PENNSYLVANIA
STATE UNIVERSITY USA
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