Chemistry 367L/392N
Macromolecular ChemistryMacromolecular Chemistry
Lecture 23Lecture 23
Yves ChauvinYves ChauvinInstitutInstitut FranFranççaisais du du PPéétroletroleRueilRueil--Malmaison, France Malmaison, France
Robert GrubbsRobert GrubbsCalifornia Institute of Technology California Institute of Technology
(Caltech) Pasadena, CA, USA (Caltech) Pasadena, CA, USA
Richard SchrockRichard SchrockMassachusetts Institute Massachusetts Institute
of Technology (MIT) of Technology (MIT) Cambridge, MA, USACambridge, MA, USA
Transition metal catalysis of polymerizationTransition metal catalysis of polymerization
Chemistry 367L/392N
HomeworkHomework
Assignment 11Assignment 11Due May 4Due May 4thth before 5PMbefore 5PM
DO: Submit a corrected copy of your midterm DO: Submit a corrected copy of your midterm examexam
Chemistry 318N
MetathesisMetathesisFrom From Dictionary.comDictionary.com
1. the transposition of letters, syllables, or sounds in a word, as in the pronunciation aksor ask.
2. In chemistry, reaction whose result is the interchange of two parts of two substances to form two new substances, as
AgNO3 + NaCl→ AgCl + NaNO3.
Chemistry 318N
Olefin MetathesisOlefin Metathesis
Chemistry 318N
Ring opening metathesis Ring opening metathesis polymerization ROMPpolymerization ROMP
* *
catalyst
Chemistry 318N
Ring strain driving forceRing strain driving force
Living!!!
Chemistry 318N
Olefin Metathesis CatalystsOlefin Metathesis Catalysts�� Schrock and GrubbsSchrock and Grubbs
–– Air sensitiveAir sensitive
–– Initially were molybdenum and ruthenium based, respectivelyInitially were molybdenum and ruthenium based, respectively
–– Shared 2005 Nobel Prize with ChauvinShared 2005 Nobel Prize with Chauvin
Images from Images from PappenfusPappenfus, T. M. Synthesis and Catalytic Activity of Ruthenium, T. M. Synthesis and Catalytic Activity of Ruthenium--IndenylideneIndenylidene Complexes for Olefin Complexes for Olefin Metathesis, Metathesis, J. Chem. Ed.J. Chem. Ed. 2007,2007, 84 (12), 199884 (12), 1998--2000.2000.
Span of Olefin Metathesis
Types of Metathesis
R1R 2 R1
R 2+
**
n
**
n
R 2
R1
+
R2
R1
cross metathesis (CM) ring closing metathesis (RCM)
ring opening cross metathesis (ROCM)
acyclic diene metathesis (ADMET)ring opening metathesis polymerization (ROMP)
C.W. Bielawski, R.H. Grubbs Prog. Polym. Sci. 32 (2007) 1.
Chemistry 318N
ADMET is step growth ADMET is step growth polymerization chemistrypolymerization chemistry
� High strength polymers can be made by ADMET
Symmetrical Diene
Symmetrical Repeat Unit
Ken Wagener
George and Josephine Butler Polymer Research Laboratory - Department of Chemistry University of Florida
Animation of ADMET MechanismThe ADMET Reaction
R
R
x
+ Gaseous Ethylene
Room Temp.
ADMET PolymerDiene Monomer
MetathesisCatalyst
+
Professor Ken Wagener, University of Florida
Chemistry 318N
Lets Practice ADMETLets Practice ADMET
Catalyst
Vacuum
* *
H2C CH2
Catalyst, BIG pressure
Chemistry 318N
Tuesday LectureTuesday LecturePolymer separation membranesPolymer separation membranes
Prof. . Benny Freeman