Odian Book Chapter 3-15, 5-3.

Slides:



Advertisements
Similar presentations
Polymerization reactions chapter 4. Fall outline Introduction Classifications Chain Polymerization (free radical initiation) Reaction Mechanism.
Advertisements

Hydrocarbon Molecules
Metallic –Electropositive: give up electrons Ionic –Electronegative/Electropositive Colavent –Electronegative: want electrons –Shared electrons along bond.
Block copolymers by combination of LAP and RAFT polymerization Wang Hui Fudan Univ. China Ellen Donkers Lab of Polymer Chemistry, TU/e Bert Klumperman.
10. Alkyl Halides Based on McMurry’s Organic Chemistry, 6 th edition.
ATRP Sandip Argekar.

RAFT Polymerization of Styrene and Acrylated Expoxidized Soy Bean Oil of Various Functionalities. By: Lucas Dunshee 1.
Polymer Synthesis CHEM 421 Chapter 3-6 (Odian). Polymer Synthesis CHEM 421 Oligomers “Oligomer” – Greek: oligos, “few” mer, “parts” Find commercial application.
Polymer Synthesis CHEM 421 Chapter 3.9 (Odian). Polymer Synthesis CHEM 421 Free Radically Polymerized Monomers.
Magnetomicelles: Nanostructures from Magnetic Nanoparticles and Cross- Linked Amphiphilic Block Copolymers Olivier Nguon Worth Reading Paper: October 2005.
Case Western Reserve University
Polymers: a chemical point of view
Polymer Chemistry CHEM List of Topics No. of Weeks Contact Hours Introduction to polymer chemistry, definitions and types of polymeric materials.
Methods of Free Radical Polymerization
John E. McMurry Paul D. Adams University of Arkansas Chapter 31 Synthetic Polymers.
© E.V. Blackburn, 2011 Alkenes and Alkynes Addition Reactions.
Part 1 Polymer Characteristics and Classifications
Ionic Polymerization.
Chapter 21 Other Organic Compounds 21.1 Functional Groups 21.2 More Classes of Organic Compounds 21.3 Organic Reactions 21.4 Polymers.
Macromer Stabilised Polystyrene Latexes
CHE 411 POLYMER TECHNOLOGY Prof. AbdulAziz A. M. Wazzan.
© 2014 Pearson Education, Inc. Synthetic Polymers Paula Yurkanis Bruice University of California, Santa Barbara Chapter 27.
Chapter 31. Synthetic Polymers
Youqing Shen Departments of Chemical Engineering and
An Introduction to Polymers Dr. Sheppard CHEM 4201 Fall 2014.
Intro to Organic Reactions. Reactions of Alkanes They burn! Hydrocarbon and Oxygen yields Carbon Dioxide and Water.
Polymeric Micelles Dr. Aws Alshamsan Department of Pharmaceutics Office: AA87 Tel:
solid polymers: ~ g/mol
Acknowledgements Department of Chemical and Biological Engineering September 26, 2013 Sri Kalluru, Lee Trask, Jace Dendor, Nacú Hernández, Eric Cochran.
Block Copolymers Block copolymers are a fascinating class of polymeric materials belonging to a big family known as ‘‘soft materials.’’ This class of polymers.
IV. Oxidation Three types A. Epoxidation B. Hydroxylation C. Oxidative cleavage.
Odian Book Chapter 3-15, 5-3.
CHEM514 COPOLYMERS AND POLYMER BLENDS Radical Copolymerization.
1 Hein * Best * Pattison * Arena Jerry Poteat Science Department Georgia Perimeter College © John Wiley and Sons, Inc. Version 1.0 Chapter 21 Polymers:
CHEM514 COPOLYMERS AND POLYMER BLENDS Graft Copolymerization.
Chap 11. Free Radical Copolymerization
Chapter 5 Reactions of Alkenes and Alkynes (Part II) Essential Organic Chemistry Paula Yurkanis Bruice.
10. Alkyl Halides Based on McMurry’s Organic Chemistry, 6 th edition ©2003 Ronald Kluger Department of Chemistry University of Toronto.
Polymerization Introduction Radical polymerization
Based on McMurry, Organic Chemistry, Chapter 31, 6th edition, (c) Chapter 31. Synthetic Polymers Based on McMurry’s Organic Chemistry, 6 th edition.
Adel F. Halasa, Ph.D. Matt Gram
Ionic Polymerization.
Polymerization.
Addition of water, H - OH + H2O major product 2-methyl-2-butene
POLYMER SCIENCE AND TECHNOLOGY
Alkenes and Alkynes Addition Reactions.
CH 14 Delocalized Pi Systems
Chapter 10 Organohalides
Chapter 10 Organohalides
Polymers ( Session 41 ).
Chapter 21 Polymers: Macromolecules 21
Polyesters Brent Strong.
Building Blocks of Life
Building Blocks of Life
Building Blocks of Life
Addition of water, H - OH + H2O major product 2-methyl-2-butene
Building Blocks of Life
Unit 1: Polymer Chemistry
Addition of water, H - OH + H2O major product 2-methyl-2-butene
CHAPTER 14: Structures of Polymers
Chapter 10 Organohalides
Engineering Materials Polymeric materials
Polymers: Macromolecules
Based on McMurry’s Organic Chemistry, 7th edition
Based on McMurry’s Organic Chemistry, 7th edition
Electropolymerizable Dendrons in Reversible Addition Fragmentation Chain-Transfer (RAFT) Polymerizations: Electrochemical Behavior and Macromolecular Assemblies.
10. Alkyl Halides Based on McMurry’s Organic Chemistry, 6th edition
Based on McMurry’s Organic Chemistry, 7th edition
Chapter 10 Organohalides
Presentation transcript:

Odian Book Chapter 3-15, 5-3

Living Polymerization (II) by Ru-Ke Bai Department of Polymer Science and Engneering University of Science and Technology of China

A Brief Review What are the major criteria for living polymerization? What is living polymerization? No termination No chain transfer What are the major criteria for living polymerization? Mn A PDI Block copolymers can be prepared by sequential addition of monomers. C B Time ln[M]0/[M]t Living polymerization is a good tool for the preparation of block copolymers.

Rankings of Anions… How to characterize the reactivity of a propagating anion?

Propagating Anions pKa of conjugate acid of prop.chain end 42 25 25 20

Propagating Anions 16-18 10-12 11-13 pKa of conjugate acid of prop.chain end 16-18 10-12 11-13

Initiators Monomer pKa Useful Initiator Styrenes.dienes 42 RLi, NH2-, Ar - Acrylates 25 RMgX, DPHL Acrylonitriles RO -, C5H5- Vinyl ketones, Aldehydes 20 RO - Cyclic oxides 16-18 Siloxanes(-D3) 10-12 HO -, RO - Cyano acrylates 11-13 H2O, HO -, RO - Nitroalkenes 10 KHCO3, H2O most nucleophilic Super glue Reactivity Least nucleophilic

Microstructure of Dienes Four different microstructures in polyisoprene cis 1-4 isomer (natural rubber) trans 1-4 isomer 1-2 isomer 3-4 isomer cis-1,4 favored in hydrocarbon solvents

Can MMA be polymerized via living process ? Side reactions 1) 2) 3)

PMMA via Living Pzn PMMA homopolymer Can not use BuLi directly Make new initiator (use 1,1-diphenylethylene) 1,1-diphenyl hexyl lithium (DPHL) Sterically hindered resonant stabilization

PMMA via Living Pzn

Block Copolymers Definition: Macromolecules consisting of homogenous segments made from different monomers (usually two or three different monomers). Ex. A-A-A-A-A-A-B-B-B-B-B-B

Some Basic Diblock Copolymer Architectures Linear Graft Ex: PS-g-PI Ex. PS-b-PI Star

Microphase Separation Most polymers are immiscible

Block Copolymer Uses Thermoplastic Elastomer Common Elastomer Poly(cis-1,4-butadiene) SBS (PS-PB-PS) Physical crosslinking Thermal reversibility Can process it repeatedly Sulfur Crosslinking heating cooling Chemical rosslinking Thermal irreversibility Can’t process it repeatedly

Self-Assembly of Block Copolymer Polym. Chem. 2011, 2, 1018–1028. PB-b-PEO PS-b-PAA cryoTEM micrographs TEM micrographs vesicles Cylindrical micelles Spherical micelles = packing parameter, v = hydrophobic volume, a = interfacial area at the hydrophobe-hydrophile/water interface, = the chain length normal to the surface per molecule.

Dispersion of Carbon Nanotubes by Block Copolymer The study of Single-Walled Carbon Nanotubes (SWNT) composite materials has been hindered by the poor solubility and processibility of SWNTs. PS-b-PAA has been used to stabilize SWNT and prevent their aggregation. The micelle-encapsulated SWNTs are compatible with a wide variety of solvent and polymer matrices, which can be used to produce carbon nanotube materials. Kang, Y. and Taton, A. T. J. Am. Chem. Soc. 2003, 125(19) 5650 – 5651.

Synthesis of Block Copolymers A-B diblock or A-B-A triblock copolymers same pKa, same reactivity; no problem any order of addition, can cross over back & forth 2) ethylene oxide/styrene copolymers styrene pKa= 42 epoxide pKa= 16-18 cross over from ethylene oxide not possible

3) Styrene & MMA Styrene-MMA Block Copolymers Styrene Then MMA, but can’t do sequential addition Styrene

Styrene-MMA Block Copolymers cap w/ 1,1-diphenylethylene (DPE) MMA @ -78 oC, THF

PMMA-PS-PMMA DFI to initiate styrene Diphenyl ethylene to initiate MMA segment Add MMA

Synthesis of Regular Star PS by Iterative Methodology Using DPE Functionality X = Y 1st Iteration 1 1st Iteration ( = ) (= ) ( = ) 1st Iteration 2st Iteration 3st Iteration 4st Iteration 5st Iteration

Synthesis of Asymmetric Star-Branched Polymers by Iterative Methodology 1

Synthesis of Asymmetric Star-Branched Polymers by Iterative Methodology 1

Synthesis of Star-Branched PS with up to 63 Arms by Iterative Methodology 5

Branched Polymers with Complex Architectures Macromol. Rapid Commun. 2010, 31,1031-1059. star-linear-star star-on-linear (dendrimer)-linear-(dendrimer) (dendrimer)-on-linear graft-on-graft graft-on-star star-on-graft star-on-star

Living/Controlled Free Radical Polymerization How to perform a living free radical polymerization? Anionic polymerization Radical polymerization kt = 0 kt = 106-108 Ri > Rp Ri < Rp Reversible termination Terminology: “controlled/living”, “pseudo-living”, “quasi-living”, and “reversible deactivation radical polymerization”

Stable Free-Radical Polymerization (SFRP) TEMPO: 2,2,6,6-tetramethyl-1-piperidinoxyl Radical was formed differently Reversible chain termination! M. K. Georges, et al, Macromolecules, 26, 2987( 1993).

Atom Transfer Radical Polymerization (ATRP) X = Br , Cl Components: Monomer: A wide variety of monomers Initiator: R-X, X = Br and Cl Catalyst: Cu, Fe, and Ru etc. Ligand: Bipyridine ect. Radical was formed differently Reversible chain termination! Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28, 7901-7910.

Reversible Addition-Fragmentation Chain Transfer (RAFT) Normal radical initiators (AIBN, etc.) Reversible chain transfer! Rizzardo, E., et al. Macromolecules 1998, 31, 5559-5562.

Advantages of Living Free Radical Polymerization Radical polymerization Anionic polymerization A variety of monomers, including the monomers with OH, COOH groups; Perform in bulk, solution, emulsion, and suspension systems; Simple and inexpensive. Styrenes, dienes, and methacrylates; Perform in solution under unaerobic and anhydrous conditions; Complex and expensive. A powerful platform for preparing a variety of well-defined polymers