This document discusses controlled radical polymerization techniques. It begins by explaining the limitations of conventional free radical polymerization in controlling properties like molecular weight and architecture. It then describes the basic principle of controlled radical polymerization, which is to reversibly trap propagating radicals to suppress termination. Three main controlled polymerization techniques are introduced: atom transfer radical polymerization, nitroxide-mediated polymerization, and reversible addition-fragmentation chain transfer polymerization. Copolymerization kinetics and the significance of reactivity ratios are also summarized.
This document discusses controlled radical polymerization techniques. It begins by explaining the limitations of conventional free radical polymerization in controlling properties like molecular weight and architecture. It then describes the basic principle of controlled radical polymerization, which is to reversibly trap propagating radicals to suppress termination. Three main controlled polymerization techniques are introduced: atom transfer radical polymerization, nitroxide-mediated polymerization, and reversible addition-fragmentation chain transfer polymerization. Copolymerization kinetics and the significance of reactivity ratios are also summarized.
This document discusses controlled radical polymerization techniques. It begins by explaining the limitations of conventional free radical polymerization in controlling properties like molecular weight and architecture. It then describes the basic principle of controlled radical polymerization, which is to reversibly trap propagating radicals to suppress termination. Three main controlled polymerization techniques are introduced: atom transfer radical polymerization, nitroxide-mediated polymerization, and reversible addition-fragmentation chain transfer polymerization. Copolymerization kinetics and the significance of reactivity ratios are also summarized.
This document discusses controlled radical polymerization techniques. It begins by explaining the limitations of conventional free radical polymerization in controlling properties like molecular weight and architecture. It then describes the basic principle of controlled radical polymerization, which is to reversibly trap propagating radicals to suppress termination. Three main controlled polymerization techniques are introduced: atom transfer radical polymerization, nitroxide-mediated polymerization, and reversible addition-fragmentation chain transfer polymerization. Copolymerization kinetics and the significance of reactivity ratios are also summarized.
radical polymerization due to the statistics and mechanism involving termination and chain transfer
Difficulty (or even impossibility) of preparing well-
defined copolymers or polymers with a predetermined functionality.
Difficulty in control of molecular and chain architecture.
Remember “Living” Anionic Polymerization (1956 by Swarc)
Absence of termination and chain transfer
Polymer chain-end remain active: ‘Living’
• Characteristics and Utility of ‘Living’ Polymer System
• Molecular weight control (chain length = [M]/[I] )
• Narrow molecular weight distribution (PDI =1.05) • Linear MW-conversion relationship
• Synthesis of block copolymers
• End-group functionalization • A variety of chain architecture possible Development of Controlled Radical Polymerization Late 1980s and 1990s
1) Atom transfer radical polymerization (ATRP)
2) Stable free radical polymerization (SFRP) or
Nitroxy-mediated radical polymerization (NMP)
3) Reversible addition–fragmentation transfer (RAFT)
The basic principle underlying all so-called Controlled/Living Radical Polymerizations:
To suppress termination to the extent that it
becomes insignificant by reversibly trapping and temporarily deactivating the chain radicals. Although the activation-deactivation cycle is rapid, the chain radicals that are free can still propagate.
…Reversible-deactivation Radical Polymerization…
Controlled/Living Radical Polymerization
Strategy 1 kact
kdeaact
Strategy 2 CI
AIKY 1 Halide 계열 트따매마
,
개시제 : 활성화제 금속리간 , :
1) Atom transfer radical polymerization (ATRP)
처음에 R X를 넣어서 pn - 시작 - 시 금솔리란드맨 가시를 떼가며 활성화 -
Copper(I) bipyridyl(bpy) complex:
측매 리간드 금속 할로겐과 어정도의 반응성 Cu(I) 배위 결합 가능 N N 두가지 산화 상태 아산가
b. initiator b. initiator (soluble in monomer) (soluble in monomer) c. water or other liquid d. stabilizer: poly(vinyl alcohol), 2) Problem & difficulty: methyl cellulose a. heat transfer 어 2) Vigorous stirring to keep b. viscosity 용매가 없기에 점도 증가 c. auto-acceleration ~
, 반응속된 suspension
3) Polymer in granular bead form
-3. Solution -4. Emulsion 1) Reactor charges: 1) Reactor charges: a. monomer 친수성 a. monomer (soluble in solvent) b. redox initiator b. initiator (soluble in solvent) c. soap or emulsifier유화제 c. solvent (usually organic) d. water e. others (see next Table) 2) Solvent must be chosen carefully, often difficult to remove 2) Polymerization in monomer from the polymer product. swollen micelle. Latex products (useful for * polymerization in … supercritical water-based paints or adhesives) solvent (CO2) … 상송유체 소액기 성질 * inverse emulsion (water-in-oil)
=⇒ 압력 > 제기 Composition of Emulsion Polymerization
Smith-Ewart Kinetics 5. Stereochemistry in Radical Polymerization
Tacticity and Cis/Trans isomerism
-1. General consideration.
a) Stereo-regular polymer: by ionic and coordination polymerization
1) Chain end in ion pair: counter ion
2) Chain end in metal-complexed active site 3) Low temperature
b) Stereo-irregular polymer: by free-radical polymerization
1) No stereo-regulating radical terminal group 2) Somewhat higher reaction temperature -2. Factors influencing stereochemistry in F/R polymerization. 1) Interaction between terminal chain carbon and approaching monomer. 2) The configuration of the penultimate repeating unit in the polymer chain. 3) Temperature.
-3. Stereo-regular free-radical polymerization of PMMA.
(ex. syndiotactic PMMA) 1) Polymerization temperature : below 0℃.
2)
3) Terminal carbon : sp2 ( planar )
penultimate repeating unit : bulky ester group. CFC - 4. Polymerization of Conjugated Dienes 두래이상 1) Radical addition to conjugated diene monomer.
1,3-butadiene
2) Propagation mode: a. 1,2-Addition : pendent vinyl group
c. 3,4-Addition (additional for substituted diene monomers)
(CH3) H2C C C CH2 H
Isoprene 6. Copolymerization
Polymerization of two or more monomers
Examples: Poly(ethylene-co-propylene) (EPR) Poly(styrene-co-butadiene) (SBR) Poly(vinylidine-co-vinyl chloride) (Saran), and many others Kinetics of Copolymerization Reactivity ratios (r1 & r2) : the relative tendency of monomer to self-propagate over cross-propagate Significance of reactivity ratio (r1, r2) Discussion on the several limiting cases:
a. r1 = r2 = ∞ : Homopolymer. b. r1 = r2 = 0 : Alternating polymer. c. r1 = r2 = 1 : Copolymer composition depending on feeding monomers in the reaction temperature. d. r1 × r2 = 1 : Ideal copolymerization like ideal liquid vaporization. e. r1 × r2 > 1 : Azeotropic copolymerization (polymer composition not depending on feeding).
* Determination of r1, r2 : by measuring copolymer composition by NMR or other
method at low conversion (<10%) <Special cases>
Purely Random Copolymer
r1 = r2 =1 * Probability of M1· or M2· react with M1 vs M2 is equal
r1 = 10 r2 = 0.1 ≈𝟎
Regardless of f1: F1 = 0.5
Copolymer Composition Curves Determination of Reactivity ratios by Q-e scheme (Alfrey and Price)
