Anti-Selective [3+2] (Hetero)annulation of Nonconjugated ...
Poly Chapter 6 - ocw.snu.ac.krocw.snu.ac.kr/sites/default/files/NOTE/1913.pdfThe addition reactions...
Transcript of Poly Chapter 6 - ocw.snu.ac.krocw.snu.ac.kr/sites/default/files/NOTE/1913.pdfThe addition reactions...
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Chapter 6Chapter 6
Polymerization of Cyclic y yOrganic Compounds
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Introduction
Two main difference from other polymerizations
1. No loss of small molucules (condensation)2. No loss of multiple bonding enthalpy (addition)
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Cyclic compounds that resists polymerization
• No suitable catalysts have not been found yet• The absence of ring strain; thermodynamically stable
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Cyclic compounds that be polymerizable
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Two general mechanisms of classical ring-opening polymerization
1. Initial ring cleavage through the attack of catalysts
2. The attack of catalysts generates a coordination intermediates (generally oxonium ion)intermediates (generally oxonium ion)
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Cyclic ethersTrioxane Polymerization using
1. Lewis acid or acid, ,2. during sublimation, 3. through γ-irradiation of the
crystalline monomer.
Protonic acidi lring cleavage
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Lewis acid
Trithian and Tetrathiane
Cationic type lcatalysts
BF or SbFBF3 or SbF3
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TetrahydrofuranVigorous purification is required
1. Polymerization using trifluoromethanesulfonic acid, CF3SO3H, 3 3
High molecular weight polymerweight polymer
or
Crown etherscoordination intermediates
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2. Polymerization using Lewis acids with a small amout of waterwater
ring cleavage
3. Polymerization using Lewis acids without water;2PCl5 → PCl4+PCl6- or 2PF5 → PF4
+PF6-2PCl5 → PCl4 PCl6 or 2PF5 → PF4 PF6
ring cleavage
4. Polymerization using Lewis acids without a cocatalysts
coordination intermediates
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Oxetanes and Oxepanes
Oxetanes
Oxepanes ; polymerization is reversible (97 8% of 29 2 3% of 28)Oxepanes ; polymerization is reversible (97-8% of 29, 2-3% of 28)
Polymerizability; Oxetanes >Tetrahydrofuran>Oxepanes
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Epoxides; ethylene oxide, propylene oxide, Both cationic and anionic mechanisms are possible
Epichlorohydrin; epoxy resins can be preparedprepared
Linear polymers can be formed
Further polymerization
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Anionic mechanism; using alkoxides, hydroxides, metal oxides, organometallic speciesoxides, organometallic species
ring cleavagering cleavage
Termination may not occur unless protonic reagents are added
Chain transfer; lower the MW
y p g
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Cationic mechanism; strong protonic acid (change)
di ti i t di tcoordination intermediates
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Lactones; polyesters are produced
Ring size effect ?
γ –butyllactone (5-membered ring); non-polymerizableδ-valerolactone (6-membered ring); polymerizable
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Glycolides and Lactides; poly(glycolic acid) and poly(lactic acid) are produced; biologically acceptable and biodegradable polymers
Cationic ; stannous chloride, antimony trifluoride….Condensation
polymerization
Low MW PolymerHigh MW Polymer
Mechanism ?
g y
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Cyclic anhydridesBiodegradable (bioerodable) polymers
Pol meri ation sing anionic cationic coordinationPolymerization using anionic, cationic, coordination initiators
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Cyclic carbonates
PC from condensation polymerization; side-products
PC from ring opening polymerization; no side-products, th l i ti i ld t d i iblthen polymerization in mold or extruder is possible
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Lactams; nylons are produced through ring iopening
caprolactam
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Strong base catalyzed polymerization
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Water catalyzed polymerization
Amino acid zwitterionAmino acid zwitterionattack the ring
Polymer
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Ethyleneimine
Cationic initiator
Carcinogenicity
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Oxazoline
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Non vinyl oxazoline
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No-catalyst copolymerizationTwo cyclic monomers of one a nucleophile and the other an electrophile can undergo a ring opening polymerization to produce a 1:1 alternating copolymerto produce a 1:1 alternating copolymer
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Free-radical ring-opening polymerizationRing opening polymerization; mostly ionic mechanism
Vinylcyclopropane, byclobutane can undergo radical polymerization due to the ring strain. (H ? S l b lf !)(How? Solve by yourself !)
In some cases unstrained cyclic monomers can undergoIn some cases, unstrained cyclic monomers can undergo radical polymerization
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A free radical ring opening polymerization with a volumeA free-radical ring-opening polymerization with a volume expansion
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CyclopolymerizationThe addition reactions of nonconjugated dienes that generate rings during the polymerization.Normally this occurs through an alternating intra-intermolecular propagation process
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Cyclopolymerizaton through γ –ray irradiation(How? Solve by yourself !)
Production of DIVEMA l i d i d fpolyanions derived from
this polymer are interferon-inducinginterferon inducing agents and pocess anitumor activity
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Poly(para-xyrene)