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Anionic polymerization of secondary aminostyrene and characterization of the polymer
Author(s) -
Se Kazunori,
Kudoh Shinichi
Publication year - 1999
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/(sici)1097-4628(19990321)71:12<2039::aid-app14>3.0.co;2-9
Subject(s) - tetrahydrofuran , trimethylsilyl , copolymer , anionic addition polymerization , polymer chemistry , molar mass distribution , polymerization , gel permeation chromatography , chemistry , isopropyl , polymer , lithium (medication) , styrene , cationic polymerization , organic chemistry , medicine , solvent , endocrinology
Preparation by anionic living technique and characterization of poly(secondary aminostyrene) having narrow molecular weight distribution were investigated. N ‐isopropyl‐ N ‐trimethylsilyl‐4‐vinylbenzylamine (SBA) was purified by use of sec ‐butylmagnesium bromide as a purging reagent under high vacuum. SBA was anionically polymerized with n ‐butyllithium or cumylpotassium in tetrahydrofuran at −78°C under high vacuum to yield the corresponding polymer (PSBA) in 100% yield. Subsequent deprotection of the trimethylsilyl group from PSBA produced poly( N ‐isopropyl‐4‐vinylbenzylamine) (PBA) of the desired molecular weights ( M n : 1.3 × 10 4 –17 × 10 4 , determined by membrane osmometry) with narrow molecular weight distribution ( M w / M n : 1.07–1.03, determined by gel permeation chromatography). The living lithium carbanion of PSBA can initiate styrene (St) to yield PSBA‐ b ‐PSt block copolymer ( M n = 4.0 × 10 4 , M w / M n = 1.05), and the polystyryllithium can initiate SBA to yield PSt‐ b ‐PSBA ( M n = 3.7 × 10 4 , M w / M n = 1.25). The deprotection of the trimethylsilyl group from the two block copolymers produced new block copolymers containing poly(secondary aminostyrene) block. Anionic reactivity of SBA and basic properties of PSBA are discussed in terms of the 13 C chemical shift of β‐carbon in the vinyl group of SBA and steric effect. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2039–2048, 1999