Synthesis of Well-Defined Functionalized Polystyrenes with a Definite Number of Chloromethylphenyl Groups at Chain Ends or in Chains by Means of Anionic Living Polymerization in Conjunction with Functional Group Transformation

Abstract

The syntheses of well-defined polystyrenes functionalized with a definite number (from one to four) of chloromethylphenyl groups at the chain ends or in the chains by means of anionic living polymerization in conjunction with functional group transformation are described. The synthetic method involves the introduction of anion-stable methoxymethylphenyl or tert-butyldimethylsilyloxymethylphenyl groups at the chain ends or in the chains and subsequent transformation reactions of these groups into chloromethylphenyl groups with BCl3. It is also possible to transform the tert-butyldimethylsilyloxymethylphenyl group into bromomethylphenyl and iodomethylphenyl groups by treatment with Me3SiCl−LiBr, and Me3SiCl−NaI, respectively. Furthermore, the synthesis of well-defined polystyrenes having two, four, and six methoxymethylphenyl and six chloromethylphenyl termini via a new iterative approach using 3-(tert-butyldimethylsilyloxy)-1-propyllithium is described. It involves repeated chemical transformations at the chain end from tert-butyldimethylsilyloxybutyl, bromobutyl, and methoxymethylphenyl groups to the chloromethylphenyl group. At each stage in the iteration, the number of chloromethylphenyl groups doubles. The resulting polymers all, after HPLC fractionation in some cases, possessed well-controlled molecular weights and narrow molecular weight distributions. Their functionalities were nearly quantitative in all cases.

Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

“…The enormous efforts aimed at developing living chain-growth polymerizations on developments of branched structures (e.g., cationic [23]/anionic [24,25] polymerization, nitroxide-mediated radical polymerization (NMRP) [26,27], atom transfer radical polymerization (ATRP) [28][29][30][31], group transfer polymerization (GTP) [32,33], UV-initiated RAFT (reversible addition-fragmentation chain-transfer) polymerization [34,35], and ring-opening (metathesis) polymerization (RO(M)P) [36,37]), have led to many novel systems being amenable to the syntheses of hyperbranched polymers. One of the most promising approaches is the synthesis of hyperbranched polymers through atom transfer radical self-condensing vinyl polymerization (AT-SCVP) of AB* inimers [28,29,38].…”

Precise synthesis of asymmetric star-shaped polymers by coupling reactions of new specially designed polymer anions with chain-end-functionalized polystyrenes with benzyl bromide moieties

“…In particular, the use of the polymer anion comprised of different three polymer anions may allow a versatile and promising procedure for asymmetric starshaped polymers that cannot be synthesized by any other methods so far reported. The availability of a variety of chain-end-and in-chain-functionalized polymers with benzyl bromide moieties is an additional advantage of the present methodology [22,27,31,32]. In forthcoming research, the synthesis of functional asymmetric star-shaped polymers consisting of amphiphilic segments and conducting polymer segments by this methodology as well as their morphologies at molecular level leading to nanoscale ordered suprastructures and nanomaterial formation will be reported.…”

Synthesis of Dendrimer‐Like Star‐Branched Poly(methyl methacrylate)s of Generations Consisting of Four Branched Polymer Chains at Each Junction by Iterative Methodology Involving Coupling and Transformation Reactions

“…[19,21] 1,1-Bis(3-hydroxymethylphenyl)ethylene, 1,1-bis(3-tert-butyldimethylsilyloxymethylphenyl)ethylene (1), and 1,1,4,4-tetra(3-bromomethylphenyl)butane were synthesized according to our procedures previously reported. [19,22] Mesurement Both 1 H and 13 C NMR spectra were measured on a Bruker DPX300 (300 MHz for 1 H and 75 MHz for 13 C) in CDCl 3 . Siceexclusion chromatograms (SEC) were measured in THF with a TOSOH HLC-8020 at 40 8C with UV (254 nm) or refractive index detection.…”