Anionic living polymerization of useful monomers that can provide intermolecular chemical links

Abstract

Anionic living polymerization of four new monomers that serve as intermolecular chemical links between polymer chains are described, along with the wide applications of the resultant polymer alloys. Examples of the first monomer include three tertiary aminostyrenes. The corresponding poly(tertiary aminostyrene)s (PtAS) having a desired molecular weight and narrow molecular weight distribution were prepared. Crosslinked films of PtAS with p, p'-bis(chloromethyl)azobenzene (CAB) were prepared by quaternization. Photochemical isomerization of CAB incorporated in PtAS was investigated. The second monomer discussed is N-isopropyl-N-trimethylsilyl-4-vinylbenzylamine (ISBA). ISBA was anionically polymerized and subsequent deprotection of the trimethylsilyl protecting group produced poly (N-isopropyl-4-vinylbenzylamine) (PIBA) with a secondary amino group. The non-thrombogenic behavior of the corresponding poly (aminostyrene)-graft-oligopeptide graft copolymers was evaluated. The third monomer, (4-vinylphenyl)dimethylvinylsilane (VS), contains a silylvinyl group. To carry out a chemoselective polymerization of the styryl group of VS, a systematic study on anionic polymerization was carried out. Lithographic characterization shows the resultant polymer (PVS) acting as a negative working resist. Three (PVS-graft-polyisoprene)-block-polystyrene block-graft copolymers were prepared by a “grafting onto” process. The fourth monomer discussed is p-butoxystyrene. The deprotection of the tert-butyl protecting group from the corresponding polymer produces poly (p-hydroxystyrene) (PHSt). Two polystyrene-block-[PHSt-graft-poly (ethylene oxide)]-block-polystyrene block-graft copolymers were prepared by a “grafting from” process. Benzene-cast films formed clear and specific lamellar structures in which poly (ethylene oxide) is not crystallized

Introduction of Azobenzenes or Vinyl Groups into Ends of Rodlike Polymers

“…8 g, M n = 1.1 0 × 10 5 , 1.6 2 × 10 -4 mol) to prepare PHIC−PAz at −5 °C for 740 h under high vacuum (10 -6 mmHg). The precursor was taken out of the glass apparatus at a given time by the same methods as for the anionic living polymerization technique, , so as to determine the coupling efficiency.…”

“…n -Hexyl isocyanate (HIC), N(C 6 H 13 )CO, was purchased from Kanto Chemical Co., Inc. (Tokyo, Japan), and distilled under 20 mmHg, dried with calcium hydride (CaH 2 ) under high vacuum (10 -6 mmHg), and then distilled into ampules with breakable seals. Just before polymerization, HIC was distilled into an ampule after being dried with an octylzenzophenone−sodium complex. , A titanium catalyst, TiCl 3 OCH 2 CF 3 , was prepared according to Novac et al , under high vacuum using a breakable-seal technique.…”

“…BTCl was sublimed several times under high vacuum . All reagents mentioned above, as well as the solvents employed in the preparation of the corresponding solutions and in polymerization, were purified by the same methods as for the anionic living polymerization technique, using breakable seals under high vacuum (10 -6 mmHg). , The polymerization and coupling reactions were carried out under high vacuum using a breakable-seal technique. , …”

One-Pot Synthesis of Hyperbranched and Star Polyketones by Palladium-Catalyzed Terpolymerization of 4-tert-Butylstyrene, Divinylbenzene, and Carbon Monoxide

“…To facilitate the tailored synthesis of both HBPs and SPs, the well-developed controlled/“living” polymerization techniques, such as controlled/“living” radical polymerization, − “living” anionic polymerization, , and cationic polymerization − techniques, have been commonly employed because of their outstanding control over the polymer molecular weight and molecular weight distribution. However, the “living” coordinative polymerization technique has only been reported in very few cases to date for the synthesis of HBPs and SPs from monomer precursors such as ethylene − ,− because of the limitation in transition-metal catalyst technologies.…”

Study on the Mechanism of a Side Coupling Reaction during the Living Anionic Copolymerization of Styrene and 1-(Ethoxydimethylsilyphenyl)-1-phenylethylene (DPE-SiOEt)

“…DPE derivatives can also reduce side reactions between the anionic active center and certain functional groups grafted to DPE units. In a previous investigation, obvious termination was observed when the living anionic homopolymerization of amino-functionalized styrene derivative was conducted at room temperature [ 13 ]. By contrast, the living anionic copolymerization of styrene and an amino-functionalized DPE derivative (DPE-NMe 2 or DPE-(NMe 2 ) 2 ) avoided the side termination reaction and maintained the narrow distribution of the product [ 14 , 15 ].…”