A well-controlled anionic polymerization of 4-diphenylaminostyrene (DAS) with alkyllithium (RLi) has been achieved for the first time. The nucleophilicity and solubility of RLi, 4-diphenylaminostyryllithium (DASLi), and poly(4-diphenylaminostyryl)lithium (PDASLi) were very important controlling factors. An initiator system of tert-butyllithium (t-BuLi)/N,N,N′,N′-tetramethylethylenediamine (TMEDA) in toluene was found to be very effective. In this system, the t-BuLi/TMEDA complex reacts with toluene to form the benzyllithium (BzLi)/ TMEDA complex, and this complex initiates the anionic polymerization of DAS. The DASLi/TMEDA and PDASLi/TMEDA complexes have sufficient nucleophilicity and stability as propagating species, without the metalation of toluene, and as a result, living anionic polymerization was achieved. The high molecular weight poly(4-diphenylaminostyrene) (PDAS), synthesized using the RLi/TMEDA system, had a syndiotactic-rich configuration, independent of the polymerization solvent.

Soluble polyphenylene (PPH) homopolymers with a controlled polymer chain structure were synthesized for the first time by the complete dehydrogenation of poly(1,3-cyclohexadiene) (PCHD) having a 1,2-addition (1,2-CHD unit) and 1,4-addition (1,4-CHD unit). The reactivity of PCHD for dehydrogenation strongly depends on the polymer chain structure. The rate of dehydrogenation is fast on a long sequence of 1,4-CHD units, while it is considerably impeded by the presence of 1,2-CHD units in the polymer chain. With a reaction temperature higher than 90 °C, complete dehydrogenation of PCHD proceeds successfully to yield soluble PPH homopolymers. The polymers obtained are soluble in polar solvents. Therefore, the soluble PPH homopolymers appear to be polar macromolecules, and the conversion of polarity occurs during the dehydrogenation process. UV and fluorescence spectra clearly indicate the nature of a conjugated PPH homopolymer.

No abstract

Tetraphenylporphyrin-end-functionalized polycyclohexane (H 2 TPP-PCHE) and its metal complexes (MTPP-PCHE) were synthesized as the first successful example of porphyrin-end-functionalized transparent and stable polymers with a well-controlled and defined polymer chain structure. Chloromethyl-end-functionalized poly(1,3-cyclohexadiene) (CM-PCHD) was synthesized as prerequisite prepolymer by the postpolymerization reaction of poly(1,3-cyclohexadienyl)lithium and chloro(chloromethyl)dimethylsilane. CM-end-functionalized PCHE (CM-PCHE) was prepared by the complete hydrogenation of CM-PCHD with p-toluenesulfonyl hydrazide. H 2 TPP was incorporated onto the polymer chain end by the addition of 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin to CM-PCHE. The complexation of H 2 TPP-PCHE and Zn(OAc) 2 (or PtCl 2 ) yielded a zinc (or platinum) complex of H 2 TPP-PCHE. H 2 TPP-PCHE and MTPP-PCHE were readily soluble in common organic solvents, and PCHE did not inhibit the optical properties of the H 2 TPP, ZnTPP, and PtTPP end groups. V C 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 5322-5329, 2011