Sulfur‐Containing Polymers

Abstract

Vol. 4 SULFUR-CONTAINING POLYMERS 337Nevertheless, the only commercial poly(monosulfide) is Ryton [Philips Petroleum Co., poly(thio-1,4-phenylene) more frequently referred to as poly(p-phenylene sulfide) or poly(phenylene sulfide) (PPS)]. Much effort has been devoted to preparing aromatic compounds in view of their significance as reactive intermediates for the synthesis of high performance linear aromatic polymers by ring-opening polymerization (ROP) (5). In an attempt to develop a novel synthetic method for the preparation of high molecular weight poly(thioarylene)s, macrocyclic aromatic sulfides and disulfides have been intensively prepared (6-14). The coordination chemistry of macrocyclic polysulfides has also received considerable attention during the past years. The thiacrown ether polymer ligands can be used as ion-exchange resins, metal ion adsorbents, and polymeric phase-transfer catalysts (15,16). Molecular systems in which tetrathiafulvalene is incorporated into macrocycles with supplementary donor atoms are potential electroactive cation sensors (17). The π -conjugated polymers have been extensively studied because of their attractive electronic properties. SULFUR-CONTAINING POLYMERSVol. 4The novel partially crystalline polymer (3) with number-average molecular weight (M n ) of up to 5700 was prepared under various conditions by catalyzed self-condensation of 3-hydroxypropyl methoxycarbonylethyl sulfide (4) or 3-hydroxypropyl carboxyethyl sulfide (5) (22). The degree of crystallinity, melting temperature (T m ), T g , and temperature of initial decomposition (T d ) were 36-46%, 37-47 • C, −61 to −70 • C, and 164-260 • C, respectively. The monomers (4) and (5) were prepared by an addition of methyl 3-mercaptopropionate and 3-mercaptopropionic acid with allyl alcohol [107-18-6] catalyzed by AIBN [2,2 -azobis(2-methylpropionitrile), azobisisobutyronitrile, azodiisobutyrodinitrile, 2,2 -azobis(2-methylpropanenitrile), α,α -azodiisobutyronitrile, 2,2 -azobis(isobutyronitrile), 2,2 -dicyano-2,2 -azopropane, Porofor-57, 2,2 -dimethyl-2,2azodipropionitrile, 2,2(-azobis(2-methylpropionitrile))] [78-67-1].An addition of conjugate 1,4-benzenedithiol (A) to 1,4-divinylbenzene (1,4diethenylbenzene, p-divinylbenzene) (B) [105-06-6] was investigated in detail in the presence of the AIBN initiator in toluene at 75 • C (23). It was found that the polymerization proceeded without an induction period, to give a white polymer with a high molecular weight [weight-average molecular weight (M w ) = 110,000] in ∼90% yield for 2 h. In addition, it was confirmed by 1 H nmr, ir, and the sulfur contents that the polymer had an alternating structure of A and B units.The synthesis and radical addition behavior of optically active cysteinebased monomers with mercapto and olefin groups have also been studied (24). N-4-vinylbenzoyl-L-cysteine methyl ester polymerized satisfactorily to afford the corresponding polysulfide (with M n in the range of 7000-23,000) in good yields.A novel one-pot synthesis of sulfur-containing polymers incl...

Alkoxide-Initiated Regioselective Coupling of Carbon Disulfide and Terminal Epoxides for the Synthesis of Strongly Alternating Copolymers

“…In addition, it confers other features such as heavy metal recognition as well as good adhesion to metals, resistance to radiation, chemicals, and bacteria. Thus, sulfur-containing polymers are interesting material for the engineering of high performance plastics. , Some synthetic routes were reported for the preparation of polymers that contain sulfur in the main chain, e.g., polythioethers, polythiosulfites, polythioesters, and polythiocarbonates. The latter can be prepared by the condensation reaction of dithiols and phosgene, ring-opening polymerization of cyclic thiocarbonates or oxetane, and polyalkylation of trithiocarbonate .…”