Thio polymers

NPCl2)n reacts with 1-hexanethiol to give the fully substituted thio polymer utilizing 4-picoline as base in thf solutions. Only degradation products are obtained when the reaction is carried out with sodium hexanethiolate as... 

Fig. 9. X-ray scattering curves for alkyloxyethylene (bottom pair) and alkylthioethylene (top pair) methacrylate polymers. The number of carbon atoms in each alkyl group is indicated. Successive curves have been shifted vertically one division for clarity. Intensity scale (per division) oxy polymers, 200 counts/s thio polymers, 100 counts/s.

Hydantoin, 5,5-diaryl-2,4-dithio-methylation, 5, 444 Hydantoin, 1,3-divinyl-polymers, 1, 280 Hydantoin, 5-methylene-polymers, 1, 280 Hydantoin, 5-phenyl-2-thio-tautomerism, 5, 370 Hydantoin, thio-... 

Thio- and seleno-compounds of the main group elements — novel inorganic oligomers and polymers. B. Krebs, Angew. Chem., Int. Ed. Engl., 1983, 22,113-134 (252),... 

Dithiocarbamate complexes of copper have been sythesized at a high rate. Reports of new complexes include the morpholine-4- (44), thio-morpholine, AT-methylpiperazine-4-, and piperidine- (291) dithiocarba-mates. Novel, polymeric complexes of the type Cu(pipdtc)2 (CuBr) in = 4, or 6) and Cu(pipdtc)2 (CuCl)4 have been prepared by reactions of[Cu(pipdtc)2] with the respective copper halide in CHCla-EtOH (418). The crystal structures of the polymers are known to consist of sheets of individual [Cu(pipdtc)2] molecules linked to polymeric CuBr chains via Cu-S bonds. A series of copper(I) dtc complexes have been the subject of a Cu and Cu NQR-spectral study (440). 

Trimethylsilyl esters of tris(thio)phosphonic acids 2070 are readily oxidized by DMSO in toluene at -30 °C to give the dimeric tetra(thia)diaphosphorinanes 2071 and HMDSO 7 [208] (cf. also the oxidation of silylated thiophenol via 2055 to diphenyl disulfide). The polymeric Se02 is depolymerized and activated by reaction with trimethylsilyl polyphosphate 195 to give the corresponding modified polymer... 

Using tandem MS (DFS with EI/FPFD source), electron impact and collision activation mass spectra of a THF extract of an orthopaedic polymer bandage identified IV-isopropyl-A/ -phcnyl-p-phenylenediamine (IPPD, m/z 226) as a cause for contact dermatitis [232]. Fl-MS of the extract of surgeons gloves indicated thio-bis (t-butylcresol) (m/z 358 343, after CID). 

B. Krebs, Thio and seleno compounds of main group elements - new inorganic ohgomers and polymers. Angew. Chem. Int. Ed. 22 (1983) 113. 

The IAD concept via p-methoxybenzylidene acetals was also shown to be suitable for polymer-supported syntheses of disaccharides (Scheme 5.107) [292], A suitable p-allyloxybenzyl group at position 2 of a 1-thio-mannosyl donor is first converted into a PEG-modified benzyl group that allows for the convenient isolation of the intermediate tethered glycosides. 

Thus, many polymers with different conductivity were synthesized. To cite a few, these are polythiophene [158], 3-methylthiophene [159], polymers of 3-thiophene-acetic acid and methyl 3-thiophene-acetate [160], poly(2,5-thienylenevinylene) [161], poly(benzo[h]-thiophene) [162], poly(naphto[2,3-c]thio-phene) [163], poly(dithieno[3,2-h 2, 3 -fii]-thiophene) [164], poly(3- -hexylthiophene)... 

The linear prodnct is obvionsly formed according to the seqnence 2,5-di(thiocyano)thio-phene potassinm 2-mercaptido-5-thiacyanonothiophene —> tristhiomaleic anhydride thio-phene-2,5-disulfenyl biradical (the diradical valence tantomer) —> the depicted (Scheme 2.18) linear polymer in which the thiophene rings are connected by dusulfide bridges. It was recently confirmed that tristhiomaleic anhydride is nnstable and polymerizes just at the moment of its formation (see Paulssen et al. 2000, Ref. 15 therein). 

Sebemk A (1998) Living free-radical block copolymerization using thio-iniferters. Prog Polym Sd 23 875-917... 

Though much effort has been spent on possible utilization of poly(thio-formaldehyde), no uses for the polymer have been developed. Most samples of the polymer cannot be melt fabricated because they are unstable in the molten state. Solvent fabrication is also impossible because the polymer is insoluble. There are two types erf poly(thioformaldehyde) that are said to be stable at high temperatures, which are polymers made by treatment of trithiane with boron trifluoride etherate and the acetylated anomalous form obtained from sodium hydrosulfide and methylene chloride. These also have not found utility. 

Because of its chemical inertness, no direct way of curing poly(thiocarbonyl fluoride) has been found. However, creep has been reduced and strength at elevated temperatures improved by milling into the polymer a free-radical generator, such as dicumyl peroxide or azobisisobutyronitrile, and a free-radical acceptor, such as N,N -m-phenylenebismaleimide or triacryloylhexahydro-s-triazine, and curing with heat and pressure (65). A better method is to mill in divinylbenzene and a small amount of benzoyl peroxide and cure with heat and pressure (66). The divinylbenzene forms a crosslinked matrix that mechanically traps poly(thio-carbonyl fluoride) molecules. Since the elastomer is in effect filled with poly(di-vinyl benzene), the final composition is less resilient than untreated poly(thio-carbonyl fluoride). 

Polyolefin poiysulfides (Thiokol) are thio analogues of polyethers which are flexible, amorphous, oil-resistant elastomers. The number of sulfur links in the repeating unit, which is called rank, is always greater than two. The solvent resistance, resistance to gaseous permeation, and flexibility of these polyolefin sulfides increase with rank. The actual strength of polymers and copolymers of olefin sulfides varies. Many of these products contain the following repeating unit ... 

Diamino-6-thio-l,3,5-triazines are potentially valuable as crosslinking agents in polymers and as accelerators in vulcanization processes (70MI22000). 

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