High-molecular-weight, synthesis

Fischer-Tropsch reaction The catalytic reaction of hydrogen and carbon monoxide (synthesis gas ) to produce high-molecular weight hydrocarbons. 

Many challenging industrial and military applications utilize polychlorotriduoroethylene [9002-83-9] (PCTFE) where, ia addition to thermal and chemical resistance, other unique properties are requited ia a thermoplastic polymer. Such has been the destiny of the polymer siace PCTFE was initially synthesized and disclosed ia 1937 (1). The synthesis and characterization of this high molecular weight thermoplastic were researched and utilized duting the Manhattan Project (2). The unique comhination of chemical iaertness, radiation resistance, low vapor permeabiUty, electrical iasulation properties, and thermal stabiUty of this polymer filled an urgent need for a thermoplastic material for use ia the gaseous UF diffusion process for the separation of uranium isotopes (see Diffusion separation methods). 

The synthesis of the high molecular weight polymer from chlorotrifluoroethylene [79-38-9] has been carried out in bulk (2 >—21 solution (28—30), suspension (31—36), and emulsion (37—41) polymerisation systems using free-radical initiators, uv, and gamma radiation. Emulsion and suspension polymers are more thermally stable than bulk-produced polymers. Polymerisations can be carried out in glass or stainless steel agitated reactors under conditions (pressure 0.34—1.03 MPa (50—150 psi) and temperature 21—53°C) that require no unique equipment. 

Polymerization ofiVIasked Disilenes. A novel approach, namely, the anionic polymerization of masked disilenes, has been used to synthesize a number of poly(dialkylsilanes) as well as the first dialkylamino substituted polysilanes (eq. 13) (111,112). The route is capable of providing monodisperse polymers with relatively high molecular weight M = lO" — 10 ), and holds promise of being a good method for the synthesis of alternating and block copolymers. 

Some apphcations require PE with a very high molecular weight nearly 10 times that of common PE materials. These resins are essentially nonbranched and require special catalysts, synthesis, and fabrication techniques. 

Processes for HDPE with Broad MWD. Synthesis of HDPE with a relatively high molecular weight and a very broad MWD (broader than that of HDPE prepared with chromium oxide catalysts) can be achieved by two separate approaches. The first is to use mixed catalysts containing two types of active centers with widely different properties (50—55) the second is to employ two or more polymerization reactors in a series. In the second approach, polymerization conditions in each reactor are set drastically differendy in order to produce, within each polymer particle, an essential mixture of macromolecules with vasdy different molecular weights. Special plants, both slurry and gas-phase, can produce such resins (74,91—94). 

There are two commercial PPS processes being practiced worldwide the Phillips process and the Kureha process. Although these processes contain some common steps, there are distinguishing features, most notably in the reagents used to faciUtate the synthesis of high molecular weight linear PPS. 

Poly(arylene vinylenes). The use of the soluble precursor route has been successful in the case of poly(arylene vinylenes), both those containing ben2enoid and heteroaromatic species as the aryl groups. The simplest member of this family is poly(p-phenylene vinylene) [26009-24-5] (PPV). High molecular weight PPV is prepared via a soluble precursor route (99—105). The method involves the synthesis of the bis-sulfonium salt from /)-dichloromethylbenzene, followed by a sodium hydroxide elimination polymerization reaction at 0°C to produce an aqueous solution of a polyelectrolyte precursor polymer (11). This polyelectrolyte is then processed into films, foams, and fibers, and converted to PPV thermally (eq. 8). 

In these types of 1,3-dipolar cycloaddition only one of two possible isomers is obtained and the pyrazole functions have different orientations by the two methods. Another classical synthesis of pyrazoles (Section 4.04.3.2.l(ii)), the reaction between hydrazines and )3-diketones, has been used with success to prepare high molecular weight polypyrazoles (Scheme 65) (81MI40400). A-Arylation (Section 4.04.2.1.3(ix)) of 4,4 -dipyrazolyl with 1,4-diiodobenzene also yields polymeric pyrazoles (69RRC1263). 

The chain extension step may then take place in the water phase. Hydrazine and ethylene diamine are commonly used chain extenders for waterborne urethane dispersions. The isocyanates react with the diamine chain extenders much faster than with the water, thus forming polyurea linkages and building a high molecular weight polymer. More detailed information regarding the synthesis and process of making waterborne polyurethane dispersions is found in Dieterich s review article [58]. 

The first polyimine was reported by Adams and coworkers [182] from terephthalaldehyde and benzidine and dianisidine. Between 1950 and 1959 Marval and coworkers [174-176] reported a number of polyimines. Suematsu and coworkers [170] reported the first successful synthesis of high molecular weight fully aromatic polyimines by solution polycondensation method using w-cresol as reaction medium. 

Polyethylene, crystallites in, 1215 high-density, 1210 high-molecular-weight, 1210 kinds of, 1210 low-density, 1210 synthesis of, 240-241 ultrahigh-molecular-weight, 1210 uses of, 242... 

Palladium-mediated catalysis has only been exploited relatively recently in the synthesis of substituted PPV derivatives. The use of aryl dibromides as monomers is particularly useful as it allows the synthesis of PPVs substituted with alkyl rather than alkoxy sidechains. The Suzuki [53, 54], Heck [55], and Stille [56] reactions have been used in the synthesis of new PPV derivatives, but attaining high molecular weight PPV derivatives by these methodologies has proved problematic. A phenyl-subslilutcd PPV material PPPV 31 was synthesized by a Suzuki coupling (Scheme 1-10) of dibromoethene and fo/.v-boronic acid 30. Its absorption (2ni ix=385 nm) and emission (2max=475 nm) maxima were strongly... 

Wayland et al. reported the use of tetramesitylporphyrin complexes (CoTMP), including 118231 and 119251 in the synthesis of high molecular weight PMA with very low dispersities (1.1-1.3). Arvanilopoulos et al.m have reported similar chemistry with alkylcobaloximes (120) as photoinitiators at low temperatures. 

Synthesis of High Molecular Weight Poly (p-Pinene)... 

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