Specialty monomers

AH the common monobasic (107) and dibasic esters (108) of tetrahydrofurfuryl alcohol have been prepared by conventional techniques the dibasic esters and some of the mono esters are effective as primary or secondary plasticizers for vinyl polymers. Tetrahydrofurfuryl acrylate [2399-48-6] and methacrjiate [2455-24-5] specialty monomers, have been produced by carbonylation (nickel carbonyl and acetylene) of the alcohol (109) as weU as by direct esterification (110—112) and ester interchange (111). 

Pure dry reactants are needed to prevent catalyst deactivation effective inhibitor systems are also desirable as weU as high reaction rates, since many of the specialty monomers are less stable than the lower alkyl acrylates. The alcohol—ester azeotrope (8) should be removed rapidly from the reaction mixture and an efficient column used to minimize reactant loss to the distillate. After the reaction is completed, the catalyst may be removed and the mixture distilled to obtain the ester. The method is particularly useful for the preparation of functional monomers which caimot be prepared by direct esterification. 

Itaconic acid is a specialty monomer that affords performance advantages to certain polymeric coatings (qv) (see Polyesters, unsaturated). Emulsion stabihty, flow properties of the formulated coating, and adhesion to substrates are improved by the acid. Acrylonitrile fibers with low levels of the acid comonomer exhibit improved dye receptivity which allows mote efficient dyeing to deeper shades (see Acrylonitrile polymers Fibers, acrylic) (10,11). Itaconic acid has also been incorporated in PAN precursors of carbon and graphite fibers (qv) and into ethylene ionomers (qv) (12). 

Divinylbenzene. This is a specialty monomer used primarily to make cross-linked polystyrene resins. Pure divinylbenzene (DVB) monomer is highly reactive polymericaHy and is impractical to produce and store. Commercial DVB monomer (76—79) is generally manufactured and suppHed as mixtures of m- and -divinylbenzenes and ethylvinylbenzenes. DVB products are designated by commercial grades in accordance with the divinylbenzene content. Physical properties of DVB-22 and DVB-55 are shown in Table 10. Typical analyses of DVB-22 and DVB-55 are shown in Table 11. Divinylbenzene [1321 -74-0] is readily polymerized to give britde insoluble polymers even at ambient temperatures. The product is heavily inhibited with TBC and sulfur to minimize polymerization and oxidation. 

OC-Methylstyrene. This compound is not a styrenic monomer in the strict sense. The methyl substitution on the side chain, rather than the aromatic ring, moderates its reactivity in polymerization. It is used as a specialty monomer in ABS resins, coatings, polyester resins, and hot-melt adhesives. As a copolymer in ABS and polystyrene, it increases the heat-distortion resistance of the product. In coatings and resins, it moderates reaction rates and improves clarity. Physical properties of a-methylstyrene [98-83-9] are shown in Table 12. 

Specialty Monomers Product Stewardship Manual, Form No. 505-0007-1290JB, Dow Chemical USA, Midland, Mich., 1990. 

A large number of compounds related to styrene have been reported in the literature, Those having the vinyl group CH2=CH—attached to the aromatic ring are referred to as styienic monomers, Several of them have been used for manufacturing small-volume specialty polymers. The specialty styreme monomers that arc manufactured in commercial quantities arc vinyl toluene, /r, -methylstyrene, or-methylstyrene. and divinylbenzene. In addition, 4-fert-butylstyrene (TBS) is a specialty monomer that is superior to vinyltoluene and pnra-methylstyrene in many applications. Other styrenic monomers produced in small quantities include chlorostyrene and vinylbenzene chloride. With the exception of a-methylstyrene, which is a by-product of the phenol-acetone process, these specialty monomers are more difficult and expensive to manufacture than styrene... 

Vinyltoluene. Vinyltoluene (VT) is a mixture of meta- and para-vinyltoluenes, typically in the ratio of 60 40. This isomer ratio results from the ratio of the corresponding ethyltoluenes in thermodynamic equilibrium. Vinyltoluene is produced for special applications. Its copolymers are more heat-resistant than the corresponding styrene copolymers, and it is used as a specialty monomer for paint, varnish, and polyester applications. 

Divinylbenzene. This is a specialty monomer used primarily to make cross-linked polystyrene resins. The largest use of divinylbenzene (DVB) is in ion-exchange resins for domestic and industrial water softening, Ion-exchange resins are also used as solid acid catalysts for certain reactions, such as esterification. Divinylbenzene is manufactured by dehydrogenation of diethylbenzene, which is an internal product in the alkylation plant for ethylbenzene production,... 

Another example in which a biocatalytic transformation has replaced a chemo-catalytic one, in a very simple reaction, is the Mitsubishi Rayon process for the production of acrylamide by hydration of acrylonitrile (Fig. 1.42). Whole cells of Rhodococcus rhodocrous, containing a nitrile hydratase, produced acrylamide in >99.9% purity at >99.9% conversion, and in high volumetric and space time yields [121]. The process (Fig. 1.42) currently accounts for more than 100000 tons annual production of acrylamide and replaced an existing process which employed a copper catalyst. A major advantage of the biocatalytic process is the high product purity, which is important for the main application of acrylamide as a specialty monomer. 

Significantly, 1,2-dichlorovinyl carbonates and carbamates may have an interesting future as specialty monomers, for example as core materials in all-plastic optical fibers. 

Performance Chemicals, specialty chemicals (surfactants, synthetic oils, rubbers specialty monomers) and emulsion polymers based on latex Agricultural Products herbicides and seeds ... 

Next-generation soft contact lenses, dental polymers, surface coatings, and similar materials are produced from compounds of varying structure and reactive functionality. For example, currently in development are new soft lenses that will be manufactured from monomers synthesized with dimethylsil-oxane backbones. The dimethylsiloxane backbone is terminated with a methacryloxy functionality that supplies the site for polymerization. The siloxane provides lens softness. Occasionally the functionality is formed on both ends of the monomer, resulting in undesired properties. The compound BisGMA is a monomer that is polymerized to form hard dental structures. In the monomer synthesis process impurities are coproduced that interfere with the polymerization. Finally, diacetone acrylamide used in a copolymerization process is another specialty monomer that is occasionally contaminated with difficult-to-remove impurities. These three monomers are quite reactive at modest temperature and cannot be purified by distillation. The three examples that are presented here derive from as yet unpublished research (Krukonis, 1982c). 

IMI has also developed a general route for the synthesis of homo- and hetero-disubstituted benzophenones such as 4,4 -difluorobenzophenone (DFBP), 4,3 -di-fluorobenzophenone, and 4,4 -diphenoxybenzophenone (DPOBP). These substituted benzophenones are important materials, with a variety of uses as specialty monomers (for polyether ketones and polyarylene ether ketones) and pharmaceutical intermediates. These benzophenones are prepared by utilizing Heck technology in conjunction with an oxidative cleavage reaction. 

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