The B. F. Goodrich Company

Louis Cohen

Donald E Witenhafer

James B Haehn

Pijus K Basu

Compositions of salts of water-soluble, carboxyl-containing polymers and surface active agents, deposited on polymerization reactor surfaces exposed to polymerization mixtures, substantially reduce or eliminate undesirable polymer build-up on reactor surfaces during aqueous polymerization of vinylidene monomers, even when the amount of carboxyl-containing polymers deposited on the reactor surfaces is very small.

Polymerization reactor coatings and use thereof

Anionic water soluble carboxyl-containing polymers, deposited and dried on polymerization reactor surfaces exposed to polymerization mixtures, substantially reduce or eliminate undesirable polymer build-up on reactor surfaces during aqueous polymerization of vinylidene monomers, even when the amount of carboxyl-containing polymers deposited on the reactor surfaces is in an amount as small as at least one ppm of monomers being polymerized, providing a layer on the polymerization surfaces as thin as about 0.1 to about one or more microns in thickness.

Coated polymerization vessels and methods for use thereof

The present invention relates to the polymerization of vinyl monomers either alone or copolymerized with ethylenically unsaturated polymerizable monomers having a terminal CH.sub.2 .dbd.C&lt; grouping using a free-radical yielding catalyst or catalyst system, wherein the polymerization reaction is effectively stopped by the addition to the reaction mixture of a shortstopping agent, such as, for example, 4,4'-thiodiphenol (TDP).

Shortstopping free radical polymerization of olefinic monomers

This invention relates to a polymerization reaction vessel having a coating on the inner surfaces thereof resulting from applying thereto an aqueous coating composition containing the reaction product of a thiodiphenol, or a derivative thereof, with a bleaching agent or material, such as, for example, sodium hypochlorite (NaOCl). When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 .dbd.C&lt; group, and mixtures thereof, polymer buildup on the inner surfaces of the reaction vessel is substantially reduced. Multiple charges or batches of polymer can be made in said internally coated reaction vessel without opening the same between charges thus preventing the escape of unreacted monomer(s) to the surrounding atmosphere.

Coating polymerization reactors with the reaction products of

Carboxyl or carboxyl salt containing polymers are prepared by polymerizing carboxyl containing monomers wherein greater than one percent of the carboxyl groups are neutralized with an alkali, ammonia or an amine, optionally copolymerized with other vinylidene monomers containing at least one terminal CH.sub.2 .dbd.CH&lt; group dissolved in a solvent for the monomers which is a non-solvent for the polymer with a free radical catalyst, so that the resulting polymer is obtained suspended as a fine, readily recoverable substantially non-swollen fine powder. The solvents used are moderately to strongly hydrogen bonded and have solubility parameters of from about 8 to 15.

Solvent polymerization of carboxyl containing monomers

This invention relates to the reduction of polymer buildup on the inner surfaces of a polymerization reaction vessel by applying a coating to the inner surfaces thereof. An approximate monolayer coating on the inner surfaces of the reactor results from applying thereto an aqueous solution of a hydrophilic polymer-inhibitor complex, for example, such as a complex of polyvinyl alcohol and the disodium salt of bisphenol A. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 .dbd.C&lt; grouping, and mixtures thereof, in the presence of said coating, polymer buildup on the inner surfaces of the reaction vessel is substantially eliminated.

Polymerization reactors coated with polymer-inhibitor complexes

This invention relates to a process of coating the internal surface of a polymerization reactor in order to substantially eliminate the buildup of polymer on said surfaces during the polymerization process. There is applied to the surfaces a coating composition containing a straight chain or branched polyaromatic amine dissolved in an aqueous acid solution and thereafter the coated surfaces are flushed or rinsed with water without drying the same.

Process for preventing polymer buildup in a polymerization reactor

This invention relates to a new and improved quiescent polymerization process which produces spherical beads of polymer having excellent porosity and unusually high bulk density. The process comprises polymerizing discrete droplets of liquid monomer containing a monomer-soluble free radical type catalyst while suspended in an aqueous mucilage having plastic flow properties and in the presence of a nonionic surfactant having the proper Hydrophile-Lipophile Balance (HLB), such as, for example, sorbitan monooleate. The porous bead polymers have the advantage of providing for lower cost bulk shipping, better extrusion feed, and for easy monomer stripping.

Method of preparing spherical porous bead-type polymers

This invention relates to a polymerization reaction vessel having a coating on the inner surfaces thereof resulting from applying thereto a coating composition containing the reaction product of (1) the self-condensation product of a polyhydric phenol, or (2) the condensation product of two or more polyhydric phenols, or (3) the self-condensation product of a polyhydric naphthol, with a bleaching material, such as, for example, sodium hypochlorite (NaOCl), dissolved in an aqueous alkaline solution. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 .dbd.C&lt; group, and mixtures thereof, polymer buildup on the inner surfaces of the reaction vessel is substantially reduced. Further, multiple charges or batches of polymer can be made in said internally coated reaction vessel without opening the same between charges thus preventing the escape of unreacted monomer(s) to the surrounding atmosphere.

Coating polymerization reactors with oligomers derived from polyhydric

This invention relates to a polymerization reaction vessel having a coating on the inner surfaces thereof resulting from applying thereto a coating composition containing, as a primary ingredient, the reaction product or oligomers of (1) an alkyl or halogen substituted phenol, such as p-chlorophenol and the like, (2) a condensing agent, such as formaldehyde, and the like, and (3) a polyhydric phenol, such as resorcinol, and the like, dissolved in water or an aqueous alkaline solution. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers, having at least one terminal ##STR1## and mixtures thereof, polymer buildup on the inner surfaces of the reaction vessel is substantially eliminated. Further, multiple charges or batches of polymer can be made in said internally coated reaction vessel without opening the same between charges thus preventing the escape of unreacted monomer(s) to the surrounding atmosphere.

Coating polymerization reactors with oligomer coatings derived from

This invention relates to a polymerization reaction vessel having an approximate monolayer coating on the inner surfaces thereof which is obtained by applying thereto an aqueous coating solution containing a tannin, such as, for example, tannic acid. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 =C&lt; grouping, in such a coated reaction vessel, polymer build-up on the inner surfaces thereof is substantially eliminated. Multiple charges of polymer can be made in said coated vessel without opening the same between charges thus preventing the escape of unreacted monomer to the atmosphere.

Internally coated reaction vessel for use in olefinic polymerization

This invention relates to a polymerization reaction vessel having an approximate monolayer coating on the inner surfaces thereof which is obtained by applying thereto an aqueous coating solution containing a tannin, such as, for example, tannic acid. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 .dbd.C&lt; grouping, in such a coated reaction vessel, polymer buildup on the inner surfaces thereof is substantially eliminated. Multiple charges of polymer can be made in said coated vessel without opening the same between charges thus preventing the escape of unreacted monomer to the atmosphere.

This invention relates to a polymerization reactionvessel having an approximate monolayer coating on the inner surface thereof resulting from applying thereto an aqueous alkali metal hydroxide coating solution containing a straight chain or branched polyaromatic amine and a dispersant operable in aqueous media, such as, for example, polyvinyl alcohol. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 .dbd.C&lt; grouping, and mixtures thereof, in the presence of said coating, polymer build-up on the inner surfaces of the reaction vessel is substantially eliminated. Further, multiple charges or batches of polymer can be made in said internally coated reaction vessel without opening the same between charges thus preventing the escape of unreacted monomer to the atmosphere.

This invention relates to a polymerization reaction vessel having a coating on the inner surfaces thereof resulting from applying thereto a coating composition containing, as a primary ingredient, (1) the self-condensation product of a polyhydric phenol, or (2) the condensation product of two or more polyhydric phenols, or (3) the self-condensation product of a polyhydric naphthol, dissolved in an aqueous alkali metal hydroxide solution. When polymerizing olefinic monomers, such as vinyl halides, vinylidene halides, and vinylidene monomers having at least one terminal CH.sub.2 .dbd.C&lt; group, and mixtures thereof, in the presence of said coating, polymer build-up on the inner surfaces of the reaction vessel is substantially eliminated. Further, multiple charges or batches of polymer can be made in said internally coated reaction vessel without opening the same between charges thus preventing the escape of unreacted monomer to the surrounding atmosphere.

In the aqueous polymerization of vinyl chloride and vinylidene chloride polymers and copolymers in reactors having exposed metal surfaces, undesirable thin polymer build up is noted on the metal surface exposed to the polymerization media. Such polymer build up is substantially reduced if before the polymerization the reactor is first mechanically cleaned to remove visible polymer deposits and then cleaned of organic materials adsorbed on the metal surfaces; and thereafter between polymerization charges as required, by treatment with a hot-alkali detergent mixture to remove organic residues from the surface of said metal surfaces.

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Avon Lake, OH, United States of America

Louis Cohen