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United States Patent (19) 11) Patent Number: 5,072,065 Sun Et Al

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United States Patent (19) 11) Patent Number: 5,072,065 Sun Et Al United States Patent (19) 11) Patent Number: 5,072,065 Sun et al. 45 Date of Patent: Dec. 10, 1991 54 NHIBITING POPCORN POLYMER FORMATION WITH ALKYL HALDES FOREIGN PATENT DOCUMENTS 63-223003 9/1988 Japan. (75) inventors: Hsiang-ning Sun, Houston, Tex.; Steven J. Potlock, Baton Rouge, La. OTHER PUBLICATIONS Liu, Plugging-Up of Equipment by Self-Polymeriza (73) Assignee: Exxon Chemical Patents Inc., tion Butadiene Production and its Prevention, China Linden, N.J. Synthetic Rubber Industry, 11(5) 356-360 (1988) & English abstract. 21 Appl. No.: 647,358 Liu et al., Determination of Traces of Diethylhydrox ylamine Inhibitor in c5 Fraction by Gas Chromatogra 22 Fied: Jan. 29, 1991 phy, China Synthetic Rubber Industry, 12(6), 408-410 (1989) & English abstract. (51 Int, C. ........................... C07C 7/20; B08B 9/00 (52) U.S. C. ..................................... 585/2; 134/22.19; Primary Examiner-Curtis R. Davis 585/3,585/950 Attorney, Agent, or Firm-Linda K. Russell (58 Field of Search ............................... 585/3, 2,950; 57 ABSTRACT 34/22.19 Inhibition of popcorn polymer growth by treatment with an alkyl halide. This compound can be admixed (56) References Cited with organic material from which popcorn polymer is U.S. PATENT DOCUMENTS formed, or added to a system for the recovery, use or 4,404,413 9/1983 Heskell ................................ 585/950 storage of such organic material. 4,941,926 7/1990 Nakajima ................................ 585/5 4,956,020 9/1990 Nakajima ................................ 585/5 16 Claims, No Drawings 5,072,065 1. 2 once present in a system. Some of the seeds become NHIBITING POPCORN POLYMER FORMATION attached to the processing and handling equipment, and WITH ALKYL HALDES cannot be readily removed by mechanical means; more over, being insoluble in most common solvents, they are CONCURRENTLY FILED APPLICATIONS virtually impossible to wash out by use of such solvents. Concurrently with this application, also filed were Even after equipment and storage facilities have been applications entitled METHOD FOR INHIBITING cleaned thoroughly, residual particles of popcorn poly POPCORN, POLYMER FORMATION BY HEAT, mer remain, and promote unwanted polymer growth. Ser. No. 07/647,365, filed Jan. 29, 1991; INHIBITING Trace particles remaining in the equipment will stay POPCORN POLYMER FORMATION WITH SUL 10 active for long periods without the presence of mono FUR-CONTAINING COMPOUNDS, Ser. No. mer, and serve to initiate polymerization when once 07/647,356, filed Jan. 29, 1991; INHIBITING POP again contacted therewith. CORN POLYMER FORMATION WITH ESTERS Different inhibitors are known for use against pop OF INORGANIC ACIDS, Ser. No. 07/647,359, filed corn polymer formation. Examples of these are the Jan. 29, 1991 and INHIBITING POPCORN POLY 5 following: t-butylcatechol; sodium nitrite, as disclosed MERFORMATION WITH COMPOUNDS INCOR in LIU, "Plugging-Up of Equipment by Self-Polymeri PORATING GROUP IV ELEMENTS, Ser. No. zation Butadiene Production and Its Prevention,' China 07/647,357, filed Jan. 29, 1991. These applications are all Synthetic Rubber Industry, 11(5) 357-360 (1988); carbon incorporated herein in their entireties, by reference disulfide and elemental phosphorous, as disclosed in thereto. 20 HASKELL, U.S. Pat. No. 4,404,413, which also refers to hydrogen sulfide, to ethane-, propane-, and hexane BACKGROUND OF THE INVENTION thiol, and to ethyl disulfide as being known in the prior . Field of the Invention art; N,N-dialkylhydroxylamines, as disclosed in The present invention is directed to inhibiting or TOKAI ELECTROCHEMICAL CO., Japanese preventing popcorn polymer growth or formation, par 25 Kokai No. 66,223,003, as well as in LIU et al., "Deter ticularly such growth or formation in organic material. mination of Traces of Diethylhydroxylamine Inhibitor The desired result is effected by treatment with one or in C5 Fraction by Gas Chromatography,” China Syn more alkyl halides. This treatment is conducted with an thetic Rubber Industry, 12(6)408-410 (1989), and in amount of such inhibitor sufficient to prevent, inhibit, retard, or stop popcorn polymer growth. 30 ALBERT, U.S. Pat. No. 3,148,225, the latter of these 2. Description of Background and Other Information also referring to nitrites, nitroso compounds, NO2, Popcorn polymers are known to form from all man N2O3, phenolic compounds, sulfur, aromatic amines, ner of organic material, particularly olefinically unsatu and hydroxylamine as being known in the prior art; rated monomers, including olefins and diolefins; espe trialkylamine oxides, as also disclosed in TOKAI cially susceptible are the conjugated diolefins, e.g., bu 35 ELECTRO-CHEMICAL CO.; N-hydroxymorpho tadiene and isoprene, and vinyl compounds, e.g., sty line, used in conjunction with N,N-dialkylhydroxyla renes and acrylates. Known as popcorn polymers be mines, as disclosed in WHITON et al., U.S. Pat, No. cause they resemble popped corn, these polymers are 3,265,752, or in conjunction with N-hydroxypiperidine, also referred to in the art as sponge polymers, granular as disclosed in McCOY et al., U.S. Pat. No. 3,265,751; polymers, cauliflower-like polymers, nodular polymers, adducts of phenols and hydroxylamines, as disclosed in fluffy polymers, proliferous polymers, and crusty poly ALBERT et al., U.S. Pat. No. 3,493,063; reaction prod e.S. ucts of nitrous acid and 1,3-dichlorobutene-2 or diiso Popcorn polymer has been considered to occur from butylene, as disclosed in BENJAMINS, U.S. Pat. No. spontaneous monomer polymerization. It can occur in 3,560,577, which also refers to nitrogen dioxide, the both liquid phase and vapor phase, and at any stage of 45 addition product of 1,3-dichloro-2-butene and nitrogen use or handling of the monomer, e.g., recovery, separa dioxide, and ion-exchange resin containing nitrite ions, tion, manufacturing, purification, storage, etc. High as being known in the prior art; butyraldoxime, as dis concentrations of monomer are particularly advanta closed in KEOWN, U.S. Pat. No. 2,947,795; and nitro geous for its formation. gen tetroxide-diisobutylene addition products, as dis Specifically, it appears that the presence of one or 50 closed in COLBERT, U.S. Pat. No. 3,175,012. more initiators - e.g., water, oxygen, hydrogen peroxide Those inhibitors known in the prior art are generally - results in the formation of popcorn polymer "seeds' in effective in stopping the formation of popcorn polymer the organic material. The seeds themselves then perpet seeds. However, they are only minimally effective in uate polymerization, without further requiring an initia stopping the growth of seeds already in existence. Fur tor and/or a crosslinking agent; they serve as sites for 55 ther, such inhibitors which are relatively heavy will further polymerization. work in liquid phase, but are of little or no use in vapor As the particular mechanism, it is believed that mono phase, because in this state their weight hinders their ner diffuses through the surface of the growing poly distribution. mer mass, and is added to the polymer at the center It has been discovered that alkyl halides will inhibit thereof. For this reason, such polymerization is referred 60 popcorn polymer formation. For instance, these com to as occurring "from the inside out.' pounds can be used to treat organic material wherein Consequently, there is continued incorporation of such popcorn polymer formation occurs. Specifically, monomer into the polymer phase, leading to buildup of they may be admixed with, or added to, such organic the popcorn polymer. The result is a hard polymeric material during the use, handling, or storage thereof. foulant, which can cause serious equipment and safety 65 SUMMARY OF THE INVENTION concerns if left unchecked. A particular problem attendant upon popcorn poly According to the invention, inhibition of popcorn mer formation is its extreme resistance to deactivation, polymer growth is effected with an inhibitor compris 5,072,065 3. 4. ing an alkyl halide. Included within the scope of the Specifically, suitable such organic material includes invention are the alkyl halides having the formula: monovinyl compounds such as styrene, acrylic acid and its esters, such as methyl acrylate, ethyl acrylate, and butyl acrylate; methacrylates such as methyl methacry 5 late, ketones such as methyl vinyl ketone, and nitriles wherein R is an alkyl group, and X is selected from the such as acrylonitrile. Appropriate divinyl compounds group consisting of fluorine, chlorine, bromine, and include 1,3-butadiene, isoprene, dimethyl-2,3-buta-1,3- iodine. diene,chloroprene, and bromoprene. Preferably, R is selected from the group consisting of Further as to the organic material, two or more mon C1-10 alkyl; methyl, ethyl, and isopropyl are particularly 10 omers, such as any combination of those discussed preferred. Suitable alkyl halides of the invention include above, as well as popcorn polymer sources or seeds methyl iodide, ethyl iodide, isopropyl iodide, ethyl bro formed from any such combination, may also be treated mide, isopropyl bromide, and methyl chloride. with the inhibitor of the invention. The process of the invention employs an amount of While retaining its ordinary meaning in the art, i.e., as the alkyl halide inhibitor sufficient to inhibit popcorn 15 the starting unit for polymerization, the term "mono polymer growth. As an aspect of the process, the inhibi mer', as used herein, is understood to encompass all tor is added to a system for organic material from which organic material suitable for treatment with the alkyl popcorn polymer is formed. halides of the invention. It is further understood as Preferably, the popcorn polymer-forming material encompassing all such organic material wherein is comprises at least one vinyl compound. More prefera 20 formed the popcorn polymer whose growth or forma bly, the at least one vinyl compound comprises at least tion is to be inhibited. one divinyl compound. The invention pertains to any process utilizing at least In a particularly preferred embodiment of the process one alkyl halide for inhibiting popcorn polymer growth of the invention, the organic material itself is treated or formation.
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