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EP-3841130-B1 - SYNERGISTIC COMBINATION FOR INHIBITING POLYMERIZATION

EP3841130B1EP 3841130 B1EP3841130 B1EP 3841130B1EP-3841130-B1

Inventors

  • SHI, Yongtao
  • ZHANG, GUIXI
  • ZHANG, MEI
  • XIE, Xiaoan

Dates

Publication Date
20260506
Application Date
20180824

Claims (13)

  1. A synergistic polymerization inhibitor composition, the composition comprising: a copper compound or a manganese compound, wherein the copper compound or manganese compound is between about 0.01 wt% and about 50 wt%; and a cationic polymer, wherein the cationic polymer is between about 0.01 wt% and about 90 wt%.
  2. The composition as recited in claim 1, wherein the copper compound is a copper salt selected from the group consisting of copper (II) acetate, copper (II) oxide, copper (II) sulfate, copper (II) chloride, copper (II) dithiocarbamate, copper (II) formate, copper (II) propionate, copper (II) oleate, or combinations thereof.
  3. The composition as recited in claim 1, wherein the manganese compound is a manganese salt selected from the group consisting of manganese (II) acetate, manganese (II) oxide, manganese (II) sulfate, manganese (II) chloride, manganese (II) dithiocarbamate, manganese (II) acetylacetonate, manganese (II) formate, manganese (II) propionate, manganese (II) oleate, tricarbonyl (methylcyclopentadienyl) manganese, cyclopentadienyl manganese tricarbonyl, or combinations thereof.
  4. The composition as recited in claim 1, wherein the cationic polymer comprises a plurality of repeating units, and wherein at least 20% of the repeating units are positively charged.
  5. The composition as recited in claim 1, wherein the cationic polymer is [Al(OH) n C 3-n ] m , where n = 1.0 to 2.5, m ≤ 20.
  6. The composition as recited in claim 1, wherein the cationic polymer is selected from the group consisting of a polydiallyldialkylammonium salt, a polymer formed from an amine and epihalohydrin or dihaloalkane, an epichlorohydrin-dialkylamine polymer, an epichlorohydrin-dialkylamine-ethylenediamine polymer, a polymer formed from a vinyltrialkylammonium salt, a polyaluminum salt, a polymer of dialkylaminoalkyl (meth) acrylates, a polymer of dialkylaminoalkyl (meth) acrylamides, a poly [2- (acryloyloxy) ethyl] trimethylammonium salt, or a polymethacryloxyethyltrimethylammonium salt.
  7. The composition as recited in claim 1, wherein the copper compound or manganese compound in the composition is at least 100 ppm, and the cationic polymer is at least 100 ppm.
  8. A method for inhibiting polymerization of unsaturated polymerizable monomers, the method comprising: adding a synergistic polymerization inhibitor composition to a monomer manufacturing system or component thereof, the composition comprising, a copper salt or a manganese salt, and a cationic polymer.
  9. The method as recited in claim 8, wherein the monomer is methacrylic acid, and the synergistic polymerization inhibitor composition inhibits methacrylic acid polymerization.
  10. The method as recited in claim 8, wherein the monomer is an acrylate, and the synergistic polymerization inhibitor composition inhibits acrylate polymerization.
  11. The method as recited in claim 8, wherein the monomer is a methacrylate, and the synergistic polymerization inhibitor composition inhibits methacrylate polymerization.
  12. The method as recited in claim 8, wherein the monomer is an acrolein, and the synergistic polymerization inhibitor composition inhibits acrolein polymerization.
  13. The method as recited in claim 8, wherein the monomer is an acrylonitrile, and the synergistic polymerization inhibitor composition inhibits acrylonitrile polymerization.

Description

FIELD OF INVENTION The disclosed technology generally described hereinafter provides for a synergistic composition for inhibiting polymerization of unsaturated polymerizable monomers, and more specifically, a synergistic composition for polymerization inhibition of acrylic acid or methacrylic acid. BACKGROUND OF THE INVENTION A major problem with the manufacturing of unsaturated polymerizable monomers is the polymerization of said monomers. In the absence of efficient polymerization inhibitors or dispersants, the undesired polymerization during manufacturing causes many problems, like fouling or blocking of the equipment, which will reduce the run time or increase cost to clean the system. Thus, an efficient polymerization inhibitor or dispersant is preferred to keep the manufacturing smooth and safe. There are many types of polymerization inhibitors or dispersants for this application, including phenols, hydroquinone, phenothiazine, copper salts, manganese salts, stable free radicals, like 4-hydroxy-(2,2,6 6-tetramethylpiperidin-1-yl)oxyl (or 4-hydroxy TEMPO), etc. Such inhibitors or dispersants can be used alone, or in combination, to inhibit polymerization. However, new inhibitors or dispersants with better inhibition efficiency are desired. US 4814493 discloses a process for the production of CI-C8 alkyl acrylate by the reaction of a C I-C8 alkyl alcohol with acrylic acid in the presence of esterification catalysts and soluble manganese or cerium ions. US 4507495 discloses a process of producing ethyl acrylate by the reaction of ethylene and acrylic acid in the presence of sulfuric acid. Using phenolic type inhibitors, soluble manganese or cerium salts. JP 2001348359 discloses a method comprises using. in a refining column as poly merization inhibitors N-nitrosophenylhydroxylamine or a salt in combination with a manganese salt compound and/or phenothiazine compound. EP 2398832 discloses a polymerization inhibitor composition and a method of inhibiting polymerization of distillable monomers in liquid and evaporated/condensed phases with the polymerization inhibitor composition. US 2010130766 discloses a method for inhibiting polymerization of (meth)acrylic acid a step of inhibiting polymerization of (meth)acrylic acid and/or the ester thereof by using a solution of a dialkyldithiocarbamic acid copper salt dissolved in an organic solvent. US5371280 discloses polymerization inhibitors against polymerization of vinyl compounds. The inhibitors may comprise joint use of a coppers salt and a manganese salt. SUMMARY OF THE INVENTION The disclosed technology generally described hereinafter provides for a composition and method for a synergistic polymerization inhibitor as set out in the appended claims. In some embodiments, the composition comprises a copper compound, and a manganese compound. In some embodiments, the copper compound is a copper salt selected from the group consisting of copper (II) acetate, copper (II) oxide, copper (II) sulfate, copper (II) chloride, copper (II) dithiocarbamate, copper (II) formate, copper (II) propionate, and copper (II) oleate. In some embodiments, the manganese compound is a manganese salt selected from the group consisting of manganese (II) acetate, manganese (II) oxide, manganese (II) sulfate, manganese (II) chloride, manganese (II) dithiocarbamate, manganese (II) acetylacetonate, manganese (II) formate, manganese (II) propionate, manganese (II) oleate, tricarbonyl (methylcyclopentadienyl) manganese, cyclopentadienyl manganese tricarbonyl, or combinations thereof. In some embodiments, the copper compound is at least 100 ppm. In some embodiments, the manganese compound is at least 100 ppm. The copper compound is between about 0.01 wt% and about 50 wt%. The manganese compound is between about 0.01 wt% and about 50 wt%. The claimed composition comprises a copper compound or a manganese compound; and a cationic polymer. In some embodiments, the copper compound is a copper salt selected from the group consisting of copper (II) acetate, copper (II) oxide, copper (II) sulfate, copper (II) chloride, copper (II) dithiocarbamate, copper (II) formate, copper (II) propionate, and copper (II) oleate. In some embodiments, the manganese compound is a manganese salt selected from the group consisting of manganese (II) acetate, manganese (II) oxide, manganese (II) sulfate, manganese (II) chloride, manganese (II) dithiocarbamate, manganese (II) acetylacetonate, manganese (II) formate, manganese (II) propionate, manganese (II) oleate, tricarbonyl (methylcyclopentadienyl) manganese, cyclopentadienyl manganese tricarbonyl, or combinations thereof. In some embodiments, the cationic polymer has molecular weight greater than 500. In some embodiments, the cationic polymer comprises a plurality of repeating units, and wherein at least 20%of the repeating units are positively charged. In some embodiments, the cationic polymer is [Al(OH)nCl3-n]m, where n = 1.0 to 2.5, m ≤ 20. In some embodiments, th