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WO2021022550A1 - Compositions inhibitrices de polymérisation et leurs utilisations - Google Patents

Compositions inhibitrices de polymérisation et leurs utilisations Download PDF

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Publication number
WO2021022550A1
WO2021022550A1 PCT/CN2019/099785 CN2019099785W WO2021022550A1 WO 2021022550 A1 WO2021022550 A1 WO 2021022550A1 CN 2019099785 W CN2019099785 W CN 2019099785W WO 2021022550 A1 WO2021022550 A1 WO 2021022550A1
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polymerization
composition
monomer
inhibiting composition
present
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Jing Jiang
Ding Wang
David Vanzin
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Rhodia Operations SAS
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Rhodia Operations SAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives

Definitions

  • the present invention relates to the field of the industrial preparation of ethylenically unsaturated monomers comprising at least one heteroatom, such as acrylic monomers.
  • Ethylenically unsaturated monomers have the property of undergoing spontaneous polymerization, more particularly under the effect of heat. This polymerization proves disruptive during monomer preparation steps, particularly during the manufacture, purification, and storage of said monomers. Unless it is prevented, it gives rise to detrimental yield losses. Frequent stops for plant maintenance are then necessary, in order to remove the deposits formed, and the production capacities are therefore reduced as a result, and in that case an extra production cost is incurred.
  • acrylic acid or acrylic esters from acrylic acid conventionally requires a distilling operation for the purposes of separating, concentrating, or purifying the monomer in question.
  • Acrylic acid when taken to a higher temperature, like that required for a distillation, exhibits a tendency to polymerize.
  • the polymeric material thus formed in liquid phase or vapor phase, then undergoes deposition on the various pieces of equipment employed for the process, and more particularly on the walls of the columns, on the plates, and on the condensers. The result of this is fouling of this equipment with, for example, substantial pressure losses in the distillation columns.
  • polymerization inhibitors are commonly employed. These are, most frequently, phenol derivatives, amine derivatives, thiazine derivatives, nitroso derivatives, and N-oxyl derivatives. Other polymerization inhibitors are also known, such as metal salts or else, particularly, quinone derivatives.
  • phenol derivatives such as, particularly, hydroquinone (HQ) , methyl ether of HQ (MEHQ) , 2, 6-di-tert-butyl-paracresol (BHT) , and 2, 4-dimethyl-6-tert-butylphenol (Topanol A) ; amine derivatives such as phenylenediamine, thiazine derivatives such as, particularly, phenothiazine (PTZ) or methylene blue; nitroso compounds such as N-nitrosodiphenylamine; N-oxyl derivatives such as, for example, 2, 2, 6, 6-tetramethyl-1-piperidine N-oxyl (TEMPO) and its derivatives: 4-hydroxy TEMPO (HTEMPO) , 4-methoxy TEMPO, 4-oxo TEMPO, or 4-amino TEMPO; metal salts such as, for example, iron sulfate
  • EP 765 856 describes the combined use of an N-oxyl derivative-type polymerization inhibitor with a phenol derivative-type polymerization inhibitor, with the aim of stabilizing acrylic acid during distillation or else during transport.
  • EP 1 273 565 discloses the use of hydroquinone, Topanol A, BHT, and phenothiazine, either alone or in combination, for preventing the risk of polymerization in the distillation column during the synthesis and purification of (meth) acrylic anhydride.
  • EP 1 805 128 describes the use of a polymerization inhibitor selected from the group consisting of (a) metal salts of thiocarbamic acid or dithiocarbamic acid and mixtures thereof with a phenol derivative or with phenothiazine and its derivatives, and (b) N-oxyl compounds in a mixture with 2, 6-di-tert-butyl 4-methylphenol (BHT) alone or in the presence of 2, 4-dimethyl 6-tert-butylphénol (Topanol A) .
  • a polymerization inhibitor selected from the group consisting of (a) metal salts of thiocarbamic acid or dithiocarbamic acid and mixtures thereof with a phenol derivative or with phenothiazine and its derivatives, and (b) N-oxyl compounds in a mixture with 2, 6-di-tert-butyl 4-methylphenol (BHT) alone or in the presence of 2, 4-dimethyl 6-tert-butylphénol (Topanol A)
  • WO 2013/026729 discloses a process for preparing a pulverulent composition which has inhibitory properties by an isothermal cogranulating process. Said composition is different from a simple juxtaposition of the elementary solids. For example, said composition has a melting point different from the melting point of anyone of the elementary solids. In addition, said composition has its own specific X-Ray diffraction spectrum: its rays are not the rays of the X-Ray diffraction spectrum of the elementary compounds. Thus, this document discloses the use of a new compound as a polymerization inhibitor, but not the combined use of the elementary solids.
  • US 5,650,072 proposes the addition of a naphthalene sulfonate-formaldehyde condensate during the production of acrylonitrile in order to control fouling on the walls of industrial plants.
  • US 8,067,629 describes the use of a styrene sulfonate polymer as a dispersant preventing the deposition of unwanted residues on the walls of industrial plants.
  • US 7,880,029 describes the employment of N-alkylsuccinimide during the formation of acrylic monomers.
  • WO2017041204A1 provides an inhibitor composition comprising para-methoxyphenol (PMP) and pyrocatechol (PC) , as well as at least one ancillary polymerization inhibitor.
  • PMP para-methoxyphenol
  • PC pyrocatechol
  • inhibitor (s) such as HQ in the monomer composition sometimes results in a precipitation in the production apparatus, for example at the injection point of a metering pump.
  • the inventors of the present invention unexpectedly discover that a combination of HQ and PC produces a synergistic effect in inhibition.
  • the combined use of HQ and PC shows improved performances in terms of polymerization inhibition compared to the use of HQ or PC alone.
  • the present invention provides a composition having at least similar inhibition properties or improved properties in terms of polymerization inhibition of various monomers, while providing a more cost efficient solution.
  • the inventors of the present invention unexpectedly discover that a combination of HQ, PC and PTZ produces a synergistic effect in inhibition in comparison to the use of HQ or PC alone.
  • the inventors of the present invention unexpectedly discover that the combinational use of PC in addition to HQ in the polymerization-inhibiting composition increases the solubility of HQ in the solvent or solvent mixture of the monomer composition, in comparison to the situation where PC is not used in combination with HQ.
  • the inventors of the present invention unexpectedly discover that the combinational use of PC in addition to HQ in the polymerization-inhibiting composition increases the solubility of HQ in the solvent or solvent mixture of the monomer composition in a larger extent, when the weight ratio of PC: HQ falls inside a specific range, in comparison to the situation where the weight ratio of PC: HQ falls outside the specific range.
  • a polymerization-inhibiting composition comprising or consisting of pyrocatechol (PC) and hydroquinone (HQ) .
  • a weight ratio of PC: HQ is in a range of (0.3-3) : 1, i.e., from 0.3: 1 to 3: 1.
  • the weight ratio of PC: HQ is in the range of (0.4-1.6) : 1, specifically for example one of 0.4: 1, 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1, 0.9: 1, 1: 1, 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1 and 1.6: 1.
  • the polymerization-inhibiting composition is used in a monomer composition to inhibit polymerization of the monomer (s) .
  • the polymerization-inhibiting composition of the present invention is generally present in the monomer composition in a range of 20-5000 ppm by weight, preferably 50-4000 ppm, more preferably 90-3000 ppm by weight, relative to the total weight of the monomer composition.
  • the amount of polymerization-inhibiting composition of the present invention is lower or equal to 2000 ppm, preferably 1000 ppm, more preferably 500 ppm, and still more preferably below 300 ppm.
  • the polymerization-inhibiting composition of the present invention is present in the monomer composition in a range of 100-200 ppm by weight, specifically for example one of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and 200 ppm, relative to the total weight of the monomer composition.
  • a combination of PC and HQ is generally present in the monomer composition in a range of 20-5000 ppm by weight, preferably 50-4000 ppm, more preferably 90-3000 ppm by weight, relative to the total weight of the monomer composition.
  • the amount of polymerization-inhibiting composition of the present invention is lower or equal to 2000 ppm, preferably 1000 ppm, more preferably 500 ppm, and still more preferably below 300 ppm.
  • a combination of PC and HQ is present in the monomer composition in a range of 100-200 ppm by weight, specifically for example one of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and 200 ppm, relative to the total weight of the monomer composition.
  • a polymerization-inhibiting composition comprising or consisting of pyrocatechol (PC) , hydroquinone (HQ) and phenothiazine (PTZ) .
  • a weight ratio of PC: HQ is in a range of (0.3-3) : 1, i.e., from 0.3: 1 to 3: 1.
  • the weight ratio of PC: HQ is in the range of (0.4-1.6) : 1, specifically for example one of 0.4: 1, 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1, 0.9: 1, 1: 1, 1.1: 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1 and 1.6: 1.
  • the polymerization-inhibiting composition is used in a monomer composition to inhibit polymerization of the monomer (s) .
  • the polymerization-inhibiting composition of the present invention is generally present in the monomer composition in a range of 20-5000 ppm by weight, preferably 50-4000 ppm, more preferably 90-3000 ppm by weight, relative to the total weight of the monomer composition.
  • the amount of polymerization-inhibiting composition of the present invention is lower or equal to 2000 ppm, preferably 1000 ppm, more preferably 500 ppm, and still more preferably below 300 ppm.
  • the polymerization-inhibiting composition of the present invention is present in the monomer composition in a range of 100-200 ppm by weight, specifically for example one of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and 200 ppm, relative to the total weight of the monomer composition.
  • a combination of PC and HQ is present in the monomer composition in a range of 20-5000 ppm by weight, preferably 50-4000 ppm, more preferably 90-3000 ppm by weight, relative to the total weight of the monomer composition.
  • the amount of polymerization-inhibiting composition of the present invention is lower or equal to 2000 ppm, preferably 1000 ppm, more preferably 500 ppm, and still more preferably below 300 ppm.
  • a combination of PC and HQ is present in the monomer composition in a range of 100-200 ppm by weight, specifically for example one of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and 200 ppm, relative to the total weight of the monomer composition.
  • PTZ is present in the monomer composition in a range of 10-50 ppm by weight, specifically for example one of 10, 15, 20, 25, 30, 35, 40, 45 and 50 ppm, relative to the total weight of the monomer composition.
  • a weight ratio of PTZ: (HQ+PC) is in a range of (0.1-0.5) : 1, i.e., a weight percent of PTZ is 10%-50%based on a weight combination of HQ and PC in the monomer composition, specifically for example one of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%and 50%by weight.
  • the monomer composition comprises one or more ethylenically unsaturated monomer (s) comprising at least one heteroatom, which are for example selected from the group consisting of halogenated unsaturated monomers, acrylic monomers, unsaturated acrylic resins, unsaturated amides, unsaturated ethers, and vinylpyridines.
  • the ethylenically unsaturated monomers comprising at least one heteroatom are acrylic monomers, specifically for example methyl methacrylate.
  • the monomer composition comprises a solvent or a solvent mixture.
  • the solvent or solvent mixture of the monomer composition is selected from one or more of the group consisting of:
  • -alcohols including methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol etc.;
  • -ketones including acetone, butyl ketone, cyclopentanone and cyclohexanone etc.
  • -ethers including ethylene glycol monobutyl ether, diethylene glycol monomethyl ether (DEGME) and diethylene glycol monobutyl ether (DEGBE) etc..
  • DEGME diethylene glycol monomethyl ether
  • DEGBE diethylene glycol monobutyl ether
  • the polymerization-inhibiting composition further comprises at least one dispersant.
  • a use of the polymerization-inhibiting composition of the present invention to limit and/or prevent fouling of industrial equipment used in the preparation of ethylenically unsaturated monomer (s) comprising at least one heteroatom, and more particularly of purifying equipment and of peripheral equipment during purification of ethylenically unsaturated monomer (s) comprising at least one heteroatom.
  • the polymerization-inhibiting composition of the present invention to limit and/or prevent fouling of industrial equipment used during distillation.
  • a polymerization inhibiting composition according to the present invention to limit and/or prevent fouling of ethylenically unsaturated monomer (s) comprising at least one heteroatom during storage and/or handling.
  • an ethylenically unsaturated monomer is a monomer comprising at least one ethylenic unsaturation.
  • a heteroatom is any atom that is not carbon or hydrogen. Typical heteroatoms are nitrogen, oxygen, sulphur, phosphorus, chlorine, bromine, and iodine.
  • Ethylenically unsaturated monomers comprising at least one heteroatom comprise, in particular, halogenated unsaturated monomers, acrylic monomers, unsaturated acrylic resins, unsaturated amides, unsaturated ethers, and vinylpyridines.
  • Halogenated unsaturated monomers include vinyl chloride, chloroprene, vinylidene chloride, vinylidene fluoride, vinyl fluoride and mixtures thereof.
  • Acrylic monomers include unsaturated acids typified by acrylic acid (AA) , methacrylic acid (MAA) , and crotonic acid; acrylates typified by methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminomethyl acrylate, or any other acrylate derivative; methacrylates (MA) , typified by methyl methacrylate, butyl methacrylate, lauryl methacrylate, dimethylaminoethyl methacrylate, and stearyl methacrylate; acrylonitrile (ACN) , acrolein, acrylic anhydride, methacrylic anhydride and
  • Unsaturated acrylic resins include acrylated epoxy resins and polyethylene glycol diacrylate.
  • Unsaturated amides include acrylamide, N, N-dimethylacrylamide, methylenebisacrylamide, and N-vinylpyrrolidone.
  • Unsaturated ethers include vinyl methyl ether.
  • ethylenically unsaturated monomers comprising at least one heteroatom include, further, vinyl acetate, diethyl vinylphosphonate, styrenesulfonic acids and sodium styrenesulfonate.
  • the ethylenically unsaturated monomer comprising at least one heteroatom for stabilization may be selected from acrylic monomers.
  • dispenser is used to name a component preventing deposits (particularly of polymers) and the fouling of industrial equipment, particularly of purifying equipment.
  • Other terms may also be employed that are equivalent to the term “dispersant” . They include, in particular: detergent, surfactant, antifouling additive, and antideposition agent.
  • the dispersant in the sense of the present invention may be composed of a mixture of two or more dispersants.
  • -sulfonates such as styrenesulfonate, naphthalenesulfonate, for instance SUPRAGIL MNS/90, which is a polyalkylnaphthalenesulfonate sold by Solvay,
  • -esters such as the methyl ester of salicylic acid, also called methyl salicylate,
  • -tristyrylphenols such as ethoxylated TSP and tristyrylphenol phosphate ethoxylate
  • -acrylates such as ethyl methacrylate, ethoxy methacrylate, and 2-ethylhexyl acrylate
  • -amides such as dimethylamides, acrylamides such as N-tert-butylacrylamide or N- (butoxymethyl) methacrylamide,
  • -phosphates such as sodium polyphosphates such as the tripolyphosphate, phosphate esters, and ethoxylated phosphate esters,
  • the dispersant may be polyalkylnaphthalenesulfonate, particularly that sold by SOLVAY under the name Supragil MNS/90.
  • All of these components may be in the form of monomers, polymers, or copolymers.
  • the total amount of dispersant may be between 10 ppm and 2%, more particularly between 50 ppm and 1%, and, for example, from 500 to 5000 ppm by weight, relative to the total weight of the ethylenically unsaturated monomer (s) comprising at least one heteroatom.
  • the increase in the rate of use of equipment via the polymerization-inhibiting activity and/or the antideposition effect may be desired in all industrial stages involving the use of ethylenically unsaturated monomer (s) comprising at least one heteroatom. Mention may be made more particularly of the stages of purification or else the stages of manufacture, storage, transport, handling, etc.
  • the purifying equipment, and more particularly distilling equipment, for which the present invention proposes, more particularly, to control fouling of their walls and their internals may be, in particular, the distillation columns themselves, scrubbing columns, absorption columns, or else all of the peripheral equipment such as condensers, pumps, boilers, phase separators, and the associated piping.
  • These inhibitor systems described in the context of the present invention may also be used in liquid/liquid extractions.
  • the polymerization inhibition systems formed by the joint presence of PC and HQ and optionally PTZ may be added entirely conventionally to the monomer to be stabilized. It is possible, moreover, to envisage the continuous or else repeated addition of said polymerization inhibition system over time, at one or more points of introduction. Furthermore, the addition of PC, HQ, PTZ, dispersants, and additives may be simultaneous or separate.
  • the dispersant in the embodiments where the dispersant is present, it may be introduced simultaneously with the polymerization inhibition system, or else separately. As for the potential points of introduction, they are identical to those envisaged customarily for polymerization inhibitors.
  • compositions specified above may further comprise a dispersant as defined earlier.
  • the polymerization-inhibiting composition may also be called a stabilizing composition.
  • the invention is directed to a process for preparing ethylenically unsaturated monomers comprising at least one heteroatom, particularly acrylic monomers, employing a distillation of said monomers, wherein said monomers are distilled in the presence of an effective amount, particularly for preventing their polymerization, of PC and HQ, and optionally PTZ.
  • the distillation temperatures at which equipment fouling is most particularly observed are commonly between 30 and 300°C, more particularly between 50 and 200°C and, for example, between 70 and 160°C, particularly at a pressure of between 0 and 3 bar in absolute pressure, more particularly between 0.1 and 2 bar, and, for example, between 0.3 and 1.5 bar in absolute pressure, and in the presence of oxygen.
  • the preset invention proves especially advantageous for these operating conditions.
  • the polymerization-inhibiting composition of the present invention may be in a solid form after having been shaped by any of various methods: powders, crystals, flakes, prills, without limitation, and obtained by mixing or by co-generation of solids (crystallizing, flaking, atomizing, prilling, granulated, pelletizing, etc. ) .
  • composition may alternatively be formulated with a solvent, and/or may be formulated with an amount of monomer in accordance with the monomer intended for treatment according to the invention.
  • the inhibitors may therefore be introduced using appropriate injection nozzles.
  • mixture comprising the monomer for stabilization is meant the whole of the phase as employed in the industrial preparation step in question–for example, at the start of a purification process, particularly distillation, particularly comprising the ethylenically unsaturated monomer or monomers comprising at least one heteroatom, such as the acrylic monomer or monomers, the polymerization inhibitors, and also any other additive there may be.
  • a composition in accordance with the invention, or the mixture for stabilization, for example for purification may further comprise one or more additives selected from detergents other than the dispersants, antioxidants, antifoams, rust inhibitors, corrosion inhibitors, and surfactants distinct from the dispersants in accordance with the invention.
  • the detergents distinct from the dispersants are advantageously selected from salicylates, phenates different from the dispersants, and sulfonates different from the dispersants.
  • the antioxidants are advantageously selected from amines different from the dispersants, and derivatives of phenol.
  • the antifoams are advantageously selected from silicones and acrylates.
  • the rust inhibitors are advantageously selected form amines different from the dispersants, esters different from the dispersants, derivatives of phenol, and sulfonates different from the dispersants.
  • the corrosion inhibitors are advantageously selected from nitrogen compounds such as triazoles and thiadiazoles.
  • the mixture to be purified and/or the polymerization inhibitors in accordance with the invention may be introduced directly into the distillation column.
  • the purification process, and particularly distillation process may more particularly be a continuous process. In that case, the supplying of monomer (s) for purification and of polymerization inhibitors takes place continuously.
  • the point at which the mixture for purification is introduced may vary according to the apparatus used. The selection of these parameters and of the apparatus is part of the general knowledge of a person skilled in the art and has no effect whatsoever on the technical effect considered in the context of the present invention.
  • the inhibitor and/or stabilizer system in accordance with the present invention may be removed at the end of the process by distillation, washing with sodium hydroxide solution, liquid-liquid extraction, or else by adsorption.
  • Figure 1 shows the apparatus used in the dynamic inhibition test.
  • Figure 2 is a schematic view of the solubility test apparatus and method.
  • Figure 3 shows the solubility curves of two solutes at different temperatures.
  • Figure 4 shows the solubility curve of HQ at different PC/HQ ratios.
  • inhibitor and/or stabilizer systems in accordance with the invention, is validated in a dynamic inhibition test, which is a reflux distillation test simulating a step of distillative purification of methyl methacrylate.
  • the apparatus used comprises a 100 ml round-bottom flask in glass, surmounted by a double-wall refrigerating column with spikes, with a height of 33 cm, and a reflux apparatus and a condenser, as shown in figure 1.
  • Table 1 shows the test conditions of the dynamic inhibition test.
  • the dynamic inhibition test comprises the following steps:
  • Distillation begins when the temperature reaches optimum settings.
  • start distillation use the reflux controller to make sure the reflux ratio is at 4: 8, meanwhile start the overhead feed to make sure the feed speed is the same to the take-off speed.
  • the inhibitors tested in the dynamic inhibition test are as follows:
  • PC -Pyrocatechol flake sold by Solvay, referred to as PC
  • PTZ -Phenothiazine prill sold by Solvay
  • Table 2 shows the compositions of the mixtures of a lab blended sample and an inhibitor or inhibitors, as well as the time passed until there is polymer forming in column plate, top of the column and condenser. The polymerization time of the composition in these positions has been assessed by visual inspection of the composition.
  • Inventors of the present invention noticed that a monomer composition with HQ as an inhibitor was prone to precipitate in the injection point of a metering pump at a low temperature between above 0°C to 10°C, in the process of MMA production.
  • the polymerization-inhibiting composition of the present invention successfully increases the low-temperature solubility of HQ and of the composition, as demonstrated by this example 2.
  • a glass reactor with a stirrer is kept at a pre-set temperature (0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C respectively for each run) , see figure 2.
  • a solvent mixture comprising 21wt%of alcohol, 76wt%of water and 2wt%of MMA is added to the reactor.
  • HQ solute
  • FIG. 2 is a schematic view of the solubility test apparatus and method.
  • the solubility of pure HQ is 7.8g, but with the help of 11g of PC, the solubility of HQ is increased to 12g, which is totally unexpected, and the solubility of the whole blend, i.e, PC+HQ, is 23g, which is three times the solubility of pure HQ.
  • the inventors of the present invention unexpectedly discover that the combinational use of PC in addition to HQ in the polymerization-inhibiting composition increases the solubility of HQ in the solvent or solvent mixture of the monomer composition in a larger extent, when the weight ratio of PC: HQ falls inside a specific range, in comparison to the situation where the weight ratio of PC: HQ falls outside the specific range.
  • a 100 ml jacket glass reactor, equipped with an oil bath and mechanical agitation is used for the test.
  • the stirrer type is a 4 blade mixing impeller.
  • the glass reactor with the stirrer is kept at 20°C temperature.
  • 50g of the solvent mixture of example 2 is prepared and then added into the reactor.
  • a certain amount of PC (as shown in table 4 for each test run) is added to the reactor to start the test, at a stirring speed of 900 rpm.
  • HQ is added in batches to dissolve, until HQ is not dissolvable any more.
  • a next run is started with addition of PC to a next amount shown in table 4.
  • the following table 4 shows the test results.
  • Figure 4 shows the solubility curve of HQ at different PC/HQ ratios at 20°C. The figure demonstrates that the solubility of HQ is increased at different extents when PC/HQ falls in different ranges. HQ solubility increases at a larger extent when the PC/HQ ratio is between about 0.4-1.3.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La composition inhibitrice de polymérisation comprenant du pyrocatéchol (PC) et de l'hydroquinone (HQ), et éventuellement de la phénothiazine (PTZ) ou constituée de ceux-ci , le rapport en poids du PC : HQ est dans la plage de (0,3-3) : 1, de préférence (0,4-1,6) : 1. La composition est utilisée pour inhiber la polymérisation d'un monomère/de monomères éthyléniquement insaturé(s) comprenant au moins un hétéroatome.
PCT/CN2019/099785 2019-08-08 2019-08-08 Compositions inhibitrices de polymérisation et leurs utilisations Ceased WO2021022550A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1111605A (zh) * 1994-01-25 1995-11-15 住友化学工业株式会社 抑制乙烯基化合物聚合的方法及其中所用的聚合阻聚剂
CN101717647A (zh) * 2009-11-26 2010-06-02 石家庄开发区永生华清液晶有限公司 一种聚合物分散液晶材料及其制备液晶薄膜的方法
US20130274519A1 (en) * 2012-03-20 2013-10-17 Basf Se Thermal separation process
CN103889939A (zh) * 2011-08-25 2014-06-25 罗地亚运作公司 用于制备包括基于至少两种聚合抑制性固体的复合物的抑制性组合物的方法
CN108026000A (zh) * 2015-09-07 2018-05-11 罗地亚经营管理公司 阻聚剂组合物的用途

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1111605A (zh) * 1994-01-25 1995-11-15 住友化学工业株式会社 抑制乙烯基化合物聚合的方法及其中所用的聚合阻聚剂
CN101717647A (zh) * 2009-11-26 2010-06-02 石家庄开发区永生华清液晶有限公司 一种聚合物分散液晶材料及其制备液晶薄膜的方法
CN103889939A (zh) * 2011-08-25 2014-06-25 罗地亚运作公司 用于制备包括基于至少两种聚合抑制性固体的复合物的抑制性组合物的方法
US20130274519A1 (en) * 2012-03-20 2013-10-17 Basf Se Thermal separation process
CN108026000A (zh) * 2015-09-07 2018-05-11 罗地亚经营管理公司 阻聚剂组合物的用途

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications

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