EP1802564A1 - Verwendung von phosphorester als ablagerungssteuermittel während der synthese, reinigung oder regenerierung von (meth)acrylmonomeren - Google Patents

Verwendung von phosphorester als ablagerungssteuermittel während der synthese, reinigung oder regenerierung von (meth)acrylmonomeren

Info

Publication number
EP1802564A1
EP1802564A1 EP05809243A EP05809243A EP1802564A1 EP 1802564 A1 EP1802564 A1 EP 1802564A1 EP 05809243 A EP05809243 A EP 05809243A EP 05809243 A EP05809243 A EP 05809243A EP 1802564 A1 EP1802564 A1 EP 1802564A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylic
use according
compounds
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05809243A
Other languages
English (en)
French (fr)
Inventor
Jean-François Croizy
Michel Fauconet
Jean-Michel Paul
René BONNAZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP1802564A1 publication Critical patent/EP1802564A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/14—Derivatives of phosphoric acid

Definitions

  • the present invention belongs to the field of synthesis, purification and regeneration of (meth) acrylic monomers such as acrylic acid and methacrylic acid as well as C 1 -C 6 alkyl acrylates and methacrylates. More particularly, the present invention relates to the suppression or at least to the limitation of the fouling phenomena due to the deposition of polymers and / or insoluble heavy products, in the installations used for the aforementioned operations of synthesis, purification or regeneration.
  • Synthetic reactions of the (meth) acrylic monomers include: catalytic gas phase oxidation of propylene or propane to produce acrylic acid; catalytic oxidation of isobutene or tertiobutanol to generate methacrylic acid; the synthesis of sulfuric methacrylamide from acetone cyanohydrin, methanol and sulfuric acid to produce methyl methacrylate; the production of (meth) acrylic esters from (meth) acrylic acid and alcohols.
  • polymerization inhibitors are added to the streams.
  • the polymerization inhibitors conventionally used in processes for purifying (meth) acrylic monomers are numerous. Mention may be made, among them, of phenolic compounds, phenothiazine and its derivatives, manganese salts, thiocarbamates and dithiocarbamates, N-oxyl compounds, amine compounds and nitroso compounds, examples of these various compounds being indicated more far.
  • polymerization inhibitors used alone or in combination, is generally increased when they are used in combination with a introduction of oxygen or a gas stream containing oxygen at the bottom of the column.
  • These polymerization inhibitors can be introduced as they are, for example when they are liquid, or in solution in a solvent and, preferably, in solution in the monomer itself.
  • the monomer purification operations are often accompanied by the formation of polymers, soluble or insoluble in the medium, depending on the nature of the monomer and the composition of the medium.
  • the polymer formed is insoluble in the medium and precipitates in the form of a solid deposit.
  • Precipitation of the polymer in the medium occurs especially when the length of the polymer chain is sufficient or when multifunctional compounds generate bridges between certain units of the polymer, by a process known as crosslinking.
  • Another source of fouling of the solid deposition facilities is the presence of heavy compounds generated during the monomer synthesis reaction step.
  • (meth) acrylic monomers is accompanied by the formation of compounds resulting from a Michael addition reaction of a molecule containing a labile hydrogen atom on the double bond of a compound ( meth) acrylic:
  • insoluble polymers or heavy compounds can occur rapidly at the point where the polymerization process or the Michael addition reaction is initiated, if the polymer or heavy compound is insoluble in the medium, or if produce during a purification process step in which these products, previously dissolved, become insoluble by modifying the composition of the original medium, for example during a concentration operation of the heavy compounds by separation of light, or during the elimination of a polar component responsible for their solubilization.
  • problems of polymer deposits frequently occur during the drying phases of the monomers.
  • Patent documents EP 839 790, DE 19 851 984 and US Pat. No. 4,440,625 disclose the use of alkyl or arylsulfonic acid derivatives as anti-fouling agents ("antifoulants") for the purpose of dispersing polymers.
  • anti-fouling agents alkyl or arylsulfonic acid derivatives
  • acrylic or heavy addition derivatives formed during the synthesis or purification of (meth) acrylic monomers, DE 19 851 984 also envisaging the case of tailing or cracking of distillation residues of (meth) acrylic monomers.
  • the tests carried out in dynamic mode with this known family of products by the applicant company did not give any results. satisfactory from the point of view of industrial application.
  • the Applicant Company has therefore sought to solve the problems of fouling due to the deposition of solids of polymeric origin or resulting from addition reactions on the (meth) acrylic double bonds, and has discovered a family of compounds soluble in the medium containing the (meth) acrylic monomer and having the property of avoiding or effectively limiting the aforementioned deposits in the equipment for synthesis, purification or regeneration of the (meth) acrylic monomer.
  • the present invention therefore firstly relates to the use of at least one compound of formula (I):
  • R 1 represents a C 3 -C 30 alkyl radical, an aryl radical or an alkylaryl radical, these radicals being able to be interrupted or connected to the oxygen of the molecule by a chain - (OR 4 ) o - where R 4 each independently represents an ethylene, propylene or butylene chain and o is an integer of 1 to 50;
  • R 2 represents R 1 , a hydrogen atom or a counterion
  • R 3 represents a hydrogen atom or a counter-ion, as an anti-deposit agent (which can also be designated as antifouling or antifouling or antifouling agent) avoiding the deposit of compounds of polymeric nature or resulting from reactions of addition to the (meth) acrylic double bonds in synthetic or purification or regeneration of (meth) acrylic monomers.
  • an anti-deposit agent which can also be designated as antifouling or antifouling or antifouling agent
  • Compounds (I) have a dispersant property and are also known as dispersants in the following.
  • the compounds of formula (I) are especially chosen from those in which R 1 and R 2 each independently represent the radical where p is an integer of 4 to 12, preferably 8 or 9, and q is an integer of 4 to 50, preferably 6 to 20; and R 3 represents a hydrogen atom or a counterion; and / or those in which R 1 represents the radical
  • R 2 and R 3 each independently represent a hydrogen atom or a counterion.
  • the compound (s) (I) can be introduced as such into the medium containing the (meth) acrylic monomer.
  • the compound (s) may be introduced at a concentration of from 0.01 to 1% by weight, especially from 0.05 to 0.5% by weight, into the medium containing the (meth) acrylic monomer to be prepared. purify or regenerate.
  • the medium containing the (meth) acrylic monomer may also contain at least one polymerization inhibitor, in particular from 0.01% to 5% by weight, in particular from 0.05% to 3% by weight, relative to the medium containing the (meth) acrylic monomer to be prepared, purified or regenerated, the polymerization inhibitor (s) which can be chosen from: phenol derivatives such as hydroquinone and its derivatives such as methyl ether of hydroquinone; 2,6-di-tert-butyl-4-methyl phenol (BHT); and 2,4-dimethyl-6-tert-butyl phenol (Topanol A); phenothiazine and its derivatives such as methylene blue; manganese salts, such as manganese acetate; salts of thiocarbamic or dithiocarbamic acid, such as metal thiocarbamates and dithiocarbamates, such as copper di-n-butyldithiocarbamate; N-oxyl compounds, such as 4-hydroxy-2
  • Z 1 and Z 2 each independently represent an alkyl, aryl, alkylaryl or arylalkyl radical, an example being N, N'-di-sec-butyl para-phenylenediamine.
  • the invention reduces solids deposition in monomer purification plants
  • a second advantage may be to reduce the amount of stabilizers introduced into the purification equipment, to reduce their cost.
  • reaction stages of acid synthesis or (meth) acrylic esters such as those listed in the preamble of the present description
  • reactive generation steps and reaction products by thermal cracking, batchwise or continuously, in the presence or absence of catalyst.
  • the compounds (I) are introduced preferentially at the top of the column.
  • Stabilizers or polymerization inhibitors - PTZ phenothiazine
  • the dispersant used in the Examples of the invention is a mixture of neutralized ethoxylated alkylphenol mono- and diphosphate, as defined in formula (I) above, dissolved in an aromatic solvent.
  • a glass distillation equipment comprising a distillation column, a boiler, a condenser and a reflux tank.
  • the column with a diameter of 38 mm, is lined with a multiknit element made of 316L stainless steel with a height of 14 cm.
  • the vapors are generated at the bottom in a thermosiphon boiler heated by electrical resistances, of volume 200 ml, into which acrylic acid stabilized with 0.2% PTZ and 0.2% PMP is introduced. A continuous flow of air is further ensured in the liquid of the boiler.
  • the vapors are condensed at the top through a water-cooled condenser and collected in a reflux tank. The assembly is placed under reduced pressure of 1.6 x 10 4 Pa
  • the condensed liquid flow at the top is 540 g / h.
  • the liquid collected in the reflux tank is returned by a pump at the top of the column, maintaining a constant level in this container.
  • the liquid level in the boiler is kept constant by withdrawing the excess liquid.
  • the mass of polymer deposited in the multiknit packing is 6.5 g.
  • Example 2 A reference Example is carried out under the same conditions as those of Example 1, but without the dispersant: the mass of polymer recovered in the packing is 25.1 g.
  • the mass of polymer deposited in the multiknit packing is 4 g.
  • Example 2 A reference Example is carried out under the same conditions as those of Example 2, but without the dispersant: the mass of polymer recovered in the packing is 28 g.
  • a Comparative Example is carried out under the same conditions as those of Example 2, but with pure acrylic acid and dodecylbenzene sulfonic acid as dispersant: the mass of polymer recovered in the packing is 15.9 g.
  • the liquid solution contained in the boiler is cloudy, with some fine solids in suspension. After draining the liquid, some solid particles remain attached to the wall of the boiler, and disappear by a simple washing with water.
  • Example 3 Under the same conditions as in Example 3, but in the absence of the dispersant, the solid particles are agglomerated into a cluster partly suspended, and partly adhered to the wall. Deposits clinging to the wall, in greater quantity than Example 3 carried out with dispersant, are not removed by washing with water.
  • This example describes the application of the present invention to the recovery of noble products by thermal cracking, from a stream obtained at the bottom of the column for removing heavy compounds from a butyl acrylate manufacturing process.
  • the mixture composed of:
  • thermosiphon circulation glass boiler heated by electrical resistors, with a volume of 90 ml, is fed at a rate of 360 g / h by the mixture of heavy.
  • the boiler is equipped with a head section at the top, consisting of a glass element filled with a 3 cm high multiknit filling.
  • the distilled stream at the top is condensed through a circulating exchanger with water, and collected in a receiver.
  • the operation is carried out under reduced pressure of 6.7 ⁇ 10 3 Pa (50 mmHg) at a temperature of 146 ° C., measured in the boiler.
  • Example 4a In a first test (Reference Example 4a), the mixture is introduced without addition of dispersant. After 5 hours of operation, the wall of the boiler is completely covered with a solid deposit very difficult to eliminate, which makes this method of recovery unusable industrially.
  • a second test (Example 4a of the invention), 0.04% of the dispersant is added to the feed medium, and it is found that the wall of the boiler is clean after 10 hours of operation. •
  • the second step of the process catalytic thermal cracking
  • the same assembly is used, the boiler having this time a function of cracking reactor.
  • the vaporizer head stream recovered in the previous step is supplemented with sulfuric acid (4% in the medium) and PTZ (1.4%), and then introduced at a rate of 180 g / h, into the reactor .
  • the temperature imposed in the cracker is 186 ° C., and 146 g / h of a mixture containing: 71.3% of butyl acrylate are condensed at the top;
  • Example 4b_ of the invention In a second test (Example 4b_ of the invention), 0.12% of the dispersant is added to the feed medium, and it is found that the wall of the boiler is clean after 6 hours of operation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP05809243A 2004-10-11 2005-10-07 Verwendung von phosphorester als ablagerungssteuermittel während der synthese, reinigung oder regenerierung von (meth)acrylmonomeren Withdrawn EP1802564A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0410687A FR2876374B1 (fr) 2004-10-11 2004-10-11 Utilisation d'esters phosphoriques comme agents anti-depots lors de la synthese, la purification ou la regeneration de monomeres (meth) acryliques
PCT/FR2005/002480 WO2006040457A1 (fr) 2004-10-11 2005-10-07 Utilisation d'esters phosphoriques comme agents anti-depots lors de la synthese, la purification ou la regeneration de monomeres (meth ) acryliques .

Publications (1)

Publication Number Publication Date
EP1802564A1 true EP1802564A1 (de) 2007-07-04

Family

ID=34951147

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05809243A Withdrawn EP1802564A1 (de) 2004-10-11 2005-10-07 Verwendung von phosphorester als ablagerungssteuermittel während der synthese, reinigung oder regenerierung von (meth)acrylmonomeren

Country Status (4)

Country Link
US (1) US20090203938A1 (de)
EP (1) EP1802564A1 (de)
FR (1) FR2876374B1 (de)
WO (1) WO2006040457A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2901272B1 (fr) * 2006-05-18 2008-06-27 Arkema France Procede perfectionne de fabrication de (meth)acrylates d'alkyle en c1-c4
FR2980476B1 (fr) 2011-09-27 2013-08-30 Arkema France Procede de valorisation de produits nobles dans un procede de production de (meth)acrylates de dialkylaminoalkyle
WO2017041204A1 (en) * 2015-09-07 2017-03-16 Rhodia Operations Use of polymerization inhibitor compositions
CN113825723A (zh) 2019-04-02 2021-12-21 埃科莱布美国股份有限公司 具有减少的酸用量的纯二氧化氯生成系统
WO2022165710A1 (en) * 2021-02-04 2022-08-11 Rhodia Operations Anti-fouling composition and uses thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1982000147A1 (en) * 1980-07-08 1982-01-21 Co B F Goodrich Hydrophilic interpolymers of acrylic acid and an acrylate
US4444649A (en) * 1982-11-15 1984-04-24 Union Oil Company Of California Antifoulant for high temperature hydrocarbon processing
US4425223A (en) * 1983-03-28 1984-01-10 Atlantic Richfield Company Method for minimizing fouling of heat exchangers
US4814514A (en) * 1986-05-07 1989-03-21 Dai-Ichi Kogyo Seiyaku Co., Ltd. Surface active compounds having a polymerizable moiety
US5710329A (en) * 1996-10-23 1998-01-20 Nalco/Exxon Energy Chemical, L. P. Antifoulant for acrylic acid purification
JP2003147005A (ja) * 2001-11-14 2003-05-21 San-Dia Polymer Ltd 逆相懸濁重合用分散剤
FR2861725B1 (fr) * 2003-11-04 2005-12-30 Arkema Procede de purification de l'acide (meth)acrylique obtenu par oxydation d'un substrat gazeux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006040457A1 *

Also Published As

Publication number Publication date
FR2876374B1 (fr) 2007-02-23
FR2876374A1 (fr) 2006-04-14
WO2006040457A1 (fr) 2006-04-20
US20090203938A1 (en) 2009-08-13

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