EP2417098A1 - Procédé de préparation continue d'alkylamino(méth)acrylamides - Google Patents

Procédé de préparation continue d'alkylamino(méth)acrylamides

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Publication number
EP2417098A1
EP2417098A1 EP10706252A EP10706252A EP2417098A1 EP 2417098 A1 EP2417098 A1 EP 2417098A1 EP 10706252 A EP10706252 A EP 10706252A EP 10706252 A EP10706252 A EP 10706252A EP 2417098 A1 EP2417098 A1 EP 2417098A1
Authority
EP
European Patent Office
Prior art keywords
meth
catalyst
acrylate
distillation column
distillation
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Withdrawn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
EP10706252A
Other languages
German (de)
English (en)
Inventor
Bardo Schmitt
Wolfgang Klesse
Martina Ebert
Dirk BRÖLL
Guido Protzmann
Joachim Knebel
Thomas Kehr
Hans-Gerhard Stadler
Gerhard Kölbl
Benedikt Laux
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.)
Evonik Roehm GmbH
Original Assignee
Evonik Roehm GmbH
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Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2417098A1 publication Critical patent/EP2417098A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/16—Amides, e.g. hydroxamic acids
    • A61K31/165—Amides, e.g. hydroxamic acids having aromatic rings, e.g. colchicine, atenolol, progabide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • H 2 C C - COOR 1 (A) + R 2 NH 2 (B)
  • H 2 C C - CONHR 2 (C) + R 1 OH (D)
  • R 1 linear or branched alkyl radical having 3 to 10
  • R 3 is hydrogen or the methyl group
  • R 2 is a linear, branched or cyclic
  • Alkyl radical an aryl radical which may also be substituted by one or more alkyl groups
  • the linear, cyclic or branched alkyl radical may have a length of 1-12 carbon atoms, and for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl and may optionally be replaced by
  • R 3 or R 4 can assume the meaning of hydrogen and where furthermore:
  • R 3 , R 4 or R 5 can either be the same or different and represent an alkyl group having 1-12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. Butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl or hydrogen.
  • R 2 can also be used
  • R 6 may be a Ci-C 4 alkyl group, which may also be branched, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert. Butyl.
  • R 7 may be the methyl group or the ethyl group.
  • Suitable amines are the following compounds: Dimethylaminoethylamine, diethylaminoethylamine, Dipropylaminoethylamin, Düsopropylaminoethylamin, dibutylaminoethylamine, Disobutylaminoehtylannin, Dimethylaminopropylannin, diethylaminopropylamine, dipropylaminopropylamine, Düsopropylaminopropylamin, dibutylaminopropylamine, Disobutylaminopropylamin, dimethylaminobutylamine, diethylaminobutylamine, Dipropylaminobutylamin, Düsopropylaminobutylamin, Dibutylaminobutylamin, Disobutylaminobutylamin, methylamine, cyclohexylamine, Dimethylaminohexylannin, Diethy
  • dimethylaminopropylannin dimethylaminoethylamine, dimethylaminobutylamine, dimethylaminopentylamine and dimethylaminohexylamine is particularly preferred.
  • the literature describes many intermittent transesterification processes (batch transesterification processes) in combination with different catalysts.
  • the continuous transesterification processes have the following advantages over the discontinuous transesterification processes: The process is easier to automate and can be operated with reduced personnel requirements, the product quality is more reproducible and less variable, the plant capacity increases due to the elimination of the sequential execution of the individual production steps (filling, reaction , Low boiler removal, product separation, emptying). The process has a higher space-time yield than a batch process.
  • EP 0 960 877 (Elf Atochem SA) describes a continuous process for the preparation of methacrylate esters of dialkylaminoalcohols. Dialkylamino alcohols are reacted with in general methyl (meth) acrylate and the dialkylaminoalkyl (meth) acrylate is obtained by the following process:
  • the mixture of the starting materials (methyl (meth) acrylate and dialkylaminoalcohol) is used together with a tetraalkyl titanate as catalyst (for example tetrabutyl, tetraethyl or tetra (2-ethylhexyl) titanate) and at least one polymerization inhibitor (for example phenothiazine, tert-butylcatechol, hydroquinone monomethyl ether or hydroquinone) continuously fed to a stirred reactor, where at a temperature of 90 0 C - 120 0 C, the reaction to dialkylaminoalkyl (meth) acrylate takes place with simultaneous continuous withdrawal of the azeotropic methyl (meth) acrylate / methanol mixture.
  • a tetraalkyl titanate for example tetrabutyl, tetraethyl or tetra (2-ethylhexyl) titanate
  • at least one polymerization inhibitor
  • the crude reaction mixture (crude ester) is fed to a first distillation column, wherein at reduced pressure at the top of the distillation column a substantially catalyst-free stream is withdrawn and withdrawn in the bottom of the distillation column of the catalyst and a little dialkylaminoalkyl (meth) acrylate.
  • the top stream of the first distillation column is then fed to a second distillation column which comprises a stream of low-boiling products containing a little dialkylaminoalkyl (meth) acrylate under reduced pressure and a stream comprising mainly dialkylaminoalkyl (meth) acrylate and polymethylation inhibitor (s) in the bottom.
  • withdrawn which is fed to a third distillation column.
  • a rectification is carried out under reduced pressure, in which the desired pure dialkylaminoalkyl (meth) acrylate ester is stripped off at the top and essentially the polymerization inhibitor or the polymerization inhibitors in the bottom.
  • the bottom stream of the first distillation column is recycled after further purification using a film evaporator as well as the top stream from the second distillation column.
  • This process dispenses with dehydration of the alcohols before use, which can lead to increased deactivation of the tetraalkyl titanate used as a result of hydrolysis up to the formation of undesired precipitation of solids.
  • the process has the disadvantage that in the first distillation column, the catalyst in the sump is thermally stressed at relatively high temperatures. This can easily lead to decomposition of the catalyst.
  • EP 0 968 995 (Mitsubishi Gas Chemical Comp.) Describes a continuous process for the preparation of alkyl (meth) acrylic acid esters using a reaction column.
  • the transesterification reaction is carried out directly in a distillation column (i.e., reactor and distillation column for withdrawing the methyl (meth) acrylate / methanol azeotrope form an apparatus) to which the starting materials (methyl (meth) acrylate and alcohol) are continuously fed.
  • the necessary catalyst here likewise preferably a titanium compound, is located in the distillation column.
  • the catalyst is continuously metered into the distillation column.
  • the use of homogeneous catalysts in a distillation column leads due to a rinsing effect by the liquid reflux in the distillation column to an increased catalyst requirement and when a
  • Catalyst precipitate for contamination of column internals In the case of a heterogeneous catalyst, the catalyst is in the reaction column. However, the positioning of the catalyst in the distillation column is disadvantageous because in the distillation column then an increased pressure loss occurs and in addition for the regular purification of the distillation column very high effort must be operated. Furthermore, heterogeneous catalysts can deactivate, for example due to undesired polymerization.
  • CN 183 71 88 (Jiangsu Feixiang Chemical Co.) describes a process for preparing N - ((- 3-dimethylamino) propyl) methacrylamide (DMAPMA) by reacting methyl methacrylate with N, N-dimethyl-1,3-propanediamine to give N - (- 3 (-3-dimethylamino) propyl) -3 - ((dimethylamino) propyl) amino) -2-methylpropanamide (BDMAPA).
  • BDMAPA is pyrolyzed in a second reaction step at 160 0 C on the metal catalyst and yields in 70 wt .-% - yield a DMAPMA with a purity of> 97%.
  • the process is described as a batch process.
  • the content of crosslinkers is quite high.
  • WO 2004/103952 (Röhm GmbH) describes a process for the continuous preparation of alkylaminoacrylamides by reaction of alkyl acrylates with high-boiling amines. Thanks to a special processing technique, previously unachieved product qualities are achieved. Furthermore, very high space-time and overall yields can be achieved. task
  • the object of the present invention is to provide a continuous process for the aminolysis of (meth) acrylic acid esters, which avoids the disadvantages of the two processes described above. Furthermore, the new process should provide a product that is better in quality than the one currently on the market. A better quality is understood to mean a lower crosslinker content or a lower content of addition products of the amines to the double bond of the starting ester or to the double bond of the product amide.
  • N-3-dimethylaminopropylmethacrylamide (Jiangsu Feixiang Chemical Co., obtained May 2008, batch number 2007/05/01) has a purity of 98.4% and a crosslinker content of 1730 ppm. The crosslinker found was N-allylmethacrylamide.
  • amino (meth) acrylates are to be prepared with as little effort and energy as possible (ie more cost-effective). The personnel costs for operating the system should be reduced. solution
  • the method is shown schematically in FIG.
  • FIG. 1 Explanations of the reference numbers FIG. 1:
  • the (meth) acrylate-feedstock (11) is fed continuously to a suitable reactor (1), wherein both a single reaction vessel and a cascade of a plurality of successively connected reaction vessels can be used.
  • a cascade may consist, for example, of 2, 3, 4, 5, 6 or optionally a plurality of individual reaction vessels.
  • a cascade of 3 consecutively operated stirred kettles is used.
  • the (meth) acrylate-feed educt (11) can be carried out in various ways. It is possible, for example, to supply the reactant stream (11) only to the first reaction vessel of the cascade or else to divide the reactant stream (11) into substreams and to supply these substreams to all or only some of the reaction vessels connected in series to the cascade. It is equally possible to carry out the feed of the feedstock stream (11) via the apparatus (2) and / or the reaction apparatuses (1). It may be advantageous to feed the educt stream (11) only into the apparatus (2) or, in another embodiment, to divide the educt stream (11) into partial streams which then both the apparatus (2) and the first or optionally a plurality of reaction vessels of the cascade be supplied.
  • the flow guidance to and from the reactors does not necessarily have to be as shown in the flow chart. It has proved advantageous in particular embodiments to introduce the discharge of a boiler of the cascade into the respective subsequent boiler of the cascade from below.
  • the amine (12) is continuously fed to the distillation column (2) for dehydration.
  • the tetraalkoxititanate required as catalyst (the tetraalkoxititanate content with respect to (meth) acrylic ester A used is preferably 0.2% by weight - 4% by weight) is likewise preferably continuously introduced into the reactor (as the polymerization inhibitor (s)). 1) added.
  • Suitable catalysts are zirconium acetylacetonate and further 1,3-diketonates of zirconium; furthermore, mixtures of alkali metal cyanates or alkali metal thiocyanates and alkali metal halides can be used, furthermore tin compounds, for example dioctyltin oxide, alkaline earth metal oxides or alkaline earth metal hydroxides, for example CaO, Ca (OH) 2 , MgO , Mg (OH) 2 or mixtures of the abovementioned compounds, furthermore alkali metal hydroxides, alkali metal alkoxides and lithium chloride and lithium hydroxide, it is also possible to use mixtures of the abovementioned compounds with the abovementioned alkaline earth compounds and the Li salts, dialkyltin oxides, for example dioctyltin oxide , Alkali metal
  • a catalyst mixture of dialkyltin oxide and alkyl titanate for example dioctyltin oxide and isopropyl titanate in a ratio of about 2.5: 1 (wt .-% / wt .-%).
  • the catalyst or the catalyst mixture is used in amounts of 0.1% by weight to 10% by weight, preferably 0.2% by weight to 7% by weight, in each case based on the (meth) acrylate used.
  • a pre-activation of the catalyst has proved to be advantageous (6).
  • the catalysts are mixed or dispersed, heated to temperatures of 90 0 C to 120 0 C and stirred for 2 to 3 hours until a homogeneous, clear solution has formed.
  • Suitable alkyl (meth) acrylates are all (meth) acrylates having a linear or branched alkyl radical having 3 to 10, preferably 3 to 6 and particularly preferably 3 or 4 carbon atoms. Typical examples thereof are propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, amyl (meth) acrylate, neopentyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, ethylhexyl (meth) acrylate or decyl (meth) acrylate.
  • the choice of starting materials is particularly advantageously such that as the alcohol is removed from the reaction mixture, the equilibrium can be shifted to the side of the products.
  • the removal of the alcohol can be carried out by distillation by its lower boiling point compared to the amine used and / or by the formation of an azeotrope.
  • polymerization inhibitors are, for example, hydroquinone, 4-hydroxy-2,2,6,6-tetra-methylpiperidinooxyl or bis (2- methoxycarbonylpropyl) sulfide or hydroquinone monomethyl ether in combination with oxygen in question.
  • the amine used may contain water.
  • the amount of water in the amine used is between 50 and 500 ppm (0.05-0.005% by weight).
  • the amine is preferably dewatered by distillation before entering the reactor, via the distillation column (2).
  • the water contained in the amine is removed overhead.
  • the task of the amine is preferably carried out in the lower part of the distillation column (2).
  • the amine used can also be dehydrated in other ways:
  • a dehydrating agent such as a molecular sieve, or
  • Dewatering is therefore important because the water in the amine can cause irreversible damage to the catalyst (e.g., tetraalkyl titanate) in the reactor.
  • the water contained in the amine leads to the formation of by-products and should therefore be strictly avoided.
  • This dewatering step avoids the hydrolysis of the catalyst and the associated costs due to increased catalyst use and problems with solid precipitates.
  • the purity of the product is increased by a reduced proportion of by-products.
  • the reaction takes place in the reactor (1) at a temperature in the range between 80 0 C and 180 0 C Depending on the material system and operating pressure. Prefers is the temperature range between 110 0 C and 160 0 C.
  • Prefers is the temperature range between 110 0 C and 160 0 C.
  • the reaction mixture which consists largely of the product alkyl (meth) acrylamide, unreacted (meth) acrylate and amine and small amounts of alcohol, the catalyst, the polymerization inhibitors and a proportion of by-products, is about 0.5 to 3 hours
  • Reactor residence time (preferably, a residence time of 1 - 2 hours) is fed to a continuously operated falling-film evaporator (5).
  • the vapors of the falling film evaporator (5) are fed to a low boiler distillation column (3).
  • the in the course of the falling film evaporator (5) obtained with catalyst, polymerization and high-boiling by-products still contaminated crude amide (15) preferably contains> 80 wt .-% product amide and is used to work up a further vacuum distillation stage, which in the preferred pressure range between 0.1 and 200 mbar works, fed.
  • the distillative separation of pure product amide takes place as a top product.
  • the by-products formed in the process are high-boiling components with respect to the reactant amine and the reactant (meth) acrylate and thus enter the product amide as an impurity, whereby the product quality is markedly lowered.
  • This problem can be solved by separating the product amide from the catalyst and the Polymerization inhibitors and the high-boiling by-products use a device with gentle film evaporation such as (5). Suitable apparatuses for this fall film, thin film and short path evaporator are known.
  • the preparation of the alkylamino (meth) acrylamides may optionally be followed by a purifying distillation unit which can also be operated under reduced pressure, for example at 500-0.1 mbar. This is particularly necessary if a particularly good separation of the high-boiling secondary components formed in the process should take place.
  • a two-stage workup is used in order to achieve a low crosslinker content.
  • the crude product (15) is heated and dosed on a column in the head to separate low boilers (16).
  • the degassed feed stream is applied to a second column (4) in the middle to separate low boiler (17).
  • the low-boiling intermediate is applied in a third column (5) and the product (18) distilled overhead to separate the high boilers in the resulting sump (19).
  • the first reaction vessel was charged with 200 kg / h of preactivated catalyst feed containing 2.0% by weight of isopropyl titanate, 5.0% by weight of dioctyltin oxide from the distillation column (2) and 144 kg / h N-dimethylaminopropylamine (DMAPA) added.
  • the pre-activation was carried out at 110 0 C for 2 h in a stirred tank.
  • the 1st reaction vessel flowed via the distillation column (2) the recycle stream from the top of the low boiler Distillation column continuously to (400 kg / h with the composition 70 wt .-% Eduktmethacrylat and methanol, DMAPA and by-products
  • the molar MMA: DMAPA ratio in the reactor feed was 1, 8: 1.
  • Furthermore ran in the distillation column (2) from Methanol was used to liberate the stirred tank vapors via the bottom of the column to the 1st reaction vessel Under these reaction conditions (pressure about 500 mbar), a reaction temperature of 138 ° C. was established in the 1st reaction vessel . 155 0 C. the distillate takeoff of the distillation column (2) was 110 kg / h.
  • the sequence of the first reaction vessel was running in the 2nd reaction vessel and the flow of the second reaction vessel was in the 3rd reaction vessel. at a residence time of For a total of about 150 minutes, the following proportions of the components were determined at the end of the third reaction vessel:
  • the course of the third reaction vessel was continuous to the thin-film evaporator of a low-boiling column in which unreacted DMAPA, MMA and methanol were withdrawn as distillate (400 kg / h) and recycled as recycle stream of the distillation column (2).
  • the bottom outlet of the low-boiling column thin-film evaporator was 240 kg / h and had the composition: about 90% by weight of product amide, 0.1% by weight of DMAPA, a higher proportion of high-boiling components and traces of the reactants.
  • the crude product is then worked up in a two-stage distillation.
  • the crude product prepared (about 90 wt .-% product amide) is conveyed via a pipeline in batches in the feed tank. There stabilizers are added.
  • the product By means of a pump, the product, heated by a heater, reaches the top of the column.
  • the separated low boilers (16) are, as far as possible condensed and fed to thermal utilization. Non-condensable fractions are absorbed in the gas scrubber in sulfuric acid.
  • the degassed feed stream is applied to the middle of the second column and freed there by an evaporator of low boiling points (17).
  • the resulting low boiler are condensed and also thermally utilized.
  • the "low-boiling product” is collected and added to the third column via a preheater
  • the pure product (18) is drawn overhead, almost completely condensed in the dephlegmator and transferred to the clean product tank.
  • Uncondensed fractions are liquefied in the downstream condenser and used thermally.
  • the high boilers are withdrawn in the bottom of the second evaporator and fed to thermal utilization (19).
  • the process according to the invention leads to a product (N-3-dimethylaminopropyl methacrylamide) having a purity of> 98%, in the example 98.9%, and a content of less than 600 ppm, in particular 500 ppm, more preferably below 400 ppm, in Example 240 ppm crosslinker.
  • the crosslinker found was N-allylmethacrylamide (analysis by GC).

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Abstract

L'invention porte sur un procédé de production continue d'alkylamino (méth)acrylamides par réaction de (méth)acrylates d'alkyle avec des amines à haut point d'ébullition. Par une activation catalytique et une technique particulière de traitement, on attend des qualités du produit non encore réalisées à ce jour. Il est en outre possible d'arriver à des valeurs très élevées du rendement espace-temps et du rendement global.
EP10706252A 2009-04-07 2010-03-03 Procédé de préparation continue d'alkylamino(méth)acrylamides Withdrawn EP2417098A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009002239A DE102009002239A1 (de) 2009-04-07 2009-04-07 Verfahren zur kontinuierlichen Herstellung von Alkylamino(meth)acrylamiden
PCT/EP2010/052689 WO2010115666A1 (fr) 2009-04-07 2010-03-03 Procédé de préparation continue d'alkylamino(méth)acrylamides

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EP2417098A1 true EP2417098A1 (fr) 2012-02-15

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US (1) US8674133B2 (fr)
EP (1) EP2417098A1 (fr)
JP (1) JP5599453B2 (fr)
KR (1) KR101689905B1 (fr)
CN (1) CN102369181A (fr)
AU (1) AU2010234280B2 (fr)
BR (1) BRPI1015290A2 (fr)
CA (1) CA2758115C (fr)
DE (1) DE102009002239A1 (fr)
RU (1) RU2546670C2 (fr)
TW (2) TWI519506B (fr)
WO (1) WO2010115666A1 (fr)
ZA (1) ZA201107331B (fr)

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CN105348130B (zh) * 2015-12-02 2017-06-06 天津久日新材料股份有限公司 一种n、n‑二甲基丙基丙烯酰胺的制备方法
CN105481698B (zh) * 2015-12-28 2017-06-13 江苏富淼科技股份有限公司 一种n,n‑二甲基‑1,3‑丙二胺回收和联产n,n,n′,n′‑四甲基‑1,3‑丙二胺的方法
ES2832577T3 (es) * 2016-06-28 2021-06-10 Evonik Operations Gmbh Producción de N,N-(di)alquilaminoalquil(met)acrilamida, o bien (met)acrilato de N,N-(di)alquilaminoalquilo, y sus sales amónicas cuaternarias como adyuvantes de floculación y gelificantes
CN108047057B (zh) * 2017-12-28 2020-06-02 山东铂源药业有限公司 一种布替萘芬的合成方法
CN111170873B (zh) * 2020-02-12 2023-07-07 四川科宏达集团有限责任公司 一种从甜菜碱废水中提取n，n-二甲基-1,3-丙二胺的方法

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EP0619295A1 (fr) * 1992-10-21 1994-10-12 KOHJIN CO. Ltd. Procede de production de (meth)acrylamide monosubstitue en position n

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JP2012522817A (ja) 2012-09-27
WO2010115666A1 (fr) 2010-10-14
US20110313195A1 (en) 2011-12-22
TW201102364A (en) 2011-01-16
AU2010234280A1 (en) 2011-10-06
AU2010234280B2 (en) 2014-02-13
CA2758115C (fr) 2017-05-02
RU2546670C2 (ru) 2015-04-10
TW201600496A (zh) 2016-01-01
CN102369181A (zh) 2012-03-07
DE102009002239A1 (de) 2010-10-14
KR20120016049A (ko) 2012-02-22
JP5599453B2 (ja) 2014-10-01
KR101689905B1 (ko) 2016-12-26
BRPI1015290A2 (pt) 2016-04-19
US8674133B2 (en) 2014-03-18
ZA201107331B (en) 2012-07-25

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