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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
  • B01J19/122—Incoherent waves
  • B01J19/126—Microwaves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J2219/12—Processes employing electromagnetic waves
  • B01J2219/1203—Incoherent waves
  • B01J2219/1206—Microwaves
  • B01J2219/1287—Features relating to the microwave source
  • B01J2219/129—Arrangements thereof

Definitions

• Amides of ethylenically unsaturated carboxylic acids are used to prepare a variety of polymers.
• the properties of the polymers produced therefrom can be adjusted in a targeted manner over a wide range.
• alkyl radicals impart oil solubility to the polymers, while more polar substituents such as polyoxyalkylene radicals or groups with a basic character increase water solubility.
• basic functionalized copolymers have many uses, as sizing aids in fiber preparation, in aqueous systems in viscosity modification, in wastewater treatment, as flocculation aids in the recovery of minerals as well as auxiliaries in metalworking and as a detergent additive in lubricating oils.
• amides have increased hydrolytic stability.
• the desirable direct thermal condensation of carboxylic acid and amine requires very high temperatures and long reaction times and does not give satisfactory results since various side reactions reduce the yield. These include, for example, a Michael addition of the amine to the double bond of the ethylenically unsaturated carboxylic acid, an uncontrolled, thermal polymerization of the ethylenically unsaturated carboxylic acid or of the amide formed, an oxidation of the amino group during long heating and in particular the thermally induced degradation of the amino group.
• Another problem is the corrosivity of the reaction mixtures of acid, amine, amide and water of reaction, which often strongly attack or dissolve metallic reaction vessels at the required high reaction temperatures.
• the carboxyl group of the underlying ethylenically unsaturated carboxylic acid must be selectively reacted with the primary or secondary amino group of the unsymmetrically substituted diamine to obtain both the ethylenic double bond and the tertiary amino group.
• ethylenically unsaturated amides carrying polyalkylene glycol groups Leave with these macromonomers.
• the rheological properties of polymers or their solutions are specifically influenced.
• the inhomogeneity of the microwave field caused by localized overheating of the reaction mixture, caused by more or less uncontrolled reflections of the microwaves irradiated into the microwave oven on the walls thereof and the reaction mixture in the commonly used multimode microwaves causes problems in scale-up.
• the microwave absorption coefficient of the reaction mixture which often changes during the reaction, presents difficulties with regard to a reliable and reproducible reaction.
• single-mode or single-mode microwave applicators are known in which a single wave mode is used, which propagates in only one spatial direction and is focused by precisely dimensioned waveguides on the reaction vessel.
• these devices allow higher local field strengths, but so far are due to the geometric requirements (eg, the intensity of the electric field at its crests largest and goes at the junctions to zero) so far limited to small reaction volumes ( ⁇ 50 ml) on a laboratory scale.
• a process has therefore been sought for the preparation of amides of ethylenically unsaturated carboxylic acids, in which carboxylic acid and amine can also be converted to the amide on an industrial scale under microwave irradiation.
• the aim is to achieve as high as possible, that is to say quantitative, conversion rates.
• the method should further enable a possible energy-saving production of carboxylic acid amides, that is, the microwave power used should be as quantitatively absorbed by the reaction mixture and thus offer the process a high energy efficiency. In this case, no or only minor amounts of by-products and in particular no or only minor amounts of Michael adduct and multiply ethylenically unsaturated compounds are obtained.
• the amides should also have the lowest possible metal content and a low intrinsic color. In addition, the process should ensure a safe and reproducible reaction.
• amides of ethylenically unsaturated carboxylic acids by direct reaction of ethylenically unsaturated carboxylic acids with amines in a continuous process by only brief heating by irradiation with microwaves in a reaction tube whose longitudinal axis is in the propagation direction of the microwaves of a single-mode microwave applicator in to produce technically relevant quantities.
• the microwave energy radiated into the microwave applicator is absorbed virtually quantitatively by the reaction mixture.
• the inventive method also has a high level of safety in the implementation and provides a high reproducibility of the set reaction conditions.
• the amides prepared by the process according to the invention show a comparison with conventional
• the invention relates to a continuous process for the preparation of amides of ethylenically unsaturated carboxylic acids by reacting at least one ethylenically unsaturated carboxylic acid of the formula I.
• R 3 is an optionally substituted alkenyl group having 2 to 4 carbon atoms, with at least one amine of formula II
• R 1 and R 2 independently of one another, are hydrogen or a hydrocarbon radical having 1 to 100 carbon atoms, are converted to an ammonium salt and / or a Michael adduct, and this ammonium salt and / or Michael adduct is subsequently subjected to microwave irradiation in a reaction tube, the longitudinal axis of which is in the propagation direction of the microwaves of a single-mode microwave applicator is converted to the ethylenically unsaturated carboxylic acid amide.
• Another object of the invention are amides of ethylenically unsaturated carboxylic acids with a low metal content, prepared by reacting at least one ethylenically unsaturated carboxylic acid of the formula I.
• R 3 is an optionally substituted alkenyl group having 2 to 4 carbon atoms, with at least one amine of the formula
• R 1 and R 2 are independently hydrogen or a hydrocarbon radical having 1 to 100 carbon atoms, to an ammonium salt and / or a Michael adduct and subsequent reaction of this ammonium salt and / or a Michael adduct to the ethylenically unsaturated carboxylic acid amide under microwave irradiation in a reaction tube whose longitudinal axis is in the propagation direction of the microwaves of a single-mode microwave applicator.
• ethylenically unsaturated carboxylic acids are understood as meaning those carboxylic acids which are converted into a carboxylic acid
• R 3 is preferably an alkenyl radical having 2, 3 or 4 C atoms and particularly preferably having 2 or 3 C atoms. This can be linear or branched.
• the alkenyl radical is an unsubstituted alkenyl radical.
• the alkenyl radical bears one or more, such as, for example, two, three or more further substituents such as carboxyl, ester, amide, cyano, nitrile, and / or C 5 -C 2 o-aryl groups such as For example, phenyl groups with the proviso that the substituents are stable under the reaction conditions and do not undergo side reactions.
• the C 5 -C 2 o-aryl groups in turn may themselves substituents such as halogen atoms, halogenated alkyl radicals, CrC 2 o-alkyl, C 2 -C 2 o-alkenyl, Ci-C 5 -Akoxy- such as methoxy, esters , Amide, carboxyl, cyano, nitrile, and / or nitro groups.
• the alkenyl radical carries at most as many substituents as it has valencies.
• the alkenyl radical R 3 carries as further substituents a carboxyl group or an optionally substituted Cs-C 2 o-aryl group.
• the inventive method is also suitable for the reaction of ethylenically unsaturated dicarboxylic acids.
• imides can also be formed.
• ethylenically unsaturated carboxylic acids which are suitable according to the invention are acrylic acid, methacrylic acid, crotonic acid, 2,2-dimethylacrylic acid, maleic acid, fumaric acid, itaconic acid, cinnamic acid and methoxycinnamic acid, and their mixtures.
• Particularly preferred ethylenically unsaturated carboxylic acids are acrylic acid and methacrylic acid.
• ethylenically unsaturated dicarboxylic acids in the form of their anhydrides such as maleic anhydride process of the invention is advantageous.
• the condensation of the amidocarboxylic acid formed intermediately from dicarboxylic acid and primary and / or secondary and tertiary amino groups leads, in contrast to thermal condensation, in high yields to imides of ethylenically unsaturated carboxylic acids carrying tertiary amino groups.
• the process according to the invention is preferably suitable for the preparation of secondary amides, ie for the reaction of carboxylic acids with amines in which R 1 is a hydrocarbon radical having 1 to 100 carbon atoms and R 2 is hydrogen.
• the process according to the invention is particularly preferably suitable for the preparation of tertiary amides, that is to say for the reaction of carboxylic acids with amines, in which both radicals R 1 and R 2 independently of one another are a hydrocarbon radical having 1 to 100 carbon atoms.
• the radicals R 1 and R 2 may be the same or different. In a particularly preferred embodiment, R 1 and R 2 are the same.
• R 1 and / or R 2 are independently an aliphatic radical. This preferably has 1 to 24, more preferably 2 to 18 and especially 3 to 6 C atoms.
• the aliphatic radical may be linear, branched or cyclic. It may also be saturated or unsaturated, preferably it is saturated.
• the aliphatic radical may carry substituents such as, for example, hydroxyl, C 1 -C 5 -alkoxy, cyano, nitrile, nitro and / or C 5 -C 2 0-aryl groups, for example phenyl radicals.
• the C 5 -C 2 o-aryl radicals may in turn optionally with halogen atoms, halogenated alkyl radicals, Ci-C 2 o-alkyl, C 2 -C 2 o-alkenyl, hydroxyl, Ci-C 5 alkoxy such as methoxy , Ester, amide, cyano, nitrile, and / or nitro groups be substituted.
• Particularly preferred aliphatic radicals are methyl, ethyl, hydroxyethyl, n-propyl, isopropyl, hydroxypropyl, n-butyl, isobutyl and tert-butyl, hydroxybutyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl and methylphenyl.
• R 1 and / or R 2 independently of one another are hydrogen, a C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or C 3 -C 6 -cycloalkyl radical and especially an alkyl radical with 1, 2, or 3 C atoms. These groups can carry up to three substituents as described above.
• R 1 and R 2 together with the nitrogen atom to which they are attached form a ring.
• This ring preferably has 4 or more, such as 4, 5, 6 or more ring members.
• Preferred further ring members are carbon, nitrogen, oxygen and sulfur atoms.
• the rings in turn may carry substituents such as alkyl radicals.
• Suitable ring structures are, for example, morpholinyl, pyrrolidinyl, piperidinyl, imidazolyl and azepanyl radicals.
• R 1 and / or R 2 independently of one another represent an optionally substituted Ce-Ci 2 -aryl group or an optionally substituted heteroaromatic group having 5 to 12 ring members.
• R 1 and / or R 2 independently of one another are an alkyl radical interrupted by heteroatoms. Particularly preferred heteroatoms are oxygen and nitrogen.
• R 1 and / or R 2 independently of one another are preferably radicals of the formula III
• R 4 is an alkylene group having 2 to 6 carbon atoms and preferably 2 to
• R 5 is hydrogen, a hydrocarbon radical having 1 to 24 C-atoms or a group of the formula -NR 10 R 11
• n is a number between 2 and 500, preferably between 3 and 200 and in particular between 4 and 50 such as between 5 and 20 and R 10
• R 11 are each independently hydrogen, an aliphatic radical
• Preferred poly (alkylene glycol) amines of the formula III are derived from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. They prefer
• R 1 and / or R 2 independently of one another are preferably radicals of the formula IV
• R 6 is an alkylene group having 2 to 6 carbon atoms and preferably 2 to
• each R 7 is independently hydrogen, an alkyl or
• Hydroxyalkyl radical having up to 24 carbon atoms such as 2 to 20 carbon atoms, a polyoxyalkylene radical - (R 4 -O) p -R 5 , or a polyiminoalkylene radical - [R 6 -N (R 7 )] q - (R 7 ), wherein R 4 , R 5 , R 6 and R 7 have the meanings given above and q and p are independently from 1 to 50 and m is a number from 1 to 20 and preferably 2 to 10 such as three, four , five or six stands.
• the radicals of the formula IV preferably contain 1 to 50, in particular 2 to 20, nitrogen atoms
• R 5 or R 7 are hydrogen
• these amines can be esterified in a specific embodiment of the method according to the invention also in addition to the ethylenically unsaturated carboxylic acid (I) or amidated several times.
• R 1 is one of the meanings given above, preferably hydrogen, an aliphatic radical having 1 to 24 C atoms or an aryl group having 6 to 12 C atoms and especially for methyl, and R 2 for a tertiary Amino groups bearing hydrocarbon radical of formula V
• A is an alkylene radical having 1 to 12 carbon atoms, a cycloalkylene radical with
• Z is a group of the formula -NR 8 R 9 or a nitrogen-containing cyclic hydrocarbon radical having at least
• R 5 ring links and R 8 and R 9 independently of one another represent Cr to C 2 o-hydrocarbon radicals or to polyoxyalkylene radicals of the formula - (R 4 -O) p -R 5 (III), where R 4 , R 5 and p have the meanings given above.
• A is preferably a linear or branched alkylene radical having 1 to 12 C atoms and s is 1.
• A is a linear or branched alkylene radical having 2, 3 or 4 C atoms, in particular an ethylene radical or a linear propylene radical.
• Z is a nitrogen-containing cyclic hydrocarbon radical, compounds are particularly preferred in which A is a linear alkylene radical having 1, 2 or 3 C atoms, in particular a methylene, ethylene or a linear propylene radical.
• Cyclic radicals which are preferred for the structural element A can be monocyclic or polycyclic and contain, for example, two or three ring systems.
• Preferred ring systems have 5, 6 or 7 ring members. Preferably, they contain a total of about 5 to 20 C-atoms, in particular 6 to 10 C-atoms.
• Preferred ring systems are aromatic and contain only C atoms.
• the structural elements A are formed from arylene radicals.
• the structural element A may carry substituents such as, for example, alkyl radicals, halogen atoms, halogenated alkyl radicals, nitro, cyano, nitrile, hydroxyl and / or hydroxyalkyl groups. If A is a monocyclic aromatic hydrocarbon, the substituents carrying amino groups or amino groups are preferably in the ortho or para position relative to one another.
• Z is preferably a group of the formula -NR 8 R 9 .
• R 8 and R 9 independently of one another are preferably aliphatic, aromatic and / or araliphatic hydrocarbon radicals having 1 to 20 carbon atoms.
• R 8 and R 9 are particularly preferred alkyl radicals. If R 8 and / or R 9 are alkyl radicals, they preferably carry 1 to 14 C atoms, for example 1 to 6 C atoms. These alkyl radicals can be linear, branched and / or cyclic.
• R 8 and R 9 are alkyl radicals having 1 to 4 C atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl.
• the radicals R 8 and / or R 9 independently of one another are polyoxyalkylene radicals of the formula III.
• R 8 and / or R 9 particularly suitable aromatic radicals include ring systems having at least 5 ring members. They may contain heteroatoms such as S, O and N.
• Particularly suitable araliphatic radicals R 8 and / or R 9 include ring systems having at least 5 ring members which are bonded to the nitrogen via a C 1 -C 6 -alkyl radical. They may contain heteroatoms such as S, O and N.
• the aromatic as well as the araliphatic radicals may carry further substituents such as, for example, alkyl radicals, halogen atoms, halogenated alkyl radicals, nitro, cyano, nitrile, hydroxyl and / or hydroxyalkyl groups.
• Z is a nitrogen-containing, cyclic hydrocarbon radical whose nitrogen atom is not capable of forming amides.
• the cyclic system can be mono-, di- or also polycyclic. It preferably contains one or more five- and / or six-membered rings.
• This cyclic hydrocarbon may contain one or more, such as two or three, nitrogen atoms which do not carry acidic protons, most preferably it contains an N atom.
• Particularly suitable are nitrogen-containing aromatics whose nitrogen is involved in the formation of an aromatic ⁇ -Elektronensextetts such as pyridine.
• nitrogen-containing heteroaliphatic compounds whose nitrogen atoms do not carry any protons and, for example, are all saturated with alkyl radicals.
• the linking of Z with A or the nitrogen of the formula (II) is preferably carried out here via a nitrogen atom of the heterocycle, for example in the case of 1- (3-aminopropyl) pyrrolidine.
• the cyclic hydrocarbon represented by Z may have further substituents, such as
• Ci-C 2 o-alkyl radicals, halogen atoms, halogenated alkyl radicals, nitro, cyano, nitrile, hydroxyl and / or hydroxyalkyl groups bear.
• one or more amino groups, each carrying at least one hydrogen atom are converted into the carboxylic acid amide.
• the primary amino groups can also be converted into imides.
• nitrogen-containing compounds which split off ammonia gas on heating instead of ammonia.
• nitrogen-containing compounds are urea and formamide.
• Suitable amines are ammonia, methylamine, ethylamine, ethanolamine, propylamine, propanolamine, butylamine, hexylamine, cyclohexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, dimethylamine, diethylamine, diethanolamine, ethylmethylamine, di-n-propylamine, di -iso-propylamine, dicyclohexylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadedcylamine, benzylamine, phenylethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and mixtures thereof. Particularly preferred are dimethyl
• Ethylmethylamine Ethylmethylamine.
• suitable amines carrying tertiary amine groups are N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dimethyl-2-methyl-1, 3-propanediamine, N, N- (2'-hydroxyethyl) -1,3-propanediamine, 1- (3-aminopropyl) pyrrolidine, 1- (3-aminopropyl) -4-methylpiperazine, 3- (4-morpholino) - 1 -propylamine, 2-aminothiazole, the various isomers of N, N-dimethylaminoaniline, aminopyridine, aminomethylpyridine, aminomethylpiperidine and aminoquinoline, as well as 2-aminopyrimidine, 3-aminopyrazole, aminopyrazine and 3-amino-1 , 2,4-triazole. Also mixtures of
• the process is particularly suitable for the preparation of N, N-dimethylmethacrylamide, N, N-dimethylacrylamide, N, N-diethymethacrylamide, N, N-diethylacrylamide, N-isopropylacryamide, N-isopropylmethacryamide, N-2-ethylhexylacrylamide, N-2-ethylhexylmethacrylamide, N-propylacrylamide, N-propylmethacrylamide, N-butylacrylamide, N-butylmethacrylamide, N-hexylacrylamide, N-hexylmethacryamide, N-octylacrylamide, N-octylmethacryamide, N-cocoylacrylamide, N- Cocoylmethacrylamide, N-laurylacrylamide, N-laurylmethacrylamide, N-mesitylacrylamide,
• tertiary amino groups-bearing amides such as N- [3- (N, N-dimethylamino) propyl] acrylamide, N- [3- (N, N-Dimethylamino) propyl] methacrylamide, N- [3- (N, N-dimethylamino) propyl] crotonylamide, N- [3- (N, N-dimethylamino) propyl] itaconylimide, N- [(Pyridin-4-yl) methyl] acrylamide and N - [(pyridin-4-yl) methyl] methacrylamide.
• tertiary amino groups-bearing amides such as N- [3- (N, N-dimethylamino) propyl] acrylamide, N- [3- (N, N-Dimethylamino) propyl] methacrylamide, N- [3- (N, N-dimethylamino) propyl
• ethylenically unsaturated carboxylic acid and amine can be reacted with one another in any ratio.
• the reaction between carboxylic acid and amine preferably takes place with molar ratios of from 10: 1 to 1: 100, preferably from 2: 1 to 1:10, especially from 1.2: 1 to 1: 3, in each case based on the molar equivalents of carboxyl groups. and amino groups.
• R 1 and / or R 2 are a hydrocarbon radical substituted by one or more hydroxyl groups
• the reaction between ethylenically unsaturated carboxylic acid and amine takes place with molar ratios of 1: 1 to 1: 100, preferably 1: 1, 001 to 1:10 and in particular from 1: 1, 01 to 1: 5, for example from 1: 1, 1 to 1: 2, in each case based on the molar equivalents of carboxyl groups and amino groups in the reaction mixture.
• carboxylic acid and amine are used equimolar.
• the preparation of the amides according to the invention is carried out by reacting carboxylic acid and amine to form the ammonium salt and subsequently irradiating the salt with microwaves in a reaction tube whose longitudinal axis is in the direction of propagation of the microwaves in a single-mode microwave applicator.
• ammonium salt formed primarily during the mixing of amine and ethylenically unsaturated carboxylic acid can, in particular at elevated temperatures, also react further by nucleophilic addition of the amine to the double bond of the carboxylic acid to form a Michael adduct, which is then converted into the amide in an equivalent manner under microwave irradiation , In the context of this invention, therefore, ammonium salt and the Michael adduct formed from the same starting materials are considered to be equivalent.
• the irradiation of the salt and / or Michael adduct with microwaves preferably takes place in a largely microwave-transparent reaction tube, which is located within a waveguide connected to a microwave generator.
• the reaction tube is aligned axially with the central axis of symmetry of the waveguide.
• the waveguide acting as a microwave applicator is preferably formed as a cavity resonator. Further preferably, the microwaves not absorbed in the waveguide are reflected at its end.
• the cavity resonator is preferably operated in the Eoi n mode, where n stands for an integer and indicates the number of field maxima of the microwave along the central axis of symmetry of the resonator. In this operation, the electric field is directed toward the central axis of symmetry of the cavity resonator.
• N is preferably an integer from 1 to 200, particularly preferably from 2 to 100, in particular from 4 to 50 and especially from 3 to 20, for example 3, 4, 5, 6, 7 or 8.
• the irradiation of the microwave energy into the waveguide acting as a microwave applicator can take place via suitably dimensioned holes or slots.
• the irradiation of the ammonium salt and / or Michael adduct with microwaves in a reaction tube which is located in a waveguide with coaxial transition of the microwaves.
• particularly preferred microwave devices are constructed of a cavity resonator, a coupling device for coupling a microwave field in the cavity and each with an opening at two opposite end walls for passing the reaction tube through the resonator.
• the coupling of the microwaves in the cavity resonator is preferably carried out via a coupling pin, which projects into the cavity resonator.
• the coupling pin is preferably shaped as a preferably metallic inner conductor tube functioning as a coupling antenna.
• this coupling pin protrudes through one of the frontal openings into the cavity resonator.
• the reaction tube connects to the inner conductor tube of the coaxial transition and in particular it is guided through its cavity into the cavity resonator.
• the reaction tube is aligned axially with a central one Symmetryeachse the cavity resonator, including the cavity resonator preferably each having a central opening at two opposite end walls for passing the reaction tube.
• Coupling antenna acting inner conductor tube can be done for example by means of a coaxial connecting cable.
• the microwave field is supplied to the resonator via a waveguide, wherein the protruding from the cavity resonator end of the coupling pin is guided into an opening which is located in the wall of the waveguide in the waveguide and the waveguide takes microwave energy and in the Resonator couples.
• the irradiation of the salt and / or Michael adduct with microwaves takes place in a microwave-transparent manner
• Reaction tube which is axially symmetric in an EOM circular waveguide with coaxial transition of the microwaves.
• the reaction tube is guided through the cavity of an inner conductor tube acting as a coupling antenna into the cavity resonator.
• Microwave generators such as the magnetron, the klystron and the gyrotron are known in the art.
• the reaction tubes used for carrying out the method according to the invention are preferably made of largely microwave-transparent, high-melting material. Non-metallic reaction tubes are particularly preferably used.
• Substantially microwave-transparent materials are understood here which absorb as little microwave energy as possible and convert it into heat.
• the dielectric loss factor tan ⁇ ⁇ 'V ⁇ 'is often used.
• the dielectric loss factor tan ⁇ is defined as the ratio of dielectric loss ⁇ "and dielectric constant ⁇ '.
• tan ⁇ values of various materials Microwave-assisted Organic Synthesis, Elsevier 2005.
• suitable reaction tubes Materials with tan ⁇ values measured at 2.45 GHz and 25 ° C. of below 0.01, in particular below 0.005 and especially below 0.001 are preferred
• thermally stable plastics such as in particular fluoropolymers such as Teflon, and engineering plastics such as polypropylene, or polyaryletherketones such as glass fiber reinforced polyetheretherketone (PEEK) are suitable as pipe materials During the reaction, minerals coated with these plastics in particular, such as quartz or aluminum oxide, have proven to be suitable as reactor materials.
• reaction tubes have an inner diameter of one millimeter to about 50 cm, especially between 2 mm and 35 cm, for example between 5 mm and 15 cm.
• Reaction tubes are understood here to be vessels whose ratio of length to diameter is greater than 5, preferably between 10 and 100,000, particularly preferably between 20 and 10,000, for example between 30 and 1,000.
• the length of the reaction tube is understood here as the distance of the reaction tube on which the microwave irradiation takes place.
• baffles and / or other mixing elements can be installed.
• particularly suitable Eor cavity resonators preferably have a diameter which corresponds to at least half the wavelength of the microwave radiation used.
• the diameter of the cavity resonator is the 1, 0- to
• the Eor cavity resonator has a round cross section, which is also referred to as Eoi round waveguide. Particularly preferably it has a cylindrical shape and especially a circular cylindrical shape.
• the reaction tube is usually provided at the inlet with a metering pump and a pressure gauge and at the outlet with a pressure holding device and a heat exchanger. This allows reactions in a very wide range of pressure and temperature.
• the reaction of amine and carboxylic acid to form the ammonium salt and / or Michael adduct can be carried out continuously, batchwise or else in semi-batch processes.
• the preparation of the ammonium salt and / or Michael adduct can be carried out in an upstream (semi) batch process such as in a stirred tank.
• the ammonium salt and / or Michael adduct is preferably generated in situ and not isolated.
• the educts amine and carboxylic acid, both independently of one another optionally diluted with solvent, are mixed shortly before they enter the reaction tube.
• the ammonium salt and / or Michael adduct may be fed into the reaction tube either at the end passed through the inner conductor tube, as well as at the opposite end.
• the reaction conditions are adjusted so that the maximum reaction temperature is reached as quickly as possible and the residence time at maximum temperature remains so short that so few side or subsequent reactions occur as possible.
• the reaction mixture can be passed through the reaction tube several times to complete the reaction, optionally after intermediate cooling. In many cases, it has proven useful if the reaction product immediately after leaving the reaction tube z. B. is cooled by jacket cooling or relaxation. With slower reactions, it has often proven useful to keep the reaction product after leaving the reaction tube for a certain time at the reaction temperature.
• the advantages of the method according to the invention lie in a very uniform irradiation of the reaction material in the center of a symmetrical microwave field within a reaction tube whose longitudinal axis is in the propagation direction of the microwaves of a single-mode microwave applicator and in particular within a E 0 i cavity resonator, for example with coaxial transition.
• the reactor design according to the invention allows reactions to be carried out even at very high pressures and / or temperatures. By temperature and / or Pressure increase is observed a significant increase in the degree of conversion and yield compared to known microwave reactors, without causing unwanted side reactions and / or discoloration.
• a very high efficiency is achieved in utilizing the microwave energy radiated into the cavity resonator, which is usually more than 50%, often more than 80%, partly over 90% and in special cases more than 95%, for example over 98% of the radiated microwave power and thus provides economic as well as environmental advantages over conventional manufacturing methods as well as prior art microwave methods.
• the inventive method also allows a controlled, safe and reproducible reaction. Since the reaction mixture is moved in the reaction tube parallel to the propagation direction of the microwaves, known overheating phenomena are compensated by uncontrollable field distributions, which lead to local overheating by changing intensities of the field, for example in wave crests and nodes, by the flow of the reaction material.
• the advantages mentioned also make it possible to work with high microwave powers of, for example, more than 10 kW or more than 100 kW and, thus, in combination with a short residence time in the cavity resonator, achieve large production quantities of 100 and more tons per year in one system.
• Ammonium salt and / or Michael adduct in the microwave field a very extensive amidation with conversions in general of over 80%, often more than 90% such as more than 95% based on the component used in the deficit occurs, without formation of appreciable amounts of by-products.
• these ammonium salts and / or Michael adducts in a flow tube of the same dimensions under thermal jacket heating extremely high wall temperatures are required to achieve suitable reaction temperatures, the formation Undefined polymers and colored species resulted, but at the same time interval cause only minor amide formation.
• the products produced by the process according to the invention have very low metal contents without the need for further processing of the crude products.
• the metal contents of the products produced by the process according to the invention based on iron as the main element are usually below 25 ppm, preferably below 15 ppm, especially below 10 ppm, such as between 0.01 and 5 ppm iron.
• the temperature rise caused by the microwave irradiation is limited to a maximum of 400 ° C., for example by controlling the microwave intensity, the flow rate and / or by cooling the reaction tube, for example by a stream of nitrogen.
• the implementation of the reaction has proven particularly useful at temperatures between 100 and 300 ° C. and especially between 120 and 280 ° C., for example at temperatures between 150 and 260 ° C.
• the duration of the microwave irradiation depends on various factors, such as the geometry of the reaction tube, the radiated microwave energy, the specific reaction and the desired
• the microwave irradiation is carried out for a period of less than 30 minutes, preferably between 0.01 seconds and 15 minutes, more preferably between 0.1 seconds and 10 minutes and in particular between one second and 5 minutes, for example between 5 seconds and 3 minutes ,
• the intensity (power) of the microwave radiation is adjusted so that the reaction material when leaving the cavity resonator has the desired maximum temperature.
• the reaction product is cooled as soon as possible after completion of the microwave irradiation at temperatures below 120 0 C, preferably below 100 0 C and especially below 80 0 C.
• the reaction is carried out at pressures between 0.01 and 500 bar and more preferably between 1 bar (atmospheric pressure) and 150 bar and especially between 1, 5 bar and 100 bar such as between 3 bar and 50 bar.
• Working under elevated pressure has proven particularly useful, the starting materials or products, the optionally present solvent and / or above the reaction water formed during the reaction being worked above the boiling point (at atmospheric pressure). More preferably, the pressure is set so high that the reaction mixture remains in the liquid state during microwave irradiation and does not boil.
• an inert protective gas such as nitrogen, argon or helium.
• the reaction is accelerated or completed in the presence of dehydrating catalysts.
• dehydrating catalysts Preferably, one works in the presence of an acidic inorganic, organometallic or organic catalyst or mixtures of several of these catalysts.
• acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel and acidic aluminum hydroxide. Furthermore, for example
• Aluminum compounds of the general formula AI (OR 15 ) 3 and titanates of the general formula Ti (OR 15 J 4 can be used as acidic inorganic catalysts, where the radicals R 15 can each be identical or different and are selected independently of one another from C 1 -C 10.
• Alkyl radicals for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexy, n-nonyl or n-decyl, C 3 -C 2 -cycloalkyl radicals, for example cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, Cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl;
• Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides (R 15 ) 2 SnO, where R 15 is as defined above.
• R 15 dialkyltin oxides
• a particularly preferred representatives of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called Oxo-tin or as Fascat ® brands.
• Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups.
• Particularly preferred sulfonic acids contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 carbon atoms and preferably having 3 to 24 carbon atoms.
• aromatic sulfonic acids especially alkylaromatic monosulfonic acids having one or more C 1 -C 28 -alkyl radicals and, in particular, those having C 3 -C 22 -alkyl radicals.
• Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid.
• Acidic ion exchangers can also be used as acidic organic catalysts, for example poly (styrene) sulfonic acid groups which are crosslinked with about 2 mol% of divinylbenzene.
• the microwave irradiation is carried out in the presence of acidic solid catalysts.
• the solid catalyst is suspended in the optionally mixed with solvent ammonium salt or advantageously passed the optionally with solvent-added ammonium salt over a fixed bed catalyst and exposed to microwave radiation.
• Suitable solid catalysts are, for example, zeolites, silica gel, montmorillonite and (partially) crosslinked polystyrenesulphonic acid, which may optionally be impregnated with catalytically active metal salts.
• Suitable acidic ion exchanger based on polystyrene sulfonic acids that can be used as solid phase catalysts are for example available from the company Rohm & Haas under the trademark Amberlyst ®.
• Solvents which are preferred for the process according to the invention have a dielectric loss ⁇ "of less than 10 and preferably less than 1, for example less than 0.5, measured at room temperature and 2450 MHz An overview of the dielectric loss of various solvents can be found, for example, in" Microwave Synthesis "by BL Hayes, CEM Publishing 2002.
• Suitable solvents for the process according to the invention are, in particular, solvents having ⁇ " values below 10, such as N-methylpyrrolidone, N, N-dimethylformamide or acetone, and in particular solvents having ⁇ "values below 1. Examples of especially preferred solvents with ⁇ "values below 1 are aromatic and / or aliphatic
• Hydrocarbons such as toluene, xylene, ethylbenzene, tetralin, hexane, cyclohexane, decane, pentadecane, decalin, and commercial hydrocarbon mixtures such as petroleum fractions, kerosene, solvent naphtha, Shellsol ® AB, Solvesso ® 150, Solvesso ® 200, Exxsol ®, Isopar ® and Shellsol ® types. Solvent mixtures which have ⁇ "values preferably below 10 and especially below 1 are equally preferred for carrying out the process according to the invention.
• the process according to the invention can also be carried out in solvents having higher ⁇ "values of, for example, 5 and higher, in particular with ⁇ " values of 10 and higher.
• ⁇ values of 10 and higher.
• the observed accelerated heating of the reaction mixture requires special measures to maintain the maximum temperature.
• reaction mixture is preferably between 2 and 95 wt .-%, especially between 5 and 90 wt .-% and in particular between 10 and 75 wt .-%, such as between 30 and 60 wt .-%.
• the reaction is carried out solvent-free.
• Microwaves are electromagnetic waves having a wavelength between about 1 cm and 1 m and frequencies between about 300 MHz and 30 GHz. This frequency range is in principle for the inventive method suitable.
• microwave radiation with the frequencies released for industrial, scientific and medical applications is preferably used, for example with frequencies of 915 MHz, 2.45 GHz, 5.8 GHz or 27.12 GHz.
• the microwave power to be radiated into the cavity resonator for carrying out the method according to the invention depends, in particular, on the geometry of the reaction tube and thus the reaction volume and the duration of the required irradiation. It is usually between 200 W and several 100 kW and in particular between 500 W and 100 kW such as between 1 kW and 70 kW. It can be generated by one or more microwave generators.
• the reaction is carried out in a pressure-resistant inert tube, wherein the water of reaction forming and optionally starting materials and, if present, solvents lead to a pressure build-up.
• the excess pressure can be used by relaxation for volatilization and separation of water of reaction, excess starting materials and, if appropriate, solvents and / or for cooling the reaction product.
• the water of reaction formed after cooling and / or venting by conventional methods such as phase separation, distillation stripping, flashing and / or absorption is separated.
• polymerization inhibitors based on phenols such as hydroquinone, hydroquinone monomethyl ether and sterically hindered phenols such as 2,6-di-tert-butylphenol or 2,6-di-tert-butyl-4-methyphenol.
• thiazines such as phenothiazine or methylene blue and nitroxides, in particular sterically hindered nitroxides, ie nitroxides of secondary amines which are each at the C atoms, which are adjacent to the nitroxide group, three alkyl groups where two of these alkyl groups, especially those not on the same carbon atom, form a saturated 5- or 6-membered ring with the nitrogen atom of the nitroxide group or the carbon atom to which they are attached, such as in 2,2,6,6-tetramethypiperidine-1-oxyl (TEMPO) or 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (OH-TEMPO).
• TEMPO 2,2,6,6-tetramethypiperidine-1-oxyl
• OH-TEMPO 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl
• mixtures of the aforementioned inhibitors, mixtures of the aforementioned inhibitors with oxygen, for example in the form of air, and mixtures of mixtures of the aforementioned inhibitors with air are suitable. These are preferably added to the reaction mixture or one of the reactants in amounts of from 1 to 1000 ppm and in particular in amounts of from 10 to 200 ppm, based on the ethylenically unsaturated carboxylic acid.
• the inventive method allows a very fast, energy-saving and cost-effective production of amides ethylenically unsaturated
• Carboxylic acids in high yields and high purity in large quantities Due to the very uniform irradiation of the ammonium salt and / or Michael adduct in the center of the rotationally symmetric microwave field, it allows a safe, controllable and reproducible reaction. It is achieved by a very high efficiency in the utilization of the radiated microwave energy, the known manufacturing process significantly superior efficiency. This process does not generate significant amounts of by-products. Such rapid and selective reactions can not be achieved by conventional methods and were not to be expected by heating to high temperatures alone.
• amides prepared via the route according to the invention usually accumulate in a purity which is sufficient for further use, so that no further working or post-processing steps are required. For However, special requirements can be further purified by customary purification processes such as, for example, distillation, recrystallization, filtration or chromatographic processes.
• the amides prepared according to the invention are particularly suitable for homopolymerization as well as for copolymerization with other ethylenically unsaturated compounds. Based on the total mass of the (co) polymers, their content of amides prepared according to the invention may be from 0.1 to 100% by weight, preferably from 20 to 99.5% by weight, particularly preferably from 50 to 98% by weight. As comonomers, it is possible to use all ethylenically unsaturated compounds whose reaction parameters permit copolymerization with the amides prepared according to the invention in the respective reaction media.
• the microwave power was adjusted over the duration of the experiment in such a way that the desired temperature of the reaction mixture was kept constant at the end of the irradiation zone.
• the microwave powers mentioned in the test descriptions therefore represent the time average of the irradiated microwave power.
• the temperature measurement of the reaction mixture was carried out directly after leaving the reaction zone (about 15 cm distance in an insulated stainless steel capillary, 0 1 cm) using PtIOO Temperature sensor made. Microwave energy not directly absorbed by the reaction mixture was reflected at the end face of the cavity resonator opposite the coupling antenna; the microwave energy which was not absorbed by the reaction mixture during the return and was reflected back in the direction of the magnetron was conducted by means of a prism system (circulator) into a vessel containing water. From the difference between incident energy and heating of this water load, the microwave energy introduced into the reaction mixture was calculated
• reaction mixture was placed in the reaction tube under such a working pressure, which was sufficient to keep all starting materials and products or condensation products always in the liquid state.
• the reaction mixtures prepared from carboxylic acid and amine were pumped through the reaction tube at a constant flow rate and the residence time in the irradiation zone was adjusted by modifying the flow rate.
• the products were analyzed by means of 1 H-NMR spectroscopy at 500 MHz in CDCl 3 .
• the determination of iron contents was carried out by atomic absorption spectroscopy.
• the mixture thus prepared was pumped through the reaction tube continuously at a working pressure of 20 bar at a flow rate of about 2 l / h and exposed to a microwave power of 1.4 kW, of which 91% was absorbed by the reaction mixture.
• the residence time of the reaction mixture in the irradiation zone was about 75 seconds.
• the reaction mixture had a temperature of 253 0 C. It was achieved a conversion of 92% based on the used in deficit N, N-dimethylaminopropylamine.
• the reaction product was virtually colorless and contained ⁇ 2 ppm iron. It also contained 5 mol% of Michael adduct.
• Example 2 Analogously to Example 2 are prepared from 3.63 kg of toluene, 1.83 kg of butylamine (25 mol), 0.9 g of phenothiazine and 1.8 kg of acrylic acid (25 mol) about 7.3 kg of reaction solution.
• the reaction solution was pumped through the reaction tube continuously at a working pressure of 20 bar at a flow rate of about 3 l / h and exposed to a microwave power of 1.5 kW, of which 93% was absorbed by the reaction mixture.
• the residence time of the reaction mixture in the irradiation zone was about 57 seconds.
• the reaction mixture had a temperature of 246 0 C.
• Example 2 Analogously to Example 2 were of 4.25 kg of toluene, 3 kg of coconut fatty amine (15 mol, Genamin ® CC 100 from Clariant), 1 g of phenothiazine, and 1, 3 kg of methacrylic acid (15 mol) 8.55 kg prepared reaction solution.
• the reaction solution was pumped through the reaction tube continuously at a working pressure of 20 bar at a flow rate of about 3 l / h and thereby exposed to a microwave power of 1.9 kW, of which 88% were absorbed by the reaction mixture.
• Irradiation zone was about 57 seconds.
• the reaction mixture had a temperature of 256 ° C.
• the preheated to 70 0 C reaction mixture was pumped at a working pressure of 25 bar continuously at a flow rate of about 4 l / h through the reaction tube and exposed to a microwave power of 1, 0 kW, of which 94% were absorbed by the reaction.
• the residence time of Reaction mixture in the irradiation zone was about 42 seconds.
• the reaction mixture had a temperature of 300 0 C.
• the crude product was cooled directly and pumped again under the same conditions through the reaction tube and irradiated with microwaves.
• the reaction product product contained about 90% (N-Methylpolyethylenglkyol) -methacrylklamid and was fed directly to further use.

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