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  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/28—Treatment by wave energy or particle radiation
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • 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
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/04—Acids, Metal salts or ammonium salts thereof
  • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/44—Preparation of metal salts or ammonium salts
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • H—ELECTRICITY
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  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B6/00—Heating by electric, magnetic or electromagnetic fields
  • H05B6/64—Heating using microwaves
  • H05B6/80—Apparatus for specific applications
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  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B6/00—Heating by electric, magnetic or electromagnetic fields
  • H05B6/64—Heating using microwaves
  • H05B6/80—Apparatus for specific applications
  • H05B6/806—Apparatus for specific applications for laboratory use
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  • 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
  • B01J2219/0873—Materials to be treated
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  • B01J2219/0884—Gas-liquid
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  • 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
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  • B01J2219/0873—Materials to be treated
  • B01J2219/0892—Materials to be treated involving catalytically active material
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  • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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  • B01J2219/1203—Incoherent waves
  • B01J2219/1206—Microwaves
  • B01J2219/1209—Features relating to the reactor or vessel
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  • B01J2219/1215—Single reactor
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  • 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
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  • B01J2219/1203—Incoherent waves
  • B01J2219/1206—Microwaves
  • B01J2219/1209—Features relating to the reactor or vessel
  • B01J2219/1221—Features relating to the reactor or vessel the reactor per se
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  • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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  • B01J2219/1203—Incoherent waves
  • B01J2219/1206—Microwaves
  • B01J2219/1287—Features relating to the microwave source

Definitions

• the present invention relates to a continuous process for modifying polymers carrying acid groups by polymer-analogous esterification of aqueous solutions of the polymers in the microwave field.
• Hydrophobically modified water-soluble synthetic polymers have gained increasing industrial importance in recent years. These are usually polymers which are composed mainly of monomers carrying hydrophilic groups and a smaller proportion of monomers carrying hydrophobic groups. These water-soluble polymers aggregate in aqueous solutions due to intra- and / or intermolecular interactions of the hydrophobic groups with micelle-like structures. As a result, the hydrophobically modified polymers cause an increase in viscosity compared with conventional water-soluble polymers by the formation of three-dimensional networks at low concentrations, without requiring extremely high molecular weights. Such "associative thickeners" effectively control the rheological properties of aqueous based fluids in many industrial applications or formulations, such as in paints and coatings, paper, drilling fluids, and oil recovery
• these polymers are used, for example, as stabilizers for colloidal dispersions, emulsions, liposomes or (nano) particles. Further, they are used as dispersing agents for pigments and dyes wherein the modified polymer acts as a hydrophobic particle dispersant by anchoring the hydrophobic polymer segments to the solid surface and by extending the charged, hydrophilic groups into the bulk phase.
• LCST polymers Liwer Critical Solution Temperature
• hydrophobically modified, water-soluble, synthetic polymers can be adjusted within wide limits, for example, by selecting the hydrophobic group and / or the degree of modification and thus adapting it to a wide variety of applications.
• An important group of hydrophobically associating water-soluble macromolecules are hydrophobically modified synthetic poly (carboxylic acids). These can be prepared, for example, by copolymerization of ethylenically unsaturated carboxylic acids with corresponding monomers carrying hydrophobic groups.
• Esters of ethylenically unsaturated carboxylic acids have proven to be useful as hydrophobic comonomers because they have comparable copolymerization parameters to the hydrophilic monomers.
• their technical availability is limited both in terms of the variation of the substituents and in terms of quantity and their synthesis is complicated and expensive.
• J. Org. Chem. 56 (1991), 1313-1314 discloses a marked acceleration of the rate of reaction in the esterification of propanol with acetic acid under the influence of microwave radiation.
• the reactants are completely miscible liquids.
• EP 0437480 discloses an apparatus for continuously carrying out various chemical reactions. Esterifications are carried out using an excess of reactant as the solvent.
• Macromolecular Chemistry and Physics 2008, 209, 1942-947 discloses the polymer-analogous esterification of an acid group-bearing poly (ether sulfone) with 1-naphthol in apolar solvents under microwave irradiation.
• Macromol. Rapid Commun. 2007, 28, 443-448 discloses the esterification of poly (ethylene-co-acrylic acid) containing 20% by weight of acrylic acid different phenols in the microwave field. Excess phenol is used as the solvent, which is separated by precipitation of the polymer.
• JP 2009/263497 A discloses the esterification of copolymers of fumaric acid and styrene with octanol under microwave irradiation.
• the invention accordingly relates to a continuous process for the reaction of synthetic poly (carboxylic acids) (A), containing per
• R 1 is hydrogen, a C 4 to C 4 alkyl group or a group of
• R 2 is hydrogen or a C 4 to C 4 alkyl group
• R 3 is hydrogen, a C 1 to C 4 alkyl group or -COOH
• R 4 is a hydrocarbon radical having 1 to 100 carbon atoms, which may be substituted or may contain heteroatoms and n is a number from 1 to 10,
• Solvent mixture containing 0.1 to 75 wt .-% of at least one water-miscible organic solvent, and wherein the organic solvent has a measured at 25 ° C dielectric constant of at least 10, is placed in a reaction zone, and exposed to microwave radiation as it flows through the reaction section is, and wherein the reaction mixture in the reaction section by the microwave irradiation to temperatures above 100 ° C is heated.
• Another object of the invention are according to the invention
• R 1 is hydrogen or a methyl group.
• R 2 is preferably hydrogen.
• R 3 is preferably hydrogen or -COOH. In a specific embodiment, R 1 , R 2 and R 3 stand for
• R 1 is a methyl group and R 2 and R 3 are hydrogen.
• R 2 and R 3 are hydrogen.
• Embodiment R 1 and R 2 are hydrogen and R 3 is a
• Synthetic poly (carboxylic acids) (A) are polymers which can be prepared by addition polymerization of ethylenically unsaturated carboxylic acids.
• Preferred synthetic poly (carboxylic acids) contain structural units derived from acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or mixtures thereof. The concept of derived
• Structural units means that the polymer contains structural units which are formed in the addition polymerization of said acids.
• Particularly preferred are homopolymers of said ethylenically unsaturated carboxylic acids such as poly (acrylic acid), and poly (methacrylic acid).
• the inventive method is also for the modification of
• the proportion of structural units derived from further ethylenically unsaturated monomers is preferably between 0.1 and 40 mol%, more preferably between 0.5 and 25 mol% and in particular between 1 and 10 mol%, for example between 2 and 5 mol%.
• Preferred further ethylenically unsaturated monomers are
• Sulfonic acid groups such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate,
• unsaturated compounds having phosphate or phosphonic acid groups such as vinylphosphoric acid, vinylphosphonic acid, allylphosphonic acid, methacrylamidomethanephosphonic acid,
• esters of acrylic and methacrylic acid with Ci-C2o alcohols and especially
• C 2 -C 6 -alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate and acrylamide and methacrylamide and their on the nitrogen with Ci-C 2 o-alkyl radicals substituted derivatives, vinyl ethers such as methyl vinyl ether,
• N-vinyl compounds such as N-vinylcaprolactam and N-vinylpyrrolidone and olefins such as ethylene, styrene and butadiene are useful as other comonomers.
• Preferred copolymers are included in the solvent mixture of water and the water-miscible organic solvent
• Temperatures above 40 ° C such as at 50 ° C, 60 ° C, 70 ° C, 80 ° C or 90 ° C homogeneously soluble or at least swellable. Furthermore, they are preferred with a concentration of at least 1 wt .-% and in particular 5 bis
• wt .-% such as 20 to 80 wt .-% at temperatures above 40 ° C such as at 50 ° C, 60 ° C, 70 ° C, 80 ° C or 90 ° C homogeneously soluble or swellable in the solvent mixture.
• preferred copolymers are copolymers of Acrylic acid or methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid
• the structural units of the formula (I) derived from ethylenically unsaturated carboxylic acids may be distributed in blocks, alternately or randomly.
• Poly (carboxylic acids) (A) which are preferred according to the invention have number-average molecular weights above 700 g / mol, more preferably between 1,000 and 500,000 g / mol and in particular between 2,000 and 300,000 g / mol, for example between 2,500 and 100,000 g / mol, in each case determined by gel permeation chromatography against poly (styrenesulfonic acid) standards.
• the poly (carboxylic acids) contain (A) on average at least 10 and in particular at least 20 such as 50 bis
• R 4 is an aliphatic radical. This has preferably 2 to 50, more preferably 3 to 24 and especially 4 to 20 C-atoms.
• the aliphatic radical may be linear, branched or cyclic. It may also be saturated or unsaturated, preferably it is saturated.
• the hydrocarbon radical may carry substituents such as, for example, halogen atoms, halogenated alkyl radicals, C 1 -C 5 -alkoxyalkyl, 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, hydroxyl, Ci-C 2 o-alkyl, C 2 -C 2 o-alkenyl, Ci-C 5 alkoxy- such as
• aliphatic radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl,
• R 4 is an optionally substituted C 6 -C 12 -aryl or an optionally substituted
• heteroaromatic group with 5 to 12 ring members.
• Preferred heteroatoms are oxygen, nitrogen and sulfur.
• the aryl or heteroaromatic group may thus be mono- or polycyclic.
• suitable substituents are halogen atoms, halogenated alkyl radicals and also alkyl, alkenyl, hydroxyalkyl, alkoxy, ester, amide, nitrile and nitro groups.
• the radical R 4 bears one or more, for example two, three, four, or more further hydroxyl groups, but not more hydroxyl groups than the radical R 4 has C atoms or as the aryl group has valencies.
• Hydroxyl groups may be attached to adjacent C atoms or to further carbon atoms of the hydrocarbon radical, but at most one OH group per carbon atom.
• n is a number between 2 and 6.
• the process according to the invention is also suitable for the esterification of poly (carboxylic acids) (A) with polyols, for example ethylene glycol,
• the alcohol has a hydroxyl group, that is, n is 1.
• R 4 is one with
• an alkylene group having 2 to 18 C atoms preferably having 2 to 12 and in particular 2 to 4 C atoms, such as, for example, ethylene, propylene, butylene or mixtures thereof,
• Hydrocarbon radical having 1 to 50 carbon atoms, or a group of the formula -R 5 -NR 7 R 8 ,
• an aliphatic radical having 1 to 24 C atoms and preferably 2 to 18 C atoms, an aryl group or heteroaryl group having 5 to 12 ring members, a
• Polyethers of the formula (III) which are suitable according to the invention are obtainable, for example, by alkoxylating alcohols of the formula R 4 -OH or fatty acids of the formula R 9 -COOH with 2 to 100 mol of ethylene oxide, propylene oxide or a mixture thereof.
• Preferred polyethers have molecular weights between 300 and 7,000 g / mol and more preferably between 500 and 5,000 g / mol, for example between 800 and 2,500 g / mol. Does R 4 stand for a remainder of
• n is equal to 1.
• suitable alcohols (B) are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, neopentanol, n-hexanol, isohexanol, cyclohexanol, heptanol, octanol , 2-ethylhexanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, ethylene glycol, 2-methoxyethanol, propylene glycol, diethylene glycol, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol,
• fatty alcohol mixtures obtained from natural raw materials such as, for example, coconut fatty alcohol, palm kernel fatty alcohol and tallow fatty alcohol and also their reaction products with alkylene oxides.
• poly (carboxylic acid) (A) and alcohol (B) can generally be reacted with one another in any desired ratios.
• the reaction with molar ratios between carboxyl groups of the poly (carboxylic acid) (A) and hydroxyl groups of the alcohol (B) preferably takes place from 100: 1 to 1: 5, preferably from 10: 1 to 1: 1, especially from 5: 1 to 2 : 1, in each case based on the equivalents of carboxyl and hydroxyl groups. If the alcohol is used in excess or is not fully reacted, portions of it remain unreacted in the polymer, depending on
• Volatile means that the alcohol has a boiling point at normal pressure of preferably below 250 ° C as
• ester for example, below 150 ° C and thus, optionally together with solvent, can be separated from the ester. This can be done for example by means of distillation, phase separation or extraction.
• Ratio of hydroxyl to carboxyl groups of the polymer may be the
• reaction conditions are preferably adjusted so that at least 10 mol%, in particular 20 to 100 mol% and especially 25 to 80 mol%, such as 30 to 70 mol% of the alcohol used (B) are reacted.
• very homogeneous products are formed, which manifests itself in a uniform solubility.
• Reaction mixture containing poly (carboxylic acid) (A), alcohol (B), water, a water-miscible solvent and optionally other auxiliaries such as emulsifier, catalyst and / or electrolyte can be carried out in various ways.
• Alcohol (B) can be carried out continuously, batchwise or else in semi-batch processes. In particular for processes on an industrial scale, it has proven useful to supply the starting materials to the process according to the invention in liquid form.
• the poly (carboxylic acid) (A) is preferably fed to the inventive method as a solution in water or as a solution in water and a water-miscible solvent.
• the poly (carboxylic acid) (A) can also be used in swollen form, provided that it is pumpable.
• the alcohol (B) optionally in a molten state, with water and / or with water mixable solvent added, for example, as a solution to use dispersion or emulsion.
• the mixing of poly (carboxylic acid) (A) with alcohol (B) can be carried out in a (semi) batch process by sequential charging of the ingredients, for example in a separate stirred tank.
• the alcohol (B) is dissolved in the water-miscible organic solvent and then added to the already dissolved or swollen polymer.
• the addition is carried out in small portions over a long time and with stirring, on the one hand, a homogeneous distribution of the alcohol
• Reaction mixture optionally after intermediate cooling, in the
• a catalyst and further auxiliaries can be added to one of the educts or else to the educt mixture before it enters the reaction zone. Also heterogeneous systems can after the
• the reaction mixture contains 10 to 99 wt .-%, particularly preferably 20 to 95 wt .-%, in particular 25 to 90 wt .-% such as 50 to 80 wt .-% of a solvent mixture of water and one or more miscible with water , organic solvents.
• water is added to reactants A and B prior to microwave irradiation so that the reaction product contains an amount of water exceeding the amount of water of reaction liberated during esterification.
• Preferred water-miscible organic solvents are polar protic and polar aprotic liquids. Preferably, these have a measured at 25 ° C dielectric constant of at least 12 and in particular at least 15.
• Preferred solvents are soluble in water to at least 100 g / l, more preferably at least 200 g / l, in particular at least 500 g / l soluble and are special they are completely miscible with water.
• Particularly preferred as solvents are heteroaliphatic compounds and in particular alcohols, ketones, end-capped polyethers, carboxylic acid amides such as
• tertiary carboxylic acid amides for example, tertiary carboxylic acid amides, nitriles, sulfoxides and sulfones.
• Preferred aprotic solvents are, for example, formamide,
• protic organic solvents are lower alcohols having 1 to 10 carbon atoms and
• Secondary and tertiary alcohols are particularly preferably used as lower alcohols. Particularly preferred are secondary and tertiary alcohols having 3 to 5 carbon atoms such as
• low-boiling liquids are preferred as the water-miscible, organic solvents and in particular those which have a boiling point at atmospheric pressure of below 150 ° C and especially below 120 ° C such as below 100 ° C and thus with little effort again from the
• modified polymers may remain in the product.
• the proportion of water-miscible organic solvent in the solvent mixture is preferably between 1 and 60 wt .-%, more preferably between 2 and 50 wt .-%, in particular between 5 and 40 wt .-% such as between 10 and 30 wt .-%, each based on the weight of the solvent mixture. Water is contained in the solvent mixture ad 100 wt .-%.
• the alcohol (B) may also function simultaneously as a water-miscible organic solvent.
• Embodiment preferably lower primary alcohols have proven useful.
• Preferred lower primary alcohols herein have 1 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms.
• the proportion of the lower alcohols in the solvent mixture is preferably between 1 and 60% by weight, more preferably between 2 and 50% by weight, in particular between 5 and 40% by weight, for example between 10 and 30% by weight. %, in each case based on the weight of the solvent mixture. Water is contained in the solvent mixture ad 00 wt .-%. To further reduce the viscosity of the reaction mixture used and / or the solution of the polymer polymer modified polymer formed in the course of the process according to the invention, it has proven itself many times
• Reaction mixture to add electrolytes Preferred are strong electrolytes which are completely dissociated, regardless of the concentration.
• Preferred strong electrolytes are salts of alkali and alkaline earth metals such as, for example, their chlorides, phosphates, sulfates, carbonates and bicarbonates. Examples of preferred strong electrolytes are NaCl, KCl, Na 2 C0 3) Na 2 S0 4 and MgS0 4 .
• the addition of electrolytes simultaneously increases the dielectric loss of the reaction medium, so that more energy can be coupled into the reaction mixture per unit of time or volume. For the continuous process according to the invention, this means an increase in the amount that can be converted per unit time, since more of the reaction mixture in the reaction zone can be heated to the desired temperature while increasing the flow rate (and simultaneously the irradiated microwave energy).
• the reaction mixture in a preferred embodiment, one or more Emulsifiers are added.
• Emulsifiers which are chemically inert towards the educts and the product are preferably used.
• the emulsifier is a reaction product from a separate preparation.
• the reactants are fed in the desired ratio of separate templates of the reaction route. In a special embodiment they will be before entering the reaction route.
• Reaction zone and / or further homogenized in the reaction section itself by means of suitable mixing elements such as static mixer and / or Archimedean screw and / or by flowing through a porous foam.
• the reaction zone comprises at least one vessel in which the reaction mixture is exposed to microwave radiation (irradiation zone) and optionally an isothermal reaction zone adjoining it in the flow direction, in which the reaction can be completed.
• the reaction zone consists of the irradiation zone.
• the reaction mixture by microwave radiation, preferably at temperatures above 110 ° C, more preferably
• Microwave irradiation reached maximum temperatures.
• the temperature can be measured, for example, on the surface of the irradiation vessel. It is preferred on the reaction mixture directly after leaving the
• the pressure in the reaction zone is preferably set so high that the reaction mixture remains in the liquid state and does not boil. Is preferred at pressures above 1 bar, preferably at pressures between 3 and 300 bar, more preferably between 5 and 200 and in particular between 10 and 100 bar such as between 15 and 50 bar worked.
• Preferred catalysts according to the invention are acidic inorganic, organometallic or organic
• Catalysts and mixtures of several of these catalysts are liquid and / or soluble in the reaction medium.
• 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 acid
• Aluminum compounds of the general formula AI (OR 15 ) 3 and titanates of the general formula Ti (OR 15 ) 4 can be used as acidic inorganic catalysts, where the radicals R 5 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, C3-Ci 2 -cycloalkyl radicals, for example cyclopropyl, cycl
• Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides (R 5 ) 2 SnO, where R 15 is as defined above.
• 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, sulfonic acid 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.
• Particularly preferred are aromatic sulfonic acids and especially alkylaromatic mono-sulfonic acids with one or more
• CrC28-alkyl radicals and especially those with C3-C22-alkyl radicals.
• Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid,
• Particularly preferred for carrying out the process according to the invention are acidic organic catalysts and in particular methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.
• Catalysts are used according to the invention 0.01 to 10 wt .-%, preferably 0.02 to 2 wt .-% catalyst.
• the microwave irradiation is carried out in the presence of acidic, solid and in the reaction medium not or not completely soluble catalysts.
• acidic, solid and in the reaction medium not or not completely soluble catalysts.
• Catalysts can be suspended in the reaction mixture and exposed to microwave irradiation together with the reaction mixture.
• the reaction mixture can be suspended in the reaction mixture and exposed to microwave irradiation together with the reaction mixture.
• 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 acid ion exchangers based on of polystyrenesulfonic acids which can be used as solid phase catalysts, for example, by the company Rohm & Haas under the
• the reaction mixture can in many cases be fed directly to another use.
• water and / or organic solvent can be separated from the crude product by conventional separation techniques such as distillation, freeze-drying or absorption.
• alcohol used in excess and optionally unreacted residual amounts of alcohol can be separated with it.
• the crude products can be further purified by conventional purification methods such as, for example, washing, reprecipitation, filtration, dialysis or chromatographic methods.
• the microwave irradiation is usually carried out in apparatuses which have an irradiation vessel made of a material which is as far as possible transparent to microwaves, in the microwave generated in a microwave generator
• Microwave radiation is coupled.
• Microwave generators like
• the magnetron, the klystron and the gyrotron are the magnetron, the klystron and the gyrotron.
• Irradiation vessels are preferably made of largely microwave-transparent, high-melting material or contain at least parts such as windows made of these materials. Non-metallic irradiation vessels are particularly preferably used. Under largely
• the dielectric loss factor tan ⁇ is defined as the ratio of dielectric loss ⁇ "and ⁇ dielectric constant '.
• tan ⁇ values of different materials are, for example, in D. Bogdal, Microwave-assisted Organic Synthesis, Elsevier 2005.
• materials with tan ⁇ values measured at 2.45 GHz and 25 ° C. of less than 0.01, in particular less than 0.005 and especially less than 0.001 are preferred.
• materials with tan ⁇ values measured at 2.45 GHz and 25 ° C. of less than 0.01, in particular less than 0.005 and especially less than 0.001 are preferred.
• Microwave-transparent and temperature-stable materials are primarily materials based on minerals such as quartz, aluminum oxide, zirconium oxide, silicon nitride and the like into consideration. Also temperature stable
• Plastics such as in particular fluoropolymers such as Teflon, and engineering plastics such as polypropylene, or polyaryletherketones such
• PEEK glass fiber reinforced polyetheretherketone
• microwaves are electromagnetic radiation having a wavelength between about 1 cm and 1m and frequencies between about 300 MHz and
• microwave radiation with frequencies released for industrial, scientific and medical applications is preferably used, such as
• the microwave irradiation of the reaction mixture can be carried out both in
• Microwave applicators that operate in mono or quasi-single mode as well as in those working in multimode done. Corresponding devices are known to the person skilled in the art.
• Irradiation vessel to be irradiated microwave power is particularly dependent on the desired reaction temperature, the geometry of the
• Irradiation vessel and the associated reaction volume and the flow rate of the reaction mixture through the irradiation vessel It is usually between 100 W and several 100 kW and in particular between 200 W and 100 kW, such as between 500 W and 70 kW. It can be applied at one or more points of the irradiation vessel. It can be generated by one or more microwave generators. The duration of the microwave irradiation depends on various factors such as the reaction volume, the geometry of the irradiation vessel, the
• the intensity (power) of the microwave radiation is adjusted so that the reaction mixture in the shortest possible time the desired
• Reaction temperature reached In a further preferred embodiment of the method according to the invention, it has proven useful to supply the reaction mixture to the irradiation vessel in heated form. To maintain the reaction temperature, the reaction product may be further irradiated with reduced and / or pulsed power or otherwise maintained at temperature. In a preferred embodiment, the reaction product is cooled as soon as possible after completion of the microwave irradiation to temperatures below 100 ° C, preferably below 80 ° C and especially below 50 ° C.
• the microwave irradiation is preferably carried out in a flow tube serving as an irradiation vessel, which is also referred to below as the reaction tube. It can also be carried out in semi-batch processes such as continuously operated stirred reactors or cascade reactors.
• the reaction is carried out in a closed, pressure-resistant and chemically inert vessel, wherein the water and optionally the alcohol (B) and the water-miscible solvent lead to a pressure build-up.
• the pressure can be reduced by venting to volatilize and separate water, organic Solvent and optionally excess alcohol (B) and / or used to cool the reaction product.
• the reaction mixture is freed as rapidly as possible from water and optionally present catalytically active species in order to avoid hydrolysis of the resulting ester.
• the water and organic solvent may be separated by conventional separation techniques such as freeze-drying, distillation or absorption.
• the reaction mixture is passed continuously through a pressure-resistant reaction tube which is inert toward the reactants and which is largely transparent to microwaves and inserted into a microwave applicator serving as an irradiation zone.
• This reaction tube preferably has a diameter of one millimeter to about 50 cm, especially between 2 mm and 35 cm, for example between 5 mm and 15 cm. Particularly preferred is the
• Diameter of the reaction tube smaller than the penetration depth of the microwaves in the reaction mixture to be irradiated. In particular, it is 1 to 70% and especially 5 to 60% such as 10 to 50% of the penetration depth. Under penetration depth is understood here the route on which the irradiated
• Microwave energy is attenuated to 1 / e.
• Irradiation zone (this is understood as the proportion of the flow tube in which the reaction mixture is exposed to microwave radiation) greater than 5, preferably between 10 and 100,000, more preferably between 20 and 10,000 such as between 30 and 1,000.
• they can be straight or bent or shaped as a tube coil.
• the reaction tube is in the form of a
• Double jacket tube designed by the inner and outer space, the reaction mixture can be performed sequentially in countercurrent, for example, the temperature control and energy efficiency of the process increase.
• the length of the reaction tube is to be understood as meaning the total distance traveled by the reaction mixture in the microwave field.
• Reaction tube is surrounded on its length by at least one, but preferably by several such as, for example, two, three, four, five, six, seven, eight or more microwave radiators.
• the microwave radiation preferably takes place via the tube jacket.
• the microwave irradiation takes place by means of at least one antenna via the tube ends.
• the reaction section 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.
• a metering pump and a pressure gauge at the outlet with a pressure-holding device and a heat exchanger.
• a solution of the polymer (A) and alcohol (B) only shortly before entering the reaction zone optionally with the aid of suitable mixing elements such as static mixer and / or Archimedean screw and / or by flowing through a porous foam mixed.
• suitable mixing elements such as static mixers and / or Archimedean screw and / or by flowing through a porous foam.
• Reaction conditions adjusted so that the maximum reaction temperature is reached as quickly as possible.
• the residence time at maximum temperature is chosen so short that as few side or subsequent reactions occur as possible.
• the continuous microwave reactor is preferably operated in monomode or quasi-monomode.
• the residence time of the reaction mixture in the irradiation zone is generally less than 20 minutes, preferably between 0.01 seconds and 10 minutes, preferably between 0.1 seconds and 5 minutes
• reaction mixture can flow through the irradiation zone several times to complete the reaction, optionally after intermediate cooling.
• the irradiation of the reaction material with microwaves is carried out in a reaction tube whose longitudinal axis is in the direction of propagation of the microwaves in a monomode microwave applicator.
• the length of the reaction material with microwaves is carried out in a reaction tube whose longitudinal axis is in the direction of propagation of the microwaves in a monomode microwave applicator.
• Irradiation zone at least half the wavelength, more preferably at least one and up to 20 times, especially 2 to 15 times, such as 3 to 0 times the wavelength of the used
• Microwave radiation With this geometry, energy from several, such as two, three, four, five, six or more consecutive maxima of the propagating parallel to the longitudinal axis of the tube microwave can be transferred to the reaction mixture, which significantly improves the energy efficiency of the process.
• the irradiation of the reaction product with microwaves preferably takes place in a substantially microwave-transparent straight reaction tube, which is located within a hollow conductor connected to a microwave generator and functioning as a microwave applicator.
• the reaction tube is aligned axially with a central axis of symmetry of this waveguide.
• the waveguide is preferably formed as a cavity resonator.
• Cavity resonator dimensioned so that it forms a standing wave. Further preferred are those not absorbed in the waveguide
• Mikrowellenapplikators as a resonator of the reflection type, a local increase in the electric field strength are achieved with the same power supplied by the generator and increased energy utilization.
• the cavity resonator is preferably operated in Eoi n mode, where n is an integer and the number of field maxima of the microwave along the indicates the central axis of symmetry of the resonator.
• the electric field is in the direction of the central axis of symmetry of the
• Cavity resonator directed. It has a maximum in the area of the central axis of symmetry and decreases to the lateral surface to the value zero.
• Field configuration is rotationally symmetrical about the central axis of symmetry.
• n is an integer
• N is preferably an integer from 1 to 200, particularly preferably from 2 to 100, in particular from 3 to 50, especially from 4 to 20, for example three, four, five, six, seven, eight, nine or ten.
• the E 0 i n mode of the cavity resonator is also referred to in English as TM 0 i n -Mode (transverse magnetic), see, for example, K. Lange, KH Löcherer, Paperback of high-frequency technology ", Volume 2, page K21 ff.
• 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 reaction material with microwaves in a reaction tube which is located in a waveguide with coaxial transition of the microwaves.
• particularly preferred microwave devices are from a cavity resonator, a coupling device for coupling a
• Microwave field in the cavity resonator and constructed with one opening at two opposite end walls for passing the reaction tube through the resonator.
• Cavity resonator is preferably via a coupling pin, in the
• the coupling pin is as a
• Forming coupling antenna preferably formed metallic inner conductor tube. In a particularly preferred embodiment, this protrudes
• 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 axis of symmetry of the cavity resonator, for which purpose the cavity resonator preferably each has a central opening on 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 fed to the resonator via a waveguide, wherein the protruding from the cavity resonator end of the coupling pin in a
• Opening which is located in the wall of the waveguide, in the waveguide
• Reaction tube which is axially symmetrical in a E 0 i n 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.
• the irradiation of the reaction mixture with microwaves in a microwave-transparent reaction tube which is passed through a Eoi n- cavity resonator with axial feeding of the microwaves, wherein the length of the
• the irradiation of the reaction mixture with microwaves takes place in one
• Microwave transparent reaction tube which is passed through an Eoi n- cavity resonator with axial feeding of the microwaves, wherein the length of the
• the irradiation of the reaction mixture with microwaves in a microwave-transparent reaction tube which is axially symmetrical in a circular cylindrical E 0 i n cavity resonator with coaxial transition of the microwaves is carried out, the length of the microwave-transparent reaction tube, which is axially symmetrical in a circular cylindrical E 0 i n cavity resonator with coaxial transition of the microwaves is carried out, the length of the microwave-transparent reaction tube, which is axially symmetrical in a circular cylindrical E 0 i n cavity resonator with coaxial transition of the microwaves is carried out, the length of the microwave-transparent reaction tube, which is axially symmetrical in a circular cylindrical E 0 i n cavity resonator with coaxial transition of the microwaves is carried out, the length of the microwave-transparent reaction tube, which is axially symmetrical in a circular cylindrical E 0 i n cavity resonator with coaxial transition of the microwaves is carried out, the length of
• Eoi 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 an EorRundhohlleiter. Particularly preferably it has a cylindrical shape and especially a circular cylindrical shape.
• the reaction of the reaction mixture is on leaving the
• reaction mixture is therefore transferred directly after passage of the irradiation zone, that is without intermediate cooling in an isothermal reaction zone, in which it continues for a certain time
• the reaction mixture is optionally relaxed and cooled.
• the direct transfer from the irradiation zone into the isothermal reaction zone is to be understood as meaning that no active measures are taken between the irradiation zone and the isothermal reaction zone for supplying and in particular for dissipating heat.
• the Temperature difference between leaving the irradiation zone to the entry into the isothermal reaction path less than ⁇ 30 ° C, preferably less than ⁇ 20 ° C, more preferably less than ⁇ 10 ° C and especially less than ⁇ 5 ° C.
• the temperature of the reaction product when entering the isothermal reaction path corresponds to the temperature when leaving the irradiation zone. This embodiment allows rapid and targeted heating of the reaction mixture to the desired reaction temperature without partial overheating and then a stay in this
• reaction temperature for a defined period of time before it is cooled.
• the reaction mixture is preferably cooled as quickly as possible directly after leaving the isothermal reaction zone to temperatures below 120 ° C, preferably below 100 ° C and especially below 60 ° C.
• Isothermal reaction zone is understood to mean that the temperature of the reaction mixture in the isothermal reaction zone is kept constant with respect to the inlet temperature at ⁇ 30 ° C., preferably ⁇ 20 ° C., more preferably ⁇ 10 ° C. and in particular ⁇ 5 ° C.
• the reaction mixture when leaving the isothermal reaction zone, has a maximum temperature of ⁇ 30 ° C, preferably ⁇ 20 ° C, more preferably ⁇ 10 ° C and especially ⁇ 5 ° C of the
• Reaction paths may consist of various materials such as metals, ceramics, glass, quartz or plastics, provided that they are mechanically stable and chemically inert under the selected temperature and pressure conditions. Thermally insulated vessels have proven to be particularly useful. The residence time of the reaction mixture in the isothermal
• Reaction distance can, for example, the volume of the isothermal
• Reaction distance are set. When using stirred containers and Container cascades, it has proven equally to adjust the residence time on the degree of filling of the container.
• the isothermal reaction zone is with active or passive mixing elements
• a tube is used as the isothermal reaction section. This may be an extension of the
• Microwave-transparent reaction tube after the irradiation zone or even a separate, related to the reaction tube tube of the same or different material act Over the length of the tube and / or its cross-section can be at a given flow rate, the
• the tube acting as an isothermal reaction section is thermally insulated in the simplest case, so that the temperature prevailing when the reaction mixture enters the isothermal reaction section is kept within the limits given above.
• the reaction mixture can in the isothermal reaction zone but also for example by means of a
• Heat transfer medium or cooling medium targeted energy to be added or removed.
• the isothermal reaction path can be configured for example as a tube coil or as a tube bundle, which is located in a heating or cooling bath or acted upon in the form of a double-walled tube with a heating or cooling medium.
• the isothermal reaction zone can also be located in a further microwave applicator in which the reaction mixture is again treated with microwaves. Both single-mode and multi-mode applicators can be used.
• the residence time of the reaction mixture in the isothermal reaction zone is preferably selected such that the thermal equilibrium state defined by the prevailing conditions is achieved. Usually that is
• Dwell time between 1 second and 10 hours, preferably between
• the ratio between residence time of the reaction mixture in the Isothermal reaction path to the residence time in the irradiation zone between 1: 2 and 100: 1, more preferably 1: 1 to 50: 1 and in particular between 1: 1.5 and 10: 1.
• the inventive method allows the polymer-analogous modification of synthetic poly (carboxylic acids) with alcohols in a continuous
• a further advantage of the process according to the invention resides in the fact that the polymer-analogous condensation reactions can be carried out in aqueous solution, since water is the solvent most suitable for poly (carboxylic acids) and, moreover, is also advantageous from an ecological point of view.
• the addition of certain polar organic solvents can counteract any increase in viscosity which may occur in the course of the process as a result of the formation of hydrophobically modified structural units and also facilitates the reaction with less water-soluble alcohols.
• the process according to the invention is suitable for partial esterifications of relatively high molecular weight synthetic poly (carboxylic acids since the reaction mixtures, despite viscosity and solubility differences between poly (carboxylic acids) (A) and alcohols (B), become homogeneous
• Aluminum oxide reaction tube (60 x 1 cm) axially symmetric in a cylindrical cavity resonator (60 x 10 cm). At one of the end faces of the cavity resonator, the reaction tube passed through the cavity of an inner conductor tube functioning as a coupling antenna.
• the microwave field generated by a magnetron with a frequency of 2.45 GHz was coupled by means of the coupling antenna in the cavity resonator
• Intensive heat exchanger cooled to the specified temperature and neutralized the catalyst.
• the microwave power was adjusted over the duration of the experiment in each case 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.
• Reaction mixture was made directly after leaving the irradiation zone by means of Pt100 temperature sensor. Microwave energy not directly absorbed by the reaction mixture was reflected at the end face of the cavity resonator opposite the coupling antenna; the ones from Reaction mixture also not absorbed in the return and mirrored back in the direction of the magnetron microwave energy was using a
• Prism system (circulator) passed into a water-containing vessel. 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 were pumped through the device at a constant flow rate and the residence time in the
• Irradiation zone adjusted by modifying the flow rate.
• reaction products were carried out by means of 1 H-NMR spectroscopy at 500 MHz in CDCl 3 .
• Poly (acrylic acid) (molecular weight 5,000 g / mol) initially charged in 4 kg of water, treated with 20 g of p-toluenesulfonic acid and heated to 40 ° C. At this temperature, 1 kg of methanol (1, 1 mol of methanol per acid function of the polymer) was added over a period of 10 minutes with stirring.
• the resulting reaction mixture was pumped at a working pressure of 35 bar continuously at 6 l / h through the reaction tube and a
• Irradiation zone was about 40 seconds.
• the reaction mixture had a temperature of 235 ° C and was transferred directly at this temperature in the isothermal reaction zone.
• the reaction mixture had a temperature of 221 ° C.
• the reaction mixture was cooled to room temperature immediately after leaving the reaction section.
• the reaction product was a homogeneous, colorless solution with lower
• Viscosity After evaporation of the solvent resulted in a viscous,
• the residence time of the reaction mixture in the Irradiation zone was about 48 seconds.
• the reaction mixture had a temperature of 257 ° C and was transferred directly at this temperature in the isothermal reaction zone.
• the reaction mixture had a temperature of 225.degree.
• the reaction mixture was cooled to room temperature immediately after leaving the reaction section and the catalyst was neutralized with sodium hydroxide solution.
• the reaction product was a slightly yellowish solution of low viscosity. After evaporation of the solvent and reprecipitation from methanol resulted in a viscous mass whose IR spectrum shows a characteristic of ester band at 1735 cm "1 and for aliphatic -CH 3 groups characteristic signals in the 1 H-NMR spectrum at 0.9 ppm. The comparison with the integrals of the backbone protons gave a conversion of about 13% of the acid functions.
• Verestanssgrad determined by 15 mol%.
• Poly (acrylic acid) (molecular weight 5,000 g / mol) presented in 4 kg of water, mixed with 20 g of methanesulfonic acid and heated to 35 ° C. At this temperature, a solution of 1 kg of methyl tetraethylene glycol (4.8 mol) in 1 kg of isopropanol was added over a period of one hour with stirring.
• the reaction mixture thus obtained was continuously pumped at a working pressure of 33 bar at 6.2 l / h through the reaction tube and a
• Irradiation zone was about 38 seconds.
• the reaction mixture had a temperature of 247 ° C and was transferred directly at this temperature in the isothermal reaction zone.
• the reaction mixture had a temperature of 234 ° C.
• the reaction mixture was cooled to room temperature immediately after leaving the reaction zone and the catalyst was neutralized with bicarbonate solution.
• the reaction product was a slightly yellowish, slightly viscous solution. After evaporation of the solvent and dropping the reaction product from methanol / acetone resulted in a viscous, extremely sticky mass whose
• Verestanssgrad determined by 8 mol% of the carboxyl groups.
• Example 4 Esterification of poly (acrylic acid) with coconut fatty alcohol ethoxylate (10 EO)
• Cocosfettalkoholethoxilat (Genapol ® C 100) about 1 mol) in 2 kg of isopropanol was added.
• the reaction mixture thus obtained was continuously pumped at a working pressure of 35 bar at 5 l / h through the reaction tube and a
• Irradiation zone was about 48 seconds.
• the reaction mixture had a temperature of 227 ° C and was transferred directly at this temperature in the isothermal reaction zone.
• the reaction mixture had a temperature of 209.degree.
• the reaction product was then neutralized by means of sodium carbonate and freed from the solvent in vacuo. By means of a Soxlet On an aliquot, the unreacted portions of the
• Cocosfettalkoholethoxilats extracted with boiling t-butanol and determined gravimetrically after removal of the solvent. By recalculation on the

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