WO2012089300A2 - Hydroxylgruppen und estergruppen tragende polymere und verfahren zu ihrer herstellung - Google Patents
Hydroxylgruppen und estergruppen tragende polymere und verfahren zu ihrer herstellung Download PDFInfo
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- WO2012089300A2 WO2012089300A2 PCT/EP2011/006176 EP2011006176W WO2012089300A2 WO 2012089300 A2 WO2012089300 A2 WO 2012089300A2 EP 2011006176 W EP2011006176 W EP 2011006176W WO 2012089300 A2 WO2012089300 A2 WO 2012089300A2
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- C—CHEMISTRY; METALLURGY
- 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
- C08F16/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/02—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/08—Allyl alcohol
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- C—CHEMISTRY; METALLURGY
- 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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
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- 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
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- C—CHEMISTRY; METALLURGY
- 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
- C08F18/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- 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
- C08F8/14—Esterification
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- 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
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- 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
Definitions
- the present invention relates to hydroxyl groups and ester group-bearing polymers and to a process for their preparation by polymer analogues
- a suitable method would be, for example, the alkoxylation of with alkylene oxides.
- the low solubility of polymers bearing hydroxyl groups in organic solvents causes considerable preparative difficulties in the reaction and in particular in the preparation of homogeneous products.
- the polymer to be reacted must be brought into a soluble or at least swollen form to ensure a homogeneous reaction. If the polymer is insoluble in the reaction medium, only
- Hydroxyl-bearing polymers such as, for example, polyvinyl alcohol are in solvent-free form solids or highly viscous masses, which must be fluidized for homogeneous chemical reactions either thermally or by means of solvents.
- Preferred solvent for most hydroxyl-bearing polymers is water.
- water is usually less suitable as a solvent because it leads primarily to the formation of glycol and polyglycols and not to the etherification of the alcoholic hydroxyl groups.
- polymers such as poly (vinyl alcohol) usually in polar aprotic solvents such as Dimethyl sulfoxide, formamide, dimethylformamide and
- Ethercarboxylic acids are at least technically not available, so that such polymer-analogous modifications are not accessible.
- the esterification requires temperatures between 150 and 250 ° C and takes 2 to 5 hours.
- the products obtained are intensely tanned in color and on the one hand contain high molecular weight crosslinked components and on the other hand
- the modification should be as homogeneous as possible, that is done in statistical distribution over the entire polymer. Furthermore, there should be no reactions on the polymer backbone, in particular polymer degradation, and no appreciable amounts of toxicologically and / or ecologically harmful by-products should arise.
- Hydroxyl-carrying polymers in aqueous solution and / or in solutions of water and water-miscible organic solvents with
- Ethercarboxylic acids under the influence of microwaves at temperatures above 100 ° C esterify. In this way, the elasticity of hydroxyl-bearing polymers can be significantly increased with comparable tensile strength. At the same time the solubility in cold water is significantly improved.
- the dissolution behavior of such modified polymers gives no indication of the presence of larger hydrophilic or hydrophobic polymer blocks. Since a large number of different ether carboxylic acids can be obtained inexpensively and in technical quantities, the properties of said polymers can be modified within wide limits in this way. It does not come to the degradation of
- esters of hydroxyl-bearing polymers containing repeating structural units of the formulas (I) and (II) in blockwise, alternating or random sequence
- R 1 is hydrogen, a hydrocarbon radical having 1 to 50 carbon atoms or an acyl radical of the formula -C (0) -R 4
- R 2 is a C 2 - to C 10 -alkylene radical
- R 3 is hydrogen or a C 1 -C 10 -alkyl radical which may carry substituents,
- R 4 is a hydrocarbon radical having 1 to 50 C atoms
- A is a C 2 -C 10 -alkylene radical
- n for a number from 0 to 4999
- n + m is a number from 10 to 5,000, with the proviso that a) the molar fraction of the structural units (I) on the polymer is between 0 and 99.9 mol%, and
- the molar fraction of the structural units (II) on the polymer is between 0.1 and 100 mol% of the repetitive units.
- Another object of the invention is a process for the preparation of esters of hydroxyl-bearing polymers containing repetitive
- R 1 is hydrogen, a hydrocarbon radical having 1 to 50 carbon atoms or an acyl radical of the formula -C (0) -R 4
- R 2 is a C 2 - to Cio-alkylene radical
- R 3 is hydrogen or a C 1 -C 10 -alkyl radical which may carry substituents,
- A is a C 2 - to C 10 -alkylene radical
- n for a number from 0 to 4999
- n + m is a number from 10 to 5,000, with the proviso that a) the molar fraction of the structural units (I) on the polymer is between 0 and
- the molar fraction of the structural units (II) on the polymer is between 0.1 and 100 mol% of the repetitive units
- R 1 -O [-A-O] k -E-COOH III
- R - O [-A-O] k -E -COOR 5 IV
- R 1 , A, E and k have the meanings given above and R 5 is a Ci-C4-alkyl radical
- Preferred hydroxyl-carrying polymers A) are main chain polymers, the polymer backbone is composed only of C-C bonds and the
- preferred hydroxyl-bearing polymers A) may have groups at the chain end
- the polymer A) contains a total of at least 5, more preferably at least 10, especially at least 15 and in particular at least 20 hydroxyl-bearing monomer units, d. H. n is at least 5, 10, 15 or 20. These monomer units may also be combined with or interspersed with structural units derived from other monomers in copolymers.
- D is preferably a direct bond between the polymer backbone and the hydroxyl group.
- the structural unit of the formula (I) is in this case from
- D stands for a linear or branched alkylene radical. This preferably has one, two, three or four carbon atoms. These are, for example, structural units derived from allyl alcohol or from 3-buten-1-ol 3-buten-1-ol, 1-penten-3-ol or 4-penten-1-ol.
- D is an oxyalkylene group in which R 2 is preferably an alkylene group having two, three or four C atoms.
- Such structural units (I) are preferably derived from hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether or
- D is an ester group.
- R 2 here preferably stands for an alkylene group having 2 or 3 C atoms.
- Such structural units (I) are derived, for example, from
- Hydroxyalkyl esters of acrylic acid and methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and
- D is an amide group which is connected via a group R 2 to the hydroxyl group.
- R 2 here preferably stands for an alkyl group having 2 or 3 C atoms.
- R 3 may, if it is an alkyl radical, carry substituents such as, for example, a hydroxyl group.
- R 3 is hydrogen, methyl, ethyl or hydroxyethyl.
- structural units (I) are derived, for example, from
- Hydroxyalkylamiden of acrylic acid and methacrylic acid such as hydroxyethylacrylamide, hydroxyethylmethacrylamide, hydroxypropylacrylamide,
- Hydroxyl-containing units of the formula (I) have structural elements which are derived from one or more further monomers which are not Wear hydroxyl groups.
- Preferred further monomers are olefins, esters and amides of acrylic acid and methacrylic acid, vinyl esters, vinyl ethers, vinylamines, allylamines, and derivatives thereof.
- Examples of preferred comonomers are ethene, propene, styrene, methyl acrylate, methyl methacrylate and esters of acrylic acid and methacrylic acid with alcohols having 2 to 24 carbon atoms.
- Preferably included Preferably included
- Copolymers more than 10 mol%, particularly preferably 15-99.5 mol%,
- suitable copolymers A) are copolymers of vinyl alcohol with vinyl esters, in particular copolymers of vinyl alcohol with vinyl acetate, as are obtainable, for example, by partial saponification of polyvinyl acetate.
- copolymers which in addition to vinyl alcohol 0.5 to 60 mol% and particularly preferably 1 to 50 mol% such as 1, 5 to 10 mol%
- copolymers A) examples are copolymers of vinyl alcohol and ethylene, vinyl alcohol and styrene and copolymers
- Preferred copolymers A) are homogeneously soluble or at least swellable in water or solvent mixtures of water and water-miscible organic solvent at temperatures above 40 ° C., for example at 50 ° C., 60 ° C., 70 ° C., 80 ° C. or 90 ° C. , Furthermore, they are preferred with a
- Particularly preferred hydroxyl-bearing main chain polymers A) are poly (vinyl alcohols). Under poly (vinyl alcohols) are understood according to the invention both homopolymers of vinyl alcohol and copolymers of vinyl alcohol with other monomers. Particularly preferred copolymers are those which contain 0.5 to 20 mol%, preferably 1 to 15 mol% vinyl ester. These are usually prepared by polymerization or copolymerization of esters of vinyl alcohol with lower carboxylic acids and subsequent hydrolysis of the ester. Preferred ester of the vinyl alcohol is vinyl acetate.
- Hydrolysis of the polymers can be complete or partial.
- copolymers are copolymers of ethylene and vinyl alcohol. Especially preferred are those which are 15-70 mol% and especially 20-60 mol%, such as 25-50 mol% of ethylene derived
- the weight-average molecular weight M w of preferred polymers A is preferably between 10,000 and 500,000, especially between 12,000 and 300,000 and in particular between 15,000 and 250,000 g / mol.
- the molecular weight of the modified polymers is according to their
- Suitable ether carboxylic acids B1 are generally compounds which have at least one carboxyl group and at least one ether group in the acid radical.
- inventive method is also for the implementation of
- Ethercarbon yarnren with, for example, two, three, four or more carboxyl groups suitable.
- Preferred ether carboxylic acids have a carboxyl group.
- Halocarboxylic acids or their alkali metal salts such as with
- E is an alkylene group having one, two, three or four C atoms and in particular a methylene group.
- Preferred ether carboxylic acids contain polyoxyalkylene groups having 2 to 70, more preferably 5 to 50 and
- Alkylene oxides for the preparation of the ether carboxylic acids B1) are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
- A is therefore preferably an alkylene radical having two, three or four C atoms.
- Formula (V) are accessible, for example, by reacting alkylene oxides with water, alcohols or carboxylic acids.
- R 1 is hydrogen.
- it may also come in the implementation of the ether carboxylic acid to the formation of double-sided carboxyl-bearing ether carboxylic acids.
- These ether carboxylic acids correspond to the formulas HOOC-E-O [-A-O] k -E-COOH (IIIa)
- R 5 OOC-E-O [-A-O] k -E-COOR 5 IVa)
- the resulting crosslinked polymers comprise a structure in which two polymer chains through their D-O structural unit of formula I by means of the group derived from the ether carboxylic acid
- R 1 is a hydrocarbon radical having preferably 2 to 36, more preferably 4 to 24 and in particular 6 to 20 carbon atoms.
- the hydrocarbon radical may be aliphatic, cycloaliphatic, aromatic or araliphatic. It is preferably aliphatic.
- Particularly preferred alcohols are lower alcohols having 1 to 6 carbon atoms such as methanol and ethanol, fatty alcohols of natural or synthetic origin having 7 to 20 carbon atoms such as oleyl, Cocosfett-, tallow fat and
- R 1 is an acyl radical of the formula -C (0) -R 4
- R 4 is a hydrocarbon radical having preferably 2 to 36, particularly preferably 4 to 24 and especially with 6 to 20 carbon atoms.
- the hydrocarbon radical R 4 may be aliphatic, cycloaliphatic, aromatic or araliphatic. It is preferably aliphatic.
- hydrocarbon radical R 4 as well as the acyl radical R 1 may independently of one another contain one or more, for example two, three, four or more further substituents, for example hydroxyalkyl, alkoxy, for example methoxy, poly (alkoxy) -,
- the hydrocarbon radical R 1 may also contain heteroatoms such as, for example, oxygen, nitrogen, phosphorus and / or sulfur, but preferably not more than one heteroatom per
- the ethercarboxylic esters B2) which are suitable according to the invention are esters of the abovementioned ethercarboxylic acids B) with alcohols of the general formula R 5 -OH.
- R 5 is preferably an alkyl radical with 1, 2 or
- Particularly preferred alcohols are methanol and ethanol.
- Ethercarbonchureester B2) are preferably used in a ratio of 100: 1 to 1: 1, more preferably in a ratio of 10: 1 to 1, 1: and especially in the ratio 8: 1 to 1, 2: used, in each case based on the molar equivalents of hydroxyl-bearing structures of the formula (I) and the carboxyl groups of the formula (III) or the ester groups of the formula (IV).
- the ratio of ether carboxylic acids B1) or Ethercarbonklastern B2) to hydroxyl groups of the polymer the degree of modification and thus the properties of the product can be adjusted. If ether carboxylic acid B1) or Ethercarbonklaester B2) im
- esterification of the free hydroxyl groups of the polymer A) can therefore take place completely or only partially.
- partial esterification preferably 1 to 99%, particularly preferably 2 to 90, in particular 5 to 70% and especially 10 to 50%, for example 20 to 40% of the hydroxyl groups, are esterified.
- Ethercarboxylic acid B1) or ether carboxylic acid ester B2) are preferably used substoichiometrically based on the total number of hydroxyl groups, in particular in a ratio of 1: 100 to 1: 2 and especially in a ratio of 1:50 to 1: 5, for example in a ratio of 1: 20 to 1 :8th. Preference is given to
- Reaction conditions thereby 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 ether carboxylic acid used or the fatty acid ester used are reacted.
- at least 10 mol%, in particular 20 to 100 mol% and especially 25 to 80 mol%, such as 30 to 70 mol% of the ether carboxylic acid used or the fatty acid ester used are reacted.
- very homogeneous products are formed, which manifests itself in good solubility and a sharp cloud point of aqueous solutions.
- the reaction mixture contains 5 to 98 wt .-%, particularly preferably 10 to 95 wt .-%, in particular 20 to 90 wt .-%, such as 50 to 80 wt .-% water, or 5 to 98 wt .-%, particularly preferably 10 to 95 wt .-%, in particular 20 to 90 wt .-% such as 50 to 80 wt .-% of a mixture of water and one or more water-miscible, organic solvent.
- water is added to the reactants A) and / or B) prior to irradiation with microwaves, so that the reaction product contains an amount of water in excess of the amount of water of reaction liberated during the esterification.
- ether carboxylic acids B1) and ether carboxylic acid esters B1) is readily water-soluble, so that their implementation with hydroxyl-bearing
- Polymer A can be carried out in aqueous solution.
- Solubility of Various Ethercarboxylic Acids B1) and Ethercarboxylic Acid Ester B2) in Water often requires the addition of one or more water-miscible organic solvents to the reaction mixture.
- 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 10 and in particular at least 12 such as at least 5.
- Preferred organic 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 and especially they are complete with water miscible.
- Particularly preferred solvents are heteroaliphatic
- aprotic solvents examples include formamide, ⁇ , ⁇ -dimethylformamide (DMF), ⁇ , ⁇ -dimethylacetamide, acetone, ⁇ -butyrolactone, acetonitrile, sulfolane and dimethyl sulfoxide (DMSO).
- Preferred protic organic solvents are lower alcohols having 1 to 10 C atoms and in particular having 2 to 5 C atoms. Examples of suitable alcohols are
- Secondary and tertiary alcohols are particularly preferably used as lower alcohols, which are inert under the chosen reaction conditions and neither tend to competing esterification nor to side reactions such as dehydration.
- Particularly preferred secondary and tertiary alcohols having 3 to 5 C 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. If water-miscible organic solvents are used, their share in the
- Solvent mixture preferably between 1 and 75 wt .-%, more preferably between 2 and 60 wt .-%, in particular between 5 and 50 wt .-%, such as between 10 and 30 wt .-%. Water is contained in the solvent mixture ad 100 wt .-%.
- one or more emulsifiers can be added to the reaction mixture in a preferred embodiment.
- Emulsifiers which are chemically inert towards the educts and the product are preferably used.
- the emulsifier is a reaction product of separate ones
- reaction mixture containing a hydroxyl-carrying polymer A), a
- Ethercarbon Textre B1) or an Ethercarbonchureester B2) water and optionally a water-miscible solvent and / or other auxiliaries such as emulsifier and / or catalyst, can be carried out in various ways.
- the mixing of polymer A) and ether carboxylic acid B1) or ether carboxylic acid ester B2) and optionally the other auxiliaries be carried out continuously, discontinuously or 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 hydroxyl-carrying polymer A) is preferably fed to the process according to the invention as a solution in water or as a solution in water and a water-miscible solvent. But it can also be used in swollen form, provided that it is pumpable.
- hydroxyl-carrying polymer A) with ether carboxylic acid B1) or ether carboxylic acid ester B2) and optionally the further auxiliaries can be carried out in a (semi) -batch process by sequential charging of the
- the ether carboxylic acid or the ether carboxylic acid ester is dissolved in a 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 to ensure a homogeneous distribution of the ether carboxylic acid or the Ethercarbonklareesters and on the other hand, a local
- the starting materials in a preferred embodiment in the desired ratio of separate templates to the vessel in which the irradiation with microwaves is carried out (hereinafter also referred to as a reaction vessel) fed.
- they are prior to entry into the reaction vessel and / or in the reaction vessel itself by means of suitable mixing elements such as static mixer and / or Archimedean screw and / or by flowing through a porous foam further homogenized.
- suitable mixing elements such as static mixer and / or Archimedean screw and / or by flowing through a porous foam further homogenized.
- a catalyst and further auxiliaries can be added to one of the educts or also to the educt mixture before it enters the reaction vessel.
- Solid, pulverulent and heterogeneous systems can also be reacted by the process according to the invention, with only corresponding technical devices for conveying the reaction mixture being required.
- Microwave radiation is preferably heated to temperatures above 110 ° C, more preferably at temperatures between 120 and 230 ° C, in particular between 130 and 210 ° C and in particular between 140 and 200 ° C such as between 150 and 195 ° C. These temperatures refer to the maximum temperatures reached during microwave irradiation.
- the temperature can be measured, for example, on the surface of the irradiation vessel. In continuous reactions, it is preferably determined on the reaction mixture directly after leaving the irradiation zone.
- the pressure in the reaction vessel is preferably set so high that the reaction mixture remains in the liquid state and does not boil. Preference is given to operating 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, for example between 15 and 50 bar.
- Preferred catalysts according to the invention are acidic inorganic,
- organometallic or organic catalysts and mixtures of several these catalysts.
- Preferred catalysts are liquid and / or im
- 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 Al (OR 15 ) 3 and titanates of the general formula Ti (OR 15 ) 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, C3-C12-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.
- a particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin or Fascat® grades.
- 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 CrC 2 8-alkyl radicals and in particular those having C 3 -C 2 2-alkyl radicals.
- Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid,
- Ion exchangers can be used as acidic organic catalysts, for example, crosslinked poly (styrene) resins carrying sulfonic acid groups. Particularly preferred for carrying out the process according to the invention are sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid,
- Titanates of the general formula Ti (OR 15 ) 4 and especially titanium tetrabutylate and titanium tetraisopropylate.
- 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. Such heterogeneous
- 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 polystyrenesulfonic acids, which are used as solid phase catalysts can be obtained for example from Rohm & Haas under the trade name Amberlyst ®.
- the basic catalyst is selected from the group of hydroxides, oxides, carbonates or alkoxides.
- the basic catalyst is selected from the group of hydroxides, oxides,
- the amount of catalyst to be used can vary within wide limits.
- Range between 0.001 and 10 wt .-%, particularly preferably in the range of 0.01 to 5 wt .-%, such as between 0.02 and 2 wt .-%, based on the amount of ether carboxylic acid B2).
- the reaction mixture can in many cases be fed directly to another use.
- water optionally present organic solvent can be separated from the crude product by conventional separation methods such as phase separation, distillation, freeze-drying or absorption. there can also be used in excess educts and optionally unreacted residual amounts of the reactants are separated with.
- Procedure be further purified. Often, it has also proved to be successful here to neutralize excess or unreacted ether carboxylic acid and remove by washing.
- the microwave irradiation is usually carried out in devices which have a reaction vessel (also referred to below as irradiation vessel) made of a material that is largely transparent to microwaves, into which microwave radiation generated in a microwave generator is coupled.
- a reaction vessel also referred to below as irradiation vessel
- Microwave generators such as the magnetron, the klystron and the gyrotron are known in the art.
- Reaction vessels are preferably made of largely microwave-transparent, high-melting material or contain at least parts such as
- Non-metallic reaction vessels are particularly preferably used. Under largely
- Microwave transparent here materials understood that absorb as little microwave energy and convert it into heat.
- the dielectric loss factor tan ⁇ is defined as the ratio of dielectric loss ⁇ "and ⁇ dielectric constant '. Examples of 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.
- microwave-transparent and temperature-stable materials come primarily materials based on minerals such as quartz, alumina, zirconia, silicon nitride and similar consideration.
- thermally stable plastics such as in particular fluoropolymers such as Teflon, and engineering plastics such
- Polypropylene, or polyaryletherketones such as glass fiber reinforced polyetheretherketone (PEEK) are suitable as vessel materials.
- PEEK glass fiber reinforced polyetheretherketone
- 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
- 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.
- the reaction vessel to be irradiated microwave power is particularly dependent on the desired reaction temperature, the geometry of the reaction vessel and the associated reaction volume as well as in continuously carried out reactions of the flow rate of the
- Reaction good through the reaction 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 reaction 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 reaction vessel, the desired Residence time of the reaction mixture at the reaction temperature and the desired degree of conversion. Usually, the microwave irradiation for a period of less than 30 minutes, preferably between
- the intensity (power) of the microwave radiation is adjusted so that the
- Reactive material in the shortest possible time reaches the desired reaction temperature.
- the reaction mixture with reduced and / or pulsed power can be further irradiated or otherwise maintained at temperature.
- 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 can be carried out batchwise or, preferably, continuously, for example in a flow tube serving as a reaction vessel, which is also referred to below as the reaction tube. You can continue in semi-batch processes like
- reaction is carried out in a closed, pressure-resistant and chemically inert vessel, wherein the water and optionally the educts lead to a pressure build-up.
- the excess pressure can be used by venting to volatilize and separate water and optionally excess acid and / or cooling of the reaction product.
- the reaction mixture after completion of the microwave irradiation or after leaving the reaction vessel as quickly as possible of water and optionally present catalytically active Species freed to avoid hydrolysis of the ester formed.
- the process according to the invention is carried out in a discontinuous microwave reactor in which a certain amount of the reaction mixture is filled into an irradiation vessel, irradiated with microwaves and subsequently worked up.
- a discontinuous microwave reactor in which a certain amount of the reaction mixture is filled into an irradiation vessel, irradiated with microwaves and subsequently worked up.
- Microwave irradiation is preferably carried out in a pressure-tight, stirred vessel.
- the coupling of the microwaves in the reaction vessel can, if the reaction vessel is made of a microwave transparent material or has transparent windows for microwave over the
- the microwaves can also be coupled via antennas, probes or waveguide systems in the reaction vessel.
- a multimode microwave applicator is preferably used here.
- Embodiment of the method according to the invention allows by varying the microwave power fast as well as slow heating rates and in particular holding the temperature for longer periods such as several hours.
- reaction mixture before starting the microwave irradiation in the irradiation vessel. It preferably has temperatures below 100 ° C as
- the reactants and water or parts thereof are supplied to the irradiation vessel only during the irradiation with microwaves.
- reaction mixture in the form of a semi-batch or cascade reactor.
- the process according to the invention is carried out in a continuous microwave reactor.
- Reaction mixture is to continuously by a pressure-resistant, inert to the reactants, for microwave largely transparent and built into a microwave applicator, serving as an irradiation vessel Reaction tube out.
- 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.
- Reaction or flow tubes are here understood to be irradiation vessels in which the ratio of length to diameter of the
- 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, to increase the temperature control and energy efficiency of the process.
- the length of the reaction tube is to be understood as meaning the total distance traveled by the reaction mixture in the microwave field.
- the reaction tube is at least one, but preferably several, such as two, three, four, five, six, seven, eight or more in length
- 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 tube is usually at the inlet with a metering pump and a pressure gauge and at the outlet with a pressure holding valve and a
- the reaction mixture is the reaction mixture
- a solution of the polymer and carboxylic acid or carboxylic acid ester only shortly before entering the reaction tube optionally mixed with the aid of suitable mixing elements such as static mixer and / or Archimedean screw and / or by flowing through a porous foam.
- suitable mixing elements such as static mixer and / or Archimedean screw and / or by flowing through a porous foam.
- they are in the reaction tube by means of suitable mixing elements such
- 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 second and 10 minutes, preferably between 0.1 second 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, for example, 3 to 10 times the wavelength of the used
- Microwave radiation With this geometry, energy can be made up of several For example, two, three, four, five, six or more successive maxima of the propagating parallel to the longitudinal axis of the tube microwave are 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 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 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 specifically from 4 to 20 such as three, four, five, six, seven, eight, nine or ten.
- the eoin mode of the cavity resonator is also known in English as
- TMoin mode transversal magnetic
- 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
- Coupling pin through one of the frontal openings in the cavity resonator inside.
- the reaction tube connects to the
- Inner conductor tube of the coaxial transition and in particular it is guided through the cavity into the cavity resonator. Preferably, this is flushed
- Reaction tube axially with a central axis of symmetry of the cavity resonator, to which the cavity resonator preferably each having 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 supplied via a waveguide to the resonator, 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
- the irradiation of the reaction mixture with microwaves in a microwave-transparent reaction tube which takes place
- 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 Itemssgut with microwaves in a microwave-transparent reaction tube which is axially symmetrical in a circular cylindrical eoin cavity resonator with coaxial transition 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 axially symmetrical in a circular cylindrical eoin cavity resonator with coaxial transition
- Eor cavity resonators preferably have a diameter that corresponds to at least half the wavelength of the microwave radiation used.
- the diameter of the cavity resonator is the 1, 0- to
- the Eoi cavity resonator has a round cross-section, which is also referred to as EorRundhohlleiter. Particularly preferably it has a cylindrical shape and especially a circular cylindrical shape.
- the reaction mixture is often not yet in chemical equilibrium when leaving the irradiation zone.
- the reaction mixture is transferred directly, that is to say without intermediate cooling, into an isothermal reaction zone in which it is kept at the reaction temperature for a certain time. Only after leaving the isothermal reaction zone, 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.
- 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
- the reaction mixture is preferably directly after leaving the Isothermal reaction path as soon as possible cooled 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 temperature which deviates at most ⁇ 30 ° C., preferably ⁇ 20 ° C., more preferably ⁇ 10 ° C. and in particular ⁇ 5 ° C. from the temperature on entry into the isothermal reaction zone.
- In addition to continuously operated Rrock historiesem and container cascades pipes are particularly suitable as an isothermal reaction zone.
- 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.
- 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 about the length of the Pipe 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 zone 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 process according to the invention allows polymer-analogous modification Hydroxyl-bearing polymers and in particular of polyvinyl alcohol with ether carboxylic acids or ether carboxylic acid esters in continuous or discontinuous processes and thus in industrially interesting amounts.
- polyvinyl alcohol with ether carboxylic acids or ether carboxylic acid esters
- a further advantage of the process according to the invention lies in the surprising observation that the polymer-analogous condensation reactions can be carried out in aqueous solution since water is the most suitable polymer bearing hydroxyl groups
- Solvent is and is also beneficial in ecological terms.
- the addition of certain polar organic solvents can counteract any increase in viscosity occurring during the course of the process and facilitate the reaction with less water-soluble ether carboxylic acids or their esters.
- the process according to the invention is suitable for partial esterifications of hydroxyl-carrying polymers, since the reaction mixtures, despite differences in viscosity between
- Ethercarbon yarnrereste lead over the entire chain length of the polymer.
- the process according to the invention permits reproducible production along its chain length of statistically modified products.
- Ether carboxylic acids and ether carboxylic acid esters opens up a wide range of modification possibilities.
- the method according to the invention can be selected by suitable choice of the ether carboxylic acid, for example, the swelling behavior, the solubility in water or organic solvents, the adhesion to different polar substrates, the mechanical strength and the
- Modified polymers are versatile as for example as Fibers, adhesives, emulsifiers, lamination for safety glass and plastics, paper coating, thickeners for latices, binders for fertilizers, as water-soluble as well as water-insoluble films such as
- Reaction vessels were closed, pressure-resistant glass cuvettes (pressure vials) with a volume of 20 ml, in which was homogenized with magnetic stirring.
- the microwave power was adjusted over the experimental period in each case in such a way that the desired temperature of the reaction mixture was reached as quickly as possible and then kept constant over the period specified in the experiment descriptions.
- the glass cuvette was cooled with compressed air.
- reaction tube 60 ⁇ 1 cm
- cylindrical cavity resonator 60 ⁇ 10 cm
- Cavity of a functioning as a coupling antenna inner conductor tube was coupled by means of the coupling antenna in the cavity resonator (Eoi cavity applicator, single mode), in which a standing wave
- 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
- Prism system (circulator) passed into a water-containing vessel. Using a high-pressure pump and a pressure relief valve, the reaction mixture was placed in the reaction tube under such a working pressure that was sufficient to all educts and products or condensation products always in the liquid state from the difference between radiated energy and heating of this water load to keep. The reaction mixtures were pumped through the device at a constant flow rate and the residence time in the reaction tube was adjusted by modifying the flow rate.
- 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 205 ° C and was transferred directly at this temperature in the isothermal reaction zone.
- the reaction mixture had a temperature of 186 ° C.
- the reaction mixture was cooled to room temperature immediately after leaving the isothermal reaction section and adjusted to pH 4 with bicarbonate solution.
- Polyvinyl alcohol (Mowiol ® 8-88, molecular weight 67,000 g / mol, degree of hydrolysis 88%) presented in 7 kg of water, treated with 10 g of p-toluenesulfonic acid and heated to 60 ° C. At this temperature, over a period of one hour with stirring, a solution of 600 g of 3,6,9-trioxodecanoic acid (3.2 mol) in 500 g 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. When leaving the irradiation zone, the reaction mixture had a temperature of 203 ° C. It was cooled to room temperature immediately after leaving the reaction zone and with
- the reaction product was a homogeneous, colorless solution with lower
- Viscosity After evaporation of the solvent resulted in a viscous mass whose IR spectrum for esters of polyvinyl alcohol at characteristic bands
- Example 3 Continuous esterification of poly (vinyl alcohol Mowiol ® 4-98 with oleic acid + 8 moles of EO-carboxylic acid
- the resulting reaction mixture was pumped continuously at 4.5 l / h through the reaction tube at a working pressure of 32 bar and a
- Irradiation zone was about 52 seconds.
- the reaction mixture had a temperature of 205 ° C and was transferred directly at this temperature in the isothermal reaction zone.
- the reaction mixture had a temperature of 189.degree.
- the reaction mixture was adjusted to pH 4 directly after leaving the reaction zone to room temperature with bicarbonate solution.
- the reaction product was a homogeneous, colorless solution with lower
- Viscosity After evaporation of the solvent resulted in a viscous mass whose IR spectrum for esters of polyvinyl alcohol at characteristic bands
- Method 4 Determination of the Mechanical Properties of the Polymer Films: From a polymer film prepared as described above (without the addition of Patent Blue V solution), a piece about 10 ⁇ 2 cm in size is cut out and subjected to a tensile elongation experiment using a commercially available apparatus. The tensile strength indicates the maximum force that will withstand the film until it breaks.
- a 4 wt .-% polymer solution (in terms of dry content) is prepared and determined its viscosity at 20 ° C with a commercial Brookfield viscometer at 20 revolutions per minute (rpm). The choice of a suitable spindle is made depending on the viscosity of the solution.
- the following data were determined for these polyvinyl alcohols and the modified polymers using these methods:
- the modified polymers show markedly improved solubility in water at 20 ° C as well as at 80 ° C compared to the underlying poly (vinyl alcohols). While the unmodified poly (vinyl alcohols) in
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112013016864A BR112013016864A2 (pt) | 2010-12-30 | 2011-11-08 | polímeros portadores de grupos hidroxila e grupos éster e processo para a sua produção |
CN201180059243.7A CN103492427A (zh) | 2010-12-30 | 2011-12-08 | 带有羟基和酯基团的聚合物及其制备方法 |
EP11794410.8A EP2658880A2 (de) | 2010-12-30 | 2011-12-08 | Hydroxylgruppen und estergruppen tragende polymere und verfahren zu ihrer herstellung |
US13/977,468 US20130289206A1 (en) | 2010-12-30 | 2011-12-08 | Polymers Comprising Hydroxyl Groups And Ester Groups And Method For The Production Thereof |
JP2013546601A JP2014504656A (ja) | 2010-12-30 | 2011-12-08 | ヒドロキシル基およびエステル基担持ポリマー、ならびにその製造方法 |
KR1020137016863A KR20140009272A (ko) | 2010-12-30 | 2011-12-08 | 하이드록실 그룹 및 에스테르 그룹을 포함하는 중합체 및 이의 제조 방법 |
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DE102010056578A DE102010056578A1 (de) | 2010-12-30 | 2010-12-30 | Hydroxylgruppen und Estergruppen tragende Polymere und Verfahren zu ihrer Herstellung |
DE102010056578.4 | 2010-12-30 |
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WO2012089300A2 true WO2012089300A2 (de) | 2012-07-05 |
WO2012089300A3 WO2012089300A3 (de) | 2012-09-27 |
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PCT/EP2011/006176 WO2012089300A2 (de) | 2010-12-30 | 2011-12-08 | Hydroxylgruppen und estergruppen tragende polymere und verfahren zu ihrer herstellung |
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US (1) | US20130289206A1 (de) |
EP (1) | EP2658880A2 (de) |
JP (1) | JP2014504656A (de) |
KR (1) | KR20140009272A (de) |
CN (1) | CN103492427A (de) |
BR (1) | BR112013016864A2 (de) |
DE (1) | DE102010056578A1 (de) |
WO (1) | WO2012089300A2 (de) |
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DE102006047617B4 (de) * | 2006-10-09 | 2008-11-27 | Clariant International Limited | Verfahren zur Herstellung basischer (Meth)acrylamide |
DE102008017216B4 (de) * | 2008-04-04 | 2013-08-14 | Clariant International Ltd. | Kontinuierliches Verfahren zur Herstellung von Fettsäureamiden |
DE102009031059A1 (de) | 2009-06-30 | 2011-01-05 | Clariant International Ltd. | Vorrichtung zur kontinuierlichen Durchführung chemischer Reaktionen bei hohen Temperaturen |
DE102009042522A1 (de) | 2009-09-22 | 2011-04-07 | Clariant International Ltd. | Kontinuierliches Umesterungsverfahren |
DE102009042523B4 (de) | 2009-09-22 | 2012-02-16 | Clariant International Ltd. | Vorrichtung und Verfahren zur kontinuierlichen Durchführung heterogen katalysierter chemischer Reaktionen bei hohen Temperaturen |
DE102010056564A1 (de) | 2010-12-30 | 2012-07-05 | Clariant International Limited | Hydroxylgruppen und Estergruppen tragende Polymere und Verfahren zu ihrer Herstellung |
DE102010056565A1 (de) | 2010-12-30 | 2012-07-05 | Clariant International Ltd. | Verfahren zur Modifizierung Hydroxylgruppen tragender Polymere |
JP7021197B2 (ja) * | 2016-09-05 | 2022-02-16 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 官能基化されたポリビニルアルコールに基づくuv硬化性接着促進剤 |
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US2601561A (en) | 1949-05-05 | 1952-06-24 | Hercules Powder Co Ltd | Synthetic drying oils from polyvinyl alcohol and method of production |
CN1749279A (zh) | 2005-10-12 | 2006-03-22 | 江南大学 | 微波法酸解与酯化改性复合变性淀粉的制备方法和应用 |
Family Cites Families (10)
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JPH022848A (ja) * | 1987-11-06 | 1990-01-08 | Asahi Chem Ind Co Ltd | 改良された再生セルロース膜及びその製造法 |
JP2543597B2 (ja) * | 1989-08-31 | 1996-10-16 | ユニ・チャーム株式会社 | 開孔を有する複合不織布の製造方法 |
JPH0545613A (ja) * | 1991-08-15 | 1993-02-26 | Asahi Chem Ind Co Ltd | 耐汚染性の改良されたコンタクトレンズ及びその製造方法 |
JPH09316127A (ja) * | 1996-03-26 | 1997-12-09 | Fuji Photo Film Co Ltd | エステル置換ポリビニルアルコールの製造方法およびそれを用いた薄膜 |
US5804653A (en) * | 1997-03-07 | 1998-09-08 | Playtex Products, Inc. | Polyvinyl alcohol compound |
US6175037B1 (en) * | 1998-10-09 | 2001-01-16 | Ucb, S.A. | Process for the preparation of (meth)acrylate esters and polyester (meth)acrylates using microwave energy as a heating source |
JP2000162601A (ja) * | 1998-11-27 | 2000-06-16 | Fuji Photo Film Co Ltd | 配向膜形成材料層付き長尺可撓性シート |
FR2839069B1 (fr) * | 2002-04-25 | 2006-04-07 | Satie Sa | Nouveaux procedes de transesterification, esterification, interesterification, par chauffage dielectrique |
WO2005037980A1 (ja) * | 2003-10-22 | 2005-04-28 | Kao Corporation | アレルゲン低減化剤と低減化方法 |
JP5300014B2 (ja) * | 2009-03-10 | 2013-09-25 | 独立行政法人産業技術総合研究所 | 流体へのマイクロ波連続照射方法及び装置 |
-
2010
- 2010-12-30 DE DE102010056578A patent/DE102010056578A1/de not_active Ceased
-
2011
- 2011-11-08 BR BR112013016864A patent/BR112013016864A2/pt not_active IP Right Cessation
- 2011-12-08 US US13/977,468 patent/US20130289206A1/en not_active Abandoned
- 2011-12-08 CN CN201180059243.7A patent/CN103492427A/zh active Pending
- 2011-12-08 EP EP11794410.8A patent/EP2658880A2/de not_active Withdrawn
- 2011-12-08 WO PCT/EP2011/006176 patent/WO2012089300A2/de active Application Filing
- 2011-12-08 JP JP2013546601A patent/JP2014504656A/ja active Pending
- 2011-12-08 KR KR1020137016863A patent/KR20140009272A/ko not_active Application Discontinuation
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US2601561A (en) | 1949-05-05 | 1952-06-24 | Hercules Powder Co Ltd | Synthetic drying oils from polyvinyl alcohol and method of production |
CN1749279A (zh) | 2005-10-12 | 2006-03-22 | 江南大学 | 微波法酸解与酯化改性复合变性淀粉的制备方法和应用 |
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Title |
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K. LANGE; K.H. LÖCHERER: "Taschenbuch der Hochfrequenztechnik", vol. 2, pages: K21 FF |
See also references of EP2658880A2 |
Also Published As
Publication number | Publication date |
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JP2014504656A (ja) | 2014-02-24 |
EP2658880A2 (de) | 2013-11-06 |
WO2012089300A3 (de) | 2012-09-27 |
KR20140009272A (ko) | 2014-01-22 |
BR112013016864A2 (pt) | 2016-10-04 |
US20130289206A1 (en) | 2013-10-31 |
DE102010056578A1 (de) | 2012-07-05 |
CN103492427A (zh) | 2014-01-01 |
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