WO2012089298A2 - 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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- C08F216/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—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
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Definitions
- the present invention relates to hydroxyl groups and ester group-bearing polymers and to a process for their preparation by polymer analogues
- Higher molecular weight synthetic polymers bearing a variety of hydroxyl groups such as poly (vinyl alcohol) are nonionic, water-soluble, thermoplastics that transition to highly viscous masses above their melting point.
- the water solubility of the polymers is dependent inter alia on the concentration of hydroxyl groups in the polymer and in the specific case of poly (vinyl alcohol) also a function of the degree of hydrolysis of the poly (vinyl acetate) used for its preparation.
- poly (vinyl alcohol) of high degree of hydrolysis is highly crystalline and soluble only in hot water.
- Poly (vinyl alcohol) has interesting physicochemical
- a suitable method would be, for example, the esterification with hydroxycarboxylic acids.
- esterification the low solubility of hydroxyl-bearing polymers in organic solvents causes considerable preparative difficulties in the reaction and especially in the
- 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 surface reactions are possible; if the polymer is swollen in the reaction medium, the reaction rate depends on the accessibility of the functional groups in the pores of the polymer matrix. Moreover, in partially crystalline polymers, reactions take place practically only in the amorphous regions, since diffusion processes in the crystalline region are very slow.
- 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, since it is the Reaction equilibrium shifts in favor of the educts.
- polymers such as poly (vinyl alcohol) usually in polar aprotic solvents such as dimethyl sulfoxide, formamide, dimethylformamide and Phosphorklatrisdimethylamid solve. Upon removal of these high-boiling solvents after the reaction, the polymer usually suffers thermal damage, which makes them often unusable for further use.
- Hydroxyalkylvinylester or hydroxyalkyl acrylates technically limited access and very expensive in most cases.
- hydrolysis of the acyl groups to hydroxyl groups and the ester groups of the comonomers are at least partially hydrolyzed.
- poly (lactic acid) is a water-insoluble thermoplastic that does not show the sought-after property profile.
- the tensile strength of the polymers should be increased while improving their solubility, especially in cold water.
- the solution viscosity of the polymers should not differ significantly from the viscosity of the underlying polymers in order to apply them to existing machines of known technology. To achieve a constant
- Hydroxyl-carrying polymers in aqueous solution and / or in solutions of water and water-miscible organic solvents with
- Modified polymer gives no indication of the presence of larger hydrophilic or hydrophobic polymer blocks. Since a large number of different hydroxycarboxylic 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 lead to the degradation of the polymer chains.
- esters of hydroxyl-bearing polymers containing repeating structural units of the formulas (I) and (II) in blockwise, alternating or random sequence
- R 2 is a C 2 - to C 0 -alkylene radical
- R 3 is hydrogen or a C 1 -C 10 -alkyl radical which may carry substituents,
- n for a number from 0 to 4999
- n + m is a number from 10 to 5,000, with the proviso that the molar fraction of the structural units (I) on the polymer is between 0 and 99.9 mol%, and
- the molar proportion 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 2 is a C 2 - to C 0 alkylene radical
- R 3 is hydrogen or a C 10 -C 10 -alkyl radical which may carry substituents
- n for a number from 0 to 4999
- n + m is a number from 10 to 5,000, with the proviso that the molar fraction of the structural units (I) on the polymer is between 0 and 99.9 mol%, and
- the molar proportion of the structural units (II) on the polymer is between 0.1 and 100 mol% of the repetitive units, hydroxyl groups carrying polymers A), which are the repetitive
- Preferred hydroxyl-carrying polymers A) are main chain polymers, the polymer backbone is composed only of C-C bonds and the
- preferred hydroxyl-carrying 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-carrying 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 in formula I or the oxygen atom in formula II
- Structural unit of formula (I) is derived in this case from vinyl alcohol.
- D is a linear or branched alkylene radical. This preferably has one, two, three or four
- C-atoms are, for example, derived from allyl alcohol or from 3-buten-1-ol 3-buten-1-ol, 1-pentene-3-ol or 4-penten-1-ol
- D stands for one Oxyalkylene group in which R 2 is preferably an alkylene group having two, three or four carbon 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 is an alkylene group with 2 or
- 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 from hydroxyethylacrylamide, hydroxyethylmethacrylamide, hydroxypropylacrylamide, hydroxypropylmethacrylamide from.
- two, three, four or more different structural units of the formula (I) containing polymers are suitable according to the invention.
- the inventive method is
- the inventive method is also suitable for the modification of
- Hydroxyl-containing units of the formula (I) have structural elements derived from one or more other monomers which do not carry 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%
- ester groups present in the copolymer A) can be completely or partially transesterified in the process according to the invention.
- suitable copolymers A) are copolymers of vinyl alcohol and ethylene, vinyl alcohol and styrene, and copolymers of
- 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
- hydroxycarboxylic acids B1 are generally suitable compounds which have at least one carboxyl group and one hydroxyl group.
- the inventive method is also suitable for the reaction of hydroxycarboxylic acids with, for example, two, three, four or more carboxyl groups.
- Preferred hydroxycarboxylic acids have a carboxyl group.
- inventive method is further for the implementation of
- Hydroxycarboxylic acids with, for example, two, three, four or more
- hydroxycarboxylic acids have a
- the hydroxycarboxylic acids may be of natural or synthetic origin. Particular preference is given to those hydroxycarboxylic acids which have a hydrocarbon radical E with 2 to 30 C atoms and in particular with 3 to 20, such as carry 4 to 12 carbon atoms. Of the
- Hydrocarbon radical is preferably aliphatic, cycloaliphatic, aromatic or araliphatic.
- the hydrocarbon radical may be one or more such
- C5-C2o-aryl groups such as phenyl groups
- the hydrocarbon radical E may also contain heteroatoms such as oxygen, nitrogen, phosphorus and / or sulfur, but preferably not more than one heteroatom per 2 C atoms.
- the polymers A) are reacted with aliphatic hydroxycarboxylic acids B1), ie with carboxylic acids which carry at least one hydroxyl group on an aliphatic hydrocarbon radical E.
- aliphatic hydrocarbon radicals can be linear, branched or cyclic.
- the carboxyl group may be bonded to a primary, secondary or tertiary C atom.
- the hydrocarbon radicals can be saturated or unsaturated. Preferably, they are saturated. unsaturated
- the aliphatic hydrocarbon radical is an unsubstituted alkylene or alkenylene radical.
- the aliphatic hydrocarbon radical carries one or more, for example two, three or more of the abovementioned substituents.
- Preferred cycloaliphatic hydrocarbon radicals E are aliphatic
- Hydrocarbon radicals having 2 to 24 and in particular having 3 to 20 carbon atoms. You can optionally one or more heteroatoms such as
- Cycloaliphatic hydrocarbon radicals have at least one ring with four, five, six, seven, eight or more ring atoms.
- the carboxyl group is bound to one of the rings.
- the hydroxyl group may be bonded to a primary, secondary or tertiary carbon atom of the aliphatic hydrocarbon radical.
- Particular preference is given to hydroxycarboxylic acid / esters which contain a hydroxyl group bonded to a secondary and especially to a tertiary C atom, and to those hydroxycarboxylic acids in which the hydroxyl group is in the ⁇ , ⁇ or ⁇ position relative to the carboxyl group.
- Carboxyl and hydroxyl groups may be bonded to the same or different C atoms of E.
- the inventive method is also suitable for the esterification of polyhydroxycarboxylic acids with, for example, two, three, four or more hydroxyl groups, but the hydroxycarboxylic acids only one hydroxyl group per carbon atom of the
- aliphatic hydrocarbon radical E may carry.
- Particularly preferred are hydroxycarboxylic acids which carry an aliphatic hydrocarbon radical R 3 having 1 to 30 C atoms and in particular having 2 to 24 C atoms, for example having 3 to 20 C atoms.
- Suitable aliphatic hydroxycarboxylic acids are, for example
- 2-hydroxy-2-methylpropionic acid 4-hydroxypentanoic acid, 5-hydroxypentanoic acid, 2,2-dimethyl-3-hydroxypropionic acid, 5-hydroxyhexanoic acid,
- 2-hydroxyoctanoic acid 2-hydroxytetradecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid as well
- Polyhydroxypolycarboxylic acids such as, for example, tartaric acid and gluconic acid can be esterified by means of the process according to the invention with the hydroxyl-carrying polymers A).
- Particularly preferred according to the invention Hydroxycarboxylic acids are hydroxyacetic acid, 2-hydroxypropionic acid,
- the polymers A) are reacted with aromatic hydroxycarboxylic acids B1), that is to say with carboxylic acids which carry at least one hydroxyl group on an aromatic hydrocarbon radical E.
- Aromatic carboxylic acids are understood as meaning compounds which carry at least one carboxyl group bonded to an aromatic system (aryl radical).
- aromatic systems are meant cyclic (4p + 2) ⁇ electron conjugated systems in which p is a natural integer and preferably 1, 2, 3, 4 or 5.
- the aromatic system may be mono- or polycyclic, such as di- or tricyclic.
- the aromatic system is preferably formed from carbon atoms. In a further preferred embodiment, it contains in addition
- aromatic systems are benzene, naphthalene, phenanthrene, furan and pyridine.
- the aromatic system may carry, in addition to the carboxyl group and the hydroxyl group, one or more, for example one, two, three or more identical or different further substituents.
- Suitable further substituents are, for example, alkyl, alkenyl and halogenated alkyl radicals, hydroxy, hydroxyalkyl, alkoxy, halogen, cyano, nitrile, nitro and / or sulfonic acid groups. These may be attached at any position of the aromatic system.
- the aryl radical carries at most as many substituents as it has valencies.
- Carboxylic acids in which the aryl group carrying the carboxyl group additionally carries at least one alkyl or alkylene radical are particularly preferred.
- Alkylbenzoic acids which carry at least one alkyl radical having 1 to 20 carbon atoms and in particular 1 to 12 carbon atoms such as 1 to 4 carbon atoms.
- Further preferred examples are aromatic carboxylic acids whose aryl radical contains one or more, for example two or three hydroxyl groups and / or Carries hydroxyalkyl groups.
- esterification with polymers A) carrying hydroxyl groups the formation of polycondensates and, in particular, of polycondensates bound to the polymer A) may occur
- Suitable aromatic carboxylic acids are, for example, the various isomers of hydroxybenzoic acid, hydroxymethylbenzoic acid,
- the carboxylic acids B1) carry, in addition to at least one hydroxyl group, araliphatic hydrocarbon radicals E.
- araliphatic carboxylic acids carry at least one over one
- the alkylene or alkenylene radical preferably has 1 to 10 C atoms and in particular 2 to 5 C atoms. It may be linear or branched, preferably it is linear. Preferred alkenylene radicals have one or more, such as one, two or three double bonds.
- Aromatic system is understood to mean the aromatic systems already defined above, to which an alkyl radical bearing at least one carboxyl group is bound. The aromatic systems can in turn turn
- Examples of preferred araliphatic carboxylic acids are
- Polycarboxylic acids can also be used as carboxylic acid B1). At least partially, this leads to an esterification of the polycarboxylic acid with hydroxyl groups of different polymer chains, which can lead to an increase in the molecular weight. Preference is given to using polycarboxylic acids in a mixture with monocarboxylic acids.
- the proportion of polycarboxylic acids is preferably between 0.1 and 70 mol%, more preferably between 0.5 and 50 mol% and in particular between 1 and 20 mol%, for example between 2 and 10 mol%, based on the total amount the carboxylic acids used for the esterification.
- Preferred polycarboxylic acids have two, three, four or five carboxyl groups. Particularly preferred are dicarboxylic acids. Suitable polycarboxylic acids are aliphatic polycarboxylic acids such as
- Lactic acid Lactic acid, malic acid and tartaric acid.
- carboxylic acid esters B2) which are suitable according to the invention are esters of the abovementioned carboxylic acids B1) with alcohols of the general formula
- R 5 is -OH.
- R 5 is preferably an alkyl radical having 1, 2 or 3 C atoms. Particularly preferred alcohols are methanol and ethanol.
- Hydroxycarboxylic acids B1) and / or hydroxycarboxylic acid esters B2) by the process according to the invention can be used to form polycondensates and, in particular, polycondensates bound to the polymer A)
- Polyhydroxycarboxylic come.
- the degree of polycondensation k is preferably between 1 and 1000, more preferably between 2 and 500
- Hydroxyl-bearing polymers A) and hydroxycarboxylic acids B1) or hydroxycarboxylic acid esters B2) are preferably used in a ratio of 100: 1 to 100: 1, particularly preferably in a ratio of 10: 1 to 1:10 and especially in a ratio of 5: 1 to 1: 5, in each case based on the molar equivalents of hydroxyl-bearing structures of the formula (I) and the carboxyl groups of the formulas (III) and / or ( IV).
- the 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.
- Hydroxycarboxylic acid B1) or hydroxycarboxylic 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 mo-% of the carboxylic acid or of the used
- 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.
- hydroxycarboxylic acids B1) and hydroxycarboxylic acid esters B1) are readily soluble in water, so that their reaction with hydroxyl-carrying polymers A) can be carried out in aqueous solution.
- Hydroxycarboxylic 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 15.
- Preferred 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 15.
- Solvents are soluble in water to at least 100 g / l, more preferably to at least 200 g / l, in particular to at least 500 g / l, and especially they are completely miscible with water.
- Particularly preferred solvents are heteroaliphatic compounds and in particular alcohols, ketones,
- carboxylic acid amides such as tertiary carboxylic acid amides, nitriles, sulfoxides and sulfones.
- Preferred aprotic solvents are, for example, formamide, ⁇ , ⁇ -dimethylformamide (DMF),
- DMSO Dimethyl sulfoxide
- 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 methanol, ethanol, n-propanol,
- Secondary and tertiary alcohols are particularly preferably used which are inert under the chosen reaction conditions and do not lead to any competing esterification or side reactions such as dehydration tend.
- Particularly preferred are secondary and tertiary alcohols having 3 to 5 carbon atoms such as isopropanol, sec-butanol, 2-pentanol and
- 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 may be added to the reaction mixture in a preferred embodiment.
- Emulsifiers which are chemically inert towards the educts and the product are preferably used. In a particularly preferred
- the emulsifier is a reaction product of separate production.
- reaction mixture containing a hydroxyl-carrying polymer A), a
- Hydroxycarboxylic acid B1) or a hydroxycarboxylic acid 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 hydroxycarboxylic acid B1) or hydroxycarboxylic 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.
- the hydroxycarboxylic acid B1) or the hydroxycarboxylic acid B2) if they are liquid or at low temperatures of preferably below 150 ° C and especially below 100 ° C are melted, can be used as such. In many cases, it has been found useful to use B1) or B2), optionally in the molten state, with water and / or a water-miscible solvent, for example as a solution, dispersion or emulsion.
- Hydroxycarboxylic acid B1) or hydroxycarboxylic acid B2) and optionally the other auxiliaries can be carried out in a (semi) -Batch process by sequential charging of the ingredients, for example in a separate stirred tank.
- the ingredients for example in a separate stirred tank.
- 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 further homogenized before entering 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.
- 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 5 ) 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, C 3 -C 12 -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 5 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 Ci-C28-Alkylresten and in particular those with C3-C22-Alkylresten.
- 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,
- 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.
- catalytic amounts of the abovementioned reaction-accelerating compounds preferably in the range from 0.001 to 10% by weight, more preferably in the range from 0.01 to 5% by weight, for example from 0.02 to 2% by weight. -%, based on the amount of hydroxycarboxylic acid ester 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 2b 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 hydroxycarboxylic 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 the dielectric loss ⁇ " and the dielectric constant ⁇ .” Examples of tan ⁇ values of different materials are described in D. Bogdal, for example.
- 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 kataiytisch 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
- Embodiment be a solution of the polymer and carboxylic acid or
- Carboxylic 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. In a further preferred embodiment, 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 mode n E i 0, where n is an integer and represents the number of field maxima of the microwave along 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 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 reaction material with microwaves in a microwave-transparent reaction tube which is axially symmetrical in a circular cylindrical Eoi n- 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 symmetric in a circular cylindrical E 0 i n cavity resonator with coaxial transition 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 E 0 i cavity resonator has a round cross-section, which is also referred to as Eoi round waveguide. Particularly preferably it has a cylindrical shape and especially a circular cylindrical shape.
- the reaction 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
- the reaction mixture is optionally expanded 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.
- stirred tanks and tank cascades pipes are particularly suitable as an isothermal reaction path.
- 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 hydroxycarboxylic acids or hydroxycarboxylic acid esters in continuous or discontinuous processes and thus in industrially interesting amounts.
- polyvinyl alcohol with hydroxycarboxylic acids or hydroxycarboxylic acid esters in continuous or discontinuous processes and thus in industrially interesting amounts.
- water or lower alcohol there are no by-products to be disposed of and polluting the environment.
- the inventive method is the surprising observation that the polymer-analogous condensation reactions in aqueous solution
- Hydroxycarboxylic acids and hydroxycarboxylic acid esters opens up a wide range of modification possibilities.
- the method according to the invention can be by suitable choice of hydroxycarboxylic acid, for example, the
- modified polymers according to the invention are versatile such as fiber sizing, adhesives, emulsifiers, laminating for safety glass and plastics, paper coating, thickeners for latices, binders for fertilizers, as water-soluble as well as water-insoluble films such as self-dissolving packaging films, as an additive to inks and concrete and as a temporary, water-removable Surface protection suitable.
- 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.
- 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.
- Polyvinyl alcohol (Mowiol ® 4-98, molecular weight 27,000 g / mol, degree of hydrolysis 98%) in 5.6 kg of water, treated with 25 g of p-toluenesulfonic acid and heated to 55 ° C. At this temperature, a solution of 0.85 kg of lactic acid in the form of lactol 90 (90% solution in water, 8.5 mol of lactic acid) in 1 kg of isopropanol was added with stirring over a period of one hour.
- the reaction mixture thus obtained was continuously pumped at a working pressure of 35 bar at 4.8 l / h through the reaction tube and a
- Irradiation zone was about 50 seconds. When leaving the irradiation zone, the reaction mixture had a temperature of 186 ° C and was transferred directly at this temperature in the isothermal reaction zone. At the end of the isothermal reaction zone, the reaction mixture had a temperature of 172 ° C. The reaction mixture was cooled to room temperature immediately after leaving the reaction section and adjusted to pH 4 with bicarbonate solution.
- the reaction product was a homogeneous, slightly yellowish, low viscosity solution. After evaporation of the solvent and reprecipitation of the residue with methanol from aqueous solution resulted in a viscous mass whose
- Methine protons of the esterified polyvinyl alcohol By comparing this signal with the signals of the remaining methane protons of the PVA backbone between 3.5 and 4.1 ppm, a degree of conversion of 17 mol% of the alcohol groups of the polyvinyl alcohol used can be estimated. A wide Multiplet at 5.2 ppm further indicates the presence of oligomeric lactic acid units.
- Example 2 Continuous esterification of poly (vinyl alcohol) Mowiol ® 18-88 with lactic acid
- Polyvinyl alcohol (Mowiol ® 18-88, molecular weight 130,000 g / mol, degree of hydrolysis 88%) in 6.5 kg of water, treated with 10 g of p-toluenesulfonic acid and heated to 50 ° C. At this temperature, a solution of 400 g of lactic acid in the form of lactol 90 (4 mol of lactic acid) in 2 kg of isopropanol was added with stirring over a period of one hour.
- 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 192 ° C and was transferred directly at this temperature in the isothermal reaction zone. At the end of the isothermal reaction zone, the reaction mixture had a temperature of 185 ° C. The reaction mixture was cooled to room temperature immediately after leaving the reaction section and adjusted to pH 4 with bicarbonate solution.
- the reaction product was a homogeneous, slightly yellowish, viscous solution. After evaporation of the solvent resulted in a viscous mass, the IR spectrum for esters shows characteristic bands at 1735 cm “1 and 1245 cm “ 1 with a relation to the polyvinyl alcohol significantly increased intensity.
- Polyvinyl alcohol (Mowiol ® 4-98, molecular weight 27,000 g / mol, degree of hydrolysis 98%) presented in 6 kg of water, treated with 20 g of p-toluenesulfonic acid and heated to 50 ° C. At this temperature, over a period of one hour with stirring, a solution of 1, 04 kg of 4-hydroxybutyric acid (10 mol) in 1 kg of isopropanol was added.
- the reaction mixture thus obtained was continuously pumped at a working pressure of 34 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 195 ° C and was transferred directly at this temperature in the isothermal reaction zone. At the end of the isothermal reaction zone, the reaction mixture had a temperature of 188 ° C. The reaction mixture was cooled to room temperature immediately after leaving the reaction zone and the catalyst was neutralized with bicarbonate solution. HO
- the reaction product was a homogeneous, colorless solution with lower
- Viscosity After evaporation of the solvent and reprecipitation of the residue with methanol from aqueous solution resulted in a viscous mass whose
- Microwave reactor heated to a temperature of 185 ° C, with a pressure of about 19 bar set. After reaching the thermal equilibrium (after about 1 minute) was held for 15 minutes under further microwave irradiation at this temperature and pressure. After completion of the
- the reaction mixture was cooled to room temperature and the catalyst was neutralized with bicarbonate solution.
- the reaction product was a homogeneous, colorless, viscous, opalescent solution. After evaporation of the solvent resulted in a homogeneous, non-sticky film whose IR spectrum for esters of polyvinyl alcohol
- 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
- Polyvinyl alcohols significantly increased tensile strength with slightly increased extensibility.
- the solution viscosity of the polymers remains largely unchanged by the modification, so that the modified polymers such as
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/977,326 US9221938B2 (en) | 2010-12-30 | 2011-12-08 | Polymers carrying hydroxyl groups and ester groups and method for the production thereof |
CN201180060563.4A CN103443134B (zh) | 2010-12-30 | 2011-12-08 | 制备带有羟基和酯基团的聚合物的方法 |
KR1020137016843A KR20140012040A (ko) | 2010-12-30 | 2011-12-08 | 하이드록실 그룹 및 에스테르 그룹을 갖는 중합체의 제조 방법 |
BR112013016852A BR112013016852A2 (pt) | 2010-12-30 | 2011-12-08 | processo para a produção de polímeros carregando grupos hidroxila e grupos éster |
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EP11796922.0A EP2658881A2 (de) | 2010-12-30 | 2011-12-08 | Hydroxylgruppen und estergruppen tragende polymere und verfahren zu ihrer herstellung |
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JP5403232B2 (ja) * | 2009-05-08 | 2014-01-29 | 独立行政法人産業技術総合研究所 | 容器内での放電を抑制したマイクロ波照射方法及び装置 |
DE102009031057A1 (de) | 2009-06-30 | 2011-01-05 | Clariant International Ltd. | Kontinuierliches Verfahren zur Herstellung von Amiden aliphatischer Carbonsäuren |
DE102009031058A1 (de) | 2009-06-30 | 2011-01-27 | Clariant International Ltd. | Kontinuierliches Verfahren zur Herstellung von Amiden aromatischer Carbonsäuren |
DE102009031059A1 (de) | 2009-06-30 | 2011-01-05 | Clariant International Ltd. | Vorrichtung zur kontinuierlichen Durchführung chemischer Reaktionen bei hohen Temperaturen |
DE102009031056A1 (de) | 2009-06-30 | 2011-01-27 | Clariant International Ltd. | Kontinuierliches Verfahren zur Acrylierung von Aminogruppen tragenden organischen Säuren |
DE102009031053A1 (de) | 2009-06-30 | 2011-01-13 | Clariant International Ltd. | Kontinuierliches Verfahren zur Herstellung von Estern aliphatischer Carbonsäuren |
DE102009031054A1 (de) | 2009-06-30 | 2011-01-13 | Clariant International Ltd. | Kontinuierliches Verfahren zur Herstellung von Estern aromatischer Carbonsäuren |
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 |
DE102010056566A1 (de) | 2010-12-30 | 2012-07-05 | Clariant International Ltd. | Kontinuierliches Verfahren zur Veresterung Säuregruppen tragender Polymere |
DE102010056578A1 (de) | 2010-12-30 | 2012-07-05 | Clariant International Ltd. | Hydroxylgruppen und Estergruppen tragende Polymere und Verfahren zu ihrer Herstellung |
DE102010056579A1 (de) | 2010-12-30 | 2012-07-05 | Clariant International Limited | Kontinuierliches Verfahren zur Umsetzung Säuregruppen tragender Polymere mit Aminen |
DE102010056565A1 (de) | 2010-12-30 | 2012-07-05 | Clariant International Ltd. | Verfahren zur Modifizierung Hydroxylgruppen tragender Polymere |
-
2010
- 2010-12-30 DE DE102010056564A patent/DE102010056564A1/de not_active Ceased
-
2011
- 2011-12-08 CN CN201180060563.4A patent/CN103443134B/zh not_active Expired - Fee Related
- 2011-12-08 US US13/977,326 patent/US9221938B2/en not_active Expired - Fee Related
- 2011-12-08 KR KR1020137016843A patent/KR20140012040A/ko not_active Application Discontinuation
- 2011-12-08 EP EP11796922.0A patent/EP2658881A2/de active Pending
- 2011-12-08 JP JP2013546599A patent/JP2014504654A/ja active Pending
- 2011-12-08 WO PCT/EP2011/006174 patent/WO2012089298A2/de active Application Filing
- 2011-12-08 BR BR112013016852A patent/BR112013016852A2/pt not_active IP Right Cessation
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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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Also Published As
Publication number | Publication date |
---|---|
EP2658881A2 (de) | 2013-11-06 |
JP2014504654A (ja) | 2014-02-24 |
US9221938B2 (en) | 2015-12-29 |
BR112013016852A2 (pt) | 2016-10-04 |
CN103443134B (zh) | 2015-05-27 |
US20140200312A1 (en) | 2014-07-17 |
DE102010056564A1 (de) | 2012-07-05 |
WO2012089298A3 (de) | 2012-09-13 |
KR20140012040A (ko) | 2014-01-29 |
CN103443134A (zh) | 2013-12-11 |
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