EP1863863A1 - Procede en deux etapes pour produire des polyesterols - Google Patents

Procede en deux etapes pour produire des polyesterols

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Publication number
EP1863863A1
EP1863863A1 EP06725186A EP06725186A EP1863863A1 EP 1863863 A1 EP1863863 A1 EP 1863863A1 EP 06725186 A EP06725186 A EP 06725186A EP 06725186 A EP06725186 A EP 06725186A EP 1863863 A1 EP1863863 A1 EP 1863863A1
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EP
European Patent Office
Prior art keywords
reaction
polyesterols
polyesterol
koh
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06725186A
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German (de)
English (en)
Inventor
Christoph Schnorpfeil
Mirko Kreitschmann
Jean-François STUMBE
Gitta Egbers
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BASF SE
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BASF SE
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Publication of EP1863863A1 publication Critical patent/EP1863863A1/fr
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Classifications

    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters

Definitions

  • the present invention relates to a two-stage process for the preparation of polyesterols with the following process steps:
  • Polymeric hydroxyl compounds such as polyesterols and polyetherols react with isocyanates to give polyurethanes which, depending on their specific mechanical properties, find a wide variety of possible uses.
  • polyesterols are used because of their favorable properties for high-quality polyurethane products.
  • the specific properties of the polyurethanes in question strongly depend on the polyesterols used.
  • polyesterols used have a low acid number (see Ullmann's Encyclopedia, Electronic Release, Wiley-VCH-Verlag GmbH, Weinheim, 2000 under the heading “polyester”, paragraph 2.3 "Quality Specifications and Testing”).
  • the acid number should be as small as possible, since the terminal acid groups react more slowly with diisocyanates than terminal hydroxyl groups. Polyesterols with high acid numbers therefore lead to a lower molecular weight during the reaction of polyesterols with isocyanates to polyurethane.
  • the polyesterols also called polyester
  • the polyesterols can be divided into two groups, the hydroxycarboxylic acid types (AB-polyester) and the dihydroxy-dicarboxylic acid types (AA-BB-polyester).
  • the former are made of only a single monomer by e.g. Polycondensation of a ⁇ -hydroxycarboxylic acid or by ring-opening polymerization of cyclic esters, so-called lactones produced.
  • the AA-BB polyester types are produced by polycondensation of two complementary monomers, typically by the reaction of polyfunctional polyhydroxyl compounds (e.g., diols or polyols) with dicarboxylic acids (e.g., adipic acid or terephthalic acid).
  • polyfunctional polyhydroxyl compounds e.g., diols or polyols
  • dicarboxylic acids e.g., adipic acid or terephthalic acid
  • the polycondensation of polyfunctional polyhydroxyl compounds and dicarboxylic acids to polyesterols of the AA-BB is a large scale usually at high temperatures of 160 - 280 0 C performed.
  • the polycondensation reactions can be carried out both in the presence and in the absence of a solvent.
  • a disadvantage of these polycondensations at high temperatures, however, is that they proceed relatively slowly. In order to accelerate the polycondensation reaction at high temperatures, esterification catalysts are therefore frequently used.
  • Organometallic compounds such as titanium tetrabutoxide, tin dioctoate or dibutyltin dilaurate, or acids, such as, for example, sulfuric acid, p-toluenesulfonic acid or bases, for example potassium hydroxide or sodium methoxide, are preferably used as conventional esterification catalysts. These esterification catalysts are homogeneous and usually remain in the polyesterol after completion of the reaction. The disadvantage here is that the esterification catalysts remaining in the polyesterol may possibly impair the subsequent conversion of these polyesterols to the polyurethane.
  • lipases are generally used here, inter alia the lipases Candida antarctica, Candida cylinderacea, Mucormeihei, Pseudomonas cepacia, Pseudomonas fluorescens.
  • a lipase-catalyzed in EP 0670906 B1 for the preparation of polyesterols AA-BB at 10 - 90 0 C which does not require the use of a solvent.
  • Either activated or non-activated dicarboxylic acid components can be used in this process.
  • the high-temperature polycondensations and the enzymatically catalyzed polycondensations for the preparation of polyesterols have the common disadvantage that the production of polyesterols is carried out by condensation reactions in plants for which a complex periphery is required.
  • the classical high-temperature polycondensation as well as for the enzymatic polycondensation devices on the reactor for the metering of liquids and / or solids are required.
  • Water must be removed from the reaction mixture under vacuum, introduction of an inert gas or by means of a entrainer distillation.
  • the water must be separated from the diols by distillation, since they must remain as reactants of the acid component in the reaction mixture.
  • the separation of water and diols is usually carried out with a distillation column.
  • membranes which are permeable to water but not to the diols to be retained can also be used.
  • Devices for generating vacuum, eg pumps, for the separation of diols and water, eg distillation columns and membranes, or for the introduction of an inert gas stream require high investments.
  • in the high-temperature condensation devices are still required to produce internal temperatures of 160-270 0 C required.
  • polyesterols The production of the largest possible and broadest range of structurally different polyesterols can be carried out in many small reactors. However, these small reactors all have to be designed with the complete periphery for vacuum generation, separation of diol-water mixtures, and possibly high temperature generation. This requires an undesirably high specific investment. Alternatively, a large assortment of many different polyesterols can be made in a few large reactors requiring less specific investment.
  • the change between polyesterols of different composition and structure requires a cleaning step in a product change, which leads to a reduction in utilization. For certain specialty products, customer demand may also be less than the reactor volume. For the production of such small quantities can thus not be prevented that not the entire reactor volume is utilized. This also leads to a capacity restriction.
  • a process for the preparation of a wide range of low acid number dihydroxy-dicarboxylic acid specialty polyesterols which avoids the hitherto required high logistical and economical expense.
  • the two-stage preparation of the polyesterols according to the invention with an actual polycondensation step a) with elimination of water and with an enzymatically catalyzed transesterification and / or glycolysis step b) has the clear advantage that in this case avoid frequent reactant and product changes in the esterification reactor or a reduced utilization in the production of smaller quantities.
  • the transesterification and / or glycolysis according to process step b) takes place in reactors which require a smaller infrastructure. In particular, the temperature range of 50-120 0 C is technically more accessible. In addition, no removal of water by vacuum, inert gas or entrainment is required for transesterification.
  • this process offers the advantages of improving the utilization of traditional manufacturing equipment by avoiding product changes and of avoiding inadequate use of reactor volume in the production of smaller quantities of specialty polyesterols. These advantages lead to a greatly reduced logistical and economic expense and thus ultimately to a lower price for special polyesterols.
  • the process according to the invention has the further advantage that polyesterols with low acid numbers are formed which are significantly better suited for the production of a large number of polyurethanes than polyesterols having high acid numbers.
  • transesterification processes already known are generally carried out exclusively in the presence of a solvent, while the transesterification step b) according to the invention can be carried out both in the presence and in the absence of a solvent.
  • the transesterification step b) according to the invention is even preferably carried out in the absence of any solvent (i.e., "in bulk").
  • WO 98/55642 describes a lipase-catalyzed process for the preparation of polyesterols.
  • the classical solvent- and catalyst-dependent high-temperature process for the preparation of polyesters would be the case (see page 8, last line to page 9, line 10 of WO 98/55642) .Thus, it can be concluded from this statement that under the conditions the enzymatic synthesis, as described in WO 98/55642, usually no transesterification reactions can take place.
  • polyesters prepared in the absence of solvents have different properties than those polyesters prepared in the presence of solvents.
  • polyesters having higher molecular weights and lower polydispersity can be prepared.
  • polymers with low polymer dispersity is meant here a polymer mixture having uniform degrees of polymerization or a polymer mixture whose individual polymer chains have a narrow range of different degrees of polymerization.
  • polyesters prepared by solvent-free enzymatic processes should have the advantage that they generally have higher molecular weights, are more uniform in their molecular weight distribution, and therefore have higher physical properties than conventionally prepared polymers. lyases may be superior in some cases.
  • One reason for this assumption might be that, according to general knowledge, most enzymes can only develop their full reactivity in the presence of a solvent, especially in the presence of water.
  • none of the prior art documents cited above disclose the possibility of a transesterification step of polyesterols in the absence of a solvent (or in bulk).
  • polyesterols having a high acid number of more than 10 mg KOH / g are formed to a much lesser extent for the production of polyurethane than polyesterols having low acid numbers of less than 3 mg KOH / g, preferably less than 2 KOH / g, in particular less than 1 mg KOH / g.
  • step a only a few base polyesterols are prepared by standard processes, preferably by high-temperature polycondensation, more preferably by esterification catalyst-assisted high-temperature polycondensation.
  • the resulting base polyesterols are then converted in the second step by enzymatic transesterification and / or glycolysis in almost any number of different special polyesterols without a costly Edukt- / product change is necessary.
  • this two-stage production process of the complex and costly step of high-temperature condensation limited only to the production of a few base polyesterols.
  • the first process step can also be carried out by an enzymatic polycondensation instead of an esterification catalyst-assisted high-temperature polycondensation.
  • the enzymatic polycondensation is preferably a lipase or hydrolase, preferably a lipase, in particular one of the lipases Candida antarctica, Candida cylinderacea, Mucor meihei, Pseudomonas cepacia, Pseudomonas fluorescens, Burkholderia plantarii at 20 - 110 0 C, preferably at 50-90 0 C. used.
  • the enzymes can also be immobilized on a carrier material.
  • the esterification catalyst used is preferably an organometallic compound such as titanium tetrabutoxide, tin dioctoate or dibutyltin dilaurate, or an acid such as sulfuric acid, Toluene sulfonic acid or a base such as potassium hydroxide or sodium methoxide used.
  • This esterification catalyst is usually homogeneous and remains after completion of the reaction generally in the polyesterol.
  • the high- temperature polycondensation is in this case at 160-280, preferably at 200-250 ° C used 0C.
  • the water released during the condensation reaction is preferably removed continuously.
  • the dicarboxylic acid used is preferably adipic acid or other aliphatic dicarboxylic acids, terephthalic acid or other aromatic dicarboxylic acids.
  • Suitable polyhydroxyl compounds are all at least dihydric alcohols, but preferably diol components such as e.g. Ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1, 5-pentanediol.
  • Process step a) can be carried out both in the presence of a solvent, but also in the absence of a solvent, i. regardless of whether an (esterification catalyst-assisted) high-temperature polycondensation or an enzymatically catalyzed polycondensation is performed.
  • the base polyesterols to be prepared in step a) are selected according to the desired properties of the end products.
  • Preferably used base polyesterols are polyesterols based on adipic acid and a diol component, preferably ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol.
  • the preferred molecular weight of the base polyesterols prepared in step a) is in the range from 200 g / mol to 10000 g / mol, more preferably in the range from 500 to 5000 g / mol.
  • the acid numbers of the base polyesterols prepared in step a) are preferably in the range of less than 3 g KOH / kg, more preferably in the range of less than 2 g KOH / kg, in particular in the range of less than 1 g KOH / kg.
  • the acid number is used to determine the content of the polyesterol on free organic acids. The acid number is determined by the number of mg KOH (or g KOH) consumed to neutralize 1 g (or 1 kg) of the sample.
  • the functionality of the base polyesterols prepared in step a) is preferably in the range of at least 1.9 to 4.0, more preferably in the range of 2.0 to 3.0.
  • the hydroxyl number (abbreviated to OHZ in the following) of the base polyesterols prepared in step a) is calculated from the number-average molecular weight M n and the functionality f of the polyesterol according to the formula
  • step b) is carried out exclusively enzymatically.
  • step b) either the
  • two or more base polyesterols from step a) are admixed with a sufficient amount of suitable enzymes, but then no additional polyvalent polyhydroxy compounds (diols, glycols) are added.
  • a new polyesterol is formed, which is ideally a random copolymer of the monomers of all the base polyesterols used.
  • step a) In enzyme-catalyzed glycolysis, only one base polyesterol from step a) is reacted with one or more polyhydroxy compounds, preferably with diols or polyols, and a suitable amount of the enzyme.
  • the average molecular weight of the base polyesterol is reduced by the glycolysis or by the alcoholysis of a part of the ester bonds.
  • a mixed reaction of enzyme-catalyzed transesterification and enzyme-catalyzed glycolysis or alcoholysis may also take place.
  • a mixture of at least two base polyesterols from step a) and at least one polyhydric polyhydroxy compound (preferably diols or polyols) is reacted with a suitable amount of the enzyme.
  • the change in the average molecular weight or the other material parameters (viscosity, acid number, melting point, etc.) of the base polyesterols in this variant of process step b) depends on the components used in the individual case, in particular on the type and amount of the base used -Polyesterol (s) and the type and amount of polyhydroxy compounds used.
  • the properties of the end product (of the polyesterol) also depend on whether the transesterification or glycolysis according to step b) has taken place completely.
  • the reaction times for the transesterification step b) are preferably selected such that ultimately polyesterols are obtained which have properties that are as similar as possible to those polyesterols which have been prepared by the classical single-stage high-temperature polycondensation process.
  • the reaction time of the transesterification or glycolysis according to step b) can thus be between 1 and 36 hours, preferably between 2 and 24 hours, depending on how much and which enzyme is used for the reaction.
  • a lipase or hydrolase preferably a lipase, particularly preferably one of the lipases Candida antarctica, Candida cylinderacea, Mucor meihei, Pseudomonas cepacia, Pseudomonas fluorescens, Burkholderia plantarii at 20 - 110 0 C, preferably at 30 - 90 0 C, more preferably at 50 - 80 ° C, in particular used at 70 0 C.
  • the lipases Candida antarctica and Burkholderia plantarii are suitable for the enzymatic transesterification or for the glycolysis of the basic polyesterols after step b).
  • Candida antarctica is "435 ® Novozym” or "525 Novozym” commercially available in immobilized form on a macroporous acrylic resin as in soluble form as.
  • the use of "Novozym 435 ®” and “Novozym 525" b in process step) is thus particularly preferred.
  • the enzymes used can thus also be immobilized on a carrier material.
  • carrier materials it is possible to use all suitable materials, but preferably solid materials with large surface areas, more preferably resins, polymers, etc., on which the enzymes can preferably be covalently bonded. NEN.
  • resin beads of a small diameter are used as support material
  • the enzymes, if they are immobilized on a support material, are preferably separated from the polyesterol can be achieved, for example, by conventional separation methods such as filtration, centrifugation or the like, which exploit the different particle size or the different particle weight
  • the separation can be carried out, for example, with magnetic carrier materials also by the application of magnetic forces
  • By separating the immobilized on support materials enzymes after completion of the method Step b) prevents these from interfering with the use of the polyesterols produced, in particular in the case of further reactions of these polyesterols, for example in the reaction of the polyesterols with isocyanates to give polyurethanes.
  • soluble enzymes are used in process step b) which are not immobilized on support materials, then it is generally not necessary to separate them from the polyesterol. In this case, it is often sufficient to inactivate the enzymes after transesterification or glycolysis in process step b).
  • the inactivation of the enzymes can be achieved by a variety of methods that lead to the denaturation of the enzyme, such as the inactivation of soluble enzymes with chemical substances, but preferably the inactivation of the enzymes via a simple heat denaturation at high temperatures. For the thermal denaturation temperatures of preferably about 110 0 C, more preferably from about 150 0 C applied.
  • reaction according to process step b) can - similar to those according to process step a) - be carried out in the presence of a solvent or in the absence of a solvent (reaction "in mass”).
  • reaction according to process step b) is carried out in the presence of a solvent
  • suitable solvents in particular the solvents toluene, dioxane, hexane, tetrahydrofuran, cyclohexane, xylene, dimethyl sulfoxide, dimethylformamide, N-methyl-pyrrolidone, chloroform.
  • the choice of solvent depends in each case on the educts used (the base polyesterols and the polyhydroxy compounds) and in particular on their solubility properties.
  • reaction according to process step b) in the presence of a solvent has the disadvantage that it comprises additional partial process steps, namely the dissolution of the at least one base polyesterol in the solvent and the removal of the solvent after the reaction. Furthermore, that can Dissolution of the at least one base polyesterol in the solvent may be problematic depending on the hydrophobicity properties of the base polyesterol and may possibly reduce the yield.
  • the reaction according to step b) is carried out in the absence of a solvent (also referred to as "reaction in bulk.") If high molecular weight base polyesterols are to be subjected to enzymatic transesterification after step b) the effectiveness of this transesterification reaction is limited by the low solubility of these high molecular weight base polyesterols in most solvents, but the number of hydroxyl groups of the solvent has only a minor influence on the effectiveness of the transesterification reaction (2004), 765 - 770 in 1,4-butanediol as the solvent no transesterification reaction takes place, although the concentration of hydroxyl groups is very high, whereas in polar solvents (dioxane, toluene) transesterification takes place.
  • a solvent also referred to as "reaction in bulk.
  • process step b preference is given to using those base polyesterols, enzymes and, if appropriate, additional polyhydroxyl compounds which together have a water content of less than 0.1% by weight, preferably less than 0.05% by weight, more preferably less than 0.03% by weight, in particular less than 0.01% by weight.
  • hydrolysis also takes place in addition to the transesterification, so that the acid number of the polyesterol would undesirably increase during step b).
  • step b) of the process according to the invention at a water content of less than 0.1% by weight, preferably less than 0.05% by weight, more preferably less than 0.03% by weight, in particular less than 0 , 01% by weight thus leads to the production of special polyesterols with low acid number as end products.
  • Low acid number polyesterols are generally more stable to hydrolysis than high acid number polyesterols because free acid groups promote the reverse reaction, i. the hydrolysis, catalyze.
  • polyesterols having water contents of more than 0.1% by weight leads to polyesterols having an acid number of greater than 10 mg KOH / g (see Comparative Examples D1 and D2).
  • polyesterols with such high acid numbers are not or only poorly suited for most industrial applications, in particular for use in the production of polyesterols.
  • enzymes can have water contents of> 0.1% by weight. Therefore, prior to the use of the enzyme in the transesterification reaction after process step b) a drying of the enzyme is required.
  • the drying of the enzyme is carried out according to the usual drying methods, for example by drying in a vacuum drying oven at temperatures of 60-120 ° C and under a pressure of 0.5 to 100 mbar or by suspending the enzyme in toluene and subsequent distillation of the toluene in Vacuum at temperatures of 50-100 ° C.
  • polyesterols also absorb at least 0.01%, but generally at least 0.02%, in some cases more than 0.05% of water. Depending on the degree of conversion and molecular weight of the base polyesterols used, this water concentration is higher than the equilibrium water concentration. If the polyester is not dried before process step b), the hydrolysis of the polyesterol inevitably begins.
  • the water content of the base polyesterols used in step b) are therefore preferably dried before the transesterification according to process step b).
  • the enzyme to be used in step b) and the polyhydric polyhydroxyl compound (for example, the diol) to be optionally used are preferably dried before the transesterification reaction in order to achieve the abovementioned low water content in the transesterification.
  • the drying can be carried out by conventional drying methods according to the prior art, for example by drying over molecular sieve or falling film evaporator.
  • base polyesterols having low water contents can also be obtained by carrying out the reaction according to process step a) as well as a possible intermediate storage step of the at least one base polyesterol completely under inert conditions, for example in an inert gas atmosphere, preferably in a nitrogen atmosphere ,
  • the base polyesterols from the beginning have no way to absorb larger amounts of water from the environment. A separate drying step could then be unnecessary.
  • the at least one base polyesterol from process step a) is temporarily stored before the reaction according to process step b), preferably in an inert gas atmosphere in order to keep the water content low.
  • a mixture of two or more basic polyesterols can then be combined in suitable proportions to obtain, after the transesterification (and after the possible additional glycolysis with polyhydroxy compounds), a certain special polyesterol with very specific physical properties and with a specific structure ,
  • a further subject of the invention relates to a polyesterol which has been prepared or preparable by one of the two-stage processes described above with the process steps a) and b).
  • These polyesterols according to the invention generally have relatively low acid numbers, namely preferably acid numbers of less than 3 mg KOH per gram of polyesterol, more preferably less than 2 mg KOH per gram of polyesterol, in particular less than 1 mg of KOH per gram of polyesterol.
  • process step b) preferably has a water content of less than 0.1% by weight, more preferably less than 0.05% by weight, more preferably less than 0.03% by weight, in particular of less than 0.01 wt.% Is performed.
  • a stirred tank reactor with stirrer and distillation column is used to carry out process step a).
  • This apparatus is usually a closed system and can generally be evacuated by means of a vacuum pump.
  • the starting materials are heated with stirring and preferably with exclusion of air (for example in a nitrogen atmosphere or under reduced pressure).
  • the water formed in the polycondensation is preferably distilled off at low pressure or a continuously decreasing pressure (see Batchwise Vacuum-Melt method, Houben-Weyl 14/2, 2).
  • the distillable products such as e.g. the reaction water is not removed by lowering the pressure, but rather by the passage of an inert gas such as nitrogen or carbon dioxide through the reaction mixture.
  • thermoplastic polyesters such as PET and PBT (see Ullmann, Chapter: Polyesters, paragraph: Thermoplastic Polyesters (Production)).
  • the reactor material must be both corrosion resistant, heat and acid resistant. These requirements are met, for example, by austenitic chromium-nickel-molybdenum alloys (e.g., V4A steel DIN1.4571).
  • process step b) is carried out in a temperature range of 50-120 0 C, preferably from 60-100 0 C, particularly preferably from 70 to 90 ° C under atmospheric pressure.
  • the reaction is carried out in an inert atmosphere with the exclusion of atmospheric moisture, for example by the transfer of nitrogen.
  • the implementation of process step b) takes place in a heated stirred tank reactor.
  • the process according to the invention can also be carried out batchwise, semicontinuously or continuously in conventional bioreactors.
  • polyesterols of adipic acid and 1,4-butadiol (1,4-butanediol adipate) having an average molecular weight of 5000 g / mol, with a base number (in hereinafter referred to as "OHZ") of 23.5 mg KOH / g and an acid number (hereinafter called "SZ”) of 1.6 mg KOH / g.
  • OHZ base number
  • SZ acid number
  • 1,4-butanediol adipates were prepared as follows for all examples and comparative examples for the glycolysis of polyesterols (process step a)): Preparation of polybutanediol adipate by means of high-temperature polycondensation:
  • the polyesterol was heated to a reaction temperature of 90 ° C. After reaching the reaction temperature, 34 g of butanediol were added through a dropping funnel heated to the reaction temperature. To determine the progress of the reaction, the acid number, OH number, the water value and the viscosity were measured as a function of the reaction time (see Table 1).
  • the viscosity which is a measure of the weight-weighted average molecular weight, remained constant throughout the reaction. There was thus no standardization of the distribution and thus no reaction between the components.
  • Comparative Example A2 Transesterification of polyesterols with diols at 200 ° C. without catalyst
  • the polyesterol was heated to a reaction temperature of 200 ° C. After reaching the reaction temperature, 34 g of butanediol were added through a dropping funnel heated to the reaction temperature. To determine the progress of the reaction, the acid number, OH number, the water value and the viscosity were measured as a function of the reaction time (see Table 2).
  • Example A3 Enzymatic glycolysis of polyesterols with diols with 1% Novozym 435 at 90 ° C.
  • Novozyms-435 To dry the Novozyms-435, a 30% suspension of Novozym-435 in toluene was prepared in a 100 ml flask. The toluene was removed immediately before the start of the reaction by distillation on a rotary evaporator under vacuum (100 mbar) at about 50-60 0 C.
  • the mixture comprising Novozyme-435 and polyesterol was heated to a reaction temperature of 90 ° C. After reaching the reaction temperature, 52 g of butanediol were added through a temperature dropping funnel heated to the reaction temperature. To determine the progress of the reaction, the acid number (SZ), the OH number (OHN), the water value and the viscosity were measured as a function of the reaction time (Table 3).
  • Example A4 Enzymatic glycolysis of polyesterols with diols with 5% Novozym 435 at 90 ° C.
  • Novozyms-435 To dry the Novozyms-435, a 30% suspension of Novozym-435 in toluene was prepared in a 100 ml flask. The toluene was removed immediately before the start of the reaction by distillation on a rotary evaporator under vacuum (100 mbar) at about 50-60 0 C.
  • the mixture comprising Novozyme-435 and polyesterol was heated to a reaction temperature of 90 ° C. After reaching the reaction temperature, 52 g of butanediol were added through a temperature dropping funnel heated to the reaction temperature. To determine the progress of the reaction, the acid number (SZ), the OH number (OHN), the water value and the viscosity were measured as a function of the reaction time (see Table 4).
  • Example A5 Enzymatic glycolysis of polyesterols with diols with 10% Novozym-435 at 90 ° C.
  • Novozyms-435 To dry the Novozyms-435, a 30% suspension of Novozym-435 in toluene was prepared in a 100 ml flask. The toluene was removed immediately before the start of the reaction by distillation on a rotary evaporator under vacuum (100 mbar) at about 50-60 0 C.
  • the mixture comprising Novozyme-435 and polyesterol was heated to a reaction temperature of 90 ° C. After reaching the reaction temperature, 52 g of butanediol were added through a temperature dropping funnel heated to the reaction temperature. To determine the progress of the reaction, the acid number (SZ), the OH number (OHN), the water content and the viscosity were measured as a function of the reaction time (see Table 5).
  • Example A6 Enzymatic glycolysis of polyesterols with diols with 10% Novozym-435 at 60 ° C.
  • Novozyms-435 To dry the Novozyms-435, a 30% suspension of Novozym-435 in toluene was prepared in a 100 ml flask. The toluene was removed immediately before the start of the reaction by distillation on a rotary evaporator under vacuum (100 mbar) at about 50-60 0 C.
  • the mixture comprising Novozyme-435 and polyesterol was heated to a reaction temperature of 60 ° C. After reaching the reaction temperature, 52 g of butanediol were added through a temperature dropping funnel heated to the reaction temperature. To determine the progress of the reaction, the acid number (SZ), the OH number (OHN), the water value and the viscosity were measured as a function of the reaction time (see Table 6).
  • polyesterols of adipic acid and ethylene glycol (polyethylene glycol adipate) and of adipic acid and 1,4-butanediol (polybutanediol adipate) were used in each of the following examples for the transesterification of polyesterols.
  • the polyethylene glycol adipate had an average molecular weight of 1000 g / mol, a base number (hereinafter called "OHZ") of 99.3 mg KOH / g, and an acid value (hereinafter called "SZ”) of 2.4 mg KOH / g.
  • the polybutanediol adipate had a mean molecular weight of 5000 g / mol, a base number of 23.5 mg KOH / g and an acid number of 1.6 mg KOH / g.
  • polyethylene glycol adipates and the polybutanediol adipates were in each case prepared as follows for all the following examples and comparative examples for the transesterification of polyesterols (process step a)):
  • the acid number of the polyesterol prepared according to step a) was 2.4 mg KOH / g after a reaction time of 24 h, the OH number was 99.8 mg KOH / g, the water content was immediately after completion of the reaction at ⁇ 0.01w% ,
  • Example B1 Enzymatic transesterification of polyesterols with 1% Novozynn-435 at 90 0 C
  • the drying of the Novozyms-435 was carried out by preparing a 30% suspension of Novozyme-435 in toluene and the subsequent removal of the solvent on a rotary evaporator at 50-60 0 C and a pressure of about 100 mbar.
  • the signal at 24.33 ppm was attributed to the triad of butanediol-adipic acid-butanediol (BAB).
  • the triad of ethylene glycol adipic acid-ethylene glycol (EAE) appeared at 24.17 ppm.
  • the signals at 24.27 ppm and 24.23 ppm corresponded to the triads butanediol - adipic acid - ethylene glycol (BAE) and ethylene glycol adipic acid-butanediol (E-AB).
  • Example B2 Enzymatic transesterification of polyesterols with 5% Novozym-435 at 90 0 C
  • the drying of the Novozyms-435 was carried out by preparing a 30% suspension of Novozyme-435 in toluene and removing the solvent on a rotary evaporator at 50-60 ° C and a pressure of about 100 mbar.
  • the microstructure of the final product was determined by 13 C-NMR. Here, the splitting of the C atom, which is in ⁇ -position to the carboxyl C atom of adipic acid, was considered.
  • the signal at 24.33 ppm was attributed to the triad of butanediol-adipic acid-butanediol (BAB).
  • the triad of ethylene glycol adipic acid ethylene glycol (EAE) appeared at 24.17 ppm.
  • the signals at 24.27 ppm and 24.23 ppm corresponded to the triads butanediol - adipic acid - ethylene glycol (BAE) and ethylene glycol adipic acid-butanediol (EAB).
  • Example B3 Enzymatic transesterification of Polvesterolen with 10% Novozym-435 at 90 0 C.
  • the drying of the Novozyms-435 was carried out by preparing a 30% suspension of Novozyme-435 in toluene and then removing the solvent on a rotary evaporator at 50-60 ° C and a pressure of about 100 mbar.
  • the microstructure of the final product was determined by 13 C-NMR.
  • the splitting of the C atom, which is in ⁇ -position to the carboxyl C atom of adipic acid was considered.
  • the following 13 C signals were observed: the signal at 24.33 ppm was attributed to the triad of butanediol-adipic acid-butanediol (BAB).
  • BAB butanediol-adipic acid-butanediol
  • EAE ethylene glycol adipic acid-ethylene glycol
  • the signals at 24.27 ppm and 24.23 ppm corresponded to the triads butanediol - adipic acid - ethylene glycol (BAE) and ethylene glycol adipic acid-butanediol (EAB).
  • BAE butanediol - adipic acid - ethylene glycol
  • EAB ethylene glycol adipic acid-butanediol
  • polyesterols of adipic acid and diethylene glycol (poly-diethylene glycol adipate) and of adipic acid and 1,4-butanediol (1,4-polybutanediol adipate) were used in each of the following examples for the transesterification and glycosylation of polyesterols.
  • the polydiethylene glycol adipate had an average molecular weight of 2600 g / mol, a base number (hereinafter referred to as "OH") of 43 mg KOH / g and an acid value (hereinafter called "SZ”) of 0.8 mg KOH / g.
  • the polybutanediol adipate had an average molecular weight of 2350 g / mol, a base number of 45 mg KOH / g and an acid value of 0.7 mg KOH / g.
  • polydiethylene glycol adipates and the polybutanediol adipates were in each case prepared as follows for all the following examples and comparative examples for the transesterification of polyesterols (process step a)):
  • Preparation of polydiethylene glycol adipate In a 250 l stirred tank reactor with column and stirrer, 57.7 kg of diethylene glycol were initially charged. At 90 0 C 73.0 kg of adipic acid were added via a filler neck. The reaction mixture was heated at 40 ° C / h to 240 0 C. The resulting water of reaction was removed by distillation from the reactor. After a reaction time of 3 h, the reactor pressure was reduced from atmospheric pressure to 30-50 mbar.
  • the acid number of the polyesterol prepared according to step a) was after a reaction time of 24 h 0.8 mg KOH / g, the OH number was 43 mg KOH / g, the water content was immediately after completion of the reaction at ⁇ 0.01w%.
  • the drying of the Novozyms-435 was carried out by storage of the enzyme in a vacuum oven at 70 ° C and a pressure of 1 mbar for 12 hours.
  • the reaction was continued at 70 ° C. for 18 h.
  • the final product had an acid number of 0.4 mg KOH / g, an OH number of 99 mg KOH / g and a water content of 0.04 wt.%.
  • the viscosity was 200 mPas at 75 ° C.
  • the decrease of the viscosity from 850 mPas to 200 mPas is an indication for the reduction of the average molecular weight of the base polyesterols and thus for the incorporation of the diols in the Polyesterol chains.
  • the drying of the Novozyms-435 was carried out by storage of the enzyme in a vacuum oven at 70 ° C and a pressure of 1 mbar for 12 hours.
  • the reaction was continued at 70 ° C. for 18 h.
  • the final product had an acid number of 0.4 mg KOH / g, an OH number of 78 mg KOH / g and a water content of 0.03 wt.%.
  • the viscosity after completion of the reaction was 350 mPas at 75 ° C.
  • the decrease in viscosity from 950 mPas to 350 mPas is an indication of the reduction in the average molecular weight of the base polyesterols and thus for the incorporation of the diols in the Polyesterol chains.
  • the reaction was continued at 70 ° C. for 10 hours.
  • the final product had an acid number of 45 mg KOH / g, an OH number of 100 mg KOH / g and a water content of 0.5 wt.%.
  • the viscosity was 150 mPas at 75 ° C. This comparison test shows that a water content of already 0.5 wt.% Leads to polyesterols having a high acid number or that a total water content of 0.8 wt.% During the enzymatic transesterification according to process step b) leads to high acid number polyesterols.
  • the reaction was continued at 70 ° C. for 10 hours.
  • the final product had an acid number of 10 mg KOH / g, an OH number of 78 mg KOH / g and a water content of 0.14 wt.%.
  • the viscosity was 150 mPas at 75 ° C.
  • This comparative experiment shows that a water content of already 0.14 wt.% Leads to polyesterols having a high acid number or that a total water content from 0.15% by weight during the enzymatic glycosylation according to process step b) to high-acid-content polyesterols.

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Abstract

L'invention concerne un procédé en deux étapes pour produire des polyestérols, comprenant les étapes suivantes : a) production d'au moins un polyestérol de base par la transformation d'au moins un acide dicarboxylique avec au moins un composé de polyhydroxyle ; b) transformation du polyestérol de base obtenu en a) ou d'un mélange de polyestérols de base obtenus en a) avec au moins une enzyme et éventuellement avec des composés de polyhydroxyle. L'invention concerne également un polyestérol, qui peut être produit selon le procédé susmentionné.
EP06725186A 2005-03-23 2006-03-21 Procede en deux etapes pour produire des polyesterols Withdrawn EP1863863A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005014032A DE102005014032A1 (de) 2005-03-23 2005-03-23 Zwei-stufiges Verfahren zur Herstellung von Polyesterolen
PCT/EP2006/060898 WO2006100231A1 (fr) 2005-03-23 2006-03-21 Procede en deux etapes pour produire des polyesterols

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EP1863863A1 true EP1863863A1 (fr) 2007-12-12

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US (1) US20080193990A1 (fr)
EP (1) EP1863863A1 (fr)
KR (1) KR20080012844A (fr)
CN (1) CN101146847B (fr)
DE (1) DE102005014032A1 (fr)
WO (1) WO2006100231A1 (fr)

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EP2059550B1 (fr) * 2006-08-30 2011-10-26 Basf Se Procédé de préparation de polyestérols
DE102008004343A1 (de) 2007-01-19 2008-07-24 Basf Se Verfahren zur Herstellung von Polyesteralkoholen
CN101781398B (zh) * 2009-01-21 2012-05-30 华东理工大学 一种酶法连续生产聚(ε-己内酯)的方法
JP5680084B2 (ja) 2009-08-20 2015-03-04 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリエステルアルコールの製造方法

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GB9711680D0 (en) * 1997-06-05 1997-08-06 Baxenden The Chemical Co Ltd Enzymatic synthesis
DE10163163A1 (de) * 2001-12-20 2003-07-03 Basf Ag Verfahren zur Herstellung hochfunktioneller, Hyperverzweigter Polyester durch enzymatische Veresterung
DE10304625A1 (de) * 2003-02-05 2004-08-26 Basf Coatings Ag Polyester, enthaltend mit aktinischer Strahlung aktivierbare Gruppen, Verfahren zu ihrer Herstellung und ihre Verwendung

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CN101146847B (zh) 2011-06-15
US20080193990A1 (en) 2008-08-14
CN101146847A (zh) 2008-03-19
WO2006100231A1 (fr) 2006-09-28
KR20080012844A (ko) 2008-02-12

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