WO2011095446A1 - Procédé de production de polyesters, en particulier de polyesters-alcools - Google Patents

Procédé de production de polyesters, en particulier de polyesters-alcools Download PDF

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Publication number
WO2011095446A1
WO2011095446A1 PCT/EP2011/051281 EP2011051281W WO2011095446A1 WO 2011095446 A1 WO2011095446 A1 WO 2011095446A1 EP 2011051281 W EP2011051281 W EP 2011051281W WO 2011095446 A1 WO2011095446 A1 WO 2011095446A1
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Prior art keywords
polyester
light
wavelength
reaction
acid
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PCT/EP2011/051281
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German (de)
English (en)
Inventor
Lionel Gehringer
Elke GÜTLICH-HAUK
Horst Binder
Original Assignee
Basf Se
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Priority to SG2012055018A priority Critical patent/SG182717A1/en
Publication of WO2011095446A1 publication Critical patent/WO2011095446A1/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
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • 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
    • C08G63/88—Post-polymerisation treatment

Definitions

  • the present invention relates to a process for the preparation of polyesters, in particular polyester alcohols, having a reduced color number, polyesters, in particular polyester alcohols, preparable by the novel process and the use of the polyester alcohols according to the invention for the production of polyurethanes.
  • polyesters in particular polyester alcohols (PESOLs), and the use of such products in polyurethane chemistry have long been known and described many times.
  • polyester alcohols are produced by polycondensation reactions of polybasic carboxylic acids and / or carboxylic acid derivatives with polyhydric alcohols or polyols.
  • the plastic handbook, Volume VII, Polyurethane, Carl-Hanser-Verlag, Kunststoff 1 may be mentioned by way of example. Edition 1966, edited by Dr. med. R Vieweg and dr. A. Höchtlen, as well as 2nd edition 1983 and the 3rd revised edition 1993, edited by Dr. med. G. Oertel.
  • polyester alcohols by polycondensation reactions of co-hydroxycarboxylic acid or by ring-opening polymerization of cyclic esters, so-called lactones. It is also possible to process polyester wastes and in particular polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) wastes. For this purpose, a whole series of methods are known and described. The basis of some processes is the conversion of the polyester into a diester of terephthalic acid, e.g. in dimethyl terephthalate. DE-A 1003714 and US Pat. No. 5,051,528 describe such transesterifications using methanol and transesterification catalysts.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • polyester alcohols in particular for the production of polyurethanes, hereinafter also referred to as PUR, in particular of flexible polyurethane foam, rigid polyurethane foam, polyisocyanurate (PIR) rigid foam, and other cellular or noncellular PUR materials, or polyurethane dispersions requires one Concrete selection of the input products and the polycondensation technology to be used. It is particularly important for the production of polyurethane that the polyester alcohols used have a low acid number (see Ullmann's Encyclopedia, Electronic Release, Wiley-VCH-Verlag GmbH, Weinheim, 2000 under the heading “polyesters”, Section 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. Polyester alcohols with high acid numbers lead therefore to a lower molecular weight during the reaction of polyester alcohols with isocyanates to polyurethane.
  • polyester alcohols with high acid numbers for the polyurethane reaction Another problem with the use of polyester alcohols with high acid numbers for the polyurethane reaction is that in the reaction of the numerous terminal acid groups with isocyanates an amide bond takes place with liberation of carbon dioxide. The gaseous carbon dioxide can then lead to undesirable bubble formation. Furthermore, free carboxyl groups deteriorate the catalysis in the polyurethane reaction and also the stability of the polyurethanes prepared to hydrolysis.
  • a known polycondensation technology for the production of polyester alcohols is the use of polyfunctional aromatic and / or aliphatic carboxylic acids or their anhydrides and di-, tri- and / or higher-functional alcohols, in particular of glycols, which at temperatures of in particular 150-280 ° C under Normal pressure and / or a slight vacuum in the presence of catalysts together with removal of the water of reaction to be reacted.
  • the usual technology is z. B. in DE-A-2904184 and consists in the addition of the reaction components at the start of the synthesis with a suitable catalyst with simultaneous temperature increase and pressure reduction. The temperatures and the vacuum are then further changed during the synthesis.
  • the polycondensation reactions can be carried out both in the presence and in the absence of a solvent.
  • polyester alcohols are produced industrially generally with the aid of the vacuum melting process, the propellant gas melting process or the azeotrope process. Further details on these methods can the Plastics Handbook Polyurethane, edited by G. Oertel, 3rd edition 1993, Carl Hanser Verlag, chap. 3.1.2, esp. Chap. 3.1 .2.3.
  • the acid number of the polyester alcohols should, as already mentioned, be as low as possible if the polyester alcohols are to be used for the production of polyurethanes;
  • the color number of the polyester alcohols should be as low as possible.
  • PESOL polyesterols
  • PU polyurethanes
  • Natural raw materials are in particular substances which are obtained by processing from plants or parts of plants (or even animals). Characteristic of raw materials from renewable sources is a significantly high proportion of the carbon isotope 14 C. By its determination, the proportion of renewable raw materials can be determined experimentally. Renewable raw materials differ from those obtained by chemical synthesis or petroleum processing in that they are less homogeneous - their composition can vary considerably more. However, these variations in the composition of natural raw materials and the presence of other, difficult-to-separate, contaminants, such as degradation products or impurities, often lead to problems in subsequent processing and therefore limit the industrial value of these substances.
  • polyester polyols by reacting educts obtained from natural raw materials is of particular interest for the production of polyurethanes, for example for the shoe industry.
  • polyester polyols thus produced have hitherto not been used industrially.
  • APHA HAZEN color evaluation done.
  • the recommendation of this procedure by the American Public Health Organization (APHA) led to the corresponding name.
  • UV light is also in the presence of an additive, for.
  • an additive for.
  • hydrogen peroxide or peracetic acid to improve the color of organic carboxylic acid esters or epoxy compounds used.
  • JP 11-171986 deals with the production of polybutylene adipate from dimethyl adipate and 1,4-butanediol under UV irradiation.
  • JP 43020268 deals with polyethylene terephthalate fibers which are irradiated with light in the range of 3500-4500 A after esterification of terephthalic acid and ethylene glycol.
  • the subject matter of the invention is thus a process for the preparation of polyesters, in particular polyester alcohols, by catalytic reaction of at least one polyfunctional carboxylic acid or derivative of a polyfunctional carboxylic acid with at least one polyhydric alcohol, characterized in that the molten monomers already before the reaction with light of the wavelength be treated in the range 100 nm to 600 nm, preferably from 200 to 600 nm and / or in that at least part of the reaction is carried out in the presence of light of the wavelength in the range from 100 nm to 600 nm, preferably from 200 to 600 nm, and / or that the polyester alcohol obtainable by the catalytic reaction after the reaction with light of wavelength in the range of 100 nm to 600 nm, preferably from 200 to 600 nm.
  • the process according to the invention can also be used for the production of polyesters as binders and also thermoplastic compositions for coating compositions and adhesives.
  • thermoplastic compositions for coating compositions and adhesives.
  • biodegradable thermoplastic polyesters it is also possible to produce biodegradable thermoplastic polyesters by the process according to the invention.
  • the process according to the invention offers the possibility of determining the color and thus the quality of the polyester alcohols obtained from the abovementioned standard processes for the preparation of polyester alcohols from dicarboxylic acids and polyols by irradiation with light of the wavelength in the range from 100 nm to 600 nm. preferably from 200 to 600 nm to improve.
  • the polyester alcohol obtained from the process described above is decolorized in the presence of light of the wavelength in the range from 100 nm to 600 nm, preferably from 200 to 600 nm.
  • the molten monomers are already treated before the polymerization with light of the wavelength in the range from 100 nm to 600 nm, preferably from 200 to 600 nm.
  • This embodiment of the method can be used for example for lactones, in particular ⁇ -caprolactone as starting material.
  • irradiation with light of the wavelength in the range from 100 nm to 600 nm preferably from 200 to 600 nm
  • all three forms of irradiation with light of the wavelength in the range from 100 nm to 600 nm preferably from 200 to 600 nm combine with each other.
  • the molten monomers (dicarboxylic acid (s) or their derivatives and polyol (s)) with light of the wavelength in the range from 100 nm to 600 nm, preferably from 200 to 600 nm, even before the polymerization, and then, in addition, irradiation with light of the wavelength in the range of 100 nm to 600 nm, preferably from 200 to 600 nm during the polymerization of at least one dicarboxylic acid (or derivatives thereof) and at least one polyol (or Roufunkti- onal alcohol) make.
  • the monomers, the reaction mixture and / or the PESOL are irradiated with light having a wavelength of 100 to 600 nm, preferably 200 to 600 nm, more preferably 220 to 500 nm, particularly preferably 220 to 450 and most preferably 220 to 420 nm.
  • UV light is used for irradiation.
  • the UV range extends from about 100 nm to about 400 nm.
  • all radiation sources which emit light of the wavelength from 100 to 600 nm, preferably from 200 nm to 600 nm, are suitable. Also suitable are all UV sources that emit electromagnetic radiation in the UV-A, UV-B and / or UV-C range.
  • the radiation source used should have at least one emission maximum in the wavelength range of 100 to 600 nm.
  • the absorbed dose is sufficient when the desired color numbers are reached or when no further color reduction is achieved by further irradiation. Upwards, the absorbed dose is not limited in principle. At very high doses, undesirable side reactions or decomposition could possibly occur, but a corresponding maximum dose can easily be determined by a person skilled in the individual case.
  • Suitable sources of radiation are, for example, low-pressure mercury lamps, medium-pressure lamps or high-pressure lamps, which may be undoped, gallium or iron doped, and fluorescent tubes, pulse emitters, metal halide emitters, Excimerstrahler, laser, LED, pulsed lamps (flash) or halogen lamps. Preference is given to medium-pressure mercury lamps with doping, in particular with iron doping. Also preferred are UV LEDs. Of course, several similar or different radiation sources can be used to achieve the desired absorbed dose or spectral distribution.
  • the temperature of the PESOL plays only a minor role in the irradiation.
  • the lower temperature limit is determined by the fact that the PESOL should be pumpable, the upper limit is determined by its temperature stability.
  • the temperature is from ambient to 240 ° C, more preferably from 60 ° C to 180 ° C, and most preferably from 80 ° C to 160 ° C.
  • the temperature is preferably 80 ° C to 120 ° C. If the irradiation of the reactants with light of the wavelength in the range of 100 nm to 600 nm, preferably from 200 to 600 nm is carried out during the reaction, this is carried out at the usual reaction temperature in the range of 150 ° C to 280 ° C, preferably in the range from 150 ° C to 260 ° C.
  • the polyester alcohols produced by the process according to the invention have, depending on the desired use, a hydroxyl number in the range between 20 and 400 mg KOH / g.
  • the hydroxyl number of polyester alcohols which are used for the production of flexible polyurethane foams or thermoplastic polyurethane elastomers preferably in the range between 20 and 250 mg KOH / g.
  • Polyester alcohols for use in rigid polyurethane foams preferably have a hydroxyl number of more than 100 mg KOH / g, in particular between 100 and 400 mg KOH / g.
  • the polyfunctional carboxylic acids or derivatives are preferably selected from the group consisting of succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic, maleic, fumaric, phthalic, isophthalic, terephthalic, dicarboxylic acid esters of alcohols having from 1 to 4 carbon atoms, dicarboxylic anhydrides or dicarboxylic acid mixtures Amber, glutaric and adipic acid or fatty acid or fatty acid derivatives selected from the group consisting of castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grape seed oil, black caraway oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, Pistachio nut oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil,
  • 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, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10-decanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 3-methyl-1,5-pentanediol.
  • diol components such as e.g. Ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10-decanediol, neopent
  • glycerol trimethylolpropane and pentaerythritol, sorbitol and sucrose. It is also possible to use oligomeric or polymeric products having at least two hydroxyl groups. Examples of these are polytetrahydrofuran, polylactones, polyglycerol, polyetherols, polyesterol or ⁇ , ⁇ -dihydroxypolybutadiene.
  • the process according to the invention is particularly well suited for the use of bio-based and / or renewable raw materials (natural raw materials), eg. B. when using a dicarboxylic acid selected from the group consisting of sebacic acid, azelaic acid, dodecanedioic acid, succinic acid and 2-methyl succinic acid, and polyhydric alcohols selected from the group consisting of 1, 3-propanediol, 1, 2-ethanediol and butanediols (in particular 1,4-butanediol).
  • a dicarboxylic acid selected from the group consisting of sebacic acid, azelaic acid, dodecanedioic acid, succinic acid and 2-methyl succinic acid
  • polyhydric alcohols selected from the group consisting of 1, 3-propanediol, 1, 2-ethanediol and butanediols (in particular 1,4-butanediol).
  • bio-based raw materials are usually more colored than comparable conventional raw materials.
  • the process according to the invention is particularly suitable here, since the color number of the resulting polyesterol can be reduced by irradiation with light of wavelength from 100 nm to 600 nm, preferably from 200 to 600 nm, before, during and / or after the reaction Thus, despite strong coloration of the starting materials can be moved to an acceptable or even good range.
  • the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are preferably polycondensed in a molar ratio of 1: (1 to 2.1), particularly preferably 1: (1, 05 to 1, 9).
  • the functionality of the polyester alcohols produced is, depending on the raw materials used, preferably in the range of at least 1.9 to 4.0, more preferably in the range of 2.0 to 3.0.
  • the number-average molecular weight of the polyester alcohols produced is preferably 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 polyester alcohols produced are preferably in the range of less than 10 g KOH / kg, more preferably in the range of less than 5 g KOH / kg, most preferably in the range of less than 2 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 catalytic reaction is preferably carried out in the presence of an esterification catalyst.
  • the esterification catalyst is preferably selected from the group comprising toluene sulfonic acids and organometallic compounds.
  • the organometallic compounds are preferably selected from compounds based on titanium or tin, particularly preferably from the group comprising the organometallic compounds titanium tetrabutoxide or tin (II) octoate, dibutyltin laurate and / or tin chloride.
  • the irradiation can be carried out according to the invention continuously or discontinuously.
  • the PESOL can rest or preferably be moved, for example by pumping or stirring.
  • the irradiation in an apparatus already takes place during the production, for example by placing a lamp in the reaction vessel, or that the monomeric starting materials are already irradiated before the esterification.
  • the color number of the resulting polyester alcohol is usually 150 Apha / Hazen, preferably at most 100 Apha / Hazen, more preferably at most 50 Apha / Hazen. If the irradiation with light having the wavelength of 100 nm to 600 nm, preferably 200 to 600 nm on the resulting polyester alcohol after the catalytic reaction, usually a reduction of the color number of the polyester alcohol before irradiation against the color number of the polyester alcohol after irradiation by at least 1%, preferably by at least 5%, more preferably by at least 20%, most preferably by at least 50%.
  • a reduction in the color number of the resulting polyester alcohol can generally be achieved by at least 1 compared with the color number of the polyester alcohol obtained by an otherwise identical method but without irradiation %, preferably at least 5%, more preferably at least 20%, most preferably at least 50%.
  • the percentage reduction of the color number of the polyester alcohol before the irradiation depends on several factors. For example, the purity of the monomers used plays a role; As a rule, in the case of monomers of low purity (and thus generally of a strong color), a particularly high percentage reduction of the color number in the end product can be achieved under otherwise identical process conditions.
  • a longer irradiation time usually results in a higher percentage reduction in the color number of the final product compared to the polyester alcohol before irradiation with light of wavelength from 100 nm to 600 nm, preferably from 200 to 600 nm.
  • the temperature during the process and the type of radiation source can also have an influence; however, irrespective of the factors mentioned, a significant improvement of the color (reduction of the color number) can always be achieved with the method according to the invention.
  • no further additives are used in addition to at least one polyfunctional carboxylic acid or derivatives thereof, at least one polyhydric alcohol and an esterification catalyst.
  • the process according to the invention thus offers numerous advantages over the processes described hitherto for improving the color of PESOLs.
  • the inventive method can be ensured by the inventive method a consistent color and thus consistent quality.
  • many of the additives that are used according to previously described methods lead to a deterioration in the quality of PESOL.
  • the method according to the invention allows the variation of the quality of the monomers without noticeable quality losses of the products (PESOL).
  • PESOL quality losses of the products
  • Another object of the invention relates to a process for preparing a polyurethane by reacting a prepared by the process according to the invention (or be prepared) polyester polyol with one or more organic diisocyanates (or polyisocyanates).
  • the polyurethane which is obtained from a polyesterpolyol prepared by the process according to the invention is in particular a thermoplastic polyurethane.
  • Thermoplastic polyurethanes are also referred to below as TPU.
  • the preparation of the polyurethanes can, in principle, be carried out by the known processes, batchwise or continuously, for example with reaction extruders or the strip process according to one-shot or the prepolymer process (also multistage prepolymer processes as in US6790916B2), preferably after the one-shot. Procedures are carried out. In these processes, the components to be reacted, polyesterol, chain extender, isocyanate (see Table 1) and, if appropriate, auxiliaries and additives (in particular UV stabilizers) may be mixed successively or simultaneously with one another, the reaction beginning immediately. Further details about the auxiliaries and additives mentioned above can be found in the specialist literature, for example from "Plastics Additive Handbook", 5th Edition, H.
  • Another object of the present invention relates to the use of a polyester polyol prepared by the process according to the invention for the production of polyurethanes (hereinafter also referred to as PUR), in particular soft polyurethane foam, rigid polyurethane foam, polyisocyanurate (PIR) hard foam, and other cellular and not cellular PUR materials or polyurethane dispersions.
  • PUR polyurethanes
  • the polyurethanes as described above can be used, inter alia, for the production of mattresses, shoe soles, gaskets, hoses, floors, profiles, paints, adhesives, sealants, skis, car seats, raceways in stadiums, instrument panels, various moldings, potting compounds, films, fibers, nonwovens. Wooven and / or cast floors are used.
  • the invention relates to the use of polyester polyols for the production of polyurethanes, the production of (foamed) flexible foam or compact casting systems.
  • Another object of the present invention relates to the use of a thermoplastic polyurethane produced by the process according to the invention for the production of moldings, tubes, films and / or fibers.
  • Another object of the present invention relates to a molded article, a film, a tube or a fiber, made of a thermoplastic polyurethane based on the inventive method.
  • FIG. 1 shows, by way of example, the spectrum of a Hönle imagesetter which can be used as the radiation source in the method according to the invention.
  • FIG. 2 shows an exemplary spectrum of a UV LED that can be used as the radiation source in the method according to the invention.
  • Example 1 Preparation of Conventional PESOL A 6040.1 g of adipic acid, 1406.8 g of ethylene glycol, 2042.6 g of 1,4-butanediol, 1 ppm of titanium tetrabutoxide and 5 ppm of tin octoate were charged into a round bottom flask having a volume of 12 liters , The mixture was heated with stirring to 180 ° C and left for 3 hours at this temperature. The resulting water was removed by distillation.
  • the resulting liquid polyester alcohol A had the following characteristics: Hydroxyl value: 58.5 mg KOH / g Acid number: 0.40 mgKOH / g
  • Viscosity 570 mPa s at 75 ° C
  • the resulting polyester polyols A were subjected to irradiation with light of the wavelength of 200 to 600 nm for 12 hours, and the resulting polyester polyol showed a color index of 10 Apha / Hazen.
  • adipic acid 6040.1 g adipic acid, 1406.8 g ethylene glycol (low quality, corresponding to a purity of ⁇ 99.5%), 2042.6 g butanediol-1, 4 (low quality, corresponding to a purity of ⁇ 99.5%), 1 ppm of titanium tetrabutoxide and 5 ppm of tin octoate were charged to a 12 liter round bottom flask. The mixture was heated with stirring to 180 ° C and left for 3 hours at this temperature. The resulting water was removed by distillation.
  • the resulting liquid polyester alcohol B had the following characteristics: hydroxyl number 56 mgKOH / g
  • Viscosity 620 mPa s at 75 ° C
  • the obtained polyester polyols B were exposed to light of the wavelength of 200 to 600 nm for 14 hours, and the resulting polyester polyol showed a color index of 1 10 Apha / Hazen.
  • a 400 W medium-pressure mercury lamp UV 400 F / 2 from Hönle was used for the irradiation.
  • the temperature of the polyester polyol rises to about 80 ° C.
  • UV meter Probe No. 724 (UV-A range) from Hönle was used.
  • Viscosity 610 mPa s at 75 ° C
  • the obtained polyester polyols C were exposed to UV irradiation for 3 hours, and the resulting polyester polyol showed a color index of 43 Hazen.
  • a 400 W medium pressure mercury lamp ES450 from Panacol was used for the irradiation.
  • the temperature of the polyester-polyol increased to about 80 ° C.
  • the polyester polyol was irradiated longer. The following results were achieved.
  • the obtained polyester polyols C were exposed to UV irradiation for 3 hours, and the resulting polyester polyol showed a color index of 50 Hazen.
  • a 400 W medium pressure mercury lamp ES460 from Panacol was used for the irradiation.
  • the temperature of the polyester-polyol increased to about 80 ° C.
  • the obtained polyester polyols C were exposed to UV irradiation for 3 hours, and the resulting polyester polyol showed a color index of 50 Hazen.
  • a 400 W medium pressure mercury lamp ES470 from Panacol was used for the irradiation.
  • the temperature of the polyester-polyol increased to about 80 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un procédé de production de polyesters par réaction catalytique d'au moins un acide carboxylique multifonctionnel ou d'un dérivé d'un acide carboxylique multifonctionnel avec au moins un alcool multifonctionnel.
PCT/EP2011/051281 2010-02-04 2011-01-31 Procédé de production de polyesters, en particulier de polyesters-alcools WO2011095446A1 (fr)

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SG2012055018A SG182717A1 (en) 2010-02-04 2011-01-31 Method for producing polyesters, in particular polyester alcohols

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EP10152691.1 2010-02-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9458277B2 (en) 2011-09-30 2016-10-04 Covestro Deutschland Ag Homogeneous extruded articles made from thermoplastically processable polyurethanes based on polyester diols formed from succinic acid and 1,3-propanediol
US11124594B2 (en) 2013-07-02 2021-09-21 Basf Se Polyurethane based on renewable raw materials

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1003714B (de) 1956-01-25 1957-03-07 Glanzstoff Ag Verfahren zum Abbau von Polyaethylenterephthalat zu Terephthalsaeuredimethylester
JPS4320268Y1 (fr) 1965-08-28 1968-08-26
US3668092A (en) 1971-02-02 1972-06-06 Ashland Oil Inc Bleaching of carboxylic acid esters and/or epoxy compounds employing ultraviolet light
US4020010A (en) * 1975-12-29 1977-04-26 Basf Wyandotte Corporation Tin titanium complexes as esterification/transesterification catalysts
DE2904184A1 (de) 1978-03-17 1979-09-20 Gaf Corp Formmasse und die daraus hergestellten spritzguss-formkoerper
DE2901774A1 (de) 1979-01-18 1980-07-24 Elastogran Gmbh Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung
US4897474A (en) 1986-07-11 1990-01-30 Huels Aktiengesellschaft Carbohydrate fatty acid esters and a process for preparing them
US5051528A (en) 1990-04-24 1991-09-24 Eastman Kodak Company Recovery process for ethylene glycol and dimethylterephthalate
JPH11171986A (ja) 1997-12-16 1999-06-29 Nippon Ester Co Ltd ポリエステルの製造方法
US6790916B2 (en) 2002-02-23 2004-09-14 Bayer Aktiengesellschaft Process for the preparation of soft, low-shrinkage, thermoplastic polyurethane elastomers which can be easily released from the mold
US20070238799A1 (en) * 2006-04-06 2007-10-11 Inolex Investment Corporation Odorless polyester polyol, odorless polyurethane foam and method for making the same

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1003714B (de) 1956-01-25 1957-03-07 Glanzstoff Ag Verfahren zum Abbau von Polyaethylenterephthalat zu Terephthalsaeuredimethylester
JPS4320268Y1 (fr) 1965-08-28 1968-08-26
US3668092A (en) 1971-02-02 1972-06-06 Ashland Oil Inc Bleaching of carboxylic acid esters and/or epoxy compounds employing ultraviolet light
US4020010A (en) * 1975-12-29 1977-04-26 Basf Wyandotte Corporation Tin titanium complexes as esterification/transesterification catalysts
DE2904184A1 (de) 1978-03-17 1979-09-20 Gaf Corp Formmasse und die daraus hergestellten spritzguss-formkoerper
DE2901774A1 (de) 1979-01-18 1980-07-24 Elastogran Gmbh Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung
US4897474A (en) 1986-07-11 1990-01-30 Huels Aktiengesellschaft Carbohydrate fatty acid esters and a process for preparing them
US5051528A (en) 1990-04-24 1991-09-24 Eastman Kodak Company Recovery process for ethylene glycol and dimethylterephthalate
JPH11171986A (ja) 1997-12-16 1999-06-29 Nippon Ester Co Ltd ポリエステルの製造方法
US6790916B2 (en) 2002-02-23 2004-09-14 Bayer Aktiengesellschaft Process for the preparation of soft, low-shrinkage, thermoplastic polyurethane elastomers which can be easily released from the mold
US20070238799A1 (en) * 2006-04-06 2007-10-11 Inolex Investment Corporation Odorless polyester polyol, odorless polyurethane foam and method for making the same

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"Kunstoff-Handbuch Polyurethane", 1993, CARL-HANSER-VERLAG
"Kunststoffhandbuch", vol. VII, 1966, CARL-HANSER-VERLAG
"Plastics Additive Handbook", 2001, HANSER PUBLISHERS
"Polyurethane", vol. VII, 1966, CARL-HANSER-VERLAG, article "Kunststoffhandbuch"
"Ullmann's Encyclopedia, Electronic Release", 2000, WILEY-VCH-VERLAG GMBH
DATABASE WPI Week 199936, Derwent World Patents Index; AN 1999-425041, XP002636551 *
H. SAUNDERS; K. C. FRISCH: "Polyurethane", vol. XVI, 1962, VERLAG INTERSCIENCE PUBLISHERS, article "High Polymers"
VON R. GACHTER; H. MULLER: "Taschenbuch für Kunststoff-Additive", 1990, HANSER VERLAG

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9458277B2 (en) 2011-09-30 2016-10-04 Covestro Deutschland Ag Homogeneous extruded articles made from thermoplastically processable polyurethanes based on polyester diols formed from succinic acid and 1,3-propanediol
US11124594B2 (en) 2013-07-02 2021-09-21 Basf Se Polyurethane based on renewable raw materials

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