WO2010120289A1 - Improved copolyether glycol manufacturing process - Google Patents
Improved copolyether glycol manufacturing process Download PDFInfo
- Publication number
- WO2010120289A1 WO2010120289A1 PCT/US2009/040642 US2009040642W WO2010120289A1 WO 2010120289 A1 WO2010120289 A1 WO 2010120289A1 US 2009040642 W US2009040642 W US 2009040642W WO 2010120289 A1 WO2010120289 A1 WO 2010120289A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oce
- glycol
- polymerization
- dalton
- tetrahydrofuran
- Prior art date
Links
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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
Definitions
- the present invention relates to a process for manufacturing polyether glycols by polymerization of tetrahydrofuran and at least one alkylene oxide in the presence of an acid catalyst and at least one compound containing reactive hydrogen atoms. More particularly, the invention relates to a process for manufacturing polyether glycols which comprises recycle to the polymerization reaction of at least a portion of the oligomeric cyclic ethers which are co-produced with the polyether glycols.
- Homopolymers of tetrahydrofuran (THF), also known as polytetramethylene ether glycols (PTMEG) 1 are well known for use as soft segments in polyurethanes and other elastomers. These homopolymers impart superior dynamic properties to polyurethane elastomers and fibers.
- Copolymers of THF and at least one cyclic ether, also known as copolyether glycols are known for use in similar applications, particularly where the reduced crystallinity imparted by the cyclic ether may improve certain dynamic properties of a polyurethane which contains such a copolymer as a soft segment.
- the cyclic ethers used for this purpose are ethylene oxide and propylene oxide.
- Copolymers of THF and at least one cyclic ether are well known in the art. Their preparation is disclosed, for example, by Pruckmayr in U.S. Pat. No. 4,139,567 and U.S. Pat. No 4,153,786. Such copolymers can be prepared by any of the known methods of cyclic ether polymerization, described for instance in "Polytetrahydrofuran" by P. Dreyfuss (Gordon & Breach, N.Y. 1982). Such polymerization methods include catalysis by strong proton or Lewis acids, by heteropoly acids, as well as by perfluorosulfonic acids or acid resins.
- a polymerization promoter such as a carboxylic acid anhydride, as disclosed in U.S. Pat. No. 4,163,115.
- the primary polymer products are diesters, which need to be hydrolyzed in a subsequent step to obtain the desired polyether glycols.
- oligomeric cyclic ethers are often co-produced with the polyether glycols.
- the polymerization product stream may have an OCE content ranging from low levels upwards to about 18 percent by weight (wt%) OCE, as disclosed for example in U.S. Pat. Nos. 4,192,943; 4,228,272; 4,564,671 ; 4,585,592; and published patent applications WO 03/076453 and WO 03/076494.
- 4,564,671 discloses a process for copolymerization of THF with a 1 ,2-alkylene oxide in the presence of a compound containing reactive hydrogen and a fixed-bed clay catalyst in which less than 30% by weight of a mixture of THF, 1 ,2-alkylene oxide, and a compound containing reactive hydrogen is added to the reaction mixture, which is then recycled to the reactor.
- the latter patent discloses that virtually no by-products, in particular no cyclic oligomers, are formed during the copolymerization.
- 4,728,722 discloses that the formation of significant amounts of OCE is avoided if the THF is polymerized batchwise with a 1 ,2-alkylene oxide in the presence of compounds containing reactive hydrogen over a bleaching earth or zeolite catalyst, the 1 ,2-alkylene oxide being fed to the reaction mixture in such a manner that the concentration of the 1 ,2-alkylene oxide in the reaction mixture is kept below 2% by weight during the polymerization.
- U.S. Pat. No. 5,268,345 discloses that in the copolymerization of THF with ethylene oxide (EO), the formation of undesirable OCE is significantly reduced when montmorillonite catalyst which has been regenerated by the process disclosed therein is used.
- 4,192,943 discloses that the OCE content of copolyether glycols based on THF and alkylene oxides varies with their method of production and further discloses that raw polymerizates usually contain from about 7 to about 15% by weight of the ethers, and in some cases may contain as much as from 15 to 18% by weight.
- the OCE in PTMEG or copolyether glycol product is generally undesirable. Lacking hydroxyl groups, OCE is an inert material, and when the copolyether glycols are reacted with diisocyanates in the preparation of polyurethanes, the inert OCE can have an adverse effect on, for example, the mechanical properties of the finished products.
- the OCE can act as softeners and in general cause deterioration in the mechanical properties of the finished polyurethane products.
- the OCE may furthermore be exuded at the surface of the finished products or be dissolved out by solvents, with the result that, for example, the dimensional stability of the finished products is adversely affected.
- the OCE is a yield loss and, if separated and isolated from the desired copolyether glycol, a waste stream that requires disposal is formed.
- U.S. Pat. No. 4,192,943 discloses, for example, that the OCE content is significantly reduced by bringing the polymerizates into contact with an acid-activated sodium or calcium montmorillonite clay.
- the OCE content of THF/alkylene oxide polymerizates can be reduced by extraction with water, as disclosed in U.S. Pat. No 4, 251 ,654, or with aliphatic and cycloaliphatic hydrocarbons, as disclosed for example in U.S. Pat. No.
- the present invention provides a simple economical process for the copolymerization of THF and alkylene oxide which minimizes or avoids OCE yield loss and/or copolyether glycol contamination with OCE.
- the process comprises the steps of:
- step b) separating a majority of the tetrahydrofuran and the dimer of the alkylene oxide from the polymerization product mixture of step a) to produce a crude product mixture comprising OCE, copolyether glycol having a mean molecular weight of from about 650 dalton to about 5000 dalton and linear short chain copolyether glycol;
- step b) separating at least a portion of the OCE and linear short chain copolyether glycol from the crude product mixture of step b) to produce an OCE stream comprising OCE and linear short chain copolyether glycol, and a product stream comprising copolyether glycol having a mean molecular weight of from about 650 dalton to about 5000 dalton;
- step d) recycling at least a portion of the OCE stream of step c) to the polymerization step a).
- the present invention therefore, provides a process for manufacturing poly(tetramethylene-co-ethyleneether) glycol having a mean molecular weight of from about 650 dalton to about 5000 dalton comprising the steps of:
- step b) separating a majority of the tetrahydrofuran and the 1 ,4-dioxane from the polymerization product mixture of step a) to produce a crude product mixture comprising OCE, poly(tetramethylene-co-ethyleneether) glycol and linear short chain copolyether glycol;
- step b) separating at least a portion of the OCE and linear short chain copolyether glycol from the crude product mixture of step b) to produce an OCE stream comprising OCE and linear short chain copolyether glycol, and a product stream comprising poly(tetramethylene-co-ethyleneether) glycol;
- step d) recycling at least a portion of the OCE stream of step c) to the polymerization step a).
- Fig. 1 shows a diagrammatic flow of an embodiment of the present process.
- Fig. 2 shows a diagrammatic flow of another embodiment of the present process including separating at least a portion of the dimer of the alkylene oxide from the tetrahydrofuran.
- the process of the invention comprises the step of polymerization of THF and at least one alkylene oxide in the presence of an acid catalyst and at least one compound containing reactive hydrogen atoms.
- the unreacted THF, unreacted alkylene oxide, dimer of the alkylene oxide, and any lower boiling components present are removed, and the copolyether glycol fraction is, for example, distilled to remove at least a portion of the OCE.
- the OCE portion removed is then recycled to the polymerization step, where it can be incorporated into the copolyether glycol product.
- PTMEG poly(tetramethylene ether glycol). PTMEG is also known as polyoxybutylene glycol.
- copolyether glycol means copolymers of tetrahydrofuran and at least one 1 ,2-alkylene oxide, which are also known as polyoxybutylene polyoxyalkylene glycols.
- An example of a copolyether glycol is a copolymer of tetrahydrofuran and ethylene oxide. This copolyether glycol is also known as poly(tetramethylene-co-ethyleneether) glycol.
- linear short chain copolyether glycol means copolyether glycols having a molecular weight of from about 130 to about 400 dalton.
- An example of a linear short chain copolyether glycol is HOCH 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OH.
- THF as used herein, unless otherwise indicated, means tetrahydrofuran and includes within its meaning alkyl substituted tetrahydrofuran capable of copolymerizing with THF 1 for example 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, and 3-ethyltetrahydrofuran.
- alkylene oxide means a compound containing two, three or four carbon atoms in its alkylene oxide ring.
- the alkylene oxide can be unsubstituted or substituted with, for example, linear or branched alkyl of 1 to 6 carbon atoms, or aryl which is unsubstituted or substituted by alkyl and/or alkoxy of 1 or 2 carbon atoms, or halogen atoms such as chlorine or fluorine.
- Examples of such compounds include ethylene oxide; 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 1 ,3-butylene oxide; 2,3-butylene oxide; styrene oxide; 2,2-bis-chloromethyl-1 ,3-propylene oxide; epichlorohydrin; perfluoroalkyl oxiranes, for example (1 H,1 H-perfluoropentyl) oxirane; and combinations thereof.
- oligomeric cyclic ether as used herein in the singular, unless otherwise indicated, means one or more of the series of cyclic compounds comprised of constituent ether fragments derived from at least one alkylene oxide and/or THF and arranged in a random fashion within the cyclic compound.
- OCE refers to the distribution of cyclic ethers formed during polymerization of the THF and at least one alkylene oxide and thus refers to a series of individual compounds.
- the term OCE excludes the dimer of the alkylene oxide co- monomer used in the polymerization, even though such a dimer is an example of cyclic ether.
- the dimer of the alkylene oxide is 1 ,4-dioxane.
- this definition of OCE may differ from that of OCE disclosed in the prior art.
- OCE comprises the series of cyclic oligomeric ethers comprised of ring- opened ethylene oxide and ring-opened THF repeat units, as represented by the formula Examples of such OCE components are shown in Table A below. Two isomers were observed for molecular weight 232. Other higher molecular weight OCE components not listed in the Table are likely formed as well.
- One embodiment of the present invention is a process for the copolymerization of THF and alkylene oxide which minimizes or avoids OCE yield loss and/or copolyether glycol contamination with OCE.
- Another embodiment of the present is a process for the copolymerization of THF and ethylene oxide which minimizes or avoids OCE yield loss and/or copolyether glycol contamination with OCE.
- the THF used as a reactant in the process of the invention can be any of those commercially available.
- the THF has a water content of less than about 0.03% by weight and a peroxide content of less than about 0.005% by weight.
- the THF contains unsaturated compounds, their concentration should be such that they do not have a detrimental effect on the polymerization process of the present invention or the polymerization product thereof.
- the copolyether glycol product of the present invention has low APHA color, such as, for example less than about 250 APHA units.
- the THF can contain an oxidation inhibitor such as butylated hydroxytoluene (BHT) to prevent formation of undesirable byproducts and color.
- BHT butylated hydroxytoluene
- one or more alkyl substituted THF's capable of copolymerizing with THF can be used as a co-reactant, in an amount from about 0.1 to about 70% by weight of the THF.
- alkyl substituted THF's include 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, and 3-ethyltetrahydrofuran.
- the alkylene oxide used as a reactant in the present process may be a compound containing two, three or four carbon atoms in its alkylene oxide ring. It may be selected from, for example, the group consisting of ethylene oxide; 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 2,3-butylene oxide; 1 ,3-butylene oxide and combinations thereof.
- the alkylene oxide has a water content of less than about 0.03% by weight, a total aldehyde content of less than about 0.01 % by weight, and an acidity (as acetic acid) of less than about 0.002% by weight.
- the alkylene oxide should be low in color and non-volatile residue.
- the alkylene oxide reactant is EO
- it can be any of those commercially available.
- the EO has a water content of less than about 0.03% by weight, a total aldehyde content of less than about 0.01 % by weight, and an acidity (as acetic acid) of less than about 0.002% by weight.
- the EO should be low in color and non-volatile residue.
- Examples of compounds containing reactive hydrogen atoms which are suitable for use in the process of this invention include water, 1 ,4- butanediol, PTMEG having a molecular weight of from about 162 to about 400 dalton, copolyether glycols having a molecular weight of from about 134 to 400 dalton, and combinations thereof.
- An example of a suitable copolyether glycol for use as a compound containing reactive hydrogen atoms is poly(tetramethylene-co-ethyleneether) glycol having a molecular weight of from about 134 to about 400 dalton.
- the acid catalyst useful in the present invention includes broadly any strong acid and super acid catalyst capable of ring-opening polymerization of cyclic ethers as generally known in the art.
- the catalyst may be homogeneous or heterogeneous. Heterogeneous catalysts may be used in extrudate form or in suspension. The use of a heterogeneous catalyst may facilitate separation of product from the catalyst, especially when the catalyst is used in extrudate form.
- Suitable homogeneous acid catalysts for use herein include, by way of example but not by limitation, heteropolyacids as disclosed, for example, in U.S. Pat. No. 4,658,065.
- Suitable heterogeneous acid catalysts for use herein include, by way of example but not by limitation, zeolites optionally activated by acid treatment, sulfate-doped zirconium dioxide, supported catalysts comprising at least one catalytically active oxygen-containing molybdenum and/or tungsten compound or a mixture of such compounds applied to an oxidic support, polymeric catalysts which contain sulfonic acid groups (optionally with or without carboxylic acid groups), and combinations thereof.
- Natural or synthetic zeolites a class of aluminum hydrosilicates (also known as crystalline aluminosilicates), having an open structure of three-dimensional networks with defined pores and channels in the crystal, may be used as heterogeneous acid catalysts in the process of the present invention.
- Suitable zeolites for use herein have a S1O 2 /AI 2 O 3 molar ratio ranging from about 4:1 to about 100:1 , for example from about 6:1 to about 90:1 , or from about 10:1 to about 80:1.
- the particle size of the zeolite may be less than about 0.5 micron, for example less than about 0.1 micron, or less than about 0.05 micron.
- the zeolites are used in the hydrogen (acid) form and may optionally be activated by acid treatment.
- heterogeneous catalysts are those comprising at least one catalytically active oxygen-containing molybdenum and/or tungsten compound or a mixture of such compounds applied to an oxidic support as disclosed, for example, in U.S. Pat. No. 6,197,979.
- suitable oxidic supports include zirconium dioxide, titanium dioxide, hafnium oxide, yttrium oxide, iron (III) oxide, aluminum oxide, tin (IV) oxide, silicon dioxide, zinc oxide or mixture of these oxides.
- the supported catalysts may be, for example, additionally doped with sulfate or phosphate groups, as disclosed in German patent application DE-A 44 33606, pretreated with a reducing agent as described in DE 196 41481 , or calcined and further comprising a promoter comprising at least one element or compound of an element of groups 2, 3 (including the lanthanides), 5, 6, 7, 8, and 14 of the periodic table of the elements, as disclosed in DE 196 49803.
- polymeric catalysts which contain sulfonic acid groups, optionally with or without carboxylic acid groups, are those whose polymer chains are copolymers of tetrafluoroethylene or chlorotrifluoroethylene and a perfluoroalkyl vinyl ether containing sulfonic acid group precursors (again with or without carboxylic acid groups) as disclosed in U.S. Pat. Nos. 4,163,115 and 5,118,869 and as supplied commercially by E. I. du Pont de Nemours and Company under the tradename National®.
- Such polymeric catalysts are also referred to as polymers comprising alpha- fluorosulfonic acids.
- a perfluorosulfonic acid resin i.e. it comprises a perfluorocarbon backbone and the side chain is represented by the formula -0-CF 2 CF(CFa)-O-CF 2 CF 2 SO 3 H.
- Polymers of this type are disclosed in U.S. Patent No.
- TFE tetrafluoroethylene
- PMMAF perfluoro (3,6-dioxa-4- methyl-7-octenesulfonyl fluoride)
- the perfluorosulfonic acid resin type of polymeric heterogeneous catalyst can be pretreated (hydrotreated) by placing it along with deionized water at a weight ratio of resin/water of from about 1/4 to about 1/10 into a clean stainless steel autoclave, heating to a temperature of, for example, from about 17O 0 C to about 21O 0 C under agitation, and holding at that temperature for up to about 12 hours, for example from about 1 hour to about 8 hours.
- heterogeneous catalysts which can be employed according to the present invention can be used in the form of powders or as shaped bodies, for example in the form of beads, cylindrical extrudates, spheres, rings, spirals, or granules.
- the polymerization step a) of the present invention may be carried out with or without a solvent.
- THF may serve as a solvent for the polymerization process step, or an inert solvent, such as one or more aliphatic, cycloaliphatic, or aromatic hydrocarbons, may be used if desired.
- an inert solvent such as one or more aliphatic, cycloaliphatic, or aromatic hydrocarbons, may be used if desired.
- dimer(s) of the alkylene oxide(s) comonomers for example 1 ,4-dioxane in the case of ethylene oxide, as a solvent, alone or in conjunction with another solvent, for example THF.
- the polymerization step of the present invention is generally carried out at from about 5O 0 C to about 8O 0 C, for example from about 56 0 C to about 72 0 C. Such a temperature range is suitable for OCE incorporation into the copolyether glycol product.
- the pressure employed is generally not critical to the result of the polymerization, and pressures such as atmospheric pressure, the autogenous pressure of the polymerization system, and elevated pressures may be used.
- the polymerization step of the present process may be conducted under an inert gas atmosphere.
- suitable inert gases for use herein include nitrogen, carbon dioxide, or the noble gases.
- the polymerization step of the present invention can also be carried out in the presence of hydrogen at hydrogen pressure of from about 0.1 to about 10 bar.
- the process of the invention can be carried out continuously, or with one or more steps of the process being carried out batchwise.
- the polymerization reaction can be carried out in conventional reactors or reactor assemblies suitable for continuous processes in a suspension or fixed-bed mode, for example in loop reactors or stirred reactors in the case of a suspension process or in tube reactors or fixed-bed reactors in the case of a fixed-bed process.
- a continually stirred tank reactor (CSTR) is desirable due to the need for good mixing in the present process, especially when the products are produced in a single pass mode.
- the catalyst can, if desired, be pretreated after it has been introduced into the reactor(s).
- catalyst pretreatments include drying by means of gases, for example air or nitrogen, which have been heated to 80-200 0 C, or, in the case of supported catalysts comprising a catalytically active amount of at least one oxygen-containing molybdenum and/or tungsten compounds, pretreatment with a reducing agent as is disclosed in DE 19641481.
- the catalyst can also be used without pretreatment.
- the polymerization reactor apparatus can be operated in the upflow mode, that is, the reaction mixture is conveyed from the bottom upward, or in the downflow mode, that is, the reaction mixture is conveyed through the reactor from the top downward.
- the polymerization reactor can be operated using a single pass without internal recirculation of product, such as in a CSTR.
- the polymerization reactor can also be operated in the circulation mode, i.e., the polymerization mixture leaving the reactor is circulated. In the circulation mode, the ratio of recycle to feed is less than 100:1 , for example less than 50:1 , or for example less than 40:1.
- Feeds can be introduced to the polymerization reactor using delivery systems common to current engineering practice either batchwise or continuously.
- a preferred method of feed delivery combines EO and THF as a liquid mixed feed to the reactor, for example a CSTR, in continuous fashion along with the other feed ingredients.
- the compound containing reactive hydrogen and recycled OCE streams are metered independently or in ratio- fashion to the reactor.
- Part of or the entire recycled THF-rich stream separated downstream of the polymerization reactor can be used in place of part of the neat THF feed.
- Ranges of EO in the feed are from about 1 to about 40 wt%, for example from about 10 to about 30 wt%.
- Ranges of THF in the feed are from about 10 to about 98 wt%, for example from about 20 to about 88 wt%.
- Ranges of OCE in the feed are from 0 (prior to recycle of OCE stream separated downstream) to about 20 wt%, for example from about 3 to about 15 wt%.
- Ranges of linear short chain copolyether glycols in the feed are from 0 (prior to recycle of OCE stream separated downstream) to about 10 wt%, for example from 0 (prior to recycle of OCE stream separated downstream) to about 5 wt%.
- Ranges of the compound containing reactive hydrogen are from about 0.1 to about 5 wt% as water, for example from about 0.1 to about 2 wt%.
- the major part of the polymerization catalyst requires separation from the polymerization product mixture in the work-up of the output from the polymerization step, for example by filtration, decantation or centrifugation.
- the resulting polymerization product mixture may be passed directly to the step of separation of THF and alkylene oxide dimer from the polymerization product mixture, or optionally it may be treated first to remove any catalyst fines or downstream products of the catalyst before being passed to the separation step.
- the output from the polymerization step may be passed directly to the separation step, or optionally it may be treated first to remove any catalyst fines or downstream products of the catalyst before being passed to the separation step.
- the molar concentration of alkylene oxide, e.g. ethylene oxide, in the copolyether glycol product from the polymerization reaction step is from about 15 to about 60 mole%.
- the concentration of the copolyether glycol in the polymerization reaction step product stream is less than about 75 wt%.
- the step b) of separating a majority of the THF and alkylene oxide dimer, and the alkylene oxide, from the polymerization product mixture can be carried out either batchwise or continuously.
- majority of THF and dimer in this step we mean from at least about 98 wt% to about 100 wt%, for example at least about 99 wt%.
- the separation is performed by distillation which separates the majority of the THF, the alkylene oxide, the alkylene oxide dimer, and any low boilers such as acetaldehyde or 2-methyl-1 ,3-dioxolane from the polymerization product mixture.
- the separation of the THF in this step can in principle be carried out in one distillation step, or it can be carried out in a plurality of distillation steps, for example two or three distillation steps followed by a stripping step. It is advantageous to carry out the distillation steps under different pressures.
- the configuration of the separation operation is dependent on the alkylene oxide and the compound(s) containing reactive hydrogen atoms used in the polymerization step.
- possible distillation apparatuses are appropriate columns or evaporators such as falling film evaporators or thin film evaporators. It may also be advantageous to use tray or packed columns.
- the polymerization product mixture from step a) usually has a THF content of from about 5 wt% to about 30 wt%, dependent upon the operating temperature and pressure selected.
- the water content is generally not more than about 150 ppm
- the alkylene oxide, e.g. EO, content is from about 20 ppm to about 500 ppm
- the 2-methyl-1 ,3-dioxolane concentration is from about 200 ppm to about 1500 ppm.
- Other compounds such as ethylene glycol (typically from about 100 ppm to about 1000 ppm) and 1 ,4-butanediol (typically from about 30 ppm to about 300 ppm) are also present.
- a circulating temperature at the top of from about 100 0 C to about 16O 0 C and a temperature at the bottom of from about 100 0 C to about 200 0 C, for example from about 100 0 C to about 12O 0 C the major part of the water, alkylene oxide, e.g., EO, and acetaldehyde in admixture with THF is distilled off via the top.
- the tetrahydrofuran fraction obtained as distillate is condensed and all or some of it, such as for example at least about 99 %, can be subsequently returned to the polymerization step after purification, for example by distillation.
- the crude product mixture obtained as distillation residue at the bottom of the evaporator comprises copolyether glycol, OCE, THF, dimer of the alkylene oxide, e.g. 1 ,4-dioxane, and other low boilers.
- the removal of the major part of the unreacted THF at atmospheric pressure can be carried out in a thin film evaporator or distillation column, for example a falling film evaporator with circulation, which is operated at from about 100 0 C to about 200 0 C, for example from about 12O 0 C to about 18O 0 C.
- a thin film evaporator or distillation column for example a falling film evaporator with circulation, which is operated at from about 100 0 C to about 200 0 C, for example from about 12O 0 C to about 18O 0 C.
- the composition of the THF fraction obtained as distillate and that of the crude product mixture obtained as distillation residue correspond to those described above.
- the distillation residue obtained from the first distillation step is subsequently freed of most of the residual THF under reduced pressure, for example in a second circulating flash evaporator operating at about 100 0 C to about 15O 0 C (for example at about 12O 0 C) and from about 80 mm Hg to about 160 mm Hg (for example at about 130 mm Hg) with the circulation temperature from about 2 0 C to about 5 0 C higher than the evaporator temperature.
- a second circulating flash evaporator operating at about 100 0 C to about 15O 0 C (for example at about 12O 0 C) and from about 80 mm Hg to about 160 mm Hg (for example at about 130 mm Hg) with the circulation temperature from about 2 0 C to about 5 0 C higher than the evaporator temperature.
- Crude product leaving from the second recovery step generally contains less than about 10 ppm EO, less than about 50 ppm water, less than about 200 ppm of 2-methyl-1 ,3-dioxolane, less than about 3000 ppm 1 ,4- dioxane, and less than about 1.5 wt% THF. All or some of the THF fraction obtained as distillate, which comprises predominantly THF, such as for example at least about 99 %, can be returned to the polymerization step after purification in the distillation column.
- a third step using ultra low vacuum, for example less than 3 torr, or inert gas stripping, for example with nitrogen can be employed.
- the third step could use thin film evaporators, wiped film evaporators, disc and donut contactors, or packed columns.
- nitrogen stripping in a packed column with- nitrogen at about 17O 0 C feed at the bottom and crude product at about 12O 0 C feed at the top the crude product leaving the bottom of the column might have only dropped by about 1to 2 0 C, for example to about 118 0 C - 119 0 C.
- the EO and water content would generally be less than about 1 ppm, the 2-methyl-1 ,3-dioxolane concentration less than about 3 ppm, the THF concentration less than about 40 ppm, and the 1 ,4-dioxane concentration less than about 250 ppm.
- Other high boiling compounds like ethylene glycol and 1 ,4-butanediol would be slightly reduced but would mainly remain in the crude product.
- the crude product mixture may be treated to remove any catalyst fines or downstream products of the catalyst before being passed to the step of separation of at least a portion of the OCE from the crude product mixture.
- Either or both of the polymerization product mixture and the crude product mixture may be treated to remove any catalyst fines or downstream products of the catalyst which may result, for example, from attrition of or leaching of the catalyst during pretreatment or during polymerization.
- examples of these include finely divided, suspended or emulsified abraded catalyst comprising unchanged catalyst, the catalyst support and/or the active catalyst component.
- the abraded material is accordingly unchanged catalyst, support material and/or active oxygen-containing molybdenum or tungsten components.
- Downstream products of the catalyst are, for example, dissolved cations or anions of the active components, for example tungsten or molybdenum cations or molybdate or tungstate anions.
- the downstream product can include fluoride ions and/or sulfonic acids; in the case of the sulfate-doped metal oxides, the downstream product can include sulfuric acid and/or metal cations or anions.
- the amount of such catalyst and/or downstream products of the catalyst is small and generally does not exceed 0.1 % by weight, for example 0.01 % by weight, based on the output from the polymerization step, this material should be removed or it would otherwise remain in the copolyether glycol and change the specification data and thereby the properties of the copolyether glycol product.
- the catalyst and/or downstream products of the catalyst can be separated from the polymerization product mixture and/or the crude product mixture by filtration, for example ultrafiltration, adsorption on solid adsorbents, for example activated carbon, and/or by means of ion exchangers, for example molecular sieves having pore sizes of from 3 to 10 angstroms. Adsorption on solid adsorbents can also be combined with neutralization using acids or bases.
- distillation can be carried out batchwise from a batch distillation apparatus, without rectification.
- Short-path distillation apparatuses for example conventional film evaporators with mechanical surface distribution or automatic distribution, are advantageous.
- the continuous procedure is generally preferred, whereas distillation from a batch distillation apparatus is carried out batchwise in most cases.
- Flash evaporators are also suitable for separating off the OCE.
- the required evaporation energy is introduced into the product in the form of sensible heat, after which the product is let down into a suitable vessel under reduced pressure. During this procedure, the OCE present therein is vaporized.
- the distillation can be reinforced by additional stripping with an inert gas, such as nitrogen or superheated steam.
- an inert gas such as nitrogen or superheated steam.
- available thin film evaporators, falling film evaporators and/or short path distillation units are useful.
- OCE and low molecular weight copolyether glycols having a mean molecular weight of from about 200 to about 700 dalton are separated in at least one distillation step at a pressure of from about 0.1 to about 130 ⁇ bar, for example from about 1 to about 90 ⁇ bar, or for example from about 10 to about 70 ⁇ bar, and at a temperature of from about 18O 0 C to about 280 0 C, for example from about 200 0 C to about 25O 0 C, or for example from about 21O 0 C to about 25O 0 C, and copolyether glycols having a mean molecular weight of from about 650 dalton to about 5000 dalton are isolated.
- step d) a majority, such as greater than about 50 wt%, for example from greater than about 50 wt% to about 100 wt%, of the OCE stream of step c) is recycled to polymerization step a).
- Fig. 1 shows an embodiment of the present invention wherein feedstock comprising, for example, 13.0 parts EO, 73.6 parts THF and 0.4 parts water enters polymerization reactor 10, containing, for example, 8 parts catalyst, via line 1.
- Polymerization product mixture exits reactor 10 and enters filtration system 11 via line 2.
- Effluent from filtration system 11 enters separation system 20 via line 3.
- From separation system 20 a majority of the THF and product dimer and low boiling compounds exit via line 5, while crude product mixture comprising OCE 1 linear short chain copolyether glycol and copolyether glycol product exit via line 4.
- the line 4 composition enters filtration system 21 and the filtered composition enters separation system 30 via line 6.
- Line 7 from separation system 30 comprises the product copolyether glycol
- line 8 from separation system 30 comprises an OCE stream comprising OCE and linear short chain copolyether glycol.
- a portion of the recovered OCE stream (for example, 13 parts) in line 8 is fed to polymerization reactor 10 via line 9.
- Fig. 2 shows another embodiment of the present invention wherein feedstock comprising, for example, 13.0 parts EO, 73.6 parts THF and 0.4 parts water enters polymerization reactor 100, containing, for example, 8 parts catalyst, via line 31.
- Polymerization product mixture exits reactor 100 and enters filtration system 101 via line 32.
- Effluent from filtration system 101 enters separation system 120 via line 33.
- From separation system 120 a majority of the THF and product dimer and low boiling compounds exit via line 35, while crude product mixture comprising OCE, linear short chain copolyether glycol and copolyether glycol product exit via line 34.
- the line 35 composition enters separation system 140 and product dimer, low boiling compounds and some THF exit the separation system 140 via line 36, while separated THF exits separator system 140 via line 37 for addition to line 31.
- the line 34 composition enters filtration system 121 and the filtered composition enters separation system 130 via line 38.
- Line 39 from separation system 130 comprises the product copolyether glycol
- line 40 from separation system 130 comprises an OCE stream comprising OCE and linear short chain copolyether glycol. A portion of the recovered OCE stream (for example, 13 parts) in line 40 is fed to polymerization reactor 100 via line 41.
- THF was obtained from Chemcentral.
- EO was purchased from ARC Specialty Products and was used without further purification.
- the NR50 Nafion® perfluorinated sulfonic acid resin was obtained from E. I. du Pont de Nemours, Wilmington, Delaware, USA, and hydrotreated (pretreated) as above indicated.
- the filter aid was purchased from Aldrich Chemical, and deionized water was used.
- OCE feed was composite material that had been obtained previously as distillate from short path distillation of filtered crude copolyether glycol samples.
- the OCE feed contained 92.7 wt% oligomeric cyclic ethers (MW range of from 188 to 404 dalton) and 7.3 wt% linear short chain copolyether glycols.
- the conversion to copolymers is defined by the weight percent of non-volatiles in the crude product mixture collected from the reactor exit, which was measured by a vacuum oven (130 0 C and about 200 mmHg) removal of the volatiles in the crude product mixture.
- the short chain glycol and OCE contents were determined by gas chromatography using a DB1701 column of 5 meter length with an FID detector. Temperature programming was commenced at 5O 0 C 1 held for 2 minutes at 5O 0 C, then ramped at 20°C/minute to 25O 0 C, held at 250 0 C for 22.5 minutes, then reduced to 5O 0 C. Sample dilution was 1 :4 by weight with toluene; and sample injection size was 1 microliter.
- %OCE made and %OCE incorporation into polymer were determined for all the examples as follows: For Example 1 discussed below, the analysis of the reactor exit mixture showed that the overall conversion was 59.0%, low molecular weight oligomers that were removed by the short path distillation unit was 18.51%, the molecular weight of the final product was 2612 g/mole and the EO incorporation in the product reached 40.7 mole%.
- Hydroxyl number was determined by titration of hydroxyl end groups per ASTM method E 222.
- the APHA color of the products was determined per ASTM method D 4890.
- the polydispersity was determined by GPC, which was performed with an HP 1090 series Il liquid chromatography with a Waters Ultrastyragel 500 A column. THF was used as eluant. Polystyrene and PTMEG standards were used for calibration. The polydispersity was calculated as the ratio between the Mw/Mn.
- the equivalent weight of water in the linear small chain copolyether glycols was determined using hydroxyl number measurement as discussed above. This is required to make adjustments to the amount of chain terminating agent to attain the desired molecular weight of the copolymer product.
- the average molecular weight of the OCE and short chain polyols recycled in the feed was 3093 g/mole.
- the agitator was energized and 1616 grams of EO was added to the THF solution with cooling water supplied to the vessel. After 0.5 hour of mixing, the mixture was transferred to a 4 gallon mixture transfer tank.
- the feed mixture was fed to a supply tank, made inert with nitrogen in the free space, and fed to a jacketed 0.5 liter stainless steel CSTR reactor system using a metering pump.
- the agitator in the reactor was equipped with a single set of impellors pitched 45 degrees to provide downward pumping of the reactor contents. The liquid feed entered at the same height as the bottom impellor.
- the jacketed 0.5 liter reactor system was loaded with 44 grams of the perfluorosulfonic acid resin catalyst.
- the reactor was filled with a solution of 0.4 wt% deionized water and 99.6 wt% THF.
- the reactor mixture was heated to 68 0 C at 500 rpm agitation and 40 psig nitrogen pressure while a feed solution was added at 160 grams/hour to give a 3 hour hold time.
- the feed solution comprised 13.79 wt% ethylene oxide, 12.42 wt% OCE, 0.97 wt% linear short chain copolyether glycol, 0.369 wt% deionized water, and the balance THF.
- the average molecular weight of the OCE added as recycle feed was 3093 dalton for a water equivalent of 9.347 grams of water. Also accounted for is the water content of the OCE feed and the THF which were 93 and 89 ppm, respectively.
- a steady-state condition was reached after about 8 turnovers in the reactor, as evidenced by constant percent conversion based on sample weight after roto-evaporation and by constant molecular weight of the copolyether glycol product.
- the sample was filtered.
- Filter aid (Celpure® 300) was added to the filter paper and to the sample.
- the sample was fed to the short path distillation unit (2 or 4 inch unit from Pope Scientific). Conditions were 190 0 C wall temperature, 0.1 torr vacuum and with feed rate around 300 to 500g/hr.
- the residue, the copolyether glycol was characterized for OCE content, MW, and mole% EO incorporated.
- the distillate, the OCE was analyzed for short chain glycol content.
- Example 13 was performed in order to use, as OCE feed, OCE which had already been through the process at least one additional cycle.
- OCE feed OCE fractions obtained from the short path distillation of product from Examples 1 , 6 and an earlier run made under similar conditions were composited and used as the OCE feed.
- the OCE feed used in Example 13 contained 96.8 wt% OCE (MW range of form 188 to 404dalton) and 3.2 wt% linear short chain copolyether glycol.
- Example 13 was run with the same batch of catalyst under the conditions shown in Table B and gave product with characteristics as shown in Table C.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2009/040642 WO2010120289A1 (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process |
MX2011010777A MX2011010777A (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process. |
JP2012505864A JP5572694B2 (en) | 2009-04-15 | 2009-04-15 | Improved preparation of copolyether glycols. |
EP09843446.7A EP2419471B1 (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process |
BRPI0924022A BRPI0924022A2 (en) | 2009-04-15 | 2009-04-15 | process for manufacturing glycol copolyether, process for manufacturing poly (tetramethylene-co-ethylene ether) glycol and process for preparing single pass preparation of glycol copolyethers |
ES09843446.7T ES2525364T3 (en) | 2009-04-15 | 2009-04-15 | Improved process for the manufacture of copolyether glycol |
KR1020117027022A KR20120018320A (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process |
CN200980159790.5A CN102459407B (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2009/040642 WO2010120289A1 (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010120289A1 true WO2010120289A1 (en) | 2010-10-21 |
Family
ID=42982749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/040642 WO2010120289A1 (en) | 2009-04-15 | 2009-04-15 | Improved copolyether glycol manufacturing process |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP2419471B1 (en) |
JP (1) | JP5572694B2 (en) |
KR (1) | KR20120018320A (en) |
CN (1) | CN102459407B (en) |
BR (1) | BRPI0924022A2 (en) |
ES (1) | ES2525364T3 (en) |
MX (1) | MX2011010777A (en) |
WO (1) | WO2010120289A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102887995A (en) * | 2011-07-19 | 2013-01-23 | 因温斯特技术公司 | Improved product recovery process in the filtration of polyether polyols |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BRPI0923998A2 (en) * | 2009-04-15 | 2016-01-26 | Invista Tech Sarl | method for treating perfluorosulfonic acid resin, perfluorosulfonic acid resin and process for making polyether glycol or copolyether glycol |
CN102850540A (en) * | 2011-07-01 | 2013-01-02 | 因温斯特技术公司 | Improved method for preventing pressure build up in a catalyst separation system |
TWI646125B (en) * | 2014-01-06 | 2019-01-01 | 盧森堡商英威達技術有限公司 | Copolyether ester polyol process |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4139567A (en) * | 1977-03-30 | 1979-02-13 | E. I. Du Pont De Nemours And Company | Method for preparing copolyether glycols |
US4153786A (en) * | 1977-03-30 | 1979-05-08 | E. I. Du Pont De Nemours And Company | Method for preparing ester end-capped copolyether glycols |
US4251654A (en) * | 1979-08-14 | 1981-02-17 | E. I. Du Pont De Nemours And Company | Copolyether glycols of tetrahydrofuran and alkylene oxides having low oligomeric cyclic ether content |
US4374970A (en) * | 1981-07-07 | 1983-02-22 | E. I. Du Pont De Nemours And Company | Sulfur-modified copolyether glycols, a method for preparing them, and polyurethanes prepared therefrom |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4224432A (en) * | 1978-12-11 | 1980-09-23 | E. I. Du Pont De Nemours And Company | Polyurethanes prepared with tetrahydrofuran-alkylene oxide polymerizates having low oligomeric cyclic ether content |
US4202964A (en) * | 1978-03-16 | 1980-05-13 | E. I. Du Pont De Nemours And Company | Method for reducing oligomeric cyclic ether content of a polymerizate |
US4306058A (en) * | 1980-11-19 | 1981-12-15 | E. I. Du Pont De Nemours And Company | Method for reducing oligomeric cyclic ether content of a polymerizate |
US5302255A (en) * | 1992-03-06 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Reducing molecular weight distribution of polyether glycols by short-path distillation |
TW550873B (en) * | 1999-05-17 | 2003-09-01 | Nec Tokin Corp | Electrodynamic type of vibration actuator and mobile communication terminal |
US6989432B2 (en) * | 2002-01-10 | 2006-01-24 | Invista North America S.A.R.L. | Copolymers of tetrahydrofuran, ethylene oxide and an additional cyclic ether |
ES2465519T3 (en) * | 2009-04-15 | 2014-06-06 | Invista Technologies S.À.R.L. | Manufacturing process of glycol copolyether |
-
2009
- 2009-04-15 KR KR1020117027022A patent/KR20120018320A/en not_active Application Discontinuation
- 2009-04-15 MX MX2011010777A patent/MX2011010777A/en not_active Application Discontinuation
- 2009-04-15 BR BRPI0924022A patent/BRPI0924022A2/en not_active IP Right Cessation
- 2009-04-15 WO PCT/US2009/040642 patent/WO2010120289A1/en active Application Filing
- 2009-04-15 EP EP09843446.7A patent/EP2419471B1/en not_active Not-in-force
- 2009-04-15 JP JP2012505864A patent/JP5572694B2/en not_active Expired - Fee Related
- 2009-04-15 ES ES09843446.7T patent/ES2525364T3/en active Active
- 2009-04-15 CN CN200980159790.5A patent/CN102459407B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4139567A (en) * | 1977-03-30 | 1979-02-13 | E. I. Du Pont De Nemours And Company | Method for preparing copolyether glycols |
US4153786A (en) * | 1977-03-30 | 1979-05-08 | E. I. Du Pont De Nemours And Company | Method for preparing ester end-capped copolyether glycols |
US4251654A (en) * | 1979-08-14 | 1981-02-17 | E. I. Du Pont De Nemours And Company | Copolyether glycols of tetrahydrofuran and alkylene oxides having low oligomeric cyclic ether content |
US4374970A (en) * | 1981-07-07 | 1983-02-22 | E. I. Du Pont De Nemours And Company | Sulfur-modified copolyether glycols, a method for preparing them, and polyurethanes prepared therefrom |
Non-Patent Citations (1)
Title |
---|
See also references of EP2419471A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102887995A (en) * | 2011-07-19 | 2013-01-23 | 因温斯特技术公司 | Improved product recovery process in the filtration of polyether polyols |
WO2013012833A3 (en) * | 2011-07-19 | 2013-09-12 | Invista Technologies S. A. R. L. | Improved product recovery process in the filtration of polyether polyols |
US9040754B2 (en) | 2011-07-19 | 2015-05-26 | Invista North America S.A R.L. | Product recovery process in the filtration of polyether polyols |
Also Published As
Publication number | Publication date |
---|---|
JP5572694B2 (en) | 2014-08-13 |
CN102459407B (en) | 2014-06-18 |
BRPI0924022A2 (en) | 2016-03-01 |
KR20120018320A (en) | 2012-03-02 |
ES2525364T3 (en) | 2014-12-22 |
CN102459407A (en) | 2012-05-16 |
JP2012524147A (en) | 2012-10-11 |
MX2011010777A (en) | 2012-01-20 |
EP2419471A1 (en) | 2012-02-22 |
EP2419471B1 (en) | 2014-09-24 |
EP2419471A4 (en) | 2013-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2513195B1 (en) | Integrated copolyether glycol manufacturing process | |
US8609805B2 (en) | Copolyether glycol manufacturing process | |
EP2419471B1 (en) | Improved copolyether glycol manufacturing process | |
KR101759358B1 (en) | Improved polyether glycol manufacturing process | |
EP2419472B1 (en) | Copolyether glycol manufacturing process | |
US20100267905A1 (en) | Copolyether glycol manufacturing process | |
EP2419214A1 (en) | Improved catalyst for manufacturing polymers of tetrahydrofuran | |
US8372946B2 (en) | Copolyether glycol manufacturing process | |
KR101874474B1 (en) | Copolyether ester polyol process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980159790.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09843446 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 7356/CHENP/2011 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2011/010777 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012505864 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20117027022 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009843446 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: PI0924022 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: PI0924022 Country of ref document: BR Kind code of ref document: A2 Effective date: 20111014 |