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  • 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
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
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  • 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
  • C08G65/2642—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 catalyst used
  • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
  • B01J31/068—Polyalkylene glycols
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
• • 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
  • C08G65/08—Saturated oxiranes
  • C08G65/10—Saturated oxiranes characterised by the catalysts used
  • C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
• • 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
  • C08G65/2642—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 catalyst used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
  • B01J2231/48—Ring-opening reactions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0213—Complexes without C-metal linkages
  • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0213—Complexes without C-metal linkages
  • B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
  • B01J2531/26—Zinc
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
  • B01J2531/31—Aluminium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
  • B01J2531/46—Titanium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/62—Chromium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/64—Molybdenum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/842—Iron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/845—Cobalt
• • 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
  • C08G2250/00—Compositions for preparing crystalline polymers

Definitions

• the invention relates to a process for the preparation of novel, partially crystalline polyether polyols having a hydroxyl functionality> 2 and the new polyether polyols and their use.
• bimetallic catalysts used for propylene oxide polymerization contain monool substituents which are then incorporated into the polypropylene oxide during the polymerization process, which leads to polypropylene oxides with a hydroxyl functionality far below 2, which are unsuitable, for example, as chain extenders for the production of polyurethanes.
• reaction of bimetallic catalysts with hydroxyl compounds with a functionality> 2 gives rise to catalysts which enable the polymerization of alkylene oxide to polyether polyols, with a functionality> 2. It is surprising here that the catalytically active bimetallic starting compounds, which according to the literature (J. of Polym. Sc .: Part A: Polym.
• Chem., 24, 1423 (1986) are sensitive to impurities and are still active for the alkylene oxide polymerization after the reaction with hydroxyl compounds, even at temperatures of 100-160 ° C.
• bimetallic catalysts which are to be regarded as polyfunctional with respect to hydroxyl compounds, do not crosslink or swell in the presence of hydroxyl compounds with a functionality> 2 and remain catalytically active.
• the invention therefore relates to a process for the preparation of novel, partially crystalline polyether polyols having a hydroxyl functionality> 2, which is characterized in that alkylene oxides in the presence of bimetallic ⁇ -oxoalkoxides corresponding to the formula (I)
• R I0 alkyl is a C, -C
• M stands for zinc, cobalt, molybdenum, iron, chromium or manganese
• M 2 means aluminum or titanium
• x represents 3 to 4, polymerized, the ⁇ -oxoalkoxides (I) previously having hydroxyl compounds of the formula (II)
• Q represents a C 2 -C 20 alkyl group
• R 1 and R 2 independently of one another are hydrogen or C 1 -C 20 -hydrocarbon radicals
• n independently of one another represent numbers from 0 to 40 and
• Preferred bimetallic ⁇ -oxoalkoxides are those in which M ⁇ is zinc and M 2 is aluminum, x is 3 and R is n- and isopropyl and n-butyl.
• bimetallic ⁇ -oxoalkoxides which are suitable for use in the process according to the invention are known and are described in more detail, for example, in the aforementioned US Pat. No. 3,432,445.
• Suitable hydroxyl compounds of the formula (II), which are reacted with the bimetallic ⁇ -oxoalkoxides used, are in particular those with a functionality of> 2, preferably 2 to 6, which have an average molecular weight of 90 to 6000, preferably 90 to 2000.
• the average molecular weight is determined in the usual way by measuring the OH number or by GPC against polystyrene as a comparison.
• Hydroxy compounds of the formula (II) include, in particular, polypropylene glycols, polyethylene glycols, polyethylene oxide-polypropylene oxide block copolymers and statistical C-O-PO copolymers, in addition to the known low molecular weight polyhydroxy compounds.
• Such connections are e.g. in Kirk-Othmer (3) j_, 754 to 789.
• reaction mixture is then stirred, if appropriate under vacuum, at elevated temperature (about 100 to 150 ° C.) for some time (about 0.5 to 5 hours).
• reaction mixture is then diluted with an organic solvent and / or diluent, for example a suitable hydrocarbon, such as xylene and / or ligroin, preferably to 80 to 50% by weight, and then the solvent and / or diluent is distilled off again under reduced pressure (about 0.01 to 1013 mbar).
• organic solvent and / or diluent for example a suitable hydrocarbon, such as xylene and / or ligroin, preferably to 80 to 50% by weight
• the bimetallic ⁇ -oxoalkoxide modified with the polyols is then reacted with suitable alkylene oxides to produce the partially crystalline polyether polyols.
• the reaction is preferably carried out at 20 to 200 ° C., in particular at 80 to 150 ° C., under normal or elevated pressure up to 20 bar.
• Suitable alkylene oxides are the alkylene oxides known for such reactions, preferably propylene oxide, 1,2-butylene oxide, epichlorohydrin, alkyl glycidyl ether and mixtures thereof. Propylene oxide and / or ethylene oxide is preferably used.
• the modified ⁇ -oxoalkoxide can also be diluted with hydroxyl compounds having a functionality> 2, preferably with hydroxyl compounds of the formula (II)
• the reaction of the modified catalyst with the alkylene oxides can be carried out in bulk or in a suitable inert organic solvent, such as toluene, xylene and / or tetrahydrofuran.
• a suitable inert organic solvent such as toluene, xylene and / or tetrahydrofuran.
• concentration and amount of the solvent is chosen so that under the given reaction conditions, good control of the reaction is possible.
• the modified bimetallic ⁇ -oxoalkoxide is generally used in amounts of 5 ⁇ 10 -2 to 60 mol%, preferably in amounts of 0.1 to 20 mol%, based on the amount of the polyether polyol to be prepared.
• the new, partially crystalline polyether polyols produced by the process according to the invention with a functionality of> 2, preferably 2 to 6, have average molecular weights M n of 500 to 100,000, preferably of 1000 to 10,000, determined according to GPC against polystyrene or via the hydroxyl content -End groups (OH-Z-ahl), and a molar fraction of isotactic which determines the crystallinity
• the present invention accordingly also relates to the new, partially crystalline polyether polyols of the type described above.
• the process according to the invention can be carried out either continuously or batchwise, for example in a batch or semi-batch process.
• the crude product is preferably worked up by dissolving the polyether polyol prepared in a solvent such as toluene, xylene, tetrahydrofuran, ethyl acetate and / or methylene chloride.
• a solvent such as toluene, xylene, tetrahydrofuran, ethyl acetate and / or methylene chloride.
• the catalyst is then destroyed by acidified water and the reaction products are extracted with aqueous acid ( ⁇ 25% by weight), preferably with water.
• aqueous acid ⁇ 25% by weight
• 1 to 2 acid equivalents are preferably used.
• the acids include Hydrochloric acid, phosphoric acid, sulfuric acid, benzoic acid, acetic acid and or lactic acid in question. Of course, other acids can also be used.
• the excess acid is removed by washing with water, optionally in the presence of an alkaline compound such as sodium bicarbonate.
• the polyol solution obtained is separated from the water, dried and freed from the solvent.
• the product can be further cleaned.
• suitable solvents e.g. Acetone
• the partially crystalline polyether polyols produced by the process according to the invention are outstandingly suitable for the production of polyurethane materials, such as PUR elastomers, PUR foams and PUR coatings.
• polyurethane materials such as PUR elastomers, PUR foams and PUR coatings.
• PUR materials is known and is used, for example, in plastic
• the preactivated polypropylene glycol was then transferred to an autoclave and reacted with 500 g of propylene oxide at a pressure of 3 bar and a temperature of 130 to 140 ° C.
• the crude product is dissolved in toluene and mixed with 2N hydrochloric acid to pH ⁇ 5, then shaken out with water.
• the product was neutralized with an aqueous carbonate solution washed.
• the organic phase was separated and dried.
• the semi-crystalline, waxy product has an OH number of 20 mg KOH / g and, according to GPC, an M n of 5900.
• the crystalline phase in the polyether polyol melted at 55 ° C.
• the product contained 64% isotactic triads.
• the catalyst solution was transferred to an autoclave and reacted with 400 g of propylene oxide at a pressure of 3 b.ar and a temperature of 130 to 140 ° C.
• the crude product was dissolved in methylene chloride and mixed with 20% phosphoric acid to pH ⁇ 5 and shaken out with water. For neutralization, the product was washed with an aqueous bicarbonate solution. The organic phase was separated off and dried.
• the semi-crystalline, waxy product had an OH number of 65 mg KOH / g and, according to GPC, an M n of 1900.
• the catalyst solution was then transferred to an autoclave and reacted with 1 kg of propylene oxide at a pressure of 3 b.ar at a temperature of 150 ° C.
• the crude product was dissolved in methylene chloride and 2N hydrochloric acid was added to a pH ⁇ 5 and d-ann shaken out with water. For neutralization, the product was washed with an aqueous bicarbonate solution. The organic phase was separated and dried.
• the semi-crystalline, waxy product has an OH number of 42 mg KOH / g and, according to GPC, an M "of 4290.
• the catalyst solution was then transferred into an autoclave and reacted with 1500 g of propylene oxide at a pressure of 3 b-ar at 130 to 140 ° C.
• the crude product is dissolved in toluene and mixed with 2N hydrochloric acid at pH ⁇ 5, then shaken out with water. For neutralization, the product was washed with an aqueous bicarbonate solution. The organic phase was separated and dried.
• the semi-crystalline, waxy product has an OH number of 14 and according to GPC
• the solution was then mixed with 10 ml of toluene and the reaction mixture was stirred at 120 to 130 ° C. for a further 2 hours.
• the toluene was then distilled off under high vacuum and the reaction mixture was heated again to 130 ° C. for 1 hour.
• the preactivated polyol was then reacted with 250 g of propylene oxide in an autoclave at a pressure of 3 bar and a temperature of 150 ° C. After the cleaning step .analog example lb, the partially crystalline product has an OH number of 135 mg KOH / g and according to GPC an M n of 2600.
• the organic phase was separated and dried.
• the semi-crystalline product has an OH number of 57 mg KOH / g and according to GPC an M n of 2000.
• the viscous product After the cleaning step - analogous to Example 1b, the viscous product has an OH number of 57.5 mg KOH / g and, according to GPC, an M n of 2000.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Polyethers (AREA)

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Citations (2)

• 1997
  • 1997-11-03 DE DE19748359A patent/DE19748359A1/de not_active Withdrawn
• 1998
  • 1998-10-21 AU AU14858/99A patent/AU1485899A/en not_active Abandoned
  • 1998-10-21 US US09/530,304 patent/US6458918B1/en not_active Expired - Fee Related
  • 1998-10-21 JP JP2000519004A patent/JP4399108B2/ja not_active Expired - Fee Related
  • 1998-10-21 CN CN98810796A patent/CN1116335C/zh not_active Expired - Fee Related
  • 1998-10-21 DE DE59810564T patent/DE59810564D1/de not_active Expired - Lifetime
  • 1998-10-21 WO PCT/EP1998/006689 patent/WO1999023135A1/de not_active Ceased
  • 1998-10-21 CA CA002308168A patent/CA2308168C/en not_active Expired - Fee Related
  • 1998-10-21 EP EP98958860A patent/EP1028990B1/de not_active Expired - Lifetime
  • 1998-10-21 ES ES98958860T patent/ES2212381T3/es not_active Expired - Lifetime
  • 1998-10-21 KR KR1020007004761A patent/KR100556175B1/ko not_active Expired - Fee Related
  • 1998-10-21 BR BR9814110-4A patent/BR9814110A/pt not_active IP Right Cessation
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