WO2006001482A1 - Procédé servant à produre un polyéther de polyol - Google Patents

Procédé servant à produre un polyéther de polyol Download PDF

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Publication number
WO2006001482A1
WO2006001482A1 PCT/JP2005/011980 JP2005011980W WO2006001482A1 WO 2006001482 A1 WO2006001482 A1 WO 2006001482A1 JP 2005011980 W JP2005011980 W JP 2005011980W WO 2006001482 A1 WO2006001482 A1 WO 2006001482A1
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Prior art keywords
polyether polyol
solid acid
amount
producing
acid catalyst
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PCT/JP2005/011980
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English (en)
Japanese (ja)
Inventor
Naoko Fujita
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Mitsubishi Chemical Corporation
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Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Priority to US11/631,015 priority Critical patent/US20080071118A1/en
Priority to KR1020067027443A priority patent/KR20070032725A/ko
Publication of WO2006001482A1 publication Critical patent/WO2006001482A1/fr

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    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing a polyether polyol by a dehydration condensation reaction of a polyol. Specifically, the present invention relates to a method for efficiently producing a polyether polyol with little coloration by carrying out this reaction in the presence of a catalyst having specific acid properties.
  • Polyether polyol is a polymer having a wide range of uses, including raw materials for soft segments such as elastic fibers and plastic elastomers.
  • Typical examples of polyether polyols include polyethylene glycol, poly (1,2-propanediol), and polytetramethylene ether glycol.
  • poly (1,2-propandiol) is widely used because it is liquid at room temperature, easy to handle, and inexpensive.
  • poly (1,2-propanediol) has a primary hydroxyl group and a secondary hydroxyl group, the physical properties of these hydroxyl groups may be problematic depending on the application.
  • polytrimethylene ether glycol which is a dehydration condensate of 1,3-propanediol, has recently attracted attention because it has only primary hydroxyl groups and has a low melting point.
  • polyether polyols can be produced by a dehydration condensation reaction of corresponding polyols.
  • ethylene glycol, 1,4-butanediol, 1,5-pentanediol, and the like produce 5- or 6-membered cyclic ethers, that is, 1,4-dioxane, tetrahydrofuran, and tetrahydropyran, respectively, during dehydration condensation.
  • a polyether polyol corresponding to a polymer of ethylene glycol and 1,4-butanediol is produced by ring-opening polymerization of a corresponding cyclic ether, that is, ethylene oxide and tetrahydrofuran.
  • Polyether polyols corresponding to 1,5-pentanediol polymers are difficult to produce because tetrahydropyran, a cyclic ether, is thermodynamically advantageous.
  • Catalysts include iodine, inorganic acids such as hydrogen iodide and sulfuric acid, and And organic acids such as para-toluene sulfonic acid (see Patent Document 1), perfluoroalkyl sulfonic acid groups having a side chain (see Patent Document 2), a combination of sulfuric acid and cuprous chloride, activity White clay, zeolite, organic sulfonic acid, heteropoly acid (see Patent Document 3) and the like have been proposed.
  • inorganic acids such as iodine, hydrogen iodide and sulfuric acid
  • organic acids such as para-toluenesulfonic acid, organic sulfonic acids and heteropolyacids are homogeneous acid catalysts.
  • the reactor used for the polymerization reaction corrodes, and the reactor corrodes, so that the metal component is eluted and the product polyether polyol
  • the eluted polyol is contained in the polyether polyol.
  • it is necessary to use a reactor that uses glass or glass-lined reactors and high-grade materials such as hastelloy. Met.
  • an ester derived from the catalyst acid may be contained at the end of the polyether polyol of the product, and the hydrolysis of the ester may be required, resulting in a large number of steps.
  • the problem of wastewater treatment also arises.
  • a uniform acid catalyst is contained in the polyether polyol, it is necessary to remove these acid catalysts by methods such as neutralization and washing with water, and there is a problem that a purification step of the polyether polyol is required for that purpose. To the eye.
  • Patent Document 2 Pamphlet of International Publication No. 92Z09647
  • Patent Document 3 U.S. Patent No. 5659089
  • Patent Document 4 US Patent Application Publication No. 2002Z0007043
  • the present invention intends to provide a method for producing a polyether polyol with high selectivity and low coloration in high yield by dehydrating condensation of a polyol using a solid catalyst.
  • the gist of the present invention is that a solid acid catalyst satisfying at least one of the following conditions (1) to (3) is used when producing a polyether polyol by a dehydration condensation reaction of a polyol.
  • Acidity function H measured by Hammett's indicator adsorption method is greater than -3
  • TPD temperature-programmed desorption analysis
  • TG thermogravimetric analysis
  • the second gist is a method for producing a polyether polyol as described above, wherein the solid acid catalyst contains 0.01 to 2.5 equivalents of a metal element and Z or an organic base with respect to the acid. Exist.
  • the third gist is the polyether polyol as described above, wherein the metal element is an alkali metal.
  • the manufacturing method is the polyether polyol as described above, wherein the metal element is an alkali metal.
  • the fourth gist lies in the method for producing a polyether polyol as described above, wherein the organic base has a pyridine skeleton.
  • the fifth gist lies in the method for producing a polyether polyol as described above, wherein the solid acid catalyst, the metal element-containing compound and Z or an organic base are used in combination.
  • the sixth gist is that the solid acid catalyst is an intercalation compound, zeolite, mesoporous material, metal composite oxide, oxide or composite oxide containing a sulfonic acid group, a carbon material containing a sulfonic acid group, And a method for producing a polyether polyol as described above, which is at least one member selected from the group consisting of a resin having a perfluoroalkylsulfonic acid group in the side chain.
  • the seventh gist is a polyol having 3 or more and 10 or less carbon atoms having two primary hydroxyl groups (excluding those forming a 5- or 6-membered cyclic ether by dehydration), or This is a mixture of this with other polyols, and the ratio of the other polyols is less than 50 mol%.
  • An eighth aspect resides in the above-described method for producing a polyether polyol, wherein the reaction is performed at 120 ° C or higher and 250 ° C or lower.
  • the solid acid catalyst used in the production method of the present invention shall satisfy at least one of the conditions described in (1) to (3) below. Among these conditions, those satisfying the two conditions are more preferable. Specifically, (1) and (2), (1) and (3), or (2) and (
  • a solid acid catalyst satisfying the condition 3) is more preferable. Furthermore, a solid acid catalyst that satisfies all the conditions (1), (2), and (3) is particularly preferred.
  • the solid acid catalyst used in the present invention must have an acid strength that is not too strong for this reaction. Yes, with acidity function H measured by Hammett's indicator adsorption method greater than -3, + 1.
  • a value larger than 5 is more preferable +2 or more.
  • the acidity function H measured by Hammett's indicator adsorption method has a stronger acid point as the value is smaller. Therefore
  • V weak it means that it is acid nature.
  • Hammett's acid strength function here is obtained by measuring acid strength in a commercially available benzene solution with Hammett's indicator after treating a solid acid catalyst in saturated steam at 25 ° C for 2 days. .
  • an indicator for measuring acidity can be conveniently measured by changing the acidity of Hammett's indicator to an acidic color on a solid acid catalyst when it shows acidity. If the solid acid catalyst power is originally colored, it is difficult to recognize a change in the color of the indicator visually, so the change in the indicator may be analyzed by, for example, a spectroscopic technique.
  • the acid amount and strength of the solid acid catalyst used in this reaction is strong, and the amount of acid sites is preferably large.
  • the temperature range is 100 to 350 ° C by temperature programmed desorption analysis (TPD) of ammonia. It is preferable that the ammonia desorption amount at 60% is 60% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C). Among these, 70% or more is more preferable.
  • the ammonia desorption amount in the region of 100 to 300 ° C is preferably 50% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C). 60% or more Is more preferable.
  • ammonia desorption amount in the region of 100 to 250 ° C is preferably 40% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C). Is more preferable.
  • the ammonia desorption amount in the region of 300 to 450 ° C is 0.6 times or less, preferably 0.5 times or less, more preferably the ammonia desorption amount in the region of 100 to 300 ° C. It is preferably 0.3 times or less, particularly 0.2 times or less. Among them, the range of 400 to 700 ° C It is particularly preferable that the amount of ammonia desorbed at 2 mmolZg or less, preferably ImmolZg or less, more preferably 0.5 mmolZg or less, even more preferably 0.4 mmolZg or less. Further, it is further preferable that the ammonia desorption amount in the region of 100 to 300 ° C. is 0.1 ImmolZg or more, preferably 0.2 mmolZg, more preferably 0.3 mmolZg or more.
  • the solid acid catalyst used in this reaction is 3% or more, more preferably 5% or more, more preferably 50 to 200 ° C of the reference weight between 32 and 250 ° C in thermogravimetric analysis (TG).
  • TG thermogravimetric analysis
  • a solid acid catalyst from which 5% or more of the standard weight of water is eliminated is preferable.
  • the TG analysis method and the reference weight are based on the method in Examples described later.
  • the solid acid catalyst used in this reaction can be selected using acid strength measurement with Hammett's indicator, temperature-programmed desorption analysis of ammonia, or thermogravimetric analysis. A polyether polyol with little coloration can be obtained.
  • a solid acid catalyst that satisfies at least one of the above conditions, a part of the acid substituted with a metal element, a metal element or an organic base modified, or the solid
  • the metal element-containing compound or organic base component is added in the form of coexistence in the reaction system, the effect increases.
  • Such a solid acid catalyst is a catalyst having an acidity function H measured by Hammett's indicator adsorption method of the present invention of greater than -3, or 100 to 350 in the temperature programmed desorption measurement of ammonia.
  • a catalyst whose ammonia desorption amount in the region of ° C is 60% or more of the total ammonia desorption amount (region of 25 ° C to 700 ° C), or between 30 and 250 ° C in thermogravimetric analysis This is a solid acid catalyst from which 3% or more of the reference weight is eliminated.
  • Any solid acid catalyst that satisfies at least one of the above conditions (1) to (3) is not particularly limited, but is preferably an intercalation compound such as activated clay, zeolite, mesoporous material, silica-alumina, silica-zircoua, etc.
  • an intercalation compound such as activated clay, zeolite, mesoporous material, silica-alumina, silica-zircoua, etc.
  • Metal complex oxides, oxides or complex oxides containing sulfonic acid groups, carbon compounds containing sulfonic acid groups, organic compounds such as ion-exchange resins, and perfluoroalkylsulfonic acid groups in the side chain Can be used.
  • intercalation compounds such as activated clay, zeolite, mesoporous materials, metal composite oxides such as silica-alumina and silica-zirconia, oxides containing sulfonic acid groups
  • intercalation compounds such as activated clay, zeolite, mesoporous materials, oxidation containing sulfonic acid groups Sulfur and composite oxides, and carbon materials containing sulfonic acid groups are more preferred.
  • Particularly preferred are oxides or composite oxides containing phonic acid groups, and carbon materials containing sulfonic acid groups.
  • Preferable metal elements that can be replaced with protons at the acid sites of solid acid catalysts or metal elements that can be modified are alkali metals, alkaline earth metals, group 3-12 transition metals, and group 13 elements.
  • Alkali metals are particularly preferred, with alkali metals and alkaline earth metals being more preferred.
  • As the alkali metal Li, Na, K, and Cs are preferable. Na is particularly preferable.
  • the content of the metal element is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, and preferably 2.5 equivalents or less, as the metal element with respect to the acid amount of the solid acid catalyst. Preferably, it is used so that it is 1 equivalent or less, more preferably 0.5 equivalent or less.
  • the acid amount refers to a theoretical acid amount or an acid amount obtained by a neutral salt decomposition method.
  • the theoretical acid amount for which the amount of A1 is calculated zeolite containing elements other than A1, mesoporous materials, sulfonic acid-containing solid catalysts, oxides, complex oxides, activated clay
  • it means the acid amount determined by the neutral salt decomposition method.
  • the neutral salt decomposition method means that a solid acid catalyst is washed with a saturated sodium chloride aqueous solution at 20 to 25 ° C.
  • the H + ion exchanged with Na + is determined by titration with an aqueous solution of sodium hydroxide and sodium hydroxide of known concentration.
  • a catalyst having an acid point substituted with a metal may be obtained in advance.
  • the content of the metal element is equivalent to the original acid amount when the metal element is not substituted with the acid point of the solid acid.
  • the acid amount when the metal is not substituted is 1 mmolZg, and the acid amount when the metal is substituted is 0.
  • the metal element content of the metal-substituted solid acid is 0.3 equivalent to the acid amount.
  • the amount of metal substitution can also be determined by elemental analysis.
  • a compound containing a metal element can be used, and metal sulfate, hydrogen sulfate, nitrate, halide, phosphate, hydrogen phosphate, borate, etc.
  • Mineral acid salt And metal salts such as organic sulfonates such as trifluoromethanesulfonate, paratoluenesulfonate, methanesulfonate, carboxylates such as formate and acetate, metal hydroxide, metal alkoxide, metal Specific examples include acetylylacetonate.
  • the organic base is preferably a nitrogen-containing organic base, particularly a nitrogen-containing organic base having a tertiary or quaternary nitrogen atom.
  • the organic base is preferably 0.01 equivalents or more, more preferably 0.05 relative to the acid amount of the solid acid catalyst (in this case, the acid amount in the case of unsubstituted as in the case of the metal element). It should be used so that it is at least equivalent, preferably 2.5 equivalent or less, more preferably 1 equivalent or less, and particularly preferably less than 1 equivalent.
  • a method for modifying an organic base to a solid acid catalyst a method in which a solid acid catalyst is mixed in a solution containing a desired base, a method in which impregnation is forcibly supported, a base-containing solution is pore-filled, and then dried.
  • the catalyst can be obtained by a known method such as a method, and these catalysts can be washed and dried as necessary.
  • a metal element and Z or an organic base are used in combination. May be. Specifically, these may be added separately to the reaction system, or these compounds may be mixed and then used in the reaction. In this case, the sum of the amounts of all metal elements and organic bases present in the reaction system should be within the above range.
  • the solid acid catalyst and the metal element or organic base may exist separately in the reaction system, or a salt may be formed between the solid acid catalyst and the metal element or organic base. Good.
  • Reaction polyols include 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,7- It is preferable to use a diol having two primary hydroxyl groups such as heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decandiol, 1,4-cyclohexanedimethanol. 1,3-propanediol is more preferred.
  • ethylene glycol, 1,4-butanediol, 1,5-pentanediol, etc. generate cyclic ether ethers by the dehydration condensation reaction as described above. Therefore, it is not preferable as a raw material for the method of the present invention.
  • the ability to use these diols alone can be used as a mixture of two or more diols if desired.
  • the main diol accounts for 50 mol% or more.
  • the oligomer of the 2-9 mer obtained by the dehydration condensation reaction of the main diol can be used together with these diols.
  • polyols of triol or higher such as trimethylolethane, trimethylolpropane, pentaerythritol, or oligomers of these polyols can be used in combination. Even in these cases, it is preferable that the main diol occupies 50 mol% or more.
  • a mixture of polyols with a ratio of other polyols of less than 50 mol% is used for the reaction.
  • a diol selected from the group consisting of 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, or another polyol and this Mixtures with a proportion of other polyols of less than 50 mol%, particularly preferably 1,3-propanediol or a mixture of this with other polyols with a proportion of other polyols of less than 50 mol% Subject to reaction.
  • the production of the polyether polyol by the dehydration condensation reaction of the polyol can be carried out either batchwise or continuously.
  • a raw material polyol and a solid acid catalyst and, if necessary, a metal element or an organic base may be charged and reacted with stirring.
  • the solid acid catalyst is usually used in the range of 0.01 to 1 times by weight with respect to the starting polyol.
  • a solid acid catalyst is retained in a reaction apparatus or a flow reaction apparatus in which a large number of stirring tanks are connected in series, and the raw material polyol is continuously supplied to the reactor.
  • a method can be used in which only the reaction solution containing no solid acid catalyst is continuously extracted from the other end. In this case, either a suspension bed or a fixed bed reaction can be employed.
  • the lower limit is usually 0.01 times by weight or more, preferably 0.1 times by weight or more, and the upper limit is usually 10,000 times by weight or less, with respect to the solid acid catalyst usually staying in the reactor.
  • a raw material polyol of 1000 times by weight or less is fed in one hour.
  • the equivalent ratio of the base to the solid acid catalyst in the reaction apparatus may decrease with time. Therefore, if necessary, the solid acid catalyst may be withdrawn little by little to charge a new catalyst, The base is supplied together with the solvent so that the equivalent ratio of organic base to acid maintains the desired value.
  • the lower limit of the temperature of the dehydration condensation reaction is usually 120 ° C or higher, preferably 140 ° C or higher, and the upper limit is usually 250 ° C, preferably 200 ° C or lower.
  • the reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen nitrogen.
  • the reaction pressure is maintained in the liquid phase of the reaction system. As long as it is within the range, it is optional and is usually carried out under normal pressure. If desired, the reaction can be carried out under reduced pressure or an inert gas can be circulated through the reaction system to promote the elimination of water produced by the reaction from the reaction system.
  • the reaction time varies depending on the amount of catalyst used, the reaction temperature, and the desired yield and physical properties of the dehydration condensate to be produced, but the lower limit is usually 0.5 hours or more, preferably 1 hour or more. Is usually 50 hours or less, preferably 20 hours or less.
  • the reaction is usually carried out in a non-solvent, but a solvent can be used if desired.
  • the solvent should be selected as appropriate according to the organic solvent power used in conventional organic synthesis reactions, taking into consideration the vapor pressure, stability, and solubility of raw materials and products under the reaction conditions.
  • Separation / recovery of the produced polyether polyol can be carried out by a conventional method.
  • the suspended solid acid catalyst is removed from the reaction solution by filtration or centrifugation.
  • a metal compound is added to the reaction system, it can be removed by washing with water or a hardly soluble salt can be formed and removed by filtration.
  • an organic base it can be removed by distillation if it can be distilled, and the extracted organic base can be returned to the reaction system. If it cannot be distilled, it can be removed by washing with water.
  • the low-boiling oligomers are removed by distillation or extraction with water to obtain the desired polyether polyol.
  • a light-boiling component or a low-boiling oligomer is removed from the taken-out reaction solution by distillation or water washing as necessary to obtain the desired polyether polyol.
  • polyether polyols can be made into products through a drying step if necessary.
  • the color of the polyether polyol obtained by the method of the present invention is so preferable that it is not colored.
  • the number average molecular weight of the polyether polyol of the present invention depends on the type of catalyst used and
  • the lower limit is usually 80 or more, preferably 600 or more, more preferably 1000 or more, and the upper limit is usually 10000 or less, preferably 7000 or less, more preferably 5000 or less.
  • the preferred upper limit is usually 3 or less, preferably 2.5 or less.
  • the polyether polyol of the present invention can be used for applications such as elastic fibers, thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and coating materials.
  • Example 1 thermoplastic polyester elastomers, thermoplastic polyurethane elastomers, and coating materials.
  • the acid amount was measured by the neutral salt decomposition method as follows. A sample lOmg was precisely weighed to the first decimal place, 30 ml of a saturated aqueous sodium chloride solution (prepared with Pure Chemical's special grade sodium chloride and demineralized water) was added, and the mixture was stirred for 15 minutes at room temperature.
  • a saturated aqueous sodium chloride solution prepared with Pure Chemical's special grade sodium chloride and demineralized water
  • the solid acid catalyst was filtered off, washed with demineralized water, and the filtrate was titrated with 0.025 M aqueous solution of sodium hydroxide and sodium to obtain the amount of protons ion-exchanged. The amount was determined.
  • Hammett indicator is anthraquinone (pKa-8. 2) ⁇ benzalacetophenone (pKa-5.
  • Anthraquinone (pKa-8.2), benzalacetophenone (pKa-5.6), and disinnamalaceton (pKa-3.0) have no discoloration to acidic color.
  • the acidity function H is smaller than ⁇ 3, for example, anthraquinone (pKa-8.2) or ben
  • the temperature programmed desorption analysis of ammonia was performed by the following method.
  • Measuring device Anelva AGS-7000 EI method 70eV
  • Sample pretreatment conditions He 80ml / min, raised from room temperature to 250 ° C at 30 ° CZmin, then kept at 250 ° C for 30 minutes.
  • Ammonia adsorption condition “After evacuating the sample with a rotary pump at 100 ° C, inject ammonia gas (purity 100%) for 90 torr at the same temperature and hold for 15 minutes” ⁇ “Vacuum exhaustion” 100 ° CX 30 minutes ” ⁇ “ He 200ml / min, 100 ° CX 30 minutes ” ⁇ “ TPD measurement starts 5 minutes after returning to room temperature. ”
  • TPD measurement temperature range room temperature to 700 ° C (temperature rise at 10 ° C Zmin)
  • Thermogravimetric analysis was performed by the following method.
  • Sample Sampling in air at room temperature after pretreatment for 2 days in saturated steam.
  • Measuring device SII Nanotechnology Co., Ltd. TG-DTA 6300
  • Sample amount about 10 mg
  • Measurement method Dry nitrogen gas (purity 99.999% or more, dew point-60 ° C) Flow through 200mlZmin, hold at 30 ° C for 30 minutes at room temperature, then heat up at 10 ° C Zmin, then heat up to 500 ° C.
  • Reference weight The weight obtained by subtracting the weight loss to 32 ° C from the weight of the measured sample shall be the reference weight.
  • Table 1 shows the results of thermogravimetric analysis (TG).
  • the amounts quantified by the following method were used for the amounts of Al, Na, and Si contained in the zeolite catalyst.
  • Example 4 The sample was melted, cooled, glass-beaded, and then quantified by fluorescent X-ray (XRF (fundamental parameter method: FP method)).
  • XRF fundamental parameter method: FP method
  • Chemical analysis method (2) The sample was dried at 120 ° C for 2 hours, allowed to cool, and collected, and the total amount was resolved by dry ashing to obtain a solution, which was quantified by AAS and calibration curve method.
  • Mn number average molecular weight
  • the light boiling components and 1,3-propanediol contained in the obtained oil layer were analyzed by gas chromatography (GC).
  • Carrier Nitrogen approx. 1.5mlZmin, split ratio approx. 40
  • Oven temperature 50 ° C- (10 ° C, min temperature rise) -230 ° C (10 minutes hold)
  • Example 1 the catalysts used in Examples 2 and 8 and Comparative Examples 1 and 3 were used after being previously dried at 300 ° C. for 12 hours.
  • the mixture was stirred at room temperature for 10 minutes, and after sufficiently removing oxygen in the reactor, the oil bath temperature was set to 200 ° C and heating was started. The temperature of the reaction solution was adjusted to 185 ° C. ⁇ 3 ° C. and held for 6 hours for reaction, and then the flask was removed from the oil bath and allowed to cool to room temperature. The water generated during the reaction was allowed to flow out with nitrogen, and a trap that had been cooled with dry ice-ethanol solution along with the by-product 1,3-propanediol was used.
  • the oil layer was measured with a gel permeation chromatography and the number average molecular weight (Mn) was determined.
  • Mn number average molecular weight
  • the amount of 1,3-propanepandiol contained in this oil layer was analyzed and quantitatively analyzed by gas chromatography.
  • the amount of unreacted 1,3-propanediol is determined for each of the light boiling component and the component in the oil reservoir.
  • the selectivity for the polyether polyol was determined from the following formula, subtracting the amount of 1,3-propanediol from the obtained oil layer and using the remainder as the polyether polyol.
  • Polytrimethyl ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table-1.
  • Polytriethylene ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table 1.
  • a polytrimethylene ether glycol was obtained in exactly the same manner as in Example 1 except that nitrogen was supplied in an amount of lOONmlZ. The results are shown in Table 1.
  • the ammonia desorption amount at 100 to 250 ° C was 0.19 mmolZg, and the total ammonia desorption amount (region of 25 ° C to 700 ° C) was 33 %Met.
  • the ammonia desorption amount at 100-300 ° C is 0.25 mmolZg
  • the ammonia desorption amount at 100-350 ° C is 0.33 mmolZg, with 43% of the ammonia desorption amount (region of 25 ° C-700 ° C), and the total (25 ° C- It was 57% of the amount of ammonia desorbed in the 700 ° C region).
  • the ammonia desorption amount in the region of 300 to 450 ° C was 0.24 mmol Zg. At this time, the ammonia desorption amount in the region of 300-450 ° C was 0.96 times the ammonia desorption amount in the region of 100-300 ° C. Desorption of NH desorbing in the region of 400 to 700 ° C
  • Example 3 Similar to the method for preparing a metal element-substituted solid acid in Example 3, except that 25 g of sodium nitrate, 280 g of demineralized water, and 30 g of ZSM-5zelite used in Comparative Example 1 were used as the solid acid catalyst. Obtained 5 zeolite.
  • Polytriethylene ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table 1.
  • the product was taken out into a 100 ml eggplant flask, the solvent was distilled off, dried, pulverized, powdered in a mortar, and then dried at 70 ° C for 3 hours at 2 mmHg.
  • the ammonia desorption amount at 100 to 250 ° C was 0.83 mmolZg, and the total ammonia desorption amount (25 ° C to 700 ° C region) 53%.
  • the ammonia desorption amount at 100-300 ° C is 1. ImmolZg, 69% of the total ammonia desorption amount (25 ° C-700 ° C region), at 100-350 ° C
  • the amount of ammonia desorbed was 1.2 mmolZg, which was 76% of the total amount of ammonia desorbed (range from 25 ° C to 700 ° C).
  • the ammonia desorption amount in the region of 300 to 450 ° C was 0.15 mmolZg. At this time, the ammonia desorption amount in the region of 300 to 450 ° C was 0.14 times the ammonia desorption amount in the region of 100 to 300 ° C.
  • Polytrimethylene ether glycol was obtained in the same manner as in Example 1 except that 5 g of the above catalyst was used as the solid acid catalyst and the reaction temperature was 189 ⁇ 3 ° C. The results are shown in Table-1.
  • Example 7 6 g of the catalyst used in Example 7 was charged with 10 g of demineralized water, and 66 ml of lN-NaOHO. Was added dropwise at room temperature while stirring at room temperature. Washed. After repeating this twice, the same operation was performed using 1.46 ml of ⁇ -NaOH aqueous solution, washed with demineralized water in the same manner, dried, dried under reduced pressure at 16 mmHg at room temperature, and Na-substituted sulfonic acid group Containing silica was obtained.
  • the acid amount by the neutral salt decomposition method was 0.70 mmol Zg. Therefore, the substitution amount of Na + is 0.45 equivalent to the original acid amount.
  • Polytrimethylene was prepared in the same manner as in Example 8, except that 0.26 g of pyridine (0.5 times the theoretical amount of acid) and 10 g of the same ZSM-5 zeolite used in Comparative Example 1 were used as the solid acid catalyst. Ether glycol was obtained. The results are shown in Table 1.
  • Example 5 0.18 g of pyridine (1 equivalent to the acid amount obtained by the neutral salt decomposition method) was used as a solid acid catalyst.
  • Preparation method of metal element-substituted solid acid in Example 5 Using the same Aldrich reagent Nafion NR50 2.5 used in the above, heat the oil bath to 182 ° C and the reaction temperature to 169 ° C ⁇ Polytrimethylene glycol was obtained in the same manner as in Example 7 except that the temperature was adjusted to 3 ° C. and the catalyst was separated by decantation. The results are shown in Table-1.
  • Polytrimethylene ether diol was obtained in the same manner as in Example 7, except that 0.036 g (0.46 mmol) of pyridine and 5 g of the same Nafion powder used in Example 10 were used as the solid acid catalyst.
  • the total amount of metal element and base is 1.1 times equivalent to the original acid amount. The results are shown in Table 1.
  • the zeolite was filtered off and washed with 80 ° C demineralized water. This was repeated twice. After air drying, it was dried in an oven at 120 ° C for 12 hours and then calcined in air at 500 ° C for 2 hours to obtain H + type fluorite.
  • a polytrimethyl compound was prepared in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. Ren ether glycol was obtained. The results are shown in Table 1.
  • Polytriethylene ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table 1.
  • Polytriethylene ether glycol was obtained in the same manner as in Example 1 except that the above catalyst was used as the solid acid catalyst. The results are shown in Table 1.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)

Abstract

Procédé servant à produire avec un rendement de production élevé et avec une sélectivité élevée un polyéther de polyol qui a une coloration réduite grâce à la condensation par déshydratation d'un polyol. Dans la production d'un polyéther de polyol grâce à la condensation par déshydratation d'un polyol, on utilise un catalyseur acide solide satisfaisant à au moins un des critères (1) à (3) suivants : (1) la fonction d'acidité H0 telle que mesurée par la méthode d'adsorption de l'indicateur de Hammet est supérieure à -3 ; (2) dans l'analyse de désorption de l'ammoniac programmée en température (TPD), la quantité d'ammoniac désorbée sur la plage de 100-350°C correspond à au moins 60 % de la quantité d'ammoniac désorbée sur la plage totale du test (plage de 25-700°C) ; et (3) dans une analyse thermogravimétrique (TG), la quantité d'eau désorbée sur la plage 32-250°C est supérieure ou égale à 3 % en poids sur la base du poids de base.
PCT/JP2005/011980 2004-06-29 2005-06-29 Procédé servant à produre un polyéther de polyol WO2006001482A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006121111A1 (fr) * 2005-05-13 2006-11-16 Mitsubishi Chemical Corporation Procede de fabrication de polyether polyol
WO2007052697A1 (fr) * 2005-11-02 2007-05-10 Mitsubishi Chemical Corporation Polyalkylene ether glycol et son procede de fabrication
WO2007083519A1 (fr) * 2006-01-20 2007-07-26 Mitsubishi Chemical Corporation Méthode de production de polyéther-polyol
WO2008118495A1 (fr) * 2007-03-27 2008-10-02 E. I. Du Pont De Nemours And Company Polytriméthylène éther glycol plus clair obtenu au moyen de métaux à valence zéro
CN111499826A (zh) * 2020-04-08 2020-08-07 上海抚佳精细化工有限公司 一种热塑性聚氨酯弹性体及其制备方法

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JPS60156630A (ja) * 1983-12-21 1985-08-16 ヘキスト・アクチエンゲゼルシヤフト ポリグリセリンの製法
JPS61123630A (ja) * 1984-11-21 1986-06-11 Asahi Chem Ind Co Ltd ポリアルキレンエ−テルポリオ−ルの製造法
JPH01125338A (ja) * 1987-11-10 1989-05-17 Nippon Oil & Fats Co Ltd グリセリン縮合物の製造法
JPH06503113A (ja) * 1990-11-27 1994-04-07 コモンウェルス・サイエンティフィック・アンド・インダストリアル・リサーチ・オーガナイゼーション ポリ（アルキレンオキシド）類
JP2003517071A (ja) * 1999-12-17 2003-05-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリトリメチレンエーテルグリコールおよびそのコポリマーの生成
JP2003517082A (ja) * 1999-12-17 2003-05-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリトリメチレンエーテルグリコールの調製のための連続的な方法
WO2004048440A1 (fr) * 2002-11-22 2004-06-10 Mitsubishi Chemical Corporation Procede permettant de produire du polyol de polyether

Patent Citations (7)

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Publication number Priority date Publication date Assignee Title
JPS60156630A (ja) * 1983-12-21 1985-08-16 ヘキスト・アクチエンゲゼルシヤフト ポリグリセリンの製法
JPS61123630A (ja) * 1984-11-21 1986-06-11 Asahi Chem Ind Co Ltd ポリアルキレンエ−テルポリオ−ルの製造法
JPH01125338A (ja) * 1987-11-10 1989-05-17 Nippon Oil & Fats Co Ltd グリセリン縮合物の製造法
JPH06503113A (ja) * 1990-11-27 1994-04-07 コモンウェルス・サイエンティフィック・アンド・インダストリアル・リサーチ・オーガナイゼーション ポリ（アルキレンオキシド）類
JP2003517071A (ja) * 1999-12-17 2003-05-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリトリメチレンエーテルグリコールおよびそのコポリマーの生成
JP2003517082A (ja) * 1999-12-17 2003-05-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリトリメチレンエーテルグリコールの調製のための連続的な方法
WO2004048440A1 (fr) * 2002-11-22 2004-06-10 Mitsubishi Chemical Corporation Procede permettant de produire du polyol de polyether

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006121111A1 (fr) * 2005-05-13 2006-11-16 Mitsubishi Chemical Corporation Procede de fabrication de polyether polyol
WO2007052697A1 (fr) * 2005-11-02 2007-05-10 Mitsubishi Chemical Corporation Polyalkylene ether glycol et son procede de fabrication
WO2007083519A1 (fr) * 2006-01-20 2007-07-26 Mitsubishi Chemical Corporation Méthode de production de polyéther-polyol
WO2008118495A1 (fr) * 2007-03-27 2008-10-02 E. I. Du Pont De Nemours And Company Polytriméthylène éther glycol plus clair obtenu au moyen de métaux à valence zéro
CN111499826A (zh) * 2020-04-08 2020-08-07 上海抚佳精细化工有限公司 一种热塑性聚氨酯弹性体及其制备方法

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