WO2015151598A1 - アルキレンオキシド重合体の製造方法 - Google Patents
アルキレンオキシド重合体の製造方法 Download PDFInfo
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- WO2015151598A1 WO2015151598A1 PCT/JP2015/053777 JP2015053777W WO2015151598A1 WO 2015151598 A1 WO2015151598 A1 WO 2015151598A1 JP 2015053777 W JP2015053777 W JP 2015053777W WO 2015151598 A1 WO2015151598 A1 WO 2015151598A1
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- alkylene oxide
- zinc
- zinc catalyst
- times equivalent
- monohydric alcohol
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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
- C08G65/02—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
- C08G65/04—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
-
- 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
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
Definitions
- the present invention relates to a method for producing an alkylene oxide polymer. More specifically, the present invention relates to a method for producing an alkylene oxide polymer capable of producing an alkylene oxide polymer having a high degree of polymerization with good industrial reproducibility.
- Patent Document 4 specifies a product obtained by reacting an organic zinc compound, an aliphatic polyhydric alcohol and a monohydric alcohol at a specific equivalent ratio. It has been proposed to use a polymer that has been heat-treated in the above temperature range as a polymerization catalyst.
- the main object of the present invention is to provide a method for producing an alkylene oxide polymer capable of producing an alkylene oxide polymer having a high degree of polymerization with good industrial reproducibility.
- the present inventor has intensively studied to solve the above problems. As a result, even if the catalyst is produced under the same conditions by the method disclosed in Patent Document 4, if the removal of unreacted monohydric alcohol by heat treatment is not uniform, the catalyst is removed by the remaining monohydric alcohol. It has been clarified that the activity changes and the polymerization time may vary.
- the zinc catalyst contains the organic zinc compound, A monohydric alcohol obtained by reacting a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organozinc compound, and in the polymerization reaction system It has been found that an alkylene oxide polymer having a high degree of polymerization can be produced industrially with high reproducibility by conducting a polymerization reaction under the condition that the amount of alcohol is 0.01 times equivalent or less with respect to the organozinc compound. It was. The present invention has been completed by further studies based on these findings.
- Item 1 A method for producing an alkylene oxide polymer by polymerizing an alkylene oxide in an inert hydrocarbon solvent in the presence of a zinc catalyst,
- the zinc catalyst is obtained by reacting an organic zinc compound with a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organic zinc compound.
- the manufacturing method of the alkylene oxide polymer which performs the said polymerization reaction on the conditions from which the quantity of the monohydric alcohol in the said polymerization reaction system becomes 0.01 times equivalent or less with respect to the said organic zinc compound.
- a method for producing an alkylene oxide polymer by polymerizing an alkylene oxide in an inert hydrocarbon solvent in the presence of a zinc catalyst A step of reacting an organic zinc compound with a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organozinc compound to prepare the reaction solution; , A step of distilling the reaction solution at a temperature of 100 ° C.
- the method for producing an alkylene oxide polymer according to any one of Items 1 to 4, wherein the aliphatic polyhydric alcohol is an aliphatic polyhydric alcohol having 2 or more carbon atoms and 2 or more hydroxyl groups in the molecule.
- Item 6 A method for producing a zinc catalyst used in a polymerization reaction of an alkylene oxide, A reaction step of reacting an organic zinc compound with a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organozinc compound; A step of distilling the reaction solution obtained in the reaction step under a normal pressure at a temperature of 100 ° C.
- a method for producing a zinc catalyst Item 7.
- a zinc catalyst used in a polymerization reaction of an alkylene oxide After reacting an organozinc compound with a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organozinc compound, the reaction solution obtained is A zinc catalyst distilled under normal pressure at a temperature of 100 ° C. or less, wherein the amount of the monohydric alcohol is 0.01 times equivalent or less with respect to the organozinc compound.
- an alkylene oxide polymer having a high degree of polymerization can be produced industrially with good reproducibility.
- the process for producing an alkylene oxide polymer of the present invention is a process for producing an alkylene oxide polymer by polymerizing an alkylene oxide in an inert hydrocarbon solvent in the presence of a zinc catalyst.
- the zinc catalyst is obtained by reacting an organic zinc compound with a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organic zinc compound. And the polymerization reaction is carried out under the condition that the amount of the monohydric alcohol in the polymerization reaction system is 0.01 times equivalent or less with respect to the organic zinc compound.
- the alkylene oxide to be subjected to the polymerization reaction as a raw material is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, epichlorohydrin and the like. It is done.
- alkylene oxides ethylene oxide, propylene oxide, and the like are preferably used because the obtained alkylene oxide polymer has high solubility in water.
- These alkylene oxides may be used alone or in combination of two or more.
- a polymer using an alkylene oxide alone is a homopolymer of the alkylene oxide, and a polymer using a combination of two or more alkylene oxides is a copolymer of these alkylene oxides.
- the alkylene oxide polymer produced by the production method of the present invention may be a block copolymer or a random copolymer.
- the inert hydrocarbon solvent used for the polymerization reaction is not particularly limited, but is preferably an aliphatic hydrocarbon such as n-pentane, n-hexane, n-heptane, or cyclohexane; an aromatic such as benzene, toluene, or xylene.
- a hydrocarbon etc. are mentioned.
- n-hexane, n-heptane, and the like are more preferably used because they are easily available industrially. These solvents may be used alone or in combination of two or more.
- the amount of the inert hydrocarbon solvent used in the polymerization reaction is not particularly limited, but from the viewpoint of efficiently proceeding the polymerization reaction, from the viewpoint of suppressing the product alkylene oxide polymer from becoming a lump,
- the amount is preferably 200 to 10000 parts by mass, more preferably 300 to 1000 parts by mass, and still more preferably 400 to 600 parts by mass with respect to 100 parts by mass of the alkylene oxide.
- the zinc catalyst used for the polymerization reaction is composed of an organic zinc compound, a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organic zinc compound. It is obtained by reacting. As described later, in the present invention, after preparing such a reaction solution, the amount of the monohydric alcohol is reduced by distilling the unreacted monohydric alcohol at a temperature of 100 ° C. or less under normal pressure. A zinc catalyst having a 0.01-fold equivalent or less with respect to the organic zinc compound is obtained, and this can be used for a polymerization reaction with the zinc catalyst.
- the amount of the monohydric alcohol in the polymerization reaction system is 0.01 times equivalent or less with respect to the organic zinc compound.
- the polymerization reaction by carrying out the polymerization reaction under such conditions, it becomes possible to produce an alkylene oxide polymer having a high degree of polymerization with good industrial reproducibility.
- the organozinc compound used for the preparation of the zinc catalyst is a compound represented by the general formula: ZnR 2 .
- each R independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a cycloalkyl group having 4 to 6 carbon atoms, or the like.
- Specific examples of the organic zinc compound include dialkyl zinc such as dimethyl zinc, diethyl zinc, di-n-propyl zinc and dibutyl zinc; diphenyl zinc and dicyclobutyl zinc. Among these, dialkyl zinc is preferable and diethyl zinc is particularly preferable.
- the monohydric alcohol used for the preparation of the zinc catalyst is an alcohol having one hydroxyl group in the molecule and no other active hydrogen.
- monohydric alcohols include primary alcohols such as methanol, ethanol, 1-propanol and 1-butanol; secondary alcohols such as 2-propanol and 2-butanol; and tertiary alcohols such as t-butanol. Grade alcohol and the like.
- aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and 2-propanol are preferably used. These monohydric alcohols may be used alone or in combination of two or more.
- the upper limit of the amount of monohydric alcohol used is such that the unreacted monohydric alcohol is removed by distillation described later, and the amount of unreacted monohydric alcohol is 0. From the viewpoint of performing a polymerization reaction with high reproducibility under the condition of 01 times equivalent or less, it is necessary to make it 12 times equivalent or less with respect to the organic zinc compound.
- As an upper limit of the usage-amount of monohydric alcohol Preferably it is 10 times equivalent or less, More preferably, 8 times equivalent or less is mentioned.
- the lower limit of the amount of monohydric alcohol used is preferably 1 equivalent or more, more preferably 2 equivalents or more, more preferably 3 with respect to the organic zinc compound, from the viewpoint of maintaining the activity of the resulting zinc catalyst. More than a double equivalent.
- a preferable range of the amount of the monohydric alcohol used is preferably 1 to 12 times equivalent, more preferably 2 to 10 times equivalent, still more preferably 3 to 8 times equivalent to the organozinc compound.
- the aliphatic polyhydric alcohol used for the preparation of the zinc catalyst is an aliphatic polyhydric alcohol having 2 or more carbon atoms and 2 or more hydroxyl groups in the molecule.
- Specific examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and 1,5-pentane. Examples thereof include diol, 2,3,4-pentanetriol, 1,6-hexanediol, glycerin, pentaerythritol and the like.
- an aliphatic polyhydric alcohol having 4 carbon atoms is preferable, and specifically, 1,3-butanediol and 1,4-butanediol are preferable. Used.
- the upper limit of the amount of the aliphatic polyhydric alcohol used is that for the organic zinc compound from the viewpoint of preventing the formation of an alkylene oxide polymer lump when the alkylene oxide polymer is produced using the obtained zinc catalyst. 0.2 to 1.1 equivalents. A preferable range of the amount of the aliphatic polyhydric alcohol used is 0.3 to 1.0 equivalents relative to the organozinc compound.
- reaction solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene.
- the solvent used for the preparation of the zinc catalyst and the inert hydrocarbon solvent used for the polymerization reaction of the alkylene oxide should be the same. Is preferred.
- the amount of the solvent used is preferably 200 to 1500 parts by weight, more preferably 300 to 1200 parts, based on 100 parts by weight of the organic zinc compound, from the economical viewpoint and from the viewpoint of controlling the heat of reaction.
- Part by mass more preferably 400 to 1000 parts by mass can be mentioned.
- the zinc catalyst when preparing the zinc catalyst, when reacting an organic zinc compound, a monohydric alcohol, and an aliphatic polyhydric alcohol, nitrogen, argon, helium or the like is used from the viewpoint of maintaining the activity of the resulting zinc catalyst. It is preferable to carry out in an active gas atmosphere.
- the method of reacting the organic zinc compound, the monohydric alcohol, and the aliphatic polyhydric alcohol is not particularly limited.
- the amount of the first monohydric alcohol to be reacted is preferably 0.2 times equivalent or more, more preferably 0.4 times equivalent to the organozinc compound. The above is mentioned.
- the amount of the first aliphatic polyhydric alcohol to be reacted is preferably 0.1 times equivalent or more, more preferably 0.2 times the amount of the organic zinc compound. More than a double equivalent.
- the reaction solution prepared by the method as described above is distilled under normal pressure at a temperature of 100 ° C. or less, and the amount of monohydric alcohol in the reaction solution is reduced to the organozinc compound.
- a zinc catalyst in which the amount of monohydric alcohol is 0.01 times equivalent or less with respect to the organozinc compound is obtained by removing it until it becomes 0.01 times equivalent or less.
- an alkylene oxide polymer having a high degree of polymerization can be industrially produced with good reproducibility.
- the upper limit of the temperature when the reaction solution is distilled the number of active sites of the obtained zinc catalyst is maintained, and in order to maintain the activity, it is preferably 100 ° C. or lower under normal pressure. More preferably, the upper limit of the distillation temperature is 90 ° C.
- the lower limit of the distillation temperature is preferably 70 ° C. .
- the range of the distillation temperature is preferably 70 to 90 ° C. In the present invention, the distillation temperature is the temperature of the heating medium heating the reaction vessel.
- count of performing distillation From a viewpoint which removes unreacted monohydric alcohol and aliphatic polyhydric alcohol fully outside a system, and prevents the activity fall and dispersion
- the amount of the solvent to be added is not particularly limited, but is preferably 400 to 1000 parts by mass with respect to 100 parts by mass of the organozinc compound from the purpose of distillation and economical viewpoint.
- the zinc catalyst may be further heat-treated.
- the upper limit of the heat treatment temperature is preferably 200 ° C. or less, more preferably 150 ° C. or less, from the viewpoint of maintaining the activity of the obtained zinc catalyst.
- the lower limit of the heat treatment temperature is preferably 100 ° C. or higher from the viewpoint of sufficiently removing unreacted monohydric alcohol and aliphatic polyhydric alcohol out of the system and suppressing the decrease in activity and variation of the zinc catalyst. More preferably, 120 degreeC or more is mentioned.
- the range of the heat treatment temperature is preferably 100 to 200 ° C, more preferably 120 ° C to 150 ° C.
- heat processing temperature is the temperature of the heating medium which is heating the reaction container.
- the time required for the heat treatment varies depending on the heating temperature, but is appropriately determined in the range of usually 5 to 180 minutes, preferably 10 to 60 minutes, from the viewpoint of suppressing the decrease in activity and variation in activity of the obtained zinc catalyst.
- the amount of monohydric alcohol in the polymerization reaction system is 0.01 times equivalent or less with respect to the organozinc compound. That is, it is necessary that the amount of monohydric alcohol in the zinc catalyst is 0.01 times equivalent or less to the organic zinc compound in the polymerization reaction.
- the amount of monohydric alcohol exceeds 0.01 times equivalent to the organozinc compound, the activity of the zinc catalyst varies, and as a result, the polymerization time of the alkylene oxide can vary, and the performance of the resulting alkylene oxide ( In particular, the viscosity can vary.
- the amount of monohydric alcohol in the zinc catalyst is a value obtained by the measurement method described later.
- the zinc catalyst prepared as described above may be used as it is for the polymerization reaction of alkylene oxide, or may be used by appropriately adjusting the concentration by adjusting the amount of the solvent.
- concentration can be adjusted, for example, by removing or adding the solvent in the above distillation or the like.
- the method for polymerizing the alkylene oxide in an inert hydrocarbon solvent in the presence of a zinc catalyst is not particularly limited.
- the above-mentioned inert hydrocarbon solvent and zinc catalyst are added to a polymerization reaction vessel, and further alkylene is added.
- a method of polymerizing in an inert gas atmosphere by adding an oxide can be mentioned.
- the polymerization reaction is preferably performed while stirring or stirring from the viewpoint of smoothly performing the polymerization reaction.
- the amount of the zinc catalyst used in the polymerization reaction is not particularly limited, but is preferably 0.01 on the basis of the zinc atom in the zinc catalyst with respect to the number of moles of alkylene oxide, from the viewpoint of efficient polymerization reaction.
- the range is ⁇ 1 mol%, more preferably 0.02 to 0.8 mol%.
- the temperature of the polymerization reaction can be arbitrarily set depending on the reaction conditions such as the type and concentration of the alkylene oxide and the concentration of the zinc catalyst, but is usually 5 to 100 ° C., preferably 20 to 50 ° C.
- the pressure in the polymerization reaction is not particularly limited, and examples thereof include 0.0 MPa to 1.0 MPa, preferably 0.01 MPa to 0.5 MPa.
- the end point of the polymerization reaction for example, the end point of the reaction can be the time when the internal pressure in the polymerization system does not change continuously for 15 minutes.
- an alkylene oxide polymer is obtained by drying and the like.
- the obtained alkylene oxide polymer is usually a fine granular material without being agglomerated, and has a viscosity of 300 mPa.s in the measurement method described later. More than s alkylene oxide polymers can be obtained with good reproducibility.
- the polymerization reaction is carried out under the condition that the amount of monohydric alcohol in the polymerization reaction system is 0.01 times equivalent or less with respect to the organic zinc compound.
- the details of the mechanism by which an alkylene oxide polymer having a high degree of polymerization can be produced industrially with good reproducibility are not clear, but can be considered as follows, for example. That is, in general, in the polymerization of alkylene oxide using an organic zinc compound, a mechanism in which alkylene oxide coordinates to zinc and sequentially undergoes ring-opening addition can be considered.
- the amount of unreacted monohydric alcohol present in the polymerization reaction is extremely small, which improves and stabilizes the catalytic activity of the zinc catalyst.
- the alkylene having a high degree of polymerization is obtained. It is considered that the oxide polymer is produced with good reproducibility.
- the alkylene oxide polymer produced by the production method of the present invention is a useful polymer for various uses.
- the ethylene oxide polymer can be used as a useful water-soluble polymer in various fields such as a papermaking dispersant, a flocculant, a water-soluble film, a water-soluble fiber, a printing paste, and a plasticizer.
- the production of the alkylene oxide polymer can be carried out with the above zinc catalyst.
- the zinc catalyst is obtained after reacting an organozinc compound with a monohydric alcohol of 12 times equivalent or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 times equivalent to the organozinc compound.
- the reaction solution was distilled under normal pressure at a temperature of 100 ° C. or less, and the amount of monohydric alcohol was 0.01 times equivalent or less with respect to the organic zinc compound.
- the said zinc catalyst can be manufactured according to the following processes.
- Reaction step of reacting an organozinc compound with a monohydric alcohol of 12 equivalents or less and an aliphatic polyhydric alcohol of 0.2 to 1.1 equivalents with respect to the organozinc compound Reaction solution obtained in the reaction step Is distilled at a temperature of 100 ° C. or less under normal pressure to make the amount of monohydric alcohol 0.01 times equivalent or less with respect to the organic zinc compound
- the alkylene oxide used for polymerization, the organic zinc compound used for producing the zinc catalyst, the monohydric alcohol, the aliphatic polyhydric alcohol, the reaction conditions, and the like are as described above.
- an alkylene oxide polymer having a high degree of polymerization can be produced industrially with good reproducibility.
- B-type rotational viscometer manufactured by TOKIMEC, rotor number 2, rotational speed 12 rpm, 3 minutes, 25 ° C.
- Asked if a viscosity is 300 mPa * s or more, it can be judged that it is an alkylene oxide polymer with a high degree of polymerization.
- the amount of monohydric alcohol was measured using a gas chromatography (GC-2014, manufactured by Shimadzu Corporation, hereinafter referred to as GC) at a vaporization temperature of 200 ° C. and a used column Thermon 1000 (length: 3). Meter), column temperature 100 ° C., detector temperature 200 ° C., and the concentration was calculated from the peak area. The amount of monohydric alcohol was calculated from a calibration curve prepared in advance.
- GC-2014 gas chromatography
- Example 1-1 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane, diethyl zinc (Et 2 Zn) 9.90 g was added, and while stirring at an inner peripheral temperature of 20 ° C.
- Et 2 Zn diethyl zinc
- the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc.
- n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0033 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, 0.975 g of zinc catalyst obtained above (in terms of zinc: 0.0004 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered out and dried at 40 ° C. under reduced pressure to obtain 81.0 g of polyethylene oxide.
- the polymerization time was 6 hours and the yield was 100% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 855 mPa.s. s.
- Example 1-2 A zinc catalyst was produced in the same manner as in Example 1-1 to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc.
- the amount of ethyl alcohol was 0.0038 times equivalent to the organozinc compound.
- 81 g (1.84 mol) of ethylene oxide was polymerized using the above zinc catalyst. As a result, 79.5 g of polyethylene oxide was obtained.
- the polymerization time was 6 hours and the yield was 98% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 825 mPa.s. s and reproducibility was good.
- Example 1-3 A zinc catalyst was produced in the same manner as in Example 1-1 to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0047 equivalents to the organozinc compound.
- 81 g (1.84 mol) of ethylene oxide was polymerized using the above zinc catalyst, resulting in 80.7 g of polyethylene oxide. The polymerization time was 6 hours and 45 minutes, and the yield was 100% by mass.
- the viscosity of the obtained 0.5% by mass aqueous solution of polyethylene oxide was 865 mPa.s. s and reproducibility was good.
- Example 2 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and the first stage was performed while stirring at an inner peripheral temperature of 20 ° C. at a tip peripheral speed of 0.97 m / sec (stirring rotation speed: 350 rpm).
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. After distillation twice, the mixture was transferred to a pressure vessel sufficiently purged with nitrogen, sealed, and heat-treated at an oil bath temperature of 130 ° C. for 15 minutes. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0093 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, 0.975 g of zinc catalyst obtained above (in terms of zinc: 0.0004 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered off and dried at 40 ° C. under reduced pressure to obtain 78.6 g of polyethylene oxide.
- the polymerization time was 6 hours and 45 minutes, and the yield was 97% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 820 mPa.s. s.
- Example 3 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and the first stage was performed while stirring at an inner peripheral temperature of 20 ° C. at a tip peripheral speed of 0.97 m / sec (stirring rotation speed: 350 rpm).
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. This operation was performed once again, and distillation was performed a total of 3 times. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0013 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, and 3.38 g of zinc catalyst obtained above (in terms of zinc: 0.0013 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered out and dried at 40 ° C. under reduced pressure to obtain 80.9 g of polyethylene oxide.
- the polymerization time was 4 hours and 15 minutes, and the yield was 100% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 810 mPa.s. s.
- Example 4 In the production of the zinc catalyst of Example 3, a zinc catalyst was produced in the same manner as in Example 3 except that all distillation temperatures were changed from 80 ° C. to 70 ° C., and 297 g of a zinc catalyst containing 1.8% by mass of zinc was added. Obtained. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0058 times equivalent to the organozinc compound. In the same manner as in Example 3, 81 g (1.84 mol) of ethylene oxide was polymerized using the zinc catalyst. As a result, 77.9 g of an alkylene oxide polymer was obtained. The polymerization time was 4 hours and 30 minutes, and the yield was 96% by mass. The viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 595 mPa.s. s.
- Example 5 In the production of the zinc catalyst of Example 3, a zinc catalyst was produced in the same manner as in Example 3 except that all distillation temperatures were changed from 80 ° C. to 100 ° C., and 297 g of zinc catalyst containing 1.8% by mass of zinc was added. Obtained. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.001 times equivalent to the organozinc compound. In the same manner as in Example 3, 81 g (1.84 mol) of ethylene oxide was polymerized using the above zinc catalyst. As a result, 80.2 g of an alkylene oxide polymer was obtained. The polymerization time was 5 hours and the yield was 99% by mass. The viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 720 mPa.s. s.
- Example 6 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and the first stage was performed while stirring at an inner peripheral temperature of 20 ° C. at a tip peripheral speed of 0.97 m / sec (stirring rotation speed: 350 rpm).
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. This operation was performed once again, and distillation was performed a total of 3 times. After distillation three times, the mixture was transferred to a pressure vessel sufficiently purged with nitrogen, sealed, and heat-treated at an oil bath temperature of 130 ° C. for 15 minutes. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of isopropyl alcohol was 0.0001 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, 0.975 g of zinc catalyst obtained above (in terms of zinc: 0.0004 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered out and dried at 40 ° C. under reduced pressure to obtain 75.7 g of polyethylene oxide.
- the polymerization time was 6 hours and 45 minutes, and the yield was 93% by mass.
- the viscosity of the obtained 0.5% by mass aqueous solution of polyethylene oxide was 575 mPa.s. s.
- Example 7 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and the first stage was performed while stirring at an inner peripheral temperature of 20 ° C. at a tip peripheral speed of 0.97 m / sec (stirring rotation speed: 350 rpm).
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. This operation was performed once again, and distillation was performed a total of 3 times. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0008 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, and 3.38 g of zinc catalyst obtained above (in terms of zinc: 0.0013 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered off and dried at 40 ° C. under reduced pressure to obtain 79.1 g of polyethylene oxide.
- the polymerization time was 5 hours and 30 minutes, and the yield was 98% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 425 mPa.s. s.
- Example 8 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and the mixture was stirred at a tip peripheral speed of 0.97 m / sec (stirring speed: 350 rpm) at an internal temperature of 20 ° C. as a first step.
- the reaction was carried out while dropwise adding 11.03 g (0.240 mol) of ethyl alcohol at 0.2 g / min.
- a mixture of 2.16 g (0.30 mol) of 1,4-butanediol and 26.54 g (0.576 mol) of ethyl alcohol was added to a reaction solution cooled to an internal temperature of 10 ° C. by 0.2 g.
- the temperature in the flask was raised to 30 ° C. for 1 hour, and then the temperature was raised to 50 ° C. for 1 hour. Then, it heated at the oil bath temperature of 80 degreeC, and removed the unreacted component by distillation.
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. This operation was performed once again, and distillation was performed a total of 3 times. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0048 equivalents with respect to the organic zinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, and 3.38 g of zinc catalyst obtained above (in terms of zinc: 0.0013 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered off and dried at 40 ° C. under reduced pressure to obtain 79.4 g of polyethylene oxide.
- the polymerization time was 3 hours and the yield was 98% by mass.
- the viscosity of the obtained 0.5% by mass aqueous solution of polyethylene oxide is 700 mPa.s. s.
- Example 9 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and the first stage was performed while stirring at an inner peripheral temperature of 20 ° C. at a tip peripheral speed of 0.97 m / sec (stirring rotation speed: 350 rpm).
- 1,4-butanediol 1.45 g (0.016 mol) was added dropwise at 0.2 g / min.
- a mixture of 5.04 g (0.056 mol) of 1,4-butanediol and 24.3 g (0.528 mol) of ethyl alcohol was added to a reaction solution cooled to an internal temperature of 10 ° C. by 0.2 g. Added dropwise at a rate of 1 minute.
- the temperature in the flask was raised to 30 ° C. for 1 hour, and then the temperature was raised to 50 ° C. for 1 hour. Then, it heated at the oil bath temperature of 80 degreeC, and removed the unreacted component by distillation.
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. This operation was performed once again, and distillation was performed a total of 3 times. After distillation three times, the mixture was transferred to a pressure vessel sufficiently purged with nitrogen, sealed, and heat-treated at an oil bath temperature of 130 ° C. for 15 minutes. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0007 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was placed in a pressure-resistant container sufficiently substituted with nitrogen, and 3.38 g of zinc catalyst obtained above (in terms of zinc: 0.0013 mol) was uniformly dispersed, and 81.0 g (1.84 mol) of ethylene oxide was obtained. ) was added and sealed, and polymerization was carried out in a constant temperature bath at 40 ° C. while stirring.
- the white product was filtered out and dried at 40 ° C. under reduced pressure to obtain 80.8 g of polyethylene oxide.
- the polymerization time was 4 hours and 30 minutes, and the yield was 100% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 815 mPa.s. s.
- Example 10 [Production of zinc catalyst] A round bottom flask having an inner diameter of 80 mm and a capacity of 500 mL equipped with a cooler, a dropping funnel, a nitrogen gas introduction tube, and a stirring blade having four (45 degree inclined) paddle blades with a blade diameter of 53 mm as a stirrer was prepared. In a flask purged with nitrogen, 87.1 g of n-hexane and 9.90 g of diethylzinc were placed, and while stirring at an inner peripheral temperature of 10 ° C.
- 1,4 -A mixed liquid of 6.49 g (0.072 mol) of butanediol and 24.3 g (0.528 mol) of ethyl alcohol was added dropwise at 0.2 g / min.
- the temperature in the flask was raised to 30 ° C. for 1 hour, and then the temperature was raised to 50 ° C. for 1 hour. Then, it heated at the oil bath temperature of 80 degreeC, and removed the unreacted component by distillation.
- the mixture was allowed to cool to room temperature, 52.4 g of n-hexane was added, and the oil was heated at an oil bath temperature of 80 ° C. to perform a second distillation. This operation was performed once again, and distillation was performed a total of 3 times. After cooling, the mixture was diluted with 264 g of n-hexane to obtain 297 g of a zinc catalyst containing 1.8% by mass of zinc. When n-hexane in the supernatant of the zinc catalyst was measured by GC, the amount of ethyl alcohol was 0.0038 times equivalent to the organozinc compound.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, and 3.38 g of zinc catalyst obtained above (in terms of zinc: 0.0013 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered off and dried at 40 ° C. under reduced pressure to obtain 76.3 g of polyethylene oxide.
- the polymerization time was 7 hours and the yield was 94% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 530 mPa.s. s.
- a pressure-resistant reaction vessel having an inner diameter of 94 mm and a volume of 1 L, equipped with a dropping funnel, a nitrogen gas introduction pipe, and a stirring blade having an impeller paddle blade with a blade diameter of 47 mm as a stirrer was prepared.
- 340 g of n-hexane was put into a pressure-resistant container sufficiently substituted with nitrogen, 0.975 g of zinc catalyst obtained above (in terms of zinc: 0.0004 mol) was uniformly dispersed, and 81 g (1.84 mol) of ethylene oxide was dispersed.
- the white product was filtered out and dried at 40 ° C. under reduced pressure to obtain 80.2 g of polyethylene oxide.
- the polymerization time was 7 hours and 30 minutes, and the yield was 99% by mass.
- the viscosity of the obtained 0.5% by weight aqueous solution of polyethylene oxide was 825 mPa.s. s.
- 1,4-BDO is not a monohydric alcohol, but is described in the monohydric alcohol column for convenience.
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Abstract
Description
本発明は、このような問題に鑑みなされた発明である。すなわち、本発明は、重合度の高いアルキレンオキシド重合体を、工業的に再現性よく製造することができるアルキレンオキシド重合体の製造方法を提供することを主な目的とする。
項1. アルキレンオキシドを、亜鉛触媒の存在下、不活性炭化水素溶媒中で重合反応させてアルキレンオキシド重合体を製造する方法であって、
前記亜鉛触媒が、有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させて得られるものであり、
前記重合反応系中における一価アルコールの量が、前記有機亜鉛化合物に対して0.01倍当量以下となる条件で前記重合反応を行う、アルキレンオキシド重合体の製造方法。
項2. アルキレンオキシドを、亜鉛触媒の存在下、不活性炭化水素溶媒中で重合反応させてアルキレンオキシド重合体を製造する方法であって、
有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させて、前記反応液を調製する工程と、
前記反応液を、常圧下、温度100℃以下で蒸留し、前記一価アルコールの量を前記有機亜鉛化合物に対して0.01倍当量以下にした亜鉛触媒を調製する工程と、
前記一価アルコールの量が前記有機亜鉛化合物に対して0.01倍当量以下となった前記亜鉛触媒を用いて、前記アルキレンオキシドを重合反応させる工程と、
を備える、アルキレンオキシド重合体の製造方法。
項3. 前記有機亜鉛化合物が、ジアルキル亜鉛である、項1または2に記載のアルキレンオキシド重合体の製造方法。
項4. 前記一価アルコールが、炭素数1~3の脂肪族アルコールである、項1~3のいずれかに記載のアルキレンオキシド重合体の製造方法。
項5. 前記脂肪族多価アルコールが、炭素数が2以上かつ分子中に水酸基を2個以上有する脂肪族多価アルコールである、項1~4のいずれかに記載のアルキレンオキシド重合体の製造方法。
項6. アルキレンオキシドの重合反応に用いられる亜鉛触媒の製造方法であって、
有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させる反応工程と、
前記反応工程で得られた反応液を、常圧下、温度100℃以下で蒸留し、前記一価アルコールの量を前記有機亜鉛化合物に対して0.01倍当量以下にする工程と、
を備える、亜鉛触媒の製造方法。
項7. アルキレンオキシドの重合反応に用いられる亜鉛触媒であって、
有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させた後、得られた反応液を、常圧下、温度100℃以下で蒸留し、前記一価アルコールの量が前記有機亜鉛化合物に対して0.01倍当量以下とされた、亜鉛触媒。
本発明のアルキレンオキシド重合体の製造方法は、アルキレンオキシドを、亜鉛触媒の存在下、不活性炭化水素溶媒中で重合反応させてアルキレンオキシド重合体を製造する方法であって、亜鉛触媒が、有機亜鉛化合物と、有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させて得られるものであり、重合反応系中における一価アルコールの量が、有機亜鉛化合物に対して0.01倍当量以下となる条件で重合反応を行うことを特徴とする。以下、本発明のアルキレンオキシド重合体の製造方法について詳述する。
本発明において、アルキレンオキシド重合体の製造は、上記の亜鉛触媒により行うことができる。当該亜鉛触媒は、有機亜鉛化合物と、当該有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させた後、得られた反応液を、常圧下、温度100℃以下で蒸留し、一価アルコールの量が有機亜鉛化合物に対して0.01倍当量以下とされていることを特徴としている。また、当該亜鉛触媒は、以下の工程により製造することができる。
反応工程で得られた反応液を、常圧下、温度100℃以下で蒸留し、一価アルコールの量を有機亜鉛化合物に対して0.01倍当量以下にする工程
各実施例及び比較例で得られたアルキレンオキシド重合体の性能を、以下の方法により測定、評価した。結果を表1及び表2に示す。
1L容のビーカーにイオン交換水497.5gを入れ、幅80mm、縦25mmの平板で先端周速が1.0m/sの条件で、攪拌しながらアルキレンオキシド重合体2.5gを投入し、攪拌を3時間継続して水溶液を調製した。得られた水溶液を、25℃の恒温槽に30分以上浸し、B型回転粘度計(TOKIMEC社製のB型粘度計、ローター番号2、回転数12rpm、3分、25℃)により水溶液の粘度を求めた。
なお、粘度が300mPa・s以上であれば、重合度の高いアルキレンオキシド重合体であると判断できる。
一価アルコール量の測定は、ガスクロマトグラフィー(GC-2014、島津製作所社製、以下GC)を使用して気化温度200℃、使用カラムThermon1000(長さ:3メートル)、カラム温度100℃、検出器温度200℃の条件にて測定し、ピーク面積から濃度を計算した。一価アルコール量は予め作成しておいた検量線から算出した。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛(Et2Zn)
9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、エチルアルコール(EtOH)11.03g(0.240モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール(1,4-BDO)6.49g(0.072モル)とエチルアルコール13.27g(0.288モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。3度の蒸留後、十分に窒素置換された耐圧容器に移し、密栓して油浴温度130℃で15分間加熱処理を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0033倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒0.975g(亜鉛換算:0.0004モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド81.0gを得た。
重合時間は6時間で、収率は100質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は855mPa.sであった。
実施例1-1と同様にして亜鉛触媒を製造し、亜鉛を1.8質量%含む亜鉛触媒297g得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0038倍当量であった。
実施例1-1と同様にして、上記亜鉛触媒を用いてエチレンオキシド81g(1.84モル)を重合させた結果、ポリエチレンオキシド79.5gを得た。
重合時間は6時間で、収率は98質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は825mPa.sであり、再現性は良好であった。
実施例1-1と同様にして亜鉛触媒を製造し、亜鉛を1.8質量%含む亜鉛触媒297g得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0047倍当量であった。
実施例1-1と同様にして、上記亜鉛触媒を用いてエチレンオキシド81g(1.84モル)を重合させた結果、ポリエチレンオキシド80.7gを得た。
重合時間は6時間45分で、収率は100質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は865mPa.sであり、再現性は良好であった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、エチルアルコール11.03g(0.240モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール6.49g(0.072モル)とエチルアルコール13.27g(0.288モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。2度の蒸留後、十分に窒素置換された耐圧容器に移し、密栓して油浴温度130℃で15分間加熱処理を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0093倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒0.975g(亜鉛換算:0.0004モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド78.6gを得た。
重合時間は6時間45分、収率は97質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は820mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、エチルアルコール1.47g(0.030モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール6.49g(0.072モル)とエチルアルコール13.27g(0.288モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0013倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒3.38g(亜鉛換算:0.0013モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド80.9gを得た。
重合時間は4時間15分、収率は100質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は810mPa.sであった。
実施例3の亜鉛触媒の製造において、全ての蒸留温度を80℃から70℃に変更した以外は実施例3と同様にして亜鉛触媒を製造し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0058倍当量であった。
実施例3と同様にして、上記亜鉛触媒を用いてエチレンオキシド81g(1.84モル)を重合させた結果、アルキレンオキシド重合体77.9gを得た。
重合時間は4時間30分、収率は96質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は595mPa.sであった。
実施例3の亜鉛触媒の製造において、全ての蒸留温度を80℃から100℃に変更した以外は実施例3と同様にして亜鉛触媒を製造し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.001倍当量であった。
実施例3と同様にして、上記亜鉛触媒を用いてエチレンオキシド81g(1.84モル)を重合させた結果、アルキレンオキシド重合体80.2gを得た。
重合時間は5時間、収率は99質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は720mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、イソプロピルアルコール(2-PrOH)14.42g(0.240モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール6.49g(0.072モル)とイソプロピルアルコール17.31g(0.288モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。3度の蒸留後、十分に窒素置換された耐圧容器に移し、密栓して油浴温度130℃で15分間加熱処理を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、イソプロピルアルコール量は有機亜鉛化合物に対して0.0001倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒0.975g(亜鉛換算:0.0004モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド75.7gを得た。
重合時間は6時間45分、収率は93質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は575mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、メチルアルコール1.02g(0.030モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール6.49g(0.072モル)とメチルアルコール(MeOH)9.22g(0.288モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0008倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒3.38g(亜鉛換算:0.0013モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド79.1gを得た。
重合時間は5時間30分、収率は98質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は425mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1gジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、エチルアルコール11.03g(0.240モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール2.16g(0.30モル)とエチルアルコール26.54g(0.576モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0048倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒3.38g(亜鉛換算:0.0013モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド79.4gを得た。
重合時間は3時間、収率は98質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は700mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、1,4-ブタンジオール1.45g(0.016モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール5.04g(0.056モル)とエチルアルコール24.3g(0.528モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。3度の蒸留後、十分に窒素置換された耐圧容器に移し、密栓して油浴温度130℃で15分間加熱処理を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0007倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒3.38g(亜鉛換算:0.0013モル)を均一に分散させ、エチレンオキシド81.0g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド80.8gを得た。
重合時間は4時間30分、収率は100質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は815mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン87.1g、ジエチル亜鉛9.90gを入れ、内温10℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら、1,4-ブタンジオール6.49g(0.072モル)とエチルアルコール24.3g(0.528モル)の混合液を、0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度80℃で加熱し、蒸留により未反応成分の除去を行った。蒸留後、室温まで放冷し、n-ヘキサン52.4gを添加し、油浴温度80℃で加熱し2度目の蒸留を行った。この操作を更にもう1度行い、合計3度の蒸留を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0038倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒3.38g(亜鉛換算:0.0013モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド76.3gを得た。
重合時間は7時間、収率は94質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は530mPa.sであった。
〔亜鉛触媒の製造〕
冷却器、滴下ロート、窒素ガス導入管、攪拌機として翼径53mmの4枚の(45度傾斜)パドル翼を有する攪拌翼を備えた、内径80mm、500mL容の丸底フラスコを準備した。
窒素置換されたフラスコ中に、n-ヘキサン55.9g、高沸点脂肪族炭化水素(商品名:日本石油製0号ソルベント)21.2g、ジエチル亜鉛9.90gを入れ、内温20℃において先端周速0.97m/秒(撹拌回転数350rpm)で攪拌しながら第一段階として、エチルアルコール11.03g(0.240モル)を0.2g/分で滴下しながら反応させた。第二段階として、1,4-ブタンジオール6.49g(0.072モル)とエチルアルコール13.27g(0.288モル)の混合液を、内温10℃まで冷却した反応液に0.2g/分で滴下した。滴下終了後、フラスコ内を30℃まで昇温して1時間反応させ、次に、50℃まで昇温して1時間反応させた。その後、油浴温度130℃で15分間、密栓せずに加熱処理を行った。冷却後、n-ヘキサン264gで希釈し、亜鉛を1.8質量%含む亜鉛触媒297gを得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0116倍当量であった。
滴下ロート、窒素ガス導入管、攪拌機として翼径47mmのいかり型パドル翼を有する攪拌翼を備えた、内径94mm、1L容の耐圧反応容器を準備した。
十分に窒素置換された耐圧容器にn-ヘキサン340gを入れ、上記で得られた亜鉛触媒0.975g(亜鉛換算:0.0004モル)を均一に分散させ、エチレンオキシド81g(1.84モル)を加えて密栓し、40℃の恒温槽中で攪拌しながら重合させた。重合終了後、白色生成物を濾過して取り出し、40℃で減圧乾燥してポリエチレンオキシド80.2gを得た。
重合時間は7時間30分、収率は99質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は825mPa.sであった。
比較例1-1と同様にして亜鉛触媒を製造し、亜鉛を1.8質量%含む亜鉛触媒297g得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.0334倍当量であった。
比較例1-1と同様にして、上記亜鉛触媒を用いてエチレンオキシド81g(1.84モル)を重合させた結果、ポリエチレンオキシド79.8gを得た。
重合時間は11時間15分で、収率は99質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は625mPa.sであった。
比較例1-1と同様にして亜鉛触媒を製造し、亜鉛を1.8質量%含む亜鉛触媒297g得た。この亜鉛触媒の上澄みのn-ヘキサンをGCにて測定したところ、エチルアルコール量は有機亜鉛化合物に対して0.00221倍当量であった。
比較例1-1と同様にして、上記亜鉛触媒を用いてエチレンオキシド81g(1.84モル)を重合させた結果、ポリエチレンオキシド78.3gを得た。
重合時間は9時間45分で、収率は97質量%であった。得られたポリエチレンオキシドの0.5質量%の水溶液の粘度は785mPa.sであった。
Claims (7)
- アルキレンオキシドを、亜鉛触媒の存在下、不活性炭化水素溶媒中で重合反応させてアルキレンオキシド重合体を製造する方法であって、
前記亜鉛触媒が、有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させて得られるものであり、
前記重合反応系中における一価アルコールの量が、前記有機亜鉛化合物に対して0.01倍当量以下となる条件で前記重合反応を行う、アルキレンオキシド重合体の製造方法。 - アルキレンオキシドを、亜鉛触媒の存在下、不活性炭化水素溶媒中で重合反応させてアルキレンオキシド重合体を製造する方法であって、
有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させて、反応液を調製する工程と、
前記反応液を、常圧下、温度100℃以下で蒸留し、前記一価アルコールの量を前記有機亜鉛化合物に対して0.01倍当量以下にした亜鉛触媒を調製する工程と、
前記一価アルコールの量が前記有機亜鉛化合物に対して0.01倍当量以下となった前記亜鉛触媒を用いて、前記アルキレンオキシドを重合反応させる工程と、
を備える、アルキレンオキシド重合体の製造方法。 - 前記有機亜鉛化合物が、ジアルキル亜鉛である、請求項1または2に記載のアルキレンオキシド重合体の製造方法。
- 前記一価アルコールが、炭素数1~3の脂肪族アルコールである、請求項1~3のいずれかに記載のアルキレンオキシド重合体の製造方法。
- 前記脂肪族多価アルコールが、炭素数が2以上かつ分子中に水酸基を2個以上有する脂肪族多価アルコールである、請求項1~4のいずれかに記載のアルキレンオキシド重合体の製造方法。
- アルキレンオキシドの重合反応に用いられる亜鉛触媒の製造方法であって、
有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させる反応工程と、
前記反応工程で得られた反応液を、常圧下、温度100℃以下で蒸留し、前記一価アルコールの量を前記有機亜鉛化合物に対して0.01倍当量以下にする工程と、
を備える、亜鉛触媒の製造方法。 - アルキレンオキシドの重合反応に用いられる亜鉛触媒であって、
有機亜鉛化合物と、前記有機亜鉛化合物に対して12倍当量以下の一価アルコール及び0.2~1.1倍当量の脂肪族多価アルコールとを反応させた後、得られた反応液を、常圧下、温度100℃以下で蒸留し、前記一価アルコールの量が前記有機亜鉛化合物に対して0.01倍当量以下とされた、亜鉛触媒。
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WO2012165199A1 (ja) * | 2011-06-03 | 2012-12-06 | 住友精化株式会社 | ポリアルキレンオキシド粒子及びその製造方法 |
WO2012165198A1 (ja) * | 2011-06-03 | 2012-12-06 | 住友精化株式会社 | ポリアルキレンオキシド粒子及びその製造方法 |
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JPH0517566A (ja) * | 1991-07-11 | 1993-01-26 | Sumitomo Seika Chem Co Ltd | アルキレンオキシド重合体の製造方法 |
WO2012165199A1 (ja) * | 2011-06-03 | 2012-12-06 | 住友精化株式会社 | ポリアルキレンオキシド粒子及びその製造方法 |
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