Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/08—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 particularly, it relates to a method for the production of an alkylene oxide polymer by which an alkylene oxide polymer having a high degree of polymerization can be produced industrially and reproducibly.
• Patent Document 4 As a solution to the above-described problems, it is proposed, for example in Patent Document 4, to use as a polymerization catalyst a material prepared by heat-treating within a certain temperature range a product obtained by reacting an organozinc compound with an aliphatic polyhydric alcohol and a monohydric alcohol in a certain equivalent ratio.
• Patent Document 1 JP-B-45-7751
• Patent Document 2 JP-B-53-27319
• Patent Document 3 JP-A-62-232433
• Patent Document 4 JP-A-5-17566
• the present invention is an invention devised in view of such a problem. That is, a main object of the present invention is to provide a method for the production of an alkylene oxide polymer by which an alkylene oxide polymer having a high degree of polymerization can be produced industrially and reproducibly.
• an alkylene oxide polymer having a high degree of polymerization can be produced industrially and reproducibly by a method for the production of an alkylene oxide polymer including making an alkylene oxide undergo a polymerization reaction in the presence of a zinc catalyst in an inert hydrocarbon solvent to produce an alkylene oxide polymer, wherein the zinc catalyst is one prepared by reacting an organozinc compound with a monohydric alcohol in an amount of 12 equivalents or less relative to the organozinc compound and an aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative to the organozinc compound, and the polymerization reaction is performed under such conditions that the amount of the monohydric alcohol in a polymerization reaction system may be 0.01 equivalents or less relative to the organozinc compound.
• the present invention has been accomplished by further repeating studies based on these findings.
• the present invention provides inventions of the following aspects.
• the zinc catalyst is one prepared by reacting an organozinc compound with a monohydric alcohol in an amount of 12 equivalents or less relative to the organozinc compound and an aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative to the organozinc compound, and
• the polymerization reaction is performed under such conditions that the amount of the monohydric alcohol in a system of the polymerization reaction may be 0.01 equivalents or less relative to the organozinc compound.
• reaction step of reacting an organozinc compound with a monohydric alcohol in an amount of 12 equivalents or less relative to the organozinc compound and an aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative to the organozinc compound, and
• an alkylene oxide polymer having a high degree of polymerization can be produced industrially and reproducibly.
• the method for the production of an alkylene oxide polymer of the present invention is a method for the production of an alkylene oxide polymer including making alkylene oxide undergo a polymerization reaction in the presence of a zinc catalyst in an inert hydrocarbon solvent to produce an alkylene oxide polymer, Characterized in that the zinc catalyst is one prepared by reacting an organozinc compound with a monohydric alcohol in an amount of 12 equivalents or less relative to the organozinc compound and an aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative to the organozinc compound, and the polymerization reaction is performed under such conditions that the amount of the monohydric alcohol in a polymerization reaction system may be 0.01 equivalents or less relative to the organozinc compound.
• the method for the production of an alkylene oxide polymer of the present invention is described in detail.
• the alkylene oxide to be subjected to a polymerization reaction as a raw material is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and epichlorohydrin.
• ethylene oxide, propylene oxide, etc. are preferably used in terms of high solubility of a resulting alkylene oxide polymer in water.
• These alkylene oxides may be used individually or two or more of them may be used in combination.
• a polymer prepared using an alkylene oxide singly is a homopolymer of the alkylene oxide, and a polymer prepared using two or more alkylene oxides in combination is a copolymer of these alkylene oxides.
• the alkylene oxide polymer to be produced by the production method of the present invention may be either a block copolymer or a random copolymer.
• the inert hydrocarbon solvent to be subjected to the polymerization reaction is not particularly limited, and preferable examples thereof include aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane, and cyclohexane; and aromatic hydrocarbons, such as benzene, toluene, and xylene.
• aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and cyclohexane
• aromatic hydrocarbons such as benzene, toluene, and xylene.
• n-hexane, n-heptane, and the like are preferably used because they are easily available in the industry. These solvents may be used individually or two or more of them may be used in combination.
• the amount of the inert hydrocarbon solvent to be used in the polymerization reaction is not particularly limited, it is preferably 200 to 10000 parts by mass, more preferably 300 to 1000 parts by mass, even more preferably 400 to 600 parts by mass, relative to 100 parts by mass of the alkylene oxide from the viewpoint of advancing the polymerization reaction efficiently and the viewpoint of inhibiting a product alkylene oxide polymer from forming a mass.
• the zinc catalyst to be used for a polymerization reaction in the present invention is one obtained by reacting an organozinc compound with a monohydric alcohol in an amount of 12 equivalents or less relative to the organozinc compound and an aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative to the organozinc compound.
• a zinc catalyst in which the amount of the monohydric alcohol has been adjusted to 0.01 equivalents or less relative to the organozinc compound can be obtained by preparing such a reaction liquid and then distilling the reaction liquid under normal pressure at a temperature of 100° C. or lower, thereby evaporating unreacted monohydric alcohol, and the product can be used for a polymerization reaction by the zinc catalyst.
• the amount of the monohydric alcohol in the polymerization reaction system is 0.01 equivalents or less relative to the organozinc compound.
• the organozinc compound to be used for the preparation of the zinc catalyst is a compound denoted by the formula: ZnR 2 .
• R each independently may be 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 organozinc compound include dialkylzinc, such as dimethylzinc, diethylzinc, di-n-propyizinc, and dibutylzinc; diphenylzinc, and dicyclobutylzinc. Of these, a dialkylzinc is preferred, and diethyl zinc is particularly preferred.
• the monohydric alcohol to be used for the preparation of the zinc catalyst is an alcohol having one hydroxy group in each molecule thereof and having no other active hydrogen.
• Specific examples of the monohydric alcohol include primary alcohols such as methanol, ethanol, 1-propanol, and 1-butanol; secondary alcohol such as 2-propanol and 2-butanol and tertiary alcohol such as tert-butanol. Of these, a monohydric alcohol having 1 to 3 carbon atoms and having a boiling point under normal pressure of 100° C.
• an aliphatic alcohol having 1 to 3 carbon atoms such as methanol, ethanol and 2-propanol, is preferably used.
• monohydric alcohols may be used individually or two or more of them may be used in combination.
• the upper limit of the use amount of the monohydric alcohol is preferably 10 equivalents or less, more preferably 8 equivalents or less.
• the lower limit of the use amount of the monohydric alcohol is preferably 1 equivalent or more, more preferably 2 equivalents or more, even more preferably 3 equivalents or more, relative to the organozinc compound.
• a preferable range of the use amount of the monohydric alcohol is preferably 1 to 12 equivalents, more preferably 2 to 10 equivalents, even more preferably 3 to 8 equivalents, relative to the organozinc compound.
• the aliphatic polyhydric alcohol to be used for the prep anon of the zinc catalyst is an aliphatic polyhydric alcohol having 2 or more carbon atoms and having 2 or more hydroxy groups in each molecule thereof.
• Specific examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanetriol, 2,3,4-pentanetriol 1,6-hexanediol, glycerol, and pentaerythritol.
• aliphatic polyhydric alcohols having 4 carbon atoms are preferable from the viewpoint of the activity of a zinc catalyst to be obtained, and specifically, 1,3-butanediol and 1,4-butariediol are suitably used.
• the upper limit of the use amount of the aliphatic polyhydric alcohol is required to be 0.2 to 1.1 equivalents relative to the organozinc compound from the viewpoint of preventing the formation of a mass of an alkylene oxide polymer in the production of an alkylene oxide polymer using the resulting zinc catalyst.
• a preferable range of the use amount of the aliphatic polyhydric alcohol may be 0.3 to 1.0 equivalent relative to the organozinc compound.
• reaction solvent in reacting the organozinc compound, the monohydric alcohol, and the aliphatic polyhydric alcohol together from the viewpoint of performing the reaction smoothly.
• the reaction solvent is not particularly limited and examples thereof include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and cyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene.
• the use amount of the solvent may be preferably 200 to 1500 parts by mass, more preferably 300 to 1200 parts by mass, even more preferably 400 to 1000 parts by mass relative to 100 parts by mass of the organozinc compound from an economical point of view and the viewpoint of controlling heat of reaction.
• the reaction When reacting the organozinc compound, the monohydric alcohol, and the aliphatic polyhydric alcohol together in the preparation of the zinc catalyst, it is preferable to perform the reaction in an inert gas atmosphere, such as nitrogen, argon, and helium, from the viewpoint of holding the activity of a zinc catalyst to be obtained.
• an inert gas atmosphere such as nitrogen, argon, and helium
• the method of reacting the organozinc compound, the monohydric alcohol, and the aliphatic polyhydric alcohol together is not particularly limited, and examples thereof include (a) a method in which a solvent and the organozinc compound are charged, then reacted with part of the monohydric alcohol, and subsequently reacted with the remainder of the monohydric alcohol and the aliphatic polyhydric alcohol, (b) a method in which a solvent and the organozinc compound are charged, then reacted with part of the aliphatic polyhydric alcohol, and subsequently reacted with the monohydric alcohol and the remainder of the aliphatic polyhydric alcohol, and (c) a method in which a solvent and the organozinc compound are charged, and then the monohydric alcohol and the aliphatic polyhydric alcohol are reacted simultaneously.
• the amount of the part of the monohydric alcohol to be reacted first may be preferably 0.2 equivalents or more, more preferably 0.4 equivalents or more relative to the organozinc compound.
• the amount of the part of the aliphatic polyhydric alcohol to be reacted first may be preferably 0.1 equivalents or more, more preferably 0.2 equivalents or more relative to the organozinc compound.
• the use of such a zinc catalyst makes it possible to perform a polymerization reaction under such conditions that the amount of the monohydric alcohol in a polymerization reaction system is adjusted to 0.01 equivalents or less relative to the organozinc compound, and an alkylene oxide polymer having a high degree of polymerization can be produced industrially and reproducibly.
• the upper limit of the temperature in distilling the reaction liquid is preferably 100° C. or lower under normal pressure in order to hold the number of active points of a zinc catalyst to be obtained and hold the activity thereof.
• the upper limit of the distillation temperature may more preferably be 90° C.
• the lower limit of the distillation temperature is preferably 70° C. from the viewpoint of fully removing unreacted monohydric alcohol and aliphatic polyhydric alcohol to the outside of the system to prevent deterioration and variation in the activity of a zinc catalyst.
• the range of the distillation temperature may preferably be 70° C. to 90° C.
• the distillation temperature is the temperature of a heating medium that is heating a reaction vessel.
• the number of times of performing distillation is not particularly limited, and it may preferably be twice or more, more preferably three times or more from the viewpoint of fully removing unreacted monohydric alcohol and aliphatic polyhydric alcohol to the outside of the system to prevent deterioration and variation in the activity of a zinc catalyst.
• the addition amount of the solvent is not particularly limited, and it may preferably be 400 to 1000 parts by mass relative to 100 parts by mass of the organozinc compound from the purpose of the distillation and the economical point of view.
• the zinc catalyst may further be heat treated after performing the above-mentioned distillation.
• the upper limit of the heat treatment temperature may preferably be 200° C. or lower, more preferably 150° C. or lower from the viewpoint of holding the activity of a zinc catalyst to be obtained.
• the lower limit of the heat treatment temperature may preferably be 100° C. or higher, more preferably 120° C. or higher from the viewpoint of fully removing unreacted monohydric alcohol and aliphatic polyhydric alcohol to the outside of the system to prevent deterioration and variation in the activity of a zinc catalyst.
• the range of the heat treatment temperature may preferably be 100 to 200° C., more preferably 120 to 150° C. in the present invention, the heat treatment temperature is the temperature of a heating medium that is heating a reaction vessel.
• the time necessary for the heat treatment varies depending on the heating temperature, and it is properly determined usually within a range of 5 to 180 minutes, preferably within a range of 10 to 60 minutes from the viewpoint of preventing deterioration in the activity of a zinc catalyst to be obtained and variation in the activity.
• the amount of the monohydric alcohol in the polymerization reaction system be equal to or less than 0.01 equivalents relative to the above-described organozinc compound. That is, it is necessary to use for the polymerization reaction the zinc catalyst in which the amount of the monohydric alcohol is equal to o less than 0.01 equivalents relative to the organozinc compound.
• the amount of the monohydric alcohol exceeds 0.01 equivalents relative to the organozinc compound, variation in the activity of the zinc catalyst results, leading to variation in the polymerization time of the alkylene oxide and variation in the performance (especially, viscosity) of an alkylene oxide to be obtained.
• the amount of the monohydric alcohol in the zinc catalyst is a value determined by the measuring method described below.
• the zinc catalyst prepared as described above may be used for a polymerization reaction of an alkylene oxide as received and can be used by adjusting its concentration through the adjustment of the amount of a solvent.
• the adjustment of the concentration can be performed, for example, by removing or adding the solvent in the distillation described above or the like.
• the method of making an alkylene oxide undergo a polymerization reaction in the presence of a zinc catalyst in an inert hydrocarbon solvent is not particularly limited, and it may be, for example, a method in which the inert hydrocarbon solvent and the zinc catalyst are added to a polymerization reaction vessel, the alkylene oxide is further added, and they are polymerized in an inert gas atmosphere. It is preferable to perform the polymerization reaction under stirring or shaking from the viewpoint of performing the polymerization reaction smoothly.
• the amount of the zinc catalyst o be used in the polymerization reaction is not particularly limited, it may preferably be 0.01 to 1 mol %, more preferably 0.02 to 0.8 mol % based on the zinc atoms in the zinc catalyst relative to the number of moles of the alkylene oxide from the viewpoint of efficient advance of the polymerization reaction.
• the temperature of the polymerization reaction can arbitrarily be set according to reaction conditions such as the type d the concentration of the alkylene oxide and the concentration of the zinc catalyst, and it is usually 5 to 100° C., preferably 20 to 50° C.
• the pressure in the polymerization reaction is not particularly limited, and it may, for example, be 0.0 MPa to 1.0 MPa, preferably 0.01 MPa to 0.5 MPa.
• the endpoint of the polymerization reaction for example, the time when the internal pressure in the polymerization system has come to no longer change continuously for 15 minutes can be regarded as the endpoint of the reaction.
• An alkylene oxide polymer is obtained by performing drying, etc. after the completion of the polymerization reaction.
• the thus-obtained alkylene oxide polymer is usually in the form of line particulates which do not agglomerate, and an alkylene oxide polymer having a viscosity of 300 mPa ⁇ s or more as measured by the measurement method described below can be obtained reproducibly.
• the mechanism of it becoming possible to produce an alkylene oxide polymer having a high degree of polymerization industrially and reproducibly in the present invention by performing a polymerization reaction using the zinc catalyst prepared as described above under such conditions that the amount of a monohydric alcohol in the polymerization reaction system is adjusted to 0.01 equivalents or less relative to the organozinc compound is not clear in detail, the mechanism can, for example, be considered as follows: That is, generally, there can be considered a mechanism in which in polymerization of an alkylene oxide using an organozinc compound, alkylene oxide molecules coordinate to zinc and undergo ring-opening addition successively.
• the alkylene oxide polymer to be produced by le production method of the present invention is a useful polymer to be used for a variety of applications.
• an ethylene oxide polymer can be used as a useful, water-soluble polymer in various fields including a dispersing agent for paper making, a coagulant, a water-soluble film, a water-soluble fiber, a sizing agent for printing, and a plasticizer.
• the production of an alkylene oxide polymer can be performed using the above-described zinc catalyst.
• the zinc catalyst is characterized in that by reacting an organozinc compound with a monohydric alcohol in an amount of 12 equivalents or less relative to the organozinc compound and an aliphatic polyhydric alcohol in an amount of 0.2 to 1.1 equivalents relative to the organozinc compound, then distilling the resulting reaction liquid under normal pressure at a temperature of 100° C. or lower, the amount of the monohydric alcohol has been adjusted to 0.01 equivalents or less relative to the organozinc compound.
• the zinc catalyst can be produced via the following steps.
• the alkylene oxide to be used for polymerization the organozinc compound, the monohydric alcohol, and the aliphatic polyhydric alcohol to be used for the production of the zinc catalyst, the reaction conditions, etc. are as described above.
• an alkylene oxide polymer having a high degree of polymerization can be produced industrially and reproducibly.
• a 1-liter beaker was charged with 497.5 g of ion-exchanged water, and 2.5 g of an alkylene oxide polymer was charged thereinto under stirred with a flat board of 80 mm in width and 25 mm in length at a tip peripheral speed of 1.0 m/s, and the stirring was continued for 3 hours to prepare an aqueous solution.
• the polymer can be judged to be an alkylene oxide polymer having a high degree of polymerization.
• the amount of a monohydric alcohol was measured using a gas chromatography (GC-2014 manufactured by Shimadzu Corporation; hereinafter GC) under conditions including an injection temperature of 200° C., a column to be used being Thermon 1000 (length: 3 meters) a column temperature of 100° C., and a detector temperature of 200° C., and a concentration was calculated from a peak area.
• the amount of a monohydric alcohol was calculated from an analytical curve prepared beforehand.
• a mixture liquid of 6.49 g (0.072 mol) of 1,4-butanediol (1,4-BDO) and 13.27 g (0.288 mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour.
• heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation.
• the residue was allowed to cool to room temperature and 52.4 g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. This operation was performed further once again and distillation was carried out three times in total.
• the residue was moved to a pressure-resistant vessel thoroughly replaced with nitrogen, and was subjected to heat treatment at an oil bath temperature of 130° C. for 15 minutes with the vessel stoppered.
• the residue was diluted with 264 g of n-hexane, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0033 equivalents relative to an organozinc compound.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 81.0 g of polyethylene oxide.
• the polymerization time was 6 hours and the yield was 100% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 855 mPa ⁇ s.
• a zinc catalyst was produced in analogy to Example 1-1, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethanol was found to be 0.0038 equivalents relative to an organozinc compound.
• the polymerization time was 6 hours and the yield was 98% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 825 mPa ⁇ s, and reproducibility was good.
• a zinc catalyst was produced in analogy to Example 1-1, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0047 equivalents relative to an organozinc compound.
• the polymerization time was 6 hours and 45 minutes and the yield was 100% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 865 mPa ⁇ s, and reproducibility was good.
• a mixture liquid of 6.49 g (0.072 mol) of 1,4-butanediol and 13.27 g (0.288 mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour.
• heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation.
• the residue was allowed to cool to room temperature and 52.4 g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. After the two-times distillation, the residue was moved to a pressure-resistant vessel thoroughly replaced with nitrogen, and was subjected to h at treatment at an oil bath temperature of 130° C. for 15 minutes/the vessel stoppered. After cooling, the residue was diluted with 264 g of n-hexane, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc. When the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0093 equivalents relative to an organozinc compound.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 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 a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 820 mPa ⁇ s.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour. Then, heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation. Following the distillation, the residue was allowed to cool to room temperature and 52.4. g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. This operation was performed further once again and distillation was carried out three times in total.
• a pressure-resistant vessel thoroughly r placed with nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 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 a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 810 mPa ⁇ s.
• a zinc catalyst was produced in analogy to Example 3 except that all the distillation temperatures where changed from 80° C. to 70′C in the production of the zinc catalyst of Example 3, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0058 equivalents relative to an organozinc compound.
• the polymerization time was 4 hours and 30 minutes and the yield was 96% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 595 mPa ⁇ s.
• a zinc catalyst was produced in analogy to Example 3 except that all the distillation temperatures where changed from 80′′C to 100° C. in the production of the zinc catalyst of Example 3, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the amount of ethyl alcohol was found to be 0.001 equivalents relative to an organozinc compound.
• the polymerization time was 5 hours and the yield was 99% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 720 mPa ⁇ s.
• a mixture liquid of 6.49 g (0.072 mol) of 1,4-butanediol and 17.31 g (0.288 mol) of isopropyl alcohol was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour.
• heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation.
• the residue was allowed to cool to room temperature and 52.4 g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. This operation was performed further once again and distillation was carried out three times in total. After the three-times distillation, the residue was moved to a pressure-resistant vessel thoroughly replaced with nitrogen, and was subjected to heat treatment at an oil bath temperature of 130° C. for 15 minutes with the vessel stoppered. After cooling, the residue was diluted with 264 g of n-hexane, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc. When the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of isopropyl alcohol was found to be 0.0001 equivalents relative to an organozinc compound.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 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 a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 575 mPa ⁇ s.
• a mixture liquid of 6.49 g (0.072 mol) of 1,4-butanediol and 9.22 g (0.288 _op of methyl alcohol (MeOH) was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour. Then, heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation.
• the residue was allowed to cool to room temperature and 52.4 g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. This operation was performed further once again and distillation was carried out three times in total. After cooling, the residue was diluted with 264 g of n-hexane, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of methyl alcohol was found to be 0.0008 equivalents relative to an organozinc compound.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, follow d by polymerization wider stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 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 a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 425 mPa ⁇ s.
• a mixture liquid of 2.16 g (0.30 mol) of 1,4-butanediol and 26.54 g (0.576 mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour.
• heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation.
• the residue was allowed to cool to room temperature and 52.4 g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. This operation was performed further once again and distillation was carried out three times in total. After cooling, the residue was diluted with 264 g of n-hexane, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0048 equivalents relative to an organozinc compound.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hex and 3.38 g (0.0013 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 79.4 g of polyethylene oxide.
• the polymerization time was 3 hours and the yield was 98% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 700 mPa ⁇ s.
• a mixture liquid of 5.04 g (0.056 mol) of 1,4-butariediol and 24.3 g (0.528 mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour.
• heating was performed at an oil bath temperature of 80° C. and unreacted components were removed by distillation.
• the residue was allowed to cool to room temperature and 52.4 g of n-hexane was added, and second distillation was carried out by heating at an oil bath temperature of 80° C. This operation was performed further once again and distillation was carried out three times in total. After the three-time distillation, the residue was moved to a pressure-resistant vessel thoroughly replaced with nitrogen, and was subjected to heat treatment at an oil bath temperature of 130° C. for 15 minutes with the vessel stoppered. After cooling, the residue was diluted with 264 g of n-hexane, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc. When the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0007 equivalents relative to an organozinc compound.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol in terms of zinc) of the zinc catalyst obtained. above was dispersed uniformly, and 81.0 g(1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 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 a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 815 mPa ⁇ s.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 3.38 g (0.0013 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 76.3 g of polyethylene oxide.
• the polymerization time was 7 hours and the yield was 94% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 530 mPa ⁇ s.
• a mixture liquid of 6.49 (0.072 mol) of 1,4-butariediol and 13.27 g (0.288 mol) of ethyl alcohol was dropped at a rate of 0.2 g/minute to the reaction liquid cooled to an internal temperature of 10° C.
• the temperature of the inside of the flask was raised to 30° C. and a reaction was carried out for 1 hour, and. subsequently the temperature was raised to 50° C. and the reaction was carried out for 1 hour.
• heat treatment was carried out without stoppering at an oil bath temperature of 130° C. for 15 minutes.
• a pressure-resistant vessel thoroughly replaced with nitrogen was charged with 340 g of n-hexane and 0.975 g (0.0004 mol in terms of zinc) of the zinc catalyst obtained above was dispersed uniformly, and 81 g (1.84 mol) of ethylene oxide was added and the vessel was stoppered, followed by polymerization under stirring in a thermostatic bath at 40° C. After the completion of the polymerization, a white product was taken out by filtration and dried at 40° C. under reduced pressure, thereby obtaining 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 a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 825 mPa ⁇ s.
• a zinc catalyst was produced in analogy to Comparative Example 1-1, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.0334 equivalents relative to an organozinc compound.
• the polymerization time was 11 hours and 15 minutes and the yield was 99% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 625 mPa ⁇ s.
• a zinc catalyst was produced in analogy to Comparative Example 1-1, thereby obtaining 297 g of a zinc catalyst containing 1.8% by mass of zinc.
• the n-hexane of the supernatant liquid of this zinc catalyst was measured by GC, the amount of ethyl alcohol was found to be 0.00221 equivalents relative to an organozinc compound.
• the polymerization time was 9 hours and 45 minutes and the yield was 97% by mass.
• the viscosity of a 0.5% by mass aqueous solution of the resulting polyethylene oxide was 785 mPa ⁇ s.

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