Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
  • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/04—Saturated ethers
  • C07C43/10—Saturated ethers of polyhydroxy compounds
  • C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10

Definitions

• the present invention relates to a method for producing a (poly)alkylene glycol monoalkyl ether. More specifically, the present invention relates to a method for producing a (poly)alkylene glycol monoalkyl ether by reacting an olefin with a (poly)alkylene glycol.
• Japanese Patent Publication No. 2703752 discloses the reaction of olefins with (poly)alkylene glycols using a BEA-type metallosilicate catalyst to obtain (poly)alkylene glycol monoalkyl ethers. It explains that the reaction can be carried out in the presence or absence of a solvent, and that the solvent can be nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, paraffin, or the like.
• the inventors conducted extensive research to solve these problems, and as a result, discovered an efficient method for producing (poly)alkylene glycol monoalkyl ethers, which takes advantage of the advantages of using a solvent for the reaction, and by lowering the temperature of the reaction liquid after the reaction to a temperature lower than the reaction temperature and separating it into an upper layer (A) containing mainly olefins and (poly)alkylene glycol monoalkyl ethers, and a lower layer (B) containing mainly (poly)alkylene glycols, dramatically reduces the total amount of upper layer (A) containing the product (poly)alkylene glycol monoalkyl ether, and enables stable distillation, thereby obtaining a highly pure product.
• a method for producing a (poly)alkylene glycol monoalkyl ether comprising: a reaction step in which an olefin and a (poly)alkylene glycol are reacted in the form of a homogeneous liquid solution in the presence of a solvent at 110 to 250°C using a crystalline metallosilicate as a catalyst; a separation step in which the reaction solution obtained in the reaction step is separated into an upper layer (A) and a lower layer (B) at a temperature lower than 110°C; and a step in which the upper layer (A) separated in the separation step is distilled to obtain a (poly)alkylene glycol monoalkyl ether.
• R 1 is a linear or branched alkyl group having 1 to 4 carbon atoms
• R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms or an acetyl group
• A is a linear or branched alkylene group having 2 to 4 carbon atoms
• n is 1 to 4.
• a method for producing a higher secondary alcohol alkoxylate adduct which comprises further adding an alkylene oxide to the (poly)alkylene glycol monoalkyl ether obtained by any one of (1) to (5).
• X to Y includes X and Y and means "X or more and Y or less.”
• operations and measurements of physical properties are performed at room temperature (20°C or more and 25°C or less) and at a relative humidity of 40% RH or more and 50% RH or less.
• One aspect of the present invention relates to a method for producing a (poly)alkylene glycol monoalkyl ether, which includes a reaction step (reaction step) in which an olefin and a (poly)alkylene glycol are reacted in the presence of a solvent at 110 to 250°C as a homogeneous liquid phase solution using a crystalline metallosilicate as a catalyst, a separation step (separation step) in which the reaction solution obtained in the reaction step is separated into an upper layer (A) and a lower layer (B) at a temperature lower than 110°C, and a step (purification step) in which the upper layer (A) separated in the separation step is distilled to obtain a (poly)alkylene glycol monoalkyl ether.
• reaction step in which an olefin and a (poly)alkylene glycol are reacted in the presence of a solvent at 110 to 250°C as a homogeneous liquid phase solution using a crystalline metal
• the solvent is removed in the separation step, the amount of solvent distilled off (distillation separation) when recovering the reaction product can be reduced, which is preferable in terms of energy.
• an olefin and a (poly)alkylene glycol can be reacted in the presence of a catalyst with high selectivity to produce a (poly)alkylene glycol monoalkyl ether in high yield.
• a (poly)alkylene glycol monoalkyl ether can be produced from an olefin and a (poly)alkylene glycol with high selectivity and high yield.
• a high-purity (poly)alkylene glycol monoalkyl ether can be produced.
• reaction step In this process, in the presence of a crystalline metallosilicate (catalyst), an olefin is reacted with a (poly)alkylene glycol at a temperature of 110 to 250° C. using a solvent that makes the liquid phase a uniform solution.
• the raw olefin is not compatible with a (poly)alkylene glycol (e.g., ethylene glycol), and therefore the reaction is easily separated into two layers. Therefore, the olefin phase containing the reaction product ((poly)alkylene glycol monoalkyl ether) is easily separated, and the (poly)alkylene glycol and the catalyst can be recovered.
• the reaction since the reaction is easily separated, the reaction needs to be carried out under strong stirring.
• a solvent is used in the reaction to promote the reaction, but the solvent must be removed (distilled separation) to recover the reaction product, which is energetically disadvantageous.
• the reaction can be carried out in a uniform solution state, and therefore the reaction can be carried out without strong stirring.
• phase separation easily occurs into an upper layer mainly containing the reaction product ((poly)alkylene glycol monoalkyl ether), unreacted olefin and solvent, and a lower layer mainly containing the solvent and unreacted (poly)alkylene glycol, which allows the reaction product to be easily and reliably recovered (in high yield/high amount).
• a solution with a homogeneous liquid phase means that the liquid phase is a single phase. Specifically, whether or not the liquid phase is homogeneous is evaluated based on whether or not the liquid phase is visually separated into two layers, and if the liquid phase is not separated into two layers and is a single phase, the liquid phase is evaluated as being homogeneous.
• the olefins used in the present invention are hydrocarbons having 2 to 40 carbon atoms and an ethylenically unsaturated bond, preferably those having 6 to 30 carbon atoms and an ethylenically unsaturated bond, more preferably those having 8 to 20 carbon atoms and one ethylenically unsaturated bond, and particularly preferably those having 12 to 16 carbon atoms and one ethylenically unsaturated bond (acyclic olefins) (dodecene, tridecene, tetradecene, pentadecene, hexadecene).
• Specific examples include ethylene, propylene, butene, isobutylene, butadiene, pentene, hexene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, henicosene, docosene, tricosene, tetracosene, etc. These may be used alone or in a mixture of two or more.
• olefins having a large number of carbon atoms such as octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, etc. are preferably used.
• These olefins can be used without any particular limitation, regardless of whether the position of the unsaturated bond is the ⁇ -position, the inner position, or both the ⁇ -position and the inner position.
• the olefin has an ⁇ -position of the unsaturated bond (e.g., 1-dodecene, 1-tridecene, 1-tetradecene).
• the olefin has an inner position of the unsaturated bond (e.g., inner dodecene, inner tridecene, inner tetradecene).
• inner position of the unsaturated bond e.g., inner dodecene, inner tridecene, inner tetradecene.
• two or more of these olefins having different positions of the unsaturated bond can be used in combination.
• the olefin is a mixture of an olefin having an ⁇ -position of the unsaturated bond and an olefin having an inner position of the unsaturated bond (e.g., a mixture of 1-dodecene and inner dodecene, a mixture of 1-tridecene and inner tridecene, a mixture of 1-tetradecene and inner tetradecene).
• a reaction occurs simultaneously in which the position of the unsaturated bond of the olefin is isomerized.
• inner olefins are thermodynamically more stable than ⁇ -olefins, so when ⁇ -olefins are used as the raw material, the olefin gradually isomerizes to the inner olefin during the reaction.
• the rate of isomerization varies depending on the reaction temperature and the type and amount of crystalline metallosilicate used as a catalyst.
• the (poly)alkylene glycol monoalkyl ethers obtained from these acyclic olefins with 6 to 30 carbon atoms are suitable as raw materials for surfactants.
• the (poly)alkylene glycols used in the present invention include monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, paraxylylene glycol, and 1,4-cyclohexanemethanediol. These may be used alone or in a mixture of two or more.
• the number of carbon atoms of the alkylene in the (poly)alkylene glycol is 1 to 8, 1 to 6, 1 to 4, or 1 to 3.
• the number of moles of alkylene oxide added in the (poly)alkylene glycol may be 1 to 20.
• the crystalline metallosilicate used in the present invention is a regular, porous substance with a certain crystal structure. In other words, it is a solid substance with a large specific surface area that has many regular voids and holes within its structure.
• the crystalline metallosilicates used in the present invention are crystalline aluminosilicates (also commonly referred to as zeolites) and compounds in which other metal elements have been introduced into the crystal lattice in place of the Al atoms of crystalline aluminosilicates.
• crystalline aluminosilicates also commonly referred to as zeolites
• other metal elements include at least one of B, Ga, In, Ge, Sn, P, As, Sb, Sc, Y, La, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn.
• crystalline aluminosilicates In terms of catalytic activity and ease of synthesis and availability, crystalline aluminosilicates, crystalline ferrosilicates, crystalline borosilicates, and crystalline gallosilicates are preferred, with crystalline aluminosilicates being more preferred.
• the specific surface area of the catalyst is 400-800 m 2 /g.
• crystalline metallosilicates used in the present invention when described using IUPAC codes, include those having structures such as MFI (ZSM-5, etc.), MEL (ZSM-11, etc.), BEA ( ⁇ -type zeolite, etc.), FAU (Y-type zeolite, etc.), MOR (mordenite, etc.), MTW (ZSM-12, etc.), and LTL (L-type zeolite, etc.).
• MFI ZSM-5, etc.
• MEL ZSM-11, etc.
• BEA ⁇ -type zeolite, etc.
• FAU Y-type zeolite, etc.
• MOR memory-type zeolite, etc.
• MTW ZSM-12, etc.
• LTL L-type zeolite, etc.
• the crystalline metallosilicate is a pentasil type metallosilicate or a BEA type metallosilicate.
• the crystalline metallosilicate used in the present invention preferably has an atomic ratio of silicon atoms to the constituent metal atoms in the range of 5 to 1500, particularly 10 to 500. Crystalline metallosilicates in which the atomic ratio of silicon atoms to the constituent metal atoms is too small or too large are not preferred because they have low catalytic activity.
• the crystalline metallosilicates used in the present invention can be synthesized by a commonly used synthesis method, for example, a hydrothermal synthesis method. Specifically, they can be synthesized by the methods described in JP-B-46-10064, U.S. Pat. No. 3,965,207, and Journal of Molecular Catalysis, Vol. 31, pp. 355-370 (1985), etc. These crystalline metallosilicates can be synthesized, for example, by heating a composition consisting of a silica source, a metallo source, and a quaternary ammonium salt such as tetrapropylammonium salt at a temperature of about 100 to 175° C.
• silica source water glass, silica sol, silica gel, alkoxysilane, etc. can be used.
• metallo source various inorganic or organic metal compounds can be used.
• metal compounds include metal salts such as metal sulfates [e.g., Al 2 (SO 4 ) 3 ], metal nitrates [e.g., Fe(NO 2 ) 2 ], and alkali metal salts of metal oxides [e.g., NaAlO 2 ]; metal halides such as metal chlorides [e.g., TiCl 4 ] and metal bromides [e.g., MgBr 2 ]; and metal alkoxides [e.g., Ti(OC 2 H 5 ) 4 ].
• metal salts such as metal sulfates [e.g., Al 2 (SO 4 ) 3 ], metal nitrates [e.g., Fe(NO 2 ) 2 ], and alkali metal salts of metal oxides [e.g., NaAlO 2 ]; metal halides such as metal chlorides [e.g., TiCl 4 ] and metal bromides [e.g., MgBr 2 ]
• the H + type cation form can be prepared by mixing and stirring the crystalline metallosilicate in an aqueous solution of HCl, NH 4 Cl, NH 3 , etc., exchanging the cation species into H + type or NH 4 + type, and then filtering the solid product, washing with water, drying, and then calcining at 350 to 600°C.
• Cationic forms other than H + can be prepared by carrying out the same procedure using an aqueous solution containing the desired cation.
• the crystalline metallosilicates used in the present invention may be commercially available products.
• commercially available products include zeolites of the HSZ-900 series (BEA), HSZ-800 series (ZSM-5), HSZ-600 series (mordenite), HSZ-500 series (L type), and HSZ-300 series (Y type) (all manufactured by Tosoh Corporation), CP series, CBV series, and ZD series (all manufactured by Zeolyst International), CZB series, CZP series, CZM series, CZC series, LiCZF series, CZA series, CZE series, and CZL series (all manufactured by Clariant).
• the crystalline metallosilicate may be calcined before the reaction. Calcination conditions are not particularly limited and may be appropriately selected depending on the desired degree of catalytic activity.
• the calcination temperature is, for example, 300 to 1000°C, particularly 500 to 700°C.
• the calcination time is, for example, 1 to 10 hours, particularly 1 to 5 hours. Calcination may be performed in air or in an inert atmosphere (e.g., nitrogen, argon).
• the catalyst in this reaction may be in any form, including powder, granules, and molded bodies having specific shapes.
• alumina, silica, titania, etc. can also be used as a carrier or binder.
• an olefin is reacted with a (poly)alkylene glycol in the presence of a crystalline metallosilicate (catalyst) using a solvent that will give a uniform liquid phase.
• the solvent that can be used in the reaction may be any solvent that will give a uniform liquid phase (that will allow the reaction to proceed uniformly).
• the solvent that can be used in the reaction preferably contains a compound represented by the following formula (I) that has a solubility parameter of 16 to 20, and more preferably, the solvent that can be used in the reaction is only a compound represented by the following formula (I) that has a solubility parameter of 16 to 20.
• the reaction between the olefin and the (poly)alkylene glycol is preferably carried out in the presence of a compound having a solubility parameter in the range of 16 to 20 and represented by the following formula (I).
• the solvent used in the reaction has a solubility parameter in the range of 16 to 20 and contains a compound having the following formula (I).
• the solvent used in the reaction has a solubility parameter in the range of 16 to 20 and is a compound having the following formula (I).
• the solvent used in the reaction has a solubility parameter in the range of 16 to 20 and is one type of compound having the following formula (I).
• R 1 is a linear or branched alkyl group having 1 to 4 carbon atoms.
• the alkyl group as R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group.
• R 1 is preferably a methyl group, an ethyl group, or a butyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• R 2 is a linear or branched alkyl group having 1 to 4 carbon atoms, or an acetyl group (CH 3 CO-).
• specific examples of the alkyl group as R 2 are the same as those of R 1 above.
• R 2 is preferably a methyl group, an ethyl group, a butyl group, or an acetyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• A is a linear or branched alkylene group having 2 to 4 carbon atoms. When a plurality of A's are present (n is 2 to 4), each A's may be the same or different.
• Examples of the alkylene group represented by A include an ethylene group (-CH 2 CH 2 -), a trimethylene group (-CH 2 CH 2 CH 2 -), a propylene group (-CH(CH 3 )CH 2 - or -CH 2 CH(CH 3 )-), and a tetramethylene group (-CH 2 CH 2 CH 2 CH 2 -).
• A is preferably an ethylene group or a propylene group, and is particularly preferably an ethylene group.
• n is 1 to 4.
• m is more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 2.
• the solubility parameter (SP value) of the solvent is 16 to 20. From the viewpoint of further uniformity of the liquid phase during the reaction, the solubility parameter is preferably 16.5 to 19.0, more preferably 17.0 or more and less than 19.0, and particularly preferably 17.5 to 18.5.
• the solubility parameter refers to the Hansen solubility parameter, which is an index that serves as a guide for the solubility of a binary solution.
• the SP value ⁇ (J/cm 3 ) of the solvent was calculated using the following formula (II).
• ⁇ d is the London dispersion force term
• ⁇ p is the molecular polarization term
• ⁇ h is the hydrogen bond term
• Particularly preferred solvents include ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. The above solvents may be used alone or in the form of a mixture of two or more kinds, but are preferably used alone.
• the reaction process in the present invention is characterized in that a crystalline metallosilicate is used as a catalyst, and an olefin and a (poly)alkylene glycol are reacted in the presence of a solvent at 110 to 250°C as a uniform liquid phase solution.
• a solvent is not used, the raw materials (poly)alkylene glycol and olefin are distributed only in amounts that are small relative to each other, and the catalyst crystalline metallosilicate is distributed in the (poly)alkylene glycol phase, while the product (poly)alkylene glycol monoalkyl ether is distributed in the olefin phase, resulting in a very slow reaction rate.
• the use of a solvent makes the liquid phase uniform, making it easier for the olefin to come into contact with the catalyst, and increasing the reaction rate with the (poly)alkylene glycol.
• the liquid phase being uniform means that the liquid phase is uniform at a reaction temperature of 110°C or higher, and that the liquid phase is uniform when the temperature is increased or the reaction progresses (for example, 120 minutes after the predetermined reaction temperature is reached), and the liquid phase does not have to be uniform when mixed at a temperature lower than 110°C.
• the amount of the solvent used to homogenize the liquid phase in this manner is preferably 35% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, and particularly preferably more than 100% by mass, based on the total amount of the olefin, (poly)alkylene glycol, and solvent.
• the upper limit of the amount of the solvent used is, for example, 300% by mass or less, preferably 250% by mass or less, and more preferably 200% by mass or less, based on the total amount of the olefin, (poly)alkylene glycol, and solvent.
• the amount of solvent added is more than 62 parts by mass per 100 parts by mass of olefin. If the amount falls below the lower limit, the liquid phase during the reaction will separate into two layers and will not be homogenous.
• the solvent is preferably provided to the reaction in a ratio of 150 to 800 parts by mass, more preferably 165 to 600 parts by mass, even more preferably more than 165 parts by mass and not more than 500 parts by mass, and particularly preferably 250 to 350 parts by mass per 100 parts by mass of olefin.
• the reaction in the present invention can be carried out by a commonly used method such as a batch reaction or a flow reaction, and is not particularly limited.
• the molar ratio of the raw materials for the reaction, olefin and (poly)alkylene glycol is not particularly limited. For example, 0.05 to 20 moles, preferably 0.1 to 10 moles, and more preferably 1 to 5 moles of (poly)alkylene glycol are used per mole of olefin.
• the reaction temperature is 110 to 250°C, preferably 110 to 200°C, more preferably 110 to 170°C, and particularly preferably 120 to 150°C. Higher reaction temperatures result in a faster reaction rate, but are not preferred because side reactions lead to the production of by-products.
• the reaction pressure may be reduced, normal or increased, but is preferably in the range of normal pressure to 2 MPa.
• the reactor When a batch reactor is used, the reactor is filled with the catalyst of the present invention and raw materials, and a mixture containing the desired (poly)alkylene glycol monoalkyl ether is obtained by stirring at a specified temperature and pressure.
• the amount (addition amount) of the crystalline metallosilicate (catalyst) used is not particularly limited and is appropriately selected depending on the desired reaction progress, etc.
• the amount of the crystalline metallosilicate (catalyst) is 0.1 to 150 mass%, preferably 0.5 to 100 mass%, more preferably 10 to 100 mass%, and particularly preferably 20.0 to 99.5 mass% relative to the olefin raw material.
• the reaction time varies depending on the reaction temperature, amount of catalyst, and raw material composition ratio, but is in the range of 0.1 to 100 hours, preferably 0.5 to 30 hours, preferably 1 to 10 hours, and more preferably 2 to 5 hours.
• reaction liquid obtained in the above reaction step is separated into an upper layer (A) and a lower layer (B) at a temperature lower than 110°C.
• the reaction solution in order to obtain a (poly)alkylene glycol monoalkyl ether from the reaction solution obtained in the reaction step, the reaction solution is cooled to a temperature lower than 110°C and allowed to stand, and separated into two layers: an upper layer (A) containing mainly the solvent, unreacted olefin, and the product (poly)alkylene glycol monoalkyl ether, and a lower layer (B) containing mainly the solvent and unreacted (poly)alkylene glycol.
• the temperature for separation may be lower than 110°C, preferably 100°C or lower, more preferably 90°C or lower, even more preferably 50°C or lower, and particularly preferably less than 40°C.
• the temperature for separation may be any temperature that does not freeze, and is, for example, -20°C or higher, preferably 10°C or higher, and more preferably 20°C or higher.
• the difference between the reaction temperature in the above reaction step and the separation temperature in this step is, for example, 10 to 200°C, preferably 30 to 150°C, more preferably 50 to 140°C, even more preferably 70 to 130°C, and particularly preferably more than 95°C and less than 120°C.
• separation may be performed after removing the catalyst by filtration or centrifugation, or may be performed while still contained. The catalyst separated by a method such as centrifugation or filtration can be used repeatedly in the reaction as it is or after being regenerated.
• the amount of solvent suitable for forming a uniform liquid phase during the reaction and separating into two layers after the reaction is preferably 35% by mass or more, more preferably 38% by mass or more, and even more preferably 40% by mass or more, based on the total amount of olefin, (poly)alkylene glycol, and solvent. If the amount of solvent is less than 35% by mass, the liquid phase of the reaction liquid will not be uniform at the reaction temperature, and the reaction rate will be slow, which is not preferable.
• the amount of solvent is more than 65% by mass, the liquid phase of the reaction liquid will be uniform, but separation will not occur even if the temperature of the reaction liquid is lowered below 110°C, and the amount of reaction liquid will increase to obtain (poly)alkylene glycol monoalkyl ether, and a large amount of distillation energy will be required to recover unreacted olefin, unreacted (poly)ethylene glycol, solvent, etc. and reuse them in the reaction, which is not preferable.
• the amount is preferably 65% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less.
• the method of adjusting the amount of solvent to be suitable for separation includes a method of adjusting the amount of solvent when preparing the reaction or a method of adjusting the amount of solvent by distillation after the reaction.
• the amount of solvent can be adjusted by removing the solvent by distillation from the reaction liquid after the reaction so that the amount of solvent is suitable for separation.
• the present invention includes a method of adjusting the amount of solvent suitable for separation in the reaction step and reacting and/or a method of distilling the solvent from the reaction liquid after the reaction to adjust the amount of solvent to be suitable for separation.
• the distillation conditions are not particularly limited, and known methods can be used.
• the temperature at the top of the distillation tower is usually 50 to 300°C.
• Distillation may be performed either under normal pressure or under reduced pressure, but is preferably performed under reduced pressure, with a preferred degree of reduced pressure being 15 kPa or less, more preferably 10 kPa or less.
• a preferred degree of reduced pressure is 50 Pa or more, more preferably 100 Pa or more.
• the process of obtaining a (poly)alkylene glycol monoalkyl ether by distillation from the upper layer (A) separated in the separation process of the present invention is a process in which low boiling points such as the solvent and unreacted olefins are distilled off by distillation to obtain a (poly)alkylene glycol monoalkyl ether, since the upper layer (A) mainly contains the solvent, unreacted olefins, and the product (poly)alkylene glycol monoalkyl ether.
• the distillation conditions are not particularly limited, and known methods, such as the same methods as those for distilling the solvent described above, can be used.
• the obtained (poly)alkylene glycol monoalkyl ether can be used as it is or after purification as a raw material for the higher secondary alcohol alkoxylate adduct described later.
• the lower layer (B) contains the desired (poly)alkylene glycol monoalkyl ether and some unreacted olefin.
• the lower layer (B) can be reused for the reaction of the (poly)alkylene glycol monoalkyl ether by adding raw olefins and (poly)alkylene glycol as necessary, and by removing the solvent component from the lower layer (B) by distillation, it can be separated into an upper layer (C) containing mainly unreacted olefins and the (poly)alkylene glycol monoalkyl ether of the reaction product, and a lower layer (D) containing mainly unreacted (poly)alkylene glycol.
• the present invention may further include a step of removing the solvent from the lower layer (B) by distillation to separate the upper layer (C) and the lower layer (D), and obtaining the (poly)alkylene glycol monoalkyl ether from the separated upper layer (C) by distillation.
• the (poly)alkylene glycol monoalkyl ether can be obtained from the lower layer (B), and the (poly)alkylene glycol monoalkyl ether produced by the reaction can be recovered without waste.
• removing the solvent component from the lower layer (B) by distillation this can be done after removing the catalyst by filtration or centrifugation, or it can be done while it is still contained.
• the catalyst separated by methods such as centrifugation or filtration can be used in repeated reactions as it is or after being regenerated.
• the method of the present invention further includes a step of distilling off the solvent component from the lower layer (B) separated in the separation step, separating the lower layer (B) into an upper layer (C) and a lower layer (D), and obtaining a (poly)alkylene glycol monoalkyl ether from the separated upper layer (C) by distillation.
• the separated upper layers (A) and (C) are distilled to obtain (poly)alkylene glycol monoalkyl ether, but the unreacted olefin and solvent are also recovered by distillation and can be reused as reaction raw materials and solvents.
• the lower layer (D) also contains unreacted (poly)alkylene glycol, which can be reused as reaction raw materials either as is or after purification.
• the distillation conditions are not particularly limited, and known methods can be used.
• the temperature at the top of the distillation tower is usually 50 to 300°C, preferably 70 to 300°C, and more preferably 70 to 250°C.
• the distillation residence time is usually within 24 hours, preferably within 12 hours, and more preferably within 6 hours.
• the distillation residence time is preferably 10 minutes or more, more preferably 20 minutes or more, and even more preferably 30 minutes or more.
• the distillation may be carried out under either normal pressure or reduced pressure, but is preferably carried out under reduced pressure, with the preferred degree of reduced pressure being 15 kPa or less, more preferably 10 kPa or less.
• the preferred degree of reduced pressure is 50 Pa or more, and more preferably 100 Pa or more.
• any of the fluidized bed, fixed bed and stirred tank types can be used.
• the reaction conditions vary depending on the raw material composition, catalyst concentration, reaction temperature, etc., but the liquid hourly space velocity (LHSV), i.e., the value obtained by dividing the volumetric flow rate of the flowing raw material by the volume of the reactor, is preferably in the range of 0.01 to 50 hr -1 , particularly 0.1 to 20 hr -1 .
• the target (poly)alkylene glycol monoalkyl ether can be recovered by the same operation as in the batch reaction.
• the present invention provides a method for producing a higher secondary alcohol alkoxylate adduct, which comprises further adding an alkylene oxide to the (poly)alkylene glycol monoalkyl ether obtained above in the presence of a catalyst.
• the method for producing the higher secondary alcohol alkoxylate adduct of the present invention is not particularly limited as long as it is a method capable of adding an alkylene oxide to a (poly)alkylene glycol monoalkyl ether, and known methods can be applied in the same manner or with appropriate modifications.
• an alkylene oxide is added to the (poly)alkylene glycol monoalkyl ether obtained by the above method in an appropriate molar ratio, and reacted in the presence of an alkali catalyst, an acid catalyst, a solid acid catalyst such as alumina magnesia, a complex metal cyanide (DMC) catalyst, or the like.
• the alkylene oxide may be only one type, or two or more types. In the latter case, two or more types of alkylene oxides may be added randomly, each may be added in a block, or a random structure and a block structure may be combined.
• alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.
• the molar ratio of the alkylene oxide to the (poly)alkylene glycol monoalkyl ether is not particularly limited, but is preferably 1 to 30, more preferably 2 to 25, and even more preferably 4 to 20, and is preferably 3 to 18, 4 to 16, or 5 to 12.
• the reaction conditions for adding alkylene oxide to (poly)alkylene glycol monoalkyl ether are a reaction temperature of usually 50 to 250°C, preferably 100 to 200°C, 110 to 180°C, or 120 to 160°C.
• the reaction time is 0.5 to 40 hours, 0.5 to 20 hours, or 1 to 10 hours.
• the reaction pressure may be either normal pressure or pressurized, but is preferably in the range of normal pressure to 2 MPa (1 MPa or less, or 0.5 MPa or less). If the reaction temperature is less than 50°C, the reaction rate may be slow, and on the other hand, if it exceeds 250°C, decomposition and an increase in by-products may occur, which is not preferable.
• the above-mentioned alkaline catalyst includes hydroxides of elements belonging to the alkali metal or alkaline earth metal, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.
• sodium hydroxide and potassium hydroxide are preferred. These may be added in the form of powder, granules, or even an aqueous solution, and dehydrated.
• the amount of the alkaline catalyst used (in terms of solids if in the form of an aqueous solution) is 0.01 to 2.0% by mass, preferably 0.02 to 0.5% by mass, based on the (poly)alkylene glycol monoalkyl ether raw material.
• Catalyst (1) was obtained by calcining BEA-type zeolite manufactured by Tosoh Corporation (product name: HSZ-930NHA, powder product, pore size: 6.5 ⁇ , cation: template, SiO 2 /Al 2 O 3 ratio: 27 (molar ratio), specific surface area: 590 m 2 /g (BET method), crystal size: 0.04 ⁇ m, particle size: 5 ⁇ m) at 500° C. for 4 hours in air.
• BEA-type zeolite manufactured by Tosoh Corporation product name: HSZ-930NHA, powder product, pore size: 6.5 ⁇ , cation: template, SiO 2 /Al 2 O 3 ratio: 27 (molar ratio), specific surface area: 590 m 2 /g (BET method), crystal size: 0.04 ⁇ m, particle size: 5 ⁇ m) at 500° C. for 4 hours in air.
• GC gas chromatography
• Example 1 40 g (0.24 mol) of 1-dodecene, 59 g (0.95 mol) of monoethylene glycol, 105.5 g of diethylene glycol dimethyl ether, and 39.3 g of catalyst (1) were charged into a 500 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen, and then the mixture was maintained in a nitrogen atmosphere at normal pressure. The temperature was then raised to 135° C. while stirring at a rotation speed of 650 rpm, and the reaction was carried out at the same temperature for 4 hours. The liquid phase during the reaction was uniform. After the reaction, the reaction liquid was cooled to 25° C. and separated into two layers.
• the upper layers (A) and (C) were distilled at 1 kPa to distill off the solvent and raw material components at a tower top temperature of less than 140°C, and 18.9 g of ethylene glycol monododecyl ether was obtained at a tower top temperature of 140 to 143°C.
• Example 2 The reaction was carried out in the same manner as in Example 1, except that the amount of diethylene glycol dimethyl ether was changed from 105.5 g to 193.9 g in Example 1. The liquid phase during the reaction was uniform. After the reaction, the mixture was cooled to 25° C., but no phase separation of the liquid phase was observed. 90.1 g of diethylene glycol dimethyl ether, which is the solvent, was distilled off from the reaction liquid by distillation (pressure: 4 kPa, tower top temperature: 80 to 100° C.). The reaction liquid was then cooled to 25° C. and separated into two layers. 122.2 g of an upper layer (A) and 118.0 g of a lower layer (B) were obtained.
• A upper layer
• B 118.0 g of a lower layer
• the upper layer (A) and the lower layer (B) were analyzed by gas chromatography, and the conversion rate of 1-dodecene, as well as the selectivity and yield of ethylene glycol monododecyl ether, are shown in Table 1.
• the separated lower layer (B) was filtered, the catalyst was removed, and 13.2 g of the solvent, diethylene glycol dimethyl ether, was distilled off by distillation (pressure: 4 kPa, tower top temperature: 80-100°C). Then, it was cooled to 25°C and separated into two layers, obtaining 19.6 g of an upper layer (C) and 46.3 g of a lower layer (D).
• the upper layers (A) and (C) were distilled at 1 kPa to distill off the solvent and raw material components at a tower top temperature of less than 140°C, and 18.7 g of ethylene glycol monododecyl ether was obtained at a tower top temperature of 140-143°C.
• Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that the amount of diethylene glycol dimethyl ether was changed from 105.5 g to 24.8 g. During the reaction, the mixture was separated into two layers, and when cooled to 25°C, the mixture was also separated into two layers. 63.3 g of an upper layer (A) and 98.4 g of a lower layer (B) were obtained. The upper layer (A) and the lower layer (B) were analyzed by gas chromatography, and the conversion rate of 1-dodecene, as well as the selectivity and yield of ethylene glycol monododecyl ether, are shown in Table 1.
• the upper layer (A) was distilled at 1 kPa to distill off the solvent and raw material components at a column top temperature of less than 140°C, and 12.3 g of ethylene glycol monododecyl ether was obtained at a column top temperature of 140 to 143°C.
• Example 3 40 g (0.20 mol) of 1-tetradecene, 50.6 g (0.82 mol) of monoethylene glycol, 105.0 g of diethylene glycol dimethyl ether, and 37.6 g of catalyst (1) were charged into a 500 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen, and then the atmosphere was maintained under nitrogen at normal pressure. The temperature was then raised to 135° C. while stirring at a rotation speed of 650 rpm, and the reaction was carried out at the same temperature for 4 hours. The liquid phase during the reaction was uniform. After the reaction, the reaction liquid was cooled to 25° C. and separated into two layers.
• the upper layers (A) and (C) were distilled at 0.5 kPa to distill off the solvent and raw material components at a tower top temperature of less than 142°C, and 15.6 g of ethylene glycol monotetradecyl ether was obtained at a tower top temperature of 142-145°C.
• Example 4 The reaction was carried out in the same manner as in Example 1, except that the amount of catalyst (1) was changed from 39.3 g to 6.6 g in Example 1. The liquid phase during the reaction was uniform. After the reaction, the reaction liquid was cooled to 25° C. and separated into two layers. 139.1 g of an upper layer (A) and 70.6 g of a lower layer (B) were obtained. The upper layer (A) and the lower layer (B) were analyzed by gas chromatography, and the conversion rate of 1-dodecene, as well as the selectivity and yield of ethylene glycol monododecyl ether, are shown in Table 1.
• the separated lower layer (B) was filtered, the catalyst was removed, and 9.1 g of diethylene glycol dimethyl ether, the solvent, was distilled off (pressure: 4 kPa, tower top temperature: 80 to 100° C.). Then, the mixture was cooled to 25° C. and separated into two layers, obtaining 14.5 g of an upper layer (C) and 40.5 g of a lower layer (D).
• the upper layer (A) and the upper layer (C) were distilled at 1 kPa to remove the solvent and raw material components at a column top temperature of less than 140°C, and 17.2 g of ethylene glycol monododecyl ether was obtained at a column top temperature of 140 to 143°C.
• Example 5 The reaction was carried out in the same manner as in Example 3, except that the amount of catalyst (1) was changed from 37.6 g to 5.6 g. The liquid phase during the reaction was uniform. After the reaction, the reaction liquid was cooled to 25° C. and separated into two layers. 128.4 g of an upper layer (A) and 70.8 g of a lower layer (B) were obtained. The upper layer (A) and the lower layer (B) were analyzed by gas chromatography, and the conversion rate of 1-tetradecene, as well as the selectivity and yield of ethylene glycol monotetradecyl ether, are shown in Table 1.
• the separated lower layer (B) was filtered, the catalyst was removed, and 11.7 g of diethylene glycol dimethyl ether, the solvent, was distilled off (pressure: 4 kPa, tower top temperature: 80 to 100° C.). Then, the mixture was cooled to 25° C. and separated into two layers, obtaining 13.6 g of an upper layer (C) and 39.9 g of a lower layer (D).
• the upper layer (A) and the upper layer (C) were distilled at 0.5 kPa to remove the solvent and raw material components at a column top temperature of less than 142°C, and 14.5 g of ethylene glycol monotetradecyl ether was obtained at a column top temperature of 142 to 145°C.
• Example 6 The reaction was carried out in the same manner as in Example 1, except that the amount of diethylene glycol dimethyl ether was changed from 105.5 g to 66 g. At the start of the reaction, the mixture was separated into two layers, but the liquid phase during the reaction (the liquid phase 120 minutes after the temperature was raised to 135° C.) was homogeneous. After the reaction, the reaction liquid was cooled to 25° C. and separated into two layers. 97.0 g of an upper layer (A) and 106.3 g of a lower layer (B) were obtained.
• the upper layer (A) and the lower layer (B) were analyzed by gas chromatography, and the conversion rate of 1-dodecene, as well as the selectivity and yield of ethylene glycol monododecyl ether, are shown in Table 1.
• the upper layer (A) was distilled at 1 kPa to distill off the solvent and raw material components at a column top temperature of less than 140° C., and 18.6 g of ethylene glycol monododecyl ether was obtained at a column top temperature of 140 to 143° C.
• the (poly)alkylene glycol monoalkyl ether obtained by the present invention is useful as a raw material for surfactants. Furthermore, the higher secondary alcohol alkoxylate adduct obtained by adding alkylene oxide is useful as a cleaning agent, emulsifier, fiber treatment agent, etc.

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