JP2003183383A - Manufacturing method of cyclic ether adduct of alcohol with less smell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a cyclic ether adduct of an alcohol having little impurities and particularly having less smell in high efficiency. <P>SOLUTION: The method of manufacturing the cyclic ether adduct of the alcohol represented by formula (1) havin little impurities is added to and reacted with a secondary and/or tertiary mono-ol and/or polyol in the presence of a catalyst (c) represented by formula (2) and/or (3). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of a ring-opening polymer having a small amount of impurities, especially an odor, which is obtained by ring-opening addition polymerization of a cyclic ether compound to a secondary or tertiary alcohol. More specifically, the secondary grade having 4 to 20 carbon atoms and /
Alternatively, a method for producing a cyclic ether adduct having a small amount of impurities, particularly an odor, which is obtained by ring-opening polymerization of a cyclic ether compound into an alcohol composed of a tertiary monool and / or polyol in the presence of a specific catalyst Regarding

[0002]

As a method for ring-opening polymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, glycidol and epichlorohydrin to secondary and tertiary alcohols, it is usually used for ring-opening polymerization of cyclic ether compounds of primary alcohols. When an alkaline catalyst such as NaOH or KOH is used, the addition rate of the cyclic ether compound to alcohol is low, and the addition molar distribution of the cyclic ether compound is wide,
Only cyclic ether adducts with a high content of unadded alcohol were obtained. Therefore, for example, as a method for producing an alkyleon oxide into a secondary or tertiary alcohol, Japanese Patent Publication No.
9268 uses a method of ring-opening polymerization in the presence of a Lewis acidic catalyst such as BF3, and JP-A-53-119809 uses a method of ring-opening polymerization in the presence of a Lewis acidic catalyst such as indium halide.

[0003]

However, the method for producing a cyclic ether adduct of a secondary or tertiary alcohol in which a cyclic ether compound is subjected to a ring-opening reaction in the presence of the above-mentioned catalyst is, for example, dioxane generation or ether chain cleavage. However, there is a problem that the yield of the cyclic ether adduct of the secondary and tertiary alcohol is low, resulting in a large amount of residual alcohol, which requires purification such as distillation, which results in cost reduction. There was a drawback to rising. Further, in order to remove these by-products, it is also necessary to remove the by-products by washing with water or alkaline water, and even if these processes such as distillation are performed, the problem of odor that is presumed to be caused by impurities containing by-products was there. In particular, when a large amount of residual alcohol is present in the cyclic ether adduct of alcohol, when the ring-opening polymer of the cyclic ether compound is used as a surfactant, it is separated as water-insoluble matter, smells, and has strong skin irritation. There were drawbacks such as. Further, it gives an unpleasant odor to the sulfated product (Japanese Patent Publication No. 51-43483) and gives an unfavorable result to the performance as a surfactant (US Pat. No. 36).
Therefore, it is necessary to reduce the residual alcohol as much as possible.

Further, depending on the use of the ring-opening polymer thus obtained, the remaining catalyst has a significant adverse effect, so that it is necessary to remove the catalyst by a treatment after the ring-opening polymerization. In view of the above-mentioned present situation, an object of the present invention is to provide a method for producing a ring-opening polymer having few impurities, particularly improved odor, by subjecting a cyclic compound to ring-opening addition polymerization in the presence of a specific catalyst.

[0005]

Means for Solving the Problems The present invention provides a second conventional method.
It is intended to solve the above-mentioned problems of a cyclic ether addition product of a primary and / or tertiary monool and / or a polyol and a method for producing the same. That is, in the present invention, when a cyclic ether compound is subjected to ring-opening addition polymerization of a secondary and / or tertiary monool and / or polyol having 4 to 20 carbon atoms, the cyclic ether compound is opened in the presence of a specific catalyst. It was found that the cycloaddition polymerization improved the yield, suppressed the production of by-products, and improved the odor, as compared with the conventional catalysts, and completed the present invention.

That is, the present invention provides a cyclic ether compound (B) represented by the general formula (1) with a secondary and / or tertiary monool and / or polyol having 4 to 20 carbon atoms. In the cycloaddition polymerization, an alcohol cyclic ether adduct having a small amount of impurities, characterized by carrying out an addition reaction in the presence of a catalyst (C) represented by the general formula (2), and a method for producing the same. And a cyclic ether adduct of alcohol having a small amount of impurities, which is obtained by purifying the alcohol cyclic ether adduct by operations such as washing with water, washing with alkaline water, distillation and adsorption. Further, using the alcohol cyclic ether adduct and / or the purified cyclic ether adduct of alcohol as a raw material, the cyclic ether compound (B) is further added with a catalyst (D) such as an alkali catalyst, an alumina magnesia catalyst, an amine catalyst or the like. Alcohol cyclic ether adduct with few impurities. Also, the present invention relates to a method for producing a sulfated product of an alcohol cyclic ether adduct having a small amount of impurities obtained by sulfating the cyclic ether adduct of each alcohol, particularly having an improved odor.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic ether adduct of alcohol having a small amount of impurities and the method for producing the same according to the present invention is an alcohol composed of a secondary and / or tertiary monool and / or polyol having 4 to 20 carbon atoms. In (A),
It can be obtained by subjecting the cyclic ether compound (B) represented by the general formula (1) to ring-opening addition polymerization in the presence of the catalyst (c) represented by the general formula (2). The secondary and / or tertiary monool and / or polyol used in the present invention has an alcohol having 4 to 20 carbon atoms, preferably 6 to 18 carbon atoms.
The range is more preferably 8 to 16, and more preferably 10 to 16.
Is more preferable, and 12-14 is the most preferable. These alkyl groups may be a mixture, and may be linear or branched. Secondary alcohols and their alkyl ethers with 3 or less carbon atoms can be
Since the cyclic ether compound can be easily added to some extent, the necessity of using the present catalyst (C) is low, which is not preferable in terms of cost. In addition, secondary monools and / or polyols are preferable to tertiary monools and / or polyols in terms of performance when used as a surfactant. The position of addition of the hydroxyl group to the secondary and / or tertiary monool and / or polyol is not particularly limited, but it is preferable to add them as evenly as possible.
It is preferable in terms of performance when used as a surfactant. The addition position is represented by the addition position of the hydroxyl group counted from the carbon at the terminal of the alkyl group. For example, in the case of a secondary alcohol having 12 carbon atoms, there are 2,3,4,5,6 positions. As a preferable hydroxyl group addition position distribution, the maximum amount of a single addition position component is 80% by weight or less, more preferably 70% by weight or less, further preferably 50% by weight or less, and most preferably 40% by weight or less. is there. The secondary and / or tertiary monool and / or polyol may be a mixture of monool and polyol. Preferably, the secondary and / or tertiary monool contains 2 to 20% by weight, preferably 4 to 15%, more preferably 4 to 10% of a polyol such as a secondary and / or tertiary diol. It is preferable to do so because when used as a surfactant or the like, the freezing point is lowered and the viscosity of the aqueous solution composition when used as a detergent composition is lowered. Examples of such secondary and / or tertiary monool include 2-octanol and C12-14 secondary alcohol (trade name: Softanol-A manufactured by Nippon Shokubai Co., Ltd.). Examples of polyols such as secondary and / or tertiary diols include C12-14 secondary diols (trade name: Softanol-D manufactured by Nippon Shokubai Co., Ltd.). Cyclic ether compound (B) of the present invention
Is represented by the following general formula (1).

[0008]

[Chemical 3]

R1 and R2 are H, a branched or straight-chain alkyl group having C = 1 to 4, an aryl group, --CH2-M
(M = OH, F, Cl, Br, -O-R3 (R3 = 1 to 1
20 functional groups represented by alkyl groups, aryl groups, and allyl groups)), and may be the same or different. Preferred cyclic ether compound (B) has R1 = R2
= H or R1 = H, R2 = methyl group. Examples of the cyclic ether compound (B) include ethylene oxide, propylene oxide, butylene oxide, glycidol, epichlorohydrin, and the like, and ethylene oxide or propylene oxide is preferable in terms of cost or when used as a surfactant. These cyclic ether compounds (B) can be used alone or in combination. In addition, it is also possible to add each block in a random manner or in combination with a random block. The average number of moles added to these secondary and / or tertiary alcohols is in the range of 1 to 100, preferably 3 to 50, and more preferably 3 to 2.
It is 0, more preferably 3 to 15. The catalyst (C) used in the present invention is represented by the following general formula (2) and / or (3).

[0010]

[Chemical 4]

X = B, Al, Ga, In atoms, R4 to R
6 are selected from the fluorine atom and the compounds represented by the general formula (4) and / or the general formula (5) and may be the same or different, but R4 to R6 are not fluorine atoms at the same time. -Finyl group- (Y) n General formula (4) Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group or a cyano group, and may be the same or different. -C- (Z) n General formula (5) Z represents an alkyl group having 1 to 5 carbon atoms and may be the same or different. _{(MSO 3) pX (D- (} R7) -Eq) in r general formula (3), M represents a perfluoroalkyl or perfluoroalkyl aryl group, X = B, Al, Ga , In atoms, D is oxygen, sulfur , Selenium, N (R8) or P (R8), wherein R8 is an H atom or an alkyl or aryl group having 1 to 20 carbon atoms, R8 can form a ring together with R7, and R7 is a carbon atom. C1 selected from the alkylene, arylene or aralkylene groups of formula 1 to 30
To 30 hydrocarbon groups, E is H, or alkyl or aryl groups having 1 to 10 carbon atoms, O (R9), N (R
9) (R10), halogen, S (R9) or P (R
9) represents (R10), provided that R9 and R10 may be the same or different from each other, and each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms selected from an alkyl, aryl or aralkyl group, and R9 is R10. Alternatively, R7 may form one or more rings with R7, and / or R10 may form one or more rings with R7 or R9, p is an integer of 0 to 3, and r is 1 to Is an integer of 3 and q is an integer of 0-10.

X in the general formula (2) is X = B, A
l, Ga, and In atoms, and preferably a boron atom. R1, R2, and R3 in the general formula (2) are selected from a fluorine atom, compounds represented by the general formula (4) and / or the general formula (5), and may be the same or different, but R1 ~ R3 is not a fluorine atom at the same time. R1
~ BF3 as a compound in which R3 is a fluorine atom at the same time
Is mentioned. Y in the general formula (4) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group or a cyano group, which may be the same or different. Among these, preferred are a hydrogen atom, a halogen atom and a cyano group, and more preferred are a halogen atom and a cyano group. Moreover, n represents the number of 0-5. Specific examples of the phenyl group or the substituted phenyl group represented by the general formula (5) include a pentafluorophenyl group, a phenyl group, a p-methylphenyl group, a p-cyanophenyl group and a p-nitrophenyl group. Preferred are pentafluorophenyl group, phenyl group and p-cyanophenyl group, more preferred are pentafluorophenyl group and phenyl group, and most preferred are pentafluorophenyl group.

Z in the general formula (5) each independently represents an alkyl group having 1 to 5 carbon atoms and may be the same or different. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like. Specific examples of the tertiary alkyl group represented by the general formula (5) include t
Examples include -butyl group and t-pentyl group.

In the present invention, in the above general formula (2),
Specific examples include triphenylborane, tri (t-butyl) borane, diphenyl-t-butylborane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, bis (pentafluorophenyl) borane. , Di (t-butyl) borane fluoride, (pentafluorophenyl) borane difluoride,
(T-Butyl) borane difluoride, triphenylaluminum, diphenyl-t-butylaluminum, tri (t
-Butyl) aluminum, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl)
-T-butylaluminum, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluorophenyl) aluminum difluoride, (t-butyl) aluminum difluoride, triphenylindium, Examples thereof include tris (pentafluorophenyl) indium, and preferred are triphenylborane, triphenylaluminum, tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, and tris (pentafluorophenyl) indium. Tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum are preferable, and tris (pentafluorophenyl) borane is particularly preferable. The method for producing the general formula (2) of the present catalyst (C) is not particularly limited, but the method disclosed in JP-A-9-227574 is preferable.

In the present invention, the above general formula (3) is
(MSO ₃ ) pX (D- (R7) -Eq) r, wherein M represents a perfluoroalkyl or perfluoroaryl group, X represents a B, Al, Ga, In atom,
D is oxygen, sulfur, selenium, N (R8) or P (R
8) in which R8 is an H atom or has 1 to 2 carbon atoms.
0 is an alkyl or aryl group, R8 can form a ring together with R7, R7 represents a C1-30 hydrocarbon group selected from an alkylene, arylene or aralkylene group having 1 to 30 carbon atoms, and E is E H, or an alkyl or aryl group having 1 to 10 carbon atoms, O (R9)
, N (R9) (R10), halogen, S (R9) or P (R9) (R10), provided that R9 and R
10's may be the same as or different from each other, each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and is selected from an alkyl, aryl or aralkyl group, R9 is R10 or R7 together with one or more rings. Can be formed,
And / or R10 together with R7 or R9 is 1
Can form more than one ring, p is an integer from 0 to 3, r is an integer from 1 to 3, and q is an integer from 0 to 10. MS
O3 is trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, heptadecanefluorooctanesulfonic acid, tridecafluoromethylcyclohexylsulfonic acid, 5-trifluoromethyldodecafluorohexanesulfonic acid or pentafluorophenylsulfone. An acid, preferably a substitution product of trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid or perfluoroarylsulfonic acid. The unit D- (R7) -E is preferably methanolate, ethanolate, i-propanolate, tert-butanolate, cyclohexanolate, benzyl alcoholate, 2-methoxyethanolate, 2- (2-piperidyl) ethanolate, 2,2,2. 2-trifluoroethanolate, 1,1,1,3,3,3-hexafluoroisopropanolate, 2- (methylmercapto) ethanolate, 3-dimethylphosphanylphenolate, 2-dimethylamino-cyclohexanolate, Ethyl thiolate, benzyl thiolate, 2-methoxyethane thiolate, methyl selenate, N-methylanilide, 6-methoxy-2,3-dihydroindolate, phenolate,
Quinoline-7-oleate, 3-methoxyphenolate,
3,5'-methoxyphenolate, 3-methyl-4-dimethyl-aminophenolate, 3-dimethylaminophenolate, 2-fluorophenolate, pentafluorophenolate, 3-tert-butylphenolate,
2,6-di-tert-butyl-4-methylphenolate, 3-methylmercaptophenolate, 3,5-trifluoromethylphenolate, 3,5-dimethoxy-phenolate, 2- (2-pyridyl) phenol Rate, 6-
Methoxyindolate, 2'-methoxybiphenyl-2
-Oleate, 2'-methoxy-1,1'-binaphthalenyl-2-oleate or 8-methoxy-2-naphtholate, more preferably 1,1,1,3,3,3, -hexafluoroisopropanolate, pheno Rate, 3-methoxyphenolate, 3,5-methoxyphenolate, 3
-Methyl-4-dimethylamino-phenolate, 3-
(N, N-dimethylamino) phenolate, 3-fluorophenolate, pentafluorophenolate, 3-methylmercaptophenolate, 3,5-trifluoromethyl-phenolate, 3,5-dimethoxyphenolate or 6- It is methoxy indole.

In the present invention, in the above general formula (3),
Specific examples include aluminum bis (trifluoromethanesulfonate) phenolate, aluminum bis (trifluoromethanesulfonate) -3-methyl-4-N,
N-dimethylaminophenolate, aluminum bis (trifluoromethanesulfonate) -3-N, N-dimethylaminophenolate, aluminum bis (trifluoromethanesulfonate) -3-methoxyphenolate, aluminum bis (trifluoromethanesulfonate) -3- Fluorophenolate, aluminum bis (trifluoro-methanesulfonate) -3,5-difluorophenolate, aluminum bis (trifluoromethane-sulfonate) -pentafluorophenolate, aluminum bis (trifluoromethane-sulfonate) -6-methoxyindolate , Aluminum bis (trifluoromethane-sulfonate) -5-tert
-Butylphenolate, aluminum bis (trifluoromethane-sulfonate) -3,5-di-tert-butylphenolate, aluminum bis (trifluoromethane-sulfonate) -3,5-dimethoxyphenolate, aluminum bis (trifluoromethane-sulfonate) ) -3-Mercaptophenolate, aluminum bis (trifluoromethanesulfonate) -3-methanolate, aluminum bis (trifluoromethanesulfonate) -3-ethanolate, aluminum bis (trifluoromethanesulfonate) -3-isopropanolate, aluminum bis ( Trifluoromethanesulfonate) -3-tert-butyrate, aluminum bis (trifluoromethanesulfonate) -3-benzylate, aluminum bi (Trifluoro - methanesulfonate) -3-cyclohexanol rate or aluminum bis (trifluoromethane - sulfonate) -3-methoxy cyclohexanol rate and the like, aluminum bis (trifluoromethanesulfonate) phenolate is preferable. The amount of the catalyst (C) to be used is not particularly limited, but is 0.0001 to 5% by weight, preferably 0.0001 to the cyclic ether adduct of the alcohol produced.
It is 1 to 0.5% by weight. Compared with the conventionally used BF3 catalyst, impurities such as dioxane and ether chain decomposition products such as polyethylene glycol are reduced, which is preferable. The cyclic ether adduct of alcohol obtained by this production method has few impurities and especially has improved odor. The dioxane content in the cyclic ether adduct of alcohol obtained by this production method is preferably 0.1 wt% or less,
It is more preferably 0.07 wt% or less, still more preferably 0.05 wt% or less. As the ether chain decomposed product, when the addition mole number of cyclic ether is 1.5 to 2 moles,
1 wt% or less is preferable, more preferably 0.7 wt%
Or less, more preferably 0.5 wt% or less. Also, secondary and / or tertiary monools and / or
Alternatively, the addition rate of the cyclic ether compound (B) to the alcohol (A) composed of a polyol is improved, and the residual rate of the unreacted alcohol (A) after the reaction is reduced, so that the yield is improved. The content of unreacted alcohol is preferably 50 wt% or less, and more preferably 40 wt% or less when the number of added moles of cyclic ether is 1.5 to 2 mol. The cyclic ether adducts of alcohols of the present invention, which are used in the present invention and have a small amount of impurities, particularly improved odor, have 4 to 2 carbon atoms.
0 secondary and / or tertiary monools and / or
Alternatively, the cyclic ether compound (B) represented by the general formula (1) is added to the alcohol (A) composed of a polyol in the presence of the catalyst (C) represented by the general formula (2) and / or (3). Obtained by cycloaddition polymerization. As the production method thereof, the cyclic ether compound (B) may be fed as a gas or a liquid in the presence of the alcohol (A) and the catalyst (C), and the catalyst (C) and the cyclic ether compound may be fed to the alcohol (A). (B) may be fed as a gas or a liquid. The alcohol (A), the cyclic ether compound (B), and the catalyst (C) may be appropriately dissolved in a solvent before use. As a method of feeding the cyclic ether compound (B) and / or the catalyst (C), the cyclic ether compound (B) may be fed into the alcohol (A) liquid, or may be fed into the gas phase portion by a showering device or the like. The reaction solution is circulated by a pump or the like and fed from the upper part of the kettle by a showering device or the like to promote the dissolution of the cyclic ether compound (B) in the gas phase into the alcohol (A), thereby increasing the reaction rate. It is possible to improve or efficiently remove the residual cyclic ether compound (B). The water content when performing the ring-opening addition polymerization is
1 for cyclic ether adduct of alcohol produced
It is 000 ppm or less, preferably 500 ppm or less, more preferably 200 ppm or less. If the water content is large, the catalyst (C) will decompose, or water and cyclic ether compound (B)
It is not preferable because the reaction product and the ether chain decomposition product increase. The addition temperature at the time of carrying out the ring-opening addition polymerization is not particularly limited, but is preferably in the range of 0 to 200 ° C, more preferably 20 to 160 ° C, further preferably 40 to 100 ° C.
C., particularly preferably in the range of 40-80.degree. If the temperature is too low, the reaction rate becomes slow and the reaction time becomes long.
In addition, there is a drawback that impurities and ether chain decomposition products increase due to a longer reaction time. On the other hand, if the temperature is too high, it is preferable that the reaction rate becomes faster and the reaction time becomes shorter, but the decomposition reaction also becomes faster and there is a drawback that impurities and ether chain decomposition products increase. The reaction apparatus for carrying out the ring-opening addition polymerization is not particularly limited, but a batch reaction vessel or a tube type continuous polymerization apparatus can be used. When using a tube-type continuous polymerization device,
It is possible to heat or remove heat by flowing the reaction solution into the bath and passing a heat medium to the outside, and the reaction heat can also be controlled by feeding the cyclic ether compound (B) from several places. The catalyst (C) in the produced cyclic ether adduct of alcohol may be subjected to a removal treatment. As the removal method, after neutralizing with an alkali such as NaOH or KOH, a method of removing by washing with water, a method of removing with an adsorbent such as synthetic silicate, alumina magnesia, activated clay, diatomaceous earth, activated carbon, an ion exchange resin There is a method of using. Further, for the purpose of removing the residual cyclic ether and light impurities from the cyclic ether adduct of alcohol, deodorization can also be carried out under reduced pressure by bubbling with an inert gas such as nitrogen, steam or water. The cyclic ether adduct of alcohol of the present invention used in the present invention has 4 to 20 carbon atoms.
To the alcohol (A) consisting of the secondary and / or tertiary monool and / or polyol of the cyclic ether compound (B) represented by the general formula (1), the general formula (2) and / or ( After ring-opening addition polymerization in the presence of the catalyst (C) represented by 3), it is desirable to remove impurities such as dioxane and ether chain decomposition products such as polyethylene glycol by washing with alkaline water.
Distillation to remove unadded alcohol and the like is desirable from the viewpoints of narrow distribution of addition moles of the cyclic ether compound to alcohol and performance and odor when used as a surfactant. At this time, the residual alcohol concentration of the purified cyclic ether adduct of alcohol and / or the concentration of the ether chain decomposition product such as polyethylene glycol is 1% or less, preferably 0.5% or less, more preferably 0%. It is 0.3% or less, and more preferably 0.1% or less. The washing method and the distillation method used in the present invention can be performed by known methods. To wash with water, cyclic ether compound (B) to alcohol (A)
It is preferable that the average number of added moles of is less than 3 moles, preferably less than 2 moles in order to prevent poor separation of the interface due to emulsification of the alcohol phase and the aqueous phase and migration of the cyclic ether adduct of alcohol to the aqueous phase. . Further, when the number of moles of the cyclic ether addition of the cyclic ether adduct of the alcohol and the cyclic ether adduct of the purified alcohol is further increased, a catalyst (D) such as an alkali catalyst, an alumina magnesia catalyst, an amine catalyst or the like which is usually used generally. It is preferable to increase the number of moles of the cyclic ether compound (B) to be added by further adding the cyclic ether compound (B) in order to reduce the cost and the generation of impurities. Further, the cyclic ether adduct of alcohol, the cyclic ether adduct of purified alcohol, and the cyclic ether adduct of alcohol in which the molar number of cyclic ether addition is further increased are known methods, for example, JP-A-10-45703.
By sulphating according to the above method, it is possible to obtain an alkyl ether sulfate having less alkyl sulfate and impurities and less odor. Further, the cyclic ether adduct of alcohol, the cyclic ether adduct of purified alcohol, and the cyclic ether adduct of alcohol in which the molar number of cyclic ether addition is further increased are used as raw materials.
842, an ether carboxylic acid compound added with monochloroacetic acid by the method of registered patent 322080 or the like and JP-A-59-1
It is also possible to produce a sulfate ester by a method such as 93863 and JP-A-57-149263, and a sulfosuccinic acid half ester salt by a method such as JP-A-54-24825. These cyclic ether adducts of alcohols and sulfated products of cyclic ether adducts of alcohols can be used as surfactants and can be blended with various detergent additives to form a detergent composition. The use in the field of is not particularly limited. For example, lubricants and metalworking oils, plasticizer raw materials, resin compositions, drilling agents, fiber oils,
It can be used in the fields of paper medicine, defoaming agents, cosmetics and the like.
Examples of miscible additives for various detergents include primary alcohol ethoxylates, primary alcohol ethoxylate propoxylates, nonylphenol ethoxylates, amine oxides, nonionic activators such as alkanolamines, anion activators such as LAS, AES, AS, AOS , Cationic activator, (meth) acrylic acid builder, (meth) acrylic acid-maleic acid copolymer builder, aspartic acid builder, crystalline aluminosilicate, sodium silicate, oil absorbing powder, optical brightener,
Enzymes, pH adjusters, bactericides, viscosity adjusters such as EtOH,
Examples thereof include water-soluble polymers such as polyethylene glycol, polyamines, and polyamine alkoxylates. The field in which the surfactant and the detergent composition can be used is not particularly limited, but includes clothing, textile products, tableware, containers, miscellaneous goods appliances, foods, foods, homes, furniture, automobiles, aircrafts, metal products. , Shampoo-, body shampoo, emulsification;
Mineral oil, animal and vegetable oil, synthetic oil, pesticide, metalworking oil, dye,
Examples include fields such as emulsifiers for emulsion polymerization.

[0017]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, parts and% are based on weight unless otherwise specified. Synthesis Example 1 1000 g of a mixture of saturated aliphatic hydrocarbon having an average molecular weight of 184 and carbon number of 12 to 14 and 25 g of metaboric acid were placed in a cylindrical reactor having a volume of 3 L and an oxygen concentration of 3.5 vol.
%, Nitrogen concentration 96.5% gas 430L per hour
Was blown in and the oxidation reaction was carried out at 170 ° C. for 2 hours under normal pressure. 50% of this oxidation reaction mixture is mixed with a large amount of hot water (9
It hydrolyzed at (5 degreeC), and isolate | separated the oil layer containing the produced | generated alcohol. By mixing the remaining 50% of the oxidation reaction liquid with this oil layer, the orthoboric acid ester equivalent was 1.0
It was adjusted so that 4 equivalents of borate ester forming compound were present. This was subjected to orthoboric acid esterification of alcohol at Pa 170 ° C. for 200 hours. The mixture containing the orthoborate ester was flash distilled at 7 hPa to remove unreacted saturated aliphatic hydrocarbons until the temperature of the residual liquid reached 170 ° C. Then, the residual liquid was hydrolyzed with a large amount of hot water at 95 ° C. to remove boric acid in the aqueous phase. The obtained oil layer was saponified and washed with water to remove the organic acid and the organic acid ester. This oil phase was fractionally distilled at 7 hPa, and the boiling point range of 95 to 120 ° C as the first fraction was a small amount of a mixture of paraffin, carbonyl compound, and monohydric primary alcohol. The boiling point range of 120 to 150 ° C. as the second fraction is a trace amount of carbonyl compound and polyhydric secondary alcohol,
Most were monohydric secondary alcohols. This second fraction is referred to as synthetic product (1). This second distillate is a monohydric secondary alcohol (trade name: Softanol-A (SOFT-A)
(Manufactured by Nippon Shokubai Co., Ltd.) and / or as a raw material for monohydric secondary alcohol alkoxylates (trade name: Softanol each series manufactured by Nippon Shokubai Co., Ltd.). This SOF
The carbon distribution of T-A is C12 / 13/14 = 20/55.
/ 25, additional position distribution is 2/3/4 / in terms of GC area ratio
The ratio was 5/6/7 position = 18/18/18/19/19/8. The bottom component was a polyhydric secondary alcohol and a resinous high boiling point compound. Bottom component is 7.3h
Pa, C12 obtained by simple distillation at 170 to 180 ° C
A polyhydric secondary alcohol containing 14 diols as a main component (trade name: Softanol-D (SOFT-D) manufactured by Nippon Shokubai) is obtained. As for the hydroxyl value of the obtained Softanol-D, a product having a range of about 425 to 465 mgKOH / g can be obtained. This is designated as a synthetic product (2). Analysis method of addition position Gas chromatography method Gas chromatogram: Shimadzu GC-17A Column: J & W Scientific, DB-5HT
(Length: 30 m inner diameter; 0.25 mm film thickness; 0.1 μm) Temperature conditions 50 ° C (hold for 10 minutes) → 5 ° C / min → 350 ° C
(Hold for 40 minutes) Sample injection amount: Analyzed under the condition of 1 μL, and calculated from the area ratio of the obtained chart. This result is in good agreement with the analysis result at the two positions by NMR analysis.

[0018]

Example 1 Synthesis product (1) of Synthesis Example 1 (second fraction SOF
TA (hydroxyl value 280 mgKOH / g) and synthetic product (2) (polyhydric secondary alcohol (hydroxyl value 440 mgK)
OH / g)) was mixed at a weight ratio of 94/6, and 1 kg was charged in a stainless steel 3 L autoclave equipped with a stirrer, a thermometer, and an EO introduction tube, and the atmosphere was replaced with nitrogen. After that, 0.49 g of tris (pentafluorophenyl) borane was charged, and 0.5 to 5 mol of ethylene oxide was fed to 1 mol of the hydroxyl group at an initial nitrogen pressure of 0.05 MPa and 50 ± 5 ° C. to add it. The alcohol cyclic ether adducts (1-1 to 6) described in 1 were obtained. Table 1 shows the amount of impurities in each addition mole number.

[0019]

Example 2 2EO adduct of the alcohol cyclic ether adduct obtained in Example 1 (cyclic ether adduct (1-
To 4)), add a NaOH solution and wash the reaction solution at 90 ° C.
Further, it was washed with water until the pH became 7 or less. Then, the oil phase was charged into a 3 L glass three-necked flask, and a distillation column (packing Dickson packing theoretical plate number 3 stages, inner diameter 40 mm, length 200 mm) was attached, and the mixture was distilled to give an average addition mole number of 3. 1 mole of an ethoxylate adduct, an alcohol cyclic ether adduct (2), was obtained. The yield was 66% based on alcohol, and the residual alcohol was 0.22%.

[0020]

Comparative Example 1 Comparative alcohols shown in Table 1 were prepared in the same manner as in Example 1 except that 0.49 g of tris (pentafluorophenyl) borane was replaced by 1.68 g of BF3-Et catalyst (BF3 concentration 46-49%). Cyclic ether adduct (1
-1 to 6) were obtained. Table 1 shows the amount of impurities in each addition mole number.

[0021]

Comparative Example 2 The 1.5 EO adduct of the alcohol cyclic ether adduct (Comparative alcohol cyclic ether adduct (1-3)) obtained in Comparative Example 1 was distilled in the same manner as in Example 2, A comparative alcohol cyclic ether adduct (2) was obtained. The average number of moles added was 3 moles per mole of hydroxyl groups. The yield was 55% based on alcohol, and the residual alcohol was 0.28%.

[0022]

Example 3 In the same manner as in Example 1 except that 0.49 g of tris (pentafluorophenyl) borane was changed to 0.025 g, 5 mol of ethylene oxide was fed to 1 mol of hydroxyl group to give an alcohol cyclic ether adduct. (3) was obtained.

[0023]

Example 4 The polyhydric secondary alcohol described in Synthesis Example 1 (hydroxyl value 440 mgKOH / g) was added to a stirrer, a thermometer,
1kg in SUS 3L autoclave with EO conduit
Charged and purged with nitrogen. After that, 0.049 g of aluminum bis (trifluoromethanesulfonate) was charged,
At an initial nitrogen pressure of 0.05 MPa and 55 ± 5 ° C., EO was added by feeding 3 feeds to 1 mol of hydroxyl groups. Then KOH
The reaction solution was washed with water at 90 ° C., and further washed with water until the pH became 7 or less. From the average addition mole number of hydroxyl groups, 3 moles of polyhydric secondary alcohol ethoxylate adducts shown in Table 1 were added. Alcohol cyclic ether adduct (4)
Got The hydroxyl value was 280 mgKOH / g.

[0024]

[Embodiment 5] SU with a stirrer, thermometer, and EO tube
Into a S 3L autoclave, 1 kg of an alcohol cyclic ether adduct (2) and an aqueous NaOH solution (49 wt%) were added.
After charging 56 g and substituting with nitrogen, dehydration was performed while bubbling nitrogen with 0.005 MPa. Then, the initial nitrogen pressure was 0.
At 05 MPa and 55 ± 5 ° C., 4 moles of EO was additionally fed to 1 mole of hydroxyl group and added. Then, acetic acid was added to neutralize the mixture to pH 7 to obtain an alcohol cyclic ether adduct (5). The residual alcohol was 0.14%.

[0025]

Comparative Example 3 A comparative alcohol cyclic ether adduct (3) was obtained by the same procedure as in Example 5, except that the alcohol cyclic ether adduct (2) was changed to the comparative alcohol cyclic ether adduct (2).

[0026]

Example 6 Into a SUS 3L autoclave equipped with a stirrer, a thermometer, and an alkylene oxide conduit tube, 1 kg of an alcohol cyclic ether adduct (2), an aqueous solution of NaOH (4
9 wt%) was charged, and the atmosphere was replaced with nitrogen.
It was dehydrated while bubbling with 005 MPa nitrogen. Then, at an initial nitrogen pressure of 0.05 MPa and 55 ± 5 ° C., 4 mol of EO was added to 1 mol of the hydroxyl group, and 2.5 mol of PO was added to 1 mol of the hydroxyl group, and added. Then, lactic acid was added to neutralize to pH 7 to obtain an alcohol cyclic ether adduct (6).

[0027]

[Example 7] Synthetic product (1) of Synthesis Example 1 (second fraction SOF
1 kg of TA (hydroxyl value 280 mgKOH / g) was charged into a stainless steel 3 L autoclave equipped with a stirrer, a thermometer, and an EO introducing tube, and the atmosphere was replaced with nitrogen. After that, 0.49 g of tris (pentafluorophenyl) borane was charged, and PO was carried out at an initial nitrogen pressure of 0.05 MPa and 55 ± 5 ° C.
An alcohol cyclic ether adduct was obtained by feeding 2 mol of hydroxyl group to 1 mol of hydroxyl group and adding. Then N
An aOH solution was added, the reaction solution was washed at 90 ° C., and further washed with water until the pH became 7 or less. Then, the oil phase was charged into a 3 L glass three-necked flask, and the distillation column (packing Dickson packing theoretical plate number 3 stages, inner diameter 40 mm, length 200 m).
m) was attached and the mixture was distilled to obtain an alcohol cyclic ether adduct (7) which was a propoxylate adduct of 3 mol per 1 mol of the average added mol number of hydroxyl groups.

[0028]

Example 8 Alcohol cyclic ether adduct (2) 25
0 g was reacted with 63 g of anhydrous sulfuric acid (trade name: Nisso sulfane, manufactured by Nippon Soda Co., Ltd.). The sulfate thus obtained was neutralized with 270 g of a 12.7% by weight sodium hydroxide aqueous solution to obtain a viscous aqueous solution of a secondary alcohol ethoxysulfate salt. The concentration of this secondary alcohol ethoxysulfate sodium salt aqueous solution (1) was 56.1% by weight, and it was liquid at room temperature.

[0029]

Comparative Example 4 Comparative secondary alcohol ethoxysulfate sodium salt aqueous solution (1) was prepared in the same manner as in Example 8 except that the alcohol cyclic ether adduct (2) was changed to the comparative alcohol cyclic ether adduct (2).
Got The concentration of the comparative secondary alcohol ethoxysulfate sodium salt aqueous solution (1) was 56.5% by weight, which was a liquid at room temperature.

[0030]

Example 9 Alcohol cyclic ether adduct (5) 21
7 g (0.67 mol) was charged into a 500 ml flask and cooled to 10 ° C. In this, chlorosulfonic acid 8
6.3 g (0.74 mol) was added dropwise over about 1 hour. During the dropping, the liquid temperature was maintained at 10 to 15 ° C. After the chlorosulfonic acid was added dropwise, nitrogen gas was passed through the reaction solution to remove the by-product hydrogen chloride gas, and then the reaction solution was added dropwise to the sodium hydroxide solution while maintaining the temperature at 20 ° C or lower. The mixture was hydrated to obtain an about 25% aqueous solution of the desired secondary dodecyl ether sulfate ester salt (1).

[0031]

Example 10 Alcohol cyclic ether adduct (1)
(7), and comparative alcohol cyclic ether adducts (1) to (3), secondary alcohol ethoxysulfate sodium salt aqueous solution (1), comparative secondary alcohol ethoxysulfate sodium salt aqueous solution (1), secondary dodecyl The odor of the ether sulfate ester salt (1) was evaluated by a sensory test in the following 5 grades. Also, the acid value,
Carbonyl number, hue and residual alcohol were analyzed by the following methods. The results are shown in Table 2.

[0032]

[Table 1]

[0033]

[Table 2]

Odor evaluation point 5 points No odor 4 points Slight odor 3 points Odor 2 points Slightly unpleasant odor Unpleasant odor analysis Method of residual alcohol gas chromatographic analysis column (DB-5H manufactured by J & W Scientific)
It diluted with the ethanol solution in (T) and quantified by creating a calibration curve with unadded alcohol.

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, cyclic ether adducts of secondary and tertiary alcohols and sulphates of cyclic ether adducts of secondary and tertiary alcohols containing few impurities and having particularly improved odor are used. Surfactant and detergent compositions can be obtained.

Claims (5)

[Claims] 1. A cyclic ether compound (B) represented by the general formula (1) in an alcohol (A) consisting of a secondary and / or tertiary monool and / or polyol having 4 to 20 carbon atoms. In the ring-opening addition polymerization of (1), an alcohol containing a small amount of impurities, particularly an odor-improved alcohol, obtained by the addition reaction in the presence of the catalyst (C) represented by the general formula (2) and / or (3) Process for producing cyclic ether adduct. [Chemical 1] R1 and R2 are H, a branched or straight-chain alkyl group having C = 1 to 4, an aryl group, -CH2-M (M = OH,
It is selected from the functional groups represented by F, Cl, Br, and -O-R3 (R3 = 1 to 20 alkyl group, aryl group, allyl group), and may be the same or different. [Chemical 2] X = B, Al, Ga, In atom, R4 to R6 are selected from a fluorine atom, a compound represented by the general formula (4) and / or the general formula (5) and may be the same or different, but R4 ~ R6 is not a fluorine atom at the same time. -Finyl group- (Y) n General formula (4) Y represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, a nitro group or a cyano group, and may be the same or different. -C- (Z) n General formula (5) Z represents an alkyl group having 1 to 5 carbon atoms and may be the same or different. _{(MSO 3) pX (D- (} R7) -Eq) in r general formula (3), M represents a perfluoroalkyl or perfluoroalkyl aryl group, X = B, Al, Ga , In atoms, D is oxygen, sulfur , Selenium, N (R8) or P (R8), provided that R8 is an H atom or an alkyl or aryl group having 1 to 20 carbon atoms, R8 can form a ring together with R7, and R7 is C1 selected from alkylene, arylene or aralkylene groups having 1 to 30 carbon atoms
To 30 hydrocarbon groups, E is H, or alkyl or aryl groups having 1 to 10 carbon atoms, O (R9), N (R
9) (R10), halogen, S (R9) or P (R
9) represents (R10), provided that R9 and R10 may be the same or different from each other, and each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms selected from an alkyl, aryl or aralkyl group, and R9 is R10. Alternatively, R7 may form one or more rings with R7, and / or R10 may form one or more rings with R7 or R9, p is an integer of 0 to 3, and r is 1 to Is an integer of 3 and q is an integer of 0-10. 2. The alcohol (A) according to claim 1 is a secondary monool and / or polyol having 4 to 20 carbon atoms, and the catalyst (C) is tris (pentafluorophenyl) borane. , Especially method for producing cyclic ether adduct of alcohol with improved odor 3. The cyclic ether adduct of alcohol obtained by the production method according to claim 1 or 2,
A process for producing a cyclic ether adduct of an alcohol, which is purified by an operation such as distillation or adsorption and has a small amount of impurities, and particularly improved odor. 4. An impurity obtained by further adding a cyclic ether compound (B) to a catalyst (D) such as an alkali catalyst, an alumina magnesia catalyst or an amine catalyst using the alcohol cyclic ether adduct of any one of claims 1 to 3 as a raw material. Method for producing an alcohol cyclic ether adduct having low odor and particularly improved odor. 5. A process for producing a sulfated product of an alcohol cyclic ether adduct containing less impurities, particularly improved odor, obtained by sulfating the alcohol cyclic ether adduct according to claim 1.