JP2013100271A - Method for producing alkylene oxide adduct - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply producing alkylene oxide adduct having excellent low-temperature flowability.SOLUTION: The method for producing an alkylene oxide adduct includes a step 1 of feeding an alkylene oxide AO and an alkylene oxide AO and then conducting addition reaction, wherein the carbon number of AO is smaller than that of AO. Assuming that the weight ratios of AO and AO fed at time points of Ts, Tf, T1 and T2 are represented by [AO/AO], [AO/AO], [AO/AO]and [AO/AO], respectively, the following expressions are simultaneously satisfied. 0<[AO/AO]<1...(A), 1<[AO/AO]<100...(B), and 0.8<[AO/AO]/[AO/AO]<10...(C).

Description

  The present invention relates to a method for producing an alkylene oxide adduct. More specifically, the present invention relates to a method for producing an alkylene oxide adduct including a step of supplying a plurality of alkylene oxides to an active hydrogen-containing compound to cause an addition reaction.

Alkylene oxide adducts obtained by adding alkylene oxide to active hydrogen-containing compounds such as alcohols are useful and versatile in various applications such as detergents, emulsifiers, dispersants, oil phase component modifiers, penetrants, and polymer raw materials. Has been.
Ethylene oxide adducts, which are typical alkylene oxide adducts, are used as surfactants in various industrial applications such as detergents, emulsifiers, dispersants, oil phase component modifiers, penetrants, and the like. However, ethylene oxide adducts are excellent in emulsification / dispersion performance, but have the disadvantage of high freezing point and poor low-temperature stability.

In order to remedy these drawbacks, multiple alkylene oxide copolymer adducts have been proposed. A typical example of such a copolymerized adduct is an ethylene oxide / propylene oxide copolymerized adduct. Generally, when propylene oxide is introduced into a polyoxyethylene chain, fluidity and stability at low temperatures are improved, and merits such as low foaming properties are produced. However, on the other hand, introduction of propylene oxide into the polyoxyethylene chain may cause disadvantages such as a decrease in emulsifying properties as compared with the ethylene oxide adduct.
Various structural designs have been studied for optimizing the performance of this ethylene oxide / propylene oxide copolymer adduct. For example, Patent Document 1 discloses a random adduct of ethylene oxide and propylene oxide; Patent Document 2 discloses a block adduct obtained by adding ethylene oxide and then propylene oxide in this order to an alcohol; Patent Document 3 Is a block adduct obtained by adding propylene oxide and then ethylene oxide in this order to alcohol; Patent Document 4 discloses that random addition of ethylene oxide and propylene oxide is first performed on alcohol; Patent Document 5 discloses a block adduct obtained by first adding ethylene oxide and propylene oxide randomly to alcohol, then adding ethylene oxide, and further adding propylene oxide. Click adduct; in Patent Document 6, first ethylene oxide and then subjected to addition of propylene oxide, then block adducts obtained by adding ethylene oxide is disclosed to alcohol.

However, these ethylene oxide / propylene oxide copolymer adducts do not sufficiently satisfy any required properties such as low foaming property, emulsifying property, dispersibility, and thickening property. In addition, the structures of Patent Documents 5 and 6 have a manufacturing problem such that the reaction process is multistage and the manufacturing time is long. Further, Patent Document 7 proposes a higher alcohol-based alkylene oxide adduct intermediate composition excellent in uniform transparency and containing water and a solvent, but does not directly contribute to performance. This is not preferable because of the contamination.
As described above, the alkylene oxide adducts of Patent Documents 1 to 7 have various problems regarding low-temperature fluidity and production thereof, but the current situation is that the conventional alkylene oxide adducts must be used. .

JP-A-7-303825 Japanese Patent Publication No. 63-12192 JP-A-53-58508 Japanese Patent Laid-Open No. 10-461189 JP-A-10-130690 JP-A-10-195499 Japanese Patent Laid-Open No. 51-13394

  An object of the present invention is to provide a method for easily producing an alkylene oxide adduct having excellent low-temperature fluidity.

In order to solve the above-mentioned problems, the present inventors diligently studied. As a result, in the step of supplying a plurality of alkylene oxides to the active hydrogen-containing compound to cause an addition reaction, the weight ratio of the plurality of alkylene oxides is changed, The knowledge of solving the above problems by controlling within a certain range was obtained, and the present invention was completed.
The method for producing an alkylene oxide adduct according to the present invention comprises the step 1 of adding an alkylene oxide A ₁ O and an alkylene oxide A ₂ O to an active hydrogen-containing compound to cause an addition reaction, thereby producing an alkylene oxide adduct. A method,

The carbon number of A ₁ O is smaller than the carbon number of A ₂ O,
The start of supply of A ₁ O and A ₂ O is Ts, the end of supply of A ₁ O is Tf ₁ , the end of supply of A ₂ O is Tf _2, and it is between Ts and Tf ₁ and Ts and Tf time T1 and T2 which is between _2, Ts <T1 <T2 <when the relation of Tf ₂ ≦ Tf ₁ and _{(T2-T1) / Tf 2} = 0.01,

Ts, and the weight ratio of the _{A 1} O and _{A 2} O is supplied at the time of each of _{Tf, T1, T2, [A} 2 O / A 1 O] Ts, [A 2 O / A 1 O] Tf2, As [A ₂ O / A ₁ O] _T1 and [A ₂ O / A ₁ O] _T2 , the following formulas (A) to (C):
0 <[A ₂ O / A ₁ O] _Ts <1 (A)
1 <[A ₂ O / A ₁ O] _Tf2 <100 (B)
0.8 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <10 (C)
To be satisfied at the same time.

It is preferable that the method for producing an alkylene oxide adduct satisfies at least one of the following (1) to (6).
(1) The following numerical formula (A-1) and / or (B-1) is further satisfied.
0.1 <[A ₂ O / A ₁ O] _Ts <0.5 (A-1)
2 <[A ₂ O / A ₁ O] _Tf2 <20 (B-1)
(2) The following numerical formula (C-1) is further satisfied.
0.9 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <1.2 (C-1)
(3) A ₁ O is ethylene oxide, and A ₂ O is one of alkylene oxides selected from propylene oxide and butylene oxide.

(4) The active hydrogen-containing compound contains at least one compound selected from alcohols, phenols, amines, carboxylic acids and amides.
(5) The addition reaction is performed in the presence of a catalyst.
(6) After the step 1, the method further includes a step 2 in which one of alkylene oxides selected from ethylene oxide, propylene oxide, and butylene oxide is supplied to cause an addition reaction.
In the above (6), it is more preferable to further include a step 3 of supplying an alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide and causing an addition reaction after the step 2.

  The method for producing an alkylene oxide adduct of the present invention can easily produce an alkylene oxide adduct having excellent low-temperature fluidity.

About the weight ratio _{[A 2 O / A 1 O} ] of the supplied A _{1 O} and A ₂ o in Example 1 is a graph showing changes with time until at the end of the supply from the start feeding. About the weight ratio _{[A 2 O / A 1 O} ] of the supplied A _{1 O} and A ₂ o in Example 11 is a graph showing changes with time until at the end of the supply from the start feeding. 6 is a graph showing the change over time from the start of supply to the end of supply with respect to the weight ratio [A ₂ O / A ₁ O] with A ₁ O and A ₂ O supplied in Comparative Example 1.

The production method of the present invention supplies alkylene oxide A ₁ O and alkylene oxide A ₂ O (wherein the carbon number of A ₁ O is smaller than the carbon number of A ₂ O) to the active hydrogen-containing compound. Thus, the production method includes an addition reaction step 1. Hereinafter, for the sake of simplicity, “A ₁ O and A ₂ O” may be referred to as “alkylene oxide A”.
Moreover, after the said process 1, it is good to further include the process 2 which supplies 1 type of the alkylene oxide chosen from ethylene oxide, a propylene oxide, and a butylene oxide, and makes it addition-react. After the step 2, it is preferable to further include a step 3 in which one of alkylene oxides selected from ethylene oxide, propylene oxide, and butylene oxide is supplied to cause an addition reaction.

[Step 1]
The active hydrogen-containing compound in the production method of the present invention may be, for example, a compound having one or more active hydrogen groups such as hydroxyl group, amino group, carboxyl group and amide group in the molecule. Examples of the active hydrogen-containing compound include alcohols, phenols, amines, carboxylic acids, amides and the like, and these compounds may be used alone or in combination of two or more.
The alcohols are not particularly limited. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, Linear alkanols such as xadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol and triacosanol; 2-ethyl Hexanol, 2-propylheptanol, 2-butyloctanol, 1-methylheptadecanol, 2-hexyloctyl Branched alkanols such as hexol, 1-hexylheptanol, isodecanol, isotridecanol, 3,5,5-trimethylhexanol; hexenol, heptenol, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol , Pentadecenol, hexadecenol, heptadecenol, octadecenol, octadecenol, nonadecenol, eisenol, docosenol, tetracosenol, pentacosenol, hexacosenol, heptacosenol, heptacosenol, octacosenol, nonacosenol and triaconsenol, and the like; isohexenol, 2-isohexenol Senol, 1-methylheptadecenol Branched alkenols such as 1-hexyl heptenol, isotridecenol and isooctadecenol; ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol acetate Alkylene glycol monoalkyl ethers such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether Butyl ethyl propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 6-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, , 15-pentadecanediol, 1,16-hexadecanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,2-cyclohexanediol, 1, 3-cyclohexanediol, 1,4-cyclohexanediol, tricyclodecane dimethyl Alkanediol having 4 to 20 carbon atoms such as diol and cyclohexanedimethanol; mono- or diesterified product of neopentyl glycol and hydroxypivalic acid, β, β, β ′, β′-tetramethyl-2,4,8,10 -Dihydric alcohols such as tetraoxaspiro [5,5] undecane-3,9-dienol, ethylene glycol, propylene glycol; trimethylol ethane, dimethylol propane, trimethylol propane, trimethylol butane, trimethylol hexane, ditri Methylolpropane, pentaerythritol, dipentaerythritol, glycerin, polyglycerin, sorbitan, sorbitol, fructose, sucrose, dextrose, fructose, methyl glucoside, hydroxyethyl glucooxide, castor oil, hardened castor Examples include trihydric or higher alcohols such as oil; polyvinyl alcohol; thioalcohols in which one or more oxygen atoms of these compounds are substituted with sulfur atoms, and the like. Good.

The phenols are not particularly limited. For example, phenol, nonylphenol, octylphenol, dinonylphenol, naphthol, hydroquinone, catechol, resorcin, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol S, triphenol, tetraphenol , Novolaks, resoles, resorcins, Mannich compounds and the like; thiophenols in which one or more oxygen atoms of these compounds are substituted with sulfur atoms, and the like may be used alone or in combination of two or more.
The amines are not particularly limited. For example, ammonia; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and butanolamine; methylamine, ethylamine, butylamine, 2-ethylhexylamine, octadecyl Dialkylamines such as amine, laurylamine, eicosylamine, coconut oil amine, beef tallow amine, palm oil amine, soybean oil amine, dimethylamine, diethylamine, methylethylamine, 2-ethylhexylmethylamine, methyloctadecylamine and octadecylethylamine, ethylenediamine , Hexamethylenediamine, octamethylenediamine, isophoronediamine, cyclohexylenediamine, diethylenetriami And aliphatic amines such as alkylene polyamines such as triethylenetetramine; aniline, N-methylaniline, o-toluidine, m-toluidine, N-ethyltoluidine, p-toluylamine, 2,3-xylinoamino, 2,4-xylinoamine Arylamines such as diphenylamine, methylphenylamine, ethylphenylamine, di-o-toluylamine and phenyltoluylamine, arylalkylamines such as benzylamine, benzylmethylamine and o-toluylmethylamine, phenylenediamine, diaminotoluene, Examples include arylene polyamines such as xylylenediamine, methylenedianiline, and diphenyletherdiamine, and one or two or more thereof may be used in combination.

The carboxylic acids are not particularly limited, and examples thereof include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, octanoic acid, lauric acid, Monocarboxylic acids such as 2-ethylhexanoic acid, octadecanoic acid, stearic acid and eicosanoic acid; dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid and maleic acid; hexanetricarboxylic acid, octanetricarboxylic acid, hexanetetracarboxylic Examples thereof include polycarboxylic acids such as acids. Examples of the aromatic carboxylic acid include monocarboxylic acids such as benzoic acid, 4-methylbenzoic acid, 2,3,4-trichlorobenzoic acid and naphthalenecarboxylic acid; for example, phthalic acid, terephthalic acid and trichlorobenzenedicarboxylic acid. Dicarboxylic acids such as acid, m-toluene dicarboxylic acid and naphthalenedicarboxylic acid; polycarboxylic acids such as trimellitic acid, 1,2,4,5-benzenetetracarboxylic acid, benzenehexacarboxylic acid and naphthalenetetracarboxylic acid 1 type or 2 types or more may be used in combination.
The amides are not particularly limited, and examples thereof include acetamide, ethylamide, propylamide, methylethylamide, butyramide, benzoamide, lauric acid diethanolamide, oleic acid diethanolamide, and the like. You may use together.

The alkylene oxide A of the present invention is not particularly limited. For example, ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO; for example, 1,2-butylene oxide, 2,3-butylene n oxide , Isobutylene oxide, etc.), 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylethylene oxide, α-olefin oxide, styrene oxide, α-methylstyrene oxide, cyclohexene oxide, epichlorohydrin, epifluorohydride Phosphorus, epibromohydrin, glycidol, methyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 2 -Chloroethyl glycidyl ether, o-chlorophenyl glycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, methacryl chloride epoxide, cyclohexene oxide, dihydronaphthalene oxide, vinylcyclohexene monooxide, oxetane, tetrahydrofuran, tetrahydropyran, 1, 4 -Epoxycyclohexane, trifluoropropylene oxide, butadiene monooxide, 1,1-diphenylethylene oxide and the like.
The alkylene oxide A is preferably two types selected from ethylene oxide, propylene oxide, and butylene oxide because of excellent versatility. Moreover, among the alkylene oxides A, when A ₁ O is ethylene oxide and A ₂ O is one of propylene oxide and butylene oxide, the resulting alkylene oxide adduct has excellent emulsifiability. Therefore, it is preferable. It is more preferable that A ₂ O is propylene oxide because it has excellent emulsifying properties.

The number of added moles of alkylene oxide A supplied to the active hydrogen-containing compound is not particularly limited, but is preferably 1 to 100 mol, more preferably 1 to 90 mol, relative to 1 mol of the active hydrogen-containing compound. More preferably, it is 1-80 mol, Most preferably, it is 1-70 mol, Most preferably, it is 2-70 mol. If the added mole number of alkylene oxide A is less than 1, the emulsifiability may not be sufficient. On the other hand, when the average number of added moles of alkylene oxide A is more than 100, handleability may be low.
The production method of the present invention may be performed in the presence of a catalyst. The catalyst is not particularly limited. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide; potassium oxide Alkali (earth) metal oxides such as sodium oxide, calcium oxide, barium oxide, magnesium oxide, strontium oxide; alkali metals such as metal potassium and metal sodium; metal hydrides such as sodium hydride and potassium hydride ; Carbonates of alkali (earth) metals such as sodium carbonate, sodium bicarbonate and potassium carbonate; sulfates of alkali (earth) metals such as sodium sulfate and magnesium sulfate; organics such as methanesulfonic acid and trifluoromethanesulfonic acid Sulfonic acid; sodium paratoluenesulfonate, patorue Aromatic sulfonates such as pyridinium sulfonate; amine compounds such as monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, and triethylamine; iron powder, aluminum powder, antimony powder, aluminum (III) chloride, Aluminum bromide (III), iron (III) chloride, iron (III) bromide, cobalt (III) chloride, antimony (III) chloride, antimony (V) chloride, antimony (III) bromide, tin tetrachloride, four Lewis acids such as titanium chloride, boron trifluoride and boron trifluoride diethyl ether; proton acids such as sulfuric acid and perchloric acid; potassium perchlorate, sodium perchlorate, calcium perchlorate, magnesium perchlorate, etc. Alkali (earth) metal perchlorate; calcium metho Alkali (earth) metal alkoxides such as sid, sodium ethoxide and lithium ethoxide; Alkali (earth) metal phenoxides such as potassium phenoxide and calcium phenoxide; Sodium silicate, potassium silicate, sodium aluminosilicate, potassium aluminosilicate, Silicates such as sodium metasilicate, orthosilicate sodium, zeolite; Al-Mg complex oxides such as calcined aluminum hydroxide and magnesium, metal ion-added magnesium oxide, calcined hydrotalcite, or surface modified products thereof, lanthanoids A complex etc. are mentioned. These catalysts may be used alone or in combination of two or more.

Although there is no limitation in particular about the usage-amount of a catalyst, Preferably it is 0.001-10 weight part with respect to 100 weight part of active hydrogen containing compounds, More preferably, it is 0.001-8 weight part, More preferably, it is 0.00. 01 to 6 parts by weight, particularly preferably 0.05 to 5 parts by weight, and most preferably 0.05 to 3 parts by weight. If the amount of the catalyst used is less than 0.001 part by weight, the addition reaction may not proceed sufficiently. On the other hand, when the amount of the catalyst used exceeds 10 parts by weight, the alkylene oxide adduct may be easily colored.
In the production method of the present invention, it is preferable that raw materials such as an active hydrogen-containing compound and a catalyst are charged into a reaction vessel, and the reaction vessel is subjected to degassing treatment or dehydration treatment. The degassing process is performed by, for example, a vacuum degassing system, a vacuum degassing system, or the like. Further, the dehydration process is performed by, for example, a heat dehydration method, a vacuum dehydration method, a vacuum dehydration method, or the like.

In the production method of the present invention, the production form is not particularly limited, and may be a continuous type or a batch type. Although there is no limitation in particular about reaction container, For example, the tank-type reaction container provided with the stirring blade, the micro reactor, etc. can be mentioned. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, a paddle multistage blade, a turbine blade, etc. can be mentioned.
In the production method of the present invention, the addition reaction may be started from a reduced pressure state, may be started from an atmospheric pressure state, or may be started from a pressurized state. When starting from an atmospheric pressure state or a pressurized state, it is preferably carried out in an inert gas atmosphere. When the addition reaction is performed in an inert gas atmosphere, it is possible to sufficiently remove impurities generated due to side reactions between alkylene oxides such as A ₁ O and A ₂ O and oxygen, and the like. This is preferable because it is useful from the viewpoint of safety. The inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, and carbon dioxide gas. These inert gases may be used alone or in combination of two or more. The oxygen concentration in the reaction vessel under an inert gas atmosphere is not particularly limited, but is preferably 10% by volume or less, more preferably 5% by volume or less, still more preferably 3% by volume or less, and particularly preferably 1% by volume. % Or less, and most preferably 0.5% by volume or less. If the oxygen concentration in the reaction vessel exceeds 10% by volume, impurities may not be sufficiently removed, and it may not be preferable from the viewpoint of safety.

The initial pressure in the reaction vessel is not particularly limited. For example, the gauge pressure is preferably 0 to 3.0 MPa, more preferably 0 to 2.0 MPa, still more preferably 0 to 1.5 MPa, and particularly preferably 0. -1.0 MPa, most preferably 0-0.5 MPa. If the initial pressure in the reaction vessel is less than 0 MPa, the amount of impurities generated may increase. On the other hand, when the initial pressure in the reaction vessel is more than 3.0 MPa, the reaction rate may be slow.
When alkylene oxide A is supplied to the active hydrogen-containing compound, an addition reaction occurs. Here, since A ₁ O and A ₂ O are supplied almost simultaneously, the polyoxyalkylene group formed in the resulting alkylene oxide adduct is likely to be generated by random addition, which is preferable.

The method for supplying the alkylene oxide A is not particularly limited. 1) A method for continuously supplying A ₁ O and A ₂ O to the active hydrogen-containing compound from different supply lines, or 2) A ₁ A method in which О and A ₂ O are supplied from different lines and mixed in-line and continuously supplied to the active hydrogen-containing compound, or 3) a part of each of A ₁ O and A ₂ O The premixed material is first supplied to the active hydrogen-containing compound at a time, and then the remaining A ₁ O and the remaining A ₂ O are continuously supplied to the active hydrogen-containing compound from different supply lines. And 4) a method in which several mixtures prepared by previously mixing A ₁ O and A ₂ O are prepared, and these mixtures are divided into several stages and sequentially supplied to alcohol.
In step 1, it is preferable to supply while changing the weight ratio of supplied A ₁ O and A ₂ O.

In step 1, at the time of the initial feed weight ratio of _{A 1} o and _{A 2} O supplied, the weight ratio of _{A 1} O is greater than _{A 2} O, the weight ratio of _{A 2} O during the second half of supply than _{A 1} O More preferably, it is controlled to be large.
Here, Ts is the start of supply of A ₁ O and A ₂ O, Tf _{1 is} the end of supply of A ₁ O, Tf ₂ is the end of supply of A ₂ O, and it is between Ts and Tf ₁ when the time T1 and T2 that is between the Ts and Tf ₂ is set to be in a relation of _{Ts <T1 <T2 <Tf 2} ≦ Tf 1 and _{(T2-T1) / Tf 2} = 0.01, Ts, The weight ratio of A ₁ O to A ₂ O supplied at each time point of Tf, T1, and T2 is expressed as [A ₂ O / A ₁ O] _Ts , [A ₂ O / A ₁ O] _{Tf 2} , [A ₂ As O / A ₁ O] _T1 and [A ₂ O / A ₁ O] _T2 , the following mathematical formulas (A) to (C) may be satisfied at the same time.
0 <[A ₂ O / A ₁ O] _Ts <1 (A)
1 <[A ₂ O / A ₁ O] _Tf2 <100 (B)
0.8 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <10 (C)

The numerical formula (A) is preferably 0.02 <[A ₂ O / A ₁ O] _Ts <0.9, more preferably 0.05 <[A ₂ O / A ₁ O] _Ts <0.8, Preferably 0.08 <[A ₂ O / A ₁ O] _Ts <0.7, and most preferably 0.1 <[A ₂ O / A ₁ O] _Ts <0.5. When [A ₂ O / A ₁ O] _Ts is 0, the low temperature fluidity of the resulting alkylene oxide adduct may not be excellent. On the other hand, when [A ₂ O / A ₁ O] _Ts is 1 or more, the emulsifiability of the resulting alkylene oxide adduct may be low.
The numerical formula (B) is preferably 1.2 <[A ₂ O / A ₁ O] _{Tf 2} <80, more preferably 1.5 <[A ₂ O / A ₁ O] _{Tf 2} <60, and particularly preferably 1. 8 <[A ₂ O / A ₁ O] _{Tf 2} <40, most preferably 2 <[A ₂ O / A ₁ O] _{Tf 2} <20. [A ₂ O / A ₁ O] When _Tf2 is 1 or less, the low temperature fluidity of the resulting alkylene oxide adduct may not be excellent. On the other hand, when [A ₂ O / A ₁ O] _Tf2 is 100 or more, it may be difficult to control the supply of A ₁ O and A ₂ O.

The numerical formula (C) is preferably 0.8 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <5.0, more preferably 0.8 <[A ₂ O / _{A 1 O] T2 / [A} 2 O / A 1 O] T1 <2.0, particularly preferably _{0.9 <[A 2 O / A} 1 O] T2 / [A 2 O / A 1 O] T1 < 1.2, most preferably 1.0 ≦ [A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <1.2. When [A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _T1 is 0.8 or less, the emulsifiability of the resulting alkylene oxide adduct may be low. When [A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _T1 is 10 or more, the handling property of the resulting alkylene oxide adduct may not be excellent.
Speaking what is meant by formula (A) ~ (C) roughly, toward the supply end time from the supply start timing of the A 1 _O and A ₂ o, as gradually increasing the weight ratio of A 2 _O Is to control. However, in a minute time range that satisfies the relationship of (T2−T1) / Tf ₂ = 0.01, the weight ratio of A ₂ O may be temporarily reduced.

The supply rate of the alkylene oxide A is not particularly limited as long as the formulas (A) to (C) are simultaneously satisfied. For example, 1) The supply rate of the alkylene oxide A at the start of supply is Fast and gradually slow the supply rate (a large amount of alkylene oxide A is supplied at the start of supply, and decrease at the end of the supply), 2) The supply rate of alkylene oxide A at the start of supply is slow and the supply is gradually A method of increasing the speed (a small amount is supplied at the start of supply of alkylene oxide A, and the amount is increased at the end of supply), and 3) the supply speed of A ₂ O is slow at the start of supply, and gradually the supply speed with time while fast, a ₁ o fast at the start feeding the feed rate of, by supplying a small amount gradually feed rate slows (a 2 _O supply start time of the over time While increasing the amount at the time of the completion of the large amount of supply at the start of supplying the A ₁ o, reducing the amount at the time of the end of the feed) method and, 4) A ₁ o maintaining the feed rate of the constant, A ₂ O at the start feed A method of slowing down the supply rate of the steel and gradually increasing the supply rate over time, 5) keeping the supply rate of A ₂ O constant, increasing the supply rate of A ₁ O at the start of the supply, and over time A method of gradually lowering the supply rate can be used. Thus, by adjusting so that numerical formula (A)-(C) may be satisfied simultaneously, an alkylene oxide adduct can be manufactured simply.
The pressure in the reaction vessel during the addition reaction is affected by the supply rate of alkylene oxide A, the reaction temperature, the amount of catalyst, and the like. The pressure in the reaction vessel during the addition reaction is not particularly limited, but is preferably 0 to 5.0 MPa, more preferably 0 to 4.0 MPa, further preferably 0 to 3.0 MPa, and particularly preferably 0 to 0 in terms of gauge pressure. 2.0 MPa, most preferably 0.1-1.0 MPa. When the pressure in the reaction vessel during the addition reaction is less than 0 MPa, the reaction rate may be slow. On the other hand, if the pressure in the reaction vessel during the addition reaction is more than 5.0 MPa, the production may be difficult.

The reaction temperature for the addition reaction of alkylene oxide A is not particularly limited, but is preferably 70 to 240 ° C, more preferably 80 to 220 ° C, still more preferably 90 to 200 ° C, particularly preferably 100 to 190 ° C, and most preferably. Is 110-180 ° C. If the reaction temperature is less than 70 ° C., the addition reaction may not proceed sufficiently. On the other hand, when the reaction temperature exceeds 240 ° C., coloring of the resulting alkylene oxide adduct and decomposition of the polyoxyalkylene group in the alkylene oxide adduct may be promoted.
The time required for the addition reaction (reaction time) is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.1 to 80 hours, still more preferably 0.1 to 60 hours, and particularly preferably. 0.1 to 40 hours, most preferably 0.5 to 30 hours. If the reaction time is less than 0.1 hour, the addition reaction may not proceed sufficiently. On the other hand, when the reaction time exceeds 100 hours, the production efficiency may deteriorate.

When the supply of the alkylene oxide A is completed, the internal pressure in the reaction vessel gradually decreases as the alkylene oxide A is consumed. The addition reaction of alkylene oxide A is preferably continued until no change in internal pressure is observed. The addition reaction of alkylene oxide A ends when no change in internal pressure is observed over a certain period of time. An unreacted alkylene oxide A may be recovered by performing a heating and decompression operation or the like as necessary.
In the addition reaction of alkylene oxide A, an inert solvent can be used as necessary. For example, when using a solid compound at room temperature such as triaconsenol as the active hydrogen-containing compound, it is preferable to use it dissolved in an inert solvent before the reaction, thereby improving the reactivity more sufficiently, High handling. In addition, if an inert solvent is used, a heat removal effect can be expected.

There are no particular limitations on the inert solvent, but examples include ethers such as diethyl ether, ethylene glycol dimethyl ether, dioxane, and tetrahydrofuran; ketones such as acetone, methyl isobutyl ketone, and methyl ethyl ketone; sulfones such as sulfolane and dimethylsulfone hydroxide. Halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as benzene, toluene and xylene; and aliphatic hydrocarbons such as pentane, hexane, cyclopentane and cyclohexane, etc. You may use the above together. Of these, aromatic hydrocarbons are preferable, and toluene is more preferable.
The amount of the inert solvent used is not particularly limited, but when used to dissolve the active hydrogen-containing compound, it is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the active hydrogen-containing compound. The amount is preferably 10 to 500 parts by weight, more preferably 10 to 400 parts by weight, particularly preferably 10 to 300 parts by weight, and most preferably 10 to 200 parts by weight. If the amount of the inert solvent is more than 1000 parts by weight with respect to 100 parts by weight of the active hydrogen-containing compound, the addition reaction may not be allowed to proceed sufficiently. On the other hand, when the amount of the inert solvent is less than 10 parts by weight, the active hydrogen-containing compound may not be sufficiently dissolved. When an inert solvent is used, it is preferably removed after the addition reaction. By removing the inert solvent, it is possible to sufficiently prevent the generation of impurities due to the remaining inert solvent, and to obtain an active hydrogen-containing compound that is superior in various physical properties. The solvent removal step is as described later.

After completion of the addition reaction of alkylene oxide A, it is preferable to neutralize and / or remove the catalyst or remove the inert solvent as necessary.
The neutralization of the catalyst is limited to the case where the catalyst is mainly an alkali catalyst, and may be performed by an ordinary method. For example, hydrochloric acid, phosphoric acid, acetic acid, lactic acid, citric acid, succinic acid, acrylic acid, methacrylic acid It is preferable to carry out by adding an acid such as.

The neutralization of the catalyst is preferably carried out in an inert gas atmosphere. Although there is no limitation in particular as an inert gas, For example, nitrogen gas, argon gas, a carbon dioxide gas etc. are mentioned, You may use 1 type (s) or 2 or more types together.
The temperature during neutralization of the catalyst is not particularly limited, but is preferably 50 to 200 ° C, more preferably 50 to 190 ° C, still more preferably 60 to 180 ° C, particularly preferably 60 to 170 ° C, and most preferably. 60-160 ° C. If the temperature during neutralization of the catalyst is less than 50 ° C., the time required for neutralization may become long. On the other hand, when the temperature during neutralization of the catalyst is higher than 200 ° C., coloring of the resulting alkylene oxide adduct and decomposition of the polyoxyalkylene group in the alkylene oxide adduct may be promoted.

By the neutralization of the catalyst, the pH of the reaction product obtained by the above addition reaction is preferably adjusted to 4 to 10, more preferably 5 to 8, particularly preferably 6 to 8. Moreover, antioxidants, such as quinones and phenols, can also be used together as necessary during catalyst neutralization.
The neutralized salt produced by neutralization may be further subjected to solid-liquid separation. Examples of the method for solid-liquid separation of the neutralized salt produced by neutralization include filtration and centrifugation. For filtration, for example, a filter paper, a filter cloth, a cartridge filter, a two-layer filter of cellulose and polyester, a metal mesh filter, a sintered metal filter, etc., under reduced pressure or pressurized conditions of 20 to 140 ° C. It is good to do. Centrifugation may be performed, for example, using a centrifuge such as a decanter or a centrifugal clarifier. Moreover, about 1-30 weight part of water can also be added with respect to 100 weight part of liquids before solid-liquid separation as needed. As the solid-liquid separation, particularly when filtration is performed, it is preferable to use a filter aid because the filtration rate is improved.

The filter aid is not particularly limited. For example, each series of Celite, High Flow Supercell, and Cell Pure (manufactured by Advanced Minerals Corporation), silica # 645, silica # 600H, silica # 600S, silica # 300S, silica # 100F Diatomaceous earth such as Daikalite (manufactured by Chuo Silica), diatomite such as Daikalite (manufactured by Grefco); Perlite such as RocaHelp (manufactured by Mitsui Mining & Smelting), Topco (manufactured by Showa Chemical Co., Ltd.); KC Flock (manufactured by Nippon Paper Industries), Fibracell ( Cellulose-based filter aids such as Advanced Minerals Corporation); silica gels such as silopute (Fuji Silysia Chemical Co., Ltd.) and the like. These filter aids may be used alone or in combination of two or more.
For the filter aid, a precoat method for forming a filter aid layer on the filter surface such as filter paper in advance may be used, or a body feed method for directly adding to the filtrate may be used, or both of these may be used in combination. Good. The amount of the filter aid used is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the liquid before solid-liquid separation. The filtration rate depends on the size of the filter surface, the degree of vacuum or pressurization, the treatment humidity, etc., but is preferably 100 kg / m ² · hr or more, more preferably 300 kg / m ² · hr or more. More preferably 500 kg / m ² · hr or more.

The removal of the alkali catalyst is not particularly limited, but for example, a method of solid-liquid separation after adsorbing the alkali catalyst to the adsorbent is preferable.
Examples of the adsorbent include silicates such as aluminum silicate and magnesium silicate, activated clay, acid clay, silica gel, ion exchange resin and the like. Examples of commercially available adsorbents include KYOWARD 600, 700 (manufactured by Kyowa Chemical Co., Ltd.), Mizuka Life P-1, P-1S, P-1G, F-1G (manufactured by Mizusawa Chemical Co., Ltd.), Tomita-AD600, 700. Silicates (Tomita Pharmaceutical Co., Ltd.), etc .; Amberlist (Rohm and Haas), Amberlite (Rohm and Haas), Diaion (Mitsubishi Chemical), Dowex (Dow Chemical) And the like, and the like. These adsorbents may be used alone or in combination of two or more.

The amount of the adsorbent used is, for example, preferably 100 to 5000 parts by weight, more preferably 300 to 3000 parts by weight with respect to 100 parts by weight of the alkali catalyst.
The conditions for removing the alkali catalyst are not particularly limited. For example, the adsorbent is stirred and mixed at a temperature of 20 to 140 ° C. for 5 to 120 minutes under any one of reduced pressure, normal pressure, and pressurized conditions, A method of separating the adsorbent on which the alkali catalyst is adsorbed by the above-mentioned solid-liquid separation method, or a column or the like is previously filled with the adsorbent, and the reaction mixture is passed at a temperature of 20 ° C to 140 ° C to adsorb the alkali catalyst. And a method of removing the alkali catalyst. At this time, if necessary, 1 to 20 parts by weight of a water-soluble solvent such as water or lower alcohol represented by ethanol may be added to 100 parts by weight of the reaction mixture.

The residual amount after removal of the alkali catalyst is not particularly limited, but is preferably 300 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less, particularly preferably 50 ppm or less, and most preferably 20 ppm or less.
The removal of the inert solvent is preferably performed by distillation, for example.

In addition, when performing neutralization and / or removal of a catalyst and removal of an inert solvent, the order of each step is not particularly limited. For example, after neutralization and / or removal of a catalyst, The removal is preferable because the resulting alkylene oxide adduct is excellent in purification efficiency.
In the production method of the present invention, the content of the active hydrogen-containing compound remaining unreacted is not particularly limited, but is preferably 1 part by weight or less, more preferably 100 parts by weight or less, based on 100 parts by weight of the resulting alkylene oxide adduct. Is 0.01 part by weight or less, more preferably 0.001 part by weight or less, particularly preferably 0.0001 part by weight or less, and most preferably 0.00001 part by weight or less. If the content of the active hydrogen-containing compound remaining unreacted is more than 1 part by weight with respect to 100 parts by weight of the alkylene oxide adduct, an odor may be generated.
The alkylene oxide adduct obtained in step 1 is also excellent in low viscosity performance and emulsifying properties.

[Step 2 and Step 3]
Next, when performing Step 2, after Step 1, one kind of alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide is supplied to the terminal hydroxyl group of the alkylene oxide adduct obtained in Step 1. Addition reaction is performed.
The number of added moles of alkylene oxide to be subjected to addition reaction in step 2 is not particularly limited, but is preferably 1 to 50 moles, more preferably 1 to 40 moles, and further preferably 1 to 1 mole of the active hydrogen-containing compound. -30 mol, particularly preferably 1-20 mol, most preferably 1-10 mol. If the added mole number of alkylene oxide is less than 1, the emulsifiability may not be sufficient. On the other hand, when the average added mole number of alkylene oxide is more than 50, the handling property may be low.

In step 2, an addition reaction may be performed on the reaction mixture obtained in step 1 as it is, and the above-described catalyst is neutralized and / or removed, or an inert solvent is removed. After the post-treatment, the addition reaction may be performed.
Furthermore, when performing Step 3, after Step 2, one kind of alkylene oxide selected from ethylene oxide, propylene oxide and butylene oxide is supplied, and the terminal hydroxyl group of the alkylene oxide adduct obtained in Step 2 is supplied. Addition reaction.

The number of added moles of alkylene oxide to be subjected to addition reaction in step 3 is not particularly limited, but is preferably 1 to 50 moles, more preferably 1 to 40 moles, and further preferably 1 to 1 mole of the active hydrogen-containing compound. -30 mol, particularly preferably 1-20 mol, most preferably 1-10 mol. If the added mole number of alkylene oxide is less than 1, the emulsifiability may not be sufficient. On the other hand, when the average added mole number of alkylene oxide is more than 50, the handling property may be low.
In Step 3, an addition reaction may be performed on the reaction mixture obtained in Step 2 as it is, and the above-mentioned catalyst is neutralized and / or removed, or an inert solvent is removed. After the post-treatment, the addition reaction may be performed.

  When the production method of the present invention further includes step 2 after step 1 or further includes step 3 after step 2, the cloud point of the resulting alkylene oxide adduct can be further increased. The use temperature range of the adduct can be widened and used for a wide variety of applications. Moreover, low viscosity and emulsification can be variously controlled and improved according to the kind of alkylene oxide to be added. When the alkylene oxide supplied in Step 2 and Step 3 is ethylene oxide, the resulting alkylene oxide adduct is excellent in emulsifying properties. Further, when the alkylene oxide supplied in Step 2 and Step 3 is propylene oxide and butylene oxide, the resulting alkylene oxide adduct is excellent in low-temperature fluidity, low viscosity and antifoaming property.

[Alkylene oxide adduct]
Although there is no limitation in particular as a weight average molecular weight of the alkylene oxide adduct obtained with the manufacturing method of this invention, Preferably it is 200-10000, More preferably, it is 200-8000, More preferably, it is 200-6000, Most preferably, it is 200- 4000, most preferably 200-2000. When the weight average molecular weight is less than 200, the emulsifiability of the alkylene oxide adduct may be low. When the weight average molecular weight is more than 10,000, handling properties may be low. The measurement method of a weight average molecular weight is demonstrated in detail in an Example.
In the present invention, as a method for measuring the cloud point of the alkylene oxide adduct, the following measurement method is selected according to the cloud point range of the alkylene oxide adduct to be measured.

The clouding point of the alkylene oxide adduct of the present invention is usually a method in which a 1% by weight aqueous solution of an alkylene oxide adduct is prepared and heated to turbidize the solution once, and then gradually cooled to eliminate the turbidity. Use to measure. As said cloud point, Preferably it is 0-95 degreeC, More preferably, it is 0-90 degreeC, More preferably, it is 0-85 degreeC, Especially preferably, it is 0-80 degreeC, Most preferably, it is the range of 0-75 degreeC. If the cloud point is less than 0 ° C., the emulsifiability of the alkylene oxide adduct may be low. On the other hand, when the cloud point is higher than 95 ° C., the handling property of the alkylene oxide adduct may be low.
In the present invention, when the cloud point is less than 40 ° C. or more than 80 ° C., the cloud point may not be measurable or the measurement value may be unreliable even if it can be measured. A measurement method shown below, which is different from the cloud point measurement method, is selected, and the value obtained by the measurement method is defined as the cloud point.

When the cloud point is lower than 40 ° C., a 1% by weight aqueous solution of an alkylene oxide adduct may already be cloudy at room temperature and may not be measured. Therefore, when the said cloud point is less than 40 degreeC, let the cloud point of an alkylene oxide adduct be the value measured by the butyl diglycol method (BDG method) demonstrated in detail below. The cloud point of the alkylene oxide adduct measured by the BDG method is preferably 0 to 95 ° C, more preferably 20 to 95 ° C, still more preferably 20 to 90 ° C, particularly preferably 20 to 85 ° C, and most preferably 20 to 80 ° C. If the cloud point measured by the BDG method is less than 0 ° C., the emulsifiability of the alkylene oxide adduct may be low. On the other hand, when the cloud point measured by the BDG method exceeds 95 ° C., the handling property of the alkylene oxide adduct may be low.
On the other hand, when the cloud point of the 1% by weight aqueous solution of the alkylene oxide adduct is higher than 80 ° C., the cloud point of the alkylene oxide adduct was measured by a method using a potassium sulfate aqueous solution as a solvent described in detail in the following examples. Value. When the cloud point of the 1% by weight aqueous solution of the alkylene oxide adduct of the present invention is more than 80 ° C., it may be measured by a method (potassium sulfate method) using an aqueous potassium sulfate solution as described in detail below. The cloud point of the alkylene oxide adduct measured by the potassium sulfate method is preferably 0 to 95 ° C, more preferably 20 to 95 ° C, still more preferably 20 to 90 ° C, particularly preferably 20 to 85 ° C, and most preferably 20 ~ 80 ° C. When the cloud point measured by the potassium sulfate method is less than 0 ° C., the emulsifiability of the alkylene oxide adduct may be low. On the other hand, when the cloud point measured by the potassium sulfate method is more than 95 ° C., the handling property of the alkylene oxide adduct may be low.

  The alkylene oxide adduct obtained in the present invention is a liquid or powder detergent for clothing, household detergent, kitchen detergent, solid detergent, active ingredient of various detergents such as shampoo, antifoaming agent, foam suppressor, Lubricant, Textile oil agent, Paper agent, Machine / metal cleaning agent, Deresin agent, Deinking agent, Degreasing agent, Water reducing agent, Flocculant, Dispersant, Emulsion polymerizer, Emulsifier, Solubilizer, Suspension agent, It can be used as a thickener, a gelling agent, an antistatic agent, a surface treatment agent, etc., and their active ingredients.

  Below, the Example of an alkylene oxide adduct is described concretely with the comparative example. The present invention is not limited to these examples.

(Weight average molecular weight)
The alkylene oxide adduct was dissolved in tetrahydrofuran so that the nonvolatile content concentration was about 0.2% by mass, and then gel permeation chromatography (GPC) was measured under the following measurement conditions. Subsequently, a calibration curve was prepared from the GPC measurement result of polyethylene glycol having a known molecular weight, and the weight average molecular weight was calculated.
(Measurement condition)
Device name: HLC-8220 (manufactured by Tosoh Corporation)
Column: KF-G, KF-402HQ, KF-403HQ each connected in series (all manufactured by Shodex)
Eluent: Tetrahydrofuran Injection volume: 10 μl
Eluent flow rate: 0.3 ml / min Temperature: 40 ° C

[Measurement of cloud point]
A 1% by weight aqueous solution of an alkylene oxide adduct was prepared, heated to make the solution turbid, and gradually cooled to measure the temperature T at which the turbidity disappeared. Here, when it was in the range of T = 40 to 80 ° C., the cloud point of the alkylene oxide adduct was taken.
In the alkylene oxide adducts of Example 5 and Comparative Example 5, since T was less than 40 ° C., the value measured by the following butyl diglycol method (BDG method) was taken as the cloud point.

(BDG method)
A cloud point test solution was prepared by adding an alkylene oxide adduct to a 25% by weight aqueous solution of n-butyl diglycol (also known as 2- (2-butoxyethoxy) ethanol, diethylene glycol mono-n-butyl ether). In that case, it adjusted so that the density | concentration of the alkylene oxide adduct in a cloud point test liquid might be 10 weight%. Subsequently, the cloud point test solution was once clouded by heating, and the temperature at which the cloud point disappeared gradually after cooling was defined as the cloud point.
(Potassium sulfate method)
A cloud point test solution was prepared by adding an alkylene oxide adduct to a 5 wt% aqueous solution of potassium sulfate. At that time, the concentration of the alkylene oxide adduct in the cloud point test solution was adjusted to 1% by weight. Subsequently, the cloud point test solution was once clouded by heating, and the temperature at which the cloud point disappeared gradually after cooling was defined as the cloud point.

[Example 1]
After charging 100 g of decanol (molecular weight 159) and 0.3 g of potassium hydroxide into a 1 L autoclave to which supply lines of ethylene oxide as alkylene oxide A ₁ O and propylene oxide as alkylene oxide A ₂ O were respectively connected. The autoclave was purged with nitrogen, and then dehydrated under reduced pressure at 80 ° C. with stirring.
Next, after the temperature was raised to 130 ° C., ethylene oxide and propylene oxide were simultaneously fed while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . With ethylene oxide, the supply was started from a supply rate of 72 g / h, the supply amount was gradually decreased, and the supply was completed at a final supply rate of 12 g / h, and a total amount of 194 g was supplied in about 170 minutes. In addition, for propylene oxide, the supply was started at a supply rate of 12 g / h, the supply amount was gradually increased, and the supply was completed at a final supply rate of 67 g / h, and a total amount of 73 g was supplied in about 160 minutes. The supply rate of ethylene oxide at the completion of the supply of propylene oxide was 25 g / h.

The weight ratio [A ₂ O / A ₁ O] _TS of ethylene oxide and propylene oxide supplied at the start of supply was 0.17. The weight ratio [A ₂ O / A ₁ O] _Tf2 between ethylene oxide and propylene oxide supplied at the end of the supply was 5.6. The supply of ethylene oxide and propylene oxide satisfied the condition of 0.9 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <1.2. FIG. 1 is a schematic diagram showing the change over time from the start of supply to the end of supply for the weight ratio [A ₂ O / A ₁ O] of ethylene oxide and propylene oxide supplied in Example 1. It can be seen that the supply time and the weight ratio [A ₂ O / A ₁ O] have a linear function relationship.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.

The resulting alkylene oxide adduct had 2 propylene oxide addition moles and 7 ethylene oxide addition moles.
The resulting alkylene oxide adduct had a weight average molecular weight of 584. The cloud point was 58 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Examples 2 to 10]
In Examples 2 to 10, an alkylene oxide adduct was obtained in the same manner as in Example 1 except that the raw materials were changed as shown in Table 1 in Example 1, and the physical properties and the like were the same as in Example 1. evaluated. The results are shown in Tables 1 and 2.
In the table shown below, EO represents ethylene oxide, PO represents 1,2-propylene oxide, and BO represents 1,2-butylene oxide.

Example 11
After charging 100 g of decanol (molecular weight 159) and 0.3 g of potassium hydroxide in a 1 L autoclave connected to a 0.5 L mixing tank, the autoclave was purged with nitrogen, and then the pressure was reduced at 80 ° C. with stirring. Dehydration was performed.
Then, after raising the temperature to 130 ° C., the reaction temperature 145 ± 5 ° C., while maintaining the reaction pressure 3.5 ± 0.5kg / cm ^2, as ethylene oxide and an alkylene oxide _{A 2} O as alkylene oxide _{A 1} O The propylene oxide mixed solution was prepared in a mixing tank in three times and supplied. First, in the first time, a liquid in which 110 g of ethylene oxide and 10 g of propylene oxide were mixed was supplied for 60 minutes. Next, in the second time, a solution in which 70 g of ethylene oxide and 20 g of propylene oxide were mixed was supplied in 50 minutes, and in the last third time, a solution in which 14 g of ethylene oxide and 43 g of propylene oxide were mixed was supplied in 50 minutes. . The total amount of ethylene oxide supplied was 194 g, and the total amount of propylene oxide supplied was 73 g.

The weight ratio [A ₂ O / A ₁ O] _Ts between ethylene oxide and propylene oxide supplied at the start of supply was 0.09. The weight ratio [A ₂ O / A ₁ O] _Tf2 of ethylene oxide and propylene oxide supplied at the end of the supply was 3.1. The supply of ethylene oxide and propylene oxide satisfied the condition of 0.8 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <10. FIG. 2 shows a schematic diagram showing the change over time from the start of supply to the end of supply for the weight ratio [A ₂ O / A ₁ O] of ethylene oxide and propylene oxide supplied in Example 11. 2 that the supply time and the weight ratio [A ₂ O / A ₁ O] have a step function relationship.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the obtained reaction mixture, and as a post-treatment, a synthetic adsorbent (KYOWARD 700, Kyowa Chemical) was added to the obtained reaction mixture. 3 g of Kogyo Co., Ltd. was added and the mixture was stirred at 90 ° C. for 1 hour under a nitrogen stream, and then the catalyst was removed by filtration to obtain an alkylene oxide adduct.

The resulting alkylene oxide adduct had an ethylene oxide addition mole number of 7, and a propylene oxide addition mole number of 2.
The resulting alkylene oxide adduct had a weight average molecular weight of 584. The cloud point was 58 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

Example 12
After charging 300 g of the alkylene oxide adduct obtained in Example 1 and 1.0 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 45 g of ethylene oxide was supplied in about 40 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. The total reaction time from the start of the ethylene oxide supply to the cooling to 80 ° C. was 140 minutes. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct obtained by adding 2 mol of ethylene oxide to the alkylene oxide adduct obtained in Example 1 was obtained.
The resulting alkylene oxide adduct had a weight average molecular weight of 691. The cloud point was 73 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

Example 13
After charging 300 g of the alkylene oxide adduct obtained in Example 12 and 0.3 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 30 g of propylene oxide was supplied in about 50 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct obtained by further adding 1 mol of propylene oxide to the alkylene oxide adduct obtained in Example 12 was obtained.
The resulting alkylene oxide adduct had a weight average molecular weight of 749. The cloud point was 77 ° C as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 1]
A 1 L autoclave was charged with 100 g of decanol (molecular weight 159) and 0.3 g of potassium hydroxide, and the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Then, after raising the temperature to 130 ° C., the reaction temperature 145 ± 5 ° C., while maintaining the reaction pressure 3.5 ± 0.5kg / cm ^2, as ethylene oxide and an alkylene oxide _{A 2} O as alkylene oxide _{A 1} O The propylene oxide was simultaneously fed. Ethylene oxide was supplied while maintaining a supply rate of 68 g / h, and a total amount of 194 g was supplied in about 170 minutes. Propylene oxide was supplied while maintaining a supply rate of 27 g / h, and a total amount of 73 g was supplied in about 160 minutes.

The weight ratio [A ₂ O / A ₁ O] of propylene oxide and ethylene oxide supplied from the supply start to the supply end was constant at 0.40. The weight ratio of the supplied ethylene oxide and propylene oxide in Comparative Example _{1 [A 2 O / A 1} O], shows a schematic diagram showing changes with time from the start feeding until the end of feed in FIG.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number of 2, and a propylene oxide addition mole number of 7. The cloud point was 57 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Examples 2 to 10]
In Comparative Examples 2 to 10, except that each of the raw materials was changed as shown in Table 2 in Comparative Example 1, an alkylene oxide adduct was obtained in the same manner as in Comparative Example 1, and the physical properties and the like were the same as in Comparative Example 1. evaluated. The results are shown in Tables 3 and 4.

[Comparative Example 11]
After charging 300 g of the alkylene oxide adduct obtained in Comparative Example 1 and 1.0 g of potassium hydroxide in a 1 L autoclave, the inside of the autoclave was purged with nitrogen and then dehydrated at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 45 g of ethylene oxide was supplied in about 40 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct obtained by further adding 1 mol of ethylene oxide to the alkylene oxide adduct obtained in Comparative Example 1 was obtained.
The resulting alkylene oxide adduct had a weight average molecular weight of 691. The cloud point was 72 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 12]
After charging 300 g of the alkylene oxide adduct obtained in Comparative Example 11 and 0.3 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 30 g of propylene oxide was supplied in about 50 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct obtained by further adding 1 mol of propylene oxide to the alkylene oxide adduct obtained in Comparative Example 11 was obtained.
The resulting alkylene oxide adduct had a weight average molecular weight of 749. The cloud point was 71 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 13]
A 1 L autoclave was charged with 100 g of decanol (molecular weight 159) and 0.3 g of potassium hydroxide, and the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Subsequently, after raising the temperature to 130 ° C., 194 g of ethylene oxide was supplied in about 120 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . After aging until the internal pressure decreased and became constant, 73 g of propylene oxide was supplied in about 140 minutes.

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. The total reaction time from the start of the supply of A ₁ O and A ₂ O to the cooling to 80 ° C. was 370 minutes. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct was a block adduct of ethylene oxide and propylene oxide, the ethylene oxide addition mole number was 7, and the propylene oxide addition mole number was 2.
The resulting alkylene oxide adduct had a weight average molecular weight of 584. The cloud point was 57 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 14]
Into a 1 L autoclave, 100 g of nonylphenol (molecular weight 220) and 0.3 g of potassium hydroxide were charged, and then the inside of the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Subsequently, after raising the temperature to 130 ° C., 100 g of ethylene oxide was supplied in about 130 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . After aging until the internal pressure decreased and became constant, 79 g of propylene oxide was supplied in about 150 minutes.

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. The total reaction time from the start of the supply of A ₁ O and A ₂ O to the cooling to 80 ° C. was 380 minutes. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct was a block adduct of ethylene oxide and propylene oxide, the number of moles of ethylene oxide added was 5, and the number of moles of propylene oxide added was 3.
The resulting alkylene oxide adduct had a weight average molecular weight of 615. The cloud point was 48 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 15]
Into a 1 L autoclave, 100 g of glycerin (molecular weight 92) and 0.3 g of potassium hydroxide were charged, and the inside of the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Subsequently, after raising the temperature to 130 ° C., 287 g of ethylene oxide was supplied in about 340 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . After aging until the internal pressure decreased and became constant, 189 g of propylene oxide was supplied in about 400 minutes.

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. The total reaction time from the start of the supply of A ₁ O and A ₂ O to the cooling to 80 ° C. was 850 minutes. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct was a block adduct of ethylene oxide and propylene oxide, the ethylene oxide addition mole number was 6, and the propylene oxide addition mole number was 3.

The resulting alkylene oxide adduct had a weight average molecular weight of 532. The cloud point was 53 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.
Using the alkylene oxide adduct of the present invention obtained in Examples 1 to 13 and the alkylene oxide adduct obtained in Comparative Examples 1 to 15 respectively, the emulsifying power (emulsifiability) and the low temperature pour point were obtained by the following methods. (Low temperature fluidity) and aqueous solution viscosity (low viscosity) were evaluated.

[Measurement of emulsification power (emulsification)]
4 g of alkylene oxide adduct was added to 40 g of xylene and 56 g of water, and the mixture was emulsified with stirring at 4500 rpm for 5 minutes at room temperature using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The emulsified performance was evaluated by measuring the emulsified layer and the water separating layer after leaving the prepared emulsion in a 50 ° C. atmosphere for 1 hour. The emulsifying power is calculated by the following formula. The larger the emulsifying power, the better the emulsifying ability.
Emulsifying power (%) = (amount of charged water−amount of water separation) (ml) / amount of charged water (ml) × 100
If the emulsifying power is 90% or more, the alkylene oxide adduct is excellent in emulsifying properties. On the other hand, if the emulsifying power is less than 90%, the alkylene oxide adduct is not sufficiently emulsifiable.

[Measurement of low temperature pour point (low temperature fluidity)]
It measured using the method based on the method of JISK2269. That is, 45 ml of alkylene oxide adduct taken in a test tube was heated to 45 ° C. and then cooled in a cooling bath using a cryogen. Each time the temperature dropped by 2.5 ° C., the test tube was removed from the cooling bath, the temperature at which the alkylene oxide adduct stopped moving at all for 5 seconds was read, and 2.5 ° C. was added to that value to obtain the low temperature pour point. The smaller the value of the low temperature pour point, the better the low temperature fluidity.

[Measurement of aqueous solution viscosity (low viscosity)]
A 50 wt% alkylene oxide adduct was prepared and measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd .: BL type) in an atmosphere at 25 ° C. The smaller the value of the aqueous solution viscosity, the better the low viscosity.
Table 5 shows the evaluation results of the alkylene oxide adduct. The basic structure of the alkylene oxide adduct of Example 1 and Example 11 corresponds to that of Comparative Example 1. The alkylene oxide adducts of Examples 2 to 10 correspond to those of Comparative Examples 2 to 10. The alkylene oxide adducts of Examples 12 and 13 correspond to those of Comparative Examples 11 and 12. Further, the alkylene oxide adducts of Examples 1 to 3 correspond to those of Comparative Examples 13 to 15.

  From the above evaluation results, Examples 1 and 11 are superior to Comparative Example 1 in low-temperature fluidity and low viscosity. In Examples 2-10, it is excellent in low-temperature fluidity | liquidity and low viscosity rather than corresponding Comparative Examples 2-10, respectively. In Examples 12 and 13, the low temperature fluidity and the low viscosity are superior to the corresponding Comparative Examples 11 and 12, respectively. Moreover, in Examples 1-3, it is excellent in emulsifiability rather than the corresponding Comparative Examples 13-15, respectively.

Claims (8)

A method for producing an alkylene oxide adduct, comprising the step 1 of adding an alkylene oxide A ₁ O and an alkylene oxide A ₂ O to an active hydrogen-containing compound to cause an addition reaction,
The carbon number of A ₁ O is smaller than the carbon number of A ₂ O,
The start of supply of A ₁ O and A ₂ O is Ts, the end of supply of A ₁ O is Tf ₁ , the end of supply of A ₂ O is Tf _2, and it is between Ts and Tf ₁ and Ts and Tf time T1 and T2 which is between _2, Ts <T1 <T2 <when the relation of Tf ₂ ≦ Tf ₁ and _{(T2-T1) / Tf 2} = 0.01,
Ts, and the weight ratio of the _{A 1} O and _{A 2} O is supplied at the time of each of _{Tf, T1, T2, [A} 2 O / A 1 O] Ts, [A 2 O / A 1 O] Tf2, As [A ₂ O / A ₁ O] _T1 and [A ₂ O / A ₁ O] _T2 , the following formulas (A) to (C):
0 <[A ₂ O / A ₁ O] _Ts <1 (A)
1 <[A ₂ O / A ₁ O] _Tf2 <100 (B)
0.8 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <10 (C)
The process for producing an alkylene oxide adduct satisfying The manufacturing method of the alkylene oxide adduct of Claim 1 which further satisfies the following numerical formula (A-1) and / or (B-1).
0.1 <[A ₂ O / A ₁ O] _Ts <0.5 (A-1)
2 <[A ₂ O / A ₁ O] _Tf2 <20 (B-1) The manufacturing method of the alkylene oxide adduct of Claim 1 or 2 which further satisfies the following numerical formula (C-1).
0.9 <[A ₂ O / A ₁ O] _{T 2} / [A ₂ O / A ₁ O] _{T 1} <1.2 (C-1) The method for producing an alkylene oxide adduct according to claim 1, wherein A ₁ O is ethylene oxide, and A ₂ O is one of alkylene oxides selected from propylene oxide and butylene oxide.   The production of an alkylene oxide adduct according to any one of claims 1 to 4, wherein the active hydrogen-containing compound contains at least one compound selected from alcohols, phenols, amines, carboxylic acids and amides. Method.   The method for producing an alkylene oxide adduct according to claim 1, wherein the addition reaction is performed in the presence of a catalyst.   The alkylene oxide according to any one of claims 1 to 6, further comprising, after the step 1, a step 2 of supplying an alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide to cause an addition reaction. Method for producing adducts.   The method for producing an alkylene oxide adduct according to claim 7, further comprising, after the step 2, a step 3 of supplying an alkylene oxide selected from ethylene oxide, propylene oxide, and butylene oxide to cause an addition reaction. .

Images