JP2009001559A - Method for producing alkylene oxide adduct and alkylene oxide adduct obtained therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an alkylene oxide adduct of an active hydrogen-containing compound containing a fluorine atom at a hydrophobic group site, in which operation such as molecular distillation is unnecessary because of slight residue of unreacted material, and to provide the alkylene oxide adduct obtained by the method. <P>SOLUTION: In the method for producing the alkylene oxide adduct comprising carrying out addition polymerization of alkylene oxides to an active hydrogen-containing compound containing a fluorine atom by using a catalyst, addition polymerization of the alkylene oxides to the active hydrogen-containing compound containing the fluorine atom is carried out by using a basic catalyst which is at least one kind of a Lewis base and addition polymerization of the resultant alkylene oxide adduct to alkylene oxides is further carried out by using an acidic catalyst which is at least one kind of Lewis acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an alkylene oxide adduct comprising addition polymerization of an alkylene oxide to an active hydrogen-containing compound using a catalyst, and an alkylene oxide adduct obtained thereby.

  The alkylene oxide adduct is a kind of important material widely used industrially. Alkylene oxide adducts are generally produced by reaction of an active hydrogen-containing compound with various alkylene oxide compounds typified by ethylene oxide in the presence of one or more catalysts. Many knowledge about the manufacturing technology has been found, and various things have been reported.

  However, in the case of an active hydrogen-containing compound containing a fluorine atom such as a fluorine alcohol, generally, when an Arrhenius base used in producing an alkylene oxide adduct is used as a catalyst, the alcohol containing the fluorine atom is decomposed and the acid is As a by-product. For this reason, there is a problem that the catalyst is deactivated, the reaction does not proceed as expected, and the reaction stops.

  In response to these problems, the active hydrogen-containing compound containing a fluorine atom as described above is synthesized by a production method using an acidic catalyst such as a Lewis acid. However, this production method has a problem that a large amount of by-products such as polyethylene glycol and dioxane are generated, and a large amount of unreacted substances remain.

  As an improvement method, for example, it is proposed to perform the reaction in the presence of an iodine source selected from alkali metal iodide, alkaline earth metal iodide, elemental iodine, and a mixture thereof.

However, these methods have problems such as the fact that harmful substances such as iodine remain in the system and the necessity of equipment such as molecular distillation equipment suitable for production in factories. (Patent Documents 1 and 2, Non-Patent Documents 1 and 2).
Japanese National Patent Publication No. 10-501810 Japanese National Patent Publication No. 11-501933 The Chemical Society of Japan, 1974 (9), p1731-1735 Oil Chemistry, Vol. 12, No. 12 (1963), p653-662

  The present invention has been made in view of the above, and is a method for producing an alkylene oxide adduct of an active hydrogen-containing compound containing a fluorine atom at a hydrophobic group site, since the residual amount of unreacted material is small, and thus molecular distillation and the like. It is an object of the present invention to provide a method for producing an alkylene oxide adduct that does not require the above operation and an alkylene oxide adduct obtained thereby.

  The method for producing an alkylene oxide adduct of the present invention is a method for producing an alkylene oxide adduct comprising subjecting an active hydrogen-containing compound containing a fluorine atom to addition polymerization of an alkylene oxide using a catalyst. In order to solve the problem, an active hydrogen compound containing a fluorine atom is first subjected to addition polymerization of an alkylene oxide using a basic catalyst which is one or two or more Lewis bases. An alkylene oxide is further subjected to addition polymerization using an acidic catalyst which is a seed or two or more Lewis acids.

  The alkylene oxide adduct of the present invention is obtained by the above-described production method of the present invention, and the content of the active hydrogen-containing compound containing a fluorine atom is less than 3% by weight.

  According to the production method of the present invention, when an alkylene oxide adduct of an active hydrogen-containing compound containing a fluorine atom at a hydrophobic group site is obtained, a target product with little remaining unreacted product is obtained. It is possible to produce an object that is easily dissolved in water without any water. Further, since the decomposition reaction does not proceed, the production of by-products can be suppressed, and the deactivation of the catalyst is not confirmed, so that the target compound can be easily prepared.

  In the production method of the present invention, alkylene oxide is first subjected to addition polymerization using a Lewis base to a predetermined active hydrogen-containing compound as described above, and the resulting alkylene oxide adduct is subjected to alkylene oxide using a Lewis acid. Is a method of addition polymerization.

  The active hydrogen-containing compound used in the present invention is a compound containing a fluorine atom. In other words, the present invention is effective when an alcohol containing a fluorine atom that promotes the decomposition of a hydrophobic group is used as an active hydrogen-containing compound in an alkali catalyst generally used for addition polymerization of alkylene oxide. . The active hydrogen-containing compound may contain an aromatic ring and an unsaturated double bond. Specific examples include perfluoroalkyl alcohols, but are not limited thereto. As the active hydrogen-containing compound, one having a single molecular weight may be used, or a mixture of compounds having different molecular weights may be used.

  The alkylene oxide used in the present invention is not particularly limited as long as it can react with the active hydrogen-containing compound to form an adduct. Preferable examples include those having an oxirane ring such as ethylene oxide, propylene oxide, butylene oxide, and particularly preferable is ethylene oxide.

  The Lewis acid used as a catalyst in the present invention is an electron pair acceptor having an empty orbital capable of receiving at least one electron pair, and is an acid that does not generate hydrogen ions. Specific examples include aluminum ethylate, aluminum isopropylate, aluminum secondary butyrate, aluminum chloride, stannic chloride (IV), aluminum chloride, titanium chloride (IV), iron chloride (III), zinc chloride, trifluoride. Boron fluoride amine complex, boron trifluoride ethyl ether complex, boron trifluoride phenol complex, boron trifluoride acetic acid complex, boron trifluoride methyl alcohol complex, borofluoric acid, stannous borofluoride, copper borofluoride, Examples thereof include lead borofluoride, zinc borofluoride, ferrous borofluoride, antimony borofluoride, indium borofluoride, potassium borofluoride, ammonium borofluoride, sodium borofluoride, and magnesium borofluoride. Among these, stannic chloride (IV), boron trifluoride amine complex, boron trifluoride ethyl ether complex, boron trifluoride phenol complex, and boron trifluoride acetic acid complex are preferable because of easy handling. These Lewis acids may be used alone or in combination of two or more.

  A Lewis base is an electron pair donor having at least one electron pair that is not shared, and is a base that does not generate hydroxide ions. Specific examples thereof include methylamine, ethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, triethanolamine, N, N-diisopropylethylamine, piperidine, piperazine, morpholine, quinuclidine, 1,4-diazabicyclo [2.2.2. ] Octane, pyridine, 4-dimethylaminopyridine, ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, aniline, catecholamine, phenethylamine, 1,8-bis (dimethylamino) naphthalene (proton sponge), amantadine, spermidine, spermine, trimethylamine N-oxide dihydrate, dimethyl (propan-2-yl) amine, etc. are mentioned. Of these, trimethylamine, triethylamine, and tributylamine are preferable from the viewpoint of easy handling. These Lewis bases may be used alone or in combination of two or more.

  Production of the alkylene oxide adduct by the production method of the present invention can be carried out in a pressure reactor such as an autoclave according to conventional operating procedures and reaction conditions. During the reaction, the temperature is preferably 0 to 150 ° C, more preferably 50 to 100 ° C. The pressure is preferably −0.1 to 5.0 MPa, more preferably −0.1 to 1.0 MPa.

  Although the usage-amount of a catalyst is not specifically limited, It is preferable that it is 0.01 to 5.0 weight% with respect to an active hydrogen containing compound about each said catalyst.

  The alkylene oxide adduct of the present invention is obtained by the production method of the present invention, and the content of the active hydrogen-containing compound containing an unreacted fluorine atom is preferably less than 3% by weight. When these requirements are satisfied, there is an advantage that the balance between hydrophobicity and hydrophilicity is not lost, and performance deterioration as a surfactant does not occur.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

  In addition, the measurement of the alkylene oxide addition mole number and the measurement of molecular weight distribution in the following were performed by GC (gas chromatography). The measurement conditions are as follows.

<GC measurement conditions>
a. Gas chromatograph: HP-5890 series II (manufactured by Hewlett-Packard Company)
b. Column: DB-1, 0.53 mmφ × 15 m, membrane pressure 0.15 μm (manufactured by J & W)
c. Detector: FID detector, 300 ° C
d. Carrier gas: helium, 0.2 bar (at 100 ° C) constant.flow.on

[Example 1]
After adding 364 g of perfluorohexylethanol and 9.0 g of tributylamine to the glass autoclave, the inside of the autoclave was replaced with nitrogen. Next, while maintaining the temperature at 70 ° C. and the pressure at 0.3 MPa, 110 g (2.5 mol) of ethylene oxide was introduced, and an aging reaction was performed for 6 hours. Subsequently, 16.4 g of stannic chloride was added, 110 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 60 ° C. and the pressure at 0.1 MPa, and an aging reaction was performed for 1 hour.

  As a result of measuring the obtained alkylene oxide adduct by GC, the average number of moles of ethylene oxide (EO) added was 4.9 mol, the amount of by-produced polyethylene glycol (PEG) was 2% by weight, and the perfluoro raw material was It was confirmed that the residual amount of alkylethanol was 1% by weight or less. The EO addition mole number distribution is shown in FIG.

[Example 2]
After adding 464 g of perfluorooctylethanol and 4.9 g of triethylamine to the glass autoclave, the inside of the autoclave was replaced with nitrogen. Next, 181 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 70 ° C. and the pressure at 0.3 MPa, and an aging reaction was performed for 6 hours. Subsequently, 8.9 g of boron trifluoride ethyl ether complex was added, 181 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 70 ° C. and the pressure at 0.1 MPa, and the aging reaction was performed for 1 hour. .

  As a result of measuring the obtained alkylene oxide adduct by GC, the average number of moles of EO addition was 4.9 mol, the amount of by-produced PEG was 2% by weight, and the residual amount of the raw material perfluoroalkylethanol was 1% by weight. It was confirmed that: The EO addition mole number distribution is shown in FIG.

[Example 3]
After adding 464 g of perfluorooctylethanol and 9.0 g of tributylamine to the glass autoclave, the inside of the autoclave was replaced with nitrogen. Next, 110 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 70 ° C. and the pressure at 0.3 MPa, and an aging reaction was performed for 6 hours. Subsequently, 8.9 g of boron trifluoride ethyl ether complex was added, 181 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 70 ° C. and the pressure at 0.1 MPa, and the aging reaction was performed for 1 hour. .

  As a result of measuring the obtained alkylene oxide adduct by GC, the average number of moles of EO addition was 4.9 mol, the amount of by-produced PEG was 2% by weight, and the residual amount of the raw material perfluoroalkylethanol was 1% by weight. It was confirmed that: The EO addition mole number distribution is shown in FIG.

[Example 4]
After adding 364 g of perfluorohexylethanol and 4.9 g of triethylamine to the glass autoclave, the inside of the autoclave was replaced with nitrogen. Next, 110 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 120 ° C. and the pressure at 0.3 MPa, and an aging reaction was performed for 6 hours. Subsequently, 9 g of boron trifluoride ethyl ether complex was added, 181 g (2.5 mol) of ethylene oxide was introduced while maintaining the temperature at 80 ° C. and the pressure at 0.1 MPa, and an aging reaction was performed for 1 hour.

  As a result of measuring the obtained alkylene oxide by GC, the average number of added EO was 4.9 mol, the by-product PEG was 2% by weight, and the residual amount of perfluoroalkylethanol as a raw material was 1% by weight or less. It was confirmed. The EO addition mole number distribution is shown in FIG.

[Comparative Example 1]
After adding 464 g of perfluorooctylethanol and 8.1 g of sodium methoxide to the glass autoclave, the inside of the autoclave was replaced with nitrogen. Next, 198 g (4.5 mol) of ethylene oxide was introduced while maintaining the temperature at 70 ° C. and the pressure of 0.3 MPa, and an aging reaction was performed for 3 hours.

  The obtained alkylene oxide had an average EO addition mole number of 2.9 moles, and the introduced EO did not react as expected. Moreover, it was recognized that the substance which the perfluoro octyl ethanol ethylene oxide adduct decomposed | disassembled was floating, and the reduction | decrease of the added alkali amount was also confirmed. Therefore, when the present catalyst is used, the decomposition reaction is also progressing, so it is clear that many by-products remain in addition to the target alkylene oxide adduct. The EO addition mole number distribution is shown in FIG.

[Comparative Example 2]
After adding 464 g of perfluorooctylethanol and 14.1 g of boron trifluoride ether complex to a glass autoclave, the inside of the autoclave was replaced with nitrogen. Next, 198 g (4.5 mol) of ethylene oxide was introduced while maintaining the temperature at 70 ° C. and the pressure of 0.1 MPa, and an aging reaction was performed for 1 hour.

  The obtained alkylene oxide had an average EO addition mole number of 4.1 moles, but the molecular weight distribution was wide and 25% by weight or more of the raw material perfluoroalkylethanol remained. The EO addition mole number distribution is shown in FIG.

  Since the alkylene oxide adduct obtained by the production method of the present invention has few unreacted fluorine atom-containing active hydrogen compounds and does not contain decomposition products, it can be used as a high-quality industrial surfactant, and moreover an anion / cation / amphoteric. It can be used in a wide range of applications as a raw material for surfactants.

2 is a graph showing the distribution of moles of EO addition of the alkylene oxide adduct obtained in Example 1. FIG. 4 is a graph showing the distribution of the number of moles of EO addition of the alkylene oxide adduct obtained in Example 2. 4 is a graph showing the distribution of the number of EO addition moles of the alkylene oxide adduct obtained in Example 3. 6 is a graph showing the distribution of the number of moles of EO addition of the alkylene oxide adduct obtained in Example 4. 4 is a graph showing a distribution of EO addition moles of the alkylene oxide adduct obtained in Comparative Example 1. 4 is a graph showing the distribution of EO addition moles of the alkylene oxide adduct obtained in Comparative Example 2.

Claims (2)

A method for producing an alkylene oxide adduct comprising subjecting an active hydrogen-containing compound containing a fluorine atom to addition polymerization of an alkylene oxide using a catalyst,
First, an alkylene oxide is addition-polymerized to an active hydrogen compound containing a fluorine atom using a basic catalyst that is one or more Lewis bases, and the resulting alkylene oxide adduct is added to one or more Lewis acids. A method for producing an alkylene oxide adduct, which further comprises addition polymerization of alkylene oxide using an acidic catalyst which is an acid.   The alkylene oxide adduct obtained by the production method according to claim 1, wherein the content of the active hydrogen-containing compound containing a fluorine atom is less than 3% by weight.

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