Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1999-04-13
2001-07-03
Keys, Rosalynd (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S606000, C568S613000, C568S623000, C568S624000, C502S162000, C502S164000, C502S167000, C502S200000, C502S208000
Reexamination Certificate
active
06255537
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for preparing a poly(alkylene oxide) by polymerizing an alkylene oxide. The poly(alkylene oxide) is an important polymer which is used as a raw material of polyurethane foam, elastomer, etc. by reacting with an isocyanate compound or a surfactant.
2. Description of the Prior Art
In the preparation of a poly(alkylene oxide) by polymerizing an alkylene compound, it is most popular that the hydration reaction between an active hydrogen compound such as polyhydric alcohol and a basic alkali metal compound such as potassium hydroxide is conducted before the initiation of the polymerization to form an alkali metal salt of the active hydrogen compound, which is used as an initiator. This process has already been put into practical use, industrially. With respect to a combination other than this combination of the initiator, U.S. Pat. No. 3,829,505 discloses that a polymer of propylene oxide is obtained by using an active hydrogen compound and a compound represented by Zn
3
[Fe(CN)
6
]
2
.H
2
O.dioxane. Japanese Patent Kokai (Laid-Open) Publication No. 276821/1990 discloses that a polymer is obtained by reacting a polyol prepared in the presence of a zinc hexacyanocobaltate complex with sodium methylate and polymerizing the reaction product with ethylene oxide. Japanese Patent Kokai (Laid-Open) Publication No. 232433/1987 discloses that a polymer is obtained by polymerizing ethylene oxide using a product obtained by adding a hexane solution of diethylzinc to a dispersion prepared by adding 1,4-butanediol and a nonionic surfactant to a hexane slurry of fumed silica. However, all of these polymers contain metallic components and an adverse influence is exerted on the reaction in the preparation of a polyurethane or physical properties of the polyurethane when these metallic components are remained in the formed poly(alkylene oxide). Therefore, in the preparation of the polyalkylene oxide, a special process or complicated step of sufficiently removing these metallic components is required.
In Japanese Patent Kokai (Laid-Open) Publication No. 159595/1975, a polymer of ethylene oxide is obtained by using, as a metal free initiator, a combination of an alkanepolyol as the active hydrogen compound and an ether adduct of boron trifluoride. Also with respect to this initiator, however, it is known that impurities in the polymer exert an adverse influence on physical properties of the polyurethane and, therefore, a complicated step is required to sufficiently remove impurities. In Japanese Patent Kokai (Laid-Open) Publication No. 12026/1982, a polymer of an alkylene oxide is obtained by using alcohols and aminophenol. In Japanese Patent Kokai (Laid-Open) Publication No. 38323/1981, a propylene oxide is polymerized by using sorbitol and tetramethyl ammonium hydroxide. However, all processes have a problem that a polymerization activity is insufficient and an odor of an amine compound is remained.
There has also been known a process for preparing a poly(alkylene oxide) by polymerizing an alkylene oxide compound in the presence of a phosphazene compound and an active hydrogen compound (EP0763555; Macromol. Rapid Commun., Vol. 17, pages 143-148, 1996; and Macromol. Symp., Vol. 107, pages 331-340, 1996).
The phosphazene compound in this process is an initiator having strong basicity, but is not at all industrially advantageous because a complicated step is required to synthesize the phosphazene compound and a stronger basic compound must be used to afford strong basicity. There is also a problem on handling that the phosphazene compound is liable to cause a change of properties by a carbon dioxide in an air because of its strong basicity.
EP0791600 discloses a process for preparing a poly(alkylene oxide) by substantially polymerizing an alkylene oxide compound in the presence of a phosphazenium salt of an active hydrogen compound. This process requires that the phosphazenium salt of the active hydrogen compound is formed by the dehydration or desalting reaction of a phosphazenium hydroxide with an active hydrogen compound or of a phosphazenium halide with an alkaline metal salt of the active hydrogen compound before the initiation of the polymerization. An inorganic salt or water formed in that case can inhibit smooth proceeding of the polymerization, sometimes, and it becomes complicated to remove the inorganic salt and, therefore, an improvement is industrially required.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a process for preparing a poly(alkylene oxide) which does not contain any metallic component and does not leave an odor, simply and efficiently, by using a polymerization initiator which does not cause any problem on preparing and handling in the preparation of the poly(alkylene oxide) by polymerizing an alkylene oxide compound and does not require a special treatment before the initiation of the polymerization.
The present inventors have studied intensively. As a result, they have found that an initiator containing a phosphine oxide compound represented by the formula (1), or said phosphine oxide compound and water or an organic compound having a specific partial structure can serve as an effective initiator which answers the above object. Thus, the present invention has been accomplished.
That is, the present invention provides a process for preparing a poly(alkylene oxide) by polymerizing an alkylene oxide compound, which comprises polymerizing the alkylene oxide compound in the presence of a phosphine oxide compound represented by the formula (1):
wherein R is the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms, and x represents an amount of water molecules contained in terms of a molar ratio and is within a range from 0 to 5.0,
or in the presence of said phosphine oxide compound and an active hydrogen compound selected from water or an organic compound having a partial structural formula —OH or —NH—.
DETAILED DESCRIPTION OF THE INVENTION
Formula (1) is a limiting structure for a phosphine oxide used in the process of this invention, where phosphorus and oxygen atoms are bound via a double bond. Alternatively, the compound may have a limiting structure where electrons are localized on the oxygen atom to form an anion while the phosphorous has a cationic form, i.e., P
+
—O
−
. The positive charge on the phosphorus atom is delocalized over the molecule via a conjugated system. It should be, therefore, noted that the phosphine oxide represented by the formula (1) is a resonance hybrid including all the limiting structures. When the phosphine oxide compound represented by the formula (1) contains water, an interaction between water and the phosphine oxide compound may be any one as far as it does not eliminate characteristics of the phosphine oxide compound and does not inhibit the process of the present invention.
In the process of the present invention, the phosphine oxide compound represented by the formula (1) may react with an alkylene oxide compound and/or an active hydrogen compound to form a derivative of the phosphine oxide compound, and the derivative may serve as a polymerization initiator. When such a derivative of the phosphine oxide compound is prepared previously or separately and is used for polymerization of the alkylene oxide compound, that idea is also included in an idea of the present invention that an alkylene oxide compound is polymerized in the presence of a phosphine oxide compound represented by the formula (1), or in the presence of the phosphine oxide compound and an active hydrogen compound selected from water or an organic compound having a partial structural formula —OH or —NH—.
The alkylene oxide compound in the process of the present invention includes epoxy compounds, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, phenyl glyci
Funaki Katsuhiko
Hara Isao
Hayashi Takaomi
Kiyono Shinji
Mizutani Kazumi
Burns Doane Swecker & Mathis L.L.P.
Keys Rosalynd
Mitsui Chemicals Inc.
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