DESCRIPTION PHOSPHONIUM SALT, CATALYST FOR ALKYLENE OXIDE COMPOUND POLYMERIZATION
AND PROCESS FOR PRODUCING POLYALKYLENE OXIDE TECHNICAL FIELD [0001]
The present invention relates to a new salt of an anion in the form obtainable by separating a proton from an active hydrogen compound More specifically, it relates to a new salt of a phosphomum cation and an anion of an active hydrogen compound, a polymerization catalyst for an alkylene oxide compound, and a process for producing a polyalkylene oxide using the polymerization catalyst It, further, relates to a polyalkylene oxide useful as a raw material for polyurethane foams or elastomers, or a surface-active agent or the like
TECHNICAL BACKGROUND [0002]
Salts of an anion of an active hydrogen compound obtainable by extracting a proton from the active hydrogen compound, and a counter cation have been known In the preparation of the salts, they are active hydrogen compound anion salts having an alkali metal or an alkali earth metal as a counter cation because of generally using a simple substance of an alkali metal or an alkali earth metal, a hydroxide, a carbonate, a hydride compound, an amide compound or an alkyl compound In order to react an anion of an active hydrogen compound effectively,

it is necessary to dissolve the active hydrogen compound in a solvent However, the solvents capable of sufficiently dissolving the salt having an alkali metal cation or an alkali earth metal cation are extremely limited Furthermore, the anion reactivity is sometimes largely influenced by the size of a counter cation Therefore, when the cation limits to an alkali metal or an alkali earth metal, the size thereof is also limited
[0003]
Therefore, in order to enhance the solubility of an anion of an active hydrogen compound with a salt of a cation paired with the anion, or in order to enhance the reactivity of the anion, an alkali metal cation which is a counter cation is stabilized using a compound having high coordinating properties such as crown ether or cryptand, or the counter cation is exchanged with an ammonium salt However, the results on the salt solubility and the anion reactivity are not sufficient in many cases
[0004]
Patent document 1 discloses a phosphazenium salt as a salt having high solubility of an anion derived from an active hydrogen compound with a counter cation The phosphazenium salt has a property such that the size of a cation part can be changed optionally It also discloses that the anion can be reacted effectively Since the phosphazenium salt, however, has a phosphorus atom represented as a cation, bonded with four substituents in total including a phosphoranilidene amino
group and an amino group, the synthesis thereof is relatively complex In particular, in the case of replacing with four phosphoranilidene amino groups, it is known that the reaction has to be carried out at a relatively high temperature for a long period of time For example, Patent document 2 discloses a process for producing tetrakis [tris (dimethylammo) phosphoranilidene ammo] phosphonium chloride which is one of the phosphazenium salts In the preparation, phosphorus pentachloride and lmmotris (dimethylammo) phosphorane have to be reacted with heat at 170°C for 9 hr Accordingly, the development of a salt capable of being synthesized simply and having the same functions has been desired [0005]
Non-patent document 1 discloses tris [tris (dimethylammo) phosphoranilidene ammol phosphonium hydroxide which is one of the polymerization catalysts of the present invention It, however, discloses only the use of the phosphonium hydroxide as a synthetic intermediate The description that the phosphonium hydroxide can be used for preparation of the polymerization catalyst described in the present invention cannot be found m it [0006]
In the preparation of a polyalkylene oxide by polymerization of an alkylene oxide compound, it is most general to employ, as an initiator, the combined use of an active hydrogen compound such as poly-valent alcohol or the like, and a basic alkali metal compound
such as potassium hydroxide or the like, and the combined use of them has been conducted industrially However, a more efficient initiator has been desired from the viewpoint of polymerization activity and physical properties of a resulting polymer Except for the initiators, the use of a metal compound is known For example, Patent document 3 discloses a process for preparing a polymer from propylene oxide using an active hydrogen compound and a compound represented by Zn3 [Fe (CN) 6J2 H20 dioxane In these processes, the remaining of metal components in a resulting polyalkylene oxide sometimes affects the reaction in preparing polyurethane or the physical properties of polyurethane Therefore, it is necessary in the preparation of polyalkylene oxide has to employ a special method or a complicated step for removing these metal components sufficiently [0007]
Patent document 4 discloses that from an ethylene oxide, its polymer is prepared by, as an initiator not containing metals, the combined use of an alkane polyol as an active hydrogen compound, and an ether adduct of boron trifluoride This initiator, however, is known that special impurities in the polymer affects the physical properties of polyurethane, so that complicated steps are required in order to remove them sufficiently Moreover, Patent document 5 discloses a process for preparing a polymer of an alkylene oxide using alcohols and ammophenol, and Patent document 6 discloses a process for polymerizing a propylene oxide using sorbitol and
triaramethylammonium hydroxide These processes, however, have
problems that the polymerization activity thereof is not sufficient
and also the odor of amines remains
Patent Document 1 JP-B-3497054
Patent Document 2 JP-A-H11(1999)-152294
Patent Document 3 USP3829505
Patent Document 4 JP-A-S50(1975)-159595
Patent Document 5 JP-A-S57(1982)-12026
Patent Document 6 JP-A-S56(1981)-38323
Non-Patent Document 1 Journal of General Chemistry of the USSR,
1984, Vol 54, P 1581
DISCLOSURE OF THE INVENTION
OBJECT OF THE INVENTION
[0008]
It is a first object of the invention to provide a salt of an anion derived from an active hydrogen compound and a counter cation wherein the cation is neither an alkali metal cation nor an alkali earth metal cation, and has a size changeable optionally, which salt is easily soluble in an organic solvent and can be prepared easily [0009]
It is a second object of the invention to provide a polymerization catalyst for a polyalkylene oxide which catalyst does not contain special metal components, does not remain odor, and has good efficiency of producing the polyalkylene oxide, in preparing the
pwyalkylene oxide by polymerizing an alkylene oxide compound [0010]
It is a third object of the invention to provide a process for preparing a polyalkylene oxide simply and efficiently using the polymerization catalyst [0011]
It is a fourth object of the invention to provide a polyalkylene oxide having high purity by the process for preparing a polyalkylene oxide
MEANS FOR SOLVING THE OBJECT [0012]
The present inventors have been earnestly studied in order to solve the problems, and found a new phosphonium salt and also found that the salt is very effective for polymerization of an alkylene oxide compound Thus, the present invention has been accomplished That is, the present invention is as follows [0013]
The first of the invention is a phosphonium salt represented by the formula (1) [0014][Chemical formula 1]
(Formula Removed)
[0015]
In the formula (1), Qn- is an anion of an n-valent active hydrogen compound having at least one carbon atom, and a form derived by separating n protons from an active hydrogen compound having at most 8 active hydrogen atoms in an oxygen atom or a nitrogen atom, a, b and c are each a positive integer of less than 3 or 0 provided that they are not zero simultaneously, R' s are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R's present in one nitrogen atom may bond each other to form a cyclic structure
In the phosphonium salt, an active hydrogen compound making Qn-is preferably an active hydrogen compound selected from the group consisting of alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms or their derivatives, polyalkylene oxides having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total, and having a molecular weight of from 100 to 50,000, carboxylic acids having 1 to 20 carbon atoms, polyvalent carboxylic acids having 2 to 8 carboxyl groups, and 2 to 20 carbon atoms, primary or secondary amines having 1 to 20 carbon atoms, polyvalent amines having 2 to 3
primary or secondary amino groups and 2 to 20 carbon atoms, saturated cyclic secondary amines having 4 to 20 carbon atoms, and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms [0016]
In the phosphomum salt represented by the formula (1), n is preferably an integer of 1 to 3 [0017]
In the phosphomum salt represented by the formula (1), a, b and c are not zero simultaneously, and are each preferably a positive integer of less than 2, or 0 [0018]
In the phosphomum salt represented by the formula (1) , R' s are each preferably an alkyl group having 1 to 10 carbon atoms [0019]
In the phosphomum salt represented by the formula (1), when two R's in one nitrogen atom are bonded to form a cyclic structure, a bivalent substituent corresponding the nitrogen atom is preferably tetramethylene or pentamethylene [0020]
The second invention is a polymerization catalyst for an alkylene oxide compound comprising a phosphomum salt represented by the formula (2) [0021] [Chemical Formula 2]

(Formula Removed)
[0022]
In the formula (2), Zn- is an anion of an n-valent active hydrogen compound having a form derived by releasing n protons from an active hydrogen compound having at most 8 active hydrogen atoms in an oxygen atom or a nitrogen atom, a, b and c are each a positive integer of less than 3 or 0 provided that they are not zero simultaneously, R' s are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R's present in one nitrogen atom may be bonded each other to form a cyclic structure
The polymerization catalyst is preferably obtainable from a phosphine compound represented by the following formula (3) , and an active hydrogen compound making Zn-[0023][Chemical Formula 3]
(Formula Removed)

[0024]
In the formula (3), a, b and c are each a positive integer of
less than 3 or 0 provided that they are not zero simultaneously, R' s are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R's present in one nitrogen atom may be bonded each other to form a cyclic structure
The polymerization catalyst is preferably obtainable from a phosphomum salt represented by the following formula (4), and an alkali metal or an alkali earth metal of an active hydrogen compound making Zn-[0025][Chemical Formula 4]
(Formula Removed)
[0026]
In the formula (4) , Ym- is an m-valent inorganic anion, a, b and c are each a positive integer of less than 3 or 0 provided that they are not zero simultaneously, R' s are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R's present m one nitrogen atom may be bonded each other to form a cyclic structure
The inorganic anion in the formula (4) is preferably an anion of an inorganic acid selected from the group consisting of a boric acid, tetrafluoroborate, hydroacid halide, phosphoric acid, hexafluorophosphorate, and perchloric acid
[0027]
The active hydrogen compound making Zn- is preferably selected from the group consisting of water, alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in totals carboxylic acids having 1 to 20 carboxyl groups, polyvalent carbolic acid groups having 2 to 8 carboxylic acids and having 2 to 20 carbon atoms, primary or secondary amines having 1 to 20 carbon atoms, polyvalent amines having 2 to 3 primary or secondary amino groups and 2 to 20 carbon atoms, saturated cyclic secondary amines having 4 to 20 carbon atoms, and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms [0028]
In the formula (2), n is preferably an integer of 1 to 3 [0029]
In the formula (2), a, b and c are each preferably a positive integer of less than 2 or 0 provided that all of them are not 0 simultaneously [0030]
In the formula (2), R is preferably an alkyl group having 1 to 10 alkyl groups [0031]
When two R's on one nitrogen atom in the formula (2) are bonded each other to form a cyclic structure, the bivalent substituent corresponding to the nitrogen atom is tetramethylene or pentamethylene [0032]
Furthermore, the polymerization catalyst preferably comprises an active hydrogen compound making Zn-[0033]
The active hydrogen compound making Zn-, which is coexisted with the polymerization catalyst represented by the formula (2) is preferably selected from the group consisting of water, alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups m total, carboxylic acids having 1 to 20 carboxyl groups, polyvalent carboxylic acid groups having 2 to 8 carboxylic acids and having 2 to 20 carbon atoms, primary or secondary amines having 1 to 20 carbon atoms, polyvalent amines having 2 to 3 primary or secondary amino groups and 2 to 20 carbon atoms, saturated cyclic secondary amines having 4 to 20 carbon atoms, and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms [0034]
The third inventions are a process for producing a polyalkylene
oxide which process comprises polymerizing an alkylene oxide compound in the presence of the polymerization catalyst represented by the formula (2), and a polyalkylene oxide prepared by the production process [0035]
In the process for producing a polyalkylene oxide, the alkylene oxide compound preferably comprises at least one of the groups consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide [0036]
The process for producing a polyalkylene oxide preferably comprises polymerizing at least two alkylene oxide compounds one by one and thereby preparing a block copolymer containing at least two polyalkylene oxide blocks EFFECT OF THE INVENTION [0037]
The phosphonium salt of the present invention is a new phosphonium salt, has properties such that the size of a cation part is changeable optionally, and the solubility in an organic solvent is high Furthermore, the production process for the phosphonium salt has a merit such that the phosphonium salt can be more simply produced for a short period of time without heating at a high temperature as compared with conventional salts [0038]

The use of the polymerization catalyst of the present invention can provide a process for producing a polyalkylene oxide simply and efficiently by polymerizing an alkylene oxide compound, and has a merit of preparing a polyalkylene oxide having high purity BEST EMBODIMENT FOR CARRYING OUT THE INVENTION [0039]
The present invention will be described m detail hereinafter [0040]
In the present invention, phosphonium cations in the phosphonium salts represented by the formula (1), the formula (2), the formula (4) and the formula (6) , are represented by a canonical structure that positive electrons are localized on a specific phosphorus atom, but they may be represented by many canonical structures other than the above formulas Actually, it is interpreted that their positive electrons are delocalized on the whole of the phosphonium cation [0041]
The first of the invention is a phosphonium salt represented by the formula (1) [0042][Chemical Formula 5]
(Formula Removed)
[0043]
In the formula (1) , Qn- is an anion of an n-valent active hydrogen compound having at least one carbon atom, and a form derived by separating n protons from an active hydrogen compound having at most 8 active hydrogen atoms in an oxygen atom or a nitrogen atom [0044]
Of the active hydrogen compounds making Qn-, examples of the compound having an active hydrogen atom in an oxygen atom may include
alcohols having 1 to 30 carbon atoms such as methanol, ethanol, normal-propanol, iso-propanol, normal-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methyl vinyl carbmol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbmol or cmnamyl alcohol,
poly-valent alcohols having 2 to 10 hydroxyl groups and 2 to 30 carbon atoms such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propane diol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, 1,4-cyclohexane diol, trimethylol propane, glycerin, diglycerm, pentaerythritol or di-pentaerythritol ,
saccharides or their derivatives such as glucose, sorbitol, dextrose, fructose or sucrose,
polyalkylene oxides having 2 to 8 end groups which groups have
1 to 8 hydroxyl groups in total, such as polyethylene oxide or polypropylene oxide,
carboxylic acids having 1 to 30 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, iso-butyric acid, lauric acid, stearic acid, oleic acid, phenylbutyric acid, dihydrocmnamic acid, cyclohexane carboxylic acid, benzoic acid, paramethyl benzoic acid or 2-carboxynaphthalene,
polyvalent carboxylic acids having 2 to 8 carboxyl groups, and 2 to 30 carbon atoms such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butane tetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyrromellitic acid,
carbamic acids such as N,N-diethyl carbamic acid, N-carboxy pyrrolidone, N-carboxy aniline or N,N'-dicarboxy-2,4-toluene diamine, and
phenolic compounds having 6 to 20 carbon atoms and 1 to 3 hydroxyl groups, such as phenol, 2-naphthol, 2,6-dihydroxy naphthalene or bisphenol A [0045]
Of the active hydrogen compounds making Qn-, examples of active hydrogen compounds having an active hydrogen atom on a nitrogen atom are
primary or secondary amines having 1 to 30 carbon atoms such as methylamme, ethylamme, normal-propylamme, isopropylamine,
normal-butylamme, isobutylamine, see-butylamine, tert-butylamine, cyclohexylarnme, benzylamme, p-phenylethyl amine, aniline, o-tolidme , m-tolidme, p-tolidme, dimethylamme, methylethylamme, diethylamme, di-normal-propylamme, ethyl-normal-butylamme, methyl-sec-butylamme, dipentylamme, dicyclohexylamme, N-methylamlme or diphenylamme,
polyvalent amines having 2 or 3 primary or secondary amino groups and 2 to 30 carbon atoms, such as ethylene diamine, di (2-aminoethyl)amme, hexamethylene diamine, 4, 4'-diammodiphenyl methane, tri (2-ammoethyl) amine, N,N'-dimethylethylene diamine, N,N'-diethyl ethylene diamine or di (2-methylammoethyl) amine,
saturated cyclic secondary amines such as pyrrolidine, piperidme, morpholme or 1, 2, 3, 4-tetrahydroqumolme,
cyclic poly-valent amines having 2 or 3 secondary ammo groups and 4 to 30 carbon atoms such as piperadme, pyrazme or 1,4,7-triazacyclononane,
unsubstituted or N-substituted acid amides having 2 to 20 carbon atoms such as acetoamide, propionic amide, N-methylpropionic amide, N-methyl benzoic acid amide or N-ethyl stearic acid amide,
5 to 7-membered ring cyclic amides such as 2-pyrrolidone or s-caprolactam,
dicarboxylic acid lmides having 4 to 10 carbon atoms such as succinic acid lmide, maleic acid imide or phthalic lmide, and
unsaturated cyclic secondary amines having 4 to 20 carbon atoms
such as 3-pyrophosphate, pyrrole, indole, carbazole, imidazole, pyrazole or purine [0046]
Of the active hydrogen compounds making Qn-, preferable examples are alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total, carboxylic acids having 1 to 20 carboxyl groups, polyvalent carboxylic acid groups having 2 to 8 carboxylic acids and having 2 to 20 carbon atoms, primary or secondary amines having 1 to 20 carbon atoms, polyvalent amines having 2 to 3 primary or secondary amino groups and 2 to 20 carbon atoms, saturated cyclic secondary amines having 4 to 20 carbon atoms, and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms More preferable examples are alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total, and primary or secondary amines having 1 to 20 carbon atoms [0047]
In the formula (1) , n represents the number of phosphonium
carbons and also represents the number of protons separating from the active hydrogen compound making Qn- n is an integer of 1 to 8, preferably 1 to 3 When the active hydrogen compound making Qn- has a plurality of active hydrogen atoms, there is a case such that all the active hydrogen atoms are separated and led to anion, or a case such that a part of the active hydrogen atoms are separated and led to anion [0048]
In the formula (1) , a, b and c are each 0 or a positive integer of less than 3 provided that all are not 0 simultaneously a, b and c are each preferably 0 or a positive integer of less than 2 provided that all are not 0 simultaneously a, b and c are each more preferably 2 or 1, and all of them are furthermore preferably 1 simultaneously [0049]
In the formula (1) , R is a hydrocarbon group having 1 to 10 carbon atoms, and two R's on one nitrogen atom may be bonded each other to form a cyclic structure Moreover, all of R' s in the phosphomum salt may be identical or different Examples of the R' s are alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, 2-butyl, n-pentyl or 2-ethylhexyl, cycloalkyl groups having 3 to 10 carbon atoms such as cyclohexyl, etc, alkenyl groups having 2 to 10 carbon atoms such as vinyl or propenyl, cycloalkenyl groups having 3 10 carbon atoms such as cyclohexenyl, etc, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms such as phenyl, naphthyl or ethylphenyl
In the case that two R' s on one nitrogen atom may be bonded each other to form a cyclic structure, examples of bivalent substituents bonding to the nitrogen atom are alkylene groups having 2 to 10 carbon atoms such as ethylene, tetramethylene or pentamethylene, cycloalkylene groups having 3 to 10 carbon atoms such as cyclohexylene, etc, alkenylene groups having 2 to 10 carbon atoms such as vmylene, etc, cycloalkenylene groups having 3 to 10 carbon atoms such as cyclohexenylene, etc, and aralkylenes having 8 to 10 carbon atoms such as phenylethylene, etc
[0050]
In the case that two R' s on one nitrogen atom do not form a cyclic structure, examples of R are preferably aliphatic hydrocarbon groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms, and particularly preferably methyl or ethyl In the case that two R' s on one nitrogen atom may be bonded each other to form a cyclic structure, examples of bivalent substituents bonding to the nitrogen atom are preferably alkylene groups having 2 to 8 carbon atoms, more preferably tetramethylene or pentamethylene
[0051]
The synthesis method of the phosphomum salt represented by the formula (1) according to the present invention is not particularly limited, for example, may include the following general method
[0052]
(I) A compound represented by the formula (5) obtainable by the
process as described in JP-B-3497054 is used [0053][Chemical Formula 6]
(Formula Removed)

[0054]
In the formula (5) , q is an integer of 0 to 3, and R's have the same meanings as in the formula (1)
(II) Three equivalents of the compounds represented by formula
(5) having different q's and/or R's, are one by one, or the compounds
represented by formula (5) having the same q's and R's are
simultaneously added to phosphorus trichloride, to prepare a
phosphonium salt represented by the formula (6)
[0055][Chemical Formula 7]
(Formula Removed)

[0056]
In the formula (6), a, b, c and R have the same meanings as in the formula (1)
(III) The resulting phosphonium salt represented by the formula
(6) is allowed to react with an alkali metal salt of an active hydrogen
compound represented by M+nQn- wherein M+n represent n alkali metal
cations, to prepare the phosphomum salt represented by the formula
(1) [0057]
In the reaction (II), three equivalents of the compounds represented by the formula (5) are added to phosphorus trichloride In the addition reaction, hydrogen chloride generates at the same time of the progress of the reaction The hydrogen chloride is reacted with the compounds represented by the formula (5) , to form a hydrogen chloride adduct of the compound represented by the formula (5) Accordingly, in order to prepare the aimed phosphomum salt represented by the formula (6) ma high yield, a method of using three or more equivalents of the compounds represented by the formula (5) to phosphorus trichloride, or a method of coexisting other basic substances is employed The reaction temperature varies according to the kind, amount and concentration of the compounds represented by the formula (5) The reaction temperature is usually lower than 150°C, preferably -50 to 100°C, more preferably 0 to 60°C The reaction time varies according to the kind, amount and concentration of the compounds represented by the formula (5) The reaction time is usually less than 24 hr, preferably 1 mm to 12 hr, more preferably 5 mm to 6 hr [0058]
In the reaction (III) , the amount ratio of the two salts, which are raw materials, is not limited as long as the aimed salt is generated, and there are no particularly problems even if any salt of them is
ecsess amounts To 1 equivalent of the phosphonium salt represented by the formula (6) , the amount of M+nQn- is usually 0 2 to 5 equivalents, preferably 0 5 to 3 equivalents, more preferably 0 7 to 1 5 equivalents In order to enhance the contact between them efficiently, it is general to use a solvent Any solvents may be used as long as they do not interfere the reaction Examples of the solvent are water, alcohols such as methanol, ethanol or propanol, ketones such as acetone or methylethyl ketone, aliphatic or aromatic hydrocarbons such as normal-pentane, normal-hexane, cyclohexane, benzene, toluene or xylene, halogenated hydrocarbons such as dichloromethane, chloroform, bromoform, carbon tetrachloride, dichloroethane, chlorobenzene, orthodichlorobenzene, fluorobenzene or benzotrifluoride, esters such as ethyl acetate, methyl propionate or methyl benzoate, ethers such as diethyl ether, tetrahydrofurane, 1,4-dioxane, ethylene glycol dimethylether or triethylene glycol dimethylether, ternary amines such as tributylamme, N,N-dimethyl aniline, pyridine or qumolme, nitroalkanes such as nitromethane or nitroethane, nitriles such as acetonitrile or propionic nitrile, and polar non-protonic solvents such as N,N-dimethyl formamide, dimethyl sulfoxide, sulforane, hexamethyl phosphoric triamide or 1,3-dimethyl-2-imidazolidmone These solvents may be selected according to the chemical stability of the raw material salt used in the reaction The solvents may be used singly or two or more of the solvents may be mixed The raw material salt is preferably dissolved, but may be in a suspension state
The reaction temperature varies according to the kind, amount and concentration of the salt The reaction temperature is usually lower than 150°C, preferably -78 to 80°C, more preferably 0 to 50°C The reaction can be carried out under reduced pressure, ordinary pressure or pressure The reaction pressure is preferably from 0 01 to 1 MPa/cm2 (absolute pressure, refers to hereinafter), more preferably 0 1 to 0 3 MPa/cm2 The reaction time varies according to the reaction temperature and reaction conditions The reaction time is usually from 1 mm to 24 hr, preferably 1 mm to 10 hr, more preferably 5 mm to 6 hr In place of the alkali metal salt M+nQn-, it is also possible to use an alkali earth metal salt having Qn- as a counter anion, an ammonium salt or an anion exchanged resin [0059]
In the separation of the phosphonium salt represented by the formula (1) from the reaction solution in the reaction, a usual method that usual means are combined is used The method varies according to the kind of the aimed salt, the kinds of the two raw material salts, the excess amount thereof and the kind or amount of the solvent In usual, a salt of alkali metal cation and chlorine anion by-produced is precipitated as a solid in the solution As it is, or after it is somewhat concentrated, the salt precipitated is removed by solid -liquid separation with filtration or centrifugal separation, and the solution is concentrated and solidified with drying, to prepare the aimed phosphonium salt When the salt by-produced is still dissolved
In the solution after the concentration, as it is, or after it is somewhat concentrated, a poor solvent is added, to precipitate a by-produced salt or an aimed salt, or after concentration and solidification with drying, one of them can be separated by a method of extracting When the raw material salt used m excess amount is contained in a large amount in the aimed salt, as it is, or after it is dissolved again, they can be separated by extraction using a proper other solvent Furthermore, it can be re-crystallized or purified by a column chromatography, etc if necessary The phosphonium salt represented by the formula (1) thus prepared is capable of changing the size of its cation part and easily soluble in an organic solvent, and is very useful as an active seed for the organic synthesis reaction concerning with anion of the active hydrogen compound [0060]
The second invention is the polymerization catalyst of the alkylene oxide compound comprising the phosphonium salt represented by the formula (2) [0061][Chemical Formula 8]
(Formula Removed)
[0062]
In the formula (2) , Zn- is an anion of an n-valent active hydrogen
compound derived by separating n protons from an active hydrogen compound having at most 8 active hydrogen atoms in an oxygen atom or a nitrogen atom [0063]
Of active hydrogen compounds making Zn-, examples of the active hydrogen compound having active hydrogen atoms on an oxygen atom are water, alcohols having 1 to 30 carbon atoms such as methanol, ethanol, normal-propanol, isopropanol, normal-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, aryl alcohol, crotyl alcohol, methyl vinyl carbmol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbmol or cmnamyl alcohol,
polyvalent alcohols having 2 to 10 hydroxyl groups and 2 to 30 carbon atoms such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propane diol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, 1,4-cyclohexane diol, trimethylol propane, glycerin, diglycerm, pentaerythritol or dipentaerythritol,
saccharides or their derivatives such as glucose, sorbitol, dextrose, fructose or sucrose,
polyalkylene oxides having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups m total, such as polyethylene oxide or polypropylene oxide,
carboxylic acids having 1 to 30 carbon atoms such as formic acid,

autic acid, propionic acid, butyric acid, iso-butyric acid, lauric acid, stearic acid, oleic acid, phenylbutyric acid, dihydrocmnamic acid, cyclohexane carboxylic acid, benzoic acid, paramethyl benzoic acid or 2-carboxyl naphthalene,
polyvalent carboxylic acids having 2 to 8 carboxyl groups and 2 to 30 carbon atoms such as oxialic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butane tetracarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyrromellitic acid,
carbamic acids such as N,N-diethyl carbamic acid^ N-carboxy pyrrolidone, N-carboxy aniline or N,N'-dicarboxy-2,4-toluene diamine, and
phenolic compounds having 6 to 20 carbon atoms and 1 to 3 hydroxyl groups, such as phenol, 2-naphthol, 2,6-dihydroxy naphthalene or bisphenol A [0064]
Of the active hydrogen compounds making Zn-, examples of the active hydrogen compound having an active hydrogen atom on a nitrogen atom are ammonia, primary or secondary amines having 1 to 30 carbon atoms such as methylamme, ethylamme, normal-propyl amine, isopropyl amine, normal-butyl amine, isobutyl amine, sec-butyl amine, tert-butyl amine, cyclohexyl amine, benzyl amine, p-phenylethyl amine, aniline, o-tolidme, m-tolidme, p-tolidme, dimethyl amine, methylethyl amine, diethyl amine, di-normal-propylamme,
exiyl-normal-butylamine, methyl-sec-butylamme, dipentylamme, dxcyclohexyl amine, N-methylanilme or diphenylamme,
polyvalent amines having 2 or 3 primary or secondary amino groups
and 2 to 30 carbon atoms, such as ethylene diamine,
di (2-aminoethyl)amine, hexamethylene diamine,
4, 4' -diammodiphenylmethane, tri (2-ammoethyl) amine,
N,N'-dimethylethylene diamine, N,N'-diethyl ethylene diamine or di(2-methylaminoethyl)amine,
saturated cyclic secondary amines such as pyrrolidine, piperidme, morpholme or 1,2, 3, 4-tetrahydroqumolme,
cyclic poly-valent amines having 2 or 3 secondary amino groups and 4 to 30 carbon atoms such as piperadme, pyrazme or 1,4, 7-tnazacyclononane,
unsubstituted or N-substituted acid amides having 2 to 20 carbon atoms such as acetoamide, propionic amide, N-methylpropionic amide, N-methyl benzoic acid amide or N-ethyl stearic acid amide,
5 to 7-membered ring cyclic amides such as 2-pyrrolidone or s-caprolactam,
dicarboxylic acid lmides having 4 to 10 carbon atoms such as succinic acid lmide, maleic acid lmide or phthalic lmide, and
unsaturated cyclic secondary amines having 4 to 20 carbon atoms such as 3-pyrophosphate, pyrrole, indole, carbazole, imidazole, pyrazole or purine [0065]
Of the active hydrogen compounds making Zn-, preferable examples are water, alcohols having 1 to 20 carbon atoms,
polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms,
saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total,
carboxylic acids having 1 to 20 carboxyl groups, polyvalent carboxylic acid groups having 2 to 8 carboxyl groups and having 2 to 20 carbon atoms,
primary or secondary amines having 1 to 20 carbon atoms, polyvalent amines having 2 to 3 primary or secondary amino groups and 2 to 20 carbon atoms,
saturated cyclic secondary amines having 4 to 20 carbon atoms, and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms More preferable examples are water, alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total, and primary or secondary amines having 1 to 20 carbon atoms [0066]
In the formula (2) , n represents the number of phosphomum cations and also represents the number of protons separating from the active hydrogen compound making Zn- n is an integer of 1 to 8, preferably 1 to 3 When the active hydrogen compound making Zn- has a plurality of active hydrogen atoms, there is a case such that all the active hydrogen atoms are separated and led to anion, or a case such that a part of the active hydrogen atoms are separated and led to anion [0067]
In the formula (2) , a, b and c are each 0 or a positive integer of less than 3 provided that all are not 0 simultaneously a, b and c are each preferably 0 or a positive integer of less than 2 provided that all are not 0 simultaneously All of a, b and c are more preferably 2 or 1 simultaneously, and all of them are furthermore preferably 1 simultaneously [0068]
In the formula (2), R is a hydrocarbon group having 1 to 10 carbon atoms, and two R's on one nitrogen atom may be bonded each other to form a cyclic structure Moreover, all of R' s in the phosphomum salt may be identical or different Examples of the R' s are alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, 2-butyl, n-pentyl or 2-ethylhexyl, cycloalkyl groups having 3 to 10 carbon atoms such as cyclohexyl, etc, alkenyl groups having 2 to 10 carbon atoms such as vinyl or propenyl, cycloalkenyl groups having 3 10 carbon atoms
such as cyclohexenyl, etc, and substituted or unsubstituted aryl groups having 6 to 10 carbon atoms such as phenyl, naphthyl or ethylphenyl In the case that two R' s on one nitrogen atom may be bonded each other to form a cyclic structure, examples of bivalent substituents bonding to the nitrogen atom are alkylene groups having 2 to 10 carbon atoms such as ethylene, tetramethylene or pentamethylene, cycloalkylene groups having 3 to 10 carbon atoms such as cyclohexylene, etc, alkenylene groups having 2 to 10 carbon atoms such as vmylene, etc, cycloalkenylene groups having 3 to 10 carbon atoms such as cyclohexenylene, etc, and aralkylenes having 8 to 10 carbon atoms such as phenylethylene, etc [0069]
In the case that two R' s on one nitrogen atom do not form a cyclic structure, examples of R are preferably aliphatic hydrocarbon groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms, and particularly preferably methyl or ethyl In the case that two R's on one nitrogen atom may be bonded each other to form a cyclic structure, examples of bivalent substituents bonding to the nitrogen atom are preferably alkylene groups having 2 to 8 carbon atoms, more preferably tetramethylene or pentamethylene [0070]
The method of preparing the polymerization catalyst represented by the formula (2) is not particularly limited, and preferable examples of the method are as follows
(I) A method of preparing the polymerization catalyst
represented by the formula (2) by allowing a phosphme compound
represented by the formula (3) to react with the active hydrogen
compound making Zn-,
[0071][Chemical Formula 9]
(Formula Removed)
[0072]
In the formula (3) , a, b and c are each 0 or a positive integer of less than 3, provided that all of them are not 0 simultaneously R' s are identical or different hydrocarbon groups having 1 to 10 carbon atoms and two R' s on one nitrogen atom are optionally bonded each other to form a cyclic structure
(II) A method of preparing the polymerization catalyst
represented by the formula (2) by allowing a phosphonium salt
represented by the formula (4) to react with a salt of an alkali metal
or alkali earth metal of the active hydrogen compound making Zn-
[0073][Chemical Formula 10]
(Formula Removed)
[0074]
In the formula (4), Ym~ is an m-valent inorganic anion a, b and c are each 0 or a positive integer of less than 3 provided that all of them are not 0 simultaneously R' s are identical or different hydrocarbon groups having 1 to 10 carbon atoms and two R's on one nitrogen atom are optionally bonded to form a cyclic structure In the formulas (3) and (4) , a, b, c and R are the same meanings as those in the formula (2) [0075]
In the formula (4), Ym~ is an m-valent inorganic anion, and m represents the number of phosphonium cation in the formula (4) and also represents the valence of the inorganic anion m is an integer of 1 to 3 Examples of the inorganic anion are hydrohalogenic acids such as hydrochloric acid or hydrobromic acid, anions of inorganic acids such as boric acid, tetrafluoro boric acid, hydrocyanic acid, thiocyanic acid, hydrofluoric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorus acid, hexaf luorophosphoric acid, carbonic acid, hexafluoroantimonic acid, hexafluorothallium acid, perchloric acid, chloric acid, chlorous acid or hypochlorous acid, HS04~ and HC03~ Of these inorganic anions, boric acid, tetrafluoro boric acid,
hydrohalogemc acid , phosphoric acid, hexafluorophosphoric acid and perchloric acid are preferred, and further chlorine anion is more preferred [0076]
The salt of an alkali metal or alkali earth metal of the active hydrogen compound making Zn-, which is allowed to react with the phosphonium salt represented by the formula (4) is a compound obtainable by replacing a part or all of active hydrogen atoms of the active hydrogen compound making Zn- with an alkali metal ion such as lithium, sodium or potassium ion, or an alkali earth metal ion such as magnesium or barium ion For example, when the active hydrogen compound making Zn- is methanol, examples of the salt are sodium methoxide and potassium methoxide [0077]
The method of preparing the polymerization catalyst represented by the formula (2) from the phosphme compound represented by the formula (3) and the active hydrogen compound making Zn- can be carried out, for example, in the following procedure [0078]
(I) The phosphonium salt represented by the formula (6) is
prepared in the same manner as in the above method, and thereafter,
(II) the phosphme compound represented by the formula (3) is
prepared in accordance with the method as described in the non patent
document 1 (Journal of general chemistry of the USSR, 1984, 54, 1581) ,

(III) the phosphme compound is allowed to react with the active hydrogen compound making Zn- and thereby the polymerization catalyst represented by the formula (2) is prepared [0079]
Since the phosphme compound represented by the formula (3) has sufficient basicity capable of separating active hydrogen from the active hydrogen compound making Zn-, the polymerization catalyst represented by the formula (2) can be prepared by simply allowing the phosphme compound represented by the formula (3) to contact with the active hydrogen compound making Zn- In this reaction, the weight ratio of the phosphme compound represented by the formula (3) to the active hydrogen compound making Zn- used as raw materials is not particularly limited as long as the aimed polymerization catalyst represented by the formula (2) is generated, and further even if any one of them may be used m excess, there is no problem For example, the amount of the active hydrogen compound making Zn- per 1 equivalent weight of the phosphme compound represented by the formula (3) is usually from 0 2 to 5 equivalent weight, preferably 0 5 to 3 equivalent weight, more preferably 0 7 to 1 5 equivalent weight Furthermore, a solvent can be used to carry out the contact of the both effectively Any solvents may be used as long as not retarding the reaction The reaction temperature varies depending on the kinds, amounts and concentrations of the phosphme compound represented by the formula (3) and the active
hydrogen compound For example, the reaction temperature is usually lower than 150° C, preferably -50°C to 80°C, more preferably 0 to 50°C The reaction can be carried out in any pressure condition of under reduced pressure, under ordinary pressure and under pressure The pressure is preferably from 0 01 to 1 MPa/cm2 (absolute pressure, refers to hereinafter) , more preferably 0 1 to 0 3 MPa/cm2 The reaction time varies depending on the reaction temperature and the reaction conditions For example, the reaction time is usually from 1 mm to 24 hr, preferably 1 mm to 10 hr, more preferably 5 mm to 6 hr [0080]
Usually, the polymerization catalyst represented by the formula (2) ma near pure condition can be prepared by using the reaction solution in the reaction as it is, or only by removing the reaction solvent in the reaction that the reaction solvent is used [0081]
When the polymerization catalyst represented by the formula (2) is prepared froin the phosphonium salt represented by the formula (4), and the salt of an alkali metal or alkali earth metal of the active hydrogen compound making Zn-, the polymerization catalyst represented by the formula (2) can be prepared using an alkali metal salt or alkali earth metal salt having Zn_as a counter anion m place of the alkali metal salt represented by M+nQn- used in the preparation of the phosphonium salt represented by the formula (1) from the phosphonium
step represented by the formula (6) The weight ratio of the phosphonium salt represented by the formula (4), to the salt of an alkali metal or alkali earth metal of the active hydrogen compound making Zn-is not particularly limited as long as the polymerization catalyst represented by the formula (2) is generated, and further even if any one of them may be used m excess, there is no problem For example, the amount of the salt of an alkali metal or alkali earth metal of the active hydrogen compound making Zn- per 1 equivalent weight of the phosphonium salt represented by the formula (4) is usually from 0 2 to 5 equivalent weight, preferably 0 5 to 3 equivalent, more preferably 0 7 to 1 5 equivalent weight Furthermore, a solvent can be used to carry out the contact of the both effectively Any solvents may be used as long as not retarding the reaction The reaction temperature varies depending on the kinds, amounts and concentrations of the phosphonium salt represented by the formula (4) and the salt of the active hydrogen compound For example, the reaction temperature is usually lower than 150° C, preferably -50°C to 80°C, more preferably 0 to 50°C The reaction can be carried out in any pressure condition of under reduced pressure, under ordinary pressure and under pressure The pressure is preferably from 0 01 to 1 MPa/cm2 (absolute pressure, refers to hereinafter), more preferably 0 1 to 0 3 MPa/cm2 The reaction time varies depending on the reaction temperature and the reaction conditions For example, the reaction time is usually from 1 mm to 24 hr, preferably 1 mm to 10 hr, more
preferably 5 mm to 6 hr [0082]
The polymerization catalyst of the present invention may contain the active hydrogen compound making Zn- together with the phosphonium salt represented by the formula (2) The active hydrogen compound making Zn- acts as a chain transfer agent m polymerization reaction of alkylene oxide, and the amount of the active hydrogen compound making Zn- controls the molecular weight of the resulting polyalkylene oxide, or the number of active hydrogen atom therein controls the number of functional group of the resulting polyalkylene oxide [0083]
Examples of the active hydrogen compound making Zn_ contained together with the phosphonium salt represented by the formula (2) may include the same compounds as described in the active hydrogen compound making Zn- in the formula (2) These active hydrogen compounds may be used singly, or two or more thereof may be mixed and submitted to use [0084]
Preferable examples of the active hydrogen compound making Zn-contained together with the phosphonium salt represented by the formula (2) may include water, alcohols having 1 to 20 carbon atoms,
polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms,
saccharides having 5 to 20 carbon atoms and their derivatives,
polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total,
carboxylic acids having 1 to 20 carboxyl groups,
polyvalent carboxylic acid groups having 2 to 8 carboxyl groups and having 2 to 20 carbon atoms,
primary or secondary amines having 1 to 20 carbon atoms,
polyvalent amines having 2 to 3 primary or secondary amino groups and 2 to 20 carbon atoms,
saturated cyclic secondary amines having 4 to 20 carbon atoms, and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms More preferable examples are water, alcohols having 1 to 20 carbon atoms, polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms, saccharides having 5 to 20 carbon atoms and their derivatives, polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups m total, and primary or secondary amines having 1 to 20 carbon atoms [0085]
The amount of the active hydrogen compound making Zn- contained together with the phosphonium salt represented by the formula (2) is usually from 0 01 to 10000 mol, preferably 0 1 to 5000 mol, per 1 mol of the phosphonium salt represented by the formula (2) Polyalkylene oxides having the desired molecular weight and number of functional
groups can be prepared by varying the kind and weight of the active hydrogen compound making Zn-, and the ratio to the alkylene oxide compound arbitrarily [0086]
The third invention is a process for producing the polyalkylene oxide by polymerizing the alkylene oxide compound in the presence of the polymerization catalyst of the present invention Specifically, it is a process for producing the polyalkylene oxide by polymerizing the alkylene oxide compound in the presence of the phosphonium salt represented by the formula (2) , or in the presence of the phosphonium salt represented by the formula (2) and the active hydrogen compound making Zn- In this process, the preparation method of the polymerization catalyst represented by the formula (2) is not particularly limited It is preferred to use the polymerization catalyst represented by the formula (2) derived from the phosphine compound represented by the formula (3) and the active hydrogen compound making Zn- or the polymerization catalyst represented by the formula (2) derived from the phosphonium salt represented by the formula (4) and the salt of an alkali metal or alkali earth metal of the active hydrogen compound making Zn-[0087]
Examples of the alkylene oxide compound used in the process of the present invention may include aliphatic alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene
oxide or cyclohexene oxide, and aromatic alkylene oxides such as styrene oxide, trans stilbene oxide, 2-phenyl propylene oxide, 2-(p-fluorophenyl) oxirane, 2-(p-chlorophenyl) oxirane or 2-(p-bromophenyl) oxirane Of these compounds, ethylene oxide, propylene oxide 1,2-butylene oxide or styrene oxide is preferred, and further ethylene oxide or propylene oxide is more preferred [0088]
In the process of the present invention, it is possible to use two or more of the alkylene oxide compounds simultaneously When plural alkylene oxide compounds are polymerized simultaneously, a copolymer having relatively high randomness is prepared although depending on the reactivity differences thereof Two or more of the alkylene oxide compounds are polymerized one by one, to prepare a block copolymer containing two or more polyalkylene oxide compound blocks For example, after the completion of the polymerization reaction of the first alkylene oxide compound as it is, the second alkylene oxide compound is polymerized, to prepare a block copolymer containing two kinds of blocks Moreover, after the completion of the polymerization reaction of the second alkylene oxide compound, the first alkylene oxide compound is polymerized again, or this procedure is repeated, to prepare an alternating block copolymer Of these copolymers, a block copolymer containing polypropylene oxide and polyethylene oxide, which is obtainable by polymerizing propylene oxide and ethylene oxide as the alkylene oxide compounds one by one, is preferred
[0089]
In the process of the present invention, when the polymerization catalyst represented by the formula (2) derived from the phosphonium salt represented by the formula (4) and the salt of an alkali metal or alkali earth metal of the active hydrogen compound is used, salts of cation of the alkali metal or alkali earth metal, and inorganic anion are co-generated When the salts are disadvantageous to the polymerization reaction, they are removed by filtration or other methods and thereafter submitted to the polymerization reaction [0090]
The amount of the polymerization catalyst represented by the formula (2) used in the polymerization reaction of the alkylene oxide compounds, which is not particularly limited, is usually from 1 x 10"15 to 5 x 10"1 mol, preferably 1 x 10"7 to 1 x 10~2 mol per 1 mol of the alkylene oxide compounds [0091]
When the polymerization catalyst of the present invention is submitted as a solution to the polymerization reaction, and the solvent is disadvantageous to the polymerization reaction, the solvent can be removed by heating under reduced pressure, or other methods [0092]
In the process of the present invention, the procedure of the polymerization reaction is not particularly limited It is usual to employ a procedure of feeding necessary amounts of the alkylene oxide
compounds together to a reactor filled with the polymerization catalyst of the present invention, and optionally the solvent, or a procedure of feeding necessary amounts of the alkylene oxide compounds intermittently or continuously.
[0093]
The reaction temperature in the polymerization reaction varies the kinds or the amounts of the alkylene oxide compounds and other components used It is usually lower than 150°C, preferably 10 to 130°C, more preferably 50 to 120°C The reaction pressure in the polymerization reaction varies the kinds or the amounts of the alkylene oxide compounds and other components used, or the polymerization temperature The pressure in the polymerization reaction is preferably lower than 3 MPa/cm2 (absolute pressure, refers to hereinafter) , more preferably 0 01 to 1 5 MPa/cm2, more preferably 0 1 to 1 MPa/cm2 The reaction time varies depending on the kinds or amounts of the substances used, the reaction temperature or the pressure For example, the reaction time is usually less than 70 hr, preferably 0 1 mm to 30 hr, more preferably 0 5 to 24 hr
[0094]
In the polymerization reaction, it is possible to use the solvent if necessary Examples of the solvent may include aliphatic hydrocarbons such as pentane, hexane, heptane or cyclohexane, aromatic hydrocarbons such as benzene or toluene, ethers such as diethyl ether, tetrahydrofurane, 1,4-dioxane or amsole, and polar non-protonic
solvents such as dimethyl sulfoxide, N,N-dimethyl formamide, hexamethyl phosphoric triamide or N,N' -dimethylimidazolidmone Except for the above solvents, any other solvents can be used as long as not retarding the polymerization reaction of the present invention In the process of the present invention, the polymerization reaction is usually carried out in the presence of an inert gas such as nitrogen or argon
[0095]
The polyalkylene oxide prepared in the process of the present invention by the polymerization reaction without the solvents, as it is, can be used, or the polyalkylene oxide prepared in the process of the present invention by the polymerization reaction with the solvents is submitted to removal of the solvent and then can be used to raw materials of polyurethane foams or elastomers, or surface active agents However, the polyalkylene oxide thus prepared is usually treated with mineral acids such as hydrochloric acid, phosphoric acid or sulfuric acid, formic acid, organic carboxylic acids such as acetic acid or propionic acid, carbon dioxide, or acid type ion-exchange resin to remove or deactivate the catalyst, and then submitted to the above uses Moreover, it may be submitted to usual purification by cleaning with water, an organic solvent or a mixture thereof
[0096]
The polyalkylene oxide of the present invention is a polyalkylene oxide prepared by the production process of the present
Invention In the production, by-products are in small amounts and the polyalkylene oxide has high purity as compared with polyalkylene oxides obtainable by conventional catalysts such as potassium hydroxide catalyst or the like For example, when a poly-valent alcohol such as glycerin is used as a chain transfer agent, it is known that a polyalkylene oxide having only one hydroxyl group at the end, which is called as mono-ol, is usually by-produced in addition to the polyalkylene oxide having a plurality of hydroxyl groups at the end, which is a main product Mono-ol has an unsaturated double bonding group (C=C group) at the molecule end The content of the mono-ol corresponds to the total unsaturation degree of the polyalkylene oxide The polyalkylene oxide of the present invention can be preferably used to raw materials for urethane foams because the amount of mono-ol by-produced is smaller in the production of the polyalkylene oxide, as compared with polyalkylene oxides prepared using a potassium hydroxide catalyst
[0097]
[EXAMPLE]
Next, the present invention will be described m more detail with reference to the following examples, but it should not be limited by the examples
[0098]
In the examples, the number average molecular weight and molecular weight distribution of polyalkylene glycol were determined
by gel permeation chromatography using polyethylene glycol as a standard substance The total degree of unsaturation, which is an index of the amount of mono-ol generated, was determined by the method described in JIS K-1557 Moreover, lmmotris (dialkylammo) phosphorane compound ( (R2N)3P=NH, R represents an alkyl group) , which is a raw material of the phosphonium salt of the present invention, was synthesized by the method as described in JP-B-3497054
[0099] Example 1
Synthesis of tris [tris (dimethylamino)phosphoranilidene
amino]phosphonium methoxide (a)
[0100][Chemical Formula 11]
(Formula Removed)

[0101]
In a 1 L flask, 25 5 g (185 6 mmol) of phosphorus trichloride was weighed out m a nitrogen atmosphere and dissolved in 360 mL of benzene To the solution, 60 mL of a benzene solution of 165 5 g (928 9 mmol) of lmmotris (dimethylamino)phosphorane was slowly dropped at 20°C, and thereafter, reacted at 20°C for 2 hr The lmmotris (dimethylamino) phosphorane was used in an amount of 5 0 times by mole per phosphorus trichloride After the completion of the
reaction, a resulting precipitate was separated with filtration and washed with benzene, and the wash solution was mixed with a filtrate Next, from the mixed solution, a product was extracted in a water phase by 90 mL of water, and from the aqueous solution, the product was extracted in an organic phase by 600 mL of methylene chloride The organic phase was washed with water and the solvent was concentrated and solidified As a result, 109 7 g of a white solid was prepared [0102]
As described below, the white solid was submitted to 31P-NMR and element analysis It was found that this compound is tris [tris (dimethylammo)phosphoranilidene amino] phosphomum chloride ( [ [ (Me2N) 3P=N] 3PH+] [Cl~]) The yield based on phosphorus trichloride was 98 7% [0103]
In the white solid tetrahydrofurane (hereinafter abbreviated to THF) -de, the 31P-NMR chemical shifts using hexamethyl phosphoramide (hereinafter abbreviated to HMPA) as an internal standard were 23 0 ppm and -27 4 ppm, and were respectively assigned on phosphorus atom of P=N and phosphorus atom of PH+ m tris [tris (dimethylamino)phosphoranilidene amino] phosphomum cation ( [ (Me2N)3P=N]3PH+) In the result of the element analysis, the C value was 35 80 %, H was9 21%, N was 28 25%, 0 was 20 70% and CI was 6 08% These values are consistent well with the calculation values of [[(Me2N)3P=N]3PH+] [Cl~] (C 36 09%, H 9 25%, N 28 06%, P 20 68%,
0.5 92%) [0104]
The resulting tris[tris(dimethylamino)phosphoranilidene ammo] phosphonrum chloride was ion exchanged in the following manner to prepare tris[tris(dimethylamino)phosphoranilidene ammo]phosphonium methoxide (a) [0105]
In a 100 mL egg-plant type flask, 30 0 g(50 0 mmol) of the tris [tris (dimethylamino) phosphoranilidene amino] phosphomum chloride synthesized was weighed out, and 50 mL of pure water was added To the solution, 60 4 g (55 mmol m terms of NaBF4) of a 10 wt% NaBF4 aqueous solution was added and stirred at room temperature for 1 hr The resulting white solid was filtrated, and the solid was washed with 100 mL of water and dried under reduced pressure to prepare 32 1 g (49 4 mmol) of tris[tris(dimethylamino)phosphoranilidene amino] phosphomum tetrafluoroborate as a white solid The yield was 98 7% [0106]
Subsequently, m a nitrogen atmosphere, 25 4 g(39 1 mmol) of tris [tris (dimethylamino) phosphoranilidene ammo] phosphomum tetrafluoroborate was weighed out and dissolved m 200 mL of methanol To the mixture, 70 mL of a methanol solution of 2 74 g (39 1 mmol) of potassium methoxide was added gradually at room temperature At the same time of the dropping, cloudiness of the solution started Furthermore, the solution was stirred at room temperature for 2 hr
After the stirring, a resulting precipitate (KBF4) was separated with
filtration, and a filtrated substance was washed with 30 mL of methanol,
and a wash solution was mixed with a filtrate From the mixed solution,
methanol was removed under reduced pressure, and thereby 22 8 g of
a slightly yellowish oily substance was prepared The substance was
submitted to measurements for 31P-NMR and element analysis, and it was
found that this compound is
tris[tris(dimethylamino)phosphoranilidene amino]phosphonium methoxide (a) The yield was 98 1% [0107]
In THF-d8, the 31P-NMR chemical shifts using HMPA as an internal standard were 20 1 ppm and -30 6 ppm, and were respectively assigned on phosphorus atom of P=N and phosphorus atom of PH+ m tris [tris (dimethylamino)phosphoramlidene amino] phosphonium cation ( [ (Me2N) 3P=N] 3PH+) In the result of the element analysis, the C value was 38 33 %, H was 9 97%, N was 26 98% and P was 19 96% These values are consistent well with the calculation values of tris [tris (dimethylammo) phosphoramlidene ammo] phosphonium methoxide (a) (C 38 38%, H 9 83%, N 28 27%, P 20 84%) [0108]
Comparative Example 1
Synthesis of [Tetrakis [tris (dimethylammo) phosphoramlidene ammo] phosphonium chloride (b) [0109][Chemical Formula 12]
(Formula Removed)
[0110]
A tetrakis [tris (dimethylamino)phosphoranilidene ammo] phosphomum chlorxde (b) was synthesized according to the method as described in Example 1 of JP-A-Hll(1999)-152294 [0111]
In a nitrogen atmosphere, to a 2 L glass reactor, 60 20 g (0 289
mol) of phosphorus pentachlonde and 585 1 g of o-dichlorobenzene were
fed The temperature was elevated to 40°C while the mixture was
stirred, and 439 3 g (2 465 mol) of lmmotris (dimethylammo)
phosphorane was dropped to the mixture over 1 hr while controlling
the temperature The limnotris (dimethylammo) phosphorane was used in
an amount of 8 5 times by mole per phosphorus pentachlonde After
the completion of the dropping, the mixture was further kept at 40°
for 1 hr Thereafter, the temperature of the solution was elevated
to 170°C over 1 hr and the solution was reacted for 9 hr A part of
the reaction solution was picked out and submitted to quantitative
analysis by 31P-NMR As a result, it was found that this reaction
solution contains 0 284 mol of
tetrakis [tris (dimethylammo) phosphoranilidene ammo] phosphomum
cycloride (b) The yield for phosphorus pentachloride was 98 2%
The resulting tetrakis[tris(dimethylammo) phosphoramlidene amino] phosphomum chloride (b) was induced to tetrakis [tris (dimethylammo) phosphoramlidene ammo] phosphomum methoxide by the ion exchange method same as m Example 1 [0112]
In order to prepare
tetrakis [tris (dimethylammo) phosphoramlidene ammo] phosphomum chloride (b), which is an intermediate of tetrakis [tris (dimethylammo) phosphoramlidene ammo] phosphomum methoxide m a high yield, it is necessary to allow phosphorus pentachloride to react with immotris (dimethylammo)phosphorane at a high temperature for a long period of time It is further necessary to use 8 5 times by mole of immotris (dimethylammo) phosphorane based on phosphorus pentachloride Therefore, it is necessary to use a larger amount of immotris (dimethylammo) phosphorane as compared with the synthesis of tris [tris (dimethylammo) phosphoramlidene ammo] phosphomum chloride (5 0 times by mole based on phosphorus trichloride) [0113] Example 2
Synthesis of [tris [tris (di-n-propylammo) phosphoramlidene ammo] phosphomum methoxide (c) [0114][Chemical Formula 13]
(Formula Removed)
[0115]
In a 100 mL flask, 253 mg (1 84 inmol) of phosphorus trichloride was weighed out m a nitrogen atmosphere and dissolved m 25 mL of pentane To the solution, a solution obtainable by dissolving 4 46 g (12 9 mmol) of uninotris (di-n-propylammo)phosphorane m 25 mL of a pentane was slowly dropped at 0°C Thereafter, the mixture was reacted at 50°C for 6 hr, and a resulting precipitate was separated After drying, 3 42 g of a white solid was prepared The mass analysis of the white solid was carried out As a result, molecule ion peaks corresponding to molecular weights of the cation parts of tris [tris (di-n-propylammo) phosphoranilidene ammo]phosphonium chloride obtainable by replacing methoxy anion with chlorine anion in the phosphonium salt (c), and ammotris (di-n-propylamino)phosphonium chloride, which is a salt of lmmotris (di-n-propylammo) phosphorane and hydrogen chloride, were observed [0116]
Next, the removal of ammotris (di-n-propylammo)phosphonium chloride in the mixture was carried out by allowing it to react with potassium methoxide and thereby making into
panotris(di-n-propylamino)phosphorane The whole amount of the resulting white solid was dissolved in 10 mL of methanol, and to the solution, 2 67 g (3 81 mmol in terms of potassium methoxide) of a methanol solution of 10 0 wt% of potassium methoxide was added at room temperature, and stirred for 15 hr A resulting potassium chloride solid was separated with filtration From the filtrate, methanol was removed, and the resulting white solid was washed with 100 mL of pentane to remove lmmotris (di-n-propylammo)phosphorane 1 80 g of a white solid was prepared [0117]
As described below, the white solid was submitted to 31P-NMR and element analysis It was found that this compound is tris [tris (di-n-propylammo)phosphoranilidene amino] phosphonium chloride The 31P-NMR chemical shifts using HMPA as an internal standard m THF-d8 were 22 0 ppm and -27 9 ppm, and were respectively assigned on phosphorus atom of P=N and phosphorus atom of PH+ in tris [tris (di-n-propylammo)phosphoranilidene amino] phosphonium cation ([ (nPr2N) 3P=N]3PH+) In the result of the element analysis, the C value was 58 81 %, H was 11 80%, N was 15 11%, P was 11 10% and CI was 3 18% These values are consistent well with the calculation values (C 58 75%, H 11 59%, N 15 22%, P 11 22%, CI 3 21%) The yield for phosphorus trichloride was 88 6% [0118]
The resulting tris [tris (di-n-propylammo)phosphoranilidene
amino phosphomum chloride was induced to tris [tris (di-n-propylamino)phosphoranilidene ammo]phosphomum methoxide (c) by the ion exchange method same as m Example 1 In the result of the element analysis of the phosphomum salt (c), the C value was 60 41 %, H was 11 88%, N was 15 20% and P was 11 57% These values are consistent well with the calculation values (C 60 08%, H 11 92%, N 15 29%, P 11 27%)
[0119]
Example 3
Synthesis of tris [tris (di-n-hexylamino)phosphoramlidene ammo]
phosphomum methoxide (d)
[0120][Chemical Formula 14]
(Formula Removed)
[0121]
The reaction and post-treatment procedures of Example 2 were repeated except that phosphorus trichloride was used in an amount of 367 mg (2 67 mmol), 8 01 g (13 4 mmol) of lmmotns (di-n-hexylammo)phosphorane was used m place of immotris (di-n-propylammo)phosphorane, and the reaction time was 8 hr, and thereby 1 60 g (0 860 mmol) of tris [tris (di-n-hexylammo)phosphoramlidene amino] phosphomum

oxioride was prepared The yield for phosphorus trichloride was
32 2%
[0122]
In tris [tris (di-n-hexylamino)phosphoramlidene amino] phosphomum chloride, the 31P-NMR chemical shifts using HMPA as an internal standard in THF-d8 were 20 4 ppm and -29 5 ppm, and were respectively assigned on phosphorus atom of P=N and phosphorus atom of PH+ in tris [tris (di-n-hexylammo)phosphoranilidene amino] phosphomum cation ([ (nHex2N) 3P=N]3PH+) In the result of the element analysis, the C value was 69 97 %, H was 13 01%, N was 8 91%, P was 6 59% and CI was 2 02% These values are consistent well with the calculation values of [ [ (nHex2N) 3P=N] 3PH+] [Cl~] (C 69 69%, H 12 72%, N 9 03%, P 6 66%, CI 1 90%) [0123]
The resulting tris [tris (di-n-hexylammo)phosphoranilidene amino] phosphomum chloride was induced to tris [tris (di-n-hexylammo) phosphoramlidene amino] phosphomum methoxide (d) by the ion exchange method same as m Example 1 In the result of the element analysis of the phosphomum salt (d), the C value was 70 80 %, H was 13 01%, N was 8 83% and P was 6 88% These values are consistent well with the calculation values (C 70 50%, H 12 92%, N 9 05%, P 6 67%) [0124]
Example 4
Synthesis of [tris[tris(pyrrolidine -1-yl) phosphoranilidene
amino]phosphonium methoxide (e)
[0125] [Chemical Formula 15]
(Formula Removed)
[0126]
The reaction and post-treatment procedures of Example 2 were repeated except that lminotris (pyrrolidme-l-yl)phosphorane was used in an amount of 3 31 g (12 9 mmol) m place of lminotris (di-n-propylammo) phosphorane, and thereby 1 11 g (1 33 mmol) of tris [tris (pyrrolidme-1-yl) phosphoranilidene amino] phosphonium chloride was prepared as a white solid The yield for phosphorus trichloride was 72 3% [0127]
In tris [tris (pyrrolidme-1-yl) phosphoranilidene amino] phosphonium chloride, the 31P-NMR chemical shifts using HMPA as an internal standard in THF-dg were 21 9 ppm and -28 0 ppm, and were respectively assigned on phosphorus atom of P=N and phosphorus atom of PH+ in tris [tris (pyrrolidme-1-yl) phosphoranilidene amino] phosphonium cation ([Py3P=N] 3PH+ wherein Py represents a pyrrolidme-1-yl group, refer to hereinafter) In the result of the
element analysis, the C value was 51 96 %, H was 9 01%, N was 20 03%, P was 14 67% and CI was 4 13% These values are consistent well with the calculation values of [Py3P=N]3PH+] [CI-] (C 51 88%, H 8 83%, N 20 17%, P 14 87%, CI 4 25%) [0128]
The resulting tris [tris (pyrrolidine-l-yl)phosphoramlidene amino] phosphomum chloride was induced to tris [tris (pyrrolidme-1-yl) phosphoranilidene amino] phosphomum methoxide (e) by the ion exchange method same as in Example 1 In the result of the element analysis of the phosphomum salt (e) , the C value was 54 02 %, H was 9 35%, N was 20 10% and P was 14 72% These values are consistent well with the calculation values (C 53 61%, H 9 24%, N 20 28%, P 14 95%) [0129] Example 5
Synthesis of tris [tris (dimethylammo) phosphoranilidene amino] phosphomum methoxide (a) by another method
Using tris [tris (dimethylammo) phosphoranilidene amino] phosphomum chloride synthesized m Example 1, tris [tris (dimethylammo) phosphoranilidene amino]phosphme (f) was synthesized m accordance with the method as described m Journal of General Chemistry of USSR, 1984, Vol 54 p 1581 [0130][Chemical Formula 16]
(Formula Removed)
[0131]
In a nitrogen atmosphere, 10 0 g (17 8 mmol) of tris [tris (dimethylammo) phosphoranilidene amino]phosphine was weighed out m a 100 mL egg-plant flask and 50 mL of THF was added therein To the mixture, 570 mg (17 8 mmol) of methanol was added accurately with a micro-syringe, and stirred After 5 mm, THF, which was a solvent, was concentrated at room temperature, and thereby 10 6 g (17 8 mmol) of tris [tris (dimethylammo) phosphoranilidene ammo] phosphonium methoxide (a) was prepared as a slightly yellowish oily substance [0132]
In the phosphonium salt (a) prepared m this example, the 31P-NMR chemical shifts m THF-de were identical with the values of Example 1 In the result of the element analysis of the phosphonium salt (a) , the C value was 38 25 %, H was 9 54%, N was 28 10% and P was 20 53% These values are consistent well with the calculation values (C 38 38%, H 9 83%, N 28 27%, P 20 84%) [0133] Examples 6 to 14
Syitheses of various phosphomum salts
Using each of phosphomum chlorides synthesized m Examples 2 to 4, tris [tris (di-isopropylammo) phosphoranilidene ammo] phosphme, tris [tris (di-n-hexylammo)phosphoramlidene amino]phosphine, and tris [tris (pyrrolidine -1-yl) phosphoranilidene amino] phosphme were synthesized in accordance with the method as described in Journal of General Chemistry of USSR, 1984, Vol 54 p 1581 [0134]
The procedure of Example 5 was repeated except that various kinds of phosphme compounds and active hydrogen compounds as described m Table 1 were used m place of tris [tris (di-methylammo) phosphoranilidene ammo]phosphme and methanol, and thereby the following phosphomum salts were prepared In Example 13, glycerin was used in an amount of 0 82 g (8 9 mmol) In Example 14, MN1000 manufactured by Mitsui Chemical Polyurethane was used as polyoxypropylene triol The analysis results are shown m Table 1
[0135]
Table
(Table Removed)
[0136] [Chemical Formula 17]
(Formula Removed)
[0137][Chemical Formula 18]
(Formula Removed)
[0138]
Example 15
Synthesis of glycerin solution of glycerin tris [tris (dimethylammo)
phosphoramlidene ammojphosphonium salt (m) ]
A solution prepared by dissolving 2 03 g (3 40 mmol) of tris [tris (dimethylammo) phosphoramlidene amino] phosphomum chloride synthesized in Example 1 in 65 mL of pure water was passed through a column having an inner diameter of 20 mm and a height of
cm, filled with 25 mL of hydroxyl group type ion exchange resin
(Lewatit® MP-500 manufactured by Bayer AG) at room temperature at a flow rate of SV = 3 Thereafter, 75 mL of pure water, further, was passed through, and all the solution was recovered and concentrated until the amount thereof was halved mostly This aqueous solution was titrated with a 0 01 N-HC1 aqueous solution, and thereby found to be an aqueous solution containing 0 0350 mmol/g of tris [tris (dimethylammo) phosphoranilidene amino] phosphonium hydroxide To 38 8 g of this aqueous solution (1 36 mmol m terms of tris [tris (dimethylammo) phosphoranilidene amino] phosphonium hydroxide), 10 4 g (113 mmol) of glycerin was added, and water was distilled off under a reduced pressure of 133 Pa at 80°C over 5 hr As a result, 11 1 g of a glycerin solution of glycerin tris [tris (dimethylammo) phosphoranilidene ammo] phosphonium salt
(m) was obtained as a colorless oily substance
[0139] Example 16
72 8 mg (0 122 mmol) of
tris [tris (dimethylammo) phosphoranilidene ammo] phosphonium methoxide (a) prepared in Example 1 and 921 mg (10 0 mmol) of glycerin were weighed out in a 100 mL autoclave equipped with a temperature measuring tube, a manometer and a stirring device, and then 49 3 g
(84 9 mmol) of propylene oxide was fed all together The system inside was pressurized with nitrogen to regulate the initial pressure to 0 07
mm Thereafter, the system inside was heated so that the inner temperature was 80°C, and the reaction was carried out It was confirmed that the reaction had mostly been completed after 22 hr from the descendent of the reaction pressure After cooling, remained and unreacted propylene oxide was removed under reduced pressure 49 0 g of propylene oxide (sometimes abbreviated to PPG) was obtained as a colorless and odorless oily substance The yield was 97 6 %, and the resulting polymer had a number average molecular weight of 4 55 X 103 (calculation molecular weight 4 90 X 103) and a molecular weight distribution of 1 03 The total degree of unsaturation was 0 022 meq/g
[0140]
The produced amount of the polypropylene oxide per weight of the catalyst and per time (hereinafter simply represented by polymerization activity) , which is an index of polymerization activity, was 30 6 g-PPG/g-catalyst h The polypropylene oxide having high purity was obtained with a low total degree of unsaturation
[0141]
Comparative Example 2
The procedure of Example 16 was repeated except for using 94 4 mg (0 122 mmol) of tetrakis [tris (dimethylamino) phosphoramlidene amino] phosphoniummethoxide prepared in Comparative Example 1 in place of tris [tris (dimethylamino) phosphoramlidene amino] phosphomum methoxide to carry out polymerization reaction of propylene oxide
After 22 hr, the reaction has mostly been completed After cooling, remained and unreacted propylene oxide was removed under reduced pressure 49 2 g of propylene oxide was obtained as a colorless and odorless oily substance The yield was 98 0 %, and the resulting polymer had a number average molecular weight of 4 58 X 103 (calculation molecular weight 4 92 X 103) and a molecular weight distribution of 1 03 The total degree of unsaturation was 0 021 meq/g
[0142]
The polymerization activity of
tetrakis [tris (dimethylanu.no) phosphoramlidene amino] phosphonium methoxide was 23 7 g-PPG/g-catalyst h The polymerization activity is lower as compared with that of the phosphonium salt (a)
[0143]
Comparative Example 3
The procedure of Example 16 was repeated except for using 8 6 mg (0 122 mmol) of potassium methoxide in place of tris [tris (dimethylammo) phosphoramlidene amino] phosphonium methoxide to carry out polymerization reaction of propylene oxide After 22 hr, the reaction solution was cooled to room temperature, and remained and unreacted propylene oxide was removed under reduced pressure 2 23 g of propylene oxide was obtained The yield had a low value of a low level of 4 4 %, and the polymerization activity had a low value of 11 8 g-PPG/g-catalyst h
[0144]
Sample 17
5 95 mg (lOmmol) of tris [tris (dimethylamino)phosphoranilidene amino] phosphomum methoxide prepared by the method as described in Example 1 was weighed out m a 100 mL autoclave equipped with a temperature measuring tube, a manometer, a stirring device and an alkylene oxide-introducing tube, and then heated with stirring until the outer temperature reached to 80°C Next, 29 0 g (500 mmol) of propylene oxide was fed intermittently so that the reaction pressure was kept to about 0 3 MPa (gauge pressure) After 10 hr, the feeding was finished and further the reaction was continued at an outer temperature of 80°C for 10 hr Thereafter, the temperature was decreased to room temperature, and remained and unreacted propylene oxide was removed under reduced pressure 34 0 g of propylene oxide was obtained as a colorless and odorless oily substance The yield was 97 3 %, and the resulting polymer had a number average molecular weight of 2 88 X 103 (calculation molecular weight 2 94 X 103) and a molecular weight distribution of 1 03 [0145] Examples 18-23
In each example, the reaction and post-treatment procedures of Example 16 were repeated except for using each of various phosphomum salts as shown in Table 2 m place of the phosphomum salt (a) The results are shown m Table 2
[0146]
Table 2
(Table Removed)
[0147] Example 24
The reaction procedure of Example 16 was repeated except for using 73 1 mg (0 122 mmol) of tris [tris (dimethylammo) phosphoramlidene amino] phosphonium chloride synthesized as a synthetic intermediate of the phosphonium salt (a) in Example 1, and 926 mg of a glycerin solution containing 0 515 wt% potassium ion (0 122 mmol of potassium ion, 10 0 mmol of glycerin) m place of the phosphonium salt (a) and glycerin After 22 hr, the reaction had mostly been completed After cooling, remained and unreacted propylene oxide was removed under reduced pressure 48 5 g of polypropylene oxide was obtained as a colorless and odorless oily substance The yield was 96 4%, and the resulting polymer had a number average molecular weight of 4 53 X 103 and a molecular weight distribution of 1 05 The total degree of unsaturation was 0 020 meq/g
[0148] Example 25
The reaction procedure of Example 16 was repeated except for using 999 mg of a glycerin solution of glycerin tris [tris(dimethylamino) phosphoranilidene amino]phosphonium salt
(m) (0 122 mmol of potassium salt (m), 10 0 mmol of glycerin) prepared in Example 15 m place of the phosphonium salt (a) and glycerin After 22 hr, the reaction had mostly been completed After cooling, remained and unreacted propylene oxide was removed under reduced pressure 49 Og of polypropylene oxide was obtained as a colorless and odorless oily substance The yield was 97 5 %, and the resulting polymer had a number average molecular weight of 4 55 X 103 and a molecular weight distribution of 1 03 The total degree of unsaturation was 0 021 meq/g
[0149] Example 26
The reaction procedure of Example 16 was repeated except for using 130 mg (0 122 mmol) of tris [tris (di-n-propylammo) phosphoranilidene amino] phosphme in place of the phosphonium salt
(a) After 22 hr, the reaction had mostly been completed After cooling, remained and unreacted propylene oxide was removed under reduced pressure 50 0 g of polypropylene oxide was obtained as a colorless and odorless oily substance The yield was 98 1 %, and the resulting polymer had a number average molecular weight of 4 56 X 103
and a molecular weight distribution of 1 07 The total degree of unsaturation was 0 021 meq/g [0150] Example 27
From the resulting aqueous solution of tris [tris (dimethylamino) phosphoramlidene amino] phosphonium hydroxide prepared as an intermediate raw material m Example 15, water was distilled off and thereby tris [tris (dimethylammo) phosphoramlidene amino] phosphonium hydroxide was prepared as a white solid [0151]
The reaction procedure of Example 16 was repeated except for using 70 8 mg (0 122 mmol) of tris [tris (dimethylammo) phosphoramlidene amino] phosphonium hydroxide m place of the phosphonium salt (a) After 22 hr, the reaction had mostly been completed After cooling, remained and unreacted propylene oxide was removed under reduced pressure 4 9 8 g of polypropylene oxide was obtained as a colorless and odorless oily substance The yield was 97 7 %, and the resulting polymer had a number average molecular weight of 4 53 X 103 and a molecular weight distribution of 1 06 The total degree of unsaturation was 0 021 meq/g [0152] Examples 28-31
In each example, the reaction and post-treatment procedures of Example 16 was repeated except for using each of compounds as shown
in Table 3 as a chain transfer agent m place of glycerin
The results are shown m Table 3 [0153]
Table 3
(Table Removed) [0154] Example 32
The procedure of Example 16 was repeated to carry out polymerization of propylene oxide Successively, 3 74 g (85 mmol) of ethylene oxide was slowly fed to the autoclave over about 1 hr without exposing the autoclave to air, and the reaction was carried out at an internal temperature of 80°C for 5 hr After cooling, remained and unreacted propylene oxide and ethylene oxide were removed under reduced pressure 52 5 g of a block copolymer of propylene oxide and ethylene oxide was obtained as a colorless and odorless oily substance The yield was 97 3 %, and the resulting polymer had a number average molecular weight of 4 85 X 103 (calculation molecular weight 5 32 X 103) and a molecular weight distribution of 1 04 The total degree of unsaturation was 0 022 meq/g
[0155] Examples 33-35
In Example 33, 138 1 g(l 50 mmol) of glycerin was added to 8 03 mg (13 5 mmol) of a phosphomum salt (a) prepared in the same manner as in Example 1 Methanol was removed at 80°C under reduced pressure (133 Pa) over 5 hr, and thereby 144 8 g of a glycerin solution of glycerin tris [tris (dimethylammo)phosphoranilidene amino] phosphomum salt was obtained as a colorless oily substance Next, in a 3 L autoclave equipped with a temperature measuring tube, a manometer, a stirring device and an alkylene oxide introducing tube, 36 2 g of the glycerin solution of glycerin tris [tris (dimethylammo) phosphoranilidene ammo] phosphomum salt was weighed out and then heated with stirring until the inner temperature reached to 90°C Next, 1650 g (28 4 mmol) of propylene oxide was fed intermittently so that the reaction pressure was not over 0 4 MPa (gauge pressure) After 13 hr, the feeding was finished and further the reaction was continued at an inner temperature of 90°C for 7 hr Thereafter, the temperature was decreased to room temperature, and remained and unreacted propylene oxide was removed under reduced pressure Into the reactor, nitrogen was fed until the gauge pressure of 0 MPa, and then the temperature was elevated again while the reaction mixture was stirred so that the inner temperature was 110°C To the reactor, 285 g (6 5 mmol) of ethylene oxide was fed intermittently so that the reaction pressure was not over 0 4 MPa (gauge pressure) After 3 5 hr, the feeding was
funished, and further, the reaction was continued for 1 5 hr with keeping the internal temperature to 110°C Thereafter, the temperature was decreased to room temperature, and remained and unreacted ethylene oxide was removed under reduced pressure 1961 g of a block copolymer of polypropylene oxide and ethylene oxide was obtained as a colorless and odorless oily substance The yield was 99 5 %, and the resulting polymer had a number average molecular weight of 5 23 X 103 (calculation molecular weight 5 26 X 103) and a molecular weight distribution of 1 03 The total degree of unsaturation was 0 019 meq/g The polymerization activity of propylene oxide was 68 0 g-polymer/g-catalyst h, and the polymerization activity of ethylene oxide was 50 9 g-polymer/g-catalyst h
[0156]
The reaction of Example 33 was carried out twice m Examples 34 and 35 The results are shown in Table 4 together with the above results
[0157]
Table 4
(Table Removed)
0158]
Comparative Examples 4 to 6
In Comparative Example 4, the procedure of Example 33 was repeated except that a glycerin solution of glycerin tetrakis [tris (dimethylamino)phosphoranilidene amino] phosphomum salt was prepared using 10 4 g (13 5 mmol) of tetrakis [tris (dimethyl ammo)phosphoranilidene amino]phosphomum methoxide synthesized in the method as described in Comparative Example 1 in place of the phosphomum salt (a) , and 36 8 g of the glycerin solution of glycerin tetrakis [tris (dimethylamino)phosphoramlidene amino] phosphomum salt was used in place of the glycerin solution of glycerin tris [tris (dimethylaitu.no) phosphoranilidene ammo]phosphomum salt, and thereby a block copolymer of polypropylene oxide and polyethylene oxide was prepared [0159]
The reaction of Comparative Example 4 was carried out twice in Comparative Examples 5 and 6 The results are shown m Table 5 together with the above results
[0160]
Table 5
(Table Removed)
POSSIBILITY OF INDUSTRIAL USE [0161]
The present invention provides new phosphonium salts that are basic catalysts effective for various organic reactions [0162]
Moreover, the present invention can provide a process for effectively and readily producing a polyalkylene oxide by polymerizing an alkylene oxide compound using the polymerization catalyst of the present invention, and further provide a polyalkylene oxide having high purity.

WE CLAIM:
1. A phosphonium salt represented by the formula (1)
(Formula Removed)
wherein Qn- is an anion of an n-valent active hydrogen compound having at least one carbon atom, and a form derived by releasing n protons from an active hydrogen compound having at most 8 active hydrogen atoms
in an oxygen atom or a nitrogen atom, a, b and c are each a positive
integer of not more than 3 or 0 provided that they are not zero simultaneously, R's are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R's present in one nitrogen atom may be bonded to each other to form a cyclic structure.
2. The phosphonium salt according to claim 1 wherein an active hydrogen compound making Qn- is an active hydrogen compound selected from the group consisting of alcohols having 1 to 20 carbon atoms; polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20 carbon atoms; saccharides having 5 to 20 carbon atoms or their derivatives; polyalkylene oxides having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total, and having a molecular weight of from 100 to 50,000; carboxylic acids having 1 to 20 carbon atoms; polyvalent
carboxylic acids having 2 to 8 carboxyl groups, and 2 to 20 carbon atoms; primary or secondary amines having 1 to 20 carbon atoms; polyvalent amines having 2 to 3 primary or secondary amino groups, and 2 to 20 carbon atoms; saturated cyclic secondary amines having 4 to 20 carbon atoms; and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms.
3. The phosphonium salt according to claim 1 or 2 wherein n in the phosphonium salt represented by the formula (1) is an integer of 1 to 3.
4. The phosphonium-salt according to any one of claims 1 to 3
wherein a, b and c in the phosphonium salt represented by the formula
(1) are not zero simultaneously, and are each a positive integer of not more than 2 or 0.
5. The phosphonium salt according to any one of claims 1 to 4 wherein R's in the phosphonium salt represented by the formula (1) are each an alkyl group having 1 to 10 carbon atoms.
6. The phosphonium salt according to any one of claims 1 to 5 wherein when two R' s present in one nitrogen atom in the phosphonium salt represented by the formula (1) are bonded to form a cyclic structure, a bivalent substituent corresponding the nitrogen atom is
tetramethylene or pentamethylene.
7. A polymerization catalyst of an alkylene oxide compound comprising a phosphonium salt represented by the formula (2),
(Formula Removed)
wherein Zn- is an anion of an n-valent active hydrogen compound having a form derived by releasing n protons from an active hydrogen compound having at most 8 active hydrogen atoms in an oxygen atom or a nitrogen
atom, a, b and c are each a positive integer of not more than 3 or 0 provided that, they are not zero simultaneously, R's are identically or
differently hydrocarbon groups having 1 to 10 carbon atoms, and two
R's present in one nitrogen atom may be bonded each other to form a
cyclic structure.
8. The polymerization catalyst according to claim 7 obtainable from a phosphine compound represented by the formula (3), and an active hydrogen compound making Zn-,
(Formula Removed)
wherein a, b and c are each a positive integer of not more than 3 or 0 provided that they are not zero simultaneously, R' s are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R' s present in one nitrogen atom may be bonded each other to form a cyclic structure.
9. The polymerization catalyst according to claim 7 obtainable from a phosphonium salt represented by the formula (4), and an alkali metal or an alkali earth metal of an active hydrogen compound making Zn-,
(Formula Removed)
wherein Ym- is an m-valent inorganic anion, a, b and c are each a positive
integer of not more than 3 or 0 provided that they are not zero
simultaneously, R' s are identically or differently hydrocarbon groups having 1 to 10 carbon atoms, and two R's present in one nitrogen atom may be bonded each other to form a cyclic structure.
13. The polymerization catalyst according to any one of claim 7 to 12 wherein in the formula (2), a, b and c are each a positive
integer of not more than 2 or 0 provided that all of them are not 0 simultaneously.
14. The polymerization catalyst according to any one of claim 7 to 13 wherein in the formula (2), R is an alkyl group having 1 to 10 alkyl groups.
15. The polymerization catalyst according to any one of claim 7 to 14 wherein when two R's on one nitrogen atom in the formula (2)
-are bonded each other to form a cyclic structure, the bivalent substituent corresponding to the nitrogen atom is tetramethylene or pentamethylene.
16. The polymerization catalyst for the alkylene oxide compound according to any one of claim 7 to 15, which further comprises an active hydrogen compound making Zn-.
17. The polymerization catalyst according to claim 16 wherein the active hydrogen compound making Zn-, which is coexisted with the polymerization catalyst represented by the formula (2) is selected from the group consisting of water; alcohols having 1 to 20 carbon atoms; polyvalent alcohols having 2 to 8 hydroxyl groups and 2 to 20
carbon atoms; saccharides having 5 to 20 carbon atoms and their derivatives; polyalkylene oxides having a molecular weight of from 100 to 50,000 and having 2 to 8 end groups which groups have 1 to 8 hydroxyl groups in total; carboxylic acids having 1 to 20 carboxyl groups; polyvalent carboxylic acid groups having 2 to 8 carboxyl groups and having 2 to 20 carbon atoms; primary or secondary amines having 1 to 20 carbon atoms; polyvalent amines having 2 to 3 primary or secondary amino groups and 2 to 20 carbon atoms; saturated cyclic secondary amines having 4 to 20 carbon atoms; and cyclic polyvalent amines having 2 or 3 secondary amino groups and 4 to 20 carbon atoms.
18. A process for producing a polyalkylene oxide which process comprises polymerizing an alkylene oxide compound in the presence of the polymerization catalyst as claimed in any one of claims 7 to 17.
19. The process for producing a polyalkylene oxide according to claim 18 wherein the alkylene oxide compound comprises at least one of the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide.
20. The process for producing a polyalkylene oxide according to claim 18 or 19 which comprises polymerizing at least two alkylene oxide compounds one by one and thereby preparing a block copolymer containing at least two polyalkylene oxide blocks.
21. A polyalkylene oxide obtainable by the process as claimed in any one of claims 18 to 20.