JP2019167480A - Polyalkylene oxide composition and polyurethane-forming composition containing the polyalkylene oxide composition - Google Patents

Abstract

To provide a polyalkylene oxide composition that reduces an amount of aldehyde volatilization, prevents the occurrence of a bad smell and turbidity, and has excellent urethanation reactivity, and a polyurethane-forming composition containing the polyalkylene oxide composition.SOLUTION: The present invention provides a polyalkylene oxide composition containing a divalent phosphazenium salt having a specific structure and a polyalkylene oxide, and a polyurethane-forming composition containing the same.SELECTED DRAWING: None

Description

  The present disclosure relates to a polyalkylene oxide composition and a polyurethane-forming composition comprising the polyalkylene oxide composition.

Polyalkylene oxide compositions containing phosphazenium salts and polyalkylene oxides are known.
In Patent Document 1, a compound having a P = N bond is used as a catalyst to produce a crude polyoxyalkylene polyol by addition polymerization of an epoxide compound to an active hydrogen compound, and then a crude polyoxyalkylene polyol, a predetermined solid acid, And the residual amount of catalyst in the polyoxyalkylene polyol is controlled to 150 ppm or less, and a polyoxyalkylene polyol obtained by the production method is disclosed.

Japanese Patent No. 42012233

However, as a result of further studies by the present inventors on the polyalkylene oxide according to Patent Document 1, it has been found that the polyalkylene oxide has room for further improvement with respect to the reduction of the volatile aldehyde amount. Reduction of aldehydes generated in living spaces such as indoors and cars is strongly required.
In addition, polyalkylene oxide is useful as a raw material for urethane and the like, and its use includes products used indoors and in vehicles. Therefore, suppression of generation of odor and turbidity is desired.

  Thus, one embodiment of the present invention is directed to providing a polyalkylene oxide composition that has a reduced amount of volatile aldehyde, suppressed generation of odor and turbidity, and is excellent in urethanization reactivity. Another aspect of the present invention is directed to providing a polyurethane-forming composition that contributes to the formation of a polyurethane with reduced odor and turbidity.

The polyalkylene oxide composition according to one aspect of the present invention is:
A divalent phosphazenium salt represented by the formula (1);
Including polyalkylene oxides:

In formula (1),
R ¹ and R ² are each independently
Hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms,
Represents a ring structure in which R ¹ and R ² are bonded to each other;
A ^n- represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;
One of n and m is 1 and the other is 2.

The polyurethane-forming composition according to another aspect of the present invention is:
(A) the polyalkylene oxide composition;
(B) an isocyanate compound.

  One embodiment of the present invention can provide a polyalkylene oxide composition in which the amount of volatile aldehyde is reduced, the generation of odor and turbidity is suppressed, and the urethanization reactivity is excellent. Another embodiment of the present invention can provide a polyurethane-forming composition that contributes to the formation of a polyurethane in which the generation of odor and turbidity is suppressed.

  Hereinafter, exemplary embodiments for carrying out the present invention will be described in detail.

<Polyalkylene oxide composition>
The polyalkylene oxide composition according to one aspect of the present invention is:
A divalent phosphazenium salt represented by the formula (1);
Including polyalkylene oxides:

In formula (1),
R ¹ and R ² are each independently
Hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms,
Represents a ring structure in which R ¹ and R ² are bonded to each other;
A ^n- represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;
One of n and m is 1 and the other is 2.

<< Polyalkylene oxide >>
The polyalkylene oxide may be any as long as it belongs to the category generally known as polyalkylene oxide, such as polyethylene oxide, polypropylene oxide, poly (1,2-butylene oxide), poly (2,3-butylene oxide), polyisobutylene oxide, polybutadiene oxide, polypentene oxide, polycyclohexene oxide, polystyrene oxide and the like. Moreover, the block copolymer and random copolymer which use these as a copolymerization component can be mentioned. Among these, polyethylene oxide, polypropylene oxide, and polypropylene oxide-polyethylene oxide block copolymers are preferable.

<< Bivalent phosphazenium salt >>
The divalent phosphazenium salt may be any as long as it belongs to the category of the phosphazenium salt represented by the above formula (1).

<<< R ¹ , R ² >>>
In formula (1), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a ring structure in which R ¹ and R ² are bonded to each other.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, vinyl group, n-propyl group, isopropyl group, cyclopropyl group, allyl group, n-butyl group, isobutyl group, t-butyl group, Cyclobutyl, n-pentyl, neopentyl, cyclopentyl, n-hexyl, cyclohexyl, phenyl, heptyl, cycloheptyl, octyl, cyclooctyl, nonyl, cyclononyl, decyl, cyclodecyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like.

Examples of the ring structure in which R ¹ and R ² are bonded to each other include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

Among these, it is preferable that R ¹ and R ² are each independently a methyl group, an ethyl group, or an isopropyl group from the viewpoint of easy availability of raw materials. It is particularly preferred that R ¹ and R ² are methyl groups.

  Specific examples of the cation species in formula (1) include tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium (hydro) dication, tetrakis [tris (diethylamino) phosphoranylideneamino] phosphonium (hydro) dication, tetrakis [ Tris (di-n-propylamino) phosphoranylideneamino] phosphonium (hydro) dication, tetrakis [tris (diisopropylamino) phosphoranylideneamino] phosphonium (hydro) dication, tetrakis [tris (di-n-butylamino) phosphoranylidene Amino] phosphonium (hydro) dication, tetrakis [tris (diphenylamino) phosphoranylideneamino] phosphonium (hydro) dication, tetrakis [tris (dibenzylamino) phospho Holanilideneamino] phosphonium (hydro) dication, tetrakis [tris (dipyrrolidinylamino) phosphoranylideneamino] phosphonium (hydro) dication, tetrakis [tris (dipyrrolylamino) phosphoranylideneamino] phosphonium (hydro) dication . Among these, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium (hydro) dication is preferable.

<<< A ^n- >>>
Wherein (1), A ^n- is a deprotonated derivative of an organic sulfonic acid or organic disulfonic acid. When an organic acid such as hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid or nitric acid; an organic carboxylic acid such as acetic acid, adipic acid, benzoic acid or oxalic acid is used in place of the organic sulfonic acid, the phosphazenium salt becomes polyalkylene oxide. It is not preferable because the polyalkylene oxide composition becomes turbid and an acid-derived odor is generated.

Any organic sulfonic acid or organic disulfonic acid may be used as long as it belongs to a category generally known as organic sulfonic acid or organic disulfonic acid.
Examples of the organic sulfonic acid include alkane sulfonic acid, α-olefin sulfonic acid, higher alcohol sulfuric acid, polyoxyethylene alkyl ether sulfuric acid, and the like.
Examples of the organic disulfonic acid include alkane disulfonic acid, α-olefin disulfonic acid, higher alcohol disulfuric acid, polyoxyethylene alkyl ether disulfuric acid, and the like.

  Specific examples of organic sulfonic acid and organic disulfonic acid include, for example, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, methoxybenzenesulfonic acid, dodecylbenzenesulfonic acid, linear alkylbenzenesulfonic acid (soft type), branched Chain alkylbenzene sulfonic acid (hard type), alkyl diphenyl ether disulfonic acid, linear alkyl naphthalene sulfonic acid, branched chain alkyl naphthalene sulfonic acid, β-naphthalene sulfonic acid formalin condensate, p-aniline sulfonic acid, o-aniline sulfonic acid, etc. Can be mentioned. Among these, dodecylbenzenesulfonic acid, linear alkylbenzenesulfonic acid (soft type), and branched alkylbenzenesulfonic acid (hard type) are preferable from the viewpoint of industrial availability.

  In formula (1), one of n and m is 1 and the other is 2. That is, when n is 1, m is 2, and when n is 2, m is 1.

  In the polyalkylene oxide composition, the content of the divalent phosphazenium salt is not particularly limited. However, since the odor and turbidity are suppressed and the polyalkylene oxide composition has a small amount of volatile aldehyde, it is 50 ppm or more and 10,000 ppm or less. Preferably, it is 100 ppm or more and 5000 ppm or less, more preferably 200 ppm or more and 3000 ppm or less.

  The polyalkylene oxide composition may contain an antioxidant. Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 2,6-di-tert-butylphenol, 6-tert-butyl- 2,4-methylphenol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate] (for example, Irganox 1010 manufactured by BASF), 3,5-bis-tert-butyl-4 Phenolic antioxidants such as -hydroxybenzenepropanoic acid octadecyl ester (for example, Irganox 1076 from BASF), 3,5-bis-tert-butyl-4-hydroxybenzenepropanoic acid isooctyl ester (for example, Irganox 1135 from BASF); n -Butyl-p Amine antioxidants such as aminophenol, 4,4-dimethyldiamine, 4,4-dioctyldiphenylamine, etc. These antioxidants may be used alone or in combination of two or more. Good.

  In the polyalkylene oxide composition according to this embodiment, generation of odor is suppressed. The polyalkylene oxide composition has 10 g of a polyalkylene oxide composition in a 20 ml sample tube, left still for 12 hours in a sealed state, and has no or almost no odor when opened.

  In the polyalkylene oxide composition according to this embodiment, the occurrence of turbidity is suppressed. When the polyalkylene oxide composition is placed in a 20 ml sample tube and 10 g of the polyalkylene oxide composition is visually observed, there is no turbidity or almost no turbidity.

  The polyalkylene oxide composition according to this embodiment is excellent in urethanization reactivity. The polyalkylene oxide composition preferably has a pH of 5 or more and 8 or less measured according to the method described in JIS K-1557-5. When the pH is 5 or more and 8 or less, the polyalkylene oxide composition and the isocyanate compound are mixed, and the reactivity when trying to synthesize a polyurethane-forming composition is further improved, which is preferable.

The polyalkylene oxide composition according to this embodiment is low in volatile aldehydes. As an index in this embodiment, when measured by the following measurement method,
The amount of acetaldehyde that volatilizes is preferably 0.9 ppm or less,
The amount of propionaldehyde that volatilizes is preferably 3.0 ppm or less.
[Measuring method]
(I): 10 g of sample is put into a container with an internal volume of 30 ml.
(II): After (I), the amount of volatilization is measured by bubbling nitrogen at 0.5 L / min under heating at 65 ° C. for 2 hours.

  More specifically, the amount of volatilized acetaldehyde when measured in the order of the following (i) to (iv) is preferably 0.9 ppm or less, more preferably 0.8 ppm or less. Moreover, it is preferable that the amount of propionaldehyde which volatilizes when measured in order of following (i)-(iv) is 3.0 ppm or less, More preferably, it is 2.5 ppm or less.

(I) The polyalkylene oxide composition is placed in an impinger having an internal volume of 30 ml, and bubbling with nitrogen trapped in a hydrocarbon trap at 65 ° C. under constant heating (65 ° C., 2 hours) (flow rate: 0. 5L / min)
(Ii) collecting the volatilized gas in a 2,4-dinitrophenylhydrazine (DNPH) cartridge;
(Iii) eluting the adsorbed components using 5 ml of eluate,
(Iv) Perform high performance liquid chromatography (HPLC) measurement.

<Polyurethane-forming composition>
The polyurethane-forming composition according to one aspect of the present invention is:
(A) a polyalkylene oxide containing a divalent phosphazenium salt represented by the above formula (1) and a polyalkylene oxide;
(B) an isocyanate compound.

  The isocyanate compound (B) may be any compound as long as it belongs to a category generally known as an isocyanate compound, such as an aromatic isocyanate compound, an aliphatic isocyanate compound, an alicyclic isocyanate compound, And polyisocyanate derivatives thereof.

  Examples of the aromatic isocyanate compound include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate, or Mixtures thereof), 4,4′-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4′-, 2,4 ′ or 2,2′-diphenylmethane diisocyanate, or mixtures thereof) (MDI), 4,4′-toluidine Diisocyanate (TODI), 4,4′-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof) (TMXDI), ω, ω′-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanate (1,5-, 1,4 -Or 1,8-naphthalene diisocyanate, or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3, Examples include 3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

  Examples of the aliphatic isocyanate compound include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene. Diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate Sulfonates, decamethylene diisocyanate.

  Examples of the alicyclic isocyanate compound include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate. Methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylene bis (cyclohexyl isocyanate (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate, or a mixture thereof)) (Hydrogenated MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, bis (iso Natemethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (water) Monocyclic alicyclic isocyanate compounds such as hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI); norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, cyisocyanate methyl bicycloheptane, di (diisocyanate) And alicyclic isocyanate compounds such as natemethyl) tricyclodecane; and the like.

  Examples of derivatives of these polyisocyanates include, for example, multimers of the above isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinediones, ureitoimines, isosinurate modified products, polycarbodiimides, etc.). , Urethane-modified products (for example, urethane-modified products obtained by modifying or reacting a part of the isocyanate groups in the isocyanate compound or multimer with monool or polyol), biuret-modified products (for example, by reaction of the isocyanate compound with water) Biuret-modified products, etc.), allophanate-modified products (for example, allophanate-modified products generated by reaction of the isocyanate compound with monool or polyol component), urea-modified products (for example, reaction of the isocyanate compound with diamine). To generate A modified product, etc.), oxadiazinetrione (e.g., oxadiazinetrione, etc.) or the like formed by the reaction between the isocyanate compound and carbon dioxide, and the like.

  In addition, said isocyanate compound or its derivative may be used independently, and may be used by 2 or more types.

The polyurethane-forming composition may contain various additives. A polyurethane-forming composition containing an additive is expected to have an effect of the additive.
Additives include catalysts, foam stabilizers, crosslinking agents, communication agents, foaming agents, dyes, organic pigments, inorganic pigments, inorganic reinforcing materials, plasticizers, processing aids, UV absorbers, light stabilizers, lubricants, Examples thereof include waxes, crystal nucleating agents, mold release agents, hydrolysis inhibitors, antifogging agents, dustproofing agents, rustproofing agents, ion trapping agents, flame retardants, flame retardant aids, inorganic fillers, and organic fillers.

EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all.
The evaluation / measurement methods used in Examples and Comparative Examples are shown.

(1) Hydroxyl value of polyalkylene oxide (unit: mgKOH / g)
It was calculated by the method described in JIS K-1557-1.

(2) Odor of Polyalkylene Oxide Composition 10 g of the polyalkylene oxide composition was put in a 20 ml sample tube, allowed to stand for 12 hours in a sealed state, and then opened to evaluate the presence or absence of odor.

(3) Turbidity of polyalkylene oxide 10 g of the polyalkylene oxide composition was placed in a 20 ml sample tube, and when visually observed, the presence or absence of turbidity was evaluated.

(4) pH of polyalkylene oxide
According to the method described in JIS K-1557-5, 10 g of polyalkylene oxide was dissolved in isopropanol / water = 10/6 mixed solvent (60 mL), and the pH / ORP meter PH72 manufactured by YOKOGAWA was used. The pH was measured.

(5) Aldehyde volatilization amount from polyalkylene oxide (unit: ppm)
Put 10 g of polyalkylene oxide in an impinger (Capacity: 30 ml, manufactured by Suenaga Chemical Co., Ltd.), heat at 65 ° C. for 2 hours, and flow nitrogen gas aerated with a carbon trap at 65 ° C. at a flow rate of 0.5 L / min. I blew in. The gas after aeration was collected on a 2,4-dinitrophenylhydrazine (DNPH) cartridge, and the adsorbed component was eluted using 5 ml of the eluent. The eluate was subjected to high performance liquid chromatography (HPLC) measurement, and the amount of aldehyde volatilized from the polyalkylene oxide was measured.

(6) Odor of polyurethane-forming composition The polyurethane-forming composition immediately after production was placed in a sample bottle and allowed to stand for 1 hour in a sealed state. The presence or absence of odor when opened was evaluated.

Synthesis Example 1 (Synthesis of monovalent phosphazenium salt)
A 100 ml Schlenk tube with a magnetic rotator was placed under a nitrogen atmosphere, and 5.7 g of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride (7.4 mmol, manufactured by Sigma-Aldrich) and 16 ml of 2-propanol were added. The solution was stirred and dissolved at 25 ° C. A solution prepared by dissolving 0.53 g (8.1 mmol, 1.1 mol equivalent to tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride) in 2-propanol while maintaining stirring. Was added. After stirring at 25 ° C. for 5 hours, the precipitated by-product salt was removed by filtration, whereby 33 g of a 2-propanol solution of a monovalent phosphazenium salt (tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide) was obtained. The concentration was 17% by mass and the yield was 98%.

Example 1
A 0.2 liter four-necked flask containing a stir bar was placed in a nitrogen atmosphere, and 50 g (11 mmol) of a 17% 2-propanol solution of a monovalent phosphazenium salt obtained in Synthesis Example 1 was added. Thereto, 7.5 g (23 mmol, 2.1 mol with respect to 1 mol of monovalent phosphazenium salt) was added while maintaining stirring. After stirring for 10 minutes, the solvent was removed under reduced pressure to obtain a divalent phosphazenium salt (R ¹ in the above formula (1) is a methyl group, R ² is a methyl group, and [A ⁿ⁻ ] _m is dodecylbenzene. A phosphazenium salt corresponding to a deprotonated form of sulfonic acid was obtained.
A 2 liter four-necked flask equipped with a stirring blade is a polypropylene oxide having acetaldehyde volatilization amount: 0.92 ppm, propionaldehyde volatilization amount: 3.1 ppm, pH: 6.4 (neutral), and a hydroxyl value of 24 mgKOH / g. By adding 1200 g of the obtained divalent phosphazenium salt 3.7 g and stirring at an internal temperature of 80 ° C. for 1 hour, the divalent phosphazenium salt (R ¹ in the above formula (1) is a methyl group, R ² is 1204 g of a polyalkylene oxide composition containing 3100 ppm of a methyl group, [A ⁿ⁻ ] _m , a phosphazenium salt corresponding to a deprotonated form of dodecylbenzenesulfonic acid), was obtained. The resulting polyalkylene oxide composition was odorless, free of turbidity, pH 7.4 (neutral), and hydroxyl value 24 mgKOH / g. The acetaldehyde volatilization amount was reduced to 0.53 ppm, and the propionaldehyde volatilization amount was reduced to 0.11 ppm.

  The obtained polyalkylene oxide composition and MDI were mixed so that the molar ratio of isocyanate group (NCO) in MDI to hydroxyl group (OH) in the polyalkylene oxide composition was 1.5, and the NCO group was completely Until it was consumed, and a polyurethane-forming composition was synthesized. The resulting polyurethane-forming composition was odorless.

Comparative Example 1
To a 2 liter autoclave equipped with a stirring blade, 100 g of polypropylene triol having a molecular weight of 600 and 11 g (2.5 mmol) of a 17 mass% 2-propanol solution of a monovalent phosphazenium salt obtained in Synthesis Example 1 were added. 2-Propanol was removed under reduced pressure at 0 ° C. and 0.5 kPa. Subsequently, while maintaining an internal temperature of 90 ° C. and a pressure of 0.3 MPa or less, 946 g of propylene oxide was intermittently supplied to carry out a polymerization reaction of propylene oxide, and then unreacted propylene oxide under a reduced pressure of 0.5 kPa. Was removed. Further, while maintaining an internal temperature of 130 ° C. and a pressure of 0.3 MPa or less, 173 g of ethylene oxide was intermittently supplied to carry out a polymerization reaction of ethylene oxide, and then unreacted ethylene oxide was removed under a reduced pressure of 0.5 kPa. Thereafter, 30 g of water and 12 g of KYOWARD 700SEN-S (manufactured by Kyowa Chemical Industry Co., Ltd., adsorbent) were added at an internal temperature of 85 ° C. and stirred for 1 hour. Further, the temperature was raised to 120 ° C., the mixture was stirred for 3 hours, dehydrated under reduced pressure of 0.5 kPa for 3 hours, the adsorbent was removed by filtration, and a polyalkylene oxide composition containing no divalent phosphazenium salt 1210 g was obtained. The resulting polyalkylene oxide composition was odorless, free of turbidity, pH 6.9 (neutral), and hydroxyl value 24 mgKOH / g. Further, the obtained polyalkylene oxide composition had a high acetaldehyde volatilization amount of 0.95 ppm and a propionaldehyde volatilization amount of 3.3 ppm.

  The obtained polyalkylene oxide composition and MDI were mixed so that the molar ratio of isocyanate group (NCO) in MDI to hydroxyl group (OH) in the polyalkylene oxide composition was 1.5, and the NCO group was completely Until it was consumed, and a polyurethane-forming composition was synthesized. The resulting polyurethane-forming composition had a slight odor.

Comparative Example 2
A 0.2 liter four-necked flask containing a stir bar was placed in a nitrogen atmosphere, and 50 g (11 mmol) of a 17% 2-propanol solution of a monovalent phosphazenium salt obtained in Synthesis Example 1 was added. Then, 3.6 g (11 mmol, 1.0 mol with respect to 1 mol of monovalent phosphazenium salt) was added while maintaining stirring. After stirring for 10 minutes, the solvent is removed under reduced pressure to remove the monovalent phosphazenium salt (cation species is tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium cation, anion species is dodecylbenzenesulfonic acid). Protonated product) was obtained.
A 2 liter four-necked flask equipped with a stirring blade is a polypropylene oxide having acetaldehyde volatilization amount: 0.92 ppm, propionaldehyde volatilization amount: 3.1 ppm, pH: 6.4 (neutral), and a hydroxyl value of 24 mgKOH / g. 1200 g and 2.8 g of the obtained monovalent phosphazenium salt were added, and the mixture was stirred at an internal temperature of 80 ° C. for 1 hour, whereby a monovalent phosphazenium salt (cation species was tetrakis [tris (dimethylamino) phosphoranylideneamino] 1203 g of a polyalkylene oxide composition containing 2300 ppm of a phosphonium cation and a deprotonated form of anionic species dodecylbenzenesulfonic acid) was obtained. The obtained polyalkylene oxide composition had odor, no turbidity, pH of 8.6, and showed basicity.

  The obtained polyalkylene oxide composition and MDI were mixed so that the molar ratio of isocyanate group (NCO) in MDI to hydroxyl group (OH) in the polyalkylene oxide composition was 1.5. Since the composition was basic, a polyurethane-forming composition could not be obtained.

Comparative Example 3
A 0.2 liter four-necked flask containing a stir bar was placed in a nitrogen atmosphere, and 50 g (11 mmol) of a 17% 2-propanol solution of a monovalent phosphazenium salt obtained in Synthesis Example 1 was added. Thereto, 23 mL of a 1.0 mol / L hydrochloric acid solution (23 mol, 2.1 mol with respect to 1 mol of a monovalent phosphazenium salt) was added while maintaining stirring. After stirring for 10 minutes, the solvent was removed under reduced pressure to obtain a divalent phosphazenium salt (R ¹ in the above formula (1) is a methyl group, R ² is a methyl group, and [A ⁿ⁻ ] _m is a chlorine anion. To the phosphazenium salt).
To a 2 liter four-necked flask equipped with a stirring blade was added 1200 g of polypropylene oxide having a pH of 6.4 (neutral) and a hydroxyl value of 24 mgKOH / g, and 2.1 g of the obtained divalent phosphazenium salt. By stirring at a temperature of 80 ° C. for 1 hour, a divalent phosphazenium salt (the phosphazenium salt in which R ¹ in the above formula (1) is a methyl group, R ² is a methyl group, and [A ⁿ⁻ ] _m is a chlorine anion) ) 1202 g of a polyalkylene oxide composition containing 2300 ppm was obtained. The resulting polyalkylene oxide composition was odorless, turbid, and pH 7.1.

  The resulting polyalkylene oxide composition and MDI were mixed so that the molar ratio of isocyanate group (NCO) in MDI to hydroxyl group (OH) in the polyalkylene oxide composition was 1.5, and a polyurethane-forming composition The product was synthesized. The resulting polyurethane-forming composition was turbid due to the turbidity of the polyalkylene oxide composition.

  The polyalkylene oxide composition according to one embodiment of the present invention is useful for polyurethane raw materials, polyester raw materials, surfactant raw materials, lubricant raw materials and the like because it is odorless and has no turbidity and has a small amount of aldehyde volatilization. In particular, by reacting with various isocyanate compounds, rigid foams used for heat insulation materials, etc., flexible foams used for automobile seats / cushions, bedding, etc., adhesives, paints, sealing materials, thermosetting elastomers, thermoplastics Expansion to elastomers is expected.

Claims (5)

A divalent phosphazenium salt represented by the formula (1);
A polyalkylene oxide composition comprising:

In formula (1),
R ¹ and R ² are each independently
Hydrogen atom,
A hydrocarbon group having 1 to 20 carbon atoms,
Represents a ring structure in which R ¹ and R ² are bonded to each other;
A ^n- represents a deprotonated form of an organic sulfonic acid or organic disulfonic acid;
One of n and m is 1 and the other is 2. When measured by the following measurement method,
The amount of volatilized acetaldehyde is 0.9 ppm or less,
The polyalkylene oxide composition according to claim 1, wherein the amount of propionaldehyde volatilized is 3.0 ppm or less.
[Measuring method]
(I): 10 g of sample is put into a container with an internal volume of 30 ml.
(II): After (I), the amount of volatilization is measured by bubbling nitrogen at 0.5 L / min under heating at 65 ° C. for 2 hours. R ¹ and R ² are methyl groups;
The ^An- is a deprotonated form of dodecylbenzenesulfonic acid, linear alkylbenzenesulfonic acid (soft type), or branched alkylbenzenesulfonic acid (hard type). A polyalkylene oxide composition.   The polyalkylene oxide according to any one of claims 1 to 3, wherein the polyalkylene oxide composition has a pH of 5 or more and 8 or less measured according to the method of JIS K-1557-5. Composition. (A) the polyalkylene oxide composition according to any one of claims 1 to 4, and
(B) A polyurethane-forming composition comprising an isocyanate compound.