JP2019218434A - Method of producing polyoxyalkylene polyol - Google Patents

Abstract

To provide a method of producing a polyoxyalkylene polyol excellent in storage stability.SOLUTION: The method of producing a polyoxyalkylene polyol comprises the (step 1) and (step 2) in the following: (step 1) adding an alkylene oxide (C) to a polyol (B) in the presence of a basic catalyst (A); and (step 2) neutralizing the product obtained in the (step 1) with a phosphoric acid ester (D).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyoxyalkylene polyol.

  The polyoxyalkylene polyol is obtained by subjecting a polyol to addition polymerization of an alkylene oxide, in which case a basic catalyst is used to promote the reaction.

  Generally, a basic catalyst is neutralized with an acid after addition polymerization, but when a short-chain fatty acid such as acetic acid is used as a neutralizing agent, the use of the obtained polyoxyalkylene polyol is limited due to the influence of odor. Will be done. On the other hand, for example, in JP-A-6-157744 (Patent Document 1), the problem of odor is avoided by using phosphoric acid as a neutralizing agent.

JP-A-6-157744

  However, when phosphoric acid is used as a neutralizing agent, for example, flake-like or particulate polyoxyalkylene polyols are sometimes solidified in a container when stored in a high-temperature environment, resulting in poor handleability. That is, when phosphoric acid is used as the neutralizing agent, there is a problem that the storage stability of the polyoxyalkylene polyol deteriorates.

  The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing a polyoxyalkylene polyol having excellent storage stability.

(1) In order to solve the above problems, a method for producing a polyoxyalkylene polyol according to an aspect of the present invention includes the following (Step 1) and (Step 2).
(Step 1) Step of adding alkylene oxide (C) to polyol (B) in the presence of basic catalyst (A) (Step 2) The product obtained in (Step 1) is converted to phosphoric acid ester (D) Neutralization process

  According to the present invention, a polyoxyalkylene polyol having excellent storage stability can be produced.

  First, the contents of the embodiment of the present invention will be listed and described.

(1) The method for producing a polyoxyalkylene polyol according to the embodiment of the present invention includes the following (Step 1) and (Step 2).
(Step 1) Step of adding alkylene oxide (C) to polyol (B) in the presence of basic catalyst (A) (Step 2) Converting the product obtained in (Step 1) to phosphoric acid ester (D) Neutralization process

  According to such a method, for example, flake-like or particulate polyoxyalkylene polyols hardly solidify even when stored in a high-temperature environment. That is, a polyoxyalkylene polyol having excellent storage stability can be produced.

  (2) Preferably, the acid value of the phosphoric ester (D) is 20 to 200 mgKOH / g.

  Thereby, a polyoxyalkylene polyol having more excellent storage stability can be produced.

  (3) Preferably, the phosphate ester (D) is used in an amount of 0.3 to 2.5 mol per 1 mol of the basic catalyst.

  Thereby, a polyoxyalkylene polyol having more excellent storage stability can be produced.

  (4) Preferably, the phosphate (D) is a polyoxyalkylene alkyl ether phosphate.

  Thereby, a polyoxyalkylene polyol having more excellent storage stability can be produced.

  (5) Preferably, the basic catalyst (A) is an alkali metal compound.

  Thereby, a polyoxyalkylene polyol having more excellent storage stability can be produced.

   Hereinafter, embodiments of the present invention will be described more specifically.

(material)
The polyol (B) used in the present embodiment is not particularly limited, but includes, for example, polyhydric alcohol, polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, polyacryl polyol, polyacetal polyol, polybutadiene polyol, and polysiloxane. Polyols, fluorine polyols and the like.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, 3-methyl-1,5-pentanediol, bisphenol A, bisphenol B, bisphenol S, hydrogenated bisphenol A, dibromo Bisphenol A, 1,4-cyclohexane dimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, pentaerythritol and the like can be mentioned.

  Examples of the polyether polyol include the oxyalkylene derivative of the polyhydric alcohol, polytetramethylene glycol, and polythioether polyol. Specifically, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene bisphenol A, polyoxypropylene bisphenol A, polyoxyethylene polyoxypropylene bisphenol A, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl Ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane, polyoxypropylene trimethylolpropane, polyoxyethylene polyoxypropylene trimethylolpropane, and the like.

  Examples of the polyester polyol include, for example, an esterified product of a hydroxyl group-containing compound such as a polyhydric alcohol and a polyether polyol, and a carboxylic acid derivative such as a polycarboxylic acid, a polycarboxylic anhydride and a polycarboxylic ester. . Specifically, at least one diol selected from ethylene glycol, butanediol, hexanediol, methylpentanol, neopentyl glycol and 1,4-cyclohexanedimethanol, adipic acid, sebacic acid, And esterified products with at least one dicarboxylic acid selected from isophthalic acid and terephthalic acid. As the polyester polyol, castor oil polyol, polycaprolactone polyol and the like can also be used.

  Examples of the polycarbonate polyol include those composed of a carbonate derivative such as dimethyl carbonate and the above-mentioned polyhydric alcohol. Specifically, a polycarbonate polyol containing dimethyl carbonate and at least one selected from ethylene glycol, butanediol, hexanediol, 3-methyl-1,5-pentanediol and 1,4-cyclohexanediol Is mentioned.

  Examples of the polyolefin polyol include polybutadiene polyol, polyisoprene polyol, and hydrogenated products thereof.

  As the polyol (B) used in the present embodiment, the above-mentioned polyhydric alcohols and polyether polyols are preferable from the viewpoint of improving the storage stability of the obtained polyoxyalkylene polyol. These polyols may be used alone or in combination of two or more.

  The basic catalyst (A) used in the present embodiment is not particularly limited, but may be an alkali metal compound such as sodium methoxide, sodium hydroxide, potassium hydroxide, lithium carbonate, potassium-t-butoxide, or triethylamine. Amine compounds can be mentioned. From the viewpoint of improving storage stability, the basic catalyst (A) is preferably an alkali metal compound, more preferably an alkali metal hydroxide, and further preferably potassium hydroxide.

  The alkylene oxide (C) used in the present embodiment is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, and butylene oxide. As the alkylene oxide (C), from the viewpoint of improving the storage stability of the obtained polyoxyalkylene polyol, ethylene oxide and propylene oxide are preferable, and it is more preferable to use ethylene oxide and propylene oxide together.

  When ethylene oxide and propylene oxide are used in combination as the alkylene oxide, from the viewpoint of improving the storage stability of the obtained polyoxyalkylene polyol, it is preferable to use 0.05 to 1 mol of propylene oxide with respect to 1 mol of ethylene oxide. It is more preferable to use 0.05 to 0.4 mol. The form of addition of ethylene oxide and propylene oxide is not particularly limited, but block addition is preferred from the viewpoint of improving the storage stability of the resulting polyoxyalkylene polyol.

  The phosphate (D) used in the present embodiment is not particularly limited, but includes alkyl phosphate, alkenyl phosphate, aryl phosphate, alkylaryl phosphate, styrenated phenyl phosphate, polyoxyphosphate, and the like. Examples thereof include an alkylene alkyl ether phosphate, a polyoxyalkylene alkenyl ether phosphate, a polyoxyalkylene aryl ether phosphate, a polyoxyalkylene alkyl aryl ether phosphate, and a polyoxyalkylene styrenated phenyl ether phosphate. These may be used alone or in combination of two or more.

As the phosphate (D) used in the present embodiment, a polyoxyalkylene alkyl ether phosphate is preferred from the viewpoint of improving the storage stability of the obtained polyoxyalkylene polyol. The polyoxyalkylene alkyl ether phosphate has, for example, a structure represented by the following formula (1).
[RO- (AO) _n ] _a -P (= O)-(OH) _3-a (1)
Here, R represents a hydrocarbon group having 4 to 25 carbon atoms, A represents an alkylene group, O represents oxygen, and H represents hydrogen. In addition, n indicating the number of repeating units of the oxyalkylene group AO is a number of 1 to 50, and a indicating the number of polyoxyalkylene alkyl groups of the polyoxyalkylene alkyl ether phosphate is 1 or 2.

In the polyoxyalkylene alkyl ether phosphate of the formula (1), the carbon number of the hydrocarbon group represented by R is more preferably 4 to 20, more preferably 4 to 18, and even more preferably 4 to 15. As the oxyalkylene group represented by AO, an oxyethylene group or an oxypropylene group is preferable, and an oxyethylene group is particularly preferable. Further, n indicating the number of repeating units of the oxyalkylene group is more preferably 1 to 40, and more preferably 1 to 30. In the polyoxyalkylene group represented by (AO) _n , the proportion of the oxyethylene group is preferably 50% or more, more preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.

  Examples of the phosphate (D) used in the present embodiment include polyoxyalkylene alkyl ether phosphates in which a in Formula (1) is 1 and polyoxyalkylene alkyl ether phosphorus in which a in Formula (1) is 2 It is preferable to use both acid esters in combination.

  In the present embodiment, the average value of the number of ester groups in the molecule of the phosphate ester (D) (hereinafter, also referred to as the average number of ester groups) is preferably from 1 to 1.5.

  The acid value of the phosphate (D) used in the present embodiment is preferably from 20 to 250 mgKOH / g, more preferably from 40 to 220 mgKOH / g, from the viewpoint of improving the storage stability of the obtained polyoxyalkylene polyol. , 50 to 200 mgKOH / g are more preferred.

  The polyoxyalkylene polyol according to the present embodiment is preferably a polyoxyalkylene polyol glycol, and more preferably a polyoxyethylene polyoxypropylene glycol, from the viewpoint of improving storage stability. Further, the polyoxyethylene polyoxypropylene glycol preferably has a polyoxyethylene group and a polyoxypropylene group having a block structure.

(Production method)

  The method for producing a polyoxyalkylene polyol according to the present embodiment includes at least the following (Step 1) and (Step 2).

  In (Step 1), an alkylene oxide (C) is added to the polyol (B) in the presence of the basic catalyst (A). Specifically, for example, in the presence of a basic catalyst (A), an alkylene oxide (C) is introduced into a polyol (B) at 80 to 140 ° C. so that the pressure becomes 0.5 MPa or less. By reacting for 5 to 10 hours, a polyoxyalkylene polyol is obtained. At this time, the polyoxyalkylene polyol is in a state containing, for example, the entire amount of the basic catalyst (A) used as an impurity.

  In (Step 2), the product obtained in (Step 1) is neutralized with a phosphate (D). Specifically, the phosphate ester (D) is added to the polyoxyalkylene polyol obtained in (Step 1), and the mixture is neutralized by, for example, mixing at 65 to 140 ° C. for 1 hour. The polyoxyalkylene polyol that has undergone (Step 2) contains, for example, almost no basic catalyst (A) as an impurity, but instead contains the generated phosphate salt.

  After neutralization, the liquid polyoxyalkylene polyol is solidified, for example, by cooling it in a room temperature environment (25 ° C.), and then crushed using a mixer or the like to obtain a flake-like polyoxyalkylene polyol. it can.

  The polyoxyalkylene polyol may be finely pulverized into particles. In addition, for example, before solidifying the liquid polyoxyalkylene polyol, a part of the phosphate ester salt generated in (Step 2) may be removed by filtration or the like.

  In (Step 2), the phosphoric acid ester (D) is preferably used in an amount of 0.3 to 2.5 mol, more preferably 0.5 to 2.0 mol, per 1 mol of the basic catalyst (A). It is more preferable to use 0.8 to 1.2 mol.

  The polyoxyalkylene polyol that can be produced by applying the method for producing a polyoxyalkylene polyol according to the present embodiment covers a wide variety such as polyethylene glycol and polyoxyethylene / oxypropylene glycol. These can be widely used as raw materials for polyurethane resins, pharmaceuticals, cosmetics, surfactants and the like.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples. In the following Examples and Comparative Examples, “parts” or “%” is based on mass unless otherwise specified.

  First, a phosphate ester (D) used in Examples is prepared according to Production Examples 1 to 9. Production Examples 1 to 9 will be described with reference to Table 1. Table 1 shows the type of monool used in each of Production Examples 1 to 9 and the amount used, and the acid value and average number of ester groups of the obtained phosphate ester (D).

The acid values described in Table 1 are measured according to JIS K0070. Further, the average number of ester groups shown in Table 1 was obtained based on the measurement results by ³¹ P-NMR. The measurement conditions of ³¹ P-NMR are shown below.

(conditions)
-Equipment used: Bruker AV-400M
-Solvent: deuterated chloroform-Measurement temperature: room temperature-Number of times of accumulation: 128

The monols 1 to 7 shown in Table 1 are shown below. Here, EO represents ethylene oxide.
Monool 1: lauryl alcohol EO (5 mol) adduct Monol 2: butanol EO (5 mol) adduct Monool 3: octanol EO (5 mol) adduct Monool 4: palmityl alcohol EO (5 mol) addition Monool 5: lauryl alcohol EO (2 mol) adduct Monool 6: lauryl alcohol EO (10 mol) adduct Monol 7: lauryl alcohol EO (20 mol) adduct

(Production Example 1)
1218 g of Monol 1 was charged into the reaction vessel, and then 142 g of phosphoric anhydride was introduced so that the reaction temperature did not exceed 50 ° C., and further reacted at 45 ° C. for 30 minutes. Subsequently, phosphate ester 1 was obtained by adding 1 g of water and reacting at 70 ° C. for 2 hours.

(Production Examples 2 to 9)
The same operations as in Production Example 1 were performed except that the monol and the amount used were shown in Table 1, and phosphoric esters 2 to 9, respectively, were obtained.

  Next, Examples 1 to 10 and Comparative Example 1 will be described with reference to Table 2. Table 2 shows the types of neutralizing agents used in Examples 1 to 10 and Comparative Example 1, and the evaluation results (storage stability) of the obtained polyoxyalkylene polyol.

(Example 1)
76 g of propylene glycol and 7.2 g of a 48% by mass aqueous solution of potassium hydroxide were charged into the autoclave, and dehydration was performed at 125 ° C. for 30 minutes under reduced pressure (2 kPa). Here, 3364 g of propylene oxide was introduced while maintaining the reaction temperature at 120 to 130 ° C. and the pressure at 0.4 MPa or less, and further reacted at 130 ° C. for 60 minutes. Subsequently, 13760 g of ethylene oxide was introduced while maintaining a reaction temperature of 120 to 130 ° C. and a pressure of 0.4 MPa or less, and the mixture was further reacted at 130 ° C. for 60 minutes. The resulting reaction product was adjusted to pH 6.5 by adding the phosphate ester 1 obtained in Production Example 1 as a neutralizing agent, and solidified by cooling in a room temperature environment. And it flaked using the mixer, and obtained polyoxyalkylene polyol.

(Examples 2 to 9)
Each polyoxyalkylene polyol was obtained by performing the same operation as in Example 1 except that the phosphoric acid ester shown in Table 2 was used as the neutralizing agent.

(Example 10)
A polyoxyalkylene polyol was obtained by performing the same operation as in Example 1 except that the amount of propylene oxide used was 2523 g and the amount of ethylene oxide used was 14620 g.

(Comparative Example 1)
A polyoxyalkylene polyol was obtained in the same manner as in Example 1, except that phosphoric acid was used as a neutralizing agent instead of the phosphoric acid ester.

(Evaluation of storage stability)
The storage stability of the polyoxyalkylene polyols of Examples 1 to 10 and Comparative Example 1 was evaluated by the following method.

  The obtained polyoxyalkylene polyol was sieved through a 10 mm × 10 mm sieve. 1 kg of the polyoxyalkylene polyol that passed through the sieve was put into a 1-L capacity plastic container, and allowed to stand still at 50 ° C. for 1 month. The preserved polyoxyalkylene polyol was passed through a 10 mm × 10 mm sieve again, and the passing ratio (% by mass) was measured. The larger the value, the better the storage stability.

  From the evaluation results described in Table 2, it can be seen that each of the polyoxyalkylene polyols obtained in Examples 1 to 10 has better storage stability than the polyoxyalkylene polyol obtained in Comparative Example 1. That is, the storage stability of the polyoxyalkylene polyol is superior when using a phosphoric acid ester than when using phosphoric acid as a neutralizing agent.

Claims (5)

A method for producing a polyoxyalkylene polyol, comprising the following (Step 1) and (Step 2).
(Step 1) Step of adding alkylene oxide (C) to polyol (B) in the presence of basic catalyst (A) (Step 2) The product obtained in (Step 1) is converted to phosphoric acid ester (D) Neutralization process   2. The method for producing a polyoxyalkylene polyol according to claim 1, wherein the phosphoric acid ester has an acid value of 20 to 200 mgKOH / g.   The method for producing a polyoxyalkylene polyol according to claim 1 or 2, wherein the phosphoric acid ester is used in an amount of 0.3 to 2.5 mol per 1 mol of the basic catalyst.   The method for producing a polyoxyalkylene polyol according to any one of claims 1 to 3, wherein the phosphate is a polyoxyalkylene alkyl ether phosphate. The method for producing a polyoxyalkylene polyol according to any one of claims 1 to 4, wherein the basic catalyst is an alkali metal compound.