JP2006233146A - Manufacturing method of alkylene oxide polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an alkylene oxide polymer which is easy in the treatment of the polymerization catalyst used therein and is reduced in the content of impurities which cause defects such as odor, discoloring, etc. even without the treatment with an adsorber as before, and the alkylene oxide polymer. <P>SOLUTION: In this manufacturing method of an alkylene oxide polymer, an alkylene oxide (B) is addition polymerized to an compound (A) containing an active hydrogen, in the presence of a catalyst (D) in a compressed fluid (C), and this alkylene oxide polymer is prepared by the manufacturing method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an alkylene oxide polymer.

Conventionally, alkylene oxide polymers have been used in various surfactants, solvents, chemical intermediates, cosmetics, pharmaceuticals, and the like. As a method for producing an alkylene oxide polymer, a method in which an alkylene oxide is addition-polymerized in the presence of a basic catalyst or an acidic catalyst and treated with an adsorbent such as activated carbon (Patent Document 1), distilled while supplying water. The method (patent document 2) etc. to perform are known.
JP 2001-342156 A JP 2001-342249 A

  However, these methods cannot sufficiently remove impurities, and these residual impurities sometimes cause problems such as odor and coloring.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention relates to a process for producing an alkylene oxide polymer, which comprises addition polymerization of an alkylene oxide (A) to an active hydrogen-containing compound (B) in the presence of a catalyst (D) in a compressible fluid (C). An alkylene oxide polymer produced by the production method.

  According to the method for producing an alkylene oxide polymer of the present invention, alkylene oxide can be polymerized in a compressive fluid, and impurities can be extracted and removed. There is an effect that a united body can be manufactured.

  The present invention is a process for producing an alkylene oxide polymer in which an alkylene oxide (A) is addition-polymerized to an active hydrogen-containing compound (B) in the presence of a catalyst (D) in a compressible stream (C).

In the present invention, alkylene oxide (hereinafter abbreviated as AO) (A) is not particularly limited,
(A1) AO having 2 to 12 carbon atoms [for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, isobutylene oxide, 1,2-butylene oxide 2,3-butylene oxide, 1,3-butylene oxide, trimethylethylene oxide, tetramethylethylene oxide, cyclohexene oxide, oxetane, tetrahydrofuran, tetrahydropyran, 1,2-pentene oxide, 1,2-hexene oxide, etc.]
(A2) C-C20 α-olefin oxide [1,2-octene oxide, 1,2-dodecene oxide, etc.],
(A3) aromatic hydrocarbon group-substituted alkylene oxide [styrene oxide, α-methylstyrene oxide, 1,1-diphenylethylene oxide, etc.],
(A4) Unsaturated aliphatic hydrocarbon group-substituted alkylene oxide (such as butadiene monoxide and vinylcyclohexene monooxide).
Of these, ethylene oxide and propylene oxide are preferable from the viewpoint of reactivity. One type of AO may be used, or two or more types may be used in combination. The addition reaction may be random addition or block addition.

The addition polymerization of alkylene oxide is a reaction of adding AO to the active hydrogen-containing compound (B). Examples of the active hydrogen-containing compound include compounds having a hydroxyl group, a carboxyl group, an amino group, a thiol group, and an acid amide group. .
Specific examples of the active hydrogen-containing compound (B) include the following (B1) to (B6), and these are one kind or a mixture of two or more kinds.

(B1) water (B2) alcohols [monohydric alcohols (alcohols selected from linear, branched, saturated, unsaturated, alicyclic and aromatic having 1 to 30 carbon atoms, such as methanol, ethanol, n or iso- Propanol, 2-ethylhexanol, n-octanol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, octadecyl alcohol, oleyl alcohol, etc., dihydric alcohol (ethylene glycol, propylene glycol, neopentyl alcohol) Trivalent alcohol (such as glycerin and trimethylolpropane), tetravalent alcohol (such as pentaerythritol and sorbitan), pentavalent alcohol (such as dipentaerythritol, glucose, and fructose), hexavalent to octavalent alcohol Call, etc.],
(B3) Carboxylic acids [monovalent carboxylic acids (acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, oleic acid, linoleic acid, etc.), divalent carboxylic acids (dimers of linoleic acid, maleic acid, itaconic acid, etc. ) Trivalent carboxylic acids (such as trimers of linoleic acid), tetravalent carboxylic acids (such as dimers such as itaconic acid and maleic acid), pentavalent carboxylic acids (such as pentamers of acrylic acid), etc.],
(B4) Amines [monovalent amine (such as diethylamine, dioleylamine), divalent amine (such as methylamine, ethylamine, propylamine, n-butylamine), trivalent amine (such as N-methylaminoethylamine), tetravalent amine (Such as ethylenediamine and propylenediamine), pentavalent amine (such as diethylenetriamine and dipropylenetriamine)],
(B5) Thiols [obtained by reacting sodium pentasulfide with a 1-5 functional thiol, epichlorohydrin or epichlorohydrin obtained by reacting the 1-5 pentahydric alcohol and thiourea of (1) above with thiourea. 1 to 5 functional thiols, etc.)],
(B6) Acid amides [oleic acid amide, dimer to pentamer of unsaturated monocarboxylic acid amide (such as acrylamide, methacrylamide, etc. as monocarboxylic acid amide)] and the like.

Of the active hydrogen-containing compound (B), from the viewpoint of ease of production, the compounds of (B1) to (B5) are preferable, more preferably (B1) and (B2), and particularly preferably (B2). is there.
The number of active hydrogens is preferably 1 to 8, more preferably 1 to 3, particularly preferably 1 or 2.

  In the present invention, examples of the compressible fluid (C) include carbon dioxide (31.0, 7.4), methane (-82.5, 4.6), ethane (31.1, 4.9), Propane (96.7, 4.2), hexane (234.2, 3.0), methanol (239.4, 8.2), ethanol (240.7, 6.1), water (374.2) 22.1) etc., fluids at temperatures and pressures above the critical point. In addition, the inside of a parenthesis is a critical temperature (degreeC) and a critical pressure (MPa) in order. A supercritical fluid is defined as a non-condensable fluid that exceeds the gas-liquid critical temperature and pressure inherent to the substance. The thermal motion of the molecule is intense because it exceeds the critical temperature, and the density can be continuously changed by changing the pressure from a dilute state close to the ideal gas to a high-density state corresponding to the liquid. .

The compressible fluid (C) is preferably used as a supercritical fluid.
Of these, carbon dioxide, methane, and ethane are preferable from the viewpoint of ease of handling, and carbon dioxide is more preferable.
The amount of (C) used in the polymerization reaction is preferably 10 to 1000 parts by weight, more preferably 30 to 800 parts by weight, and particularly preferably 50 to 500 parts by weight with respect to 100 parts by weight of AO.

In the present invention, the catalyst (D) is an alkaline catalyst [alkali metal and alkaline earth metal hydroxide (for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, hydroxide) Alkali metal and alkaline earth metal alkoxides such as calcium and barium hydroxide (sodium ethoxide, potassium methoxide, lithium ilopropoxide, calcium methoxide, barium ethoxide, etc.), acidic catalyst [Lewis acid catalyst (tin tetrachloride , Tin tetrafluoride, antimony pentachloride, antimony pentafluoride, iron trichloride, iron trifluoride, boron trifluoride, etc.), Bronsted acids (eg perchloric acid, sulfuric acid, phosphoric acid, nitric acid, fluorosulfuric acid, Hydrofluoric acid, etc.) or salts thereof (eg, barium perchlorate, calcium perchlorate) , Magnesium perchlorate, manganese perchlorate, lead perchlorate, strontium perchlorate, zinc perchlorate, zirconium perchlorate, ferric perchlorate, barium fluorosulfate, calcium fluorosulfate, magnesium fluorosulfate , Manganese fluorosulfate, lead fluorosulfate, strontium fluorosulfate, zinc fluorosulfate, aluminum fluorosulfate, etc.).
Among these, from the viewpoint of catalyst removal efficiency, a fluorine-containing catalyst is preferable, and antimony pentafluoride and aluminum fluorosulfate are more preferable.

In addition, when the AO addition reaction is performed in a plurality of steps (block addition or the like), the catalyst used in the first step and the catalyst used in the subsequent step may be different or the same.
The amount of the catalyst (C) used is preferably 0.001 to 1 part by weight per 100 parts by weight of the finished product from the viewpoint of reaction rate and economy. More preferably, it is 0.003-0.8 weight part, Most preferably, it is 0.005-0.5 weight part.

In the method for producing an alkylene oxide polymer of the present invention, an active hydrogen-containing compound (B) and a catalyst (D) are charged into a pressure vessel, and then the alkylene oxide (A) is charged into the compressive fluid (C) to react. This can be done.
Examples of the charging method of (B) and (C) include continuous dripping, splitting, batch, and the like, and a batch loading method is preferable from the viewpoint of productivity.

Examples of the charging method of the alkylene oxide (A) include continuous dropping, splitting, and batching, and a method of continuously dropping and charging is preferable from the viewpoint of reaction rate control.
For example, a predetermined amount of lauryl alcohol and antimony pentafluoride is charged into a reaction vessel 500 having a stirring device and a temperature measuring device, and can be set up to a pressure of 30 MPa and a temperature of 290 ° C., and adjusted to a temperature of 70 ° C. and a pressure of 10 MPa. To do. A predetermined amount of carbon dioxide is charged, and supercritical carbon dioxide at a temperature of 30 ° C. and a pressure of 10 MPa is added dropwise with stirring at a temperature of 150 ° C. and a pressure of 10 MPa while stirring. After the dropwise addition, the reaction is carried out for 0.5 to 5 hours. After completion of the reaction, the supercritical carbon dioxide can be removed to obtain an alkylene oxide polymer.

In the production method of the present invention, a known solvent (for example, described in JP-A-2002-284881) or the like can be added to the compressive fluid (C). For example, an ester solvent (ethyl acetate, butyl acetate, etc.) ), Ketone solvents (acetone, methyl ethyl ketone, etc.), alcohol solvents (methanol, ethanol, etc.), alkane solvents (hexane, cyclohexane), and the like.
When the solvent is used, the amount used (parts by weight) is preferably from 0.1 to 50, more preferably from 0.5 to 100, based on a total of 100 weights of alkylene oxide (A) + active hydrogen-containing compound (B). 20, particularly preferably 1-10.

In the production method of the present invention, a known surfactant (for example, JP 2001-504752 A, JP 10-102088 A, JP 2004-315675 A, JP 10-504602 etc.) can be added, and examples thereof include polyperfluoroether (trade name: KRYTOX157FSL, manufactured by DuPont).
The use amount (parts by weight) when using the surfactant is preferably 0.01 to 500 with respect to a total of 100 weights of the alkylene oxide (A) + the active hydrogen-containing compound (B) from the viewpoint of productivity. More preferably, it is 0.05-300, Most preferably, it is 0.1-200.

The temperature (° C.) during the reaction is in the supercritical region temperature range of the compressible fluid (C), and is preferably 31 to 250, more preferably 50 to 230, particularly preferably 70 in the case of carbon dioxide from the viewpoint of molecular weight control. ~ 220 ° C.
The pressure (MPa) during the reaction is in the supercritical region pressure range of (C), preferably from 7 to 70 in the case of carbon dioxide from the viewpoint of molecular weight control, more preferably from 8 to 50, particularly preferably from 9 to 30. is there.
The reaction time (time) may be adjusted according to the reaction temperature, but is preferably 0.1 to 15, more preferably 0.3 to 12, and particularly preferably 0.5 to 10 from the viewpoint of productivity.

  Further, the compressive fluid (C) used for the reaction is removed from the polymer, and impurities such as the catalyst (D) and the unreacted active hydrogen-containing compound (B) are extracted and removed by newly supplying (C). Thus, the desired polymer can be obtained. The amount of catalyst remaining in the obtained alkylene oxide polymer is 1 ppm or less, and can be reduced to 0.1 ppm or less by increasing the number of extractions in (C) after the reaction.

  The alkylene oxide polymer of the present invention is an alkylene oxide polymer produced by addition polymerization of an alkylene oxide (A) to an active hydrogen-containing compound (B) in the presence of a catalyst (D) in a compressible fluid (C). It is a coalescence.

  The alkylene oxide polymer that can be produced by the production method of the present invention is not particularly limited, and the alkylene oxide polymer described in “Alkylene Oxide Polymer” (published on November 20, 1990, Kaibundo Publishing Co., Ltd.). And (1) polyalkylene glycol, (2) alcohol alkylene oxide adduct, (3) phenol alkylene oxide adduct, and (4) carboxylic acid alkylene oxide adduct.

(1) As polyalkylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxyethylene glycol (number average molecular weight 2000), polyoxypropylene glycol (number average molecular weight 1000), polyoxyethylene polyoxypropylene glycol (oxy) And ethylene / oxypropylene: weight ratio 90/10, block, number average molecular weight 4000) and polyoxyethylene polyoxybutylene glycol (oxyethylene / oxybutylene: weight ratio 50/50, random, number average molecular weight 2000). .

(2) Alcohol alkylene oxide adducts include methanol tetraethylene oxide adduct, methanol tripropylene oxide adduct, ethanol polyethylene oxide polypropylene oxide adduct (oxyethylene / oxypropylene: weight ratio 90/10, number average molecular weight 4000, random ) And glycerin polyethylene oxide adduct (number average molecular weight 2000).

(3) As a phenol alkylene oxide adduct, phenol polyethylene oxide adduct (number average molecular weight 3000), phenol polyethylene oxide polypropylene oxide adduct (oxyethylene / oxypropylene: weight ratio 80/20, number average molecular weight 4000, random) And bisphenol polyethylene polypropylene oxide oxide adduct (oxyethylene / oxypropylene: weight ratio 90/10, number average molecular weight 6000, random) and the like.

(4) As carboxylic acid alkylene oxide adduct, lauric acid polyethylene oxide adduct (number average molecular weight 8000), stearic acid polypropylene oxide adduct (number average molecular weight 3000), oleic acid polyethylene oxide polypropylene oxide adduct (oxyethylene / Oxypropylene: weight ratio 85/15, number average molecular weight 4000, random) and the like.

The weight average molecular weight (Mw) of the alkylene oxide polymer obtained by the production method of the present invention is preferably 200 to 100,000, more preferably 240 to 80000, and particularly preferably 261 to 50000. It is a value obtained by converting a standard material polystyrene measured by a gel permeation chromatograph (GPC) method. ].
Moreover, the residual catalyst amount contained in the alkylene oxide polymer is 1 ppm or less as described above, and it is a high-purity alkylene oxide polymer.

Since the alkylene oxide polymer of the present invention has high purity, it is extremely useful for pharmaceuticals.
It can also be used in cosmetics, pH-dependent agricultural chemicals, binders for electronic materials, building materials, surfactants, detergents, antifoaming agents, emulsifiers, lubricating oils, brake fluids, synthetic resins, and the like.

[Example]
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples without departing from the gist of the present invention. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<Example 1>
A reactor equipped with a stirrer, a circulation tank, and a temperature measuring device, and charged with 186 parts of lauryl alcohol and 0.1 part of antimony pentafluoride into a reaction tank that can be set up to a pressure of 70 MPa in the tank and a temperature in the tank of 290 ° C., a temperature of 70 ° C., The pressure was adjusted to 8 MPa. While charging 300 parts of carbon dioxide and circulating in a circulation tank, 3000 parts of ethylene oxide was dropped for 3 hours while maintaining a temperature of 70 ° C. and a pressure of 10 MPa. Reaction was performed after dripping for 3 hours.
After completion of the reaction, supercritical carbon dioxide is continuously supplied at 80 ° C. at a flow rate of 50 parts / minute, and unreacted substances and impurities are extracted for 1 hour to remove supercritical carbon dioxide, and the weight average molecular weight is 4000. The alkylene oxide polymer (1) was obtained.

<Example 2>
An alkylene oxide polymer (2) having a weight average molecular weight of 600 was obtained in the same manner as in Example 1 except that the amount of ethylene oxide added was changed from 3000 parts to 308 parts.

<Example 3>
An alkylene oxide polymer (3) having a weight average molecular weight of 11,000 was obtained in the same manner as in Example 1 except that the amount of ethylene oxide added was changed from 3000 parts to 8000 parts.

<Example 4>
An alkylene oxide polymer (4) having a weight average molecular weight of 3500 was obtained in the same manner as in Example 1 except that the reaction temperature was changed from 70 ° C to 100 ° C.

<Example 5>
An alkylene oxide polymer (5) having a weight average molecular weight of 3500 was obtained in the same manner as in Example 1 except that the reaction pressure was changed from 10 MPa to 30 MPa.

<Example 6>
An alkylene oxide polymer (6) having a weight average molecular weight of 3500 was obtained in the same manner as in Example 1 except that the reaction pressure was changed from 10 MPa to 50 MPa.

<Example 7>
An alkylene oxide polymer (7) having a weight average molecular weight of 3,500 was obtained in the same manner as in Example 1 except that 186 parts of lauryl alcohol was changed to 18 parts of water.

<Example 8>
An alkylene oxide polymer (8) having a weight average molecular weight of 3500 was obtained in the same manner as in Example 1 except that 3000 parts of ethylene oxide was changed to 4000 parts of propylene oxide.

<Example 9>
An alkylene oxide polymer (9) having a weight average molecular weight of 3,500 was obtained in the same manner as in Example 1 except that 0.1 part of antimony pentafluoride was changed to 0.1 part of aluminum fluorosulfate.

<Comparative Example 1>
186 parts of lauryl alcohol and 0.4 part of potassium hydroxide were poured into an autoclave reaction vessel, and after nitrogen substitution, 3000 parts of ethylene oxide were added at 150 ° C. and 0.2 MPa over 3 hours to be reacted. 3 parts of an adsorbent (KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)) was added to the reaction product, and the catalyst was adsorbed at 90 ° C. for 30 minutes, followed by filtration to an alkylene oxide polymer having a weight average molecular weight of 3500 ( 10) was obtained.

<Residual catalyst evaluation>
1 g of each of the resulting alkylene oxide polymers (1) to (10) was taken, 1 ml of hydrochloric acid (35 wt%) was added, and water was added to a total volume of 100 ml and dissolved. The residual catalyst content was measured by measuring using AA-860, an atomic absorption flame light spectrum analyzer manufactured by Nippon Jarrell-Ash Co., Ltd. (wavelength 217.6 nm: antimony, 303.3 nm: aluminum, 766.5 nm: potassium). evaluated. The results are shown in Table 1.
<Molecular weight measurement method>
Polymers (1) to (14) were each dissolved in tetrahydrofuran at a concentration of 2.5 g / L and measured by GPC using polystyrene as a standard substance.
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: TSKgel GMHXL) + 2 TSKgel Multipore HXL-M (made by Tosoh Corporation)

From the above evaluation results, it can be seen that the alkylene oxide polymer obtained by the production method of the present invention has a very high purity as compared with the comparative example.

Since the alkylene oxide polymer of the present invention has high purity, it is extremely useful for pharmaceuticals.
For pharmaceutical use, it can be used for coating agents such as tablets, granules and pills, ointment bases, moisture-proof coating bases, sustained-release coating agents, bitterness masking agents and the like.
It can also be used in cosmetics, pH-dependent agricultural chemicals, binders for electronic materials, building materials, surfactants, detergents, antifoaming agents, emulsifiers, lubricating oils, brake fluids, synthetic resins, and the like.

Claims (6)

  A method for producing an alkylene oxide polymer, comprising subjecting an active hydrogen-containing compound (B) to addition polymerization of an alkylene oxide (A) in the presence of a catalyst (D) in a compressible fluid (C).   The production method according to claim 1, wherein (B) is carbon dioxide in a supercritical state.   The production method according to claim 1 or 2, wherein (C) is a fluorine group-containing catalyst.   The production method according to any one of claims 1 to 3, wherein the polymerization reaction is performed at a pressure of 7 to 70 MPa and a temperature of 31 to 250 ° C.   The alkylene oxide polymer manufactured with the manufacturing method in any one of Claims 1-4. The alkylene oxide polymer according to claim 5, wherein the content of (D) is 1 ppm or less of the alkylene oxide polymer.