TW200835719A - Process for production of polyether polyol containing material derived from natural oil-and-fat - Google Patents

Abstract

Disclosed is a process for producing a polyether polyol having good compatibility with an isocyanate compound at low cost by using a raw material derived from a natural oil-and-fat. Specifically disclosed is a process for producing a polyether polyol containing a material derived from a natural oil-and-fat by conducting the ring-opening polymerization of an alkylene oxide with an initiator in the presence of a polymerization catalyst, wherein the initiator is a polyol derived from a natural oil-and-fat which is produced by adding a hydroxy group to a natural oil-and-fat by a chemical reaction and which has a hydroxy value of 20 to 250 mgKOH/g and a ratio between the number average molecular weight in terms of polystyrene to the weight average molecular weight [i.e., a (Mw)/(Mn) ratio] of 1.2 or greater, and wherein the polymerization catalyst does not accelerate the hydrolysis of a glyceride structure derived from a natural oil-and-fat.

Description

200835719 IX. Description of the Invention [Technical Field to Which the Invention Is Ascribed] The present invention relates to a process for producing a polyether polyol derived from nature. [Prior Art] Generally, a polyether polyol which is used as a raw material of a polyamic oil agent such as a foamed urethane, a binder, a sealant or the like, is a starting agent and, for example, ethylene oxide or propylene oxide. Made by the same. These polyether polyols and the polyurethane products obtained by the polyethers are derived from the final incineration process to cause air in recent years, based on the effect of the global warming, do not increase the carbon dioxide of nature. For example, when the carbamic acid is used as a raw material in the air to produce a carbamate-burning treatment, the carbon burning of the derived automatic plant does not increase the carbon dioxide in the natural world as a natural animal or vegetable oil having a hydroxyol or the like. Patent Document 1 discloses that in the presence of a conjugate catalyst, castor oil and/or a polyalcohol which is subjected to a ring-opening addition reaction of a monoepoxide as a starting agent, a polyurethane elastomer, a urethane The acid ester product is functionally added to the alkylene oxide having an active hydrogen atom for addition polymerization. The alcohol and the isocyanate are reacted to obtain a chemical derived from petroleum, so that the carbon dioxide is increased. The concern is that the benefits of waste disposal are required. The carbon ester compound of the carbon-immobilized compound, the carbon dioxide produced by the burning of the product is self-evident. The base has castor oil and a method in which the plant is solidified in a composite metal cyanide-modified castor oil as a starter to produce a polyether. However -5 - 200835719 However, due to the high price of castor oil, it is difficult to put it into practical use. Therefore, a method of attaching a hydroxyl group to a natural fat having no hydroxyl group by chemical reaction has been proposed. For example, Patent Document 2 listed below discloses a base-containing high molecular weight-containing compound and a derivative thereof formed by injecting oxygen and/or air, and reacting it with an isocyanate to produce a urethane product. The method 〇® is also described in the following Patent Document 3, which discloses that the above-described double bond derived from natural fats and oils is subjected to a step of injecting oxygen or air to obtain a modified hydroxyl group-containing high molecular weight compound imparted thereto. After a metal catalyzed reaction such as an amine or potassium hydroxide is subjected to an alcoholization reaction and a hydrolysis reaction, the carboxyl group and the hydroxyl group of the resulting oil and fat are subjected to ring-opening polymerization with an alkylene oxide to increase the number of alcoholic hydroxyl groups. Patent Document 4 listed below discloses a method of producing a epoxidized soybean oil by using a double bond of soybean oil to obtain an epoxidized soybean oil by a peroxidation. The method comprises the following steps: ring-opening the epoxidized soybean oil in the presence of excess alcohol to obtain a hydroxyl group-added soybean oil which is used as a starting agent, and an anionic catalyst of potassium hydroxide as an epoxy After the propane reaction, a block polymerization catalyst is further carried out with ethylene oxide. Patent Document 5 listed below discloses a method in which a double bond of soybean oil is reacted with carbon monoxide and hydrogen in the presence of a special metal catalyst to form a carbonyl group, and then reacted with hydrogen to introduce a first-order hydroxyl group. [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-524627 [Patent Document No. 2] Japanese Patent Application Publication No. 22003/0 1 9 1 274 [Patent Document 4] Japanese Patent Laid-Open No. 2005-32043 No. 1 [Patent Document 5] International Patent Publication No. 2005/03 3 1 67 (pamphlet) [Invention] (Problems to be Solved by the Invention) Patent Literature The soybean oil (usually referred to as aerated soybean oil) modified by injecting oxygen and/or empty fluorine to the hydroxyl group as described in 2, or the epoxidized soybean oil described in Patent Document 3 is Raw materials that are cheaper than castor oil, especially aerated oils, can be manufactured inexpensively. However, for example, the polyalkylene oxide polyol produced by the method described in Patent Document 3 may not sufficiently obtain the compatibility with the isocyanate compound which is important in the production of polyurethane, and is a problem. The present invention has been made in view of the above circumstances, and an object of the invention is to provide a process for producing a polyether polyol containing a natural fat or oil which is produced by using a raw material derived from a natural oil to inexpensively produce a polyether polyol which is excellent in compatibility with an isocyanate compound. (Means for Solving the Problem) The gist of the present invention is as follows: 1 * A method for producing a polyether polyol containing a natural oil and fat derivative, 200835719, which is an alkylene oxide as a starting agent in the presence of a polymerization catalyst A method for producing a polyether polyol by ring-opening polymerization; characterized in that as the initiator, a hydroxyl group is formed by using a chemical reaction to impart a hydroxyl group to a natural fat, and the hydroxyl value is 20 to 25 mg/g' and the weight average molecular weight is relatively A polyalcohol derived from natural fats and oils having a ratio of polystyrene-equivalent number average molecular weight (Mw/Mn) of 1.2 or more, which does not promote a catalyst derived from structural hydrolysis of glycerides derived from natural fats and oils. Φ 2 The method for producing a polyether polyol containing a natural fat or oil derivative according to the above, wherein the polymerization catalyst is one or more selected from the group consisting of a coordination anion polymerization catalyst and a cationic polymerization catalyst. 3. The method for producing a polyether polyol containing a natural oil or fat derivative according to the above 1 or 2, wherein the polymerization catalyst contains a solid catalyst component, and contains the polymerization catalyst, the initiator, and the alkylene oxide. The content of the solid catalyst component in the polymerization raw material is 10 to 150 Ppm. 4. The method for producing a polyether polyol II containing a natural fat or oil derivative according to the above 1 to 3, wherein the weight average molecular weight (Mw) derived from the natural fat or oil is 1 500 or more. The method for producing a polyether polyol containing a natural fat or oil derivative according to any one of the above 1 to 4, wherein the ratio (Mw/Mn) of the polyalcohol derived from the natural fat or oil is 2 or more. 6. The method according to any one of the above 1 to 5, wherein the polymerization catalyst is a double metal cyanide complex catalyst and the one or more selected from the group consisting of tert-butyl Alcohol, η-butyl oxime, iso-butanol tert-pentanol 'iso-pentanol, dimethyl acetam 200835719 amine, ethylene glycol mono ter-butyl ether, ethylene glycol dimethyl ether, diethylene glycol A group of dimethyl ether, triethylene glycol dimethyl ether, iso-propanol, and dioxane as an organic ligand. 7. The method for producing a polyether polyol containing a natural fat or oil derivative according to the above 6, wherein the double metal cyanide complex catalyst is a zinc hexacyanocobaltate complex. The method for producing a poly-Φ ether polyol containing a natural oil and fat derivative according to any one of the above 1 to 7, wherein the alkylene oxide contains propylene oxide. 9. The method for producing a polyether polyol containing a natural oil or fat derivative according to any one of the above 1 to 8, wherein the initiator is a method for producing a hydroxyl group on a natural fat by (1) injecting air or v oxygen. And/or (2) a polyol derived from a natural fat obtained by epoxidizing a natural fat or oil and then forming a hydroxyl group by ring-opening the epoxy. The method for producing a polyether polyol containing a natural oil or fat derivative according to any one of the above 1 to 9, wherein the initiator is derived from soybean oil. (Effects of the Invention) According to the present invention, a polyether polyol which is excellent in compatibility with an isocyanate compound can be produced at low cost by using a raw material derived from natural fats and oils. [Embodiment] In the present invention, the number average molecular weight (?n) and the weight average molecular weight (Mw) of the starting agent and the polyether polyol containing the natural oil-and-fat derivative are polyphenylene oxide-based molecular weights. Specifically, it is measured by the following. Gel permeation chromatography (GPC) of several monodisperse polystyrene polymers having different polymerization degrees, which are commercially available as standard samples for the measurement of sub--9-200835719, using a commercially available GPC measuring device, The relationship between the molecular weight of polystyrene and the residence time (retenti ο ntime) is made into a quantitative line. Using this quantitative line, the number average molecular weight and the weight average molecular weight of the sample compound were determined by computer analysis on the GPC spectrum of the sample compound to be measured. This assay is well known. <Polyol derived from natural fats and oils> The polyalcohol derived from natural fats and oils used as an initiator in the present invention is a high molecular weight body which imparts a hydroxyl group to a natural fat or oil by a chemical reaction. Natural oils and fats may be used without a base, and preferred are castor oil and natural oils other than refined phytosterols. However, phytosterols are phytosterols derived from plants and are contained in trace amounts in vegetable oils such as soybean oil and rapeseed. Mixing of this range is tolerable. #又' Natural fats and oils are preferably those containing a fatty acid having an unsaturated double bond. Preferred examples of the natural fat or oil having an unsaturated double bond include linseed oil, sunflower oil, soybean oil, tung oil, meso oil, rapeseed oil, sesame oil, rice bran oil, camellia oil, olive oil, and tall oil. , palm oil, cottonseed oil, corn oil, fish oil, butter, lard, etc. Further, in order to impart an OH group by an unsaturated bond, the reactivity is high and more OH groups can be introduced, and it is preferable that the iodine value is high. Therefore, the iodine value is preferably 50 or more, and specific examples thereof include linseed oil, sunflower oil, soybean oil, tung oil 'mesons oil, rapeseed oil, sesame oil, rice bran oil, camellia oil-10-200835719, olive oil, Tall oil, cottonseed oil, corn oil, fish oil, butter, lard, etc. Further, the iodine value is preferably 1 〇〇 or more, and specific examples thereof include linseed oil, sunflower oil, soybean oil, tung oil, meson oil, vegetable oil, sesame oil, rice bran oil, tall oil, cottonseed oil, Corn oil, fish oil, etc. In particular, the consideration of soybean oil at a low price is particularly good. The valence of the hydroxyl group derived from the natural fat and oil which can be used in the present invention is 20 to 25 mgKOH/g. The valence of the hydroxy group of castor oil is usually 155 to 177 mgKOH/g, and the natural oil other than castor oil and phytosterol has no hydroxyl group, so the valence of the hydroxyl group is 1 〇 mgKOH/g or less. By imparting a hydroxyl group to a hydroxyl group-free natural oil by a chemical reaction, the hydroxyl group can be made to be 20 to 250 mgKOH/g. If the base price is less than 20 mgKOH/g, the shell [J lacks cross-linking reactivity, and there is a possibility that sufficient physical properties cannot be exhibited. On the other hand, even if all of the double bonds are converted into a hydroxyl group, the valence of the hydroxyl group cannot be raised to the iodine value. The maximum iodine value is 1 90 of linseed, but hydrolysis may occur during the reaction, which may result in the formation of a glyceride-derived radical as a constituent alcohol of the glyceride. If the base is significantly larger, it means that the glyceride is broken, which causes the molecular weight to decrease, become highly polar, and the compatibility and physical properties are lowered. Further, if the hydroxyl group is too high, the flexibility is lowered by the addition of a crosslinking agent, and the amount of the plant material used is reduced. For the above reasons, the valence of the hydroxyl group derived from the natural fat or oil of the present invention is 250 mgKOH/g or more, preferably 30 to 200 mgKOH/g. The polyol derived from natural oils used in the invention of Φ is an index of molecular weight distribution. The ratio (Mw/Mn) of the weight average molecular weight (Mw) logarithmic average molecular weight (?η) is 1.2 or more. Castor oil and phytosterol-11 - 200835719 Μw/Mn is 1.1 or less, and if a natural oil other than castor oil and phytosterol is chemically reacted to impart a hydroxyl group, the Mw/Mn becomes 1.2 or more. It is less difficult than the current technology. The Mw/Mn is preferably 2 or more. The upper limit of the Mw/Mn is not particularly limited, and the viewpoint of ensuring fluidity is preferably 20 or less, more preferably 15 or less. The weight average molecular weight (Mw) of the polyol derived from natural fats and oils in the present invention is preferably 15,000 or more in terms of compatibility and mechanical properties, more preferably 1700 or more, and more preferably 2000 or more. good. The upper limit of the M w of the polyphenol derived from natural fats and oils is not particularly limited, and is preferably more than 500,000, and more than 100,000 or less, which is preferable because of low viscosity and good fluidity. A known method can be suitably used for a method in which a natural fat is imparted to a hydroxyl group by a chemical reaction to produce a polyol derived from a natural fat. As a specific example, the following method can be considered: (1) a method of forming a hydroxyl group by injecting air or oxygen into a natural fat (hereinafter also referred to as a gas filling method); (2) a ring by oxidizing a natural fat or oil a method in which an oxygen ring is opened to form a hydroxyl group (hereinafter also referred to as a base method after epoxidation); (3) in the presence of a special metal catalyst, a double bond of a natural oil is reacted with carbon monoxide and hydrogen to form a carbonyl group, and then a method of introducing a hydroxyl group into a first-order hydroxyl group; (4) a method of performing (2) or (3) after the above (1); (5) a method after the above (2) or (3) (1) . Among these methods, the methods of (1) and (2) alone are preferable in terms of cost. -12- 200835719 The following is a description of the methods of (1) and (2). [(1) Gas infusion method] A method of imparting a hydroxyl group to an oxidized parent at the same time by injecting air or oxygen into a natural fat. Further, the polyol may be introduced by the ester parent exchange reaction. In this method, the molecular weight and the base value of the product (polyol derived from natural fats and oils) can be changed by the type of the oil and fat used as the raw material and the oxidized state by the gas. The weight average molecular weight (Mw) of the polyol derived from natural oils produced by the method using soybean oil as a raw material is usually 1,500 or more, preferably 5,000 to 50,000 Å to 1 〇 00 〇 1 〇〇〇〇〇 For better. Mw/Mn is usually 2 or more, preferably 3 to 15. If the weight average molecular weight is too low, the oxidative polymerization and the formation of a hydroxyl group may be insufficient to cause crosslinkability, and too high may cause a decrease in fluidity. An example of a product derived from Urethane Soy System, s〇yol series, is an example of a polyalcohol derived from natural fats and oils (hereinafter also referred to as aerated soybean oil) which is obtained by imparting a hydroxyl group to a soybean oil by a gas filling method. [(2) Method for imparting hydroxyl group after epoxidation] A method in which an unsaturated double bond of a natural fat or oil is epoxidized by an oxidizing agent, and a cation-polymerizing catalyst is used to open-loop a hydroxyl group in the presence of an alcohol. As the oxidizing agent, a peroxide such as peracetic acid can be used. The epoxy equivalent in the epoxidized natural fats and oils can be controlled by the ratio of the iodine value of the fats and oils used as the raw materials to the use ratio of the oxidizing agent to the iodine value, and the reaction rate, etc. -13-200835719. The hydroxyl value of the product (polyol derived from natural oil) can be controlled by the epoxy equivalent in the epoxidized natural fat. The molecular weight of the product (polyol derived from natural fats and oils) is changed depending on the amount of alcohol of the ring-opening initiator at the time of giving a hydroxyl group. Although the alcohol is significantly excessive, the molecular weight is small, but the reaction efficiency is poor and there is no economic benefit. In the case where the amount of alcohol is small, the ring-opening addition polymerization reaction between the epoxidized soybean oil molecules is carried out, so that the molecular weight is rapidly increased and there is a possibility of gelation. Φ For example, the epoxidized soybean oil which oxidizes soybean oil is commercially available, and specifically, the product name: Ai Di Casseza O-130P, etc., which is manufactured by Asahi Kasei Kogyo Co., Ltd. The cationic polymerization catalyst can be used as the cationic polymerization catalyst which is the same as the polymerization catalyst used in the ring-opening polymerization of alkylene oxide in the present invention for the polyol derived from natural fats and oils. For example, boron trifluoride diethyl ether (BFgEtsO) can be used. As the alcohol, for example, dehydration methanol can be used to open-loop the epoxidized soybean oil to the hydroxyl group, and the mixed solution of the cationic polymerization catalyst and the alcohol can be added to the epoxidized soybean oil, and the catalyst adsorption can be removed by filtration. method. The weight average molecular weight (Mw) of the polyol derived from natural fat produced by the present method using epoxidized soybean oil as a raw material is usually 1 500 or more, preferably 1800 to 5,000. Mw/Mn is usually 1.2 to 1.9. <Alkylene oxide> The alkylene oxide used in the present invention is not particularly limited as long as it is a ring-opening polymerizable alkylene oxide. Specific examples thereof include ethylene oxide (hereinafter also referred to as E 0 ), -14-200835719 propylene oxide (hereinafter also referred to as p〇), phenylethylene oxide, butylene oxide, and epoxy. A glycidyl compound such as cyclohexane, glycidyl ether or glycidyl acrylate, and oxetane. In the present invention, only one type of alkylene oxide may be used, or two or more kinds of alkylene oxides may be used. In the case where two or more kinds of alkylene oxides are used, block polymerization and random polymerization may be used, and both a block polymerization and a random polymerization may be combined to produce a polyether polyol. As the alkylene oxide in the present invention, it is preferred to use an alkylene oxide containing propylene oxide, more preferably ethylene oxide and/or propylene oxide, or a cyclopropane/ethylene oxide. The mass ratio is preferably 100/0 to 25/7, and the range of 95/5 to 5 0/5 0 is particularly good. <Other cyclic compounds> When a polyether polyol is produced, a monomer composed of a cyclic compound other than alkylene oxide may be present in the reaction system. Examples of the cyclic compound include cyclic esters such as ε-caprolactone and lactide; and cyclic carbonates such as ethylene carbonate, propylene carbonate and neopentyl carbonate. These can be subjected to random polymerization or block polymerization. In particular, if a lactide derived from lactic acid derived from fermentation of a plant-derived saccharide is used, the content ratio of the non-petroleum-based component in the polyalcohol (the ratio of the mass of the biological component (bi 〇mass) described later can be higher). Therefore, it is better. <Polymerization Catalyst> -15-

200835719 In the present invention, a catalyst which does not promote hydrolysis of a glyceride structure derived from fats and oils is used as a polymerization catalyst. A preferred polymerization catalyst is one or more of a complex anionic polymerization catalyst and a cationic polymerization catalyst. The preferred catalyst is a coordination anionic polymerization catalyst. [Coordination Anionic Polymerization Catalyst] A complex anion polymerization catalyst can be suitably used. In particular, a composite metal cyanide complex catalyst (hereinafter also referred to as DMC (Double Metal Cyanide)) having an organic ligand can be produced by a public method using a composite metal cyanide complex having an organic ligand. . For example, it can be produced by the method described in JP-A-2003-165836, JP-A-2005-15786, JP-A-7-196778, and JP-A-2000-513647. Specifically, it can be produced by the following method: (1) a reaction product obtained by reacting a halogenated metal salt with an alkali metal cyanide metal salt (alkali cyanometallate) in a solution, which is compounded with a site a method of separating the solid component and then washing the separated solid component with an organic aqueous solution; (2) reacting the metal halide salt with the alkali metal cyanide metal salt in an aqueous solution of the organic solution to prepare a reaction product ( The solid component is separated, and a method of washing the separated solid component with an organic aqueous solution is further carried out. In the method of (1) or (2), the cake obtained by the above reaction formation is filtered and the cake is redispersed in a content selected from the group selected from the natural one. It is also known as the special public notice. It is obtained from the water metal machine with the ruthenium base group. The base 7 is washed with the f block to be -16-200835719. The organic ligand of the polyether compound is less than 3 mass%. In the aqueous solution, the volatile component is then distilled off, whereby a slurry-like composite metal cyanide complex catalyst can be prepared. In order to produce a polyether polyol having a high activity and a narrow molecular weight distribution, it is particularly preferable to use the slurry catalyst. As the polyether compound used for preparing the slurry-like catalyst, a polyether polyol or a polyether monool is preferred. Specifically, it is preferred that the average number of hydroxyl groups per molecule produced by ring-opening polymerization of an alkylene oxide with an alkali catalyst or a cationic catalyst is selected from the group consisting of a base catalyst and a cationic catalyst. A polyether monool or a polyether polyol having a number average molecular weight of 300 to 5,000. Further, as the DMC catalyst, a zinc hexacyanocobaltate complex is preferred. As the organic ligand in the DMC catalyst, an alcohol, an ether, a ketone, an ester, an amine, a decylamine or the like can be used. Preferred examples of the organic ligand include tert-butanol, η-butanol 'iso-butanol, tert-pentanol, iso-pentanol, hydrazine, hydrazine-dimethylacetamide, and ethylene glycol. Mono-tert-butanol, ethylene glycol dimethyl ether (also known as glyme), diethylene glycol dimethyl ether (also known as diglyme), triethylene glycol dimethyl ether ( Also known as triglyme, iso-propanol, or dioxane. The dioxane may be 1,4-dioxane or may be 1,3-dioxane '1,4-dioxane. Organic ligands are available! It is also possible to use two or more types in combination. Among these, as the organic ligand, tert-butanol is preferred. Therefore, it is preferred to use at least a part of the organic ligand as a complex metal cyanide complex catalyst having tert-butanol. The complex metal cyanide complex catalyst having such an organic ligand can be highly active, and can produce a total of -17-200835719 low poly-polyol. The polyethers obtained by the use of a small amount of a highly reactive double metal cyanide complex catalyst to obtain a polyether after purification can be obtained by a small amount of a residue of the polyether after purification. [iw ionomerization catalyst] Examples of the cationic polymerization catalyst include lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, and trichlorination. ® ammonium, metal acetate acetate, phosphorus pentafluoride 'ammonium pentafluoride, boron trifluoride, boron trifluoride coordination compound (for example, boron trifluoride diethyl ether, boron trifluoride dibutyl ether) , boron trifluoride dioxane, boron trifluoride acetate anhydride, boron trifluoride triethylamine complex compound, etc.; perchloric acid, acetyl perchlorate, tert-butyl perchloric acid Inorganic and organic acids such as ester, hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.; metal salts of organic acids, diethyloxo (0X0niuin) tetrafluoroborate, a complex salt compound of triphenylmethyl hexafluoroantimonate-alcodide (azonium) hexafluorodiester, ® allyldiazepine tetrafluoroborate, etc.; diethyl zinc, three An alkyl metal salt such as ethyl aluminum or diethyl aluminum chloride; heteropolyacid, isopolyacid; (Mo 〇2) (dione) Cl, (Mo02) (two ) 〇S02CF3; at least one element of fluorine-containing aromatic hydrocarbon group or Wu Ming-containing boron compound or an aromatic hydrocarbon group of the fluorine element and the like. Among them, (Mo02) (dione) Cl, (Mo〇2) (diketone) oso2cf3, trifluoromethanesulfonic acid, boron trifluoride, boron trifluoride diethyl ether, boron trifluoride Boron trifluoride complex compound such as butyl ether, boron trifluoride dioxane, boron trifluoride-18-200835719 acetic anhydride, and boron trifluoride triethylamine complex compound. Further, in the present invention, as the cationic polymerization catalyst, aluminum or a boron compound having at least one aromatic hydrocarbon group containing a fluorine element or an aromatic hydrocarbon oxygen group containing a fluorine element is preferable. As the aromatic hydrocarbon group containing a fluorine element, selected from the group consisting of pentafluorophenyl, tetrafluorophenyl 'trifluorophenyl, 3,5-bis(trifluoromethyl)trifluorophenyl, 3,5-bis (three) One or more of the group consisting of a fluoromethyl)phenyl group, a fluorenyl-perfluoronaphthyl group, and a 2,2',2"-perfluorobiphenyl group is preferred as the aromatic hydrocarbon group containing a fluorine element. The alkoxy group having an oxygen-containing element on the aromatic hydrocarbon group containing a fluorine element is preferred. The aluminum or boron compound having at least one aromatic hydrocarbon group containing a fluorine element or an aromatic hydrocarbonoxy group containing a fluorine element is preferred. The preferred one is a boron compound or an aluminum compound as a Lewis acid, which is described in, for example, JP-A-2000-344881, JP-A-2005-82732, or International Publication No. 03/0007-50 (pamphlet). The boron compound or the aluminum compound of the onium salt described in Japanese Laid-Open Patent Publication No. 2003-501524 or JP-A-2003-510374.

I Specific examples of the Lewis acid include tris(pentafluorophenyl)borane, tris(pentafluorophenyl)aluminum, tris(pentafluorophenoxy)borane, and tris(pentafluorophenoxy). ) Aluminum and the like. Among them, tris(pentafluorophenyl)borane is particularly preferred as a catalyst for ring-opening polymerization of alkylene oxide. As the counter anion of the key salt, a trityl cation or an anilium cation is preferred, and as the oxy tin salt, it is triphenylmethyltetrakis(pentafluorophenyl). ) borate or n, n, monodimethylaniline salt tetrakis(pentafluorophenyl) borate. [Other catalysts which do not promote the hydrolysis derived from the glyceride structure derived from natural oils and fats] As the above-mentioned coordination anionic polymerization catalyst and cationic polymerization catalyst, it does not promote the structure derived from the glyceride structure derived from natural oils and fats. The hydrolysis catalyst can be exemplified by a phosphazenium catalyst. The phosphazene salt catalyst can be obtained by a known method (for example, the method described in Japanese Patent Laid-Open Publication No. Hei No. Hei 6 No. 5). Specifically, tetrakis[tris(dimethylamino)phosphoranilide (amino acid) sulfonate or the like can be mentioned. <Method for Producing Polyol> In the present invention, a polyether polyol is produced by ring-opening polymerization in the presence of a catalyst in the presence of a catalyst. The ring-opening polymerization reaction of the epoxy compound can be suitably carried out by a known method. Specifically, first, an initiator is introduced into a pressure-resistant reactor equipped with a stirrer and a cooling interlayer, and a polymerization catalyst is added. Then, by adding an alkylene oxide to a mixture of a starter and a polymerization catalyst to produce a polyether polyol oxime, in the present invention, an alkylene oxide can be separately polymerized by using an initiator, or Two or more alkylene oxides are subjected to block and/or random polymerization. The amount of the catalyst used in the polymerization reaction may be any amount necessary for the ring-opening polymerization, -20-200835719, preferably as small as possible. Hereinafter, (1) the case of using a coordinating anion polymer such as a DMC catalyst, and (2) the case of using a cationic polymerization catalyst, respectively. (1) In the case of using a coordination anionic polymerization catalyst, the less the amount of the polymerization catalyst in the polymerization, the less the amount of the catalyst contained in the polyether polyol of the product. Thereby, the reactivity of the polymerization catalyst to the polyisocyanate and the polyisocyanate by the polymerization reaction, or the physical properties of the polyurethane product and the functional oil agent produced by using the polyalcohol as a raw material can be Smaller. Usually, after the ring-opening polymerization of the alkylene oxide of the initiator, the polyether polyol is subjected to the operation of removing the polymerization catalyst, and the amount of the polymerization catalyst in the polyether polyol is small as shown. Moreover, the step of removing the polymerization catalyst can be carried out without the step of removing the polymerization catalyst, and the polyether polyol can be directly used for the next step, thereby improving the production of the polyether polyol and performing the alkylene oxide. The amount of the polymerization catalyst used in the polymerization catalyst is preferably set to include the polymerization catalyst (which means that the polymerization contains a solid catalyst component, and the solid catalyst in the polymerization catalyst is a slurry catalyst). The content of the polyether compound and the excess ligand in the above) and the polymerization starting material of the above-mentioned initiator and the alkylene oxide (in the polymerized polymer) are 10 to 150 ppm by mass, J ~120ppm is preferred. By making the polymerized solid catalyst component contained in the polymerization raw material to be at least Oppm, a sufficient contact can be obtained, and the reaction polymerization can be carried out to obtain an efficiency of self-sufficiency, such as ether polymerization, which is more effective than the catalyst. After the Vs 2 0 catalyst media activity-21 - 200835719, and sufficient catalyst activity can be obtained below 1 5 Oppm, so the above amount is not economical. However, even if a catalyst containing a solid catalyst component having a content of 150 ppm or more relative to the obtained compound is used, the ring-opening polymerization temperature of the alkylene oxide is preferably 30 to 180 ° C, preferably 7 0 160 °. C is better, especially 90~140 °C. When the polymerization temperature is below °C, the ring-opening polymerization of the alkylene oxide cannot be started, and if it is at least 180 °C, the polymerization activity of the polymerization catalyst may be lowered. After the completion of the polymerization reaction of the alkylene oxide, the polymerization catalyst contained in the reaction formation to be obtained is removed, and as a method thereof, preferably, it is selected from the group consisting of synthetic bismuth citrate (magnesium citrate, aluminum oleate). Etc., an ion exchange grease, and an adsorbent such as activated clay to adsorb the catalyst, and then filter the adsorbent. Further, a method of neutralizing a catalyst with a neutralizing agent selected from the group consisting of an amine, an alkali metal hydroxide organic acid, and a mineral acid, followed by filtration can be mentioned. The method of using the former adsorbent is preferred because hydrolysis is not carried out. (2) In the method of producing a polyether polyol by using a cationic polymerization catalyst, in particular, when the (2 -1 ) alkylene oxide has a carbon number of 3 or more, it is preferred to use at least one as a cationic polymerization catalyst. A method of 1 or more of the group consisting of a fluorine-substituted group or a fluorine-substituted phenoxy aluminum or a boron compound is selected. In the method of (2-1), the cationic polymerization catalyst is preferably used in an amount of from 10 to 120 ppm, more preferably from 20 to 100 ppm. For the purification and cost consideration of the polyether polyol obtained, the catalyst is used as the material of the problem. The tree is used as the amount of benzene. -22- 200835719 is less preferred, but the amount of cationic catalyst is specified. When it is 10 ppm or more, a moderately rapid polymerization rate of alkylene oxide can be obtained. In particular, it is preferred that the hydroxy group of each of the initiators is subjected to ring-opening polymerization of 1 to 30 oxoxanes, more preferably from 1 to 20, particularly preferably from 2 to 15. By making the alkylene oxide added to the hydroxyl group of each of the starter agents two or more, the ratio of the first-order hydroxyl group in the terminal hydroxyl groups of the polyether polyol obtained can be easily more than 45%. Moreover, the amount of multi-component by-products can be suppressed to a lesser extent. In the method of (2-1), the reaction is carried out to adjust the rate at which the alkylene oxide is supplied to the reaction vessel in conjunction with the cooling of the reaction vessel, so that the internal temperature of the reaction vessel is maintained at a desired temperature. The temperature in the reaction vessel is usually preferably from -15 to 140 ° C, preferably from 〇 to 120 ° C, particularly preferably from 20 to 90 ° C. The polymerization time is usually 〇 5 to 24 hours, preferably 1 to 1 2 hours. In the case where the anionic polymerization catalyst is used in the above (1) and (2) the cationic polymerization catalyst is used, it is preferred that the polymerization of the alkylene oxide is carried out under good stirring conditions. In the case of using a stirring method using a usual stirring blade, it is preferred that the stirring speed of the stirring blade is as high as possible within a range in which the gas in the gas phase is not generated in the reaction liquid to lower the stirring efficiency. Further, in the polymerization of alkylene oxide, the molecular weight distribution of the polymer can be made narrow, and the rate at which the alkylene oxide is supplied into the reaction vessel is preferably as slow as possible. On the other hand, if the supply speed is too slow, the production efficiency is lowered, and it is preferable to set the supply speed of the alkylene oxide by weighing the consideration. The polymerization of the alkylene oxide can also be carried out using a reaction solvent. Examples of the preferred reaction solvent of 23-200835719 include aliphatic hydrocarbons such as hexane, pentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and chloroform, dichloromethane, and the like. Halogen solvent. Further, the amount of the solvent to be used is not particularly limited, and a desired amount of the solvent can be used. Further, the addition of an antioxidant, an anticorrosive agent or the like to the obtained polyether polyol can prevent deterioration during long-term storage. The polyether polyol containing the natural oil and fat derivative of the present invention thus obtained is preferably environmentally friendly by a manufacturer of an initiator derived from natural fats and oils. Further, as shown in the examples to be described later, since it has good compatibility with an isocyanate compound, it is suitable as a raw material of polyurethane. Further, since a person who imparts a hydroxyl group by a chemical reaction to a natural fat or oil is used as a starter, it is possible to suppress the cost of the raw material at a low price. Therefore, a polyether polyol containing a natural oil derivative can be produced inexpensively. Further, as shown in the examples described later, since it has good compatibility with other polyalcohol compounds, it is also suitable for use in combination with polyalcohol. Further, it can be used for the production of a cured urethane film, and a film having good flexibility and toughness can be obtained. [Use of Polyether Polyol] The polyether polyol containing a natural oil and fat derivative of the present invention is used as a raw material for reacting a polyisocyanate compound to produce a polyurethane resin, an elastomer, a binder, and a sealant. It is better. Examples of the polyisocyanate include aromatic-24-200835719 polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyisocyanate, and hexamethylene diisocyanate 'xylene diisocyanate vinegar. An aliphatic polyisocyanate such as dicyclohexylmethane diisocyanate, diazonic acid diisocyanate or tetramethylxylene diisocyanate; an alicyclic polyisocyanate such as isophorone diisocyanate; and such a polyisocyanate compound a derivative. The raw material of the polyether polyol containing a natural oil-and-fat derivative of the present invention is reacted with a polyisocyanate compound to produce a polyurethane product such as a foam, an elastomer, a sealing material or a bonding agent. Further, the polyether polyol containing the natural oil and fat derivative of the present invention can also be used for the use of a surfactant and a functional oil agent, and further, it can also be used as a raw material for dispersing a polyether polyol of a polymer containing polymer microparticles. . In the case where the polyether polyol produced by the method of the present invention is used in various applications as described above, the weight average molecular weight of the polyether polyol is preferably from 15,000 to 500,000, more preferably from 2,000 to 100,000. The present invention is more specifically described by way of examples and comparative examples, but the present invention is not limited thereto. [Starting agent A] The product name: Soyol R2-052F, manufactured by Urethane Soy System Co., Ltd., which is derived from natural oils and fats, which is produced by a gas filling method using soybean oil as a raw material. The hydroxyl value derived from the natural oil was -25-200835719. The hydroxyl value was 45.3 [mgKOH/g], the acid value was 4.3 [mgKOH/g], and the Μη (number average molecular weight) was 1578, Mw (weight average molecular weight). For 65 62 , the ratio of Mw/Mn is 4.16. The polyol derived from natural oils is used as the initiator A. [Starting agent B] Soybean oil is used as a raw material, and a polyol derived from natural fats and oils is prepared by a hydroxyl group imparting method after epoxidation. First, 232 g of epoxidized soybean oil (trade name: Ai Di Kasaiza O-130P, manufactured by Asahi Kasei Kogyo Co., Ltd.) was dropped into 3 g of BF3Et20 of cationic polymerization catalyst at room temperature for 2 hours. In a mixed solution of methanol 3 80 ml. To this, for the purpose of removing the catalyst, a synthetic magnesium oxide salt adsorbent (product name: Qiu Waide 6 0 0 S) manufactured by Kyowa Industrial Co., Ltd. was added, and the mixture was further stirred at room temperature for 2 hours. Then, the mixture was filtered under pressure, and methanol was removed under reduced pressure at 95 ° C to obtain a polyol derived from natural fats and oils. The obtained polyol derived from natural fats had a hydroxyl group value of 169 [mgKOH/g], an oxygen value of 1.1 [mgKOH/g], a Mw of 2299, a Μη of 1,720, and a Mw/Mn of 1.34. The polyol derived from natural oils is used as the initiator B. [Reference Example 1: Preparation of DMC-TBA Catalyst] As a polymerization catalyst, a slurry of a mixture of a zinc hexacyanocobaltate complex (DMC catalyst) coordinated with terl butanol and a polyether polyol was used. It was prepared by the following method. The concentration (active ingredient concentration) of the DMC catalyst (solid catalyst component) contained in the slurry was 5.33 mass%. -26- 200835719 An aqueous solution of 10.2 g of zinc chloride and 10 g of water was placed in a 500 mL flask. An aqueous solution of 4.2 g of potassium hexacyanocobaltate (K3Co(CN)6) and 75 g of water was added dropwise to the zinc chloride aqueous solution in the flask while stirring at 300 rpm for 30 minutes. The mixed solution in the flask was maintained at 40 °C. After the completion of the dropwise addition of the potassium hexacyanocobaltate aqueous solution, the mixture in the flask was further stirred for 30 minutes, and then 80 g of tert-butanol (hereinafter abbreviated as TBA), 80 g of water, and 0.6 g of the following polyol P were added. The resulting mixture was stirred at 40 ° C for 30 minutes and then at 60 ° C for 60 minutes. The above-mentioned polyphenol P is a polycyclopropanediol having a hydroxyl equivalent of 501 which is obtained by addition polymerization of propylene glycol to propylene glycol using a KOH catalyst. The mixture thus obtained was filtered with a circular filter paper having a diameter of 25 mm and a quantitative filter paper (N0.5C manufactured by ADVANTEC Co., Ltd.) under pressure (0.2 5 MPa) to contain a composite metal cyanide complex. The solid (cake) is separated. Then, the obtained cake containing the double metal cyanide complex was transferred into a flask, and a mixture of TBA 3 6 g and water 8 4 g was added thereto, and after stirring for 30 minutes, pressure filtration was carried out under the same conditions as above. Get the cake. The obtained cake was transferred into a flask, and a mixture of 108 g of TBA and 12 g of water was further added, and the mixture was stirred for 30 minutes to obtain a slurry in which a mixed metal cyanide complex catalyst (DMC catalyst) was dispersed in a TBA-water mixed solution ( s 1 urry ). Adding 120 g of the above polyphenol P to the slurry and mixing them, maintaining at 8 ° C for 3 hours under reduced pressure, and then maintaining at 3 to 15 ° C for 3 -27-200835719 hours. The volatile component was distilled off to obtain a slurry-like DMC catalyst (DMD-TBA catalyst). [Production of Polyether Polyol] (Example 1) Using the above-mentioned initiator A as a starting agent, a DMC catalyst of Reference Example 1 was used as a polymerization catalyst, and a polyether was produced by the formulation and reaction conditions shown in Table 1. Polyol. The reaction time in the table indicates the time from the start of supply of the alkylene oxide to the fact that the pressure in the reactor is no longer lowered (the same applies hereinafter). That is, using a 500 ml pressure-resistant reactor made of stainless steel with a stirrer as a reactor, 248.2 g of the initiator A and the DMC-TBA catalyst prepared in the above Reference Example 1 were 682 mg (the solid catalyst component was 36 mg) was placed in the reactor. After replacing the inside of the reactor with nitrogen, the temperature was raised to 1200 ° C, and vacuum dehydration was carried out for 2 hours. Thereafter, a mixed liquid of 2 4.1 g of propylene oxide and 12.2 g of ethylene oxide was prepared in a pressure tank, and the whole amount was supplied to the reactor over a period of 40 minutes, and stirring was continued for 2 hours and 30 minutes. The pressure is no longer falling for confirmation. In the meantime, the reaction was carried out while maintaining the internal temperature of the reactor at a rate of 1 20 C 's with a rate of 5 〇 r p m . The appearance of the polyether polyol obtained by this reaction is a transparent liquid at normal temperature. The characteristics 値 (Mw, Mn, Mw/Mn, base price, and biological component mass ratio) of the polylactic acid are shown in Table 1. The content of the solid catalyst component contained in the DMC-TBA catalyst in the polymerization raw material calculated from the polymerization raw material composition of Example 1 was n2 ppm on a mass basis. -28- 200835719 The mass ratio of the biological component of the polyether polyol is an index of the content ratio of the non-petroleum component in the polyether polyol, so in the following examples and comparative examples, it is used as a relative polyether The mass ratio (unit %) of the initiator of the total mass of the raw material (starting agent and monomer) of the polyol was determined. The greater the enthalpy, the greater the proportion of ingredients derived from natural sources. The valence of the hydroxyl group in this example was 43.8, which was 1.01 times the predicted hydroxyl value (= 43.3 ) from the feedstock. (Comparative Example 1) Using the above-mentioned initiator A as a starting agent and KOH as a polymerization contact age, a polyether polyol was produced in the formulation and reaction conditions shown in Table 1. In the same manner as in Example 1, 2 1 5 · 8 g of the initiator A and 6.25 g of KOH (concentration: 95% by mass) as a polymerization catalyst were placed in the reactor. The temperature was raised to 120 ° C, and vacuum dehydration was carried out for 2 hours to carry out alcoholization. Then, a mixture of propylene oxide 2 0 · 9 g and ethylene oxide 10 6 g was supplied to the reactor at a time of 3 hours, and then reacted at 120 ° C for 7 hours, the pressure was no longer lowered. Confirm. After the completion of the reaction, the above-mentioned Qiawad 600S (trade name, synthetic magnesium oxide adsorbent) was added in an amount of 5% by mass relative to the amount of the catalyst, and the water was vacuumed at 120 ° C. In addition, the catalyst was removed by adsorption for 2 hours. The properties of the polyether polyol thus obtained are shown in Table 1. [Preparation of Composition and Film Forming] The polyether polyols obtained in Example 1 and Comparative Example 1 were respectively prepared into a composition according to the formulation shown in Table -29-200835719. The compatibility in the table is such that 5 drops of the composition are dropped onto a glass plate to be hardened and dried, and the physical properties of the cured product are visually evaluated. '〇 (good) means that the cured product is transparent, and X (bad) means hardened material. It is turbid. That is, after adding 1 part by mass of DBTDL (dibutyltin dilaurate) as a hardening catalyst to 100 g of a polyether polyol, a solution of 2 g of methyl ethyl ketone (MIBK) diluted by 100 parts by mass is added so that As a product of Asahi Kasei Co., Ltd., which is a hydroxy group of hexamethylene diisocyanate of an isocyanate compound, was added as a NCO/OH (equivalent ratio) of 1 to the product name: DANA-100 (NCO content: 23.1% by mass) ), mix it. In the composition thus prepared, the polyether polyol obtained in Example 1 showed good compatibility, and the polyether polyol obtained in Comparative Example 1 was inferior in compatibility, and the composition was cloudy. The mass ratio of the biological components of the obtained composition is shown in Table 1. The mass ratio of the biological component of the composition is an index of the content ratio of the non-petroleum component in the product, and is used as a raw material (polyether polyol) constituting the composition in the following examples and comparative examples. The mass ratio (unit %) of the initiator in the total mass of the isocyanate compound was determined. The obtained composition was coated on a substrate composed of an OPP (stretched polypropylene) film by a coater having a spacing of 120 //m to form a film, and the composition containing the polyether polyol of Example 1 was used. A transparent film is formed. The elongation and breaking strength of the obtained film were measured by the following methods. The results are shown in Table 1 in the film formation evaluation column (good), indicating that the film -30-200835719 has good flatness, and x (bad) indicates that the film has abnormalities such as eye hole separation and collection. On the other hand, the film composed of the composition containing the polyether polyol of Comparative Example 1 was too brittle to be peeled off normally from the substrate. The method for measuring the elongation and breaking strength of the film is to punch the film into a dumbbell shape according to JIS K-625 1-3, and then use the tensile testing machine SS-207D-UA manufactured by Toyo Bodwin Co., Ltd. (trade name) The breaking strength was measured at a stretching speed of 1 〇mm/min. The % elongation is measured by the change in the distance between the lines. -31 - 200835719 [Table i] Example 1 Comparative Example 1 Starting material A (g) 248.2 215.8 Slurry catalyst (DMC catalyst) (5.33% active ingredient) (g) 0.682 - Catalyst 95% KOH (g - 6.25 P〇(g) 24.1 20.9 EO (g) 12.2 10.6 Reaction conditions Reaction temperature rc] 120 120 Reaction time [hrs] 4 10 Characteristics 値Mw 8516 6593 Mn 2338 1117 Mw/Mn 3.64 5.90 Hydroxyl (mgKOH/g) *l 43.8 85.4 Biomass mass ratio (%)*2 87 85 Composition formula NCO/OH (equivalent ratio) 1 1 Polyether polyol (g) 10 10 Hardening catalyst (g) 0.2 0.2 Isocyanate compound (g) 1.42 2.77 Compatible 〇X composition of raw material 3 component mass ratio (%) 74.9 65.6 film film forming 〇X elongation % 29.2 - breaking strength (kN/m) 3.6 — * 1 JIS-K-l557 *2 Sexual component mass ratio = l〇〇x (quality of raw materials derived from automatic plants) / (all raw material quality) From the results of Table 1, it can be known that even if the starting agent is similarly derived from soybean oil, it is used. In Comparative Example 1 in which KOH was used as a polymerization catalyst, the polyether polyol obtained was inferior in compatibility with an isocyanate compound, and no -32-20 The 0835719 method is used for film forming. On the other hand, the polyether polyol of Example 1 obtained by using a D M C catalyst has good compatibility with an isocyanate compound, and therefore can be suitably applied to film formation. (Example 2) Using the above-mentioned initiator A as a starting agent, a DM C catalyst was used as a polymerization catalyst, and a polyether polyol was produced in the formulation and reaction conditions shown in Table 2. The difference between this example and Example 1 is that ethylene oxide is not used, and only propylene oxide is used as the alkylene oxide. In the same manner as in Example 1, 120 kg of the initiator A and 600 mg of the DMC-TBA catalyst (solid catalyst component: 32 mg) similar to those in Example 1 were placed in the reactor. After the reactor was replaced with nitrogen, the temperature was raised to 120 ° C and vacuum dehydration was carried out for 2 hours. Thereafter, 24 g of propylene oxide was supplied to the reactor to cause a reaction. After the pressure in the reactor was lowered, 122.8 g of propylene oxide was supplied to the reactor for reaction for 4 hours, and stirring was continued for 1 hour, and the pressure was not lowered for confirmation. In the meantime, the internal temperature of the reactor was maintained at 120 ° C, and the stirring speed was maintained at 500 rpm to carry out the reaction. The appearance of the polyether polyol obtained by this reaction is a transparent liquid at normal temperature. The properties 値 (Mw, Mn, Mw/Mn, hydroxyl value, and biological component mass ratio) of the polyether polyol are shown in Table 2. The content of the solid catalyst component contained in the DMC-TBA catalyst in the polymerization raw material calculated from the polymerization raw material composition of Example 2 was 112 ppm on a mass basis. -33-200835719 (Comparative Example 2) A polyether polyol was produced by using the above-mentioned initiator A as a starting agent and KOH as a polymerization catalyst under the formulation and reaction conditions shown in Table 2. The difference between this example and Comparative Example 1 is that ethylene oxide is not used, and only propylene oxide is used as the alkylene oxide. In the same manner as in Example 1, 12 g of the starting agent A and 6.4 g of the same KOH as in Comparative Example 1 were placed in the reactor. The temperature was raised to 120 ° C, and the mixture was vacuum dehydrated for 2 hours to carry out alcoholization. Thereafter, 24.2 g of propylene oxide was supplied to the reactor to cause a reaction. After the pressure in the reactor was lowered, 122.6 g of propylene oxide was supplied to the reactor over a period of 3 hours and 50 minutes, and then reacted at 120 ° C for 40 minutes, and the pressure was no longer lowered for confirmation. After the completion of the reaction, in the same manner as in Comparative Example 1, a synthetic magnesium oxide base adsorbent was added in an amount of 5% by mass based on the amount of the product, and the water was vacuum-distilled at 120 ° C for 2 hours. Time removes the adsorbent from the catalyst. The properties of the polyether polyol thus obtained are shown in Table 2. [Preparation of Composition and Mixing of Other Polyols] The polyether polyols obtained in Example 2 and Comparative Example 2 were prepared in the same manner as in Example 1 in the same manner as in Example 1 to prepare a composition. However, in Example 2 and Comparative Example 2, an adduct (adduct) of a hexamethylene diisocyanate as an isocyanate compound was added so that NCO/OH (mole ratio) = 1 (a partial modification of a cyanate group) The product name of the Asahi Kasei Co., Ltd. product, Dallas TSA-100 (NCO content: 20.1% by mass - 34 - 200835719) In the composition thus prepared, the polyether polyol obtained in Example 2 showed good compatibility. The polyether polyol of Comparative Example 2 was poor in compatibility, and the composition was turbid. The mass ratio of the biological components of the obtained composition is shown in Table 2. The respective polyethers of Example 2 and Comparative Example 2 were also obtained. The compatibility of the polyalcohol with other polyether polyols is examined separately. That is, as an example of a trifunctional polyalcohol commonly used in the manufacture of carbamates, propylene oxide is used for glycerol using a ruthenium catalyst. The ring-opening polymerization produces a polyether polyol having a molecular weight of 700, and is compared with the polyether polyol obtained in Example 2 (or Comparative Example 2) at a mass ratio of 1 /; [compatibility at the time of mixing. The polyol of Example 2 was shown to have good compatibility, while the polymerization of Example 2 The compatibility is poor, the cloudy.

-35- 200835719 [Table 2]

Example 2 Comparative Example 2 Starting material A (g) 120 120 Slurry catalyst (DMC catalyst) (5.33% active ingredient) (g) 0.6 - Catalyst 95% KOH (g) - 6.4 PO (8) 146.8 146.8 Reaction conditions Reaction temperature [°c] 120 120 Reaction time [hrs] 5 8.5 Characteristics 値Mw 14316 5238 Μη 3707 1363 Mw/Mn 3.86 3.84 Hydroxyl (mgKOH/g) 30.2 84 Biological component mass ratio (%) 45 44 Composition Formulation NCO/OH (equivalent ratio) 1 1 Polyether polyol (g) 10 10 Hardening catalyst (g) 0.2 0.2 Isocyanate compound (g) 1.12 3.13 Compatible 〇X Composition Biological component mass ratio (%) 35.4 25.5 Compatibility with other polyhydric alcohols 〇X From the result 2 of the table, it is understood that even if the starting agent is similarly a polyalcohol derived from soybean oil, in the comparative example 2 using KOH as a polymerization catalyst, the obtained polycondensation An ether polyol which is inferior in compatibility with an isocyanate compound and which is inferior in compatibility with a trifunctional group. On the other hand, the polyether polyol of Example 2 obtained by using a DMC catalyst had good compatibility with an isocyanate compound and good compatibility with other polyether polyols (trifunctional polyalcohol). (Example 3) -36- 200835719 A polyether polyol was produced by using the above-mentioned initiator B as a starting agent, using a DMC catalyst as a polymerization catalyst, and the formulation and reaction conditions shown in Table 3. In this example, only propylene oxide was used as the alkylene oxide. In the same manner as in Example 1, 30 g of the initiator B and 125.1 mg of the DMC-TBA catalyst (7 mg of the solid catalyst component) similar to those of Example 1 were placed in the reactor. After the reactor was replaced with nitrogen, the temperature was raised to 120 ° C, and vacuum dehydration was carried out for 2 hours. Thereafter, 6.7 g of propylene oxide was supplied to the reactor to cause a reaction. After the pressure in the reactor was lowered, 30 g of propylene oxide was supplied to the reactor over a period of 1 hour. Then continue to stir for 1 hour. In the meantime, the internal temperature of the reactor was maintained at 丨 20 ° C, and the stirring speed was maintained at 500 rpm to carry out the reaction. The properties of the polyether polyol obtained by this reaction are shown in Table 3. In this example, the hydroxyl value is 82.2, which is 1.07 times the predicted hydroxyl value of 76.5 from the feedstock. The content of the solid catalyst component contained in the DMC-TBA catalyst in the polymerization raw material calculated from the polymerization raw material composition of Example 3 was 1,100 ppm on a mass basis. (Comparative Example 3) Using the above-mentioned initiator B as a starting agent, KOH was used as a polymerization catalyst, and a polyether polyol was produced in the formulation and reaction conditions shown in Table 3. In the same manner as in Example 1, 30 g of the initiator B and 25 g of KOH equivalent to that of Comparative Example 1 were placed in a reactor, and the temperature was raised to 120 ° C, and vacuum dehydration was carried out for 2 hours to carry out alcoholization. Thereafter, 3 6.7 g of the total amount of epoxypropane was supplied to the reactor over 8 hours, and then reacted at -120 ° C for 1 hour, and the pressure was no longer lowered for confirmation. After the completion of the reaction, in the same manner as in Comparative Example 1, a synthetic magnesium oxide salt adsorbent having a yield of 5 mass% was added in the same manner as in Comparative Example 1, and the moisture was vacuum-exposed at 1 20 ° C to 2 The adsorbent is removed by the time of the hour. The properties of the polyether polyol thus obtained are shown in Table 3. [Preparation of Composition and Formation of Film] # The composition of the polyether polyol obtained in Example 3 and Comparative Example 3 was prepared in the same manner as in Example 1 in the same manner as in Example 1 except that the composition was as shown in Table 3. As the isocyanate, in the same manner as in Example 1, TP A-1 00 as an isocyanate compound was added so that NCO / OH (mole ratio) = 1. In the composition thus prepared, the polyether polyols obtained in Example 3 and Comparative Example 3 were free from compatibility. The biomass component mass ratio of the obtained composition is shown in Table 3. Using the obtained composition, a thin film was formed under the same film as in Example 1, and a transparent film was formed. The results of measurement of the elongation and breaking strength of the film are shown in Table 3. -38 - 200835719

[Table 3] Example 3 Comparative Example 3 Starting material B (g) 30 30 Slurry catalyst (DMC catalyst) (5.33% active ingredient) (g) 0.1251 - Catalyst 95% KOH (g) - 0.25 P 〇(g) 36.7 36·7 Reaction conditions Reaction temperature [°c] 120 120 Reaction time [hrs] 5 9 Characteristic 値Mw 5091 6723 Μη 3099 2678 Mw/Mn 1.64 2.51 Hydroxyl (mgKOH/g) 82.2 88.4 Biomass quality Ratio (%) 45 45 Composition formula NCO/OH (equivalent ratio) 1 1 Polyether polyol (g) 10 10 Hardening catalyst (g) 0.2 0.2 Isocyanate compound (g) 2.66 2.87 Coherent 〇〇 composition 3rd material mass ratio (%) 34.9 34.3 Film film forming 〇〇 elongation % 56.7 53.3 breaking strength UN / m) 9.1 3.4 From the results of Table 3, it is known that the compatibility between Example 3 and Comparative Example 3 did not occur significantly. The difference was found, but the breaking strength of the film was inferior to that of Example 3 in Comparative Example 3. (Industrial Applicability) According to the present invention, a polyether polyol which is excellent in compatibility with an isocyanate compound can be produced at low cost by using a raw material derived from natural fats and oils. The present invention contains -39-200835719 a polyether polyol having a natural oil-and-fat derivative, which is reacted with a polyisocyanate compound, and can be used to produce a polyurethane resin, a foamed elastomer, a binder, a sealant, etc., and is useful. Raw materials. In addition, the contents of this specification are the contents of the specification and the abstract of the Japanese Patent Application No. 2006-2622^4 filed in Japan on September 27, 2006.

-40-

Claims (1)

.200835719 X. Patent Application Scope 1. A method for producing a polyether polyol containing a natural oil and fat derivative, which is a method for producing a polyether by ring-opening polymerization of an initiator and an alkylene oxide in the presence of a polymerization catalyst. A method for forming an alcohol, which is characterized by using a chemical reaction to impart a hydroxyl group to a natural fat or oil as a starting agent, a hydroxyl group having a valence of 20 to 250 mgKOH/g, and a weight average molecular weight relative to a polystyrene-equivalent number average molecular weight. The ratio (Mw/Mn) is a polyalcohol derived from natural oils and fats, and the polymerization catalyst does not promote a catalyst derived from structural hydrolysis of glycerides derived from natural oils and fats. 2. The method for producing a polyether polyol containing a natural fat or oil derivative according to the first aspect of the invention, wherein the polymerization catalyst is one or more selected from the group consisting of a coordination anionic polymerization catalyst and a cationic polymerization catalyst. . 3. The method for producing a polyether polyol containing a natural fat or oil derivative according to claim 1 or 2, wherein the polymerization catalyst contains a solid catalyst component, and the polymerization catalyst, the initiator, and the catalyst are contained. The content of the solid catalyst component in the polymerization raw material of the alkylene oxide is 10 to 150 Ppm. The method for producing a polyether polyol containing a natural fat or oil derivative according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) of the polyol derived from the natural fat or oil is 1 50,000. the above. 5. The method for producing a polyether polyol containing a natural fat or oil derivative according to any one of claims 1 to 4, wherein the ratio (Mw/Mn) of the polyalcohol derived from natural fats and oils is 2 or more . 6 · If any of the patent applications range 1 to 5 contains natural -41 - .200835719 and I is the ert medium t. Moreover, the alcoholic polymerized polyether compound is a biochemical derivative of cyanohydrin, gold butanol, η-butanol, iso-butanol, tert-pentanol, iso-p-pentanol, ν, ν-dimethyl a group of ethionamide, ethylene glycol single tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, iso-propanol, and dispiro As an organic ligand. A method for producing a polyether polyol containing a natural oil or fat derivative according to claim 6, wherein the double metal cyanide complex catalyst is a hexaamino-acid dry complex. The method for producing a polyether polyol containing a natural oil or fat derivative according to any one of claims 1 to 7, wherein the alkylene oxide contains epoxypropane. 9. The method for producing a polyether polyol containing a natural oil or fat derivative according to any one of claims 1 to 8, wherein the initiator is natural by (1) by injecting air or oxygen. A method of producing a hydroxyl group on a fat or oil and/or (2) a polyol derived from a natural fat or oil obtained by epoxidizing a natural fat or oil and then forming a hydroxyl group by ring-opening the epoxy ring. The method for producing a polyether polyol containing a natural oil or fat derivative according to any one of claims 1 to 3, wherein the initiator is derived from soybean oil. -42- 200835719 VII. Designated representative map: (1) The designated representative figure of this case is ··· (2), the representative symbol of the representative figure is simple: no 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none