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WO2008038596A1 - Procédé pour la production d'un polyol de polyéther contenant une matière dérivée d'une matière grasse/huile naturelle - Google Patents

Procédé pour la production d'un polyol de polyéther contenant une matière dérivée d'une matière grasse/huile naturelle Download PDF

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Publication number
WO2008038596A1
WO2008038596A1 PCT/JP2007/068439 JP2007068439W WO2008038596A1 WO 2008038596 A1 WO2008038596 A1 WO 2008038596A1 JP 2007068439 W JP2007068439 W JP 2007068439W WO 2008038596 A1 WO2008038596 A1 WO 2008038596A1
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Prior art keywords
polyether polyol
derived
natural
catalyst
oil
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PCT/JP2007/068439
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English (en)
Japanese (ja)
Inventor
Yasuyuki Sasao
Shigeru Ikai
Chitoshi Suzuki
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Asahi Glass Company, Limited
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Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Priority to JP2008536358A priority Critical patent/JP5287246B2/ja
Publication of WO2008038596A1 publication Critical patent/WO2008038596A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids

Definitions

  • the present invention relates to a method for producing a polyether polyol using a polyol derived from natural fats and oils as an initiator.
  • polyether polyols used as raw materials for polyurethane products and functional oils such as urethane foam, polyurethane elastomers, adhesives, and sealants are used as initiators having active hydrogen atoms, such as ethylene oxide and Manufactured by addition polymerization of alkylene oxides such as propylene oxide.
  • Patent Document 1 discloses castor oil and / or modified castor oil in the presence of a complex metal cyanide complex catalyst.
  • a method for producing a polyether by a ring-opening addition reaction of a monoepoxide as an initiator is disclosed.
  • castor oil is expensive and difficult to put into practical use.
  • Patent Document 2 a hydroxyl group-containing high molecular weight compound in which a hydroxyl group is generated by blowing oxygen and / or air into a double bond of a natural oil and fat, and a derivative thereof.
  • a method for producing a urethane product by reacting an isocyanate with an isocyanate is described.
  • Patent Document 3 uses a hydroxyl group-containing high molecular weight compound in which a double bond of the above-mentioned naturally-derived fats and oils is imparted and modified by oxygen and / or air blowing process, and amines such as potassium hydroxide are used. It has been shown that the number of alcoholic hydroxyl groups can be increased by ring-opening polymerization of alkylene oxides to carboxyl groups and hydroxyl groups derived from fats and oils after alcoholation reaction and hydrolysis reaction using the above metal catalyst.
  • Patent Document 4 describes a method for producing a polyoxyalkylene polyol using epoxidized soybean oil obtained by epoxidizing a double bond of soybean oil with a peroxide.
  • the epoxidized soybean oil is ring-opened in the presence of excess alcohol to obtain a hydroxyl group-added epoxy soybean oil having a hydroxyl group added thereto, and this is used as an initiator and potassium hydroxide as an anion catalyst is used.
  • a method of block copolymerizing ethylene oxide after reacting propylene oxide is described.
  • Patent Document 5 carbonyl is produced by reacting carbon monoxide with hydrogen in the presence of a special metal catalyst for the double bond of soybean oil, and then further reacting with hydrogen to react with primary hydroxide. It also describes how to introduce groups!
  • Patent Document 1 Japanese Patent Laid-Open No. 5-163342
  • Patent Document 2 Japanese Translation of Special Publication 2002-524627
  • Patent Document 3 US Patent Application Publication No. 2003/0191274
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-320431
  • Patent Document 5 International Publication No. 2005/033167 Pamphlet
  • soybean oil modified by adding hydroxyl groups by blowing oxygen and / or air (generally referred to as aerated soybean oil) and Patent Document 3
  • aerated soybean oil soybean oil modified by adding hydroxyl groups by blowing oxygen and / or air
  • Patent Document 3 The epoxidized soybean oil is a raw material that is considerably less expensive than castor oil, and in particular, aerated soybean oil can be produced at a low cost.
  • polyoxyalkylene produced by the method described in Patent Document 3! / Polyols are not compatible with isocyanate compounds, which is important in the production of polyurethanes.
  • the present invention has been made in view of the above circumstances, and it is possible to produce a polyether polyol having good compatibility with an isocyanate compound at low cost by using a raw material derived from natural fat.
  • An object of the present invention is to provide a method for producing a product-containing polyether polyol.
  • the present invention has the following gist.
  • a polyol derived from natural fats and oils having a hydroxyl value of 20 to 250 mgKOH / g and a ratio of the weight average molecular weight to the number average molecular weight in terms of polystyrene (Mw / Mn) of 1.2 or more.
  • the polymerization catalyst is a double metal cyanide complex catalyst and as an organic ligand tert-butinoreanoreconole, n-butinoreanoreconole, iso-butinoreanoreconole, tert-pentylalcohol, iso-pentylalcohol, N, N-dimethylacetamide, ethylenic glycomonoremonoter tert- Having at least one selected from the group consisting of butinoleethenore, ethyleneglycolenoresimethinoleethenore, diethyleneglyconoresimethinoleethenore, triethyleneglyconoresimethinoleetenore, iso-propyl alcohol, and dioxane 1 to 5! /, A method for producing a polyether polyol-containing polyether polyol according to any one of the above.
  • the initiator (1) generates hydroxyl groups by blowing air or oxygen into natural fats and / or (2) generates hydroxyl groups by opening the epoxy ring after epoxidizing natural fats and oils.
  • a polyether polyol having good compatibility with an isocyanate compound can be produced at low cost by using a raw material derived from natural fats and oils.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the initiator and the natural polyol-containing polyether polyol are polystyrene-equivalent molecular weights. Specifically, it is a value measured by the following method.
  • Several types of monodisperse polystyrene polymers with different degrees of polymerization are sold as standard samples for molecular weight measurement! / Gel permeation chromatography (GPC) and commercially available GPC measurement equipment
  • GPC Gel permeation chromatography
  • a calibration curve is created based on the relationship between the molecular weight of polystyrene and the retention time. Using the calibration curve, the GPC spectrum of the sample compound to be measured By analyzing, the number average molecular weight and the weight average molecular weight of the sample compound are determined. Methods for measuring force and cues are known.
  • the polyol derived from natural fats and oils used as an initiator in the present invention is a high molecular weight product obtained by adding a hydroxyl group to natural fats and oils using a chemical reaction.
  • Natural fats and oils that do not naturally have a hydroxyl group can be used, and natural fats and oils other than castor oil and purified phytosterol are preferably used.
  • fistosterol is a plant-derived sterol, and is contained in trace amounts in vegetable oils such as soybean oil and rapeseed oil. Any contamination within that range shall be permitted.
  • Natural oils and fats preferably contain fatty acid glycerides having unsaturated double bonds.
  • natural fats and oils having an unsaturated double bond include linseed oil, safflower oil, soybean oil, persimmon oil, poppy oil, rapeseed oil, sesame oil, rice oil, coconut oil, olive oil, tall oil, palm oil, Examples include cottonseed oil, corn oil, fish oil, beef tallow, and pork tallow.
  • iodine having an iodine value of 50 or more are linseed oil, safflower oil, soybean oil, persimmon oil, poppy oil, rapeseed oil, sesame oil, rice oil, rice bran oil, olive oil, tall oil. Cottonseed oil, corn oil, fish oil, pork fat and the like.
  • soybean oil is preferable because it is inexpensive.
  • the polyol derived from natural fats and oils used in the present invention has a hydroxyl value of 20 to 250 mgKOH / g.
  • the hydroxyl value of castor oil is usually from 155 to 177 mgKOH / g, and natural fats and oils other than castor oil and phytosterol have no hydroxyl group, so the hydroxyl value is 10 mg KOH / g or less.
  • the hydroxyl value can be adjusted to 20 to 250 mgKOH / g. If the hydroxyl value is less than 20 mgKOH / g, the crosslinking reactivity is poor and sufficient physical properties may not be exhibited.
  • the maximum iodine value is 190 of linseed oil. Hydrolysis occurs during the reaction, and glycerin-derived hydroxyl group, which is a constituent alcohol of glyceride, may be generated. When the hydroxyl value is significantly increased, it means that the glyceride bond is broken, and there is a concern that the molecular weight is lowered to be highly polar and compatibility and physical properties are lowered. On the other hand, if the hydroxyl value is too high, a large amount of cross-linking agent is added, so that flexibility is reduced and the amount of plant material used is reduced. From these facts, the hydroxyl value of the polyol derived from natural fats and oils in the present invention is 250 mgKOH / g or less, more preferably in the range of 30 to 200 mgKOH / g.
  • the polyol derived from natural fats and oils used in the present invention has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), which is an index of molecular weight distribution, of 1.2 or more.
  • Mw / Mn of castor oil and phytosterol is less than 1 ⁇ 1.
  • the Mw / Mn is preferably 2 or more.
  • the upper limit of the Mw / Mn is not particularly limited, but is preferably 20 or less, more preferably 15 or less, from the viewpoint of securing fluidity.
  • the weight-average molecular weight (Mw) of the polyol derived from natural fats and oils in the present invention is preferably 1500 or more from the viewpoint of compatibility and mechanical properties, more preferably 1700 or more, and further preferably 2000 or more.
  • the upper limit of Mw of the polyol derived from natural fats and oils is not particularly limited. 1S 500,000 or less is preferred 100,000 or less force S, more preferable because of low viscosity and good fluidity
  • blowing method A method for generating hydroxyl groups by blowing air or oxygen into natural fats and oils (hereinafter sometimes referred to as blowing method), (2) Hydroxyl groups by opening epoxy rings after epoxidizing natural fats and oils (3) After reacting carbon monoxide and hydrogen in the presence of a special metal catalyst to the double bond of natural fats and oils to form carbonyl
  • blowing method a method for generating hydroxyl groups by blowing air or oxygen into natural fats and oils
  • the methods (1) and (2) performed independently are preferable from the viewpoint of cost merit.
  • the methods (1) and (2) will be further described.
  • the molecular weight and hydroxyl value of the product can vary depending on the type of fat used as a raw material and the oxidation state at the time of blowing.
  • the weight average molecular weight (Mw) of the polyol derived from natural fats and oils produced using soybean oil as a raw material is generally 1500 or more, preferably 5000 to 500000, and more preferably 10 000 to 00000.
  • Mw / Mn is generally 2 or more, preferably 3 to 15; If the value of the weight average molecular weight is too low, oxidative polymerization and hydroxyl group formation are insufficient and the crosslinkability is poor, and if it is too high, the fluidity is lowered.
  • soybean oil As an example of a polyol derived from natural fats and oils obtained by adding a hydroxyl group to soybean oil (hereinafter also referred to as aerated soybean oil), there is a product name manufactured by Urethane Soy Systems: Soyol series.
  • an oxidant is allowed to act on an unsaturated double bond of natural fats and oils and then epoxidized, and then a ring is opened in the presence of alcohol using a cationic polymerization catalyst to give a hydroxyl group.
  • a peroxide such as peracetic acid is used as the oxidizing agent.
  • the epoxy equivalent in the epoxidized natural fat / oil can be controlled by the iodine value of the fat / oil used as a raw material, the ratio of the oxidizing agent to the iodine value, the reaction rate, and the like.
  • the hydroxyl value of the product (natural oil-derived polyol) can be controlled by the epoxy equivalent in the epoxidized natural oil.
  • the molecular weight of the product (natural oil-derived polyol) varies depending on the amount of alcohol that is a ring-opening initiator at the time of providing a hydroxyl group. The ability to reduce the molecular weight when alcohol is extremely high, the reaction efficiency is poor, and the cost merit is low. It is poor. When the amount of alcohol is small, ring-opening addition polymerization reaction between epoxidized soybean oil molecules proceeds, and the molecular weight may increase rapidly to cause gelation.
  • epoxidized soybean oil obtained by epoxidizing soybean oil is available from commercial products, and specific examples include Product Name: Air Dekasizer I-130P manufactured by Asahi Denka Kogyo Co., Ltd.
  • the cationic polymerization catalyst the same cationic polymerization catalyst as that used for ring-opening polymerization of an alkylene oxide to the polyol derived from natural fats and oils in the present invention can be used.
  • the alcohol for example, dehydrated methanol can be used.
  • the reaction of opening the epoxidized soybean oil to give a hydroxyl group can be performed by dropping the epoxidized soybean oil into a mixed solution of the cationic polymerization catalyst and alcohol and then removing the catalyst by adsorption filtration. .
  • the weight average molecular weight (Mw) of the polyol derived from natural fats and oils produced by epoxidized soybean oil as a raw material is generally 1500 or more, preferably 1800 to 5000.
  • Mw / Mn is generally 1 ⁇ 2 ⁇ ;! ⁇ 9.
  • the alkylene oxide used in the present invention is not particularly limited as long as it is an alkylene oxide capable of ring-opening polymerization.
  • ethylene oxide hereinafter sometimes referred to as EO
  • propylene oxide hereinafter also referred to as PO
  • styrene oxide butylene oxide
  • cyclohexene oxide glycidinoreether
  • glycidino rare acrylate examples include ethylene oxide (hereinafter sometimes referred to as EO), propylene oxide (hereinafter also referred to as PO), styrene oxide, butylene oxide, cyclohexene oxide, glycidinoreether, and glycidino rare acrylate.
  • Glycidinole compounds such as oxetane and the like.
  • two or more types of alkylene oxides may be used in combination, which may use only one type of alkylene oxide.
  • block polymerization or random polymerization may be used, and block polymerization and random polymerization may be combined to produce a kind of polyether polyol.
  • block polymerization and random polymerization may be combined to produce a kind of polyether polyol.
  • alkylene oxide in the present invention it is preferable to use ethylene oxide and / or propylene oxide, which preferably includes an alkylene oxide containing propylene oxide. It is more preferable to use it, and it is more preferable that the mass ratio of propylene oxide / ethylene oxide is in the range of 100/0 to 25/75, and it is particularly preferably in the range of 95/5 to 50/50.
  • a monomer composed of another cyclic compound other than alkylene oxide may be present in the reaction system.
  • cyclic compounds examples include cyclic esters such as ⁇ -force prolatatone and ratatide, and cyclic carbonates such as ethylene carbonate, propylene carbonate, and pentenole carbonate. These can be random polymerization or block polymerization.
  • lactide derived from lactic acid obtained by fermenting plant-derived saccharides is preferable in that the content ratio of non-petroleum components (the degree of biomass described later) in the polyol can be increased.
  • a catalyst that does not promote hydrolysis of a glyceride structure derived from natural fats and oils is used as a polymerization catalyst.
  • a more preferred polymerization catalyst is at least one selected from a coordination anion polymerization catalyst and a cationic polymerization catalyst.
  • a more preferred polymerization catalyst is a coordination anion polymerization catalyst.
  • a double metal cyanide complex catalyst having an organic ligand (hereinafter sometimes referred to as DMC (Double Metal Cyanide) catalyst) is preferred.
  • the double metal cyanide complex having an organic ligand can be produced by a known production method. For example, it can be produced by the methods described in JP-A No. 2003-165836, JP-A No. 2005-15786, JP-A No. 7196778 and JP-T No. 2000-513647.
  • an organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt and an alkali metal cyanate in an aqueous solution, and then the solid component is separated, Method of further washing the components with an organic ligand aqueous solution, (mouth) organic ligand It can be produced by reacting a metal halide salt and an alkali metal cyanate in an aqueous solution, separating the resulting reaction product (solid component), and further washing the separated solid component with an organic ligand aqueous solution.
  • the cake (solid component) obtained by washing and filtering and separating the reaction product according to the method (i) or (mouth) is used in a method comprising 3% by mass or less of the cake.
  • a slurry-like double metal cyanide complex catalyst can also be prepared by redispersing in an organic ligand aqueous solution containing an ether compound and then distilling off the volatile components. In order to produce a polyether polyol having a high activity and a narrow molecular weight distribution, it is particularly preferable to use this slurry-like catalyst.
  • the polyether compound used for preparing the slurry catalyst is preferably polyether polyol or polyether monool.
  • the average number of hydroxyl groups per molecule produced by ring-opening polymerization of alkylene oxide with an initiator selected from monoalcohol and polyhydric alcohol using a cationic catalyst or a cationic catalyst is 1 to 1.
  • Polyether monool or polyether polyol having a number average molecular weight of 300 to 5,000 is preferred.
  • a zinc hexocyanocobalt complex is preferable.
  • organic ligand in the DMC catalyst alcohol, ether, ketone, ester, amine, amide and the like can be used.
  • Preferred organic ligands include tert butyl alcohol, n butyl alcohol, is o butino oleanoleno cornole, tert penteno eno eno coleno ole, iso pentino eno eno coleno ole, N, N dimethylacetamide, ethylene glycol mono tert Examples include butyl ether, ethylene glycoloresimethinoleatenore (also referred to as glyme), diethyleneglycolinoresimethylinol ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), isopropyl alcohol, or dioxane. It is done.
  • the dioxane may be 1,4-di-aged xanthone or 1,3-di-aged xanthone, but 1,4-di-aged xylene is preferred.
  • One kind of organic ligand may be used, or two or more kinds may be used in combination.
  • tert butyl alcohol as the organic ligand.
  • tert butyl alcohol as at least part of the organic ligand
  • a double metal cyanide complex catalyst has high activity and can produce a polyether polyol having a low total unsaturation.
  • Pre-purification polyethers obtained by ring-opening polymerization of alkylene oxides using small amounts of highly active double metal cyanide complex catalysts have less catalyst residues and therefore less catalyst residues in polyethers after purification be able to.
  • Examples of the cationic polymerization catalyst include lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trichloride, metal acetyl cetate, phosphorus pentafluoride, antimony pentafluoride, Boron trifluoride, boron trifluoride coordination compounds (for example, boron trifluoride jetyl etherate, boron trifluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride amorphous unhydrate, Boron fluoride triethylamine complex, etc.); inorganics such as perchloric acid, acetyl chloride monochlorate, t-butyl peroxyphosphate, hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, p-toluene
  • organic acids metal salts of organic acids; triethyloxonium Complex salt compounds such as trough mouth roborate, triphenylmethylhexafluoroantimonate, allyldiazohexafluorophosphate, allyldiazoditetrafluoroborate; alkyl metal salts such as jetylzinc, triethylaluminum, and ethylaluminum chloride Heteropolyacids, isopolyacids; MoO (dik)
  • an aluminum or boron compound having at least one aromatic hydrocarbon oxy group containing a hydrogen group or a fluorine element.
  • MoO (diketonate) Cl MoO (diketonate) OSO CF
  • MoO (diketonate) OSO CF MoO (diketonate) Cl
  • MoO (diketonate) OSO CF MoO (diketonate) OSO CF
  • an aromatic hydrocarbon containing a fluorine element as a cationic polymerization catalyst.
  • Aluminum or boron compounds having at least one aromatic hydrocarbon oxy group containing a group or elemental fluorine are preferred.
  • Aromatic hydrocarbon groups containing elemental fluorine include pentafluorophenyl, tetrafluorophenyl, trifluorophenyl, 3,5-nyl, ⁇ -perfluoronaphthyl, 2, 2 ', 2' perfluorobi One or more selected from the group consisting of phenyl are preferred.
  • the aromatic hydrocarbon oxy group containing a fluorine element a hydrocarbon oxy group in which an oxygen element is bonded to the aromatic hydrocarbon group containing the fluorine element is preferable.
  • Examples of the aluminum or boron compound having at least one aromatic hydrocarbon group containing an elemental fluorine or an aromatic hydrocarbonoxy group containing an elemental fluorine include, for example, JP-A-2000-344881 and JP-A-2005-82732. Boron compounds and aluminum compounds as Lewis acids are preferred, as described in Japanese Patent Publication No. WO 03/000750! Alternatively, boron compounds and aluminum compounds, which are onium salts described in Japanese Patent Application Laid-Open No. 2003-501524 or Japanese Patent Application Laid-Open No. 2003-510374, are preferable.
  • Lewis acid examples include tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyloxy) borane, tris (pentafluorophenyloxy) aluminum, Etc.
  • tris (pentafluorophenyl) borane is a particularly preferred catalyst having a large catalytic activity for ring-opening polymerization of alkylene oxide.
  • a trityl cation or an anilium cation is preferable.
  • the onium salt trityltetrakis (pentafluorophenyl) borate or N′dimethylaniliniumtetrakis (pentafluorophenyl) borate is used. Particularly preferred.
  • a phosphazenium catalyst can be mentioned as a catalyst that does not promote hydrolysis of the natural oil-derived dalyceride structure.
  • the phosphazenium catalyst is prepared by a known method such as JP-A-11-106500. It can be obtained by the method described in the publication.
  • a polyether polyol is produced by ring-opening polymerization of an alkylene oxide as an initiator in the presence of a polymerization catalyst in a reaction vessel.
  • the ring-opening polymerization reaction of alkylene oxide can be performed using a known method as appropriate.
  • an initiator is introduced into a pressure-resistant reactor equipped with a stirrer and a cooling jacket, and a polymerization catalyst is added.
  • a polyether polyol is produced by adding an alkylene oxide to the mixture of the initiator and the polymerization catalyst and reacting them.
  • one kind of alkylene oxide may be homopolymerized using an initiator, or two or more kinds of alkylene oxide may be block polymerized and / or randomly polymerized.
  • the amount of the polymerization catalyst used in the polymerization reaction is preferably as small as possible as long as it is necessary for the ring-opening polymerization of alkylene oxide! /, But it is preferable that it be as small as possible! /.
  • the amount of the polymerization catalyst used in the polymerization reaction of the alkylene oxide is such that the polymerization catalyst contains a solid catalyst component and the solid catalyst component in the polymerization catalyst (polyester compound or excess in the slurry catalyst).
  • the content of the polymerization raw material (in the polymer immediately after polymerization) containing the polymerization catalyst, the initiator, and the alkylene oxide is 10 on a mass basis. It is preferably set to be ⁇ 150ppm, more preferably 20 ⁇ ; 120ppm. Sufficient polymerization catalyst activity can be obtained by setting the solid catalyst component of the polymerization catalyst contained in the polymerization raw material to 1 Oppm or more, and further sufficient polymerization activity can be obtained at 150 ppm or less. It is not economical to use. However, there is no problem even if a catalyst containing 150 ppm or more of the solid catalyst component is used with respect to the obtained polymer.
  • the ring-opening polymerization temperature of the alkylene oxide is 30-; 180 ° C is preferred 70-; 160 ° C is preferred 90-; 140 ° C is particularly preferred.
  • the polymerization temperature is 30 ° C or less, the ring-opening polymerization of alkylene oxide may not start, and when it is 180 ° C or more, the polymerization activity of the polymerization catalyst may decrease.
  • the amount of the cationic polymerization catalyst used is preferably 10 to 120 ppm force S, more preferably 20 to; OOppm force S based on the initiator. Obtained polyether polyol From the viewpoint of purification and cost, it is preferable that the amount of catalyst used is as small as possible. However, when the amount of cationic catalyst used is 10 ppm or more, a moderately fast alkylene oxide polymerization rate can be obtained.
  • ring-opening polymerization of 1 to 30, more preferably !! to 20, particularly 2 to 15 alkylene oxides per hydroxyl group of the initiator.
  • the ratio of primary hydroxyl groups to all terminal hydroxyl groups of the resulting polyether polyol can easily be made higher than 45%! /, .
  • the amount of force and the amount of multimeric by-products can be reduced.
  • the reaction is carried out by adjusting the temperature inside the reaction vessel by adjusting the supply rate of alkylene oxide into the reaction vessel in combination with cooling the reaction vessel. It is preferable to carry out while maintaining the desired temperature.
  • the temperature in the reaction vessel is usually ⁇ 15 to; 140 ° C., preferably 0 to; 120 ° C., particularly preferably 20 to 90 ° C.
  • the polymerization time is usually 0.5 to 24 hours, preferably 1 to 12 hours.
  • the polymerization reaction of alkylene oxide should be carried out under good stirring conditions. Is preferred. When using a general stirring method using a stirring blade, a large amount of gas in the gas phase will be taken into the reaction solution and the stirring efficiency will not be reduced! It is preferable to do.
  • the supply rate of the alkylene oxide into the reaction vessel is preferably as slow as possible from the viewpoint that the molecular weight distribution of the resulting polymer can be narrowed. On the other hand, if it is too slow, the production efficiency decreases, so it is preferable to set the supply rate of alkylene oxide by comparing these.
  • the polymerization reaction of alkylene oxide can also be performed using a reaction solvent.
  • Preferred reaction solvents include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated solvents such as chloroform and dichloromethane. It can be illustrated.
  • the amount of solvent used is not particularly limited, and a desired amount of solvent can be used.
  • antioxidants and anticorrosives can be added to the resulting polyether polyol to It is also possible to prevent deterioration during storage of the period.
  • the natural polyol-containing product-containing polyether polyol of the present invention thus obtained is produced using a natural fat-derived initiator and is environmentally preferable. Further, as shown in the examples described later, since the compatibility with the isocyanate compound is good, it is suitable as a raw material for polyurethane. Furthermore, the raw material cost can be kept low because the initiator is a natural fat / oil that has been subjected to a chemical reaction to give a hydroxyl group. Therefore, natural oil-derived substance-containing polyether polyol can be produced at low cost.
  • the polyether polyol-containing polyether polyol of the present invention is preferable as a raw material for producing a polyurethane resin, an elastomer, an adhesive, a sealant and the like by reacting with a polyisocyanate compound.
  • polyisocyanate compound examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexane.
  • aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, dicyclohexane.
  • An aliphatic polyisocyanate of xinolemeta an alicyclic polyisocyanate such as isophorone diisocyanate
  • modified products of these polyisocyanate compounds examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, hex
  • a polyurethane product such as a foam, an elastomer, a sealing material, and an adhesive by reacting the raw material containing the polyether polyol derived from the natural fat and oil of the present invention with a polyisocyanate compound.
  • the natural polyol-containing polyether polyol of the present invention can be used in applications such as surfactants and functional oils, and further as a raw material for polymer-dispersed polyether polyols containing polymer fine particles. Can be used.
  • Polyether polyols produced using the method of the present invention can be used in various applications as described above.
  • the weight average molecular weight of the polyether polyol is preferably 1500 to 500,000 ⁇ , 2000 to; more preferably 100,000, more preferably 2000 to 20,000.
  • Soyol R2-052F manufactured by Urethane Soy Systems Co., Ltd. was used as a natural oil-derived polyol produced from soybean oil by a blowing method.
  • the measured hydroxyl value of this natural fat-derived polyol was 45.3 [mgKOH / g]
  • the acid value was 4.3 [mgKOH / g]
  • Mn (number average molecular weight) was 1578
  • Mw weight average molecular weight
  • the ratio of Mw / Mn was 4.16.
  • This natural fat-derived polyol is called initiator A.
  • a soybean oil-derived polyol was prepared from soybean oil as a raw material by the hydroxylation method after epoxidation.
  • 232g of epoxidized soybean oil (Asahi Denka Kogyo Co., Ltd., trade name: Air Dekasizer I O 130P), 3g of BF Et O, a cationic polymerization catalyst, and dehydrated methanol
  • the mixture was added dropwise to 380 ml of the mixed solution at room temperature over 2 hours.
  • a synthetic magnesium oxide base adsorbent product name: Kiyoward 60 OS manufactured by Kyowa Chemical Industry was added thereto, and the mixture was further stirred at room temperature for 2 hours. Then, pressure filtration was performed, and methanol removal was further performed at 95 ° C. under reduced pressure to obtain a polyol derived from natural fats and oils.
  • the resulting polyol derived from natural fats and oils had a hydroxyl value of 169 [mgKOH / g], an acid value of 1 ⁇ l [mgKOH / g], Mw of 2299, Mn of 1720, and Mw / Mn of 1 ⁇ 34.
  • This natural fat-derived polyol is used as an initiator.
  • a slurry mixture of zinc hexocyanocobaltate complex (DMC catalyst) coordinated with tert-butyl alcohol and polyether polyol P was prepared by the following method.
  • the concentration (effective component concentration) of DMC catalyst (solid catalyst component) contained in the slurry is 5.33% by mass.
  • An aqueous solution consisting of 10.2 g of zinc chloride and 10 g of water was placed in a 500 mL flask. Potassium hexanocobaltate (K Co (CN)) 4.2
  • the solution was added dropwise to the aqueous zinc chloride solution in the flask over 30 minutes while stirring at a rotation speed of (minutes). During this time, the mixed solution in the flask was kept at 40 ° C.
  • the mixture in the flask was stirred for another 30 minutes, and then composed of 80 g of tert butyl alcohol (hereinafter abbreviated as TBA), 80 g of water, and 0.6 g of the following polyol P.
  • TBA tert butyl alcohol
  • the mixture was added and stirred at 40 ° C for 30 minutes and then at 60 ° C for 60 minutes
  • the polyol P is a polyoxypropylenediol having a hydroxyl group equivalent of 501, which is obtained by subjecting propylene oxide to addition polymerization of propylene glycol using a KOH catalyst and dealkal purification.
  • the mixture thus obtained was filtered under a pressure (0.25 MPa) using a 125 mm diameter circular filter plate and a quantitative filter paper for fine particles (No. 5C manufactured by ADV ANTEC) to obtain a composite metal cyanide complex.
  • a solid (cake) containing was isolated.
  • the cake containing the obtained double metal cyanide complex was transferred to a flask, a mixture of 6 g of TBA3 and 84 g of water was added and stirred for 30 minutes, and then pressure filtration was performed under the same conditions as above to obtain a cake.
  • Transfer the resulting cake to a flask add a mixture of 108 g of TBA and 12 g of water and stir for 30 minutes to obtain a liquid (slurry) in which a double metal cyanide complex catalyst (DMC catalyst) is dispersed in a TBA water mixed solvent. It was.
  • the volatile components were distilled off under reduced pressure at 80 ° C. for 3 hours and further at 115 ° C. for 3 hours to obtain a slurry-like DMC catalyst (DMC — TBA catalyst) was obtained.
  • DMC catalyst double metal cyanide complex catalyst
  • a polyether polyol was produced under the composition and reaction conditions shown in Table 1.
  • the reaction time in the table indicates the time from the start of supplying the alkylene oxide until the pressure drop in the reactor disappears (the same applies hereinafter).
  • a stainless steel 500 ml pressure-resistant reactor with a stirrer was used as the reactor, The reactor was charged with 248.2 g of initiator A and 682 mg of the DMC-TBA catalyst prepared in Reference Example 1 (36 mg as a solid catalyst component). After the atmosphere in the reactor was replaced with nitrogen, the temperature was raised to 120 ° C and vacuum dehydration was carried out for 2 hours. Thereafter, a mixed liquid of 24. lg of propylene oxide and 12.2 g of ethylene oxide was adjusted to a pressurized tank, and this whole amount was fed into the reactor over 40 minutes, and further stirred for 2 hours 30 minutes. Continuing, it was confirmed that there was no pressure drop. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C and the stirring speed at 500 rpm.
  • the appearance of the polyether polyol obtained by this reaction was a transparent liquid at room temperature.
  • the characteristic values (Mw, Mn, Mw / Mn, hydroxyl value, and biomass degree) of the polyether polyol are shown in Table 1.
  • the content of the solid catalyst component contained in the DM C TBA catalyst in the polymerization raw material calculated from the polymerization raw material composition of Example 1 was 112 ppm on a mass basis.
  • the degree of biomass of the polyether polyol is an index of the content ratio of non-petroleum components in the polyether polyol.
  • the raw materials constituting the polyether polyol initiator and It was calculated as a ratio (unit:%) of the mass of the initiator to the total mass of the monomer. The larger the value, the higher the content of naturally derived components.
  • a polyether polyol was produced according to the formulation and reaction conditions shown in Table 1.
  • compositions were prepared with the formulations shown in Table 1.
  • the compatibility in the table indicates that 5 drops of the composition are dropped on a glass plate, cured and dried, and the transparency of the cured product is evaluated by visual observation.
  • ⁇ (good) means that the cured product is transparent.
  • X (Poor) means that the cured product has turbidity.
  • Table 1 shows the degree of biomass in the composition obtained.
  • the degree of biomass of the composition is an index of the content ratio of non-petroleum components in the product.
  • the raw materials (polyether polyol and isocyanate) constituting the composition are used. It was calculated as a ratio (unit:%) of the mass of the initiator in the total mass of the phenate compound).
  • the method for measuring the elongation and breaking strength of the film is specified in JIS K-6251-3. It was punched into the specified dumbbell shape, and the breaking strength was measured at a pulling speed of 10 mm / min using a tensile tester SS — 207D—UA (product name) manufactured by Toyo Baldwin. Moreover, elongation% was measured from the change of the distance between marked lines.
  • a polyether polyol was produced under the composition and reaction conditions shown in Table 2. This example is significantly different from Example 1 in that ethylene oxide is not used as alkylene oxide, but only propylene oxide is used.
  • Example 2 In the same reactor as in Example 1, 120 g of initiator A and 600 mg of the same DMC-TBA catalyst as in Example 1 (32 mg as a solid catalyst component) were charged. After replacing the reactor 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 fed into the reactor to react. After the pressure in the reactor dropped, 122.8 g of propylene oxide was fed into the reactor over 4 hours to react, and stirring was continued for 1 hour to confirm that the pressure drop disappeared. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C and the stirring speed at 500 rpm.
  • the appearance of the polyether polyol obtained by this reaction was a transparent liquid at room temperature.
  • the characteristic values (Mw, Mn, Mw / Mn, hydroxyl value, and biomass degree) 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.
  • a polyether polyol having a molecular weight of 700 obtained by ring-opening polymerization of propylene oxide using glycerol and a KOH catalyst was used, and this was used in Example 2 (or The compatibility when the polyether polyol obtained in Comparative Example 2) was mixed at a mass ratio of 1/1 was examined. As a result, the polyol of Example 2 showed good compatibility. Comparative Example 2 was poorly compatible and became turbid.
  • Composition Polyether polyol (g) 10 10 Formulation Curing catalyst (g) 0.2 0.2
  • Polyether polyols were prepared using the initiator B described above as an initiator and a DMC catalyst as a polymerization catalyst under the formulation and reaction conditions shown in Table 3.
  • alkylene oxide In the same reactor as in Example 1, 30 g of initiator B and 125. lmg of the same DMC-TBA catalyst as in Example 1 (7 mg as a solid catalyst component) were charged. After replacing the inside of the reactor 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 fed into the reactor to react. After the pressure in the reactor dropped, 30 g of propylene oxide was fed into the reactor over 1 hour. Stirring was continued for another hour. Meanwhile, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C and the stirring speed at 500 rpm.
  • Table 3 shows the characteristic values of the polyether polyol obtained by this reaction.
  • the hydroxyl value was 82.2, 1.07 times the hydroxyl value of 76.5 expected from the raw material balance.
  • 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 lOOppm on a mass basis.
  • Polyether polyols were produced using the initiator B described above as an initiator and KOH as a polymerization catalyst under the formulation and reaction conditions shown in Table 3.
  • Table 3 shows the characteristic values of the polyether polyol thus obtained.
  • a film was produced in the same manner as in Example 1 using the obtained composition. A transparent film was formed. Table 3 shows the measurement results of the elongation and breaking strength of the film.
  • a polyether polyol having good compatibility with an isocyanate compound can be produced at low cost by using a raw material derived from natural fats and oils.
  • a raw material derived from natural fats and oils Contains natural fat and oil-derived material of the present invention
  • the polyether polyol is useful as a raw material for producing a polyurethane resin, a foam elastomer, an adhesive, a sealant and the like by reacting with a polyisocyanate compound.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyethers (AREA)

Abstract

L'invention concerne un procédé servant à produire un polyol de polyéther ayant une bonne compatibilité avec un composé isocyanate à faible coût en utilisant une matière première dérivée d'une matière grasse/huile naturelle. L'invention concerne précisément un procédé servant à produire un polyol de polyéther contenant une matière dérivée d'une matière grasse/huile naturelle en effectuant la polymérisation par ouverture de cycle d'un oxyde d'alkylène avec un initiateur en présence d'un catalyseur de polymérisation, caractérisé en ce que l'initiateur est un polyol dérivé d'une matière grasse/huile naturelle qui est produit en ajoutant un groupe hydroxy à une matière grasse/huile naturelle par une réaction chimique et qui a un indice d'hydroxyle de 20 à 250 mg de KOH/g et un rapport entre le poids moléculaire moyen en nombre en termes de polystyrène et le poids moléculaire moyen en poids [c'est-à-dire un rapport (Mw)/(Mn)] supérieur ou égal à 1,2 et en ce que le catalyseur de polymérisation n'accélère pas l'hydrolyse d'une structure de glycéride dérivée d'une matière grasse/huile naturelle.
PCT/JP2007/068439 2006-09-27 2007-09-21 Procédé pour la production d'un polyol de polyéther contenant une matière dérivée d'une matière grasse/huile naturelle WO2008038596A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009001783A1 (fr) * 2007-06-22 2008-12-31 Asahi Glass Company, Limited Procédé de fabrication de polyol dispersé dans un polymère et procédé de fabrication d'une mousse de polyuréthanne flexible
JP2012532948A (ja) * 2009-07-10 2012-12-20 ビーエーエスエフ ソシエタス・ヨーロピア 再生可能な資源からポリオールを製造する方法
JP2014136751A (ja) * 2013-01-17 2014-07-28 Asahi Kasei Chemicals Corp 組成物及び重合物
CN119286463A (zh) * 2024-12-13 2025-01-10 济南西电特种变压器有限公司 一种高导热低膨胀系数的聚氨酯灌封胶及其制备方法

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JPH05163342A (ja) * 1991-12-11 1993-06-29 Asahi Glass Co Ltd ポリエーテル類の製造方法
JP2005320431A (ja) * 2004-05-10 2005-11-17 Honda Motor Co Ltd 大豆油由来の軟質ポリウレタンフォームからなる自動車シート用クッション
US20060167125A1 (en) * 2002-08-28 2006-07-27 Basf Aktiengesellschaft Method for the production of low-emission polyurethane soft foams
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JPH04506962A (ja) * 1989-07-14 1992-12-03 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン 水酸基官能カルボン酸誘導体及び／又はカルボン酸のアルコキシル化生成物
JPH05163342A (ja) * 1991-12-11 1993-06-29 Asahi Glass Co Ltd ポリエーテル類の製造方法
US20060167125A1 (en) * 2002-08-28 2006-07-27 Basf Aktiengesellschaft Method for the production of low-emission polyurethane soft foams
JP2005320431A (ja) * 2004-05-10 2005-11-17 Honda Motor Co Ltd 大豆油由来の軟質ポリウレタンフォームからなる自動車シート用クッション
JP2007146163A (ja) * 2005-11-26 2007-06-14 Bayer Materialscience Ag 天然油に基づくポリオールの製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009001783A1 (fr) * 2007-06-22 2008-12-31 Asahi Glass Company, Limited Procédé de fabrication de polyol dispersé dans un polymère et procédé de fabrication d'une mousse de polyuréthanne flexible
JP5201141B2 (ja) * 2007-06-22 2013-06-05 旭硝子株式会社 ポリマー分散ポリオールおよび軟質ポリウレタンフォームの製造方法
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JP2012532948A (ja) * 2009-07-10 2012-12-20 ビーエーエスエフ ソシエタス・ヨーロピア 再生可能な資源からポリオールを製造する方法
JP2014136751A (ja) * 2013-01-17 2014-07-28 Asahi Kasei Chemicals Corp 組成物及び重合物
CN119286463A (zh) * 2024-12-13 2025-01-10 济南西电特种变压器有限公司 一种高导热低膨胀系数的聚氨酯灌封胶及其制备方法

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