WO2014069556A1 - レジンプレミックス組成物、硬質ポリウレタンフォーム用組成物および硬質ポリウレタンフォーム - Google Patents
レジンプレミックス組成物、硬質ポリウレタンフォーム用組成物および硬質ポリウレタンフォーム Download PDFInfo
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- WO2014069556A1 WO2014069556A1 PCT/JP2013/079501 JP2013079501W WO2014069556A1 WO 2014069556 A1 WO2014069556 A1 WO 2014069556A1 JP 2013079501 W JP2013079501 W JP 2013079501W WO 2014069556 A1 WO2014069556 A1 WO 2014069556A1
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- polyol
- fatty acid
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
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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
- 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
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
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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
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/52—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type obtained by dehydration of polyhydric alcohols
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/52—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type obtained by dehydration of polyhydric alcohols
- C08G2650/54—Polyglycerols
Definitions
- the present invention relates to a resin comprising a polyol containing a polyether ester polyol obtained by condensing a polyether polyol obtained by dehydrating condensation of a trihydric or higher alcohol and a fatty acid and / or a fatty acid ester, and a hydrocarbon-based blowing agent.
- the present invention relates to a premix composition, a composition for a rigid polyurethane foam comprising the resin premix composition and a polyisocyanate, and a rigid polyurethane foam obtained by reacting these.
- Polyether polyol which is a raw material for rigid polyurethane foam, has been conventionally produced by a method of ring-opening polymerization of a cyclic ether compound such as ethylene oxide, propylene oxide, and tetrahydrofuran to an active hydrogen compound that is an initiator.
- This method is an excellent method in which the reaction is possible under relatively mild conditions because of the high activity of the cyclic ether compound, and the polyether polyol produced by this method is excellent in that the molecular weight distribution is narrow.
- cyclic ether compounds have a low boiling point and are highly toxic, they have the disadvantage that they are difficult to store and synthesize.
- the average number of hydroxyl groups of the polyether polyols obtained from these cyclic ether compounds is not higher than the number of active hydrogens in the initiator due to the nature of the reaction, and in some cases, the average number of hydroxyl groups due to side reactions during the reaction. May be reduced. Therefore, when preparing polyether polyols for rigid polyurethane foams that require a particularly high number of hydroxyl groups, it is necessary to select an initiator having many hydroxyl groups such as pentaerythritol, sorbitol, and saccharides in the production method. However, an initiator having many hydroxyl groups is often in a solid state, and there is a problem that handling as an initiator is difficult.
- a polyether polyol can also be produced by dehydrating and condensing alcohol.
- the number of hydroxyl groups per molecule of polyether polyol can theoretically be increased by using a polyol compound having three or more hydroxyl groups in one molecule as the alcohol.
- a polyether polyol obtained by dehydration condensation of a polyol compound having three or more hydroxyl groups in one molecule polyglycerol obtained by dehydration condensation of glycerin in the presence of an alkali can be mentioned (Patent Document 1).
- Patent Document 2 when used as a polyol for rigid polyurethane foam, it is necessary to use polyglycerin having a high degree of condensation.
- polyglycerin has a very high viscosity when the degree of condensation increases, it can be used alone as a polyol for rigid polyurethane foam. It is difficult to use. Therefore, a technique for obtaining a polyether polyol having a low viscosity by adding a monovalent or divalent alcohol to glycerin and condensing has been developed (Patent Documents 3 and 4).
- chlorofluorocarbons that have been used for a long time as foaming agents for rigid polyurethane foams have high ozone depletion potential and global warming potential, so their use is restricted and suppressed, and pentane, isopentane, cyclopentane, etc. are representative.
- Hydrocarbon blowing agents, or water have been used as blowing agents.
- foaming is caused by carbon dioxide gas generated by the reaction between isocyanate and water, but at the same time, there is a problem that the foam becomes brittle due to the formation of urea bonds, and hydrocarbon-based foaming agents are used.
- the present invention seeks to solve the problems associated with the prior art as described above, and uses a polyol obtained without using a ring-opening polymerization reaction of a cyclic ether.
- a resin premix composition having good storage stability even when it is contained is provided.
- a resin premix composition comprising at least a polyol and a hydrocarbon foaming agent,
- the polyol is Containing a polyether polyol (A) obtained by reacting a polyether polyol obtained by condensing a polyhydric alcohol containing at least 50 mol% of a trihydric or higher alcohol with a fatty acid and / or a fatty acid ester.
- Resin premix composition characterized.
- the polyol is (1) including at least 10 parts by weight of the polyether ester polyol (A) and (2) 0 to 90 parts by weight of other polyols (provided that the total of (1) and (2) is 100 parts by weight)
- the resin premix composition as described in [1] above.
- a composition for rigid polyurethane foam comprising the resin premix composition according to any one of [1] to [4] above and a polyisocyanate.
- a rigid polyurethane foam obtained by reacting the resin premix composition according to any one of [1] to [4] above with a polyisocyanate.
- a polyether ester polyol having a large number of hydroxyl groups and a low viscosity can be easily obtained.
- a hydrocarbon-based blowing agent By mixing this with a hydrocarbon-based blowing agent, the compatibility is excellent and the storage stability is also excellent.
- a resin premix composition can be prepared.
- This resin premix composition is useful for the production of rigid polyurethane foam, and the rigid polyurethane foam obtained by using this resin premix composition is used as a heat insulating material such as a building material panel, a refrigerator, a freezer, a pipe, a house, a vehicle. It can be used for structural support materials such as.
- the resin premix composition of the present invention comprises at least a polyol and a hydrocarbon-based foaming agent, and the polyol contains 50 mol% or more of a trihydric or higher alcohol. It includes a polyether polyol (A) obtained by reacting a polyether polyol obtained by condensing (all the polyhydric alcohol is 100 mol%) with a fatty acid and / or a fatty acid ester. Moreover, the resin premix composition here is used for rigid polyurethane foam, and means a composition containing no polyisocyanate described later.
- the polyether ester polyol (A) is a polyol for rigid polyurethane foam obtained without using a ring-opening polymerization reaction of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
- the resin premix composition containing the polyol (A) and the hydrocarbon-based blowing agent is excellent in storage stability. The reason is presumed that the polyether ester polyol (A) obtained by condensing a specific fatty acid with a polyether compound can increase the hydrophobicity of the polyol.
- the polyether ester polyol (A) is usually prepared by dehydrating condensation etherification of a polyhydric alcohol containing 50 mol% of a trihydric or higher alcohol, and then preparing the polyether polyol, and then the fatty acid and / or fatty acid. It can be obtained by dehydrating condensation esterification with an ester.
- the polyhydric alcohol is not particularly limited, but is preferably a polyhydric alcohol having a boiling point of 160 ° C. or higher which is the lower limit of the reaction temperature.
- a polyol having a sufficient number of functional groups for use in rigid polyurethane foam by containing a trivalent or higher alcohol, a polyol having a sufficient number of functional groups for use in rigid polyurethane foam can be obtained.
- the trihydric or higher alcohol is preferably 50 mol% or more with respect to 100 mol% of the polyhydric alcohol, preferably 70 to 100 mol% from the viewpoint that the number of functional groups can be designed high, and 90 to 100 mol%. Is more preferable. If the trihydric or higher alcohol is less than 50 mol%, the number of functional groups of the polyol will not be sufficiently high, and foam shrinkage will occur when used in rigid polyurethane foam applications.
- trivalent or higher alcohols examples include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, methylglucoside, glucose, and the like. Since it is easy in handling to use a liquid trihydric alcohol, glycerol and diglycerol are preferably used, and glycerol having a lower viscosity is more preferable.
- the divalent alcohol is 50 mol% to 0 mol%, preferably 30 to 0 mol%, more preferably 10 to 0 mol%, based on 100 mol% of the polyhydric alcohol.
- the dihydric alcohol is not particularly limited, but ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, hexylene glycol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, isosorbide, bisphenol A, catechol, 4-t-butylcatechol, hydroquinone, 2-t-butylhydroquinone, resorcin, p Hydroxy pheneth
- dihydric alcohols for example, Actol KB-280, Actol KB-300, Actol ES-41, Actol ES-01, Actol manufactured by Mitsui Chemicals, Inc. D-280, Actcall D-400 and the like.
- These polyhydric alcohols may be used alone or in combination of two or more.
- glycerin is preferable because it is a liquid at the time of preparation and is easy to handle, and a polyol having a sufficient number of functional groups can be easily obtained by condensation.
- condensation etherification catalyst used when the polyhydric alcohol is subjected to a dehydration condensation reaction, it is preferable to use a known catalyst used for the glycerin condensation reaction, such as an alkali catalyst, an acid catalyst, and a solid acid catalyst.
- the catalyst concentration is not particularly limited, but for example, it is not particularly limited with respect to all hydroxyl groups of all alcohol components such as glycerin, but is usually preferably 0.01 to 10 mol%.
- alkali catalyst examples include tris [tris (dimethylamino) phosphoranylidene] phosphoric such as alkali metal or alkaline earth metal hydroxide, carbonate or oxide such as sodium, lithium, potassium, calcium, cesium or magnesium.
- phosphazene catalysts such as triamide (PZO), tetrakis [tris (dimethylamino) phosphoranideneamino] phosphonium hydroxide (PZN), tris [tris (dimethylamino) phosphoranylideneamino] phosphine sulfide (PZS), and the like. .
- the acid catalyst examples include iodine, hydrogen iodide, sulfuric acid, phosphoric acid, fluorosulfuric acid, phosphotungstic acid, methanesulfonic acid, trifluoromethanesulfonic acid, octanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid. Benzenesulfonic acid, paratoluenesulfonic acid and the like.
- the solid acid catalyst is not particularly limited as long as it is generally used.
- smectite silicate, acid clay, activated clay, vermiculite and other silicates are impregnated with inorganic acid or organic acid and dried.
- inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, phosphorous acid, perchloric acid, and the like.
- organic acids include formic acid, acetic acid, oxalic acid, monochloroacetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, boric acid, tungstic acid, molybdic acid, vanadic acid, chromic acid, and heteropolyacid. Can be mentioned.
- Any reaction apparatus may be used as the reaction apparatus used for the polyhydric alcohol condensation reaction as long as the apparatus is equipped with an instrument capable of distilling the produced water.
- a reaction apparatus in which a distillation column is connected to the upper part of the reactor and a condenser is further connected.
- the distillation column is a raw material such as polyhydric alcohol, water and low polymer produced by the reaction, etc., necessary components such as raw material and low polymer are refluxed to the reactor, and unnecessary components such as water are condensed in the condenser. Used to discharge.
- the number of theoretical plates in the distillation column is not particularly limited, but is usually 1 to 20 plates.
- the packing in the distillation column is not particularly limited, but usually Raschig ring, Berle saddle, McMahon, Cannon, Stepman, Sruza packing, Dixon and the like are used.
- the temperature of the distillation column is not particularly limited, and can be set to an arbitrary temperature using a refrigerant or a heat medium.
- the condenser is used to condense water and the low boiling point produced by the side reaction. Condensation is usually performed using a refrigerant, and the temperature of the refrigerant is not particularly limited, but is usually about ⁇ 30 ° C. to 60 ° C.
- the reaction temperature in the dehydration condensation is not particularly limited as long as it is a temperature at which dehydration condensation starts, but is usually 160 to 280 ° C., and preferably 200 to 270 ° C.
- the pressure during the reaction is not particularly limited, and the reaction may be carried out under normal pressure, reduced pressure, or increased pressure as long as most of the polyhydric alcohol is not distilled together with water.
- the catalyst may be added to react with the batch mixture, or the reaction may be performed by condensing only a portion of the alcohol first, then adding another type of alcohol in the middle and dropping to condense. May be.
- the hydroxyl value of the polyether polyol after completion of etherification is not particularly limited as long as the hydroxyl value of the polyether ester polyol (A) after esterification is 200 to 600 mgKOH / g, but is 400 to 1400 mgKOH / g. It is preferably 600 to 1200 mgKOH / g.
- the hydroxyl value is too low, the viscosity will be very high, and the viscosity of the polyol after esterification will be high. If the hydroxyl value is too high, condensation will not proceed sufficiently and it will be difficult to express the hardness required for rigid polyurethane foam. It becomes.
- the obtained polyether polyol may be purified to remove the catalyst, or may be subjected to condensation esterification as the next step without being purified.
- a purification method a known method can be used according to the type of catalyst used.
- an alkali catalyst such as potassium hydroxide, sodium hydroxide, potassium carbonate, or phosphazene catalyst
- neutralize with an acid such as hydrochloric acid, acetic acid, or oxalic acid
- the catalyst can be removed, for example, by removing cations by using an exchange resin.
- an acidic catalyst such as sulfuric acid, para-toluenesulfonic acid, hydrochloric acid, or phosphoric acid
- neutralize with a base such as sodium hydroxide, potassium hydroxide, or potassium carbonate, and then filter the anion exchange resin.
- the catalyst can be removed, for example, by removing anions.
- the colored component may be adsorbed and removed by activated carbon or the like.
- the fatty acid and / or fatty acid ester is not particularly limited, but is preferably an esterified product of a fatty acid having 10 to 24 carbon atoms and / or a fatty acid having 10 to 24 carbon atoms.
- Such fatty acids and / or fatty acid esters include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid or these Fatty acid esterified products or fatty acids obtained by hydrolysis from soybean oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, coconut oil fatty acids, sunflower oil fatty acids, rapeseed oil fatty acids, cottonseed oil fatty acids or the like, or these fatty acids It is possible to use the esterified product.
- esterified products include methylated products, ethylated products, and propylated products.
- a fatty polyol and / or a fatty acid ester satisfying the carbon number can be made into a liquid polyol having high compatibility with a hydrocarbon-based blowing agent with respect to the total amount of the fatty acid and / or the fatty acid ester.
- 50 wt% or more is preferable, 70 wt% or more is more preferable, and 80 wt% or more is more preferable.
- the fatty acid and / or fatty acid ester when a fatty acid having 9 or less carbon atoms is used in excess of 50 wt%, the hydrophobicity is low and may be separated when a hydrocarbon-based foaming agent is mixed. .
- the resulting polyether ester polyol (A) may be solidified.
- a saturated fatty acid ester it is preferable to contain 50 wt% or more of a saturated fatty acid having 10 to 14 carbon atoms and / or an esterified product of a saturated fatty acid having 10 to 14 carbon atoms.
- the fatty acid or fatty acid ester which contains 50 wt% or more of unsaturated fatty acid and / or unsaturated fatty acid ester.
- the reaction apparatus for the esterification reaction only needs to have a device for distilling the produced water or alcohol out of the system, and these condensations are carried out, for example, under an inert gas such as nitrogen gas, without solvent-free high temperature condensation.
- an inert gas such as nitrogen gas
- other known polymerization methods such as solution polymerization may be used.
- the temperature at the time of high-temperature condensation in the absence of a solvent may be any number as long as dehydration condensation or dealcoholization condensation occurs, but it is usually preferably 160 ° C to 260 ° C.
- the pressure during the reaction may be any of pressurization, normal pressure, and reduced pressure as long as dehydration or dealcohol condensation is possible, but it is preferable from the viewpoint of reaction efficiency to proceed the reaction under normal pressure or reduced pressure. .
- esterification catalyst a tin catalyst such as tin octylate or dibutyltin dilaurate, a titanium catalyst such as titanium tetranormal butoxide, titanium tetraisopropoxide, or titanium lactate may be used.
- a tin catalyst such as tin octylate or dibutyltin dilaurate
- titanium catalyst such as titanium tetranormal butoxide, titanium tetraisopropoxide, or titanium lactate
- Other catalysts such as a bismuth catalyst
- a known esterification catalyst may be used.
- the acid value of the polyether ester polyol (A) of the present invention is 0 to 5 mgKOH / g, preferably 0 to 3 mgKOH / g, more preferably 0 to 2 mgKOH / g.
- An acid value exceeding 5 mgKOH / g is not preferable because the reactivity is delayed when the urethanization reaction is performed.
- the hydroxyl value of the polyether ester polyol (A) of the present invention is preferably 200 to 600 mgKOH / g, more preferably 300 to 550 mgKOH / g. If it is below 200 mg KOH / g, the foam becomes soft and it becomes difficult to prepare a rigid foam. If it exceeds 600 mg KOH / g, the amount of fatty acid to be added is small, and there is a possibility that the fatty acid and unreacted polyether polyol remain and the polyol is separated. There is.
- the viscosity of the polyether ester polyol (A) of the present invention is preferably 50,000 mPa ⁇ s or less at 25 ° C., and more preferably 20,000 mPa ⁇ s or less.
- the viscosity exceeds 50,000 mPa ⁇ s, it is not preferable because the viscosity of the polyol is too high and it becomes difficult to prepare a polyurethane foam, and handling is easier if the polyol viscosity is 20,000 mPa ⁇ s or less. Therefore, it is preferable.
- the average number of functional groups of the polyetherester polyol (A) is preferably 3 or more, and more preferably 3.5 or more. When the average number of functional groups is less than 3, it is not preferable because the number of functional groups is too low to maintain the necessary strength as a rigid polyurethane foam. An average functional group number of 3.5 or more is more preferable because sufficient strength can be obtained as a polyurethane foam.
- the polyol of the present invention contains the polyether ester polyol (A), and may be the polyether ester polyol (A) alone or a combination of two or more of these with other polyols. Good.
- the polyether ester polyol (A) is at least 10 parts by weight (10 to 100 parts by weight), preferably 20 to 100 parts by weight, based on 100 parts by weight of the polyol of the present invention.
- the other polyol is preferably used in an amount of 0 to 90 parts by weight, preferably 0 to 80 parts by weight.
- the other polyol is not particularly limited as long as it is different from the polyether ester polyol (A) and has a hydroxyl group at the end, and known polyether polyol, polyester polyol, polymer polyol (polymer dispersed polyol), etc. I can give you.
- polyether polyols used as other polyols include polyether polyols obtained by addition polymerization of alkylene oxides with polyhydric alcohols, aromatic amines, and aliphatic amines.
- Any polyhydric alcohol can be used as long as it can be used for producing a polyether polyol.
- aromatic amine examples include tolylenediamine (hereinafter abbreviated as “TDA”) and / or crude TDA, diphenylmethanediamine (hereinafter abbreviated as “MDA”) and / or crude MDA.
- TDA tolylenediamine
- MDA diphenylmethanediamine
- aliphatic amine examples include ethylenediamine, triethanolamine, and isopropanolamine. These can be used alone or in combination.
- the alkylene oxide may be any alkylene oxide used in the production of polyether polyol, and examples thereof include alkylene oxides having 2 to 8 carbon atoms. More specifically, ethylene oxide, propylene oxide, butylene oxide and the like can be mentioned, and among these, propylene oxide and butylene oxide are preferably used. These can be used alone or in combination.
- polyether polyols examples thereof include GR-84T, DA-401P, GR-33F, T-700S (trademark, Actol: manufactured by Mitsui Chemicals, Inc.).
- polyester polyols used as other polyols those obtained by semi-esterifying an anhydride such as an aromatic carboxylic acid or an aliphatic carboxylic acid with a polyhydric alcohol or an aliphatic amine and then polymerizing an alkylene oxide, Or what was obtained by condensation-reacting aromatic carboxylic acid or aliphatic carboxylic acid with a polyhydric alcohol is mentioned.
- aromatic carboxylic acid examples include phthalic acid, terephthalic acid, isophthalic acid, and pyromellitic acid.
- aromatic carboxylic acid anhydride examples include phthalic anhydride and pyromellitic acid anhydride. Is mentioned.
- Examples of the aliphatic carboxylic acid include adipic acid, succinic acid, and maleic acid
- examples of the aliphatic carboxylic acid anhydride include succinic anhydride and maleic anhydride.
- polyester polyols commercially available products may be used, and examples thereof include RMK-342 (trademark: Maximol: manufactured by Kawasaki Kasei Co., Ltd.).
- the polymer polyol include a polymer polyol obtained from a polyether polyol.
- the polymer polyol is a dispersion in which vinyl polymer particles are dispersed in a polyether polyol by dispersing and polymerizing a compound having an unsaturated bond in the polyether polyol using a radical initiator such as azobisisobutyronitrile.
- a radical initiator such as azobisisobutyronitrile.
- the vinyl polymer particles may be vinyl polymer particles made of a polymer of a compound having an unsaturated bond, but at the time of dispersion polymerization, at least a part of the compound having an unsaturated bond is grafted to a polyether polyol as a dispersion medium. Polymer particles are preferred.
- the compound having an unsaturated bond is a compound having an unsaturated bond in the molecule, and examples thereof include acrylonitrile, styrene, and acrylamide. These compounds having an unsaturated bond can be used singly or in combination of two or more.
- a dispersion stabilizer, a chain transfer agent, or the like may be used in combination.
- the hydroxyl value of these other polyols is not limited as long as a rigid polyurethane foam can be prepared, but is preferably 200 mgKOH / g or more and 800 mgKOH / g or less.
- Urethane catalyst As the catalyst mixed in the resin premix composition of the present invention, amines, aziridines, quaternary ammonium compounds, alkali metal salts, lead compounds, tin compounds, which are usually used for urethane foaming, Any urethane catalyst such as an alcoholate compound, a phenolate compound, a metal halide, or a metal complex compound can be used.
- amines include trimethylaminoethylpiperazine, triethylamine, tripropylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylene.
- aziridines examples include 2-ethylaziridine.
- quaternary ammonium compounds include tertiary amine carboxylates.
- alkali metal salts examples include potassium octylate and sodium acetate.
- Examples of the lead compound include lead naphthenate and lead octylate.
- Examples of tin compounds include dibutyltin diacetate and dibutyltin dilaurate.
- Examples of the alcoholate compound include sodium methoxide and sodium ethoxide.
- Examples of the phenolate compound include potassium phenoxide, lithium phenoxide, sodium phenoxy and the like.
- metal halide examples include iron chloride, zinc chloride, zinc bromide, tin chloride and the like.
- metal complex compound examples include metal complex compounds such as acetylacetone metal salts.
- catalysts can be used alone or in combination of two or more, and the amount used is preferably 0.001 to 10 parts by weight, more preferably 100 parts by weight of the total polyol used in the present invention. Is preferably 0.1 to 5 parts by weight.
- hydrocarbon foaming agent As the hydrocarbon foaming agent contained in the resin premix composition of the present invention, a hydrocarbon having 3 to 8 carbon atoms can be preferably used. Specific examples include propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, isoheptane, cyclopentane, cyclohexane, cycloheptane and the like. These can be used alone or in combination. Among these, cyclopentane and isopentane can be preferably used, and cyclopentane is particularly preferable.
- water can be used in combination as a foaming agent.
- ion-exchanged water or distilled water is usually used, but industrial water can be used as it is depending on circumstances.
- a chlorofluorocarbon compound can be used in combination as a foaming agent.
- the chlorofluorocarbon compounds include HCFC-141b, HFC-245fa, HFC-365mfc and the like.
- the amount of the foaming agent used can be 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the total polyol. preferable.
- a foam stabilizer can be used in the resin premix composition of the present invention as necessary.
- conventionally known silicon-containing organic surfactants are used. Specifically, silicone derivatives (alkylene oxide-modified polydimethylsiloxane having an alkoxy group or an active OH group at the terminal) are used. Can be mentioned. Also, so-called nonionic surfactants such as polyoxyethylene octadecylamine and long-chain fatty acid alkylol amide can be used as the foam stabilizer.
- foam stabilizer examples include, for example, SZ-1127, SZ-1142, SZ-1605, SZ-1642, SZ-1645, SZ-1649, SZ-1655, SZ-1675, SZ-1694, SZ-1711. , L-580, L-5740, L-5420, L-5421, L-5440, SF-2935F, SF-2938F, SF-2940F, SF-2945F, SF-2908, SRX-294A, SH-190, SH -192, SH-193, etc. (above, trade names, manufactured by Toray Dow Corning Silicone Co., Ltd.), F-327, F-345, F-305, F-388, F-394, etc.
- foam stabilizers can be used alone or in combination of two or more, and the amount used is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total polyol. Part is preferred.
- a chain extender or crosslinking agent can be used in the resin premix composition of the present invention as necessary. When these are used, it is preferable to use 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of polyol.
- chain extender examples include dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, and 1,4-butanediol.
- crosslinking agent examples include polyhydric alcohols such as glycerin and diglycerin, alkanolamines such as triethanolamine, diethanolamine, and monoethanolamine, aliphatic amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetraamine, aniline, 2, Aromatic amines such as 4-tolylenediamine, 2,6-tolylenediamine, bisphenol A, bisphenol F, hydroquinone, resorcinol, novolak, resole and other aromatic alcohols, pentaerythritol, and sorbitol.
- polyhydric alcohols such as glycerin and diglycerin
- alkanolamines such as triethanolamine, diethanolamine, and monoethanolamine
- aliphatic amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetraamine
- aniline 2,
- Aromatic amines such as 4-tolylenediamine, 2,6-tolylenediamine,
- additives Various other additives can be added to the resin premix composition of the present invention depending on applications and purposes. Examples of such additives include flame retardants, antioxidants, colorants, and viscosity reducing agents.
- the resin premix composition of the present invention is excellent in compatibility with a hydrocarbon-based foaming agent and excellent in storage stability.
- the rigid polyurethane foam composition of the present invention comprises a polyisocyanate in addition to the resin premix composition.
- the polyisocyanate is not particularly limited as long as it is a bifunctional or higher functional polyisocyanate.
- diphenylmethane diisocyanate hereinafter abbreviated as “MDI”
- polymeric MDI polymeric MDI
- tolylene diisocyanate hereinafter abbreviated as “TDI”
- HDI hexamethylene Diisocyanate
- XDI xylene diisocyanate
- NBDI norbornene diisocyanate
- H12MDI dicyclohexylmethane diisocyanate
- H6XDI hydrogenated Xylylene diisocyanate
- IPDI isophorone diisocyanate
- TDI TDI
- crude TDI containing a multifunctional tar for example, TDI-TRC manufactured by Mitsui Chemicals, Inc.
- MDI is mainly composed of 4,4'-isomer (4,4'-MDI), and polymeric MDI containing trinuclear or higher polynuclear (for example, Cosmonate series manufactured by Mitsui Chemicals, Inc.) Can be suitably used.
- modified polyisocyanate compounds such as nurate modification, carbodiimide modification, prepolymer modification (prepolymer having an isocyanate group at the molecular end obtained from polyisocyanate and the above-mentioned polyol), uretdione modification, and the like can also be used as the polyisocyanate.
- These polyisocyanates and modified products thereof can be used singly or in combination of two or more.
- the ratio of the resin premix composition and the polyisocyanate used in the present invention is not particularly limited, but the molar ratio of the isocyanate groups contained in the polyisocyanate and the active hydrogen groups contained in the resin premix composition is usually 50: The range is 100 to 300: 100, preferably 90: 100 to 150: 100.
- the molar ratio of isocyanate groups when the number of moles of active hydrogen groups contained in the resin premix composition is 100 is expressed as an NCO index.
- the rigid polyurethane foam of the present invention comprises a composition for rigid polyurethane foam (that is, the resin premix composition and polyisocyanate), a urethanization catalyst and a hydrocarbon-based foaming agent, and if necessary, a foam stabilizer. In the presence, it can be produced by reacting and foaming by a conventionally known method.
- foaming may be carried out in any state, a method of carrying out in the mold similar to the shape or shape of the molded product is preferable.
- the polyisocyanate and the resin premix composition are preferably mixed immediately before foaming.
- mixing method of each component either dynamic mixing or static mixing may be used, or both mixing methods may be used in combination.
- a mixing method by dynamic mixing a method of mixing with a stirring blade or the like can be mentioned.
- a mixing method by static mixing a method of mixing in a machine head mixing chamber of a foaming machine, a method of mixing in a liquid feeding pipe using a static mixer or the like, and the like can be mentioned.
- the mixing temperature and pressure can be arbitrarily set according to the quality of the desired rigid polyurethane foam, the type and composition of the raw material, and can be heated as necessary prior to mixing.
- each starting component is stirred and mixed at a liquid temperature of 10 to 50 ° C., preferably 15 to 30 ° C., and then introduced into an open mold or a closed mold whose temperature can be controlled as necessary under high pressure.
- the mold temperature is 20 to 110 ° C., preferably 30 to 60 ° C., particularly preferably 45 to 55 ° C.
- the rigid polyurethane foam is a polyurethane foam having a hydroxyl value (OHV) of 200 or more and a glass transition degree (Tg) of 100 ° C. or more.
- the rigid polyurethane foam obtained from the composition for rigid polyurethane foam of the present invention is excellent in compressive strength, dimensional stability, thermal conductivity, heat insulating performance, and moldability. For this reason, the rigid polyurethane foam of this invention can be utilized for structural support materials, such as heat insulating materials, such as a building material panel, a refrigerator, a freezer, piping, a house, vehicles, such as a motor vehicle.
- structural support materials such as heat insulating materials, such as a building material panel, a refrigerator, a freezer, piping, a house, vehicles, such as a motor vehicle.
- Hydroxyl value Defined in terms of mg of potassium hydroxide corresponding to the hydroxyl group in 1 g of polyether polyol, and measured according to JIS K1557, Section 6.4 “Hydroxyl value”. Acid value: The acid value was measured according to JIS K6901 5.3.2 “Partial acid value”.
- a resin premix composition containing cyclopentane as a blowing agent was prepared by mixing the raw materials shown in Table 1 as a resin premix composition formulation. After mixing the raw materials, let stand in a room at 25 ° C. for one week, and visually check whether the resin premix composition is separated. Table 1 shows the non-separated one as “AA” and the separated one as “BB”. Described.
- Cream time, gel time, and tack-free time were evaluated with the mixing start time of the polyol and polyisocyanate in the resin premix composition as 0 seconds.
- TFT Tack-free time
- Low-temperature dimensional change rate The dimensional change rate of a test piece after measuring a rigid polyurethane foam test piece of 80 mm ⁇ 80 mm ⁇ 20 mm in a thermostatic chamber at ⁇ 30 ° C. for 48 hours was determined.
- Example 1 Preparation of polyether polyol 600 g of diethylene glycol (27.0 mol% in polyhydric alcohol) and 22.6 g of sodium hydroxide were charged into a flask equipped with a distillation column and a condenser, and the temperature was raised to 250 ° C. in a nitrogen atmosphere. After the temperature increase, 1406 g of glycerin (73.0 mol% in the polyhydric alcohol) was added dropwise over 5 hours, and dehydration condensation was performed at normal pressure for 18 hours. Thereafter, oxalic acid dihydrate was added so as to be half the number of moles of sodium hydroxide, and neutralization was performed at 120 ° C. for 1 hour. The hydroxyl value of this polyether polyol was 806 mgKOH / g.
- the resulting polyether ester polyol (1) was a brown turbid liquid with a hydroxyl value of 420 mg KOH / g, an acid value of 0.39 mg KOH / g, and a viscosity at 25 ° C. of 2670 mPa ⁇ s. Moreover, the average functional group number of this polyol was 3.8.
- a resin premix composition was prepared with the composition described in Table 1 below, sealed in a sealable glass bottle and stored at 25 ° C. for 1 week. Then, it was confirmed visually whether the resin premix composition was separated. Since no separation was confirmed, Cosmonate M-200 as an isocyanate was added to the resin premix composition adjusted to 20 ° C. in an amount such that the NCO index was 110, and the mixture was stirred with a stirring blade for 5 seconds.
- the stirred mixed solution was added to a foamed BOX of 200 ⁇ 200 ⁇ 200 mm, and cream time (CT), gel time (GT), and tack free time (TFT) were measured.
- CT cream time
- GT gel time
- TFT tack free time
- a predetermined amount of the mixed liquid stirred was poured into a 400 ⁇ 300 ⁇ 50 mm vertical panel heated in advance to 40 ° C., then covered and cured for 5 minutes, and then demolded.
- the core density, thermal conductivity, compressive strength, and low temperature dimensional stability of this sample were measured by the above methods. The measurement results are shown in Table 1.
- Example 2 Preparation of polyether polyol 500 g of diethylene glycol (22.4 mol% in polyhydric alcohol) and 22.6 g of sodium hydroxide were charged into a flask equipped with a distillation column and a condenser, and the temperature was raised to 250 ° C. in a nitrogen atmosphere. After the temperature increase, 1500 g of glycerin (77.6 mol% in the polyhydric alcohol) was added dropwise over 5 hours, and dehydration condensation was further performed at normal pressure for 18 hours. Thereafter, sulfuric acid was added so that the number of moles of sodium hydroxide was half that of sodium hydroxide, neutralization was performed at 120 ° C. for 1 hour, and then dehydration was performed at 110 ° C. under reduced pressure for 4 hours. The hydroxyl value of this polyether polyol was 795 mgKOH / g.
- the resulting polyether ester polyol (2) was a brown turbid liquid having a hydroxyl value of 430 mg KOH / g, an acid value of 0.48 mg KOH / g, and a viscosity at 25 ° C. of 5100 mPa ⁇ s. Moreover, the average functional group number of this polyol was 4.1.
- Example 3 (Preparation of polyether polyol) 667 g of diethylene glycol (30.3 mol% in polyhydric alcohol) and 22.6 g of sodium hydroxide were charged into a flask equipped with a distillation column and a condenser, and the temperature was raised to 250 ° C. in a nitrogen atmosphere. After the temperature increase, 1333 g of glycerin (69.7 mol% in the polyhydric alcohol) was added dropwise over 5 hours, and dehydration condensation was performed at normal pressure for 24 hours. Thereafter, oxalic acid dihydrate was added so as to be half the number of moles of sodium hydroxide, neutralized at 120 ° C. for 1 hour, and then dehydrated at 110 ° C. under reduced pressure for 4 hours. The neutralized salt precipitated was removed using 5B filter paper at a pressure of 0.35 MPa. The hydroxyl value of this polyether polyol was 791 mgKOH / g.
- Example 4 (Preparation of polyether polyol) Dipropylene glycol 667 g (25.6 mol% in polyhydric alcohol) and sodium hydroxide 22.6 g were charged into a flask equipped with a distillation column and a condenser, and the temperature was raised to 250 ° C. in a nitrogen atmosphere. After the temperature increase, 1333 g of glycerin (74.4 mol% in the polyhydric alcohol) was added dropwise over 5 hours, followed by dehydration condensation at normal pressure for 18 hours. Thereafter, oxalic acid dihydrate was added so as to be half the number of moles of sodium hydroxide, neutralized at 120 ° C. for 1 hour, and then dehydrated at 110 ° C. under reduced pressure for 4 hours. The hydroxyl value of this polyether polyol was 777 mgKOH / g.
- the resulting polyether ester polyol (4) was a brownish liquid with a hydroxyl value of 432 mgKOH / g, an acid value of 0.39 mgKOH / g, and a viscosity at 25 ° C. of 2160 mPa ⁇ s. Moreover, the average functional group number of this polyol was 3.9.
- Example 5 Preparation of polyether polyol 2024 g of glycerin and 7.05 g of sodium hydroxide were charged into a flask equipped with a distillation column and a condenser, heated to a temperature of 260 ° C. in a nitrogen atmosphere, and subjected to dehydration condensation at normal pressure for 17 hours. Thereafter, oxalic acid dihydrate was added so as to be half the number of moles of sodium hydroxide, neutralized at 120 ° C. for 1 hour, and then dehydrated at 110 ° C. under reduced pressure for 4 hours. The neutralized salt precipitated was removed using 5B filter paper at a pressure of 0.35 MPa. The hydroxyl value of this polyether polyol was 1044 mgKOH / g.
- the resulting polyether ester polyol (5) was a brown turbid liquid with a hydroxyl value of 449 mg KOH / g, an acid value of 0.56 mg KOH / g, and a viscosity at 25 ° C. of 19600 mPa ⁇ s. Moreover, the average functional group number of this polyol was 4.2.
- Example 6 Preparation of polyether polyol 5060 g of glycerin and 17.63 g of sodium hydroxide were charged into a flask equipped with a distillation column and a condenser, heated to a temperature of 260 ° C. in a nitrogen atmosphere, and dehydrated and condensed at normal pressure for 21 hours. Thereafter, oxalic acid dihydrate was added so as to be half the number of moles of sodium hydroxide, neutralized at 120 ° C. for 1 hour, and then dehydrated at 120 ° C. and atmospheric pressure for 4 hours. The neutralized salt precipitated was removed using 5B filter paper at a pressure of 0.35 MPa. The hydroxyl value of this polyether polyol was 990 mgKOH / g.
- the resulting polyether ester polyol (6) was a brown turbid liquid with a hydroxyl value of 400 mgKOH / g, an acid value of 0.58 mgKOH / g, and a viscosity at 25 ° C. of 15300 mPa ⁇ s.
- the average functional group number of this polyol was 4.6.
- Example 7 Preparation of polyether polyol 5060 g of glycerin and 17.63 g of sodium hydroxide were charged into a flask equipped with a distillation column and a condenser, heated to a temperature of 260 ° C. in a nitrogen atmosphere, and subjected to dehydration condensation at normal pressure for 27 hours. Thereafter, oxalic acid dihydrate was added so as to be half the number of moles of sodium hydroxide, neutralized at 120 ° C. for 1 hour, and then dehydrated at 120 ° C. and atmospheric pressure for 4 hours. The neutralized salt precipitated was removed using 5B filter paper at a pressure of 0.35 MPa. The hydroxyl value of this polyether polyol was 951 mgKOH / g.
- the resulting polyether ester polyol (7) was a brown transparent liquid, having a hydroxyl value of 396 mgKOH / g, an acid value of 0.6 mgKOH / g, and a viscosity at 25 ° C. of 14400 mPa ⁇ s.
- the average functional group number of this polyol was 4.5.
- the precipitated neutralized salt was removed using 5B filter paper at a pressure of 0.35 MPa to obtain a polyether polyol (8).
- the polyether polyol (8) had a hydroxyl value of 783 mgKOH / g and a viscosity at 25 ° C. of 3050 mPa ⁇ s.
- the average functional group number of this polyol was 4.9.
- Comparative Example 2 (Production of rigid polyurethane foam) With the composition shown in Table 1, a rigid polyurethane foam was prepared in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 1. In addition, the foam obtained by the comparative example 2 had high heat conductivity compared with the foam obtained by the Example, and was inferior as a foam.
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Abstract
Description
一方、レジンプレミックス組成物の貯蔵安定性を確保するために発泡剤とポリオールの相溶性を良くしすぎると発泡時に熱伝導率が悪化するということが報告されている(非特許文献1)。
[1] ポリオールおよび炭化水素系発泡剤を少なくとも含んでなるレジンプレミックス組成物であって、
前記ポリオールが、
50モル%以上の3価以上のアルコールを含む多価アルコールを縮合させて得られるポリエーテルポリオールと、脂肪酸および/または脂肪酸エステルとを反応させて得られるポリエーテルエステルポリオール(A)を含むことを特徴とするレジンプレミックス組成物。
(1)前記ポリエーテルエステルポリオール(A)を少なくとも10重量部と
(2)その他のポリオールを0~90重量部(ただし、(1)と(2)の合計を100重量部とする)を含むことを特徴とする上記[1]に記載のレジンプレミックス組成物。
[4] 前記多価アルコールが、グリセリンであることを特徴とする前記[1]に記載のレジンプレミックス組成物。
[6] 上記[1]~[4]の何れか一項に記載のレジンプレミックス組成物とポリイソシアネートとを反応させることにより得られる硬質ポリウレタンフォーム。
[8] 前記ポリエーテルエステルポリオール(A)の粘度が、25℃で50,000mPa・s以下であることを特徴とする上記[1]~[4]の何れか一項に記載のレジンプレミックス組成物。
[10] 前記脂肪酸および/または脂肪酸エステルが、不飽和脂肪酸および/または不飽和脂肪酸エステルを50wt%以上含むことを特徴とする上記[1]~[4]の何れ一項かに記載のレジンプレミックス組成物。
本発明のレジンプレミックス組成物は、ポリオールおよび炭化水素系発泡剤を少なくとも含んでなるものであり、前記ポリオールが、50モル%以上の3価以上のアルコールを含む多価アルコール(多価アルコール全体を100モル%とする)を縮合させて得られるポリエーテルポリオールと、脂肪酸および/または脂肪酸エステルとを反応させて得られるポリエーテルエステルポリオール(A)を含むものである。
また、ここでいうレジンプレミックス組成物とは、硬質ポリウレタンフォームに用いるものであり、後述するポリイソシアネートを含まないものを意味する。
[ポリエーテルエステルポリオール(A)]
本発明において、ポリエーテルエステルポリオール(A)は、エチレンオキサイドやプロピレンオキサイド、ブチレンオキシド、テトラヒドロフランなどの環状エーテル化合物の開環重合反応を用いることなく得られる硬質ポリウレタンフォーム用ポリオールであり、ポリエーテルエステルポリオール(A)および炭化水素系発泡剤を含むレジンプレミックス組成物は、貯蔵安定性に優れる。この理由は、ポリエーテル化合物に特定の脂肪酸を縮合することにより得られるポリエーテルエステルポリオール(A)は、ポリオールの疎水性を高めることができるためと推定される。
(多価アルコール)
多価アルコールは、特に制限されないが、沸点が反応温度の下限である160℃以上の多価アルコールが好ましい。
2価のアルコールは、多価アルコール100モル%に対して、50モル%~0モル%、好ましくは30~0モル%、さらに好ましくは10~0モル%である。
これらの多価アルコールは、1種単独で用いても2種以上を組み合わせて用いてもよい。
なお、多価アルコールとしては、グリセリンであることが仕込み時に液体であるため取扱いが容易であり、また縮合により充分な官能基数のポリオールを得やすいため好ましい。
前記多価アルコールを脱水縮合反応させる際に使用される縮合エーテル化触媒としては、アルカリ触媒、酸触媒、固体酸触媒などのグリセリンの縮合反応に用いられる公知の触媒を使用することが好ましい。触媒濃度は、特に制限されないが、例えば、グリセリンなどアルコール全成分の全水酸基に対して、特に限定されないが、通常0.01~10モル%が好ましい。
多価アルコールの縮合反応に使用する反応装置は、生成する水を留出させることができる器具を備えた装置であれば、どのような反応装置を用いてもよい。例えば、反応器上部に蒸留塔を連結し、さらに凝縮器を連結した反応装置が挙げられる。
前記脱水縮合における反応温度は、脱水縮合が始まる温度であれば特に制限されないが、通常160~280℃であり、200~270℃が好ましい。また、反応時の圧力も特に制限はなく多価アルコールの大部分が水とともに留出しない条件であれば、常圧、減圧、加圧のどの条件で反応を行なってもよい。
得られたポリエーテルポリオールは、精製を行って触媒を除去してもよいし、特に精製を行わずそのまま次工程である縮合エステル化を行ってもよい。精製の手法は使用した触媒の種類に応じて、既知の方法を用いることができる。
脂肪酸および/または脂肪酸エステルは、特に限定されないが、好ましくは、炭素数10~24の脂肪酸および/または炭素数10~24の脂肪酸のエステル化物である。このような脂肪酸および/または脂肪酸エステルとしては、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、アラキジン酸、アラキドン酸、ベヘン酸、リグノセリン酸あるいはこれらの脂肪酸のエステル化物、もしくは大豆油脂肪酸、パーム油脂肪酸、パーム核油脂肪酸、ヤシ油脂肪酸、ひまわり油脂肪酸、ナタネ油脂肪酸、綿実油脂肪酸などの天然油脂より加水分解して得られる脂肪酸、あるいはこれらの脂肪酸のエステル化物を用いることが可能である。なお、エステル化物としては、メチル化物、エチル化物、プロピル化物などが挙げられる。
また、不飽和脂肪酸および/または不飽和脂肪酸エステルを50wt%以上含む脂肪酸もしくは脂肪酸エステルを用いることも好ましい。
エステル化反応の反応装置は生成する水、もしくはアルコールを系外に留出させる装置を具備していれば良く、これらの縮合は例えば、窒素ガスなどの不活性ガス下において、無溶剤下高温縮合をしてもよいし、溶液重合などの他の公知の重合方法を用いても良い。無溶剤下の高温縮合時の温度は、脱水縮合もしくは脱アルコール縮合が起こる温度なら何度でもかまわないが、通常160℃~260℃が好ましい。また、反応中の圧力は脱水、もしくは脱アルコール縮合が可能であれば、加圧、常圧、減圧のいずれでもかまわないが、常圧もしくは減圧下に反応を進めることが反応効率の点から好ましい。
本発明のポリエーテルエステルポリオール(A)の酸価は、0~5mgKOH/g、好ましくは0~3mgKOH/g、さらに好ましくは0~2mgKOH/gである。酸価が5mgKOH/gを超えるとウレタン化反応を行うにあたって反応性が遅延するため好ましくない。
本発明のポリオールは、前記ポリエーテルエステルポリオール(A)を含有するものであり、前記ポリエーテルエステルポリオール(A)単独でも、これと他のポリオールとを2種以上組み合わせたものを用いたものでもよい。その他のポリオールを併用する場合は、本発明のポリオールの合計100重量部に対して、ポリエーテルエステルポリオール(A)が少なくとも10重量部(10~100重量部)、好ましくは20~100重量部、その他のポリオールが0~90重量部、好ましくは0~80重量部となる量で用いることが好ましい。
ポリマーポリオールとしては、例えば、ポリエーテルポリオールから得られるポリマーポリオールが挙げられる。
これら他のポリオールの水酸基価については硬質ポリウレタンフォームを調製できるものであれば制限はないが、200mgKOH/g以上800mgKOH/g以下であることが好ましい。
本発明のレジンプレミックス組成物中に混合される触媒としては、通常ウレタン発泡に用いられるアミン類、アジリジン類、4級アンモニウム化合物、アルカリ金属塩、鉛化合物、錫化合物、アルコラート化合物、フェノラート化合物、金属ハロゲン化物、金属錯体化合物等のウレタン化触媒であればいずれでも使用することができる。
4級アンモニウム化合物としては3級アミンのカルボン酸塩等を挙げることができる。
アルカリ金属塩類としては、オクチル酸カリウム、酢酸ナトリウムなどを例示することができる。
錫化合物としてはジブチル錫ジアセテート、ジブチル錫ジラウレート等を挙げることができる。
フェノラート化合物としては、カリウムフェノキシド、リチウムフェノキシド、ナトリウムフェノキシ等を挙げることができる。
金属錯体化合物としてはアセチルアセトン金属塩等の金属錯化合物等を挙げることができる。
本発明のレジンプレミックス組成物中に含有される炭化水素系発泡剤としては、炭素原子数3~8の炭化水素を好ましく用いることができる。具体的には、プロパン、n-ブタン、イソブタン、n-ペンタン、イソペンタン、ネオペンタン、n-ヘキサン、イソヘキサン、n-ヘプタン、イソヘプタン、シクロペンタン、シクロヘキサン、シクロヘプタンなどが挙げられる。これらは単独で、または複数を併用して用いることができる。このうち、シクロペンタン、イソペンタンを好ましく用いることができ、特にシクロペンタンが好ましい。
このような発泡剤の使用量は、全ポリオール100重量部に対して、1~50重量部用いることができ、更に好ましくは2~40重量部、特に好ましくは5~30重量部であることが好ましい。
[整泡剤]
本発明のレジンプレミックス組成物には必要に応じて整泡剤を用いることができる。整泡剤としては、従来公知の含珪素有機系の界面活性剤が用いられ、具体的には、シリコーン誘導体(アルキレンオキサイド変性ポリジメチルシロキサンで末端にアルコキシ基または活性のOH基などを有する)が挙げられる。また、ポリオキシエチレンオクタデシルアミン、長鎖脂肪酸アルキロールアマイドなど、いわゆるノニオン系の界面活性剤も整泡剤として使用可能である。整泡剤の具体例としては、例えば、SZ-1127、SZ-1142、SZ-1605、SZ-1642、SZ-1645、SZ-1649、SZ-1655、SZ-1675、SZ-1694、SZ-1711、L-580、L-5740、L-5420、L-5421、L-5440、SF-2935F、SF-2938F、SF-2940F、SF-2945F、SF-2908、SRX-294A、SH-190、SH-192、SH-193等(以上、商品名、東レ・ダウコーニング・シリコーン(株)製)、F-327、F-345、F-305、F-388、F-394等(以上、商品名、信越化学工業(株)製)、TG-B-8404、TG-B-8461、TG-B-8462、TG-B-8466、TG-B-8467、TG-B-8474(以上、商品名、エボニック社製、シリコーン整泡剤)が挙げられる。これら整泡剤は、単独または2種以上併用して用いることができ、その使用量は、全ポリオール100重量部に対して、0.1~10重量部が好ましく、さらに好ましくは1~5重量部が好ましい。
本発明のレジンプレミックス組成物には必要に応じ、鎖延長剤あるいは架橋剤を用いることができる。これらを用いる場合は、ポリオール100重量部に対し、0.1~5重量部、好ましくは0.5~3重量部を用いることが好ましい。
本発明のレジンプレミックス組成物には、用途や目的に応じて、その他の各種添加剤を添加することができる。このような添加剤としては、例えば、難燃剤、酸化防止剤、着色剤、低粘度化剤などが挙げられる。
本発明のレジンプレミックス組成物は、炭化水素系発泡剤との相溶性に優れ、貯蔵安定性にも優れる。
本発明の硬質ポリウレタンフォーム用組成物は、前記レジンプレミックス組成物に、さらにポリイソシアネートを含むものである。
ポリイソシアネートとしては、2官能以上のポリイソシアネートであれば制限はないが、例えばジフェニルメタンジイソシアネート(以下、「MDI」と略す)、ポリメリックMDI、トリレンジイソシアネート(以下、「TDI」と略す)、ヘキサメチレンジイソシアネート(以下、「HDI」と略す)、キシレンジイソシアネート(以下、「XDI」と略す)、ノルボルネンジイソシアネート(以下、「NBDI」と略す)、ジシクロヘキシルメタンジイソシアネート(以下、「H12MDI」と略す)、水添キシリレンジイソシアネート(以下、「H6XDI」と略す)、イソホロンジイソシアネート(以下、「IPDI」と略す)などが挙げられる。これらポリイソシアネートは、単独でも2種類以上を混合して用いてもよい。中でも、硬質ポリウレタンフォーム用ポリイソシアネートとしては、TDIおよび/またはMDIが好ましい。
本発明の硬質ポリウレタンフォームは、前記硬質ポリウレタンフォーム用組成物(すなわち、前記レジンプレミックス組成物とポリイソシアネート)を、ウレタン化触媒および炭化水素系発泡剤、要すれば整泡剤の存在下で、従来公知の方法で反応および発泡させることにより製造することができる。
ダイナミックミキシングによる混合方法としては、攪拌翼等により混合する方法が挙げられる。また、スタティックミキシングによる混合方法としては、発泡機のマシンヘッド混合室内で混合を行う方法、あるいはスタティックミキサー等を用いて送液配管内で混合を行う方法等が挙げられる。
なお、「部」は、特に断らない限り、「重量部」を表す。また、実施例、比較例における分析、測定は以下の方法に従って行った。
水酸基価:ポリエーテルポリオール1g中の水酸基に相当する水酸化カリウムのmg数で定義し、測定はJIS K1557、6.4項「水酸基価」に従って行った。
酸価:酸価の測定はJIS K6901 5.3.2項「部分酸価」に従って行った。
分子量:得られたポリエーテルポリオールを0.05g程度精秤し、N,O-ビス(トリメチルシリル)アセトアミド0.5gを加えた後、ジメチルホルムアミド(以下、「DMF」と略す)/テトラヒドロフラン(以下、「THF」と略す)混合液(DMF:THF=1:9(重量比))を加えて10mLにメスアップした。これをゲルパーミエーションクロマトグラフィー(GPC)HLC-8020(東ソー(株)製)を用いて以下の条件で測定した。
溶離液:THF
溶離液流量:0.8ml/min
溶離液温度:40℃
カラム温度:40℃
カラム:東ソー(株)製TSKgel G-3000H、G-2000H、G-1000Hを直列につないで使用
検出器:RI(示差屈折率)検出器
標準試料:ポリスチレン
平均官能基数=(分子量×水酸基価)/(56108+74×水酸基価)
レジンプレミックス組成物処方として表1に示された原料を混合することによって発泡剤としてシクロペンタンを含むレジンプレミックス組成物を調製した。原料混合後、25℃の室内に1週間静置し、目視にてレジンプレミックス組成物の分離の有無を確認し、分離しないものを「AA」、分離するものを「BB」として表1に記載した。
レジンプレミックス組成物中のポリオールとポリイソシアネートとの混合開始時刻を0秒として、クリームタイム、ゲルタイムおよびタックフリータイムを評価した。
クリームタイム(CT)(秒):ポリオールとポリイソシアネートとの混合液が泡立ちを始めるまでの時間。
タックフリータイム(TFT)(秒):発泡が終了し、フォームにベトツキが無くなるまでの時間。
コア密度:JIS K-6400記載の方法により測定を実施した。JIS規格での見かけ密度を指す。本発明では、フォームサンプルから直方体フォームサンプルを切り出したものを測定サンプルとした。
熱伝導率:JIS A-1412-2に従い、Anacon社製モデルTCA-8を用いて測定した。
圧縮強度:JIS K-7220、硬質発泡プラスチック-硬質材料の圧縮試験-に従い、発泡したフォームを80×80×40mmに切断し、発泡方向と平行な方向の圧縮強度を測定した。
低温寸法変化率:80mm×80mm×20mmの硬質ポリウレタンフォーム試験片を-30℃の恒温室内に48時間静置した後の試験片寸法変化率を測定して求めた。
(ポリエーテルポリオールの調製)
ジエチレングリコール600g(多価アルコール中27.0モル%)と水酸化ナトリウム22.6gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度250℃まで昇温した。昇温後グリセリン1406g(多価アルコール中73.0モル%)を5時間かけて滴下し、さらに常圧にて18時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した。このポリエーテルポリオールの水酸基価は806mgKOH/gであった。
このポリエーテルポリオール750gと純度72.1%のオレイン酸(和光純薬工業製)424.6gとを、凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.1g仕込んだ。反応温度200℃にて15時間エステル化反応を実施した後、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。得られたポリエーテルエステルポリオール(1)は褐色のにごった液体であり、水酸基価は420mgKOH/g、酸価0.39mgKOH/g、25℃での粘度は2670mPa・sであった。また、このポリオールの平均官能基数は3.8であった。
下記表1に記載した組成にて、レジンプレミックス組成物を調製し、密閉可能なガラス瓶に密閉して25℃で1週間保管した。その後、目視にてレジンプレミックス組成物が分離したか否かを確認した。分離が確認されなかったため、20℃に調整したこのレジンプレミックス組成物にイソシアネートとしてコスモネートM-200をNCOインデックスが110となる量で加え、攪拌翼にて5秒間攪拌した。
(ポリエーテルポリオールの調製)
ジエチレングリコール500g(多価アルコール中22.4モル%)と水酸化ナトリウム22.6gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度250℃まで昇温した。昇温後グリセリン1500g(多価アルコール中77.6モル%)を5時間かけて滴下し、さらに常圧にて18時間脱水縮合させた。その後、硫酸を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した後、110℃減圧下で4時間脱水を実施した。このポリエーテルポリオールの水酸基価は795mgKOH/gであった。
このポリエーテルポリオール750gと純度72.1%のオレイン酸(和光純薬工業製)423.3gとを、凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.1g仕込んだ。反応温度200℃にて14.5時間エステル化反応を実施した後、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。得られたポリエーテルエステルポリオール(2)は褐色のにごった液体であり、水酸基価は430mgKOH/g、酸価0.48mgKOH/g、25℃での粘度は5100mPa・sであった。また、このポリオールの平均官能基数は4.1であった。
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。
(ポリエーテルポリオールの調製)
ジエチレングリコール667g(多価アルコール中30.3モル%)と水酸化ナトリウム22.6gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度250℃まで昇温した。昇温後グリセリン1333g(多価アルコール中69.7モル%)を5時間かけて滴下し、さらに常圧にて24時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した後、110℃減圧下で4時間脱水を実施し、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。このポリエーテルポリオールの水酸基価は791mgKOH/gであった。
このポリエーテルポリオール630gと純度72.1%のオレイン酸(和光純薬工業製)373.5gとを、凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.1g仕込んだ。反応温度200℃にて13時間エステル化反応を実施した。得られたポリエーテルエステルポリオール(3)は褐色のにごった液体であり、水酸基価は424mgKOH/g、酸価0.49mgKOH/g、25℃での粘度は1990mPa・sであった。また、このポリオールの平均官能基数は3.7であった。
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。
(ポリエーテルポリオールの調製)
ジプロピレングリコール667g(多価アルコール中25.6モル%)と水酸化ナトリウム22.6gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度250℃まで昇温した。昇温後グリセリン1333g(多価アルコール中74.4モル%)を5時間かけて滴下し、さらに常圧にて18時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した後、110℃減圧下で4時間脱水を実施した。このポリエーテルポリオールの水酸基価は777mgKOH/gであった。
このポリエーテルポリオール700gと純度72.1%のオレイン酸(和光純薬工業製)379.7gとを凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.1g仕込んだ。反応温度200℃にて13.5時間エステル化反応を実施し、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。得られたポリエーテルエステルポリオール(4)は褐色のにごった液体であり、水酸基価は432mgKOH/g、酸価0.39mgKOH/g、25℃での粘度は2160mPa・sであった。また、このポリオールの平均官能基数は3.9であった。
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。
(ポリエーテルポリオールの調製)
グリセリン2024gと水酸化ナトリウム7.05gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度260℃まで昇温し常圧にて17時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した後、110℃減圧下で4時間脱水を実施し、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。このポリエーテルポリオールの水酸基価は1044mgKOH/gであった。
このポリエーテルポリオール540gと純度72.1%のオレイン酸(和光純薬工業製)496.5gとを凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.1g仕込んだ。反応温度240℃にて4時間エステル化反応を実施しポリエーテルエステルポリオールを得た。得られたポリエーテルエステルポリオール(5)は褐色のにごった液体であり、水酸基価は449mgKOH/g、酸価0.56mgKOH/g、25℃での粘度は19600mPa・sであった。また、このポリオールの平均官能基数は4.2であった。
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。
(ポリエーテルポリオールの調製)
グリセリン5060gと水酸化ナトリウム17.63gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度260℃まで昇温し常圧にて21時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した後、120℃常圧で4時間脱水を実施し、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。このポリエーテルポリオールの水酸基価は990mgKOH/gであった。
このポリエーテルポリオール2100gと純度72.1%のオレイン酸(和光純薬工業製)2163gとを凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.4g仕込んだ。反応温度240℃にて7時間エステル化反応を実施しポリエーテルエステルポリオールを得た。得られたポリエーテルエステルポリオール(6)は褐色のにごった液体であり、水酸基価は400mgKOH/g、酸価0.58mgKOH/g、25℃での粘度は15300mPa・sであった。なお、このポリオールの平均官能基数は4.6であった。
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。
(ポリエーテルポリオールの調製)
グリセリン5060gと水酸化ナトリウム17.63gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度260℃まで昇温し常圧にて27時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施した後、120℃常圧で4時間脱水を実施し、圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行った。このポリエーテルポリオールの水酸基価は951mgKOH/gであった。
実施例6で作成したポリエーテルポリオール561gとパーム核油脂肪酸(C10の飽和脂肪酸0.1%、C12の飽和脂肪酸52.3%、C14の飽和脂肪酸17.3%、C16の飽和脂肪酸9.1%、C18の飽和脂肪酸2.4%、不飽和脂肪酸18.8%含有)500gを、凝縮器を備えたフラスコに仕込み、触媒としてチタンテトラノルマルブトキシドを0.1g仕込んだ。反応温度240℃にて6.5時間エステル化反応を実施し、ポリエーテルエステルポリオールを得た。得られたポリエーテルエステルポリオール(7)は褐色透明液体であり、水酸基価は396mgKOH/g、酸価0.6mgKOH/g、25℃での粘度は14400mPa・sであった。なお、このポリオールの平均官能基数は4.5であった。
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。
(ポリエーテルポリオールの調製)
ジエチレングリコール650gと水酸化ナトリウム45.2gとを蒸留塔および凝縮器を備えたフラスコに仕込み、窒素雰囲気下、温度250℃まで昇温した。昇温後グリセリン1300gを5時間かけて滴下し、さらに常圧にて8時間脱水縮合させた。その後、シュウ酸二水和物を水酸化ナトリウムモル数に対して半分のモル数となるように加え120℃で1時間中和を実施したのち、110℃、10mmHgにて4時間脱水をし、その後圧力0.35MPaにて、5Bろ紙を用いて析出した中和塩の除去を行いポリエーテルポリオール(8)を得た。このポリエーテルポリオール(8)の水酸基価は783mgKOH/g、粘度は25℃での粘度は3050mPa・sであった。なお、このポリオールの平均官能基数は4.9であった。
表1の組成にて、レジンプレミックス組成物を調製し、25℃で1週間静置して貯蔵安定性を確認したところ分離が認められたので発泡体の調製ができなかった。
(硬質ポリウレタン発泡体の作製)
表1の組成にて、実施例1と同様にして硬質ポリウレタンフォームを調製し、各種物性を測定した。結果を表1に示す。なお、比較例2で得た発泡体は、熱伝導率が実施例で得られた発泡体と比べて高く、発泡体として劣っていた。
Claims (11)
- ポリオールおよび炭化水素系発泡剤を少なくとも含んでなるレジンプレミックス組成物であって、
前記ポリオールが、
50モル%以上の3価以上のアルコールを含む多価アルコールを縮合させて得られるポリエーテルポリオールと、脂肪酸および/または脂肪酸エステルとを反応させて得られるポリエーテルエステルポリオール(A)を含むことを特徴とするレジンプレミックス組成物。 - 前記ポリオールが、
(1)前記ポリエーテルエステルポリオール(A)を少なくとも10重量部と
(2)その他のポリオールを0~90重量部(ただし、(1)と(2)の合計を100重量部とする)を含むことを特徴とする請求項1に記載のレジンプレミックス組成物。 - 前記3価以上のアルコールが、グリセリンであることを特徴とする請求項1に記載のレジンプレミックス組成物。
- 前記多価アルコールが、グリセリンであることを特徴とする請求項1に記載のレジンプレミックス組成物。
- 請求項1~4の何れか一項に記載のレジンプレミックス組成物とポリイソシアネートとからなる硬質ポリウレタンフォーム用組成物。
- 請求項1~4の何れか一項に記載のレジンプレミックス組成物とポリイソシアネートとを反応させることにより得られる硬質ポリウレタンフォーム。
- 前記ポリエーテルエステルポリオール(A)の水酸基価が、200~600mgKOH/gであることを特徴とする請求項1~4の何れか一項に記載のレジンプレミックス組成物。
- 前記ポリエーテルエステルポリオール(A)の粘度が、25℃で50,000mPa・s以下であることを特徴とする請求項1~4の何れか一項に記載のレジンプレミックス組成物。
- 前記ポリエーテルエステルポリオール(A)の平均官能基数が、3以上であることを特徴とする請求項1~4の何れか一項に記載のレジンプレミックス組成物。
- 前記脂肪酸および/または脂肪酸エステルが、不飽和脂肪酸および/または不飽和脂肪酸エステルを50wt%以上含むことを特徴とする請求項1~4の何れ一項かに記載のレジンプレミックス組成物。
- 前記脂肪酸および/または脂肪酸エステルが、炭素数10~14の飽和脂肪酸および/または炭素数10~14の飽和脂肪酸のエステル化物を50wt%以上含むことを特徴とする請求項1~4の何れか一項に記載のレジンプレミックス組成物。
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KR1020157009660A KR101754063B1 (ko) | 2012-11-05 | 2013-10-31 | 레진 프리믹스 조성물, 경질 폴리우레탄 폼용 조성물 및 경질 폴리우레탄 폼 |
CN201380056364.5A CN104755557B (zh) | 2012-11-05 | 2013-10-31 | 树脂预混合组合物、硬质聚氨酯泡沫用组合物及硬质聚氨酯泡沫 |
EP13850391.7A EP2915850A4 (en) | 2012-11-05 | 2013-10-31 | COMPOSITION BASED ON RESIN PREMIXING, COMPOSITION FOR RIGID POLYURETHANE FOAM, AND RIGID POLYURETHANE FOAM |
US14/438,693 US20150299376A1 (en) | 2012-11-05 | 2013-10-31 | Resin premix composition, rigid polyurethane foaming composition and rigid polyurethane foam |
PH12015500951A PH12015500951A1 (en) | 2012-11-05 | 2015-04-28 | Resin premix composition, rigid polyurethane foaming composition and rigid polyurethane foam |
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WO2015183070A1 (en) * | 2014-05-26 | 2015-12-03 | Universiti Kebangsaan Malaysia (Ukm) | Method to produce natural oil-based polyurethane prepolymer |
WO2020195641A1 (ja) * | 2019-03-28 | 2020-10-01 | 三菱ケミカル株式会社 | ポリアルキレンエーテルグリコール組成物及びそれを用いたポリウレタンの製造方法 |
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CN110452544A (zh) * | 2019-08-21 | 2019-11-15 | 上海麦浦新材料科技有限公司 | 一种有机硅稳泡剂、硬质聚氨酯泡沫用组合物及其用途 |
US11407874B2 (en) | 2019-10-07 | 2022-08-09 | Covestro Llc | Polyol premixes, thermally insulating rigid polyurethane foams and methods for their production |
CN112831040A (zh) * | 2020-12-31 | 2021-05-25 | 烟台市顺达聚氨酯有限责任公司 | 一种合成聚酯醚多元醇的方法 |
KR102577410B1 (ko) * | 2021-02-03 | 2023-09-13 | 주식회사 풍산 | 겔화반응 시간 조절을 통한 상온에서의 폴리우레탄 폼 합성방법 |
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JPWO2014069556A1 (ja) | 2016-09-08 |
EP2915850A4 (en) | 2016-06-22 |
KR20150058348A (ko) | 2015-05-28 |
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