WO2015111497A1 - Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition - Google Patents

Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition Download PDF

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Publication number
WO2015111497A1
WO2015111497A1 PCT/JP2015/050925 JP2015050925W WO2015111497A1 WO 2015111497 A1 WO2015111497 A1 WO 2015111497A1 JP 2015050925 W JP2015050925 W JP 2015050925W WO 2015111497 A1 WO2015111497 A1 WO 2015111497A1
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compound
titanium
urethane resin
group
aluminum
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PCT/JP2015/050925
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English (en)
Japanese (ja)
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岡田　貴之
浩志 坂根
和則 難波
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日東化成株式会社
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Priority to JP2015513939A priority Critical patent/JP5894704B2/ja
Publication of WO2015111497A1 publication Critical patent/WO2015111497A1/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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds

Definitions

  • the present invention relates to a catalyst for producing a urethane resin, a urethane resin composition produced in the presence of the catalyst, and a method for producing the urethane resin composition.
  • silicone rubber silicone rubber, urethane rubber, polysulfide rubber and the like are known.
  • urethane rubber is widely used as a flooring material, a waterproofing agent for coating film, a casting material, a sealing material and the like because it has economical efficiency and excellent elasticity.
  • the first part contains the polyol and in most cases the catalyst and other conventional additives, and the second part contains the polyisocyanate crosslinker.
  • the two liquids are usually mixed immediately before application of the coating. When the two liquids are mixed, a chemical reaction between the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate begins and eventually gels.
  • Metal catalysts and tertiary amines are used as catalysts for urethane resins.
  • Tertiary amines promote the reaction to form urethane bonds from polyols and organic polyisocyanates, while water and organic polyisocyanates. It is usually used for urethane foam because it has the effect of promoting the reaction with carbon dioxide and generating carbon dioxide gas.
  • metal catalysts are mainly used in the non-foamed urethane field because they promote the urethanization reaction.
  • organic tin compounds organic carboxylic acid tin salts, lead carboxylates, bismuth carboxylates, titanium compounds, zirconium compounds and the like are generally used. These compounds are economical in terms of quantitative levels to be used, discoloration of the resulting urethane cured composition, other side effects are minimal, and are particularly excellent in terms of high catalytic activity. It is considered a standard catalyst and is used in a wide range of applications.
  • Bismuth organic carboxylate is excellent in that it has little environmental toxicity and does not significantly change the physical properties of the cured product (Patent Documents 1 to 4).
  • the pot life is relatively short due to its high activity, and if the amount of catalyst slightly varies due to measurement errors during adjustment of the cured composition, the pot life greatly fluctuates accordingly. End up. If this pot life is short, the cured composition starts to gel or harden before construction, and if it is long, it affects the moldability and physical properties after enforcement, and thus there are various problems during construction.
  • Patent Documents 5 to 7 propose a urethane cured composition using a urethane prepolymer in order to solve the problem of pot life when a bismuth carboxylate salt is used.
  • Patent Document 8 proposes an attempt to prepare a pot life with a mixed catalyst system.
  • the pot life is greatly affected by the slight variation in the amount of the curing catalyst blended in the urethane cured composition, a stable pot life cannot be obtained as described in these publications, which is not practical.
  • Titanium compounds and zirconium compounds have a relatively high urethanization activity, and the development of new catalysts has become active. Examples of these include a tetradiketone complex of zirconium containing a ⁇ -diketone ligand having 7 or more carbon atoms (Patent Document 9), a zirconium compound having a specific ⁇ -diketone ligand and an allyloxy group (Patent Document 10). ), A zirconium compound having a ketoamide ligand (Patent Document 11), a mixture of a titanium alkoxide and a coordinating compound such as a ketone, aldehyde, or carboxylic acid (Patent Document 12).
  • these zirconium compounds and titanium compounds have high initial activity, they are easily decomposed by the moisture contained in the polyols, additives and fillers in the composition, and the curing rate varies depending on the humidity during construction. Or sufficient curability may not be obtained. Further, since the catalyst activity is strong, the color tone of the resin obtained when the polymer residence time or the polycondensation time is long or after annealing is deteriorated. In addition, the titanium compound has a strong tendency to be colored from yellow to red, and this may shift to a resin and increase the initial color tone. Because of these problems, there are cases where it cannot be used particularly in clear paints.
  • JP-A-56-155220 Japanese Patent Laid-Open No. 11-60678 Japanese Patent Publication No. 5-56769 US 3714077 Japanese Patent Laid-Open No. 4-65417 Japanese Patent Laid-Open No. 02-258877 Japanese Unexamined Patent Publication No. 03-91520 Japanese Patent Laid-Open No. 04-227620 JP-T-2001-524142 JP 2007-197506
  • a Special table 2008-545058 gazette Japanese Patent No. 4041459 Japanese Patent Laid-Open No. 11-60678 Japanese Patent Publication No. 5-56769 US 3714077 Japanese Patent Laid-Open No. 4-65417 Japanese Patent Laid-Open No. 02-258877 Japanese Unexamined Patent Publication No. 03-91520 Japanese Patent Laid-Open No. 04-227620 JP-T-2001-524142 JP 2007-197506
  • the present invention has been made for the purpose of solving the problems of the prior art in view of the above points. That is, the problem to be solved by the present invention shows high stability when stored with a curing agent component.
  • Another object of the present invention is to provide a urethane resin production catalyst for producing a urethane resin having a good color tone.
  • a urethane resin production catalyst containing a titanium compound A having at least one Ti—O—Ti bond and an aluminum compound B having at least one Al—O—Al bond.
  • a titanium compound having a Ti—O—Ti bond portion and an Al—O—Al bond as a polycondensation catalyst in the polycondensation reaction of a urethane resin.
  • the catalyst for producing a urethane resin of the present invention contains a titanium compound A having at least one Ti—O—Ti bond and an aluminum compound B having at least one Al—O—Al bond.
  • the titanium compound A used in the present invention is a compound having at least one Ti—O—Ti bond, and the number of titanium atoms in the titanium compound A is preferably 2 to 15, more preferably 2 to 10, and still more preferably. Is 2 to 8, specifically, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15. Any of the numerical values exemplified here Or within a range between the two.
  • the titanium compound preferably includes a titanium structural unit composed of at least one Ti—O—Ti bond and at least one Ti—R 1 bond.
  • R 1 each independently represents a mono- or polyvalent alkoxy group having 1 to 10 carbon atoms, a phenoxy group, a benzyloxy group, an amino group-containing mono- or polyvalent alkoxy group, or a carboxylic acid residue having 2 to 18 carbon atoms. Or a triorganosiloxy group having 2 to 18 carbon atoms.
  • R 1 is a polyvalent alkoxy group and an amino group-containing polyvalent alkoxy group, a plurality of R 1 may be linked by a polyvalent alkoxy group.
  • Examples of the mono- or polyvalent alkoxy group having 1 to 10 carbon atoms represented by R 1 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, Examples include pentyloxy group, hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, ethylene-1,2-dioxy group, cyclohexyloxy group and the like.
  • Examples of the amino group-containing monoalkoxy group or polyvalent alkoxy group include 2-aminoethoxy group and aminotriethoxy group.
  • Examples of the carboxylic acid residue having 2 to 18 carbon atoms include acetate, lactate, 2-ethylhexanoate, neodecanate, laurate, oleate, and stearate.
  • Examples of the triorganosiloxy group having 2 to 18 carbon atoms include trimethylsiloxy group, triethylsiloxy group, triisopropylsiloxy group, triphenylsiloxy group and the like.
  • the carbon number of the alkoxy group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the carbon number of the carboxylic acid residue or the triorganosiloxy group is, for example, 2, 3 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18. These carbon numbers are between any two of the numerical values exemplified here. It may be within the range.
  • the number of titanium atoms contained in the titanium structural unit is preferably 2 to 5, for example 2, 3, 4, or 5, and is within a range between any two of the numerical values exemplified here. Also good.
  • the number of titanium structural units contained in the titanium compound A is preferably 1 to 3, for example 1, 2 or 3. When the titanium compound A includes a plurality of titanium structural units, these titanium structural units are bonded by a polyvalent alkoxy group or the like.
  • the titanium structural unit is preferably represented by the general formula (1) and / or the general formula (2).
  • X is —R 1 , —O—Ti—X 3 .
  • a represents an integer of 1 to 3.
  • b represents an integer of 0 to 3.
  • X may be —R 1 or —O—Ti—X 3 .
  • a titanium atom is bonded to the X position via an oxygen atom, and three X atoms are bonded to the titanium atom.
  • X may be —R 1 or —O—Ti—X 3 .
  • X is interpreted recursively.
  • the number of titanium atoms contained in the titanium structural unit is 2 to 5, the recursion of X is not repeated infinitely.
  • titanium compound represented by the formula (1) or (2) specifically, Hexamethoxymonotitanoxane, octamethoxydititanoxane, decamethoxytrititanoxane, dodecamethoxytetratitanoxane, Hexaethoxymonotitanoxane, octaethoxydititanoxane, decaethoxytrititanoxane, dodecaethoxytetratitanoxane, Hexaisopropoxymonotitanoxane, octaisopropoxydititanoxane, decaisopropoxytrititanoxane, dodecaisopropoxytetratitanoxane, Hexabutoxy monotitanoxane, octabutoxy dititanoxane, decabutoxy trititanoxane, dodecabutoxy tetratitanoxane,
  • titanium compounds can be synthesized by known methods. For example, 1 to 11 mol of water is added to 1 mol of tetraalkoxytitanium in the presence or absence of a solvent and reacted at 60 to 100 ° C. for 0.5 to 3 hours to distill alcohol derived from tetraalkoxytitanium. It can be synthesized by the method of leaving. In addition, after synthesizing the titanoxane compound by the above-described method, an alcohol other than the alcohol bonded to the tetraalkoxytitanium is added at an arbitrary ratio and reacted at 60 to 100 ° C. for 0.5 to 3 hours. It can be synthesized by a method of distilling off alcohol.
  • the aluminum compound B used in the present invention is a compound having at least one Al—O—Al bond, and the number of aluminum atoms in the aluminum compound B is preferably 2 to 15, more preferably 2 to 10, and still more preferably. Is 2 to 8, specifically, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15. Any of the numerical values exemplified here Or within a range between the two.
  • the aluminum compound preferably includes an aluminum structural unit composed of at least one Al—O—Al bond and at least one Al—R 2 bond.
  • R 2 each independently represents a mono- or polyvalent alkoxy group having 1 to 10 carbon atoms, a phenoxy group, a benzyloxy group, an amino group-containing mono- or polyvalent alkoxy group, or a carboxylic acid residue having 2 to 18 carbon atoms. Or a triorganosiloxy group having 2 to 18 carbon atoms.
  • R 2 is a polyvalent alkoxy group and an amino group-containing polyvalent alkoxy group, a plurality of R 2 may be linked by a polyvalent alkoxy group.
  • Examples of the mono- or polyvalent alkoxy group having 1 to 10 carbon atoms represented by R 2 include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, pentyl Examples thereof include an oxy group, a hexyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an ethylene glycol dioxy group, and a cyclohexyloxy group.
  • Examples of the amino group-containing mono- or polyvalent alkoxy group include 2-aminoethoxy group and 2-aminotriethoxy group.
  • Examples of the carboxylic acid residue having 2 to 18 carbon atoms include acetate, lactate, 2-ethylhexanoate, neodecanate, laurate, oleate, and stearate.
  • Examples of the triorganosiloxy group having 2 to 18 carbon atoms include trimethylsiloxy group, triethylsiloxy group, triisopropylsiloxy group, triphenylsiloxy group and the like.
  • the carbon number of the alkoxy group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the carbon number of the carboxylic acid residue or the triorganosiloxy group is, for example, 2, 3 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18. These carbon numbers are between any two of the numerical values exemplified here. It may be within the range.
  • the number of aluminum atoms contained in the aluminum structural unit is preferably 2 to 5, for example 2, 3, 4, or 5, and is within the range between any two of the numerical values exemplified here. Also good.
  • the number of aluminum structural units contained in the aluminum compound B is preferably 1 to 3, for example 1, 2 or 3. When the aluminum compound B includes a plurality of aluminum structural units, these aluminum structural units are bonded by a polyvalent alkoxy group or the like.
  • this aluminum structural unit is preferably represented by the general formula (3) and / or the general formula (4).
  • Y is —R 2 , —O—Al—Y 2 .
  • c represents an integer of 1 to 3.
  • d represents an integer of 0 to 3.
  • Y may be —R 2 or —O—Al—Y 2 . In the latter case, an aluminum atom is bonded to the Y position via an oxygen atom, and two Y atoms are bonded to the aluminum atom.
  • Y may be —R 2 or —O—Al—Y 2 .
  • Y is interpreted recursively. However, since there is a limitation that the number of aluminum atoms contained in the aluminum structural unit is 2 to 5, the recursion of Y is not repeated infinitely.
  • aluminum compound represented by the general formula (3) or (4) include: Tetraisopropoxymonoaluminoxane, pentaisopropoxydialuminoxane, hexaisopropoxytrialuminoxane, Tetrabutoxy monoaluminoxane, pentaboxydialuminoxane, hexabutoxytrialuminoxane, Tetra (2-ethylhexyloxy) monoaluminoxane, penta (2-ethylhexyloxy) dialuminoxane, hexa (2-ethylhexyloxy) trialaluminoxane,
  • Tetrabenzyloxymonoaluminoxane pentabenzyloxydialuminoxane, hexabenzyloxytrialuminoxane, Tetra (2-aminoethoxy) monoaluminoxane, penta (2-aminoethoxy) dialuminoxane, hexa (2-aminoethoxy) trialuminoxane,
  • Tetraacetyloxymonoaluminoxane isopropoxytriacetyloxymonoaluminoxane, diisopropoxydiacetyloxymonoaluminoxane, triisopropoxyacetyloxymonoaluminoxane, Tetra (2-ethylhexanoyl) oxymonoaluminoxane, isopropoxytriacetyloxymonoaluminoxane, diisopropoxydiacetyloxymonoaluminoxane, triisopropoxyacetyloxymonoaluminoxane, Tetraneodecanoyloxy monoaluminoxane, isopropoxy trineodecanoyloxy monoaluminoxane, diisopropoxy dineodecanoyloxy monoaluminoxane, triisopropoxyneodecanoyloxy monoaluminoxane,
  • Tetra (trimethylsiloxy) monoaluminoxane penta (trimethylsiloxy) dialuminoxane, hexa (trimethylsiloxy) trialuminoxane, Tetra (triisopropylsiloxy) monoaluminoxane, penta (triisopropylsiloxy) dialuminoxane, hexa (triisopropylsiloxy) trialuminoxane, Tetra (triphenylsiloxy) monoaluminoxane, penta (triphenylsiloxy) dialuminoxane, hexa (triphenylsiloxy) trialuminoxane, Etc.
  • monoaluminoxane compounds and dialuminoxane compounds are preferred from the viewpoint of ease of production and ease of handling of the compounds, and monoaluminoxane compounds are particularly preferred.
  • These aluminum compounds can be synthesized by known methods. For example, 1 to 11 mol of water is added to 1 mol of trialkoxyaluminum in the presence or absence of a solvent and reacted at 60 to 100 ° C. for 0.5 to 3 hours to distill alcohol derived from trialkoxyaluminum. It can be synthesized by the method of leaving. In addition, after synthesizing the aluminoxane compound by the above-mentioned method, an alcohol other than the alcohol bonded to trialkoxyaluminum is added at an arbitrary ratio, and reacted at 60 to 100 ° C. for 0.5 to 3 hours. It can be synthesized by a method of distilling off alcohol.
  • the content ratio of the titanium compound A and the aluminum compound B is preferably such that the ratio of titanium atom to aluminum atom in each compound is in the range of 9/1 to 1/9 in terms of molar ratio. When it is in the above range, the colorability of the urethane resin is reduced, and good curability can be obtained.
  • This molar ratio is preferably 8/2 to 2/8, more preferably 7/3 to 3/7, and still more preferably 6/4 to 4/6.
  • the amount used when the titanium compound A and the aluminum compound B of the present invention are used for producing a polyurethane resin is the sum of the titanium compound A and the aluminum compound B when the active hydrogen-containing organic compound used is 100 parts by mass. Is usually in the range of 0.001 to 20 parts by mass, preferably in the range of 0.01 to 10 parts by mass.
  • the catalyst for production of the urethane resin composition of the present invention can contain components other than the titanium compound A and the aluminum compound B, and can contain additives such as the following other curing catalysts, for example.
  • the catalyst for production of the urethane resin composition of the present invention can be used as a curing catalyst in a one-pack type or two-pack type urethane resin (curable) composition.
  • a urethane resin (curable) composition is used for a sealing agent, an adhesive, and the like.
  • the polyurethane resin composition of the present invention is obtained by reacting a main agent component and a curing agent component in the presence of the urethane resin production catalyst.
  • an active hydrogen-containing organic compound is used, and is not particularly limited as long as it is generally used for the production of urethane.
  • polyether polyol, polyester polyol, polymer polyol, Examples include flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols. These polyols can be used alone, or can be used by appropriately mixing them.
  • polyether polyol for example, ethylene glycol, propylene glycol, glycerin, pentaerythritol, ethylenediamine, ethanolamine, diethanolamine and the like are used as initiators.
  • examples thereof include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran or the like.
  • polyester polyol examples include a polybasic carboxylic acid such as maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid, and a polyhydric alcohol.
  • a polyhydric alcohol examples thereof include those obtained by a condensation reaction and polymers of lactones.
  • the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, and 1,6-hexane.
  • the lactone polymer include those obtained by ring-opening polymerization of ⁇ -caprolactam, ⁇ -methyl- ⁇ -caprolactam, ⁇ -methyl- ⁇ -caprolactam, and the
  • polymer polyol examples include, for example, a polymerizable monomer containing a hydroxyl group such as hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane acrylic acid monoester, or a monomer copolymerizable with these, such as acrylic acid. And compounds obtained by polymerization or copolymerization with methacrylic acid, styrene, acrylonitrile, ⁇ -methylstyrene and the like.
  • a polymerizable monomer containing a hydroxyl group such as hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane acrylic acid monoester, or a monomer copolymerizable with these, such as acrylic acid.
  • a polymerizable monomer containing a hydroxyl group such as hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane acrylic acid monoester, or a monomer
  • Examples of the flame retardant polyol include a phosphorus-containing polyol obtained by adding alkylene oxide to a phosphoric acid compound, a polyol obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide, a polyether polyol, a polyester polyol, and an acrylic polyol. And halogen-containing polyols in which the hydrogen atoms are partially or completely substituted with fluorine atoms.
  • These polyols usually have a weight average molecular weight (M w ) in the range of 62 to 15000.
  • M W weight average molecular weight
  • the flexible polyurethane foam those having a molecular weight (M W ) in the range of 1000 to 15000 are usually used, and polyether polyols and polymer polyols having a molecular weight (M W ) in the range of 3000 to 15000 are preferable.
  • M W molecular weight
  • M W molecular weight
  • M W molecular weight
  • M W molecular weight
  • M W molecular weight
  • More preferred is a flexible polyurethane foam using a polyether polyol and a polymer polyol in combination.
  • the polymer polyol has the effect of increasing the strength (hardness and elasticity) of the resin and facilitates molecular design.
  • a weight average molecular weight (Mw) shows the weight average molecular weight (polystyrene conversion) by GPC.
  • the rigid polyurethane foam those having a weight average molecular weight (M W ) in the range of 62 to 8000 are usually used, and a polyether polyol having a molecular weight (M W ) in the range of 62 to 1500 is preferable.
  • the polyol for the rigid polyurethane foam those having a large number of functional groups (4 to 8) and having a low molecular weight are preferred.
  • an isocyanate component is used and is not particularly limited as long as it is generally used.
  • Alkylene diisocyanate bis (isocyanatemethyl) cyclohexane, cyclopentane diisocyanate, cyclohexane diisocyanate, cycloalkylene diisocyanate such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, diphenyl ether diisocyanate, aromatic diisocyanate, xylylene diisocyanate, diisocyanate Diethylbenze Polymerized polyisocyanates such as diisocyanate dimers and trimers, such as araliphatic diisocyanates such as triisocyanate such as triphenylmethane triisocyanate, triisocyanate benzene, triisocyanate toluene, tetraisocyanate such as diphenyldimethylmethane tetraisocyanate Low molecular active hydrogen-containing organic compounds such as ethylene glyco
  • the polyurethane resin composition of the present invention further includes other curing catalysts, foaming agents, fillers, surfactants, colorants, plasticizers, curing retarders, anti-sagging agents, anti-aging agents, solvents, and various titanate types. Or you may add adhesion imparting agents, such as a silane coupling agent, the reaction product of a coupling agent, and an isocyanate, an ultraviolet absorber, etc.
  • other curing catalysts in the polyurethane resin composition of the present invention, other curing catalysts other than the titanium compound can be used in combination without departing from the gist of the present invention.
  • other curing catalysts include known acidic components, organometallic catalysts, tertiary amine catalysts, and quaternary ammonium salt catalysts.
  • the acidic component for example, one or more kinds of saturated or unsaturated linear or branched aliphatic carboxylic acids having 2 to 18 carbon atoms are preferably used.
  • saturated aliphatic carboxylic acids such as acetic acid, propionic acid, caproic acid, caprylic acid, octylic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, linolenic acid
  • unsaturated aliphatic carboxylic acids such as arachidonic acid, and saturated or unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid.
  • an acidic component is used in combination, it is preferably blended in an amount of 40 to 60% by mass with respect to the tin compound.
  • organometallic catalyst examples include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel octoate, cobalt octoate, and iron octoate.
  • tertiary amines include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ′′, N '' -Pentamethyldiethylenetriamine, N, N, N ′, N ′′, N ′′ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ′′, N ′′ -pentamethyldi Propylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] ]
  • Undecene-7 triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methyl
  • Examples of the quaternary ammonium salt catalyst include tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, and tetraalkylammonium 2-ethylhexanoate. Examples include alkylammonium organic acid salts. Among these, in the polyurethane resin composition of the present invention, a tertiary amine catalyst is preferably used in combination with the titanium compound A and the aluminum compound B.
  • the foaming agent is water and / or a low boiling point organic compound.
  • the low boiling point organic compound include low boiling point organic compounds such as hydrocarbons and halogenated hydrocarbons.
  • specific examples of the hydrocarbons include known methane, ethane, propane, butane, pentane, hexane and the like.
  • Specific examples of the halogenated hydrocarbons include known halogenated methanes, halogenated ethanes, and fluorinated hydrocarbons (eg, methylene chloride, HCFC-141b, HFC-245fa, HFC-356mfc, etc.). It is done.
  • water and a low-boiling organic compound may be used alone or in combination, but water is a particularly preferable foaming agent in terms of the environment.
  • the amount used varies depending on the density of the target product, but is usually 0.1 parts by mass or more, preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the polyol.
  • filler examples include calcium carbonate, kaolin, talc, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, shirasu balloon, and glass fiber. , Asbestos, glass filament, pulverized quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium dioxide, and the like.
  • the surfactant is not particularly limited, and for example, a conventionally known organosilicone surfactant is preferable, and the amount used is usually 0.1 to 100 parts by mass of the polyol. The range is 10 parts by mass.
  • Coloring agent Specifically, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, and the like are used as the colorant.
  • plasticizer examples include phthalates such as dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, and butyl benzyl phthalate, dioctyl adipate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, and butyl oleate.
  • Aliphatic carboxylic acid esters such as pentaerythritol ester, phosphate esters such as trioctyl phosphate, tricresyl phosphate, epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate, chlorinated paraffin, etc. used.
  • the manufacturing method of the polyurethane resin composition of the present invention uses a catalyst containing the titanium compound A and the aluminum compound B, and the main component and the curing agent component are not particularly limited.
  • the active hydrogen-containing organic compound (main component), the titanium compound A and the aluminum compound B (curing catalyst) are sufficiently kneaded and uniformly dispersed, and then the isocyanate component ( Examples thereof include a method of producing a polyurethane resin composition by mixing and reacting a curing agent component).
  • the ratio of the active hydrogen-containing organic compound and the curing catalyst in the production process is preferably in the range of 0.001 to 20 parts by mass with respect to the former 100 parts by mass, from the viewpoint of obtaining a good curing rate. A range of ⁇ 10 parts by mass is more preferred.
  • the blending ratio of the active hydrogen-containing organic compound and the isocyanate component in the production process is not particularly limited, but is represented by an isocyanate index (isocyanate group / active hydrogen group capable of reacting with an isocyanate group ⁇ 100). 50 to 800 is preferable, and 70 to 400 is more preferable. Within this range, the resin strength is good, and the possibility of remaining unreacted isocyanate groups also decreases.
  • the mixture was concentrated to a final pressure of 80 ° C. and a reduced pressure of 40 torr or less to obtain 261.45 g (95%) of a light yellow liquid titanium compound a4.
  • the appearance of absorption of Ti—O—Ti (775 to 785 cm ⁇ 1 ) that does not exist in the raw material tetrabutoxy titanium can be confirmed by FT-IR, and the Ti content measured by the ICP method is 9.0. % Substantially coincided with the theoretical Ti content of 8.7%, confirming the formation of hexabutoxymonotitanoxan.
  • the mixture was concentrated to a final pressure of 80 ° C. and a reduced pressure of 40 torr or less to obtain 216.75 g (95%) of a light yellow liquid titanium compound a5.
  • the appearance of absorption of Ti—O—Ti (775 to 785 cm ⁇ 1 ) that does not exist in the raw material tetrabutoxy titanium can be confirmed by FT-IR, and the Ti content measured by the ICP method is 19.3. % Substantially coincided with the theoretical Ti content of 18.9%, confirming the formation of octabutoxydititanoxane.
  • Production Example 7 Production of aluminum compound b1 204.24 g (1 mol) of triisopropoxyaluminum and 104.24 g of isopropanol were weighed into a 1000 ml eggplant-shaped flask equipped with a nitrogen introduction tube, and mixed in advance while stirring with a magnetic stirrer. A solution of 9.01 g (0.5 mol) of water and 100 g of isopropanol was added dropwise. After the exotherm subsided, the mixture was heated to 90 to 100 ° C. and isopropanol was distilled off at normal pressure for 1 hour. Subsequently, isopropanol was distilled off under reduced pressure. Concentration was carried out to a final pressure of 80 ° C.
  • Production Example 8 Production of aluminum compound b2 To a 1000 ml eggplant-shaped flask equipped with a nitrogen introduction tube, weighed 306.36 g (1.5 mol) of triisopropoxyaluminum and 206.36 g of isopropanol, and stirred them with a magnetic stirrer. A premixed solution of 18.02 g (1 mol) of water and 100 g of isopropanol was added dropwise. After the exotherm subsided, the mixture was heated to 90 to 100 ° C. and isopropanol was distilled off at normal pressure for 1 hour. Subsequently, isopropanol was distilled off under reduced pressure. Concentration was carried out to a final pressure of 80 ° C.
  • Production Example 9 Production of aluminum compound b3 To a 1000 ml eggplant-shaped flask equipped with a nitrogen inlet tube, 245.09 g (1.2 mol) of triisopropoxyaluminum and 144.09 g of isopropanol were weighed and stirred with a magnetic stirrer. A premixed solution of 16.22 g (0.9 mol) of water and 100 g of isopropanol was added dropwise. After the exotherm subsided, the mixture was heated to 90 to 100 ° C. and isopropanol was distilled off at normal pressure for 1 hour. Subsequently, isopropanol was distilled off under reduced pressure. The mixture was concentrated to a final pressure of 80 ° C.
  • Production Example 10 Production of aluminum compound b4 To a 1000 ml eggplant-shaped flask equipped with a nitrogen introduction tube, weigh 204.32 g (1 mol) of triisopropoxyaluminum and 222.36 g (3 mol) of n-butanol, and stir with a magnetic stirrer. The mixture was heated to reflux for 1 hour. After cooling until the reflux subsided, a premixed solution of 9.01 g (0.5 mol) of water and 100 g of isopropanol was added dropwise. After the exotherm subsided, the mixture was heated to 90 to 100 ° C. and isopropanol was distilled off at normal pressure for 1 hour.
  • Production Example 11 Production of Titanium Compound a7 233.13 g (0.5 mol) of a pale yellow transparent liquid titanium compound a1 synthesized by the method of Production Example 1 was weighed into a 1000 ml eggplant type flask equipped with a nitrogen introduction tube, While stirring with a tic stirrer, 324.42 g (3 mol) of benzyl alcohol was added and reacted at 100 to 120 ° C., and isopropyl alcohol as a reaction byproduct was distilled off at normal pressure. Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium compound a7.
  • the compound was analyzed by FT-IR, absorption of Ti-O-Ti in 775 ⁇ 785cm -1, 1600cm -1 derived from benzyl alcohol, it was confirmed the absorption of phenyl group near 1500 cm -1. Further, the disappearance of the absorption of the hydroxyl group around 3630 cm ⁇ 1 derived from benzyl alcohol was confirmed. Furthermore, the formation of hexabenzyloxymonotitanoxane was confirmed by the fact that the Ti content of 12.2% measured by the ICP method substantially coincided with the theoretical Ti content of 12.7%.
  • Production Example 12 Production of Titanium Compound a8 233.13 g (0.5 mol) of a pale yellow transparent liquid titanium compound a1 synthesized by the method of Production Example 1 was weighed into a 1000 ml eggplant type flask equipped with a nitrogen inlet tube, While stirring with a tic stirrer, 15.52 g (0.25 mol) of ethylene glycol was added and reacted at 100 to 120 ° C., and the reaction by-product isopropyl alcohol was distilled off at normal pressure. Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium compound a8.
  • This compound was analyzed by FT-IR, and absorption of Ti—O—Ti was confirmed at 775 to 785 cm ⁇ 1 . Further, disappearance of absorption of a hydroxyl group near 3630 cm ⁇ 1 derived from ethylene glycol was confirmed. Furthermore, the formation of bis (pentaisopropoxymonotitanoxane) ethylene glycolate was confirmed by the fact that the Ti content 22.4% measured by the ICP method almost coincided with the theoretical Ti content 21.9%.
  • Production Example 13 Production of Titanium Compound a9 233.13 g (0.5 mol) of a pale yellow transparent liquid titanium compound a1 synthesized by the method of Production Example 1 was weighed into a 1000 ml eggplant type flask equipped with a nitrogen introduction tube, While stirring with a tic stirrer, 24.86 g (0.17 mol) of triethanolamine was added and reacted at 100 to 120 ° C., and isopropyl alcohol as a reaction byproduct was distilled off at normal pressure. Further, the mixture was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium compound a9.
  • This compound was analyzed by FT-IR, and absorption of Ti—O—Ti at 775 to 785 cm ⁇ 1 and absorption of methylene adjacent to the tertiary amino group in the vicinity of 1425 cm ⁇ 1 derived from triethanolamine were confirmed. Further, the disappearance of absorption of a hydroxyl group in the vicinity of 3630 cm ⁇ 1 derived from triethanolamine was confirmed. Furthermore, since the Ti content 21.5% measured by the ICP method almost coincided with the theoretical Ti content 21.0%, tris (pentaisopropoxymonotitanoxane) -N, N, N-triethyleneoxy Production of amine was confirmed.
  • Production Example 14 Production of Titanium Compound a10 233.13 g (0.5 mol) of a pale yellow transparent liquid titanium compound a1 synthesized by the method of Production Example 1 was weighed into a 1000 ml eggplant-shaped flask equipped with a nitrogen inlet tube, While stirring with a tic stirrer, 344.52 g (2 mol) of neodecanoic acid was added and reacted at 100 to 120 ° C., and the reaction by-product isopropyl alcohol was distilled off at normal pressure. Further, it was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium compound a10.
  • This compound was analyzed by FT-IR, and absorption of Ti—O—Ti at 775 to 785 cm ⁇ 1 and absorption of the carbonyl group of neodecanoic acid bonded to titanium were confirmed around 1550 cm ⁇ 1 . Further, the disappearance of the absorption of the carbonyl group around 1770 cm ⁇ 1 derived from neodecanoic acid was confirmed. Furthermore, the formation of diisopropoxytetraneodecanoyloxymonotitanoxan was confirmed by the fact that the Ti content 10.8% measured by the ICP method almost coincided with the theoretical Ti content 10.5%.
  • Production Example 15 Production of Titanium Compound a11 233.13 g (0.5 mol) of a pale yellow transparent liquid titanium compound a1 synthesized by the method of Production Example 1 was weighed into a 1000 ml eggplant-shaped flask equipped with a nitrogen introduction tube, While stirring with a tic stirrer, 523.08 g (3 mol) of triisopropylsilanol was added and reacted at 100 to 120 ° C., and isopropyl alcohol as a reaction byproduct was distilled off at normal pressure. Further, it was concentrated under reduced pressure at 100 ° C. to obtain a light yellow transparent liquid titanium compound a11.
  • This compound was analyzed by FT-IR, and absorption of Ti—O—Ti was confirmed at 775 to 785 cm ⁇ 1 . Further, the disappearance of absorption of a hydroxyl group around 3600 cm ⁇ 1 derived from triisopropylsilanol was confirmed. Furthermore, the formation of hexa (triisopropylsiloxy) monotitanoxan was confirmed by confirming that the Ti content 8.6% measured by the ICP method substantially coincided with the theoretical Ti content 8.3%.
  • Production Example 16 Production of Aluminum Compound b5
  • DBDG diethylene glycol dibutyl ether
  • 216.28 g (2 mol) of benzyl alcohol was added, and the mixture was reacted at 100 to 120 ° C. while stirring with a magnetic stirrer to distill off isopropyl alcohol as a reaction by-product at normal pressure. . Further, the solution was concentrated under reduced pressure at 100 ° C. to obtain a 50% DBDG solution of a light yellow transparent aluminum compound b5.
  • the compound was analyzed by FT-IR, absorption of Al-O-Al to 800 ⁇ 850cm -1, 1600cm -1 derived from benzyl alcohol, it was confirmed the absorption of phenyl group near 1500 cm -1. Further, the disappearance of the absorption of the hydroxyl group around 3630 cm ⁇ 1 derived from benzyl alcohol was confirmed. Furthermore, the formation of tetrabenzyloxymonoaluminoxane was confirmed by confirming that the Al content of 5.7% measured by the ICP method substantially coincided with the theoretical Al content of 5.4%.
  • Production Example 17 Production of aluminum compound b6
  • a white solid aluminum compound b1 synthesized by the method of Production Example 7 in a 1000 ml eggplant-shaped flask equipped with a nitrogen introduction tube was mixed with 233.13 g (0.5 mol), diethylene glycol dibutyl ether (DBDG). 138.63 g was added, ethylene glycol g (0.25 mol) was added, and the mixture was reacted at 100 to 120 ° C. while stirring with a magnetic stirrer to distill off isopropyl alcohol as a reaction by-product at normal pressure. .
  • the solution was further concentrated under reduced pressure at 100 ° C. to obtain a 50% DBDG solution of a light yellow transparent aluminum compound b6.
  • This compound was analyzed by FT-IR, and absorption of Al—O—Al was confirmed at 800 to 850 cm ⁇ 1 . Further, disappearance of absorption of a hydroxyl group near 3630 cm ⁇ 1 derived from ethylene glycol was confirmed. Furthermore, the production of bis (triisopropoxymonoaluminoxane) ethylene glycolate was confirmed by the fact that the Al content of 10.0% measured by the ICP method almost coincided with the theoretical Al content of 9.8%.
  • Production Example 18 Production of Aluminum Compound b7
  • DBDG diethylene glycol dibutyl ether
  • 24.87 g (0.17 mol) of triethanolamine was added, and the mixture was allowed to react at 100 to 120 ° C. while stirring with a magnetic stirrer. Distilled off. Further, the solution was concentrated under reduced pressure at 100 ° C. to obtain a 50% DBDG solution of a light yellow transparent aluminum compound b7.
  • This compound was analyzed by FT-IR, and absorption of Al—O—Al at 800 to 850 cm ⁇ 1 and absorption of methylene adjacent to the tertiary amino group in the vicinity of 1425 cm ⁇ 1 derived from triethanolamine were confirmed. Further, the disappearance of absorption of a hydroxyl group in the vicinity of 3630 cm ⁇ 1 derived from triethanolamine was confirmed. Furthermore, since the Al content of 9.6% measured by the ICP method almost coincided with the theoretical Al content of 9.1%, tris (triisopropoxymonoaluminoxane) -N, N, N-triethyleneoxyamine Confirmed generation.
  • Production Example 19 Production of Aluminum Compound b8 233.13 g (0.5 mol) of white solid aluminum compound b1 synthesized by the method of Production Example 7 and diethylene glycol dibutyl ether (DBDG) were added to a 1000 ml eggplant-shaped flask equipped with a nitrogen introduction tube. 265.33 g was added, 172.26 g (1 mol) of neodecanoic acid was added, and the mixture was reacted at 100 to 120 ° C. while stirring with a magnetic stirrer, and isopropyl alcohol as a reaction by-product was distilled off at normal pressure. . Furthermore, it concentrated under 100 degreeC pressure reduction, and obtained the 50% DBDG solution of the pale yellow transparent aluminum compound b8.
  • DBDG diethylene glycol dibutyl ether
  • This compound was analyzed by FT-IR, and absorption of Al—O—Al at 800 to 850 cm ⁇ 1 and absorption of a carbonyl group of neodecanoic acid bonded to aluminum were confirmed around 1550 cm ⁇ 1 . Further, the disappearance of the absorption of the carbonyl group around 1770 cm ⁇ 1 derived from neodecanoic acid was confirmed. Furthermore, the production of diisopropoxydineodecanoyloxymonoaluminoxane was confirmed by the fact that the Al content of 5.5% measured by the ICP method almost coincided with the theoretical Al content of 5.1%.
  • Production Example 20 Production of Aluminum Compound b9
  • DBDG diethylene glycol dibutyl ether
  • 348.72 g (2 mol) of triisopropylsilanol were added and reacted at 100 to 120 ° C. while stirring with a magnetic stirrer to distill off isopropyl alcohol as a by-product at normal pressure. did.
  • the solution was further concentrated under reduced pressure at 100 ° C. to obtain a 50% DBDG solution of a light yellow transparent aluminum compound b9.
  • This compound was analyzed by FT-IR, and absorption of Al—O—Al was confirmed at 800 to 850 cm ⁇ 1 . Further, the disappearance of absorption of a hydroxyl group around 3600 cm ⁇ 1 derived from triisopropylsilanol was confirmed. Furthermore, the production of tetra (isopropylsiloxy) monoaluminoxane was confirmed by the fact that the Al content 3.8% measured by the ICP method almost coincided with the theoretical Al content 3.5%.
  • Liquid A was prepared by kneading 16 parts by mass of tolylene diisocyanate with 100 parts by mass of polypropylene glycol (Mitsui Toatsu Co., Ltd. Mitsui Polyol NM-3050, average polymerization degree 3,000, hydroxyl value 56.1 mgKOH / g). Obtained.
  • the test shown below was done using the obtained A liquid and B liquid.
  • Mitsui Polyol NM-3050 Polypropylene glycol (Mitsui Toatsu Co., Ltd.) Tolylene diisocyanate: Isocyanate (Reagent of Tokyo Chemical Industry Co., Ltd.) Sumoyle P-350: Liquid paraffin (Muramatsu Oil Co., Ltd.) Tinuvin 327: UV absorber (LF-101 manufactured by Tokyo Fine Chemical Co., Ltd.) DINP: Diisononyl phthalate (manufactured by CG Esther) Tetraisopropoxytitanium: Titanium compound (Tokyo Chemical Co., Ltd. reagent) Triisopropoxyaluminum: Aluminum compound (Kishida Chemical Co., Ltd. reagent) Sunny Cat T-100: Diisopropoxy titanium bis (ethyl acetoacetate) (manufactured by Nitto Kasei Co., Ltd.)
  • ⁇ Test method> "Preparation of long-term stability test sample”
  • the curing agent component was allowed to stand in an incubator at 50 ° C., sampled at the start and after 30 days, and the following tests were performed.
  • the urethane cured composition using the catalyst for producing the polyurethane resin of the present invention has a higher stability in the curing agent and a cured product having an excellent color tone as compared with conventionally known catalysts and the like.
  • a urethane curable composition makes it possible to obtain a polyurethane resin useful as a heat insulating material or a cushioning material as a paint, a sealing agent, a coating agent, an elastic adhesive, or a polyurethane foam.

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  • Health & Medical Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention fournit un catalyseur pour fabrication de résine uréthane destiné à fabriquer une résine uréthane qui présente une grande stabilité lors d'une conservation à l'aide d'un composant durcisseur, et dont le ton de couleur est satisfaisant. Le catalyseur pour fabrication de résine uréthane de l'invention comprend un composé titane (A) possédant au moins une partie liaison Ti-O-Ti, et un composé aluminium (B) possédant au moins une partie liaison Al-O-Al.
PCT/JP2015/050925 2014-01-21 2015-01-15 Catalyseur pour fabrication de résine uréthane, composition de résine uréthane fabriquée en présence dudit catalyseur, et procédé de fabrication de ladite composition WO2015111497A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5937754B2 (ja) * 2014-04-01 2016-06-22 日東化成株式会社 有機重合体又はオルガノポリシロキサン用硬化触媒、湿気硬化型組成物、硬化物及びその製造方法
CN114621470A (zh) * 2020-12-10 2022-06-14 柏瑞克股份有限公司 用于缩合反应的催化剂及合成催化剂的方法

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WO2003018662A1 (fr) * 2001-08-25 2003-03-06 Johnson Matthey Plc Catalyseurs et compositions durcissables
JP2006509070A (ja) * 2002-12-04 2006-03-16 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 有機金属触媒組成物及び前記触媒を用いるポリウレタン製造プロセス
JP2010530917A (ja) * 2007-06-18 2010-09-16 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー ポリウレタン製造用の水に安定な触媒
JP2011501774A (ja) * 2007-10-17 2011-01-13 ビーエーエスエフ ソシエタス・ヨーロピア 有機金属化合物を主成分とする光潜伏性触媒

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WO2003018662A1 (fr) * 2001-08-25 2003-03-06 Johnson Matthey Plc Catalyseurs et compositions durcissables
JP2006509070A (ja) * 2002-12-04 2006-03-16 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 有機金属触媒組成物及び前記触媒を用いるポリウレタン製造プロセス
JP2010530917A (ja) * 2007-06-18 2010-09-16 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー ポリウレタン製造用の水に安定な触媒
JP2011501774A (ja) * 2007-10-17 2011-01-13 ビーエーエスエフ ソシエタス・ヨーロピア 有機金属化合物を主成分とする光潜伏性触媒

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5937754B2 (ja) * 2014-04-01 2016-06-22 日東化成株式会社 有機重合体又はオルガノポリシロキサン用硬化触媒、湿気硬化型組成物、硬化物及びその製造方法
CN114621470A (zh) * 2020-12-10 2022-06-14 柏瑞克股份有限公司 用于缩合反应的催化剂及合成催化剂的方法

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