JP2014234392A - Catalyst for producing polyurethane resin and method for producing polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for producing a polyurethane resin which achieves both water resistance and high catalytic activity without using a metal causing high environmental loading, and to provide a method for producing a polyurethane resin using the catalyst.SOLUTION: There is provided a catalyst for producing a polyurethane resin, which contains a zirconium compound represented by the following general formula (1) and β-diketones. Zr(L)(1) [where Ls each independently represent a diketonate ligand represented by the structure of the following general formula (2)] [where Rand Reach independently represent an alkyl group having 2 to 10 carbon atoms; and Rrepresents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.]

Description

  The present invention relates to a catalyst useful for producing a polyurethane resin. The present invention also relates to a method for producing a polyurethane resin by reacting a polyol with an organic polyisocyanate and / or a urethane prepolymer in the presence of the catalyst and, if necessary, a solvent, a diluent, a pigment, a crosslinking agent and the like. .

  The polyurethane resin is produced by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, additives such as a foaming agent, a surfactant, and a crosslinking agent. Polyurethane resins are widely used in applications such as automobiles, architecture, home appliances, heavy anticorrosion, plastic paints, adhesives and the like because of their excellent adhesion to substrates, flexibility and weather resistance.

  Tertiary amines and metal catalysts are used as catalysts for polyurethane resin production. Tertiary amines promote water and organic reaction at the same time as promoting the reaction to form urethane bonds from polyols and organic polyisocyanates. Since it has the effect | action which accelerates | stimulates reaction with polyisocyanate and generate | occur | produces a carbon dioxide gas, it is normally used for foaming urethane use. On the other hand, metal catalysts are mainly used in the non-foamed urethane field because they promote the urethanization reaction. Aliphatic isocyanates are often used in urethane coatings and adhesives for non-foaming applications, and metal catalysts, particularly organotin compounds, have been used as catalysts from the viewpoint of reactivity. However, organotin compounds are highly toxic, and dibutyltin dilaurate (hereinafter sometimes referred to as DBTDL), which is a typical organotin catalyst, contains tributyltin, which has been pointed out as harmful as an environmental hormone. It remains a problem that it remains as an impurity.

  As an alternative catalyst for the organotin catalyst, a zirconium compound having a high activity with respect to aliphatic isocyanate, low coloring property, and low toxicity is promising, and many studies have been conducted so far.

  Improvement of reactivity has been attempted by using a tetradiketonate complex of zirconium containing a β-diketonate ligand having 7 or more carbon atoms as a urethane catalyst (see, for example, Patent Document 1). As a mixed complex containing a β-diketonate ligand, it is disclosed that a titanium / zirconium compound combining a specific β-diketonate ligand, an alkoxide group or a carboxylate group is useful as a delayed urethane catalyst. (For example, refer to Patent Document 2).

  Moreover, as a catalyst composition, it is reported that a highly active catalyst can be obtained by combining a zirconium diketonate complex and a specific amine compound (for example, refer patent document 3).

  However, since these catalysts have low water resistance, they are easily deactivated by water remaining in the polyol, so that it is extremely difficult to store them in the polyol. Further, since it is also deactivated by moisture in the air, for example, when used as a paint or sealant, there are problems that the resin is not sufficiently cured or the surface is sticky.

Special table 2001-524142 International Patent Publication No. 2004/044027 Pamphlet JP 2004-300430 A

Tetsuo Yokoyama, “Structure / Physical Properties of Polyurethanes, Higher Functionality, and Application Development” published by Technical Information Association, 1998, page 325

  The present invention has been made in view of the above-mentioned background art, and its purpose is to provide a polyurethane resin production catalyst that is compatible with water resistance and high catalytic activity and does not use a metal with a high environmental load. And it is providing the manufacturing method of the polyurethane resin using this catalyst.

  In view of the above circumstances, the present inventors have intensively studied a novel catalyst for producing a polyurethane resin, and as a result, use a composition containing a zirconium compound containing a specific β-diketonate ligand and a specific β-diketone. Thus, the inventors have found that both water resistance and high reactivity can be achieved, and have completed the present invention.

  That is, the present invention is a polyurethane resin production catalyst and a polyurethane resin production method as described below.

  [1] A polyurethane resin production catalyst comprising a zirconium compound represented by the following general formula (1) and a β-diketone represented by the following general formula (3).

Zr (L) ₄ (1)
[In the above formula (1), each L independently represents a diketonate ligand represented by the structure of the following general formula (2). ]

［上記式（２）中、Ｒ_１及びＲ_３は各々独立して炭素数２〜１０のアルキル基を表し、Ｒ_２は水素原子又は炭素数１〜７のアルキル基を表す。］

[In the above formula (2), R ₁ and R ₃ each independently represents an alkyl group having 2 to 10 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ]

［上記式（３）中、Ｒ_４及びＲ_６は各々独立して炭素数２〜１０のアルキル基を表し、Ｒ_５は水素原子又は炭素数１〜７のアルキル基を表す。］
［２］一般式（２）で示されるβ−ジケトネート配位子が、３，５−ヘプタンジオネート、３，５−オクタンジオネート及び２−メチル−３，５−ノナンジオネートからなる群より選ばれることを特徴とする上記［１］に記載のポリウレタン樹脂製造用触媒。

[In the above formula (3), R ₄ and R ₆ each independently represent an alkyl group having 2 to 10 carbon atoms, and R ₅ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ]
[2] The β-diketonate ligand represented by the general formula (2) is selected from the group consisting of 3,5-heptanedionate, 3,5-octanedionate, and 2-methyl-3,5-nonandionate. The catalyst for producing a polyurethane resin as described in [1] above.

  [3] The β-diketone represented by the general formula (3) is selected from the group consisting of 3,5-heptanedione, 3,5-octanedione and 2-methyl-3,5-nonanedione. The polyurethane resin production catalyst according to the above [1] or [2].

  [4] The molar ratio of the β-diketone represented by the general formula (3) to the zirconium compound represented by the general formula (1) (β-diketone / zirconium compound) is in the range of 0.5 to 50. The polyurethane resin production catalyst according to any one of the above [1] to [3], wherein

  [5] A method for producing a polyurethane resin, comprising reacting a polyol and an organic polyisocyanate in the presence of the polyurethane resin production catalyst according to any one of [1] to [4].

  [6] A method for producing a polyurethane resin comprising reacting a polyol and an organic polyisocyanate in the presence of the polyurethane resin production catalyst and additive according to any one of [1] to [4].

  [7] The method for producing a polyurethane resin according to the above [5] or [6], wherein the organic polyisocyanate is an aliphatic isocyanate.

  The catalyst for producing a polyurethane resin of the present invention is superior in water resistance as compared with a conventional zirconium catalyst. For this reason, since it is hard to deactivate by the water | moisture content in a polyol or air | atmosphere, high curability is obtained. Moreover, since it is not necessary to contain a heavy metal, it is easy to handle and an environmentally friendly polyurethane resin can be produced.

  Hereinafter, the present invention will be described in more detail.

  The catalyst for producing a urethane resin according to the present invention includes a zirconium compound (zirconium tetradiketone complex) represented by the general formula (1) and a β-diketone represented by the general formula (3).

  In the present invention, the zirconium compound represented by the general formula (1) contains 4 molecules of β-diketonate ligand represented by the general formula (2) in one molecule.

In the general formula (2), R ₁ and R ₃ each independently represents an alkyl group having 2 to 10 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. When either R ₁ or R ₃ is an alkyl group having 1 carbon atom (methyl group), the water resistance of the zirconium compound itself is significantly reduced.

  Although it does not specifically limit as a C2-C10 alkyl group, For example, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t -Butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3- Dimethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, 1-methylhexyl, cycloheptyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2- Propylpentyl group, cyclooctyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, , 5,5-trimethyl-hexyl group, n- decyl group.

  Although it does not specifically limit as (beta) -diketonate ligand represented by the said General formula (2), For example, 3,5-heptanedione, 3,5-octanedione, 2-methyl-3,5 -Heptanedione, 4-methyl-3,5-heptanedione, 3,5-nonanedione, 4,6-nonanedione, 2-methyl-3,5-octanedione, 2,6-dimethyl-3,5-heptanedione 7-methyl-3,5-heptanedione, 2,2-dimethyl-3,5-heptanedione, 3,5-decanedione, 4,6-decanedione, 2-methyl-3,5-nonanedione, 2,7 -Dimethyl-3,5-octanedione, 2,2-dimethyl-3,5-octanedione, 2,2,6-trimethyl-3,5-heptanedione, 3,5-undecanedione, 4,6-undeca Dione, 2-methyl-3,5-undecanedione, 2-methyl-4,6-undecanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,7-trimethyl-3,5-octanedione An anion of a β-diketone compound such as 2,2,6,6-tetramethyl-3,5-heptanedione is preferred. Of these, 3,5-heptanedionate, 3,5-octanedionate and 2-methyl-3,5-nonanedionate are particularly preferred.

  In the present invention, the zirconium compound represented by the general formula (1) is not particularly limited. Specifically, tetrakis (3,5-heptanedionate) zirconium, tetrakis (3,5-octanedionate) are used. ) Zirconium, tetrakis (2-methyl-3,5-heptanedionato) zirconium, tetrakis (4-methyl-3,5-heptanedionato) zirconium, tetrakis (3,5-nonandionato) zirconium, tetrakis (4,6-nonandionato) zirconium , Tetrakis (2-methyl-3,5-octandionato) zirconium, tetrakis (2,6-dimethyl-3,5-heptanedionato) zirconium, tetrakis (7-methyl-3,5-heptanedionato) zirconium, tetrakis (2 , 2-Dimethyl −3,5-heptanedionato) zirconium, tetrakis (3,5-decanedionato) zirconium, tetrakis (4,6-decanedionato) zirconium, tetrakis (2-methyl-3,5-nonandionato) zirconium, tetrakis (2,7-dimethyl) -3,5-octanedionate) zirconium, tetrakis (2,2-dimethyl-3,5-octanedionate) zirconium, tetrakis (2,2,6-trimethyl-3,5-heptanedionate) zirconium, tetrakis (3 , 5-Undecanedionato) zirconium, tetrakis (4,6-undecanedionato) zirconium, tetrakis (2-methyl-3,5-undecanedionato) zirconium, tetrakis (2-methyl-4,6-undecanedionato) ) Zirconium, Tet Kis (2,2-dimethyl-3,5-nonandionato) zirconium, tetrakis (2,2,7-trimethyl-3,5-octanedionate) zirconium, tetrakis (2,2,6,6-tetramethyl-3) , 5-heptanedionato) zirconium and the like. Among these zirconium compounds, tetrakis (3,5-heptanedionato) zirconium and tetrakis (3,5-octanedionato) zirconium are preferably used because of their high catalytic activity when used as a composition.

  The zirconium compound represented by the general formula (1) can be produced by a conventionally known general method. For example, zirconium tetrapropoxide or zirconium tetrabutoxide is dissolved in an appropriate solvent (for example, methylene chloride, toluene, ethyl acetate, etc.), and then a β-diketone compound as a ligand is dropped at 0 to 100 ° C. Then, it is exchanged with alkoxide by reacting for 1 to 24 hours. Next, the by-produced alcohol and solvent are distilled off under reduced pressure to obtain the target compound. Since zirconium tetraalkoxide is easily hydrolyzed, it is necessary to perform the reaction in an inert gas and use a dehydrated solvent.

  Moreover, it can manufacture similarly also using a zirconium oxychloride octahydrate as a raw material. Zirconium oxychloride octahydrate is dissolved in an appropriate solvent (for example, water, methanol, ethanol, etc.), a β-diketone compound as a ligand is dropped at room temperature, and reacted for 1 to 2 hours. By adding water and subsequently an organic base such as triethylamine, it is precipitated as a solid or liquid insoluble in water. The target product can be obtained by extracting the precipitate with a solvent such as methylene chloride and drying under reduced pressure.

  In the catalyst composition of the present invention, β-diketones represented by the above general formula (3) are used to ensure water resistance. These β-diketones stabilize the zirconium compound represented by the above general formula (1) in a chemical equilibrium and react with residual water or moisture in the atmosphere to generate a hydroxyl complex (low activity). Suppress.

In the general formula (3), R ₄ and R ₆ each independently represent an alkyl group having 2 to 10 carbon atoms, and R ₅ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. When either R ₄ or R ₆ is an alkyl group having 1 carbon atom (methyl group), the water resistance of the zirconium compound produced by ligand exchange is significantly reduced.

  Although it does not specifically limit as a C2-C10 alkyl group, For example, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t -Butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3- Dimethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, 1-methylhexyl, cycloheptyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2- Propylpentyl group, cyclooctyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, , 5,5-trimethyl-hexyl group, n- decyl group.

  The β-diketone compound represented by the general formula (3) is not particularly limited, and examples thereof include 3,5-heptanedione, 3,5-octanedione, 2-methyl-3,5-heptane. Dione, 4-methyl-3,5-heptanedione, 3,5-nonanedione, 4,6-nonanedione, 2-methyl-3,5-octanedione, 2,6-dimethyl-3,5-heptanedione, 7 -Methyl-3,5-heptanedione, 2,2-dimethyl-3,5-heptanedione, 3,5-decanedione, 4,6-decanedione, 2-methyl-3,5-nonanedione, 2,7-dimethyl -3,5-octanedione, 2,2-dimethyl-3,5-octanedione, 2,2,6-trimethyl-3,5-heptanedione, 3,5-undecanedione, 4,6-undecanedi , 2-methyl-3,5-undecanedione, 2-methyl-4,6-undecanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,7-trimethyl-3,5-octanedione 2,2,6,6-tetramethyl-3,5-heptanedione and the like. Among these β-diketones, 3,5-heptanedione, 3,5-octanedione, 2-methyl-3,5-nonanedione and 2,2-dimethyl-3,5-heptanedione are added in small amounts. It can be preferably used because it can improve water resistance.

  Although there is no restriction | limiting in particular as a synthesis method of (beta) -diketone represented by the said General formula (3), For example, it can synthesize | combine as follows. That is, a metal base such as sodium hydride, sodium ethoxide, and tertiary butoxy potassium is dissolved or dispersed in an aprotic solvent such as dimethylformamide, and a mixed solution of the corresponding ester and ketone is added dropwise to 20 to 100. The reaction (Claisen condensation) is carried out at 1 ° C. for 1 to 10 hours. After completion of the reaction, hydrochloric acid is added, and beta diketones are extracted with an organic solvent. The target β-diketone can be obtained by concentrating and distilling the organic layer.

  In the present catalyst composition, the molar ratio of the β-diketone represented by the general formula (3) to the zirconium compound represented by the general formula (1) (β-diketone / zirconium compound) is particularly limited. Although it does not do, the range of 0.5-50 is preferable, for example, More preferably, it is the range of 2-20. If the molar ratio is less than 0.5, sufficient water resistance may not be obtained, and if it exceeds 20, the catalytic activity may be lowered.

  The method for producing a polyurethane resin of the present invention is characterized in that a polyol and an organic polyisocyanate are reacted in the presence of the above-described catalyst for producing a polyurethane resin of the present invention.

  The amount of the polyurethane resin production catalyst of the present invention when used for polyurethane resin production is not particularly limited, but when the polyol is 100 parts by weight, the amount of the metal compound is in the range of 0.001 to 1 part by weight. Is preferred.

  When the polyurethane resin is produced, the catalyst for producing the polyurethane of the present invention may be used as the catalyst, and it is not necessary to use any other catalyst. However, other organometallic catalysts and tertiary amine catalysts may be used in combination with the polyurethane production catalyst of the present invention as long as it does not depart from the spirit of the present invention.

  Examples of other organometallic catalysts include, but are not limited to, for example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyl Examples thereof include organic tin catalysts such as tin dichloride and dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, and bismuth naphthenate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate.

  Further, the other tertiary amine catalyst is not particularly limited. For example, triethylenediamine, 2-methyltriethylenediamine, 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 ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethyl Isopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxyethyl) ) Ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 3-quinuclidinol, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N-methyl-N '-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2 -Methylimidazole, 1-dimethylaminopropyl Dazole, N, N-dimethylhexanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxypropyl) imidazole, 1- (2- Hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, quinuclidine, 2-methylquinuclidine and the like.

  In the present invention, when other organometallic catalyst or tertiary amine catalyst is used, the amount used is not particularly limited, but is usually 0.0001 to 5 weight when the polyol is 100 parts by weight. Parts by weight, more preferably 0.001 to 3 parts by weight.

  Since the catalyst for producing a polyurethane resin of the present invention is very highly active, the pot life may not be ensured depending on the application. In this case, the pot life can be adjusted by adding carboxylic acid as a retarder. Specific examples of effective retarders include formic acid, acetic acid, propanoic acid, octylic acid, 2-hydroxyethanoic acid (glycolic acid), 2-phenyl-2-hydroxyethanoic acid (mandelic acid), 2-hydroxypropanoic acid (Lactic acid) can be exemplified. The addition amount of these retarders depends on the required pot life and is not particularly limited, but is usually 0.01 to 100 parts by weight with respect to 1 weight of the polyurethane resin production catalyst of the present invention. The range is more preferably 0.1 to 10 parts by weight.

  In the present invention, the polyol used is not particularly limited. For example, conventionally known polyether polyols, polyester polyols, acrylic polyols, polycarbonate polyols, acrylic polyols, polybutadiene polyols, polyolefin polyols. Caprolactone-modified polyol, polyesteramide polyol, polyurethane polyol, epoxy polyol, epoxy-modified polyol, alkyd-modified polyol, castor oil, fluorine-containing polyol, and the like can be used. These polyols can be used alone or in combination as appropriate.

  Examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, and aliphatic amine compounds such as ethylenediamine. A compound having two or more active hydrogen groups such as aromatic amine compounds such as toluenediamine and diphenylmethane-4,4-diamine, alkanolamines such as ethanolamine and diethanolamine, It can be produced by addition reaction with alkylene oxides such as ethylene oxide and propylene oxide (for example, Gunter Oertel, “Polyurethane Handbook” ( (1985 edition) Hanser Publishers (Germany), p. 42-53).

  Examples of the polyester polyol include condensates of polybasic acids such as maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, adipic acid and isophthalic acid with polyhydric alcohols, wastes from the production of nylon, and trimethylolpropane. , Pentaerythrole waste, phthalic polyester waste, polyester polyol derived by treating waste, etc. (see, for example, Keiji Iwata, "Polyurethane Resin Handbook" (first edition in 1987), Nikkan Kogyo Shimbun, p. 117). Can be mentioned.

  Examples of the acrylic polyol include a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, or a lactone modified by adding a lactone such as ε-caprolactam to the hydroxyl group-containing unsaturated monomer. Examples thereof include polyols obtained by polymerizing an unsaturated monomer, or both of them, and an unsaturated monomer such as styrene, methyl acrylate, methyl methacrylate, butyl acrylate, or butyl methacrylate.

  The average molecular weight of the polyol is preferably in the range of 200 to 10,000. If the average molecular weight is less than 200, the distance between cross-linking points is short, the flexibility when used as a coating film is not sufficient, the crack resistance may be insufficient, and if it exceeds 10,000, the cross-linking density becomes low, When the coating film is used, the toughness and hardness are insufficient, and the effects of the present invention may not be exhibited.

  In the present invention, examples of the organic polyisocyanate used include aromatic diisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl diisocyanate, Aliphatic polyisocyanates such as isophorone diisocyanate, or a mixture thereof. Of these, aliphatic isocyanates are preferred for the purpose of providing excellent coating film properties and weather resistance.

  In the present invention, examples of the aliphatic isocyanate used include conventionally known isocyanates such as linear aliphatic, cycloaliphatic, and alicyclic. Specifically, hexamethylene diisocyanate (HDI), hydrogenated diphenylmethane diisocyanate (H-MDI), hydrogenated xylylene diisocyanate (H-XDI), isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI), 1,3 -Isocyanates such as bis (isocyanatemethyl) cyclohexane (H6XDI), L-lysine diisocyanate (LDI), 1,6,11-undecane triisocyanate, or dimer, trimer and burette modifications of these isocyanates And allophanate-modified bodies, and block isocyanate bodies of these organic polyisocyanate compounds are exemplified, and used alone or in combination.

  Examples of the blocked isocyanate include alcohols such as ethanol, isopropanol and n-butanol, phenols such as phenol and p-nitrophenol, lactams such as ε-caprolactam, oximes such as acetoxime and methylethylketoxime, and malonic acid. Examples include active methylene-containing compounds such as diethyl, ethyl acetoacetate, and acetylacetone that block active isocyanate groups.

  In the production method of the present invention, a urethane prepolymer can be used instead of the organic isocyanate. The urethane prepolymer is produced by reacting the aforementioned polyol and polyisocyanate. Here, the reaction is desirably performed at a high temperature, for example, the reaction is desirably performed in the range of 60 ° C to 150 ° C. The equivalent ratio of polyisocyanate to polyol is preferably set between about 0.8 and about 3.5.

  In the production method of the present invention, the isocyanate index is not particularly limited, but is usually in the range of 50 to 250, more preferably in the range of 70 to 150. If it is less than 50, there is a possibility that the crosslink density is lowered and the resin strength is lowered. The isocyanate index is defined by the total amount of isocyanate groups / total amount of hydroxyl groups (molar ratio) × 100.

  In the production method of the present invention, additives can be used as necessary. Examples of such additives include cross-linking agents or chain extenders, pigments, colorants, flame retardants, anti-aging agents, antioxidants, fillers, thickeners, thickeners, plasticizers and sagging prevention. Agents, suspending agents, antifoaming agents, UV absorbers, solvents, thixotropic agents, adsorbents, and other conventionally known additives. About the kind and addition amount of these additives, unless it deviates from a conventionally well-known form and procedure, it can fully apply to this invention in the range normally used.

  In the production method of the present invention, examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols (specifically, ethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6 -Hexanediol, glycerin, etc.), low molecular weight amine polyols (specifically, diethanolamine, triethanolamine, etc.), polyamines (specifically, ethylenediamine, diethylenetriamine, piperazine, N-aminoethylpiperazine, xylylenediamine, Methylenebisorthochloroaniline, etc.).

  In the production method of the present invention, a solvent can be used to dissolve and dilute raw materials such as isocyanate and polyol. Examples of such solvents include hydrocarbons such as toluene, xylene and mineral terpenes, esters such as ethyl acetate, butyl acetate, methyl glycol acetate and cellosolve, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, Examples include organic solvents of amides such as N, N-dimethylformamide and N, N-dimethylacetamide.

  Hereinafter, although demonstrated based on an Example and a comparative example, this invention is not limited only to these Examples. The compounds synthesized in the examples were analyzed under the following conditions.

(GC analysis conditions)
Apparatus: GC-2014 (manufactured by Shimadzu Corporation), column: DB-5 (inner diameter 0.32 mm, length 30 m, film thickness 0.25 μm) (manufactured by GL Sciences), carrier: helium, split ratio: 40, injector Temperature: 280 ° C., detection method: FID, injection amount: 1 μL, temperature program: temperature is increased from 50 ° C. to 200 ° C. at 10 ° C./min.

(Elemental analysis)
The solid sample was dissolved and the metal concentration was analyzed by ICP-AES method. Apparatus: OPTIMA 3000 DV (manufactured by PerkinElmer Japan)
The contents of carbon (C) and hydrogen (H) were measured by CHN analysis. Apparatus: 2400II (manufactured by PerkinElmer Japan).

(NMR analysis)
Using deuterated chloroform as a solvent, ¹ H and ¹³ C-NMR spectra were measured at room temperature. Apparatus: Gemini-200 (manufactured by Varian).

  The raw materials used in the examples and comparative examples are specifically shown below.

(Raw materials for metal compounds)
2,4-pentanedione: a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
3,5-heptanedione: a reagent manufactured by Aldrich Co. 6-methyl-2,4-heptanedione: a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
2,6-dimethyl-3,5-heptanedione: a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
2-methyl-3,5-nonanedione and other β-diketones: preparations,
Zirconium oxychloride octahydrate: Reagent manufactured by Kishida Chemical Co., Ltd.

(Raw material of polyurethane)
Polyoxypropylene triol: number average molecular weight 3000, hydroxyl value 56.5 mg / KOH / g (manufactured by Sanyo Kasei Co., Ltd., trade name “SANIX GP3000”),
Hexamethylene diisocyanate: Reagent manufactured by Tokyo Chemical Industry Co., Ltd.

Synthesis Example <Preparation of 2-methyl-3,5-nonanedione and other β-diketones>
67.3 g (0.6 mol) of tertiary butoxypotassium and 100.0 g of dimethylformamide were added to a flask in a nitrogen atmosphere, and heated to 50 ° C. to dissolve. To this solution, a mixed solution of 116.2 g (1.0 mol) of methyl valerate and 43.1 g (0.5 mol) of 3-methyl-2-butanone was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 5 hours.

  To the total amount of the reaction solution, 100.0 g of distilled water was added, followed by 28.0 g of 12N hydrochloric acid. After the liquid temperature returned to room temperature, 50.0 g of diethyl ether was added to recover the organic layer.

  The organic layer was concentrated and distilled under reduced pressure to obtain a pale yellow liquid. This liquid was analyzed by GC and contained 52.8 g of 2-methyl-3,5-nonanedione. The yield based on 3-methyl-2-butanone was 62%.

  Other β-diketones (3,5-octanedione, 2-methyl-3,5-heptanedione, 2,4-dimethyl-3,5-heptanedione) were prepared using the ester and ether raw materials shown in Table 1. And synthesized as above.

  The synthesis results or suppliers of diketones are summarized in Table 1.

実施例１ ＜触媒１Ａの調製＞
オキシ塩化ジルコニウム８水和物１０．０ｇ（０．０３１ｍｏｌ）をメタノール２５．０ｇに加え、続いて３，５−ヘプタンジオン１７．９０ｇ（０．１４０ｍｏｌ）を加えて均一溶液を得た。次に、蒸留水５０．０ｇさらにトリエチルアミン１０．０ｇを加えた。析出物をジクロロメタン３０．０ｇで抽出し、８０℃で減圧乾燥することで淡黄色の固体を得た。元素分析及びＮＭＲによって、得られた化合物がテトラキス（３，５−ヘプタンジオネート）ジルコニウムであることを確認した。

Example 1 <Preparation of Catalyst 1A>
Zirconium oxychloride octahydrate 10.0 g (0.031 mol) was added to methanol 25.0 g, followed by 3,5-heptanedione 17.90 g (0.140 mol) to obtain a homogeneous solution. Next, 50.0 g of distilled water and 10.0 g of triethylamine were added. The precipitate was extracted with 30.0 g of dichloromethane and dried under reduced pressure at 80 ° C. to obtain a pale yellow solid. It was confirmed by elemental analysis and NMR that the obtained compound was tetrakis (3,5-heptanedionate) zirconium.

  Elemental analysis value C: 57.2% (56.1), H: 7.8% (7.4), Zr: 14.9% (15.2). The values in parentheses represent theoretical values.

  The catalyst 1A was prepared by dissolving 2.0 g of the obtained tetrakis (3,5-heptanedionate) zirconium in 2.14 g of 3,5-heptanedione. The composition ratios and the like are summarized in Table 2.

Examples 2 to 8 <Preparation of catalysts 2A to 8A>
In the same manner as in Example 1, catalysts 2A to 8A were prepared with the compositions shown in Table 2 or Table 3.

比較例１〜比較例７ ＜触媒の調製＞
実施例１と同様にして、触媒１Ｂ〜７Ｂを表４又は表５に示した組成で調製した。

Comparative Examples 1 to 7 <Preparation of Catalyst>
In the same manner as in Example 1, catalysts 1B to 7B were prepared with the compositions shown in Table 4 or Table 5.

評価例１ ＜耐水性の評価＞
１３０℃で１時間減圧脱水したポリオキシプロピレントリオール１０．０ｇをポリエチレンカップに入れ、上記で調製した触媒１Ａを１１．３ｍｇ（金属化合物分としてウレタン樹脂に対して５００ｐｐｍ）加えて溶解させた。この溶液にヘキサメチレンジイソシアネート０．８９ｇを加え３０秒間撹拌した。混合液を６０℃に温調した金型上の円形のくぼみ（直径１ｃｍ、深さ２ｍｍ）に流し込み、硬化挙動を評価した。混合液を流し込んでから、混合液がゲル化するまでの時間をゲルタイム、指で触ってベトツキが無くなるまでの時間をタックフリータイムとした。これらを脱水ポリオール中における硬化性とする。

Evaluation Example 1 <Evaluation of water resistance>
10.0 g of polyoxypropylene triol dehydrated under reduced pressure at 130 ° C. for 1 hour was put in a polyethylene cup, and 11.3 mg of the catalyst 1A prepared above (500 ppm with respect to the urethane resin as a metal compound) was added and dissolved. To this solution, 0.89 g of hexamethylene diisocyanate was added and stirred for 30 seconds. The mixed solution was poured into a circular depression (diameter 1 cm, depth 2 mm) on a mold whose temperature was adjusted to 60 ° C., and the curing behavior was evaluated. The time from pouring the mixed solution to gelation of the mixed solution was defined as gel time, and the time from touching with a finger to the absence of stickiness was defined as tack-free time. These are set to be curable in the dehydrated polyol.

  A hydrous polyol was prepared by adding 0.5 parts by weight of distilled water to 100 parts by weight of the dehydrated polyol. 11.3 mg of catalyst 1A was added to 10.0 g of the hydrated polyol, put in a sample bottle, sealed and allowed to stand at room temperature for 24 hours, and then the gel time and tack free time were evaluated in the same manner as described above. These are set to be curable in the water-containing polyol. The curability in the dehydrated polyol and hydrous polyol is shown as Evaluation Example 1 in Table 6.

[Reactivity evaluation method]
Gel time: Time required for the reaction to proceed to change from a liquid material to a resinous material,
Tack-free time: The time until the resin hardens and touches with a finger to eliminate stickiness.

Evaluation Examples 2 to 8 <Evaluation of water resistance>
Evaluation Examples 2 to 8 were carried out in the same manner as Evaluation Example 1 except that the catalyst composition and the amount added were changed as shown in Tables 6 and 7 (corresponding to Examples 2 to 7, respectively). The results are shown in Table 6 and Table 7.

触媒組成物の耐水性 「○」：耐水性が良好である。「×」：耐水性が不良である。以下の表でも同じである。

Water resistance of catalyst composition “◯”: Water resistance is good. "X": Water resistance is poor. The same applies to the following tables.

  As shown in Evaluation Examples 1 to 8, it can be seen that the catalyst of the present invention has excellent water resistance since the difference in curability between the anhydrous polyol and the hydrated polyol is small.

Evaluation Examples 9 to 16 <Evaluation of water resistance>
Evaluation Examples 9 to 16 were carried out in the same manner as Evaluation Example 1 except that the catalyst composition and the amount added were changed as shown in Tables 8 and 9 (corresponding to Comparative Examples 1 to 8, respectively). The results are shown in Table 8 and Table 9.

評価例９（比較例１に対応）は、ジルコニウムジケトン錯体をβ−ジケトン類と併用しないで使用した場合であるが、耐水性が著しく低い。

Evaluation Example 9 (corresponding to Comparative Example 1) is a case where a zirconium diketone complex is used without being used in combination with β-diketones, but the water resistance is remarkably low.

Evaluation Examples 10 to 14 (corresponding to Comparative Examples 2 to 6, respectively) are cases where a diketone complex in which at least one of R ₁ or R ₃ is a methyl group (1 carbon number) is used in combination with the same diketones, The property is extremely low. The diketone complex in which at least one of R ₁ or R ₃ is a methyl group (carbon number 1) has low water resistance of the complex itself, and water resistance is insufficient even when diketones are used in combination.

Evaluation Example 15 (corresponding to Comparative Example 7) is a combination of a diketone complex in which R ₁ and R ₃ have 2 or more carbon atoms and β-diketone in which at least one of R ₄ or R ₆ is a methyl group (1 carbon atom). However, the water resistance is remarkably low.

  Evaluation Example 16 (corresponding to Comparative Example 8) is a case where DBTDL is used as a catalyst. DBTDL has high water resistance. However, organotin compounds are difficult to handle because of their high toxicity.

Evaluation Example 17 <Evaluation of room temperature curability>
15.0 g of polyoxypropylene triol dehydrated under reduced pressure at 130 ° C. for 1 hour was placed in a polyethylene cup, 6.8 mg of catalyst 1A prepared above (500 ppm relative to the urethane resin as a metal compound), and then hexamethylene diisocyanate 1 .33 g was added and stirred for 30 seconds. The mixture was put into an incubator whose temperature was adjusted to 20 ° C., and the resin hardness and surface tack were evaluated after 24 hours as evaluation of room temperature curability. The results are shown as Evaluation Example 17 in Table 10.
[Evaluation method of room temperature curability]
Resin hardness: Hardness was measured with a JIS K6253 standard type A durometer.

  Surface tack: The surface of the resin was lightly touched with a fingertip, and “stickiness” was evaluated as follows. “1: Very sticky” <“3: Stickiness remains” <“5: No stickiness”.

評価例１８〜２６ ＜常温硬化性の評価＞
触媒組成物及び添加量を表１０に示したように変更した以外は、評価例１７と同様にして評価例１８〜２６を実施した（実施例２〜８にそれぞれ対応）。結果を表１０にあわせて示す。

Evaluation Examples 18 to 26 <Evaluation of room temperature curability>
Evaluation Examples 18 to 26 were carried out in the same manner as Evaluation Example 17 except that the catalyst composition and the addition amount were changed as shown in Table 10 (corresponding to Examples 2 to 8, respectively). The results are shown in Table 10.

  As shown in Evaluation Examples 17 to 26, the polyurethane resin prepared using the catalyst of the present invention has high hardness and little stickiness, so that it can be seen that the room temperature curability is very good.

Evaluation Examples 27 to 35 <Evaluation of room temperature curability>
Evaluation Examples 27 to 35 were carried out in the same manner as Evaluation Example 17 except that the catalyst composition and the addition amount were changed as shown in Table 11 (corresponding to Comparative Examples 1 to 8, respectively). The results are shown in Table 11.

評価例２７（比較例１に対応）は、ジルコニウムジケトン錯体をβ−ジケトン化合物と併用しないで使用した場合であるが、常温硬化性が著しく低い。

Evaluation Example 27 (corresponding to Comparative Example 1) is a case where the zirconium diketone complex is used without being used in combination with the β-diketone compound, but the room temperature curability is extremely low.

Evaluation Examples 28 to 32 (corresponding to Comparative Examples 2 to 6) are cases where a diketone complex in which at least one of R ₁ or R ₃ is a methyl group (carbon number 1) and the same diketone as the raw material of the diketone complex are used in combination. However, the room temperature curability is extremely low.

Evaluation Example 33 (corresponding to Comparative Example 7) used a combination of a diketone complex in which R ₁ and R ₃ have 2 or more carbon atoms and a β-diketone in which at least one of R ₄ and R ₆ is a methyl group (1 carbon atom). In some cases, the room temperature curability is extremely low.

  Evaluation Examples 34 to 35 (corresponding to Comparative Example 8) are cases where DBTDL is used as a catalyst, and show high room temperature curability. However, organotin compounds are difficult to handle because of their high toxicity.

  The catalyst of this invention is used suitably for manufacture of a polyurethane resin.

Claims (7)

A catalyst for producing a polyurethane resin, comprising a zirconium compound represented by the following general formula (1) and a β-diketone represented by the following general formula (3).
Zr (L) ₄ (1)
[In the above formula (1), each L independently represents a diketonate ligand represented by the structure of the following general formula (2). ]

[In the above formula (2), R ₁ and R ₃ each independently represents an alkyl group having 2 to 10 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ]

[In the above formula (3), R ₄ and R ₆ each independently represent an alkyl group having 2 to 10 carbon atoms, and R ₅ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ] The β-diketonate ligand represented by the general formula (2) is selected from the group consisting of 3,5-heptanedionate, 3,5-octanedionate and 2-methyl-3,5-nonanedionate. The catalyst for producing a polyurethane resin according to claim 1. The β-diketone represented by the general formula (3) is selected from the group consisting of 3,5-heptanedione, 3,5-octanedione and 2-methyl-3,5-nonanedione. A catalyst for producing a polyurethane resin according to claim 1 or 2. The molar ratio of the β-diketone represented by the general formula (3) to the zirconium compound represented by the general formula (1) (β-diketone / zirconium compound) is in the range of 0.5 to 50. The polyurethane resin production catalyst according to any one of claims 1 to 3, wherein the catalyst is a polyurethane resin production catalyst. A method for producing a polyurethane resin, comprising reacting a polyol and an organic polyisocyanate in the presence of the catalyst for producing a polyurethane resin according to any one of claims 1 to 4. A process for producing a polyurethane resin, comprising reacting a polyol and an organic polyisocyanate in the presence of the catalyst and additive for polyurethane resin production according to any one of claims 1 to 4. The method for producing a polyurethane resin according to claim 6, wherein the organic polyisocyanate is an aliphatic isocyanate.