JP2019104808A - Amine catalyst composition for producing polyurethane foamed by haloalkane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst composition for improving the storage stability of a polyol-based compounded liquid for producing a polyurethane foam containing a hydrohaloolefin as a blowing agent and initiating a rapid foaming reaction with a small addition amount. Furthermore, the manufacturing method of the polyurethane foam using the polyol type compounding liquid composition containing this catalyst composition is provided. A dihydric alcohol obtained by addition polymerization of one or more epoxy compounds selected from the group consisting of ethylene oxide and propylene oxide using one or more compounds selected from the group consisting of ethylene glycol and propylene glycol as an initiator. (1) or a polyhydric alcohol containing a trihydric alcohol (2) obtained by addition polymerization of one or more epoxy compounds selected from the group consisting of ethylene oxide and propylene oxide using glycerin as an initiator, and having an average molecular weight thereof A polyhydric alcohol having an A of 100 to 2000, hexamethyltriethylenetetramine, N, N, N′-trimethylaminoethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethyl-N ′, N ′ -Di (2-hydroxypropyl) Propylenediamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, and N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methyl A catalyst composition containing one or more tertiary amine compounds selected from the group consisting of aminoisopropanol is used.

Description

  The present invention relates to an amine catalyst composition used in the production of polyurethane foam and its use.

  The polyurethane resin is produced by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, a blowing agent, a surfactant, a crosslinking agent and the like. Conventionally, it is known to use a large number of metal compounds and tertiary amine compounds as catalysts in the production of this polyurethane resin. These catalysts are also widely used industrially by using alone or in combination. In particular, tertiary amine compounds are widely used as catalysts for polyurethane foam production due to their excellent productivity and moldability.

  The formation reaction of polyurethane foam and isocyanurate modified polyurethane foam (hereinafter referred to as "polyurethane foam") is mainly composed of a polyol (so-called, a main component of the second component) and an isocyanate (so-called, a main component of the first component) The reaction consists of two reactions: urethane group formation reaction (resinification reaction) by reaction, urea group formation reaction by reaction of isocyanate and water, and carbon dioxide gas generation reaction (foaming reaction), and the catalyst has not only these reaction rates, The curing speed of the polyurethane foam, the moldability, the reduction in density of the polyurethane foam, physical properties, etc. are greatly affected.

  On the other hand, fluorocarbons have been used as one of the representative physical blowing agents for polyurethane foam. Fluorocarbons not only function as a blowing agent due to their volatility, but also are enclosed in the closed cell structure of rigid polyurethane foam, particularly when used for rigid polyurethane foam, and contribute to the low thermal conductivity properties of rigid polyurethane foam Do. That is, by selecting fluorocarbons as the foaming agent, it is possible to form a rigid polyurethane foam having an extremely low thermal conductivity, that is, excellent in heat insulation performance.

  Among fluorocarbons, reduction of chlorofluorocarbons (so-called CFCs such as trichloromonofluoromethane and dichlorodifluoromethane) and hydrochlorofluorocarbons (so-called HCFCs such as dichloromonofluoroethane) which cause ozone layer depletion And environmental issues such as improvement of working environment and suppression of the scattering of volatile substances from products are of great interest. At present, hydrofluorocarbons (tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-penta, which do not destroy the ozone layer or have a small ozone layer destruction) So-called HFCs) such as fluorobutane are used.

  In recent years, hydrohaloolefins containing hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) having low global warming potentials as compared with the above-mentioned hydrofluorocarbons with low ozone depletion are preferable blowing agents As newly proposed. As such hydrofluoroolefins, trans-1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO- Examples of hydrochlorofluoroolefins include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).

  In many applications, the first component is comprised of raw materials compatible with polyisocyanate and any isocyanate. The other second component (hereinafter referred to as a polyol-based mixed solution) is composed of a polyol or a mixture of polyols, a surfactant, a catalyst, a foaming agent, and other isocyanate-reactive and non-reactive components. Therefore, the polyurethane foam is easily prepared by foaming reaction by mixing the first component and the second component described above by a method such as manual stirring or mechanical stirring.

  Components such as flame retardants, colorants, auxiliary blowing agents, and other polyols (so-called third components) can also be added to the mixing head of the mechanical stirring device using a separate stream. However, it is most convenient to incorporate them all into the second component.

  By mixing the first component and the second component and causing a foaming reaction, usually, a good polyurethane foam is obtained. However, in the case where the polyol-based mixed solution of the second component is deteriorated before reacting with the polyisocyanate contained in the first component, there is a problem that the speed of the foaming reaction becomes slow, or a polyurethane foam inferior in quality is formed. It causes a problem. Further, if the deterioration progresses significantly, polyurethane foam formation may cause collapse before the foaming reaction is completed. In general, since this polyol-based compounded liquid may be used after several weeks to about 3 months have passed since it is compounded, it is an extremely important task to secure its storage stability.

  In particular, since certain hydrohaloolefins, including HFO-1234ze and HCFO-1233zd, react and decompose with the amine catalyst generally used for polyurethane foam, they have the drawback of having a short shelf life of the polyol-based formulation There is. When foaming is carried out using an old polyol-based compounded liquid, the reactivity of foam formation / resin reaction is reduced, and cell roughening of the foam occurs.

  As a method to solve this problem, when using an organic acid-containing amine catalyst for a specific foaming agent such as hydrohaloolefins including HFO-1234ze and HCFO-1233zd, good quality polyurethane foam is formed even after storage What can be done is disclosed in Patent Document 1.

  As another solution, it is known to utilize a sterically hindered amine as a catalyst (Patent Document 2).

Japanese Patent Publication No. 2011-500893 WO 2009/048807 pamphlet

  The invention based on the organic acid-containing amine catalyst disclosed in Patent Document 1 does not have a sufficient effect of suppressing the decomposition of the hydrohaloolefin. For this reason, in summer, the shelf life of the hydrohaloolefin-containing polyol-based mixed solution may be less than several weeks in some cases, and an improvement is required.

  The invention based on the sterically hindered amine disclosed in Patent Document 2 has a serious problem of causing dripping in the spray method because the initial reactivity of urethane foam is poor.

  The present invention has been made in view of the above problems.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, in order to solve the above-mentioned subject, the present inventors discover the following catalyst composition, and came to complete this invention.

That is, the present invention provides an amine catalyst composition for producing a polyurethane foam as shown below, a polyol-based compounding solution for producing a polyurethane foam using the amine catalyst composition, and a polyurethane foam using the polyol-based compounding solution The manufacturing method of
[1]
A dihydric alcohol (1) obtained by addition polymerization of one or more epoxy compounds selected from ethylene oxide and propylene oxide using, as an initiator, one or more compounds selected from ethylene glycol and propylene glycol as an initiator; Or a polyhydric alcohol containing a trihydric alcohol (2) obtained by addition polymerization of at least one epoxy compound selected from the group consisting of ethylene oxide and propylene oxide using glycerin as an initiator, and having an average molecular weight of 100 to 2000 Polyhydric alcohols which are the same as above, as well as hexamethyltriethylenetetramine, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethyl-N ', N'-di (2 -Hydroxypropyl) propylene diamide N, N, N'-trimethyl-N '-(2-hydroxyethyl) bis (2-aminoethyl) ether, and N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoisopropanol A catalyst composition containing one or more tertiary amine compounds selected from the group consisting of
[2]
Polyhydric alcohol is one or two or more selected from the group consisting of dihydric alcohol (1) represented by the following general formula (1) and trihydric alcohol (2) represented by the following general formula (2) The catalyst composition according to [1], which is a polyhydric alcohol containing a polyhydric alcohol having an average molecular weight of 100 to 2,000.

(In the formula, A represents ethylene or propylene. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a methyl group. A + b + x + y represents an integer of 7 to 17 in total.)

(Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a methyl group. A + b + c + x + y + z represents an integer of 6 to 22 in total)
[3]
The polyhydric alcohol is a polyhydric alcohol comprising one or more selected from the group consisting of polyoxypropylene glycol, polyethylene glycol, and polyoxypropylene glyceryl ether, and having an average molecular weight of 100 to 2,000. The catalyst composition according to [1] or [2], which is a polyhydric alcohol.
[4]
One or more types of tertiary amine compounds selected from the group consisting of hexamethyltriethylenetetramine, N, N, N'-trimethylaminoethylethanolamine, and N, N-dimethylaminoethoxyethanol The catalyst composition according to [1] to [3], which is a tertiary amine compound.
[5]
The tertiary amine compound is characterized in that it is one or two tertiary amine compounds selected from the group consisting of hexamethyltriethylenetetramine and N, N, N'-trimethylaminoethylethanolamine. The catalyst composition according to any one of [1] to [4].
[6]
A polyol-based liquid mixture composition comprising a polyol, a hydrohaloolefin, and the catalyst composition according to [1] to [5].
[7]
The polyol-based liquid mixture composition according to [6], wherein the hydrohaloolefin is a fluoroalkene, a chlorofluoroalkene or a chloroalkene consisting of 3 or 4 carbon atoms.
[8]
Characterized in that the hydrohaloolefin is trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorodifluoropropene, chlorotrifluoropropene or chlorotetrafluoropropene, or a combination thereof, [6] or [7] ] The polyol-type liquid mixture composition as described in [].
[9]
Hydrohaloolefins are 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, 1,2,3,3,3 -Pentafluoropropene, 1,1,1-trifluoropropene, 3,3,3-trifluoropropene, 1,1,1,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropene 1,1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene, 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3 Trifluoropropene, or 1,1,1,4,4,4-hexafluorobut-2-ene, their structural isomers, stereoisomers, or a combination thereof, [6 ] To [8] Polyol blend liquid composition.
[10]
The polyol-based mixed liquid composition according to [6] to [9], wherein the hydrohaloolefin is trans-1-chloro-3,3,3-trifluoropropene.
[11]
A method for producing a polyurethane, comprising reacting the polyol-based mixed liquid composition according to any one of [6] to [10] with an organic polyisocyanate.

  The catalyst composition of the present invention exhibits an effect of significantly improving the shelf life of the hydrohaloolefin-containing polyol-based mixed solution or being excellent in initial foamability, as compared with the background art.

  Incidentally, the organic acid-containing amine catalyst, which is one of the prior art, reduces the reactivity with the hydrohaloolefin by neutralizing the tertiary amine compound with the organic acid, and is for producing a polyurethane foam containing the hydrohaloolefin. The storage stability of the polyol-based compounding solution of The catalyst composition of the present invention is, surprisingly, significantly enhancing the storage stability of a polyol-based compounding fluid for producing a polyurethane foam containing a hydrohaloolefin, although not neutralizing the amine compound. The invention achieves the effects of the invention based on a configuration that can not easily be conceived from the prior art in that

  The catalyst composition of the present invention is remarkably excellent in the urethane foam initial reactivity of the hydrohaloolefin-containing polyol-based mixed solution as compared with the background art, and exhibits an effect of preventing dripping in the spray method.

  Furthermore, since the addition amount of the catalyst composition of the present invention can be reduced as compared with the background art, the effect of reducing the work environment load by the amine compound can be achieved.

  Next, the present invention will be described in detail.

  The catalyst composition of the present invention is one or more polyhydric alcohols selected from the group consisting of the dihydric alcohol (1) and the trihydric alcohol (2), and the average molecular weight of the catalyst composition is Polyhydric alcohols with 100 to 2000 and hexamethyltriethylenetetramine, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethyl-N ', N'- Di (2-hydroxypropyl) propylenediamine, N, N, N'-trimethyl-N '-(2-hydroxyethyl) bis (2-aminoethyl) ether, and N, N-dimethylaminoethyl-N'-methyl Containing one or more tertiary amine compounds selected from the group consisting of aminoethyl-N ′ ′-methylaminoisopropanol A catalyst composition.

  The dihydric alcohol (1) of the present invention is obtained by adding one or more epoxy compounds selected from the group consisting of ethylene oxide and propylene oxide using one or more compounds selected from the group consisting of ethylene glycol and propylene glycol as an initiator. The dihydric alcohol (1) to be polymerized is ethylene glycol and propylene oxide, which are glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol as starting materials. Polyalkylene glycols obtained by addition are preferred. Examples thereof include polyethylene glycol 400, Primepol PX-1000 manufactured by Sanyo Chemical Industries, or Sannix PP-1000.

  The trihydric alcohol (2) of the present invention is a trihydric alcohol (2) obtained by addition polymerization of at least one epoxy compound selected from the group consisting of ethylene oxide and propylene oxide using glycerin as an initiator. As the polyhydric alcohol (2), polyoxyalkylene glyceryl ethers obtained by adding ethylene oxide or propylene oxide using glycerin or the like as a starting material are preferable. For example, Sannix GP-1000 manufactured by Sanyo Chemical Industries, Ltd. and the like can be mentioned.

  The polyhydric alcohol of the present invention is characterized in that the urethane foam initial reactivity is remarkably excellent, and the dihydric alcohol (1) represented by the following general formula (1) and the trihydric alcohol (2) represented by the following general formula (2) )

(In the formula, A represents ethylene or propylene. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a methyl group. A + b + x + y represents an integer of 7 to 17 in total.)

(Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a methyl group. A + b + c + x + y + z represents an integer of 6 to 22 in total)
It is preferable that it is a polyhydric alcohol containing 1 type, or 2 or more types selected from the group which consists of.

  In addition, the polyhydric alcohol of the present invention is one or more selected from the group consisting of polyoxypropylene glycol, polyethylene glycol, and polyoxypropylene glyceryl ether in that it is remarkably excellent in urethane foam initial reactivity. It is more preferable that it is a polyhydric alcohol containing, Comprising: It is the polyhydric alcohol whose average molecular weight is 100-2000.

  The polyhydric alcohol of the present invention has an average molecular weight of 100 to 2,000, but preferably has an average molecular weight of 250 to 2,000, and an average molecular weight of 500, because the urethane foam initial reactivity is remarkably excellent. It is more preferable that it is -2000.

  A commercial item can also be used about the polyhydric alcohol of this invention, and what was newly manufactured based on those skilled in the art common sense can also be used.

  Examples of the tertiary amine compound include hexamethyltriethylenetetramine, N, N, N'-trimethylaminoethyl ethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethyl-N ', N'-di (2-hydroxypropyl) propylenediamine, N, N, N'-trimethyl-N '-(2-hydroxyethyl) bis (2-aminoethyl) ether, and N, N-dimethylaminoethyl-N'-methylamino It is not particularly limited as long as it is one or more tertiary amine compounds selected from the group consisting of ethyl-N ′ ′-methylaminoisopropanol, and is not particularly limited, but for producing polyurethane foams containing hydrohaloolefins. Hexamethyltriethylenetetramine, N from the viewpoint of improving the storage stability of the polyol-based compounding solution One or more tertiary amine compounds selected from the group consisting of N, N'-trimethylaminoethyl ethanolamine and N, N-dimethylaminoethoxyethanol are preferred, and the size of the catalytic activity is further preferred. From the viewpoint, one or two tertiary amine compounds selected from the group consisting of hexamethyltriethylenetetramine and N, N, N′-trimethylaminoethylethanolamine are more preferable.

  The content ratio of the polyhydric alcohol and the tertiary amine compound is not particularly limited, but preferably, [polyhydric alcohol] / [tertiary amine compound] = 90/10 to 10/90 (weight Ratio is more preferably in the range of [polyhydric alcohol] / [tertiary amine compound] = 80/20 to 20/80 (weight ratio), and more preferably [polyhydric alcohol] / Tertiary amine compound] = 70/30 to 30/70 (weight ratio).

  As the above-mentioned tertiary amine compounds, commercially available ones can be used, or they can be easily produced by methods known in the literature. For example, a method by reaction of a diol and a diamine, amination of an alcohol, a method by reductive methylation of a monoamino alcohol or a diamine, a method by reaction of an amine compound and an alkylene oxide, and the like can be mentioned.

  The catalyst composition of the present invention can be used as a catalyst for promoting the reaction of isocyanate and polyol.

  In general, the amount of the catalyst composition of the present invention used is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the polyol used. More preferably, it is 0.1 to 10 parts by weight. It is preferable to increase the amount of use of the tertiary amine compound in terms of improving the curability and productivity of the polyurethane resin.

  The catalyst composition of the present invention may contain other components. Examples of the other components include conventionally known organic metal catalysts, quaternary ammonium salt catalysts, solvents and the like.

  The organometallic catalyst is not particularly limited, and, for example, stanas diacetate, stanas dioctoate, stanas dioleate, stanas dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride And dioctyltin dilaurate, lead octanoate, lead naphthenate, nickel naphthenate, or cobalt naphthenate.

  Further, the quaternary ammonium salt catalyst is not particularly limited. For example, tetraalkyl ammonium halides such as tetramethyl ammonium chloride, tetraalkyl ammonium hydroxides such as tetramethyl ammonium hydroxide, tetramethyl Hydroxyalkylammonium organic acids such as ammonium acetate, tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, or 2-hydroxypropyltrimethylammonium 2-ethylhexanoate Acid salts are mentioned.

  Although it does not specifically limit as said solvent, For example, dipropylene glycol, ethylene glycol, 1, 4- butanediol, or water etc. are mentioned.

  Also, the content of other components (for example, the above-mentioned organometallic catalyst, quaternary ammonium salt catalyst, solvent, etc.) that can be contained in the catalyst composition of the present invention is not particularly limited, In general, the range of 0.1 to 90% by weight of the catalyst composition of the present invention is preferred.

  The polyol-based mixed liquid composition of the present invention is characterized by containing a polyol, a hydrohaloolefin and the catalyst composition of the present invention.

  As the polyol, commonly known polyester polyols, polyether polyols, polymer polyols and mixtures thereof can be used. The known polyester polyols are not particularly limited. For example, those obtained from the reaction of a dibasic acid and a hydroxy compound (such as glycol) or Keiji Iwata "Polyurethane resin handbook" (first edition of 1987) Nikkan Kogyo Shinbun DMT residue described on pages 116 to 117, polyester polyol starting from phthalic anhydride, waste from nylon production, TMP, waste from pentaerythritol, waste from phthalic acid polyester, waste And derived polyester polyols. In addition to these, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, waste products thereof, and products obtained by subjecting an aromatic dicarboxylic acid or a derivative thereof to an esterification reaction from waste products can be exemplified.

  As a dibasic acid used as a raw material of polyester polyol, adipic acid, phthalic acid, succinic acid, azelaic acid, sebacic acid, ricinoleic acid etc. are illustrated.

  The known polyether polyols are not particularly limited, but, for example, polyhydric alcohols such as glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, sucrose, fats such as ammonia, ethylenediamine, ethanolamines, etc. Examples thereof include those obtained by adding ethylene oxide or propylene oxide to aromatic amine compounds such as aromatic amine compounds, toluene diamine, diphenylmethane-4, 4'-diamine and / or mixtures thereof.

  The polymer polyol known in the art is not particularly limited. For example, it is obtained by reacting a polyether polyol with an ethylenically unsaturated monomer (eg, butadiene, acrylonitrile, styrene etc.) in the presence of a radical polymerization catalyst. Polymer polyols and the like.

  Of these, polyether and / or polyester polyols are preferred as polyols for the production of rigid polyurethane foams. The average functionality of the polyol is preferably 4 to 8, and the average hydroxyl value is preferably 200 to 800 mg KOH / g, more preferably 300 to 700 mg KOH / g.

  The hydrohaloolefin used in the present invention is not particularly limited, but its Global Warming Potential (GWP) is preferably 150 or less, more preferably 100 or less, and even more preferably. Is less than 75. The "GWP" described herein is described in "The Scientific Assessment of Ozone Depletion, 2002, a Report of the World Meteorological Association's Global Ozone Research and Monitoring Project (Scientific Assessment of Ozone Depletion, 2002, Measured relative to the GWP of carbon dioxide on a 100-year time scale, as defined in the World Meteorological Association's Global Ozone Survey and Monitoring Plan.

  The hydrohaloolefin used in the present invention is not particularly limited, but the ozone destruction coefficient (ODP; Ozone Depletion Potential) is preferably 0.05 or less, more preferably 0.02 or less. Even more preferably, it is about zero. The "ODP" described herein is described in "The Scientific Assessment of Ozone Depletion, 2002, A Report of the World Meteorological Association's Global Ozone Research and Monitoring Project (Scientific Assessment of Ozone Depletion, 2002, As defined by the World Meteorological Association's Global Ozone Survey and Monitoring Plan.

  The hydrohaloolefin used in the present invention is not particularly limited, but is preferably a fluoroalkene having 3 or 4 carbon atoms, a chlorofluoroalkene or a chloroalkene. Preferred hydrohaloolefins include, but are not limited to, trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorotrifluoropropene, chlorodifluoropropene, or chlorotetrafluoropropene, or mixtures thereof. More preferably, it is tetrafluoropropene, pentafluoropropene or chlorotrifluoropropene, or a mixture thereof.

  As for the hydrohaloolefins of the present invention, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoro Propene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluoro But-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3, 3,3-trifluoropropene (HFCO-1233zd) or 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), Mixtures thereof, or structural isomers thereof, geometric isomers or stereoisomers, and the like. Among these, trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd (E)) is preferable from the viewpoint of heat insulation performance and availability.

  The content of the hydrohaloolefin in the polyol-based mixed liquid composition is not particularly limited, but is preferably 1 to 50% by weight, and more preferably 3 to 30% by weight. Preferably, it is 5% by weight to 20% by weight.

  The polyol-based mixed liquid composition of the present invention may contain components other than the polyol, the hydrohaloolefin and the catalyst composition of the present invention. The components are not particularly limited, but include organic metal catalysts, quaternary ammonium salt catalysts, solvents, foaming agents, foam stabilizers, crosslinking agents, chain extenders, coloring agents, flame retardants, anti-aging agents, Or other additives and the like.

  The organometallic catalyst, quaternary ammonium salt catalyst or solvent shown as other components which can be contained in the catalyst composition of the present invention is not necessarily required to be contained in the catalyst composition of the present invention, As mentioned above, it can also be contained as a component of the polyol-based mixed liquid composition of the present invention.

The foaming agent is not particularly limited, but in addition to the above hydrohaloolefins, organic acids, hydrocarbons, ethers, halogenated ethers, pentafluorobutane which generate CO ₂ when reacted with water, formic acid and isocyanates Pentafluoropropane, hexafluoropropane, heptafluoropropane, trans-1,2-dichloroethylene, methyl formate, 1-chloro-1,2,2,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1-chloro-1,1-difluoroethane, 1,1,1,3,3-pentafluorobutane, 1 1,1,1,2,3,3,3-heptafluoropropane, trichlorofluoromethane, dichlorodifluorometa 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane, difluoromethane, difluoroethane, 1,1,1,3,3-penta Examples thereof include fluoropropane, 1,1-difluoroethane, isobutane, normal pentane, isopentane, or cyclopentane, and mixtures thereof.

  Examples of the foam stabilizer include known silicone foam stabilizers, and examples thereof include nonionic surfactants such as organosiloxane-polyoxyalkylene copolymer, silicone-grease copolymer, or the like, or A mixture etc. are mentioned. The amount used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyol.

  The foaming agent is not particularly limited, but is preferably contained in an amount of 1 to 50% by weight, more preferably 3 to 30% by weight, in the polyol-based mixed liquid composition, and more preferably In an amount of 5% to 20% by weight.

  Thus, when the hydrohaloolefin and the foaming agent coexist in the polyol-based mixed liquid composition, the amount of the hydrohaloolefin is 5% by weight to 90% by weight based on the “total amount of the hydrohaloolefin and the foaming agent”. It is preferably 7 to 80% by weight, more preferably 10 to 70% by weight.

  Examples of the foam stabilizer may include known silicone foam stabilizers, and are not particularly limited. For example, nonionic agents such as organosiloxane-polyoxyalkylene copolymer, silicone-grease copolymer, etc. A system surfactant, or a mixture of these, etc. may be mentioned. Although the usage-amount of the said foam stabilizer is not specifically limited, 0.1-10 weight part is preferable with respect to 100 weight part of polyols.

  The crosslinker or chain extender is not particularly limited, and examples thereof include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol and glycerin, diethanolamine, triethanolamine and the like. And low molecular weight amine polyols, or polyamines such as ethylene diamine, xylylene diamine, methylene bis orthochloroaniline and the like.

  The colorant, the flame retardant, the antiaging agent, the other known additives and the like are not particularly limited, but conventionally known ones can be used. The addition amount of these agents is not particularly limited, but can be used within a general range.

  The catalyst composition of the present invention can be used to produce polyurethane foams, and can be suitably used, for example, to produce rigid polyurethane foams and isocyanurate-modified rigid polyurethane foams.

The rigid polyurethane foam is a non-reversibly deformable foam, which is a highly cross-linked closed-cell structure, as described in Polyurethanes Handbook 234-313 and Polyurethane Resin Handbook pages 224-283. And semi-rigid foams have totally different properties. The properties of the rigid foam are not particularly limited, but generally, the density is in the range of ²⁰ to 100 kg / m ³ and the compressive strength is in the range of 0.5 to 10 kgf / cm ² (50 to 1000 kPa) preferable.

  The method for producing a polyurethane of the present invention is characterized in that the polyol-based mixed liquid composition is reacted with an organic polyisocyanate.

  For example, known polyisocyanates can be used as the organic polyisocyanate, and examples thereof include, but are not limited to, toluene diisocyanate (TDI), 4,4'- or 4,2'-diphenylmethane diisocyanate (MDI) ), Aromatic polyisocyanates such as naphthalene diisocyanate, xylylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, or free isocyanates by reaction of these with polyols Prepolymers, modified polyisocyanates such as carbodiimide modification, and mixtures thereof can be used.

  As TDI and its derivative, a mixture of 2,4-TDI and 2,6-TDI, or a terminal isocyanate prepolymer derivative of TDI can be mentioned. As MDI and its derivative, the mixture of MDI and the polyphenyl polymethylene diisocyanate of the polymer, and / or the diphenylmethane diisocyanate derivative which has a terminal isocyanate group can be mentioned.

  Of these, rigid polyurethane foams are preferably MDI or derivatives of MDI, which may be used in combination.

  Components other than the polyol, the hydrohaloolefin and the catalyst composition of the present invention (organic metal catalyst, quaternary ammonium salt catalyst, solvent, blowing agent, which may be contained in the polyol-based mixed liquid composition of the present invention described above) The foam stabilizer, crosslinking agent, chain extender, coloring agent, flame retardant, anti-aging agent, and other additives etc.) are not necessarily required to be contained in the polyol-based mixed liquid composition, and It can also be added as a third component at the time of the reaction with the polyol-based mixed liquid composition and the organic polyisocyanate in the method for producing a polyurethane of the present invention.

  The polyurethane foam products produced using the catalyst composition of the present invention, the polyol-based mixed liquid composition, or the method for producing polyurethane can be used in various applications. For example, in the case of rigid polyurethane foam, foams such as heat insulation building materials, freezers, refrigerators and the like can be mentioned.

  EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

  In the following examples and comparative examples, the measurement method of each measurement item is as follows.

Examples 1 to 5 and Comparative Examples 1 to 4
Polyisocyanate whose part number is adjusted to be a predetermined isocyanate index in a polyol-based raw material blending solution (20 ° C.) containing a polyol, a foam stabilizer, a catalyst composition, and a foaming agent (water and hydrohaloolefin) shown in Table 1 (20.degree. C.) was added, and immediately after that, the mixture was stirred and mixed at 7,000 rpm for 3 seconds using a laboratory mixer to cause a foaming reaction to produce a rigid polyurethane foam. The addition amount of the amine catalyst composition was adjusted so that the gel time was in the range of 29 to 40 seconds.

  The cream time (CT) and the gel time (GT) at this time were measured visually. These were considered as initial reactivity. In addition, cream time (CT) and gel time (GT) were defined as follows.

  Cream time (CT): The laboratory mixer agitation start was made into zero time (zero second), the foaming reaction progressed, and the time (second) which foaming started was measured.

  Gel time (GT): The laboratory mixer agitation start was made zero time (zero second), resinification reaction advanced, and the time (seconds) which a reactant changes from a liquid substance to a resinous substance was measured.

  Further, the appearance of the obtained rigid polyurethane foam was confirmed, and the state of the cell and the presence or absence of collapse were examined.

  Next, the polyol-based raw material blending solution containing a polyol, a foam stabilizer, a catalyst composition, and a foaming agent (water and hydrohaloolefin) shown in Table 1 was placed in a closed container and heated at 40 ° C. for 28 days Thereafter, the temperature was adjusted to 20 ° C., and the polyisocyanate (20 ° C.), the number of which was adjusted so as to obtain a predetermined isocyanate index, was added, mixed and foamed similarly to the evaluation of initial reactivity. The CT and GT at this time were measured. These were made reactive after storage.

  Further, the appearance of the obtained rigid polyurethane foam was confirmed, and the state of the cell and the presence or absence of collapse were examined.

  These measurements and survey results are shown in Table 1.

  About 1)-12) of Table 1, it is as follows.

1) Sannix HS-209 (Sucrose-based polyether polyol manufactured by Sanyo Chemical Industries, Ltd., OH number = 447 mg KOH / g)
2) Niax-L-5420 (Momentive's silicone surfactant)
3) Prime pole PX-1000 (Sanyo Chemical Industries, Ltd.)
4) Sannix PP-1000 (Sanyo Chemical Industries, Ltd.)
5) Polyethylene glycol 400 (Tokyo Chemical Industry Co., Ltd.)
6) Preparation product prepared by reacting formalin with triethylenetetramine for reductive methylation 7) Special grade reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
8) Preparation prepared by reacting formalin with triethylenetetramine to reduce and methylate 9) TOYOCAT-RX5 (Tosoh Corporation)
10) Reagents (Tokyo Chemical Industry Co., Ltd.)
11) trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell Solstice-LBA)
12) Polymeric MDI (Millionated MR200, manufactured by Tosoh Corporation, NCO content = 31.0%)
As apparent from Comparative Examples 1 and 2 in Table 1, when the polyhydric alcohol contained in the amine catalyst composition of the present invention is not used, the decrease in reactivity after storage is large. Furthermore, the stock solution after storage was disintegrated during the foaming reaction, and the obtained rigid polyurethane foam was not practical.

  As apparent from Comparative Example 3, when a mixture of an organic acid and an amine according to the prior art was used as a catalyst, although the decrease in reactivity was not large, some foam collapse occurred during the foaming reaction. Furthermore, since the catalyst activity is low, the addition amount of the catalyst composition required to obtain the equivalent reactivity is about 1.7 times as large as in Examples 1 to 5.

  As apparent from Comparative Example 4, when the sterically hindered amine of the prior art was used as a catalyst, no decrease in reactivity was observed, and the appearance of the obtained foam was suitable, but it was against the foaming reaction of the sterically hindered amine. CT is extremely slow at 14 seconds because of low catalyst activity. For this reason, in the spraying method in which a rapid foaming reaction is required in particular, the practicability is extremely poor.

  On the other hand, as apparent from Examples 1 to 5, when the amine catalyst composition of the present invention was used, the CT before storage was short and the foaming reaction was rapidly initiated. In any case, the decrease in reactivity after storage is small, and the rate of change in GT is small as compared with the case where only the same tertiary amine compound is used. In addition, the appearance of the obtained rigid polyurethane foam and the degree of cell roughening are also in a sufficiently suitable range.

  In the production of a polyurethane foam containing hydrohaloolefin as a blowing agent, the amine catalyst composition of the present invention has high catalytic activity and can exhibit sufficient reactivity even with a small addition amount. Furthermore, the storage stability of the polyol-based mixed solution to which the amine catalyst composition of the present invention is added is significantly improved as compared with the conventionally known catalyst composition. Therefore, the amine catalyst composition of the present invention is expected to be used particularly as a catalyst for producing polyurethane foam containing hydrohaloolefin as a blowing agent.

Claims (11)

A dihydric alcohol (1) obtained by addition polymerization of one or more epoxy compounds selected from ethylene oxide and propylene oxide using, as an initiator, one or more compounds selected from ethylene glycol and propylene glycol as an initiator; Or a polyhydric alcohol containing a trihydric alcohol (2) obtained by addition polymerization of at least one epoxy compound selected from the group consisting of ethylene oxide and propylene oxide using glycerin as an initiator, and having an average molecular weight of 100 to 2000 Polyhydric alcohols which are the same as above, as well as hexamethyltriethylenetetramine, N, N, N'-trimethylaminoethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethyl-N ', N'-di (2 -Hydroxypropyl) propylene di Min, N, N, N'-trimethyl-N '-(2-hydroxyethyl) bis (2-aminoethyl) ether, and N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylamino A catalyst composition comprising one or more tertiary amine compounds selected from the group consisting of isopropanol. Polyhydric alcohol is one or two or more selected from the group consisting of dihydric alcohol (1) represented by the following general formula (1) and trihydric alcohol (2) represented by the following general formula (2) The catalyst composition according to claim 1, which is a polyhydric alcohol containing polyhydric alcohol having an average molecular weight of 100 to 2,000.

(In the formula, A represents ethylene or propylene. R ^{1 to} R ⁴ each independently represent a hydrogen atom or a methyl group. A + b + x + y represents an integer of 7 to 17 in total.)

(Wherein, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a methyl group. A + b + c + x + y + z represents an integer of 6 to 22 in total) The polyhydric alcohol is a polyhydric alcohol comprising one or more selected from the group consisting of polyoxypropylene glycol, polyethylene glycol, and polyoxypropylene glyceryl ether, and having an average molecular weight of 100 to 2,000. The catalyst composition according to claim 1 or 2, which is a polyhydric alcohol. One or more types of tertiary amine compounds selected from the group consisting of hexamethyltriethylenetetramine, N, N, N'-trimethylaminoethylethanolamine, and N, N-dimethylaminoethoxyethanol The catalyst composition according to any one of claims 1 to 3, which is a tertiary amine compound. The tertiary amine compound is characterized in that it is one or two tertiary amine compounds selected from the group consisting of hexamethyltriethylenetetramine and N, N, N'-trimethylaminoethylethanolamine. The catalyst composition according to any one of claims 1 to 4. A polyol-based liquid mixture composition comprising a polyol, a hydrohaloolefin and the catalyst composition according to any one of claims 1 to 5. 7. The polyol-based liquid mixture composition according to claim 6, wherein the hydrohaloolefin is a fluoroalkene, a chlorofluoroalkene or a chloroalkene having 3 or 4 carbon atoms. 8. The method according to claim 6, wherein the hydrohaloolefin is trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorodifluoropropene, chlorotrifluoropropene, or chlorotetrafluoropropene, or a mixture thereof. Polyol-based blended liquid composition as described. Hydrohaloolefins are 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, 1,2,3,3,3 -Pentafluoropropene, 1,1,1-trifluoropropene, 3,3,3-trifluoropropene, 1,1,1,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropene 1,1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene, 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3 Trifluoropropene, or 1,1,1,4,4,4-hexafluorobut-2-ene, their structural isomers, stereoisomers, or a combination thereof, 6 to 8 Polyol blend composition of the mounting. 10. The polyol-based mixed liquid composition according to claim 6, wherein the hydrohaloolefin is trans-1-chloro-3,3,3-trifluoropropene. A method for producing polyurethane, comprising reacting the polyol-based mixed liquid composition according to any one of claims 6 to 10 with an organic polyisocyanate.