WO2020196666A1 - Polyol blend liquid for producing haloalkene polyurethane foam - Google Patents

Abstract

Regarding polyol blend liquids for producing haloalkene polyurethane foam, storage stability has been a problem for polyol blend compositions. The present invention uses a polyol blend liquid composition which is for producing polyurethane foam and which contains a polyol, a hydrohaloolefin, and a compound represented by formula (1) (in the formula, Ar1 represents a monocyclic, linked-ring, or fused-ring aromatic group having 3-20 carbon atoms and optionally having a substituent, R1 represents a linear, branched, or cyclic divalent alkyl group having 2-6 carbon atoms, each R2 independently represents an alkyl group having 2-4 carbon atoms or a hydroxy alkyl group having 2-4 carbon atoms, two R2s may be bound to each other to form a heterocycle including at least a nitrogen atom, and n represents 0 or 1).

Description

Polyurethane compound liquid for producing haloalkene foamed polyurethane

The present invention relates to a polyol-based compounding solution used in producing polyurethane foam. More specifically, the present invention relates to a polyol-based compounding solution containing a polyol, hydrohaloolefins, and a specific amine catalyst and having excellent storage stability, and a method for producing a polyurethane foam using the polyol-based compounding solution and an organic polyisocyanate.

The present invention also relates to an amine compound that contributes to improving the storage stability of the polyol compounding solution.

The polyurethane resin can be produced by reacting a polyol with an isocyanate, but typically, it is produced by reacting a polyol-based compounding solution containing an amine catalyst, a foaming agent, a surfactant, or the like with an organic polyisocyanate. The method can be mentioned. In the method for producing the polyurethane resin, it is important that the polyol-based compounding solution and the organic polyisocyanate are mixed and contacted to cause a rapid foam molding reaction. For example, in the method of spraying a heat insulating polyurethane resin, a good polyurethane foamed resin heat insulating layer can be obtained by rapidly starting a foam molding reaction of a mixed solution spray-applied to a wall surface or the like.

In recent years, hydrohaloolefins containing hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) having a low global warming potential have begun to be used as the above-mentioned foaming agents. As specific examples of such foaming agents, as hydrofluoroolefins, trans-1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,1,4,4,4-hexafluorobuta -2-ene (HFO-1336mzz) and hydrochlorofluoroolefins include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd).

It is known that these foaming agents are decomposed over time under the action of the amine catalyst described above, and the reaction between the polyol-based compound composition and the organic polyisocyanate is delayed due to the decomposition. It has been known. Therefore, there is a problem that the polyol-based compounding solution containing the hydrohaloolefin-based foaming agent is difficult to store for a long period of time and is difficult to be used industrially.

As a method for solving the above problems, an example using an organic acid-containing amine catalyst (Patent Document 1) and an example using a steric hindrance amine catalyst (Patent Document 2) have been proposed.

Further, although unrelated to the above-mentioned problems, a catalyst containing an imine bond and a tertiary amine has been proposed (Patent Document 3).

Japan Special Table 2011-500893 International Publication No. 2009/048807 Japan Special Table 2007-516339 Gazette

In the example using the organic acid-containing amine catalyst described in Patent Document 1, there is a problem that the storage stability of the polyol-based compounding composition is not sufficiently improved.

In the example using the steric hindrance amine catalyst described in Patent Document 2, there is a problem that the foam molding reaction does not proceed rapidly, and there is a problem that liquid dripping is caused in the spraying method.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found an amine catalyst composed of a reaction product of a specific tertiary amine and an aldehyde, and have completed the present invention.

That is, the present invention relates to a polyol-based compounding solution for producing a polyurethane foam as shown below, a method for producing a polyurethane foam using the polyol-based compounding solution, or an amine compound that can be used in the polyol-based compounding solution. That is, the present invention exists in the following [1] to [11].
[1] polyol, hydrohaloolefin and the following formula (1)

(In the formula, Ar ¹ represents a monocyclic, linked ring, or condensed ring aromatic group having 3 to 20 carbon atoms which may have a substituent.
R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
n represents 0 or 1. )
A polyol-based compounding liquid composition for producing a polyurethane foam containing the compound represented by.
[2] The group represented by -NR ² R ² is a diethylamino group, an ethyl (n-propyl) amino group, a di (n-propyl) amino group, or a morpholino group, [1]. The composition according to.
[3] The composition according to [1] or [2], wherein both R ² are ethyl groups (that is, the group represented by -NR ² R ² is a diethylamino group).
[4] The composition according to any one of [1] to [3], wherein Ar ¹ is a phenyl group which may have a substituent.
[5] The composition according to any one of [1] to [3], wherein Ar ¹ is a group represented by any of the following formulas (2) to (6).

(In the formula, * represents a connecting site in the formula (1). R ¹ , R ² , and n are synonymous with the formula (1). Note that the formula (1) and the formula (5) are combined. In this case, R ¹ , R ² , and n may be the same or different from each other, and the formula (5) is limited to those having a total carbon number of 20 or less.)
[6] Of [1] to [5], wherein the hydrohaloolefin is hydrofluoropropene, hydrofluorobutene, hydrochlorofluoropropene, hydrochlorofluorobutene, hydrochloropropene, or hydrochlorobutene. The composition according to any one item.
[7] Of [1] to [5], wherein the hydrohaloolefin is trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorodifluoropropene, chlorotrifluoropropene, or chlorotetrafluoropropene. The composition according to any one item.
[8] 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, 1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene, 1,1,1,2,3-pentafluoropropene, 1-chloro-3, It is characterized by being 3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, or 1,1,1,4,4,4-hexafluorobut-2-ene. The composition according to any one of [1] to [5].
[9] The composition according to any one of [1] to [5], wherein the hydrohaloolefin is trans-1-chloro-3,3,3-trifluoropropene.
[10] A method for producing a polyurethane foam, which comprises reacting the composition according to any one of [1] to [9] with a polyisocyanate compound.
[11] The following equation (1')

(In the formula (1'), Ar ¹ represents a group represented by any of the above formulas (2) to (6).
In formulas (2) to (6), * represents a connecting site in formula (1').
In the formula, R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
When Ar ¹ is any of the formulas (2) to (5), n independently represents 0 or 1, and when Ar ¹ is formula (6), n represents 1.
When the formula (1') and the formula (5) are combined, R ¹ , R ² , and n may be the same or different from each other, and the formula (5) may be different. Limited to those with a total carbon number of 20 or less. )
The compound represented by.

Surprisingly, the catalyst of the present invention can significantly improve the storage stability of the polyol-based compounding solution for producing polyurethane foam containing hydrohaloolefin, as compared with the organic acid-containing amine catalyst which is one of the prior arts. it can. Further, since the catalyst composition of the present invention has remarkably high foaming activity as compared with the steric hindrance amine catalyst which is one of the prior arts, a rapid foaming reaction can be started, and dripping in the spraying method can be prevented. It can be suppressed.

For the above reasons, if the catalyst composition of the present invention is used, the polyol-based compounding solution can be stored for a long period of time, and a high-quality haloalkene foamed polyurethane can be produced, which is a special effect.

Next, the present invention will be described in detail.

The present invention is a polyol-based compounding liquid composition for producing polyurethane foam, which comprises a polyol, a hydrohaloolefin, and the following formula (1).

(In the formula, Ar ¹ represents a monocyclic, linked ring, or condensed ring aromatic group having 3 to 20 carbon atoms which may have a substituent.
R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
n represents 0 or 1. )
It is characterized by containing a compound represented by.

The compound represented by the above formula (1) in the polyol-based compounding liquid composition of the present invention is as follows.

The linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms in R ¹ is not particularly limited, and is, for example, an ethylene group, a propane-1,3-diyl group, or a propane-. 1,2-Diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, 2-methylpropane-1,3-diyl group, hexane-1, 6-Diyl group, hexane-1,5-diyl group, hexane-1,4-diyl group, hexane-1,3-diyl group, hexane-1,2-diyl group and the like can be mentioned.

The above-mentioned R ¹ is preferably an ethylene group or a propane-1,3-diyl group, and more preferably a propane-1,3-diyl group because it is excellent in the effect of storage stability.

The above-mentioned R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.

The above-mentioned alkyl group having 2 to 4 carbon atoms is not particularly limited, but for example, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or tert-butyl. The basis can be mentioned.

The hydroxyalkyl group having 2 to 4 carbon atoms is not particularly limited, but for example, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 1-hydroxypropyl group, or a 4-hydroxy group. Butyl groups and the like can be mentioned.

The heterocycle formed by bonding ^two R2s to each other and containing at least a nitrogen atom is not particularly limited, and examples thereof include a pyrrolidinyl group (pyrrolidin ring), a morpholino group (morpholine ring), and the like. it can.

The R ² is preferably an ethyl group, a hydroxyethyl group, or an n-propyl group independently of each other in terms of excellent storage stability effect, and is used as a group represented by -NR ² R ^2. it is a diethylamino group, an ethyl (n- propyl) amino group, preferably a di (n- propyl) amino group, or a morpholino group, a diethylamino group (i.e., a two R ² are both an ethyl group) Is more preferable.

The monocyclic, linked ring, or condensed ring aromatic group having 3 to 20 carbon atoms which may have a substituent in Ar ¹ described above represents a group having a total carbon number of 3 to 20 and is particularly limited. Although not, for example, it may have a monocyclic, linked ring, or condensed ring aromatic hydrocarbon group having a total carbon number of 3 to 20 or a substituent which may have a substituent. Heteroaromatic groups of monocyclic, linked or fused rings having 3 to 20 carbon atoms can be mentioned.

The substituent which the above aromatic group, aromatic hydrocarbon group or heteroaromatic group may have is not particularly limited, but for example, a methyl group, an ethyl group, a tert-butyl group, and the like. Vinyl group, allyl group, methoxy group, ethoxy group, tert-butoxy group, hydroxy group, hydroxymethyl group, hydroxyethyl group, phenyl group, tosyl group, benzyl group, pyridyl group, epoxy group, glycidyl group, glycidyl ether group, Carboxy group, methoxycarboxy group, ethoxycarboxy group, carbamoyl group, nitro group, amino group, isocyanate group, formyl group, sulfo group, nitrile group, acetyl group, mercapto group, fluorine group, chlorine group, bromine group, iodine group, Examples thereof include a trifluoromethylsulfonyl group and a p-toluenesulfonyl group.

The aromatic hydrocarbon group having a total carbon number of 3 to 20 and which may have the above-mentioned substituents is not particularly limited, but is, for example, a phenyl group or a trill. Group, 2,4,6-trimethylphenyl group, ethylphenyl group, cumenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, formylphenyl group, carboxyphenyl group, methoxycarbonyloxyphenyl group, ethoxycarbonyloxyphenyl group , Carbamoylphenyl group, nitrile group, hydroxyphenyl group, biphenylyl group (2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group), turphenylyl group, naphthyl group, phenylnaphthyl group, naphthylphenyl group, anthracenyl group, or anthryl Group etc. can be mentioned.

The heteroaromatic group having a monocyclic, linking ring, or condensed ring having a total carbon number of 3 to 20 which may have the above-mentioned substituent is not particularly limited, and is, for example, a phenylyl group or an imidazolyl group. , Thienyl group, pyridyl group, methylpyridyl group, phenylpyridyl group and the like can be exemplified.

Ar ¹ is preferably a phenyl group having a total carbon number of 20 or less, which may have a substituent, from the viewpoint of excellent storage stability, and a phenyl group (the group has a total carbon number of 6 to 6 to In the range of 20, methyl group, phenyl group, methoxy group, formyl group, carboxy group, methoxycarboxy group, ethoxycarboxy group, carbamoyl group, nitrile group, hydroxy group, or-(CH = CH) _n -CH = N- _{^{CH 2 -CH 2 -R 1 -N (}} R 2) groups represented by ₂ (n, ^{R 1,} and ^{R 2} is the formula (n in 1), ^{R 1,} and ^{R 2} as defined) substituted with It is more preferable that the group is represented by any of the following formulas (2) to (6).

(In the formula, * represents a connecting site in the formula (1). R ¹ , R ² , and n are synonymous with the formula (1). Note that the formula (1) and the formula (5) are combined. In this case, R ¹ , R ² , and n may be the same or different from each other, and the formula (5) is limited to those having a total carbon number of 20 or less.)
In the formula (1), n independently represents 0 or 1, but is preferably 0 in terms of excellent storage stability.

In the compound represented by the formula (1), the above formulas (4), (5), and (6) are suitable for industrial production, respectively, and the following formulas (4') and (5'), respectively. ) And (6') are preferable.

(In the formula, * represents a connecting site in the formula (1). R ¹ , R ² , and n are synonymous with the formula (1). Note that the formula (1) and the formula (5') are combined. In this case, R ¹ , R ² , and n may be the same or different from each other, and the formula (5') is limited to those having a total carbon number of 20 or less.)
The polyol in the polyol-based compounding liquid composition of the present invention is not particularly limited, and examples thereof include generally known polyester polyols, polyether polyols, and polymer polyols. The polyol can be used alone or as a mixture.

Known polyester polyols usually include polymerization reactions of dibasic acids (eg, adipic acid, phthalic acid, succinic acid, azelaic acid, sebacic acid, ricinoleic acid, etc.) and hydroxy compounds (eg, glycol, etc.). .. Specific examples of the polyester polyol are not particularly limited, but for example, a polyester polyol using DMT (dimethyl terephthalate) production residue or phthalic acid anhydride production residue as a starting material, waste products during nylon production, and the like. Examples thereof include waste products during the production of TMP (trimethylol propane), waste products during the production of pentaerythritol, polyester polyols derived from waste products during the production of phthalic acid-based polyesters, and the like.

Known polyether polyols include polyhydric alcohols (eg, glycols, glycerin, pentaerythritol, trimethylolpropane, sorbitol, shoe cloth, etc.), aliphatic amine compounds (eg, ammonia, ethylenediamine, ethanolamine, etc.), or aromatics. Examples thereof include those obtained by reacting a group amine compound (for example, toluenediamine, diphenylmethane-4, 4'-diamine, etc.) with ethylene oxide or propylene oxide.

Examples of known polymer polyols include those obtained by reacting the above-mentioned polyether polyol with an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) in the presence of a radical polymerization catalyst.

Of these polyols, polyether or polyester polyols are preferable in that they are suitable for producing rigid polyurethane foam. Further, from the viewpoint of being suitable for producing a rigid polyurethane foam, the average functional value of the polyol is preferably 4 to 8, and the average hydroxyl value of the polyol is preferably 200 to 800 mgKOH / g, more preferably. It is 300 to 700 mgKOH / g.

The hydrohaloofrefin in the above-mentioned polyol-based compounding liquid composition is not particularly limited, but for example, the one having a global warming potential (GWP; Global Warming Potential) of 150 or less is preferable and more preferable. Is 100 or less, and even more preferably 75 or less.

The hydrohaloolefin used in the present invention is not particularly limited, but for example, its ozone depletion potential (ODP; Ozone Depletion Potential) is preferably 0.05 or less, more preferably 0.02. It is less than or equal to, and even more preferably about 0.

The hydrohaloolefin used in the present invention is not particularly limited, but is preferably hydrofluoropropene, hydrofluorobutene, hydrochlorofluoropropene, hydrochlorofluorobutene, or hydrochloro from the viewpoint of heat insulating performance of polyurethane foam. Propene, or hydrochlorobutene. More preferably, trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorotrifluoropropene, chlorodifluoropropene, or chlorotetrafluoropropene can be mentioned. More preferably, tetrafluoropropene, pentafluoropropene, or chlorotrifluoropropene can be mentioned. More preferably, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye) ), 1,1,1-Trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene , 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yz), 1-chloro-3,3,3-tri With fluoropropene (HFCO-1233zd), 1-chloro-2,3,3,3-tetrafluoropropene, or 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz). is there. Particularly preferred is trans-1-chloro-3,3,3-trifluoropropene (HFCO-1233zd (E)). The hydrohaloolefins exemplified above can be used alone or as a mixture of two or more kinds. Further, the hydrohaloolefins exemplified above include all structural isomers, geometric isomers, and stereoisomers.

The foaming agent used in the present invention is not particularly limited, and examples thereof include the above-mentioned hydrohaloolefin. Other effervescent agents include organic acids that generate CO ₂ when reacted with water, formic acid, and isocyanate, hydrocarbons, ethers, halogenated ethers, pentafluorobutane, pentafluoropropane, hexafluoropropane, heptafluoropropane, and 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, 1,1,1,2,3,3,3-hepta Fluoropropane, trichlorofluoromethane, dichlorodifluoromethane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoropropane, difluoromethane, difluoroethane, 1, Included are 1,1,3,3-pentafluoropropane, 1,1-difluoroethane, isobutane, normalpentane, isopentane, or cyclopentane. The above-exemplified foaming agents may be used alone or in combination of two or more.

The foaming agent is usually preferably present in the polyol-based compounding solution composition in an amount of 1% by weight to 50% by weight, more preferably 3% by weight to 30% by weight, more preferably, based on the weight of the polyol-based compounding solution composition. The amount is preferably 5% by weight to 20% by weight.

The total amount of the foaming agent may be the above-mentioned hydrohaloolefin or a mixture of the above-mentioned hydrohaloolefin and other foaming agents. When the hydrohaloolefin is used as a mixture with other foaming agents, the content of the hydrohaloolefin is preferably 5% by weight to 90% by weight, more preferably 7% by weight to 80% by weight of the weight of the foaming agent. It is by weight%, more preferably 10% by weight to 70% by weight. On the contrary, the content of the foaming agent other than the hydrohaloolefin is preferably 95% by weight to 10% by weight, more preferably 93% by weight to 20% by weight, and more preferably 90% by weight of the weight of the foaming agent. It is from% by weight to 30% by weight.

In the polyol-based compounding liquid composition of the present invention, the content of the compound represented by the formula (1) can be 0.1 to 100 parts by weight when the polyol is 100 parts by weight. It is preferably 0.1 to 50 parts by weight, and more preferably 0.1 to 10 parts by weight.

In the polyol-based compounding liquid composition of the present invention, the content of hydrohaloolefin can be 0.1 to 100 parts by weight when the polyol is 100 parts by weight, but the heat insulating performance of the polyurethane foam is improved. From the viewpoint, it is preferably 0.1 to 50 parts by weight, and more preferably 0.1 to 20 parts by weight.

The polyol-based compounding liquid composition of the present invention may contain components other than the above, and is not particularly limited, but for example, a quaternary ammonium compound, an organometallic catalyst compound, a foam stabilizer, a cross-linking agent, and the like. Examples thereof include chain extenders, solvents, colorants, flame retardants, antiaging agents, and other known additives.

The above-mentioned quaternary ammonium compound is not particularly limited, but for example, a tetraalkylammonium halide such as tetramethylammonium chloride, a tetraalkylammonium hydroxide such as tetramethylammonium hydroxide salt, or tetramethylammonium acetate. Salts, tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanate, hydroxyalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate Can be mentioned.

The organic metal catalyst compound is not particularly limited, but for example, stanus diacetate, stanus dioctate, stanus dioleate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, and the like. Examples thereof include dibutyltin dichloride, dioctyltin dilaurate, lead octanate, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.

The foam stabilizer is not particularly limited, but for example, a known silicone foam stabilizer can be exemplified, and more specifically, for example, an organosiloxane-polyoxyalkylene copolymer or silicone. -A nonionic surfactant such as a grease copolymer can be exemplified. These silicone foam stabilizers can be used alone or as a mixture.

The above-mentioned cross-linking agent, chain extender, or solvent is not particularly limited, but is, for example, low molecular weight polyhydric alcohols such as water, ethylene glycol, diethylene glycol, 1,4-butanediol, and glycerin, and diethanolamine. , Low molecular weight amine polyols such as triethanolamine, polyamines such as ethylenediamine, xylylenediamine and methylenebis orthochloroaniline, and polyols such as polyethylene glycol and polypropylene glycol.

The type of additive described as described above and the content in the polyol-based compounding liquid composition are preferably used within the range generally used.

The content of the quaternary ammonium salt catalyst is not particularly limited, but can be 0.1 to 100 parts by weight when the polyol is 100 parts by weight.

The content of the cross-linking agent, the chain extender, or the solvent is not particularly limited, but is preferably 70 parts by weight or less when the polyol is 100 parts by weight.

The polyol-based compounding liquid composition of the present invention can produce a polyurethane resin by reacting with polyisocyanate. The polyurethane resin is not particularly limited, and examples thereof include rigid polyurethane foams and isocyanurate-modified rigid polyurethane foams.

As the above-mentioned polyisocyanate, known polyisocyanates can be exemplified, and more specifically, for example, toluene diisocyanate (TDI), TDI derivative, diphenylmethane diisocyanate (MDI), MDI derivative, naphthylene diisocyanate, or xylyl. Aromatic polyisocyanates such as range isocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, free isocyanate-containing prepolymers by reaction between them and polyol, carbodiimide modification, etc. Examples of the modified polyisocyanates of the above, and further examples thereof include mixed polyisocyanates thereof.

Examples of the toluene diisocyanate (TDI) include 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, which may be used alone or as a mixture. Examples of the TDI derivative include a TDI prepolymer having a terminal isocyanate group which is a reaction product of TDI and a polyol.

Examples of the diphenylmethane diisocyanate (MDI) include 4,4'-diphenylmethane diisocyanate and 4,2'-diphenylmethane diisocyanate, which may be used alone or as a mixture. Examples of the MDI derivative include polyphenylpolymethylene diisocyanate, which is a polymer of MDI, and an MDI prepolymer having a terminal isocyanate group, which is a reaction product of MDI and a polyol.

Of these, MDI or MDI derivatives are preferable because they are suitable for producing rigid polyurethane foam, and these may be mixed and used.

Rigid polyurethane foam usually has a highly crosslinked closed cell structure, is a foam that cannot be reversibly deformed, and has properties completely different from those of soft and semi-rigid foam. The physical properties of the hard foam are not particularly limited, but in general, the density is preferably in the range of 20 to 100 kg / m3, and the compressive strength is 0.5 to 10 kgf / cm2 (50 to 1000 kPa). It is preferably in the range of.

The polyurethane foam product produced by using the polyol-based compounding liquid composition of the present invention can be used for various purposes. For example, there are applications such as heat insulating building materials, heat insulating materials for freezers, and heat insulating materials for refrigerators.

Among the compounds represented by the above formula (1), the compounds limited within the range of the following formula (1') can significantly improve the storage stability of the polyol-based compounding liquid composition of the present invention. It is preferable in that it can be done.

(In the formula (1'), Ar ¹ represents a group represented by any of the above formulas (2) to (6).
In formulas (2) to (6), * represents a connecting site in formula (1').
In the formula, R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
When Ar ¹ is any of the formulas (2) to (5), n independently represents 0 or 1, and when Ar ¹ is formula (6), n represents 1.
When the formula (1') and the formula (5) are combined, R ¹ , R ² , and n may be the same or different from each other, and the formula (5) may be different. Limited to those with a total carbon number of 20 or less. )
Each substituent in the formula (1') (straight, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms, alkyl group having 2 to 4 carbon atoms, hydroxyalkyl group having 2 to 4 carbon atoms, at least nitrogen A heterocycle containing an atom, a group represented by -NR ² R ² , etc.) has the same meaning as each substituent in the formula (1) and is not particularly limited, but for example, in the formula (1). The groups exemplified by each substituent can be exemplified.

The preferable range of Ar ¹ , R ¹ , R ² , and n in the formula (1') is the same as the preferable range of Ar ¹ , R ¹ , R ² , and n described in the formula (1). ..

In addition, in terms of being suitable for industrial production, the above formulas (4), (5), and (6) are the following formulas (4'), (5'), and (6'), respectively. Is preferable.

(In the formula, * represents the connecting part in the formula (1').
R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
When the formula (1') and the formula (5') are combined, R ¹ , R ² , and n may be the same or different from each other, and the formula (5') may be different. Is limited to those having a total carbon number of 20 or less. )
Hereinafter, a method for synthesizing the compound represented by the above formula (1') will be described.

The compound represented by the above formula (1') is the following formula (7).

(In the formula (7), Ar ¹ represents a group represented by the above formulas (2), (3), (4), or (6).
In formulas (2), (3), (4), and (6), * represents a connecting site in formula (7).
When Ar ¹ is any of the formulas (2) to (4), n independently represents 0 or 1, and when Ar ¹ is formula (6), n represents 1. )
Aldehyde compound represented by, or the following formula (8)

(In the formula, n independently represents 0 or 1).
The aldehyde compound represented by and the following formula (9)

(In the formula, R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom. )
It can be produced by reacting an amine compound represented by.

The aldehyde compound represented by the formula (7) is not particularly limited, but specifically, syringaldehyde, 3,4-dimethoxybenzaldehyde, 2-hydroxy-1-naphthaldehyde, 4-amyloxybenzaldehyde. , P-Tolualdehyde, benzaldehyde, perylaldehyde, salicylaldehyde, 4-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, vanillin, o-anisaldehyde, p-anisaldehyde, m-anisaldehyde, cuminaldehyde, 4-isobutylbenzaldehyde And cinnamaldehyde. From the viewpoint of availability, salicylaldehyde, benzaldehyde, vanillin, p-anisaldehyde, and cinnamaldehyde are preferable, and salicylaldehyde, benzaldehyde, and cinnamaldehyde are more preferable.

That is, it is preferable that the formulas (4) and (6) in the formula (7) are the following formulas (4') and (6'), respectively.

(In the formula, * represents the connecting part in the formula (7).)
The aldehyde compound represented by the formula (8) is not particularly limited, and specific examples thereof include orthophthalaldehyde, terephthalaldehyde and isophthalaldehyde. From the viewpoint of availability, terephthalaldehyde and isophthalaldehyde are preferable, and isophthalaldehyde is more preferable.

That is, the aldehyde compound represented by the formula (8) is preferably the aldehyde compound represented by the following formula (8').

(In the formula, n independently represents 0 or 1).
The amine compound represented by the formula (9) is not particularly limited, but is N- (3-aminopropyl) from the viewpoint of improving the storage stability of the polyol-based compound for producing polyurethane foam containing hydrohaloolefin. ) Morpholine, N, N-diethylethylenediamine, and N, N-diethyl-1,3-diaminopropane are preferred. Further, from the viewpoint of the magnitude of catalytic activity, N, N-diethylethylenediamine and N, N-diethyl-1,3-diaminopropane are particularly preferable.

The aldehyde compound represented by the formula (7) or the formula (8) can be easily produced by a method known in the literature. For example, a method of oxidizing the corresponding alcohol, a method of reducing the corresponding ester, amide, and nitrile compound, and the like can be mentioned.

The amine compound represented by the formula (9) can be easily produced by a method known in the literature. For example, a method of catalytically hydrogenating the corresponding nitrile compound using a nickel catalyst or a cobalt catalyst can be mentioned.

When the aldehyde compound and the amine compound are reacted, the ratio thereof is not particularly limited, but is preferably [formyl group] / [primary amino group] = 9/1 to 1/9. It is in the range of (molar ratio), particularly preferably in the range of [formyl group] / [primary amino group] = 5/1 to 1/5 (molar ratio), and more preferably [formyl group]. / [Primary amino group] = 2/1 to 1/2 (molar ratio).

The compound represented by the formula (1') can be produced by dehydrating and condensing the aldehyde compound represented by the formula (7) or (8) and the amine compound represented by the formula (9).

For the dehydration condensation, the reaction can proceed by mixing the above amine compound and aldehyde compound and heating them.

The reaction can be carried out without a solvent or in a solvent. The solvent is not particularly limited, but for example, methanol, ethanol, 2-propanol, 1-butanol, ethylene glycol, diethylene glycol, propylene glycol, diethyl ether, diisopropyl ether, diglyme, tetrahydrofuran, dioxane, hexane, heptane, etc. Examples thereof include octane, benzene, toluene, xylene, pyridine, acetonitrile, 2-pyrrolidone, methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide and the like.

The above reaction can also be carried out in the presence of a catalyst. The catalyst is not particularly limited, but an acid catalyst is preferable, and for example, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, tris borate (2,2,2-trifluoroethyl), pyrrolidine, or orthotitanic acid. Examples thereof include tetraethyl. The amount of the catalyst added is not particularly limited, but is preferably in the range of 0.01 to 5 parts by weight, preferably in the range of 0.2 to 2 parts by weight, based on 100 parts by weight of the amine compound. More preferred.

For the above reaction, a dehydration operation step may be performed to promote the reaction. At this time, a dehydrating agent may be added. The dehydrating agent is not particularly limited, and examples thereof include molecular sieves and magnesium sulfate.

Regarding the above reaction, the liquid property is not particularly limited, but neutral to weakly acidic is preferable, pH 2 to 8 is more preferable, and pH 3 to 6 is more preferable.

The above reaction can be performed continuously or in batch.

The above reaction is not limited in pressure and can be performed under reduced pressure, atmospheric pressure, or pressurized. Industrially, it is preferably under pressure and is not particularly limited, but for example, it is preferably in the range of 0 to 10 MPaG (megapascal gauge), and more preferably a plate of 0 to 2 MPaG. ..

The above reaction is not limited in temperature and can be performed at any temperature. The temperature is not particularly limited, but is preferably in the range of 90 to 150 ° C, preferably 100 to 130 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The analytical instruments and measurement methods used in this example are listed below.

[NMR measurement]
Measuring device: Gemini200 manufactured by Varian
Example 1.
1. Add 13.0 g (0.10 mol) of N, N-diethyl-1,3-diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) to a 100 cc eggplant flask, replace with nitrogen, and then cinnamaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 13. 2 g (0.10 mol) was added dropwise over 1 hour with stirring. Then, after aging reaction at room temperature for 24 hours, 26 g of a reaction solution was obtained.

The ¹ H-NMR analysis data of the reaction solution is as follows.
^{1 1} H-NMR (CDCl ₃ ): 1.03 (t, 6H), 1.83 (tt, 2H), 2.48-2.55 (m, 6H), 3.54 (t, 2H), 6 .90-6.92 (m, 2H), 7.31-7.38 (m, 3H), 7.46-7.49 (m, 2H), 8.04 (d, 1H) [ppm].

The above ^{1 1} H-NMR analysis data supports the following structure of the reaction solution. This compound is referred to as (A-1).

Example 2.
The same procedure as in Example 1 was carried out except that 15.2 g (0.10 mol) of vanillin (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 13.2 g (0.10 mol) of cinnamaldehyde, and 28 g of the reaction solution was used. Obtained.

The ¹ H-NMR analysis data of the reaction solution is as follows.
^{1 1} H-NMR (CDCl ₃ ): 1.03 (t, 6H), 1.83 (dd, 2H), 2.52-2.60 (m, 6H), 3.57 (t, 2H), 3 .88 (s, 3H), 4.46 (br, 1H), 6.87 (d, 1H), 7.05 (dd, 1H), 7.40 (s, 1H), 8.15 (s, 1H) [ppm]
The above ^{1 1} H-NMR analysis data supports the following structure of the reaction solution. This compound is referred to as (A-2).

Example 3.
The same procedure as in Example 1 was carried out except that 13.4 g (0.10 mol) of isophthalaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 13.2 g (0.10 mol) of cinnamaldehyde to prepare the reaction solution. I got 26g.

The ¹ H-NMR analysis data of the reaction solution is as follows.
^{1 1} H-NMR (CDCl ₃ ): 1.05 (m, 6H), 1.84-1.95 (m, 2H), 2.55-2.62 (m, 6H), 3.68 (m, 2H), 7.45 (t, 0.18H), 7.58 (t, 0.55H), 7.74 (t, 0.14H), 7.80 (d, 0.39H), 7.94 (D, 0.52H), 8.00-8.03 (m, 0.73H), 8.16 (d, 0.28H), 8.22 (s, 0.55H), 8.33 (s) , 0.37H), 8.38 (s, 0.71H), 10.07 (s, 0.51H), 10.12 (0.25H) [ppm]
The above ^{1 1} H-NMR analysis data supports the following structure of the reaction solution. This compound composition is referred to as (A-3).

Production example 1.
The same procedure as in Example 1 was carried out except that 12.2 g (0.10 mol) of salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 13.2 g (0.10 mol) of cinnamaldehyde, and 25 g of the reaction solution was used. Got

The ¹ H-NMR analysis data of the reaction solution is as follows.
^{1 1} H-NMR (CDCl ₃ ): 1.02 (t, 6H), 1.85 (tt, 2H), 2.50-2.54 (m, 6H), 3.63 (t, 2H), 6 .86 (dd, 1H), 6.95 (d, 1H), 7.23 (d, 1H), 7.29 (dd, 1H), 8.35 (s, 1H) [ppm]
The above ^{1 1} H-NMR analysis data supports the following structure of the reaction solution. This compound is referred to as (A-4).

The polyurethane foam production and evaluation results will be described below. The following raw materials were used as raw materials related to the present invention other than the above compounds.

Polyester A: Maximol RDK-133 (aromatic polyester polyol, OH value = 319 mgKOH / g, manufactured by Kawasaki Kasei Chemicals Co., Ltd.)
Polypoly B: DK polyol 3776 (Mannich-based polyether polyol, OH value = 349 mgKOH / g, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Flame Retardant: TMCPP (Halogen-containing phosphoric acid ester, manufactured by Daihachi Chemical Industry Co., Ltd.)
Foam regulator: NIAX SILICONE L-5420 (Silicone foam stabilizer, manufactured by Momentive Performance Materials Japan LLC)
Foaming agent A: Solstice LBA (1-chloro-3,3,3-trifluoropropene, manufactured by Honeywell Japan Ltd.)
Foaming agent B: Water Polyisocyanate solution: Polymeric MDI (Millionate MR200 manufactured by Tosoh Corporation, NCO content = 31.0%)
Example 4.
A rigid polyurethane foam was produced using the catalyst for producing polyurethane foam of the present invention.

Weigh 50 parts by weight of polyol A, 50 parts by weight of polyol B, 20 parts by weight of flame retardant, 1.0 part by weight of foam stabilizer, 40 parts by weight of foaming agent A, and 1.0 part by weight of foaming agent B, and sufficiently The polyol-based compounding solution composition was prepared by stirring and mixing. Next, 48.6 g of the prepared polyol-based compounding solution composition was placed in a 300 ml polyethylene cup, and 6.58 parts by weight of the above compound (A-1) was further added as a catalyst, stirred and mixed, and the temperature was adjusted to 15 ° C. .. The amount of the catalyst added was adjusted so that the reactivity would be about 30 seconds in the following gel time. A polyisocyanate solution whose temperature has been adjusted to 15 ° C. is placed in a cup of the raw material compounding solution in an amount such that the isocyanate index [[isocyanate group] / [OH group] (molar ratio) × 100)] is 110, and then The mixture was quickly stirred with a stirrer at 7000 rpm for 3 seconds. The mixed solution mixed and stirred was transferred to a 1 L polyethylene cup whose temperature was adjusted to 23 ° C., and the reactivity during foaming was measured by the method shown below. In addition, the appearance of the obtained rigid polyurethane foam was confirmed and the state of the cell was recorded.

[Measurement of reactivity]
・ Cream time: Visually measure the time when the foaming reaction progresses and foaming starts ・ Gel time: Visually measure the time when the reaction progresses and changes from a liquid substance to a resinous substance [Polyurethane foam molding state]
◯: The appearance and the inside are all normal ×: There is an abnormal part in the appearance or the inside.

The terms indicating abnormalities are explained below.

Cell roughness: Bubbles are coalesced and coarsened. Next, the above-mentioned polyol-based compounding composition is placed in a closed container and heated at 50 ° C. for 7 or 14 days, and then the same foaming reaction as above is carried out. [Measurement of reactivity] and [Molded state of polyurethane foam] were evaluated.

Example 5.
An experimental operation was carried out in the same manner as in Example 4 except that 7.09 parts by weight of the above compound (A-2) was used instead of 6.58 parts by weight of the compound (A-1), and evaluation data were obtained.

Example 6.
The experimental operation was carried out in the same manner as in Example 4 to obtain evaluation data, except that the above compound composition (A-3) was used in an amount of 6.63 parts by weight instead of 6.58 parts by weight of the compound (A-1). did.

Example 7.
An experimental operation was carried out in the same manner as in Example 4 except that 6.34 parts by weight of the above compound (A-4) was used instead of 6.58 parts by weight of the compound (A-1), and evaluation data were obtained.

Comparative example 1.
Same as Example 4 except that N, N-diethyl-1,3-diaminopropane / formic acid 11.1 parts by weight / 3.9 parts by weight was used instead of 6.58 parts by weight of compound (A-1). An experimental operation was carried out in 1 and evaluation data was acquired.

Comparative example 2.
The experimental operation was carried out in the same manner as in Example 4 except that 20.0 parts by weight of N, N-dicyclohexylmethylamine was used instead of 6.58 parts by weight of compound (A-1), and evaluation data were obtained.

Comparative example 3.
Performing the same operation as in Example 2 of Patent Document 3 (Japanese Patent Laid-Open No. 2007-516339), from the adduct of N, N-dimethyl-1,3-diaminopropane and salicylaldehyde represented by the following formula. An amine catalyst (hereinafter referred to as compound (A-5)) was obtained.

Evaluation data was obtained by performing the experimental operation in the same manner as in Example 4 except that the dehydrated and dried compound (A-5) was used in an amount of 3.24 parts by weight instead of 6.58 parts by weight of the compound (A-1). ..

These results are shown in Tables 1 to 4.

As is clear from Tables 1 to 4, in Examples 4 to 7 using the amine catalyst of the present invention or the polyol-based compounding liquid composition for producing a polyurethane foam prepared by combining an aldehyde compound and an amine compound, the initial foamability It has the feature of fast (cream time) and the feature that the decrease in reactivity after storage is small. Moreover, the appearance of the obtained rigid polyurethane foam was good.

Comparative Example 1 is an example of a polyol-based compounding solution composition containing a conventionally known organic acid-containing amine catalyst, but the reactivity is greatly reduced after storage, and the obtained rigid polyurethane foam has a poor appearance. The cell roughness appeared greatly.

Comparative Example 2 is an example of a polyol-based compounding solution composition containing a conventionally known steric hindrance amine catalyst, but the initial foaming property (cream time) was slow.

Comparative Example 3 is an example of a polyol-based compounding solution composition containing an amine catalyst composed of an adduct of N, N-dimethyl-1,3-diaminopropane and salicylaldehyde, but the reactivity is significantly reduced after storage. Moreover, the appearance of the obtained rigid polyurethane foam was poor, and the cell roughness appeared significantly. The effect of the dimethylamino group is suggested.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the essence and scope of the invention.

The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2019-058437 filed on March 26, 2019 are cited here and incorporated as disclosure of the specification of the present invention. It is a thing.

The composition of the present invention can be used as a raw material for polyurethane foam.

Claims (11)

1. Polyols, hydrohaloolefins and the following formula (1)
   

   

   (In the formula, Ar ¹ represents a monocyclic, linked ring, or condensed ring aromatic group having 3 to 20 carbon atoms which may have a substituent.
   R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
   R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
   n represents 0 or 1. )
   A polyol-based compounding liquid composition for producing a polyurethane foam containing the compound represented by.
2. The group according to claim 1, wherein the group represented by -NR ² R ² is a diethylamino group, an ethyl (n-propyl) amino group, a di (n-propyl) amino group, or a morpholino group. Composition.
3. The composition according to claim 1 or 2, wherein both R ² are ethyl groups (that is, the group represented by -NR ² R ² is a diethylamino group).
4. The composition according to any one of claims 1 to 3, wherein Ar ¹ is a phenyl group which may have a substituent.
5. The composition according to any one of claims 1 to 3, wherein Ar ¹ is a group represented by any of the following formulas (2) to (6).
   

   

   (In the formula, * represents a connecting site in the formula (1). R ¹ , R ² , and n are synonymous with the formula (1). Note that the formula (1) and the formula (5) are combined. In this case, R ¹ , R ² , and n may be the same or different from each other, and the formula (5) is limited to those having a total carbon number of 20 or less.)
6. The present invention according to any one of claims 1 to 5, wherein the hydrohaloolefin is hydrofluoropropene, hydrofluorobutene, hydrochlorofluoropropene, hydrochlorofluorobutene, hydrochloropropene, or hydrochlorobutene. The composition described.
7. The present invention according to any one of claims 1 to 5, wherein the hydrohaloolefin is trifluoropropene, tetrafluoropropene, pentafluoropropene, chlorodifluoropropene, chlorotrifluoropropene, or chlorotetrafluoropropene. The composition described.
8. 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 , 1,1,2,3,3-pentafluoropropene, 1,1,1,2-tetrafluoropropene, 1,1,1,2,3-pentafluoropropene, 1-chloro-3,3,3 -A claim, characterized by being trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, or 1,1,1,4,4,4-hexafluorobut-2-ene. Item 2. The composition according to any one of Items 1 to 5.
9. The composition according to any one of claims 1 to 5, wherein the hydrohaloolefin is trans-1-chloro-3,3,3-trifluoropropene.
10. A method for producing a polyurethane foam, which comprises reacting the composition according to any one of claims 1 to 9 with a polyisocyanate compound.
11. The following formula (1')
    

    

    

    (In the formula (1'), Ar ¹ represents a group represented by any of the following formulas (2) to (6).
    In formulas (2) to (6), * represents a connecting site in formula (1').
    In the formula, R ¹ represents a linear, branched, or cyclic divalent alkyl group having 2 to 6 carbon atoms.
    R ² independently represents an alkyl group having 2 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms. The two R ^2s may be bonded to each other to form a heterocycle containing at least a nitrogen atom.
    When Ar ¹ is any of the formulas (2) to (5), n represents 0 or 1, and when Ar ¹ is formula (6), n represents 1.
    When the formula (1) and the formula (5) are combined, R ¹ , R ² , and n may be the same or different from each other, and the total of the formula (5) is the total. Limited to those with 20 or less carbon atoms. )
    The compound represented by.