JP2001026627A - Catalyst for producing polyurethane and method for producing polyurethane using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem on the transfer of a catalyst, fogging and stimulant odor by using 5-dimethylamino-3-methylpentanol when polyurethane is produced by reaction of a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surface active agent, a crosslinking agent and the like. SOLUTION: The structure of 5-dimethylamino-3-methylpentanol is represented by the formula. This catalyst is obtained by reaction between 3-methyl-1,5- pentanediol and dimethylamine. The amount of the catalyst used ranges from 0.01 to 10 pts.wt., preferably from 0.05 to 5 pts.wt. per 100 pts.wt. of the polyol used. This catalyst may be used in combination with other type of catalyst. Other type of catalyst includes, for example, an organometallic catalyst, a tertiary amine, a quaternary ammonium salt or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst used for producing polyurethane such as soft, hard, semi-hard and elastomer. More specifically, the present invention relates to a novel tertiary amine catalyst for producing polyurethane which has a low odor having an OH group in a molecule and is non-migratory in a polyurethane resin, and has excellent moldability on a polyurethane surface.

[0002]

2. Description of the Related Art Polyurethane is produced by reacting a polyisocyanate and an organic polyol in the presence of a catalyst and, if necessary, a foaming agent, a surfactant and a crosslinking agent. Conventionally, a large number of organotin compounds and tertiary amine compounds have been known as catalysts for this polyurethane reaction, and are often used industrially either alone or by mixing several compounds.

In particular, tertiary amine compounds are widely used as catalysts for producing polyurethanes, for example, triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2- Compounds such as dimethylaminoethyl) ether, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, and N, N-dimethylethanolamine are known as catalysts. ing.

In the production of polyurethane, the above compounds are used alone or in combination as a catalyst. For example, in the case of flexible, rigid and semi-rigid foams, among these polyurethane production catalysts, a catalyst which relatively accelerates the reaction between an organic polyol and an isocyanate, such as an organic tin compound,
As the primary amine compound, a catalyst for promoting the reaction between water and an isocyanate with a resin catalyst such as triethylenediamine, for example, bis (2-dimethylaminoethyl) ether, N, N, N ', N ", N" -pentane It is common to use in combination with a foaming catalyst such as methyldiethylenetriamine. Also, N-methylmorpholine, N-
A catalyst such as ethyl morpholine is often used for the purpose of improving the moldability of the polyurethane surface.

[0005]

However, the amine compounds which have been developed so far for polyurethane production are:
There are various problems. That is, N-methylmorpholine, N-ethylmorpholine and the like are effective in improving the moldability of the polyurethane surface, but have an extremely strong irritating odor. Causes environmental degradation. Furthermore, when polyurethane is manufactured using these compounds, for example, in an automotive instrument panel which is a semi-rigid polyurethane foam having polyvinyl chloride (PVC) as a skin,
The urethane production catalyst remaining in the product migrates to the PVC in contact with the polyurethane and causes discoloration, deterioration, and the like of the PVC. In addition, in recent years, a polyurethane production catalyst has been a factor in the problem of so-called fogging, in which volatile components of polyurethane foam migrate to window glass of automobiles and fog the window glass. In contrast to these transfer-type catalysts, non-transfer-type catalysts having active hydrogen that reacts with polyisocyanate in the molecule are used for the purpose of preventing the above problems from occurring because they are fixed in polyurethane. N, N-dimethylethanolamine has an OH group in the molecule and is the most common non-transferable catalyst, but it has a strong pungent odor, and further has a moldability on the polyurethane surface. It has insufficient functions in terms of improvement.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst for producing polyurethane in which the problems associated with the transfer of the catalyst, the problem of fogging and the problem of irritating odor are solved, and the moldability of the polyurethane surface is improved. It is.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that OH is contained in the molecule.
A specific tertiary amine compound having a group has a suitable performance as a catalyst for polyurethane production, is particularly effective for improving the moldability of the polyurethane surface portion, and has an extremely low odor. I came to.

That is, the present invention relates to a polyurethane production catalyst comprising a compound represented by the following general formula and a polyurethane production method using the same.

[0009]

Embedded image

Hereinafter, the present invention will be described in detail.

The present invention provides a catalyst for producing a polyurethane comprising the compound represented by the aforementioned general formula and a method for producing a polyurethane using the same. The catalyst of the present invention is obtained by reacting 3-methyl-1,5-pentadiol with dimethylamine.
3-methyl-1-pentanol.

The polyurethane production catalyst of the present invention is considered to have a low odor because it has a relatively large molecular weight and a higher boiling point than the amine compound usually used as a polyurethane production catalyst. Further, since the catalyst of the present invention is a tertiary amine compound having an OH group in the molecule, it has an appropriate activity as a catalyst for producing polyurethane, and by the end of the polyurethane reaction, the polyisocyanate which is a raw material of polyurethane is used. It reacts and is fixed in the polyurethane molecules, so that the catalyst does not migrate to the product surface after the polyurethane formation reaction is completed, and various problems caused by this phenomenon, such as discoloration of PVC skin and fogging, are to be prevented. Becomes possible. Furthermore, when the catalyst of the present invention is used for the production of polyurethane, it exhibits excellent moldability such as improvement of cell roughness on the surface.

Usually, the amount of the catalyst of the present invention is 0.01 to 1 with respect to 100 parts by weight of the polyol used.
0 parts by weight, preferably 0.05 to 5 parts by weight. The catalyst of the present invention can be used in combination with other catalysts. Other catalysts include, for example, conventionally known organic metal catalysts, tertiary amines and quaternary ammonium salts.

Examples of the organometallic catalyst include stannas diacetate, stannas dioctoate, stannas dioleate, stannas dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, octane Lead acid, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like. Among these, preferred compounds are organotin catalysts, and more preferred are stannas dioctoate and dibutyltin dilaurate.

The tertiary amines may be those known in the art, such as N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine. , N, N, N ', N ", N"-
Pentamethyldiethylenetriamine, N, N, N ',
N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ', N ", N" -pentamethyldipropylenetriamine, N, N, N', N'-tetramethylguanidine, 1 , 3,5-Tris (N, N-
Dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N ′
-(2-dimethylaminoethyl) piperazine, N, N '
-Dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1 Tertiary amine compounds such as -dimethylaminopropylimidazole;

Examples of the quaternary ammonium salts include conventionally known tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, and tetramethylammonium-2-ethylhexane. And tetraalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

The method for producing the polyurethane is not particularly limited, and may be a conventional method. For example, it is synthesized by a polyaddition reaction between an organic polyisocyanate and an organic polyol. Various kinds of polyurethane products are manufactured by stirring and mixing a liquid in which a foaming agent, a foam stabilizer, a flame retardant, and the like are mixed with an organic isocyanate, if necessary.

As the polyol used in the production of the polyurethane in the present invention, conventionally known polyether polyols, polyester polyols, polymer polyols, and flame-retardant polyols such as phosphorus-containing polyols and halogen-containing polyols can be used. These polyols can be used alone, or can be used by being appropriately mixed and used in combination.

Examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and pentaerythritol, amines such as ethylenediamine, and alkanolamines such as ethanolamine and diethanolamine. At least two such as
A compound having at least two active hydrogen groups is used as a starting material, and an alkylene oxide typified by ethylene oxide or propylene oxide is added to the starting material to give, for example, P
oligourethane Handbook (Gunt
er Oertel, 1985 edition) pp. 42-53. Particularly preferred are those having glycerin as a starting material and a weight average molecular weight of about 3,000 to 12,000.

As polyester polyols, for example, as described in Polyurethane Resin Handbook (Keiji Iwata, 1987, first edition), p. 117, waste from the production of nylon, trimethylolpropane (TMP), waste of pentaerythrol, phthalic acid Wastes of polyester-based polyesters and polyester polyols obtained by treating and deriving waste products are exemplified.

Examples of the polymer polyol include a polymer polyol obtained by reacting the polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, and styrene in the presence of a radical polymerization catalyst. Particularly preferred polymer polyols have a weight average molecular weight of about 5,000 to 12,000.

Examples of the flame-retardant polyol include a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, and a phenol polyol. .

The polyisocyanate used in the present invention may be any known organic polyisocyanate, such as toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate and the like. And polyaliphatic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof. Examples of TDI and its derivatives include a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate or a terminal isocyanate prepolymer derivative of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer, polyphenyl-polymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group. Particularly preferred in the production of flexible foams are mixtures of TDI and MDI,
Preferred in the production of semi-rigid foams, integral skin foams and rigid foams is MDI.

The isocyanate index of the present invention is:
Although not particularly limited, generally a flexible foam,
In the production of semi-rigid foams and integral skin foams, it is generally in the range of 70-130, and in the production of rigid foams and urethane elastomers, it is generally in the range of 70-130.
It is in the range of 250.

In the present invention, a foaming agent can be used if necessary. As the foaming agent used, water and / or
Alternatively, halogenated hydrocarbons can be used. As the halogenated hydrocarbon, known halogenated methane and halogenated ethanes such as methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichlorotrifluoromethane, and dichloromonofluoromethane can be used. A particularly preferred blowing agent is water, and the amount used may vary depending on the density of the intended foam, but is usually 2 parts by weight or more, more preferably 3.0 to 8.0 parts by weight, per 100 parts by weight of the polyol. Parts by weight.

In the present invention, a foam stabilizer can be used if necessary. The foam stabilizer used in the present invention is a conventionally known organosilicone surfactant,
The amount used is 0.1 parts by weight per 100 parts by weight of the polyol.
To 10 parts by weight.

In the present invention, a crosslinking agent or a chain extender can be added as required. As a crosslinking agent or a chain extender, a low molecular weight polyhydric alcohol, for example,
Examples thereof include low molecular weight amine polyols such as ethylene glycol, 1,4-butanediol, and glycerin, such as diethanolamine and triethanolamine, and polyamines such as ethylenediamine, xylylenediamine, and methylenebisorthochloroaniline.
Of these, diethanolamine and triethanolamine are preferred.

If necessary, a coloring agent, a flame retardant, an antioxidant and other known additives can be used. The types and amounts of these additives can be used in a range usually used as long as they do not deviate from known types and procedures.

[0029]

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

<Synthesis Example 5-dimethylamino-3-methyl-1-pentanol> 300 g of 3-methyl-1,5-pentanediol was placed in a 500 ml flask equipped with a condenser for separating water produced by the reaction. And Ni / Cu (molar ratio = 1/1) supported alumina as catalyst (pulverized product)
Was charged with 10 g, and the system was replaced with nitrogen while stirring and the temperature was raised. The catalyst used was one obtained by impregnating and supporting nickel nitrate and copper sulfate on an alumina carrier and calcining at 600 ° C.

When the temperature of the flask reaches about 100 ° C., hydrogen gas is blown into the system at a flow rate of 1 l / min.
The temperature was further raised to 90 ° C. At this temperature, dimethylamine was blown into the system at 1.5 g / min to start the reaction.

After 4 hours, the reaction was terminated and analyzed by gas chromatography. As a result, the conversion of 3-methyl-1-pentanediol was 60.0%, and 5-dimethylamino-
The yield of 3-methyl-1-pentanol was 49.5%.

After the catalyst was separated by filtration, distillation under reduced pressure (116
C./56 mmHg) to obtain 135 g of the target product. The purity by gas chromatography analysis was 98.6%. The target compound was determined by GC-Mass analysis to have a molecular weight of 5-dimethylamino-3-methyl-1-pentanol of 145.
showed that.

Example 1 86.6 g of a mixture prepared by mixing a polyol, water, a surfactant, and a cross-linking agent at the raw material mixing ratios shown in Table 1 was placed in a 300 ml polyethylene cup, and a catalyst was synthesized in Synthesis Example 5- 1.15 pbw (0.92 g by weight) of dimethylamino-3-methyl-1-pentanol (AMP)
Add and adjust the temperature to 20 ° C. A polyisocyanate solution (TM80) is placed in a separate container, and the temperature is adjusted to 20 ° C. The amount of the catalyst was adjusted so that the following gel time was 60 seconds.

[0035]

[Table 1]

The polyisocyanate solution was added to the above 300 ml polyethylene cup and the isocyanate index (isocyanate group / OH group (molar ratio) × 100) was 10
5 and stirred with a stirrer at 6000 rpm for 5 seconds. The mixed and stirred liquid was transferred to a 2 l polyethylene cup whose temperature was adjusted to 50 ° C., and the following reactivity, foam surface moldability, foam core density, and foam odor were measured.
The results are shown in Table 2.

Cream time: foaming start time. The time at which the foam starts to rise is measured visually using a stopwatch.

Gel time: The time during which the reaction proceeds and changes from a liquid substance to a resinous property is visually measured using a stopwatch.

Rise time: The time at which the rise of the form stops is visually measured using a stopwatch.

Formability of foam surface part: One hour after completion of foaming, the completed foam was removed from the 2 l polyethylene cup, and the state of the foam surface, that is, whether or not the foam skin had peeled off, and the surface cell roughness were visually observed. .
It can be said that a foam having no foam surface peeling and no surface cell roughening has good foam surface part moldability.

Foam core density: The skin part of the foam removed from the 2 l polyethylene cup was cut off, and a 5 × 5 × 10 cm foam was cut out from the core, and the dimensions and weight were measured accurately. The foam density was calculated.

Foam odor: In the evaluation of odor, the skin of the foam was cut off, the density of the foam core was measured, and at the same time, the odor of the foam was measured by asking 10 monitors to smell the odor.

[0043]

[Table 2]

Comparative Examples 1 to 4 86.6 g of a mixture prepared by mixing a polyol, water, a surfactant, and a crosslinking agent at the raw material mixing ratio shown in Table 1 was placed in a 300 ml polyethylene cup. Reactivity, foam surface formability, foam core density, and foam odor were measured in the same manner as in Example 1 by adding a predetermined amount of each catalyst of Example 4. The results are shown in Table 2.

[0045]

According to the catalyst of the present invention, the polyisocyanate reacts with the OH group in the molecule at the end of the polyurethane formation reaction and is fixed in the polyurethane molecule, and the catalyst does not transfer to the resin surface or the like. This is effective for preventing the discoloration of PVC of the automotive instrument panel and the fogging of the window glass due to the transfer of volatile components from the foam. Further, the compound itself has an extremely low odor, and the foam produced in combination with the property of being fixed in the polyurethane molecule also has a reduced odor, which greatly contributes to the improvement of the environment at the foaming site. In addition, it has the same catalytic activity as conventional catalysts and can improve the moldability of the polyurethane surface, and is a very effective catalyst for producing polyurethane such as soft, hard, semi-hard, and elastomer. .

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Claims (2)

[Claims] 1. A catalyst for producing polyurethane comprising a compound represented by the following general formula. Embedded image 2. The method according to claim 1, wherein the polyol and the organic polyisocyanate are reacted in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a crosslinking agent and the like to produce a polyurethane. A method for producing a polyurethane, comprising using as a catalyst.