JPH0770275A - Amine catalyst for polyurethane production - Google Patents

Abstract

PURPOSE:To obtain an amine catalyst for polyurethane production having a long-chain aliphatic group and an active hydrogen group reactive with isocyanate in the molecule, emitting low odor, having improved curing rate of the foam and effective for decreasing the migration from the foam. CONSTITUTION:This catalyst is composed of an amine compound of the formula (A is a >=5C long-chain aliphatic alkyl; each C atom of the group may have a 1-6C alkyl; R1 and R2 are each H, a 1-6C alkyl, a hydroxyalkyl; R3 to R5 each is H, a 1-6C alkyl; (1) is <=5; (m) is 1 or 2). Preferably, the catalyst [concretely, N-(2-hydroxypropyl)-N,N',N'-trimethylhexamethylenediamine, etc.] can be produced e.g. by adding an alkylene oxide to a long-chain aliphatic diamine and tertiary-aminating the synthesized N-hydroxyalkyl long-chain aliphatic diamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel tertiary amine compound useful as a catalyst for producing polyurethanes such as soft, rigid, semi-rigid and elastomers. For more details,
The present invention relates to a novel catalyst having a long-chain aliphatic group and an active hydrogen group capable of reacting with isocyanate, having extremely low odor, excellent curing characteristics, and non-migrating in a polyurethane resin, for producing polyurethane.

[0002]

2. Description of the Related Art Organometallic catalysts and tertiary amine catalysts have hitherto been used as catalysts for producing polyurethanes, and it is widely known that tertiary amine catalysts are already excellent catalysts for producing polyurethanes. Has been. Among the tertiary amine compounds, the following triethylenediamine, N, N, N ', is used as a catalyst for industrially used polyurethane.
N ", N" -pentamethyldiethylenetriamine, N,
N, N ', N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)
Examples thereof include piperazine, triethylamine, N-methylmorpholine and N-ethylmorpholine. Among these catalysts for polyurethane, a catalyst having a relatively low molecular weight and a high volatility has an important effect that greatly affects the curing rate of polyurethane and the physical properties of foam. Examples of such a catalyst include N-methylmorpholine, N-ethylmorpholine and triethylamine. When a polyurethane is produced using these tertiary amine compounds, the amine catalyst remaining in the product migrates to a skin material such as PVC that comes into contact with the polyurethane resin, causing a dehydrochlorination reaction, resulting in discoloration and There are problems such as fogging, which causes deterioration and forms a salt with an acid component in the atmosphere by an amine catalyst that scatters from an automobile seat or the like to fog the glass. To solve this problem, compounds having an active hydrogen group capable of reacting with isocyanate in the molecule have been used. Examples of the compound having an active hydrogen group capable of reacting with isocyanate in the molecule include compounds having a short chain aliphatic group such as N, N-dimethylethanolamine and N, N-dimethylaminoethoxyethanol.

[0003]

However, the polyurethane production catalysts that have been developed so far have various problems. That is, the tertiary amines have a strong amine odor, and especially N-methylmorpholine, N-ethylmorpholine and triethylamine have extremely strong irritating odors, and the bad odor of the foaming process deteriorates the working environment, resulting in polyurethane products. There was a problem of leaving a foul odor to myself.

N, N- which is a compound having an active hydrogen group
Dimethylethanolamine, N, N-dimethylaminoethoxyethanol and the like also have a bad odor, and since they react with isocyanate itself and lose their activity remarkably quickly, their catalytic activity is insufficient in the latter stage of the polyurethane forming reaction, Since the curing speed was slow, the mold release time could not be shortened and there was a problem with moldability.

[0005]

Means for Solving the Problems As a result of intensive studies to solve various problems of known catalysts, the present inventors have found that an activity capable of reacting with a long-chain aliphatic amino group and an isocyanate in the molecule. It was found that a specific compound having a hydrogen group has a desired activity as a catalyst, has a low odor, has an excellent effect of improving the curing rate of the foam and reducing the migration from the foam, and arrived at the present invention. It is a thing.

That is, the present invention provides a catalyst for producing a polyurethane, which comprises a compound represented by the following formula.

[0007]

[Chemical 2]

(In the formula, A is a long-chain aliphatic alkyl group having 5 or more carbon atoms, and each carbon may have a C _{1 to} C ₆ alkyl group. R ₁ and R ₂ Is hydrogen, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group, R
₃ , R ₄ and R ₅ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, 1 is an integer of 5 or less, and m is an integer of 1 or 2. ) Next, the present invention will be described in detail.

The amine catalyst of the present invention is a long-chain aliphatic amine catalyst having active hydrogen of the above general formula and can be produced by a known method. For example, an alkylene oxide may be added to a long-chain aliphatic diamine to synthesize an N-hydroxyalkyl long-chain aliphatic diamine, and this may be further tertiary aminated. As the alkylene oxides, ethylene oxide and propylene oxide are preferable, but higher order oxides can also be used.

As the method for tertiary amination, for example, the Leukart-Warach reaction described in US Pat. No. 4,026,840 or the reductive methylation reaction described in West German Patent No. 2618580 can be used. Examples of the long-chain aliphatic diamines include 2-methylpentamethylenediamine, hexamethylenediamine, octamethylenediamine, nonanediamine, decanediamine, undecadiamine, dodecanediamine, tetradecyldiamine, hexadecyldiamine, octadecyldiamine and the like. .

The catalyst of the present invention can be used as a mixture of two or more kinds.

The amine catalyst of the present invention can also be used as a co-catalyst in combination with other tertiary amine compounds and organometallic compounds to produce polyurethane.

Other tertiary amine compounds include, for example, triethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl. Propylenediamine, 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, N-methylpiperazine, N-methylmorpholine,
N-ethylmorpholine, N, N-dimethylethanolamine, N, N-dimethylaminopropylamine, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-trioxyethylene-N, N- Dimethylamine, 1,3-bis (N, N
-Dimethylamino) -2-propanol, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-
2-Methylimidazole, 1-dimethylaminopropylimidazole and the like are exemplified, but preferably triethylenediamine, N-methyl-N '-(2-dimethylaminoethyl) piperazine, bis (2-dimethylaminoethyl) ether. .

Examples of the organometallic compound 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 can be mentioned. Of these, preferred compounds are organotin catalysts, and more preferred are stannas dioctoate and dibutyltin dilaurate.

The amount of catalyst usually used in the production of polyurethane is not particularly limited. Generally, it is 0.01 to 10 parts by weight based on 100 parts by weight of the polyol. It is preferably 0.05 to 5.0 parts by weight. Further, the organic carboxylic acid salt of the amine compound of the present invention and the above-mentioned organic carboxylic acid salt of the tertiary amine compound can be appropriately used as a catalyst and a co-catalyst as long as the catalytic function of the present invention is not lost.

The amine catalyst of the present invention may be used alone or as a mixture with other amine catalysts as described above, but in the preparation of the mixture, if necessary, a solvent such as dipropylene glycol, ethylene glycol, 1,4 may be used as a solvent. -Butanediol and water etc. can be used. The amount of the solvent is not particularly limited, but it is preferably 70% or less with respect to the total amount of the catalyst. The catalyst thus prepared may be used by adding it to a polyol, or various amine catalysts may be added separately to a polyol and used, but it is not particularly limited.

As the polyol that can be used when producing a polyurethane using the novel catalyst of the present invention, generally known polyester polyols, polyether polyols, polymer polyols and mixtures thereof can be used. Known polyester polyols usually include compounds derived from dibasic acids and polyhydric alcohols. Known polyether polyols are, for example,
Polyhydric alcohols such as glycol, glycerin, pentaerythritol, trimethylolpropane and sucrose; aliphatic amine compounds such as ammonia and ethylenediamine; toluenediamine, diphenylmethane-4,
It is obtained by adding ethylene oxide or propylene oxide to an aromatic amine compound such as 4'-diamine and / or a mixture thereof. Known polymer polyols include polymer polyols obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, styrene, etc. in the presence of a radical polymerization catalyst.

The polyisocyanate that can be used when producing a polyurethane using the novel catalyst of the present invention may be any known polyisocyanate, for example, toluene diisocyanate, diphenylmethane 4,4'-.
Diisocyanates, aromatic polyisocyanates such as their polymerized isocyanates; cycloaliphatic polyisocyanates such as isophorone diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; or free isocyanate-containing prepolymers by the reaction of them with polyols; carbodiimide modification, etc. And modified polyisocyanates thereof can be exemplified.

A foaming agent can be used, if desired, when producing a polyurethane using the novel catalyst of the present invention. The foaming agent may be any known physical foaming agent or chemical foaming agent, and is not particularly limited. Examples of the physical foaming agent include low-boiling halogenated hydrocarbons such as chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons and methylene chloride; hydrocarbons such as pentane and cyclopentane; air, A gas mixture of nitrogen and carbon dioxide can be exemplified. Known chemical foaming agents include
Water, organic acids, inorganic acids such as boric acid, alkali carbonates,
Examples thereof include cyclic carbonates and dialkyl carbonates, and those that react with the polyurethane resin component or decompose by heat or the like to generate gas.

The foam stabilizer used in the present invention may be any known foam stabilizer such as a nonionic surfactant such as an organosiloxane-polyoxyalkylene copolymer and a silicone-grease copolymer, Alternatively, a mixture thereof or the like can be exemplified, and the amount used is usually 10
It is 0.1 to 10 parts by weight with respect to 0 parts by weight.

In the present invention, a crosslinking agent or a chain extender can be added if necessary. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine and xylylenediene. Examples thereof include amines and polyamines such as methylenebis orthochloroaniline.

If desired, colorants, flame retardants, antioxidants and other known additives can be used. The types and the amounts of these additives can be sufficiently used within the range usually used.

[0023]

INDUSTRIAL APPLICABILITY The novel amine catalyst for polyurethane of the present invention has a relatively high molecular weight and a high boiling point as compared with conventional amine catalysts, and therefore has extremely little odor and remarkably improves the working environment in the polyurethane production process, thus producing foam It has the advantage that it does not leave a foul odor, and has an extremely high industrial value. In addition, since it has an active hydrogen group in the molecule and reacts with the isocyanate group that is a raw material of polyurethane during the polyurethane formation reaction and is taken into the polyurethane molecule, the catalyst may migrate or scatter on the surface of the production foam or in the atmosphere. It is possible to reduce deterioration and discoloration of other materials that come into contact with the foam.

Further, since the foam curing rate is increased as compared with the conventional non-transfer type catalyst having active hydrogen in the molecule, it is possible to remarkably improve the foam productivity.

[0025]

The present invention will be described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 N- (2-hydroxypropyl) -N, N ', N'-trimethylhexamethylenediamine and N, N'-bis (2-hydroxypropyl) -N, N'-dimethylhexamethylenediamine Preparation of a mixture (80/20) of N, N-bis (2-hydroxypropyl) -N ', N'-dimethylhexamethylenediamine (810/20) Hexamethylenediamine (910 g) was charged into a 10-liter autoclave and purged with nitrogen. After the reaction temperature was raised to 80 ° C., 350 g of propylene oxide was supplied for 1 hour and aged for 1 hour to obtain a propylene oxide adduct.
Subsequently, 40 g of Raney nickel was charged, the atmosphere was replaced with nitrogen, and then the reaction temperature was 60 ° C. and 30 kg / cm ^2.
2352 g of 37% formalin was fed for 4.5 hours under hydrogen pressure, and the mixture was aged for 1 hour for tertiary amination. The reaction solution was distilled as it was, and 553 g of a colorless and transparent N- (2-hydroxypropyl) -N, N ′, N′-trimethylhexamethylenediamine at a fraction of 105 ° C./2 Torr (purity 99.
2%), distillate 128-149 ° C / 2 Torr, colorless and transparent N, N'-bis (2-hydroxypropyl) -N, N
198 g of a mixture of'-dimethylhexamethylenediamine and N, N-bis (2-hydroxypropyl) -N ', N'-dimethylhexamethylenediamine (80/20)
(Purity of 96.1%) was obtained.

Example 2 Production of N- (2-hydroxypropyl) -N, N ', N'-trimethyldecanediamine 1035 g of decanediamine was charged into a 10-liter autoclave and purged with nitrogen. After the reaction temperature was raised to 80 ° C., 270 g of propylene oxide was supplied in 1 hour, 1
After aging for a time, a propylene oxide adduct was obtained. Subsequently, 45 g of Raney nickel was charged, and after substituting with nitrogen and hydrogen, 1802 g of 37% formalin was fed for 4.5 hours under a hydrogen pressure of 30 Kg / cm ^{2 at} a reaction temperature of 60 ° C. and aged for 1 hour to carry out a tertiary amination. . The reaction solution is distilled as it is, and a colorless transparent N- at a distillation fraction of 150 ° C / 1 Torr.
530 g (purity 99.0%) of (2-hydroxypropyl) -N, N ', N'-trimethyldecanediamine was obtained.

Example 3 Production of N- (2-hydroxypropyl) -N, N ', N'-trimethyldodecanediamine 1100 g of dodecanediamine was charged into a 10-liter autoclave and purged with nitrogen. After the reaction temperature was raised to 80 ° C., 245 g of propylene oxide was supplied for 1 hour and aged for 1 hour to obtain a propylene oxide adduct.
Subsequently, after charging 48 g of Raney nickel and purging with nitrogen and hydrogen, the reaction temperature was 60 ° C., 30 Kg / cm ²
1650 g of 37% formalin was fed for 4.5 hours under the pressure of hydrogen, and the mixture was aged for 1 hour for tertiary amination. The reaction solution was distilled as it was, and a colorless transparent N- (2-hydroxypropyl) -N, N ', N at a fraction of 160 ° C / 0.6 Torr
′ -Trimethyldecanediamine 490 g (99.1%)
Got

Examples 4 to 7 and Comparative Examples 1 to 4 Polyurethane foaming was performed under the following composition and foaming conditions, and the physical properties of the resulting foams were measured. The evaluation of the moldability of the produced polyurethane foam and the measurement of the curing rate were carried out by the following methods. The results are shown in Table 1.

A. Formulation (parts by weight) Polyol 1) 100 water 2.8 Crosslinking agent 2) 3.0 Amine catalyst 3) Change Isocyanate 4) 61.2 (Index = 105) 1) Polyether polyol (FA, Sanyo Kasei Co., FA -7
03 OH value = 33 mg KOH / g) 2) Triethanolamine (special grade manufactured by Wako Pure Chemical Industries, Ltd.) 3) Explanation of catalyst abbreviations in the table NEM; N-ethylmorpholine TEA; triethylamine DMEA; N, N-dimethylaminoethanol HPTMHD N- (2-hydroxypropyl)-
N, N ', N'-trimethylhexamethylenediamine BHPTMHD; N, N'-bis (2-hydroxypropyl) -N, N'-dimethylhexamethylenediamine and N, N-bis (2-hydroxypropyl) -N
Mixture of ', N'-dimethylhexamethylenediamine (80/20) HPTMDD; N- (2-hydroxypropyl)-
N, N ', N'-trimethyldecanediamine HPTMDOD; N- (2-hydroxypropyl)-
N, N ′, N′-trimethyldodecanediamine 4) Crude MDI, NCO concentration = 31.0% (Nippon Polyurethane Co., Ltd., MR-200) b. Foaming conditions Raw material liquid temperature 25 ± 1 ° C. Stirring speed 6000 rpm (7 seconds) c. Measurement item At room temperature (20 to 25 ° C.), a polyurethane raw material was poured into a 2 liter polyethylene cup to cause foaming, and reactivity, foam density, and curing rate were measured.

Reactivity Cream time; Foaming start time (seconds) Gel time; Resinification time (seconds) Rise time; Time to reach maximum foaming height of foam (seconds) Foam density 6x from center of foam Measure the density of a test piece with a size of 6 x 8 cm.

Evaluation of moldability Voids generated at the bottom of the generated foam
Was evaluated according to the following three grades.

1: Almost no voids 2: Medium voids 3: Large voids ・ Measurement method of curing rate Polyurethane raw material was poured into an aluminum mold (dimensions: 12 × 50 × 2 cm) whose temperature was adjusted to 40 ° C. to foam, The foam hardness at the time of demolding for 5.5 minutes was measured by a Shore C hardness meter.

Evaluation of odor of amine catalyst The amine catalyst was dissolved in FA703 in an amount of 2 parts by weight, and the odor of the amine catalyst was determined by 10 panelists according to the following evaluation criteria.

Large ... Everyone feels a strong odor.

Medium: Five or more out of ten people feel a weak odor.

Small: 3 or less than 10 people feel a weak odor.

None: No one feels an odor.

[0039]

[0040]

[Table 1]

As is clear from Table 1, by using an amine compound having a specific long-chain aliphatic active hydrogen as the amine catalyst, the odor of the catalyst can be reduced, and the foam moldability and curing rate are excellent. The foam could be manufactured.

On the other hand, NEM and TE of Comparative Examples 1, 2 and 3
Catalysts such as A and DMEA have a problem in working environment because they have a low foam moldability and a low curing rate and have a high catalyst odor. Further, the conventional active hydrogen-containing amine catalysts shown in Comparative Examples 3 and 4 also have a problem that the odor is relatively high, the moldability and the curing rate are extremely poor, and the production rate and the yield are lowered.

Claims (1)

[Claims] 1. A catalyst for polyurethane production comprising an amine compound represented by the following general formula. [Chemical 1] (In the formula, A is a long-chain aliphatic alkyl group having 5 or more carbon atoms, and each carbon may have a C _{1 to} C ₆ alkyl group. R ₁ and R ₂ are hydrogen. , A C 1-6 alkyl group or a hydroxyalkyl group, R ₃ , R ₄ and R ₅ represent hydrogen or a C 1-6 alkyl group, 1 is an integer of 5 or less, and m is 1 or 2 Represents an integer.)