JP2001213929A - Catalyst composition for manufacturing polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst composition for manufacturing a polyurethane which is highly reactive, remaining liquid without solidifying at a low temperature and excellent in handling properties by effectively utilizing 1,2- dimethylimidazole having a high catalytic activity. SOLUTION: The catalyst composition for manufacturing a polyurethane comprises an N-substituted imidazole compound solid at 10 deg.C, a compound represented by the formula: R1N(CH2CHR2OH)2, wherein R1 is a 1-18C linear or branched alkyl or alkenyl group; and R2 is a hydrogen atom or a methyl group, and a compound represented by the formula: HO-R-OH, wherein R is -CHR3CHR4-(OCHR3CHR4)n-, wherein R3 and R4 are each independently a hydrogen atom or a methyl group; and n is an integer of 0-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a catalyst composition for producing polyurethane. More specifically, the present invention relates to a catalyst composition for producing polyurethane, which can be used when producing polyurethane foam suitably used as a building material, an insulating material for electric refrigerators, freezing warehouses, bathtubs, etc., interior materials for automobiles, and the like.

[0002]

2. Description of the Related Art From the viewpoint of protecting the global environment, specific fluorocarbons such as CFC-11 have already been banned from production and use. In recent years, reduction of alternative chlorofluorocarbons such as hydrochlorofluorocarbon has been called for, and HCFC-141
The use of b has been banned in Japan since 2004. Under such circumstances, a system that uses a larger amount of water as a foaming agent for a polyurethane foam than a conventional formulation, and a formulation system in which all of the foaming agent is water are being studied.

However, when a large amount of water is used as a foaming agent, there is a disadvantage that urea bonds in the polyurethane increase and the resin becomes brittle. In particular, the surface to be adhered to an adherend such as a steel plate becomes brittle, which causes a problem that the so-called flyability deteriorates. In order to solve such a problem, it has been proposed to use N-substituted imidazoles as a catalyst to improve the surface brittleness and improve the adhesiveness (JP-A-3-95212, JP-A-3-95212).
-97713, JP-A-3-122108,
JP-A-4-55419 and JP-A-4-16141
No. 7).

[0004] Among the N-substituted imidazoles, 1,2-dimethylimidazole has the highest catalytic activity per unit weight. However, 1,2-dimethylimidazole has a melting point of about 38 ° C. and shows a solid crystalline state at normal temperature. When used as a polyurethane production catalyst, it is heated and dissolved or diluted with a solvent such as ethylene glycol each time. There is a drawback that it must be used.

[0005]

DISCLOSURE OF THE INVENTION The present invention makes effective use of 1,2-dimethylimidazole having high catalytic activity, is highly reactive, is liquid without solidifying even in a low temperature range,
An object of the present invention is to provide a catalyst composition for producing polyurethane excellent in handleability.

[0006]

The present invention SUMMARY OF THE INVENTION may, N- substituted imidazole compound which is solid at 10 ° C., the formula ^{(I): R 1 N (} CH 2 CHR 2 OH) 2 (I) ( wherein, R ¹ is A linear or branched alkyl or alkenyl group having 1 to 18 carbon atoms, R ² represents a hydrogen atom or a methyl group), and a compound represented by the formula (II): HO—R—OH (II) [ In the formula, R represents —CHR ³ CHR ⁴ — (OCHR ³ CHR
⁴ ) _n- (R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 2)]. About.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The N-substituted imidazole compound is
When used as a catalyst in the production of polyurethane foam in a system that uses a large amount of water as a foaming agent, it has excellent properties of improving the flyability properties such as surface brittleness and adhesion of the obtained polyurethane foam It is.

Examples of the N-substituted imidazole compound which is solid at 10 ° C. include 1,2-dimethylimidazole, 1-benzylimidazole, 1-phenylimidazole, 1-hydroxyethyl-2-methylimidazole and the like. By using an N-substituted imidazole compound which is solid at ℃, the effect of the present invention becomes remarkable. These can be used alone or in combination of two or more. Among these, 1,2-dimethylimidazole can be suitably used from the viewpoint of catalytic activity per unit weight.

The content of the N-substituted imidazole compound which is solid at 10 ° C. in the catalyst composition is from 50 to 85% by weight, preferably from 50 to 85% by weight, from the viewpoint of improving reactivity, surface brittleness and adhesion and liquid stability at low temperatures. It is desirably 60 to 80% by weight.

The compound represented by the formula (I) has a function as a urethanization catalyst and a solid N- at 10 ° C. at a low temperature.
It has the property of accelerating the liquefaction of the substituted imidazole compound.

Specific examples of the compound represented by the formula (I) include N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine,
Butyldiethanolamine, N-hexyldiethanolamine, N-octyldiethanolamine, N-dodecyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, and the like. These may be used alone or in combination of two or more. Can be. Among these, N-methyldiethanolamine and N-ethyldiethanolamine can be suitably used from the viewpoints of catalytic activity and maintaining liquidity at low temperatures.

The content of the compound represented by the formula (I) in the catalyst composition improves the liquefaction of the solid N-substituted imidazole compound at 10 ° C. at a low temperature, and sufficiently enhances the catalytic performance of the catalyst composition. From the viewpoint of expression,
It is desirably 40% by weight, preferably 15 to 35% by weight.

Specific examples of the compound represented by the formula (II) include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol. These may be used alone or in combination of two or more. Can be used in combination. Among them, ethylene glycol and dipropylene glycol can be suitably used from the viewpoint of suppressing the influence on the properties of the polyurethane foam, maintaining the liquidity at low temperature, and being inexpensive.

The content of the compound represented by the formula (II) in the catalyst composition depends on the amount of the compound represented by the formula (I). In general, from 3 to 15
%, Preferably 3 to 10% by weight.

The catalyst composition of the present invention is a solid N.sub.2 at 10.degree.
-It can be easily prepared by mixing a substituted imidazole compound, a compound represented by the formula (I) and a compound represented by the formula (II). The temperature for mixing is 10
The temperature may be at least the melting point of the solid N-substituted imidazole compound at ° C.

Since the catalyst composition of the present invention exhibits liquidity even at a very low temperature of -10 ° C., it is not necessary to preheat the polyol premix even when preparing and mixing the polyol premix in winter. It is extremely excellent in handleability and exhibits excellent properties of improving surface brittleness and adhesiveness of a polyurethane foam obtained by a system using a large amount of water as a foaming agent.

Accordingly, the catalyst composition of the present invention can be suitably used as a catalyst for producing a polyurethane foam.

The amount of the catalyst composition used for producing the polyurethane foam is 0.3 parts by weight or more from the viewpoint of increasing the reactivity between the polyol component and the isocyanate component based on 100 parts by weight of the polyol component as the raw material. Preferably, the content is 0.5 part by weight or more. From the viewpoint of maintaining the strength of the polyurethane foam, the polyol component 1
It is desirable that the content be 10 parts by weight or less, preferably 8 parts by weight or less based on 00 parts by weight. Therefore, in consideration of these circumstances, the desirable amount of the polyurethane production catalyst is 0.3 to 1 with respect to 100 parts by weight of the polyol component.
0 parts by weight, preferably 0.5 to 8 parts by weight.

Incidentally, other urethanization catalysts may be used as long as the object of the present invention is not impaired. Other urethanization catalysts include, for example, 1,4-diazabicyclo (2.2.2) octane, 2-methyl-1,4-diazabicyclo (2.2.2) octane, N-methylmorpholine, N-ethyl Morpholine, N- (dimethylaminoethyl) morpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N'- Tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, N, N ′, N′-trimethylaminoethylpiperazine, tris (3-dimethylaminopropyl) amine,
N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,8-diazabicyclo (5 .
4.0) Undecen-7, N, N ', N "-Tris (3
-Dimethylaminopropyl) hexahydro-s-triazine, 1-methylimidazole, 1-isobutyl-2-
Methylimidazole, 6-dimethylamino-1-hexanol, N, N-dimethylethanolamine, N, N-
Dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethoxyethanol, N- (3-dimethylaminopropyl) -N-methylaminoethanol, N
Tertiary amine catalysts such as-(2-dimethylaminoethyl) -N-methylaminoethanol and derivatives thereof, salts thereof with acids such as carboxylic acid and carbonic acid; organometallic compounds represented by organotin compounds and the like Is mentioned. Further, for the purpose of imparting flame retardancy to the polyurethane foam, a potassium salt such as potassium acetate or potassium octylate or an isocyanuration catalyst represented by a quaternary ammonium salt may be used in combination. The amounts of other urethanization catalysts and isocyanuration catalysts are not particularly limited, and may be usually adjusted appropriately within a range that does not impair the purpose of the present invention.

The polyurethane foam can be produced by reacting a polyol component and an isocyanate component in the presence of the catalyst composition of the present invention, a foaming agent, and if necessary, a foam stabilizer.

The polyol component may be any of those conventionally used when producing a polyurethane foam.
There is no particular limitation. Representative examples of the polyol component include a polyester polyol and a polyether polyol having 2 to 8 functional groups and a hydroxyl value of 200 to 700.

The polyester-based polyol can be produced by a condensation reaction between a dicarboxylic acid and a polyhydric alcohol.

Examples of the dicarboxylic acid used in the polyester polyol include a saturated aliphatic dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; a saturated aliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid; Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; halogen-containing dicarboxylic acids such as tetrabromophthalic acid; These acid anhydrides and the like can be mentioned, and these can be used alone or in combination of two or more. The dicarboxylic acid may optionally contain a tribasic or higher polybasic acid such as trimellitic acid.

Polyhydric alcohols constituting the polyester polyol include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol-1,6-hexanediol, and trimethylol. Examples thereof include propane, glycerin, pentaerythritol, diglycerin, dextrose, and sorbitol, and these can be used alone or as a mixture of two or more.

Representative examples of polyether polyols include polyoxypropylene polyols, polyoxytetramethylene glycol, and mixtures thereof.

The polyoxypropylene-based polyol has the following properties:
Starting from a compound having at least two active hydrogen-containing groups, ethylene oxide, propylene oxide, 1,2-
It can be produced by a ring-opening addition reaction of an alkylene oxide such as butylene oxide, 1,3-butylene oxide, and styrene oxide.

Compounds having two or more active hydrogen-containing groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Neopentyl glycol, 1,4-butanediol,
Dihydric alcohols such as 1,6-hexanediol; trihydric or higher alcohols such as glycerin, trimethylolpropane, pentaerythritol, diglycerin, dextrose, sorbitol, and sucrose; polyhydric alcohols such as resorcinol, hydroquinone, and bisphenol A Phenol;
Polyamines such as ethylenediamine, tolylenediamine, 1,3-propanediamine, and isophoronediamine; alkanolamines such as diethanolamine and triethanolamine; and modified products thereof. These may be used alone or in combination of two or more. Can be used in combination.

Polyoxytetramethylene glycol is
It can be produced by ring-opening polymerization of tetrahydrofuran.

As the polyol component, the polyester-based polyol and the polyether-based polyol can be used alone or in combination of two or more.

As the isocyanate component, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate,
Aromatic polyisocyanates such as 2,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, naphthylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate Alicyclic polyisocyanates such as isocyanate and isophorone diisocyanate; and the above-mentioned modified polyisocyanates containing one or more of urethane bond, carbodiimide bond, uretoimine bond, allophanate bond, urea bond, buret bond, isocyanurate bond and the like. These can be used alone or in combination of two or more.

The ratio between the polyol component and the isocyanate component is usually in the range of 95 to 3 for the isocyanate index.
It is preferably adjusted to be 00, preferably 95 to 120.

Examples of the foaming agent include water, low-boiling hydrocarbons such as isopentane, normal pentane and cyclopentane, nitrogen gas, gas such as air and carbon dioxide, and HCFC.
-141b, HCFC-142b, HCFC-22, H
FC-134a, HFC-152a, HFC-245f
a, HFC-245ca, HFC-236ea, HFC
-365mfc and the like, and these can be used alone or in combination of two or more.

Since the amount of the foaming agent varies depending on its type and the density of the intended polyurethane foam, it cannot be unconditionally determined. Therefore, it is desirable to appropriately adjust the amount according to the type of the foaming agent.

The foam stabilizer can be used as needed, but any foam stabilizer may be used as long as it is generally used when producing a polyurethane foam. Representative examples of foam stabilizers include silicone surfactants such as dimethylpolysiloxane and polyoxyalkylene-modified dimethylpolysiloxane, and anionic surfactants such as fatty acid salts, sulfate esters, phosphate esters, and sulfonates. Is mentioned.

Since the amount of the foam stabilizer varies depending on the type and the density of the intended polyurethane foam, it cannot be unconditionally determined. Therefore, it is desirable to appropriately adjust the amount according to the kind of the foam stabilizer. .

Further, any other components other than those described above, for example, other auxiliaries such as a crosslinking agent, a flame retardant, a filler and the like can be used within a range not to impair the object of the present invention.

As the crosslinking agent, a hydroxyl group, a primary amino group,
Low molecular weight compounds having two or more active hydrogen-containing groups capable of reacting with a secondary amino group or another isocyanate group are exemplified. Examples thereof include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, and alkylene oxides of bisphenol A. Examples thereof include polyhydric alcohols such as adducts, and polyamines such as diethyltoluenediamine, chlorodiaminobenzene, ethylenediamine, and 1,6-hexanediamine. These can be used alone or in combination of two or more.

As the flame retardant, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3
-Dichloropropyl) phosphate, tris (2,3-
And halogen-based flame retardants such as dibromopropyl) phosphate.

Examples of the filler include inorganic compounds such as silica-based fine particles and alumina-based fine particles, and organic compounds such as melamine-based resins and phenol-based resins.

In the case of producing a polyurethane foam, for example, a polyol component is mixed with a foaming agent, a catalyst composition, a foam stabilizer, and other auxiliaries, and the resulting polyol mixture is mixed with:
The isocyanate component can be molded by mixing and stirring with a molding machine or the like, injecting into a molding die, and foaming. More specifically, for example, after adjusting the temperature of the polyol mixture to about 20 ° C. using a tank or the like, the isocyanate component is mixed with a foaming machine such as an automatic mixing injection foaming machine and an automatic mixing injection foaming machine. By reacting, a polyurethane foam can be produced.

When the catalyst composition of the present invention is used, a polyurethane foam having improved flyability characteristics can be produced even in a system using a large amount of water as a blowing agent. In addition, the catalyst composition of the present invention comprises-
It is liquid without solidifying even at a low temperature of 10 ° C., and is extremely excellent in handleability.

Accordingly, the polyurethane foam produced by using the catalyst composition of the present invention can be used as a heat insulating material or a panel for building materials formed by directly spraying on a wall or ceiling of a house or a building. It can be suitably used as a heat insulating material for boards, electric refrigerators, frozen stockers, and the like.

[0043]

Examples 1 to 5 and Comparative Examples 1 to 6 N-substituted imidazole compounds, compounds represented by the formula (I), compounds represented by the formula (II) and the like are weighed as shown in Table 1. The mixture was sufficiently mixed and stirred to obtain a catalyst composition. Note that 1,
Since 2-dimethylimidazole is a solid at room temperature, it was heated and liquefied before use. The liquidity of the obtained catalyst composition was examined according to the following method. Table 1 shows the results.

[Liquidity] The catalyst composition was placed in a 100-ml glass bottle and kept at -10 ° C for 2 days.
The state of the catalyst composition at ℃ was observed.

Next, the composition of the catalyst composition shown in Table 1 was used as shown in Table 2.
And a polyol component [a sucrose polyether polyol (hydroxyl value: 380 mg KOH / g, manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name: polyol) 17
03) 45% by weight, 45% by weight of tolylenediamine-based polyether polyol (hydroxyl value: 450 mg KOH / g, trade name: Exenol 455AR, manufactured by Asahi Glass Co., Ltd.) and glycerin-based polyether polyol (hydroxyl value: 235 mg KOH / g; 100% by weight of Mitsui Chemicals, Inc., trade name: polyol MN-700) 10% by weight, and a foam stabilizer [trade name: L-53, manufactured by Nippon Unicar Co., Ltd.]
40: silicone-based foam stabilizer] 1.5 parts by weight of water and 3.5 parts by weight of water as a foaming agent were mixed with a laboratory mixer to obtain a polyol mixture.

Next, the obtained polyol mixture and an isocyanate component (Sumitomo Bayer Urethane Co., Ltd., trade name: Sumidur 44V20) were mixed and stirred with a lab mixer at 20 ° C. so that the isocyanate index became 105. Then, the following physical properties were examined using the obtained mixture. Table 2 shows the results.

A. Reactivity The mixture 4 stirred in a 300 ml polycup.
0 g of cream time in free foaming (hereinafter referred to as CT
), Gel time (hereinafter referred to as GT) and rise time (hereinafter referred to as RT).

B. Core density Mixture 25 of polyol mixture and isocyanate component
0 g in a mold [inner size: 150 x 150 x 300 (height)
mm] to form a rigid polyurethane foam free foam. After leaving the free foam of the obtained rigid polyurethane foam for one day, a test piece having a size of 100 × 100 × 100 mm was cut out from the core portion. The weight of the test piece was measured and determined according to the formula: [core density] = [weight of test piece] ÷ [volume of test piece].

C. Foam fluidity Mold for measuring foam fluidity adjusted to 45 ° C (aluminum, vertical part: width 200 x length 550 x
A predetermined amount (230 g) of the mixture was poured into a lower part of a mold in a 35 mm thick, horizontal portion: an inverted L-shape having a width of 200 × length 450 × a thickness of 35 mm, and molded into a polyurethane foam for 7 minutes. After the lapse of time, the mold was released, and as shown in FIG. 1, the length of the linear portion on the upper surface of the polyurethane foam 1, X and the intermediate value Y (the width of 2)
When a straight line parallel to the 00 mm side divides the area of the bulging portion into two parts, the sum (X + Y) of the straight line and the length of the bulging end is measured (X + Y), and “500 + X + Y” is calculated as the foam fluidity. Index.

D. Flyability characteristics Vertical mold temperature controlled to 45 ° C (inner size: 300 × 30
The mixture was cast into a 0 × 50 mm (provided that a polyethylene sheet was stuck on the entire inner wall of the mold) such that the pack ratio became 110%, and a polyurethane foam was molded. After 5 minutes, the mold was released. The flyability characteristics were evaluated based on the amount of polyurethane foam adhered to the mold based on the following evaluation criteria. [Evaluation Criteria] ：: When the surface skin is not brittle and there is no adhesion of the polyurethane foam to the mold. Δ: When the surface skin is slightly brittle and there is some adhesion of the polyurethane foam to the mold. X: Surface When the skin is very brittle and the amount of polyurethane foam adhering to the mold is very large

E. Catalyst cost The catalyst cost was determined by the product of the amount of the catalyst in the polyurethane foam and the catalyst price, and evaluated based on the following evaluation criteria. (Evaluation criteria) High: Higher cost than when 1,2-dimethylimidazole alone is used as the catalyst Medium: Cost approximately equal to that when 1,2-dimethylimidazole is used alone as the catalyst Low : One which is lower in cost than when 1,2-dimethylimidazole is used alone as a catalyst

[0052]

[Table 1]

[0053]

[Table 2]

From the results shown in Table 1, all of the catalyst compositions obtained in each of the examples show liquidity even at a low temperature of -10 ° C., and are therefore excellent in handleability. You can see that there is.

From the results shown in Table 2, it can be seen that the catalyst compositions used in each of the examples have both high fluidity and flyability of the foam. Also, the catalyst cost required in a polyurethane foam system is:
It is about the same as the case where 1,2-dimethylimidazole is used alone as a catalyst, and it can be seen that the catalyst composition utilizes the high catalytic activity of 1,2-dimethylimidazole as it is.

[0056]

Industrial Applicability The catalyst composition for producing polyurethane of the present invention effectively utilizes 1,2-dimethylimidazole having high catalytic activity, is highly reactive, is not solidified even in a low temperature range, and is liquid. It has excellent properties.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a method for measuring the fluidity of a foam when molding a polyurethane foam in each of Examples and Comparative Examples.

[Explanation of symbols]

 1 polyurethane foam

Continued on the front page (72) Inventor Masayoshi Morii 1334 Minato, Wakayama City F-term in Kao Corporation Research Laboratories 4T034 CA01 CA04 CA12 CA15 CB08 CC03 CC44 DA01 DB03 DB04 DF01 DF16 DF20 DF21 DG04 DG06 HA01 HA07 HC03 HC12 HC17 HC22 KA01 KB02 KD01 KD07 KD11 KD12 NA02 NA03 NA05 NA06

Claims (5)

[Claims] 1. An N-substituted imidazole compound which is solid at 10 ° C., formula (I): R ¹ N (CH ₂ CHR ² OH) ₂ (I) wherein R ¹ is a straight chain having 1 to 18 carbon atoms. Or a branched alkyl or alkenyl group, R ² represents a hydrogen atom or a methyl group), and a compound represented by the formula (II): HO—R—OH (II) wherein R is —CHR ³ CHR ⁴ — (OCHR ³ CHR
⁴ ) _n- (R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 2)]. . 2. The N-substituted imidazole compound which is solid at 10 ° C. is 1,2-dimethylimidazole.
A catalyst composition as described. 3. The catalyst composition according to claim 1, wherein the compound represented by the formula (I) is N-methyldiethanolamine or N-ethyldiethanolamine. 4. The compound represented by the formula (II) is one or more glycol compounds selected from the group consisting of ethylene glycol and dipropylene glycol.
The catalyst composition according to any one of the above. 5. An N-substituted imidazole compound which is solid at 10 ° C. in an amount of 50 to 85% by weight, a compound 10 represented by the formula (I)
The catalyst composition according to any one of claims 1 to 4, comprising from about 40% by weight to about 3% by weight of the compound represented by the formula (II).