JP3392793B2 - Polyurethane manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for producing polyurethane, and a method for producing polyurethane such as soft, rigid, semi-rigid foam or elastomer using the catalyst. More specifically, a method for producing polyurethane that can be suitably used as a building material, an electric refrigerator, a frozen warehouse, a heat insulating material for a bathtub, an interior material for automobiles, a cushioning material for furniture, bedding, and various sealing materials, and the method used therefor. The present invention relates to a catalyst for producing polyurethane.

[0002]

2. Description of the Related Art As a catalyst used in the production of polyurethane, N,
N, N ', N'-tetramethylethylenediamine, N,
N, N ′, N′-tetramethylpropylenediamine and the like are widely used. However, not only do they have a bad pungent odor, but they also have a major drawback in terms of environmental hygiene due to the eye rainbow caused by the catalyst vapor during the manufacturing operation.

In order to overcome these drawbacks, 1,4-diazabicyclo (2,2,2) octane, N, N, N ',
Although tertiary amine catalysts such as N′-tetramethylhexamethylenediamine have been proposed and some effects are recognized, it is still not sufficient. In addition, since these tertiary amine catalysts are not incorporated into polyurethane during the urethanization reaction by chemical bonding, they are diffused from the polyurethane and cause discoloration of the vinyl chloride resin sheet of the adherend such as "vinyl stain" and automobiles. However, there is a drawback in that it causes inconvenience such as "fogging" in which the window glass of the above becomes cloudy.

As an amine catalyst incorporated into polyurethane during the urethanization reaction, a tertiary amine catalyst having a hydroxyl group and an amino group which react with an isocyanate group in the molecule has been proposed. However, when such a tertiary amine catalyst is used, the problems of vinyl stain and fogging are solved, but the molecular structure of the polyurethane is changed, and particularly when it is exposed to a high temperature for a long time, the strength is reduced and the coloring is reduced. There is a drawback in terms of heat resistance that it occurs.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a catalyst for producing a low-odor polyurethane, and a method for producing a polyurethane excellent in vinyl stain resistance, fogging resistance and heat resistance using the catalyst for producing polyurethane. The challenge is to provide.

[0006]

That is, the gist of the present invention is as follows: (1) Formula (I): R ¹ R ² N- (CH ₂ ) _n -OH (I) (wherein R ¹ and R ² Each independently has 1 to 4 carbon atoms
Alkyl radical, n is a polyurethane producing catalyst comprising dialkylaminoalkyl alcohol represented by an integer of 9-12), and (2) ^{(I): R 1 R 2} N- (CH 2) n - OH (I) (In the formula, R ¹ and R ² each independently have 1 to 4 carbon atoms.
Of the alkyl group, n is an integer of 9 to 12) in the presence of a catalyst for polyurethane production, which comprises a dialkylaminoalkyl alcohol.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A catalyst for producing a polyurethane comprising a dialkylaminoalkyl alcohol represented by the formula (I) of the present invention has an extremely low odor, and the resulting polyurethane has vinyl stain resistance, fogging resistance and It has an excellent property of imparting heat resistance.

In the formula (I), R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, and of these, a methyl group is preferable. n is an integer of 9 to 12, and 9 is preferable among them. Among the dialkylaminoalkyl alcohols represented by formula (I), preferred are 9-dimethylamino-1-nonanol and 1
It is 2-dimethylamino-1-dodecanol, and 9-dimethylamino-1-nonanol is particularly preferable in terms of catalytic activity.

The dialkylaminoalkyl alcohol represented by the formula (I) can be easily produced by reacting an alkanediol having 9 to 12 carbon atoms with a dialkylamine.

In a polyurethane production catalyst comprising a dialkylaminoalkyl alcohol represented by the formula (I), "consisting of" when only the dialkylaminoalkyl alcohol represented by the formula (I) is used,
And two concepts when other catalysts for polyurethane production are included within the range not impairing the object of the present invention.

Other catalysts for producing polyurethane include
1,4-diazabicyclo (2,2,2) octane, 2-
Methyl-1,4-diazabicyclo (2,2,2) octane, N-ethylmorpholine, N- (dimethylaminoethyl) morpholine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N, N', N'-trimethylaminoethylpiperazine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N,
N, N ', N ", N" -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether,
1,8-diazabicyclo (5,4,0) undecene-
7, N, N ′, N ″ -tris (3-dimethylaminopropyl) hexahydro-s-triazine, 6-dimethylamino-1-hexanol, N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol,
Examples thereof include tertiary amine catalysts such as N, N-dimethylaminoethoxyethoxyethanol and derivatives thereof, salts of these with acids such as carboxylic acid and carbonic acid; and organometallic compounds represented by organotin compounds. Further, for the purpose of imparting flame retardancy to the polyurethane foam, a potassium salt such as potassium acetate or potassium octylate or a catalyst for producing polyisocyanurate represented by a quaternary ammonium salt may be used in combination. The amounts of other polyurethane production catalysts and polyisocyanurate production catalysts are not particularly limited and may be appropriately adjusted within a range that does not impair the object of the present invention.

The amount of the catalyst for producing a polyurethane comprising the dialkylaminoalkyl alcohol represented by the formula (I) cannot be unconditionally determined because it depends on the type of polyurethane. Usually, the amount of the polyurethane-producing catalyst is the amount of the polyol component 1 which is the raw material of the polyurethane.
From the viewpoint of increasing the reactivity of the polyol component and the isocyanate component with respect to 00 parts by weight, 0.3 parts by weight or more,
The amount is preferably 0.5 parts by weight or more, and from the viewpoint of maintaining the strength of the polyurethane, 10 parts by weight or less, preferably 8 parts by weight, relative to 100 parts by weight of the polyol component.
It is desirable that the amount is not more than parts by weight. Therefore, in consideration of these circumstances, the desirable amount of the catalyst for producing polyurethane is 0.3 to 1 with respect to 100 parts by weight of the polyol component.
It is 0 part by weight, preferably 0.5 to 8 parts by weight.

There is no particular limitation on the type of polyurethane to which the catalyst for polyurethane production comprising the dialkylaminoalkyl alcohol represented by the formula (I) can be applied. Examples of polyurethane include soft, rigid and semi-rigid polyurethane foams and polyurethane elastomers,
The present invention is not limited to such examples.
Of these, flexible, rigid and semi-rigid polyurethane foams are preferred.

Polyurethane can be produced by reacting a polyol component and an isocyanate component in the presence of a catalyst for producing a polyurethane comprising a dialkylaminoalkyl alcohol represented by the formula (I). Among polyurethanes, in the case of producing a polyurethane foam, a catalyst for producing a polyurethane comprising a dialkylaminoalkyl alcohol represented by the formula (I),
By reacting the polyol component and the isocyanate component in the presence of a foaming agent and, if necessary, a foam stabilizer,
Polyurethane foam can be manufactured.

The polyol component is not particularly limited as long as it has been conventionally used for producing polyurethane. The polyol component has 2 to 8 functional groups.
And polyester-based polyols and polyether-based polyols.

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

Examples of the dicarboxylic acid used in the polyester-based polyol include saturated aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; saturated aliphatic dicarboxylic acids 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; ester forming derivatives thereof, These acid anhydrides etc. are mentioned, These can be used individually or in mixture of 2 or more types. The dicarboxylic acid may optionally contain a trifunctional or higher polybasic acid such as trimellitic acid or pyromellitic acid.

Examples of the polyhydric alcohol 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 in combination of two or more.

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

The polyoxypropylene-based polyol is 2
Starting materials are compounds having one or more 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.

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

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 may be used alone or in combination of two or more.

The number of functional groups and the hydroxyl value of the polyol component cannot be unconditionally determined because they vary depending on the type of the desired polyurethane, the required physical properties, etc. Therefore, it is desirable to appropriately select them according to these.

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 and 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; examples thereof include 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 may be used alone or in admixture of two or more.

The ratio of the polyol component to the isocyanate component is usually such that the isocyanate index is 95 to 3
00, preferably 95 to 120 is preferably adjusted.

The blowing agent used in producing the polyurethane foam is water, low-boiling point hydrocarbons such as isopentane, normal pentane and cyclopentane, gases such as nitrogen gas, air and carbon dioxide, HCFC-141b and HCF.
C-142b, HCFC-22, HFC-134a, H
FC-152a, HFC-245fa, HFC-245
ca, HFC-236ea, HFC-365mfc and the like, and these may be used alone or in combination of two or more.

The amount of the foaming agent cannot be unconditionally determined because it depends on the type and the density of the desired polyurethane foam, and it is desirable to appropriately adjust the amount according to the type of these foaming agents.

The foam stabilizer, which is optionally used in the production of the polyurethane foam, may be one generally used in the production of the polyurethane foam.
Examples of the foam stabilizer include silicone surfactants such as dimethylpolysiloxane and polyoxyalkylene-modified dimethylpolysiloxane, and anionic surfactants such as fatty acid salts, sulfate ester salts, phosphate ester salts, and sulfonates. .

The amount of the foam stabilizer cannot be unconditionally determined because it depends on the type and the density of the desired polyurethane foam, and therefore it is desirable to appropriately adjust it depending on the type of the foam stabilizer.

Further, any component other than the above, for example, other auxiliary agents such as a crosslinking agent, a stabilizer, a pigment, a flame retardant, a filler and the like can be used within a range not hindering the object of the present invention.

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

As the stabilizer, dibutylhydroxytoluene, pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, and other hindered phenolic radical scavengers; phosphorous acid, triphenylphosphite, triethyl Antioxidants such as phosphorous acid compounds such as phosphite and triphenylphosphine; 2- (5-methyl-2-hydroxyphenyl) benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzo Triazol-2-yl) -4-hydroxyphenyl] A UV absorber such as a condensate of propionate and polyethylene glycol can be used, and these can be used alone or in admixture of two or more. Among these stabilizers, phosphite compounds, especially triphenyl phosphite and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], are of foam strength. From the viewpoint of improvement, it can be preferably used. In particular, triphenyl phosphite and pentaerythrityl-tetrakis [3- (3,5-di
-t-Butyl-4-hydroxyphenyl) propionate]
When used in combination with, there is an advantage that the foam strength can be further enhanced.

Examples of the pigment include inorganic pigments represented by transition metal salts, organic pigments represented by azo compounds, carbon powder, etc. These pigments may be used alone or in admixture of two or more. You can

Examples of the flame retardant include halogen type flame retardants such as tris (chloropropyl) phosphate.

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

In the case of producing a polyurethane foam, for example, a polyol component is mixed with a foaming agent, a polyurethane production catalyst, a foam stabilizer and other auxiliaries, and the obtained polyol mixture and an isocyanate component are molded into a molding machine or the like. Due to
It can be molded by mixing, stirring, pouring into a mold and foaming. More specifically, for example,
After controlling the temperature of the polyol mixture to about 20 ° C. using a tank or the like, a polyurethane foam is obtained by reacting with the isocyanate component using a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection type foaming machine. It can be manufactured.

As explained above, since the catalyst for producing polyurethane of the present invention has an extremely low odor, it is very excellent in the working environment during the production of polyurethane, and moreover, from the produced polyurethane. Also exhibits an excellent effect that no odor is generated due to the polyurethane production catalyst. Further, when the catalyst for producing polyurethane of the present invention is used, a polyurethane having excellent vinyl stain resistance, fogging resistance and heat resistance can be produced. Therefore, the polyurethane produced by the production method of the present invention, for example, when formulated into a rigid polyurethane foam, is suitable as a heat insulating material for walls and ceilings of houses and buildings, and is suitable for construction at a construction site. Can be applied. When it is formulated into semi-rigid polyurethane foam, it can be suitably used for automobile interior materials such as headrests and armrests. Further, when it is formulated into a flexible polyurethane foam, it has almost no odor derived from a catalyst, and therefore it can be suitably used as a cushion material mainly for furniture, bedding, etc., and an interior seat cushion material for automobiles.

[0039]

Examples Examples 1 and 2 and Comparative Examples 1 to 6 Branched polyether polyol, which is a polypropylene glycol having ethylene oxide added to the terminal [Sumitomo Bayer Urethane Co., Ltd., trade name: Sumifene 306]
3, hydroxyl value: 28 mg KOH / g] 100 parts by weight, triethanolamine 1.5 parts by weight, water as a foaming agent 3.
6 parts by weight and a catalyst for polyurethane production shown in Table 1 (the catalyst amount was adjusted so that the gel time was constant in each experimental example and each comparative example) were mixed with a lab mixer to obtain a polyol mixture.

Next, the obtained polyol mixture and an isocyanate component [Sumitomo Bayer Urethane Co., Ltd., trade name: Sumidule 44V20] were mixed and stirred with a lab mixer at 15 ° C. so that the isocyanate index was 105. 250 g of the obtained mixture was molded into a molding die [internal dimensions:
150 mm × 150 mm × 300 mm (height)] to mold a semi-rigid polyurethane foam free foam.

The odor of the catalyst for producing polyurethane and the physical properties of polyurethane foam were examined for strength retention (heat resistance), haze value (fogging resistance) and core density of foam based on the following methods. The results are shown in Table 1.

A. In a glass bottle with a lid having an odor of 140 ml, 2 g of the catalyst for producing polyurethane used in each of Examples and Comparative Examples was precisely weighed, put on a lid, and allowed to stand in a thermostatic chamber at 25 ° C. for 20 hours.
Odor sensor [New Cosmos Electric Co., Ltd., XP-32
9], the odor was measured. In Table 1, the smaller the value, the less the odor.

B. Strength retention rate (heat resistance) After the polyurethane foam was manufactured, it was allowed to stand at room temperature for 24 hours, and then the polyurethane foam was subjected to JIS K 630.
According to 1, the No. 2 type test pieces for tensile test measurement were cut out and 10 test pieces were cut out at room temperature for 5 test pieces [autograph manufactured by Shimadzu Corporation, product number: DCS-50M. ] And the pulling speed is 125 mm /
The average value of the strength (initial strength) when the tensile test was carried out at min, and the average value of the strength when the tensile test was carried out in the same manner as above after leaving the remaining 5 test pieces for 24 hours in an atmosphere of 120 ° C. (Strength at high temperature) is measured and the formula:
[Strength retention rate (%)] = [High temperature strength] / [Initial strength]
It was determined according to × 100 and used as an index of heat resistance.

C. Haze value (fogging resistance) After the polyurethane foam was manufactured and left at room temperature for 24 hours, a test piece (50 mm x 50 mm x
100 mm) is cut out and the test piece is put in a 500 ml glass bottle containing 0.1 ml of 2N hydrochloric acid, the opening is sealed with a transparent glass plate, and about 2/3 of the glass bottle is cut.
Was immersed in a hot water bath kept at 80 ° C for 100 hours, and then the haze value of the glass plate was measured by a haze meter (color difference meter).
It was measured with [Nippon Denshoku Industries Co., Ltd., product number: NDH-20D] and used as an index of fogging resistance. In Table 1, the smaller the haze value, the smaller the degree of haze.

D. Foam core density After manufacturing a free foam of polyurethane foam, leave it for 1 day, then from the core part, 100 mm x 100
A test piece having a size of mm × 100 mm is cut out, the weight of the test piece is measured, and the weight is divided by the volume for measurement.

[0046]

[Table 1]

From the results shown in Table 1, it is understood that according to Examples 1 and 2, the odor of the catalyst for producing polyurethane is very weak, so that the working environment for producing polyurethane is improved. The polyurethane foams obtained in Examples 1 and 2 have relatively high strength retention rates,
Further, since the haze value at high temperature (80 ° C.) is small, it can be seen that fogging is unlikely to occur.

Among Comparative Examples 1 to 6, Comparative Example 6 in which 14-dimethylamino-1-tetradecanol was used as the catalyst for producing polyurethane was excellent in odor. However, in Comparative Example 6, in order to obtain the same gel time as in the other Examples, a large amount of catalyst is required, so that the mechanical strength (strength retention rate) is low and the cost is high. I understand.

The vinyl stain resistance has not been tested. However, in Examples 1 and 2, a dialkylaminoalkyl alcohol represented by the formula (I) is used as a catalyst for producing polyurethane.
Since this dialkylaminoalkyl alcohol has a dimethylamino group and a primary hydroxyl group in the molecule and is incorporated into the polyurethane foam by a chemical bond, it has an anti-fogging property, that is, a haze value, in terms of vinyl stain resistance. Similar results are obtained. Therefore, from the results of the haze values shown in Table 1, it can be seen that the polyurethane foams obtained in Examples 1 and 2 are also excellent in vinyl stain resistance.

[0050]

EFFECT OF THE INVENTION When the catalyst for producing polyurethane comprising the dialkylaminoalkyl alcohol represented by the formula (I) of the present invention is used, there is little odor, vinyl stain resistance,
It is possible to produce polyurethane having excellent fogging resistance and heat resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 2001-172350 (JP, A) JP 62-115017 (JP, A) JP 2000-302833 (JP, A) (58) Fields investigated ( Int.Cl. ⁷ , DB name) C08G 18/16-18/18

Claims (5)

(57) [Claims] 1. Formula (I): R ¹ R ² N— (CH ₂ ) _n —OH (I) (wherein R ¹ and R ² are each independently a carbon number of 1 to 4).
Of the dialkylaminoalkyl alcohol represented by the formula (4), wherein n represents an integer of 9 to 12). 2. The catalyst for polyurethane production according to claim 1, wherein the compound represented by the formula (I) is 9-dimethylamino-1-nonanol. 3. Formula (I): R ¹ R ² N— (CH ₂ ) _n —OH (I) (wherein R ¹ and R ² are each independently a carbon number of 1 to 4).
The alkyl group, n is an integer of 9 to 12), and the polyol component and the isocyanate component are reacted with each other in the presence of a polyurethane production catalyst comprising a dialkylaminoalkyl alcohol. 4. The method for producing a polyurethane foam according to claim 3, wherein the polyol component and the isocyanate component are reacted in the presence of a polyurethane production catalyst comprising a dialkylaminoalkyl alcohol represented by the formula (I) and a blowing agent. . 5. The method according to claim 3, wherein the dialkylaminoalkyl alcohol represented by the formula (I) is 9-dimethylamino-1-nonanol.