JP3031699B2 - Polyol composition and use thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polyoxyalkylene polyol (hereinafter, referred to as polyol) composition and use thereof.

More specifically, the present invention relates to a polyol composition having good workability during polyurethane resin production and polyurethane foaming, a polyurethane resin having excellent physical properties, a polyurethane foam, and a method for producing the same.

The polyol composition (A) of the present invention is a hydrochlorofluorocarbon (hereinafter abbreviated as HCFC) 2,2-
Dichloro-1,1,1-trifluoroethane (HCFC-123),
1,1-dichloro-1-fluoroethane (HCFC-141b),
1-chloro-1,1-difluoroethane (HCFC-142b),
1-chloro-1,1-difluoromethane (HCFC-22) and hydrofluorocarbons (hereinafter abbreviated as HFC)
1,1,1,2-tetrafluoroethane (HFC-134a), 1,1
-Not only can it be used as a raw material for polyurethanes that are resistant to dissolution in difluoroethane (HFC-152a), but it has a moderate viscosity as a
Uses trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12), which are chlorofluorocarbons (hereinafter abbreviated as CFC) when urethane foaming because of their excellent dispersibility in FC and HFC. Since the same workability and foam properties as the conventional method can be obtained, electric refrigerators, freezers, heat insulation panels, composites with other materials,
It is extremely useful as a heat insulating material for ships or vehicles or a heat insulating structural material.

[Conventional technology]

Currently, when producing polyurethane foam, CFCs such as CFC-11 and CFC-12 are used as foaming means, but these are taken up as environmental destructive substances that decompose the ozone layer and increase the greenhouse effect. Is regulated for manufacture and use. At the same time, HCFC-123, HCFC-141b, HCFC-142b, HFC
CFC-22, HFC-134a and HFC-152a have attracted attention,
It has been found that these foaming agents have a higher dissolving power than CFC-11 and CFC-12, and tend to greatly reduce the physical properties of the polyurethane foam, such as a decrease in the closed cell ratio and a decrease in foam strength. In particular, the heat insulating effect, which is a property of rigid polyurethane foam, is significantly reduced during foaming because the foaming agent dissolves the closed cell walls in the foam.

Therefore, the necessity of a new polyurethane resin or polyurethane foam has emerged. There is no example of a conventional polyol used as a raw material of a polyurethane resin in which an alkylene oxide is added to aminophenol.

In general, the polyol decreases in viscosity with an increase in the amount of alkylene oxide added, and the operation of producing a polyurethane resin is easy.However, if the alkylene oxide is added excessively, the polyurethane resin is dissolved in HCFC and HFC. There was a tendency to be virtually unusable.
Conversely, when the added amount of the alkylene oxide is reduced, the polyol becomes solid or excessively viscous, so that the handling becomes extremely difficult.

As described above, when trying to maintain the dissolution resistance of the polyurethane resin to HCFC and HFC, the workability during urethane foaming becomes extremely poor, the workability during foaming has a good viscosity, and the above HCFC And a polyol excellent in mixing dispersibility in HFC was not found.

[Problems to be solved by the invention]

The object of the present invention is to improve the workability especially in the production of a rigid polyurethane foam, and even when HCFC or HFC having a strong resin dissolving power is used as a foaming agent, the foam properties are the same as those of a conventional CFC.
An object of the present invention is to provide a rigid polyurethane foam which is equivalent to the case where FC is used and has excellent resistance to dissolution in HCFC and HFC.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and have reached the present invention.

 That is, the present invention is as follows (1) to (4).

(1) An aminophenol-based polyol (A) obtained by adding 1.0 to 4.5 mol of alkylene oxide per equivalent of active hydrogen of aminophenol.

(2) A polyurethane resin obtained by mixing and reacting the polyol (A) as described in (1) wholly or partially with a polyol and an organic polyisocyanate.

(3) In a rigid polyurethane foam obtained by mixing and reacting a polyol, a foaming agent, a catalyst, a foam stabilizer, other auxiliaries and an organic polyisocyanate, the polyol (A) described in (1) is all as the polyol. Rigid polyurethane foam using a polyol that is or part thereof, and using, as the foaming agent, a foaming agent containing at least one selected from the group consisting of hydrochlorofluorocarbons and hydrofluorocarbons and, if necessary, a foaming aid. .

(4) The method for producing a rigid polyurethane foam described in (3).

The aminophenol-based polyol (A) of the present invention has p
It is a polyol obtained by adding 1.0 to 4.5 mol of alkylene oxide per equivalent of active hydrogen of-or m-form aminophenol.

Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, and butylene oxide, and these can be used alone or in combination of two or more.

In the aminophenol-based polyol (A) of the present invention, a polyurethane foam containing less than 1.0 mol of alkylene oxide per equivalent of active hydrogen of aminophenol, that is, having a large amount of active hydrogen remaining therein, has poor foam properties. Further, when the alkylene oxide is added in an amount exceeding 4.5 mol, the viscosity is lowered and the mixing and dispersibility in HCFC and / or HFC is improved, but the physical properties of the foam are inferior.

In the present invention, the catalyst used for adding the alkylene oxide to the active hydrogen of the aminophenol used as the initiator is an amine-based catalyst represented by the following general formula (I) or (II)
Are the amine compounds shown in FIG.

NR ₁ R ₁ R ₂ (I) R ₁ R ₂ N (CH ₂ ) _n NR ₁ R ₂ (II) (wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, And represents one atom or group selected from the group consisting of a hydroxyethyl group and a hydroxyisopropyl group, provided that, in the formula (I), R ₁ and R ₂ are not hydrogen atoms.

Or, n is an integer of 1 to 6. Examples of the amine compound include dibutylamine, ethylenediamine, tetramethylenediamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, triethylamine, tri-n-propylamine, di-n-propylamine, and n-amine.
Examples thereof include propylamine, n-amylamine, N, N-dimethylethanolamine, isobutylamine, isoamylamine, and methyldiethylamine.

Further, as the metal hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide,
Examples thereof include calcium hydroxide and barium hydroxide. Each of the above catalysts can be used alone or in combination of two or more.

The amount of these catalysts used was 100 aminophenol initiators.
0.1 to 2.0 parts by weight per part by weight.

In the method for producing the polyol of the present invention, an aminophenol as an initiator and a catalyst are charged into an autoclave, and then an alkylene oxide is gradually added and reacted. The reaction temperature is preferably from 90 to 130C. When the temperature is lower than 90 ° C., the reaction does not easily proceed, and when it exceeds 130 ° C., a side reaction tends to occur easily.

Other polyols that can be used in combination with the polyol of the present invention include, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3,6-hexanetriol, pentaerythritol, sorbitol, Sucrose, bisphenol A,
Polyhydric alcohols such as novolak, hydroxylated 1,2-polybutadiene and hydroxylated 1,4-polybutadiene, and / or a hydroxyl value 200 obtained by addition-polymerizing an alkylene oxide to these polyhydroxy compounds.
~ 800mgKOH / g polyether polyol.

In addition to the above, a hydroxyl group-containing higher fatty acid ester such as a polyester polyol obtained by reacting a higher resin acid ester polyol and a polycarboxylic acid with a low molecular weight polyol and a polyester polyol obtained by polymerizing caprolactone, a castor oil, and a dehydrated castor oil. Etc. can also be used.

The amount of other polyols that can be used in combination is 0 to 40% by weight of the total polyol.

The organic polyisocyanate used in the production of the polyurethane resin and the rigid polyurethane foam in the present invention is not particularly limited as long as it is conventionally known, and is aromatic, aliphatic, alicyclic polyisocyanate and a modified product thereof,
For example, phenyl diisocyanate, diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, triphenylmethylene triisocyanate, tolylene triisocyanate, polymethylene polyphenyl polyisocyanate, modified (carbodiimide, etc.)
Obtained by reacting an excess of diphenylmethane diisocyanate or the like and a mixture thereof and an organic polyisocyanate thereof with a polyol (for example, a low molecular weight polyol and / or a polymer polyol) with NCO / active hydrogen (equivalent ratio) of 2 to 20. These include NCO group prepolymers (NCO content, eg, 5 to 35%), etc. These organic polyisocyanates are used alone or in combination of two or more. The equivalent ratio to the hydroxyl groups in the solution is adjusted to 0.8 to 5.0.

If the equivalent ratio exceeds 5.0, unreacted organic polyisocyanate remains. On the other hand, when the equivalent ratio is less than 0.8, a large amount of unreacted polyol remains, so that the above range is preferable.

The blowing agent used in the present invention is HCFC and / or HFC.

As HCFC, HCFC-123, HCFC-141b, HCFC-142
b, HCFC-22 and HFC include HFC-134a and HFC-152a. These may be used alone or in combination of two or more.

If necessary, water and / or a low-boiling compound or a foaming aid containing the compound may be used in combination.

The amount of water used is usually 0.5 to 5.0 in 100 parts by weight of the resin stock solution.
Parts by weight. The low-boiling compounds include methylene chloride, low-boiling hydrocarbons (boiling point: 10 to 50 ° C.), and mixtures thereof. Conventional chlorofluorocarbons can also be used in combination.

Examples of the foaming catalyst that can be used to obtain the rigid polyurethane foam in the present invention include amine-based urethanization catalysts (triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N- Methyl morpholine, N-ethyl morpholine, N-octadecyl morpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, diethylenetriamine, N, N, N ', N'-tetramethyl Ethylenediamine, N, N, N ', N'-tetramethylpropylenediamine,
N, N, N ', N'-tetramethylbutanediamine, N, N, N',
N'-tetramethyl-1,3-butanediamine, N, N, N ',
N'-tetramethylhexamethylenediamine, bis [2
-(N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, triethylenediamine, triethylenediamine Formate and other salts of ethylenediamine, oxyalkylene adducts of amine groups of primary and secondary amines, azacyclic compounds such as N, N-dialkylpiperazines, various N, N ', N "-trialkyl Aminoalkylhexahydrotriazines (β-aminocarbonyl catalyst of JP-B-52-0443517, JP-B-53
-014279 β-aminonitrile catalyst, etc.), organometallic urethanization catalysts (tin acetate, tin octylate, tin oleate,
Tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octanoate,
Lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.). These catalysts are used alone or as a mixture, and the amount used is 0.001 to 100 parts by weight of the polyol.
10.0 parts by weight.

The foam stabilizer in the present invention is a conventionally known organosilicon surfactant, for example, Nippon Unicar L-520,
L-540, L-5340, L-5410, L-5420, L-5710,
L-5720, etc. and SH-19 manufactured by Toray Silicone Co., Ltd.
0, SH-192, SH-193, SH-194, SH-195, etc.
Shin-Etsu Silicone F-305, F-306, F-317, F
-341, F-345, etc.
−4200, and so on. The amount of these foam stabilizers used is based on 100 parts by weight of the total of the polyol and the organic polyisocyanate.
0.1 to 20 parts by weight.

As a flame retardant, for example, tris (2-chloroethyl)
Phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, CR-505 and CR-507 manufactured by Daihachi Chemical Co., Fyro manufactured by Akzo Japan
l-6 or the like can be used.

In addition, stabilizers such as plasticizers, fillers, antioxidants, and ultraviolet absorbers, and colorants commonly used in urethane chemistry can be added as necessary.

In the case of producing the polyurethane resin of the present invention, usually, a predetermined amount of a polyol as a main raw material and an organic polyisocyanate are rapidly mixed, poured into a mold, and cured at room temperature.

In the case of producing a rigid polyurethane foam, a predetermined amount of the HCFC and / or HFC as a polyol, a catalyst, a foam stabilizer, a flame retardant, other auxiliaries, and a foaming agent is mixed to prepare a stock resin solution.

The above polyol composition includes the polyol composition (A) described above.
Use the one containing.

Using a polyurethane foaming machine, the resin stock solution and the organic polyisocyanate are continuously and rapidly mixed at a constant ratio.

The obtained rigid polyurethane foam stock solution is injected into a void or a mold. At this time, the flow ratio between the organic polyisocyanate and the resin stock solution is adjusted so that the equivalent ratio NCO / active hydrogen (equivalent ratio) between the organic polyisocyanate and the polyol is 0.8 to 5.0.

After injection, the rigid polyurethane foam stock solution foams and hardens within a few minutes.

If necessary, a batch process may be used instead of the continuous process.

The rigid polyurethane foam obtained in the present invention can be used as an electric refrigerator, a heat insulating panel, a composite with other materials, a heat insulating material or a structural material for ships or vehicles, and the like.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

In the following examples, the polyol is referred to as a polyol composition.

(1) Aminophenol-based polyol composition (A)
(Table 1) The measuring method of hydroxyl value (OH value) and viscosity is JIS K15
Followed 57.

Example 1 327 g of p-aminophenol was charged into an autoclave of No. 2 and heated to 120 ° C. with nitrogen replacement. Triethylamine 2.5
g was added and mixed, and 522 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed. OH value 595mmKOH / g, viscosity 32200CP / 25
° C polyoxyalkylene polyol composition (A-1)
830 g was obtained.

The propylene oxide addition number per active hydrogen of the polyoxyalkylene polyol composition (A-1) was 1.0 mol.

Examples 2 to 7 Comparative Examples 1 and 2 Various polyol compositions were prepared in the same manner as in the examples, and the OH values and viscosities of these polyol compositions were measured.

 Table 1 shows the measurement results.

(2) Polyurethane resin (Table-2) Next, according to the formulation shown in Table-2, the polyol composition, MDI-CR (crude diphenylmethane diisocyanate,
Mitsui Toatsu Chemicals Co., Ltd.) and Kaorizer No. 1 (Amine-based catalysts, Kao Co., Ltd. products)) are mixed rapidly, poured into a mold, left for one day and night, and the resin is removed from the mold and foamed. The absorption for the agent was measured.

 Table 2 shows the measurement results.

(3) Polyurethane foam (1) (Table-3) 1.0 g of water and 100 g of the silicone foam stabilizer L- were added to 100 g of each of the polyol compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2.
A resin premix consisting of 1.5 g of 5420 (manufactured by Nippon Yunika Co., Ltd.), 3.0 g of an amine-based catalyst chaolyzer No. 1 and 31.3 g of each of the blowing agents shown in Table 3 was prepared in advance, and then an organic polyisocyanate was prepared. A hard polyurethane foam was produced by mixing and reacting Nart (112.9 g of Mitsui Toatsu Chemicals Co., Ltd. MDI-CR).

Table 3 shows the mixing dispersibility (workability) of the foaming agent and the polyol composition when preparing the resin premix.

Further, the closed cell ratio of the manufactured rigid polyurethane foam was measured. The results are shown in Table-3.

(4) Rigid polyurethane foam (2) (Table 4) Here, a rigid polyurethane foam was prepared according to the following method, and the physical properties thereof were confirmed. A resin premix was prepared according to the polyol composition having the formulation shown in Table 1 and the formulation shown in Table 4, and a resin premix was rapidly mixed with a predetermined amount of an organic polyisocyanate at 5000 rpm for 8 seconds.
Each of the vertical wooden boxes of 0 × 200 mm and 380 × 380 × 35 (thickness) mm was injected and foamed. After standing at room temperature for one day and night, a foam of 80 × 80 × 30 mm is cut out of the rigid polyurethane foam obtained from the former, and the density, compressive strength, dimensional stability at low temperature and the rigid polyurethane foam obtained from the latter are cut out according to JIS A9514. A 200 × 200 × 25 mm foam was cut out from this, and the thermal conductivity of the foam was measured in accordance with JIS A1412. The measurement results were as shown in Table-4.

[Effect of the Invention] Aminophenol-based polyol composition (A) of the present invention
Has an appropriate viscosity, and has good mixing and dispersibility with an organic polyisocyanate. Also, the obtained polyurethane resin has high solubility resistance to HCFC or HFC with extremely low pollution, and rigid polyurethane foam using these foaming agents has the same foam properties and properties as those using conventional high pollution CFC. Has workability.

Accordingly, such polyol compositions, polyurethane resins and rigid polyurethane foams are extremely useful in the urethane industry.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Nozawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (56) References JP-A-62-30120 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) C08G 18 / 32,65 / 26,65 / 28 C07C 217/86 C08J 9/04-9/14

Claims (9)

(57) [Claims] An alkylene oxide is added to an aminophenol in an amount of 1.0 to 4.5 per equivalent of active hydrogen of the aminophenol.
Aminophenol-based polyol (A) obtained by molar addition. 2. Polyurethane characterized in that the polyol (A) according to claim 1 is obtained by mixing and reacting all or a part of the polyol with an organic polyisocyanate. resin. 3. The polyurethane resin according to claim 2, wherein the equivalent ratio of the isocyanate group of the organic polyisocyanate to the hydroxyl group of the polyol is 0.8 to 5.0. 4. The polyurethane resin according to claim 2, wherein a part or all of the organic polyisocyanate is a prepolymer having a terminal isocyanate group. 5. A rigid polyurethane foam obtained by mixing and reacting a polyol, a foaming agent, a catalyst, a foam stabilizer, other auxiliaries and an organic polyisocyanate, wherein the polyol (A) according to claim 1 is used as the polyol. All or a part of the polyol is used, and as the foaming agent, hydrochlorofluorocarbons, a foaming agent containing at least one selected from the group consisting of hydrofluorocarbons and, if necessary, a foaming aid are used. Rigid polyurethane foam characterized by the above. 6. The method of claim 1, wherein the hydrochlorofluorocarbon is 2,2.
2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane or 1-chloro-1,1-difluoromethane; hydrofluorocarbon The rigid polyurethane foam according to claim 5, wherein the class is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane. 7. The rigid polyurethane foam according to claim 5, wherein the foaming aid is water and / or a low-boiling compound. 8. The rigid polyurethane foam according to claim 5, wherein a part or all of the organic polyisocyanate is a prepolymer having a terminal isocyanate group. 9. The rigid polyurethane foam according to claim 7, wherein the equivalent ratio of the isocyanate group of the organic polyisocyanate to the hydroxyl group of the polyol is 0.8 to 5.0.