JPH04298520A - Polyol and its use - Google Patents

Abstract

PURPOSE:To obtain a rigid polyurethane foam excellent in dimensional stability at low temperatures and adhesion to a substrate by effecting the addition reaction of an alkanolamine with a lactone and an alkylene oxide in a specified ratio. CONSTITUTION:An alkanolamine is optionally mixed with at least one member selected between a polyalcohol and a polyoxyalkylene polyol to obtain an active hydrogen compound (A). The addition reaction of component A with 0.01-2.0mol, per mol of the hydroxyl groups of component A, of a lactone and 0.5-3.0mol, per mol of the hydroxyl groups of component A, of an alkylene oxide is effected to obtain the title polyol. A stock resin solution comprising this polyol, a blowing agent, a catalyst, a foam stabilizer and other assistants is mixed with an organic polyisocyanate and foamed to obtain a rigid polyurethane foam.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyol for rigid polyurethane and a rigid polyurethane foam using the polyol as a raw material.

The polyol of the present invention has a low viscosity and
Due to its rapid reactivity with organic polyisocyanates, workability during spray foaming and board molding is extremely good, and low-temperature dimensional stability when made into polyurethane foam.
It also has excellent adhesive and heat insulating properties, making it extremely useful as a heat insulating structural material and building material.

0003

[Prior Art] Conventionally, as polyols for rigid polyurethanes used in spray foaming and board molding, polyols using aromatic amines or aliphatic amines as initiators have been used (Japanese Patent Publication No. 39-15549, Special Public Sho 3
Publication No. 9-22617, Japanese Patent Publication No. 13659/1973, Publication No. 22504/1973, Japanese Patent Publication No. 46-353
Publication No. 86, Special Publication No. 48-32597, Special Publication No. 5
1-8676, Special Publication No. 12238/1983)
.

However, although these polyols obtained by adding alkylene oxide to an amine compound have excellent reactivity with organic polyisocyanates, they have a relatively high viscosity and cannot be mixed with other low molecular weight or low viscosity polyols. It has the disadvantage that it must be used in a
-151613, JP-A-57-151614).

[0005]Although polyols using aliphatic amines as initiators have relatively good low-temperature dimensional stability, they are insufficient in terms of performance, and there is still room for improvement in terms of adhesiveness and the like.

[0006]

[Problems to be Solved by the Invention] The object of the present invention is to provide a hard polyol that has a low viscosity, high reactivity with organic polyisocyanates, and excellent workability during foaming, and a polyol that can be obtained by the reaction of this polyol with an organic polyisocyanate. The purpose of the present invention is to provide a rigid polyurethane foam that has excellent low-temperature dimensional stability and adhesion to base materials.

[0007]

[Means for Solving the Problems] The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have arrived at the present invention.

That is, the present invention is as follows.

[0009] This is a polyol for rigid polyurethane, which is prepared by adding 0.01 to 2.0 moles of lactone and 0.5 to 3.0 moles of alkylene oxide per mole of hydroxyl group of alkanolamines.

[0010] And 0.01 to 2.0 moles of lactone and alkylene per mole of hydroxyl group of an active hydrogen compound prepared by adding one or more components selected from polyhydric alcohols and polyoxyalkylene polyols to alkanolamines. This is a polyol for rigid polyurethane to which 0.5 to 3.0 moles of oxide are added.

[0011] Further, in a rigid polyurethane foam obtained by mixing and foaming a resin stock solution obtained by adding a blowing agent, a catalyst, a foam stabilizer, and other auxiliary agents to a polyol and an organic polyisocyanate, the polyol as claimed in claim 1 or This is a rigid polyurethane foam characterized by using the polyol described in No. 2.

Polyol for rigid polyurethane The alkanolamines used in the present invention include monoethanolamine, methylethanolamine, ethylethanolamine, methylisopropanolamine, methyl-2-hydroxybutylamine, phenylethanolamine, diethanolamine, diisopropanolamine, Screw(
Examples include 2-hydroxypropyl)amine, ethanolisopropanolamine, triethanolamine, triisopropanolamine, and the like. These alkanolamines can be used alone or in combination of two or more.

[0013] In addition, as an active hydrogen compound used as an initiator, it is also possible to use one or more types of polyhydric alcohols and polyoxyalkylene polyols together with alkanolamines. When polyhydric alcohol and polyoxyalkylene polyol are used together, the alkanolamine content in the initiator composition is preferably 50% by weight or more. When the alkanolamine content is less than 50% by weight, a rigid polyol with low viscosity and quick reactivity with organic polyisocyanate, which is a feature of the present invention, cannot be obtained. Stability, adhesion to base materials, etc. tend to deteriorate.

Polyhydric alcohols that can be used in combination with the alkanolamine used in the present invention include glycerin, trimethylolpropane, 1,2,6-hydroxyhexane, pentaerythritol, tetramethylolcyclohexane, α-methylglucoside, 2,2 , 6,6-tetrahydroxycyclohexanol, sorbitol, mannitol, dulcitol, sucrose and the like.

Further, as polyoxyalkylene polyols that can be used in combination with the alkanolamine used in the present invention, glycerin, trimethylolpropane, 1,2,
6-hydroxyhexane, pentaerythritol, tetramethylolcyclohexane, α-methylglucoside,
Polyhydric alcohols such as 2,2,6,6-tetrahydroxycyclohexanol, sorbitol, mannitol, dulcitol, and sucrose, aliphatic amines such as ethylenediamine, diethylenetriamine, tetraethylenetriamine, and tris(2-aminoethyl)amine, and alkylene Examples include polyether polyols and polyester polyols to which oxides have been added.

The alkylene oxide used in the present invention includes ethylene oxide, propylene oxide, butylene oxide, etc., and these may be used alone or in combination of two or more.

The amount of lactone addition reaction per mole of hydroxyl group of the active hydrogen compound obtained by adding alkanolamines alone or to alkanolamines with one or more components selected from polyhydric alcohols and polyoxyalkylene polyols is 0. .01 to 2.0 mol is preferred. If the amount of lactone addition reaction is less than 0.01 mol, the low temperature dimensional stability and adhesiveness of the polyurethane foam after reaction with organic polyisocyanate tend to decrease, and if it exceeds 2.0 mol, However, the viscosity of the polyol is high and workability is poor.

[0018] Also, 1 mole of hydroxyl groups of an active hydrogen compound or a lactone addition reaction product thereof, which is obtained by adding alkanolamines alone or to alkanolamines with one or more components selected from polyhydric alcohols and polyoxyalkylene polyols. The number of alkylene oxides added per unit is 0.
5 to 3.0 mol is preferred. When the amount is less than 0.5 mol, the mixing and dispersibility with the organic isocyanate is poor, and the polyurethane foam becomes brittle. Also, 3
．． When the amount exceeds 0 mol, not only the reactivity with the organic polyisocyanate tends to decrease, but also the compressive strength of the resulting urethane foam tends to decrease.

Therefore, the preferred range of the hydroxyl value of the polyol used in the present invention is 200 to 700 mgKOH/
It is g.

In the present invention, a component 1 selected from polyhydric alcohols and polyoxyalkylene polyols is added to alkanolamines alone or to alkanolamines.
The catalyst used for adding an alkylene oxide to the hydroxyl group of an active hydrogen compound or its lactone addition product is an amine-based catalyst represented by the following general formula (1) [Chemical formula 1] or (2) [Chemical formula 1] or (2) It is an amine compound represented by the following formula.

[0021]

[Chemical formula 1]

[0022]

[Formula 2] (In the above formula, R1 and R2 are hydrogen atoms, alkyl groups having 1 to 16 carbon atoms, -CH2CH2OH groups, or -CH2CH
(CH3) represents an OH group. Moreover, n is 1-6. However, in general formula (1), cases where both R1 and R2 are hydrogen atoms are excluded. ) Examples of amine compounds include dibutylamine, dimethylpalmitylamine, tetramethylenediamine, triethylamine, tri-n-propylamine, di-n-propylamine, n-propylamine, n-amylamine,
Examples include N,N-dimethylethanolamine, isobutylamine, isoamylamine, and methyldiethylamine.

Examples of the alkali hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.

Each of the above catalysts can be used alone or in combination of two or more. When an amine compound is used, no post-treatment is required, whereas when an alkali hydroxide catalyst is used, hydrochloric acid,
The polyol is purified by neutralizing the catalyst with an acid such as sulfuric acid, phosphoric acid or acetic acid, and filtering out the generated salt.

The organic polyisocyanates used in the present invention include aromatic, aliphatic, and cycloaliphatic polyisocyanates and their modified products, dimers, and trimers, such as hexamethylene diisocyanate, isophorone diisocyanate (IPDI), Tolylene diisocyanate (T
DI), diphenylmethane diisocyanate, xylylene diisocyanate (XDI), dicyclohexylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (MDI-CR), triphenylmethylene triisocyanate, uretidione, isocyanurate, modified (carbodiimide) diphenylmethane diisocyanate, etc. .

These organic polyisocyanates may be used alone or in combination of two or more. The amount used is such that the equivalent ratio of isocyanate groups to active hydrogen in the resin liquid is 0.8.
Make it so that it becomes ~5.0.

[0027] As a method for producing the polyol used in the present invention, alkanolamines alone in an autoclave,
Alternatively, polyhydric alcohols and one or more components selected from polyoxyalkylene polyols are added to alkanolamines, and a lactone, a catalyst, and an alkylene oxide are added thereto and then reacted. In this case, the lactone, the catalyst, and the alkylene oxide may be charged at the same time, or the catalyst and the alkylene oxide may be charged after the addition reaction of only the lactone is carried out in advance.

[0028] The reaction temperature in the addition reaction of lactone and alkylene oxide is preferably 60 to 150°C. If the reaction temperature is less than 60°C, the reaction will not proceed, and if it exceeds 150°C, side reactions will become noticeable, which is not preferred.

Rigid polyurethane foam Also, the polyols, organic polyisocyanates, etc. used in this section are those mentioned above, and of course, all of them can be used as they are.

As a blowing agent, chlorofluorocarbons such as trichlorofluoromethane (CFC-11), lower hydrocarbon compounds such as heptane, or low-boiling chlorinated hydrocarbons such as methylene chloride, water, or hydrochlorofluorocarbons ( HCFC), e.g. 2,2-
Dichloro-1,1,1-trifluoroethane (HCFC
-123) and 1,1-dichloro-1-fluoroethane (
HCFC-141b) can be used alone or in combination of two or more.

Catalysts that can be used in the present invention include, for example, amine compounds (triethylamine, tripropylamine, triisopropanolamine, tributylamine,
trioctylamine, hexadecylmethylamine, N-
Methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, diethylenediamine, N,N,N',N'-tetra Methylethylenediamine, 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-dimethylamine, N,N-dimethylcyclohexylamine, N,
N,N',N'',N'''-pentamethyldiethylenetriamine, triethylenediamine, organic acid salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines, N,N-dialkylpiperazines azacyclic compounds such as, various N,N',N''-trialkylaminoalkylhexahydrotriazines,
β-aminocarbonyl catalyst disclosed in Japanese Patent Publication No. 52-43517, β-aminonitrile catalyst disclosed in Japanese Patent Publication No. 53-14279, organometallic compounds (tin acetate, tin octylate,
tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride,
lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.).

These catalysts may be used alone or in combination, and the amount used is 0.0001 to 10.0 parts by weight per 100 parts by weight of the compound having active hydrogen.

The foam stabilizer in the present invention is a conventionally known organosilicon surfactant, such as L-501, L-532, L-540, L-544, manufactured by Nippon Unicar Co., Ltd.
L-3550, L-5302, L-5305, L-53
20, L-5340, L-5410, L-5420, L
-5421, L-5710, SZ-1642, etc.
SH-190, SH-192 manufactured by Toray Silicone
, SH-193, SH-194, SH-195, SH-
200, SPX-253, etc., and F-114, F-121, F-122, F-220, manufactured by Shin-Etsu Silicone Co., Ltd.
F-230, F-258, F-260B, F-317,
F-341, F-345, etc., and TFA-4200, TFA-4202, etc. manufactured by Toshiba Silicone Corporation.

The amount of these foam stabilizers used is 0.1 to 20 parts by weight based on 100 parts by weight of the compound having active hydrogen and the organic polyisocyanate.

Examples of flame retardants include tris(2-chloropropyl) phosphate, tris(dichloropropyl) phosphate, tris(dibromopropyl) phosphate, CR-505 and CR-507 manufactured by Daihachi Kagaku Co., Ltd.
, Phosgard 2XC-2 manufactured by Monsanto Chemical Co., Ltd.
0 and C-22-R (Phosgard is a trademark of Monsanto Chemical Company), Fyrol6 (Fyrol6 manufactured by Stouffer Chemical Company)
yrol (trademark of Stouffer Chemical Co., Ltd.) can be used.

Other materials known in urethane chemistry, such as plasticizers, fillers, stabilizers, and colorants, may be added as required.

In an example of carrying out the present invention, a resin solution is prepared by mixing predetermined amounts of a polyol, a catalyst, a blowing agent, a flame retardant, and other auxiliaries.

[0038] This resin solution and organic polyisocyanate are rapidly mixed at a predetermined ratio using a polyurethane foaming machine with a mixing head or the like. The obtained rigid polyurethane foam raw material liquid is molded by methods such as spray foaming and composite board formation to produce insulating structural materials and building materials.

At this time, the flow rate ratio of the organic polyisocyanate and the resin liquid is adjusted so that the equivalent ratio of the organic polyisocyanate to the active hydrogen in the polyol is 0.8 to 5.0.

[0040]

[Examples] The present invention will be explained below with reference to Examples. still,
The hydroxyl value and viscosity were measured in accordance with JIS K1557. Measurement of low temperature dimensional stability and compressive strength of polyurethane foam is performed using JIS A-1412, JIS
It was carried out according to A-9514.

Example 1 Isopropanolamine (hereinafter abbreviated as IPOA) 70
0g, glycerin (hereinafter abbreviated as G) 300g and β-propiolactone (hereinafter abbreviated as β-PL) 90g
7 g was charged into a 5 liter autoclave equipped with a thermometer and a stirrer, and after purging with nitrogen, the temperature was raised to 100°C. Dimethylpalmitylamine (manufactured by Kao Corporation, hereinafter referred to as DM-60)
After adding and mixing 4.0 g of propylene oxide (hereinafter abbreviated as PO) and ethylene oxide (hereinafter abbreviated as PO),
1140 g of each (abbreviated as O) were gradually charged in this order. 7
After the reaction for an hour, unreacted PO and EO in the system were removed under reduced pressure. Hydroxyl value 400mgKOH/g, viscosity 400cp/25
4140 g of polyol was obtained.

Example 2 800 g of diethanolamine (hereinafter abbreviated as DEOA)
, polyoxyalkylene polyol Su450L (
(manufactured by Mitsui Toatsu Chemical Co., Ltd.) and 1,810 g of ε-caprolactone (hereinafter abbreviated as ε-CL) were placed in a 5-liter autoclave equipped with a thermometer and a stirrer, and after purging with nitrogen, the temperature was raised to 110°C. After adding and mixing DM-608.5 g, 700 g of PO and then 1050 g of EO were gradually charged. After 5 hours of reaction, unreacted PO and EO in the system
was removed under reduced pressure. 4,520 g of polyol having a hydroxyl value of 300 mgKOH/g and a viscosity of 600 cp/25°C was obtained.

Example 3 Triethanolamine (hereinafter abbreviated as TEOA) 100
0 g and 58 g of γ-butyrolactone (hereinafter abbreviated as γ-BL) were placed in a 5 liter autoclave equipped with a thermometer and a stirrer, and after purging with nitrogen and raising the temperature, the mixture was heated to 60°C for 30 minutes.
Allowed time to react. After adding and mixing 3.5 g of DM-60, the temperature was raised to 100° C., and 580 g of PO was gradually charged. After 3 hours of reaction, unreacted PO in the system was removed under reduced pressure. Hydroxyl value 690mgKOH/g, viscosity 350cp/25℃
1628 g of polyol was obtained.

Example 4 1000 g of TEOA and 2300 g of ε-CL were charged into an 8-liter autoclave equipped with a thermometer and a stirrer, and after purging with nitrogen, the autoclave was reacted at 80° C. for 2 hours. DM-
After adding and mixing 10g of 60 and 10g of KOH,
1390 g of EO was gradually charged. After 3 hours of reaction, 12
The temperature was raised to 0°C, and 980 g of PO was gradually charged. After 4 hours of reaction, unreacted PO and EO in the system were removed under reduced pressure. 90
The temperature was lowered to 0.degree. C., and after neutralization using 90 g of 7% HCl, dehydration was performed under reduced pressure. As a result of removing the generated salt by filtration, the hydroxyl value was 200 mgKOH/g, and the viscosity was 200 cp/2.
5630 g of polyol at 5° C. was obtained.

Example 5 500 g of TEOA, 500 g of polyoxyalkylene polyol AE-300 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) and 440 g of γ-BL were placed in a 5 liter autoclave equipped with a thermometer and a stirrer, and the autoclave was replaced with nitrogen at 120°C.
The temperature rose to . After adding and mixing 4.3 g of DM-60, 890 g of PO was gradually charged. After 3 hours of reaction, unreacted PO in the system was removed under reduced pressure. Next, 385 g of EO was gradually charged. After 2 hours of reaction, unreacted EO in the system was removed under reduced pressure. Hydroxyl value 350mgKOH/g, viscosity 6
2710 g of polyol having a temperature of 00 cp/25° C. was obtained.

Example 6 1000 g of TEOA and 290 g of γ-BL were charged into a 5 liter autoclave equipped with a thermometer and a stirrer, and after purging with nitrogen, the temperature was raised to 90° C. and reacted for 2 hours. After adding and mixing 4.0 g of DM-60 and 4.0 g of KOH, 2330 g of PO2 and then 885 g of EO were gradually charged. After 7 hours of reaction, unreacted PO and EO in the system were removed under reduced pressure. After neutralization using 36 g of 7% HCl, dehydration was performed under reduced pressure. As a result of removing the generated salt by filtration, the hydroxyl value was 250 mgKOH/g, and the viscosity was 200 cp/2.
4480 g of polyol at 5° C. was obtained.

Comparative Example 1 700 g of IPOA and 300 g of G were charged into a 5 liter autoclave, the autoclave was purged with nitrogen, and the temperature was raised to 110°C. After adding and mixing 3.0g of DM-60, PO, EO
1140 g of each was gradually charged in this order. After 7 hours of reaction, unreacted PO and EO in the system were removed under reduced pressure. 3268 g of polyol having a hydroxyl value of 450 mgKOH/g and a viscosity of 1200 cp/25°C was obtained.

Comparative Example 2 IPOA 450g, G550g and β-PL86
0 g was placed in a 5 liter autoclave equipped with a thermometer and a stirrer, and after purging with nitrogen, the temperature was raised to 100°C. D
After 5.5 g of M-60 was added and mixed, 1200 g of each of PO and EO were gradually charged in that order. After 7 hours of reaction,
Unreacted PO and EO in the system were removed under reduced pressure. Hydroxyl value 3
4245 g of polyol having a viscosity of 56 mg KOH/g and a viscosity of 1000 cp/25° C. was obtained.

The results of Examples 1 to 6 and Comparative Examples 1 and 2 above and the hydroxyl group 1 of the active hydrogen compound formed by alkanolamines alone or by adding and mixing polyhydric alcohols or polyoxyalkylene polyols with alkanolamines The number of moles of lactone and alkylene oxide added per mole is shown in [Table 1].

[0050]

[Table 1] For 100 g of polyol obtained in the above example, [
According to the formulation shown in Table 2], silicone foam stabilizer SZ-1
642 (Nippon Unicar product) 1.5g, R-11 (Freon 11B; manufactured by Mitsui Fluorochemical Co., Ltd.) 26g, T
CPP (tris(2-chloropropyl)phosphate)
Mix 10g and 3.0g of water to make a resin stock solution,
The temperature was adjusted to ℃. To this was added the amount of polymethylene polyphenyl polyisocyanate (MDI-CR200 NCO% 31.3 manufactured by Mitsui Toatsu Chemical Co., Ltd.) whose temperature was adjusted to 15°C as shown in the table, and the mixture was stirred using a stirrer with a rotation speed of 5000 rpm. Rapid mixing was performed for 5 seconds. Immediately pour this mixture vertically into 2
The mixture was poured into a box measuring 5 cm x width 25 cm x height 10 cm, allowed to foam freely, and the cream time and gel time after foaming started were measured. In addition, samples were cut out from polyurethane foam after being left at room temperature for 24 hours, and JIS-A-
Compressive strength (longitudinal direction) according to the method of J.
Low temperature dimensional stability (-
The dimensional change in the thickness direction after being left at 20° C. for 24 hours was measured. The above results are shown in [Table 2].

[0051]

[Table 2]

[0052]

[Effect of the invention] The polyol of the present invention has a low viscosity and
The reactivity with the organic polyisocyanate is extremely fast, and by using this, a polyurethane foam with excellent low-temperature dimensional stability etc. was obtained.

That is, it can be seen that the polyurethane foam obtained by spray foaming or board molding using the polyol of the present invention is extremely useful industrially as a heat insulating structural material or building material.

Claims (3)

[Claims] 1. A polyol for rigid polyurethane, which is obtained by adding 0.01 to 2.0 moles of lactone and 0.5 to 3.0 moles of alkylene oxide per mole of hydroxyl group of alkanolamines. 2. 0.01 to 2.0 moles of lactone and 0.01 to 2.0 moles of lactone per mole of hydroxyl group of an active hydrogen compound obtained by adding one or more components selected from polyhydric alcohols and polyoxyalkylene polyols to alkanolamines. A polyol for rigid polyurethane containing 0.5 to 3.0 moles of alkylene oxide. 3. In a rigid polyurethane foam obtained by mixing and foaming a resin stock solution prepared by adding a blowing agent, a catalyst, a foam stabilizer, and other auxiliary agents to a polyol and an organic polyisocyanate, the polyol according to claim 1 or A rigid polyurethane foam characterized by using the polyol described in 2.