JPH0370734A - Polyoxyalkylenepolyol - Google Patents

Abstract

PURPOSE:To provide the subject polyol having excellent workability in a polyurethane-foaming process, giving foams having excellent physical properties and having excellent miscibility and dispersibility with a foaming agent by reacting an aliphatic amine with a lactone and an alkylene oxide in the presence of an amine catalyst or an alkali hydroxide catalyst. CONSTITUTION:An aliphatic amine having 2-6 moles of amino groups in the molecule is subjected to an addition reaction with a lactone and an alkylene oxide in amounts of 0.166-1.0 mole and 1.0-3.0 moles, respectively, per amino group of the aliphatic amine to provide the objective polyol. The aliphatic amine is preferably a compound of the formula (R is 1-4C alkyl: (n) is 1-4) and the reaction is preferably carried out in the presence of an amine catalyst of formula: NR1R1R2 or R1R2N(CH2)nNR1R2 [R1 is H, 1-6C alkyl, CH2CH2OH or CH2CH2CH(CH3)OH; R2 is 1-6C alkyl, CH2CH2OH or CH2CH(CH3)OH; (n) is 1-6] and/or an alkali hydroxide catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyoxyalkylene polyol.

More specifically, the present invention relates to a polyoxyalkylene polyol that has excellent workability and foam properties during urethane foaming.

The polyoxyalkylene polyols obtained by the present invention are hydrochlorofluorocarbons (hereinafter abbreviated as HCFC), HCFC-123 and HCFC-141.
b. Not only can it be used as a raw material for polyurethane resins that are resistant to dissolution, but it also has an appropriate viscosity as a polyoxyalkylene polyol, and has HCFC-1
It has excellent mixing and dispersibility in 23 and HCFC-14lb, and has workability equivalent to conventional ones during urethane foaming.

[Conventional technology]

Traditionally, when producing urethane foam, fluorocarbons, especially chlorofluorocarbons (hereinafter referred to as CFCs) have been used as a foaming means.
CFC-11 and CFC-12 (abbreviated as ) are used, but these have been cited as environmentally destructive substances that decompose the ozone layer and increase the greenhouse effect, and recently there has been a trend to regulate their production and use. It's here. At the same time, C
HCFC-1 as a replacement for FC-11 and CFC-12
23 and HCFC-14l b have been attracting attention, but these CFCs have resin-dissolving power that is higher than that of CFC-11 and CFC-12.
The physical properties of the urethane foam, such as a decrease in closed cell ratio and foam strength, tended to decrease significantly.

In particular, the heat insulating effect, which is a characteristic of rigid urethane foam, was significantly reduced because the fluorocarbon dissolved the closed cells in the foam during foaming.

Therefore, the need for a new polyurethane resin emerged. Among polyoxyalkylene polyols, which are the raw materials for conventional urethane resins, the viscosity decreases as the amount of alkylene oxide added decreases, making it easy to manufacture polyurethane resins, but if too much alkylene oxide is added, the polyurethane resins become HCFC. -123 and HCFC-1
Since it dissolves in 4 liters of water, it tends to become virtually unusable. On the other hand, if the amount of alkylene oxide added is small, in the case of an amide skeleton-containing polyol, it becomes very difficult to handle because it is solid or viscous.

As mentioned above, when trying to maintain the dissolution resistance of polyurethane resin to HCFC-123 and HCFC-14lb, the workability during urethane foaming becomes extremely poor. No polyoxyalkylene polyol has been found that has the following properties and has excellent mixing and dispersibility in HCFC-123 and HCFC-14lb.

[Problem to be solved by the invention]

The purpose of the present invention is to:
The object of the present invention is to provide a novel polyoxyalkylene polyol whose workability and foam properties during urethane foaming are equivalent to those of conventional polyols even when HCFC-123 or HCFC-141b is used as a blowing agent.

[Means to solve the problem]

In order to achieve the above object, the present inventors conducted extensive studies and arrived at the present invention.

That is, the present invention provides 0.166 to 1 lactone per amino group of an aliphatic amine having 2 to 6 moles of amino groups in one molecule.
．． 0 mol and alkylene oxide from 1.00 to 3.0
It is a polyoxyalkylene polyol obtained by molar addition.

The aliphatic amine used in the present invention contains 2 to 6 amines per molecule.
It has a mole of amino groups, and this amino group reacts with lactone to form an amide bond, and further reacts with alkylene oxide to form a polyoxyalkylene polyol having an amide skeleton.

In the present invention, the aliphatic amine used when synthesizing the polyoxyalkylene polyol having an amide skeleton in the molecule is preferably a compound represented by the following general formula (1).

Hz N-R(NHR)nNHx... (1) (In the above formula, R represents a C1-C4 alkyl group, and n is 1-4.) For example, ethylenediamine (EDA), diethylenetriamine (DETA), triamine Ethylene tetra millet (TE
TA), tetraethylene pentamine (TEPA), pentaethylene hexagon (PEHA), etc., and these can be used alone or in combination of two or more.

Lactones used in the present invention include β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-
Examples include caprolactone.

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

The polyoxyalkylene polyol of the present invention contains 0.166 to 1.0 moles of lactone and 1.0 to 3.0 moles of alkylene oxide per amino group of an aliphatic amine having 2 to 6 moles of amino groups in one molecule. It was added.

If the number of amino groups per molecule of the aliphatic amine is less than 2 moles, the strength of the polyurethane foam tends to be weak. On the other hand, if the number of amino groups per molecule exceeds 6 moles, the number of amide bonds per molecule increases, which increases the viscosity of the polyoxyalkylene polyol and impairs workability during foaming.

HCFC-123 and HCFC-1 when less than 0.166 moles of lactone are reacted per amino group.
The mixing and dispersibility in 41b is equivalent to that of conventional polyoxyalkylene polyols, but the foam properties of the urethane foam obtained by reacting with polyisocyanate tend to deteriorate. The viscosity of the alkylene polyol is high, the mixing and dispersibility with HCFC is poor, and the urethane foam obtained by reacting with the polyisocyanate becomes brittle.

If less than 1.0 alkylene oxide is reacted per amino group, reactivity tends to deteriorate when producing a urethane foam because the compatibility with polyisocyanate is poor and layer separation occurs. Also, 3.0
If it exceeds , the viscosity will be low and the mixing and dispersibility in HCFC-123 and HCFC-141b will be good, but
The physical properties of the urethane foam obtained by reacting with polyisocyanate tend to deteriorate.

In the present invention, the catalyst that can be used as necessary when adding a lactone and an alkylene oxide to the amino group of an aliphatic amine is an amine compound represented by the following general formula (2) or (3) as an amine type catalyst. .

NR+ R5Rx... (2)R
r Rz N CCHx)n NR+ Rt...
(3) (In the above formula, R1 is an alkyl group up to tt, C, -Ch and CHtCHzOH, CH and CH(CHs)OH
, R1 is a C3 to C- alkyl group and C
)1ffiCH! OH,C)12C)l(C11riOR
, and n is an integer of 1 to 6. ) Examples of amine compounds include dibutylamine, ethylenediamine, tetramethylenecyamine, monoethanolamine, jetanolamine, triethanolamine,
isopropanolamine, triethylamine, tri-n
-propylamine, jetanolamine, n-propylamine, n-amylamine, N,N-dimethylethanol-
Examples include luane, isobutylamine, isoamylamine, methyldiethylamine, and the like.

Further, examples of the alkali hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and the like. Each of the above catalysts can be used alone or in combination of two or more.

In the method for producing the polyoxyalkylene polyol of the present invention, an aliphatic amine and a lactone are charged in an autoclave and reacted, and then a catalyst is charged if necessary, and an alkylene oxide is gradually added and reacted. The reaction temperature between the aliphatic amine and the lactone is preferably about 60 to 100°C. If it is less than 60°C, the reaction will be difficult to proceed, and if it exceeds 100°C, side reactions will easily occur. After the reaction between the aliphatic amine and the lactone, the temperature at which the alkylene oxide is added is preferably 90 to 130°C. 90°C
If the temperature is below 130°C, the reaction will be difficult to proceed, and if it exceeds 130°C, side reactions will tend to occur.

〔Example〕

The present invention will be explained below with reference to Examples.

The method for measuring hydroxyl value (OH value) and viscosity is JIS
According to K1557.

Example 1 40 g of HD Al and 200 g of T-butyrolactone were charged into a No. 21 autoclave, and the autoclave was purged with nitrogen and then heated to 80'C. Triethylamine 1.8 after reacting for 2 hours
After the mixture was further heated to 120° C., 270 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed. O
H number 642mgKOH/g, viscosity 34000cp/25
601 g of polyoxyalkylene polyol were obtained.

Example 2 240 g of DET A and 20 g of T-butyrolactone
0g was placed in a 22 autoclave and heated to 80° after replacing with nitrogen.
The temperature was raised to C. After reacting for 2 hours, 2.3 g of triethylamine was added and mixed, and after the temperature was raised to 120''C, 405 g of propylene oxide was gradually charged.

After reacting for 3 hours, propylene oxide in the system was removed. OH number 620s+gKOH/g, viscosity 35000
cp/25°C polyoxyalkylene polyol 83
2g was obtained.

Example 3 240 g of DET A and 20 g of T-butyrolactone
0g was placed in a 22 autoclave and heated to 80°C after replacing with nitrogen.
The temperature rose to . After reacting for 2 hours, triethylamine 3
．． 8g of propylene oxide was added and mixed, the temperature was further raised to 120°C, and 810g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed. OH
Value 552mgKOH/g, viscosity 21000cp/25°
1220 g of polyoxyalkylene polyol C was obtained.

Example 4 240 g of DET A and 20 g of T-butyrolactone
0g was placed in autoclave No. 21 and heated to 80° after nitrogen purging.
The temperature was raised to C. After reacting for 2 hours, 2.5 g of triethylamine and 2.5 g of potassium hydroxide were added and mixed,
Furthermore, after raising the temperature to 120°C, propylene oxide 1
215 g was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and filtered under reduced pressure. 1,630 g of polyoxyalkylene polyol having an OH value of 30 hgKOH/g and a viscosity of 15,000 cp/25°C was obtained.

Example 5 300 g of T E T A and 20 g of γ-wotyrolactone
0g was placed in a 22 autoclave and heated to 80° after replacing with nitrogen.
The temperature was raised to C. After reacting for 2 hours, 3.1 g of triethylamine was added and mixed, the temperature was further raised to 120°C, and then 540 g of propylene oxide was gradually charged.

After reacting for 3 hours, propylene oxide in the system was removed.・OH value 612i+g 0) 1/g, viscosity 3700
0cρ/25℃ polyoxyalkylene polyol 10
00g was obtained.

Example 6 300 g of T E T A and 2 o of γ-butyrolactone
Charge Og into a 22 autoclave and change nitrogen i1 to 0.
The temperature was raised to °C. After reacting for 2 hours, triethyl 75
73.2 g and 3.2 g of potassium hydroxide were added and mixed, and after the temperature was raised to 120° C., 1620 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and filtered under reduced pressure. OH value 205s+gKOH/
2101 g of polyoxyalkylene polyol having a viscosity of 9500 cp/25° C. was obtained.

Example 7 340 g of P E HA and 200 g of γ-butyrolactone
g was charged into a No. 21 autoclave, and the temperature was raised to 80° C. after purging with nitrogen. After reacting for 2 hours, 4.7 g of dimethylethanolamine was added and mixed, and after the temperature was further raised to 120°C, 810 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed. OH number 563a+gKO1l/g, viscosity 370
1520 g of polyoxyalkylene polyol of 00 cp/25°C was obtained.

Example 8 340 g of P E HA and 200 g of T-butyrolactone
2j for g! After the autoclave was replaced with nitrogen, the temperature was 80'.
The temperature was raised to C. After reacting for 2 hours, 3.5 g of triethylamine and 3.5 g of potassium hydroxide were added and mixed,
After further increasing the temperature to 120°C, propylene oxide 1
620 g was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and filtered under reduced pressure. OH value 355mgKOIl/g
, 2315 g of polyoxyalkylene polyol having a viscosity of 11000 cp/25° C. was obtained.

Example 9 120 g of DETA and 300 g of γ-butyrolactone were charged into a 2"l autoclave, and the temperature was raised to 80°C after purging with nitrogen. After reacting for 2 hours, triethyl 7173.
After the temperature was raised to 120°C, 607 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed. OH
Value 185mgKOH/g, viscosity 36500cp/25℃
Obtained from 1005g of polyoxyalkylene polyol *Example 10 240g of DET A and 20g of T-butyrolactone
0g to 2j! The mixture was charged into an autoclave, and after reducing the pressure, the temperature was raised to 80°C. After reacting for 2 hours, the pressure inside the system was reduced.

Add and mix 3.2 g of triethylamine, and further add 12 g of triethylamine.
After raising the temperature to 0° C., 614 g of ethylene oxide was gradually charged. After reacting for 3 hours, ethylene oxide in the system was removed. OH number 487mgKOH/g, viscosity 21
1021 g of polyoxyalkylene polyol having a temperature of 000cρ/25°C was obtained.

Example 11 240 g of DET A and 26 ε-caprolactone
6 g was charged into a No. 21 autoclave, the pressure was reduced, and the temperature was raised to 80°C. After reacting for 2 hours, triethylamine 3°9
g was added and mixed, the temperature was further raised to 120'C, and then 809 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed. O
H number 39h+gKOH/g, viscosity 28000cp/25
1287 g of polyoxyalkylene polyol 'C was obtained.

From a comparative example: 240 g of ET A and 20 g of γ-butyrolactone
0g was placed in autoclave No. 21 and heated to 80° after nitrogen purging.
The temperature was raised to C. After reacting for 2 hours, 1.7 g of triethylamine was added and mixed, the temperature was further raised to 120°C, and then 135 g of propylene oxide was gradually charged.

After reacting for 3 hours, propylene oxide in the system was removed. OT (value 897 mg K OII / g,
554 g of polyoxyalkylene polyol having a viscosity of 157,000 cp/25° C. was obtained.

Comparative Example 2 240 g of DET A and 60 g of T-butyrolactone
0g was placed in a 21 autoclave and after nitrogen purging, 80'
The temperature was raised to C. After reacting for 2 hours, 3.7 g of triethylamine was added and mixed, and after the temperature was further raised to 120"C, 405 g of propylene oxide was gradually charged.

After reacting for 3 hours, propylene oxide in the system was removed. OH number 325mgKOt(/g, viscosity 28900
0cp/25°C polyoxyalkylene polyol 1
230g was obtained.

Comparative Example 3 240 g of DETA and 60 g of T-butyrolactone were
The autoclave No. 1 was charged and the temperature was raised to 80° C. after purging with nitrogen. After reacting for 2 hours, 2.1 g of triethylamine was added and mixed, the temperature was further raised to 120° C., and then 405 g of propylene oxide was gradually charged.

After reacting for 3 hours, propylene oxide in the system was removed. OH number 721mgKOH/g, viscosity 75000c
692 g of polyoxyalkylene polyol at p/25°C
I got it.

Comparative Example 4 240 g of DETA and 200 g of γ-butyrolactone were charged into an autoclave No. 21, and the temperature was raised to 80° C. after purging with nitrogen. After 2 hours of reaction, triethylamine 3.1
g and 3.1 g of potassium hydroxide were added and mixed, the temperature was further raised to 120°C, and propylene oxide 1619 g was added and mixed.
g was gradually charged. After reacting for 3 hours, the propylene oxide in the system was removed, then neutralized with acetic acid, and further filtered under reduced pressure. OH value 236 melon gKOH/g, viscosity 250
0cp/25℃ polyoxyalkylene polyol 20
13g was obtained.

Polyurethane foam production example 100g of various polyoxyalkylene polyols obtained in the above examples, 1.0g of water, silicone foam stabilizer L-54
20 (manufactured by Nippon Unicar) 1.5 g, amine catalyst kaolizer No. 1 (manufactured by Kao ■) 3° Og and No. 2
After preparing in advance a resin blend consisting of 31.3 g of each of the fluorocarbons shown in the table, polyisocyanate (MDI-CR200H12,9 manufactured by Mitsui Toatsu Chemical Co., Ltd.) was prepared in advance.
A polyurethane foam was produced by mixing and reacting with g.

Table 2 shows the measurement results of the mixing dispersibility (workability) of Freon and polyoxyalkylene polyol and the closed cell ratio of the produced urethane foam when preparing the resin premix.

〔Effect of the invention〕

Polyoxyalkylene polyol, which is made by reacting lactone and alkylene oxide with aliphatic amine, which is generally used in rigid polyurethane foam, uses HCFC-123 and HCF as blowing agents during urethane foaming.
It has been shown that a system using C-141b can maintain the same form properties and workability as the CFC-11 system. Such polyoxyalkylene polyols are extremely useful in the urethane industry.

Claims (1)

[Claims] 1. Obtained by adding 0.166 to 1.0 moles of lactone and 1.0 to 3.00 moles of alkylene oxide per amino group of an aliphatic amine having 2 to 6 moles of amino groups per molecule. A polyoxyalkylene polyol. 2. The polyoxyalkylene polyol according to claim 1, wherein the aliphatic amine is represented by general formula (1). H_2N-R(NH-R)_nNH_2...(1) (In the above formula, R represents an alkyl group of C_1 to C_6, and n is 1 to
It is 4. 3. The polyoxyalkylene polyol according to claim 1, obtained by reaction using an amine catalyst and/or an alkali hydroxide catalyst represented by the general formula (2) or (3). NR_1R_1R_2...(2) R_1R_2N(CH_2)_nNR_1R_2...(
3) (In the above formula, R_1 is H, an alkyl group from C_1 to C_6, and CH_2CH_2OH, CH_2CH (C
H_3) OH, R_2 is an alkyl group from C_1 to C_6, and CH_2CH_2OH, CH_2CH
(CH_3) Indicates OH. Moreover, n is 1-6. )