JP2003183224A - Method of producing chlorendic acid alkylene oxide adduct and flame-retardant polyol for urethane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing an alkylene oxide adduct to chlorendic acid that has excellent economy and gives urethane foam having excellent flame retardancy, dimensional stability and compressive strength and shows good handleability and color tone. <P>SOLUTION: The polyaddition reaction of an alkylene oxide to chlorendic acid is carried out in the presence of a trihydric alcohol alkylene oxide adduct and a dihydric alcohol alkylene oxide adduct by using a tertiary amine as a catalyst whereby the chlorendic acid alkylene oxide adduct is obtained. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an alkylene oxide adduct of chlorendic acid, which is preferably used as a raw material for a flame-retardant polyurethane resin, and a flame-retardant polyol for urethane.

[0002]

2. Description of the Related Art Conventionally, flame retardancy has been mentioned as an important technical problem in polyurethane resins, particularly polyurethane resins (urethane foam) used as heat insulating materials for building materials. Until now, imparting flame retardancy to urethane has been carried out by adding a non-reactive flame retardant such as tris (β-chloropropyl) phosphate, but this non-reactive flame retardant is incorporated into the urethane skeleton. Because it does not
There are problems that the flame retardant migrates to the surface of the product and causes poor adhesion to the surface material, and that the physical properties of urethane (such as dimensional stability) deteriorate.

Therefore, the present applicants have conducted extensive studies in order to solve the above-mentioned problems, and have added a alkylene oxide in the coexistence of a polyhydric alcohol and chlorendic acid, and a reaction in which a flame-retardant component is incorporated in a urethane skeleton. It has been found that the use of the flame-retardant polyol as a raw material does not cause the above-mentioned problems such as poor adhesion and deterioration of urethane physical properties (JP-A-11-228803).

[0004]

However, the above-mentioned reactive flame-retardant polyol is superior to conventional flame-retardant agents in terms of the adhesiveness of the urethane obtained from the raw material with the face material and the urethane physical properties. Although it has improved and practically no problems, it is not sufficiently satisfactory, so it exhibits more excellent properties in terms of flame retardancy, urethane physical properties, and product handling properties. At present, there is a demand for a flame-retardant polyol that can be used.

The present invention has been made in view of the above circumstances, and provides an adduct having a good handling property and a good color tone, which gives a urethane foam excellent in flame retardancy, dimensional stability and compression strength. It is an object of the present invention to provide a method for producing an alkylene oxide adduct of chlorendic acid, which is excellent in economical efficiency, and a flame-retardant polyol for urethane.

[0006]

Means for Solving the Problems and Embodiments of the Invention
The present inventors, as a result of intensive studies to achieve the above object, by adding alkylene oxide to chlorendic acid using a mixture of alkylene oxide adducts of a predetermined alcohol as a solvent, flame retardant performance, It was found that an alkylene oxide adduct of chlorendic acid with good handling property and color tone, which gives a urethane foam excellent in dimensional stability and compressive strength, can be obtained, and in this case, by using a predetermined catalyst, after the reaction, The present invention has been completed based on the finding that the purification step is unnecessary, cost reduction can be achieved, and the adduct can be produced economically advantageously.

That is, the present invention provides the following: 3) under the coexistence of an alkylene oxide adduct of a monohydric alcohol and an alkylene oxide adduct of a dihydric alcohol.
A method for producing an alkylene oxide adduct of chlorendic acid, which comprises adding an alkylene oxide to chlorendic acid using a primary amine as a catalyst, and a chlorendic acid obtained by the method for producing an alkylene oxide adduct of chlorendic acid according to 2.1. A flame-retardant polyol for urethanes, which comprises the alkylene oxide adduct of

The present invention will be described in more detail below. The alkylene oxide adduct of trihydric alcohol in the present invention is a compound obtained by adding an alkylene oxide to a compound containing three hydroxyl groups. Here, as the compound containing three hydroxyl groups, for example, glycerin,
Trimethylolpropane, trimethylolethane, 1,
2,3-butanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,3-
Examples thereof include trialkanolamines such as cyclohexanetriol and triethanolamine, and triols containing a halogen atom.

Examples of the added alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide. A compound to which one kind or a mixture of two or more kinds is added can also be used. Among these, it is particularly preferable to use ethylene oxide, 1,2-propylene oxide and a mixture thereof. The number of moles of these alkylene oxide adducts added is preferably 1 to 10 moles, and more preferably 1 to 5 moles, per mole of the trihydric alcohol. The amount used is preferably 0.1 to 10 mol, and more preferably 0.2 to 5 mol, based on 1 mol of chlorendic acid.

The alkylene oxide adduct of the dihydric alcohol is a compound obtained by adding an alkylene oxide to a compound containing two hydroxyl groups. Here, as the compound containing two hydroxyl groups, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol, polypropylene glycol,
1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
Neopentyl glycol, 1,6-hexanediol,
Examples thereof include monoalkyl dialkanol amines, cyclohexane dimethanol, and diols containing halogen atoms.

Examples of the added alkylene oxide include ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide. A compound to which one kind or a mixture of two or more kinds is added can also be used. Among these, it is particularly preferable to use ethylene oxide, 1,2-propylene oxide and a mixture thereof. The number of moles of these alkylene oxide adducts added is preferably 1 to 10 moles, more preferably 1 to 5 moles, per mole of the dihydric alcohol. The amount used is preferably 0.1 to 10 mol, and more preferably 0.2 to 5 mol, based on 1 mol of chlorendic acid.

The tertiary amine used as a catalyst in the present invention includes trimethylamine, triethylamine, tripropylamine, tributylamine, dimethyldecylamine, dimethyldodecylamine, dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine, dimethyldiamine. Trialkylamines such as oleylamine and methyldidecylamine, trialkanolamines such as triethanolamine and tripropanolamine, dialkylmonoalkanolamines such as diethylaminoethanol, 1-methylpyrrolidine, N-
Examples thereof include cyclic amines such as methylmorpholine and polyamines such as triethylenediamine and tetramethylethylenediamine. Among these, it is preferable to use trialkylamines such as dimethyldodecylamine and triethylamine.

The amount of the catalyst added is not particularly limited and can be appropriately set according to the raw materials used, etc., but 0.002 to 5% by weight relative to the reaction product,
In particular, it is preferably used in the range of 0.01 to 1% by weight. Here, when the catalyst amount is less than 0.002% by weight,
There is a risk that the reaction will proceed insufficiently. On the other hand, if it exceeds 5% by weight, the reaction will proceed too quickly and temperature control may become difficult.

The method for producing an alkylene oxide adduct of chlorendic acid of the present invention can be carried out, for example, under the following conditions. First, 0.1 to 10 mol of an alkylene oxide adduct of a trihydric alcohol and 0.1 to 10 mol of an alkylene oxide adduct of a dihydric alcohol are charged into a reaction vessel, and the temperature is 40 to 100 ° C, preferably 60 to 80.
Raise the temperature to ℃. To this, 1 mol of chlorendic acid and a tertiary amine as a catalyst are added in an amount of 0.002 to 5% by weight based on the reaction product. After substituting the inside of the reaction system with an inert gas such as nitrogen, the temperature is raised to 60 to 150 ° C, preferably 80 to 130 ° C, and 2 to 10 mol of alkylene oxide is adjusted to 0.
It is added over 2 to 6 hours and aged for 0.2 to 3 hours, preferably 0.4 to 1.5 hours.

Thereafter, excess alkylene oxide is removed under reduced pressure and the mixture is cooled to 30 to 70 ° C. to obtain the desired alkylene oxide adduct of chlorendic acid. After the reaction, it is preferable to measure the acid value of the product and add 1.0 to 1.5 equivalents of amine to the measured acid value for neutralization. In this case, the amine used for neutralization is not particularly limited and may be any of primary to tertiary amines.

According to such a production method, since the alkylene oxide adduct of trihydric alcohol and the alkylene oxide adduct of dihydric alcohol are used as the solvent, the handling property of the obtained alkylene oxide adduct of chlorendic acid is improved. It is possible to sufficiently impart flame retardancy to the urethane foam obtained by using the adduct as a raw material without causing deterioration, and the urethane physical properties such as dimensional stability and compressive strength of the foam become good. In addition, since a tertiary amine is used as a catalyst, a purification step such as a catalyst removal step is not required for pretreatment for urethanization, urethane production cost can be reduced, and an economical method is also provided. I can say.

The flame-retardant polyol for urethane according to the present invention comprises a chlorendic acid alkylene oxide adduct obtained by the above-mentioned method for producing a chlorendic acid alkylene oxide adduct. Here, this flame-retardant polyol, as an optional component other than the chlorendic acid alkylene oxide adduct, other polyols, flame retardants, antioxidants, colorants, plasticizers, fillers, lubricants and other auxiliary agents. The total amount may be 0 to 50% by weight.

As a method for producing a polyurethane foam from the above-mentioned flame-retardant polyol for urethane, all conventionally used molding methods can be used.
For example, a method in which a mixture of a flame-retardant polyol for urethane, a catalyst, a foam stabilizer and a foaming agent and isocyanate are stirred and mixed at a high speed rotation of 3,000 to 5,000 rpm to foam in a specific container or the like. Etc.
At this time, the catalyst, foam stabilizer, foaming agent, and isocyanate used are not particularly limited, and those conventionally used can be used. In this case,
It is also possible to add auxiliary agents such as the above-mentioned other polyols and flame retardants.

[0019]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 230 g (1 mol) of EO 3 mol adduct of glycerin and EO of dipropylene glycol
232 g (1 mol) of the 2 mol adduct was charged into a 4 L autoclave, and the temperature was raised to 70 ° C. To this was added 389 g (1 mol) of chlorendic acid, and 1.07 g of dimethyldodecylamine (0.1% by weight based on the reaction product) was added as a catalyst. After purging the inside of the autoclave with nitrogen, the temperature was raised to 100 ° C., and 215 g (3.7 mol) of propylene oxide was fed at this temperature over 1 hour.

The resulting mixture was aged for 45 minutes and then sampled to measure the acid value, which was 8.8 KO.
It was Hmg / g. Then, after removing excess propylene oxide under reduced pressure, the mixture was cooled to 60 ° C., and at this point, sampling was performed again to measure the acid value.
It was KOH mg / g. Therefore, the acid value is 1.2
32.5 g of dimethyldodecylamine corresponding to an equivalent amount was added as a neutralizing agent, and the mixture was stirred at 60 ° C. for 30 minutes, and then the propylene oxide adduct of chlorendic acid, which was the target, was added to 1.0
Obtained 50 g. The properties of the obtained adduct are shown in Table 1. In addition, in Table 1, moisture is a trace moisture measuring device AQ-7.
The viscosity is a value measured by a B-type viscometer (manufactured by Tokimec Co., Ltd.) by Hiranuma Sangyo Co., Ltd.

[0022]

[Table 1]

[Example 2] Propylene oxide adduct of chlorendic acid obtained in Example 1 (flame-retardant polyol)
0.5 parts by weight of tin octylate and triethylamine as catalysts and 100 parts by weight of a silicone foam stabilizer as a foam stabilizer (L-5420, Nippon Unicar Co., Ltd.)
1.2 parts by weight, 1.0 parts by weight of water as a foaming agent and 5.0 parts by weight of CFC substitute (HCFC-141b), diphenylmethane diisocyanate as an isocyanate component (crude MDI, Millionate MR100,
112 parts by weight of Nippon Polyurethane Industry Co., Ltd. was blended. Here, the NCO index was 110.

The above components were subjected to high-speed stirring and mixing (3,000 rpm, mixing time: 10 seconds) with a homomixer at 20 ° C., and a foaming test was conducted. As a result, the obtained foam was a light yellow hard urethane foam. The flame retardancy, dimensional stability, and compression strength of this rigid urethane foam were measured and evaluated, and the results are shown in Table 2.

[0025]

[Table 2]

Here, flame retardancy, dimensional stability and compressive strength were measured by the following methods. [1] The degree of combustion when the rigid urethane foam was ignited was visually observed with a flame retardant lighter. (◯: Good flame retardancy) [2] Dimensional stability The dimensional change rate of the foam cut to 10 cm × 10 cm × 4 cm after 70 hours at 70 ° C. was measured. (○:
Dimensional change rate is less than 3%) [3] Compressive strength A foam cut to 5 cm square was measured by a compression tester (manufactured by Orientec Co., Ltd.) (○: 1)
Compressive strength at 0% deformation is 0.15 MPa or more).

As shown in Table 2, the rigid urethane foam obtained in Example 2 was prepared by using glycerol adduct and dipropylene glycol EO adduct as solvents, and using dimethyldodecylamine as a catalyst, chlorendic acid. Since it is a rigid urethane foam produced from a polyol obtained by adding propylene oxide to, as a raw material, it is clear that it has good flame retardancy, dimensional stability, and compressive strength.

[0028]

As described above, according to the present invention, an alkylene oxide adduct of chlorendic acid (urethane, which is excellent in flame retardancy, physical properties of urethane, handling property and economical efficiency and has a good color tone). Flame-retardant polyol) can be obtained. This adduct can be used as a flame retardant for polyurethane resin, and can be particularly preferably used as a raw material for a rigid polyurethane foam used for a heat insulating material for building materials including spray foaming in the field, a heat insulating panel, and other applications.

Continued front page    (72) Inventor Mitsuhiko Takei             1-3-7 Honjo, Sumida-ku, Tokyo Rio             Within the corporation (72) Inventor Masato Tamura             1-3-7 Honjo, Sumida-ku, Tokyo Rio             Within the corporation F-term (reference) 4H006 AA02 AA03 AB46 AC48 BA69                       BJ30 KA19 KC20 KF22                 4H039 CA66 CF90                 4J005 AA11 BB02

Claims (2)

[Claims] 1. In the coexistence of an alkylene oxide adduct of a trihydric alcohol and an alkylene oxide adduct of a dihydric alcohol, an alkylene oxide is added to chlorendic acid using a tertiary amine as a catalyst. Process for producing alkylene oxide adduct. 2. A flame-retardant polyol for urethanes, comprising the alkylene oxide adduct of chlorendic acid obtained by the production method according to claim 1.