JPH0597871A - Method for stabilizing organotin alkoxide and stable composition containing organotin alkoxide - Google Patents

Abstract

PURPOSE:To stabilize an organotin alkoxide stable to moisture without deteriorating catalyst activity for a long period by adding a specific triglyceride to the organotin alkoxide. CONSTITUTION:An organotin alkoxide expressed by formula I or II (R is 1-18C alkyl or benzyl; R<1> and R<2> are 1-12C alkyl or phenyl) such as dibutyltin distearyl oxide is stabilized by adding a triglyceride, expressed by formula III (R<1> is 3-36C alkyl or alkenyl) such as soybean oil to the organotin alkoxide. The composition ratio of the organotin alkoxide is preferably 1-70wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for stabilizing an organotin alkoxide compound which is effective as a catalyst, and a stable organotin alkoxide-containing composition.

[0002]

Organotin alkoxide compounds are useful as catalysts for silicone curing catalysts, urethane curing catalysts, esterification catalysts, transesterification catalysts and the like.

However, the organic tin alkoxide is an extremely unstable compound. For example, when it is exposed to the air in a solution state, a film is immediately formed on the surface and a solid precipitate is deposited within a few minutes. By the way, if an insoluble matter is deposited in terms of quality control, the product value will be impaired, and eventually the catalytic activity will be reduced in use.

Therefore, the organic tin alkoxide compound is
Despite having a remarkable catalytic activity, it is currently used only in a limited industrial field.

[0005]

As a result of intensive studies, the present inventors have found a method for stabilizing an organotin alkoxide compound by using a specific composition containing an organotin alkoxide, and have found the present invention. I arrived.

That is, the present invention relates to the general formula [7] or [8]

[Chemical 7]

[Chemical 8] (Wherein R represents an alkyl group having 1 to 18 carbon atoms or a benzyl group, and R ¹ or R ² represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, respectively). formula

[9]

[Chemical 9] (In the formula, R'represents an alkyl group or an alkenyl group having 3 to 36 carbon atoms.) A method for stabilizing an organic tin alkoxide, which comprises adding a triglyceride represented by the formula: It is a composition.

The organotin alkoxide used in the present invention is not particularly limited, and examples of the diorganotin alkoxide among the organotin alkoxides include, for example, dibutyltin distearyl oxide, dibutyltin dibenzyloxide, dibutyltin dioctyl oxide and dibutyltin di (2). -Ethylhexyl oxide), dibutyltin dibutoxide, dibutyltin dimethoxide, dioctyltin distearyl oxide, dioctyltin dibenzyloxide, dioctyltin dioctyloxide, dioctyltin di (2-ethylhexyloxide), dioctyltin dibutoxide, dioctyltin dimethoxide, diphenyltin dioctyloxide. Alternatively, these dimers, trimers and the like, and as monoorganotin alkoxide, for example, monobutyltin trioctyl oxide, monobutyltin tri (2- Ethylhexyl oxide) include mono octyl tin trioctyl oxide, and the like. These organic tin alkoxides are unstable compounds which are easily hydrolyzed and sensitively react to moisture in the air.

Examples of the triglyceride having a function of stabilizing the organic tin alkoxide include soybean oil, epoxidized soybean oil, coconut oil, linseed oil, castor oil, dehydrated castor oil, cottonseed oil, olive oil and rapeseed oil. And saturated or unsaturated fats and oils or processed fats such as sardine oil, cinnamon oil, peppermint oil, esterified oil, and maleated oil.

The composition ratio of the organic tin alkoxide in the stable composition of the organic tin alkoxide and the triglyceride of the present invention is preferably 1 to 70% by weight, and particularly 40% by weight or less exhibits a remarkable stabilizing effect. To do.

The composition ratio of the organic tin alkoxide is 70.
If it exceeds 5% by weight, precipitation or the like is likely to occur due to the relationship with solubility, but if precipitation or solidification occurs due to the properties of fats and oils, dilute with a solvent such as xylene to obtain a stable composition that is sufficiently practical. Obtainable.

[0012]

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

Example 1 Dibutyltin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer under a nitrogen stream.
2.5 g (0.05 mol), 2-ethylhexanol 13.0 g (0.1 mol) and xylene 150 g were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Then, xylene was distilled off under reduced pressure to obtain 23.3 g of dibutyltin di (2-ethylhexyl oxide) (yield 95%). Next, 100 g of soybean oil was added to 23.3 g of the obtained dibutyltin di (2-ethylhexyl oxide), and after substituting with nitrogen, the mixture was stirred at 50 to 70 ° C. for 1 hour to obtain a pale yellow liquid (A).

Example 2 Dibutyltin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer in a nitrogen stream.
2.5 g (0.05 mol), 2-ethylhexanol 13.0 g (0.1 mol) and xylene 150 g were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Then, xylene was distilled off under reduced pressure to obtain 23.3 g of dibutyltin di (2-ethylhexyl oxide) (yield 95%). Next, 23.3 g of dibutyltin di (2-ethylhexyl oxide) obtained was added to 40 g of olive oil.
Was added and the atmosphere was replaced with nitrogen, followed by stirring at 50 to 70 ° C. for 1 hour to obtain a pale yellow liquid (B).

Example 3 Dibutyltin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer under a nitrogen stream.
2.5 g (0.05 mol), benzyl alcohol 1
0.8 g (0.1 mol) and 150 g of xylene were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Next, 100 g of dehydrated castor oil was added, the atmosphere was replaced with nitrogen, and the mixture was stirred at 50 to 70 ° C. for 1 hour, and then xylene was distilled off under reduced pressure to obtain a pale yellow liquid (C).

Example 4 Dibutyltin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer under a nitrogen stream.
2.5 g (0.05 mol), octanole 13.0
g (0.1 mol) and 150 g of xylene were charged, 1
The reaction was carried out at 40 ° C. for 3 hours, and the produced water was azeotropically dehydrated.
Then, xylene was distilled off under reduced pressure to obtain 23.4 g (yield 95%) of dibutyltin dioctyl oxide. Next, 30 g of linseed oil and 70 g of soybean oil were added to 23.4 g of the obtained dibutyltin dioctyl oxide, and after substituting with nitrogen, the mixture was stirred at 50 to 70 ° C. for 1 hour to obtain a pale yellow liquid (D).

Example 5 In a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, dibutyltin oxide 1 was added in a nitrogen stream.
2.5 g (0.05 mol), stearyl alcohol 2
7.1 g (0.1 mol) and 150 g of xylene were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Then, 200 g of olive oil was added, the atmosphere was replaced with nitrogen, and the mixture was stirred at 50 to 70 ° C. for 1 hour, and then xylene was distilled off under reduced pressure to obtain a pale yellow liquid (E).

Example 6 Dioctyltin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer in a nitrogen stream.
8.1 g (0.05 mol), 2-ethylhexanol 13.0 g (0.1 mol) and xylene 150 g were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Then add 120 g of coconut oil, replace with nitrogen and
After stirring at 0-70 ° C. for 1 hour, xylene was distilled off under reduced pressure to obtain a pale yellow liquid (F).

Example 7 Diphenyl tin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer in a nitrogen stream.
4.4 g (0.05 mol), 2-ethylhexanol 13.0 g (0.1 mol) and xylene 150 g were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Next, add 120 g of soybean oil and replace with nitrogen to obtain 5
After stirring at 0 to 70 ° C for 1 hour, xylene was distilled off under reduced pressure to obtain a pale yellow liquid (G).

Example 8 Monobutyltin oxide 1 was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer in a nitrogen stream.
0.4 g (0.05 mol), 2-ethylhexanol 19.5 g (0.15 mol) and xylene 150 g were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Then, xylene was distilled off under reduced pressure to give 26.8 g of monobutyltin tri (2-ethylhexyl oxide).
(Yield 94%) was obtained. Next, 26.8 g of monobutyltin tri (2-ethylhexyl oxide) thus obtained was added to
100 g of bubu oil was added, the atmosphere was replaced with nitrogen, and the mixture was stirred at 50 to 70 ° C. for 1 hour, and then xylene was distilled off under reduced pressure to obtain a pale yellow liquid (H).

Example 9 15 g of commercially available dibutyltin dimethoxide (0.05 mo)
135 g of olive oil was added to l), and after substituting with nitrogen, 40
It stirred at -50 degreeC for 1 hour, and obtained the pale yellow liquid (I).

Example 10 To 15 g (0.05 mol) of dibutyltin dimethoxide, 135 g of soybean oil was added, and the atmosphere was replaced with nitrogen.
After stirring for a time, a pale yellow liquid (J) was obtained.

Example 11 135 g of castor oil was added to 15 g (0.05 mol) of dibutyltin dimethoxide, and after substituting with nitrogen, the mixture was stirred at 40-50 ° C. for 1 hour to obtain a pale yellow liquid (K).

Comparative Example 1 A 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with dibutyltin oxide 1 in a nitrogen stream.
2.5 g (0.05 mol), 2-ethylhexanol 13.0 g (0.1 mol) and xylene 150 g were charged and reacted at 140 ° C. for 3 hours, and the produced water was azeotropically dehydrated. Then, xylene was distilled off under reduced pressure to obtain 23.3 g of dibutyltin di (2-ethylhexyl oxide) (yield 95%). Next, 23.3 g of dibutyltin di (2-ethylhexyl oxide) obtained was added with 100 g of xylene.
Was added and the atmosphere was replaced with nitrogen, followed by stirring at 50 to 70 ° C. for 1 hour to obtain a colorless liquid (L).

Comparative Example 2 15 g of commercially available dibutyltin dimethoxide (0.05 mo)
l) was used as a colorless liquid (M).

Comparative Example 3 135 g of dioctyl phthalate (DOP) was added to 15 g (0.05 mol) of dibutyltin dimethoxide, and after substituting with nitrogen, the mixture was stirred at 40-50 ° C. for 1 hour to obtain a colorless liquid (N).
Got

1. Stability test Compositions obtained in Examples 1-11 and Comparative Examples 1-3 (A-
N) was tested for stability in air. The results are shown in [Table 1]. Test method: In a thermostatic chamber maintained at an air temperature of 25 ° C. and a humidity of 50 ± 5%, put 5 g of each composition obtained in Examples and Comparative Examples into a 50 cc beaker having a bottom area of about 15 cm ² , and liquid surface. The time (minutes) until skinning occurred on the skin was measured.

[Table 1]

2. Catalytic activity test Compositions obtained in Examples 1-11 and Comparative Examples 1-3 (A-
N) was tested for activity as a urethane catalyst. The results are shown in [Table 2]. Test method: In a thermostatic chamber maintained at a temperature of 25 ° C. and a humidity of 50 ± 5%, 500 ml Juar bottle [Thermocut D-500, manufactured by Nippon Oxygen Co., Ltd.] equipped with a thermometer and a stirrer was added to phenylisocyanate. 23.8 g (0.2 mol) of net and 100 ml of toluene were added, and then each composition obtained in Examples and Comparative Examples (immediately after opening in a 50 cc beaker having a bottom area of about 15 cm ² and 20 minutes after opening). , 2 hours after opening) and 12.0 g (0.2 mol) of isopropyl alcohol
Then, the mixture was immediately stirred and the time (minute) until the maximum heat generation was measured.

[Table 2]

[0029]

[Effect] As is clear from [Table 1], the stabilization method of the present invention can highly stabilize the organotin alkoxide compound. Further, as shown in [Table 2], a stable composition comprising an organic tin alkoxide and a triglyceride can maintain the catalytic activity for a long period of time, and in the industrial field where the organic tin alkoxide compound can be used as a curing catalyst, an esterification catalyst or the like. Widespread use is possible.

Claims (3)

[Claims] 1. A compound represented by the general formula [1] or [2]: [Chemical 2] (Wherein R represents an alkyl group having 1 to 18 carbon atoms or a benzyl group, and R ¹ or R ² represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, respectively). Formula [3] A method for stabilizing an organotin alkoxide, comprising adding a triglyceride represented by the formula (wherein R'represents an alkyl group or an alkenyl group having 3 to 36 carbon atoms). 2. The triglyceride according to claim 1,
A method for stabilizing an organotin alkoxide, which is soybean oil, coconut oil, castor oil, linseed oil, olive oil or dehydrated castor oil. 3. A compound represented by the general formula [4] or [5]: [Chemical 5] (Wherein R represents an alkyl group having 1 to 18 carbon atoms or a benzyl group, and R ¹ or R ² represents an alkyl group having 1 to 12 carbon atoms or a phenyl group) and a general organic tin alkoxide Formula [6] A stable composition comprising a triglyceride represented by the formula: wherein R'represents an alkyl group or an alkenyl group having 3 to 36 carbon atoms.