阅读说明：本技术 一种异辛烯酸亚锡的制备方法及应用 (Preparation method and application of stannous isooctenoate ) 是由 郭华 王珊 李春阳 刘宇 于 2020-12-31 设计创作，主要内容包括：本发明提供了一种异辛烯酸亚锡的制备方法及应用,其解决了现有辛酸亚锡制备工艺复杂、安全要求和成本高的技术问题,本发明制备的异辛烯酸亚锡为一种新的化合物,可以替代辛酸亚锡作为聚氨酯及中碳脂肪酸酯的催化剂,是由异辛烯醛作为反应物在碱性溶液中发生歧化反应,生成异辛烯酸盐和异辛烯醇,再加入氯化亚锡,发生复分解反应得到。本发明可广泛应用于辛酸亚锡技术领域。(The invention provides a preparation method and application of stannous isooctoate, which solve the technical problems of complex preparation process, safety requirement and high cost of the existing stannous octoate. The invention can be widely applied to the technical field of stannous octoate.)

1. A preparation method of stannous isooctoate is characterized by comprising the following steps:

(1) disproportionation reaction: adding the alkaline solution into a reaction kettle, controlling the reaction temperature, slowly adding isooctenal into the reaction kettle under stirring, and carrying out disproportionation reaction to obtain isooctoate;

(2) double decomposition reaction: adding a stannous chloride solution under the protection of nitrogen, stirring, controlling the reaction temperature, carrying out double decomposition reaction, standing for layering, collecting the upper mother liquor, carrying out reduced pressure distillation, controlling the distillation temperature and time, reducing the nitrogen to be empty after the distillation is finished, reducing the nitrogen to 25-30 ℃ under the protection of the nitrogen, and filtering to obtain the stannous isooctoate.

2. The method of claim 1, wherein the alkaline solution is one of sodium hydroxide and potassium hydroxide.

3. The method for preparing stannous isooctoate according to claim 1, wherein the mass fraction of the alkaline solution is 30-50%.

4. The method for preparing stannous isooctoate of claim 1, wherein the molar ratio of the alkaline solution to isooctenal is 1 (1-5).

5. The method for preparing stannous isooctoate according to claim 1, wherein the disproportionation reaction temperature is 25-80 ℃.

6. The method for preparing stannous isooctoate according to claim 1, wherein the metathesis reaction temperature is 40-90 ℃.

7. The method for preparing stannous isooctoate according to claim 1, wherein the vacuum degree of the negative pressure distillation is 1-10 mmHg.

8. The method for preparing stannous isooctoate according to claim 1, wherein the distillation temperature is 150-250 ℃ and the distillation time is 20-40 min.

9. Use of stannous isooctenoate according to claims 1-8 as a catalyst in polyester reactions.

Technical Field

The invention belongs to the technical field of stannous octoate, and particularly relates to a preparation method and application of stannous isooctenoate.

Background

The chemical name of stannous octoate is 2-ethyl stannous hexanoate, which is a chemical product of tin. Because stannous octoate is easy to hydrolyze in acidic and alkaline aqueous solutions, has a small stable pH value range, is easy to be oxidized and decomposed by oxygen and other oxidants in the air, and has high difficulty in preparation, stannous octoate is widely used as a catalyst of polyurethane and medium carbon fatty acid ester, and a commercial isooctyl acid preparation process is complex; the other is that isooctyl aldehyde obtained by aldol condensation is hydrogenated into isooctyl alcohol, then alkalization dehydrogenation is carried out, and isooctyl acid is obtained by acidification. Both methods have complex process, high process safety requirement and high cost. The sodium isooctanoate is saponified by using the isooctanoate prepared by the two methods, and then the sodium isooctanoate reacts with stannous chloride to obtain stannous octoate.

At present, most of stannous octoate prepared at home and abroad adopts an aldehyde disproportionation method, an acid anhydride method, a double decomposition method and the like, and the methods have the defects of unstable process control, complex operation and low stannous content, so that the industrial production of stannous octoate is limited. Therefore, there is a need for a new catalyst that can replace stannous octoate.

Disclosure of Invention

The invention aims to solve the defects of the background technology, and provides a preparation method of stannous isooctoate, which has simple process and low cost.

The invention provides a preparation method of stannous isooctoate, which comprises the steps of taking isooctenal as a raw material, carrying out disproportionation reaction in an alkaline solution, adding stannous chloride, and carrying out double decomposition reaction to obtain the stannous isooctoate.

The specific process comprises the following steps:

the method specifically comprises the following steps:

(1) disproportionation reaction: adding the alkaline solution into a reaction kettle, controlling the reaction temperature, slowly adding isooctenal into the reaction kettle under stirring, and carrying out disproportionation reaction to obtain isooctoate;

(2) double decomposition reaction: adding a stannous chloride solution under the nitrogen protection atmosphere, stirring, controlling the reaction temperature, carrying out double decomposition reaction, standing for layering, collecting the upper mother liquor, carrying out reduced pressure distillation, controlling the distillation temperature and time, after the distillation is finished, breaking the nitrogen, reducing the temperature to 25-30 ℃ under the nitrogen protection, and filtering to obtain the stannous isooctenoate.

Preferably, the alkaline solution is one of sodium hydroxide solution and potassium hydroxide solution.

Preferably, the mass fraction of the alkaline solution is 30% to 50%.

Preferably, the molar ratio of the alkaline solution to the isooctylaldehyde is 1 (1-5).

Preferably, the disproportionation reaction temperature is 25-80 ℃.

Preferably, the temperature of the double decomposition reaction is 40-90 ℃.

Preferably, the vacuum degree of the negative pressure distillation is 1-10 mmHg.

Preferably, the distillation temperature is 150-250 ℃, and the distillation time is 20-40 min.

The stannous isooctoate prepared by the preparation method can be used as a catalyst in polyester reaction.

The invention has the beneficial effects that:

(1) the stannous isooctoate prepared by the invention is a new catalyst for polyester reaction, and is prepared by taking isooctenal as a reactant to perform disproportionation reaction in an alkaline solution to generate isooctoate, adding stannous chloride to perform double decomposition reaction, wherein the tin content of the prepared stannous isooctoate reaches over 29 percent.

(2) The stannous isooctanoate prepared by the method shows good catalytic activity to polyester reaction, can be used as a catalyst in the polyester reaction, and when the stannous isooctanoate is used as a catalyst for preparing isooctanol isooctanoate, the conversion rate of isooctanol isooctanoate can reach 99.7 percent, so that the economic benefit is obviously improved, and the stannous isooctanoate is suitable for industrial production.

(3) The stannous isooctenoate prepared by the invention contains isooctanol and unreacted isooctenal generated by disproportionation reaction, and the isooctanol and the unreacted isooctenal are removed by organic phase vacuum distillation. Therefore, the post-treatment process is simple, free of three wastes, safe, nontoxic and suitable for industrial production.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

Example 1

A preparation method of stannous isooctoate comprises the following specific steps:

(1) disproportionation reaction: adding 58.88g of sodium hydroxide with the mass fraction of 30% into a 500ml four-diameter bottle with a stirrer, controlling the reaction temperature to be 25 ℃, slowly adding 100g of isooctenal into the four-diameter bottle under stirring, and carrying out disproportionation reaction to obtain isooctoate;

(2) double decomposition reaction: dissolving 88.5 g of stannous chloride dihydrate in 1L of water, adding a stannous chloride solution into the isooctoate prepared in the step (1) under the nitrogen protection atmosphere, controlling the reaction temperature to be 40 ℃, stirring for 20min, carrying out double decomposition reaction, standing for layering, collecting an upper mother solution, carrying out reduced pressure distillation for 1mmHg, controlling the distillation temperature to be 150 ℃, continuing for 10min, stopping distillation, breaking the nitrogen, reducing the nitrogen protection to 25-30 ℃, and filtering to obtain a clear, transparent and viscous liquid, namely stannous isooctoate, wherein the stannous content in the prepared stannous isooctoate is 29%, and the process yield is 90.6%.

Example 2

A preparation method of stannous isooctoate comprises the following specific steps:

(1) disproportionation reaction: adding 78.5g of sodium hydroxide with the mass fraction of 40% into a 500ml four-diameter bottle with a stirrer, controlling the reaction temperature to be 40 ℃, slowly adding 100g of isooctenal into the four-diameter bottle under stirring, and carrying out disproportionation reaction to obtain isooctoate;

(2) double decomposition reaction: dissolving 88.5 g of stannous chloride dihydrate in 1L of water, adding a stannous chloride solution into the isooctoate prepared in the step (1) under the nitrogen protection atmosphere, controlling the reaction temperature to be 65 ℃, stirring for 30min to perform double decomposition reaction, standing for layering, collecting upper mother liquor, distilling under reduced pressure for 5mmHg, controlling the distillation temperature to be 200 ℃, continuing for 10min, stopping distillation, breaking the nitrogen, reducing the nitrogen to be empty, reducing the nitrogen protection temperature to be 25-30 ℃, and filtering to obtain clear, transparent and viscous liquid, namely stannous isooctoate, wherein the stannous content in the prepared stannous isooctoate is 29%, and the process yield is 92.5%.

Example 3

(1) Disproportionation reaction: adding 98.13g of sodium hydroxide with the mass fraction of 60% into a 500ml four-diameter bottle with a stirrer, controlling the reaction temperature to be 80 ℃, slowly adding 100g of isooctenal into the four-diameter bottle under stirring, and carrying out disproportionation reaction to obtain isooctoate;

(2) double decomposition reaction: dissolving 88.5 g of stannous chloride dihydrate in 1L of water, adding a stannous chloride solution into the isooctoate prepared in the step (1) under the nitrogen protection atmosphere, controlling the reaction temperature to be 90 ℃, stirring for 30min to perform double decomposition reaction, standing for layering, collecting an upper mother solution, distilling under reduced pressure for 10mmHg, controlling the distillation temperature to be 250 ℃, continuing for 10min, stopping distillation, breaking the nitrogen, reducing the nitrogen to be 25-30 ℃ under the nitrogen protection, and filtering to obtain a clear, transparent and viscous liquid, namely stannous isooctoate, wherein the content of stannous in the prepared isooctenoic acid is 31% and the process yield is 91.8%.

Test for catalytic Performance

EXAMPLE 4 preparation of isooctanol isooctanoate as catalyst

150g of isooctanoic acid and 100g of isooctanol are added into a 500ml four-diameter bottle, 1.9g of the stannous isooctenoate prepared in the example 1 is taken as a catalyst, the stannous isooctenoate is added into the four-diameter bottle, the temperature is raised to 225-240 ℃, and the reaction is carried out for 3.5 hours. The light fraction is removed under negative pressure, washed with sodium hydroxide solution and then with distilled water to obtain 173.2g of isooctyl isooctanoate, the yield of isooctyl isooctanoate is 99.7%.

EXAMPLE 5 preparation of triethylene glycol Diethyloctanoate as catalyst

150g of isooctanoic acid and 55g of triethylene glycol are added into a 500ml four-diameter bottle, 1.9g of stannous isooctanoate in example 2 is taken as a catalyst, stannous isooctanoate is added into the four-diameter bottle, the temperature is raised to 225-240 ℃, the reaction is carried out for 5.5 hours, light components are removed under negative pressure, and the mixture is washed by alkali and water to obtain 120.3g of triethylene glycol diethyl octanoate, wherein the yield of the triethylene glycol diethyl octanoate is 80.88%.

EXAMPLE 6 preparation of monolaurin as catalyst

166g of lauric acid and 74g of glycerol are added into a four-diameter bottle of 500ml, 2.4g of the stannous isooctenoate prepared in the embodiment 3 is taken as a catalyst, the temperature is raised to 225-240 ℃, the vacuum degree is 50mmHg, the water temperature of a condenser is 65 ℃, after 2 hours of reaction, the vacuum degree is gradually increased, and the reaction is continued for 3.5 hours under 5 mmHg. Cooling to 70 ℃, adding 20g of sodium hydroxide solution with the mass fraction of 40%, stirring for 5 minutes, standing for layering, pouring out supernatant, controlling the temperature to be 70 ℃, washing twice with saturated saline solution, decompressing and dehydrating, and filtering at the constant temperature to obtain 192g of lauric acid monoglyceride with the yield of 87.6%.

Comparative example 1

150g of isooctanoic acid and 100g of isooctanol are added into a 500ml four-diameter bottle, the temperature is raised to 225-240 ℃, and the reaction is carried out for 3.5 hours. The light fraction is removed under negative pressure, and after alkali washing by using sodium hydroxide solution, 125.8.2g of isooctyl isooctanoate is obtained by washing by using distilled water, and the yield of isooctyl isooctanoate is 71.98%.

Comparative example 2

Adding 150g of isooctanoic acid and 55g of triethylene glycol into a 500ml four-diameter bottle, heating to 225-240 ℃, reacting for 5.5 hours, removing light components under negative pressure, and carrying out alkali washing and water washing to obtain 101.23g of triethylene glycol diethyl octanoate, wherein the yield of the triethylene glycol diethyl octanoate is 68.06%.

Comparative example 3

166g of lauric acid and 74g of glycerol are added into a four-diameter bottle of 500ml, the temperature is raised to 225-240 ℃, the vacuum degree is 50mmHg, the water temperature of a condenser is 65 ℃, after 2 hours of reaction, the vacuum degree is gradually increased, and the reaction is continued for 3.5 hours under 5 mmHg. Cooling to 70 ℃, adding 20g of sodium hydroxide solution with the mass fraction of 40%, stirring for 5 minutes, standing for layering, pouring out supernatant, controlling the temperature to be 70 ℃, washing twice with saturated saline solution, decompressing and dehydrating, and filtering at the constant temperature to obtain 168.60g of lauric monoglyceride, wherein the yield of the lauric monoglyceride is 76.92%.

And (4) experimental conclusion: of these, comparative example 1 is isooctyl isooctanoate prepared without adding tin isooctoate, comparative example 2 is triethylene glycol diethyloctanoate prepared without adding tin isooctoate, and comparative example 3 is monoglycerol laurate prepared without adding tin isooctoate.

From examples 1 to 3, the stannous isooctanoate prepared by the method is a new catalyst for polyester reaction, and is prepared by carrying out disproportionation reaction on isooctenal serving as a reactant in an alkaline solution to generate isooctoate, adding stannous chloride, and carrying out double decomposition reaction, wherein the tin content of the prepared stannous isooctanoate is more than 29%.

As can be seen from comparative example 1 and example 4, the yield of isooctyl isooctanoate obtained after addition of tin isooctanoate was higher than that obtained without addition of tin isooctanoate, and it is sufficiently demonstrated that tin isooctanoate can be used as a catalyst for accelerating the esterification reaction of isooctanoic acid and isooctanol.

As can be seen from comparative example 2 and example 5, the yield of triethylene glycol diethyl octanoate obtained after the addition of tin isooctoate was higher than that of triethylene glycol diethyl octanoate without the addition of tin isooctoate, and it is sufficiently demonstrated that tin isooctoate can be used as a catalyst to accelerate the esterification reaction rate of isooctanoic acid and triethylene glycol.

As is apparent from comparative example 3 and example 5, the yield of monoglycerol laurate obtained after addition of tin isooctenoate is higher than that of monoglycerol laurate without addition of tin isooctenoate, and it is sufficiently demonstrated that tin isooctenoate can be used as a catalyst for accelerating the esterification reaction rate of lauric acid and glycerin.

The stannous isooctanoate prepared by the method shows good catalytic activity to polyester reaction, can be used as a catalyst in the polyester reaction, and when the stannous isooctanoate is used as a catalyst for preparing isooctanol isooctanoate, the conversion rate of isooctanol isooctanoate can reach 99.7 percent, so that the economic benefit is obviously improved, and the stannous isooctanoate is suitable for industrial production.

In addition, the stannous isooctenoate prepared by the invention contains isooctanol and unreacted isooctenal generated by disproportionation reaction, and the isooctanol and the unreacted isooctenal are removed by organic phase vacuum distillation. Therefore, the post-treatment process is simple, free of three wastes, safe, nontoxic and suitable for industrial production.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.