CN1299821C - Use of zirconium inorganic salt and zirconium-oxygen inorganic salt as esterification catalyst - Google Patents

Abstract

The present invention relates to the application of zirconium inorganic salts and zirconium oxygen inorganic salts as catalysts in esterification and transesterification reactions, wherein the zirconium inorganic salts and zirconium oxygen inorganic salts are Zr(NO ₃ ) ₄ , ZrOCl ₂ , ZrO(NO ₃ ) ₂ .

Description

Application of Zirconium Inorganic Salt and Zirconium Oxygen Inorganic Salt as Esterification Catalyst

technical field

The invention relates to the application of zirconium inorganic salt and zirconium oxygen inorganic salt as esterification reaction catalyst.

Background technique

Acrylate compounds are a series of important organic chemical raw materials and important monomers in the polymer synthesis industry. They are widely used in coatings, adhesives, photosensitive curing agents, plastic modification, thinners, fiber treatment, leather processing, and rubber, etc. many ways. Acrylic acid ester synthesis generally adopts the method of direct esterification of sulfuric acid as catalyst in industry, (description method operation process) (referring to, the 337-340 page of " fine organic chemical raw material and intermediate handbook ", Xu Kexun, Chemical Industry Press, 1998) .

However, the methods disclosed in these documents have disadvantages such as serious corrosion of equipment, difficulty in controlling polymerization phenomenon, complicated post-treatment, high pollution, etc., and the product needs post-processing steps such as neutralization, water washing, and drying. Therefore, there is still a need for a better and simpler industrial method for preparing acrylates.

People have been looking for a new catalytic system to solve these problems. Current research mainly focuses on the following aspects:

Sulfuric acid catalyst: The research on sulfuric acid catalyst is still a hotspot, mainly focusing on the kinetics of sulfuric acid catalyzed esterification. [Grzesik M，Skrzypek J，Witczak M，Kinetics of esterificationof acrylic acid with C-3 and C-4 aliphatic alcohols in the presence of sulfuric acidas a catalyst，Reaction Kinetics and the Development of Catalytic ProcessesStudies in Surface Science and Catalysis 122：415 -418 1999], [Kinetics of theliquid phase esterification of acrylic acid with n-octanol and 2-ethylhexanolcatalyzed by sulfuric acid, Nowak P, Reaction Kinetics and Catalysis Letters 66(2): 375-380 Mar 1999], both For the main purpose, it has little to do with industrial production.

Solid acid catalyst: As a new type of catalyst, solid superacid has the advantages of high activity, good selectivity, easy separation, and low pollution. The research on its application in the esterification reaction system is a hot topic at home and abroad. Various catalytic systems, such as zirconium-based solid acid CZ catalysts with simple preparation process [Zhang Jingchang, Cao Weiliang, Lu Qing, etc., Application of Solid Acid Catalysts in Acrylation Reaction, Journal of Beijing University of Chemical Technology, 26(1999), 72-75] , has high catalytic activity for the esterification reaction of acrylic acid, and the catalyst and product are easy to separate and can be recycled. Similar to solid superacid SO ₄ ^2- /ZrO ₂ -TiO ₂ catalyst [Yang Shidi, Tang Fayou, Huang Qiang, Catalytic Synthesis of Acrylic Ester, Journal of Northwest University (Natural Science Edition), 30(2000), 393-396] It also has a good catalytic effect on the esterification of acrylic acid, but the preparation conditions of this catalyst are relatively harsh and it is easy to deactivate. It needs to be activated and reprocessed before it can be reused, which has caused great difficulties for its industrial application. The sulfonic acid resin composite AciplexSiO2 can also catalyze the esterification of acrylic acid [Kazuo Okuyama, Xin Chen, Katsumi Takata, Daisuke Odawara, Tetsuo Suzuki, Shin-ichi Nakata, Toshio Okuhara; Water-tolerant catalysis of a silica composite of a sulfonic acid resin, Aciplex; Applied catalysis.A, 190(2000), No.1-2, 253-260], and its catalytic effect is better than Cs _2.5 H _0.5 PW ₁₂ O ₄₀ , SO ₄ ^2- /ZrO ₂ etc. Solid acid catalyst, but will produce the corresponding addition products, the selectivity still needs to be improved.

Molecular sieves and ion exchange resins can also be used as catalysts for acrylated reactions. [Altiokka MR.; Citak A., Kinetics study of esterification of acetic acid withisobutanol in the presence of amberlite catalyst, Applied catalyst. A, General, 239(2003), No.1-2, 141-148], [O.Darge , F.C.Thyrion, Kenetics of the LiquidPhase Esterification of Acrylic acid with Butanol Catalysed by Cation Exchange Resin.J.Chem.Tech.Biotechnol.58(1993), 351] but the catalytic activity of ion exchange resin is inhibited by water and alcohol, wherein water Equivalent to 10 times the effect of alcohol, it is very unfavorable for the full progress of the reaction.

Heteropoly acid and heteropoly salt: Phosphotungstic acid and phosphotungstate also have a good catalytic effect on the esterification of acrylic acid [Xin Chen, Zheng Xu, Toshio Okuhara, Liquid phase esterification of acrylic acid with 1-butanol catalyzed by solid acid catalysts, Applied Catalysis A: General 180(1999) 261-269], Cs _2.5 H _0.5 PW ₁₂ O ₄₀ is also a good solid acid catalyst, but the selectivity of this type of catalyst is not higher than that of sulfuric acid.

Inorganic salt: there are not many studies on this type of catalytic system, and the literature records mainly contain metal salt sulfonic acid catalysts [(Tang Xun et al., fine chemical intermediates, novel catalytic synthesis of n-butyl acrylate, 32(2002), 24 )], titanium tetrachloride etc. supported on polymer [Kinetics of esterification of acrylic acid with n-butanol using polymer supported titanium tetrachloride as catalyst, Balakrishnan T, Rajendran V, Journal of Polymer Science part A-PolymerChemistry, 35 (4) : 727-733 Mar 1997]. Other inorganic salts such as stannous chloride [Zhao literature, Niu Meiju, solid inorganic chloride catalyzed synthesis of butyrate, Hunan Chemical Industry, 29 (1999), 6, 36-38] also have certain catalytic action to esterification, but The catalytic effect of simple inorganic salts on acrylated reactions has not been reported yet.

Aiming at the deficiencies in the prior art, the inventor has studied the existing catalytic esterification reaction, especially the industrial method for producing acrylate, and found that the use of zirconium inorganic salt and zirconium oxygen inorganic salt to catalyze the esterification reaction system, can obtain high-yield, high-purity products, and is very suitable for industrial production, thereby completing the present invention.

Summary of the invention

The invention relates to a zirconium inorganic salt and zirconium oxygen inorganic salt catalyst used for esterification.

Contents of the invention

The object of the present invention is to provide a zirconium inorganic salt and zirconium oxygen inorganic salt catalyst for esterification.

Specifically, the present invention provides a method that uses cheap inorganic zirconium salts containing crystal water, such as ZrOCl ₂ , ZrO(NO ₃ ) ₂ , Zr(NO ₃ ) ₄ and heteropolyacids, etc. to replace sulfuric acid in traditional methods. When the inorganic acid is used as a catalyst, the reaction can be carried out at room temperature without adding a polymerization inhibitor. After the reaction, the organic phase and the water phase are automatically separated, the catalyst remains in the water phase, and the water can be easily recovered by evaporating the water. , the catalyst is easy to recycle, and the product is easy to separate. It is an environmentally friendly catalytic system. And without using any water-carrying agent, a higher conversion rate can also be achieved. The prices of these zirconium salts are very low, such as ZrOCl ₂ with the best catalytic effect.

The present invention comprises the following steps:

Add the catalyst, carboxylic acid and alcohol into the reaction flask in a ratio of, for example, a molar ratio of 1 to 10:200:200 to 1000, stir and react at 0-60°C for 24 hours, leave to stand after the reaction, and separate layers, the lower layer is the water phase, The upper layer is an organic phase, the main component is C ₁ -C ₁₀ organic ester of carboxylic acid, and the reaction yield can reach 92%. The catalyst stays in the lower aqueous phase and can be reused.

The above-mentioned acid may be a carboxylic acid such as acrylic acid (acrylic acid or methacrylic acid), propionic acid, or the like. The catalysts are zirconium inorganic salts and zirconium oxygen inorganic salts, mainly ZrOCl ₂ , ZrO(NO ₃ ) ₂ ·2H ₂ O, Zr(NO ₃ ) ₄ ·5H ₂ O.

The aforementioned alcohols are aliphatic alcohols such as C ₁ -C ₁₀ aliphatic alcohols.

The present invention adopts the synthetic method of inorganic zirconium salt catalyzed esterification to prepare acrylate and propionate compounds compared with the method of sulfuric acid catalyzed synthesis of acrylate compounds currently widely used in industrialization, the former has the following advantages:

1. The conversion rate is significantly increased when the acid-alcohol ratio is 1:1 or close to 1:1;

2. Do not use solvents and water-carrying agents;

3. The catalyst can be easily recycled;

4. The pure product can be obtained by directly separating, precipitating or rectifying the product without washing, and there is no three wastes;

5. The catalytic reaction is a low-temperature reaction, no polymerization reaction occurs, energy consumption is reduced, and high-quality products can be obtained.

6. Zirconium inorganic salt and zirconium oxygen inorganic salt catalysts can be recycled and reused, which greatly reduces production costs. It is a green reaction system that conforms to the national environmental protection policy.

Detailed ways

Hereinafter, the present invention will be described in more detail without limitation by way of examples.

Example 1:

Weigh 402 mg of ZrOCl ₂ ·8H ₂ O catalyst into a reaction flask, then add 1.30 ml of methanol and 1.70 ml of acrylic acid in sequence, seal it, and stir at room temperature for reaction. The reaction time is 24 hours. The reaction result is: the yield of methyl acrylate is 83%. The reaction time was 48 hours, and the yield of methyl acrylate was 90%.

Example 2:

In the aqueous phase recovered in Example 1, 406 μl of methanol and 686 μl of acrylic acid were added successively, sealed, and stirred at room temperature for reaction. The reaction time was 48 hours. The reaction result was: the yield of methyl acrylate was 74%.

Example 3:

Weigh 322 mg of ZrOCl ₂ 8H ₂ O catalyst in a reaction flask, then add 1.42 ml of ethanol and 1.70 ml of methacrylic acid in sequence, seal it, and stir the reaction at room temperature. The reaction time is 24 hours, and the yield of ethyl methacrylate is 78%.

Example 4:

Weigh 32 mg of ZrOCl ₂ 8H ₂ O catalyst in a reaction flask, then add 1.42 ml of ethanol and 1.70 ml of methacrylic acid in sequence, seal it, and stir the reaction at room temperature. The reaction time is 24 hours, and the yield of ethyl methacrylate is 35%.

Example 5:

Weigh 161 mg of ZrOCl ₂ 8H ₂ O catalyst into a reaction bottle, then add 406 μl of methanol and 852 μl of methacrylic acid in sequence, seal it, and stir the reaction at room temperature. The reaction time is 48 hours. The reaction result is: the production of methyl methacrylate The rate is 70%.

Embodiment 6:

Weigh 80 mg of ZrOCl ₂ 8H ₂ O catalyst into a reaction tube, then add 295 μl of ethanol and 343 μl of acrylic acid in sequence, seal the reaction tube, stir and react under heating at 57°C, the reaction time is 24 hours, and the reaction result is: production of ethyl acrylate The rate is 69%.

Embodiment 7:

Weigh 80 mg of ZrOCl ₂ 8H ₂ O catalyst into a reaction tube, then add 375 μl of propanol and 343 μl of acrylic acid in sequence, seal the reaction tube, stir and react at 25°C, and the reaction time is 24 hours. The reaction result is: the production of propyl acrylate The rate is 61%.

Embodiment 8:

Weigh 80 mg of ZrOCl ₂ ·8H ₂ O catalyst into a reaction tube, then add 458 μl of butanol and 343 μl of acrylic acid in sequence, seal the reaction tube, stir and react at 35°C, and the reaction time is 24 hours. The reaction result is: production of butyl acrylate The rate is 63%.

Embodiment 9:

Weigh 80 mg of ZrOCl ₂ 8H ₂ O catalyst into a reaction tube, then add 544 μl of amyl alcohol and 343 μl of acrylic acid in sequence, seal the reaction tube, stir and react at 56°C, and the reaction time is 24 hours. The reaction result is: the production of amyl acrylate The rate is 82%.

Example 10:

Weigh 48 mg of ZrOCl ₂ 8H ₂ O catalyst into a reaction tube, then add 378 μl of hexanol and 206 μl of acrylic acid in sequence, seal the reaction tube, stir and react at 48°C, and the reaction time is 24 hours. The reaction result is: the production of hexyl acrylate The rate is not less than 92%.

Example 11:

Weigh 48 mg of ZrOCl ₂ ·8H ₂ O catalyst into a reaction tube, then add 476 μl of octanol and 206 μl of acrylic acid in sequence, seal the reaction tube, stir and react at 60°C, and the reaction time is 24 hours. The reaction result is: the production of octyl acrylate The rate is 84%.

Example 12:

Add 1.6g of ZrOCl ₂ 8H ₂ O catalyst into a 50ml single-necked round bottom flask, then add 7.7g of acrylic acid and 9.4g of n-amyl alcohol in turn, and stir the reaction at 51°C. The reaction time is 24 hours, and the reaction result is: pentyl acrylate The yield was 71%.

Example 13:

Add 1.6g of ZrOCl ₂ 8H ₂ O catalyst into a 50ml single-necked round bottom flask, then add 7.21g of acrylic acid and 11.6g of n-heptanol in turn, and stir the reaction at 45°C. The reaction time is 24 hours, and the reaction result is: heptyl acrylate The yield was 61%.

Example 14:

Add 1.6g of ZrOCl ₂ 8H ₂ O catalyst into a 50ml single-necked round bottom flask, then add 7.21g of acrylic acid and 11.6g of n-octanol in sequence, and stir the reaction at 50°C. The reaction time is 24 hours, and the reaction result is: octyl acrylate The yield was 60%.

Example 15:

Add 1.6g of ZrOCl ₂ 8H ₂ O catalyst into a 50ml single-necked round bottom flask, then add 7.21g of acrylic acid and 13.0g of n-nonanol in sequence, and stir the reaction at 52°C. The reaction time is 24 hours, and the reaction result is: nonyl acrylate The yield was 61%.

Example 16:

Add 1.6g of ZrOCl ₂ 8H ₂ O catalyst into a 50ml single-necked round bottom flask, then add 7.21g of acrylic acid and 14.4g of n-decyl alcohol in turn, and stir the reaction at 55°C. The reaction time is 24 hours, and the reaction result is: decyl acrylate The yield was 60%.

Example 17:

Add 1.6g of ZrOCl ₂ 8H ₂ O catalyst into a 50ml single-necked round bottom flask, then add 7.41g of propionic acid and 11.6g of n-octanol in turn, and stir the reaction at 50°C. The reaction time is 24 hours, and the reaction result is: octyl propionate The yield of ester was 92%.

Example 18

Weigh 331 mg of ZrO(NO ₃ ) ₂ ·2H ₂ O catalyst into a reaction flask, then add 1.30 ml of methanol and 1.70 ml of acrylic acid in sequence, seal it, and stir the reaction at room temperature for 24 hours. The reaction result is: the yield of methyl acrylate is 44%.

Example 19::

Weigh 194 mg of Zr(NO ₃ ) ₄ ·5H ₂ O catalyst into a reaction flask, then add 243 μl of methanol and 343 μl of acrylic acid in sequence, seal it, and stir the reaction at room temperature for 24 hours. The reaction result is: the yield of methyl acrylate is 54%.

Example 20:

Weigh 133 mg of ZrO(NO ₃ ) ₂ ·2H ₂ O catalyst into the reaction bottle, then add 406 μl of methanol and 852 μl of methacrylic acid in sequence, seal it, stir and react at room temperature, and the reaction time is 48 hours. The reaction result is: methacrylic acid The yield of methyl ester was 17.9%.

Example 21:

Weigh 215 mg of Zr(NO ₃ ) ₄ 5H ₂ O catalyst into a reaction bottle, then add 406 μl of methanol and 852 μl of methacrylic acid in sequence, seal it, and stir the reaction at room temperature. The reaction time is 48 hours, and the reaction result is: methacrylic acid The yield of methyl ester was 29.5%.

Comparative Example 1:

Weigh 76 mg of phosphomolybdic acid catalyst in the reaction bottle, then add 406 μl of methanol and 852 μl of methacrylic acid in sequence, seal it, stir and react at room temperature, and the reaction time is 48 hours. The reaction result is: the yield of methyl methacrylate is 20.5 %.

Comparative example 2:

Weigh 135 mg of phosphotungstic acid catalyst into the reaction bottle, then add 406 μl of methanol and 852 μl of methacrylic acid in sequence, seal it, and stir the reaction at room temperature. The reaction time is 48 hours. The reaction result is: the yield of methyl methacrylate is 30.7 %.

Comparative example 3:

Weigh 223 mg of silicotungstic acid catalyst into the reaction bottle, then add 406 μl of methanol and 852 μl of methacrylic acid in sequence, seal it, and stir the reaction at room temperature. The reaction time is 48 hours. The reaction result is: the yield of methyl methacrylate is 30.1 %.

Comparative example 4:

0.5 g of sulfuric acid was added to a 50 ml single-necked round bottom flask, followed by 7.21 g of acrylic acid and 7.4 g of butanol, and the reaction was stirred at 80°C. The reaction time was 4 hours. The reaction result was: the yield of butyl acrylate was 61%.

Comparative example 5:

Add 2.1g of tin chloride to a 50ml single-necked round bottom flask, then add 8.8g of butyric acid, 7.4g of butanol, and 2g of cyclohexane in sequence, and stir the reaction at 80°C. The reaction time is 2 hours, and the reaction result is: butyric acid The yield of butyl ester was 75%.

Claims (10)

1. The application of zirconium inorganic salts and zirconium oxygen inorganic salts as catalysts in esterification and transesterification reactions. 2. The use according to claim 1, wherein the zirconium inorganic salt is Zr(NO ₃ ) ₄ . 3. Use according to claim 1 or 2, wherein the esterification reaction is the esterification and transesterification of acrylic acid, methacrylic acid or propionic acid with C ₁ -C ₁₀ -aliphatic alcohols. 4. The application according to claim 3, wherein the molar ratio of the catalyst, carboxylic acid and alcohol used in the reaction is 1-10:200:200-1000. 5. The use according to claim 3, the reaction temperature is 0-100°C. 6. The application of zirconium oxide inorganic salt as a catalyst in esterification and transesterification reactions. 7. The use according to claim 6, wherein the zirconium oxide inorganic salt is ZrOCl ₂ , ZrO(NO ₃ ) ₂ . 8. Use according to claim 6 or 7, wherein the esterification reaction is the esterification and transesterification of acrylic acid, methacrylic acid or propionic acid with C ₁ -C ₁₀ -aliphatic alcohols. 9. The application according to claim 8, wherein the molar ratio of the catalyst, carboxylic acid and alcohol used in the reaction is 1-10:200:200-1000. 10. The use according to claim 8, the reaction temperature is 0-100°C.