High-activity organic metal catalyst dibutyl vegetable oil tin acid and preparation method thereof
Through two esterification reactions and the introduction of CQDs, a high-activity and high-stability dibutyl vegetable tin oleate catalyst was prepared, which solved the problem of insufficient activity and stability in the prior art, and achieved long-term stable catalytic activity in industrial production.
Patent Information
- Application Number
- CN202411823696.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-12
- Publication Date
- 2025-03-11
AI Technical Summary
In the prior art, the activity and stability of dibutyl vegetable tin oleate are insufficient, which affects its long-term stable catalytic activity in industrial production.
The highly reactive organometallic catalyst dibutyl tin vegetable oleate was prepared by two esterification reactions, and CQDs were introduced and stannous octoate was grafted on their surface, thereby improving the stability and activity of the catalyst.
It significantly improves the stability and activity of the catalyst, can show excellent catalytic activity under lower temperature conditions, and is suitable for the synthesis of silicone glue.
Smart Images
Figure CN119588422A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of catalyst synthesis, and specifically relates to a high-activity organic metal catalyst dibutyltin vegetable oleate and a preparation method thereof. Background Art
[0002] As a common catalyst in many fields such as modern chemical industry, materials science and organic synthesis, organometallic catalysts are compounds with unique chemical properties that can effectively reduce the activation energy of chemical reactions, thereby accelerating the reaction rate, improving the reaction selectivity, and promoting the chemical reaction to proceed in the desired direction.
[0003] Among many organometallic catalysts, dibutyltin oleate, as a tin-based organometallic catalyst, has attracted attention due to its special chemical structure and properties. Although the preparation method of dibutyltin oleate has been studied to a certain extent, there are still some limitations, such as activity and stability problems, which is not conducive to industrial production processes that require long-term stable catalytic activity.
[0004] In summary, the preparation of highly active organic metal catalyst dibutyltin vegetable oleate, its research and development and improved preparation method have important practical significance, and can provide more efficient, environmentally friendly and sustainable catalytic solutions for related industrial fields. Summary of the invention
[0005] In view of the defects of the prior art, the present invention discloses a high-activity organic metal catalyst dibutyl tin oleate. The high-activity organic metal catalyst dibutyl tin oleate is prepared through two esterification reactions. The introduction of CQDs greatly enhances the stability of the catalyst, and stannous octoate is grafted on the surface of CQDs through the esterification reaction, thereby improving the catalytic activity of the entire reaction process. In addition, during the reaction process, when some CQDs break bonds, their surfaces are rich in amino groups, which can be used as a cross-linking agent in the silicone glue synthesis process, thereby improving the performance of the product.
[0006] To achieve the above object, the technical solution adopted by the present invention is a highly active organic metal catalyst dibutyltin vegetable oleate, which is prepared from the following raw materials in parts by weight: 4-8 parts of dibutyltin chloride, 6-9 parts of distilled coconut oil fatty acid, 1 part of octanoic acid and 0.5-1 part of CQDs-alcoholized stannous octoate;
[0007] The preparation method of CQDs-alcoholized stannous octoate comprises the following steps:
[0008] (1) Weigh citric acid, urea, alcoholized stannous octoate, acetone and deionized water in a mass ratio of 3-6:1-2:0.5-1:3:40, add citric acid and urea to deionized water, stir for 30 minutes at a power of 0.3 kW to obtain solution A, add alcoholized stannous octoate to acetone, stir for 30 minutes at a power of 0.3 kW to obtain solution B;
[0009] (2) Slowly adding the solution B obtained in step (1) into the solution A, ultrasonicating for 25 min at a power of 5-15 kHz, and stirring for 30 min at a power of 0.5 kW to obtain a mixed solution, adding the mixed solution into a reactor, heating the temperature from room temperature to 80-120°C, at a heating rate of 5°C / min, for 15 h, and then naturally cooling to room temperature to obtain a CQDs-alcoholized stannous octoate precursor;
[0010] (3) The CQDs-alcoholized stannous octoate precursor obtained in step (2) was centrifuged at a speed of 10000 r / min for 20 min to obtain a supernatant, and then the supernatant was dialyzed using a dialysis bag with a molecular weight cutoff of 1500D-2500D for 24 h to obtain a dialysate, which was dried in a blast drying oven at a drying temperature of 55 ° C for 24 h to obtain CQDs-alcoholized stannous octoate.
[0011] Furthermore, the preparation method of alcoholized stannous octoate comprises the following steps:
[0012] (i) Weigh stannous octoate, glycidyl alcohol and toluene in a mass ratio of 1-3:3.5-7.5:10, add toluene into a three-necked flask reactor, then add stannous octoate into toluene, and stir for 30 minutes at a power of 0.3 kW to obtain a homogeneous liquid;
[0013] (ii) slowly adding the glycidyl alcohol weighed in step (i) to the homogenous solution obtained in step (i), heating the mixture to 110-140° C. and stirring the mixture for 4 hours at a stirring power of 0.5 kW, and then naturally cooling the mixture to room temperature to obtain a homogenous reaction solution;
[0014] (iii) adding the reaction mixture obtained in step (ii) into a separator, adding water for washing, removing the aqueous phase after the solution is separated into layers, repeating the washing operation three times to obtain an organic phase, and drying and removing water from the organic phase to obtain a composite phase;
[0015] (vi) using a rotary evaporator to distill the composite phase obtained in step (iii) to remove toluene, the distillation speed is 100-150 r / min, the distillation pressure is 5-10 kPa, and the distillation temperature is 60-80° C. to obtain an alcoholized stannous octoate precursor, and then purifying the alcoholized stannous octoate precursor, the purification pressure is 0.3-0.8 kPa, and the purification temperature is 180-220° C. to obtain alcoholized stannous octoate.
[0016] Furthermore, the preparation method of stannous octoate comprises the following steps:
[0017] (a) Weigh anhydrous stannous chloride, triethanolamine, anhydrous ethanol, isooctanoic acid and n-hexane in a mass ratio of 1-3:1.2-1.8:10:3-5:0.7-1.2;
[0018] (b) adding the anhydrous stannous chloride weighed in step (a) to anhydrous ethanol, treating for 30 minutes under an ultrasonic power of 0.3 kW to obtain a mixed solution I, slowly adding the triethanolamine weighed in step (a) to the mixed solution I, heating in an oil bath at 40-60° C. and stirring for 2 hours at a stirring power of 0.3 kW to obtain a stannous octoate intermediate, then adding the isooctanoic acid weighed in step (a) to the stannous octoate intermediate, heating for a second time and stirring for 6 hours, and then naturally cooling to room temperature to obtain a stannous octoate mixed solution;
[0019] (c) washing the stannous octoate mixed solution obtained in step (b), collecting the organic phase and drying it in a vacuum drying oven at a temperature of 70° C. for a drying time of 24 h to obtain a stannous octoate crude solution;
[0020] (d) heating the n-hexane weighed in step (a) and maintaining the temperature at 50-70° C., then slowly adding the crude stannous octoate solution obtained in step (c) into the n-hexane, stirring at a power of 0.5 kW for 40 min, and then filtering to remove impurities to obtain a mixed solution II;
[0021] (e) treating the mixed solution II obtained in step (d) in an ice-water bath at 2-5° C. to obtain a crystalline mixture, then filtering the crystalline mixture with n-hexane as the filtrate to obtain crystals, repeating the filtration operation on the crystals three times to obtain crystals, collecting the crystals and drying them at a drying temperature of 55° C. for 24 h to obtain stannous octoate.
[0022] The present invention also provides a method for preparing a high-activity organic metal catalyst dibutyl tin oleate, comprising the following steps:
[0023] Step 1: Weigh 4-8 parts of dibutyltin chloride, 6-9 parts of distilled coconut oil fatty acids, 1 part of octanoic acid and 0.5-1 part of CQDs-alcoholized stannous octoate, wherein the distilled coconut oil fatty acids are composed of octadecanoic acid, decadecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid in a mass percentage of 5%:10%:45%:20%:8%:12%, and the octanoic acid is composed of octanoic acid and decanoic acid in a mass percentage of 55%:45%;
[0024] Step 2: The distilled coconut oil fatty acid and octanoic acid weighed in step 1 are stirred and mixed, the stirring power is 0.5 kW, the stirring time is 30 min, and a mixed acid solution is obtained. The dibutyltin chloride weighed in step 1 is added to the mixed acid solution, the temperature is heated to 35-45°C and stirred, the heating time is 40 min, and a mixed reaction solution is obtained. Then, a sodium hydroxide solution is slowly dripped into the mixed reaction solution, the concentration of the sodium hydroxide solution is 2.5 mol / L, the temperature is increased to 60-110°C and the pH range is adjusted to 5-8.5, the reaction is carried out for 1 hour, and then CQDs-alcoholized stannous octoate is added thereto, the reaction is continued for 5 hours, and then naturally cooled to room temperature, the aqueous phase is removed by standing and stratification, and an organic phase mixture is obtained;
[0025] Step 3: drying the organic phase mixture obtained in step 2 in a vacuum drying oven at a drying temperature of 55° C. for 24 h to obtain a crude material of dibutyltin oleate, a highly active organic metal catalyst;
[0026] Step 4: The crude material of the highly active organic metal catalyst dibutyl tin oleate obtained in step 3 is subjected to reduced pressure filtration using a vacuum pump, the reduced pressure is 3-8 kPa, and the filtration time is 2 h, to obtain the highly active organic metal catalyst dibutyl tin oleate.
[0027] The beneficial effects achieved by the present invention are as follows:
[0028] The high-activity organic metal catalyst dibutyl tin oleate prepared by the present invention is firstly prepared by a chemical combination reaction to obtain stannous octoate, and the stannous octoate is subjected to an alcoholization reaction to obtain a stannous octoate compound rich in hydroxyl groups, and the alcoholized stannous octoate has better compatibility, providing a basic structure for a subsequent esterification reaction; the stannous octoate compound is further grafted on the surface of CQDs through an esterification reaction to obtain CQDs-alcoholized stannous octoate, providing more tin active sites for the synthesis process of silicone glue; under the premise of not affecting the tin catalytic active sites, the organic metal catalyst dibutyl tin oleate is introduced into CQDs-alcoholized stannous octoate through an esterification reaction to obtain a catalyst body with higher stability, and CQDs contain a small amount of amino groups, and when some bonds are broken, the amino groups can be used as cross-linking agents in the synthesis process of silicone glue, thereby improving the performance of the product.
[0029] The high-activity organic metal catalyst dibutyl tin oleate prepared by the present invention is the first to prepare the high-activity and high-stability organic metal catalyst dibutyl tin oleate through two esterification reactions. In the preparation process, materials with low toxicity, safety and no threat to the environment are selected. Compared with the organic metal catalysts dibutyl tin oleate and stannous octoate in the prior art, it can also show better catalytic activity in the synthesis process of silicone glue under lower temperature conditions.
[0030] The highly active organic metal catalyst dibutyltin vegetable oil acid prepared by the present invention provides more theoretical insights for the research on catalysts used in the subsequent silicone rubber synthesis process. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 A diagram showing a preparation method according to an embodiment of the present invention;
[0032] Figure 2 This is the adhesion-concentration standard curve made with silicone adhesive as the product of the present invention;
[0033] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION
[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0035] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.
[0036] The preparation methods in the following examples are referred to Figure 1 , unless otherwise specified, are conventional methods; the materials used in the following embodiments, unless otherwise specified, are all new materials purchased from the market, and the parts in the embodiments are all parts by mass, wherein the distilled coconut oil fatty acid is composed of octadecanoic acid, decadecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid and octadecanoic acid in a mass percentage of 5%:10%:45%:20%:8%:12%, and the caprylic and capric acid is composed of caprylic acid and capric acid in a mass percentage of 55%:45%.
[0037] Example 1: The highly active organic metal catalyst dibutyltin oleate provided in this example is prepared from the following raw materials in parts by weight: 4 parts of dibutyltin chloride, 6 parts of distilled coconut oil fatty acid, 1 part of octanoic acid and 0.5 parts of CQDs-alcoholized stannous octoate;
[0038] The raw materials for preparing CQDs-alcoholized stannous octoate include citric acid, urea, alcoholized stannous octoate and acetone, the raw materials for preparing alcoholized stannous octoate include stannous octoate, glycidyl alcohol and toluene, and the raw materials for preparing stannous octoate include anhydrous stannous chloride, triethanolamine, anhydrous ethanol, isooctanoic acid and n-hexane.
[0039] The preparation method of stannous octoate comprises the following steps:
[0040] (a) Weigh 1 part of anhydrous stannous chloride and add it to 10 parts of anhydrous ethanol, and perform ultrasonic treatment for 30 minutes under the condition of ultrasonic power of 0.3 kW to obtain a mixed solution I, weigh 1.2 parts of triethanolamine and slowly add it to the mixed solution I, heat the temperature to 40°C in an oil bath and keep stirring under the condition of power of 0.3 kW for 2 hours to obtain a stannous octoate intermediate, weigh 3 parts of isooctanoic acid and add it to the stannous octoate intermediate, heat it for a second time for 6 hours with stirring, and then naturally cool it to room temperature to obtain a stannous octoate mixed solution;
[0041] (b) washing the stannous octoate mixed solution obtained in step (a), collecting the organic phase and drying it in a vacuum drying oven for 24 hours at a drying temperature of 70° C. to obtain a stannous octoate crude solution;
[0042] (c) weighing 0.7 parts of n-hexane for heating treatment to 50° C., then slowly adding the crude stannous octoate solution obtained in step (b) into the n-hexane, stirring for 30 minutes at a stirring power of 0.5 kW, and then filtering to remove impurities to obtain a mixed solution II;
[0043] (d) treating the mixed solution II obtained in step (c) in an ice-water bath at 2°C to obtain a crystalline mixture, then filtering the crystalline mixture with n-hexane as the filtrate to obtain crystals, repeating the filtration operation on the crystals three times to obtain crystals, collecting the crystals and drying them for 24 hours at a drying temperature of 55°C to obtain stannous octoate.
[0044] The preparation method of alcoholized stannous octoate comprises the following steps:
[0045] (i) Weigh 10 parts of toluene and add it into a three-necked flask reactor, then weigh 1 part of stannous octoate and add it into the toluene, and stir for 30 minutes at a stirring power of 0.3 kW to obtain a homogeneous liquid;
[0046] (ii) weighing 3.5 parts of glycidyl alcohol and slowly adding it to the homogenous solution obtained in step (i), heating the temperature to 110° C. and maintaining it for 4 hours, stirring it at a stirring power of 0.5 kW, and then naturally cooling it to room temperature to obtain a reaction homogenous solution;
[0047] (iii) adding the reaction mixture obtained in step (ii) into a separator, adding water for washing, removing the aqueous phase after the solution is separated into layers, repeating the washing operation three times to obtain an organic phase, and drying and removing water from the organic phase to obtain a composite phase;
[0048] (vi) using a rotary evaporator to distill the composite phase obtained in step (iii) to remove toluene, the distillation speed is 100 r / min, the distillation pressure is 5 kPa, and the distillation temperature is 60° C. to obtain an alcoholized stannous octoate precursor, and then purifying the alcoholized stannous octoate precursor, the purification pressure is 0.3 kPa, and the purification temperature is 180° C. to obtain alcoholized stannous octoate.
[0049] The preparation method of CQDs-alcoholized stannous octoate comprises the following steps:
[0050] (1) Weigh 3 parts of citric acid and 1 part of urea, add them to 40 parts of deionized water, stir for 30 minutes at a stirring power of 0.3 kW, and obtain solution A; weigh 0.5 parts of stannous octoate alcohol, add them to 3 parts of acetone, and stir for 30 minutes at a stirring power of 0.3 kW, and obtain solution B;
[0051] (2) Slowly adding the solution B obtained in step (1) into the solution A, ultrasonically treating for 25 min at an ultrasonic power of 5 kHz, and stirring for 30 min at a stirring power of 0.5 kW to obtain a mixed solution, adding the mixed solution into a reactor, heating the temperature from room temperature to 80 ° C at a heating rate of 5 ° C / min for 15 h, and then naturally cooling to room temperature to obtain a CQDs-alcoholized stannous octoate precursor;
[0052] (3) The CQDs-alcoholized stannous octoate precursor obtained in step (2) was centrifuged at a centrifugal speed of 10000 r / min for 20 min to obtain a supernatant, and then the supernatant was dialyzed using a dialysis bag with a molecular weight cutoff of 1500D for 24 h to obtain a dialysate, and the dialysate was dried in a forced air drying oven at 55° C. for 24 h to obtain CQDs-alcoholized stannous octoate.
[0053] This embodiment also provides a method for preparing a highly active organic metal catalyst dibutyltin oleate, comprising the following steps:
[0054] Step 1: Weigh 6 parts of distilled coconut oil fatty acid and 1 part of octanoic acid and stir and mix them for 30 minutes under a stirring power of 0.5 kW to obtain a mixed acid solution, weigh 4 parts of dibutyltin chloride and add them to the mixed acid solution, heat the temperature to 35°C, maintain for 40 minutes and stir to obtain a mixed reaction solution, then slowly drip a 2.5 mol / L sodium hydroxide solution into the mixed reaction solution, increase the temperature to 60°C and adjust the pH to 5, react for 1 hour, then add 0.5 parts of CQDs-alcoholized stannous octoate thereto, continue to react for 5 hours, then naturally cool to room temperature, stand for stratification to remove the aqueous phase, and obtain an organic phase mixture;
[0055] Step 2: drying the organic phase mixture obtained in step 1 in a vacuum drying oven at 55° C. for 24 hours to obtain a crude material of dibutyltin oleate, a highly active organic metal catalyst;
[0056] Step 3: The crude material of the highly active organic metal catalyst dibutyl tin oleate obtained in step 2 is subjected to reduced pressure filtration at a pressure of 3 kPa for 2 hours using a vacuum pump to obtain the highly active organic metal catalyst dibutyl tin oleate.
[0057] Example 2: The highly active organic metal catalyst dibutyltin oleate provided in this example is prepared from the following raw materials in parts by weight: 6 parts of dibutyltin chloride, 7.5 parts of distilled coconut oil fatty acid, 1 part of octanic acid and 0.8 parts of CQDs-alcoholized stannous octoate.
[0058] The raw materials for preparing CQDs-alcoholized stannous octoate include citric acid, urea, alcoholized stannous octoate and acetone, the raw materials for preparing alcoholized stannous octoate include stannous octoate, glycidyl alcohol and toluene, and the raw materials for preparing stannous octoate include anhydrous stannous chloride, triethanolamine, anhydrous ethanol, isooctanoic acid and n-hexane.
[0059] The preparation method of stannous octoate comprises the following steps:
[0060] (a) Weigh 2 parts of anhydrous stannous chloride and add them to 10 parts of anhydrous ethanol. Under the condition of ultrasonic power of 0.3 kW, ultrasonic treatment is performed for 30 min to obtain a mixed solution I. Weigh 1.5 parts of triethanolamine and slowly add them to the mixed solution I. Heat the temperature to 50° C. in an oil bath and keep stirring under the condition of power of 0.3 kW for 2 h to obtain a stannous octoate intermediate. Weigh 4 parts of isooctanoic acid and add them to the stannous octoate intermediate. Heat for a second time for 6 h and stir. Then naturally cool to room temperature to obtain a stannous octoate mixed solution.
[0061] (b) washing the stannous octoate mixed solution obtained in step (a), collecting the organic phase and drying it in a vacuum drying oven for 24 hours at a drying temperature of 70° C. to obtain a stannous octoate crude solution;
[0062] (c) weighing 0.7 parts of n-hexane for heating treatment to 60° C., then slowly adding the crude stannous octoate solution obtained in step (b) into the n-hexane, stirring for 30 minutes at a stirring power of 0.5 kW, and then filtering to remove impurities to obtain a mixed solution II;
[0063] (d) treating the mixed solution II obtained in step (c) in an ice-water bath at 4°C to obtain a crystalline mixture, then filtering the crystalline mixture with n-hexane as the filtrate to obtain crystals, repeating the filtration operation on the crystals three times to obtain crystals, collecting the crystals and drying them for 24 hours at a drying temperature of 55°C to obtain stannous octoate.
[0064] The preparation method of alcoholized stannous octoate comprises the following steps:
[0065] (i) Weigh 10 parts of toluene and add it into a three-necked flask reactor, then weigh 2 parts of stannous octoate and add it into the toluene, and stir for 30 minutes at a stirring power of 0.3 kW to obtain a homogeneous liquid;
[0066] (ii) weighing 5.5 parts of glycidyl alcohol and slowly adding it to the homogenous solution obtained in step (i), heating the temperature to 125° C. and maintaining it for 4 hours, stirring it at a stirring power of 0.5 kW, and then naturally cooling it to room temperature to obtain a reaction homogenous solution;
[0067] (iii) adding the reaction mixture obtained in step (ii) into a separator, adding water for washing, removing the aqueous phase after the solution is separated into layers, repeating the washing operation three times to obtain an organic phase, and drying and removing water from the organic phase to obtain a composite phase;
[0068] (vi) using a rotary evaporator to distill the composite phase obtained in step (iii) to remove toluene, the distillation speed is 130 r / min, the distillation pressure is 8 kPa, and the distillation temperature is 70° C. to obtain an alcoholized stannous octoate precursor, and then purifying the alcoholized stannous octoate precursor, the purification pressure is 0.5 kPa, and the purification temperature is 200° C. to obtain alcoholized stannous octoate.
[0069] The preparation method of CQDs-alcoholized stannous octoate comprises the following steps:
[0070] (1) Weigh 4.5 parts of citric acid and 1.5 parts of urea, add them to 40 parts of deionized water, stir for 30 minutes at a stirring power of 0.3 kW, and obtain solution A; weigh 0.8 parts of stannous octoate alcohol, add them to 3 parts of acetone, and stir for 30 minutes at a stirring power of 0.3 kW, and obtain solution B;
[0071] (2) Slowly adding the solution B obtained in step (1) into the solution A, ultrasonicating for 25 min at an ultrasonic power of 10 kHz, and stirring for 30 min at a stirring power of 0.5 kW to obtain a mixed solution, adding the mixed solution into a reactor, heating the temperature from room temperature to 100 ° C at a heating rate of 5 ° C / min, the heating time is 15 h, and then naturally cooling to room temperature to obtain a CQDs-alcoholized stannous octoate precursor;
[0072] (3) The CQDs-alcoholized stannous octoate precursor obtained in step (2) was centrifuged at a centrifugal speed of 10000 r / min for 20 min to obtain a supernatant, and then the supernatant was dialyzed using a dialysis bag with a molecular weight cutoff of 2000D for 24 h to obtain a dialysate, and the dialysate was dried in a forced air drying oven at 55° C. for 24 h to obtain CQDs-alcoholized stannous octoate.
[0073] This embodiment also provides a method for preparing a highly active organic metal catalyst dibutyltin oleate, comprising the following steps:
[0074] Step 1: Weigh 7.5 parts of distilled coconut oil fatty acid and 1 part of octanoic acid and stir and mix them for 30 minutes under a stirring power of 0.5 kw to obtain a mixed acid solution, weigh 6 parts of dibutyltin chloride and add them to the mixed acid solution, heat the temperature to 40°C, keep it for 40 minutes and stir to obtain a mixed reaction solution, then slowly drip a 2.5 mol / L sodium hydroxide solution into the mixed reaction solution, increase the temperature to 90°C and adjust the pH to 6.5, react for 1 hour, then add 0.8 parts of CQDs-alcoholized stannous octoate thereto, continue to react for 5 hours, then naturally cool to room temperature, stand for stratification to remove the aqueous phase, and obtain an organic phase mixture;
[0075] Step 2: drying the organic phase mixture obtained in step 1 in a vacuum drying oven at 55° C. for 24 hours to obtain a crude material of dibutyltin oleate, a highly active organic metal catalyst;
[0076] Step 3: The crude material of the highly active organic metal catalyst dibutyl tin oleate obtained in step 2 is subjected to reduced pressure filtration at a pressure of 5 kPa for 2 hours using a vacuum pump to obtain the highly active organic metal catalyst dibutyl tin oleate.
[0077] Example 3: The highly active organic metal catalyst dibutyltin oleate provided in this example is prepared from the following raw materials in parts by weight: 6 parts of dibutyltin chloride, 7.5 parts of distilled coconut oil fatty acid, 1 part of octanoic acid and 0.8 parts of CQDs-alcoholized stannous octoate.
[0078] The raw materials for preparing CQDs-alcoholized stannous octoate include citric acid, urea, alcoholized stannous octoate and acetone, the raw materials for preparing alcoholized stannous octoate include stannous octoate, glycidyl alcohol and toluene, and the raw materials for preparing stannous octoate include anhydrous stannous chloride, triethanolamine, anhydrous ethanol, isooctanoic acid and n-hexane.
[0079] The preparation method of stannous octoate comprises the following steps:
[0080] (a) Weigh 3 parts of anhydrous stannous chloride and add them to 10 parts of anhydrous ethanol, and perform ultrasonic treatment for 30 minutes under an ultrasonic power of 0.3 kW to obtain a mixed solution I, weigh 1.8 parts of triethanolamine and slowly add them to the mixed solution I, heat the temperature to 60°C in an oil bath and keep stirring under a power of 0.3 kW for 2 hours to obtain a stannous octoate intermediate, weigh 5 parts of isooctanoic acid and add them to the stannous octoate intermediate, heat for a second time for 6 hours with stirring, and then naturally cool to room temperature to obtain a stannous octoate mixed solution;
[0081] (b) washing the stannous octoate mixed solution obtained in step (a), collecting the organic phase and drying it in a vacuum drying oven for 24 hours at a drying temperature of 70° C. to obtain a stannous octoate crude solution;
[0082] (c) weighing 1.2 parts of n-hexane and heating it to 70° C., then slowly adding the crude stannous octoate solution obtained in step (b) into the n-hexane, stirring for 30 minutes at a stirring power of 0.5 kW, and then filtering to remove impurities to obtain a mixed solution II;
[0083] (d) treating the mixed solution II obtained in step (c) in an ice-water bath at 4°C to obtain a crystalline mixture, then filtering the crystalline mixture with n-hexane as the filtrate to obtain crystals, repeating the filtration operation on the crystals three times to obtain crystals, collecting the crystals and drying them for 24 hours at a drying temperature of 55°C to obtain stannous octoate.
[0084] The preparation method of alcoholized stannous octoate comprises the following steps:
[0085] (i) Weigh 10 parts of toluene and add it into a three-necked flask reactor, then weigh 3 parts of stannous octoate and add it into the toluene, and stir for 30 minutes at a stirring power of 0.3 kW to obtain a homogeneous liquid;
[0086] (ii) weighing 7.5 parts of glycidyl alcohol and slowly adding it to the homogenous solution obtained in step (i), heating the temperature to 140° C. and maintaining it for 4 hours, stirring it at a stirring power of 0.5 kW, and then naturally cooling it to room temperature to obtain a reaction homogenous solution;
[0087] (iii) adding the reaction mixture obtained in step (ii) into a separator, adding water for washing, removing the aqueous phase after the solution is separated into layers, repeating the washing operation three times to obtain an organic phase, and drying and removing water from the organic phase to obtain a composite phase;
[0088] (vi) using a rotary evaporator to distill the composite phase obtained in step (iii) to remove toluene, the distillation speed is 150 r / min, the distillation pressure is 10 kPa, and the distillation temperature is 80° C. to obtain an alcoholized stannous octoate precursor, and then purifying the alcoholized stannous octoate precursor, the purification pressure is 0.8 kPa, and the purification temperature is 220° C. to obtain alcoholized stannous octoate.
[0089] The preparation method of CQDs-alcoholized stannous octoate comprises the following steps:
[0090] (1) Weigh 6 parts of citric acid and 2 parts of urea, add them to 40 parts of deionized water, stir for 30 minutes at a stirring power of 0.3 kW, and obtain solution A; weigh 1 part of stannous octoate alcohol, add it to 3 parts of acetone, and stir for 30 minutes at a stirring power of 0.3 kW, and obtain solution B;
[0091] (2) Slowly adding the solution B obtained in step (1) into the solution A, ultrasonically treating for 25 min at an ultrasonic power of 15 kHz, and stirring for 30 min at a stirring power of 0.5 kW to obtain a mixed solution, adding the mixed solution into a reactor, heating the temperature from room temperature to 120° C. at a heating rate of 5° C. / min for 15 h, and then naturally cooling to room temperature to obtain a CQDs-alcoholized stannous octoate precursor;
[0092] (3) The CQDs-alcoholized stannous octoate precursor obtained in step (2) was centrifuged at a centrifugal speed of 10000 r / min for 20 min to obtain a supernatant, and then the supernatant was dialyzed using a dialysis bag with a molecular weight cutoff of 2500D for 24 h to obtain a dialysate, and the dialysate was dried in a forced air drying oven at 55° C. for 24 h to obtain CQDs-alcoholized stannous octoate.
[0093] This embodiment also provides a method for preparing a highly active organic metal catalyst dibutyltin oleate, comprising the following steps:
[0094] Step 1: Weigh 9 parts of distilled coconut oil fatty acid and 1 part of octanoic acid and stir and mix them for 30 minutes under a stirring power of 0.5 kW to obtain a mixed acid solution, weigh 8 parts of dibutyltin chloride and add them to the mixed acid solution, heat the temperature to 40°C, maintain for 45 minutes and stir to obtain a mixed reaction solution, then slowly drip a 2.5 mol / L sodium hydroxide solution into the mixed reaction solution, increase the temperature to 110°C and adjust the pH to 8.5, react for 1 hour, then add 1 part of CQDs-alcoholized stannous octoate thereto, continue to react for 5 hours, then naturally cool to room temperature, stand for stratification to remove the aqueous phase, and obtain an organic phase mixture;
[0095] Step 2: drying the organic phase mixture obtained in step 1 in a vacuum drying oven at 55° C. for 24 hours to obtain a crude material of dibutyltin oleate, a highly active organic metal catalyst;
[0096] Step 3: The crude material of the highly active organic metal catalyst dibutyl tin oleate obtained in step 2 is subjected to reduced pressure filtration at a pressure of 8 kPa for 2 hours using a vacuum pump to obtain the highly active organic metal catalyst dibutyl tin oleate.
[0097] Comparative Example:
[0098] The difference between Comparative Example 1 and Example 2 is that CQDs-alcoholized stannous octoate is not added, and the rest is the same as Example 2;
[0099] The difference between Comparative Example 2 and Example 2 is that alcoholized stannous octoate is not added, and the prepared single CQDs are directly added to the preparation process of the highly active organic metal catalyst dibutyltin oleate, and the rest is the same as Example 2;
[0100] The difference between Comparative Example 3 and Example 2 is that no CQDs are added, and the prepared alcoholized stannous octoate is directly added to the preparation process of the highly active organic metal catalyst dibutyl tin oleate, and the rest is the same as Example 2;
[0101] The difference between Comparative Example 4 and Example 2 is that no CQDs are added, and stannous octoate is not alcoholized, and the prepared stannous octoate is directly added to the preparation process of the highly active organic metal catalyst dibutyl tin vegetable oil acid, and the rest is the same as Example 2;
[0102] The high-activity organic metal catalyst dibutyl tin oleate prepared in the embodiment was used for the synthesis and conversion test analysis of silicone rubber:
[0103] The base polymer, crosslinking agent, catalyst, filler, coupling agent and dehydrating agent were weighed according to the mass fractions of 50, 4, 0.07, 80, 0.8 and 4. The base polymer and dehydrating agent were first added to the reactor and stirred evenly. Then the temperature was heated to 110°C for 5 hours, and then the temperature was lowered to 15°C. The crosslinking agent, catalyst, filler and coupling agent were added in sequence. The temperature was maintained and stirred for 5 minutes and 15 minutes. 5 mL of the reaction solution was collected and the viscosity of the reaction solution was measured. Figure 2 The standard adhesion curve tested under different concentration conditions is prepared according to the standard solution of silicone glue, where the unit of adhesion y is mPa·s, and the unit of concentration x is %; the base polymer is α,ω-dihydroxypolydimethylsiloxane, the cross-linking agent is methyl tributylidene oxime silane, the catalyst is a highly active organic metal catalyst dibutyl tin vegetable oil, the filler is nano calcium carbonate-55% and heavy calcium carbonate-45%, the coupling agent is KH-550 silane coupling agent, and the dehydrating agent is dimethyl silicone oil.
[0104] Table 1 shows the concentration test of the high-activity organic metal catalyst dibutyl tin oleate prepared in the example for silicone glue:
[0105]
[0106] It can be seen from Table 1 that when the reaction time is 15 minutes, the concentrations of silicone glue are 91.88%, 98.77% and 96.74% respectively. From the data, it can be seen that the prepared high-activity organic metal catalyst dibutyl tin vegetable oil acid shows high catalytic activity and stability, and the catalyst does not decompose during the reaction.
[0107] Table 2 shows the concentration test of the highly active organic metal catalyst dibutyl tin oleate prepared in the comparative example for silicone glue:
[0108]
[0109] The test conditions of the comparative example are the same as those of the embodiment. It can be seen from Table 2 that when no CQDs-alcoholized stannous octoate or alcoholized stannous octoate is added, although a higher catalytic activity is exhibited during the reaction, the reaction time is significantly prolonged compared to the high-activity organometallic catalyst dibutyltin vegetable oil acid prepared in the embodiment.
[0110] Obviously, the above comparative examples and embodiments are only a part of comparative examples and embodiments of the present invention, and they and the comparative examples and embodiments based on such references are all within the scope of protection of the present invention.
[0111] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
[0112] The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.
Claims
1. Highly active organic metal catalyst dibutyl tin oleate, characterized in that: It is prepared from the following raw materials in parts by weight: 4-8 parts of dibutyltin chloride, 6-9 parts of distilled coconut oil fatty acid, 1 part of octanoic acid and 0.5-1 part of CQDs-alcoholized stannous octoate; The raw materials for preparing the CQDs-alcoholized stannous octoate include citric acid, urea, alcoholized stannous octoate and acetone; The preparation method of CQDs-alcoholized stannous octoate comprises the following steps: (1) Weighing citric acid, urea, alcoholized stannous octoate and acetone in a mass ratio of 3-6:1-2:0.5-1:3, adding citric acid and urea to deionized water, stirring to obtain solution A, adding alcoholized stannous octoate to acetone, stirring to obtain solution B; (2) slowly adding the solution B obtained in step (1) into the solution A, ultrasonicating and stirring to obtain a mixed solution, heating the mixed solution, and naturally cooling it to room temperature to obtain a CQDs-alcoholized stannous octoate precursor; (3) The CQDs-alcoholized stannous octoate precursor obtained in step (2) is centrifuged to obtain a supernatant, and then the supernatant is dialyzed to obtain a dialysate, and the dialysate is dried to obtain CQDs-alcoholized stannous octoate.
2. The highly active organic metal catalyst dibutyl tin oleate according to claim 1, characterized in that: The mass ratio of citric acid, urea and deionized water in step (1) is 3-6:1-2:40, the ultrasonic power in step (2) is 5-15kHz, the heating temperature is 80-120°C, and the dialysis treatment in step (3) uses a dialysis bag with a molecular weight cutoff of 1500D-2500D.
3. The highly active organic metal catalyst dibutyltin oleate according to claim 1, characterized in that: The raw materials for preparing the alcoholized stannous octoate include stannous octoate, glycidyl alcohol and toluene; The preparation method of alcoholized stannous octoate comprises the following steps: (i) weighing stannous octoate, glycidyl alcohol and toluene in a mass ratio of 1-3:3.5-7.5:10, adding stannous octoate to toluene, stirring to obtain a homogeneous solution; (ii) slowly adding the glycidyl alcohol weighed in step (i) to the homogenous solution obtained in step (i), heating and stirring, and naturally cooling to room temperature to obtain a reaction homogenous solution; (iii) washing the reaction mixture obtained in step (ii) with deionized water, separating the solution into layers, removing the aqueous phase, repeating the washing operation to obtain an organic phase, and drying the organic phase to obtain a composite phase; (vi) distilling the composite phase obtained in step (iii) to remove toluene to obtain alcoholated stannous octoate precursor, and then purifying the alcoholated stannous octoate precursor to obtain alcoholated stannous octoate.
4. The highly active organic metal catalyst dibutyltin oleate according to claim 3, characterized in that: The heating temperature in step (ii) is 110-140°C, the distillation pressure in step (vi) is 5-10 kPa, the distillation temperature is 60-80°C, the purification pressure is 0.3-0.8 kPa, and the purification temperature is 180-220°C.
5. The highly active organic metal catalyst dibutyltin oleate according to claim 3, characterized in that: The raw materials for preparing the stannous octoate include anhydrous stannous chloride, triethanolamine, anhydrous ethanol, isooctanoic acid and n-hexane; The preparation method of stannous octoate comprises the following steps: (a) Weigh anhydrous stannous chloride, triethanolamine, anhydrous ethanol, isooctanoic acid and n-hexane in a mass ratio of 1-3:1.2-1.8:10:3-5:0.7-1.2; (b) adding the anhydrous stannous chloride weighed in step (a) to anhydrous ethanol, ultrasonically treating to obtain a mixed solution I, slowly adding the triethanolamine weighed in step (a) to the mixed solution I, heating and stirring to obtain a stannous octoate intermediate, then adding the isooctanoic acid weighed in step (a) to the stannous octoate intermediate, heating and stirring for a second time, and naturally cooling to room temperature to obtain a stannous octoate mixed solution; (c) washing the stannous octoate mixed solution obtained in step (b), collecting and drying the organic phase to obtain a stannous octoate crude solution; (d) heating the n-hexane weighed in step (a) while maintaining the temperature, then slowly adding the crude stannous octoate solution obtained in step (c) into the n-hexane, stirring, and then filtering to remove impurities, thereby obtaining a mixed solution II; (e) treating the mixed solution II obtained in step (d) in an ice-water bath to obtain a crystalline mixture, then filtering the crystalline mixture to obtain crystals, repeating the filtration operation on the crystals to obtain crystals, collecting and drying the crystals to obtain stannous octoate.
6. The highly active organic metal catalyst dibutyltin oleate according to claim 5, characterized in that: The heating temperature in step (b) is 40-60° C., the temperature in step (d) is 50-70° C., and the filtrate used in the filtration in step (e) is n-hexane.
7. A method for preparing the highly active organic metal catalyst dibutyltin oleate according to any one of claims 1 to 6, characterized in that: The steps include: Step 1: Weigh dibutyltin chloride, distilled coconut oil fatty acid, octanoic acid, and CQDs-alcoholized stannous octoate; Step 2: The distilled coconut oil fatty acid and octanoic acid weighed in step 1 are stirred and mixed to obtain a mixed acid solution, the dibutyltin chloride weighed in step 1 is added to the mixed acid solution, heated and stirred to obtain a mixed reaction solution, the temperature is increased and a sodium hydroxide solution is added dropwise to adjust the pH to react, and then CQDs-alcoholized stannous octoate is added thereto, the reaction is continued, the mixture is naturally cooled to room temperature, the aqueous phase is removed by standing and stratification, and an organic phase mixture is obtained; Step 3: drying the organic phase mixture obtained in step 2 to obtain a crude material of dibutyltin oleate, a highly active organic metal catalyst; Step 4: subjecting the crude material of the highly active organic metal catalyst dibutyl tin oleate obtained in step 3 to vacuum filtration to obtain the highly active organic metal catalyst dibutyl tin oleate.
8. The method for preparing the highly active organic metal catalyst dibutyltin oleate according to claim 7, characterized in that: The sodium hydroxide solution in step 2 has a concentration of 2.5 mol / L, a heating temperature of 35-45° C., a heating temperature of 60-110° C., and a pH range of 5-8.5.