CN112574025B - Synthesis method of stannous ricinoleate - Google Patents
Synthesis method of stannous ricinoleate Download PDFInfo
- Publication number
- CN112574025B CN112574025B CN201910926847.5A CN201910926847A CN112574025B CN 112574025 B CN112574025 B CN 112574025B CN 201910926847 A CN201910926847 A CN 201910926847A CN 112574025 B CN112574025 B CN 112574025B
- Authority
- CN
- China
- Prior art keywords
- reaction
- solvent
- stannous
- ricinoleate
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
Abstract
The invention discloses a synthesis method of stannous ricinoleate. The invention adopts two steps of reaction, wherein in the first step of reaction, ricinoleic acid is used as a raw material, and a solvent A is used for reacting with sodium hydroxide, sodium methoxide or sodium methoxide methanol solution under certain reaction conditions to synthesize sodium ricinoleate; a second step of reaction, namely reacting sodium ricinoleate serving as a raw material with anhydrous stannous chloride, hydrated stannous chloride or stannous sulfate under a heating condition by using a solvent B to synthesize stannous ricinoleate; wherein, the solvent A is an alcohol solvent; the solvent B is an alcohol solvent, an aromatic solvent or a polar aprotic solvent; the solvent A and the solvent B can be recovered by a distillation method and recycled. The method has the advantages of low raw material cost, simple and convenient operation, less three-waste discharge, high reaction efficiency and the like.
Description
Technical Field
The invention relates to a synthesis method of stannous ricinoleate, belonging to the technical field of chemical organic synthesis.
Background
The polyurethane foam material has the advantages of light weight, good heat insulation performance, excellent flexibility, wear resistance, heat resistance, elasticity, mechanical property, high strength and the like, and is widely applied to the fields of refrigerators, freezers, building insulation boards, pipeline insulation, logistics cold chains, modern automobile manufacturing and the like. Because of the wide variety of requirements for making polyurethane foams, catalysts are used in many cases. Besides accelerating the reaction, the catalyst can also control the relative speed of parallel reaction, influence the fluidity of reaction mixture, the physical and mechanical properties of finished products, technological parameters and the like.
Stannous octoate and dibutyltin dilaurate are the most widely used polyurethane foaming catalysts at present and are mainstream fine chemical products in the market. However, stannous octoate can generate harmful gas of 2-ethylhexanoic acid in the process of catalyzing polyurethane foaming, and causes concern of people due to potential risks of harming human bodies, especially fetal health. Dibutyltin dilaurate is gradually eliminated or used in a limited manner because of its toxicity to human health and ecological environment.
In recent years, regulations have been issued by the national environmental protection agency, and emission of Volatile Organic Compounds (VOC) from materials such as polyurethane foams, paints, and decorative building materials has been strictly regulated. Therefore, in order to meet the requirements of polyurethane foam suppliers, it is urgent to develop a novel environment-friendly polyurethane foaming catalyst system to replace the traditional stannous octoate or dibutyltin dilaurate catalyst system.
Stannous ricinoleate (CAS number 71828-07-4), also called stannic ricinoleate, is a reddish brown viscous oily liquid, insoluble in water and alcohol, and easily soluble in organic solvents such as dichloromethane and ethyl acetate. The stannous ricinoleate is an organic tin catalyst, can replace stannous octoate, stannous isooctanoate or dibutyltin dilaurate, and is used for preparing various polyurethane foam products. Stannous ricinoleate and Amine LD are used cooperatively to form a non-volatile and green catalytic system. In 2012, germany won the patent application of high schmidt ltd (CN102952249A), disclosing a polyurethane catalytic system based on tin salt of ricinoleic acid and its use, where the catalytic system is superior to the traditional polyurethane catalytic system. Although stannous ricinoleate is a known compound, the preparation method thereof is rarely reported. The U.S. Pat. No. 4,3222 (US4532262) relates to a method for preparing organic stannous compound C2-C18, which is carried out by a one-pot two-step method, wherein sodium salt is prepared from acid and sodium hydroxide, and then the sodium salt and hydrated stannous chloride react in a water solvent at 75-85 ℃ to obtain the organic stannous compound. Although the process can effectively prepare organic acid stannous, a large amount of wastewater containing stannum, weak acid and high salt is generated in the production process. The direct discharge of wastewater causes serious environmental pollution, and if the wastewater is treated, the operation is more complicated and the treatment cost is higher.
In 2003, U.S. Kruppon corporation (CN1452626A) disclosed a method for preparing stannous carboxylate by direct reaction of tin powder or tin beads with carboxylic acid, and attempted preparation of stannous octoate, stannous oleate, stannic stearate, and stannous cocoate, all with good yield and [ Sn 1452626A ]2+]And (4) content. Although the process provides an economical and simple tin carboxylate production method without tin halide, the process still has the defects of harsh reaction conditions, high energy consumption, potential safety hazard and the like。
Ricinoleic acid is a C18 linear unsaturated fatty acid, contains active groups of carbon-carbon double bonds and hydroxyl groups, and is weak in acidity, more in reaction sites and poor in reaction specificity, so that the method can be used for effectively preparing stannous carboxylate, but is not suitable for preparing stannous ricinoleate. The method of the U.S. Pat. No. 4,32262 (US4532262) is adopted to prepare the stannous ricinoleate, and the yield and the content of the stannous are low. This is because ricinoleic acid is weak in acidity and has a slow reaction rate with stannous chloride, but stannous chloride rapidly reacts with water to form stannous hydroxide or stannous oxide under heating (80-100 ℃), which results in that stannous chloride cannot sufficiently react with ricinoleic acid. Moreover, the formation of stannous oxide also results in intramolecular esterification of ricinoleic acid, producing a significant amount of ricinoleic acid lactone as a by-product (see comparative example 1).
Since simple substance tin or tin oxide can catalyze the esterification reaction, ricinoleic acid and simple substance tin or tin oxide are reacted at high temperature by adopting the method of U.S. Klupyton corporation (CN1452626A), only ricinoleic acid lactone by-product is obtained, and almost no stannous ricinoleate is generated (see comparative examples 2 and 3).
Disclosure of Invention
The invention starts from the structural characteristics and chemical properties of ricinoleic acid, and aims to provide a method for synthesizing stannous ricinoleate, which has the advantages of low raw material cost, simple and convenient operation, high reaction efficiency, less side reaction, less three-waste discharge, high product purity, simplicity, convenience and high efficiency.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention adopts two steps of reaction, the first step of reaction: ricinoleic acid is used as a raw material, and reacts with alkali in a solvent A under room temperature or heating condition to synthesize sodium ricinoleate; wherein the alkali is sodium hydroxide, solid sodium methoxide or sodium methoxide methanol solution; the second step of reaction: taking sodium ricinoleate synthesized in the first step as a raw material, and reacting the sodium ricinoleate with a stannous compound in a solvent B under the heating condition to synthesize stannous ricinoleate; wherein, the solvent A is an alcohol solvent; the solvent B is an alcohol solvent, an aromatic solvent or a polar aprotic solvent; the synthetic route is shown as the following reaction formula:
according to the above technical scheme, preferably, the alcohol solvent in the first step is methanol, ethanol or isopropanol.
According to the above technical scheme, the molar ratio of ricinoleic acid to sodium hydroxide or sodium methoxide in the first step is preferably 1:1 to 1:1.5, and preferably 1:1.00 to 1: 1.03.
According to the technical scheme, preferably, the concentration of the sodium methoxide methanol solution in the first step is 20-30% by mass.
According to the above technical scheme, the ricinoleic acid in the first step is preferably reacted at a molar concentration of 0.2-2.0M, preferably 1.0M.
According to the above technical scheme, the reaction temperature of the first step reaction is preferably 30-82 ℃, and preferably 30-64 ℃.
According to the above technical scheme, the reaction time of the first step reaction is preferably 2-4 hours.
According to the above technical scheme, preferably, the stannous compound in the second step is anhydrous stannous chloride, hydrated stannous chloride or stannous sulfate.
According to the above technical solution, preferably, the alcohol solvent in the second step is methanol, ethanol or isopropanol, the aromatic solvent is toluene or o-xylene, and the polar aprotic solvent is acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide or hexamethylphosphoramide.
According to the above technical scheme, the molar ratio of the sodium ricinoleate to the stannous compound in the second step reaction is preferably 2.0:1-2.2: 1.
According to the above technical solution, the molar concentration of the sodium ricinoleate in the second reaction step is preferably 0.2-2.0M, preferably 0.5-0.8M.
According to the above technical scheme, the reaction temperature of the second step reaction is preferably 30-120 ℃, and preferably 64-100 ℃.
According to the above technical scheme, the reaction time of the second step reaction is preferably 1 to 10 hours, preferably 2 to 5 hours.
According to the above technical scheme, preferably, when the first-step reaction solvent a and the second-step reaction solvent B are methanol, ethanol or isopropanol, and the solvent a is the same as the solvent B, the sodium ricinoleate prepared by the first-step reaction can be directly used for preparing stannous ricinoleate without separation and distillation for recovering the solvent.
According to the above technical scheme, preferably, in the second step of the reaction, an antioxidant is added or not added, wherein the addition amount of the antioxidant is 1-2 mol% of the theoretical yield of stannous ricinoleate.
According to the above technical scheme, the antioxidant can be p-methyl phenol or p-tert-butyl phenol in a preferable case.
According to the above technical scheme, preferably, the solvent A and the solvent B can be recovered by a distillation method and recycled.
In a word, the method utilizes ricinoleic acid, sodium hydroxide, solid sodium methoxide or a methanol solution of sodium methoxide, anhydrous stannous chloride, hydrated stannous chloride or stannous sulfate in a stannous compound as raw materials, adopts two-step reaction to synthesize the ricinoleic acid stannous, and has the advantages of low raw material cost, simple and convenient operation, high reaction efficiency, less side reaction, less three-waste emission, high product purity, capability of recycling and reusing the solvent A and the solvent B by a distillation method, and the like, wherein the yield of the ricinoleic acid stannous is 90.0-99.3%, the content of divalent tin is 12.8-14.0%, and the content of total tin is 13.0-15.0%.
Detailed Description
The invention uses ricinoleic acid, sodium hydroxide, solid sodium methoxide or methanol solution of sodium methoxide, anhydrous stannous chloride, hydrated stannous chloride or stannous sulfate in stannous compound as raw materials, and adopts two-step reaction to synthesize the ricinoleic acid stannous. The first step of reaction takes ricinoleic acid as raw material, in solvent A, under room temperature or heating, the ricinoleic acid reacts with sodium hydroxide, solid sodium methoxide or methanol solution of sodium methoxide to synthesize sodium ricinoleate, and the second step of reaction takes sodium ricinoleate as raw material, in solvent B, under heating, the sodium ricinoleate reacts with anhydrous stannous chloride, hydrated stannous chloride or stannous sulfate in stannous compound to synthesize stannous ricinoleate; wherein, the solvent A is methanol, ethanol or isopropanol in alcohol solvent; the solvent B is methanol, ethanol or isopropanol in an alcohol solvent, or toluene or o-xylene in an aromatic solvent, or acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or hexamethylphosphoramide in a polar aprotic solvent; the solvent A and the solvent B can be recovered by a distillation method and recycled; the following examples are provided to aid in the further understanding of the present invention, but the invention is not limited thereto.
Example 1
The first step of reaction, preparing sodium ricinoleate: ricinoleic acid (107.4g,0.36mol), sodium hydroxide (14.4g,0.36mol) was added to ethanol (360mL) at a molar concentration of ricinoleic acid of 1.0M. The reaction was stirred at 64 ℃ for 4 hours. After the reaction is finished, the system is a clear system. Collecting reaction liquid, and carrying out post-treatment operation: the solvent (which can be recycled) is recovered by reduced pressure distillation, and then the solvent is dried in vacuum by an oil pump and ground to obtain a light yellow powdery solid which is the target product sodium ricinoleate (114.3g) with the yield of 99.0%.
Example 2
The procedure of the reaction was the same as in example 1, except that the reaction solvent was methanol (360 mL). The reaction was stopped and the desired product, sodium ricinoleate (114.4g, yield 99.1%) was obtained by work-up.
Example 3
The reaction procedure was the same as in example 1, except that the reaction solvent was isopropanol (360 mL). The reaction was stopped and the desired product, sodium ricinoleate, was obtained by work-up (114.1g, yield 98.9%).
Example 4
The procedure was the same as in example 1, except that the reaction solvent was isopropanol (360mL) and the reaction temperature was 82 ℃. The reaction was stopped and the desired product, sodium ricinoleate (114.2g, yield 99.0%) was obtained by workup.
Example 5
The procedure is as in example 1, except that sodium hydroxide is replaced by solid sodium methoxide (19.4g, 0.36 mol). The reaction was stopped and the desired product, sodium ricinoleate (114.4g, yield 99.1%) was obtained by work-up.
Example 6
The reaction procedure and operation were the same as in example 1, except that sodium hydroxide was replaced with sodium methoxide methanol solution (194.5g, 0.36mol) (20% by mass concentration) in example 1. The reaction was stopped and the desired product, sodium ricinoleate, was obtained by work-up (110.7g, yield 95.9%).
Example 7
The reaction procedure was the same as in example 1, except that sodium hydroxide was replaced with a sodium methoxide methanol solution (38.8g, 0.36mol) (30% by mass concentration) in the same manner as in example 1. The reaction was stopped and the desired product, sodium ricinoleate, was obtained by work-up (111.8g, yield 96.9%).
Example 8
The reaction procedure and operation were the same as in example 1, except that the molar ratio of sodium ricinoleate to sodium hydroxide in the reaction was 1:1.5, and the charge amount of sodium hydroxide (21.6g,0.54mol) was used in the reaction, as in example 1. The reaction was stopped and the desired product, sodium ricinoleate (113.1g, yield 98.0%) was obtained by workup.
Example 9
The reaction procedure and operation were the same as in example 1, except that the molar ratio of sodium ricinoleate to sodium hydroxide in the reaction was 1:1.03, and the charge amount of sodium hydroxide (14.8g,0.37mol) was used in the reaction, as in example 1. The reaction was stopped and the desired product, sodium ricinoleate, was obtained by work-up (114.1g, yield 98.9%).
Example 10
The reaction procedure was the same as in example 1, except that the molar concentration of ricinoleic acid in the reaction was 0.2M and the amount of ethanol charged (1800mL) was used in the reaction, as in example 1. The reaction was stopped and the desired product, sodium ricinoleate, was obtained by workup (114.2g, yield 99.0%).
Example 11
The reaction procedure and operation were the same as in example 1, except that the molar concentration of ricinoleic acid in the reaction was 2.0M and the amount of ethanol charged (180mL) was used in the reaction, as in example 1. The reaction was stopped and the desired product, sodium ricinoleate (114.3g, yield 99.0%) was obtained by workup.
Example 12
The procedure and operation were the same as in example 1 except that the reaction temperature in the reaction was 30 ℃. The reaction was stopped and the desired product, sodium ricinoleate, was obtained by work-up (92.5g, yield 80.2%).
Example 13
The procedure of the reaction was the same as in example 1, except that the reaction temperature in the reaction was 78 ℃ as in example 1. The reaction was stopped and the desired product, sodium ricinoleate (113.8g, yield 98.6%) was obtained by workup.
Example 14
The procedure and operation were the same as in example 1, except that the reaction temperature in the reaction was 50 ℃. The reaction was stopped and the desired product, sodium ricinoleate (114.4g, yield 99.1%) was obtained by work-up.
Example 15
The reaction procedure and operation were the same as in example 1, except that the reaction time in the reaction was 2 hours, as in example 1. The reaction was stopped and the desired product, sodium ricinoleate (112.9g, 97.8% yield) was obtained by workup.
Example 16
And (3) performing a second-step reaction to prepare stannous ricinoleate: in a three-necked flask equipped with a reflux condenser, sodium ricinoleate (100.0g,0.312mol) (sodium ricinoleate is selected from any one of examples 1 to 15), anhydrous stannous chloride (29.6g,0.156mol) and o-xylene (624mL), sodium ricinoleate molar concentration is 0.5M, and the reaction system is heated to 110 ℃ under nitrogen with stirring for 5 hours. After the reaction is finished, carrying out post-treatment operation: the solvent was recovered by filtration and distillation (which could be recycled) to give a translucent or transparent viscous reddish brown oil, the target product stannous ricinoleate (110.2g, 99.0% yield), 13.8% stannous (stannous) and 14.2% total tin (stannous).
Example 17
The reaction procedure and operation were the same as in example 16, except that the stannous compound in the reaction was stannous chloride hydrate (35.2g,0.156mol), in contrast to example 16. The reaction was stopped, and the target product stannous ricinoleate (109.1g, yield 98.0%), stannous 13.4% and total tin 14.0% were obtained by post-treatment.
Example 18
The reaction procedure and operation were the same as in example 16, except that the stannous compound in the reaction was stannous sulfate (33.5g,0.156 mol). The reaction was stopped and the target product stannous ricinoleate (110.2g, yield 99.0%), stannous content 13.8% and total tin content 14.2% were obtained by post-treatment.
Example 19
The procedure of the reaction was the same as in example 16, except that the reaction solvent was methanol (624mL) and the reaction temperature was 64 ℃. The reaction was stopped and the target product stannous ricinoleate (108.5g, yield 97.5%), stannous content 13.0% and total tin content 13.8% were obtained by post-treatment.
Example 20
The procedure of the reaction was the same as in example 16, except that the reaction solvent was ethanol (624mL) and the reaction temperature was 78 ℃. The reaction was stopped and the target product stannous ricinoleate (109.4g, yield 98.3%), stannous content 13.3% and total tin content 13.8% were obtained by post-treatment.
Example 21
The procedure of the reaction was the same as in example 16, except that the reaction solvent was isopropyl alcohol (624mL) and the reaction temperature was 82 ℃. The reaction was stopped and the target product stannous ricinoleate (109.8g, yield 98.6%), stannous content 13.4% and total tin content 14.0% were obtained by post-treatment.
Example 22
The procedure of the reaction was the same as in example 16, except that the reaction solvent was acetonitrile (624mL) and the reaction temperature was 82 ℃. The reaction was stopped and the target product stannous ricinoleate (109.9g, yield 98.7%), stannous content 13.3% and total tin content 14.1% were obtained by post-treatment.
Example 23
The procedure is as in example 16, except that the reaction solvent is toluene (624 mL). The reaction was stopped and the target product stannous ricinoleate (110.0g, yield 98.8%), stannous content 13.6% and total tin content 14.3% were obtained by post-treatment.
Example 24
The procedure is as in example 16, except that the reaction solvent is N, N-dimethylformamide (624 mL). The reaction was stopped and the target product stannous ricinoleate (109.6g, yield 98.5%), stannous content 13.8% and total tin content 14.2% were obtained by post-treatment.
Example 25
The procedure of the reaction was the same as in example 16, except that the reaction solvent was dimethyl sulfoxide (624 mL). The reaction was stopped and the target product stannous ricinoleate (109.8g, yield 98.6%), stannous content 13.5% and total tin content 14.5% were obtained by post-treatment.
Example 26
The procedure was as in example 16 except that the reaction solvent was hexamethylphosphoramide (624 mL). The reaction was stopped, and the target product stannous ricinoleate (106.8g, yield 96.0%), stannous 13.1% and total tin 13.8% were obtained by post-treatment.
Example 27
The procedure and operation were the same as in example 16, except that the reaction temperature was 100 ℃ in example 16. The reaction was stopped and the target product stannous ricinoleate (110.3g, yield 99.1%), stannous content 13.7% and total tin content 14.2% were obtained by post-treatment.
Example 28
The reaction procedure and operation were the same as in example 16, except that the molar ratio of sodium ricinoleate to anhydrous stannous chloride was 2.2:1, as compared to example 16. The reaction was stopped and the target product stannous ricinoleate (110.5g, yield 99.3%), stannous content 13.4% and total tin content 14.0% were obtained by post-treatment.
Example 29
The reaction procedure was the same as that of example 16, except that the molar concentration of sodium ricinoleate was 2.0M, o-xylene (156 mL). The reaction was stopped, and the target product stannous ricinoleate (109.8g, yield 98.6%), stannous 13.6% and total tin 14.4% were obtained by post-treatment.
Example 30
The procedure was as in example 16 except that sodium ricinoleate was used in a molar concentration of 0.2M, o-xylene (1560 mL). The reaction was stopped and the target product stannous ricinoleate (107.8g, yield 96.8%), stannous content 13.2% and total tin content 14.0% were obtained by post-treatment.
Example 31
The reaction procedure was the same as that of example 16, except that the molar concentration of sodium ricinoleate was 0.8M, o-xylene (390 mL). The reaction was stopped and the target product stannous ricinoleate (110.1g, yield 98.9%), stannous content 13.7% and total tin content 14.3% were obtained by post-treatment.
Example 32
The procedure and operation were the same as in example 16, except that the reaction temperature was 30 ℃ in example 16. The reaction was stopped, and the target product stannous ricinoleate (96.3g, yield 86.5%), stannous 2.6% and total tin 3.4% were obtained by post-treatment.
Example 33
The procedure and operation were the same as in example 16, except that the reaction temperature was 120 ℃ in example 16. The reaction was stopped and the target product stannous ricinoleate (107.0g, yield 96.1%), stannous content 12.8% and total tin content 13.9% were obtained by post-treatment.
Example 34
The procedure of the reaction was the same as in example 16, except that the reaction was carried out for 1 hour, unlike in example 16. The reaction was stopped and the target product stannous ricinoleate (99.1g, yield 89.0%) was obtained by post-treatment with a stannous content of 10.1% and a total tin content of 11.6%.
Example 35
The procedure of the reaction was the same as in example 16, except that the reaction was carried out for 2 hours, unlike in example 16. The reaction was stopped and the target product stannous ricinoleate (109.1g, yield 98.0%), stannous content 13.0%, total tin content 13.8% was obtained by post-treatment.
Example 36
The procedure was as in example 16 except that the reaction was carried out for 10 hours, unlike example 16. The reaction was stopped and the target product stannous ricinoleate (110.2g, yield 99.0%), stannous content 13.7% and total tin content 14.3% were obtained by post-treatment.
Example 37
The procedure is as in example 16, except that p-methylphenol (0.17g,1 mol%) is added as an antioxidant in the reaction, as in example 16. The reaction was stopped and the target product stannous ricinoleate (110.2g, yield 99.0%), stannous content 13.7% and total tin content 14.3% were obtained by post-treatment.
Example 38
The procedure is as in example 16, except that p-tert-butylphenol (0.23g,1 mol%) as an antioxidant is added. The reaction was stopped and the target product stannous ricinoleate (110.1g, yield 98.9%), stannous content 13.5% and total tin content 14.0% were obtained by post-treatment.
Example 39
The procedure is as in example 16, except that p-tert-butylphenol (0.47g,2 mol%) as an antioxidant is added. The reaction was stopped and the target product stannous ricinoleate (110.3g, yield 99.1%), stannous content 13.8% and total tin content 14.2% were obtained by post-treatment.
Example 40
The two-step reaction is carried out continuously to prepare the stannous ricinoleate: ricinoleic acid (107.4g,0.36mol) was dissolved in ethanol (540mL) to form a ricinoleic acid solution. Sodium hydroxide (14.4g,0.36mol) was dissolved in ethanol (180mL) to form a base: ethanol solution of sodium hydroxide. An ethanol solution of sodium hydroxide was added dropwise to a ricinoleic acid solution at 78 ℃ with stirring. The reaction was continued for 5 hours at 78 ℃ with stirring. To the above system, anhydrous stannous chloride (34.1g,0.18mol) was added. The reaction system was reacted at 78 ℃ for 5 hours. After the reaction is finished, carrying out post-treatment operation: filtration and distillation gave a translucent or transparent viscous reddish brown oil as stannous ricinoleate (123.9g, 96.5% yield), stannous 13.1% and total tin 13.8%.
EXAMPLE 41
The procedure and operation were the same as in example 40, except that the reaction solvent was methanol (720 mL in total) and the reaction temperature was 64 ℃. The reaction was stopped and the target product stannous ricinoleate (123.3g, yield 96.0%), stannous content 13.0% and total tin content 13.7% was obtained by post-treatment.
Example 42
The procedure of the reaction was the same as in example 40, except that the reaction solvent was isopropyl alcohol (720 mL in total) and the reaction temperature was 82 ℃. The reaction was stopped, and the target product stannous ricinoleate (124.8g, yield 97.2%), stannous content 13.2%, total tin content 14.0% was obtained by post-treatment.
Example 43
The reaction procedure was the same as in example 1, except that the reaction solvent was the ethanol solvent (320mL) recovered in example 1, and was different from example 1. The reaction was stopped and the desired product, sodium ricinoleate, was obtained by work-up (114.0g, yield 98.8%).
Example 44
The procedure was as in example 16 except that the reaction solvent was the o-xylene solvent (600mL) recovered in example 16. The reaction was stopped and the target product stannous ricinoleate (109.8g, yield 98.6%), stannous content 13.4% and total tin content 14.2% were obtained by post-treatment.
Example 45
The procedure of the reaction was the same as in example 20, except that the reaction solvent was ethanol (600mL) recovered in example 20. The reaction was stopped and the target product stannous ricinoleate (109.5g, yield 98.4%), stannous content 13.5% and total tin content 14.2% were obtained by post-treatment.
Example 46
The procedure and operation were the same as in example 25, except that the reaction solvent was dimethyl sulfoxide (600mL) recovered in example 25. The reaction was stopped and the target product stannous ricinoleate (109.7g, yield 98.6%), stannous content 13.5% and total tin content 14.5% were obtained by post-treatment.
Example 47
The procedure of the reaction was the same as in example 40, except that the reaction solvent was ethanol (700 mL in total) recovered in example 40. The reaction was stopped and the target product stannous ricinoleate (124.2g, yield 96.7%), stannous content 13.2% and total tin content 13.8% were obtained by post-treatment.
Comparative example 1
Ricinoleic acid (107.4g,0.36mol) was added to water (60mL) and was either insoluble or slightly soluble in water and stirred to form an emulsion. To the above system was added a solution of sodium hydroxide (14.4g,0.36 mol)/water (60mL) under stirring, and the addition was completed over about 20 minutes. After the addition, the reaction system was heated to 75 ℃ and stirred for 30 minutes. Stannous chloride hydrate (40.6g,0.18mol) was added to the system with stirring at 75 ℃. The reaction system was reacted at 75 ℃ for 30 minutes. After the reaction is finished, carrying out post-treatment operation: the solution was separated, washed and distilled to give a translucent or transparent viscous reddish brown oil which was found by NMR to be a mixture of stannous ricinoleate, ricinoleic acid and ricinoleic lactone (114.8g, yield 89.4%), stannous 8.7% and total tin 9.8%.
Comparative example 2
Ricinoleic acid (107.4g,0.36mol), tin beads (21.4g,0.18mol), 4-tert-butylcatechol (0.5g) and dipropylene glycol (0.5g) were added to a 250 ml reactor and mixed. The reaction was mixed with stirring and heated to 60 ℃. After stirring at 60 ℃ for 10 minutes, air was blown into the bottom of the reaction solution, and the reaction system was heated to 165 ℃. After 4 hours of reaction at 165 ℃, nitrogen was introduced into the reaction system to displace air, and the reaction was continued for 1.5 hours. After the reaction, the reaction system was subjected to vacuum to remove low-boiling substances, and filtered to obtain a reddish brown viscous oil (98.7g), which was detected by NMR to be ricinoleic acid lactone only.
Comparative example 3
Ricinoleic acid (107.4g,0.36mol), stannous oxide (24.2g,0.18mol) were added to and mixed in a 250 ml reactor under nitrogen. The reaction was mixed with stirring and heated to 140 ℃. Stirred at 140 ℃ for 5 hours. After the reaction, the reaction system was subjected to vacuum to remove low boiling point substances, and filtered to obtain a reddish brown viscous oil (99.2g), which was detected by NMR to be ricinoleic acid lactone only.
Claims (10)
1. A method for synthesizing stannous ricinoleate is characterized by comprising the following steps: adopts two-step reaction, and adopts the following steps of reaction,
the first step of reaction: ricinoleic acid is used as a raw material, and is reacted with sodium hydroxide, sodium methoxide or sodium methoxide methanol solution in a solvent A under the room temperature or the heating condition to synthesize sodium ricinoleate;
the second step of reaction: taking sodium ricinoleate synthesized by the first step as a raw material, and reacting the sodium ricinoleate with a stannous compound in a solvent B under the heating condition to synthesize stannous ricinoleate;
wherein, the solvent A is an alcohol solvent; the solvent B is an alcohol solvent, an aromatic solvent or a polar aprotic solvent;
in the second step of reaction, the alcohol solvent is methanol, ethanol or isopropanol, the aromatic solvent is toluene or o-xylene, and the polar aprotic solvent is acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or hexamethylphosphoramide;
in the second step of reaction, when an alcohol solvent is used, the reaction temperature is 64-82 ℃; when a polar aprotic solvent is used, the reaction temperature is 82-110 ℃; when the aromatic solvent is used, the reaction temperature is 100 ℃ to 120 ℃.
2. The method of synthesis according to claim 1, characterized in that: in the first step of reaction, the alcohol solvent is methanol, ethanol or isopropanol; the molar ratio of the ricinoleic acid to the sodium hydroxide or the sodium methoxide is 1:1-1: 1.5; the mass percentage concentration of the sodium methoxide methanol solution is 20-30%; the molar concentration of the ricinoleic acid is 0.2-2.0M; the reaction temperature is 30-82 ℃; the reaction time is 2-4 hours.
3. The method of synthesis according to claim 1, characterized in that: in the second step of reaction, the stannous compound is anhydrous stannous chloride, hydrated stannous chloride or stannous sulfate.
4. A synthesis method according to claim 1 or 3, characterized in that: in the second step of reaction, the molar ratio of the sodium ricinoleate to the stannous compound is 2.0:1-2.2: 1; the molar concentration of the sodium ricinoleate is 0.2-2.0M, and the reaction time is 1-10 hours.
5. The method of synthesis according to claim 1, characterized in that: when the solvent A in the first step reaction and the solvent B in the second step reaction are methanol, ethanol or isopropanol, and the solvent A is the same as the solvent B, the sodium ricinoleate prepared in the first step reaction can be directly used for preparing stannous ricinoleate without separation.
6. The method of synthesis according to claim 1, characterized in that: in the second step of reaction, an antioxidant is required to be added or not added, wherein the antioxidant is a phenol derivative, and the addition amount of the antioxidant is 1-2 mol% of the theoretical yield of the stannous ricinoleate.
7. The method of synthesis according to claim 6, characterized in that: the phenol derivative is p-methyl phenol or p-tert-butyl phenol.
8. The method of synthesis according to claim 1, characterized in that: and recovering the solvent A and the solvent B by a distillation method, and recycling.
9. The method of synthesis according to claim 2, characterized in that: in the first step, the molar ratio of the ricinoleic acid to the sodium hydroxide or the sodium methoxide is 1:1.00-1: 1.03; the molar concentration of the ricinoleic acid is 1.0M; the reaction temperature is 30-64 ℃.
10. The method of synthesis according to claim 4, characterized in that: the second step, the molar concentration of the sodium ricinoleate is 0.5-0.8M; the reaction time is 2-5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910926847.5A CN112574025B (en) | 2019-09-27 | 2019-09-27 | Synthesis method of stannous ricinoleate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910926847.5A CN112574025B (en) | 2019-09-27 | 2019-09-27 | Synthesis method of stannous ricinoleate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112574025A CN112574025A (en) | 2021-03-30 |
| CN112574025B true CN112574025B (en) | 2022-07-08 |
Family
ID=75110534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910926847.5A Active CN112574025B (en) | 2019-09-27 | 2019-09-27 | Synthesis method of stannous ricinoleate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112574025B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702637A (en) * | 2022-04-01 | 2022-07-05 | 国科广化韶关新材料研究院 | Preparation method and application of environment-friendly polyurethane catalyst |
| CN114702382A (en) * | 2022-05-05 | 2022-07-05 | 河间市熙泰化工产品有限公司 | Processing production process of zinc ricinoleate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532262A (en) * | 1984-03-21 | 1985-07-30 | Gloskey Carl R | Process for the preparation of urethane foam |
| CN102971259A (en) * | 2010-06-29 | 2013-03-13 | 皇家飞利浦电子股份有限公司 | Synthesis and use of iron oleate |
| CN103012109A (en) * | 2012-12-12 | 2013-04-03 | 南京工业大学 | Preparation method for metal oleate |
| CN103601632A (en) * | 2013-11-28 | 2014-02-26 | 山东省高密市友和助剂有限公司 | Synthetic method for stannous stearate |
| CN105598462A (en) * | 2015-10-23 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Preparation method of micro-nano Sn and application of micro-nano Sn |
-
2019
- 2019-09-27 CN CN201910926847.5A patent/CN112574025B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532262A (en) * | 1984-03-21 | 1985-07-30 | Gloskey Carl R | Process for the preparation of urethane foam |
| CN102971259A (en) * | 2010-06-29 | 2013-03-13 | 皇家飞利浦电子股份有限公司 | Synthesis and use of iron oleate |
| CN103012109A (en) * | 2012-12-12 | 2013-04-03 | 南京工业大学 | Preparation method for metal oleate |
| CN103601632A (en) * | 2013-11-28 | 2014-02-26 | 山东省高密市友和助剂有限公司 | Synthetic method for stannous stearate |
| CN105598462A (en) * | 2015-10-23 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Preparation method of micro-nano Sn and application of micro-nano Sn |
Non-Patent Citations (1)
| Title |
|---|
| Facile Synthesis of Tin(IV) Carboxylates;Ikuko Wakeshima et al.;《Chemistry Letters》;19851231(第3期);第395-396页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112574025A (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4440937A (en) | Cyclic carbonic acid derivatives | |
| JP6505917B6 (en) | Process for preparing cyclic oligomers, and cyclic oligomers obtained thereby | |
| CN112574025B (en) | Synthesis method of stannous ricinoleate | |
| US3579591A (en) | 4,4'-bis-(hydroxyarloxy)-phenylsulfone | |
| JP5596258B2 (en) | Calixarene dimer compound and method for producing the same | |
| US9850340B2 (en) | Apopinene as a biorenewable monomer for ring-opening metathesis polymerization | |
| CN1696096A (en) | Method for synthesizing Idebenone | |
| CN109535120B (en) | Preparation method of 7-substituted-3, 4,4, 7-tetrahydrocyclobutane coumarin-5-ketone | |
| JP4596680B2 (en) | Bisthiophenol fluorenes and method for producing the same | |
| CN113024375B (en) | Preparation method of trans, trans-4-alkyl-4' -amyl-3 (E) alkene-bicyclohexane liquid crystal monomer | |
| JP4140792B2 (en) | Chlorosulfonic acid derivatives of cyclic phenol sulfides and process for producing the same | |
| JPS5822108B2 (en) | Method for producing aromatic diurethane | |
| CN108264449B (en) | Preparation method of 2, 6-diethyl-4-methylphenol | |
| CN110563568B (en) | Preparation method of trifluoroacetylacetone | |
| CN113004144B (en) | Synthesis method of perfluorobisphenol A | |
| KR101627406B1 (en) | Novel neodymium compound and catalysts for polymerizing diene comprising the same | |
| CN110028660B (en) | Method for preparing aliphatic copolymerized carbonate polyol by using stannous chloride complex as catalyst | |
| JP2003055280A (en) | Method for producing condensed ring-containing compound | |
| WO2017191282A1 (en) | New adipate-type compounds and a process of preparing it | |
| JP4304758B2 (en) | Method for producing para-acetoxystyrene | |
| JPH09227503A (en) | Production of poly(phenol sulfide) | |
| US2555599A (en) | 1-hydroxy-6-alkoxy-4-methylhexadiene-2, 4- and carboxylic acid esters thereof | |
| CN115279725A (en) | Efficient and selective route for the synthesis of alkyl 2-benzoyl benzoates | |
| CN115028521A (en) | Synthesis method of 2, 2-dichloro-3, 3, 3-trifluoropropionaldehyde | |
| US5808133A (en) | Alicyclic bifunctional compounds and processes for their preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230303 Address after: 201507 building 3, No. 88, pingye Road, Caojing Town, Jinshan District, Shanghai Patentee after: Shanghai Mahou New Material Technology Co.,Ltd. Address before: No. 457, Zhongshan Road, Shahekou District, Dalian City, Liaoning Province Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right |