CN112759522A - High-carbon-chain alkane diamine terephthalate and preparation method and application thereof - Google Patents
High-carbon-chain alkane diamine terephthalate and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of preparation of high-carbon-chain alkane diamine terephthalate, and discloses high-carbon-chain alkane diamine terephthalate and a preparation method and application thereof. The preparation method of the high carbon chain alkane diamine terephthalate comprises the following stepsComprising the steps of 1) reacting a compound of formula COOH- (CH) under amidation reaction conditions2)nReacting high carbon chain alkane diacid shown as-COOH with an ammonia-containing compound to obtain CONH2‑(CH2)n‑CONH2The high carbon chain diamide shown; 2) under alkaline conditions, in the presence of water and sodium hypochlorite and/or sodium hypobromite, reacting a compound of formula CONH2‑(CH2)n‑CONH2The high carbon chain diamide undergoes rearrangement degradation reaction to obtain the formula NH2‑(CH2)m‑NH2The high carbon chain alkane diamine is shown in the formula, wherein n is 9-13, and m is 9-13; in the presence of a solvent, carrying out a salt forming reaction on high carbon chain alkane diamine shown in a formula (3) and terephthalic acid. The method is safe, convenient, simple and feasible, and is particularly suitable for industrial preparation of the high-carbon-chain alkane diamine terephthalate.
Description
Technical Field
The invention relates to the field of preparation of high-carbon-chain alkane diamine terephthalate, and particularly relates to high-carbon-chain alkane diamine terephthalate and a preparation method and application thereof.
Background
Polyamide, also known as nylon (PA), is a nitrogen-containing heterochain polymer containing polyamide characteristic groups (-NHCO-) in the main chain, and is called five general-purpose engineering plastics together with polycarbonate, polyformaldehyde, polybutylene terephthalate and polyphenyl ether. The polyamide has excellent characteristics of wear resistance, impact resistance, fatigue resistance, corrosion resistance and the like, and with the continuous emergence of high value-added modified products, the polyamide engineering plastic is widely applied to automobiles, electronics, electrics and transportation industries, and typical products comprise parts such as pump impellers, bearings, automobile electrical appliances and instruments and the like.
The high carbon chain nylon variety has the advantages of low density, low water absorption, low temperature resistance, wear resistance, impact resistance and the like. Therefore, downstream chemicals of high-carbon chain alkane diamine have no way to put new requirements on the quality of the high-carbon chain alkane diamine, and the quality of the product is required to be higher.
The preparation of long-chain diamines, including nonanediamine, and particularly represented by decanediamine, has continued the original synthesis: the long-chain dinitrile is prepared by taking long-chain dibasic acid as a raw material and carrying out high-temperature ammoniation and dehydration, and the catalytic production is carried out by selecting metal alloys such as Raney nickel and the like as catalysts and selecting an intermittent hydrogenation mode. The traditional synthetic method has the advantages of mature process control and convenient operation. In addition, as for nonanediamine, there is also reported an industrial process for producing nonanediamine by aminating and hydrogenating nonanediamine as a raw material in the presence of ammonia using a metal such as nickel as a catalyst.
However, the above-mentioned conventional processes involve dangerous processes such as high temperature, high pressure, hydrogenation, etc., and have problems in terms of safety, and the conventional processes have problems in that the processes are complicated.
Disclosure of Invention
The invention aims to overcome the problems of safety and complex process in the prior art and provide a safe, convenient, simple and feasible preparation method of high-carbon-chain alkane diamine terephthalate.
In order to achieve the above objects, the present invention provides, in a first aspect, a method for preparing a high carbon chain alkanediamine terephthalate, comprising the steps of,
1) under the amidation reaction condition, reacting the high-carbon-chain alkane diacid shown in the formula (1) with an ammonia-containing compound to obtain high-carbon-chain diamide shown in the formula (2);
2) under alkaline conditions, in the presence of water and sodium hypochlorite and/or sodium hypobromite, carrying out rearrangement degradation reaction on the high-carbon-chain diamide shown in the formula (2) to obtain high-carbon-chain alkane diamine shown in the formula (3);
3) in the presence of an organic solvent, high carbon chain alkane diamine shown in a formula (3) and terephthalic acid are subjected to contact reaction,
COOH-(CH2)n-COOH formula (1) CONH2-(CH2)n-CONH2Formula (2)
NH2-(CH2)m-NH2Formula (3)
In formulae (1) to (3), n is 11 to 13, and m is 9 to 13.
Preferably, the product of step 2) is used directly for the reaction in step 3).
Preferably, the ammonia-containing compound is ammonia and/or urea.
Preferably, the molar ratio of the high carbon chain alkane diacid shown in the formula (1) to the ammonia-containing compound is 1: 1-10.
Preferably, the amidation reaction conditions include: the reaction temperature is 150 ℃ and 280 ℃, and the reaction time is 3-18 hours.
Preferably, the molar ratio of the high carbon chain diamide represented by the formula (2) to the sodium hypochlorite and/or the sodium hypobromite is 1: 1.8-3.5.
Preferably, step 2) is carried out in the presence of a solvent.
Preferably, the weight ratio of the high carbon chain diamide represented by the formula (2) to the solvent is 1: 5-15.
Preferably, the solvent is one or more of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol.
Preferably, in step 2), the pH of the reaction system is above 9.
Preferably, the high carbon chain alkanediamine represented by formula (3) is nonanediamine, decanediamine, undecanediamine, dodecanediamine, or tridecanediamine.
Preferably, in the step 3), the molar ratio of the high carbon chain alkane diamine represented by the formula (3) to the terephthalic acid is 1: 0.95-1.05.
Preferably, the organic solvent is one or more of methanol, ethanol and isopropanol.
According to a second aspect of the present invention, there is provided a high carbon chain alkanediamine terephthalate prepared by the process of the present invention.
According to a third aspect of the present invention, there is provided a use of the high carbon chain alkanediamine terephthalate prepared by the process of the present invention for preparing polyamides.
Through the technical scheme, the invention can provide a safe, convenient, simple and feasible preparation method of the high-carbon-chain alkane diamine salt.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The preparation method of the high carbon chain alkane diamine terephthalate provided by the invention comprises the following steps,
1) under the amidation reaction condition, reacting the high-carbon-chain alkane diacid shown in the formula (1) with an ammonia-containing compound to obtain high-carbon-chain diamide shown in the formula (2);
2) under alkaline conditions, in the presence of water and sodium hypochlorite and/or sodium hypobromite, carrying out rearrangement degradation reaction on the high-carbon-chain diamide shown in the formula (2) to obtain high-carbon-chain alkane diamine shown in the formula (3);
3) in the presence of an organic solvent, high carbon chain alkane diamine shown in a formula (3) and terephthalic acid are subjected to contact reaction,
COOH-(CH2)n-COOH formula (1) CONH2-(CH2)n-CONH2Formula (2)
NH2-(CH2)m-NH2Formula (3)
In formulae (1) to (3), n is 9 to 13, and m is 9 to 13.
According to the invention, n in formulae (1) to (3) may be 9, 10, 11, 12 or 13.
According to the invention, m in formulae (1) to (3) may be 9, 10, 11, 12 or 13.
According to the invention, step 1) is carried out under amidation reaction conditions, and the high carbon chain diamide shown in formula (2) is obtained by carrying out amidation reaction on the high carbon chain alkane diacid shown in formula (1) and an ammonia-containing compound.
In the invention, the high-carbon-chain alkane diacid shown in the formula (1) and the ammonia-containing compound are subjected to amidation reaction, so that the method has the advantages of simple operation, less by-products and high yield, and can be directly used for the next reaction without post-treatment after the reaction is finished, thereby greatly simplifying the process.
According to the present invention, the ammonia-containing compound may be various ammonia-containing compounds generally used in the art for carboxylic acid amidation, for example, one or more of ammonia gas, urea, and the like, preferably ammonia gas and/or urea, and more preferably ammonia gas, since there are advantages in that the reaction is simple and the operation is convenient by using ammonia gas.
According to the present invention, the high carbon chain alkanedioic acid represented by formula (1) can be obtained commercially or synthesized according to a conventional method in the art.
Examples of the high carbon chain alkanedioic acid include: undecyl diacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid or pentadecanedioic acid.
According to the present invention, preferably, the molar ratio of the high carbon chain alkanedioic acid represented by the formula (1) to the ammonia-containing compound is 1: 1-10, more preferably 1: 2-10, more preferably 1: 2.5 to 5, more preferably 1: 3-4.
Preferably, the amidation reaction conditions include: the reaction temperature is 150 ℃ and 280 ℃, and the reaction time is 3-18 hours; more preferably, the amidation reaction conditions include: the reaction temperature is 160-240 ℃, and the reaction time is 10-16 hours.
According to the invention, after step 1) is completed, only cooling to room temperature is required to obtain the high carbon chain diamide represented by formula (2), and the obtained high carbon chain diamide represented by formula (2) can be directly used in step 2). For example, the reaction of step 2) can be carried out directly in the reaction vessel of step 1) to thereby realize the above-mentioned two-step reaction in one reactor, which is extremely useful industrially.
According to the invention, in the step 2), the high carbon chain diamide shown in the formula (2) is subjected to rearrangement degradation reaction in the presence of water and sodium hypochlorite and/or sodium hypobromite under alkaline conditions to obtain the high carbon chain alkane diamine shown in the formula (3). In the step, when the high-carbon-chain diamide shown in the formula (2) and the alkali solution of sodium hypochlorite and/or sodium hypobromite act, an isonitrile acid ester is generated by rearrangement reaction, and then the high-carbon-chain alkane diamine shown in the formula (3) is prepared by hydrolysis. That is, in step 2), the rearrangement reaction and the hydrolysis reaction (degradation reaction) are also carried out in the same reaction vessel, whereby the industrial scale can be greatly simplified and is extremely useful industrially.
In the present invention, water is usually used in excess, and for example, the weight ratio of the high carbon chain diamide represented by the formula (2) to water may be 1: 5-100, preferably 1: 6-50, more preferably 1:6 to 15, more preferably 1:6 to 10, still more preferably 1: 7-8.
In addition, water may be used in the form of an aqueous sodium hypochlorite solution or an aqueous sodium hypobromite solution.
Preferably, the molar ratio of the high carbon chain diamide represented by the formula (2) to sodium hypochlorite and/or sodium hypobromite is 1: 1.8-3.5, more preferably 1: 2.6-3.2.
The sodium hypochlorite or sodium hypobromite can be obtained commercially or can be prepared in the reaction field. When the catalyst is prepared in the reaction site, chlorine and sodium hydroxide solution can be used as raw materials for preparing in the site, and bromine and sodium hydroxide can also be used as raw materials for preparing in the site.
Further, it is preferable that the step 2) is carried out in the presence of a solvent, which is used to facilitate the reaction, and the amount of the solvent to be used may be specifically selected according to the amount of the high carbon chain diamide represented by the formula (2), for example, the weight ratio of the high carbon chain diamide represented by the formula (2) to the solvent may be 1: 5-15, preferably 1: 8-10.
Preferably, the solvent is one or more of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol; more preferably dioxane, and the use of dioxane has the excellent effects of simple operation and good reaction selectivity.
Preferably, in step 2), the pH of the reaction system is 9 or more, more preferably 10 to 12.
According to the present invention, the pH of the reaction system can be adjusted by adding a base as required, for example, an inorganic base and an organic base can be added, and preferably an inorganic base is added. The inorganic base may be, for example, sodium hydroxide, potassium hydroxide or the like, and sodium hydroxide is preferred.
According to the invention, step 2) can be carried out at a temperature of between 5 and 80 ℃, more preferably in the following manner: dropwise adding an aqueous solution containing sodium hypochlorite and/or sodium hypobromite to a solution containing a high carbon chain diamide represented by the formula (2) at 0 to 10 ℃ and maintaining at that temperature for 0.5 to 3 hours; then heating to 20-35 ℃ and reacting for 1-5 hours at the temperature; then, the temperature is raised to 60 to 75 ℃ and the reaction is carried out at the temperature for 0.5 to 5 hours.
According to the present invention, after the reaction of step 2), a high purity product can be obtained only by layering the reaction solution and concentrating the organic phase, and the post-treatment step is extremely simple and industrially extremely useful.
According to the present invention, it is preferable that the high carbon chain alkanediamine represented by the formula (3) is nonanediamine, decanediamine, undecanediamine, dodecanediamine or tridecanediamine.
According to the invention, in step 3), the molar ratio of the high carbon chain alkanediamine represented by formula (3) to terephthalic acid is 1: 0.95-1.05;
preferably, the organic solvent is one or more of ethanol, methanol and isopropanol.
According to the invention, the product obtained in step 2) can be used directly in step 3) for the reaction.
According to a second aspect of the present invention, there is provided a high carbon chain alkanediamine terephthalate prepared by the process of the present invention.
According to a third aspect of the present invention, there is provided a use of the high carbon chain alkanediamine terephthalate prepared by the process of the present invention for preparing polyamides.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples. The reagents used in the following examples are all commercially available unless otherwise specified.
Example 1
This example illustrates the preparation of 1, 9-nonanediamine terephthalate
1) Synthesis of 1, 11-undecanediamide
Adding 100 g of undecanedioic acid into a 250ml three-mouth reaction bottle, heating to a melting point of a raw material to melt the raw material, introducing ammonia (the introduction amount of the ammonia is about 3mol relative to 1 mol of undecanedioic acid), keeping the reaction temperature at 160 ℃ first, reacting the raw material and the ammonia to form a salt, then raising the reaction temperature to 220 ℃, increasing the reaction dehydration amount, raising the final reaction temperature to 260 ℃, keeping the flow rate of the ammonia to ensure that the reaction dehydration can be smoothly carried out, keeping the dehydration reaction time at 12 hours, cooling after the reaction is finished, crystallizing to form a solid, and drying to obtain 1, 11-undecanedioic amide: 93 g (94% yield) was used in the next step.
2) Synthesis of 1, 9-nonanediamine
Adding 1, 11-undecane diamide (10 g) and 190ml of dioxane into a reaction bottle, stirring and cooling with an ice bath, after the temperature of the reaction solution is reduced to about 10 ℃, dropwise adding a mixed solution of sodium hydroxide and sodium hypochlorite (the molar ratio of the sodium hydroxide to the sodium hypochlorite is 2: 1, and the amount of the sodium hypochlorite is 3 moles relative to 1 mole of 1, 11-undecane diamide), controlling the dropwise adding speed to maintain the reaction temperature at about 10 ℃, and controlling the pH value of the reaction system at 10-12. After the dropwise addition, the reaction is carried out for 1 hour under the condition of heat preservation, then the ice bath is removed to allow the temperature to naturally return to the original temperature, the reaction is carried out for 3 hours under the condition of controlling the temperature to be 30 ℃, then the reaction is carried out for 1.5 hours under the condition of heat preservation after the temperature is heated to 75 ℃. After cooling, an organic layer is separated out, the organic layer is concentrated to remove dioxane, a small amount of solid is removed by filtration, the filtrate is continuously concentrated to obtain 6.7g of a light yellow oily product, the obtained product is 1, 9-nonanediamine according to nuclear magnetic data, and in addition, the purity is 95 percent and the yield is 91 percent by gas phase quantitative sample injection detection.
Nuclear magnetic data:1H NMR(MeOD,ppm)δ2.65,(t,18Hz,CΗ2,4Η),1.4-1.6(b,CH2,4H),1.3-1.4(b,CH2,10H).
3) synthesis of 1, 9-nonanediamine terephthalate
In a reaction flask, 5.8 g of the 1, 9-nonanediamine obtained in the above step was added, followed by 32 ml of ethanol. Heating the reaction solution to 55-60 ℃ under stirring to obtain light-colored transparent liquid, adding 6.1 g of terephthalic acid in batches, and detecting the content of nonanediamine in the liquid by chromatography. After the reaction was completed, the temperature was reduced to room temperature, and 8.83 g of nonanediamine terephthalate was collected by filtration, yield: 82.6% (based on terephthalic acid), purity: 99.1 percent.
Example 2
This example illustrates the preparation of 1, 9-nonanediamine
1) Synthesis of 1, 11-undecanediamide
Adding 100 g of undecanedioic acid into a 250ml three-mouth reaction bottle, heating to a melting point of the raw material to melt the raw material, introducing ammonia (the introduction amount of the ammonia is about 3.5 mol relative to 1 mol of undecanedioic acid), keeping the reaction temperature at 180 ℃ first, reacting the raw material and the ammonia to form a salt, then raising the reaction temperature to 200 ℃, raising the final reaction temperature to 220 ℃ along with the increase of the reaction dehydration amount, keeping the flow rate of the ammonia to smoothly take out the reaction dehydration, keeping the dehydration reaction time at 10 hours, cooling after the reaction is finished, crystallizing to form a solid, and drying to obtain the 1, 11-undecanedioic amide (the yield is 95%) which can be directly used in the next step.
2) Synthesis of 1, 9-nonanediamine
Adding 1, 11-undecane diamide (10 g) and 190ml of dioxane into a reaction bottle, stirring and cooling with an ice bath, after the temperature of the reaction solution is reduced to about 10 ℃, dropwise adding a mixed solution of sodium hydroxide and sodium hypochlorite (the molar ratio of the sodium hydroxide to the sodium hypochlorite is 2: 1, and the amount of the sodium hypochlorite is 2.6 moles relative to 1 mole of 1, 11-undecane diamide), controlling the dropwise adding speed to maintain the reaction temperature at about 13 ℃, and controlling the pH value of the reaction system to be 10-11. After the dropwise addition, the reaction is carried out for 1 hour under the condition of heat preservation, then the ice bath is removed to allow the ice bath to naturally return to the temperature, the temperature is controlled at 25 ℃ for reaction for 3 hours, then the reaction is carried out for 1 hour under the condition of heat preservation after the temperature is controlled to 75 ℃. After cooling, an organic layer is separated out, the organic layer is concentrated to remove dioxane, a small amount of solid is removed by filtration, the filtrate is continuously concentrated to obtain 6.6g of a light yellow oily product, the obtained product is 1, 9-nonanediamine according to nuclear magnetic data, in addition, the gas phase quantitative sample injection detection shows that the purity is 95 percent, and the yield is 89.5 percent.
3) Synthesis of 1, 9-nonanediamine terephthalate
In a reaction flask, 3.30 g of the 1, 9-nonanediamine obtained in the above step was added, followed by 20 ml of ethanol. The reaction solution was heated to 55-60 ℃ with stirring to obtain a light-colored transparent liquid, 3.46 g of terephthalic acid was added in portions, and the content of nonanediamine in the liquid was detected by chromatography. After the reaction was completed, the temperature was reduced to room temperature, and 5.73 g of 1, 9-nonanediamine terephthalate was collected by filtration, with the yield: 85% (based on terephthalic acid), purity: 99.2 percent.
Example 3
This example illustrates the preparation of 1, 9-nonanediamine
1) Synthesis of 1, 11-undecanediamide
Adding 100 g of undecanedioic acid into a 250ml three-mouth reaction bottle, heating to the melting point of the raw material to melt the raw material, introducing ammonia (the introduction amount of the ammonia is 4mol relative to 1 mol of undecanedioic acid), keeping the reaction temperature at 160 ℃ first, reacting the raw material and the ammonia to form salt, then raising the reaction temperature to 190 ℃, raising the final reaction temperature to 210 ℃ along with the increase of the reaction dehydration amount, keeping the flow rate of the ammonia to smoothly take out the reaction dehydration, keeping the dehydration reaction time at 13 hours, cooling after the reaction is finished, crystallizing to form solid, and drying to obtain the 1, 11-undecanedioic amide (the yield is 94%) which can be directly used in the next step.
2) Synthesis of 1, 9-nonanediamine
Adding 1, 11-undecane diamide (10 g) and 190ml of dioxane into a reaction bottle, stirring and cooling with an ice bath, after the temperature of the reaction solution is reduced to about 10 ℃, dropwise adding a mixed solution of sodium hydroxide and sodium hypochlorite (the molar ratio of the sodium hydroxide to the sodium hypochlorite is 2: 1, and the amount of the sodium hypochlorite is 3.2 moles relative to 1 mole of 1, 11-undecane diamide), controlling the dropwise adding speed to maintain the reaction temperature at about 10 ℃, and controlling the pH value of the reaction system to be 10-11. After the dropwise addition, the reaction is carried out for 1 hour under the condition of heat preservation, then the ice bath is removed to allow the ice bath to naturally return to the temperature, the temperature is controlled at 30 ℃ for reaction for 1 hour, then the reaction is carried out for 1 hour under the condition of heat preservation after the temperature is controlled to 75 ℃. After cooling, an organic layer is separated, the organic layer is concentrated to remove the solvent, a small amount of solid is removed by filtration, the filtrate is continuously concentrated to obtain 6.8g of a light yellow oily product, the obtained product is 1, 9-nonanediamine according to nuclear magnetic data, in addition, the gas phase quantitative sample injection detection shows that the purity is 94.5 percent, and the yield is 92 percent.
3) Synthesis of 1, 9-nonanediamine terephthalate
In a reaction flask, 4.95 g of 1, 9-nonanediamine obtained in the above step was added, followed by 30 ml of ethanol. The reaction solution was heated to 55-60 ℃ with stirring to obtain a light-colored transparent liquid, 5.53 g of terephthalic acid was added in portions, and the content of nonanediamine in the liquid was detected by chromatography. After the reaction was completed, the temperature was reduced to room temperature, and 9.0 g of 1, 9-nonanediamine terephthalate was collected by filtration, with the yield: 86% (based on terephthalic acid), purity: 99.1 percent.
Example 4
1) Synthesis of 1, 12-dodecanediamide
The procedure is as for the preparation of example 1, except that the starting undecanedioic acid is replaced by dodecanedioic acid in the same molar amount to give 1, 12-dodecanediamide: 90 g (91% yield) was used directly in the next step.
2) Synthesis of 1, 10-sebacic diamine
10 g (0.044mol) of dodecanedioic acid diamide are introduced into a reaction flask, followed by addition of 190ml (2.23mol) of 1, 4-dioxane with stirring and cooling in an ice bath. A mixed solution of 11.2g (0.28mol) of sodium hydroxide and 160g (0.135mol) of sodium hypochlorite was prepared. The temperature of the reaction solution is reduced to about 10 ℃, the mixed solution of sodium hydroxide and sodium hypochlorite is dripped, and the reaction temperature is controlled to about 10 ℃. The reaction solution is a turbid solid-liquid mixture. After the dropwise addition, the reaction is carried out for 30 minutes under the condition of heat preservation, and the temperature is naturally returned. Controlling the temperature to be about 30 ℃ and reacting for 3 hours; heating to 75 ℃ by using an oil bath, stirring for about 10 minutes for reaction, clarifying the reaction solution, carrying out heat preservation for 1 hour, layering at about 60-65 ℃, concentrating an organic layer to obtain a viscous solid-liquid mixture, removing a small amount of solid, concentrating the filtrate to obtain 5.7g of light yellow oily matter, and obtaining the product 1, 10-sebacic diamine according to nuclear magnetic data, wherein the purity is 98% and the yield is 74% by gas phase quantitative sample injection detection.
Nuclear magnetic data:1H NMR(CDCl3,ppm)δ2.65(t,18Hz,CH2,4Η),1.4-1.6(b,CH2,4H),1.25-1.3(b,CH2,8H),1.15-1.25(b,CH2,4H).
3) synthesis of 1, 10-sebacic diamine terephthalate
In a reaction flask, 4.30 g of the 1, 10-decanediamine obtained in the above step was added, followed by 30 ml of ethanol. Heating the reaction solution to 55-60 ℃ under stirring to obtain light-colored transparent liquid, adding 4.50 g of terephthalic acid in batches, and detecting the content of nonanediamine in the liquid by chromatography. After the reaction was completed, the temperature was reduced to room temperature, 6.85 g of 1, 10-heptanediamine terephthalate was collected by filtration, yield: 78.0% (by terephthalic acid); purity: 99.2 percent.
Example 5
1) Synthesis of 1, 11-undecanediamide
The preparation was carried out according to the procedure of step 1) of example 1.
2) Synthesis of 1, 9-nonanediamine
700 g (3.27mol) of undecanedioic acid diamide were placed in a 30L reactor, followed by 13.3Kg (155.93mol) of 1, 4-dioxane which was stirred, jacketed and cooled by brine. A mixed solution of 788g (19.7mol) of sodium hydroxide and 11.2Kg (9.45mol) of sodium hypochlorite was prepared. The temperature of the reaction solution is reduced to about 10 ℃, the mixed solution of sodium hydroxide and sodium hypochlorite is dripped, and the reaction temperature is controlled to about 10 ℃. The reaction solution is a turbid solid-liquid mixture. After the dropwise addition, the reaction was carried out for 30 minutes while maintaining the temperature. The temperature is controlled to be about 30 ℃ and the reaction is carried out for 3 hours. Heating the mixture to 75 ℃ by using a jacket, stirring the mixture for reaction for about 10 minutes, clarifying the reaction solution, carrying out heat preservation reaction for 1 hour, then layering the mixture at about 60-65 ℃, concentrating an organic layer, removing a small amount of solid, concentrating the filtrate to obtain 465g of light yellow oily matter, obtaining the product 1, 9-nonanediamine through nuclear magnetic data, and detecting the product by gas-phase quantitative sample injection with the purity of 96 percent and the yield of 88.3 percent.
3) Synthesis of 1, 9-nonanediamine terephthalate
Into a reaction flask, 330.0 g of the 1, 9-nonanediamine obtained in the above step was charged, followed by 2000 ml of ethanol. The reaction solution was heated to 55-60 ℃ with stirring to obtain a light-colored transparent liquid, 346.0 g of terephthalic acid was added in portions, and the content of nonanediamine in the liquid was detected by chromatography. After the reaction was completed, the temperature was reduced to room temperature, and 580 g of 1, 9-nonanediamine terephthalate was collected by filtration, yield: 86% (based on terephthalic acid), purity: 99.3 percent.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A preparation method of high carbon chain alkane diamine terephthalate is characterized by comprising the following steps,
1) under the amidation reaction condition, reacting the high-carbon-chain alkane diacid shown in the formula (1) with an ammonia-containing compound to obtain high-carbon-chain diamide shown in the formula (2);
2) under alkaline conditions, in the presence of water and sodium hypochlorite and/or sodium hypobromite, carrying out rearrangement degradation reaction on the high-carbon-chain diamide shown in the formula (2) to obtain high-carbon-chain alkane diamine shown in the formula (3);
3) in the presence of a solvent, carrying out salt-forming reaction on high-carbon-chain alkane diamine shown in a formula (3) and terephthalic acid,
COOH-(CH2)n-COOH formula (1) CONH2-(CH2)n-CONH2Formula (2)
NH2-(CH2)m-NH2Formula (3)
In formulae (1) to (3), n is 9 to 13, and m is 9 to 13.
2. The method of claim 1, wherein the product obtained in step 2) is directly used for the reaction in step 3).
3. The method according to claim 1, wherein the ammonia-containing compound is ammonia gas and/or urea.
4. The method according to claim 1, wherein the molar ratio of the high carbon chain alkanedioic acid represented by formula (1) to the ammonia-containing compound is 1: 1-10.
5. The process of any of claims 1-4, wherein the amidation reaction conditions include: the reaction temperature is 150 ℃ and 280 ℃, and the reaction time is 3-18 hours.
6. The method according to any one of claims 1 to 4, wherein the molar ratio of the high carbon chain diamide represented by formula (2) to the sodium hypochlorite and/or the sodium hypobromite is 1: 1.8-3.5.
7. The process according to any one of claims 1 to 4, wherein step 2) is carried out in the presence of a solvent;
preferably, the weight ratio of the high carbon chain diamide represented by the formula (2) to the solvent is 1: 5-15;
preferably, the solvent is one or more of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol.
8. The process according to any one of claims 1 to 4, wherein in the step 2), the pH of the reaction system is 9 or more.
9. The method according to any one of claims 1 to 4, wherein the high carbon chain alkanediamine represented by formula (3) is nonanediamine, decanediamine, undecanediamine, dodecanediamine or tridecanediamine.
10. The method according to any one of claims 1 to 4, wherein in the step 3), the molar ratio of the high carbon chain alkanediamine represented by the formula (3) to terephthalic acid is 1: 0.95-1.05;
preferably, the organic solvent is one or more of methanol, ethanol and isopropanol.
11. A high carbon chain alkanediamine terephthalate, prepared by the process of any one of claims 1 to 10.
12. Use of a high carbon chain alkanediamine terephthalate prepared by the process according to any one of claims 1 to 10 or a high carbon chain alkanediamine terephthalate according to claim 11 for the preparation of polyamides.
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| DE3529240A1 (en) * | 1985-08-16 | 1987-02-26 | Basf Ag | IMPACT POLYAMIDE MOLDING MATERIALS AND THEIR PRODUCTION |
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