WO2020093949A1 - High-carbon chain alkane diamine, preparation method therefor and application thereof - Google Patents

High-carbon chain alkane diamine, preparation method therefor and application thereof Download PDF

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WO2020093949A1
WO2020093949A1 PCT/CN2019/115090 CN2019115090W WO2020093949A1 WO 2020093949 A1 WO2020093949 A1 WO 2020093949A1 CN 2019115090 W CN2019115090 W CN 2019115090W WO 2020093949 A1 WO2020093949 A1 WO 2020093949A1
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formula
reaction
carbon
represented
carbon chain
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PCT/CN2019/115090
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French (fr)
Chinese (zh)
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周波
王磊
刘媛
张玉龙
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昆山博科化学有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/54—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions
    • C07C209/58—Preparation of compounds containing amino groups bound to a carbon skeleton by rearrangement reactions from or via amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids

Definitions

  • the invention relates to the field of preparation of high-carbon paraffinic diamines, in particular to a high-carbon paraffinic diamine, and its preparation method and application.
  • Polyamide also known as nylon (PA) is a nitrogen-containing hetero-chain polymer containing a polyamide characteristic group (-NHCO-) in the main chain, and is compatible with polycarbonate, polyoxymethylene, and polybutylene terephthalate And polyphenylene oxide are also called five general engineering plastics.
  • Polyamide has excellent characteristics such as wear resistance, impact resistance, fatigue resistance, corrosion resistance, etc. With the continuous emergence of high value-added modified products, polyamide engineering plastics are widely used in the automotive, electronic, electrical, and transportation industries. Typical products are pumps Impeller, bearing, automobile electrical instrument and other parts.
  • High-carbon chain nylon varieties have the advantages of low density, low water absorption, low temperature resistance, wear resistance and impact resistance. Therefore, the downstream chemicals of high-carbon paraffinic diamines invariably put forward new requirements for the quality of high-carbon paraffinic diamines, which require higher quality products.
  • Long-chain diamines include nonanediamine, especially the preparation represented by decanediamine, which has continued the original synthesis process: long-chain diacid as a raw material, high-temperature ammoniation and dehydration of long-chain dinitrile , Select metal alloys such as Raney nickel as the catalyst, and choose intermittent hydrogenation method for catalytic production.
  • the advantage of the traditional synthesis method is that it is relatively mature to master the process and easy to operate.
  • nonadiamine there has also been reported an industrial process for producing nonanediamine by amination hydrogenation using nonadialdehyde as a raw material, in the presence of ammonia, using nickel and other metals as catalysts.
  • the purpose of the present invention is to overcome the problems of safety and complicated processes in the prior art, and to provide a safe, convenient and simple preparation method of high-carbon paraffin diamine.
  • the first aspect of the present invention provides a method for preparing a high-carbon alkane diamine.
  • the structure of the high-carbon alkane diamine is represented by formula (3). The method includes the following steps.
  • the ammonia-containing compound is ammonia gas and / or urea.
  • the molar ratio of the higher-carbon alkane diacid to the ammonia-containing compound represented by formula (1) is 1: 2-10.
  • the amidation reaction conditions include: a reaction temperature of 150-250 ° C, a reaction time of 3-18 hours, preferably 3-15 hours, and more preferably 8-15 hours.
  • reaction time examples include: 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours and 18 hours.
  • the molar ratio of the high-carbon chain diamide represented by formula (2) to sodium hypochlorite and / or sodium hypobromite is 1: 1.8-3.5.
  • step 2) is carried out in the presence of a solvent.
  • the weight ratio of the high-carbon chain diamide represented by formula (2) to the solvent is 1: 5-15.
  • the solvent is one of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol One or more.
  • step 2) the pH value of the reaction system is above 9.
  • the high-carbon alkane diamine represented by formula (3) is nonanediamine, sunflower diamine, undecane diamine, dodecane diamine or tridecane diamine.
  • a high-carbon paraffin diamine which is prepared by the method of the present invention.
  • the application of the high-carbon paraffin diamine prepared by the method of the present invention in the preparation of polyamide is provided.
  • the present invention can provide a safe, convenient and simple preparation method of high-carbon alkane diamine.
  • the method for preparing a high-carbon alkane diamine provided by the present invention is a method for preparing a high-carbon alkane diamine represented by formula (3).
  • the method includes the following steps,
  • n may be 9, 10, 11, 12, or 13.
  • m may be 9, 10, 11, 12, or 13.
  • step 1) is carried out under amidation reaction conditions, and the high-carbon alkane diacid represented by formula (1) is reacted with an ammonia-containing compound to obtain the high-carbon represented by formula (2) Chain diamide.
  • the high-carbon alkane diacid represented by formula (1) to perform an amidation reaction with an ammonia-containing compound, it has the advantages of simple operation, few by-products, and high yield, and, after the completion of the reaction The post-treatment can be directly used for the next reaction, which greatly simplifies the process.
  • the ammonia-containing compound may be various ammonia-containing compounds commonly used in the art for amidation of carboxylic acids, for example, it may be one or more of ammonia gas, urea, etc., preferably ammonia gas and / or Or urea, because the use of ammonia gas has the advantages of simple reaction and convenient operation, it is more preferably ammonia gas.
  • the higher-carbon alkane diacid represented by formula (1) can be obtained commercially or can be synthesized according to conventional methods in the art.
  • high-carbon alkane diacid examples include undecyl diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, and hexadecane diacid. Or heptadecanedioic acid.
  • the molar ratio of the higher-carbon alkane diacid represented by formula (1) to the ammonia-containing compound is 1: 2-10, more preferably 1: 2.5-5, still more preferably 1: 3 -4.
  • the amidation reaction conditions include: a reaction temperature of 150-250 ° C and a reaction time of 8-18 hours; more preferably, the amidation reaction conditions include: a reaction temperature of 160-240 ° C and a reaction time of 10-16 hours.
  • step 1) after step 1) is completed, only the high-carbon chain diamide represented by formula (2) can be obtained by cooling to room temperature, and the obtained high-carbon chain diamide represented by formula (2) can be used directly Step 2).
  • step 2) under alkaline conditions, in the presence of water, sodium hypochlorite and / or sodium hypobromite, the higher carbon chain diamide represented by formula (2) undergoes rearrangement and degradation reaction, The higher-carbon paraffin diamine represented by formula (3) is obtained.
  • the rearrangement reaction when the high-carbon chain diamide represented by formula (2) reacts with an alkaline solution of sodium hypochlorite and / or sodium hypobromite, the rearrangement reaction generates isocyanate, which is then hydrolyzed to prepare formula (3) High carbon paraffin diamine shown. That is, in step 2), the rearrangement reaction and the hydrolysis reaction (downgrade reaction) are also performed in the same reaction vessel, thereby greatly simplifying the industry and extremely useful in the industry.
  • the weight ratio of the high-carbon chain diamide represented by formula (2) to water may be 1: 5-100, preferably 1: 6-50, more preferably 1: 6-15, more preferably 1: 6-10, further preferably 1: 7-8.
  • water can be used in the form of an aqueous solution of sodium hypochlorite or an aqueous solution of sodium hypobromite.
  • the molar ratio of the high-carbon chain diamide represented by formula (2) to sodium hypochlorite and / or sodium hypobromite is 1: 1.8-3.5, more preferably 1: 2.6-3.2.
  • the above sodium hypochlorite or sodium hypobromite can be obtained commercially, or can be prepared at the reaction site.
  • chlorine gas and sodium hydroxide solution can be used for on-site preparation, or bromine and sodium hydroxide can be used for on-site preparation.
  • step 2) is carried out in the presence of a solvent, and the use of a solvent facilitates the reaction.
  • the amount of the solvent can be specifically selected according to the amount of the high-carbon chain diamide represented by formula (2), for example, 2)
  • the weight ratio of the high-carbon chain diamide shown to the solvent may be 1: 5-15, preferably 1: 8-10.
  • the solvent is one of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol
  • dioxane ethylene glycol dimethyl ether
  • ethylene glycol diethyl ether diethylene glycol dimethyl ether
  • diethylene glycol diethyl ether diethylene glycol dimethyl ether
  • tetrahydrofuran methanol, ethanol and propanol
  • the pH value of the reaction system is above 9, more preferably 10-12.
  • the pH value of the reaction system can be adjusted by adding a base as needed, for example, an inorganic base and an organic base can be added to adjust, preferably an inorganic base is added to adjust.
  • a base for example, an inorganic base and an organic base can be added to adjust, preferably an inorganic base is added to adjust.
  • the inorganic base include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferred.
  • step 2) can be performed at a temperature of 5-80 ° C, more preferably, it can be performed in the following manner: at 0-10 ° C, an aqueous solution containing sodium hypochlorite and / or sodium hypobromite is added dropwise to In the solution containing the high-carbon chain diamide represented by formula (2), and maintained at this temperature for 0.5-3 hours; then heated to 20-35 °C and reacted at this temperature for 1-5 hours; 60-75 ° C and react at this temperature for 0.5-5 hours.
  • step 2) the reaction is completed, it is only necessary to layer the reaction solution and concentrate the organic phase to obtain a high-purity product.
  • the post-processing step is extremely simple and extremely useful in industry.
  • the higher-carbon alkane diamine represented by formula (3) is nonanediamine, sunflower diamine, undecane diamine, dodecane diamine, or tridecane diamine.
  • a high-carbon paraffin diamine which is prepared by the method of the present invention.
  • the application of the high-carbon paraffin diamine prepared by the method of the present invention in the preparation of polyamide is provided.
  • 1,11-undecanediamide (10g) and 190ml of dioxane to the reaction flask, stir and cool down with an ice bath. After the temperature of the reaction solution drops to about 10 °C, add sodium hydroxide and sodium hypochlorite dropwise Of the mixed solution (the molar ratio of sodium hydroxide and sodium hypochlorite is 2: 1, and the amount of sodium hypochlorite is 3 moles relative to 1 mole of 1,11-undecanediamide), the drip acceleration is controlled to maintain the reaction temperature at 10 ° C About, and control the pH value of the reaction system to 10-12.
  • the reaction was kept for 1 hour, and then the ice bath was removed to allow it to return to temperature naturally, and the temperature was controlled at 30 ° C for 3 hours, and then heated to 75 ° C for 1.5 hours.
  • the organic layer was separated, the organic layer was concentrated to remove dioxane, and a small amount of solid was removed by filtration. The filtrate was further concentrated to obtain 6.7 g of light yellow oily product. From the nuclear magnetic data, the product obtained was 1,9-nonanediamine.
  • the gas-phase quantitative injection detection showed that the purity was 95% and the yield was 91%.
  • 1,11-undecanediamide (10g) and 190ml of dioxane to the reaction flask, stir and cool down with an ice bath. After the temperature of the reaction solution drops to about 10 °C, add sodium hydroxide and sodium hypochlorite dropwise Of the mixed solution (the molar ratio of sodium hydroxide and sodium hypochlorite is 2: 1, and the amount of sodium hypochlorite is 2.6 moles relative to 1 mole of 1,11-undecanediamide), and the drop acceleration is controlled to maintain the reaction temperature at 13 ° C Around, and control the pH value of the reaction system to 10-11.
  • the reaction was kept for 1 hour, and then the ice bath was removed to allow it to naturally return to temperature, and the temperature was controlled at 25 ° C for 3 hours, and then heated to 75 ° C, and kept for 1 hour.
  • the organic layer was separated, the organic layer was concentrated to remove dioxane, and a small amount of solids were removed by filtration. The filtrate was further concentrated to obtain 6.6 g of light yellow oily product. From the nuclear magnetic data, the product obtained was 1,9-nonanediamine.
  • the gas-phase quantitative injection detection showed that the purity was 95% and the yield was 89.5%.
  • 1,11-undecanediamide (10g) and 190ml of dioxane to the reaction flask, stir and cool down with an ice bath. After the temperature of the reaction solution drops to about 10 °C, add sodium hydroxide and sodium hypochlorite dropwise Of the mixed solution (the molar ratio of sodium hydroxide and sodium hypochlorite is 2: 1, and the amount of sodium hypochlorite is 3.2 moles relative to 1 mole of 1,11-undecanediamide), the drip acceleration is controlled to maintain the reaction temperature at 10 ° C Around, and control the pH value of the reaction system to 10-11.
  • the reaction was kept for 1 hour, and then the ice bath was removed to let it return to temperature naturally, and the temperature was controlled at 30 ° C for 1 hour, and then heated to 75 ° C for 1 hour.
  • the organic layer was separated, the organic layer was concentrated to remove the solvent, and a small amount of solid was removed by filtration. The filtrate was further concentrated to obtain 6.8 g of light yellow oily product. From the nuclear magnetic data, the product obtained was 1,9-nonanediamine. Quantitative sample detection showed a purity of 94.5% and a yield of 92%.
  • Example 1 According to the preparation method of Example 1, except that the raw material undecanedioic acid was replaced with the same molar amount of dodecanedioic acid to obtain 1,11-dodecanediamide: 90 g (yield 91 %), Can be directly used for the next step.
  • the temperature is controlled at about 30 ° C, and the reaction is carried out for 3 hours; then it is heated to 75 ° C with an oil bath, and the reaction is stirred for about 10 minutes.
  • the reaction solution is clear, and the reaction is kept for 1 hour, and then the layers are separated at about 60-65 ° C, and the organic layer is concentrated , A viscous solid-liquid mixture was obtained, a small amount of solids were removed, and the filtrate was concentrated to obtain 5.7g of light yellow oil.
  • the product obtained was 1,10-kuaidiamine.
  • the temperature was controlled at about 30 ° C and the reaction was conducted for 3 hours.
  • the jacket was then heated to 75 ° C with a water bath, and the reaction was stirred for about 10 minutes.
  • the reaction solution was clear, and the reaction was kept for 1 hour.
  • the layers were separated at about 60-65 ° C.
  • the organic layer was concentrated to remove a small amount of solids.
  • the yellow oily substance can be known from the nuclear magnetic data.
  • the obtained product is 1,9-nonanediamine.
  • the gas phase quantitative injection detection has a purity of 96% and a yield of 88.3%.
  • the difference is that the organic solvent used in step 2) is diethylene glycol dimethyl ether to obtain 5.4g of light yellow oily product.
  • the product obtained is 1,9-noni
  • the amine in addition, was detected by gas-phase quantitative injection, with a purity of 91% and a yield of 73.0%.

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Abstract

The present invention relates to the field of high-carbon chain alkane diamine preparation, and disclosed thereby are a high-carbon chain alkane diamine, a preparation method therefor and an application thereof. The preparation method for a high-carbon chain alkane diamine as described in the present invention is characterized in that the structure of the high-carbon chain alkane diamine is represented by the formula NH2-(CH2)m-NH2; the method comprises the following steps: 1) under amidation reaction conditions, reacting a high-carbon chain alkane diacid represented by the formula COOH-(CH2)n-COOH with an ammonia-containing compound to obtain a high-carbon chain diamide represented by the formula CONH2-(CH2)n-CONH2; 2) under basic conditions, in the presence of water, sodium hypochlorite and/or sodium hypobromite, causing the high-carbon chain diamide represented by the formula CONH2-(CH2)n-CONH2 to undergo a rearrangement and degradation reaction to obtain a high-carbon chain alkane diamine represented by the formula NH2-(CH2)m-NH2, wherein n=9-13 and m=9-13. The method of the present invention is a safe, convenient, simple, and easy-to-implement method for preparing a high-carbon chain alkane diamine.

Description

高碳链烷烃二胺及其制备方法和应用High-carbon paraffin diamine, preparation method and application thereof 技术领域Technical field
本发明涉及高碳链烷烃二胺制备领域，具体涉及一种高碳链烷烃二胺及其制备方法和应用。The invention relates to the field of preparation of high-carbon paraffinic diamines, in particular to a high-carbon paraffinic diamine, and its preparation method and application.
背景技术Background technique
聚酰胺，又称尼龙(PA)，是主链中含有聚酰胺特征基团(-NHCO-)的含氮杂链聚合物，与聚碳酸酯、聚甲醛、聚对苯二甲酸丁二醇酯和聚苯醚并称为五大通用工程塑料。聚酰胺具有耐磨、耐冲击、耐疲劳、耐腐蚀等优异特性，随着高附加值改性产品的不断涌现，聚酰胺工程塑料广泛应用于汽车、电子电气及交通运输业，典型制品有泵叶轮、轴承、汽车电器仪表等零部件。Polyamide, also known as nylon (PA), is a nitrogen-containing hetero-chain polymer containing a polyamide characteristic group (-NHCO-) in the main chain, and is compatible with polycarbonate, polyoxymethylene, and polybutylene terephthalate And polyphenylene oxide are also called five general engineering plastics. Polyamide has excellent characteristics such as wear resistance, impact resistance, fatigue resistance, corrosion resistance, etc. With the continuous emergence of high value-added modified products, polyamide engineering plastics are widely used in the automotive, electronic, electrical, and transportation industries. Typical products are pumps Impeller, bearing, automobile electrical instrument and other parts.
高碳链尼龙品种，具有密度小、吸水率低、耐低温、耐磨、耐冲击等优点。所以高碳链烷烃二胺的下游化工品不约而同地对高碳链烷烃二胺的品质提出了新的要求，要求产品的质量要更高。High-carbon chain nylon varieties have the advantages of low density, low water absorption, low temperature resistance, wear resistance and impact resistance. Therefore, the downstream chemicals of high-carbon paraffinic diamines invariably put forward new requirements for the quality of high-carbon paraffinic diamines, which require higher quality products.
长链二元胺包括壬二胺，特别是以癸二胺代表的制备，一直以来延续了原始的合成工艺：以长链二元酸为原料，经高温氨化，脱水制的长链二腈，选取雷尼镍等金属合金当作催化剂，选择间歇式的加氢方式来进行催化生产。传统合成方法的优势是对于工艺掌握比较成熟，操作便于进行。另外，对于壬二胺，也有报道通过以壬二醛为原料， 在氨的存在下，以镍等金属作催化剂，氨化氢化生产壬二胺的工业化工艺。Long-chain diamines include nonanediamine, especially the preparation represented by decanediamine, which has continued the original synthesis process: long-chain diacid as a raw material, high-temperature ammoniation and dehydration of long-chain dinitrile , Select metal alloys such as Raney nickel as the catalyst, and choose intermittent hydrogenation method for catalytic production. The advantage of the traditional synthesis method is that it is relatively mature to master the process and easy to operate. In addition, for nonadiamine, there has also been reported an industrial process for producing nonanediamine by amination hydrogenation using nonadialdehyde as a raw material, in the presence of ammonia, using nickel and other metals as catalysts.
但是，上述现有的工艺涉及高温、高压，氢化等危险工艺，存在安全性上的问题，并且现有的工艺存在工艺复杂的问题。However, the above-mentioned existing processes involve dangerous processes such as high temperature, high pressure, hydrogenation, etc., and have safety problems, and the existing processes have a problem of complicated processes.
发明内容Summary of the invention
本发明的目的是为了克服现有技术存在的安全性和工艺复杂的问题，提供一种安全方便，简单易行的高碳链烷烃二胺的制备方法。The purpose of the present invention is to overcome the problems of safety and complicated processes in the prior art, and to provide a safe, convenient and simple preparation method of high-carbon paraffin diamine.
为了实现上述目的，本发明第一方面提供一种高碳链烷烃二胺的制备方法，所述高碳链烷烃二胺的结构如式(3)所示，所述方法包括以下步骤，In order to achieve the above object, the first aspect of the present invention provides a method for preparing a high-carbon alkane diamine. The structure of the high-carbon alkane diamine is represented by formula (3). The method includes the following steps.
1)在酰胺化反应条件下，将式(1)所示的高碳链烷烃二酸与含氨化合物反应，得到式(2)所示的高碳链二酰胺；1) Under the conditions of amidation reaction, react the high-carbon alkane diacid represented by formula (1) with an ammonia-containing compound to obtain the high-carbon chain diamide represented by formula (2);
2)在碱性条件下，在水与、次氯酸钠和/或次溴酸钠的存在下，使式(2)所示的高碳链二酰胺发生重排降级反应，得到式(3)所示的高碳链烷烃二胺，2) Under alkaline conditions, in the presence of water, sodium hypochlorite and / or sodium hypobromite, the high-carbon chain diamide represented by the formula (2) undergoes rearrangement and degradation reaction to obtain the formula (3) Of high-carbon paraffinic diamines,
COOH-(CH 2) n-COOH 式(1)  CONH 2-(CH 2) n-CONH 2式(2) COOH- (CH 2 ) n -COOH formula (1) CONH 2- (CH 2 ) n -CONH 2 formula (2)
NH 2-(CH 2) m-NH 2  式(3) NH 2- (CH 2 ) m -NH 2 formula (3)
式(1)～式(3)中，n＝9-13，m＝9-13。In formula (1) to formula (3), n = 9-13 and m = 9-13.
优选地，所述含氨化合物为氨气和/或尿素。Preferably, the ammonia-containing compound is ammonia gas and / or urea.
优选地，式(1)所示的高碳链烷烃二酸与含氨化合物的摩尔比为1：2-10。Preferably, the molar ratio of the higher-carbon alkane diacid to the ammonia-containing compound represented by formula (1) is 1: 2-10.
优选地，所述酰胺化反应条件包括：反应温度为150-250℃，反应时间为3-18小时，优选为3-15小时，更优选为8-15小时。Preferably, the amidation reaction conditions include: a reaction temperature of 150-250 ° C, a reaction time of 3-18 hours, preferably 3-15 hours, and more preferably 8-15 hours.
作为反应时间例如可以举出：3小时、4小时、5小时、6小时、7小时、8小时、9小时、10小时、11小时、12小时、13小时、14小时、15小时、16小时、17小时和18小时等。Examples of the reaction time include: 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours and 18 hours.
优选地，式(2)所示的高碳链二酰胺与、次氯酸钠和/或次溴酸钠的摩尔比为1：1.8-3.5。Preferably, the molar ratio of the high-carbon chain diamide represented by formula (2) to sodium hypochlorite and / or sodium hypobromite is 1: 1.8-3.5.
优选地，步骤2)在溶剂存在下进行。Preferably, step 2) is carried out in the presence of a solvent.
优选地，式(2)所示的高碳链二酰胺与所述溶剂的重量比为1：5-15。Preferably, the weight ratio of the high-carbon chain diamide represented by formula (2) to the solvent is 1: 5-15.
优选地，所述溶剂为二氧六环、乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、四氢呋喃、甲醇、乙醇和丙醇的一种或多种。Preferably, the solvent is one of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol One or more.
优选地，步骤2)中，反应体系的pH值在9以上。Preferably, in step 2), the pH value of the reaction system is above 9.
优选地，式(3)所示高碳链烷烃二胺为壬二胺、葵二胺、十一烷二胺、十二烷二胺或十三烷二胺。Preferably, the high-carbon alkane diamine represented by formula (3) is nonanediamine, sunflower diamine, undecane diamine, dodecane diamine or tridecane diamine.
根据本发明的第二方面，提供一种高碳链烷烃二胺，其通过本发明的方法制备得到。According to the second aspect of the present invention, there is provided a high-carbon paraffin diamine, which is prepared by the method of the present invention.
根据本发明的第三方面，提供本发明的方法制备得到的高碳链烷烃二胺在制备聚酰胺中的应用。According to the third aspect of the present invention, the application of the high-carbon paraffin diamine prepared by the method of the present invention in the preparation of polyamide is provided.
通过上述技术方案，本发明能够提供一种安全方便，简单易行的高碳链烷烃二胺的制备方法。Through the above technical solution, the present invention can provide a safe, convenient and simple preparation method of high-carbon alkane diamine.
具体实施方式detailed description
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the end points of each range, between the end points of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values The scope should be considered as specifically disclosed herein.
本发明提供的高碳链烷烃二胺的制备方法，其为式(3)所示的高碳链烷烃二胺的制备方法，该方法包括以下步骤，The method for preparing a high-carbon alkane diamine provided by the present invention is a method for preparing a high-carbon alkane diamine represented by formula (3). The method includes the following steps,
1)在酰胺化反应条件下，将式(1)所示的高碳链烷烃二酸与含氨化合物反应，得到式(2)所示的高碳链二酰胺；1) Under the conditions of amidation reaction, react the high-carbon alkane diacid represented by formula (1) with an ammonia-containing compound to obtain the high-carbon chain diamide represented by formula (2);
2)在碱性条件下，在水与、次氯酸钠和/或次溴酸钠的存在下，使式(2)所示的高碳链二酰胺发生重排降级反应，得到式(3)所示的高碳链烷烃二胺，2) Under alkaline conditions, in the presence of water, sodium hypochlorite and / or sodium hypobromite, the high-carbon chain diamide represented by the formula (2) undergoes rearrangement and degradation reaction to obtain the formula (3) Of high-carbon paraffinic diamines,
COOH-(CH 2) n-COOH 式(1)  CONH 2-(CH 2) n-CONH 2式(2) COOH- (CH 2 ) n -COOH formula (1) CONH 2- (CH 2 ) n -CONH 2 formula (2)
NH 2-(CH 2) m-NH 2  式(3) NH 2- (CH 2 ) m -NH 2 formula (3)
式(1)～式(3)中，n＝9-13，m＝9-13。In formula (1) to formula (3), n = 9-13 and m = 9-13.
根据本发明，式(1)～式(3)中，n可以为9、10、11、12或13。According to the present invention, in formulas (1) to (3), n may be 9, 10, 11, 12, or 13.
根据本发明，式(1)～式(3)中，m可以为9、10、11、12或13。According to the present invention, in formula (1) to formula (3), m may be 9, 10, 11, 12, or 13.
根据本发明，步骤1)在酰胺化反应条件下进行，通过使式(1)所示的高碳链烷烃二酸与含氨化合物进行酰胺化反应，从而得到式(2) 所示的高碳链二酰胺。According to the present invention, step 1) is carried out under amidation reaction conditions, and the high-carbon alkane diacid represented by formula (1) is reacted with an ammonia-containing compound to obtain the high-carbon represented by formula (2) Chain diamide.
在本发明中，通过使用式(1)所示的高碳链烷烃二酸与含氨化合物进行酰胺化反应，具有操作简单、副产物少和收率高的优点，并且，反应完成后无需经过后处理可以直接用于下一步反应，极大地简化了工艺。In the present invention, by using the high-carbon alkane diacid represented by formula (1) to perform an amidation reaction with an ammonia-containing compound, it has the advantages of simple operation, few by-products, and high yield, and, after the completion of the reaction The post-treatment can be directly used for the next reaction, which greatly simplifies the process.
根据本发明，所述含氨化合物可以为本领域通常用于羧酸酰胺化的各种含氨化合物，例如，可以为氨气、尿素等中的一种或多种，优选为氨气和/或尿素，由于通过使用氨气具有反应简单，操作方便的优点，因此更优选为氨气。According to the present invention, the ammonia-containing compound may be various ammonia-containing compounds commonly used in the art for amidation of carboxylic acids, for example, it may be one or more of ammonia gas, urea, etc., preferably ammonia gas and / or Or urea, because the use of ammonia gas has the advantages of simple reaction and convenient operation, it is more preferably ammonia gas.
根据本发明，式(1)所示的高碳链烷烃二酸可以通过商购获得，也可以按照本领域常规方法合成得到。According to the present invention, the higher-carbon alkane diacid represented by formula (1) can be obtained commercially or can be synthesized according to conventional methods in the art.
作为所述高碳链烷烃二酸例如可以举出：十一烷基二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸或十七烷二酸。Examples of the high-carbon alkane diacid include undecyl diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, and hexadecane diacid. Or heptadecanedioic acid.
根据本发明，优选地，式(1)所示的高碳链烷烃二酸与含氨化合物的摩尔比为1：2-10，更优选为1：2.5-5，更进一步优选为1：3-4。According to the present invention, preferably, the molar ratio of the higher-carbon alkane diacid represented by formula (1) to the ammonia-containing compound is 1: 2-10, more preferably 1: 2.5-5, still more preferably 1: 3 -4.
优选地，所述酰胺化反应条件包括：反应温度为150-250℃，反应时间为8-18小时；更优选地，所述酰胺化反应条件包括：反应温度为160-240℃，反应时间为10-16小时。Preferably, the amidation reaction conditions include: a reaction temperature of 150-250 ° C and a reaction time of 8-18 hours; more preferably, the amidation reaction conditions include: a reaction temperature of 160-240 ° C and a reaction time of 10-16 hours.
根据本发明，步骤1)完成后，仅需要冷却到室温即可得到式(2)所示的高碳链二酰胺，并且得到的式(2)所示的高碳链二酰胺可以 直接用于步骤2)。According to the present invention, after step 1) is completed, only the high-carbon chain diamide represented by formula (2) can be obtained by cooling to room temperature, and the obtained high-carbon chain diamide represented by formula (2) can be used directly Step 2).
根据本发明，步骤2)中，在碱性条件下，在水与、次氯酸钠和/或次溴酸钠的存在下，使式(2)所示的高碳链二酰胺发生重排降级反应，得到式(3)所示的高碳链烷烃二胺。在该步骤中，式(2)所示的高碳链二酰胺与、次氯酸钠和/或次溴酸钠的碱溶液作用时，重排反应生成异腈酸酯，然后水解制备得到式(3)所示的高碳链烷烃二胺。也即，在步骤2)中，重排反应和水解反应(降级反应)也是在同一个反应容器中进行，由此可以大大简化工业，在工业上极其有用。According to the present invention, in step 2), under alkaline conditions, in the presence of water, sodium hypochlorite and / or sodium hypobromite, the higher carbon chain diamide represented by formula (2) undergoes rearrangement and degradation reaction, The higher-carbon paraffin diamine represented by formula (3) is obtained. In this step, when the high-carbon chain diamide represented by formula (2) reacts with an alkaline solution of sodium hypochlorite and / or sodium hypobromite, the rearrangement reaction generates isocyanate, which is then hydrolyzed to prepare formula (3) High carbon paraffin diamine shown. That is, in step 2), the rearrangement reaction and the hydrolysis reaction (downgrade reaction) are also performed in the same reaction vessel, thereby greatly simplifying the industry and extremely useful in the industry.
在本发明中，水通常过量使用，例如，式(2)所示的高碳链二酰胺与水的重量比可以为1：5-100，优选为1：6-50，更优选为1：6-15，更优选为1:6-10，进一步优选为1：7-8。In the present invention, water is usually used in excess, for example, the weight ratio of the high-carbon chain diamide represented by formula (2) to water may be 1: 5-100, preferably 1: 6-50, more preferably 1: 6-15, more preferably 1: 6-10, further preferably 1: 7-8.
此外，水可以次氯酸钠水溶液或次溴酸钠水溶液的形式使用。In addition, water can be used in the form of an aqueous solution of sodium hypochlorite or an aqueous solution of sodium hypobromite.
优选地，式(2)所示的高碳链二酰胺与次氯酸钠和/或次溴酸钠的摩尔比为1：1.8-3.5，更优选为1：2.6-3.2。Preferably, the molar ratio of the high-carbon chain diamide represented by formula (2) to sodium hypochlorite and / or sodium hypobromite is 1: 1.8-3.5, more preferably 1: 2.6-3.2.
上述次氯酸钠或次溴酸钠可以通过商购获得，也可以在反应现场制备得到。在反应现场制备得到时，可以以氯气和氢氧化钠溶液为原料现场制备使用，也可以以溴素和氢氧化钠为原料现场制备使用。The above sodium hypochlorite or sodium hypobromite can be obtained commercially, or can be prepared at the reaction site. When prepared at the reaction site, chlorine gas and sodium hydroxide solution can be used for on-site preparation, or bromine and sodium hydroxide can be used for on-site preparation.
此外，优选步骤2)在溶剂存在下进行，使用溶剂有助于反应的进行，所述溶剂的用量可以根据式(2)所示的高碳链二酰胺的量来具体选择，例如，式(2)所示的高碳链二酰胺与所述溶剂的重量比可以为1：5-15，优选为1：8-10。In addition, it is preferred that step 2) is carried out in the presence of a solvent, and the use of a solvent facilitates the reaction. The amount of the solvent can be specifically selected according to the amount of the high-carbon chain diamide represented by formula (2), for example, 2) The weight ratio of the high-carbon chain diamide shown to the solvent may be 1: 5-15, preferably 1: 8-10.
优选地，所述溶剂为二氧六环、乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、四氢呋喃、甲醇、乙醇和丙醇的一种或多种；更优选为二氧六环，通过使用二氧六环具有操作简便，反应选择性好的优异效果。Preferably, the solvent is one of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol One or more species; more preferably dioxane, by using dioxane has the advantages of simple operation and good reaction selectivity.
优选地，步骤2)中，反应体系的pH值在9以上，更优选为10-12。Preferably, in step 2), the pH value of the reaction system is above 9, more preferably 10-12.
根据本发明，根据需要反应体系的pH值可以通过加入碱来调节，例如可以加入无机碱和有机碱来调节，优选加入无机碱来调节。作为所述无机碱例如可以为氢氧化钠和氢氧化钾等，优选为氢氧化钠。According to the present invention, the pH value of the reaction system can be adjusted by adding a base as needed, for example, an inorganic base and an organic base can be added to adjust, preferably an inorganic base is added to adjust. Examples of the inorganic base include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferred.
根据本发明，步骤2)可以在5-80℃的温度下进行，更优选地，可以按照以下方式进行：在0-10℃下，将含有次氯酸钠和/或次溴酸钠的水溶液滴加到含有式(2)所示的高碳链二酰胺的溶液中，并在该温度下保持0.5-3小时；然后升温至20-35℃并在该温度下反应1-5小时；接着，升温到60-75℃并在该温度下反应0.5-5小时。According to the present invention, step 2) can be performed at a temperature of 5-80 ° C, more preferably, it can be performed in the following manner: at 0-10 ° C, an aqueous solution containing sodium hypochlorite and / or sodium hypobromite is added dropwise to In the solution containing the high-carbon chain diamide represented by formula (2), and maintained at this temperature for 0.5-3 hours; then heated to 20-35 ℃ and reacted at this temperature for 1-5 hours; 60-75 ° C and react at this temperature for 0.5-5 hours.
根据本发明，步骤2)反应完成后，仅需要将反应液进行分层后、将有机相浓缩即可获得高纯度的产物，其后处理步骤极其简单，在工业上极其有用。According to the present invention, after step 2) the reaction is completed, it is only necessary to layer the reaction solution and concentrate the organic phase to obtain a high-purity product. The post-processing step is extremely simple and extremely useful in industry.
根据本发明，优选地，式(3)所示高碳链烷烃二胺为壬二胺、葵二胺、十一烷二胺、十二烷二胺或十三烷二胺。According to the present invention, preferably, the higher-carbon alkane diamine represented by formula (3) is nonanediamine, sunflower diamine, undecane diamine, dodecane diamine, or tridecane diamine.
根据本发明的第二方面，提供一种高碳链烷烃二胺，其通过本发明的方法制备得到。According to the second aspect of the present invention, there is provided a high-carbon paraffin diamine, which is prepared by the method of the present invention.
根据本发明的第三方面，提供本发明的方法制备得到的高碳链烷烃二胺在制备聚酰胺中的应用。According to the third aspect of the present invention, the application of the high-carbon paraffin diamine prepared by the method of the present invention in the preparation of polyamide is provided.
以下将通过实施例对本发明进行详细描述，但本发明并不仅限于下述实施例。以下实施例中所使用的试剂如无特别说明时均为市售品。The present invention will be described in detail below through examples, but the present invention is not limited to the following examples. Unless otherwise specified, the reagents used in the following examples are all commercially available products.
实施例1Example 1
本实施例用于说明1,9-壬二胺的制备This example is used to illustrate the preparation of 1,9-nonanediamine
1)1,11-十一烷二酰胺的合成1) Synthesis of 1,11-undecanediamide
将100克十一烷二酸加入250ml的三口反应瓶中，加热至原料熔点使之熔化，通入氨气(相对于1摩尔的十一烷二酸，氨气通入量约为3摩尔)，反应温度先保持在160℃，使原料和氨气反应成盐，随后反应温度升至220℃，随着反应脱水的量增加，最终反应温度升高至240℃，氨气流速保持此反应脱水能够顺利带出，脱水反应时间为12小时，反应结束后，降温后结晶成固体，烘干得1,11-十一烷二酰胺：93克(收率为94％)，可直接供下一步使用。Add 100 grams of undecanedioic acid to a 250ml three-neck reaction flask, heat to the melting point of the raw material to melt it, and introduce ammonia gas (relative to 1 mole of undecanedioic acid, the amount of ammonia gas is about 3 moles) , The reaction temperature is first maintained at 160 ℃, so that the raw materials and ammonia gas react to form a salt, and then the reaction temperature rises to 220 ℃, as the amount of reaction dehydration increases, the final reaction temperature rises to 240 ℃, the ammonia flow rate keeps this reaction dehydrated It can be taken out smoothly. The dehydration reaction time is 12 hours. After the reaction is completed, it is crystallized into a solid after cooling and dried to obtain 1,11-undecanediamide: 93 g (94% yield), which can be directly used for the next step. use.
2)1,9-壬二胺的合成2) Synthesis of 1,9-nonanediamine
将1,11-十一烷二酰胺(10克)和190ml的二氧六环加入反应瓶中，搅拌并用冰浴降温，在反应液温度降至10℃左右后，滴加氢氧化钠和次氯酸钠的混合溶液(氢氧化钠和次氯酸钠的摩尔比为2：1，并且相对于1摩尔的1,11-十一烷二酰胺，次氯酸钠用量为3摩尔)，控制滴加速度以维持反应温度在10℃左右，并控制反应体系的pH值为10-12。滴加完毕后，保温反应1小时，然后撤除冰浴让其自然回温，并将温度控制在30℃反应3小时，然后加热至75℃，保温反应1.5小时。冷却后，分出有机层，有机层浓缩除去二氧六环，过滤除去少量固体，滤液继续浓缩得到6.7g浅黄色油状产品，通过核磁数 据可知，得到的产品为1,9-壬二胺，另外，气相定量进样检测，纯度为95％，收率为91％。Add 1,11-undecanediamide (10g) and 190ml of dioxane to the reaction flask, stir and cool down with an ice bath. After the temperature of the reaction solution drops to about 10 ℃, add sodium hydroxide and sodium hypochlorite dropwise Of the mixed solution (the molar ratio of sodium hydroxide and sodium hypochlorite is 2: 1, and the amount of sodium hypochlorite is 3 moles relative to 1 mole of 1,11-undecanediamide), the drip acceleration is controlled to maintain the reaction temperature at 10 ° C About, and control the pH value of the reaction system to 10-12. After the dropwise addition, the reaction was kept for 1 hour, and then the ice bath was removed to allow it to return to temperature naturally, and the temperature was controlled at 30 ° C for 3 hours, and then heated to 75 ° C for 1.5 hours. After cooling, the organic layer was separated, the organic layer was concentrated to remove dioxane, and a small amount of solid was removed by filtration. The filtrate was further concentrated to obtain 6.7 g of light yellow oily product. From the nuclear magnetic data, the product obtained was 1,9-nonanediamine. In addition, the gas-phase quantitative injection detection showed that the purity was 95% and the yield was 91%.
核磁数据： 1H NMR(MeOD,ppm)δ2.65,(t,18Hz,CΗ 2,4Η),1.4-1.6(b,CH 2,4H),1.3-1.4(b,CH 2,10H). Nuclear magnetic data: 1 H NMR (MeOD, ppm) δ 2.65, (t, 18 Hz, CH 2 , 4Η), 1.4-1.6 (b, CH 2 , 4H), 1.3-1.4 (b, CH 2 , 10H).
实施例2Example 2
本实施例用于说明1,9-壬二胺的制备This example is used to illustrate the preparation of 1,9-nonanediamine
1)1,11-十一烷二酰胺的合成1) Synthesis of 1,11-undecanediamide
将100克十一烷二酸加入250ml的三口反应瓶中，加热至原料熔点使之熔化，通入氨气(相对于1摩尔的十一烷二酸，氨气通入量约为3.5摩尔)，反应温度先保持在180℃，使原料和氨气反应成盐，随后反应温度升至200℃，随着反应脱水的量增加，最终反应温度升高至220℃，氨气流速保持此反应脱水能够顺利带出，脱水反应时间为10小时，反应结束后，降温后结晶成固体，烘干得1,11-十一烷二酰胺(收率95％)，可直接供下一步使用。Add 100 grams of undecanedioic acid to a 250ml three-necked reaction flask, heat to the melting point of the raw material to melt it, and introduce ammonia gas (relative to 1 mole of undecanedioic acid, the amount of ammonia gas is about 3.5 moles) , The reaction temperature is first maintained at 180 ℃, so that the raw materials and ammonia gas react to form a salt, and then the reaction temperature rises to 200 ℃, as the amount of reaction dehydration increases, the final reaction temperature increases to 220 ℃, the ammonia flow rate keeps this reaction dehydrated It can be taken out smoothly. The dehydration reaction time is 10 hours. After the reaction is completed, it is crystallized into a solid after cooling down and dried to obtain 1,11-undecanediamide (yield 95%), which can be directly used for the next step.
2)1,9-壬二胺的合成2) Synthesis of 1,9-nonanediamine
将1,11-十一烷二酰胺(10克)和190ml的二氧六环加入反应瓶中，搅拌并用冰浴降温，在反应液温度降至10℃左右后，滴加氢氧化钠和次氯酸钠的混合溶液(氢氧化钠和次氯酸钠的摩尔比为2：1，并且相对于1摩尔的1,11-十一烷二酰胺，次氯酸钠用量为2.6摩尔)，控制滴加速度以维持反应温度在13℃左右，并控制反应体系的pH值为10-11。滴加完毕后，保温反应1小时，然后撤除冰浴让其自然回 温，并将温度控制在25℃反应3小时，然后加热至75℃，保温反应1小时。冷却后，分出有机层，有机层浓缩除去二氧六环，过滤除去少量固体，滤液继续浓缩得到6.6g浅黄色油状产品，通过核磁数据可知，得到的产品为1,9-壬二胺，另外，气相定量进样检测，纯度为95％，收率为89.5％。Add 1,11-undecanediamide (10g) and 190ml of dioxane to the reaction flask, stir and cool down with an ice bath. After the temperature of the reaction solution drops to about 10 ℃, add sodium hydroxide and sodium hypochlorite dropwise Of the mixed solution (the molar ratio of sodium hydroxide and sodium hypochlorite is 2: 1, and the amount of sodium hypochlorite is 2.6 moles relative to 1 mole of 1,11-undecanediamide), and the drop acceleration is controlled to maintain the reaction temperature at 13 ° C Around, and control the pH value of the reaction system to 10-11. After the dropwise addition, the reaction was kept for 1 hour, and then the ice bath was removed to allow it to naturally return to temperature, and the temperature was controlled at 25 ° C for 3 hours, and then heated to 75 ° C, and kept for 1 hour. After cooling, the organic layer was separated, the organic layer was concentrated to remove dioxane, and a small amount of solids were removed by filtration. The filtrate was further concentrated to obtain 6.6 g of light yellow oily product. From the nuclear magnetic data, the product obtained was 1,9-nonanediamine. In addition, the gas-phase quantitative injection detection showed that the purity was 95% and the yield was 89.5%.
实施例3Example 3
本实施例用于说明1,9-壬二胺的制备This example is used to illustrate the preparation of 1,9-nonanediamine
1)1,11-十一烷二酰胺的合成1) Synthesis of 1,11-undecanediamide
将100克十一烷二酸加入250ml的三口反应瓶中，加热至原料熔点使之熔化，通入氨气(相对于1摩尔的十一烷二酸，氨气通入量为4摩尔)，反应温度先保持在160℃，使原料和氨气反应成盐，随后反应温度升至190℃，随着反应脱水的量增加，最终反应温度升高至210℃，氨气流速保持此反应脱水能够顺利带出，脱水反应时间为13小时，反应结束后，降温后结晶成固体，烘干得1,11-十一烷二酰胺(收率94％)，可直接供下一步使用。Add 100 grams of undecanedioic acid to a 250ml three-neck reaction flask, heat to the melting point of the raw material to melt it, and introduce ammonia gas (relative to 1 mole of undecanedioic acid, the amount of ammonia gas is 4 moles) The reaction temperature is first maintained at 160 ° C, so that the raw materials and ammonia gas react to form a salt, and then the reaction temperature is raised to 190 ° C. As the amount of dehydration increases, the final reaction temperature increases to 210 ° C. The ammonia flow rate keeps this reaction dehydration capable Taken out smoothly, the dehydration reaction time is 13 hours. After the reaction is completed, it crystallizes into a solid after cooling, and is dried to obtain 1,11-undecanediamide (yield 94%), which can be directly used for the next step.
2)1,9-壬二胺的合成2) Synthesis of 1,9-nonanediamine
将1,11-十一烷二酰胺(10克)和190ml的二氧六环加入反应瓶中，搅拌并用冰浴降温，在反应液温度降至10℃左右后，滴加氢氧化钠和次氯酸钠的混合溶液(氢氧化钠和次氯酸钠的摩尔比为2：1，并且相对于1摩尔的1,11-十一烷二酰胺，次氯酸钠用量为3.2摩尔)，控制滴加速度以维持反应温度在10℃左右，并控制反应体系的pH值 为10-11。滴加完毕后，保温反应1小时，然后撤除冰浴让其自然回温，并将温度控制在30℃反应1小时，然后加热至75℃，保温反应1小时。冷却后，分出有机层，有机层浓缩除去溶剂，过滤除去少量固体，滤液继续浓缩得到6.8g浅黄色油状产品，通过核磁数据可知，得到的产品为1,9-壬二胺，另外，气相定量进样检测，纯度为94.5％，收率为92％。Add 1,11-undecanediamide (10g) and 190ml of dioxane to the reaction flask, stir and cool down with an ice bath. After the temperature of the reaction solution drops to about 10 ℃, add sodium hydroxide and sodium hypochlorite dropwise Of the mixed solution (the molar ratio of sodium hydroxide and sodium hypochlorite is 2: 1, and the amount of sodium hypochlorite is 3.2 moles relative to 1 mole of 1,11-undecanediamide), the drip acceleration is controlled to maintain the reaction temperature at 10 ° C Around, and control the pH value of the reaction system to 10-11. After the dropwise addition, the reaction was kept for 1 hour, and then the ice bath was removed to let it return to temperature naturally, and the temperature was controlled at 30 ° C for 1 hour, and then heated to 75 ° C for 1 hour. After cooling, the organic layer was separated, the organic layer was concentrated to remove the solvent, and a small amount of solid was removed by filtration. The filtrate was further concentrated to obtain 6.8 g of light yellow oily product. From the nuclear magnetic data, the product obtained was 1,9-nonanediamine. Quantitative sample detection showed a purity of 94.5% and a yield of 92%.
实施例4Example 4
1)1,12-十二烷二酰胺的合成1) Synthesis of 1,12-dodecanediamide
按照实施例1的制备方法进行，不同的是，将原料十一烷二酸替换为相同摩尔量的十二烷二酸，得到1,11-十二烷二酰胺：90克(收率为91％)，可直接供下一步使用。According to the preparation method of Example 1, except that the raw material undecanedioic acid was replaced with the same molar amount of dodecanedioic acid to obtain 1,11-dodecanediamide: 90 g (yield 91 %), Can be directly used for the next step.
2)1,10-葵二胺的合成2) Synthesis of 1,10-kuaidiamine
取10克(0.044mol)十二碳二酸二酰胺加入反应瓶中，随后加入190ml(2.23mol)1,4-二氧六环搅拌并用冰浴降温。配制氢氧化钠11.2g(0.28mol)和160g(0.135mol)次氯酸钠的混合溶液。反应液温度降至10℃左右，滴加氢氧化钠和次氯酸钠的混合溶液，控制反应温度在10℃左右。反应液为浑浊状固液混合体。滴加完毕后，保温反应30分钟，让其自然回温。温度控制在30℃左右，反应3小时；随后用油浴加热至75℃，搅拌反应约10分钟，反应液澄清，保温反应1小时，随后在在60-65℃左右下分层，有机层浓缩，得到粘状固液混合体，除去少量固体，滤液浓缩得到5.7g浅黄色油状物，通过核 磁数据可知，得到的产品为1,10-葵二胺，另外，气相定量进样检测，纯度98％，收率74％。10 grams (0.044 mol) of dodecanedioic acid diamide was added to the reaction flask, followed by the addition of 190 ml (2.23 mol) of 1,4-dioxane and stirring and cooling with an ice bath. A mixed solution of 11.2 g (0.28 mol) of sodium hydroxide and 160 g (0.135 mol) of sodium hypochlorite was prepared. The temperature of the reaction solution drops to about 10 ° C, and a mixed solution of sodium hydroxide and sodium hypochlorite is added dropwise to control the reaction temperature at about 10 ° C. The reaction liquid is a turbid solid-liquid mixture. After the dropwise addition, the reaction was incubated for 30 minutes and allowed to return to temperature naturally. The temperature is controlled at about 30 ° C, and the reaction is carried out for 3 hours; then it is heated to 75 ° C with an oil bath, and the reaction is stirred for about 10 minutes. The reaction solution is clear, and the reaction is kept for 1 hour, and then the layers are separated at about 60-65 ° C, and the organic layer is concentrated , A viscous solid-liquid mixture was obtained, a small amount of solids were removed, and the filtrate was concentrated to obtain 5.7g of light yellow oil. According to the nuclear magnetic data, the product obtained was 1,10-kuaidiamine. In addition, the gas phase quantitative injection detection, purity 98 %, Yield 74%.
核磁数据： 1H NMR(CDCl 3,ppm)δ2.65(t,18Hz,CH 2,4Η),1.4-1.6(b,CH 2,4H),1.25-1.3(b,CH 2,8H),1.15-1.25(b,CH 2,4H). Nuclear magnetic data: 1 H NMR (CDCl 3 , ppm) δ 2.65 (t, 18 Hz, CH 2 , 4Η), 1.4-1.6 (b, CH 2, 4H), 1.25-1.3 (b, CH 2 , 8H), 1.15-1.25 (b, CH 2 , 4H).
实施例5Example 5
1)1,11-十一烷二酰胺的合成1) Synthesis of 1,11-undecanediamide
按照实施例1的步骤1)的方法进行制备。It was prepared according to the method of step 1) of Example 1.
2)1,9-壬二胺的合成2) Synthesis of 1,9-nonanediamine
将700克(3.27mol)十一碳二酸二酰胺加入30L反应釜中，随后加入13.3Kg(155.93mol)的1,4-二氧六环搅拌夹套通盐水降温。配制氢氧化钠788g(19.7mol)和11.2Kg(9.45mol)次氯酸钠的混合溶液。反应液温度降至10℃左右，滴加氢氧化钠和次氯酸钠的混合溶液，控制反应温度在10℃左右。反应液为浑浊状固液混合体。滴加完毕后，保温反应30分钟。温度控制在30℃左右，反应3小时。随后夹套改用水浴加热至75℃，搅拌反应约10分钟，反应液澄清，保温反应1小时，随后在60-65℃左右下分层，有机层浓缩，除去少量固体，滤液浓缩得到465g浅黄色油状物，通过核磁数据可知，得到的产品为1,9-壬二胺，另外，气相定量进样检测，纯度96％，收率88.3％。700 g (3.27 mol) of undecanedioic acid diamide was added to the 30 L reactor, followed by addition of 13.3 Kg (155.93 mol) of 1,4-dioxane stirred jacket to cool the brine. A mixed solution of sodium hydroxide 788g (19.7mol) and 11.2Kg (9.45mol) sodium hypochlorite was prepared. The temperature of the reaction solution drops to about 10 ° C, and a mixed solution of sodium hydroxide and sodium hypochlorite is added dropwise to control the reaction temperature at about 10 ° C. The reaction liquid is a turbid solid-liquid mixture. After the dropwise addition, the reaction was incubated for 30 minutes. The temperature was controlled at about 30 ° C and the reaction was conducted for 3 hours. The jacket was then heated to 75 ° C with a water bath, and the reaction was stirred for about 10 minutes. The reaction solution was clear, and the reaction was kept for 1 hour. Then, the layers were separated at about 60-65 ° C. The organic layer was concentrated to remove a small amount of solids. The yellow oily substance can be known from the nuclear magnetic data. The obtained product is 1,9-nonanediamine. In addition, the gas phase quantitative injection detection has a purity of 96% and a yield of 88.3%.
实施例6Example 6
按照实施例1的方法进行，不同的是步骤2)使用的有机溶剂为二乙二醇二甲醚，得到5.4g浅黄色油状产品，通过核磁数据可知，得到的产品为1,9-壬二胺，另外，气相定量进样检测，纯度为91％，收率为73.0％。According to the method of Example 1, the difference is that the organic solvent used in step 2) is diethylene glycol dimethyl ether to obtain 5.4g of light yellow oily product. According to the nuclear magnetic data, the product obtained is 1,9-noni The amine, in addition, was detected by gas-phase quantitative injection, with a purity of 91% and a yield of 73.0%.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosure of the present invention. All belong to the protection scope of the present invention.

Claims (11)

  1. 一种高碳链烷烃二胺的制备方法，其特征在于，所述高碳链烷烃二胺的结构如式(3)所示，所述方法包括以下步骤，A method for preparing a high-carbon alkane diamine, characterized in that the structure of the high-carbon alkane diamine is as shown in formula (3), the method includes the following steps,
    1)在酰胺化反应条件下，将式(1)所示的高碳链烷烃二酸与含氨化合物反应，得到式(2)所示的高碳链二酰胺；1) Under the conditions of amidation reaction, react the high-carbon alkane diacid represented by formula (1) with an ammonia-containing compound to obtain the high-carbon chain diamide represented by formula (2);
    2)在碱性条件下，在水与、次氯酸钠和/或次溴酸钠的存在下，使式(2)所示的高碳链二酰胺发生重排降级反应，得到式(3)所示的高碳链烷烃二胺，2) Under alkaline conditions, in the presence of water, sodium hypochlorite and / or sodium hypobromite, the high-carbon chain diamide represented by the formula (2) undergoes rearrangement and degradation reaction to obtain the formula (3) Of high-carbon paraffinic diamines,
    COOH-(CH 2) n-COOH 式(1)  CONH 2-(CH 2) n-CONH 2 式(2) COOH- (CH 2 ) n -COOH formula (1) CONH 2- (CH 2 ) n -CONH 2 formula (2)
    NH 2-(CH 2) m-NH 2    式(3) NH 2- (CH 2 ) m -NH 2 formula (3)
    式(1)～式(3)中，n＝9-13，m＝9-13。In formula (1) to formula (3), n = 9-13 and m = 9-13.
  2. 根据权利要求1所述的方法，其中，步骤1)和步骤2)在同一反应容器中进行。The method according to claim 1, wherein step 1) and step 2) are performed in the same reaction vessel.
  3. 根据权利要求1所述的方法，其中，所述含氨化合物为氨气和/或尿素。The method according to claim 1, wherein the ammonia-containing compound is ammonia gas and / or urea.
  4. 根据权利要求1所述的方法，其中，式(1)所示的高碳链烷烃二酸与含氨化合物的摩尔比为1：2-10。The method according to claim 1, wherein the molar ratio of the higher-carbon alkane diacid to the ammonia-containing compound represented by formula (1) is 1: 2-10.
  5. 根据权利要求1-4中任意一项所述的方法，其中，所述酰胺化反应条件包括：反应温度为150-250℃，反应时间为8-18小时。The method according to any one of claims 1-4, wherein the amidation reaction conditions include: a reaction temperature of 150-250 ° C, and a reaction time of 8-18 hours.
  6. 根据权利要求1-4中任意一项所述的方法，其中，式(2)所示的高碳链二酰胺与、次氯酸钠和/或次溴酸钠的摩尔比为1：1.8-3.5。The method according to any one of claims 1 to 4, wherein the molar ratio of the high-carbon diamide represented by the formula (2) to sodium hypochlorite and / or sodium hypobromide is 1: 1.8-3.5.
  7. 根据权利要求1-4中任意一项所述的方法，其中，步骤2)在溶剂存在下进行；The method according to any one of claims 1 to 4, wherein step 2) is carried out in the presence of a solvent;
    优选地，式(2)所示的高碳链二酰胺与所述溶剂的重量比为1：5-15；Preferably, the weight ratio of the high-carbon chain diamide represented by formula (2) to the solvent is 1: 5-15;
    优选地，所述溶剂为二氧六环、乙二醇二甲醚、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇二乙醚、四氢呋喃、甲醇、乙醇和丙醇的一种或多种。Preferably, the solvent is one of dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, methanol, ethanol and propanol One or more.
  8. 根据权利要求1-4中任意一项所述的方法，其中，步骤2)中，反应体系的pH值在9以上。The method according to any one of claims 1 to 4, wherein in step 2), the pH value of the reaction system is above 9.
  9. 根据权利要求1-4中任意一项所述的方法，其中，式(3)所示高碳链烷烃二胺为壬二胺、葵二胺、十一烷二胺、十二烷二胺或十三烷二胺。The method according to any one of claims 1 to 4, wherein the high-carbon alkane diamine represented by formula (3) is nonanediamine, sunflower diamine, undecanediamine, dodecanediamine or Tridecanediamine.
  10. 一种高碳链烷烃二胺，其特征在于，通过权利要求1-9中任 意一项所述的方法制备得到。A high-carbon paraffin diamine, which is prepared by the method according to any one of claims 1-9.
  11. 权利要求1-9中任意一项所述的方法制备得到的高碳链烷烃二胺或权利要求10所述的高碳链烷烃二胺在制备聚酰胺中的应用。Use of the high-carbon alkane diamine prepared by the method according to any one of claims 1-9 or the high-carbon alkane diamine according to claim 10 in the preparation of a polyamide.
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