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WO2017088218A1 - 长链末端氨基酸和二元酸的联产方法 - Google Patents

长链末端氨基酸和二元酸的联产方法 Download PDF

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WO2017088218A1
WO2017088218A1 PCT/CN2015/097705 CN2015097705W WO2017088218A1 WO 2017088218 A1 WO2017088218 A1 WO 2017088218A1 CN 2015097705 W CN2015097705 W CN 2015097705W WO 2017088218 A1 WO2017088218 A1 WO 2017088218A1
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acid
reaction
long
derivative
solvent
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PCT/CN2015/097705
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English (en)
French (fr)
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胡松洲
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希锐科技（北京）有限公司
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Priority to US15/601,556 priority Critical patent/US10239821B2/en
Priority to EP15909129.7A priority patent/EP3381888A4/en
Priority to BR112018008166A priority patent/BR112018008166A2/pt
Priority to JP2018519013A priority patent/JP2018535201A/ja
Publication of WO2017088218A1 publication Critical patent/WO2017088218A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/06—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid amides

Definitions

  • the invention relates to a method for producing a long-chain nylon monomer, in particular to a method for co-production of a long-chain terminal amino acid and a dibasic acid.
  • Nylon is a type of high molecular polymer containing an amide group in the main chain of the molecule. Nylon is the most expensive, most diverse and most versatile of engineering plastics.
  • Long-chain nylon has good comprehensive properties due to its unique molecular structure, higher strength than metal, low water absorption, good oil resistance, low temperature resistance, abrasion resistance, chemical resistance, flame retardancy and self-slip property, friction coefficient Low and easy to process.
  • Long-chain nylon can be processed into a variety of plastic products, but also can be drawn into fibers, can be made into films, coatings and thermal adhesives, widely used in automotive, electrical and electronic, machinery, communications, petrochemical, aerospace.
  • Nylon 9, nylon 11 and nylon 12 were industrially produced from long chain amino acids or lactams.
  • nylon 610, nylon 612, nylon 1010, and nylon 1212 have been industrially produced from long chain dibasic acids and diamines.
  • the monomer 9-aminononanoic acid of nylon 9 is obtained from a series of chemical reactions from oleic acid or oleic acid (for a detailed description, see J. Am Oil Chemist's Soc., 1975, Vol. 52, No. 11, pp 473-477).
  • oleic acid is subjected to ozone oxidation and hydrogenation reduction to prepare a methyl phthalate intermediate.
  • methyl 9-aminodecanoate is formed, hydrolyzed, and purified to obtain a 9-aminononanoic acid monomer.
  • the total yield is approximately 35%.
  • the monomer of nylon 11 and 11-aminoundecanoic acid are derived from castor oil, methanolized, pyrolyzed at high temperature, anhydrous hydrogen bromide radical addition, and finally aminolysis (detailed process is described in In the literature A. Chauvel & G. Lefebvre, Petrochemical Processes 2: Major Oxygenated, Chlorinated and Nitrated Derivatives, pages 274-278). The total yield does not exceed 55%.
  • Azelaic acid is a crude product which is prepared by decomposing ricinoleic acid at a high temperature (200 ° C - 250 ° C) with a strong base, and a qualified product is refined through a series of purification.
  • the bio-fermentation process is used to produce dodecanedioic acid and other long-chain dibasic acids, and although the reaction conditions are mild, the crude product contains a large amount of biomass and degraded short-chain diacid impurities.
  • the crude product In order to obtain a qualified product suitable for the production of nylon, the crude product must undergo a large number of complex refining.
  • Various refining methods are described in a large number of patent documents. For a detailed process, see U.S. Patent No. 6,218,574; US Pat. No. 8,729,298 and Chinese Patent No.
  • the present invention provides a method of co-producing long chain amino acids and dibasic acids. Compared with the existing industrial production technology, the production method provided by the invention has mild reaction conditions, high overall yield, and greatly improved product quality, and is suitable for industrial production.
  • the invention adopts the long-chain keto acid derivative (I) as a raw material, and co-produces the long-chain terminal amino acid (V) and the dibasic acid (IV), and proceeds according to the following steps:
  • keto acid derivative (I) in a solvent with a hydroxylation reaction, or a keto acid derivative (I) in a solvent with ammoxidation to produce a phthalic acid derivative (II);
  • a citric acid derivative is subjected to Beckmann rearrangement under the catalysis of a catalyst to form a mixed amide derivative, which comprises a compound represented by the formula (IIIa) and the formula (IIIb);
  • the X is OR or NR1R2;
  • the OR is a C1-C8 unit alcohol or a polyol such as ethylene glycol, propylene glycol, butylene glycol or glycerin.
  • R 1 and R 2 are each hydrogen and C 1 -C 8 alkyl.
  • m is an integer from 0 to 10.
  • n is a 6 to 20 integer.
  • X is OR, ie keto ester.
  • the starting material is a 12-keto stearic acid derivative.
  • a monomer of nylon 11 and 11-aminoundecanoic acid can be produced, and a very important dodecanedioic acid is also produced, which is used for producing nylon 612 and nylon 1212.
  • the starting material is a 10-keto stearic acid derivative.
  • the obtained product is 9-aminononanoic acid, which is a nylon 9 monomer. It is also co-produced with sebacic acid for the production of nylon 610 and nylon 1010.
  • the starting material is a 14-keto-arachidic acid derivative.
  • the product obtained by the above reaction was 13-aminotridecanoic acid, which was used for the synthesis of nylon 13. At the same time, tetradecanedioic acid is produced.
  • the keto acid derivative (I) is reacted with an aqueous solution of hydroxylamine in an organic solvent or subjected to an ammoxidation reaction to form a citric acid derivative (II).
  • the organic solvent may be water-soluble or may be a water-insoluble organic solvent.
  • the solvent selection requirement for the deuteration reaction is that both the keto acid derivative (I) and the decanoic acid derivative (II) are easily soluble in the solvent and do not react with the reactants, products, and hydroxylamine.
  • aldehydes and ketones cannot be used in the deuteration reaction because they themselves react with hydroxylamine.
  • Nitrile solvents also react with hydroxylamine and are not suitable.
  • Ammonia solvents react with ketones to form Schiff bases, and are not suitable.
  • the alcohol solvent is preferably not used because it can undergo an ester conversion reaction with the keto acid derivative (I).
  • the solvent is required to have a good solubility for the citric acid derivative (II) and the amide derivative (III), and the Beckmann rearrangement catalyst can be dissolved without reacting with the catalyst.
  • the solvent required for the deuteration and Beckmann rearrangement reaction must be stable and easy to recycle.
  • the deuteration reaction and the Beckmann rearrangement reaction can use different solvents to meet the requirements of each reaction.
  • the preferred solvent should meet the requirements of both reactions, which reduces solvent use and recovery.
  • the preferred organic solvent is preferably insoluble in water, so that after deuteration and rearrangement, it is convenient to separate the product.
  • the amount of the solvent is not particularly limited because the solvent in the present invention functions only as a diluent and a dispersion reactant.
  • the solvent which satisfies the above requirements is an inert solvent such as an ester, an alkane, an aromatic hydrocarbon or an ether.
  • preferred solvents are, butyl acetate, ethyl acetate, benzene, toluene, xylene, cumene, anisole, Ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, methyl tetrahydrozolium, petroleum ether, cyclohexane, dichloroethane, dichloromethane, chloroform, tetrachloro Carbon, trifluorotoluene.
  • solvents may be used singly or in combination of two or more.
  • the temperature of the deuteration reaction is from 0 ° C to 100 ° C, but it can also be carried out under higher temperature. This reaction is preferably carried out at a normal pressure of from 0 ° C to 100 ° C. If the temperature is too low, the reaction rate is slow and the reaction time is lengthened.
  • the preferred reaction temperature is from 60 ° C to 80 ° C.
  • the deuteration reaction can be carried out in air, but it can also be carried out under an inert gas such as nitrogen, argon or helium.
  • the oximation reaction time is temperature dependent and is usually from 0.5 hours to 24 hours. Preferably, the time is from 1 to 6 hours, and the reaction temperature is controlled between 0 and 100 °C. If the reaction time is too short, the amount of residual keto acid derivative is too large to lower the reaction yield. The residual keto acid derivative can be recovered at the time of post-treatment, but it is necessary to increase the recovery equipment. The long-term reaction can reduce the residual amount of the keto acid derivative, but the reaction equipment must be increased.
  • the deuteration reactor can be a conventional reactor such as a batch reactor, a semi-continuous reactor, a tubular reactor, or a flow reactor.
  • a continuous stirred flow reactor is preferred. If a CSTR reactor is employed, the aqueous solution of aqueous hydroxylamine and the organic solvent of the keto acid derivative (I) can be introduced into the first reactor and then passed to the remaining reactor to complete the reaction.
  • a hydroxylamine salt such as a sulfate, a hydrochloride or an aqueous solution
  • a basic substance preferably ammonia water
  • the aqueous solution can be used to recover an ammonium salt such as ammonium sulfate.
  • the deuteration reaction can also be carried out by an ammoxidation deuteration reaction, which can be carried out according to a conventionally disclosed process, that is, the oxidation of ammonia with hydrogen peroxide and the keto acid derivative (I).
  • the molar ratio of the keto acid derivative (I) to hydroxylamine can be controlled to be between 0.1 and 10.0, preferably between 1.0 and 2.0, to ensure conversion of the keto acid derivative (I) to the decanoic acid derivative (II).
  • the citric acid derivative (II) is dissolved in the organic phase.
  • the aqueous phase is separated and the organic phase is washed.
  • a desiccant or a dehydrating agent may be used in order to remove a small amount of water. But the preferred method is to distill off a little solvent to water Remove. Evaporation of the solvent can be used directly in the deuteration reaction section without drying. The remaining anhydrous citric acid derivative solution can be used directly in the Beckmann rearrangement reaction.
  • the above-mentioned dehydrated citric acid derivative (II) is subjected to Beckmann rearrangement by heating under the action of a catalyst to form an amide derivative (III).
  • the catalyst used is sulfuric acid or a mixture containing an acidic active halogen compound or an acidic active halogen compound and a Lewis acid.
  • the acid active halogen compound can be used alone to catalyze the Beckmann rearrangement reaction. However, a combined catalyst with a Lewis acid can achieve a better reaction effect.
  • the acidic active halogen compound is preferably a chlorine-containing compound.
  • Suitable acidic active chlorine compounds are thionyl chloride, chlorinated sulfone, chlorosulfonic acid, various sulfonyl chlorides: methanesulfonyl chloride, benzenesulfonyl chloride, p-toluenesulfonyl chloride, various acid chlorides such as formyl chloride, acetyl chloride, benzene. Any of a mixture of formyl chloride, oxalyl chloride, phosgene, diphosgene, triphosgene, and boron trichloride, or a mixture of two or more thereof in any ratio, and various chlorine-containing phosphorus compounds.
  • a reactive acidic chlorine heterocyclic compound particularly a trimeric chloronitrile or a phosphazene, can also be used as a catalyst.
  • the Lewis acid may be a metal halide such as zinc chloride, iron chloride, cobalt chloride, tin chloride, aluminum chloride, titanium chloride or boron trichloride, or two or more thereof. Mixtures mixed in any ratio.
  • the acidic active chlorine compound is used in an amount of not more than 10% by mole based on the mole of the phthalic acid derivative, preferably 0.1 to 5% by mole of the phthalic acid derivative.
  • the amount of the acidic active chlorine compound and the Lewis acid is also the amount of the catalyst, i.e., not more than 10% by mole of the decanoic acid derivative, and preferably 0.1 to 5% by mole of the citric acid derivative.
  • the amount of sulfuric acid can be used according to a conventionally disclosed process.
  • the molar ratio of Lewis acid to acidic active chlorine is from 1:0.01 to 1:100, preferably from 1:0.3 to 1:1.5.
  • the amount of catalyst used, the temperature at the reaction, the reaction pressure, and the reaction time are related to each other. Increasing the amount of catalyst at a particular reaction temperature can shorten the reaction time.
  • the Beckmann reaction temperature of the citric acid derivative is not strictly limited, and can be completed from room temperature to reflux temperature. It can also be completed by heating under pressure. However, if the temperature is too high, the color of the product will be deeper, which is not conducive to post-treatment.
  • the rearrangement reaction can be carried out in the atmosphere or under the protection of an inert gas such as nitrogen, argon or helium.
  • the reaction is preferably carried out under dry air.
  • the rearrangement reaction is not limited by pressure and can be carried out under normal pressure or under reduced pressure and pressure.
  • the rearrangement reaction also has no limitations on the reactor. Commonly used reactors and tubular reactors can be used. The reaction can be carried out batchwise, semi-continuously, or continuously.
  • the active catalyst can be quenched, and the product can be separated and recycled. If needed
  • the reaction can be completed by adding a small amount of water.
  • the added water may also carry a small amount of an acid or a base, and some inorganic salts may be added.
  • the amide derivative formed by the Beckmann reaction is a mixture of two amides, (IIIa) and (IIIb), and their molar ratios are almost the same.
  • this mixture can be purified to obtain a pure amide derivative and then passed to the hydrolysis step, but the crude product can also be directly hydrolyzed, and the introduced impurities are removed after hydrolysis.
  • the purity of the phthalic acid ester (II) is high, the rearranged product is very pure.
  • the hydrolysis of the amide derivative can be carried out in an acid.
  • the acid to be used may be any one of sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, or the like, or a mixture of two or more thereof in any ratio.
  • the amount of the acid and the reaction conditions in the hydrolysis reaction can be in accordance with a conventionally disclosed process.
  • an organic solvent such as methanol, ethanol, formic acid, acetic acid or the like may be added.
  • the crystallization is cooled to separate an almost pure saturated diacid. After the mother liquor is neutralized to neutral, long-chain amino acids can be isolated. The long-chain dibasic acid and amino acid are recrystallized to obtain a qualified product.
  • Long chain mixed amide derivatives including compounds of formula (IIIa) and formula (IIIb), may also be hydrolyzed with a base.
  • the amount of the base and the reaction conditions in the hydrolysis reaction may be in accordance with a conventionally disclosed process.
  • the base which may be used may be any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and barium hydroxide, or a mixture of two or more thereof in any ratio.
  • the hydrolyzed solution may be a mixed solvent of water or a mixture of water and an organic solvent in an arbitrary ratio.
  • the organic solvent is any one of methanol, ethanol, isopropanol, tetrahydrofuran, dioxane, and the like, or a mixture of two or more thereof in any ratio.
  • the temperature of the hydrolysis reaction is preferably from 50 ° C to 200 ° C, and the pressure is preferably a self-generated pressure from a normal pressure to a hydrolysis temperature, and may be pressurized.
  • the hydrolysis reaction is preferably carried out in air or under the protection of an inert gas.
  • the hydrolysis time is determined by the alkali concentration and the reaction temperature, from 1 hour to 24 hours. The preferred time is 2 to 4 hours. The reaction time is too short and the hydrolysis reaction cannot be completed. If the reaction time is too long, the volume of the reactor increases, increasing unnecessary investment.
  • the organic solvent is removed, and the pH is adjusted to neutral with an acid to precipitate a long-chain amino acid.
  • the acids used are sulfuric acid, hydrochloric acid, nitric acid, and organic acids such as acetic acid, propionic acid, citric acid, tartaric acid, and the like.
  • a mineral acid is preferred.
  • the mother liquor is continuously adjusted to a pH of less than 5 to precipitate a long-chain dibasic acid.
  • the product is separated by filtration.
  • long-chain dibasic acid and amino acid prepared by the present invention are very pure and do not contain any other impurities such as dibasic acid and iminodibasic acid.
  • the water phase is separated. After the organic phase was distilled off 50 mL of water, 0.8 g of triphosgene and 1.2 g of zinc chloride were added. The reaction was stirred at 90 ° C for 3 hours until the end of the rearrangement reaction. The reaction was stopped by the addition of 50 mL of water. The solvent is recovered after the aqueous phase is separated. An off-white mixed methyl amide was obtained.
  • the mother liquor was heated to 85 ° C and continued to acidify to pH 1 with 30% hydrochloric acid to form a large solid. Cool to room temperature, filter, wash with water, wash with methanol, and dry to give 70.6 g of tetradecanedioic acid. HPLC analysis indicated a product purity of 99.7%.
  • Example 1 20 g of dry 12-methyl stearate was added to 100 ml of 98% sulfuric acid, and the raw material was dried according to the procedure of Example 1.
  • the HPLC analysis showed a purity of 99.2%. Slowly heat to 100 ° C, keep warm for 1 hour, cool to room temperature, pour into 200 g of crushed ice, stir and filter to get 18g The amide ester is mixed. Subsequent to the procedure in Example 1, 8.9 g of 11-aminoundecanoic acid was obtained. HPLC analysis indicated a product purity of 99.2%; 9.6 g of dodecanedioic acid. HPLC analysis indicated a product purity of 99.4%.

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Abstract

一种长链末端氨基酸和二元酸的联产方法。该方法由下列步骤组成：(a)将酮酸衍生物在溶剂中与羟氨反应或进行氨氧化肟化反应生成肟酸衍生物；(b)将生成的肟酸衍生物进行贝克曼重排反应生成混合的酰胺衍生物；(c)将得到的混合酰胺衍生物水解生成长链末端氨基酸和长链二元酸。

Description

长链末端氨基酸和二元酸的联产方法 技术领域
本发明涉及长链尼龙单体的生产方法，特别是长链末端氨基酸和二元酸的联产方法。
背景技术
长链饱和脂肪末端氨基酸，内酰胺，和二元酸是工业生产长链尼龙工程塑料的重要单体。尼龙是分子主链上含有酰胺基团的一类高分子聚合物。尼龙是工程塑料中消耗最大，品种最多，用途最广的一种。
长链尼龙由于其特有的分子结构，具有良好的综合性能，强度高于金属，吸水率低，耐油性好，耐低温，耐摩损性，耐化学性，阻燃性及自滑性，摩擦系数低而且容易加工。长链尼龙可以加工制成各种塑料制品，也可拉丝成纤维，可以制成薄膜，涂料和热胶粘剂，广泛用于汽车，电子电气，机械，通讯，石油化工，航空航天领域。
以长链氨基酸或内酰胺为单体工业上生产了尼龙9，尼龙11和尼龙12。
以长链二元酸和二元胺为原料工业上生产了重要的尼龙610，尼龙612，尼龙1010，和尼龙1212。
在现在有工业生产技术中，尼龙9的单体9-氨基壬酸是从油酸或油腈经过一系列化学反应得到的(详细的描述可见文献J.Am Oil Chemist's Soc.,1975,Vol.52,No.11,pp 473-477)。首先，油酸经臭氧氧化，氢化还原制备壬醛酸甲酯中间体。经还原氨解后生成9-氨基壬酸甲酯，水解，精制得到9-氨基壬酸单体。总收率大约为35％。
尼龙11的单体，11-氨基十一烷酸则是从蓖麻油为原料，经甲醇化，高温热解，无水溴化氢自由基加成，最后氨解得到(详细的工艺过程描述在文献中A.Chauvel&G.Lefebvre,Petrochemical Processes 2:Major Oxygenated,Chlorinated and Nitrated Derivatives,pages 274-278)。总收率不超过55％。
尼龙12的单体，月桂内酰胺，在工业上是丁二烯出发，经过催化三聚，加氢还原，氧化成环十二烷酮,肟化反应，贝克曼重排一系列反应得到(详细的工艺过程描述在文献中A.Chauvel&G.Lefebvre Petrochemical Processes 2:Major Oxygenated,Chlorinated and Nitrated Derivatives,pages 279-286)。
在长链二元酸的工业生产中，壬二酸是从油酸经完全氧化得到。癸二酸则是用强碱在高温下(200℃-250℃)分解蓖麻酸制备粗产品，经一系列提纯精制出合格成品。
对于重要的十二碳二酸来说，工业上釆用了二种十分不同的路线。一种是化学合成，从丁二烯出发，经过催化三聚，氢化还原，氧化化成醇和酮，再经硝酸完全氧化生产。但是目前更多的是用生物发酵的方法氧化高纯度的正十二烷烃或者月桂酸酯生产。
在用化学合成方法生产这些单体时，目前的方法存在的主要问题是反应收率低(9-氨基酸壬酸仅为35％，11-氨基十一烷酸仅为55％，壬二酸仅为80％),反应条件剧烈并且非常不安全。例如生产9-氨基壬酸时用到臭氧化反应，生产11-氨基十一烷酸用到高温热解，以及生产月桂内酰胺和十二碳二酸时用的无水无氧三聚反应，生产癸二酸的高温碱解。
生物发酵法用于生产十二碳二酸和其它长链二元酸，尽管反应条件温和，但是粗产品中含有大量的生物质和降解的短链二酸杂质。为了获得适合用于生产尼龙的合格产品，粗产品必须经过大量的复杂精制。各种精制方法描述在大量的专利文献中.详细的过程可见美国专利U.S.6,218,574；U.S.8,729,298和中国专利CN 104591998A；CN 102476990A；CN 102329224A；CN 103497100A；CN 102795989A；CN 104447274A；CN 104447280A；CN 104496793A；CN 104529741A；CN 104529747A.
发明内容
针对现有技术的不足，本发明提供了一个联产长链氨基酸和二元酸的方法。与现有工业生产技术相比，本发明所提供的生产方法反应条件温和，整体收率高，产品质量大幅度提高，适合于工业化生产。
本发明采用长链酮酸衍生物(I)为原料,联产长链末端氨基酸(V)和二元酸(IV)，依以下步骤进行：
(1)酮酸衍生物(I)在溶剂中与羟氨进行肟化反应，或者酮酸衍生物(I)在溶剂中与进行氨氧化肟化反应生产肟酸衍生物(II)；
(2)肟酸衍生物在催化剂的催化下进行贝克曼重排生成混合酰胺衍生物，包括式(IIIa)和式(IIIb)所示的化合物；
(3)水解贝克曼重排产物，混合酰胺衍生物，包括式(IIIa)和式(IIIb)所示的化合物，得到长链氨基酸(V)和二元酸(IV)。水解反应同时还附产短链伯胺和短链烷酸。
上述的反应过程如下：
Figure PCTCN2015097705-appb-000001
反应方程式中，所述的X为OR或者NR1R2；所述的OR为C1-C8的单元醇或者为多元醇，如乙二醇、丙二醇、丁二醇或者甘油等。R1和R2分别为氢和C1-C8烷基。m为0到10整数。n为6到20整数。优选的X为OR,即酮酸酯.
值得指出的是，当m＝5，n＝10时，原料为12-酮基硬脂酸衍生物。经过本发明公开的生产方法，可以生产出尼龙11的单体，11-氨基十一烷酸，同时还联产十分重要的十二碳二酸，用于生产尼龙612和尼龙1212。
当m＝7，n＝8时，原料为10-酮基硬脂酸衍生物。经过本发明的过程，得到的产物为9-氨基壬酸，即为尼龙9单体。同时也联产癸二酸，用于生产尼龙610和尼龙1010。
当m＝5，n＝12时，原料为14-酮基花生酸衍生物。经上述反应得到的产品为13-氨基十三烷酸，用于合成尼龙13。同时生产出十四碳二酸。
在肟酸衍生物(II)形成步骤，酮酸衍生物(I)在有机溶剂中与羟氨的水溶液反应或进行氨氧化肟化反应生成肟酸衍生物(II)。有机溶剂可为水溶性，也可为不溶于水有机溶剂。肟化反应的溶剂选择要求是酮酸衍生物(I)和肟酸衍生物(II)都易溶于该溶剂，并且不和反应物、产物、羟氨发生反应。例如醛和酮类是不能用于肟化反应，因为它们本身会与羟氨反应。腈类溶剂也会与羟氨反应，也不适合。氨类溶剂会与酮反应生成席夫碱,亦不适用。醇类溶剂由于能与酮酸衍生物(I)发生酯变换反应，最好也不采用。
对于贝克曼重排反应而言，要求溶剂对肟酸衍生物(II)和酰胺衍生物(III)有较好的溶解性，并且能溶解贝克曼重排催化剂并不与催化剂发生反应。
对于肟化和贝克曼重排反应所需的溶剂，必需稳定并且易于回收。肟化反应和贝克曼重排反应可采用不同的溶剂来满足各反应的本身要求。但是优选的溶剂应同时满足二个反应的要求，这样可减少溶剂的使用和回收。优选的有机溶剂最好不溶于水，这样肟化和重排反应后，便于分离产品。溶剂量不需要特别限定，因为本发明中溶剂仅起到稀释和分散反应物的作用。
能满足上述要求的溶剂有:酯，烷烃，芳烃，醚类等惰性溶剂。例如，优选的溶剂有，乙酸丁酯，乙酸乙酯，苯，甲苯，二甲苯，异丙基苯，茴香醚， 乙醚，异丙醚，丁醚，甲基叔丁基醚，乙基叔丁基醚，甲基四氢唑喃，石油醚，环己烷，二氯乙烷，二氯甲烷，氯仿，四氯化碳，三氟甲苯。
这些溶剂可单独使用，也可二个或多个混合使用。
肟化反应的温度是0℃-100℃，但也可在更高的温度下加压进行。这个反应优选在0℃-100℃常压进行。如果温度太低则反应速度很慢，反应时间加长。优选的反应温度为60℃到80℃。
肟化反应可以在空气中进行，但也可在惰性气体，如氮气，氩气，氦气保护下进行。
肟化反应时间与温度有关，通常为0.5小时到24小时。优选时间为1到6小时，反应温度控制在0～100℃之间。如果反应时间太短，残余的酮酸衍生物量太大，降低反应收率。残余的酮酸衍生物可以在后处理时回收，但需要增加回收设备。长反应时可以减少酮酸衍生物的残留量，但反应设备必需增大。
肟化反应器可以是常用反应器，如批次反应釜，半连续反应釜，管式反应器，或流动反应釜。优选连续搅拌流动反应器(CSTR)。如果采用CSTR反应器，羟氨水溶液和酮酸衍生物(I)有机溶剂可同进入第一个反应器，再流到剩余的反应器中完成反应。
肟化反应中如果使用羟氨盐，如硫酸盐，盐酸盐，水溶液，要用碱性物质，优选氨水，调节反应的pH值在3到14之间来保证反应的进行。反应完后，水溶液可用来回收铵盐，如硫酸铵。肟化反应也可釆氨氧化肟化反应,氨氧化肟化反应可以按照传统的公开的工艺方法进行，即用双氧水氧化氨与酮酸衍生物(I)进行肟化。
酮酸衍生物(I)和羟氨的摩尔比可控制在0.1～10.0之间，优选1.0～2.0之间来保障酮酸衍生物(I)转化为肟酸衍生物(II)。
反应完后，肟酸衍生物(II)溶在有机相中。分出水相并洗涤有机相。尽管水在有机相的溶解度很小，但会破坏贝克曼重排催化剂的活性，所以必须除去。为了除去少量的水，可选用干燥剂或脱水剂。但优选的方法是蒸除少许溶剂将水 除去。蒸发走溶剂不经干燥可直接用于肟化反应段。留下的无水肟酸衍生物溶液可直接用于贝克曼重排反应。
上述的经脱水的肟酸衍生物(II)经加热在催化剂作用下经过贝克曼重排生成酰胺衍生物(III)。所用的催化剂为硫酸或含有酸性活泼卤素化合物或含有酸性活泼卤素化合物和路易斯酸的混合物。酸性活泼卤素化合物可单独用催化贝克曼重排反应。但与路易斯酸的组合催化剂可以取得更好的反应效果。酸性活泼卤素化合物优选含氯化合物。
适用的酸性活泼氯化合物有氯化亚砜，氯化砜，氯磺酸,各种磺酰氯:甲磺酰氯，苯磺酰氯，对甲苯磺酰氯，各种酰氯，如甲酰氯，乙酰氯，苯甲酰氯，草酰氯，光气，二光气，三光气,三氯化硼中的任意一种，或两种及其以上以任意比例混合而成的混合物，还有各种含氯的磷化合物，如三氯化磷，五氯化磷，三氯氧磷中的任意一种，或两种及其以上以任意比例混合而成的混合物。另外，含有活泼酸性氯杂环化合物，特别是三聚氯腈，磷腈，也可用作催化剂。
可用路易斯酸有金属卤化物，如氯化锌，氯化铁，氯化钴，氯化锡，氯化铝，氯化钛，三氯化硼中的任意一种，或两种及其以上以任意比例混合而成的混合物。
在上述的贝克曼重排反应中，酸性活泼氯化合物的用量为催化剂量，即不大于肟酸衍生物摩尔量的10％，优选肟酸衍生物摩尔量的0.1～5％。酸性活泼氯化合物和路易斯酸的用量也为催化剂量，即不大于肟酸衍生物摩尔量的10％，优选肟酸衍生物摩尔量的0.1～5％。用硫酸催化重排时，硫酸用量按照传统的公开的工艺方法即可。
路易斯酸和酸性活性氯的摩尔比为1：0.01到1：100，优选1：0.3到1：1.5之间。
催化剂的用量，反应时温度，反应压力，和反应时间有相互的关联。在特定的反应温度下，增加催化剂的用量可以缩短反应时间。
肟酸衍生物的贝克曼反应温度没有严格的限制，常温到回流温度就可完成。也可在加压下升温完成。但温度太高，产物的颜色会加深，不利于后处理。
重排反应可以在大气中完成，也可在惰性气体，如氮气、氩气、氦气保护下进行。本反应优选在干燥的空气下完成。重排反应不受压力的限制，可在常压、也可在减压和加压下进行。
重排反应对反应器也没有限制。常用的反应釜、管式反应器都可使用。反应可以间歇式进行、半连续进行、或连续进行。
反应完后，活性的催化剂可以淬灭，也可分出产品后继续循环使用。如果需要
Figure PCTCN2015097705-appb-000002
灭反应加入少量的水就可完成。加入的水中也可带有少量的酸或碱，可加些无机盐。
经过贝克曼反应生成的酰胺衍生物是二种酰胺的混合物,(IIIa)和(IIIb)，它们的摩尔比几乎相同。在回收溶剂后，这个混合物可经提纯得到纯的酰胺衍生物再进入水解步骤，但粗产品也可直接水解，引入的杂质在水解后再除去。事实上，如果肟酸酯(II)的纯度很高的话，重排产物非常纯。
酰胺衍生物的水解可以在酸中进行。所用的酸可以为硫酸、盐酸、氢溴酸、氢碘酸、硝酸等中的任意一种，或两种及其以上以任意比例混合而成的混合物。水解反应中酸的用量及反应条件按照传统的公开的工艺方法即可。反应时，为了增加混合酰胺衍生物，包括式(IIIa)和式(IIIb)所示的化合物的溶解度，可以加入有机溶剂，如甲醇、乙醇、甲酸、乙酸等。
在水解完后，冷却结晶即可分离出几乎为纯的饱和二酸。母液经中和到中性后，即可分离出长链氨基酸。长链二元酸和氨基酸经重结晶精制得到合格产品。
长链的混合酰胺衍生物，包括式(IIIa)和式(IIIb)所示的化合物，也可用碱水解。水解反应中碱的用量及反应条件按照传统的公开的工艺方法即可。可以选用的碱可以为氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、和氢氧化钡等中的任意一种，或两种及其以上以任意比例混合而成的混合物。水解的溶液可以用水，也可采用水、有机溶剂以任意比例混合而成的混合溶剂。所述的有机溶剂为甲醇、乙醇、异丙醇、四氢呋喃、二氧六环等中的任意一种，或两种及其以上以任意比例混合而成的混合物。
水解反应的温度优选为50℃～200℃，压力优选为从常压到水解温度的自生压力,也可加压。水解反应优选在空气中进行，也可在隋性气体保护下进行。
水解时间由碱浓度、反应温度确定，从1小时到24小时。优选时间为2～4小时。反应时间太短水解反应不能进行完成。反应时间过长，则反应器的体积增大，增加不必要的投资。
水解结束后，除去有机溶剂，用酸调pH到中性，析出长链氨基酸。所用的酸为硫酸、盐酸、硝酸、和有机酸，如乙酸、丙酸、柠檬酸、酒石酸等。优选无机酸。
分出氨基酸后，母液继续调pH到小于5，即可析出长链二元酸。过滤分离出产品。
值得指出的是，由本发明制备出的长链二元酸和氨基酸纯度非常高，不含任何其它二元酸和亚氨基二元酸等杂质。
具体实施方式
下面结合具体实例对本发明所述方案作进一步的详细描述,但本发明并不限于这些实施例.
实例1.尼龙11单体和十二碳二酸的联产
94克12-酮基硬脂酸甲酯溶于500毫升甲苯中，加入含有13.5克羟氨的硫酸羟氨水溶液(～8％)。在70～85℃剧烈搅拌，并用氨水保持体系的pH在4.5～5.0之间，6小时后HPLC分析表明原材料反应完全转换成12-肟硬脂酸甲酯。
反应完后，静置分层，排出水相。然后加入1.1克三聚氯腈和1.5克氯化锌。在90～105℃搅拌反应2小时至贝克曼重排完成。加入50mL水终止反应。分走水相后回收甲苯，得到类白色混合酰胺酸甲酯。
将上述固体加热溶解在500mL 10％氢氧化钠水溶液中，置入高压釜内，在150℃下保温4小时，HPLC分析表明水解完成。
在水解液中加入500mL水，加入2g活性碳在90℃脱色30分钟后，用稀硫酸中和至pH 7.5。冷却至室温后，经过滤、洗涤、烘干得到55.8g 11-氨基十一烷酸。HPLC分析表明产物纯度为99.7％。
母液加热至85℃，继续用硫酸酸化至pH 1，大量固体析出。冷却至室温,过滤，蒸馏水洗三次，甲醇洗涤一次。烘干得到62.4g十二碳二酸。HPLC分析表明产物纯度为99.5％。
实例2.尼龙9单体和癸二酸的联产
94克10-酮基硬脂酸甲酯溶于500毫升醋酸丁酯中，加入含有12.5克羟氨的硫酸羟氨水溶液(～8％浓度)。在70～80℃度剧烈搅拌6小时，并用氨水保持体系的pH在4.5～5.0之间。HPLC分析表明原材料全部转化为10-肟硬脂酸甲酯。
分出水相。有机相蒸出50mL除水后，加入0.8g三光气和1.2g氯化锌。在90℃度下搅拌反应3小时到重排反应结束。加入50mL水终止反应。分出水相后回收溶剂。得到类白色混合酰胺酸甲酯。
将上述固体溶于200mL乙酸中，再加入200mL 30％盐酸，回流48小时至水解完成。加入500mL水，冷却结晶。过滤，烘干得54.6g癸二酸。HPLC分析表明产物纯度为99.5％。
毋液减圧蒸干。将固体溶于800mL水中，加热到80℃。用氨水中和至pH 6.5-7.0。冷却，过滤，烘干。得到45.6g 9-氨基壬酸。HPLC分析表明产物纯度为99.6％。
实例3.尼龙13单体和十四碳二酸的联产
102.2g 14-酮基花生酸甲酯溶于500mL茴香醚中，加入含有16.5g羟氨的硫酸羟氨水溶液(8％浓度)。在75～85℃下剧烈搅拌8小时，并用氨水保持体系的pH在4.5～5.0之间。HPLC分析表明原材料全部转化为14-肟花生酸甲酯。
分走水相。有机相减压蒸出50mL除水后，加入1.2g对甲苯磺酰氯和1.5g氯化锌，在90～105℃度搅拌反应2小时完成贝克曼重排反应，加入50mL水终止反应。分出水相后减压回收苯甲醚，残余物冷却后固化为混合酰胺酸甲酯。
将上述固体加热溶解在700mL 8％的氢氧化钠水溶液中，置于高压釜内，在150℃下水解5小时。HPLC分析表明水解完成。
在水解液中加入600mL水，2g活性碳，在90℃下脱色45分钟。过滤除碳后，在80～90℃下用30％盐酸中和至pH 7.0-7.5。冷却到室温，过滤，水洗，烘干得到62.7g 13-氨基十三烷酸。HPLC分析表明产物纯度为99.5％。
母液加热到85℃，继续用30％盐酸酸化到pH 1，大量固体生成。冷却至室温，过滤，水洗，甲醇洗，烘干得到70.6g十四碳二酸。HPLC分析表明产物纯度为99.7％。
实例4.12-酮基硬脂酸甲酯的氨氧化肟化反应
将95克12-酮基硬脂酸甲酯溶于500ml甲苯中，加入20g钛硅分子筛，搅拌升温到70℃，在2小时内同时均匀滴加50ml质量分数为27.5％的双氧水和70ml质量分数为25％的氨水。在75℃下搅拌反应60分钟后冷却，静置分层。HPLC分析表明原材料完全转换成为12-肟硬脂酸甲酯。后续按照实施例1中的操作，得到56.5g 11-氨基十一烷酸。HPLC分析表明产物纯度为99.5％；63.7g十二碳二酸。HPLC分析表明产物纯度为99.3％。
实例5.硫酸催化12-肟硬脂酸甲酯的贝克曼重排反应
在100ml 98％的硫酸中，加入20g干燥的12-肟硬脂酸甲酯，该原料按照实施例1中的操作经干燥后制备得到，HPLC分析表明其纯度为99.2％。缓慢加热到100℃，保温1小时，冷却到室温后倒入200g碎冰上，搅拌后过滤得到18g 混合酰胺酯。后续按照实施例1中的操作，得到8.9g 11-氨基十一烷酸。HPLC分析表明产物纯度为99.2％；9.6g十二碳二酸。HPLC分析表明产物纯度为99.4％。
上述实例只是为说明本发明的技术构思以及技术特点，并不能以此限制本发明的保护范围。凡根据本发明的实质所做的等效变换或修饰，都应该涵盖在本发明的保护范围之内。

Claims (10)

  1. 一种联产长链氨基酸和二元酸的方法，其特征在于包括以下步骤：
    (1)将具有下式的酮酸衍生物(I)
    Figure PCTCN2015097705-appb-100001
    在溶剂中与羟氨进行肟化反应，或者酮酸衍生物(I)在溶剂中与进行氨氧化肟化反应，生产肟酸衍生物(II)；
    Figure PCTCN2015097705-appb-100002
    在上述式中，所述的X为OR或者NR1R2；所述的OR为C1-C8的单元醇或者为多元醇，如乙二醇、丙二醇、丁二醇或者甘油等。R1和R2分别为氢和C1-C8烷基。m为0到10整数。n为6到20整数。
    (2)将经过脱水干燥过的肟酸衍生物在溶剂中进行贝克曼重排反应生成具有下式的混合酰胺衍生物(IIIa)和(IIIb)
    Figure PCTCN2015097705-appb-100003
    (3)将上述的混合酰胺衍生物水解生成具有下式的长链氨基酸(V)和二元酸(IV)。
    Figure PCTCN2015097705-appb-100004
  2. 如权利要求1，肟化反应的温度保持在0℃到100℃之间，pH在3到14之间。
  3. 如权利要求1，贝克曼重排反应的催化剂为硫酸，或含有酸性活泼卤素化合物，或含有酸性活泼卤素化合物和路易斯酸的混合物。
  4. 如权利要求1，肟化反应和贝克曼重排反应所用的溶剂可用不同溶剂或同一种溶剂。
  5. 如权利要求1，贝克曼重排反应的产物是混合的酰胺衍生物(IIIa)和(IIIb)。
  6. 如权利要求1，混合酰胺衍生物经酸水解生成长链氨基酸(V)和二元酸(IV)。
  7. 如权利要求1，混合酰胺衍生物经碱水解生成长链氨基酸(V)和二元酸(IV)。
  8. 如权利要求1，长链氨基酸和二元酸从水解混合物中经分步中和法分离和提纯。
  9. 如权利要求1，长链氨基酸可作为生产长链尼龙的单体。
  10. 如权利要求1，长链二元酸可作为生产长链尼龙的单体。
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9969676B1 (en) 2017-06-28 2018-05-15 Vitaworks Ip, Llc Process for the separation of long chain amino acids and dibasic acids
US10053416B1 (en) 2017-07-12 2018-08-21 Vitaworks Ip, Llc Process for producing long chain amino acids and dibasic acids
WO2019005631A1 (en) 2017-06-28 2019-01-03 Vitaworks Ip, Llc PROCESS FOR THE SEPARATION OF LONG CHAIN AMINO ACIDS AND LONG CHAIN DIBASIC ACIDS
WO2019005633A1 (en) 2017-06-28 2019-01-03 Vitaworks Ip, Llc METHOD FOR SEPARATING LONG-CHAIN AMINO ACIDS AND DIBASIC ACIDS
WO2019010016A1 (en) * 2017-07-07 2019-01-10 Vitaworks Ip, Llc PROCESS FOR THE PRODUCTION OF AMINO ACIDS AND LONG CHAIN DIBASIC ACIDS
US20190010116A1 (en) * 2017-06-28 2019-01-10 Vitaworks Ip, Llc Process for the separation of long chain amino acids and dibasic acids
WO2019118072A1 (en) * 2017-12-14 2019-06-20 Vitaworks Ip, Llc Process for purifying long chain amino acids
US10343978B2 (en) 2017-07-07 2019-07-09 Vitaworks Ip, Llc Process for producing long chain amino acids and dibasic acids
US10822300B2 (en) 2017-07-07 2020-11-03 Vitaworks Ip, Llc Process for producing long chain amino acids and dibasic acids
WO2020251613A1 (en) 2019-06-10 2020-12-17 Vitaworks Ip, Llc Producing long chain amino and dibasic acids

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10239823B2 (en) * 2017-08-25 2019-03-26 Vitaworks Ip, Llc Process for purifying long chain amino acids
CN110386877B (zh) * 2018-04-16 2022-08-05 湖北金鹤化工有限公司 一种水解混合物的分离方法
EP4214266A1 (de) * 2020-09-16 2023-07-26 Evonik Operations GmbH Verfahren zur sauren hydrolyse von reinem polylaurinlactam

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6218574B1 (en) 1998-12-03 2001-04-17 China Petrochemical Corporation Process for purifying long-chain dicarboxylic acid
CN102089272A (zh) * 2008-07-10 2011-06-08 阿克马法国公司 由天然不饱和脂肪酸合成9-氨基壬酸或其酯的方法
US20110251414A1 (en) * 2008-12-19 2011-10-13 Arkema France Process for the ammonolysis of 11-bromoundecanoic acid
CN102329224A (zh) 2011-09-13 2012-01-25 淮安清江石油化工有限责任公司 十二碳二元酸的提纯方法
CN102476990A (zh) 2010-11-29 2012-05-30 中国石油化工股份有限公司 一种萃取精制长链二元酸粗产品的方法
CN102795989A (zh) 2012-08-28 2012-11-28 淄博广通化工有限责任公司 十二烷二酸精制方法
CN103497100A (zh) 2013-09-23 2014-01-08 中国石油化工股份有限公司 长链二元酸水相双阶段提纯方法
US8729298B2 (en) 2011-03-28 2014-05-20 Cathay Industrial Biotech Ltd. Method for separation and purification of long-chain diacids
CN103804209A (zh) * 2014-02-08 2014-05-21 中北大学 一种由10-十一烯酸制取11-氨基十一酸的方法
CN104447274A (zh) 2014-12-26 2015-03-25 淄博广通化工有限责任公司 长碳链二元酸提纯精制结晶母液的回收利用方法
CN104447280A (zh) 2014-12-26 2015-03-25 淄博广通化工有限责任公司 十二烷二酸提纯精制结晶母液的回收利用方法
CN104496793A (zh) 2014-12-26 2015-04-08 淄博广通化工有限责任公司 长碳链二元羧酸的精制方法
CN104529741A (zh) 2014-12-26 2015-04-22 淄博广通化工有限责任公司 长碳链二元羧酸的提纯方法
CN104529747A (zh) 2014-12-26 2015-04-22 淄博广通化工有限责任公司 十二烷二酸的纯化方法
CN104591998A (zh) 2013-11-03 2015-05-06 中国石油化工股份有限公司 一种纯化长链二元酸的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2462855A (en) 1944-04-21 1949-03-01 Alais & Froges & Camarque Cie Method for preparing the 11-amino-undecylic acid
US5498733A (en) 1993-07-19 1996-03-12 Howard University Synthesis of nylon-11 monomer
CN101757945B (zh) * 2009-12-25 2013-04-24 湘潭大学 一种用于催化酮类肟化反应的钛硅分子筛ts-1催化剂

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6218574B1 (en) 1998-12-03 2001-04-17 China Petrochemical Corporation Process for purifying long-chain dicarboxylic acid
CN102089272A (zh) * 2008-07-10 2011-06-08 阿克马法国公司 由天然不饱和脂肪酸合成9-氨基壬酸或其酯的方法
US20110251414A1 (en) * 2008-12-19 2011-10-13 Arkema France Process for the ammonolysis of 11-bromoundecanoic acid
CN102476990A (zh) 2010-11-29 2012-05-30 中国石油化工股份有限公司 一种萃取精制长链二元酸粗产品的方法
US8729298B2 (en) 2011-03-28 2014-05-20 Cathay Industrial Biotech Ltd. Method for separation and purification of long-chain diacids
CN102329224A (zh) 2011-09-13 2012-01-25 淮安清江石油化工有限责任公司 十二碳二元酸的提纯方法
CN102795989A (zh) 2012-08-28 2012-11-28 淄博广通化工有限责任公司 十二烷二酸精制方法
CN103497100A (zh) 2013-09-23 2014-01-08 中国石油化工股份有限公司 长链二元酸水相双阶段提纯方法
CN104591998A (zh) 2013-11-03 2015-05-06 中国石油化工股份有限公司 一种纯化长链二元酸的方法
CN103804209A (zh) * 2014-02-08 2014-05-21 中北大学 一种由10-十一烯酸制取11-氨基十一酸的方法
CN104447274A (zh) 2014-12-26 2015-03-25 淄博广通化工有限责任公司 长碳链二元酸提纯精制结晶母液的回收利用方法
CN104447280A (zh) 2014-12-26 2015-03-25 淄博广通化工有限责任公司 十二烷二酸提纯精制结晶母液的回收利用方法
CN104496793A (zh) 2014-12-26 2015-04-08 淄博广通化工有限责任公司 长碳链二元羧酸的精制方法
CN104529741A (zh) 2014-12-26 2015-04-22 淄博广通化工有限责任公司 长碳链二元羧酸的提纯方法
CN104529747A (zh) 2014-12-26 2015-04-22 淄博广通化工有限责任公司 十二烷二酸的纯化方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Dodecanedioic Acid Made from Butadiene", PETROCHEMICAL TECHNOLOGY, vol. 6, no. 6, 30 June 1977 (1977-06-30) *
A. CHAUVEL; G. LEFEBVRE: "Petrochemical Processes 2: Major Oxygenated", CHLORINATED AND NITRATED DERIVATIVES, pages 274 - 278
A. CHAUVEL; G. LEFEBVRE: "Petrochemical Processes 2: Major Oxygenated", CHLORINATED AND NITRATED DERIVATIVES, pages 279 - 286
J. AM OIL CHEMIST'S SOC., vol. 52, no. 11, 1975, pages 473 - 477
See also references of EP3381888A4

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US10899700B2 (en) 2017-06-28 2021-01-26 Vitaworks Ip, Llc Process for the separation of long chain amino acids and dibasic acids
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