Method for preparing N-(2-acyloxyalkyl) amide and application thereof

Abstract

The invention relates to the technical field of oilfield exploitation, and discloses a method for preparing N-(2-acyloxyalkyl) amide and application of the N-(2-acyloxyalkyl) amide, in the method, reaction raw materials and products are non-corrosive, the requirement for materials of reaction instruments and equipment is low, loss is low, and the preparation method only needs one-step reaction, has good economical efficiency and is suitable for industrial production. And the reaction does not involve a high-temperature and high-pressure process, does not generate a large amount of acidity, and is high in safety.

Description

Technical Field

[0001] The present invention belongs to the technical field of oilfield exploitation, and specifically relates to a preparation method and application of N-(2-acyloxyalkyl)amide. Background Art

[0002] N-alkenylamide is a highly active water-soluble monomer and a key raw material for producing amine compounds. The polymers obtained by its copolymerization / homopolymerization are widely used in the fields of oil exploitation, water treatment, adhesives, etc. At present, its production processes all involve pyrolysis, and the reaction temperature is too high, resulting in the decomposition of N-alkenylamide during the reaction, and the product purity and yield are low.

[0003] In view of the problem of the decomposition of N-alkenylamide caused by the high pyrolysis temperature, Zhejiang Xinyong Biochemical Co., Ltd. has disclosed a synthesis method of N-vinylformamide, which uses formamide and ethylene oxide to react to prepare N-(2-hydroxyethyl)formamide, which is esterified with acid anhydride to obtain N-(2-acetoxyethyl)formamide, and the latter is eliminated at 70 °C to obtain N-vinylformamide. This method has the problems of low boiling point and poor stability of the raw material ethylene oxide.

[0004]

[0005] Guangzhou Boxing has disclosed a method for preparing N-(2-carboxyethyl)formamide by reacting formamide with vinyl acetate and then pyrolyzing it to obtain N-vinylformamide. This method has a short reaction step, but the acid substances obtained in the first step will seriously corrode the production equipment; in addition, greenhouse gas carbon dioxide will be generated during the subsequent pyrolysis process.

[0006]

[0007] Although the above N-vinylamide synthesis methods can reduce the pyrolysis reaction temperature and improve the product yield and purity, they have problems such as poor stability of the reaction raw materials, generation of a large amount of waste gas and waste liquid. In addition, a large amount of acidic substances will be generated when preparing the pyrolysis raw materials by the above methods, which requires high requirements for the equipment material, resulting in a large increase in the process cost. Summary of the Invention

[0008] The purpose of the present invention is to overcome the problems existing in the prior art and provide a preparation method and application of N-(2-acyloxyalkyl)amide.

[0009] To achieve the above purpose, in the first aspect of the present invention, a preparation method of N-(2-acyloxyalkyl)amide is provided, which is characterized in that the preparation method includes: in the presence of an acid, mixing an alkanolamine represented by formula (I) with an amide represented by formula (II) for an acylation reaction;

[0010]

[0011] Among them, R 1 is selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 2 is selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 3 is selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 4 is selected from hydrogen or an alkyl group having 1 to 5 carbon atoms; R 5 is selected from hydrogen or an alkyl group having 1 to 5 carbon atoms.

[0012] In the second aspect of the present invention, a method for preparing an N-alkenylamide is provided, which is characterized in that the preparation method includes:

[0013] (1) Prepare N-(2-acyloxyalkyl)amide according to the method described in any one of claims 1-8;

[0014] (2) Crack the N-(2-acyloxyalkyl)amide obtained in step (1) to obtain a cracking product containing N-alkenylamide and organic acid.

[0015] By the above technical solutions, the present invention can at least obtain the following beneficial effects:

[0016] (1) For the preparation method provided by the present invention, the raw material amide and alkanolamine are cheap, have high stability and are easy to store;

[0017] (2) The preparation method of N-(2-acyloxyalkyl)amide provided by the present invention only requires one-step reaction, has good economy, and the reaction does not involve high temperature and high pressure processes, has high safety and does not produce a large amount of acid;

[0018] (3) For the preparation method provided by the present invention, both the reaction raw materials and products are non-corrosive, have low requirements for the material of the reaction instrument and equipment, and have low loss;

[0019] (4) In the preferred embodiment of the present invention, by recovering ammonia or organic amine in the acylation reaction product and organic acid in the cracking product, and contacting the recovered organic acid with ammonia or organic amine for reaction, the raw material amide is recovered, significantly reducing the process cost, recycling the waste ammonia or organic amine and organic acid, and reducing pollution. Detailed Embodiments

[0020] In the ranges disclosed herein, the endpoints and any values are not limited to the exact 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 endpoint values of each range, between the endpoint values 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, and these numerical ranges should be regarded as specifically disclosed herein.

[0021] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only for the purpose of illustrating and explaining the present invention, and are not intended to limit the present invention.

[0022] In the first aspect of the present invention, there is provided a method for preparing an N-(2-acyloxyalkyl)amide, which is characterized in that the preparation method includes: in the presence of an acid, mixing an alkanolamine represented by formula (I) with an amide represented by formula (II) to carry out an acylation reaction;

[0023]

[0024] wherein, R 1 is selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 2 is selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 3 is selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R 4 is selected from hydrogen or an alkyl group having 1 to 5 carbon atoms; R 5 is selected from hydrogen or an alkyl group having 1 to 5 carbon atoms.

[0025] In the present invention, in the preparation method, the amide and the alkanolamine are used as raw materials, which are low in price and high in stability, and have the advantages of easy storage and easy operation. Moreover, neither the reaction raw materials nor the products are corrosive, the requirements for the materials of the reaction instruments and equipment are low, and the process cost is low.

[0026] In the present invention, there is no particular limitation on the amounts of the respective raw materials in the preparation process of the compound. Preferably, the molar ratio of the alkanolamine to the amide can be 1:1.8 - 10, and the molar ratio of the alkanolamine to the acid can be 1:0.05 - 1; more preferably, the molar ratio of the alkanolamine to the amide can be 1:3 - 5, and the molar ratio of the alkanolamine to the acid can be 1:0.1 - 0.3.

[0027] In the present invention, the acid can be an acid commonly used in the art for preparing N-(2-acyloxyalkyl)amide. Preferably, the acid can be at least one of a Lewis acid and a protonic acid; more preferably, the acid can be selected from at least one of ferric chloride, aluminum chloride, titanium tetrachloride, tin tetrachloride, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid; further preferably, it can be at least one of ferric chloride, aluminum chloride, sulfuric acid or p-toluenesulfonic acid.

[0028] In the present invention, the alkanolamine only needs to satisfy the structure of formula (I). Preferably, the alkanolamine can be selected from at least one of 2-hydroxyethylamine, N-methyl-2-hydroxyethylamine, N-ethyl-2-hydroxyethylamine, N-propyl-2-hydroxyethylamine, N-butyl-2-hydroxyethylamine, N-pentyl-2-hydroxyethylamine, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-1-pentanol, 2-amino-1-hexanol, 2-amino-1-heptanol, 2-methylamino-1-propanol, 2-methylamino-1-butanol, 2-methylamino-1-pentanol, 2-methylamino-1-hexanol, and 2-methylamino-1-heptanol.

[0029] In the present invention, the amide only needs to satisfy the structure of formula (II). Preferably, the amide can be selected from at least one of formamide, acetamide, propionamide, butyramide, valeramide, N-methylformamide, N-ethylformamide, N-n-propylformamide, N-n-butylformamide, N-n-pentylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-di-n-propylformamide, N,N-dibutylformamide, N-methylacetamide, N-ethylacetamide, N-n-propylacetamide, N-n-butylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-di-n-propylacetamide, N,N-dibutylpropylacetamide, N-methylpropionamide, N-ethylpropionamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, N-methylbutyramide, N-ethylbutyramide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-methylvaleramide, N-ethylvaleramide, N,N-dimethylvaleramide, and N,N-diethylvaleramide.

[0030] In the present invention, there are no special requirements for the conditions of the acylation reaction, as long as the raw materials can react. Preferably, the conditions of the acylation reaction include: the reaction temperature is 50 - 180 °C, and the reaction time is 5 - 10 h; more preferably, the conditions of the acylation reaction include: the reaction temperature is 80 - 140 °C, and the reaction time is 6 - 8 h.

[0031] In a preferred embodiment of the present invention, the acylation reaction is carried out in the presence of a protective gas; more preferably, the protective gas can be at least one of nitrogen and argon, and further preferably it can be nitrogen.

[0032] In a preferred embodiment of the present invention, the method further includes recovering ammonia or organic amine in the acylation reaction product, wherein the structure of the organic amine can be NHR 4 R 5 。

[0033] In a preferred embodiment of the present invention, the method further includes quenching the reaction system. There are no special requirements for the quenching conditions, as long as the reaction can be terminated. The reaction system can be naturally cooled to room temperature first, and then a quenching reagent is added. The quenching reagent can be at least one of sodium carbonate or sodium bicarbonate.

[0034] In the present invention, the method may further include the step of purifying N-(2-acyl-oxyalkyl)amide from the acylation reaction product. The purification can be carried out in a common manner in the art. For example, the purification may include sequentially extracting, dehydrating, and distilling under reduced pressure the acylation reaction product. In a preferred embodiment of the present invention, the quenched reaction system is extracted. The extraction can be a commonly used method in the art for extracting N-(2-acyl-oxyalkyl)amide. Preferably, the extraction liquid is selected from at least one of dichloromethane and dichloroethane. More preferably, the extraction is carried out by multiple extractions.

[0035] In a preferred embodiment of the present invention, the method may further include dehydrating the organic phase after extraction. The dehydration can be carried out in a common manner in the art. Preferably, the dehydrating agent is selected from at least one of Na 2 SO 4 and MgSO 4 .

[0036] In a preferred embodiment of the present invention, the method may further include the step of removing impurities from the dehydrated substance. The removal of impurities can be carried out in a common manner in the art. Preferably, the method for removing impurities can be one of extraction or distillation under reduced pressure.

[0037] In a second aspect of the present invention, there is provided a method for preparing N-alkenylamide, characterized in that the preparation method includes:

[0038] (1) Under acidic conditions, mixing an alkanolamine represented by formula (I) with an amide represented by formula (II) for an acylation reaction;

[0039] (2) Cleaving the N-(2-acyl-oxyalkyl)amide obtained in step (1) to obtain a cleavage product containing N-alkenylamide and an organic acid.

[0040] The reaction process of the present invention is as follows:

[0041]

[0042] In a preferred embodiment of the present invention, the method further includes recovering the organic acid in the cleavage reaction product, wherein the structure of the organic acid can be R 1 COOH.

[0043] In the present invention, there are no special requirements for the conditions of the cleavage reaction, as long as the N-(2-acyloxyalkyl)amide can be cleaved. Preferably, the conditions for the cleavage include: a temperature of 100 - 180 °C and a time of 3 - 10 h; more preferably, the conditions for the cleavage include: a temperature of 130 - 160 °C and a time of 5 - 8 h; preferably, the cleavage is carried out in the presence of a cleavage catalyst, and the cleavage catalyst is at least one of ZSM-35 molecular sieve or NAY molecular sieve, more preferably ZSM-35 molecular sieve; more preferably, relative to 1 mol of N-(2-acyloxyalkyl)amide, the amount of the cleavage catalyst used is 5 - 100 g, further preferably 10 - 50 g.

[0044] In a preferred embodiment of the present invention, the method further includes: recovering ammonia or organic amine in the acylation reaction product and organic acid in the cleavage product, and contacting the recovered organic acid with ammonia or organic amine for reaction to obtain the amide for reuse in step (1). By reusing the amide, the amount of raw materials can be significantly reduced. And the contact between the organic acid and ammonia or organic amine needs to be heated to about 100 °C.

[0045] The present invention also relates to a method for preparing a polymer, which includes: preparing N-alkenylamide according to the method described above; then mixing the obtained N-alkenylamide as monomer D' with monomer A', monomer B', monomer C' and an initiator and carrying out a polymerization reaction under solution polymerization reaction conditions. The polymer prepared by this method has both the ability to thicken in the aqueous phase and the performance of emulsifying viscous oil with low dynamic viscosity, can achieve viscosity reduction of viscous oil, and is applicable to water flooding reservoir exploitation. Among them, monomer A', monomer B', monomer C', initiator, polymerization reaction, etc. are detailed in CN202311522670.5, CN202311522771.2 or CN202311519415.5, which are hereby incorporated herein by reference in their entirety.

[0046] The present invention will be described in detail below through examples. For those not specifying specific conditions in the following examples and comparative examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0047] Yield = actual yield of the target product / theoretical production amount of the target product × 100%. The yield of N-alkenylamide is calculated based on the theoretical production amount calculated with alkanolamine / amide.

[0048] The detection method for the purity of N-vinylamide is to use the internal standard method of nuclear magnetic resonance hydrogen spectrum for detection.

[0049] Examples 1 - 8

[0050] (1) Preparation of N-(2-acyloxyalkyl)amide

[0051] Take the amide. After purging with nitrogen to remove oxygen, add acid and alkanolamine, and raise the temperature for reaction. After the reaction is completed, cool it naturally to room temperature, then quench the reaction system with a 10% saturated sodium bicarbonate solution (50 mL), and extract the reaction product three times with dichloroethane. The amount of dichloroethane used for each extraction is 100 mL, and MgSO 4 Dry the organic phase, and remove other impurities by distillation under reduced pressure to obtain N-(2-acyloxyalkyl)amide. After the reaction is completed, purge the reaction kettle with nitrogen, and then absorb the tail gas to recover ammonia with organic acid R 1 COOH; for the recovery of organic amine, recover the organic amine by distillation under reduced pressure.

[0052] (2) Preparation of N-alkenylamide

[0053] Heat the obtained product N-(2-acyloxyalkyl)amide to pyrolyze under the condition of ZSM-35 molecular sieve (purchased from Zhuoyue Environmental Protection New Materials Co., Ltd., product number NA-H35-P02M) to obtain a crude alkenylamide compound. After distillation under reduced pressure, an alkenylamide compound and an organic acid are obtained. Contact the obtained organic acid with ammonia or organic amine generated by the acylation reaction to recover the amide compound.

[0054] The raw materials selected in the reaction system, the amounts of raw materials used, the reaction time, the reaction temperature, and the yields and purities of the obtained product N-(2-acyloxyalkyl)amide are shown in Tables 1 and 2.

[0055] Example 9

[0056] Prepare N-(2-acyloxyalkyl)amide in the same manner as in Example 1, except that ZSM-35 molecular sieve is not used in step (2). The yield of the obtained N-alkenylamide is 4.5%, and the purity of the N-alkenylamide is 11.9%.

[0057] Comparative Example 1

[0058] Prepare N-(2-acyloxyalkyl)amide in the same manner as in Example 1, except that acid is not used. N-(2-acyloxyalkyl)amide was not detected in the product.

[0059] Table 1

[0060]

[0061]

[0062] Table 2

[0063]

[0064] The product of Example 3, N-(2-acyloxyalkyl)amide, was analyzed by 1H NMR spectroscopy, and the results were as follows: 1 H NMR(500MHz,CDCl 3 )δ5.07(br s,1H,NH),4.13(m,2H,CH 2 -O),3.49(m,2H,CH 2 -N),2.06(s,3H,CH 3 CO),1.98(s,3H,CH 3 CO), and its structure is as shown in Formula (III).

[0065] Among them, R 1 is methyl, and R 2 , R 3 are both hydrogen.

[0066] The N-alkenylamide of Example 1 was analyzed by 1H NMR spectroscopy, and the results were as follows: 1 H NMR(500MHz,DMSO)δ10.13–9.81(m,2H,NH),8.29(d,J=10.9Hz,1H,H-C(O)),8.02(s,1H,H-C(O)),6.93–6.78(m,1H,CH=CH 2 ),6.74–6.59(m,1H,CH=CH 2 ),4.71(d,J=16.0Hz,1H,CH=CH 2 ),4.52(d,J=15.5Hz,1H,CH=CH 2 ),4.40–4.36(m,1H,CH=CH 2 ),4.19(t,J=9.6Hz,1H,CH=CH 2 ), and its structure is as shown in Formula (IV).

[0067] Among them, R 1 and R 3 are both hydrogen.

[0068] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing N-(2-acyloxyalkyl)amide, characterized in that: The preparation method comprises: under acidic conditions, mixing an alcohol amine represented by formula (I) and an amide represented by formula (II) to carry out an acylation reaction; Among them, R 1 R is selected from a hydrogen atom or a C1-C5 alkyl group; 2 R is selected from a hydrogen atom or a C1-C5 alkyl group; 3 R is selected from a hydrogen atom or a C1-C5 alkyl group; 4 R is selected from hydrogen, C1-C5 alkyl; 5 Selected from hydrogen, C1-C5 alkyl.

2. The preparation method according to claim 1, wherein The molar ratio of the alcoholamine to the amide is 1:1.8-10; preferably 1:3-5.

3. The preparation method according to claim 1 or 2, wherein The molar ratio of the alcohol amine to the acid is 1:0.05-1; preferably 1:0.1-0.

3.

4. The preparation method according to any one of claims 1 to 3, wherein The acidic condition is provided by at least one of a Lewis acid and a protonic acid; preferably provided by at least one of ferric chloride, aluminum chloride, titanium tetrachloride, tin tetrachloride, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid; further preferably provided by at least one of ferric chloride, aluminum chloride, sulfuric acid or p-toluenesulfonic acid.

5. The preparation method according to any one of claims 1 to 4, wherein: The alcoholamine is selected from at least one of 2-hydroxyethylamine, N-methyl-2-hydroxyethylamine, N-ethyl-2-hydroxyethylamine, N-propyl-2-hydroxyethylamine, N-butyl-2-hydroxyethylamine, N-pentyl-2-hydroxyethylamine, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-1-pentanol, 2-amino-1-hexanol, 2-amino-1-heptanol, 2-methylamino-1-propanol, 2-methylamino-1-butanol, 2-methylamino-1-pentanol, 2-methylamino-1-hexanol and 2-methylamino-1-heptanol.

6. The preparation method according to any one of claims 1 to 5, wherein: The amide is selected from formamide, acetamide, propionamide, butyramide, valeramide, N-methylformamide, N-ethylformamide, N-n-propylformamide, N-n-butylformamide, N-n-pentylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-di-n-propylformamide, N,N-dibutylformamide, N-methylacetamide, N-ethylacetamide, N-n-propylacetamide, N-n-butylacetamide, N,N-dimethylacetamide At least one of amine, N,N-diethylacetamide, N,N-di-n-propylacetamide, N,N-dibutylpropylacetamide, N-methylpropionamide, N-ethylpropionamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, N-methylbutanamide, N-ethylbutanamide, N,N-dimethylbutanamide, N,N-diethylbutanamide, N-methylvaleramide, N-ethylvaleramide, N,N-dimethylvaleramide and N,N-diethylvaleramide.

7. The preparation method according to any one of claims 1 to 6, wherein: The conditions of the acylation reaction include: reaction temperature of 50-180°C, reaction time of 5-10h; Preferably, the conditions of the acylation reaction include: the reaction temperature is 80-140° C., and the reaction time is 6-8 h.

8. The preparation method according to any one of claims 1 to 7, wherein: The acylation reaction is carried out in the presence of a protective gas; preferably, the protective gas is at least one of nitrogen and argon; more preferably, nitrogen; And / or, the method further comprises recovering ammonia or organic amine in the acylation reaction product.

9. A method for preparing N-alkenyl amide, characterized in that: The preparation method comprises: (1) preparing N-(2-acyloxyalkyl)amide according to the method according to any one of claims 1 to 8; (2) cracking the N-(2-acyloxyalkyl)amide obtained in step (1) to obtain a cracking product containing N-alkenylamide and organic acid.

10. The preparation method according to claim 9, wherein: In step (2), the cracking conditions include: temperature of 100-180°C and time of 3-10h; Preferably, the cracking conditions include: temperature of 130-160°C and time of 5-8h; Preferably, the cracking is carried out in the presence of a cracking catalyst, wherein the cracking catalyst is at least one of a ZSM-35 molecular sieve or a NAY molecular sieve, preferably a ZSM-35 molecular sieve; Preferably, the amount of the cleavage catalyst used is 5-100 g, more preferably 10-50 g, relative to 1 mol of N-(2-acyloxyalkyl)amide.

11. The preparation method according to claim 9 or 10, wherein: The method further comprises: recovering ammonia or organic amine in the acylation reaction product and organic acid in the cleavage product, and contacting the recovered organic acid with ammonia or organic amine to react to obtain the amide for recycling in step (1).

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