CN110746379B - Functional monomer for synthesizing polymer oil displacement agent and preparation method thereof - Google Patents

Functional monomer for synthesizing polymer oil displacement agent and preparation method thereof Download PDF

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CN110746379B
CN110746379B CN201910987777.4A CN201910987777A CN110746379B CN 110746379 B CN110746379 B CN 110746379B CN 201910987777 A CN201910987777 A CN 201910987777A CN 110746379 B CN110746379 B CN 110746379B
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伍晓林
韩培慧
冯玉军
孙刚
陈国�
李勃
潘峰
刘宏生
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Petrochina Co Ltd
Daqing Oilfield Co Ltd
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Daqing Oilfield Co Ltd
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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Abstract

The invention relates to a functional monomer for synthesizing a polymer oil-displacing agent and a preparation method thereof. The method is characterized in that: has the following structural general formula:
Figure DDA0002237242650000011
wherein: r1is-H or-CH3；R2is-CH3or-CH2CH3or-CH2CH2CH3or-CH (CH)3)2(ii) a The preparation method comprises the following steps: 1) uniformly mixing a certain amount of dichloromethane and acyl chloride under stirring, controlling the temperature of a mixed system to be 0-10 ℃, dropwise adding a certain amount of piperazine derivative into the mixed system, and raising the temperature of the system to 20-40 ℃ to continue reacting for 1-6 hours; 2) after the reaction is finished, adjusting the pH value of the reaction liquid to 8-14, then adding dichloromethane with 2-5 times of the volume of the reaction liquid for extraction, collecting an organic phase, drying, filtering, removing the organic solvent at 40-50 ℃, obtaining a product, and calculating the yield. The method can improve the yield and purity of the functional monomer and the polymerization success rate of the polymerized monomer through strict control and reasonable improvement of process parameters, and particularly can keep higher yield, purity and monomer polymerization rate under the condition of mass production.

Description

Functional monomer for synthesizing polymer oil displacement agent and preparation method thereof
Technical Field
The invention relates to the technical field of tertiary oil recovery in oilfield development, in particular to a functional monomer for synthesizing a polymer oil-displacing agent and a preparation method thereof.
Background
The polymer flooding technology can effectively improve the crude oil recovery ratio of the oil layer after water flooding. The Daqing oil field increases crude oil yield by nearly 1300 ten thousand tons in years of polymer flooding and alkali-surfactant-polymer ternary combination flooding, and the Shengli oil field increases crude oil yield by over 160 ten thousand tons in years of polymer flooding and polymer-surfactant binary combination flooding.
Because partially Hydrolyzed Polyacrylamide (HPAM) has good water solubility, easily available raw materials and low cost, the partially hydrolyzed polyacrylamide is the most widely used polymer for tertiary oil recovery at present. The main roles of HPAM solutions in tertiary oil recovery are: the viscosity of the injected water is increased, and the water phase permeability is reduced, so that the oil-water flow ratio is reduced, the planar sweep efficiency is improved, the finger advance phenomenon of the injected water and the channeling phenomenon in a high permeable layer are reduced, the vertical sweep efficiency is improved, and the water absorption thickness is increased; meanwhile, the polymer solution still has certain residual resistance after passing through, and the elasticity of the polymer solution is beneficial to improving the microcosmic oil displacement efficiency, thereby achieving the purpose of improving the recovery ratio.
Although the HPAM for tertiary oil recovery has good effect in improving the recovery ratio of oil fields in China, particularly in Daqing oil fields, with the popularization and application of the chemical flooding tertiary oil recovery technology, the underground oil reservoir environment is more and more complex and harsh, and the HPAM for tertiary oil recovery has the characteristics of high oil reservoir temperature, high oil reservoir mineralization degree (salinity) and low oil reservoir permeability, and the application of the ordinary partially Hydrolyzed Polyacrylamide (HPAM) is limited. Under the condition of high-temperature and high-salinity oil reservoir, the viscosity of HPAM is greatly reduced, the effect of improving the crude oil recovery efficiency cannot be well achieved, and the economic benefit of tertiary oil recovery is reduced. The disadvantages of partially Hydrolyzed Polyacrylamide (HPAM) are characterized in that: (1) carboxyl in HPAM molecules is greatly influenced by cations, and is easily precipitated in the presence of divalent ions or high-valent ions of formation water, resulting in phase separation (Kulkami, R, A, Guidian S.solution Behavior of hydrogenated Polyacrylamides in 0.12M NaCl. Makrol Chem,1984,185,957); (2) amide groups in HPAM molecules are more affected by temperature, and are highly susceptible to hydrolysis at temperatures exceeding 70 ℃ and are difficult to apply in high temperature formations (Peng s., Wu c.light scattering test of the formation and structure of particulate hydrogenated poly (acrylamide)/calcium (ii) complexes, macromolecules,1999,32, 585). Therefore, the development of temperature-resistant and salt-resistant polymers is an important issue for the research of oilfield workers.
The temperature-resistant and salt-resistant monomer copolymer is prepared by copolymerizing one or more temperature-resistant and salt-resistant monomers with acrylamide, and the obtained polymer is limited in hydrolysis under the conditions of high temperature and high salt, and cannot be precipitated due to the reaction with calcium and magnesium ions, so that the purposes of temperature resistance and salt resistance are achieved. There are two broad classes of nonionic water-soluble monomers that inhibit acrylamide hydrolysis: one is water soluble N-substituted acrylamide or alpha-alkyl substituted acrylamide; the other is N-vinyl pyrrolidone (NVP), and the five-membered ring structure of the N-vinyl pyrrolidone can effectively inhibit the hydrolysis of amide groups and increase the rigidity of chains, thereby improving the temperature resistance and salt resistance of the polymer. The existence of N-substituted acrylamide monomer enhances the salt resistance of the polymer (Wang Yanling, research on novel high-efficiency active polymer oil-displacing agent, fine and special chemicals 2001, 9, 45). Wangchua et al adopt copolymerization of N-vinyl-2-pyrrolidone and acrylamide monomer, and the synthesized binary copolymer solution still maintains higher solution viscosity after aging for 180 days at 90 ℃ (synthesis and performance of Quaternary copolymer of Wangchua, AM/AMPS/MAA/DADMAC. development of fine petrochemical industry, 2001,2, 10). acrylamide/N-vinyl pyrrolidone (AM/NVP) polymers can be adapted to high temperatures of 120 ℃, can maintain high application performance under high-temperature and high-mineralization conditions, and can keep 74 months without precipitation when the ratio of the monomers AM and NVP is 1:1 (Shinobu Koda, Tatsum Amano, Hiroyasu Nomura polymerization of Sodium Styrene Sulphonate and vinylirrolidone under Ultrasonic Irradiation. ultrasonics 1996,3, S91). The structural unit of the NVP five-membered ring has the effects of inhibiting hydrolysis, complexing high-valence cations, improving the rigidity and hydration capacity of a macromolecular chain and the like in polyacrylamide, so that the NVP acrylamide copolymer has better high-temperature thermal stability and salt and high-valence metal ion resistance.
An article entitled synthesis and solution performance of novel piperazine amide polymer oil displacement agent is disclosed by Song and He Yang, and 1-acryloyl-4-methyl is synthesized and used for preparing the oil displacement agent, and the structure of rigid six-membered ring of the 1-acryloyl-4-methyl is introduced to a polyacrylamide main chain, so that the resistance of the copolymer to high temperature, high salt and high shear is improved to a certain extent, and the hydrolysis of acrylamide group is inhibited. However, the synthesis yield of the monomer is 86.9%, the purity is 91.5%, and the method is a laboratory preparation with a very small amount, and if the method is used in actual production, the yield is likely to be further reduced due to the increased difficulty in controlling the process in mass production. Meanwhile, when the monomer is used for polymerization, the monomer has the problems of insufficient polymerization activity, poor polymerization effect or unsuccessful polymerization due to insufficient purity.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background art, and provides a functional monomer for synthesizing a polymer oil-displacing agent, wherein the monomer is used for being introduced to a polyacrylamide main chain to prepare the oil-displacing agent, so that the resistance of a copolymer to high temperature, high salt and high shear is improved, and the hydrolysis of an acrylamide group is inhibited. The invention also provides a preparation method of the functional monomer for synthesizing the polymer oil-displacing agent, which can improve the yield and purity of the monomer and improve the polymerization activity of the monomer and the acrylamide monomer, thereby ensuring better polymerization in mass production and improving the polymerization efficiency.
The invention can solve the problems by the following technical scheme: a functional monomer for synthesizing a polymer oil displacement agent has the following structural general formula:
Figure BDA0002237242630000031
wherein: r1is-H or-CH3；
R2is-CH3or-CH2CH3or-CH2CH2CH3or-CH (CH)3)2。
The invention also provides a preparation method of the functional monomer for synthesizing the polymer oil-displacing agent, which comprises the following steps:
(1) uniformly mixing a certain amount of dichloromethane and acyl chloride under stirring, controlling the temperature of a mixed system to be 0-10 ℃, dropwise adding a certain amount of piperazine derivative into the mixed system, after dropwise adding is completed, raising the temperature of the system to 20-40 ℃, and continuously reacting for 1-6 hours under stirring;
(2) after the reaction is finished, adding deionized water, adding NaOH solution to adjust the pH value of the reaction solution to 8-14, continuously stirring for 5-10 min, adding dichloromethane with the volume 2-5 times that of the reaction solution for extraction, collecting an organic phase, adding a drying agent, and drying for 8-16 h; filtering, removing the organic solvent at 40-50 ℃, further removing the organic solvent by using a freeze drying method to obtain a product, and calculating the yield.
Further, the ratio of the volume usage of dichloromethane to the molar usage of acid chloride is 0.25: 0.6, wherein the volume unit is L.
Further, the acyl chloride is acryloyl chloride or methacryloyl chloride.
Further, the piperazine derivative is at least one of N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine and N-isopropylpiperazine.
Further, the molar ratio of the piperazine derivative to the acyl chloride is 0.5: 0.6.
further, the mass concentration of the NaOH solution is 10-saturated sodium hydroxide solution.
Further, in the step (2), the pH value is adjusted to 12.
Further, the step (2) of filtering adopts a sand core funnel.
Further, the solvent removal is performed by rotary evaporation.
Further, the freeze drying is carried out by adopting a freeze drying device
Compared with the background technology, the invention has the following beneficial effects:
1. the invention provides a novel six-membered ring functional monomer for synthesizing a polymer oil-displacing agent, and realizes effective application of modified polyacrylamide in high-temperature and high-salt environments. The functional monomer has a rigid six-membered ring structure, is introduced to a polyacrylamide main chain, can improve the resistance of the copolymer to high temperature, high salt and high shear, inhibits the hydrolysis of an amide group, has a stable chemical structure, and meets the application requirements of severe environments such as high temperature, high salt and the like.
2. The method is beneficial to large-scale production, the yield and the purity of the obtained product are still high by carrying out 10L reaction kettle preparation through the improved method for large-scale production, the yield is 93.3 percent, the purity is 99 percent, and the method is more suitable for industrial large-scale production.
3. The monomer has high polymerization activity, can be polymerized with acrylamide to obtain a copolymer with high molecular weight, can be polymerized with the acrylamide to obtain a polymer with higher molecular weight due to high monomer purity, and is more favorable for being used as an oil displacement agent.
The preparation method of the functional monomer provided by the invention can improve the yield and purity of the functional monomer and the polymerization success rate of the polymerized monomer through strict control and reasonable improvement of process parameters, and particularly can keep higher yield, purity and monomer polymerization rate under the condition of mass production.
Drawings
FIG. 1 is an IR spectrum of 1- (4-methylpiperazin-1-yl) prop-2-en-1-one in inventive example 1;
FIG. 2 shows the preparation of 1- (4-methylpiperazin-1-yl) prop-2-en-1-one in inventive example 11H NMR spectrum;
FIG. 3 is an MS spectrum of 1- (4-methylpiperazin-1-yl) prop-2-en-1-one in inventive example 1;
FIG. 4 is a gas chromatogram of 1- (4-methylpiperazin-1-yl) prop-2-en-1-one in inventive example 1;
FIG. 5 is a block of polymer gum obtained by polymerization of example 14 of the invention before lyophilization;
FIG. 6 shows a block of polymer gel obtained by freeze-drying and polymerizing the monomers in inventive example 14.
Detailed Description
The present invention will be further described with reference to the following drawings and examples, but the present invention is not limited to the following examples.
In the following examples, the concentrations and the content percentages are mass percentages.
The chemical reaction formula for preparing the functional monomer for synthesizing the polymer oil displacement agent is as follows:
Figure BDA0002237242630000051
in the formula, R1is-H or-CH3，R2is-CH3or-CH2CH3or-CH2CH2CH3or-CH (CH)3)2。
The method is used for preparing a functional monomer for synthesizing a polymer oil displacement agent in a laboratory, and comprises the following specific steps:
(1) sequentially adding a certain amount of dichloromethane and acyl chloride into a 500ml three-neck flask, and stirring by adopting a vertical stirrer at the speed of 150rpm until the dichloromethane and the acyl chloride are fully mixed and dissolved;
(2) controlling the temperature of the system to be 0-10 ℃, and dropwise adding a certain amount of piperazine derivative by using a constant-pressure dropping funnel;
(3) after the dripping of the piperazine derivative is finished, slowly raising the temperature of the system to 20-40 ℃, and continuously reacting for 1-6 h at the stirring speed of 150 rpm;
(4) after the reaction is finished, firstly adding deionized water, then adding NaOH solution to adjust the pH value of the reaction solution to 8-14, adjusting the speed of a vertical stirrer to 300rpm, and violently stirring for 5 min;
(5) adding dichloromethane with the volume 2-5 times that of the reaction liquid for extraction, collecting an organic phase, adding a drying agent, and drying for 8-16 h;
(6) separating an organic phase containing dichloromethane by using a sand core funnel, and removing an organic solvent at 40-50 ℃ by using a rotary evaporator to obtain a product and calculating the yield;
the amount of dichloromethane used was 250 ml.
The acyl chloride is one of acryloyl chloride or methacryloyl chloride, and the using amount is 0.6 mol.
The piperazine derivative is one of N-methyl piperazine, N-ethyl piperazine, N-propyl piperazine or N-isopropyl piperazine, and the dosage of the piperazine derivative is 0.5 mol.
The concentration of the NaOH solution is 10-13%.
The desiccant is anhydrous Na2SO4Or anhydrous MgSO4One kind of (1).
Example 1(10L Mass production reaction)
In this example, R1is-H, the corresponding acid chloride is acryloyl chloride; r2is-CH3The corresponding piperazine derivative is N-methylpiperazine. The specific implementation steps of this embodiment are as follows:
(1) to a 10L reactor were added 5L of methylene chloride and 1.1kg of acryloyl chloride (12mol) in that order. 1kg of N-methylpiperazine (10mol) was added slowly at 5 ℃ using a constant pressure dropping funnel.
(2) After the dropwise addition is finished, slowly heating to room temperature, and continuously reacting for 10 hours; during the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was completed, 1L of deionized water was added, followed by addition of a saturated NaOH solution and vigorous stirring until the pH of the reaction solution reached 12. Then adding dichloromethane with 3 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding a large amount of anhydrous Na2SO4Drying for 14 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 40 ℃ to obtain a yellow oily crude product with the purity of 91%. The crude product was dried using freeze drying equipment (Ningbo New Ganoderma Scientz-10N bench lyophilizer). The product purity, calculated as functional monomer yield, was 93.3% with a purity of 99%.
The functional monomer prepared in this example is 1- (4-methylpiperazin-1-yl) prop-2-en-1-one, and its structural representation is as follows:
IR spectrum: FIG. 1 is an infrared spectrum of 1- (4-methylpiperazin-1-yl) propan-2-en-1-one at 2950 and 2800cm-1The peak of (A) is ascribed to C-H stretching vibration at the double bond, 1641cm-1Is attributed to the vibration of the carbonyl group, 1450cm-1Is attributed to bending vibration of C-H, 1250 and 1140cm-1The peak of (a) is attributed to C-C vibration. From the infrared spectrum, the sample contained an alkane structure, a carbonyl structure, and the like.
1H NMR spectrum: FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of 1- (4-methylpiperazin-1-yl) prop-2-en-1-one, in which three groups of peaks between 5.0 and 6.5ppm are peaks of three protons on the double bond, respectively, and a doublet of 3.2ppm is CH near the carbonyl group in the piperazine structure2And the doublet of 2.0ppm is near the NCH in the piperazine structure3CH (A) of2A single peak of 1.9ppm is NCH3The proton peak of (1). The nuclear magnetic resonance hydrogen spectrogram shows that the molecular structure of the product is completely consistent with the theoretical structure.
MS spectrogram: FIG. 3 is a mass spectrum of 1- (4-methylpiperazin-1-yl) propan-2-en-1-one, wherein 155.08 is 1- (4-methylpiperazin-1-yl) propan-2-en-1-one in combination with an H+The latter mass, and 177.08 is 1- (4-methylpiperazin-1-yl) prop-2-en-1-one in combination with a Na+The latter quality. By combining the infrared spectrogram, the nuclear magnetic spectrogram and the mass spectrogram, the fact that the 1- (4-methylpiperazin-1-yl) prop-2-en-1-one is successfully prepared can be concluded.
Gas chromatogram map: FIG. 4 is a gas chromatogram of 1- (4-methylpiperazin-1-yl) propan-2-en-1-one, in which a peak having a retention time of 17.0min was a peak of 1- (4-methylpiperazin-1-yl) propan-2-en-1-one and a small amount of impurities were present in addition, and the purity of 1- (4-methylpiperazin-1-yl) propan-2-en-1-one in the sample was 99% as calculated from the integrated area of the peaks.
Example 2
In this example, R1is-CH3The corresponding acid chloride is methacryloyl chloride; r2is-CH3The corresponding piperazine derivative is N-methylpiperazine. The specific implementation steps of this embodiment are as follows:
(1) into a 500mL three-necked flask were sequentially added 250mL of methylene chloride and 62.72g of methacryloyl chloride (0.6 mol). 50g of N-methylpiperazine (0.5mol) were added dropwise at 0 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 6 hours. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was complete, 50mL of deionized water was added followed by addition of saturated NaOH solution and vigorous stirring until the reaction solution reached pH 14. Then adding dichloromethane with 4 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding anhydrous Na2SO4Drying for 12 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 40 ℃ to obtain a yellow oily crude product with the purity of 92%. And drying the crude product by adopting freeze drying equipment. The calculated yield of the functional monomer is 89 percent, and the calculated purity is 98.5 percent
Example 3
In this example, R1is-H, the corresponding acid chloride is acryloyl chloride; r2is-CH2CH3The corresponding piperazine derivative is N-ethylpiperazine. The specific implementation steps of this embodiment are as follows:
(1) into a 500mL three-necked flask were added 250mL of methylene chloride and 54.3g of acryloyl chloride (0.6mol) in this order. 57.1g of N-ethylpiperazine (0.5mol) were added dropwise at 0 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 1 hour. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was completed, 50mL of deionized water was added, followed by addition of saturated NaOH solution and vigorous stirring until the reaction solution reached pH 8. Then adding dichloromethane with 3 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding anhydrous Na2SO4Drying for 14 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 40 ℃ to obtain a yellow oily crude product with the purity of 91.5%. And drying the crude product by adopting freeze drying equipment. The yield of functional monomer was calculated to be 91.5% and the purity 98.5%.
Example 4
In this example, R1is-CH3The corresponding acid chloride is methacryloyl chloride; r2is-CH2CH3The corresponding piperazine derivative is N-ethylpiperazine. The specific implementation steps of this embodiment are as follows:
(1) into a 500mL three-necked flask were sequentially added 250mL of methylene chloride and 62.72g of methacryloyl chloride (0.6 mol). 57.1g of N-ethylpiperazine (0.5mol) were added dropwise at 5 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 6 hours. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was completed, 50mL of deionized water was added, followed by addition of saturated NaOH solution and vigorous stirring until the reaction solution reached pH 11. Then adding dichloromethane with 4 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding anhydrous Na2SO4Drying for 12 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 50 ℃ to obtain a yellow oily crude product with the purity of 93%. And drying the crude product by adopting freeze drying equipment. The yield of functional monomer was calculated to be 93% and the purity 99%.
Example 5
In this example, R1is-H, the corresponding acid chloride is acryloyl chloride; r2is-CH2CH2CH3The corresponding piperazine derivative is N-propylpiperazine. The specific implementation steps of this embodiment are as follows:
(1) into a 500mL three-necked flask were added 250mL of methylene chloride and 54.3g of acryloyl chloride (0.6mol) in this order. 64.11g of N-propylpiperazine (0.5mol) were added dropwise at 3 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 3 hours. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was completed, 50mL of deionized water was added, followed by addition of saturated NaOH solution and vigorous stirring until the pH of the reaction solution reached 10. Then adding dichloromethane with 4 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding anhydrous Na2SO4Drying for 8 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 40 ℃ to obtain a yellow oily crude product with the purity of 91%. And drying the crude product by adopting freeze drying equipment. The yield of functional monomer was calculated to be 91% and the purity 99%.
Example 6
In this example, R1is-CH3The corresponding acid chloride is methacryloyl chloride; r2is-CH2CH2CH3The corresponding piperazine derivative is N-propylpiperazine. The specific implementation steps are as follows:
(1) into a 500mL three-necked flask were sequentially added 250mL of methylene chloride and 62.72g of methacryloyl chloride (0.6 mol). 64.11g of N-propylpiperazine (0.5mol) were added dropwise at 0 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 6 hours. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was complete, 50mL of deionized water was added followed by addition of saturated NaOH solution and vigorous stirring until the reaction solution reached pH 12. Then adding dichloromethane with 2 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding anhydrous Na2SO4Drying for 10 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 40 ℃ to obtain a yellow oily crude product with the purity of 92%. And drying the crude product by adopting freeze drying equipment. The yield of functional monomer was calculated to be 90% and the purity 97.5%.
Example 7
In this example, R1is-H, the corresponding acid chloride is acryloyl chloride; r2is-CH (CH)3)2The corresponding piperazine derivative is N-isopropylpiperazine. The specific implementation steps of this embodiment are as follows:
(1) into a 500mL three-necked flask were added 250mL of methylene chloride and 54.3g of acryloyl chloride (0.6mol) in this order. 64.11g of N-isopropylpiperazine (0.5mol) were added dropwise at 1 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 5 hours. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was completed, 50mL of deionized water was added, followed by addition of saturated NaOH solution and vigorous stirring until the pH of the reaction solution reached 9. Then adding 4 times of reaction liquidThe accumulated dichloromethane is extracted, a separating funnel separates and collects an organic phase containing dichloromethane, and anhydrous Na is added2SO4Drying for 8 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 45 ℃ to obtain a yellow oily crude product with the purity of 92%. And drying the crude product by adopting freeze drying equipment. The yield of functional monomer was calculated to be 93% and the purity 98%.
Example 8
In this example, R1is-CH3The corresponding acid chloride is methacryloyl chloride; r2is-CH (CH)3)2The corresponding piperazine derivative is N-isopropylpiperazine. The specific implementation steps are as follows:
(1) into a 500mL three-necked flask were sequentially added 250mL of methylene chloride and 62.72g of methacryloyl chloride (0.6 mol). 64.11g of N-isopropylpiperazine (0.5mol) were added dropwise at 5 ℃ using a constant pressure dropping funnel.
(2) After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was continued for 4 hours. During the addition, yellow flocculent insolubles were gradually generated due to the low solubility in dichloromethane after the reaction by-product HCl formed with the functional monomer hydrochloride.
(3) After the reaction was complete, 50mL of deionized water was added followed by addition of saturated NaOH solution and vigorous stirring until the reaction solution reached pH 12. Then adding dichloromethane with 3 times of reaction liquid volume for extraction, separating by a separating funnel, collecting dichloromethane-containing organic phase, and adding anhydrous Na2SO4Drying for 14 h.
(4) And (3) carrying out suction filtration by using a sand core funnel, separating solid in the organic phase, collecting the organic phase containing dichloromethane, and removing the dichloromethane by using a rotary evaporator at about 40 ℃ to obtain a yellow oily crude product with the purity of 90%. Finally, after column chromatography purification, the yield of the functional monomer is calculated to be 93.4%, and the purity is calculated to be 98.2%.
Comparative example 1
Synthesized by a literature method. The yield of functional monomer was calculated to be 86% and the purity 90%.
Comparative example 2
The synthetic feed was amplified 100-fold according to the procedure of comparative example 1. The yield was calculated to be 81% and the purity 85%.
Examples 9 to 13
The pH in step (2) was adjusted to the value shown in Table 1, and the molar ratio of acryloyl chloride/N-methylpiperazine was controlled to 1.2:1, and the other conditions and steps were the same as in example 1. The yield was calculated at the end of the reaction and the results are shown in table 1 below as the yield of functional monomer at different pH values.
TABLE 1
Figure BDA0002237242630000111
Through the research of the inventor of the application, the following results are found: when the pH value is less than 12, the product is easy to dissolve in water, and the product is difficult to extract in the subsequent extraction step; at pH >12, the yield is reduced due to the product being susceptible to decomposition under strong base. However, the comparative example did not control the pH, but rather the saturated sodium hydroxide was added directly (it can be said that the comparative example did not recognize that pH may have an effect on the yield), resulting in a product yield of only 86%.
Example 14
The functional monomers obtained before and after freeze-drying in examples 1-8 were polymerized with acrylamide under the same reaction conditions: acrylamide/functional monomer ═ 10:0.2(g/g), polymerization temperature 40 ℃, reaction time 10 h. The properties of the polymer prepared with the functional monomer and acrylamide before freeze-drying are shown in table 2; the properties of the polymer prepared from the functional monomer after freeze-drying and acrylamide are shown in Table 3:
TABLE 2
Figure BDA0002237242630000121
TABLE 3
Figure BDA0002237242630000122
Figure BDA0002237242630000131
The polymer gel blocks obtained by the functional monomer before and after freeze drying are respectively shown in fig. 5 and fig. 6, the gel blocks obtained by the functional monomer without freeze drying after polymerization are softer, which indicates that the molecular weight of the polymer is lower, while the gel blocks obtained by the monomer after freeze drying after polymerization are harder, which indicates that the molecular weight of the polymer is obviously increased. The results show that the product purity can be further improved by freeze drying, the polymerization of the monomer and acrylamide can be easier, the molecular weight of the obtained polymer is higher, the dosage can be reduced when the polymer is used as a polymer oil displacement agent, the concentration required for reaching the same viscosity is smaller, and the cost is reduced.
Example 15
Following the procedure of example 1, varying the reaction temperature, reaction time, purity results are shown in Table 4 below as yields of functional monomer under different reaction temperature and time conditions:
TABLE 4
Figure BDA0002237242630000132
The above results illustrate that: by adopting the method, the reaction can be smoothly carried out at room temperature, the required time is shorter, and the purity of the product is higher; and the reaction time is longer at low temperature, and the purity of the product is lower. This is probably because the reaction time at low temperature is too long and impurities are generated by side reactions. Meanwhile, the preparation reaction at room temperature can reduce the difficulty of temperature condition control, and is more suitable for actual production.
Example 16
In this example, acid chloride was added dropwise to piperazine, and the remaining steps were the same as in example 1, and the yield and purity of the obtained product were 86% and 89%, respectively.
The method of the invention improves the yield and purity by changing the dropping sequence, and obtains the expected effect.

Claims (8)

1. A preparation method of a functional monomer for synthesizing a polymer oil-displacing agent is disclosed, wherein the functional monomer for synthesizing the polymer oil-displacing agent has the following structural general formula:
Figure FDA0003452545310000011
wherein: r1is-H or-CH3；
R2is-CH3or-CH2CH3or-CH2CH2CH3or-CH (CH)3)2；
The method is characterized in that: the method comprises the following steps:
(1) uniformly mixing a certain amount of dichloromethane and acyl chloride under stirring, controlling the temperature of a mixed system to be 0-10 ℃, dropwise adding a certain amount of piperazine derivative into the mixed system, after dropwise adding is completed, raising the temperature of the system to 20-40 ℃, and continuously reacting for 1-6 hours under stirring;
(2) after the reaction is finished, adding deionized water, adding NaOH solution to adjust the pH value of the reaction solution to 12, continuously stirring for 5-10 min, adding dichloromethane with the volume 2-5 times that of the reaction solution for extraction, collecting an organic phase, adding a drying agent, and drying for 8-16 h; filtering, removing the organic solvent at 40-50 ℃, further removing the organic solvent by using a freeze drying method to obtain a product, and calculating the yield.
2. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the acyl chloride in the step (1) is acryloyl chloride or methacryloyl chloride.
3. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the piperazine derivative in the step (1) is one of N-methyl piperazine, N-ethyl piperazine, N-propyl piperazine and N-isopropyl piperazine.
4. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the molar use ratio of the piperazine derivative and the acyl chloride in the step (1) is 1: 1.2.
5. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the ratio of the volume usage of the dichloromethane in the step (1) to the molar usage of the acyl chloride is 0.25: 0.6, wherein the volume unit is L.
6. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the mass concentration of the NaOH solution in the step (2) is 10-saturated sodium hydroxide solution; the addition of deionized water was 5% of the total mass of the reaction.
7. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the step (2) adopts a sand core funnel for filtration, and the organic solvent removal adopts a rotary evaporation method.
8. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, characterized in that: the freeze drying equipment adopted by the freeze drying is a freeze dryer.
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