CN110746379A - 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 PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 71
- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006073 displacement reaction Methods 0.000 title description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 180
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000012074 organic phase Substances 0.000 claims abstract description 29
- 150000004885 piperazines Chemical class 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- 238000004108 freeze drying Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 11
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 11
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 8
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 claims description 7
- WHKWMTXTYKVFLK-UHFFFAOYSA-N 1-propan-2-ylpiperazine Chemical compound CC(C)N1CCNCC1 WHKWMTXTYKVFLK-UHFFFAOYSA-N 0.000 claims description 7
- QLEIDMAURCRVCX-UHFFFAOYSA-N 1-propylpiperazine Chemical compound CCCN1CCNCC1 QLEIDMAURCRVCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000002274 desiccant Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012043 crude product Substances 0.000 description 15
- YVNNRQCAABDUMX-UHFFFAOYSA-N 1-(4-methylpiperazin-1-yl)prop-2-en-1-one Chemical compound CN1CCN(C(=O)C=C)CC1 YVNNRQCAABDUMX-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 12
- 229920002401 polyacrylamide Polymers 0.000 description 12
- 238000011084 recovery Methods 0.000 description 11
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 10
- 239000007832 Na2SO4 Substances 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 241000222336 Ganoderma Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- -1 N-substituted acrylamide Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- IVXQBCUBSIPQGU-UHFFFAOYSA-N piperazine-1-carboxamide Chemical compound NC(=O)N1CCNCC1 IVXQBCUBSIPQGU-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- Oil, Petroleum & Natural Gas (AREA)
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- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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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:
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 mixing system to be 0-10 ℃, and dropwise adding a certain amount of piperazine derivative into the mixtureIn the system combination, the temperature of the system is raised to 20-40 ℃ and the reaction is continued for 1-6 h; 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
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 HydrolysedPolyacrylamide 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 ℃, making them difficult to use 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.
A heat-resistant salt-tolerant monomer copolymer is prepared by copolymerizing one or more heat-resistant salt-tolerant monomers with acrylamide to obtain a polymer, wherein the obtained polymer is limited in hydrolysis under high-temperature and high-salt conditions, and does not generate precipitation phenomenon due to reaction with calcium and magnesium ions, so that the purposes of temperature resistance and salt resistance are achieved, nonionic water-soluble monomers capable of inhibiting hydrolysis of acrylamide groups are classified into water-soluble N-substituted acrylamide or α -alkyl substituted acrylamide, and N-vinyl pyrrolidone (NVP) with a five-membered ring structure capable of effectively inhibiting amide group hydrolysis and increasing chain rigidity, so that the heat-resistant and salt-resistant performance of the polymer is improved, and the high-resistant performance of the polymer is improved, and salt-resistant performance is improved, and the high-resistant performance of the polymer is improved, and the polymer can be maintained after the high-temperature-resistant performance of the polymer is stabilized and the copolymer of the polymer is stabilized by high-temperature-resistant polyacrylamide (high-resistant polyacrylamide (DMAc) when the polymer is synthesized by using N, N-vinyl pyrrolidone, N-2-acrylamide, NV monomer, N-acrylamide, N-2-acrylamide copolymer under high-substituted acrylamide and high-acrylamide-substituted acrylamide and high-resistant performance of the high-12-crosslinking monomer synthesis conditions of the high-crosslinking polymerization of the high-crosslinking polyacrylamide (NV copolymer under high-crosslinking conditions of the high-crosslinking polymerization conditions of the high-crosslinking polymer, high-crosslinking polymer.
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:
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:
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 a second reaction solution with the volume 4 times that of the reaction solutionExtracting with chloromethane, separating with separating funnel, collecting organic phase containing dichloromethane, 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, R1for-H, the corresponding acid chloride isAcryloyl 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 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 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
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
TABLE 3
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
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 (10)
1. A functional monomer for synthesizing a polymer oil-displacing agent is characterized in that: has the following structural general formula:
wherein: r1is-H or-CH3；
R2is-CH3or-CH2CH3or-CH2CH2CH3or-CH (CH)3)2。
2. A method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 1, 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 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.
3. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, characterized in that: the acyl chloride in the step (1) is acryloyl chloride or methacryloyl chloride.
4. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, 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.
5. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, characterized in that: the molar use ratio of the piperazine derivative and the acyl chloride in the step (1) is 1: 1.2.
6. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, 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.
7. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, 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.
8. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, characterized in that: in the step (2), the pH is controlled to be 12.
9. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, characterized in that: the step (2) adopts a sand core funnel for filtration, and the organic solvent removal adopts a rotary evaporation method.
10. The method for preparing a functional monomer for synthesizing a polymer oil-displacing agent according to claim 2, characterized in that: the freeze drying equipment adopted by the freeze drying is a freeze dryer.
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