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WO2023193313A1 - Amino acid polymer, and preparation method therefor and use thereof as natural gas hydrate kinetic inhibitor - Google Patents

Amino acid polymer, and preparation method therefor and use thereof as natural gas hydrate kinetic inhibitor Download PDF

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WO2023193313A1
WO2023193313A1 PCT/CN2022/088646 CN2022088646W WO2023193313A1 WO 2023193313 A1 WO2023193313 A1 WO 2023193313A1 CN 2022088646 W CN2022088646 W CN 2022088646W WO 2023193313 A1 WO2023193313 A1 WO 2023193313A1
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amino acid
random copolymer
natural gas
present
homopolymer
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Chinese (zh)
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张倩
卢海龙
李臻超
李媛媛
管文
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Peking University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/10—Alpha-amino-carboxylic acids
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes

Definitions

  • the invention belongs to the technical field of chemical production, and specifically relates to an amino acid polymer, its preparation method and its application as a natural gas hydrate kinetic inhibitor.
  • Natural gas hydrate is a solid substance formed from water and light hydrocarbons (methane, ethane, etc.) under high pressure and low temperature conditions. Because it looks like ice and can burn, it is commonly known as flammable ice and is a potential new energy source. According to reports, the reserves of combustible ice are huge, twice as much as all proven fossil fuels combined, so it is expected to become an alternative energy source to petroleum and other sources.
  • oil and gas pipelines can easily meet the high-pressure and low-temperature environment for the formation of natural gas hydrates. However, once natural gas hydrates are generated, it will at least reduce the flow rate and affect production operations; at worst, it will block the pipeline and force the shutdown to rest, causing huge consequences. Economic losses and high safety risks, therefore the formation of natural gas hydrates needs to be avoided. Therefore, in the fields of oil and gas transportation and flammable ice mining, it is necessary to prevent the formation of natural gas hydrates.
  • the main methods to prevent and control the formation of natural gas hydrate include: (1) pressure reduction method, (2) temperature increase method, (3) water removal method, and (4) chemical inhibition method.
  • the pressure reduction method, the temperature increase method, and the water removal method are not practical.
  • Preventing the formation of natural gas hydrates through chemical inhibition is a relatively efficient, fast, low-cost and reliable method.
  • Chemical inhibition methods can prevent the nucleation, growth, and aggregation of natural gas hydrates so that they will not cause blockage during oil and gas pipeline transportation, thereby achieving safe transportation of oil and gas products.
  • Natural gas hydrate inhibitors mainly fall into three categories: thermodynamic inhibitors, kinetic inhibitors, and polymerization inhibitors.
  • Hydrate thermodynamic inhibitors can change the thermodynamic conditions for hydrate formation, shifting the formation conditions to higher pressure and lower temperature, making hydrates unable to exist stably.
  • Alcohols methanol, ethylene glycol, etc.
  • inorganic salts sodium chloride, etc.
  • Thermodynamic inhibitors can not only prevent the formation of hydrates, but also accelerate the decomposition of already formed hydrates. However, a higher addition amount (10-50wt%) of hydrate thermodynamic inhibitors is usually required to achieve the desired inhibitory effect.
  • thermodynamic inhibitors will lead to higher costs and a greater burden on the environment.
  • low-cost, relatively environmentally friendly low-dose hydrate inhibitors emerged.
  • Hydrate kinetic inhibitors and polymerization inhibitors are low-dose inhibitors.
  • the addition amount only needs 0.1 to 2wt% to achieve a good natural gas hydrate inhibition effect, which greatly reduces the cost.
  • Hydrate dynamics can extend the nucleation and growth time of natural gas hydrates, allowing oil and gas products to be transported safely to their destinations.
  • hydrate kinetic inhibitors have a wider range of applications, and they can inhibit the nucleation of hydrates, so they are more favored by the industry.
  • Common hydrate kinetic inhibitors are amide or non-amide soluble polymers (such as polyvinylpyrrolidone, polyvinylcaprolactam, etc.), or some natural polymer products (such as polysaccharides, antifreeze protein, etc.).
  • amide or non-amide soluble polymers such as polyvinylpyrrolidone, polyvinylcaprolactam, etc.
  • some natural polymer products such as polysaccharides, antifreeze protein, etc.
  • the present invention provides an amino acid polymer and its preparation method and its application as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer provided by the present invention has good inhibitory effect, low dosage, low cost, and applicability. wide advantages.
  • the present invention provides an amino acid homopolymer having a first polymerization unit with a structure shown in Formula 1:
  • the initiator used to prepare the amino acid homopolymer is a water-soluble initiator.
  • the degree of polymerization n of the amino acid homopolymer is 10 to 10,000.
  • the invention provides an amino acid random copolymer, which includes a first polymerized unit having a structure shown in Formula 1 and a second polymerized unit having a structure shown in Formula 2:
  • the average molecular weight of the amino acid random copolymer is 1,000 to 1,000,000 g/mol.
  • the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is 1: (0.1-10).
  • the invention provides a method for preparing the amino acid homopolymer described in the above technical solution, which includes the following steps:
  • valine-N-carboxyl intracyclic acid anhydride In a protective gas, valine-N-carboxyl intracyclic acid anhydride, a water-soluble initiator and an organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain the polyamine homopolymer.
  • the invention provides a method for preparing the amino acid random copolymer described in the above technical solution, which includes the following steps:
  • ring-opening polymerization occurs by mixing valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride, water-soluble initiator or oil-soluble initiator and organic solvent. reaction to obtain the polyamide random copolymer.
  • the present invention provides the application of an amino acid polymer as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer is the amino acid homopolymer described in the above technical solution or the amino acid random copolymer described in the above technical solution.
  • the amino acid polymer is used in the form of an aqueous amino acid polymer solution, and the mass concentration of the aqueous amino acid polymer solution is 0.1 to 10%.
  • the applied pressure is 1 to 25 MPa, and the applied temperature is -25 to 50°C.
  • the present invention provides an amino acid homopolymer, which has a first polymerized unit with a structure shown in Formula 1:
  • the initiator used to prepare the amino acid homopolymer is a water-soluble initiator.
  • the amino acid homopolymer provided by the invention has the first polymerization unit of the structure shown in Formula 1.
  • the amino acid homopolymer contains an isopropyl side chain group.
  • the isopropyl group has strong hydrophobicity, and the hydrophobic isopropyl group
  • the propyl group can solidify the structure of water molecules, thus binding the water molecules around the isopropyl group, making it difficult for the cage water structure of natural gas hydrate to form, thus inhibiting the nucleation of natural gas hydrate.
  • the size of the isopropyl side chain is equivalent to the size of the natural gas hydrate cage structure. It can enter the inside of the natural gas hydrate cage structure and interfere with the structure of the natural gas hydrate, affecting the stability of the natural gas hydrate structure.
  • Natural gas hydrate nucleation cannot stably grow to a critical size, making it difficult for natural gas hydrate crystals to nucleate.
  • the main chain of the amino acid homopolymer shown in Formula 1 contains an amide group.
  • the N and O atoms in the amide group can be adsorbed on the surface of natural gas hydrate through hydrogen bonds, thereby inhibiting the further growth of natural gas hydrate crystals. Therefore, the amino acid polymer provided by the present invention can effectively delay the nucleation of natural gas hydrate and reduce the formation rate of natural gas hydrate under low dose concentration conditions and high supercooling environment, and has good inhibitory effect, low dosage, It has the advantages of low cost and wide applicability.
  • the invention provides an amino acid random copolymer, which includes a first polymerized unit having a structure shown in Formula 1 and a second polymerized unit having a structure shown in Formula 2:
  • the amino acid random copolymer provided by the invention uses the second polymerization unit of the structure shown in Formula 2 to enhance the water solubility of the amino acid polymer, which can expand the types of amino acid polymer initiators and reduce the difficulty of preparation.
  • the present invention provides the application of an amino acid polymer as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer is the amino acid homopolymer described in the above technical solution or the amino acid random copolymer described in the above technical solution.
  • the usage concentration of the amino acid polymer provided by the present invention as a natural gas hydrate inhibitor is much lower than that of traditional thermodynamic inhibitors. Generally, a good inhibitory effect can be achieved by adding a mass concentration of 0.1 to 2.0%, and the reagent cost is greatly reduced.
  • the amino acid polymer provided by the present invention can effectively delay the nucleation/growth of hydrates, so that oil and gas products do not generate hydrates within a certain period of time, so that they can be safely transported to their destinations.
  • the amino acid polymer provided by the invention is suitable for oil-gas-water three-phase or oil-water or gas-water two-phase coexistence systems. It can be used to inhibit the generation of natural gas hydrates during oil and gas transportation and combustible ice mining processes, and can achieve good results. The inhibitory effect is small, the cost is reduced, and it has broad application prospects.
  • the amino acid polymer provided by the invention uses a water-soluble initiator to enhance the water solubility of the amino acid polymer, so that it can be used as a natural gas hydrate kinetic inhibitor in a water-soluble form, which is green and environmentally friendly.
  • amino acid polymers with a main chain composed of N and O heteroatoms have greater biological potential than vinyl polymers or propylene-based polymers (the main chain is composed of pure C-C bonds). Degradability potential.
  • Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 1 of the present invention.
  • Figure 2 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 2 of the present invention.
  • Figure 3 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 3 of the present invention.
  • Figure 4 is an example diagram of the time-temperature and time-pressure curves of the system in the reaction kettle of Application Example 1 of the present invention.
  • the present invention provides an amino acid homopolymer, which has a first polymerized unit with a structure shown in Formula 1:
  • the initiator used to prepare the amino acid homopolymer is a water-soluble initiator.
  • the initiator of the amino acid homopolymer is specifically preferably methoxy polyethylene glycol amine.
  • the structural formula of the amino acid homopolymer is preferably represented by Formula 1-1:
  • n in the formula 1-1 is the degree of polymerization of the first polymerization unit.
  • the degree of polymerization n of the amino acid homopolymer is 10 to 10,000, more preferably 20 to 8,000, and even more preferably 35 to 5,000.
  • the degree of polymerization of the amino acid homopolymer is preferably 46 or 40.
  • the methoxy polyethylene glycol amine has the structure shown in Formula 3:
  • the methoxy polyethylene glycol amine has the structure shown in Formula 4 or Formula 5:
  • the average molecular weight of the amino acid homopolymer is specifically preferably 5561g/mol or 5966g/mol.
  • the invention provides an amino acid random copolymer, which includes a first polymerized unit having a structure shown in Formula 1 and a second polymerized unit having a structure shown in Formula 2:
  • the average molecular weight of the amino acid random copolymer is 1,000 to 1,000,000 g/mol, more preferably 3,000 to 800,000 g/mol, and even more preferably 5,000 to 200,000 g/mol.
  • the average molecular weight of the amino acid random copolymer is preferably 17874 g/mol.
  • the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is 1: (0.1-10), more preferably 1: (0.2-8), further preferably 1 :(0.25 ⁇ 5).
  • the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is preferably 118:48.
  • the initiator for preparing the amino acid random copolymer is preferably a water-soluble initiator or an oil-soluble initiator, and more preferably an oil-soluble initiator.
  • the initiator for preparing the amino acid random copolymer is specifically preferably benzylamine.
  • the amino acid homopolymer or amino acid random copolymer provided by the invention When used as a new type of natural gas hydrate kinetic inhibitor, the amino acid homopolymer or amino acid random copolymer provided by the invention has a good inhibitory effect, and has the advantages of low dosage, low cost and wide source.
  • the added amount of the amino acid polymer provided by the present invention is much smaller than that of traditional thermodynamic inhibitors. Generally, a good inhibitory effect can be achieved by adding a mass concentration of 0.1 to 10%, and the reagent cost is greatly reduced.
  • the invention provides a method for preparing the amino acid homopolymer described in the above technical solution, which includes the following steps:
  • valine-N-carboxyl intracyclic acid anhydride In a protective gas, valine-N-carboxyl intracyclic acid anhydride, a water-soluble initiator and an organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain the polyamine homopolymer.
  • the reaction monomer is preferably valine-N-carboxylic intracyclic anhydride
  • the water-soluble initiator is specifically preferably methoxy polyethylene glycol amine
  • the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the water-soluble initiator is preferably (10-60):1, more preferably (15-50):1, and further preferably ( 20 ⁇ 45):1.
  • the organic solvent is preferably N,N-dimethylformamide.
  • the organic solvent is preferably an anhydrous solvent.
  • the present invention has no special requirements on the amount of the organic solvent, as long as the raw materials for the ring-opening polymerization reaction are completely dissolved.
  • the ratio of the mass of the valine-N-carboxylic intracyclic acid anhydride to the volume of the organic solvent is specifically preferably 0.5g:10mL.
  • the mixing sequence is preferably: mixing the valine-N-carboxyl intracyclic acid anhydride, organic solvent and water-soluble initiator in sequence.
  • the ring-opening polymerization reaction is an N-carboxyl intracyclic acid anhydride ring-opening polymerization reaction.
  • the temperature of the ring-opening polymerization reaction is preferably 20 to 60°C, and more preferably 25 to 50°C.
  • the heat preservation time of the ring-opening polymerization reaction is preferably 8 to 48 hours, more preferably 10 to 45 hours.
  • the protective gas is preferably nitrogen or an inert gas, and more preferably nitrogen.
  • the invention before performing the ring-opening polymerization reaction, preferably repeatedly evacuates and passes protective gas through the container for the ring-opening polymerization reaction three times.
  • the ring-opening polymerization reaction obtains a polymerization reaction liquid.
  • the post-treatment preferably includes: precipitation, solid-liquid separation and drying in sequence.
  • the precipitation is preferably washed out by mixing the polymerization reaction solution and diethyl ether.
  • the present invention has no special requirements on the amount of diethyl ether, as long as the homopolymer product is completely precipitated.
  • the solid-liquid separation is preferably centrifugal separation, and the present invention has no special requirements on the specific implementation of the centrifugal separation.
  • the drying temperature is preferably room temperature, and the drying time is preferably 24 hours.
  • the invention provides a method for preparing the amino acid random copolymer described in the above technical solution, which includes the following steps:
  • ring-opening polymerization occurs by mixing valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride, water-soluble initiator or oil-soluble initiator and organic solvent. reaction to obtain the polyamide random copolymer.
  • the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the glutamic acid-5-benzyl ester-N-carboxylic intracyclic acid anhydride is preferably 1:(0.1 ⁇ 10), more preferably It is 1: (0.2-8), and it is more preferable that it is 1: (0.25-5).
  • the molar ratio of the valine-N-carboxy intracyclic acid anhydride and the glutamic acid-5-benzyl ester-N-carboxyl intracyclic acid anhydride is specifically preferably 118:48.
  • the oil-soluble initiator is specifically preferably benzylamine.
  • the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the oil-soluble initiator or water-soluble initiator is preferably (4-60):1, and more preferably (6-50):1 , more preferably (8-40):1.
  • the organic solvent is preferably N,N-dimethylformamide.
  • the organic solvent is preferably an anhydrous solvent.
  • the present invention has no special requirements on the amount of the organic solvent, as long as the raw materials for the ring-opening polymerization reaction are completely dissolved.
  • the ratio of the mass of the valine-N-carboxylic intracyclic acid anhydride to the volume of the organic solvent is specifically preferably 0.5g:10mL.
  • the mixing sequence is preferably: the valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride, organic solvent and water-soluble initiator Or water-soluble initiators are mixed in sequence.
  • the ring-opening polymerization reaction is an N-carboxyl intracyclic acid anhydride ring-opening polymerization reaction.
  • the temperature of the ring-opening polymerization reaction is preferably 20 to 60°C, and more preferably 25 to 50°C.
  • the heat preservation time of the ring-opening polymerization reaction is preferably 8 to 48 hours, more preferably 10 to 45 hours.
  • the protective gas is preferably nitrogen or an inert gas, and more preferably nitrogen.
  • the invention before performing the ring-opening polymerization reaction, preferably repeatedly evacuates and passes protective gas through the container for the ring-opening polymerization reaction three times.
  • the ring-opening polymerization reaction obtains a polymerization reaction liquid.
  • the post-treatment preferably includes: precipitation, solid-liquid separation and drying in sequence.
  • the precipitation is preferably washed out by mixing the polymerization reaction solution and diethyl ether.
  • the present invention has no special requirements on the amount of diethyl ether, as long as the homopolymer product is completely precipitated.
  • the solid-liquid separation is preferably centrifugal separation, and the present invention has no special requirements on the specific implementation of the centrifugal separation.
  • the drying temperature is preferably room temperature, and the drying time is preferably 24 hours.
  • the present invention obtains the polymerization reaction liquid and performs the above post-treatment to obtain a post-processed product.
  • the present invention preferably further includes subjecting the post-processed product to a first post-processing to obtain the amino acid fruitless copolymer.
  • the first post-treatment preferably includes: hydrolysis reaction, water dialysis purification and freeze-drying in sequence.
  • the hydrolysis reaction is preferably: the post-treatment product, the first organic solvent and the NaOH aqueous solution are mixed for a second time to react.
  • the first organic solvent is specifically preferably 1,4-dioxane.
  • the molar concentration of the NaOH aqueous solution is preferably 1 mol/L.
  • the molar ratio of NaOH in the NaOH aqueous solution to the ester group in the post-treatment product is preferably (1.2-2):1.
  • the second mixing preferably includes the following steps:
  • the NaOH aqueous solution was added dropwise to the post-treatment product solution.
  • the temperature of the hydrolysis reaction is preferably room temperature, and the holding time of the hydrolysis reaction is preferably 4 to 24 hours, more preferably 5 to 23 hours.
  • the water dialysis purification is preferably as follows: putting the reaction liquid of the hydrolysis reaction into a dialysis bag, and immersing the dialysis bag containing the reaction liquid in water to perform dialysis.
  • the water is preferably pure water.
  • the time for water dialysis and purification is preferably 24 to 48 hours, and more preferably 48 hours.
  • the dialysis membrane used in the dialysis bag has a molecular weight cutoff of 1000 Da.
  • the freeze-drying temperature is preferably -60°C.
  • the present invention provides the application of an amino acid polymer as a natural gas hydrate kinetic inhibitor.
  • the amino acid polymer is the amino acid homopolymer described in the above technical solution or the amino acid random copolymer described in the above technical solution.
  • the amino acid polymer is preferably used in the form of an aqueous amino acid polymer solution.
  • the mass concentration of the amino acid polymer aqueous solution is preferably 0.1 to 10%, and more preferably 0.1 to 2%.
  • the applied pressure is preferably 1 to 25 MPa.
  • the applied temperature is preferably -25 to 50°C.
  • the amino acid polymer provided by the invention is suitable for oil-gas-water three-phase or oil-water or gas-water two-phase coexistence systems, and can be used to inhibit natural gas in the process of oil and gas transportation and flammable ice mining.
  • the formation of hydrates can achieve good inhibitory effect, and the dosage is small, the cost is reduced, and it has broad application prospects.
  • valine-N-carboxylic intracyclic anhydride Into a Schlenk flask with a volume of 50 mL, add 0.5 g of valine-N-carboxylic intracyclic anhydride, 10 mL of anhydrous N, N-dimethylformamide, and methoxy polyethylene glycol amine (the structural formula is as shown in Formula 4). shown, the weight average molecular weight is 1000, the molar ratio of methoxy polyethylene glycol amine and valine-N-carboxylic intracyclic acid anhydride is 1:15), vacuum-pass nitrogen 3 times, and start under nitrogen protection
  • the ring-opening polymerization reaction temperature is 25°C, and the holding time of the ring-opening polymerization reaction is 48 hours.
  • valine polymer 1 The reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain valine polymer 1.
  • the data molecular weight of valine polymer 1 is 5561g/mol, and the 1 H of valine polymer 1 is The NMR (using CF 3 COOD as solvent) spectrum is shown in Figure 1:
  • the structural formula of valine polymer 1 calculated from Figure 1 is shown in Formula 6:
  • valine-N-carboxylic intracyclic acid anhydride Into a Schlenk flask with a volume of 50 mL, 0.5 g of valine-N-carboxylic intracyclic acid anhydride, 10 mL of anhydrous N, N-dimethylformamide, and methoxy polyethylene glycol amine (the structural formula is as shown in Formula 5) were added in sequence. shown, the weight average molecular weight is 2000, the molar ratio of methoxy polyethylene glycol amine and valine-N-carboxylic intracyclic acid anhydride is 1:15), vacuum-pass nitrogen 3 times, and start under nitrogen protection
  • the ring-opening polymerization reaction temperature is 25°C, and the holding time of the ring-opening polymerization reaction is 48 hours.
  • valine polymer 2 The reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain valine polymer 2.
  • the data molecular weight of valine polymer 2 is 5966g/mol, and the 1 H of valine polymer 2 is The NMR (using CF 3 COOD as solvent) spectrum is shown in Figure 2:
  • the structural formula of valine polymer 2 calculated from Figure 2 is shown in Formula 7:
  • valine-N-carboxylic intracyclic acid anhydride Into a Schlenk flask with a volume of 50 mL, 0.5 g of valine-N-carboxylic intracyclic acid anhydride and glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride (glutamic acid-5-benzyl ester-N-
  • the molar ratio of carboxyl intracyclic anhydride and valine-N-carboxylic intracyclic anhydride is 1:0.45), 10 mL anhydrous N,N-dimethylformamide, benzylamine (benzylamine and valine-N-carboxylic acid anhydride)
  • the molar ratio of the intracyclic acid anhydride is 1:6), evacuate and pass nitrogen three times, and perform ring-opening polymerization under nitrogen protection.
  • the ring-opening polymerization reaction temperature is 25°C, and the ring-opening polymerization holding time is 48 hours
  • reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a solid product.
  • the amino acid polymer prepared in the embodiment of the present invention is used as a natural gas hydrate kinetic inhibitor.
  • the experimental equipment for testing the inhibitory effect of the natural gas hydrate kinetic inhibitor provided by the present invention is a high-pressure stirring test device.
  • the main components of the high-pressure stirring test device are: Parts include stainless steel high-pressure reactors, circulating water baths, magnetic stirrers, temperature sensors, pressure sensors, high-pressure gas bottles, vacuum pumps, data acquisition instruments, etc.
  • the stainless steel high-pressure reactor has a maximum working pressure of 20MPa and a working temperature range of -20 to 80°C.
  • the pressure inside the stainless steel high-pressure reaction kettle can be freely adjusted through the air valve.
  • the circulating water bath can provide a temperature environment of -20 ⁇ 80°C for the high-pressure reactor.
  • the system collects and stores parameters such as pressure and temperature in the high-pressure reaction kettle in real time.
  • the formation of natural gas hydrate in the reactor can be judged by sudden changes in temperature or pressure during the reaction.
  • After filling the high-pressure reaction kettle with the aqueous amino acid polymer solution prepared in the Example introduce high-pressure gas, close the valve to seal the system in the high-pressure reaction kettle, turn on stirring, and then lower the temperature at a constant rate (1°C/h) to allow the natural gas to flow. Hydrate formation.
  • the system in the high-pressure reactor will gradually reach the conditions for the formation of natural gas hydrate. In a closed system, the pressure decreases linearly as the temperature decreases.
  • the inhibitory effect of the natural gas hydrate kinetic inhibitor provided by the present invention is quantified based on the natural gas hydrate formation temperature at which the kinetic inhibitor aqueous solution prepared in the Example is added to the reactor system. The lower the formation temperature of natural gas hydrate in the high-pressure reactor system, the better the inhibitory effect of the kinetic inhibitor.
  • the specific implementation process is: before running the experiment, clean the high-pressure reactor with detergent, ethanol, and deionized water in sequence, and then blow dry the water in the reactor with nitrogen to ensure it is dry.
  • vacuum pass in 0.5MPa high-purity methane gas, remove the gas, and then vacuum again. Repeat this three times to remove as much air as possible from the reactor and pipelines.
  • the time-temperature and time-pressure curves measured during the experiment show that when the aqueous solution of valine polymer 1 prepared in Example 1 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 8.9 °C, has a better inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of valine polymer 2 with a mass concentration of 0.15% is added to the reaction kettle, and the time-temperature and time-pressure measured during the experiment are used.
  • the curve shows that when the aqueous solution of valine polymer 2 prepared in Example 2 with a mass concentration of 0.15% is used as a kinetic inhibitor, the generation temperature of natural gas hydrate is 8.7°C, which has a good Inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of valine polymer 3 with a mass concentration of 0.15% is added to the reaction kettle, and the time-temperature and time-pressure measured during the experiment are used.
  • the curve shows that when the aqueous solution of valine polymer 3 prepared in Example 3 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 7.5°C, which has a good inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that pure water is added to the reaction kettle.
  • the time-temperature and time-pressure curves measured during the experiment show that when pure water is a kinetic inhibitor, , the formation temperature of natural gas hydrate is 10.3°C.
  • the reaction device and method are basically the same as those in Application Example 1, except that a methoxy polyethylene glycol amine aqueous solution with a mass concentration of 0.15% and a molecular weight of 2000g/mol is added to the reaction kettle.
  • the time-temperature and time-pressure curves show that when a methoxy polyethylene glycol amine aqueous solution with a mass concentration of 0.15% and a molecular weight of 2000g/mol is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 9.8°C, inhibiting Less effective.
  • the reaction device and method are basically the same as those in Application Example 1. The difference is that a polyglutamic acid aqueous solution with a mass concentration of 0.15% and a molecular weight of 3722g/mol is added to the reaction kettle.
  • the time-temperature, The time-pressure curve shows that when a polyglutamic acid aqueous solution with a mass concentration of 0.15% and a molecular weight of 3722g/mol is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 10.6°C, with almost no inhibitory effect.
  • the reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is added to the reaction kettle, and the The time-temperature and time-pressure curves measured during the experiment show that when an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is used as a kinetic inhibitor, natural gas
  • the formation temperature of hydrate is 8.5°C, which has a good inhibitory effect.

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Abstract

Provided are an amino acid polymer, and a preparation method therefor and the use thereof as a natural gas hydrate kinetic inhibitor. The provided amino acid polymer structure contains an isopropyl side chain group. The isopropyl has relatively strong hydrophobicity, whereby the hydrophobic isopropyl can solidify the structure of water molecules, such that water molecules around the isopropyl can be bound, and the cage-shaped water structure of a natural gas hydrate is not easy to form, thereby inhibiting the nucleation of the natural gas hydrate. Therefore, the nucleation of the natural gas hydrate can be effectively delayed and the generation rate of the natural gas hydrate can be reduced under the condition of a low dosage concentration and a high supercooling degree environment, and the present invention has the advantages of a good inhibition effect, a small dosage, a low cost, wide applicability, etc.

Description

一种氨基酸聚合物及其制备方法与作为天然气水合物动力学抑制剂的应用An amino acid polymer, its preparation method and its application as a natural gas hydrate kinetic inhibitor

本申请要求于2022年04月08日提交中国专利局、申请号为CN202210365759.4、发明名称为“一种氨基酸聚合物及其制备方法与作为天然气水合物动力学抑制剂的应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires a Chinese patent submitted to the China Patent Office on April 8, 2022, with the application number CN202210365759.4 and the invention title "An amino acid polymer and its preparation method and application as a natural gas hydrate kinetic inhibitor" claim of priority, the entire contents of which are incorporated herein by reference.

技术领域Technical field

本发明属于化工生产技术领域，具体涉及一种氨基酸聚合物及其制备方法与作为天然气水合物动力学抑制剂的应用。The invention belongs to the technical field of chemical production, and specifically relates to an amino acid polymer, its preparation method and its application as a natural gas hydrate kinetic inhibitor.

背景技术Background technique

天然气水合物是在高压、低温的条件下由水和轻质烃类(甲烷、乙烷等)所形成的固体物质。因其外形似冰并且能够燃烧，俗称可燃冰，是一种潜在的新能源。据报道，可燃冰的储量巨大，是所有已探明化石燃料总和的2倍之多，因此有望成为石油等的接替能源。在油气输运过程中，油气管道中极易满足天然气水合物的高压、低温生成环境，但是天然气水合物一旦生成轻则降低流速、影响生产作业；重则堵塞管道、迫使停运休整，造成巨大的经济损失且极具安全隐患，因此需要避免天然气水合物的生成。因此，在油气输运和可燃冰开采领域，需要防止天然气水合物的生成。Natural gas hydrate is a solid substance formed from water and light hydrocarbons (methane, ethane, etc.) under high pressure and low temperature conditions. Because it looks like ice and can burn, it is commonly known as flammable ice and is a potential new energy source. According to reports, the reserves of combustible ice are huge, twice as much as all proven fossil fuels combined, so it is expected to become an alternative energy source to petroleum and other sources. In the process of oil and gas transportation, oil and gas pipelines can easily meet the high-pressure and low-temperature environment for the formation of natural gas hydrates. However, once natural gas hydrates are generated, it will at least reduce the flow rate and affect production operations; at worst, it will block the pipeline and force the shutdown to rest, causing huge consequences. Economic losses and high safety risks, therefore the formation of natural gas hydrates needs to be avoided. Therefore, in the fields of oil and gas transportation and flammable ice mining, it is necessary to prevent the formation of natural gas hydrates.

天然气水合物生成的防治方法主要有：(1)降压法，(2)升温法，(3)除水法，(4)化学抑制法。前三种方法：降低压力、升高温度、除去水分，能够使体系无法满足天然气水合物的生成条件，因此理论上可以杜绝天然气水合物的形成。然而，在实际操作中，考虑到节约成本、保护环境以及场地适用性等问题，降压法、升温法以及除水法并不实用。通过化学抑制法来防止天然气水合物的生成是一种相对高效快捷、成本较低的可靠方法。化学抑制法能够防止天然气水合物的成核、生长、聚集，使其在油气管道运输过程中不产生堵塞，从而实现油气产品的安全输运。The main methods to prevent and control the formation of natural gas hydrate include: (1) pressure reduction method, (2) temperature increase method, (3) water removal method, and (4) chemical inhibition method. The first three methods: reducing pressure, increasing temperature, and removing water can make the system unable to meet the conditions for the formation of natural gas hydrates, so in theory, the formation of natural gas hydrates can be eliminated. However, in actual operation, considering issues such as cost savings, environmental protection, and site suitability, the pressure reduction method, the temperature increase method, and the water removal method are not practical. Preventing the formation of natural gas hydrates through chemical inhibition is a relatively efficient, fast, low-cost and reliable method. Chemical inhibition methods can prevent the nucleation, growth, and aggregation of natural gas hydrates so that they will not cause blockage during oil and gas pipeline transportation, thereby achieving safe transportation of oil and gas products.

天然气水合物抑制剂主要有热力学抑制剂、动力学抑制剂、阻聚剂三大类。水合物热力学抑制剂能够改变水合物生成的热力学条件，使其生成 条件向更高的压力和更低的温度偏移，从而使水合物不能稳定存在。醇类(甲醇、乙二醇等)以及无机盐(氯化钠等)是工业上常用的天然气水合物热力学抑制剂。热力学抑制剂不止能够预防水合物的生成，而且还能使已经生成的水合物加速分解。但是，通常需要较高的加入量(10～50wt％)，水合物热力学抑制剂才能达到理想的抑制效果，因此热力学抑制剂的添加会导致成本较高、对环境造成较大负担。由此，成本较低、相对较环保的低剂量水合物抑制剂应运而生。水合物动力学抑制剂、阻聚剂均属于低剂量抑制剂，通常加入量只需要0.1～2wt％即能达到较好的天然气水合物抑制效果，大大降低了成本。水合物动力学能够延长天然气水合物的成核以及生长时间，从而使油气产品安全输运至目的地。相对阻聚剂而言，水合物动力学抑制剂的适用范围更为广泛，而且其能抑制水合物的成核，因此更受工业界的青睐。Natural gas hydrate inhibitors mainly fall into three categories: thermodynamic inhibitors, kinetic inhibitors, and polymerization inhibitors. Hydrate thermodynamic inhibitors can change the thermodynamic conditions for hydrate formation, shifting the formation conditions to higher pressure and lower temperature, making hydrates unable to exist stably. Alcohols (methanol, ethylene glycol, etc.) and inorganic salts (sodium chloride, etc.) are commonly used thermodynamic inhibitors of natural gas hydrates in industry. Thermodynamic inhibitors can not only prevent the formation of hydrates, but also accelerate the decomposition of already formed hydrates. However, a higher addition amount (10-50wt%) of hydrate thermodynamic inhibitors is usually required to achieve the desired inhibitory effect. Therefore, the addition of thermodynamic inhibitors will lead to higher costs and a greater burden on the environment. As a result, low-cost, relatively environmentally friendly low-dose hydrate inhibitors emerged. Hydrate kinetic inhibitors and polymerization inhibitors are low-dose inhibitors. Usually, the addition amount only needs 0.1 to 2wt% to achieve a good natural gas hydrate inhibition effect, which greatly reduces the cost. Hydrate dynamics can extend the nucleation and growth time of natural gas hydrates, allowing oil and gas products to be transported safely to their destinations. Compared with polymerization inhibitors, hydrate kinetic inhibitors have a wider range of applications, and they can inhibit the nucleation of hydrates, so they are more favored by the industry.

常见的水合物动力学抑制剂为酰胺类或非酰胺类的可溶性高分子聚合物(比如，聚乙烯基吡咯烷酮、聚乙烯基己内酰胺等)，或者一些天然的高分子产物(比如，多糖、抗冻蛋白等)。近年来，因水合物动力学抑制剂效率高、对环境污染小、成本低、适用范围广等优点，水合物动力学抑制剂的研究受到了世界范围内的广泛关注。Common hydrate kinetic inhibitors are amide or non-amide soluble polymers (such as polyvinylpyrrolidone, polyvinylcaprolactam, etc.), or some natural polymer products (such as polysaccharides, antifreeze protein, etc.). In recent years, the research on hydrate kinetic inhibitors has received widespread attention around the world due to its advantages such as high efficiency, low environmental pollution, low cost, and wide application range.

目前，市场上常见的水合物动力学抑制剂(比如，聚乙烯基吡咯烷酮、聚乙烯基己内酰胺等)，仍存在成本高、难生物降解的缺陷，使其应用受到限制。Currently, common hydrate kinetic inhibitors on the market (such as polyvinylpyrrolidone, polyvinylcaprolactam, etc.) still have the disadvantages of high cost and difficulty in biodegradation, which limits their application.

发明内容Contents of the invention

有鉴于此，本发明提供了一种氨基酸聚合物及其制备方法与作为天然气水合物动力学抑制剂的应用，本发明提供的氨基酸聚合物具有抑制效果好、用量少、成本低、适用性广的优点。In view of this, the present invention provides an amino acid polymer and its preparation method and its application as a natural gas hydrate kinetic inhibitor. The amino acid polymer provided by the present invention has good inhibitory effect, low dosage, low cost, and applicability. wide advantages.

为了解决上述技术问题，本发明提供了一种氨基酸均聚物，具有式1所示结构的第一聚合单元：In order to solve the above technical problems, the present invention provides an amino acid homopolymer having a first polymerization unit with a structure shown in Formula 1:

Figure PCTCN2022088646-appb-000001
Figure PCTCN2022088646-appb-000001

制备所述氨基酸均聚物的引发剂为水溶性引发剂。The initiator used to prepare the amino acid homopolymer is a water-soluble initiator.

优选的，所述氨基酸均聚物的聚合度n为10～10000。Preferably, the degree of polymerization n of the amino acid homopolymer is 10 to 10,000.

本发明提供一种氨基酸无规共聚物，包括具有式1所示结构的第一聚合单元和具有式2所示结构的第二聚合单元：The invention provides an amino acid random copolymer, which includes a first polymerized unit having a structure shown in Formula 1 and a second polymerized unit having a structure shown in Formula 2:

Figure PCTCN2022088646-appb-000002
Figure PCTCN2022088646-appb-000002

优选的，所述氨基酸无规共聚物的平均分子量为1000～1000000g/mol。Preferably, the average molecular weight of the amino acid random copolymer is 1,000 to 1,000,000 g/mol.

优选的，所述氨基酸无规共聚物中第一聚合单元和第二聚合物单元的摩尔比为1:(0.1～10)。Preferably, the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is 1: (0.1-10).

本发明提供了上述技术方案所述氨基酸均聚物的制备方法，包括以下步骤：The invention provides a method for preparing the amino acid homopolymer described in the above technical solution, which includes the following steps:

在保护气体中，将缬氨酸-N-羧基环内酸酐、水溶性引发剂和有机溶剂混合发生开环聚合反应，得到所述聚氨酸均聚物。In a protective gas, valine-N-carboxyl intracyclic acid anhydride, a water-soluble initiator and an organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain the polyamine homopolymer.

本发明提供了上述技术方案所述的氨基酸无规共聚物的制备方法，包括以下步骤：The invention provides a method for preparing the amino acid random copolymer described in the above technical solution, which includes the following steps:

在保护气体中，将缬氨酸-N-羧基环内酸酐、谷氨酸-5-苄酯-N-羧基环内酸酐、水溶性引发剂或油溶性引发剂和有机溶剂混合发生开环聚合反应，得到所述聚氨酸无规共聚物。In a protective gas, ring-opening polymerization occurs by mixing valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride, water-soluble initiator or oil-soluble initiator and organic solvent. reaction to obtain the polyamide random copolymer.

本发明提供了氨基酸聚合物作为天然气水合物动力学抑制剂的应用，所述氨基酸聚合物为上述技术方案所述氨基酸均聚物或上述技术方案所述的氨基酸无规共聚物。The present invention provides the application of an amino acid polymer as a natural gas hydrate kinetic inhibitor. The amino acid polymer is the amino acid homopolymer described in the above technical solution or the amino acid random copolymer described in the above technical solution.

优选的，所述氨基酸聚合物以氨基酸聚合物水溶液的形式使用，所述氨基酸聚合物水溶液的质量浓度为0.1～10％。Preferably, the amino acid polymer is used in the form of an aqueous amino acid polymer solution, and the mass concentration of the aqueous amino acid polymer solution is 0.1 to 10%.

优选的，所述应用的压力为1～25MPa，所述应用的温度为-25～50℃。Preferably, the applied pressure is 1 to 25 MPa, and the applied temperature is -25 to 50°C.

本发明提供一种氨基酸均聚物，具有式1所示结构的第一聚合单元：The present invention provides an amino acid homopolymer, which has a first polymerized unit with a structure shown in Formula 1:

Figure PCTCN2022088646-appb-000003
Figure PCTCN2022088646-appb-000003

制备所述氨基酸均聚物的引发剂为水溶性引发剂。The initiator used to prepare the amino acid homopolymer is a water-soluble initiator.

本发明提供的氨基酸均聚物具有式1所示结构的第一聚合单元，所述氨基酸均聚物中含有异丙基侧链基团，异丙基有较强的疏水性，疏水性的异丙基能固化水分子的结构，从而对异丙基周围的水分子起到束缚作用，使天然气水合物的笼状水结构不易形成，从而抑制天然气水合物的成核。同时，异丙基侧链的尺寸与天然气水合物笼状结构的尺寸相当，能够进入天然气水合物笼状结构内部对天然气水合物的结构产生干扰作用，影响天然气水合物结构的稳定型，从而使天然气水合物形核不能稳定长大至临界尺寸，从而使天然气水合物晶体不易成核。而且式1所示氨基酸均聚物的主链上含有酰胺基，酰胺基中的N、O原子能够通过氢键吸附在天然气水合物表面，从而抑制天然气水合物晶体的进一步生长。因此，本发明提供的氨基酸聚合物能够在低剂量浓度条件下、高过冷度的环境中，有效延缓天然气水合物的成核、降低天然气水合物生成速率，具有抑制效果好、用量少、成本低、适用性广等优点。The amino acid homopolymer provided by the invention has the first polymerization unit of the structure shown in Formula 1. The amino acid homopolymer contains an isopropyl side chain group. The isopropyl group has strong hydrophobicity, and the hydrophobic isopropyl group The propyl group can solidify the structure of water molecules, thus binding the water molecules around the isopropyl group, making it difficult for the cage water structure of natural gas hydrate to form, thus inhibiting the nucleation of natural gas hydrate. At the same time, the size of the isopropyl side chain is equivalent to the size of the natural gas hydrate cage structure. It can enter the inside of the natural gas hydrate cage structure and interfere with the structure of the natural gas hydrate, affecting the stability of the natural gas hydrate structure. Natural gas hydrate nucleation cannot stably grow to a critical size, making it difficult for natural gas hydrate crystals to nucleate. Moreover, the main chain of the amino acid homopolymer shown in Formula 1 contains an amide group. The N and O atoms in the amide group can be adsorbed on the surface of natural gas hydrate through hydrogen bonds, thereby inhibiting the further growth of natural gas hydrate crystals. Therefore, the amino acid polymer provided by the present invention can effectively delay the nucleation of natural gas hydrate and reduce the formation rate of natural gas hydrate under low dose concentration conditions and high supercooling environment, and has good inhibitory effect, low dosage, It has the advantages of low cost and wide applicability.

本发明提供一种氨基酸无规共聚物，包括具有式1所示结构的第一聚合单元和具有式2所示结构的第二聚合单元：The invention provides an amino acid random copolymer, which includes a first polymerized unit having a structure shown in Formula 1 and a second polymerized unit having a structure shown in Formula 2:

Figure PCTCN2022088646-appb-000004
Figure PCTCN2022088646-appb-000004

本发明提供的氨基酸无规共聚物以式2所示结构的第二聚合单元增强氨基酸聚合物的水溶性，能够扩展氨基酸聚合物引发剂的种类，降低制备难度。The amino acid random copolymer provided by the invention uses the second polymerization unit of the structure shown in Formula 2 to enhance the water solubility of the amino acid polymer, which can expand the types of amino acid polymer initiators and reduce the difficulty of preparation.

本发明提供了氨基酸聚合物作为天然气水合物动力学抑制剂的应用，所述氨基酸聚合物为上述技术方案所述氨基酸均聚物或上述技术方案所述的氨基酸无规共聚物。The present invention provides the application of an amino acid polymer as a natural gas hydrate kinetic inhibitor. The amino acid polymer is the amino acid homopolymer described in the above technical solution or the amino acid random copolymer described in the above technical solution.

本发明提供的氨基酸聚合物作为天然气水合物抑制剂的使用浓度远远小于传统热力学抑制剂，一般添加的质量浓度为0.1～2.0％即能达到较好的抑制效果，试剂成本大大降低。本发明提供的氨基酸聚合物能够有效延缓水合物的成核/生长，使油气产品在一定时间内不生成水合物，从而能够被安全输送至目的地。本发明提供的氨基酸聚合物适用于油-气-水三相或油-水或气-水两相共存体系，应用于油气输运和可燃冰开采过程中抑制天然气水合物的生成，能取得良好抑制效果，且用量少，成本降低，具有广阔的应用前景。The usage concentration of the amino acid polymer provided by the present invention as a natural gas hydrate inhibitor is much lower than that of traditional thermodynamic inhibitors. Generally, a good inhibitory effect can be achieved by adding a mass concentration of 0.1 to 2.0%, and the reagent cost is greatly reduced. The amino acid polymer provided by the present invention can effectively delay the nucleation/growth of hydrates, so that oil and gas products do not generate hydrates within a certain period of time, so that they can be safely transported to their destinations. The amino acid polymer provided by the invention is suitable for oil-gas-water three-phase or oil-water or gas-water two-phase coexistence systems. It can be used to inhibit the generation of natural gas hydrates during oil and gas transportation and combustible ice mining processes, and can achieve good results. The inhibitory effect is small, the cost is reduced, and it has broad application prospects.

本发明提供的氨基酸聚合物以水溶性引发剂增强氨基酸聚合物的水溶性，能够使其以水溶性的形式作为天然气水合物动力学抑制剂使用，绿色环保。同时，具有由N、O杂原子构成的主链的氨基酸聚合物，比乙烯基聚合物或者丙烯基聚合物类天然气水合物动力学抑制剂(主链由纯C-C键构成)具有更大的生物可降解性潜能。The amino acid polymer provided by the invention uses a water-soluble initiator to enhance the water solubility of the amino acid polymer, so that it can be used as a natural gas hydrate kinetic inhibitor in a water-soluble form, which is green and environmentally friendly. At the same time, amino acid polymers with a main chain composed of N and O heteroatoms have greater biological potential than vinyl polymers or propylene-based polymers (the main chain is composed of pure C-C bonds). Degradability potential.

说明书附图Instructions with pictures

图1为本发明实施例1制备的氨基酸聚合物的核磁共振氢谱图；Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 1 of the present invention;

图2为本发明实施例2制备的氨基酸聚合物的核磁共振氢谱图；Figure 2 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 2 of the present invention;

图3为本发明实施例3制备的氨基酸聚合物的核磁共振氢谱图；Figure 3 is a hydrogen nuclear magnetic resonance spectrum of the amino acid polymer prepared in Example 3 of the present invention;

图4为本发明应用例1反应釜内体系的时间-温度、时间-压力曲线示例图。Figure 4 is an example diagram of the time-temperature and time-pressure curves of the system in the reaction kettle of Application Example 1 of the present invention.

具体实施方式Detailed ways

本发明提供一种氨基酸均聚物，具有式1所示结构的第一聚合单元：The present invention provides an amino acid homopolymer, which has a first polymerized unit with a structure shown in Formula 1:

Figure PCTCN2022088646-appb-000005
Figure PCTCN2022088646-appb-000005

制备所述氨基酸均聚物的引发剂为水溶性引发剂。The initiator used to prepare the amino acid homopolymer is a water-soluble initiator.

在本发明中，所述氨基酸均聚物的引发剂具体优选为甲氧基聚乙二醇胺。In the present invention, the initiator of the amino acid homopolymer is specifically preferably methoxy polyethylene glycol amine.

在本发明中，所述氨基酸均聚物的结构式具体优选为式1-1所示：In the present invention, the structural formula of the amino acid homopolymer is preferably represented by Formula 1-1:

Figure PCTCN2022088646-appb-000006
Figure PCTCN2022088646-appb-000006

在本发明中，所述式1-1中的n为第一聚合单元的聚合度。In the present invention, n in the formula 1-1 is the degree of polymerization of the first polymerization unit.

在本发明中，所述氨基酸均聚物的聚合度n为10～10000，更优选为20～8000，进一步优选为35～5000。In the present invention, the degree of polymerization n of the amino acid homopolymer is 10 to 10,000, more preferably 20 to 8,000, and even more preferably 35 to 5,000.

在本发明的具体实施例中，所述氨基酸均聚物聚合度具体优选为46或40。In specific embodiments of the present invention, the degree of polymerization of the amino acid homopolymer is preferably 46 or 40.

在本发明中，所述甲氧基聚乙二醇胺具有式3所示结构：In the present invention, the methoxy polyethylene glycol amine has the structure shown in Formula 3:

Figure PCTCN2022088646-appb-000007
Figure PCTCN2022088646-appb-000007

在本发明的具体实施例中，所述甲氧基聚乙二醇胺具有式4或式5所示结构：In specific embodiments of the present invention, the methoxy polyethylene glycol amine has the structure shown in Formula 4 or Formula 5:

Figure PCTCN2022088646-appb-000008
Figure PCTCN2022088646-appb-000008

在本发明中，所述氨基酸均聚物的平均分子量具体优选为5561g/mol或5966g/molIn the present invention, the average molecular weight of the amino acid homopolymer is specifically preferably 5561g/mol or 5966g/mol.

本发明提供一种氨基酸无规共聚物，包括具有式1所示结构的第一聚合单元和具有式2所示结构的第二聚合单元：The invention provides an amino acid random copolymer, which includes a first polymerized unit having a structure shown in Formula 1 and a second polymerized unit having a structure shown in Formula 2:

Figure PCTCN2022088646-appb-000009
Figure PCTCN2022088646-appb-000009

在本发明中，所述氨基酸无规共聚物的平均分子量为1000～1000000g/mol，更优选为3000～800000g/mol，进一步优选为5000～200000g/mol。In the present invention, the average molecular weight of the amino acid random copolymer is 1,000 to 1,000,000 g/mol, more preferably 3,000 to 800,000 g/mol, and even more preferably 5,000 to 200,000 g/mol.

在本发明的具体实施例中，所述氨基酸无规共聚物的平均分子量具体优选为17874g/mol。In specific embodiments of the present invention, the average molecular weight of the amino acid random copolymer is preferably 17874 g/mol.

在本发明中，所述氨基酸无规共聚物中第一聚合单元和第二聚合物单元的摩尔比为1:(0.1～10)，更优选为1:(0.2～8)，进一步优选为1:(0.25～5)。In the present invention, the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is 1: (0.1-10), more preferably 1: (0.2-8), further preferably 1 :(0.25～5).

在本发明的具体实施例中，所述氨基酸无规共聚物中第一聚合单元和第二聚合物单元的摩尔比具体优选为118:48。In a specific embodiment of the present invention, the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is preferably 118:48.

在本发明中，制备所述氨基酸无规共聚物的引发剂优选为水溶性引发剂或油溶性引发剂，更优选为油溶性引发剂。In the present invention, the initiator for preparing the amino acid random copolymer is preferably a water-soluble initiator or an oil-soluble initiator, and more preferably an oil-soluble initiator.

在本发明中，制备所述氨基酸无规共聚物的引发剂具体优选为苄胺。In the present invention, the initiator for preparing the amino acid random copolymer is specifically preferably benzylamine.

本发明提供的氨基酸均聚物或氨基酸无规共聚物作为新型天然气水合物动力学抑制剂应用时，具有较好的抑制效果，并且具有用量少、成本低、来源广的优势。本发明提供的氨基酸聚合物加入量远远小于传统热力学抑制剂，一般添加的质量浓度为0.1～10％即能达到较好的抑制效果，试剂成本大大降低。When used as a new type of natural gas hydrate kinetic inhibitor, the amino acid homopolymer or amino acid random copolymer provided by the invention has a good inhibitory effect, and has the advantages of low dosage, low cost and wide source. The added amount of the amino acid polymer provided by the present invention is much smaller than that of traditional thermodynamic inhibitors. Generally, a good inhibitory effect can be achieved by adding a mass concentration of 0.1 to 10%, and the reagent cost is greatly reduced.

本发明提供了上述技术方案所述所述的氨基酸均聚物的制备方法，包括以下步骤：The invention provides a method for preparing the amino acid homopolymer described in the above technical solution, which includes the following steps:

在保护气体中，将缬氨酸-N-羧基环内酸酐、水溶性引发剂和有机溶剂混合发生开环聚合反应，得到所述聚氨酸均聚物。In a protective gas, valine-N-carboxyl intracyclic acid anhydride, a water-soluble initiator and an organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain the polyamine homopolymer.

在本发明中，若无特殊说明，所用原料均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art.

在本发明中，所述反应单体优选为缬氨酸-N-羧基环内酸酐，所述水溶性引发剂具体优选为甲氧基聚乙二醇胺。In the present invention, the reaction monomer is preferably valine-N-carboxylic intracyclic anhydride, and the water-soluble initiator is specifically preferably methoxy polyethylene glycol amine.

在本发明中，所述缬氨酸-N-羧基环内酸酐和水溶性引发剂的摩尔比优选为(10～60):1，更优选为(15～50):1，进一步优选为(20～45):1。In the present invention, the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the water-soluble initiator is preferably (10-60):1, more preferably (15-50):1, and further preferably ( 20～45):1.

在本发明的具体实施例中，所述有机溶剂具体优选为N,N-二甲基甲酰胺。In specific embodiments of the present invention, the organic solvent is preferably N,N-dimethylformamide.

在本发明的具体实施例中，所述有机溶剂优选为无水溶剂。In specific embodiments of the present invention, the organic solvent is preferably an anhydrous solvent.

本发明对所述有机溶剂的用量没有特殊要求，将所述开环聚合反应的原料完全溶解即可。The present invention has no special requirements on the amount of the organic solvent, as long as the raw materials for the ring-opening polymerization reaction are completely dissolved.

在本发明中，所述缬氨酸-N-羧基环内酸酐的质量和有机溶剂的体积之比具体优选为0.5g:10mL。In the present invention, the ratio of the mass of the valine-N-carboxylic intracyclic acid anhydride to the volume of the organic solvent is specifically preferably 0.5g:10mL.

在本发明中，所述混合的顺序优选为：将所述缬氨酸-N-羧基环内酸酐、有机溶剂和水溶性引发剂依次混合。In the present invention, the mixing sequence is preferably: mixing the valine-N-carboxyl intracyclic acid anhydride, organic solvent and water-soluble initiator in sequence.

在本发明中，所述开环聚合反应为N-羧基环内酸酐开环聚合反应。In the present invention, the ring-opening polymerization reaction is an N-carboxyl intracyclic acid anhydride ring-opening polymerization reaction.

在本发明中，所述开环聚合反应的温度优选为20～60℃，更优选为 25～50℃。In the present invention, the temperature of the ring-opening polymerization reaction is preferably 20 to 60°C, and more preferably 25 to 50°C.

在本发明中，所述开环聚合反应的保温时间优选为8～48h，更优选为10～45h。In the present invention, the heat preservation time of the ring-opening polymerization reaction is preferably 8 to 48 hours, more preferably 10 to 45 hours.

在本发明中，所述保护气体优选为氮气或惰性气体，更优选为氮气。In the present invention, the protective gas is preferably nitrogen or an inert gas, and more preferably nitrogen.

在本发明中，进行所述开环聚合反应之前，本发明优选对所述开环聚合反应的容器重复进行抽真空-通保护气体3次。In the present invention, before performing the ring-opening polymerization reaction, the invention preferably repeatedly evacuates and passes protective gas through the container for the ring-opening polymerization reaction three times.

在本发明中，所述开环聚合反应得到聚合反应液，本发明优选对所述聚合反应液进行后处理，得到所述氨基酸均聚物。在本发明中，所述后处理优选包括：依次进行沉淀析出、固液分离和干燥。在本发明中，所述沉淀洗出优选为：将所述聚合反应液和乙醚混合，本发明对所述乙醚的用量没有特殊要求，确保均聚产物完全析出即可。在本发明中，所述固液分离优选为离心分离，本发明对所述离心分离的具体实施方式没有特殊要求。本发明优选对固液分离后的固体产物进行干燥，在本发明中，所述干燥的温度优选为室温，所述干燥的时间优选为24h。In the present invention, the ring-opening polymerization reaction obtains a polymerization reaction liquid. In the present invention, it is preferable to perform post-treatment on the polymerization reaction liquid to obtain the amino acid homopolymer. In the present invention, the post-treatment preferably includes: precipitation, solid-liquid separation and drying in sequence. In the present invention, the precipitation is preferably washed out by mixing the polymerization reaction solution and diethyl ether. The present invention has no special requirements on the amount of diethyl ether, as long as the homopolymer product is completely precipitated. In the present invention, the solid-liquid separation is preferably centrifugal separation, and the present invention has no special requirements on the specific implementation of the centrifugal separation. In the present invention, it is preferred to dry the solid product after solid-liquid separation. In the present invention, the drying temperature is preferably room temperature, and the drying time is preferably 24 hours.

本发明提供了上述技术方案所述的氨基酸无规共聚物的制备方法，包括以下步骤：The invention provides a method for preparing the amino acid random copolymer described in the above technical solution, which includes the following steps:

在保护气体中，将缬氨酸-N-羧基环内酸酐、谷氨酸-5-苄酯-N-羧基环内酸酐、水溶性引发剂或油溶性引发剂和有机溶剂混合发生开环聚合反应，得到所述聚氨酸无规共聚物。In a protective gas, ring-opening polymerization occurs by mixing valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride, water-soluble initiator or oil-soluble initiator and organic solvent. reaction to obtain the polyamide random copolymer.

在本发明中，所述缬氨酸-N-羧基环内酸酐和所述谷氨酸-5-苄酯-N-羧基环内酸酐的摩尔比优选为1:(0.1～10)，更优选为1:(0.2～8)，进一步优选为1:(0.25～5)。In the present invention, the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the glutamic acid-5-benzyl ester-N-carboxylic intracyclic acid anhydride is preferably 1:(0.1~10), more preferably It is 1: (0.2-8), and it is more preferable that it is 1: (0.25-5).

在本发明的具体实施例中，所述缬氨酸-N-羧基环内酸酐和所述谷氨酸-5-苄酯-N-羧基环内酸酐的摩尔比具体优选为118:48。In a specific embodiment of the present invention, the molar ratio of the valine-N-carboxy intracyclic acid anhydride and the glutamic acid-5-benzyl ester-N-carboxyl intracyclic acid anhydride is specifically preferably 118:48.

在本发明中，所述油溶性引发剂具体优选为苄胺。In the present invention, the oil-soluble initiator is specifically preferably benzylamine.

在本发明中，所述缬氨酸-N-羧基环内酸酐和油溶性引发剂或水溶性引发剂的摩尔比优选为(4～60):1，更优选为(6～50):1，进一步优选为(8～40):1。In the present invention, the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the oil-soluble initiator or water-soluble initiator is preferably (4-60):1, and more preferably (6-50):1 , more preferably (8-40):1.

在本发明的具体实施例中，所述有机溶剂具体优选为N,N-二甲基甲 酰胺。In specific embodiments of the present invention, the organic solvent is preferably N,N-dimethylformamide.

在本发明的具体实施例中，所述有机溶剂优选为无水溶剂。In specific embodiments of the present invention, the organic solvent is preferably an anhydrous solvent.

本发明对所述有机溶剂的用量没有特殊要求，将所述开环聚合反应的原料完全溶解即可。The present invention has no special requirements on the amount of the organic solvent, as long as the raw materials for the ring-opening polymerization reaction are completely dissolved.

在本发明中，所述缬氨酸-N-羧基环内酸酐的质量和有机溶剂的体积之比具体优选为0.5g:10mL。In the present invention, the ratio of the mass of the valine-N-carboxylic intracyclic acid anhydride to the volume of the organic solvent is specifically preferably 0.5g:10mL.

在本发明中，所述混合的顺序优选为：将所述缬氨酸-N-羧基环内酸酐、谷氨酸-5-苄酯-N-羧基环内酸酐、有机溶剂和水溶性引发剂或水溶性引发剂依次混合。In the present invention, the mixing sequence is preferably: the valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride, organic solvent and water-soluble initiator Or water-soluble initiators are mixed in sequence.

在本发明中，所述开环聚合反应为N-羧基环内酸酐开环聚合反应。In the present invention, the ring-opening polymerization reaction is an N-carboxyl intracyclic acid anhydride ring-opening polymerization reaction.

在本发明中，所述开环聚合反应的温度优选为20～60℃，更优选为25～50℃。In the present invention, the temperature of the ring-opening polymerization reaction is preferably 20 to 60°C, and more preferably 25 to 50°C.

在本发明中，所述开环聚合反应的保温时间优选为8～48h，更优选为10～45h。In the present invention, the heat preservation time of the ring-opening polymerization reaction is preferably 8 to 48 hours, more preferably 10 to 45 hours.

在本发明中，所述保护气体优选为氮气或惰性气体，更优选为氮气。In the present invention, the protective gas is preferably nitrogen or an inert gas, and more preferably nitrogen.

在本发明中，进行所述开环聚合反应之前，本发明优选对所述开环聚合反应的容器重复进行抽真空-通保护气体3次。In the present invention, before performing the ring-opening polymerization reaction, the invention preferably repeatedly evacuates and passes protective gas through the container for the ring-opening polymerization reaction three times.

在本发明中，所述开环聚合反应得到聚合反应液，本发明优选对所述聚合反应液进行后处理，得到所述氨基酸均聚物。在本发明中，所述后处理优选包括：依次进行沉淀析出、固液分离和干燥。在本发明中，所述沉淀洗出优选为：将所述聚合反应液和乙醚混合，本发明对所述乙醚的用量没有特殊要求，确保均聚产物完全析出即可。在本发明中，所述固液分离优选为离心分离，本发明对所述离心分离的具体实施方式没有特殊要求。本发明优选对固液分离后的固体产物进行干燥，在本发明中，所述干燥的温度优选为室温，所述干燥的时间优选为24h。In the present invention, the ring-opening polymerization reaction obtains a polymerization reaction liquid. In the present invention, it is preferable to perform post-treatment on the polymerization reaction liquid to obtain the amino acid homopolymer. In the present invention, the post-treatment preferably includes: precipitation, solid-liquid separation and drying in sequence. In the present invention, the precipitation is preferably washed out by mixing the polymerization reaction solution and diethyl ether. The present invention has no special requirements on the amount of diethyl ether, as long as the homopolymer product is completely precipitated. In the present invention, the solid-liquid separation is preferably centrifugal separation, and the present invention has no special requirements on the specific implementation of the centrifugal separation. In the present invention, it is preferred to dry the solid product after solid-liquid separation. In the present invention, the drying temperature is preferably room temperature, and the drying time is preferably 24 hours.

本发明得到聚合反应液进行上述后处理，得到后处理产物，本发明优选还包括将所述后处理产物继续进行第一后处理，得到所述氨基酸无果共聚物。在本发明中，所述第一后处理优选包括：依次进行水解反应、水透析纯化和冻干。The present invention obtains the polymerization reaction liquid and performs the above post-treatment to obtain a post-processed product. The present invention preferably further includes subjecting the post-processed product to a first post-processing to obtain the amino acid fruitless copolymer. In the present invention, the first post-treatment preferably includes: hydrolysis reaction, water dialysis purification and freeze-drying in sequence.

在本发明中，所述水解反应优选为：将所述后处理产物、第一有机溶剂和NaOH水溶液第二混合进行反应。In the present invention, the hydrolysis reaction is preferably: the post-treatment product, the first organic solvent and the NaOH aqueous solution are mixed for a second time to react.

在本发明中，所述第一有机溶剂具体优选为1,4-二氧六环。In the present invention, the first organic solvent is specifically preferably 1,4-dioxane.

在本发明中，所述NaOH水溶液的摩尔浓度优选为1mol/L。In the present invention, the molar concentration of the NaOH aqueous solution is preferably 1 mol/L.

在本发明中，所述NaOH水溶液中NaOH与所述后处理产物中酯基的摩尔比优选为(1.2～2):1。In the present invention, the molar ratio of NaOH in the NaOH aqueous solution to the ester group in the post-treatment product is preferably (1.2-2):1.

在本发明中，所述第二混合优选包括以下步骤：In the present invention, the second mixing preferably includes the following steps:

将所述后处理产物溶解于所述第一有机溶剂中，得到后处理产物溶液；Dissolve the post-treatment product in the first organic solvent to obtain a post-treatment product solution;

将所述NaOH水溶液滴加至所述后处理产物溶液中。The NaOH aqueous solution was added dropwise to the post-treatment product solution.

在本发明中，所述水解反应的温度优选为室温，所述水解反应的保温时间优选为4～24h，更优选为5～23h。In the present invention, the temperature of the hydrolysis reaction is preferably room temperature, and the holding time of the hydrolysis reaction is preferably 4 to 24 hours, more preferably 5 to 23 hours.

在本发明中，所述水透析纯化具体优选为：将所述水解反应的反应液装入透析袋中，将装有反应液的透析袋浸渍于水中进行透析。In the present invention, the water dialysis purification is preferably as follows: putting the reaction liquid of the hydrolysis reaction into a dialysis bag, and immersing the dialysis bag containing the reaction liquid in water to perform dialysis.

在本发明中，所述水优选为纯水。In the present invention, the water is preferably pure water.

在本发明中，所述水透析纯化的时间优选为24～48h，更优选为48h。In the present invention, the time for water dialysis and purification is preferably 24 to 48 hours, and more preferably 48 hours.

在本发明中，所述透析袋使用的透析膜截留分子量为1000Da。In the present invention, the dialysis membrane used in the dialysis bag has a molecular weight cutoff of 1000 Da.

在本发明中，所述冻干的温度优选为-60℃。In the present invention, the freeze-drying temperature is preferably -60°C.

本发明提供了氨基酸聚合物作为天然气水合物动力学抑制剂的应用，所述氨基酸聚合物为上述技术方案所述氨基酸均聚物或上述技术方案所述的氨基酸无规共聚物。The present invention provides the application of an amino acid polymer as a natural gas hydrate kinetic inhibitor. The amino acid polymer is the amino acid homopolymer described in the above technical solution or the amino acid random copolymer described in the above technical solution.

在本发明中，所述氨基酸聚合物优选以氨基酸聚合物水溶液的形式使用。In the present invention, the amino acid polymer is preferably used in the form of an aqueous amino acid polymer solution.

在本发明中，所述氨基酸聚合物水溶液的质量浓度优选为0.1～10％，更优选为0.1～2％。In the present invention, the mass concentration of the amino acid polymer aqueous solution is preferably 0.1 to 10%, and more preferably 0.1 to 2%.

在本发明中，所述应用的压力优选为1～25MPa。In the present invention, the applied pressure is preferably 1 to 25 MPa.

在本发明中，所述应用的温度优选为-25～50℃。In the present invention, the applied temperature is preferably -25 to 50°C.

本发明提供的氨基酸聚合物作为天然气水合物动力学抑制剂适用于油-气-水三相或油-水或气-水两相共存体系，应用于油气输运和可燃冰开 采过程中抑制天然气水合物的生成，能取得良好抑制效果，且用量少，成本降低，具有广阔的应用前景。As a natural gas hydrate kinetic inhibitor, the amino acid polymer provided by the invention is suitable for oil-gas-water three-phase or oil-water or gas-water two-phase coexistence systems, and can be used to inhibit natural gas in the process of oil and gas transportation and flammable ice mining. The formation of hydrates can achieve good inhibitory effect, and the dosage is small, the cost is reduced, and it has broad application prospects.

为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.

实施例1Example 1

在容积为50mL的Schlenk烧瓶中依次加入0.5g缬氨酸-N-羧基环内酸酐，10mL无水N,N-二甲基甲酰胺，甲氧基聚乙二醇胺(结构式如式4所示，重均分子量为1000，甲氧基聚乙二醇胺与缬氨酸-N-羧基环内酸酐的摩尔比为1:15)，抽真空-通氮气3次，于氮气保护下进行开环聚合反应，开环聚合反应温度为25℃，开环聚合反应的保温时间为48h。Into a Schlenk flask with a volume of 50 mL, add 0.5 g of valine-N-carboxylic intracyclic anhydride, 10 mL of anhydrous N, N-dimethylformamide, and methoxy polyethylene glycol amine (the structural formula is as shown in Formula 4). shown, the weight average molecular weight is 1000, the molar ratio of methoxy polyethylene glycol amine and valine-N-carboxylic intracyclic acid anhydride is 1:15), vacuum-pass nitrogen 3 times, and start under nitrogen protection For ring polymerization reaction, the ring-opening polymerization reaction temperature is 25°C, and the holding time of the ring-opening polymerization reaction is 48 hours.

将开环聚合反应得到的反应液加入乙醚进行沉淀、离心分离、干燥后得缬氨酸聚合物1，缬氨酸聚合物1的数据分子量为5561g/mol，缬氨酸聚合物1的 1H NMR(以CF 3COOD作溶剂)谱图如图1所示：由图1计算得到缬氨酸聚合物1的结构式如式6所示： The reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain valine polymer 1. The data molecular weight of valine polymer 1 is 5561g/mol, and the 1 H of valine polymer 1 is The NMR (using CF 3 COOD as solvent) spectrum is shown in Figure 1: The structural formula of valine polymer 1 calculated from Figure 1 is shown in Formula 6:

Figure PCTCN2022088646-appb-000010
Figure PCTCN2022088646-appb-000010

实施例2Example 2

在容积为50mL的Schlenk烧瓶中依次加入0.5g缬氨酸-N-羧基环内酸酐，10mL无水N,N-二甲基甲酰胺，甲氧基聚乙二醇胺(结构式如式5所示，重均分子量为2000，甲氧基聚乙二醇胺与缬氨酸-N-羧基环内酸酐的摩尔比为1:15)，抽真空-通氮气3次，于氮气保护下进行开环聚合反应，开环聚合反应温度为25℃，开环聚合反应的保温时间为48h。Into a Schlenk flask with a volume of 50 mL, 0.5 g of valine-N-carboxylic intracyclic acid anhydride, 10 mL of anhydrous N, N-dimethylformamide, and methoxy polyethylene glycol amine (the structural formula is as shown in Formula 5) were added in sequence. shown, the weight average molecular weight is 2000, the molar ratio of methoxy polyethylene glycol amine and valine-N-carboxylic intracyclic acid anhydride is 1:15), vacuum-pass nitrogen 3 times, and start under nitrogen protection For ring polymerization reaction, the ring-opening polymerization reaction temperature is 25°C, and the holding time of the ring-opening polymerization reaction is 48 hours.

将开环聚合反应得到的反应液加入乙醚进行沉淀、离心分离、干燥后得缬氨酸聚合物2，缬氨酸聚合物2的数据分子量为5966g/mol，缬氨酸聚合物2的 1H NMR(以CF 3COOD作溶剂)谱图如图2所示：由图2计算得到缬氨酸聚合物2的结构式如式7所示： The reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain valine polymer 2. The data molecular weight of valine polymer 2 is 5966g/mol, and the 1 H of valine polymer 2 is The NMR (using CF 3 COOD as solvent) spectrum is shown in Figure 2: The structural formula of valine polymer 2 calculated from Figure 2 is shown in Formula 7:

Figure PCTCN2022088646-appb-000011
Figure PCTCN2022088646-appb-000011

实施例3Example 3

在容积为50mL的Schlenk烧瓶中依次加入0.5g缬氨酸-N-羧基环内酸酐，谷氨酸-5-苄酯-N-羧基环内酸酐(谷氨酸-5-苄酯-N-羧基环内酸酐与缬氨酸-N-羧基环内酸酐的摩尔比为1:0.45)、10mL无水N,N-二甲基甲酰胺，苄胺(苄胺与缬氨酸-N-羧基环内酸酐的摩尔比为1:6)，抽真空-通氮气3次，于氮气保护下进行开环聚合反应，开环聚合反应温度为25℃，开环聚合反应的保温时间为48h。Into a Schlenk flask with a volume of 50 mL, 0.5 g of valine-N-carboxylic intracyclic acid anhydride and glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride (glutamic acid-5-benzyl ester-N- The molar ratio of carboxyl intracyclic anhydride and valine-N-carboxylic intracyclic anhydride is 1:0.45), 10 mL anhydrous N,N-dimethylformamide, benzylamine (benzylamine and valine-N-carboxylic acid anhydride) The molar ratio of the intracyclic acid anhydride is 1:6), evacuate and pass nitrogen three times, and perform ring-opening polymerization under nitrogen protection. The ring-opening polymerization reaction temperature is 25°C, and the ring-opening polymerization holding time is 48 hours.

将开环聚合反应得到的反应液加入乙醚进行沉淀、离心分离、干燥后得固体产物。The reaction solution obtained by the ring-opening polymerization reaction is added to diethyl ether for precipitation, centrifugal separation, and drying to obtain a solid product.

将固体产物溶解于1,4-二氧六环中，得到固体产物溶液后，将NaOH水溶液滴加至所述固体产物溶液中，NaOH水溶液的摩尔浓度为1mol/L，NaOH水溶液中NaOH与固体产物中酯基的摩尔比优选为1.2:1，在常温条件下反应24h，将得到的反应液装入透析袋中，将装有反应液的透析袋浸渍于纯水中进行透析48h后，取出冷冻干燥，得到缬氨酸聚合物3，缬氨酸聚合物3的数据分子量为17874g/mol，缬氨酸聚合物3的 1H NMR(以CF 3COOD作溶剂)谱图如图3所示：由图3计算得到缬氨酸聚合物3中，谷氨酸结构单元与缬氨酸结构单元的摩尔比为48:118。 Dissolve the solid product in 1,4-dioxane to obtain a solid product solution, then add the NaOH aqueous solution dropwise to the solid product solution. The molar concentration of the NaOH aqueous solution is 1 mol/L. The NaOH and solid content in the NaOH aqueous solution are The molar ratio of ester groups in the product is preferably 1.2:1. The reaction is carried out for 24 hours at room temperature. The obtained reaction solution is put into a dialysis bag. The dialysis bag containing the reaction solution is immersed in pure water for dialysis for 48 hours and then taken out. After freeze-drying, valine polymer 3 is obtained. The data molecular weight of valine polymer 3 is 17874g/mol. The 1 H NMR (using CF 3 COOD as solvent) spectrum of valine polymer 3 is shown in Figure 3 : Calculated from Figure 3, the molar ratio of glutamic acid structural units to valine structural units in valine polymer 3 is 48:118.

应用例1Application example 1

将本发明实施例制备的氨基酸聚合物作为天然气水合物动力学抑制剂使用，检验本发明提供的天然气水合物动力学抑制剂的抑制效果的实验设备为高压搅拌试验装置，高压搅拌试验装置主要组成部分包括不锈钢高压反应釜、循环式水浴、磁力搅拌器、温度传感器、压力传感器、高压气瓶、真空泵、数据采集仪等。所述不锈钢高压反应釜最高工作压力20MPa，工作温度范围为-20～80℃。所述不锈钢高压反应釜釜内压力可通过气阀自由调节。循环式水浴可为高压反应釜提供-20～80℃的温度环境。数据采集 系统实时采集和储存高压反应釜釜内压力、温度等参数。反应釜内天然气水合物的生成可通过反应时的温度或压力的骤变进行判断。在高压反应釜内装入实施例制备的氨基酸聚合物水溶液后，通入高压气体，关闭阀门使高压反应釜内的体系封闭，开通搅拌，然后以恒定的速率(1℃/h)降低温度使天然气水合物生成。在降温的过程中，高压反应釜内的体系会逐渐达到天然气水合物的生成条件。在封闭体系内，随着温度的降低压力也随之线性降低。当天然气水合物生成时，会消耗部分气体分子，因此体系内的压力会偏离原来的压降曲线；同时，因为天然气水合物的生成是放热反应，体系的温度会上升。本发明提供的天然气水合物动力学抑制剂的抑制效果根据反应釜体系内添加添加实施例制备的动力学抑制剂水溶液的天然气水合物生成温度来量化。高压反应釜体系内的天然气水合物的生成温度越低，表明该动力学抑制剂的抑制效果则越好。The amino acid polymer prepared in the embodiment of the present invention is used as a natural gas hydrate kinetic inhibitor. The experimental equipment for testing the inhibitory effect of the natural gas hydrate kinetic inhibitor provided by the present invention is a high-pressure stirring test device. The main components of the high-pressure stirring test device are: Parts include stainless steel high-pressure reactors, circulating water baths, magnetic stirrers, temperature sensors, pressure sensors, high-pressure gas bottles, vacuum pumps, data acquisition instruments, etc. The stainless steel high-pressure reactor has a maximum working pressure of 20MPa and a working temperature range of -20 to 80°C. The pressure inside the stainless steel high-pressure reaction kettle can be freely adjusted through the air valve. The circulating water bath can provide a temperature environment of -20~80℃ for the high-pressure reactor. Data collection: The system collects and stores parameters such as pressure and temperature in the high-pressure reaction kettle in real time. The formation of natural gas hydrate in the reactor can be judged by sudden changes in temperature or pressure during the reaction. After filling the high-pressure reaction kettle with the aqueous amino acid polymer solution prepared in the Example, introduce high-pressure gas, close the valve to seal the system in the high-pressure reaction kettle, turn on stirring, and then lower the temperature at a constant rate (1°C/h) to allow the natural gas to flow. Hydrate formation. During the cooling process, the system in the high-pressure reactor will gradually reach the conditions for the formation of natural gas hydrate. In a closed system, the pressure decreases linearly as the temperature decreases. When natural gas hydrate is generated, some gas molecules will be consumed, so the pressure in the system will deviate from the original pressure drop curve; at the same time, because the generation of natural gas hydrate is an exothermic reaction, the temperature of the system will rise. The inhibitory effect of the natural gas hydrate kinetic inhibitor provided by the present invention is quantified based on the natural gas hydrate formation temperature at which the kinetic inhibitor aqueous solution prepared in the Example is added to the reactor system. The lower the formation temperature of natural gas hydrate in the high-pressure reactor system, the better the inhibitory effect of the kinetic inhibitor.

具体实施过程为：实验运行前，依次用洗涤剂、乙醇、去离子水清洗高压反应釜，再用氮气吹干反应釜内的水，确保其干燥。将50.0mL(约为反应釜容积的1/3)、质量浓度为0.15％的缬氨酸聚合物1的水溶液加入反应釜中，盖上釜盖，反应釜放入水浴中，连上温度和压力传感器。然后，抽真空，通入0.5MPa高纯度甲烷气体，排除气体后再抽真空，如此反复3次以尽量去除反应釜和管线内的空气。当温度在14.5℃时，在反应釜内通入9.1MPa(此压力稍低于14.5℃时的甲烷水合物的相平衡压力)高纯度甲烷气体，关闭阀门。然后，以1℃/h的降温速率使反应釜内的温度从14.5℃降到2.5℃，降温过程中保持磁力搅拌器的搅拌速率为400rpm。根据降温过程中采集到的时间-温度、时间-压力曲线分析水合物的生成，从检测水合物动力学抑制剂的抑制效果。通过实验过程中测量的时间-温度、时间-压力曲线表明，在质量浓度为0.15％的实施例1制备的缬氨酸聚合物1水溶液为动力学抑制剂时，天然气水合物的生成温度为8.9℃，具有较好的抑制效果。The specific implementation process is: before running the experiment, clean the high-pressure reactor with detergent, ethanol, and deionized water in sequence, and then blow dry the water in the reactor with nitrogen to ensure it is dry. Add 50.0 mL (approximately 1/3 of the volume of the reaction kettle) of an aqueous solution of valine polymer 1 with a mass concentration of 0.15% into the reaction kettle, cover the kettle lid, put the reaction kettle into a water bath, and connect the temperature and Pressure Sensor. Then, vacuum, pass in 0.5MPa high-purity methane gas, remove the gas, and then vacuum again. Repeat this three times to remove as much air as possible from the reactor and pipelines. When the temperature is 14.5°C, high-purity methane gas of 9.1MPa (this pressure is slightly lower than the phase equilibrium pressure of methane hydrate at 14.5°C) is introduced into the reaction kettle and the valve is closed. Then, the temperature in the reaction kettle was lowered from 14.5°C to 2.5°C at a cooling rate of 1°C/h. During the cooling process, the stirring rate of the magnetic stirrer was maintained at 400 rpm. The generation of hydrate is analyzed based on the time-temperature and time-pressure curves collected during the cooling process to detect the inhibitory effect of the hydrate kinetic inhibitor. The time-temperature and time-pressure curves measured during the experiment show that when the aqueous solution of valine polymer 1 prepared in Example 1 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 8.9 ℃, has a better inhibitory effect.

应用例2Application example 2

与应用例1的反应装置和方法基本相同，不同之处在于：将质量浓度为0.15％的缬氨酸聚合物2的水溶液加入反应釜中，通过实验过程中测量 的时间-温度、时间-压力曲线(如图2所示)表明，在质量浓度为0.15％的实施例2制备的缬氨酸聚合物2水溶液为动力学抑制剂时，天然气水合物的生成温度为8.7℃，具有较好的抑制效果。The reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of valine polymer 2 with a mass concentration of 0.15% is added to the reaction kettle, and the time-temperature and time-pressure measured during the experiment are used. The curve (shown in Figure 2) shows that when the aqueous solution of valine polymer 2 prepared in Example 2 with a mass concentration of 0.15% is used as a kinetic inhibitor, the generation temperature of natural gas hydrate is 8.7°C, which has a good Inhibitory effect.

应用例3Application example 3

与应用例1的反应装置和方法基本相同，不同之处在于：将质量浓度为0.15％的缬氨酸聚合物3的水溶液加入反应釜中，通过实验过程中测量的时间-温度、时间-压力曲线表明，在质量浓度为0.15％的实施例3制备的缬氨酸聚合物3水溶液为动力学抑制剂时，天然气水合物的生成温度为7.5℃，具有较好的抑制效果。The reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of valine polymer 3 with a mass concentration of 0.15% is added to the reaction kettle, and the time-temperature and time-pressure measured during the experiment are used. The curve shows that when the aqueous solution of valine polymer 3 prepared in Example 3 with a mass concentration of 0.15% is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 7.5°C, which has a good inhibitory effect.

对比例1Comparative example 1

与应用例1的反应装置和方法基本相同，不同之处在于：将纯水加入反应釜中，通过实验过程中测量的时间-温度、时间-压力曲线表明，在纯水为动力学抑制剂时，天然气水合物的生成温度为10.3℃。The reaction device and method are basically the same as those in Application Example 1. The difference is that pure water is added to the reaction kettle. The time-temperature and time-pressure curves measured during the experiment show that when pure water is a kinetic inhibitor, , the formation temperature of natural gas hydrate is 10.3℃.

对比例2Comparative example 2

与应用例1的反应装置和方法基本相同，不同之处在于：将质量浓度为0.15％、分子量为2000g/mol的甲氧基聚乙二醇胺水溶液加入反应釜中，通过实验过程中测量的时间-温度、时间-压力曲线表明，在质量浓度为0.15％、分子量为2000g/mol的甲氧基聚乙二醇胺水溶液为动力学抑制剂时，天然气水合物的生成温度为9.8℃，抑制效果较差。The reaction device and method are basically the same as those in Application Example 1, except that a methoxy polyethylene glycol amine aqueous solution with a mass concentration of 0.15% and a molecular weight of 2000g/mol is added to the reaction kettle. The time-temperature and time-pressure curves show that when a methoxy polyethylene glycol amine aqueous solution with a mass concentration of 0.15% and a molecular weight of 2000g/mol is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 9.8°C, inhibiting Less effective.

对比例3Comparative example 3

与应用例1的反应装置和方法基本相同，不同之处在于：将质量浓度为0.15％、分子量为3722g/mol的聚谷氨酸水溶液加入反应釜中，通过实验过程中测量的时间-温度、时间-压力曲线表明，在质量浓度为0.15％、分子量为3722g/mol的聚谷氨酸水溶液为动力学抑制剂时，天然气水合物的生成温度为10.6℃，几乎没有抑制效果。The reaction device and method are basically the same as those in Application Example 1. The difference is that a polyglutamic acid aqueous solution with a mass concentration of 0.15% and a molecular weight of 3722g/mol is added to the reaction kettle. The time-temperature, The time-pressure curve shows that when a polyglutamic acid aqueous solution with a mass concentration of 0.15% and a molecular weight of 3722g/mol is used as a kinetic inhibitor, the formation temperature of natural gas hydrate is 10.6°C, with almost no inhibitory effect.

对比例4Comparative example 4

与应用例1的反应装置和方法基本相同，不同之处在于：将质量浓度为0.15％、分子量为10000g/mol的聚乙烯基吡络烷酮(PVP K15-K19)水溶液加入反应釜中，通过实验过程中测量的时间-温度、时间-压力曲线表 明，在质量浓度为0.15％、分子量为10000g/mol的聚乙烯基吡络烷酮(PVP K15-K19)水溶液为动力学抑制剂时，天然气水合物的生成温度为8.5℃，具有较好的抑制效果。The reaction device and method are basically the same as those in Application Example 1, except that an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is added to the reaction kettle, and the The time-temperature and time-pressure curves measured during the experiment show that when an aqueous solution of polyvinylpyrrolidone (PVP K15-K19) with a mass concentration of 0.15% and a molecular weight of 10000g/mol is used as a kinetic inhibitor, natural gas The formation temperature of hydrate is 8.5°C, which has a good inhibitory effect.

尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。Although the above embodiments describe the present invention in detail, they are only part of the embodiments of the present invention, not all embodiments. People can also obtain other embodiments based on this embodiment without any inventive step. These embodiments All belong to the protection scope of the present invention.

Claims (20)

一种氨基酸均聚物，其特征在于，具有式1所示结构的第一聚合单元：An amino acid homopolymer, characterized in that it has a first polymerized unit with a structure shown in Formula 1:
Figure PCTCN2022088646-appb-100001
Figure PCTCN2022088646-appb-100001
 制备所述氨基酸均聚物的引发剂为水溶性引发剂。The initiator used to prepare the amino acid homopolymer is a water-soluble initiator. 根据权利要求1所述的氨基酸均聚物，其特征在于，所述氨基酸均聚物的聚合度n为10～10000。The amino acid homopolymer according to claim 1, wherein the degree of polymerization n of the amino acid homopolymer is 10 to 10,000. 根据权利要求1或2所述的氨基酸均聚物，其特征在于，所述氨基酸均聚物的引发剂为甲氧基聚乙二醇胺。The amino acid homopolymer according to claim 1 or 2, characterized in that the initiator of the amino acid homopolymer is methoxy polyethylene glycol amine. 根据权利要求3所述的氨基酸均聚物，其特征在于，所述甲氧基聚乙二醇胺具有式4或式5所示结构：The amino acid homopolymer according to claim 3, wherein the methoxy polyethylene glycol amine has a structure shown in Formula 4 or Formula 5:
Figure PCTCN2022088646-appb-100002
Figure PCTCN2022088646-appb-100002
 根据权利要求4所述的氨基酸均聚物，其特征在于，所述氨基酸均聚物具有式6或式7所示结构：The amino acid homopolymer according to claim 4, characterized in that the amino acid homopolymer has a structure shown in Formula 6 or Formula 7:
Figure PCTCN2022088646-appb-100003
Figure PCTCN2022088646-appb-100003
 一种氨基酸无规共聚物，其特征在于，包括具有式1所示结构的第一聚合单元和具有式2所示结构的第二聚合单元：An amino acid random copolymer, characterized in that it includes a first polymerized unit with a structure shown in Formula 1 and a second polymerized unit with a structure shown in Formula 2:
Figure PCTCN2022088646-appb-100004
Figure PCTCN2022088646-appb-100004
 根据权利要求6所述的氨基酸无规共聚物，其特征在于，所述氨基酸无规共聚物的平均分子量为1000～1000000g/mol。The amino acid random copolymer according to claim 6, wherein the average molecular weight of the amino acid random copolymer is 1,000 to 1,000,000 g/mol. 根据权利要求7所述的氨基酸无规共聚物，其特征在于，所述氨基酸无规共聚物的平均分子量为17874g/mol。The amino acid random copolymer according to claim 7, wherein the average molecular weight of the amino acid random copolymer is 17874g/mol. 根据权利要求6～8任一项所述的氨基酸无规共聚物，其特征在于，所述氨基酸无规共聚物中第一聚合单元和第二聚合物单元的摩尔比为1:(0.1～10)。The amino acid random copolymer according to any one of claims 6 to 8, wherein the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is 1:(0.1-10 ). 根据权利要求9所述的氨基酸无规共聚物，其特征在于，所述氨基酸无规共聚物中第一聚合单元和第二聚合物单元的摩尔比为118:48。The amino acid random copolymer according to claim 9, wherein the molar ratio of the first polymer unit and the second polymer unit in the amino acid random copolymer is 118:48. 权利要求1～5任一项所述的氨基酸均聚物的制备方法，其特征在于，包括以下步骤：The preparation method of the amino acid homopolymer according to any one of claims 1 to 5, characterized in that it includes the following steps: 在保护气体中，将缬氨酸-N-羧基环内酸酐、水溶性引发剂和有机溶 剂混合发生开环聚合反应，得到所述聚氨酸均聚物。In a protective gas, valine-N-carboxylic intracyclic acid anhydride, water-soluble initiator and organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain the polyamine homopolymer. 根据权利要求11所述的制备方法，其特征在于，所述缬氨酸-N-羧基环内酸酐和水溶性引发剂的摩尔比为(10～60):1。The preparation method according to claim 11, characterized in that the molar ratio of the valine-N-carboxyl intracyclic acid anhydride and the water-soluble initiator is (10-60):1. 根据权利要求11所述的制备方法，其特征在于，所述开环聚合反应的温度为20～60℃。The preparation method according to claim 11, characterized in that the temperature of the ring-opening polymerization reaction is 20 to 60°C. 权利要6～10任一项所述的氨基酸无规共聚物的制备方法，其特征在于，包括以下步骤：The preparation method of the amino acid random copolymer according to any one of claims 6 to 10, characterized in that it includes the following steps: 在保护气体中，将缬氨酸-N-羧基环内酸酐、谷氨酸-5-苄酯-N-羧基环内酸酐、引发剂和有机溶剂混合发生开环聚合反应，得到所述聚氨酸无规共聚物，所述引发剂为水溶性引发剂或油溶性引发剂。In a protective gas, valine-N-carboxylic intracyclic acid anhydride, glutamic acid-5-benzyl ester-N-carboxylic intracyclic acid anhydride, initiator and organic solvent are mixed to undergo a ring-opening polymerization reaction to obtain the polyurethane Acid random copolymer, the initiator is a water-soluble initiator or an oil-soluble initiator. 根据权利要求14所述的制备方法，其特征在于，所述缬氨酸-N-羧基环内酸酐和所述谷氨酸-5-苄酯-N-羧基环内酸酐的摩尔比为1:(0.1～10)。The preparation method according to claim 14, characterized in that the molar ratio of the valine-N-carboxylic intracyclic acid anhydride and the glutamic acid-5-benzyl ester-N-carboxycyclic intracyclic acid anhydride is 1: (0.1～10). 根据权利要求14所述的制备方法，其特征在于，所述缬氨酸-N-羧基环内酸酐和引发剂的摩尔比为(4～60):1。The preparation method according to claim 14, characterized in that the molar ratio of the valine-N-carboxyl intracyclic acid anhydride and the initiator is (4-60):1. 根据权利要求14所述的制备方法，其特征在于，所述开环聚合反应的温度为20～60℃。The preparation method according to claim 14, characterized in that the temperature of the ring-opening polymerization reaction is 20 to 60°C. 氨基酸聚合物作为天然气水合物动力学抑制剂的应用，所述氨基酸聚合物为权利要求1～5任一项所述氨基酸均聚物或权利要求6～10任一项所述的氨基酸无规共聚物。Application of amino acid polymer as a natural gas hydrate kinetic inhibitor, the amino acid polymer being the amino acid homopolymer described in any one of claims 1 to 5 or the random copolymer of amino acids described in any one of claims 6 to 10 things. 根据权利要求18所述的应用，其特征在于，所述氨基酸聚合物以氨基酸聚合物水溶液的形式使用，所述氨基酸聚合物水溶液的质量浓度为0.1～10％。The application according to claim 18, characterized in that the amino acid polymer is used in the form of an aqueous amino acid polymer solution, and the mass concentration of the aqueous amino acid polymer solution is 0.1 to 10%. 根据权利要求18所述的应用，其特征在于，所述应用的压力为1～25MPa，所述应用的温度为-25～50℃。The application according to claim 18, characterized in that the application pressure is 1 to 25 MPa, and the application temperature is -25 to 50°C.
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