Maleimide / α-olefin multipolymer, maleimide / α-olefin multipolymer oil-soluble drag reducer, and preparation method and application thereof

Abstract

The invention discloses a maleimide / α-olefin multipolymer, a maleimide / α-olefin multipolymer oil-soluble drag reducer, and a preparation method and application thereof, and belongs to the technical field of oilfield chemical additives. The maleimide / α-olefin multipolymer is obtained by olefin coordination polymerization of maleimide in a polymerization monomer mixture and double bonds in α-olefins under the catalytic action of a Ziegler-Natta catalyst; the polymerization monomer mixture is composed of the following components in molar percentage: 10% to 15% maleimide, 50% to 70% α-olefins with a chain length of C6-C9, and 10% to 20% α-olefins with a chain length of C6-C9. 10 ‑C 11 10% to 20% of the chain length of α-olefins, the rest is C 12 ‑C 15 The present invention uses maleimide / alpha-olefin multipolymer as a component of the drag reducer, which is beneficial to improving the drag reduction performance.

Description

Technical Field

[0001] The present invention relates to the technical field of oilfield chemical additives, and more specifically to a maleimide / alpha-olefin multipolymer, a maleimide / alpha-olefin multipolymer oil-soluble drag reducer, and a preparation method and application thereof. Background Art

[0002] Pipeline transportation is one of the main means of crude oil transportation. When the demand for crude oil transportation occurs: 1) seasonal fluctuations in oil transportation tasks; 2) temporary peaks in oil transportation tasks; 3) changes in market demand and increased transportation volume; 4) pipeline transportation volume exceeds the rated value and cannot be expanded; 5) multiple oil products are transported in sequence; 6) oil pipelines are built in areas with harsh conditions, etc., the above problems can be solved by adding oil-soluble drag reducers to the oil products. Drag reducers can greatly reduce the friction loss associated with the turbulence of fluids passing through pipelines, inhibit the growth of turbulent vortices, and thus obtain higher flow at a constant pumping pressure.

[0003] Drag reducers can be divided into water-soluble drag reducers and oil-soluble drag reducers. Oil-soluble drag reducers are divided into two categories according to their working principle: one is highly flexible linear polymers with ultra-high molecular weight, mainly olefin homopolymers or copolymers, polymethacrylates, etc.; the other is surface-active compounds. A large number of studies and practices have proved that α-olefin polymers, especially poly α-octene and poly α-decene, have the best drag reduction effect and are the most widely used.

[0004] Therefore, most of the current commercial drag reducers are mainly composed of α-olefin polymers with a chain length of C6-C9. However, since the α-olefin polymers with a chain length of C6-C9 are short, their solubility and dispersibility in oil products are relatively low, and they are only composed of alkyl carbon chains, the drag reducer effect of α-olefin homopolymers is not ideal in crude oil pipelines with high asphalt, paraffin, and colloid content. Summary of the invention

[0005] In view of the above problems, the present invention provides a maleimide / α-olefin multipolymer, a maleimide / α-olefin multipolymer oil-soluble drag reducer, and a preparation method and application thereof. Using the maleimide / α-olefin multipolymer as a component of the drag reducer is beneficial to improving the drag reduction performance.

[0006] In a first aspect, the present invention provides a maleimide / α-olefin multipolymer, wherein the maleimide / α-olefin multipolymer is obtained by olefin coordination polymerization of maleimide in a polymerization monomer mixture and double bonds in α-olefin under the catalytic action of a Ziegler-Natta catalyst;

[0007] The polymerization monomer mixture is composed of the following components in molar percentage: maleimide 10-15%, C6-C9 chain length α-olefin 50-70%, C10 -C 11 Chain length α-olefins 10-20%, the rest is C 12 -C 15 Chain length alpha-olefins, totaling 100%.

[0008] For example, the molar percentage of maleimide is 10%, 11%, 12%, 13%, 14%, 15%, etc.;

[0009] The mole percentages of alpha olefins with a chain length of C6-C9 are 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, etc.;

[0010] C 10 -C 11 The mole percentage of the chain length alpha olefin is 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.;

[0011] C 12 -C 15 The molar percentage of the chain length of α-olefins is 10%, 11%, 12%, 13%, 14%, 15%, etc.; but it is not limited to the listed values, and other values ​​not listed within the above range are also applicable.

[0012] In a preferred embodiment of the present invention, the amount of catalyst added is 0.15% to 1.3% of the mass of the polymerization monomer mixture, but it is not limited to the listed values, and other values ​​not listed in the above range are also applicable.

[0013] In a preferred embodiment of the present invention, the polymerization monomer mixture is composed of the following components in molar percentage: maleimide 10%, C6-C9 chain length α-olefin 70%, C 10 -C 11 Chain length α-olefin 10%, C 12 -C 15 Chain length alpha-olefins 10%.

[0014] In a second aspect, the present invention provides a method for preparing the maleimide / α-olefin multipolymer, comprising the following steps:

[0015] The components of the polymerization monomer mixture are weighed according to the following molar percentages: maleimide 10% to 15%, C6-C9 chain length α-olefin 50% to 70%, C 10 -C 11 Chain length α-olefins 10% to 20%, the rest is C12 -C 15 Chain length of alpha-olefins, totaling 100%;

[0016] Maleimide, C6-C9 chain length α-olefin, C 10 -C 11 Chain length of α-olefins and C 12 -C 15 After the α-olefins of different chain lengths are uniformly mixed, a Ziegler-Natta catalyst is added under a protective atmosphere, and an olefin coordination polymerization reaction occurs at room temperature to obtain a reactant;

[0017] The reactants and the separator are crushed in a liquid nitrogen environment to obtain a maleimide / α-olefin multipolymer.

[0018] In a preferred embodiment of the present invention, the reaction time of the olefin coordination polymerization reaction is 0.1 to 10 hours. For example, the reaction time is 0.1 hours, 1 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc. However, it is not limited to the listed values, and other values ​​not listed in the above numerical range are also applicable.

[0019] In a preferred embodiment of the present invention, the amount of the separator added is 2 to 10% of the amount of the reactants;

[0020] For example, the amount of the release agent added is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10% of the mass of the reactants; however, it is not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable.

[0021] The isolation agent is one or more of nano calcium carbonate, calcium stearate and magnesium stearate.

[0022] Typical but non-limiting examples of the combination include a combination of nano-calcium carbonate and calcium stearate, a combination of calcium stearate and magnesium stearate, a combination of nano-calcium carbonate and magnesium stearate, etc.;

[0023] In a third aspect, the present invention provides the use of the maleimide / α-olefin multipolymer in the preparation of a drag reducer for crude oil transportation.

[0024] In a fourth aspect, the present invention provides a maleimide / α-olefin multipolymer oil-soluble drag reducer, which is composed of a mixture of the following raw materials in percentage by mass: 30-50% of the above-mentioned maleimide / α-olefin multipolymer, 45%-69% of an organic solvent, 0.5-2% of a surfactant, and the rest being a thickener, totaling 100%.

[0025] For example, the mass percentage of maleimide / α-olefin multipolymer is 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, etc.;

[0026] The mass percentage of the organic solvent is 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, etc.;

[0027] The mass percentage of the surfactant is 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, etc.;

[0028] The mass percentage of the thickener is 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, etc.; but are not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable.

[0029] In a preferred embodiment of the present invention, the organic solvent is one or more of n-hexanol, n-octanol, ethylene glycol methyl ether, ethylene glycol butyl ether, and N,N-dimethylformamide; typical but non-limiting examples of the combination include a combination of n-hexanol and n-octanol, a combination of n-hexanol and ethylene glycol methyl ether, a combination of n-hexanol and ethylene glycol butyl ether, a combination of n-hexanol and N,N-dimethylformamide, a combination of n-octanol and ethylene glycol methyl ether, a combination of n-hexanol, n-octanol and ethylene glycol methyl ether, a combination of n-hexanol, n-octanol and N,N-dimethylformamide, a combination of n-hexanol, N,N-dimethylformamide and ethylene glycol methyl ether, a combination of n-hexanol, N,N-dimethylformamide and ethylene glycol butyl ether, and the like;

[0030] The surfactant is one or more of Tween-40, OP-10, and TX-100; typical but non-limiting examples of the combination include a combination of Tween-40 and OP-10, a combination of Tween-40 and TX-100, a combination of OP-10 and TX-100, a combination of Tween-40, OP-10 and TX-100, and the like;

[0031] The thickener is one or more of polyvinyl alcohol, hydroxypropyl cellulose, and gelatin; typical but non-limiting examples of the combination include a combination of polyvinyl alcohol and hydroxypropyl cellulose, a combination of polyvinyl alcohol and gelatin, a combination of hydroxypropyl cellulose and gelatin, a combination of polyvinyl alcohol, hydroxypropyl cellulose and gelatin, and the like.

[0032] In a preferred embodiment of the present invention, the maleimide / α-olefin multipolymer oil-soluble drag reducer is added to the crude oil transportation pipeline at 20-100 ppm.

[0033] For example, the content of maleimide / α-olefin multipolymer oil-soluble drag reducer is 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, etc.; but it is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The maleimide / α-olefin multipolymer provided by the present invention is a copolymer of maleimide, an α-olefin having a chain length of C6-C9, and C 10 -C 11 Chain length of α-olefins, C 12 -C 15 The alpha-olefin of chain length is a polymerization monomer, and the molecular weight of the polymerization obtained by olefin coordination polymerization can reach the million level. Compared with the alpha-olefin homopolymer, the present invention is a multi-polymer of polymerization monomers with alpha-olefins of different chain lengths and different functional groups (imide groups, 5-membered ring heterocycles), and the polymer dispersibility is easy to adjust, and it is more likely to obtain a large molecular weight polymer, increase the rapid solubility and drag reduction of the polymer. And other functional groups of the polymer (imide groups, 5-membered ring heterocycles) can enrich the function of the drag reducer and expand the application range of the drag reducer. Maleimide is the main monomer component of the pour point and viscosity reducer. The polar groups containing N and O heteroatoms in the molecule will not only act with the polar parts of colloids, asphaltene, etc. in crude oil, play the role of dispersing asphaltene and adsorbing on the surface of wax crystals to prevent the growth of wax crystals, but also reduce the crystallinity of the polymer, thereby reducing the drag reduction performance.

[0036] (2) The maleimide / α-olefin multipolymer oil-soluble drag reducer provided by the present invention is mainly composed of maleimide / α-olefin multipolymer, supplemented by organic solvents, surfactants and thickeners. The synergistic effect of multiple factors enables the drag reducer to significantly reduce the friction resistance of crude oil transportation, and is particularly suitable for crude oil transportation pipelines containing paraffin, asphalt and colloid.

[0037] The maleimide / α-olefin multipolymer oil-soluble drag reducer was stored at room temperature for 6 months without any stratification or precipitation, indicating good stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a molecular weight performance diagram of the maleimide / α-olefin multipolymer prepared in Example 6. DETAILED DESCRIPTION

[0039] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0041] The brands and abbreviations of all raw materials of the present invention are conventional brands and abbreviations in the art. Each brand and abbreviation is clear and definite in the field of its related use. Those skilled in the art can purchase them from the market or prepare them by conventional methods according to the brands, abbreviations and corresponding uses.

[0042] As described in the background technology, the main component of most of the current commercial drag reducers is α-olefin polymers with a chain length of C6-C9. However, since the α-olefin polymers with a chain length of C6-C9 are short, their solubility and dispersibility in oil products are relatively low, and they are only composed of alkyl carbon chains, the drag reducer effect of α-olefin homopolymers is not ideal in crude oil pipelines with high asphalt, paraffin, and colloid content. Based on this, the present invention provides a maleimide / α-olefin multipolymer and uses it in a drag reducer. The specific technical scheme is as follows:

[0043] A maleimide / α-olefin multipolymer is obtained by olefin coordination polymerization of a polymerization monomer mixture under the catalytic action of a Ziegler-Natta catalyst;

[0044] The polymerization monomer mixture is composed of the following components in molar percentage: maleimide 10-15%, C6-C9 chain length α-olefin 50-70%, C 10 -C 11 Chain length α-olefins 10-20%, C 12 -C 15 The chain length of α-olefin is 10-15%. In the preparation process, maleimide and the double bonds in α-olefin undergo olefin coordination polymerization under the action of a catalyst to form a high molecular polymer.

[0045] During the preparation process, maleimide, C6-C9 chain length α-olefin, C 10 -C 11 Chain length of α-olefins and C 12 -C 15 The chain length of α-olefin needs to be weighed according to the above molar percentage. If it exceeds the above parameter range, it will affect the performance of the maleimide / α-olefin multipolymer. Specifically, maleimide has a small molecular weight and fewer saturated carbon atoms, so it can only be added in small amounts. If the amount added is too much, it will affect the polymer solubility. The solubility of C6-C9 chain length α-olefins is moderate and the polymerization activity is high. Therefore, the present invention selects C6-C9 chain length α-olefins as the main component in order to ensure that the polymer molecular weight can reach a higher value. 10 -C 11 Chain length and C 12 -C 15 Chain-length α-olefins have better solubility due to their longer chain length and can increase the solubility of the polymer, but their polymerization activity will become worse, so the amount added should not be too much to avoid affecting the molecular weight of the polymer.

[0046] Further, the catalyst used in the present invention is a Ziegler-Natta catalyst, and the amount of the catalyst added is 0.15% to 1.3%. The amount of the catalyst added needs to be weighed according to the above parameter range, because too little addition of the catalyst will lead to incomplete polymerization of the monomers, which will lead to a low conversion rate and waste of raw materials, while too much addition of the catalyst will increase the side reactions and reduce the molecular weight of the prepared maleimide / α-olefin multipolymer. It is understandable that the catalyst used in the present invention can be purchased conventionally through commercial channels, and the present invention is not particularly limited here. For example, it can be purchased from Yingkou Xiangyang Chemical and Beijing Aoda Branch of Sinopec Catalyst Co., Ltd.

[0047] It is understood that the Ziegler-Natta catalyst is used for olefin coordination polymerization, and the Ziegler-Natta catalyst mechanism determines that the metal catalyst, co-catalyst, and electron donor need to work together. It is understood that the amount of Ziegler-Natta catalyst added is the sum of the metal catalyst, co-catalyst, and electron donor.

[0048] Specifically, the Ziegler-Natta catalyst is composed of a metal catalyst, a co-catalyst, and an electron donor. In order to better carry out olefin coordination polymerization reaction on the polymerization monomer mixture, during preparation, the amount of the metal catalyst added is 0.05-0.5% of the total mass of the polymerization monomer mixture; the amount of the co-catalyst added is 0.05-0.5% of the total mass of the polymerization monomer mixture; and the amount of the electron donor added is 0.05-0.3% of the total mass of the polymerization monomer mixture.

[0049] Further, the metal catalyst is one or more of TiCl4 or TiCl3, CpTiCl3, Cp2TiCl2, Cp2ZrCl2 loaded with MgCl2, SiO2, or ZnCl2; wherein the metal catalyst can be purchased conventionally through commercial channels or prepared with reference to the prior art, and the present invention does not make any special restrictions here. For example, the TiCl4 loaded with MgCl2, the TiCl4 loaded with SiO2, and the TiCl3 loaded with ZnCl2 used in the present invention are purchased from Yingkou Xiangyang Chemical and Beijing Aoda Branch of Sinopec Catalyst Co., Ltd.

[0050] The co-catalyst is one or more of AlEt3, Al(i-Bu)3, AlEt2Cl, AlEtCl2, and methyl alkoxyaluminum;

[0051] The electron donor is one or more of cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, ethyl benzoate and ethyl phthalate.

[0052] The present invention also provides a method for preparing a maleimide / α-olefin multipolymer, comprising the following steps:

[0053] The components of the polymerization monomer mixture are weighed according to the following molar percentages: maleimide 10% to 15%, C6-C9 chain length α-olefin 50% to 70%, C 10 -C 11 Chain length α-olefins 10% to 20%, the rest is C 12 -C 15 Chain length of alpha-olefins, totaling 100%;

[0054] Maleimide, C6-C9 chain length α-olefin, C 10 -C 11 Chain length of α-olefins and C 12 -C 15 After the α-olefins of different chain lengths are uniformly mixed, a catalyst is added under a protective atmosphere, and an olefin coordination polymerization reaction occurs at room temperature to obtain a reactant;

[0055] The reactants and the separator are crushed in a liquid nitrogen environment to obtain a maleimide / α-olefin multipolymer.

[0056] Furthermore, the reaction time of the olefin coordination polymerization reaction is 0.1-10h.

[0057] It is understandable that the reactant prepared after the olefin coordination polymerization reaction is an elastomer, which is easy to agglomerate after crushing and cannot be crushed. Based on this, an isolation agent needs to be added during the crushing process. Preferably, the amount of the isolation agent added is 2 to 10% of the mass of the reactant; the isolation agent is one or more of nano calcium carbonate, calcium stearate, and magnesium stearate.

[0058] The present invention uses a low-temperature pulverizer for pulverization. Specifically, the low-temperature pulverizer used in the present invention is a liquid nitrogen low-temperature pulverizer. After adding an isolation agent, liquid nitrogen is used as a cold source, and the reactants are cooled in a low-temperature environment to achieve embrittlement and pulverization of the elastomeric polymer.

[0059] The maleimide / α-olefin multipolymer prepared by the present invention using α-olefins of different chain lengths and polymerized monomers of different functional groups has rapid solubility and drag reduction. In addition, other functional groups of the polymer can enrich the function of the drag reducer and expand the application range of the drag reducer. Maleimide, as the main monomer component of the pour point and viscosity reducer, contains polar groups of N and O heteroatoms in the molecule, which not only reacts with the polar parts of colloids, asphaltene, etc. in crude oil, plays a role in dispersing asphaltene and adsorbing on the surface of wax crystals to prevent the growth of wax crystals, but also reduces the crystallinity of the polymer, thereby reducing the drag reduction performance. Based on this, the present invention also provides the use of maleimide / α-olefin multipolymer in the preparation of drag reducers for crude oil transportation. Maleimide / α-olefin multipolymer reduces friction and drag.

[0060] Specifically, the maleimide / α-olefin multipolymer oil-soluble drag reducer (hereinafter referred to as drag reducer) is composed of a mixture of the following raw materials in percentage by mass: 30% to 50% maleimide / α-olefin multipolymer, 45% to 69% organic solvent, 0.5% to 2% surfactant, and the rest is thickener, totaling 100%. Maleimide / α-olefin multipolymer is used as the main agent to reduce the friction resistance of crude oil transportation. The organic solvent is used to increase the stability of the polymer powder in the solution, while ensuring a lower freezing point and a higher flash point of the solvent to ensure a safe temperature range for use. The surfactant is used to disperse the polymer powder. The thickener is used to increase the viscosity of the solution, stabilize the dispersion of the polymer powder, and form a suspension.

[0061] In the process of preparing maleimide / α-olefin multipolymer oil-soluble drag reducer, maleimide / α-olefin multipolymer is dispersed by organic solvent. When selecting organic solvent, it is necessary to consider the stability of maleimide / α-olefin multipolymer in organic solvent and the safety of use. Therefore, when selecting organic solvent, the density, freezing point and flash point of organic solvent need to be considered. Preferably, the organic solvent is one or more of n-hexanol, n-octanol, ethylene glycol methyl ether, ethylene glycol butyl ether, N, N-dimethylformamide; the density of organic solvent is close to the density of maleimide / α-olefin multipolymer, which can increase the stability of maleimide / α-olefin multipolymer, and the lower freezing point and flash point of the solution are ensured by appropriate solution ratio, ensuring the safe temperature range for use. When selecting multiple organic solvents for mixing, it is necessary to ensure that the density of the organic solvent mixture is between 0.7-0.9g / cm 3 between, thereby ensuring the stability of the maleimide / α-olefin multipolymer in organic solvents.

[0062] The surfactant added in the present invention mainly plays an emulsifying role, and an oil-soluble surfactant can be selected. Preferably, the surfactant used in the present invention is one or more of Tween-40, OP-10, and TX-100;

[0063] In order to further stabilize the dispersibility of the maleimide / α-olefin multipolymer, based on this, the present invention adds a thickener, the purpose of which is to increase the viscosity of the solution, so that the maleimide / α-olefin multipolymer is stably dispersed to form a suspension. When selecting the thickener, it only needs to be soluble in an organic solvent. Preferably, the thickener is one or more of polyvinyl alcohol, hydroxypropyl cellulose, and gelatin.

[0064] Furthermore, the maleimide / α-olefin multipolymer oil-soluble drag reducer is added into the crude oil transportation pipeline at 20-100 ppm.

[0065] Example 1

[0066] Maleimide (0.38 mol, i.e. 36.69 g), 1-hexene (1.26 mol, i.e. 106.03 g), 1-undecene (0.50 mol, i.e. 77.75 g) and 1-pentadecene (0.38 mol, i.e. 79.52 g) were added into a sealed container and mixed evenly. Nitrogen was introduced, and then MgCl2-loaded TiCl4 (0.15 g), AlEt3 (0.15 g) and cyclohexylmethyldimethoxysilane (0.15 g) were added. The mixture was reacted at room temperature for 0.1 h to obtain a maleimide / α-olefin multipolymer block solid.

[0067] 250 g of maleimide / α-olefin multipolymer block solid and 5 g of magnesium stearate were added into a low-temperature pulverizer and pulverized in a liquid nitrogen environment at -196°C until the solid passed a 200-mesh sieve to obtain maleimide / α-olefin multipolymer powder.

[0068] Take 30 g of the maleimide / α-olefin multipolymer powder, 68 g of n-hexanol, 1 g of Tween-40, and 1 g of polyvinyl alcohol, stir and mix them evenly to obtain a drag reducer.

[0069] Example 2

[0070] Maleimide (0.26 mol, 25.04 g), 1-heptene (1.55 mol, 151.95 g), 1-decene (0.52 mol, 72.36 g) and 1-tetradecene (0.26 mol, 50.65 g) were added into a sealed container and mixed evenly. Nitrogen was introduced, and SiO2-loaded TiCl4 (0.3 g), Al(i-Bu)3 (0.3 g) and diphenyldimethoxysilane (0.15 g) were added. The mixture was reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0071] 250 g of maleimide / α-olefin multipolymer block solid and 15 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0072] Take 30 g of the maleimide / α-olefin multipolymer powder, 48 g of n-hexanol, 20 g of N,N-dimethylformamide, 1 g of Tween-40, and 1 g of hydroxypropyl cellulose, and mix them evenly to obtain a drag reducer.

[0073] Example 3

[0074] Maleimide (0.24 mol, 23.61 g), 1-octene (1.46 mol, 163.78 g), 1-decene (0.49 mol, 61.42 g) and 1-tridecene (0.24 mol, 44.36 g) were added into a sealed container and mixed evenly. Nitrogen was introduced, and ZnCl2-loaded TiCl3 (0.6 g), AlEt2Cl (0.6 g) and ethyl benzoate (0.3 g) were added. The mixture was reacted at room temperature for 10 h to obtain a maleimide / α-olefin multipolymer block solid.

[0075] 250 g of maleimide / α-olefin multipolymer block solid and 25 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0076] Take 30 g of the maleimide / α-olefin multipolymer powder, 30 g of n-hexanol, 20 g of n-octanol, 19 g of N,N-dimethylformamide, 0.5 g of OP-10, and 0.5 g of hydroxypropyl cellulose, and mix them evenly to obtain a drag reducer.

[0077] Example 4

[0078] Maleimide (0.23 mol, 22.55 g), 1-nonene (1.63 mol, 205.29 g), 1-decene (0.23 mol, 32.59 g), and 1-dodecene (0.23 mol, 39.57 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and CpTiCl3 (0.9 g), AlEt2Cl (0.9 g) and ethyl benzoate (0.6 g) were added, and the mixture was reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0079] 250 g of maleimide / α-olefin multipolymer block solid and 20 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0080] Take 40 g of the maleimide / α-olefin multipolymer powder, 10 g of n-hexanol, 30 g of ethylene glycol methyl ether, 15 g of N,N-dimethylformamide, 2 g of OP-10, and 3 g of gelatin, and mix them evenly to obtain a drag reducer.

[0081] Example 5

[0082] Maleimide (0.35 mol, 34.03 g), 1-nonene (1.40 mol, 177.00 g), 1-decene (0.35 mol, 49.17 g), 1-dodecene (0.23 mol, 39.57 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and Cp2TiCl2 (1.2 g), AlEt2Cl (1.2 g) and diphenyldimethoxysilane (0.9 g) were added and reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0083] 250 g of maleimide / α-olefin multipolymer block solid and 12.5 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0084] Take 40 g of the maleimide / α-olefin multipolymer powder, 10 g of n-hexanol, 30 g of ethylene glycol butyl ether, 15.5 g of N,N-dimethylformamide, 1.5 g of TX-100, and 3 g of gelatin, and mix them evenly to obtain a drag reducer.

[0085] Example 6

[0086] Maleimide (0.23 mol, 21.87 g), 1-nonene (1.58 mol, 199.11 g), 1-decene (0.22 mol, 31.61 g), 1-pentadecene (0.23 mol, 47.41 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and then MgCl2-loaded TiCl4 (0.3 g), methyl alkoxyaluminum (0.3 g) and diphenyldimethoxysilane (0.3 g) were added and reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0087] 250 g of maleimide / α-olefin multipolymer block solid and 5 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0088] Take 40 g of the maleimide / α-olefin multipolymer powder, 10 g of n-hexanol, 30 g of ethylene glycol butyl ether, 17.2 g of N,N-dimethylformamide, 0.8 g of OP-10, and 2 g of gelatin, and mix them evenly to obtain a drag reducer.

[0089] Example 7

[0090] Maleimide (0.23 mol, 21.87 g), 1-nonene (1.58 mol, 199.11 g), 1-decene (0.22 mol, 31.61 g), 1-pentadecene (0.23 mol, 47.41 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and Cp2ZrCl2 (1.5 g), methyl alkoxyaluminum (1.5 g) and diphenyldimethoxysilane (0.9 g) were added, and the mixture was reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0091] 250 g of maleimide / α-olefin multipolymer block solid and 25 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0092] Take 50 g of the maleimide / α-olefin multipolymer powder, 5 g of n-hexanol, 20 g of ethylene glycol butyl ether, 22.2 g of N,N-dimethylformamide, 0.8 g of OP-10, and 2 g of gelatin, and mix them evenly to obtain a drag reducer.

[0093] Example 8

[0094] Maleimide (0.23 mol, 21.87 g), 1-nonene (1.58 mol, 199.11 g), 1-decene (0.22 mol, 31.61 g), 1-pentadecene (0.23 mol, 47.41 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and Cp2ZrCl2 (1.5 g), methyl alkoxyaluminum (1.5 g) and diphenyldimethoxysilane (0.9 g) were added, and the mixture was reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0095] 250 g of maleimide / α-olefin multipolymer block solid and 15 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0096] Take 50 g of the maleimide / α-olefin multipolymer powder, 5 g of n-hexanol, 20 g of ethylene glycol butyl ether, 20.5 g of N,N-dimethylformamide, 1.5 g of OP-10, and 3 g of gelatin, and mix them evenly to obtain a drag reducer.

[0097] Example 9

[0098] Maleimide (0.23 mol, 21.87 g), 1-nonene (1.58 mol, 199.11 g), 1-decene (0.22 mol, 31.61 g), 1-pentadecene (0.23 mol, 47.41 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and Cp2ZrCl2 (0.3 g), methyl alkoxyaluminum (0.3 g) and diphenyldimethoxysilane (0.15 g) were added, and the mixture was reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0099] 250 g of maleimide / α-olefin multipolymer block solid and 7.5 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0100] Take 50 g of the maleimide / α-olefin multipolymer powder, 5 g of n-hexanol, 20 g of ethylene glycol butyl ether, 20 g of N,N-dimethylformamide, 2 g of OP-10, and 3 g of hydroxypropyl cellulose, and mix them evenly to obtain a drag reducer.

[0101] Example 10

[0102] Maleimide (0.23 mol, 21.87 g), 1-nonene (1.58 mol, 199.11 g), 1-decene (0.22 mol, 31.61 g), 1-pentadecene (0.23 mol, 47.41 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and then MgCl2-loaded TiCl4 (0.3 g), methyl alkoxyaluminum (0.3 g) and diphenyldimethoxysilane (0.3 g) were added and reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0103] 250 g of maleimide / α-olefin multipolymer block solid, 2.5 g of calcium stearate and 2.5 g of magnesium stearate were added into a low-temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0104] Take 40 g of the maleimide / α-olefin multipolymer powder, 10 g of n-hexanol, 30 g of ethylene glycol butyl ether, 17.2 g of N,N-dimethylformamide, 0.4 g of OP-10, 0.4 g of Tween-40, and 2 g of gelatin, and mix them evenly to obtain a drag reducer.

[0105] Example 10

[0106] Maleimide (0.23 mol, 21.87 g), 1-nonene (1.58 mol, 199.11 g), 1-decene (0.22 mol, 31.61 g), 1-pentadecene (0.23 mol, 47.41 g) were added to a sealed container and mixed evenly, nitrogen was introduced, and then MgCl2-loaded TiCl4 (0.3 g), methyl alkoxyaluminum (0.3 g) and diphenyldimethoxysilane (0.3 g) were added and reacted at room temperature for 8 h to obtain a maleimide / α-olefin multipolymer block solid.

[0107] 250 g of maleimide / α-olefin multipolymer block solid, 7.5 g of nano calcium carbonate and 7.5 g of magnesium stearate were added into a low temperature pulverizer, and the maleimide / α-olefin multipolymer powder was prepared after pulverization and dispersion.

[0108] Take 40 g of the maleimide / α-olefin multipolymer powder, 10 g of n-hexanol, 30 g of ethylene glycol butyl ether, 15.5 g of N,N-dimethylformamide, 1 g of OP-10, 0.5 g of Tween-40, 2 g of gelatin, and 1 g of hydroxypropyl cellulose, and mix them evenly to obtain a drag reducer.

[0109] Taking Examples 1 to 9 as examples, the performance of maleimide / α-olefin multipolymers and maleimide / α-olefin multipolymer oil-soluble drag reducers are analyzed.

[0110] During the test, an ultra-high performance gel permeation chromatograph, model WATERSACQUITYAPC, MALVERNOMNISECREVEAL, with tetrahydrofuran as solvent, was used to record the system refractive index, molecular weight, intrinsic viscosity, Rh(η) at different retention volumes, and the polymer molecular weight data was automatically derived through the instrument to obtain Tables 1-2 and Figure 1 result.

[0111] Table 1 Molecular weight of maleimide / α-olefin copolymers prepared in different embodiments

[0112]

[0113]

[0114] As can be seen from Table 1, the ratio of comonomers, catalyst selection and addition in Example 6 are optimal, the molecular weight is as high as one million, and the number average molecular weight and weight average molecular weight are 1.282*10 7 g / mol and 1.3841*10 7 g / mol( Figure 1 ), the increase in molecular weight and the narrower molecular weight distribution of the maleimide / α-olefin multipolymer are beneficial to improving the drag reducing effect of the drag reducer.

[0115] Table 2 Stability of drag reducers prepared in different embodiments

[0116]

[0117] The stability of the drag reducer samples of different embodiments at room temperature is shown in Table 2. From the results in Table 2, it can be seen that the compounded drag reducers prepared by the present invention have good stability, and no obvious stratification is observed after being placed at room temperature for 6 months. This is because the solvent, surfactant and thickener work together to stably disperse the maleimide / α-olefin multipolymer, so that the prepared drag reducer forms a suspension with good stability, which is convenient for subsequent use.

[0118] Table 3 Drag reduction rate of drag reducers prepared in different embodiments

[0119] Example 1 2 3 4 5 6 7 8 9 Drag reduction rate 28％ 33％ 39％ 37％ 42％ 55％ 48％ 34％ 31％

[0120] When the drag reducer described in Examples 1-9 is added in an amount of 40 ppm in ordinary crude oil, the corresponding drag reduction rate comparison is shown in Table 3. As can be seen from Table 3, the change rule of the drag reduction rate is consistent with the change trend of the molecular weight of the maleimide / α-olefin multipolymer. As the molecular weight of the maleimide / α-olefin multipolymer increases, the drag reduction rate increases, among which Example 6 has the best drag reduction effect, which can reach 55%.

[0121] A commercially available drag reducer (with polyalphaolefin as the main agent) and the drag reducer in Example 6 were selected, and the drag reduction rates of the two in ordinary crude oil and crude oil containing 10% paraffin, 3% asphaltene, and 0.5% colloid were tested at an addition amount of 40 ppmm. The test results are shown in Table 4.

[0122] Table 4 Drag reduction rate of drag reducer in different crude oils

[0123]

[0124]

[0125] As can be seen from Table 4, in common crude oil, the drag reducer prepared by the present invention has a similar effect to the commercially available drag reducer, but as the content of paraffin, asphaltene and colloid in crude oil increases, the drag reducer of the present invention has a significant advantage, and the drag reduction rate increases by 22%. This is because the maleimide / α-olefin multipolymer prepared by the present invention has a large molecular weight and excellent rapid solubility and drag reduction.

[0126] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0127] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A maleimide / α-olefin multipolymer oil-soluble drag reducer, characterized in that: The method is composed of a mixture of the following raw materials in percentage by mass: 30% to 50% of maleimide / α-olefin multipolymer, 45% to 69% of an organic solvent, 0.5% to 2% of a surfactant, and the rest being a thickener, which totals 100%; The maleimide / α-olefin multipolymer is obtained by olefin coordination polymerization of maleimide in the polymerization monomer mixture and double bonds in α-olefin under the catalytic action of Ziegler-Natta catalyst; The polymerization monomer mixture is composed of the following components in molar percentage: maleimide 10% to 15%, C6-C9 chain length α-olefin 50% to 70%, C 10 -C 11 Chain length α-olefins 10% to 20%, the rest is C 12 -C 15 Chain length alpha-olefins, totaling 100%.

2. A maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 1, characterized in that: The added amount of the catalyst is 0.15% to 1.3% of the mass of the polymerization monomer mixture.

3. The maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 1, characterized in that: The polymerization monomer mixture is composed of the following components in molar percentage: maleimide 10%, C6-C9 chain length α-olefin 70%, C 10 -C 11 Chain length α-olefin 10%, C 12 -C 15 Chain length alpha-olefins 10%.

4. The maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 1, characterized in that: The maleimide / α-olefin multipolymer comprises the following steps: The components of the polymerization monomer mixture are weighed according to the following molar percentages: maleimide 10% to 15%, C6-C9 chain length α-olefin 50% to 70%, C 10 -C 11 Chain length α-olefins 10% to 20%, the rest is C 12 -C 15 Chain length of alpha-olefins, totaling 100%; Maleimide, C6-C9 chain length α-olefin, C 10 -C 11 Chain length of α-olefins and C 12 -C 15 After the α-olefins of different chain lengths are uniformly mixed, a Ziegler-Natta catalyst is added under a protective atmosphere, and an olefin coordination polymerization reaction occurs at room temperature to obtain a reactant; The reactants and the separator are crushed in a liquid nitrogen environment to obtain a maleimide / α-olefin multipolymer.

5. The maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 4 is characterized in that: The reaction time of the olefin coordination polymerization reaction is 0.1 to 10 hours.

6. The maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 4 is characterized in that: The added amount of the isolation agent is 2-10% of the mass of the reactants; the isolation agent is one or more of nano calcium carbonate, calcium stearate and magnesium stearate.

7. The maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 1, characterized in that: The organic solvent is one or more of n-hexanol, n-octanol, ethylene glycol methyl ether, ethylene glycol butyl ether, and N,N-dimethylformamide; The surfactant is one or more of Tween-40, OP-10, and TX-100; The thickener is one or more of polyvinyl alcohol, hydroxypropyl cellulose and gelatin.

8. The maleimide / α-olefin multipolymer oil-soluble drag reducer according to claim 1, characterized in that: The maleimide / α-olefin multipolymer oil-soluble drag reducer is added into the crude oil transportation pipeline at 20-100 ppm.

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