CN103030853B - Drag reduction composition and preparation method thereof - Google Patents

Abstract

The present invention provides a drag reduction composition and a preparation method thereof. The drag reduction composition comprises poly-alpha-olefin, silicone oil, a release agent and a dispersing agent, wherein the release agent is one or more selected from the group consisting of stearic acid, stearate salt, stearamide and stearate; and the dispersing agent is an organic solvent insolubilizing the poly-alpha-olefin. The drag reduction composition of the present invention has the advantages of good storage stability, low viscosity, good fluidity and easy injection.

Description

A kind of drag-reducing composition and preparation method thereof

technical field

The invention relates to a drag reducing composition and a preparation method thereof.

Background technique

Oil-soluble polyalphaolefins are widely used as drag reducers for pipeline transportation of oil products. Oil-soluble drag reducer is a polymer chemical additive used in crude oil and refined oil pipeline transportation. Dissolving the oil-soluble drag reducer in the oil can greatly reduce the flow rate of the fluid without changing the delivery volume. Reduce the loss of frictional resistance, reduce the pressure of pipeline operation; and increase the delivery volume of pipeline under the condition of constant pipeline operation pressure. The use of drag reducers does not require additional fixed equipment for pipelines, and is a convenient and economical way to adjust pipeline delivery volume. Since the drag reducer produced by Connock Corporation of the United States was first successfully applied to the Alaska crude oil pipeline in 1979, two methods of obtaining polyalphaolefin drag reducer have been developed, namely solution polymerization and bulk polymerization.

Initially, drag reducers were prepared by solution polymerization. Solution polymerization refers to dissolving α-olefin monomers and catalysts in a solvent for polymerization, and the resulting poly α-olefin is dissolved in a solvent to form a polymer solution. Due to the low monomer conversion rate of the polyalpha-olefin produced by this method, the molecular weight of the polymer and its content in the polymer are very low, and the drag reducing effect of the drag reducer is relatively poor. At the same time, the product of solution polymerization has extremely high viscosity, which brings great difficulties to the injection of drag reducer.

After the 1990s, the method of obtaining polyalphaolefin by bulk polymerization was developed. Bulk polymerization does not add other media, but only polymerizes the monomer under the initiation of the catalyst. The method greatly increases the conversion rate of the polymerization product and the molecular weight of the polymer. However, due to the extremely high reaction heat generated by bulk polymerization and the high viscosity of the system, it is necessary to divide the polymerization reactants into relatively small reaction containers during polymerization, and then place them in a low temperature environment for reaction. The operation process is very complicated. cumbersome. In addition, since the bulk polymerization product is a viscoelastic solid substance, it is necessary to process the resulting polyalphaolefin into a fluid state in order to inject it into a pipeline. The processing method usually includes the following two steps: first, the polyalphaolefin in the solid state is pulverized into a certain fineness powder under ultra-low temperature conditions (in order to prevent the pulverized polymer from agglomerating again, it is necessary to add an appropriate amount of dispersant, The dispersant may include: calcium stearate, aluminum oxide, clay, calcium phosphate, zinc stearate, graphite and various stearic acid amides, etc.), generally not less than 100 mesh. The dispersant itself does not promote the drag reduction effect. Therefore, under the premise of keeping the polymer powder from agglomerating, it should be added as little as possible, and then suspended in the aqueous alcohol solution by various chemical additives to form a slurry fluid , the whole process is loaded down with trivial details and complexity, and production cost is extremely high, can cause serious environmental pollution simultaneously. In addition, the resulting slurry drag reducer product has poor standing stability, and polyalphaolefin is easily phase-separated from the aqueous alcohol solution. Therefore, it must be used after proper stirring.

CN1530377A discloses a preparation method of poly-alpha-olefin drag reducer, the method includes firstly adding polymerized monomers into the reactor, adding the catalyst under the condition of cutting off the air and stirring, and adding slowly within 20 hours after the reaction starts Oil-soluble polyester, polyether or ester-ether copolymer reactive base liquid in which α-olefin polymer is insoluble, and react at -50°C to 20°C for 3-10 days. The polyalpha-olefin polymer drag reducer slurry prepared by the method has low viscosity, good drag reduction effect and good standing stability, and can be directly used in oil transportation production without stirring.

CN1673237A discloses a method for preparing high-grade α-olefin low-viscoelasticity bulk polymers. Under the condition of low temperature and air isolation, the refined polymerization monomers are added to the reactor, and the main catalyst is added in proportion under the condition of stirring. Reaction with cocatalyst, characterized in that, within 1-3 hours of starting the reaction, add a certain proportion of anti-sticking agent powder, continue to stir and react for 3-6 hours, and then continue to react for 3-10 hours in a higher temperature environment sky. The high-grade α-olefin low-viscoelastic bulk polymer product prepared by the method is relatively easy to pulverize and has increased stability after pulping. CN101268128A discloses a method of preparing a stabilized polymeric drag reducer slurry comprising combining a fatty acid wax and a liquid carrier to form a dispersion; pretreating the dispersion by heating to partially dissolve the fatty acid wax in said liquid carrier; and heating the particulate polymeric drag reducing agent therein to form a stabilized polymeric drag reducing slurry. The slurry prepared by this method is relatively stable to settling, separation and coalescence. However, in the above two methods, the bulk polymerization product needs to be pulverized into fine particles at a temperature lower than its glass transition temperature, so that the drag reducing slurry can be prepared. The process is complex and the operation is cumbersome.

Contents of the invention

The object of the present invention is to provide a new drag-reducing composition and a preparation method thereof. The drag-reducing composition provided by the present invention can be well used for drag reduction of oil pipelines.

The invention provides a drag reducing composition, wherein, the drag reducing composition is a suspension containing polyalphaolefin, silicone oil, release agent and solvent; the release agent is selected from stearic acid, stearate , one or more in stearic acid amine and stearic acid ester; Described solvent is polar solvent.

The present invention also provides a preparation method of the drag-reducing composition, wherein the method comprises uniformly mixing polyalpha-olefin with silicone oil, a release agent and a solvent to obtain a suspension; the release agent is selected from stearic acid, stearic acid, One or more in fatty acid salt, stearic acid amine and stearic acid ester, described solvent is polar solvent.

The present invention also provides a preparation method of the drag reducing composition, wherein the method comprises the following steps:

(1) Under olefin polymerization conditions and in the presence of silicone oil, the α-olefin monomer is contacted with the olefin polymerization catalyst system, so that a mixture of poly α-olefin and silicone oil with an intrinsic viscosity of 10 dL/g or more is obtained;

(2) the mixture of the polyalpha-olefin and silicone oil that step (1) obtains is mixed homogeneously with release agent and solvent, obtains suspension; Described release agent is selected from stearic acid, stearate, stearic acid amine and One or more of stearic acid esters; the solvent is a polar solvent.

Furthermore, the present invention also provides the drag reducing composition prepared by the above method.

The drag reducing composition provided by the invention has the advantages of good storage stability, low viscosity, good fluidity and easy injection. The drag-reducing composition prepared according to the preferred preparation method of the present invention can be directly applied to drag-reducing oil pipelines without complicated post-treatment processes such as low-temperature crushing or grinding. The preparation process is simple, easy to produce, and convenient to use.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

According to the present invention, the drag reducing composition is a suspension containing polyalphaolefin, silicone oil, release agent and solvent; the release agent is selected from stearic acid, stearate, stearic acid amine and stearic acid One or more of the esters, the solvent is a polar solvent.

According to the present invention, although the content range of each component in the drag reducing composition can be changed within a relatively wide range, preferably, in order to obtain a drag reducing composition with better drag reducing effect, the Based on the total weight of the barrier composition, the content of the polyalpha-olefin can be 5-45% by weight, the content of the silicone oil can be 1-50% by weight, and the content of the release agent can be 0.1-10% by weight %, the content of the solvent can be 0.1-90% by weight; more preferably, based on the total weight of the drag reducing composition, the content of the polyalphaolefin is 10-40% by weight, the The content of the silicone oil is 5-45% by weight, the content of the release agent is 1-8% by weight, and the content of the solvent is 10-80% by weight.

According to the present invention, the polyalpha-olefins may be various polyalpha-olefins conventionally used in the field of drag reduction for oil pipelines. The polyalphaolefins have "ultrahigh molecular weight". It is estimated that a polyalphaolefin having an intrinsic viscosity of 10 dL/g roughly corresponds to a viscosity average molecular weight of at least 2 million to 3 million. For the present invention, an Ubbelohde viscometer (0.02g polymer/50mL toluene, 40°C) can be used to measure the intrinsic viscosity of polyα-olefin to characterize the viscosity average molecular weight of polyα-olefin. Preferably, the poly α-olefin is a polymer formed by polymerization of α-olefin monomers and has an intrinsic viscosity of 10 dL/g or more, more preferably 10-25 dL/g.

Wherein, the α-olefin monomer can be various α-olefin monomers used in the preparation of various poly α-olefins conventionally used in the field of drag reduction for oil pipelines, for example, it can be selected from C ₂ - One or more of C ₃₀ α-olefin monomers, preferably one or more of C ₄ -C ₂₀ α-olefin monomers. In other words, the polyα-olefin used in the present invention can be obtained by self-polymerization of one type of α-olefin monomer, or can be obtained by copolymerization of multiple α-olefin monomers; that is, the polyα-olefin Can be α-olefin homopolymer and/or α-olefin copolymer (for example, can be α-olefin binary copolymer, α-olefin terpolymer or α-olefin terpolymer; The copolymer Including one or more of block copolymers, random copolymers and alternating copolymers).

According to the present invention, the α-olefin monomers include linear linear α-olefin monomers and non-linear α-olefin monomers.

For example, the α-olefin monomers include vinyl aromatic monomers, such as styrene, and monomers such as alkyl styrene and vinyl naphthalene having an alkyl group of 1 to 10 carbon atoms.

Preferably, the α-olefin monomer is selected from one or more of C ₂ -C ₃₀ linear linear α-olefins; further preferably, the α-olefin monomer is selected from C ₄ - one or more of C ₂₀ linear linear α-olefins.

According to the present invention, preferably, typical α-olefin homopolymers can be selected from poly-1-butene, poly-1-hexene, poly-1-octene, poly-1-decene, poly-1-dodecene, One or more of poly-1-hexadecene and poly-1-eicosene. Typical α-olefin binary copolymers can be selected from propylene-1-dodecene copolymer, 1-butene-1-dodecene copolymer, 1-hexene-1-decene copolymer, 1-hexene One or more of ene-1-dodecene copolymer, 1-octene-1-tetradecene copolymer, and the like.

According to the present invention, the silicone oil generally refers to a linear polysiloxane product that maintains a liquid state at room temperature (20°C-30°C). After cracking and rectification, the low ring body is obtained, and then the ring body, end-capping agent, and catalyst are telomerized together to obtain a mixture of various degrees of polymerization, and the low boiling matter is removed by vacuum distillation to obtain silicone oil. Described silicone oil has following structural formula:

In the formula, R ₁ -R ₈ and X ₁ and X ₂ can be independently hydrogen, alkyl, alkyl substituted by halo, alkoxy, alkenyl, aryl, substituted by alkyl or halo One of aryl, acyloxy, halo, hydroxyl, cyano and polyether chain; among them, alkyl, halo-substituted alkyl, alkoxy, alkenyl, acyloxy, polyether chain The number of carbon atoms in can be 2-5; n and m are integers.

According to the present invention, preferably, R ₁ -R ₈ and X ₁ and X ₂ can be the same or different; R ₁ -R ₈ can be each independently hydrogen, methyl, ethyl, phenyl, halo, chlorine One of phenyl, ethoxy, vinyl and trifluoropropyl; X _{and X} can each independently be one of hydrogen, methyl, ethyl, hydroxyl, cyano and halo.

According to the chemical structure, the commonly used silicone oils are methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl Trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen silicone oil, hydroxyl hydrogen silicone oil, cyano silicone oil, etc. Further preferably, the silicone oil is selected from one or more of methyl silicone oil, ethyl silicone oil, methylphenyl silicone oil, methylchlorophenyl silicone oil and phenyl silicone oil. With the number of segments n, the molecular weight increases, and the viscosity of the silicone oil also increases. Therefore, the silicone oil can have various viscosities. Preferably, the silicone oil has a viscosity at 25° C. of 5 centipoise to 5000 centipoise, more preferably 10 centipoise to 2000 centipoise.

More preferably, the silicone oil is methyl silicone oil, that is, when R ₁ -R ₈ are all methyl groups, it is called methyl silicone oil.

According to the present invention, the release agent can be various release agents routinely used in the art, as long as it can play an isolation role, preferably, the release agent can be selected from stearic acid (the stearic acid is also One or more of octadecanoic acid), stearate, stearic acid amide and stearate. Wherein, the stearate can be one or more stearic acid metal salts selected from the IA main group, the IIA main group, the IIIA main group and the IIB subgroup of the periodic table of elements ; The stearate is selected from C1-C5 monohydric alcohol stearate and/or C1-C5 polyol stearate. Preferably, the stearate is selected from one or more of magnesium stearate, zinc stearate, calcium stearate, aluminum stearate, sodium stearate, potassium stearate; Described stearic acid amide is ethylene bis stearamide and/or stearamide; Described stearate is selected from ethylene glycol monostearate, ethylene glycol distearate, propylene glycol monostearate One or more of propylene glycol distearate, glyceryl stearate, glyceryl distearate, glyceryl tristearate, diethylene glycol distearate and stearic anhydride.

According to the present invention, the solvent can be various polar solvents, and can make the poly-alpha-olefin form a suspension. Preferably, the solvent is selected from alcohols, ethers, ketones, aqueous solutions of alcohols, ether At least one of aqueous solutions of ketones and aqueous solutions of ketones. For example, the alcohol can be selected from one or more of isopropanol, n-butanol, sec-butanol, n-pentanol, n-hexanol, n-octanol, etc.; the ether can be selected from dimethyl ether, ether etc.; the ketone can be selected from one or more of methyl ethyl ketone, butanone, etc. In addition, the selectable range of the concentration of the aqueous alcohol solution or the aqueous ether solution or the aqueous solution of the ketone is relatively wide, usually, the mass percentage concentration of the aqueous solution of the alcohol or the aqueous solution of the ether or the aqueous solution of the ketone can generally be 20- 95% by weight.

According to the present invention, in order to further stabilize the drag reducing composition, the drag reducing composition may also contain a surfactant, and the surfactant may be various oil-soluble surfactants, preferably , in order to better stabilize the drag reducing composition, the surfactant is selected from one or more of Tween surfactant, Span surfactant and nonylphenol polyoxyethylene ether surfactant. In addition, when the surfactant is one or more kinds, various surfactants may be mixed in any ratio. The amount of the surfactant can be selected in a wide range, preferably, based on the total weight of the drag reducing composition, the content of the surfactant can be 0.01-10% by weight, more preferably 0.1- 5% by weight, more preferably 1-3% by weight.

According to the present invention, in addition to the main components of the above-mentioned drag reducing composition of the present invention, the drag reducing composition can also contain other additives known in the art that can be used in drag reducing compositions, for example, emulsifiers ( Can be selected from stearyl alcohol, sodium dodecylbenzenesulfonate and alkyl aryl polyether alcohol) and other additives to further stabilize the drag reducing composition, so that Based on the total weight of the drag reducing composition, the content of the other additives may be 0.1-10% by weight.

According to the present invention, the preparation method of the drag reducing composition is not particularly limited, as long as the polyα-olefin can be uniformly dispersed in the silicone oil, release agent and solvent. For example, the mixing of the polyalpha-olefin, silicone oil, release agent and solvent can be carried out simultaneously or step by step. In the process, the silicone oil containing poly-alpha-olefin is uniformly mixed with a release agent and a solvent to obtain a suspension. Further preferably, the method also includes mixing polyalphaolefin, silicone oil, release agent, solvent and surfactant, for example, first polyalphaolefin is uniformly mixed with silicone oil, so that polyalphaolefin is uniformly dispersed in silicone oil , and then uniformly mix the polyalpha-olefin-containing silicone oil with a release agent, a solvent, and preferably a surfactant to obtain a suspension. Preferably, based on the total weight of the drag reducing composition, the amount of the surfactant is such that the content of the surfactant in the drag reducing composition is 0.01-10% by weight, preferably 0.1- 5% by weight, more preferably 1-3% by weight.

According to the present invention, in order to disperse the polyalpha-olefin more uniformly in the drag reducing composition, preferably, the particle diameter of the polyalpha-olefin is less than 1000 microns, more preferably less than 500 microns, for example, 10 -500 microns (usually can be measured by electron microscopy).

More preferably, in order to generate polyalphaolefin in situ and ensure that it can be directly and uniformly dispersed without low-temperature pulverization, according to a preferred embodiment of the present invention, the preparation method of the drag-reducing composition includes the following step:

(1) Under olefin polymerization conditions and in the presence of silicone oil, the α-olefin monomer is contacted with the olefin polymerization catalyst system, so that a mixture of poly α-olefin and silicone oil with an intrinsic viscosity of 10 dL/g or more is obtained;

(2) the mixture of polyalpha-olefin and silicone oil that step (1) obtains is mixed with release agent and solvent; Described release agent is selected from stearic acid, stearate, stearic acid amine and stearate One or more of them; the solvent is a polar solvent.

Although the dosage range of each substance in the drag reducing composition can be changed within a wide range, preferably, in order to obtain a drag reducing composition with better drag reducing effect, the total amount of the drag reducing composition Based on weight, the amount of each substance is such that in the obtained drag reducing composition, the content of polyalphaolefin is 5-45 wt%, the content of silicone oil is 1-50 wt%, and the content of release agent is 0.1-10 wt%. , the content of the solvent is 0.1-90% by weight; more preferably, based on the total weight of the drag-reducing composition, the amount of each material is such that in the obtained drag-reducing composition, the content of polyalpha-olefin is 10% -40% by weight, the content of silicone oil is 5-45% by weight, the content of release agent is 1-8% by weight, and the content of solvent is 10-80% by weight.

Preferably, in order to further stabilize polyalpha-olefins, in step (2), the method also includes mixing the mixture of polyalpha-olefins and silicone oil obtained in step (1) with release agent, solvent and surfactant The agent is mixed evenly; the surfactant can be various oil-soluble surfactants. Based on the total weight of the drag reducing composition, the amount of the surfactant is such that the content of the surfactant in the drag reducing composition is 0.01-10% by weight, preferably 0.1-5% by weight, More preferably, it is 1 to 3% by weight.

According to the present invention, the olefin polymerization catalyst system may be various olefin polymerization catalyst systems commonly used in the field of olefin polymerization, for example, Ziegler-Natta catalyst system and/or metallocene catalyst system.

It is well known to those skilled in the art that the Ziegler-Natta catalyst system includes a carrier magnesium compound (magnesium chloride), and a titanium compound (titanium tetrachloride and/or titanium trichloride) supported on the carrier and an internal electron donor. Catalysts with spherical morphology.

According to the present invention, the internal electron donor compound in the Zieglar-Natta catalyst system can be various internal electron donor compounds commonly used in the field of olefin polymerization. Preferably, the internal electron donor compound is one or more of di-n-butyl phthalate, diisobutyl phthalate, diethyl succinate and fluorene diether.

According to the present invention, the molar ratios of the titanium compound, the internal electron donor compound and the magnesium compound are known to those skilled in the art. Generally, the molar ratio of the titanium compound, the internal electron donor compound and the magnesium compound may be 0.5-150:0.02-0.4:1, preferably 2-50:0.06-0.2:1.

In the Zieglar-Natta catalytic system, also contain cocatalyst, described cocatalyst can be the organoaluminum compound that can be used as the cocatalyst in the Zieglar-Natta catalytic system of various known to those skilled in the art, for example, alkylaluminum, haloalkane aluminum or alkylaluminoxanes. Preferably, the organoaluminum compound can be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, monochlorodiethylaluminum, trioctylaluminum and tridecylaluminum one or more. More preferably, the aluminum alkyl is one or more of trimethylaluminum, triethylaluminum and diethylaluminum chloride.

The amount of the co-catalyst organoaluminum compound can be a conventional amount in the art. Usually, the molar ratio of titanium to aluminum in the co-catalyst organoaluminum compound can be 1:20-800. Preferably, the molar ratio of the titanium to the aluminum in the co-catalyst organoaluminum compound is 1:20-500. More preferably, the molar ratio of the titanium to the aluminum in the cocatalyst organoaluminum compound is 1:20-300.

In the Ziegler-Natta catalytic system, an external electron donor can also be included to control the isotacticity of the polymer.

The external electron donor can be various external electron donors known to those skilled in the art that can be used in the Ziegler-Natta catalytic system, for example, the external electron donor is preferably of the general formula R ₁ R ₂ Si (OR ) ₂ alkoxysilane, wherein, R can be C ₁ -C ₅ alkyl; R ₁ and R ₂ are the same or different, each is C ₁ -C ₅ alkyl or C ₃ -C ₁₀ cycloalkane base. More preferably, R is a C ₁ -C ₃ alkyl group, R ₁ and R ₂ are the same or different, and each is a C ₁ -C ₃ alkyl group or a C ₄ -C ₆ cycloalkyl group. Most preferably, the alkoxysilane is selected from one or more of cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane and dicyclohexyldimethoxysilane.

According to the present invention, the amount of the external electron donor compound can be the conventional amount in the art. Generally, the molar ratio of the titanium to the silicon in the external electron donor compound may be 1:10-500. Preferably, the molar ratio of the titanium to the silicon in the external electron donor compound is 1:25-250.

It is well known to those skilled in the art that the metallocene catalyst system generally contains a metallocene compound and a cocatalyst.

The metallocene compound may be various metallocene compounds known to those skilled in the art, for example, the metallocene compound may be a compound having the following general formula: R _n ¹ R _2-n ² MCl ₂ ; wherein R ¹ , R ² are respectively Me ₂ Si(Ind) ₂ , Me ₂ Si(2-Me-4-Ph-Ind) ₂ , Me ₂ Si(2-Me-Ind) ₂ , Me(Me ₃ Si)Si(2- Me-4-Ph-Ind) ₂ , Me ₂ Si(IndR ₂ ) ₂ , Et(Ind) ₂ , Me ₂ SiCp, MeCp, CpInd, Cp, Ph ₂ C(Cp)(Flu), Ph ₂ C(Cp )(2-Me ₂ NFlu) or Ph ₂ C(Cp)(2-MeOFlu); R in the molecular formula Me ₂ Si(IndR ₂ ) ₂ is an alkyl group with 1-3 carbon atoms.

Where Me is CH ₃ , Ind is indenyl, Ph is benzene ring, Et is ethyl, Cp is cyclopentadiene, and Flu is fluorene. M is Zr, Ti, Hf, V, Cr, Fe or La; n is an integer of 0-2.

The co-catalyst in the metallocene catalyst system can be various conventional co-catalysts in the metallocene catalyst system, for example, alkylaluminoxane. Generally, the alkyl group in the alkylaluminoxane can be a C ₁ -C ₁₂ alkyl group, more preferably a C ₁ -C ₅ alkyl group. Preferably, the alkylalumoxane may be selected from one or more of methylalumoxane, ethylalumoxane, isobutylalumoxane and alkyl-modified methylalumoxane. Wherein, the alkyl-modified methylalumoxane refers to a mixture of methylalumoxane and _C2 - _C5 alkylalumoxane, or a mixture of trimethylaluminum and _C2 - _C5 alkyl Methylalumoxane obtained by hydrolyzing a mixture of aluminum, for example: ethyl-modified methylalumoxane, isobutyl-modified methylalumoxane. Most preferably, the alkylaluminoxane is methylaluminoxane and/or alkyl-modified methylaluminoxane. The alkyl-modified methylaluminoxane can be obtained commercially, or can be synthesized by methods known to those skilled in the art.

According to the method of the present invention, there is no particular limitation on the usage amount of the cocatalyst alkyl aluminoxane, which may be a conventional usage amount in the art. Preferably, the molar ratio of the metal in the metallocene compound to the aluminum in the alkylaluminoxane is 1:50-5000. More preferably, the molar ratio of the metal of the metallocene compound to the aluminum in the alkylaluminoxane is 1:100-2500. Further preferably, the molar ratio of the metal in the metallocene compound to the aluminum in the alkylaluminoxane is 1:2000-2500.

According to the present invention, the selection and dosage of the catalyst system used to prepare polyalphaolefins are also described in detail in various documents, such as US5442019, US5416179, CN101230111, CN1310728, CN1310728A, etc., which will not be detailed here. stated. Typically, the catalyst system is used in an amount of about 100-1500 μg/g based on the total weight of all components supplied to the reactor.

According to the present invention, in step (1), the preparation conditions of the poly-alpha-olefin can be polymerization conditions known to those skilled in the field of olefin polymerization. Usually, the preparation of poly-alpha-olefin needs to be carried out under the conditions of air isolation and low-temperature stirring, for example, under the protection of inert gas and stirring, the alpha-olefin monomer is contacted with the olefin polymerization catalyst system.

Preferably, the polymerization temperature can be minus 20°C to 40°C, preferably minus 10°C to 10°C; the polymerization pressure can be 0.01-10MPa, preferably 0.01-2MPa, more preferably 1-2MPa; In order to obtain a higher olefin conversion rate, the contact time is usually more than 10 hours, preferably 12-36 hours.

The inert gas can be various gases that do not chemically interact with the carrier, the alkylaluminoxane, or the metallocene compound. For example, the inert gas may be nitrogen or argon.

Usually, under the conditions of olefin polymerization and in the presence of silicone oil, the way of contacting the α-olefin monomer with the olefin polymerization catalyst system is to combine the silicone oil, α-olefin monomer, and olefin polymerization catalyst system under the protection of an inert gas. The cocatalyst in the mixture is mixed with the external electron donor, the temperature of the system is controlled at a suitable polymerization temperature, and the contact reaction is carried out with the main catalyst in the olefin polymerization catalyst system under stirring.

According to the present invention, in step (2), the time for mixing the mixture of polyalphaolefin and silicone oil obtained in step (1) with release agent, solvent and preferably contained surfactant is not particularly limited, as long as it can be made Mix evenly to disperse the polyalphaolefin evenly to obtain a suspension.

According to the present invention, the types and amounts of the α-olefin monomer, silicone oil, release agent, solvent and surfactant have been introduced in detail above, and will not be repeated here.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

The present invention will be further described in detail through specific examples below.

In the following examples, the preparation method of the Ziegler-Natta catalyst used is:

Add 2.0 grams of ethoxymagnesium particle carrier (particle diameter of 40-50 microns) and 30 ml of toluene into the reaction flask to disperse evenly, then lower the temperature to -10°C, add 10 ml (6.0 mol) of TiCl ₄ , and stay for 0.5 hours. Heat up to 80°C, add 0.6ml (0.39mol) diisobutyl phthalate, heat up to 110°C, react for 2 hours, settle, filter, heat wash twice with toluene (20ml each time), add titanium twice, add 5ml (3.0mmol) TiCl ₄ was reacted with 30ml toluene for 1 hour, settled, filtered, washed 4 times with hexane, and dried at 72°C to obtain the catalyst solid component. The mass percent content of titanium in the catalyst is 2.87%.

In the following examples, the particle diameter of the polyα-olefin is obtained by measuring with an electron microscope.

Example 1

This example is used to illustrate the preparation of polyalphaolefin and drag reducing composition.

1) Preparation of polyalphaolefin:

Mix 21.3 g of 1-octene refined with molecular sieves (purchased from ACROS Reagent Company) with 9.6 g of methyl silicone oil refined with molecular sieves (purchased from Beijing Dingye Industry and Trade Co., Ltd., viscosity at 25°C is 300 centipoise) , under the protection of nitrogen, add 0.68mL 1.1M triisobutylaluminum toluene solution and 0.08mL 1.0M cyclohexylmethyldimethoxysilane solution, and stir for 10 minutes at -7°C and pressure 0.1MPa Afterwards, 25.2 mg of Ziegler-Natta catalyst was added, and the reaction was stirred for 6 hours at -7°C under a pressure of 0.1 MPa to obtain a polyα-olefin/methyl silicone oil slurry (polyα-olefin particle diameter is 150 microns), recorded as mixture A1. At 25°C, mix and stir the polyα-olefin/methyl silicone oil slurry with isopropanol, wash 4-5 times, remove the methyl silicone oil, and dry at 70°C to obtain polyα-olefin, weighing 0.02 gram of polyα-olefin and mixed with 50 milliliters of toluene solution, at 40°C, its intrinsic viscosity measured with Ubbelohde viscometer was 19.2dL/g, and the monomer conversion rate of 1-octene was 92.4%.

2) Preparation of drag reducing composition:

First 2.5g Tween-80 was added in 15.7g isopropanol, after fully dissolving, will be dissolved with the isopropanol solution of Tween-80, 1.5g zinc stearate (purchased from Nanjing Jinling Chemical Factory Co., Ltd. ) into the above mixture A1, fully stirred for 30 minutes to obtain 48.98g of stable poly-α-olefin drag-reducing composition C1, and there was no obvious layering and aggregation phenomenon after 3 months. The composition and properties of the composition are shown in Table 1.

Example 2

This example is used to illustrate the preparation of polyalphaolefin and drag reducing composition.

1) Preparation of polyalphaolefin:

Take 21.3g of 1-octene (purchased from ACROS Reagent Company) refined by molecular sieves and mix with 4.8g of methylphenyl silicone oil (purchased from ACROS Reagent Company, whose viscosity at 25° C. is 2000 centipoise) purified by molecular sieves, Under the protection of nitrogen, add 1.0mL 1.1M triisobutylaluminum toluene solution and 0.09mL 1.0M cyclohexylmethyldimethoxysilane solution, and stir for 10 minutes at -7°C under a pressure of 0.1MPa , add 32.4mg Ziegler-Natta catalyst, at -7 ℃, under the pressure of 0.1MPa, stir and react for 6 hours to obtain polyα-olefin/methylphenyl silicone oil slurry (polyα-olefin particle diameter is 200 microns), denoted as Mixture A2. At 25°C, mix and stir the polyα-olefin/methyl silicone oil slurry with isopropanol, wash 4-5 times, remove the methyl silicone oil, and dry at 70°C to obtain polyα-olefin, weighing 0.02 gram polyalpha-olefin and mix with 50 milliliters of toluene solution, at 40 ℃, measure its intrinsic viscosity with Ubbelohde viscometer to be 18.5dL/g, the monomer conversion rate of 1-octene is 90.1%.

2) Preparation of drag reducing composition:

First 1.01g Span-80 was added to 32.4g butanol, after fully dissolving, the butanol solution having Span-80 and 8g calcium stearate (purchased from Nanjing Jinling Chemical Factory Co., Ltd.) were added to the above-mentioned Mixture A2 was fully stirred for 30 minutes to obtain 65.4 g of stable poly-α-olefin drag reducer composition C2, and there was no obvious layering and aggregation after 3 months. The composition and properties of the composition are shown in Table 1.

Example 3

This example is used to illustrate the preparation of polyalphaolefin and drag reducing composition.

1) Preparation of polyalphaolefin:

Take 21.3g of 1-octene (purchased from ACROS Reagent Company) refined by molecular sieves and 28.8g of ethyl silicone oil refined by molecular sieves (purchased from Beijing Dingye Industry and Trade Co., Ltd., the viscosity at 25°C is 10 centipoise) Mixed, under the protection of nitrogen, add 0.7mL 1.1M triisobutylaluminum toluene solution and 0.08mL 1.0M cyclohexylmethyldimethoxysilane solution, stir at -10°C and pressure 0.1MPa for 10 Minutes later, 25.8 mg of Ziegler-Natta catalyst was added, and at -10° C. and a pressure of 0.1 MPa, the reaction was stirred for 24 hours to obtain a granular polyα-olefin/ethyl silicone oil slurry (polyα-olefin particle diameter is 150 microns), Recorded as mixture A3. At 25°C, mix and stir the polyα-olefin/methyl silicone oil slurry with isopropanol, wash 4-5 times, remove the methyl silicone oil, and dry at 70°C to obtain polyα-olefin, weighing 0.02 gram polyalpha-olefin and mix with 50 milliliters of toluene solution, at 40 ℃, measure its intrinsic viscosity with Ubbelohde viscometer to be 17.3dL/g, the monomer conversion rate of 1-octene is 86.4%.

2) Preparation of drag reducing composition:

First add 2g nonylphenol polyoxyethylene ether to 19.6g isopropyl ether, after fully dissolving, dissolve the isopropyl ether solution with nonylphenol polyoxyethylene ether, 3g ethylene glycol monostearate and 3g Glyceryl distearate (both purchased from Wuhan Huamei Technology Co., Ltd.) was added to the above-mentioned mixture A3, and fully stirred for 30 minutes to obtain 74.8g of stable polyα-olefin drag reducer composition C3. After 3 months, there was no obvious layered aggregation phenomenon. The composition and properties of the composition are shown in Table 1.

Example 4

This example is used to illustrate the preparation of polyalphaolefin and drag reducing composition.

1) Preparation of polyalphaolefin:

Add 14.2 g of 1-octene (purchased from ACROS Reagent Company) refined by molecular sieves into a three-necked flask previously replaced with high-purity N ₂ , and add 0.5 mL of 1.1 M triisobutylaluminum toluene solution and 0.06 mL of 1.0M cyclohexylmethyldimethoxysilane solution, stirred at -7°C and pressure of 0.1MPa for 10 minutes, then added 20.0mg of Ziegler-Natta catalyst, stirred at -7°C and pressure of 0.1MPa Reacted for 24 hours to obtain 13.5g block polymer, and the monomer conversion rate of 1-octene was 95%. Olefin and mixed with 50 milliliters of toluene solution, at 40°C, its intrinsic viscosity was 13.7dL/g measured by Ubbelohde viscometer.

2) Preparation of drag reducing composition:

Take 3g of the above-prepared massive polymer, crush it into 80-mesh (187 micron particle diameter) particles at -100°C, add 9.6g of methyl chlorophenyl silicone oil (purchased from Beijing Dingye Industry and Trade Co., Ltd., the viscosity at 25°C is 1000 centipoise), 40.5g methyl ethyl ketone, 2g ethylene bisstearamide (purchased from Sichuan Tianyu Oleochemical Co., Ltd.), stir evenly to obtain 55.1g Polyalphaolefin drag reducer composition. After 3 months, there was no obvious delamination. The composition and properties of the composition are shown in Table 1.

Comparative example 1

This comparative example serves to illustrate the preparation of prior art polyalphaolefin compositions.

1) Preparation of polyalphaolefin:

Add 21.3 g of 1-octene (purchased from ACROS Reagent Co., Ltd.) purified by molecular sieves into the reaction vessel, and add), 0.64 mL of 1.1 M triisobutylaluminum toluene solution and 0.05 mL of 1.0M solution of cyclohexylmethyldimethoxysilane, stirred at -7°C and pressure of 0.1MPa for 10 minutes, then added 23.6mg of catalyst, stirred and reacted for 24 hours at -7°C and pressure of 0.1MPa , obtained polyalpha-olefin, the monomer conversion rate of 1-octene is 70%; At 25 ℃, described polyalpha-olefin is dried at 70 ℃, weighs 0.02 gram polyalpha-olefin and mixes with 50 Milliliter toluene solution was mixed, and at 40°C, the intrinsic viscosity was measured with an Ubbelohde viscometer to be 13.4dL/g.

2) Preparation of drag reducing composition:

Get 5g of the block polymer prepared above and 2g of zinc stearate (purchased from Nanjing Jinling Chemical Factory Co., Ltd.), and grind them into 80 mesh (187 micron in particle diameter) particles at -100°C. ℃), add 15.7 g of isopropanol and 0.2 g of Tween-80, and stir evenly to obtain a drag-reducing composition containing poly-α-olefin. The drag-reducing composition will aggregate after being placed for two weeks, and the layering will be obvious , poor mobility. The composition and properties of the composition are shown in Table 1.

Example 5-8

This example is used to illustrate the drag reducing performance test of the drag reducing composition.

The drag reduction ratios of the drag reducing compositions prepared in Examples 1-4 were measured. According to the industry standard compiled by the China Petroleum and Natural Gas Pipeline Science and Technology Research Center, the drag reduction rate of the drag reduction is measured, the standard number: SY/T6578-2003. Test conditions: temperature 20°C, flow rate 57L/min. Before the test, make the drag reducer into a diesel solution with a mass concentration of 3mg/g, then place it in the dilution tank, and dilute it to a mass concentration of 16μg/g. When the flow in the pipeline is stable, read the blank pressure from the differential pressure gauge. The pressure drop and the pressure drop after adding the drag reducing agent, the formula for calculating the drag reduction rate is as follows:

$\mathrm{<span\; class="notranslate">\; DR</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; \&Delta;P</span>}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; \&Delta;P</span>}}_{\mathrm{<span\; class="notranslate">\; d</span>}}}{\mathrm{<span\; class="notranslate">\; \&Delta;P</span>}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span>$

ΔP is the pressure drop without adding drag reducer, and ΔP _d is the pressure drop after adding drag reducer. The measured drag reduction ratio of the drag reducing composition is shown in Table 1.

Comparative example 2

This comparative example is used to illustrate the drag reducing performance test of the drag reducing composition.

The drag-reducing performance of the drag-reducing composition was tested according to the method of Examples 5-8, except that the drag-reducing composition prepared by the method of Comparative Example 1 was tested, and the results are shown in Table 1.

Table 1

From the data in Table 1 above, it can be seen that compared with the prior art, the drag reducing composition provided by the present invention has a higher drag reduction rate, good storage stability, low viscosity and good fluidity. The drag-reducing composition prepared according to the preferred preparation method of the present invention can be directly applied to drag-reducing oil pipelines without complicated post-treatment processes such as low-temperature crushing or grinding, and the preparation process is simple.

Claims (22)

1. an anti-drag composition, is characterized in that, described anti-drag composition is the suspension containing poly-alpha olefins, silicone oil, separant and solvent; Described separant be selected from stearic acid, stearate, stearic amide and stearate one or more; Described solvent is polar solvent; With the gross weight of described anti-drag composition for benchmark, the content of described poly-alpha olefins is 5-45 % by weight, and the content of described silicone oil is 1-50 % by weight, and the content of described separant is 0.1-15 % by weight, and the content of described solvent is 0.1-90 % by weight.

2. anti-drag composition according to claim 1, wherein, with the gross weight of described anti-drag composition for benchmark, the content of described poly-alpha olefins is 10-40 % by weight, the content of described silicone oil is 5-45 % by weight, the content of described separant is 1-15 % by weight, and the content of described solvent is 10-80 % by weight.

3. anti-drag composition according to claim 1, wherein, the particle diameter of described poly-alpha olefins is for being less than 1000 microns.

4. according to the anti-drag composition in claim 1-3 described in any one, wherein, described poly-alpha olefins is that to be polymerized by 'alpha '-olefin monomers the limiting viscosity formed be the polymkeric substance of more than 10dL/g.

5. anti-drag composition according to claim 4, wherein, described 'alpha '-olefin monomers is selected from C ₂-C ₃₀line style linear alpha-olefin in one or more.

6. anti-drag composition according to claim 1 and 2, wherein, described silicone oil has following structural formula:

Wherein, R ₁-R ₈and X ₁and X ₂be hydrogen independently of one another, one in alkyl, the halogen alkyl, alkoxyl group, alkenyl, aryl, the aryl replaced by alkyl or halogen, acyloxy, halogen, hydroxyl, cyano group and the polyether chain that replace; Wherein, alkyl, halogen replace alkyl, alkoxyl group, alkenyl, acyloxy, carbonatoms in polyether chain can be 2-5; N and m is integer.

7. anti-drag composition according to claim 6, wherein, described silicone oil be selected from methyl-silicone oil, ethyl silicon oil, methyl phenyl silicone oil, methylchlorophenyl silicone oil and phenyl silicone oil one or more; The viscosity of 25 DEG C of described silicone oil is 5 centipoise-5000 centipoises.

8. anti-drag composition according to claim 1 and 2, wherein, described stearate is be selected from one or more the Metallic stearates in the periodic table of elements the Ith A main group, the IIth A main group, the IIIth A main group and the IIth B subgroup; Described stearate is selected from the monohydroxy-alcohol stearate of C1-C5 and/or the polyvalent alcohol stearate of C1-C5.

9. anti-drag composition according to claim 1 and 2, wherein, described solvent is selected from least one in the aqueous solution of alcohol, ether, ketone, the aqueous solution of alcohol, the aqueous solution of ether and ketone.

10. anti-drag composition according to claim 1 and 2, wherein, described anti-drag composition is also containing tensio-active agent, and described tensio-active agent is oil soluble surfactant.

11. anti-drag compositions according to claim 10, wherein, with the gross weight of described anti-drag composition for benchmark, the content of described tensio-active agent is 0.01-10 % by weight.

12. anti-drag compositions according to claim 10 or 11, wherein, described oil soluble surfactant be selected from tween surfactants, SPAN surfactants and polyoxyethylene nonylphenol ether tensio-active agent one or more.

The preparation method of 13. 1 kinds of anti-drag compositions, is characterized in that, the method comprises poly-alpha olefins and silicone oil, separant and solvent even, obtains suspension; Described separant be selected from stearic acid, stearate, Stearyl Amine and stearate one or more; Described solvent is polar solvent; With the gross weight of described anti-drag composition for benchmark, the consumption of each material makes in the anti-drag composition obtained, and the content of poly-alpha olefins is 5-45 % by weight, and the content of silicone oil is 1-50 % by weight, the content of separant is 0.1-10 % by weight, and the content of solvent is 0.1-90 % by weight.

14. preparation methods according to claim 13, wherein, the limiting viscosity of described poly-alpha olefins is more than 10dL/g, and particle diameter is for being less than 1000 microns.

15. preparation methods according to claim 13, wherein, the method also comprises and mixing containing the suspension of poly-alpha olefins with silicone oil, separant and solvent with tensio-active agent; Described tensio-active agent is oil soluble surfactant.

The preparation method of 16. 1 kinds of anti-drag compositions, is characterized in that, the method comprises the steps:

(1) under olefin polymerization conditions and under the existence of silicone oil, contacted by 'alpha '-olefin monomers with olefin polymerization catalyst system, making to obtain limiting viscosity is the poly-alpha olefins of more than 10dL/g and the mixture of silicone oil;

(2) poly-alpha olefins step (1) obtained and the mixture of silicone oil and separant and solvent even, obtain suspension; Described separant be selected from stearic acid, stearate, Stearyl Amine and stearate one or more; Described solvent is polar solvent; With the gross weight of described anti-drag composition for benchmark, the consumption of each material makes in the anti-drag composition obtained, and the content of poly-alpha olefins is 5-45 % by weight, and the content of silicone oil is 1-50 % by weight, the content of separant is 0.1-10 % by weight, and the content of solvent is 0.1-90 % by weight.

17. preparation methods according to claim 13 or 16, wherein, with the gross weight of described anti-drag composition for benchmark, the consumption of each material makes in the anti-drag composition obtained, the content of poly-alpha olefins is 10-40 % by weight, the content of silicone oil is 5-45 % by weight, and the content of separant is 1-8 % by weight, and the content of solvent is 10-80 % by weight.

18. preparation methods according to claim 16, wherein, in step (2), the mixture that the method also comprises poly-alpha olefins and silicone oil step (1) obtained mixes with separant, solvent and tensio-active agent; Described tensio-active agent is oil soluble surfactant.

19. preparation methods according to claim 15 or 18, wherein, with the gross weight of described anti-drag composition for benchmark, the consumption of described tensio-active agent makes the content of this tensio-active agent in described anti-drag composition be 0.01-10 % by weight.

20. preparation methods according to claim 16, wherein, described olefin polymerization catalyst system is Ziegler-Natta catalyst system and/or metallocene catalyst system.

21. preparation methods according to claim 16; wherein; in step (1); described olefin polymerization conditions comprises: under protection of inert gas also under agitation; 'alpha '-olefin monomers is contacted with olefin polymerization catalyst system; Contact Temperature is subzero 20 DEG C to 40 DEG C, and contact pressure is 0.01-10MPa, and duration of contact is more than 10 hours.

22. 1 kinds of anti-drag compositions, is characterized in that, this anti-drag composition is prepared by the method in claim 16-21 described in any one.