A self-stabilizing precipitation polymerization process for a fischer-tropsch synthesis product

Abstract

The present application relates to a self-stabilizing precipitation polymerization method of Fischer-Tropsch synthesis products. The self-stabilizing precipitation polymerization method of the present application comprises the following steps: subjecting a reaction system comprising Fischer-Tropsch synthesis products, electron-accepting monomers, low-carbon-number olefins, initiators and solvents to self-stabilizing precipitation polymerization; the low-carbon-number olefins are ethylene and / or propylene; the Fischer-Tropsch synthesis products comprise electron-donating monomers. The self-stabilizing precipitation polymerization method of the present application realizes the self-stabilizing precipitation polymerization of Fischer-Tropsch synthesis products by adding low-carbon-number olefins as the third monomers.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis, and specifically relates to a self-stabilizing precipitation polymerization method for Fischer-Tropsch synthesis products. Background Technology

[0002] Fischer-Tropsch Synthesis (FTS) is a chemical process developed in 1925 by German scientists Franz Fischer and Hans Tropsch. It aims to convert carbon- and hydrogen-rich gases (syngas) into liquid fuels and other chemical products. The initial research objective was to explore a method for producing liquid fuels from solid carbon resources (such as coal), especially in the face of the challenge of scarce petroleum resources. With technological advancements and the passage of time, Fischer-Tropsch Synthesis has evolved from a coal-dependent fuel production process into a more widely applicable technology capable of utilizing various hydrocarbon resources, including natural gas and biomass, to convert low-value hydrocarbon resources into high-value liquid fuels. Currently, this technology is not only widely used in the production of liquid fuels but also plays a crucial role in the production of chemical feedstocks and products, holding significant strategic importance for promoting energy diversification and the substitution of fossil fuels.

[0003] Fischer-Tropsch synthetic oils have a complex composition, mainly consisting of alpha-olefins, n-alkanes, and oxygen-containing compounds, with a carbon number distribution ranging from C5 to C30. Long-chain alpha-olefins have high added value, accounting for approximately 60% of the synthetic oil. Typically, Fischer-Tropsch synthetic oils require hydrogenation before use as a blending component in gasoline. They are characterized by low sulfur, low aromatics, and high cetane number, complementing natural petroleum products. Heavy oils and heavy waxes can be used as feedstocks for hydrocracking and the synthesis of lubricating oils. However, these processing methods are complex and costly.

[0004] Current research on the value enhancement and utilization of Fischer-Tropsch synthetic oils mainly includes the separation and extraction of individual α-olefins. Individual α-olefins have industrial applications; for example, 1-hexene and 1-octene can be used as comonomers for polyethylene. α-olefins with higher carbon numbers can be oxidized to prepare oxygen-containing compounds such as alcohols, and sulfonates can be prepared for use as detergents. There are also some reports on the polymerization of individual α-olefins with maleic anhydride; through free radical polymerization, α-olefins can be converted into polymer resources.

[0005] Patent document 1 discloses a method and apparatus for separating 1-octene from Fischer-Tropsch synthetic oil-washed naphtha, wherein the oil-washed naphtha is subjected to distillation, deoxygenation, etherification, and distillation to obtain 1-octene.

[0006] Patent Documents 2 and 3 disclose methods and apparatus for separating and purifying 1-decene and 1-dodecene from Fischer-Tropsch stable heavy oil. The stable heavy oil is divided into narrow fractions and subjected to a series of reactions to obtain 1-decene and 1-dodecene.

[0007] In non-patent literature 1-4, copolymers of 1-hexene-maleic anhydride, 1-octene-maleic anhydride, 1-dodecene-maleic anhydride, 1-tetradecene-maleic anhydride, and 1-octadecene-maleic anhydride were prepared by using initiators such as benzoyl peroxide and azobisisobutyronitrile, solvents such as toluene, xylene, acetone, and dioxane, and precipitants such as methanol and n-hexane.

[0008] Patent document 4 proposes that by copolymerizing Fischer-Tropsch synthetic oil with electron-withdrawing functional monomers, functional copolymers can be obtained directly without separation, avoiding the problem that the allyl radical effect of α-olefins makes it difficult to self-polymerize by free radical polymerization methods, and achieving a higher yield.

[0009] References:

[0010] Patent documents:

[0011] Patent Document 1: CN 114805005 A;

[0012] Patent Document 2: CN 114685235 A;

[0013] Patent document 3: CN 114644543 A;

[0014] Patent document 4: CN 117417481 A.

[0015] Non-patent literature:

[0016] Non-patent document 1: Nifant'ev IE et al., "Copolymers of Maleic Anhydride and Methylene Alkanes: Synthesis, Modification, and Pour Point Depressant Properties", Polymer Science, Series B, 2018, 60(4): 469-480;

[0017] Non-patent document 2: Demircan D et al., "Preparation of Poly(MA-alt-α-olefin-C6,8,12,18) / Silica Nanohybrids via in situ generated nanofillers for use as a dualfunction organonanofiller", Journal of Chemical Sciences, 2015, 127(11): 1993-2003;

[0018] Non-patent document 3: Davies MC et al., "Molar mass determination of poly(octadecene-alt-maleic anhydride)copolymers by size exclusion chromatography and dilute solution viscometry", Polymer, 2002, 43(15): 4311-4314;

[0019] Non-patent document 4: Chen Y et al., "A novel hyper-cross-linked polymer for high-efficient fluid-loss control in oil-based drilling fluid", Colloids and Surfaces A Physicochemical and Engineering Aspects, 2021, 626: 127004. Summary of the Invention

[0020] The problem the invention aims to solve

[0021] Patent documents 1-3 involve methods for separating α-olefins from Fischer-Tropsch synthetic oils, but separating individual α-olefins before utilization would complicate the entire process and increase costs.

[0022] Non-patent literature 1-4 describes copolymerizing α-olefins with maleic anhydride to obtain alternating copolymers. The anhydride groups are then modified through esterification and amination reactions to obtain functionalized polymers containing long-chain alkyl groups, demonstrating the significant potential application value of these copolymers. However, the polymerization methods described in non-patent literature 1-4 are all solution polymerizations, making product separation difficult and requiring the addition of large amounts of precipitating agents.

[0023] In the method of Patent Document 4, the long alkyl chain of the long-chain α-olefin means that its polymerization process can only be solution polymerization, making product separation difficult. Alkyl alcohols must be used as precipitants to separate the products. On the one hand, alkyl alcohols can cause ring-opening esterification of maleic anhydride; on the other hand, separation methods that rely heavily on precipitants are not suitable for industrial production.

[0024] In addition, Fischer-Tropsch synthesis products also include Fischer-Tropsch waxes, which contain less than 10% α-olefins, and the effective utilization of these olefins is also an issue that needs to be addressed.

[0025] The technical problem to be solved by the present invention is to provide an effective method for utilizing Fischer-Tropsch synthesis products that is simple in process, easy in product separation, high in production efficiency and low in cost.

[0026] Solution for solving the problem

[0027] To address the aforementioned problems, the inventors conducted long-term and in-depth research and discovered that by adding a low-carbon-number olefin as a third monomer, the self-stabilizing precipitation polymerization of the Fischer-Tropsch synthesis product and the electron-accepting monomer can be achieved. The polymerized system can be separated into solid and liquid phases by simple centrifugation, yielding alternating copolymer microspheres of electron-donating and electron-accepting monomers, thus completing this invention.

[0028] Specifically, the present invention solves the problems of the present invention through the following solutions.

[0029] [1] A self-stabilizing precipitation polymerization method, comprising the following steps:

[0030] To enable a reaction system containing Fischer-Tropsch synthesis products, electron-accepting monomers, low-carbon olefins, initiators, and solvents to undergo self-stabilizing precipitation polymerization;

[0031] The low-carbon-number olefin is ethylene and / or propylene;

[0032] The Fischer-Tropsch synthesis product contains electron-donating monomers.

[0033] [2] According to the self-stabilizing precipitation polymerization method described in [1], wherein,

[0034] The electron-accepting monomer is selected from one or more of maleic anhydride, maleimide, itaconic anhydride and their derivatives;

[0035] The Fischer-Tropsch synthetic products are Fischer-Tropsch synthetic oils and / or Fischer-Tropsch synthetic waxes;

[0036] The initiator is one or more selected from azo compound initiators and peroxide initiators;

[0037] The solvent is an organic solvent.

[0038] [3] According to the self-stabilizing precipitation polymerization method described in [2], wherein,

[0039] The Fischer-Tropsch synthetic oil is preferably Fischer-Tropsch synthetic oil washed naphtha and / or Fischer-Tropsch synthetic stabilized heavy oil; the mass content of electron-donating monomers in the Fischer-Tropsch synthetic product is 1-70%; the electron-donating monomers are one or more combinations selected from olefins having 4 to 40 carbon atoms, preferably α-olefins;

[0040] The solvent is selected from one or more of ketone solvents, carboxylic acid ester solvents, and ether solvents;

[0041] The azo compound initiator is azobisisobutyronitrile (AIBN) or azobisisoheptanenitrile (AIHH)nitrile.

[0042] The peroxide initiator is benzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide, and dicyclohexyl peroxide.

[0043] [4] The self-stabilizing precipitation polymerization method according to any one of [1] to [3], wherein,

[0044] In the reaction system, the total mass concentration of electron-donating and electron-accepting monomers is 5% to 75%, preferably 10% to 60%.

[0045] Based on the total mass of electron-donating monomers, electron-accepting monomers and low-carbon olefins as 100%, the mass fraction of low-carbon olefins is 1-50%, preferably 3-40%, and more preferably 5-40%.

[0046] The mass ratio of the electron-accepting monomer to the Fischer-Tropsch synthesis product is 1:30 to 5:1, preferably 1:8 to 5:4;

[0047] The amount of the initiator is 0.05 to 10 wt%, preferably 1 to 5 wt%, based on the total mass of the electron-accepting monomer, electron-donating monomer, and the low-carbon-number olefin, which is 100%.

[0048] [5] The self-stabilizing precipitation polymerization method according to any one of [1] to [3], wherein the electron-accepting monomer, the initiator and the Fischer-Tropsch synthesis product are mixed and then the low carbon number olefin is added, so that the resulting reaction system undergoes self-stabilizing precipitation polymerization.

[0049] [6] The self-stabilizing precipitation polymerization method according to any one of [1] to [3], wherein the electron-accepting monomer and the initiator are respectively added to the solvent for mixing, the Fischer-Tropsch synthesis product is added, then an inert gas is introduced into the system, followed by the introduction of ethylene and / or propylene, and then the reaction system is heated to the polymerization reaction temperature for self-stabilizing precipitation polymerization.

[0050] [7] The self-stabilizing precipitation polymerization method according to any one of [1] to [3], wherein the self-stabilizing precipitation polymerization is carried out in an inert gas, the polymerization reaction temperature is 50 to 120°C, and the polymerization reaction time is 1 to 24 hours.

[0051] [8] The self-stabilizing precipitation polymerization method according to any one of [1] to [3] further includes a step of post-treatment of the reaction system after self-stabilizing precipitation polymerization, wherein the post-treatment preferably includes one or more of solid-liquid separation, washing or drying.

[0052] [9] A copolymer obtained by a self-stabilizing precipitation polymerization method according to any one of [1] to [8].

[0053]

[10] According to the copolymer described in [9], wherein the copolymer is copolymer microspheres with a number-average particle size of 0.1 to 10 μm and a particle size distribution coefficient of 1.001 to 1.2.

[0054] The effects of the invention

[0055] The self-stabilizing precipitation polymerization method for Fischer-Tropsch synthesis products of the present invention has the characteristics of simple process, easy product separation, high production efficiency and low cost, and provides an effective solution to the problem of high-value utilization of long-chain α-olefins in Fischer-Tropsch synthesis products.

[0056] Specifically, the present invention has the following beneficial effects:

[0057] (1) The method of the present invention is simple. Only a low carbon number olefin is added to achieve self-stabilized precipitation polymerization. After polymerization, solid-liquid separation can be achieved through simple treatment. The solvent in the supernatant obtained by separation can be recycled again, and the remainder is unreacted long-chain alkanes, which is suitable for industrial production.

[0058] (2) The method of the present invention can directly use unseparated Fischer-Tropsch synthesis products or the fractions of Fischer-Tropsch synthesis products as raw materials, without the need for refining and separation, which greatly reduces costs.

[0059] (3) The copolymer prepared by the method of the present invention has a high content of functional groups, which can be further modified to be functionalized, thus broadening the application range of functional copolymers and making effective use of Fischer-Tropsch synthesis product resources.

[0060] (4) The method of the present invention overcomes the problem that the application of Fischer-Tropsch synthesis products is limited because of their very complex composition, close boiling points, and high difficulty in separation.

[0061] (5) In the method of the present invention, by adjusting the monomer ratio or different types of Fischer-Tropsch products, copolymers containing alkyl chains with different carbon numbers can be obtained, thereby making it easy to control the hydrophilicity and lipophilicity of the product copolymer. Attached Figure Description

[0062] Figure 1 Here is a SEM image of the copolymer microspheres obtained in Example 1;

[0063] Figure 2 Here is a SEM image of the copolymer microspheres obtained in Example 2;

[0064] Figure 3 Here is a SEM image of the copolymer microspheres obtained in Example 7;

[0065] Figure 4 Here is a SEM image of the lower sediment obtained in Comparative Example 2;

[0066] Figure 5 This is a SEM image of the lower sediment obtained in Comparative Example 4. Detailed Implementation

[0067] The present invention will now be described in detail. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.

[0068] <Terminology and Definitions>

[0069] In this specification, "Fischer-Tropsch synthesis product" refers to the product obtained by Fischer-Tropsch synthesis technology.

[0070] In this specification, "self-stabilizing precipitation polymerization" refers to a polymerization method in which no emulsifier is used in the polymerization system and the polymerization product is suspended in the reaction medium.

[0071] In this specification, "particle size" refers to the number-average particle size of the described particles, which can be obtained by the methods described in the Examples section.

[0072] In this specification, "electron-accepting monomer" refers to a monomer that has an electron-withdrawing group on its carbon-carbon double bond participating in the polymerization reaction.

[0073] In this specification, "electron-donating monomer" refers to a monomer that has an electron-donating group on its carbon-carbon double bond participating in the polymerization reaction.

[0074] In this specification, unless otherwise expressly stated, “alkyl” means straight-chain, branched or cyclic alkyl.

[0075] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0076] In this specification, the numerical range indicated by "above" or "below" refers to the numerical range that includes the stated number.

[0077] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0078] In this specification, the terms "optionally" or "optionally" are used to indicate the use or non-use of certain substances, components, procedures, application conditions, etc.

[0079] All unit names used in this manual are international standard unit names, and unless otherwise stated, the "%" used refers to weight or mass percentage content.

[0080] In this specification, references to "preferred embodiments," "implementation methods," etc., mean that a specific element (e.g., feature, structure, property, and / or characteristic) related to that embodiment is included in at least one of the embodiments described herein, and may or may not be present in other embodiments. Furthermore, it should be understood that the elements may be combined in any suitable manner in various embodiments.

[0081] <Self-stabilizing precipitation polymerization method>

[0082] One object of the present invention is to provide a self-stabilizing precipitation polymerization method, characterized by comprising the following steps:

[0083] To enable a reaction system containing Fischer-Tropsch synthesis products, electron-accepting monomers, low-carbon olefins, initiators, and solvents to undergo self-stabilizing precipitation polymerization;

[0084] The low-carbon-number olefin has 2 to 4 carbon atoms;

[0085] The Fischer-Tropsch synthesis product contains electron-donating monomers.

[0086] In previous studies, the copolymerization of Fischer-Tropsch products with electron-accepting monomers could only be achieved through solution polymerization. This solution polymerization method suffers from difficulties in product separation, requiring the use of alkyl alcohols as precipitants. Due to the long-chain alkyl groups, α-olefins result in excessively low cohesive energy density in copolymers. The inventors attempted to modify solvent solubility parameters, monomer concentration, and increase molecular weight, but none of these methods could achieve self-stabilizing precipitation polymerization of Fischer-Tropsch products with electron-accepting monomers. However, in a recent study, the inventors unexpectedly discovered that using low-carbon-number olefins as a third monomer for copolymerization enabled the self-stabilizing precipitation polymerization of Fischer-Tropsch products, thus completing this invention.

[0087] In the method of the present invention, the low carbon number olefins and α-olefins have similar polymerization rates and participate in polymerization simultaneously to obtain an alternating copolymer of electron-donating and electron-accepting monomers. By adding a low carbon number olefin as a third monomer, the solubility parameter of the polymer is improved, thereby realizing the self-stabilizing precipitation polymerization of Fischer-Tropsch synthesis products and α-olefins.

[0088] The method of this invention is simple and low-cost, providing a new approach to solving the problem of high-value utilization of 60% of long-chain α-olefins in Fischer-Tropsch synthetic oils.

[0089] The self-stabilizing precipitation polymerization method of the present invention is described in detail below.

[0090] reaction system

[0091] The reaction system of the self-stabilizing precipitation polymerization method of the present invention comprises Fischer-Tropsch synthesis product, electron-accepting monomer, low-carbon olefin, initiator and solvent.

[0092] Fischer-Tropsch synthesis products are products of Fischer-Tropsch synthesis technology. Their components include n-alkanes, n-olefins, branched alkanes, branched olefins, and n-alcohols, among which n-alkanes and n-olefins are the main components, and the olefin components are mostly α-olefins.

[0093] This invention does not impose any particular limitation on the composition of Fischer-Tropsch synthesis products, as long as they include electron-donating monomers capable of copolymerizing with electron-accepting monomers. Those skilled in the art can select the appropriate composition as needed. Fischer-Tropsch synthesis products can be unseparated Fischer-Tropsch oils, different fractions of Fischer-Tropsch oils, or Fischer-Tropsch waxes, as long as they contain electron-donating monomers.

[0094] Preferably, the electron-donating monomer content in the Fischer-Tropsch synthesis product is 1-70% by mass, more preferably 5-65%, and even more preferably 20-65%, such as 30%, 40%, 50%, 60%, etc.

[0095] Preferably, the electron-donating monomer is one or more combinations selected from olefins having 4 to 40 carbon atoms, preferably α-olefins, and more preferably selected from 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadene, 1-hexadecene, 1-heptadecene, 1-heptadecene, 1-heptadecene, 1-octadecene, 1-nonadene, 1-eicosene, 1-timodec ...

[0096] In one embodiment, the Fischer-Tropsch synthesis product is a Fischer-Tropsch synthetic oil and / or a Fischer-Tropsch synthetic wax, wherein the Fischer-Tropsch synthetic oil is preferably a Fischer-Tropsch synthetic oil washed naphtha and / or a Fischer-Tropsch synthetic stabilized heavy oil. The Fischer-Tropsch synthetic oil washed naphtha mainly contains C4 to C14 components, including about 60 to 70% α-olefins. The Fischer-Tropsch synthetic stabilized heavy oil mainly contains C8 to C30 components, including about 55 to 65% α-olefins. The Fischer-Tropsch synthetic heavy wax mainly contains components with a higher carbon number (C30 and above), including about 1 to 10% α-olefins.

[0097] The inventors have discovered that components other than α-olefins in Fischer-Tropsch synthesis products, such as n-alkanes, branched alkanes and alkenes, and other components, can serve as media in the reaction system. These media can also be separated after polymerization and used as products such as gasoline and diesel.

[0098] In this invention, an electron-accepting monomer is polymerized with an electron-donating monomer from a Fischer-Tropsch synthesis product to obtain a functional copolymer with functional groups. Furthermore, the functional groups can be anhydride groups, imide groups, etc.

[0099] In one embodiment, the electron-accepting monomer is one or more combinations selected from maleic anhydride, maleimide, itaconic anhydride, and their derivatives.

[0100] Preferably, the electron-accepting monomer is one or a combination of two or more selected from maleic anhydride, itaconic anhydride, maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, and N-(1-naphthyl)maleimide.

[0101] In one embodiment, the total mass concentration of electron-donating and electron-accepting monomers in the reaction system is 5% to 75%, preferably 10% to 60%, for example: 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 65%, etc. By keeping the total mass concentration of electron-donating and electron-accepting monomers within the above range, the polymerization reaction can proceed more effectively.

[0102] In one embodiment, the mass ratio of the electron-receiving monomer to the Fischer-Tropsch synthesis product is 1:30 to 5:1, preferably 1:8 to 5:4, for example: 1:25, 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, etc.

[0103] In one embodiment, the mass fraction of the low-carbon olefin is 1 to 50%, preferably 3 to 40%, more preferably 5 to 40%, for example 8%, 10%, 15%, 20%, 22%, 23%, 25%, 27%, 30%, etc., based on the total mass of the electron-donating monomer, electron-accepting monomer and low-carbon olefin as 100%.

[0104] In this invention, an initiator is used to polymerize electron-accepting monomers with electron-donating monomers in a Fischer-Tropsch synthesis product. In one embodiment, the initiator is one or more selected from azo compound initiators and peroxide initiators. Preferably, the peroxide initiator is benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide, dicyclohexyl peroxide, etc.; the azo compound initiator is azobisisobutyronitrile, azobisisoheptanenitrile, etc.

[0105] In one embodiment, the initiator content is 0.05–10 wt%, preferably 0.5–5 wt%, more preferably 1–5 wt%, based on 100% of the total mass of the electron-accepting monomer, the electron-donating monomer in the Fischer-Tropsch synthesis product, and the low-carbon-number olefin; for example: 0.1 wt%, 0.5 wt%, 1 wt%, 2.5 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 7 wt%, 9 wt%, etc. When the initiator content is 0.05–10 wt%, the desired functional copolymer can be obtained.

[0106] The present invention does not impose any particular limitation on the solvent, and it can be a solvent commonly used in the art. Specifically, the solvent is an organic solvent, and preferably, the organic solvent includes one or more of ketone solvents, carboxylic acid ester solvents, and ether solvents.

[0107] Carboxylic acid ester solvents can have the structure shown in formula (I):

[0108]

[0109] In formula (2), R4 is a hydrogen atom, a C1-C6 alkyl or a C6-C10 aryl, and R5 is a C1-C8 alkyl or a C6-C10 aryl; specifically, the C6-C10 aryl can be phenyl, benzyl, phenethyl, etc.

[0110] Specific examples of carboxylic acid ester solvents can be ester solvents consisting of one or more combinations of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, isoamyl phenylacetate, etc.

[0111] Ketone solvents can be selected from one or more of acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, etc.

[0112] Ether solvents may be selected from one or more combinations of dimethyl ether, methyl ethyl ether, ethyl ether, ethyl propyl ether, dipropyl ether, dibutyl ether, methyl propyl ether, methyl butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopentyl ether, methyl tert-amyl ether, methyl cyclopentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, etc.

[0113] The present invention does not impose any particular limitation on the amount of solvent used, and it can be added as needed, as long as the electron-accepting monomer, Fischer-Tropsch synthesis product, low carbon number olefin and initiator can be fully dissolved, and the polymerization product is insoluble in the solvent.

[0114] Preferably, the mass ratio of solvent to electron-accepting monomer is (10-1):1, more preferably (8-2):1, for example (7-3):1 or (6-4):1.

[0115] Preferably, by selecting a solvent, the solubility parameter of the copolymer as the polymerization product is 1 to 7 MPa greater than the solubility parameter of the organic solvent. 1 / 2 Preferably 2-5 MPa 1 / 2 .

[0116] The solubility parameter of a polymer has the conventional meaning in the art and can be calculated indirectly using the contribution values ​​of each group in the molecular structure, by the following formula:

[0117] δ=ρ∑F i / M

[0118] Where δ is the solubility parameter of the polymer; F i ρ is the molar attraction constant of each functional group in the polymer molecule; M is the polymer density; and M is the molecular weight of the polymer repeating unit.

[0119] The solubility parameters of solvents can be found in technical manuals or published literature in this field. For example, the solubility parameters of various solvents are recorded in "Polymer Physics" (Hua Youqing, Jin Riguang, Chemical Industry Press, 2013, p. 83).

[0120] Polymerization process

[0121] In this invention, there are no particular restrictions on the mixing order and method of the components in the reaction system; they can be carried out in any suitable manner and order.

[0122] In a specific implementation, the self-stabilizing precipitation polymerization method of the present invention includes the following steps: mixing the electron-accepting monomer, initiator, and Fischer-Tropsch synthesis product and then adding it to the low-carbon-number olefin, so that the resulting reaction system undergoes self-stabilizing precipitation polymerization.

[0123] In a specific implementation, the self-stabilizing precipitation polymerization method of the present invention includes the following steps: mixing the electron-accepting monomer with the initiator, adding the Fischer-Tropsch synthesis product, and then adding the low-carbon-number olefin, so that the resulting reaction system undergoes self-stabilizing precipitation polymerization.

[0124] The solvent can be added to the reaction system at any suitable time. Preferably, the electron-accepting monomer and the initiator are added separately to the solvent and mixed.

[0125] The polymerization reaction is initiated by heating the reaction system to the polymerization temperature. The polymerization temperature can be 50-120°C, preferably 60-110°C, for example: 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, etc. The polymerization time can be 1-24 hours, for example: 2 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, etc. Furthermore, the polymerization reaction is carried out under the protection of an inert gas, specifically, nitrogen or argon.

[0126] In a more specific embodiment, the electron-accepting monomer and the initiator are respectively added to a solvent for mixing, the Fischer-Tropsch synthesis product is added, then an inert gas is introduced into the reaction system, followed by the introduction of ethylene and / or propylene, and then the reaction system is heated to the polymerization reaction temperature for self-stabilizing precipitation polymerization.

[0127] Based on the characteristics of the self-stabilizing precipitation polymerization reaction method, the reaction medium has a good solubility for electron-accepting monomers and initiators, and is miscible with low-carbon-number olefin monomers to ensure that the system is homogeneous before the reaction. However, the reaction medium cannot dissolve the copolymers generated. When the polymer molecular chains reach a certain critical length, they precipitate out of the reaction medium. However, the precipitated polymer cannot settle down as powder or block as in precipitation polymerization. Instead, it is stably suspended in the reaction medium in the form of microspheres or particles, forming a stable dispersion system similar to a polymer emulsion.

[0128] In a specific implementation, the self-stabilizing precipitation polymerization method of the present invention further includes a post-treatment step of the reaction system after self-stabilizing precipitation polymerization, wherein the post-treatment preferably includes one or more of solid-liquid separation, washing or drying.

[0129] Based on the characteristics of the self-stabilizing precipitation polymerization reaction method, the reaction system obtained after polymerization is a dispersion system of copolymer microspheres. Therefore, no precipitant is needed, and the copolymer microspheres can be separated by solid-liquid separation alone.

[0130] More specifically, after the polymerization reaction, the reaction system is subjected to solid-liquid separation, and optionally the separated solid (polymer microspheres) is dried.

[0131] Solid-liquid separation can be performed using known methods, such as filtration, centrifugation, and solvent evaporation.

[0132] Washing can be carried out by rinsing the separated solids with a washing solvent, dispersing the separated solids in a washing solvent, and then performing solid-liquid separation again. The washing solvent is preferably the solvent used in the reaction.

[0133] Drying can be carried out by methods known in the art, such as heating to dissolve and evaporate the residue. The drying temperature can be 40–150°C, for example 40–100°C, and the drying time can be 1–48 hours, for example 4–40 hours or 8–30 hours.

[0134] <Copolymer>

[0135] The present invention also relates accordingly to copolymers obtained by the method of the present invention. The copolymers of the present invention are copolymers of olefins and electron-accepting monomers, wherein the olefins include low-carbon-number olefins and olefins derived from Fischer-Tropsch synthesis products.

[0136] The copolymer of the present invention is a copolymer microsphere with a number-average particle size of 0.1-10 μm, preferably 0.2-8 μm, more preferably 0.3-5 μm, and even more preferably 0.4-3 μm; for example, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.2 μm, 1.4 μm, 1.5 μm, 1.6 μm, 0.5 μm, 1.9 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm, 2.9 μm, etc.

[0137] The particle size distribution coefficient is 1.001 to 1.2, preferably 1.003 to 1.15, more preferably 1.005 to 1.1, for example 1.006 to 1.06.

[0138] The copolymer microspheres obtained by the method of the present invention have a residual solvent content of 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, and even 1% by mass or less.

[0139] In one embodiment, the number-average molecular weight of the polymer, as determined by gel permeation chromatography, can be 1,000 to 500,000, preferably 2,000 to 200,000, and even more preferably 2,500 to 100,000, such as 50,000, 20,000, 10,000, 8,000, etc.

[0140] Example

[0141] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0142] The composition of the Fischer-Tropsch synthetic oil-washed naphtha (also referred to as "oil-washed naphtha") used in the following examples is shown in Table 1 below:

[0143] Table 1

[0144]

[0145] The composition of the Fischer-Tropsch stabilized heavy oil (also referred to as "stabilized heavy oil") used in the following examples is shown in Table 2 below:

[0146] Table 2

[0147]

[0148] The composition (average carbon number 22.13) of the Fischer-Tropsch synthetic waxes used in the following examples is shown in Table 3 below:

[0149] Table 3

[0150] α-olefins 10.53％ Internal olefins 13.19％ n-Alkanes 76.28％

[0151] Example 1

[0152] 18g of maleic anhydride and 1.65g of benzoyl peroxide (BPO) were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres were obtained as a white solid.

[0153] Example 2

[0154] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 10g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 9g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0155] Example 3

[0156] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of isoamyl acetate solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres were obtained as a white solid.

[0157] Example 4

[0158] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in a mixed solvent of 27g of ethyl acetate and 63g of cyclohexane. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres were obtained as a white solid.

[0159] Example 5

[0160] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in a mixed solvent of 27g of butanone and 63g of cyclohexane. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres were obtained as a white solid.

[0161] Example 6

[0162] 18g of maleic anhydride and 1.65g of azobisisobutyronitrile (AIBN) were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. Nitrogen gas was introduced into the system for 10 minutes, followed by 3g of propylene gas. The reaction was carried out at 70℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 70℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0163] Example 7

[0164] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 15g of Fischer-Tropsch synthesis stabilized heavy oil was added. The system was purged with nitrogen for 10 minutes, followed by 6g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0165] Example 8

[0166] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of isoamyl acetate solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 15g of Fischer-Tropsch stabilized heavy oil was added. The system was purged with nitrogen for 10 minutes, followed by 6g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0167] Example 9

[0168] 18g itaconic anhydride and 1.65g benzoyl peroxide were dissolved in 90g methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, itaconic anhydride and α-olefin copolymer microspheres were obtained as a white solid.

[0169] Example 10

[0170] 18g of maleimide and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleimide and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0171] Example 11

[0172] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 20g of Fischer-Tropsch synthetic oil was added to wash naphtha. The system was purged with nitrogen for 10 minutes, followed by the introduction of 3g of ethylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres were obtained as a white solid.

[0173] Example 12

[0174] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 15g of Fischer-Tropsch synthesis stabilized heavy oil was added. The system was purged with nitrogen for 10 minutes, followed by 6g of ethylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0175] Example 13

[0176] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated and mixed evenly to obtain a transparent solution. Then, 15g of Fischer-Tropsch wax (purchased from Ningxia Coal Group) was added. The system was purged with nitrogen for 10 minutes, followed by 6g of propylene gas. The reaction was carried out at 80℃ for 6 hours to obtain a dispersion system of maleic anhydride and α-olefin copolymer microspheres. After centrifugation and vacuum drying at 80℃ for 24 hours, maleic anhydride and α-olefin copolymer microspheres in the form of a white solid were obtained.

[0177] Comparative Example 1

[0178] 0.49 g of maleic anhydride and 0.024 g of azobisisobutyronitrile were dissolved in 0.50 g of cyclohexanone. The solution was sonicated until dissolved and mixed thoroughly to obtain a clear solution. Then, 1.01 g of Fischer-Tropsch synthetic oil washed naphtha was added. The system was purged with nitrogen for 10 minutes and reacted at 70 °C for 6 hours to obtain a clear reaction solution. The reaction solution was added to anhydrous ethanol for precipitation to obtain a precipitate. The precipitate was centrifuged at 7000 rpm for 5 minutes, washed with ethanol, and centrifuged three times. Finally, it was vacuum dried to constant weight to obtain 0.59 g of Fischer-Tropsch synthetic oil washed naphtha-maleic anhydride copolymer, with a yield of 53%.

[0179] Comparative Example 2

[0180] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated until dissolved and mixed thoroughly to obtain a clear solution. Then, 25g of Fischer-Tropsch synthetic oil washed naphtha was added. The system was purged with nitrogen for 10 minutes and reacted at 80℃ for 6 hours, resulting in a layered system of a hard precipitate and a supernatant. The hard precipitate was removed and dried to constant weight to obtain 20.5g of Fischer-Tropsch synthetic oil washed naphtha-maleic anhydride copolymer, with a precipitate yield of 62%. The supernatant was then added to anhydrous ethanol for precipitation, obtaining a small amount of supernatant precipitate. The supernatant precipitate was centrifuged at 7000 rpm for 5 minutes, washed with ethanol, centrifuged three times, and vacuum dried to constant weight to obtain 1.98g of Fischer-Tropsch synthetic oil washed naphtha-maleic anhydride copolymer, with a supernatant yield of 6% and a total yield of 68%.

[0181] Comparative Example 3

[0182] 0.72 g of maleic anhydride and 0.088 g of azobisisobutyronitrile were dissolved in 2.4716 g of isoamyl acetate. The solution was sonicated until dissolved and mixed thoroughly to obtain a clear solution. Then, 1.81 g of Fischer-Tropsch stabilized heavy oil was added. The system was purged with nitrogen for 10 minutes and reacted at 70 °C for 8 hours to obtain a clear reaction solution. The reaction solution was added to anhydrous ethanol for precipitation to obtain a precipitate. The precipitate was centrifuged at 7000 rpm for 5 minutes, washed with ethanol, and centrifuged three times. Finally, it was vacuum dried to constant weight to obtain 1.21 g of Fischer-Tropsch stabilized heavy oil-maleic anhydride copolymer, with a yield of 69%.

[0183] Comparative Example 4

[0184] 18g of maleic anhydride and 1.65g of benzoyl peroxide were dissolved in 90g of methyl tert-butyl ether solvent. The solution was sonicated until dissolved and mixed thoroughly to obtain a clear solution. Then, 25g of Fischer-Tropsch stabilized heavy oil was added. The system was purged with nitrogen for 10 minutes and reacted at 80℃ for 6 hours, resulting in a layered system of a hard precipitate and a supernatant. A small amount of the hard precipitate was removed and dried to constant weight, yielding 2.97g of Fischer-Tropsch stabilized heavy oil-maleic anhydride copolymer, with a precipitate yield of 9%. The supernatant was then added to anhydrous ethanol for precipitation, yielding a large amount of supernatant precipitate. The supernatant precipitate was centrifuged at 7000 rpm for 5 minutes, washed with ethanol, centrifuged three times, and dried under vacuum to constant weight, yielding 27.4g of Fischer-Tropsch stabilized heavy oil-maleic anhydride copolymer, with a supernatant yield of 83% and a total yield of 91%.

[0185] <Tests and Evaluations>

[0186] SEM analysis

[0187] Small amounts of the dried copolymer microspheres obtained in Examples 1, 2, and 7, and the lower precipitates obtained in Comparative Examples 2 and 4, were dispersed in appropriate amounts of polymerization solvent. After ultrasonic dispersion, the dispersions were dropped onto coverslips and allowed to air dry. The morphology was observed using a field emission scanning electron microscope (JEOL, model JSM7401). SEM images of the copolymer microspheres from Examples 1, 2, and 7 were obtained, as shown below. Figures 1-3 As shown; SEM images of the lower sediment layers in Comparative Examples 2 and 4 are shown below. Figure 4 and Figure 5 As shown.

[0188] Particle size analysis

[0189] The particle size and distribution data of the copolymer microspheres obtained in Examples 1-13 were obtained by the following methods:

[0190] First, the particle size and distribution of microspheres in the scanning electron microscope images are measured using measurement and statistical software. The particle size and distribution of the measured microspheres can then be obtained by calculation using formulas 1 to 3.

[0191]

[0192] U=D w / D n Equation (3)

[0193] in:

[0194] D n —Number-average particle size of polymer microspheres;

[0195] D w —Weight-average particle size of polymer microspheres:

[0196] D i —The particle size of the i-th microsphere;

[0197] N – Total number of microspheres;

[0198] U – Dispersion coefficient of microsphere size.

[0199] Molecular weight test

[0200] Using tetrahydrofuran as the eluent, copolymer sample solutions obtained in Examples 1-13 and Comparative Examples 1-4 were precisely prepared with a concentration of 5 mg / mL, and the molecular weight of the copolymers was determined by gel permeation chromatography.

[0201] The properties and evaluation results of the copolymer microspheres obtained in Examples 1-11 and Comparative Examples 1-4 are shown in Table 4.

[0202] Table 4

[0203]

[0204] As shown in Table 4, by adding ethylene or propylene as low-carbon olefins, different types of Fischer-Tropsch synthesis products can achieve self-stabilized precipitation polymerization in different solvents, obtaining microspheres with particle sizes ranging from 1 to 2.5 μm, with product yields all exceeding 50%. The method of this invention can achieve self-stabilized precipitation polymerization of Fischer-Tropsch synthesis oils or Fischer-Tropsch synthesis waxes.

[0205] Industrial availability

[0206] The method of this invention can be widely used in the industrial preparation of functional copolymer microspheres.

Claims

1. A self-stabilizing precipitation polymerization method, characterized in that, Includes the following steps: Electron-accepting monomers and initiators are added to a solvent and mixed, followed by the addition of Fischer-Tropsch synthesis products, and then low-carbon olefins, so that the resulting reaction system undergoes self-stabilizing precipitation polymerization. The low-carbon-number olefin is ethylene and / or propylene; The Fischer-Tropsch synthesis product is a Fischer-Tropsch stabilized heavy oil; the Fischer-Tropsch synthesis product contains an electron-donating monomer; the mass content of the electron-donating monomer in the Fischer-Tropsch synthesis product is 50-70%; the electron-donating monomer is one or more of α-olefins selected from those having 7-40 carbon atoms. The electron-accepting monomer is selected from one or more of maleic anhydride, maleimide, and itaconic anhydride; Based on the total mass of electron-donating monomers, electron-accepting monomers, and low-carbon-number olefins as 100%, the mass fraction of low-carbon-number olefins is 15-40%. The mass ratio of the electron-accepting monomer to the Fischer-Tropsch synthesis product is 1:2 to 2:

1.

2. The self-stabilizing precipitation polymerization method according to claim 1, characterized in that, The initiator is one or more selected from azo compound initiators and peroxide initiators; The solvent is an organic solvent.

3. The self-stabilizing precipitation polymerization method according to claim 2, characterized in that, The solvent is selected from one or more of ketone solvents, carboxylic acid ester solvents, and ether solvents; The azo compound initiator is azobisisobutyronitrile (AIBN) or azobisisoheptanenitrile (AIHH)nitrile. The peroxide initiator is benzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide, and dicyclohexyl peroxide.

4. The self-stabilizing precipitation polymerization method according to any one of claims 1 to 3, characterized in that, In the reaction system, the total mass concentration of electron-donating and electron-accepting monomers is 5% to 75%. Based on the total mass of electron-donating monomers, electron-accepting monomers, and low-carbon-number olefins as 100%, the mass fraction of low-carbon-number olefins is 15-30%. The mass ratio of the electron-accepting monomer to the Fischer-Tropsch synthesis product is 1:1 to 2:1; The amount of initiator is 0.05 to 10 wt%, based on the total mass of the electron-accepting monomer, electron-donating monomer and the low-carbon-number olefin.

5. The self-stabilizing precipitation polymerization method according to claim 4, characterized in that, In the reaction system, the total mass concentration of electron-donating and electron-accepting monomers is 10% to 60%. The amount of the initiator is 1 to 5 wt% based on the total mass of the electron-accepting monomer, electron-donating monomer and the low-carbon olefin, which is 100%.

6. The self-stabilizing precipitation polymerization method according to any one of claims 1 to 3, characterized in that, The electron-accepting monomer and the initiator are respectively added to the solvent for mixing, and then the Fischer-Tropsch synthesis product is added. Then an inert gas is introduced into the system, followed by the introduction of ethylene and / or propylene. The reaction system is then heated to the polymerization temperature for self-stabilizing precipitation polymerization.

7. The self-stabilizing precipitation polymerization method according to any one of claims 1 to 3, characterized in that, The self-stabilizing precipitation polymerization is carried out in an inert gas, with a polymerization temperature of 50~120℃ and a polymerization time of 1~24 hours.

8. The self-stabilizing precipitation polymerization method according to any one of claims 1 to 3, characterized in that, It also includes a post-treatment step for the reaction system after self-stabilizing precipitation polymerization.

9. The self-stabilizing precipitation polymerization method according to claim 8, characterized in that, The post-processing includes one or more of the following: solid-liquid separation, washing, or drying.

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