A Conjugated Diene Coordination Polymerization System and Its Application

Abstract

This invention belongs to the field of olefin polymerization and relates to a conjugated diene coordination polymerization system and its application. It includes a cobalt compound (A), an organoaluminum compound (B), a silicon-containing compound (C), a conjugated diene monomer (D), and a solvent (E). In this cobalt-based catalytic conjugated diene polymerization system, the silicon-containing compound acts as both a catalyst component and participates in the polymerization reaction, effectively improving the catalytic activity of the polymerization reaction and allowing for adjustment of the microstructure content within a certain range.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization, and relates to a conjugated diene coordination polymerization system, and more specifically, to a transition metal-catalyzed conjugated diene polymerization system, and the application of the conjugated diene polymerization system in the in-situ preparation of conjugated diene polymer-based complexes. Background Technology

[0002] Conjugated dienes (such as butadiene and isoprene) are two important monomers for producing polymer materials. Taking butadiene as an example, under the action of different types of initiators or catalysts, it can undergo 1,4- and 1,2-addition polymerization reactions to generate corresponding cis-1,4-, trans-1,4-, and 1,2-structural units. Catalyst systems typically include titanium-based, iron-based, molybdenum-based, nickel-based, cobalt-based, and neodymium-based catalysts. Using titanium-based, nickel-based, and neodymium-based catalysts to catalyze the polymerization of butadiene or isoprene usually synthesizes polymers with high cis or high trans structures. Iron-based and molybdenum-based catalysts can be used to obtain atactic polybutadiene rich in 1,2-structure. For example, the coordination polymerization of butadiene catalyzed by the iron naphthenate / AlR3 / AlEt2Cl system can prepare polybutadiene with a 1,2-structure content of 39% to 56%. The polymerization of butadiene catalyzed by tris[di(2-ethylhexyl)phosphate]ferric / dihexylaluminum hydride / dioctylaluminum hydride / diethyl phosphite can prepare atactic polybutadiene with a 1,2-structure content of 76% to 80%. (See: Shen Qi, Guo Xiaoguang, Liu Guozhi, Study on butadiene polymerization catalyzed by ferrous naphthenate-alkylaluminum-o-phenanthroline-halides, Acta Polymerica Sinica, 1989, 2: 152-156); Shandong Heze Yuhuang Chemical Co., Ltd., Preparation method of atactic 1,2-polybutadiene. CN110343203A. Random 1,2-polybutadiene with a 1,2-structure content higher than 75% can be prepared by initiating butadiene polymerization using a molybdenum pentachloride (MoCl5) / tributyl phosphate (TBP) / triethylaluminum (AlEt3) catalytic system. See: Zhao Xuan, Liu Jinhui, Hua Jing, Preparation of crystalline high-vinyl polybutadiene by butadiene polymerization initiated by MoCl5 / TBP / AlEt3 system. Polymer Materials Science and Engineering, 2019, 35: 7-12.

[0003] Nickel-based, cobalt-based, and neodymium-based catalysts are commonly used to prepare highly cis-1,4-polybutadiene, atactic 1,2-polybutadiene, and syndiotactic 1,2-polybutadiene. Zigeler-Natta type cobalt-based catalyst systems typically consist of cobalt halides or organic acid salts and alkyl aluminum chlorides, such as: cobalt chloride (CoCl2) / dichloroisobutylaluminum (Al(i-Bu)Cl2) / monochlorodiisobutylaluminum (Al(i-Bu)2Cl), cobalt isooctanoate (Co(oct)2) / (Al(i-Bu)Cl2) / (Al(i-Bu)2Cl), CoCl2 / Al(i-Bu)Cl2 or diethylaluminum chloride (AlEt2Cl), Co(oct)2 / AlEt2Cl / H2O or Co(oct)2 / AlEt2Cl / H2O / cyclooctadiene. These systems can prepare high-cis polybutadiene with a cis-1,4 structure content higher than 90%. See Goodrich-Gulf Chemicals, Inc. Polymerization process for aliphatic conjugated dienes, US3094514; Goodrich-Gulf Chemicals, Inc. Process of Polymerizing conjugated dienes with acobalt salt-hydrocarbyl aluminum compound catalyst, US3135725; Firestone Tire & Rubber Co. Catalytic production of polybutadiene high in 1,4-cis structure, CA716170; Goodrich-Gulf Chemicals, Inc. Water modification of hydrocarbylaluminum compounds employed in Ziegler catalysts used to produce stereoregulated polymerizations of monomeric diolefins, CA795860; Goodrich Company, Improved solvent system for butadiene-1,3 polymerization, CA1094248; Ube Industries, Inc. Method for preparing polybutadiene rubber and rubber compositions, CN101084265B.Using cobalt complex / alkylaluminum systems, such as cobalt chloride 2,6-bis[1-(iminophenyl)ethyl]pyridine / methylaluminoxane (MAO) system, bis(benzimidazol-2-yl)methylamine cobalt complex / MAO system, etc., high cis-polybutadiene products with cis-1,4 content greater than 95% can be obtained by adjusting the content of each component. See: Ai PF, Chen L, Jie SY, Li B G. Polymerization of 1,3-butadiene catalyzed by ion-pair cobalt complexes with (benzimidazolyl)pyridine alcohol ligands. J Mol Catal A-Chem, 2013, 380, 1-9; Cariou R, Chirinos J, Gibson VC, Jacobsen G, Tomov AK, Elsegood MR J. 1,3-butadiene polymerization by bis(benzimidazolyl)amine metal complexes: remarkable microstructural control and a protocol For in-reactor blending of trans-1,4-,cis-1,4- and cis-1,4-co-1,2-Vinylpolybutadiene. Macromolecules, 2009, 42: 1443-1444. High 1,4-structure content polyisoprene can also be prepared using cobalt complexes / alkylaluminum systems, such as the preparation of high 1,4-structure content polyisoprene using a cobalt 1,2-bis(phenyl)acenaphthene complex / alkylaluminum catalyst system. See Wang XX, Fan LL, Huang CB, Liang TL, Guo CY, Sun WH. Highly cis-1,4-selective polymerization of isoprene promoted by α-diimine cobalt(II)chlorides. J Polym Sci Part A: PolymChem, 2016, 54: 3609-3615.A cobalt compound / alkylaluminum / carbon disulfide catalyst system can be used to obtain 1,2-polybutadiene with a 1,2-structure content of over 90% and a melting point above 190℃. The crystallinity of 1,2-polybutadiene can be adjusted by adding nitrogen- or phosphine-containing compounds to the catalyst system, such as cobalt compound / phosphine-containing compound / triethylaluminum / H2O / cobalt isooctanoate / triethylaluminum / carbon disulfide / amine compound, cobalt isooctanoate / triethylaluminum / carbon disulfide / acetonitrile, etc. See Japan Synthetic Rubber Co., Ltd. Process for the catalytic preparation of 1,2-polybutadiene having a high percentage of vinyl configuration, US3498963; UBE, Industries Ltd. Method of producing 1,2-polybutadiene, US4153767; UBE, Industries Ltd. Process for the preparation of 1,2-polybutadiene, US3778424.

[0004] In summary, in existing technologies, when using cobalt carboxylate compounds and alkyl aluminum as the main catalyst and co-catalyst, respectively, butadiene polymerization cannot be initiated without the addition of water or carbon disulfide as a third component. Furthermore, with the addition of water or carbon disulfide as a third component, only polybutadiene with high cis-1,4-polybutadiene or polybutadiene with high 1,2-structure content can be obtained, making it difficult to adjust the microstructure content. Summary of the Invention

[0005] The purpose of this invention is to provide a cobalt-based catalytic polymerization system for conjugated dienes, with cobalt compounds as the main catalyst and organoaluminum as the co-catalyst, and its application.

[0006] Specifically, the present invention provides a conjugated diene coordination polymerization system, comprising a cobalt compound (A), an organoaluminum compound (B), a silicon-containing compound (C), a conjugated diene monomer (D), and a solvent (E).

[0007] According to a preferred embodiment of the present invention, the molar ratio of the cobalt compound (A) to the conjugated diene monomer (D) is (1 × 10⁻⁶). -6 ~6×10 -4 :1, preferably (5×10 -5 ~5×10 -4 ):1, more preferably (9×10 -4 ~3×10 -4):1; The molar ratio of the organoaluminum compound (B) to the conjugated diene monomer (D) is (6 × 10⁻⁶). -4 ~7×10 -3 ):1, preferably (8×10 -4 ~6×10 -3 ):1, more preferably (9×10 -4 ~5×10 -3 ):1; The mass ratio of the silicon-containing compound (C) to the conjugated diene monomer (D) is (0.1 × 10⁻⁶). -2 ~23×10 -2 ):1, preferably (0.3×10 -2 ~20×10 -2 ):1, more preferably (0.4×10 -2 ~16×10 -2 ):1; The mass-to-volume ratio of the conjugated diene monomer (D) to the monomer and solvent (D+E) is 40-560 g:1 L, preferably 80-500 g:1 L, and more preferably 100-450 g:1 L.

[0008] According to a preferred embodiment of the present invention, the cobalt compound (A) is selected from cobalt organic acid salts and / or cobalt acetylacetonate, preferably selected from at least one compound selected from diacetylacetonate cobalt, triacetylacetonate cobalt, cobalt naphthenate, cobalt neodecanoate, cobalt benzoate, cobalt stearate, cobalt octanoate, cobalt isooctanoate, cobalt oleate, and cobalt linoleate; more preferably at least one compound selected from cobalt naphthenate, cobalt octanoate, cobalt neodecanoate, and cobalt isooctanoate.

[0009] According to a preferred embodiment of the present invention, the organoaluminum compound (B) is of the general formula AlR 1 3 and / or general formula AlHR 2 Compound 2, R 1 and R 2 Each of the alkyl groups is independently C1-C6, preferably selected from ethyl, propyl, or butyl; the organoaluminum compound (B) is preferably selected from at least one compound selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, diethylaluminum hydride, dibutylaluminum hydride, and diisobutylaluminum hydride; more preferably selected from at least one compound selected from triethylaluminum, triisobutylaluminum, diethylaluminum hydride, dibutylaluminum hydride, and diisobutylaluminum hydride.

[0010] According to a preferred embodiment of the present invention, the silicon-containing compound (C) is selected from polysiloxanes and / or silicon dioxide.

[0011] Further, the polysiloxane is a silicone oil (linear polysiloxane), preferably selected from at least one compound selected from 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, hydroxy hydrogen silicone oil and cyanide silicone oil; more preferably selected from at least one compound selected from methyl silicone oil, ethyl silicone oil, methyl hydrogen silicone oil, ethyl hydrogen silicone oil and hydroxy hydrogen silicone oil.

[0012] Further, the silica is silica obtained by precipitation or gas phase method; preferably, the specific surface area of ​​the silica is 150-450 m². 2 / g, more preferably 175-350m 2 / g; the surface double bond content is preferably 0.01 to 300 mmol / kg, more preferably 0.05 to 260 mmol / kg.

[0013] According to a preferred embodiment of the present invention, the conjugated diene monomer (D) is selected from at least one of butadiene, isoprene, 2-methyl-1,3-pentadiene, 2,4-hexadiene, styrene and methylstyrene, preferably at least one of butadiene, isoprene, styrene and methylstyrene, more preferably at least one of butadiene, isoprene and styrene.

[0014] According to a preferred embodiment of the present invention, the solvent (E) is a hydrocarbon compound, preferably at least one of aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, more preferably at least one of butane, pentane, hexane, cyclohexane, heptane, octane, methylcyclohexane, benzene, toluene, xylene, and trimethylbenzene, and even more preferably at least one of butane, pentane, hexane, cyclohexane, and toluene. Since the catalyst is used in small quantities, it needs to be diluted with a solvent for convenient use; the solvent used is usually the same as the solvent in the polymerization reaction system.

[0015] The present invention also provides the application of the above-mentioned conjugated diene polymerization system in the in-situ preparation of conjugated diene polymer-based composites.

[0016] According to one embodiment of the present invention, the preparation of the conjugated diene polymer-based composite includes the following steps: contacting and mixing the cobalt compound (A), organoaluminum compound (B), silicon-containing compound (C), conjugated diene monomer (D), and solvent (E) to carry out a polymerization reaction; after the reaction is completed, precipitating and drying the polymerization product to obtain the conjugated diene polymer-based composite.

[0017] In this invention, the components of the catalyst are mixed with a conjugated diene monomer / olefin solvent solution in a specific order and at a specific temperature for reaction. The order of addition has a certain influence on the catalyst activity and catalytic effect. The mixing method is selected from any one of C-(A+E)-(D+E)-(B+E), (C+A+E)-(D+E)-(B+E), C-(D+E)-(A+E)-(B+E), C-(D+E)-(B+E)-(A+E), (D+E)-C-(A+E)-(B+E), (D+E)-C-(B+E)-(A+E), (D+E)-(A+E)-C-(B+E), and (D+E)-(A+E)-BC.

[0018] According to the preparation method provided by the present invention, preferably, the polymerization reaction temperature is -60℃ to 120℃, more preferably -30℃ to 110℃, and even more preferably 0℃ to 105℃; the reaction time is 30 min to 30 h, more preferably 1 h to 20 h, and even more preferably 30 min to 3 h. When the polymerization reaction temperature is low, the polymerization time can be extended; when the polymerization reaction temperature is high, the polymerization time can be shortened.

[0019] In the copolymerization process of this invention, all operations are carried out under inert gas protection, preferably under nitrogen protection. At the end of the polymerization reaction, water, alcohols, phenols, or other compounds can be used as terminators to terminate the reaction; auxiliaries such as carboxylic acids, amines, and esters may also be added to the terminator.

[0020] The coordination polymerization reaction can be carried out in a single polymerization reactor, a multi-polymerization reactor in series, or a tubular reactor, and can be operated in a batch polymerization or continuous polymerization mode.

[0021] The beneficial effects of the solution provided by this invention are as follows:

[0022] A cobalt-based catalytic polymerization system for conjugated dienes is provided, wherein a silicon-containing compound serves as both a catalyst component and participates in the polymerization reaction, effectively improving the catalytic activity of the polymerization reaction. In the in-situ prepared conjugated diene polymer-based composite, the microstructure content is adjusted within a certain range, wherein the content of cis-1,4-structure is 40%–70%, the content of 1,2-structure is 20%–50%, the content of trans-1,4-structure is 5%–20%, the mass content of SiO2 is 1%–25%, and the SiO2 is uniformly dispersed in the composite.

[0023] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0024] The above and other objects, features and advantages of the present invention will become more apparent from the more detailed description of exemplary embodiments of the invention in conjunction with the accompanying drawings.

[0025] Figure 1 The dispersion of silica in the composite of Example 3 is shown. Detailed Implementation

[0026] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0027] The characterization method involved in this invention:

[0028] (1) The infrared spectrum of the soluble fraction was determined using a Nicolet 6700 Fourier transform infrared spectrometer (FTIR) from Nicolet Corporation, with the scanning range set at 400–2000 cm⁻¹. -1 Calculate the microstructure content of the polymer.

[0029] (2) The dispersion of silica in the composite was observed using an Olympus-BX51 phase contrast microscope (PCM).

[0030] Example 1

[0031] Under nitrogen protection, 292 mg of modified nano-SiO2 (with a specific surface area of ​​339 m²) was added to a dry polymerization reactor. 2 SiO2 (with a surface double bond content of 0.5 mmol / kg) was reacted with a hexane solution of cobalt neodecanoate at 50 °C for 1 h. Butadiene / hexane solution and triisobutylaluminum were then added. This resulted in a SiO2 to monomer mass ratio of 1.5% and a cobalt to monomer molar ratio of 1 × 10⁻⁶. -4 :1, The molar ratio of aluminum to monomer is 1.0 × 10⁻⁶ -3 The monomer to (monomer + solvent) mass-to-volume ratio was 131 g:1 L. Polymerization was carried out at 50 °C for 3 h. The reaction was then terminated by adding a hexane solution containing 1 wt% octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate to the polymerization reactor. The product was precipitated with ethanol, washed clean, and dried in a vacuum oven at 40 °C to constant weight. A polybutadiene / silica composite was obtained with a yield of 60.6% and a catalyst activity of 3.27 × 10⁻⁶. 5 g product / mol Co.

[0032] In the obtained polybutadiene / silica composite, the polybutadiene content was 97.5% by mass, the silica content was 2.5% by mass, and they were uniformly dispersed in the composite. Furthermore, the polybutadiene structural units contained 54.8% cis-1,4-, 10.3% trans-1,4-, and 34.9% 1,2-.

[0033] Compared with Comparative Example 1, the catalyst activity was increased by 2.11 times, the catalyst cost was reduced, and the polymerization efficiency was significantly improved. In the polybutadiene structural unit, the content of cis-1,4 structure increased by 27.8 times, the content of 1,2- structure decreased by 56.3%, and the content of trans-1,4 structure decreased by 43.1%. The change in microstructure led to a change in the properties of the polymerization product, changing from the synthetic resin product of the Comparative Example to the synthetic rubber product of Example 1.

[0034] Example 2

[0035] The catalyst and polymerization process were the same as in Example 1, except that 389 mg of modified SiO2 was added to the dry polymerization reactor, making the mass ratio of SiO2 to monomer 2.0%. The post-treatment method was the same as in Example 1. A polybutadiene / silica composite was obtained with a yield of 89.3% and a catalyst activity of 4.82 × 10⁻⁶. 5 g product / mol Co.

[0036] In the obtained polybutadiene / silica composite, the mass content of polybutadiene was 97.8%, and the mass content of silica was 2.2%, both uniformly dispersed in the composite. The polybutadiene structural units contained 55.4% cis-1,4-, 10.7% trans-1,4-, and 33.9% 1,2-.

[0037] Compared with Comparative Example 1, the catalyst activity was increased by 3.11 times, the catalyst cost was reduced, and the polymerization efficiency was significantly improved. In the polybutadiene structural unit, the content of cis-1,4 structure increased by 28.2 times, the content of 1,2- structure decreased by 57.6%, and the content of trans-1,4 structure decreased by 46.2%. These changes in microstructure led to changes in the properties of the polymerization product, changing from the synthetic resin product of the Comparative Example to the synthetic rubber product of Example 2.

[0038] Example 3

[0039] The catalyst and polymerization process are the same as in Example 1, except that cobalt isooctanoate is used as the main catalyst, and 778 mg of modified nano-SiO2 (with a specific surface area of ​​293 m²) is added to the dry polymerization reactor. 2 / g, with a surface double bond content of 0.1mmol / kg), resulting in a SiO2 to monomer mass ratio of 15% and a cobalt to monomer molar ratio of 1×10.-4 :1, The molar ratio of aluminum to monomer is 1.5 × 10 -3 1. The post-processing method is the same as in Example 1. A polybutadiene / silica composite was obtained with a yield of 75.1% and a catalyst activity of 4.06 × 10⁻⁶. 5 gproduct / mol Co.

[0040] In the obtained polybutadiene / silica composite, the mass content of polybutadiene was 80.0%, and the mass content of silica was 20.0%, both uniformly dispersed in the composite without obvious agglomeration. Figure 1 As shown, the polybutadiene structural unit contains 60.6% cis-1,4-, 15.3% trans-1,4-, and 24.6% 1,2-.

[0041] Compared with Comparative Example 1, the catalyst activity was increased by 2.61 times, the catalyst cost was reduced, and the polymerization efficiency was significantly improved. In the polybutadiene structural unit, the content of cis-1,4 structure increased by 30.9 times, the content of 1,2- structure decreased by 69.2%, and the content of trans-1,4 structure decreased by 14.4%. These changes in microstructure led to changes in the properties of the polymerization product, changing from the synthetic resin product of the Comparative Example to the synthetic rubber product of Example 3.

[0042] Example 4

[0043] The catalyst and polymerization process were the same as in Example 1, except that cobalt compound A was cobalt isooctanoate and the monomer was isoprene. The amount of modified SiO2 added was 1.17 g, the mass ratio of silicon to monomer was 11.4%, and the molar ratio of cobalt to monomer was 2 × 10⁻⁶. -4 1. The molar ratio of aluminum to monomer is 4.5 × 10⁻⁶. -3 The monomer to (monomer + solvent) mass-to-volume ratio was 408 g: 1 L. Polymerization was carried out at 30°C for 2 hours. The post-treatment method was the same as in Example 1. A polyisoprene / silica composite was obtained with a yield of 95.1% and a catalyst activity of 3.28 × 10⁻⁶. 5 g product / mol Co.

[0044] In the obtained polybutadiene / silica composite, the mass content of polyisoprene was 88.0%, and the mass content of silica was 12.0%, both uniformly dispersed in the composite without obvious agglomeration. The content of cis-1,4- in the polyisoprene structural units was 53.7%, and the content of 3,4- was 46.3%.

[0045] Compared with Comparative Example 1, the catalyst activity was increased by 2.64 times, the catalyst cost was reduced, the polymerization efficiency was significantly improved, and rubber products were obtained.

[0046] Example 5

[0047] The catalyst and polymerization process are the same as in Example 1, except that 26 mg of nano-SiO2 (with a specific surface area of ​​293 m²) is added to the dry polymerization reactor. 2 A solution of cobalt neodecanoate (containing 0.1 mmol / kg of surface double bonds) and a hexane solution were mixed at 50 °C for 1 h, followed by the addition of a butadiene / hexane solution and a triisobutylaluminum solution. This resulted in a SiO2 to monomer mass ratio of 0.5% and a cobalt to monomer molar ratio of 1 × 10⁻⁶. -4 :1, The molar ratio of aluminum to monomer is 1.0 × 10⁻⁶ -3 Polymerization was carried out at 50°C for 3 hours. The post-treatment method was the same as in Example 1. A polybutadiene / silica composite was obtained with a yield of 30.5% and a catalyst activity of 1.64 × 10⁻⁶. 5 gproduct / mol Co.

[0048] In the obtained polybutadiene / silica composite, the mass content of polybutadiene is 98.4%, the mass content of silica is 1.6%, and they are uniformly dispersed in the composite; in addition, the content of cis-1,4 in the polybutadiene structural units is 62.0%, the content of trans-1,4 is 9.1%, and the content of 1,2- is 28.9%.

[0049] Compared with Comparative Example 1, the catalyst activity was increased by 1.06 times, the catalyst cost was reduced, the polymerization efficiency was significantly improved, and rubber products were obtained.

[0050] Example 6

[0051] The catalyst and polymerization process are the same as in Example 1, except that 52 mg of modified nano-SiO2 (with a specific surface area of ​​328 m²) is added to the dry polymerization reactor. 2 / g, with a surface double bond content of 250mmol / kg), resulting in a SiO2 to monomer mass ratio of 1wt%.

[0052] In the obtained polybutadiene / silica composite, the mass content of polybutadiene is 95.4%, the mass content of silica is 4.6%, and they are uniformly dispersed in the composite. In addition, the content of cis-1,4 in the polybutadiene structural units is 60.1%, the content of trans-1,4 is 12.0%, and the content of 1,2- is 27.9%.

[0053] Comparative Example 1

[0054] Under nitrogen protection, 40 mL of a hexane solution of butadiene was added to a dry polymerization reactor, followed by a hexane solution of cobalt neodecanoate, triisobutylaluminum, and a hexane solution of carbon disulfide. This resulted in a cobalt to monomer molar ratio of 2 × 10⁻⁶. -4 1. The molar ratio of aluminum to monomer is 4.5 × 10⁻⁶.-3 :1, The molar ratio of carbon disulfide to monomer is 2.5 × 10 -3 The monomer to (monomer + solvent) mass-to-volume ratio was 131 g:1 L. The system was then subjected to polymerization at 30°C for 3 hours, with post-treatment following the same method as in Example 1. The polybutadiene yield was 57.4%, and the catalyst activity was 1.55 × 10⁻⁶. 5 The polybutadiene obtained by applying g product / mol Co had a 1,2-structure content of 79.9%, a cis-1,4-structure content of 1.9%, and a trans-1,4-structure content of 18.1%. Due to the high content of the 1,2-structure and its syndiotactic structure, the polymer exhibits crystalline resin characteristics.

[0055] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A conjugated diene coordination polymerization system, comprising a cobalt compound (A), an organoaluminum compound (B), a silicon-containing compound (C), a conjugated diene monomer (D), and a solvent (E); The silicon-containing compound (C) is selected from polysiloxanes and / or silicon dioxide; The molar ratio of the cobalt compound (A) to the conjugated diene monomer (D) is (1 × 10⁻⁶). -6 ~6×10 -4 ):1; The molar ratio of the organoaluminum compound (B) to the conjugated diene monomer (D) is (6 × 10⁻⁶). -4 ~7×10 -3 ):1; The mass ratio of the silicon-containing compound (C) to the conjugated diene monomer (D) is (0.1 × 10⁻⁶). -2 ~23×10 -2 ):1; The mass-to-volume ratio of the conjugated diene monomer (D) to the monomer and solvent (D+E) is 40-560 g: 1 L.

2. The conjugated diene coordination polymerization system according to claim 1, wherein, The molar ratio of the cobalt compound (A) to the conjugated diene monomer (D) is (5 × 10⁻⁶). -5 ~5×10 -4 ):1; The molar ratio of the organoaluminum compound (B) to the conjugated diene monomer (D) is (8 × 10⁻⁶). -4 ~6×10 -3 ):1; The mass ratio of the silicon-containing compound (C) to the conjugated diene monomer (D) is (0.3 × 10⁻⁶). -2 ~20×10 -2 ):1; The mass-to-volume ratio of the conjugated diene monomer (D) to the monomer and solvent (D+E) is 80-500 g: 1 L.

3. The conjugated diene coordination polymerization system according to claim 2, wherein, The molar ratio of the cobalt compound (A) to the conjugated diene monomer (D) is (9 × 10⁻⁶). -5 ~3×10 -4 ):1; The molar ratio of the organoaluminum compound (B) to the conjugated diene monomer (D) is (9 × 10⁻⁶). -4 ~5×10 -3 ):1; The mass ratio of the silicon-containing compound (C) to the conjugated diene monomer (D) is (0.4 × 10⁻⁶). -2 ~16×10 -2 ):1; The mass-to-volume ratio of the conjugated diene monomer (D) to the monomer and solvent (D+E) is 100-450 g: 1 L.

4. The conjugated diene coordination polymerization system according to claim 1, wherein, The cobalt compound (A) is selected from cobalt organic acid salts and / or cobalt acetylacetonate.

5. The conjugated diene coordination polymerization system according to claim 4, wherein, The cobalt compound (A) is selected from at least one compound selected from diacetylacetonate cobalt, triacetylacetonate cobalt, naphthenate cobalt, neodecanoate cobalt, cobalt benzoate, cobalt stearate, cobalt octanoate, cobalt isooctanoate, cobalt oleate, and cobalt linoleate.

6. The conjugated diene coordination polymerization system according to claim 5, wherein, The cobalt compound (A) is selected from at least one compound selected from cobalt naphthenate, cobalt octanoate, cobalt neodecanoate and cobalt isooctanoate.

7. The conjugated diene coordination polymerization system according to claim 1, wherein, The organoaluminum compound (B) is of the general formula AlR 1 3 and / or general formula AlHR 2 Compound 2, R 1 and R 2 Each is an alkyl group that is independently C1-C6.

8. The conjugated diene coordination polymerization system according to claim 7, wherein, R 1 and R 2 Each is independently selected from ethyl, propyl, or butyl.

9. The conjugated diene coordination polymerization system according to claim 8, wherein, The organoaluminum compound (B) is selected from at least one compound selected from trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, diethylaluminum hydride, dibutylaluminum hydride, and diisobutylaluminum hydride.

10. The conjugated diene coordination polymerization system according to claim 9, wherein, The organoaluminum compound (B) is selected from at least one compound selected from triethylaluminum, triisobutylaluminum, diethylaluminum hydride, dibutylaluminum hydride, and diisobutylaluminum hydride.

11. The conjugated diene coordination polymerization system according to claim 1, wherein, The polysiloxane is silicone oil; The silicon dioxide is obtained by precipitation or gas phase method.

12. The conjugated diene coordination polymerization system according to claim 11, wherein, The polysiloxane is selected from at least one compound selected from 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, hydroxy hydrogen silicone oil, and cyanide silicone oil.

13. The conjugated diene coordination polymerization system according to claim 12, wherein, The polysiloxane is selected from at least one compound selected from methyl silicone oil, ethyl silicone oil, methyl hydrogen silicone oil, ethyl hydrogen silicone oil and hydroxyl hydrogen silicone oil.

14. The conjugated diene coordination polymerization system according to claim 11, wherein, The specific surface area of ​​the silicon dioxide is 150–450 m². 2 / g.

15. The conjugated diene coordination polymerization system according to claim 14, wherein, The specific surface area of ​​the silicon dioxide is 175–350 m². 2 / g.

16. The conjugated diene coordination polymerization system according to claim 11, wherein, The surface double bond content of the silica is 0.01–300 mmol / kg.

17. The conjugated diene coordination polymerization system according to claim 16, wherein, The surface double bond content of the silica is 0.05–260 mmol / kg.

18. The conjugated diene coordination polymerization system according to claim 1, wherein, The conjugated diene monomer (D) is selected from at least one of butadiene, isoprene, 2-methyl-1,3-pentadiene, 2,4-hexadiene, styrene, and methylstyrene.

19. The conjugated diene coordination polymerization system according to claim 18, wherein, The conjugated diene monomer (D) is selected from at least one compound selected from butadiene, isoprene, styrene and methylstyrene.

20. The conjugated diene coordination polymerization system according to claim 19, wherein, The conjugated diene monomer (D) is selected from at least one compound selected from butadiene, isoprene and styrene.

21. The conjugated diene coordination polymerization system according to claim 1, wherein, The solvent (E) is a hydrocarbon compound.

22. The conjugated diene coordination polymerization system according to claim 21, wherein, The solvent (E) is at least one of aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

23. The conjugated diene coordination polymerization system according to claim 22, wherein, The solvent (E) is selected from at least one of butane, pentane, hexane, cyclohexane, heptane, octane, methylcyclohexane, benzene, toluene, xylene, and trimethylbenzene.

24. The conjugated diene coordination polymerization system according to claim 23, wherein, The solvent (E) is selected from at least one of butane, pentane, hexane, cyclohexane and toluene.

25. The use of the conjugated diene coordination polymerization system according to any one of claims 1-24 in the in-situ preparation of conjugated diene polymer-based complexes.

26. The application according to claim 25, wherein, The preparation of the conjugated diene polymer-based composite includes the following steps: contacting and mixing the cobalt compound (A), organoaluminum compound (B), silicon-containing compound (C), conjugated diene monomer (D), and solvent (E) to carry out a polymerization reaction; after the reaction is completed, the polymerization product is precipitated and dried to obtain the conjugated diene polymer-based composite; the mixing method is selected from any one of C-(A+E)-(D+E)-(B+E), (C+A+E)-(D+E)-(B+E), C-(D+E)-(A+E)-(B+E), C-(D+E)-(B+E)-(A+E), (D+E)-C-(A+E)-(B+E), (D+E)-C-(B+E)-(A+E), (D+E)-(A+E)-C-(B+E), and (D+E)-(A+E)-BC.

27. The application according to claim 26, wherein, The polymerization reaction temperature is -60℃ to 120℃; the reaction time is 30 min to 30 h. All steps were performed under inert gas protection.

28. The application according to claim 27, wherein, The polymerization reaction temperature is -30℃ to 110℃; the reaction time is 1h to 20h.

29. The application according to claim 28, wherein, The polymerization reaction is carried out at a temperature of 0℃ to 105℃ and for a reaction time of 30 min to 3 h.

30. The application according to claim 27, wherein, All steps were performed under nitrogen protection.

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