A method for preparing a soluble cation-based borate and its use in iron-based catalyzed polymerization of conjugated dienes

Abstract

A preparation method of a soluble positive ion based borate and its application in iron-based catalytic conjugated diene polymerization. The present application belongs to the field of iron-based catalytic polymerization of conjugated dienes. The purpose of the present application is to provide the application of a soluble carbon and silicon positive ion based borate in the research of iron-based catalytic conjugated diene polymerization, which can realize high-efficiency polymerization of conjugated dienes in aliphatic solvents, and simultaneously provides a preparation method of a soluble carbon and silicon positive ion based borate, which provides more possibilities for the expansion of soluble borates. The borate system can realize high-activity polymerization of conjugated dienes, and the reaction yield is greater than or equal to 90%. The polymerization process is simple and suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of iron-catalyzed polymerization of conjugated dienes, specifically relating to a method for preparing soluble cation-based borates and their application in iron-catalyzed polymerization of conjugated dienes. Background Technology

[0002] Rubber is one of the most important strategic resources for a nation. Along with steel, coal, and oil, rubber is considered one of the four major industrial raw materials, with global demand exceeding 30 million tons per year, making it a cornerstone of modern civilization. my country's demand for rubber materials exceeds 10 million tons per year, with a market size exceeding one trillion yuan per year, impacting the national economy and people's livelihoods. While the demand for natural rubber is enormous, it faces geographical limitations, posing a serious national strategic security concern. Synthetic rubber has emerged as an effective solution to this problem, attracting considerable attention from researchers.

[0003] Currently, highly reactive borate systems, such as triphenylcarbium tetrafluoroborate ([Ph3C]), are commonly used in synthetic rubber research. + [B(C6F5)4] - Borates exhibit high activity in the polymerization of conjugated dienes by utilizing their alkylation and stabilizing effects on iron-containing active centers. However, the poor solubility of this catalytic system is a limiting problem for its industrial application. Therefore, developing a new borate system for the industrial application of iron-based catalytic polymerization of conjugated dienes is of great significance. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide an application of borates based on soluble carbon and silicon cations in the study of iron-catalyzed conjugated diene polymerization. This borate can achieve efficient polymerization of conjugated dienes in aliphatic solvents. At the same time, it provides a method for preparing borates based on soluble carbon and silicon cations, which provides more possibilities for the development of soluble borates.

[0005] The technical solution of the present invention is as follows:

[0006] One objective of this invention is to provide an application of soluble cation-based borates in iron-catalyzed conjugated diene polymerization. The soluble cation-based borates serve as a third component in an aliphatic hydrocarbon solvent to activate an iron-metal catalyst for conjugated diene polymerization. The general structural formula of the soluble cation-based borates is:

[0007] In the formula, X is C or Si, and R1, R2, and R3 are each independently selected from the following groups: hydrogen atom, phenyl, C1-C30 straight-chain or non-straight-chain alkyl, C1-C30 substituted straight-chain or substituted non-straight-chain alkyl, C7-C30 substituted aryl, and the total number of carbon atoms in R1, R2, and R3 is >10.

[0008] Further specifying, the soluble cation-based borate specifically comprises one of the following structures:

[0009]

[0010]

[0011] Further specifying, the aliphatic hydrocarbon solvent is one or more of n-hexane, cyclohexane, methylcyclohexane, petroleum ether, gasoline, and kerosene in any proportion.

[0012] Further specifying, the general structural formula of the iron metal catalyst is as follows: Where R1 and R2 are alkyl, alkoxy, nitrogen-containing or sulfur-containing substituents, and X is EHA. - or Naph - or acac - n is 2 or 3.

[0013] To further specify, the iron metal catalyst is specifically selected from one of the following structures:

[0014]

[0015] A second objective of this invention is to provide a method for preparing borates based on soluble positive ions as described in the above applications, wherein the preparation method is carried out according to the following steps:

[0016] S1: Pentafluorobromobenzene reacts with boron trichloride or boron tribromide in the presence of butyllithium to give tetra(pentafluorophenyl)lithium salt;

[0017] S2: The monochloride of carbon or silicon reacts with a tetra(pentafluorophenyl)lithium salt to give a borate based on a soluble positive ion.

[0018] The third objective of this invention is to provide an industrial production method for catalytic conjugated diene polymerization, the method comprising the following steps:

[0019] Conjugated diene, iron metal catalyst, borates and alkyl aluminum as described in the above applications are added to an aliphatic hydrocarbon solvent and subjected to coordination polymerization at 10℃-70℃ for 10 min-3 h. After the reaction is completed, the mixture is quenched, precipitated, washed and dried to obtain a conjugated diene rubber material.

[0020] Further specifying, the alkylaluminum is one or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum hydride in any proportion.

[0021] Further specifying, the conjugated diene is one or both of isoprene and butadiene.

[0022] Further specifying, the molar ratio of the conjugated diene to the iron element in the iron metal catalyst is (1000-30000):1, preferably 10000:1.

[0023] Further specified, the molar ratio of boron in the borate to iron in the iron metal catalyst is (0.1-20):1, preferably 1:1.

[0024] Further specifying, the molar ratio of aluminum in the alkylaluminum to iron in the iron metal catalyst is (10-100):1, preferably 40:1.

[0025] Further, coordination polymerization was carried out at 30°C for 2 hours.

[0026] The fourth objective of this invention is to provide a conjugated diene rubber material prepared by the above method, wherein the conjugated diene rubber material has a number-average molecular weight of 30,000-2,000,000 g / mol and a molecular weight distribution of 1.5-3.0, wherein the molar content of 3,4-structure is 60-80% and the molar content of 1,4-structure is 20-40%.

[0027] The fifth objective of this invention is to provide an application of the conjugated diene rubber material prepared by the above method in tire manufacturing.

[0028] The significant advantages of this invention compared to existing technologies are:

[0029] (1) This invention is based on the fact that soluble carbon and silicon cations in borate can activate iron metal catalysts in aliphatic solvents to achieve highly active polymerization of conjugated dienes, with a reaction yield of ≥99%. The polymerization process is simple and suitable for industrial production.

[0030] (2) The present invention is based on a simple preparation process of soluble carbon and silicon cations borates, which can achieve the preparation of soluble borates under relatively mild reaction conditions. Attached Figure Description

[0031] Figure 1 It is the polyisoprene prepared in Example 1. 1 H NMR spectrum;

[0032] Figure 2 This is the GPC spectrum of the polyisoprene prepared in Example 1. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0034] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0035] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0036] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range. In this specification and claims, range definitions may be combined and / or interchanged, unless otherwise stated, these ranges include all subranges contained therein.

[0037] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0038] According to the present invention, the polymerization reactions are all carried out under an inert atmosphere, such as one or more inert atmospheres such as nitrogen, helium, and argon.

[0039] Preparation of borates based on soluble positive ions

[0040] Example 1

[0041] The preparation method of soluble positive ion-based borates in this embodiment is carried out according to the following steps:

[0042] S1: Pentafluorobromobenzene (1.3 mL, 10 mmol, 4 equiv.) reacted with boron trichloride (0.22 mL, 2.5 mmol, 1 equiv.) in the presence of butyllithium (0.25 mL, 2.5 mmol, 1 equiv.) at -78 °C for 2 h to give tetra(pentafluorophenyl)lithium salt;

[0043] S2: 3,3',3”-tris(dodecyl)-triphenylchloromethane (7.9 g, 10 mmol, 1 equiv.) and tetra(pentafluorophenyl)lithium salt (6.7 g, 10 mmol, 1 equiv.) were reacted at 25 °C for 2 h to give a borate based on a soluble positive ion, abbreviated as borate A, with the following structure:

[0044]

[0045] Example 2

[0046] The preparation method of soluble positive ion-based borates in this embodiment is carried out according to the following steps:

[0047] S1: Pentafluorobromobenzene (1.3 mL, 10 mmol, 4 equiv.) reacted with boron trichloride (0.22 mL, 2.5 mmol, 1 equiv.) in the presence of butyllithium (0.25 mL, 2.5 mmol, 1 equiv.) at -78 °C for 2 h to give tetra(pentafluorophenyl)lithium salt;

[0048] S2: 3,3',3”-tridecyltriphenylchloromethane (6.9 g, 10 mmol, 1 equiv.) and tetra(pentafluorophenyl)lithium salt (6.7 g, 10 mmol, 1 equiv.) were reacted at 25 °C for 2 h to give a borate based on a soluble positive ion, abbreviated as borate B, with the following structure:

[0049]

[0050] Example 3

[0051] The preparation method of soluble positive ion-based borates in this embodiment is carried out according to the following steps:

[0052] S1: Pentafluorobromobenzene (1.3 mL, 10 mmol, 4 equiv.) reacted with boron trichloride (0.22 mL, 2.5 mmol, 1 equiv.) in the presence of butyllithium (0.25 mL, 2.5 mmol, 1 equiv.) at -78 °C for 2 h to give tetra(pentafluorophenyl)lithium salt;

[0053] S2: 2,2',2”--tris(dodecyl)triphenylchloromethane (7.9 g, 10 mmol, 1 equiv.) and tetra(pentafluorophenyl)lithium salt (6.7 g, 10 mmol, 1 equiv.) were reacted at 25 °C for 2 h to give a borate based on a soluble positive ion, abbreviated as borate C, with the following structure:

[0054]

[0055] Example 4

[0056] The preparation method of soluble positive ion-based borates in this embodiment is carried out according to the following steps:

[0057] S1: Pentafluorobromobenzene (1.3 mL, 10 mmol, 4 equiv.) reacted with boron trichloride (0.22 mL, 2.5 mmol, 1 equiv.) in the presence of butyllithium (0.25 mL, 2.5 mmol, 1 equiv.) at -78 °C for 2 h to give tetra(pentafluorophenyl)lithium salt;

[0058] S2: 3,3',3”-trihexyltriphenylchloromethane (5.4 g, 10 mmol, 1 equiv.) and tetra(pentafluorophenyl)lithium salt (6.7 g, 10 mmol, 1 equiv.) were reacted at 25 °C for 2 h to give a borate based on a soluble positive ion, abbreviated as borate D, with the following structure:

[0059]

[0060] Example 5

[0061] The preparation method of soluble positive ion-based borates in this embodiment is carried out according to the following steps:

[0062] S1: Pentafluorobromobenzene (1.3 mL, 10 mmol, 4 equiv.) reacted with boron trichloride (0.22 mL, 2.5 mmol, 1 equiv.) in the presence of butyllithium (0.25 mL, 2.5 mmol, 1 equiv.) at -78 °C for 2 h to give tetra(pentafluorophenyl)lithium salt;

[0063] S2: Octadecyldimethylchlorosilane (3.5 g, 10 mmol, 1 equiv.) and tetra(pentafluorophenyl)lithium salt (6.7 g, 10 mmol, 1 equiv.) were reacted at 25 °C for 2 h to give a borate based on a soluble positive ion, abbreviated as borate E, with the following structure:

[0064]

[0065] Example 6

[0066] The preparation method of soluble positive ion-based borates in this embodiment is carried out according to the following steps:

[0067] S1: Pentafluorobromobenzene (1.3 mL, 10 mmol, 4 equiv.) reacted with boron trichloride (0.22 mL, 2.5 mmol, 1 equiv.) in the presence of butyllithium (0.25 mL, 2.5 mmol, 1 equiv.) at -78 °C for 2 h to give tetra(pentafluorophenyl)lithium salt;

[0068] S2: Trihexylchlorosilane (3.2 g, 10 mmol, 1 equiv.) and tetra(pentafluorophenyl)lithium salt (6.7 g, 10 mmol, 1 equiv.) were reacted at 25 °C for 2 h to give a borate based on a soluble positive ion, abbreviated as borate F, with the following structure:

[0069]

[0070] Industrial production methods in catalytic conjugated diene polymerization

[0071] Example 7

[0072] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0073] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0074] Results: Yield: >99%, Number-average molecular weight (M) n ): 148×105 g / mol, molecular weight distribution (PDI): 2.0. Molar content of different structures: 32% for 1,4-structure and 68% for 3,4-structure.

[0075] Example 8

[0076] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0077] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate C (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0078] Results: Yield: >99%, Number-average molecular weight (M) n ): 13.2×10 5 g / mol, molecular weight distribution (PDI): 2.3. Molar content of different structures: 1,4-structure molar content is 28%, 3,4-structure molar content is 72%.

[0079] Example 9

[0080] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0081] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate B (10.4 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0082] Results: Yield: >99%, Number-average molecular weight (M) n ): 14.7×10 5g / mol, molecular weight distribution (PDI): 2.2. Molar content of different structures: 30% for the 1,4-structure and 70% for the 3,4-structure.

[0083] Example 10

[0084] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0085] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate D (10.3 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0086] Results: Yield: >99%, Number-average molecular weight (M) n ): 10.3×10 5 g / mol, molecular weight distribution (PDI): 2.1. Molar content of different structures: 1,4-structure molar content is 27%, 3,4-structure molar content is 73%.

[0087] Example 11

[0088] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0089] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate E (12.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0090] Results: Yield: >99%, Number-average molecular weight (M) n ): 13.7×10 5g / mol, molecular weight distribution (PDI): 2.5. Molar content of different structures: 1,4-structure molar content is 31%, 3,4-structure molar content is 69%.

[0091] Example 12

[0092] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0093] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate F (10.0 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0094] Results: Yield: >99%, Number-average molecular weight (M) n ): 9.5×10 5 g / mol, molecular weight distribution (PDI): 2.5. Molar content of different structures: 30% for 1,4-structure and 70% for 3,4-structure.

[0095] Example 13

[0096] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0097] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (3.2 mg, 3 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0098] Results: Yield: >99%, Number-average molecular weight (M) n ): 7.9×10 5g / mol, molecular weight distribution (PDI): 2.3. Molar content of different structures: 1,4-structure molar content is 27%, 3,4-structure molar content is 73%.

[0099] Example 14

[0100] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0101] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (1.1 mg, 1 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0102] Results: Yield: 99%, Number-average molecular weight (M) n ): 5.2×10 5 g / mol, molecular weight distribution (PDI): 2.5. Molar content of different structures: 1,4-structure molar content is 26%, 3,4-structure molar content is 74%.

[0103] Example 15

[0104] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0105] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 40 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0106] Results: Yield: >99%, Number-average molecular weight (M) n ): 6.9×10 5g / mol, molecular weight distribution (PDI): 2.2. Molar content of different structures: 30% for the 1,4-structure and 70% for the 3,4-structure.

[0107] Example 16

[0108] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0109] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 50 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0110] Results: Yield: >99%, Number-average molecular weight (M) n ): 5.1×10 5 g / mol, molecular weight distribution (PDI): 2.0. Molar content of different structures: 1,4-structure molar content is 31%, 3,4-structure molar content is 69%.

[0111] Example 17

[0112] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0113] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triethylaluminum (45.6 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0114] Results: Yield: >99%, Number-average molecular weight (M) n ): 6.6×10 5g / mol, molecular weight distribution (PDI): 2.4. Molar content of different structures: 1,4-structure molar content is 29%, 3,4-structure molar content is 71%.

[0115] Example 18

[0116] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0117] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10.2 g, 150.0 mmol), triethylaluminum (45.6 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0118] Results: Yield: >99%, Number-average molecular weight (M) n ): 10.6×10 5 g / mol, molecular weight distribution (PDI): 2.2. Molar content of different structures: 1,4-structure molar content is 26%, 3,4-structure molar content is 74%.

[0119] Example 19

[0120] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0121] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex II (6.4 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0122] Results: Yield: >99%, Number-average molecular weight (M) n ): 17.1×10 5g / mol, molecular weight distribution (PDI): 2.3. Molar content of different structures: 30% for the 1,4-structure and 70% for the 3,4-structure.

[0123] Example 20

[0124] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0125] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex V (5.5 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0126] Results: Yield: 99%, Number-average molecular weight (M) n ): 8.1×10 5 g / mol, molecular weight distribution (PDI): 2.5. Molar content of different structures: 1,4-structure molar content is 29%, 3,4-structure molar content is 71%.

[0127] Example 21

[0128] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0129] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex VI (5.8 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0130] Results: Yield: 99%, Number-average molecular weight (M) n ): 9.3×10 5g / mol, molecular weight distribution (PDI): 2.5. Molar content of different structures: 30% for 1,4-structure and 70% for 3,4-structure.

[0131] Example 22

[0132] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0133] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex IX (5.3 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polyisoprene.

[0134] Results: Yield: 99%, Number-average molecular weight (M) n ): 13.9×10 5 g / mol, molecular weight distribution (PDI): 2.4. Molar content of different structures: 1,4-structure molar content is 31%, 3,4-structure molar content is 69%.

[0135] Example 23

[0136] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0137] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex X (5.1 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0138] Results: Yield: >99%, Number-average molecular weight (M) n ): 10.1×10 5g / mol, molecular weight distribution (PDI): 2.3. Molar content of different structures: 30% for the 1,4-structure and 70% for the 3,4-structure.

[0139] Example 24

[0140] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0141] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (6.8 g, 100.0 mmol), triisobutylaluminum (39.6 mg, 0.2 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was dried under vacuum at 40 °C to constant weight to obtain polyisoprene.

[0142] Results: Yield: 99%, Number-average molecular weight (M) n ): 15.7×10 5 g / mol, molecular weight distribution (PDI): 2.2. Molar content of different structures: 1,4-structure molar content is 29%, 3,4-structure molar content is 71%.

[0143] Example 25

[0144] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0145] Under an argon atmosphere, anhydrous cyclohexane (100 mL), butadiene (5.4 g, 100 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added, and the reaction was terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol, and the resulting polymer was vacuum dried at 40 °C to constant weight to obtain polybutadiene.

[0146] Results: Yield: >99%, Number-average molecular weight (M) n ): 8.3×10 5g / mol, molecular weight distribution (PDI): 2.4. Molar content of different structures: 1,4-structure molar content is 33%, 1,2-structure molar content is 67%.

[0147] Example 26

[0148] The industrial production method for catalytic conjugated diene polymerization in this embodiment follows these steps:

[0149] Under an argon atmosphere, anhydrous cyclohexane (100 mL), butadiene (1.6 g, 30 mmol), isoprene (4.8 g, 70 mmol), triisobutylaluminum (79.3 mg, 0.4 mmol), iron metal complex I (6.7 mg, 10 μmol), and borate A (10.5 mg, 10 μmol) were added to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. Then, 4 mL of a 1% (w / w) ethanol solution of 2,6-di-tert-butyl-4-methylphenol was added. The reaction was then terminated with an acidified methanol quencher (V(methanol):V(hydrochloric acid) = 50:1). The polymer was washed three times with ethanol and dried under vacuum at 40 °C to constant weight to obtain the isoprene / butadiene copolymer.

[0150] Results: Yield: >99%, Number-average molecular weight (M) n ): 8.2×10 5 g / mol, molecular weight distribution (PDI): 2.4. Molar content of different structures in polyisoprene: 1,4-structure molar content is 25%, 3,4-structure molar content is 75%. Molar content of different structures in polybutadiene: 1,4-structure molar content is 34%, 1,2-structure molar content is 66%.

[0151] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An industrial production method for catalytic conjugated diene polymerization, characterized in that, The method is performed according to the following steps: Conjugated diene, an iron metal catalyst, a soluble cation-based borate, and alkyl aluminum were added to an aliphatic hydrocarbon solvent and subjected to coordination polymerization at 10℃-70℃ for 10 min-3 h. After the reaction was completed, the mixture was quenched, precipitated, washed, and dried to obtain a conjugated diene rubber material. The soluble cation-based borate specifically has one of the following structures: The general structural formula of the iron metal catalyst is: or Where R1 and R2 are alkyl, alkoxy, nitrogen-containing or sulfur-containing substituents, and X is EHA. - or Naph - or acac - n is 2 or 3.

2. The method according to claim 1, characterized in that, The aliphatic hydrocarbon solvent is one or a mixture of several of the following: n-hexane, cyclohexane, methylcyclohexane, petroleum ether, gasoline, and kerosene.

3. The method according to claim 1, characterized in that, The iron metal catalyst is specifically selected from one of the following structures: 。 4. The method according to claim 1, characterized in that, The preparation method of borates based on soluble positive ions is carried out according to the following steps: S1: Pentafluorobromobenzene reacts with boron trichloride or boron tribromide in the presence of butyllithium to give tetra(pentafluorophenyl)lithium salt; S2: The monochloride of silicon reacts with the tetra(pentafluorophenyl)lithium salt to give a borate based on a soluble positive ion.

5. The method according to claim 1, characterized in that, Alkyl aluminum is one or a mixture of several of the following: trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, diethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum hydride.

6. The method according to claim 1, characterized in that, The conjugated diene is one or both of isoprene and butadiene.

7. The method according to claim 1, characterized in that, The molar ratio of conjugated diene to iron in iron metal catalyst is (1000-30000):1; the molar ratio of boron in borate to iron in iron metal catalyst is (0.1-20):1; and the molar ratio of aluminum in alkylaluminum to iron in iron metal catalyst is (10-100):

1.

8. The method according to claim 7, characterized in that, The molar ratio of conjugated diene to iron in the iron metal catalyst is 10000:1, the molar ratio of boron in borates to iron in the iron metal catalyst is 1:1, and the molar ratio of aluminum in alkylaluminum to iron in the iron metal catalyst is 40:

1.

9. The method according to claim 1, characterized in that, Coordination polymerization was carried out at 30 °C for 2 h.

10. The conjugated diene rubber material prepared by the method according to any one of claims 1-9, characterized in that, Its number-average molecular weight is 30,000-2,000,000 g / mol, and its molecular weight distribution is 1.5-3.

0. The molar content of the 3,4-structure is 60-80%, and the molar content of the 1,4-structure is 20-40%.

11. The use of the conjugated diene rubber material obtained by the method of any one of claims 1-9 in tire manufacturing.

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