Phosphonium-based borate / phosphate salts, methods of making and use in iron-based catalyzed conjugated diene polymerization

Abstract

The application relates to a borate / phosphate based on phosphonium cation and a preparation method thereof and application of the borate / phosphate based on phosphonium cation in iron-based catalytic conjugated diene polymerization. The application belongs to the field of iron-based catalytic olefin polymerization. The purpose of the application is to develop a new type of cocatalyst system which has mild reaction conditions, simple operation, low cost, good polymerization regulation effect and is beneficial to industrial production. The application provides the borate / phosphate based on phosphonium cation and a preparation method thereof, provides more selection and development direction of cocatalysts for polymerization of olefin monomers, simultaneously provides application of the borate / phosphate based on phosphonium cation in catalytic conjugated diene polymerization, and the borate / phosphate based on phosphonium cation can realize efficient and controllable polymerization of petroleum-based conjugated diene and bio-based terpene. The preparation process of the borate / phosphate based on phosphonium cation is simple, the production cost is low, the borate / phosphate based on phosphonium cation has high activity, and the borate / phosphate based on phosphonium cation meets the demand of batch industrial production.

Description

Technical Field

[0001] This invention belongs to the field of iron-based catalytic polymerization, specifically relating to a phosphate / borate based on phosphocations, its preparation method, and its application in iron-based catalytic conjugated diene polymerization. Background Technology

[0002] With the ever-increasing demand for rubber materials, the current annual production of natural rubber is clearly insufficient to meet the growing demand. To alleviate the pressure on natural rubber production capacity and effectively protect biodiversity, synthetic rubber has become the only viable option.

[0003] Methylaluminoxane (MAO) is one of the earliest and most widely used cocatalysts in synthetic rubber. However, the structure of MAO is somewhat uncertain. Researchers hope to find cocatalyst systems with well-defined molecular structures to prepare synthetic rubber, so that the final polymerization product can be verified on a valid theoretical basis. Under this premise, highly active borate cocatalyst systems with well-defined molecular structures have begun to be studied and applied. However, the preparation conditions of existing borate cocatalysts are harsh, the reaction process is complex, and the production cost is high. The borate salts obtained cannot effectively and comprehensively control the polymerization process, and often cause sticking to the reactor due to the high molecular weight of the product. These are all unfavorable for large-scale industrial production. Therefore, developing a new cocatalyst system with mild reaction conditions, simple operation, low cost, good polymerization control effect, and conducive to industrial production has extremely high scientific research value and industrial application value. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a phosphate / borate based on phosphonocations and its preparation method, which provides more choices and development directions for the polymerization of olefins and terpene monomers. At the same time, it provides an application of phosphate / borate based on phosphonocations in iron-based catalytic polymerization research. This phosphate / borate can achieve efficient and controllable homopolymerization or random copolymerization of conjugated dienes and bio-based terpenes.

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

[0006] One objective of this invention is to provide a phosphonocation-based borate / phosphate, wherein the general structural formula of the phosphonocation-based borate / phosphate is:

[0007]

[0008] In the formula, X is F, Cl or Br, and R1, R2, R3, R4, R5 and R6 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 of R1, R2, R3 or R4, R5 and R6 is ≥10.

[0009] Preferably, the phosphate-based borate is selected from one of formulas B1 to B13:

[0010]

[0011]

[0012] Phosphophosphates based on phosphonates are selected from one of formulas P1 to P9:

[0013]

[0014] A second objective of this invention is to provide a method for preparing the above-mentioned phosphate-based borate / phosphate, the preparation method comprising the following steps:

[0015] S1: Dissolve the corresponding organophosphorus compound in a suitable organic solvent, add an equimolar amount of hydrochloric acid aqueous solution, and stir for a certain period of time;

[0016] S2: Subsequently, an equimolar amount of aqueous haloborate or hexafluorophosphate solution was added and stirred for a certain period of time. The organic phase was then separated, and the organic solvent was removed by rotary evaporation to obtain borate / phosphate based on phosphocation.

[0017] Preferably, the general structural formula of the organophosphorus compound is:

[0018]

[0019] In the formula, R1, R2, R3, R4, R5, and R6 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, R3 or R4, R5, and R6 is ≥10;

[0020] Preferably, the haloborate is one or more of tetrafluoroboric acid, sodium tetrafluoroborate, tetrachloroboric acid, sodium tetrachloroborate, tetrabromoboric acid, or sodium tetrabromoborate.

[0021] Preferably, the organic solvent is one or more selected from n-hexane, cyclohexane, dichloromethane, diethyl ether, toluene, ethylbenzene, and THF.

[0022] Preferably, the molar ratio of the organophosphorus compound to hydrochloric acid is (1-3):1. More preferably, the molar ratio of the organophosphorus compound to hydrochloric acid is 1:1.

[0023] Preferably, the molar ratio of the haloborate or hexafluorophosphate to the organophosphorus compound is (1-3):1. More preferably, the molar ratio of the haloborate or hexafluorophosphate to the organophosphorus compound is 1:1.

[0024] Preferably, the stirring time for adding hydrochloric acid in step S1 is >10 min. More preferably, the stirring time for adding hydrochloric acid in step S1 is >20 min.

[0025] Preferably, the reaction temperature in step S2 is 0–50°C, and the reaction time is >10 min. More preferably, the reaction temperature in step S2 is 25°C, and the reaction time is 20 min.

[0026] A third objective of this invention is to provide an application of the above-mentioned phosphate-based borate / phosphate as a third component in the polymerization of conjugated dienes catalyzed by activated iron catalysts.

[0027] The polymerization method steps are as follows:

[0028] Under anhydrous and oxygen-free conditions, solvent, conjugated diene monomer, alkyl aluminum, iron catalyst, and the above-mentioned phosphate-based borate / phosphate were added to the reactor. The polymerization reaction was carried out by stirring at 0–100°C for 10–120 min. After the reaction was completed, quenching agent and anti-aging agent were added. After washing, the product was vacuum dried to constant weight to obtain the conjugated diene polymer.

[0029] Preferably, the general structural formula of the iron catalyst is:

[0030]

[0031] Wherein, R7 and R8 are alkyl, alkoxy, nitrogen-containing or sulfur-containing substituents, and X is EHA-, NDA- or acac-, wherein EHA- is NDA - for acac- for n is 2 or 3.

[0032] More preferably, the iron catalyst has one of the following structures:

[0033]

[0034] Preferably, the alkylaluminum is one or more selected from diethylaluminum chloride, diethylaluminum chloride, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, and diisobutylaluminum hydride;

[0035] The conjugated diene is selected from one or more of petroleum-based conjugated dienes and bio-based terpenes.

[0036] More preferably, the petroleum-based conjugated diene is at least one of 1,3-butadiene and isoprene.

[0037] More preferably, the bio-based terpene is one or more of α-myrcene, β-myrcene, α-farnesene, and β-farnesene. Most preferably, the bio-based terpene is β-myrcene or β-farnesene.

[0038] Preferably, the volume ratio of solvent to monomer is (1-15):1, more preferably, the volume ratio of solvent to monomer is (3-10):1.

[0039] Preferably, the molar ratio of the monomer to the iron element in the iron catalyst is (100-50000):1, more preferably, the molar ratio of the monomer to the iron catalyst is (1000-25000):1.

[0040] Preferably, the molar ratio of boron or phosphorus in the phosphate-based borate / phosphate to iron in the iron catalyst is (0.1-20):1. More preferably, the molar ratio of boron or phosphorus in the phosphate-based borate / phosphate to iron in the iron catalyst is (0.1-5):1.

[0041] Preferably, the molar ratio of aluminum in the alkylaluminum to iron in the iron catalyst is (10-100):1; more preferably, the molar ratio of aluminum in the alkylaluminum to iron in the iron catalyst is (20-40):1.

[0042] Preferably, the reaction temperature is 0–50°C and the reaction time is 30–120 min.

[0043] The fourth objective of this invention is to provide a conjugated diene polymer prepared by the above-mentioned application method, wherein the conjugated diene polymer has a number-average molecular weight of 200,000 to 700,000 g / mol, a molecular weight distribution of 1.5 to 5.0, a molar content of 3,4-structure in the petroleum-based conjugated diene polymer unit of 50 to 90% and / or a molar content of 1,2-structure of 50 to 70%, a molar content of 3,4-structure in the bio-based terpene polymer unit of 40 to 70%, and a glass transition temperature range of -80°C to 10°C.

[0044] Preferably, the conjugated diene polymer has a molecular weight distribution of 2.5 to 2.9, the molar content of 3,4-structure in the petroleum-based conjugated diene polymer unit is 63 to 79% and / or the molar content of 1,2-structure is 63 to 66%, the molar content of 3,4-structure in the bio-based terpene polymer unit is 53 to 58%, and the glass transition temperature range is -70°C to -8°C.

[0045] The fifth objective of this invention is to provide a vulcanization method for the above-mentioned conjugated diene polymer, wherein the method includes:

[0046] Weigh out 100 parts of conjugated diene polymer, 1-60 parts of carbon black, 10-100 parts of silica, 1-3 parts of vulcanizing accelerator, 0.1-12 parts of vulcanizing agent, 1-10 parts of stearic acid and 1-10 parts of zinc oxide by mass, mix and knead.

[0047] Preferably, the carbon black is one or more of N110, N234, N324, and N330, the vulcanizing accelerator is one or more of NS, NOBS, and TT, and the vulcanizing agent is sulfur.

[0048] The sixth objective of this invention is to provide a vulcanized rubber prepared by the above method, wherein the vulcanized rubber has a tensile strength >16MPa, an elongation at break >300%, a stress at 300% constant elongation >6MPa, a resilience of 20-35%, and, according to DMA test results, a damping temperature range above 30°C when tanδ >0.3.

[0049] Preferably, the vulcanized rubber has a tensile strength >18MPa, an elongation at break >400%, a stress at 300% constant elongation >8MPa, a resilience of 24-29%, and a damping temperature range of 38℃ when tanδ >0.3, according to DMA test results.

[0050] The seventh objective of this invention is to provide an application of the vulcanized rubber prepared by the above method in tire manufacturing, noise reduction and damping, and shock absorption.

[0051] The advantages of this invention compared to existing technologies are:

[0052] (1) The phosphate cation borate / phosphate provided by this invention can be prepared in large quantities under simple and mild reaction conditions, which greatly reduces the overall industrial production cost. The purchase price of traditional borates such as triphenylcarbium tetra(pentafluorophenyl) borate is about RMB30 / g. Under the preparation method proposed in this invention, the production cost of the new borate / phosphate can be reduced to RMB2.5 / g, which greatly saves the cost of borate preparation and subsequent polymerization production.

[0053] (2) The catalytic system provided by the present invention has high activity. When the amount of borate / phosphate added is only 0.1 equivalent, the polymerization conversion rate can still be guaranteed to reach more than 99%. At the same time, the monomer can be completely converted under high monomer concentration, thus achieving the purpose of cost reduction and efficiency improvement in industrial production.

[0054] (3) The catalytic polymerization system provided by the present invention has a better polymerization control effect, which is more conducive to obtaining polymer products with a lower molecular weight than before. The reduction in molecular weight is conducive to improving the processing performance of the product in the later stage, which meets the needs of mass industrial production. Attached Figure Description

[0055] Figure 1 The isoprene homopolymer obtained in Example 23 1 H NMR spectrum;

[0056] Figure 2 The GPC spectrum of the isoprene homopolymer obtained in Example 23 is shown below.

[0057] Figure 3 The image shows the DSC spectrum of the isoprene homopolymer obtained in Example 23. Detailed Implementation

[0058] 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.

[0059] 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.

[0060] 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.

[0061] The test method for the damping temperature range in the following embodiments is as follows: the product test heating rate is 1℃ / min, the frequency is 1Hz, the strain is 0.3%, and the sample measurement size is 1×5×20mm.

[0062] Preparation examples of phosphate cation borate

[0063] Example 1: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0064] S1: Dissolve di-tert-butyl(phenyl)phosphine (3.35 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0065] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B1, with the following structure:

[0066]

[0067] Example 2: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0068] S1: Dissolve trihexylphosphine (4.83 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL) and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0069] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B2, with the following structure:

[0070]

[0071] Example 3: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0072] S1: Dissolve tri-tert-butylphosphine (3.3 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0073] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B3, with the following structure:

[0074]

[0075] Example 4: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0076] S1: Dissolve triphenylphosphine oxide (3.9 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0077] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B4, with the following structure:

[0078]

[0079] Example 5: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0080] S1: Dissolve tert-butylphosphine (3.1 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL) and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0081] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B5, with the following structure:

[0082]

[0083] Example 6: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0084] S1: Dissolve tricyclohexylphosphine (4.2 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0085] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphocation-based borate, abbreviated as borate B6, with the following structure:

[0086]

[0087] Example 7: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0088] S1: Dissolve 8.7 g, 14 mmol, 1 equiv. of dihexadecanyl(phenyl)phosphine in 50 mL of dichloromethane and add 2.4 mL, 14 mmol, 1 equiv. of 18% wt hydrochloric acid aqueous solution and stir for 20 min.

[0089] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B7, with the following structure:

[0090]

[0091] Example 8: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0092] S1: Dissolve tricyclohexylphosphide (4.3 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0093] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphocation-based borate, abbreviated as borate B8, with the following structure:

[0094]

[0095] Example 9: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0096] S1: Dissolve tert-butyldicyclohexylphosphide (3.8 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0097] S2: Tetrafluoroboric acid (2 mL, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphocation-based borate, abbreviated as borate B9, with the following structure:

[0098]

[0099] Example 10: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0100] S1: Dissolve tricyclohexylphosphine (4.2 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0101] S2: Tetrachloroboric acid (2.2 g, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B10, with the following structure:

[0102]

[0103] Example 11: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0104] S1: Dissolve trioctylphosphine (6.25 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL) and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0105] S2: Tetrachloroboric acid (2.2 g, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate-based borate, abbreviated as borate B11, with the following structure:

[0106]

[0107] Example 12: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0108] S1: Dissolve tert-butyldicyclohexylphosphide (3.8 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0109] S2: Tetrabromoboric acid (4.6 g, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphocation, abbreviated as borate B12, with the following structure:

[0110]

[0111] Example 13: The preparation method of phosphoborate based on phosphate ions in this example is as follows:

[0112] S1: Dissolve triphenylphosphine oxide (3.9 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0113] S2: Tetrabromoboric acid (4.6 g, 14 mmol, 1 equiv., 48 vol%) was then added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphocation, abbreviated as borate B13, with the following structure:

[0114]

[0115] Example 14: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0116] S1: Dissolve tricyclohexylphosphide (4.3 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0117] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus cation, abbreviated as phosphate P1, with the following structure:

[0118]

[0119] Example 15: The preparation method of phosphate based on phosphorus ions in this example is as follows:

[0120] S1: Dissolve trihexylphosphine (4.83 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL) and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0121] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus ion, abbreviated as phosphate P2, with the following structure:

[0122]

[0123] Example 16: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0124] S1: Dissolve tert-butyldicyclohexylphosphide (3.8 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0125] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus ion, abbreviated as phosphate P3, with the following structure:

[0126]

[0127] Example 17: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0128] S1: Dissolve tri-tert-butylphosphine (3.3 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0129] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus cation, abbreviated as phosphate P4, with the following structure:

[0130]

[0131] Example 18: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0132] S1: Dissolve tri-tert-butylphosphine (3.1 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0133] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus ion, abbreviated as phosphate P5, with the following structure:

[0134]

[0135] Example 19: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0136] S1: Dissolve tricyclohexylphosphine (4.2 g, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0137] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus cation, abbreviated as phosphate P6, with the following structure:

[0138]

[0139] Example 20: The preparation method of phosphate based on phosphorus cations in this example is as follows:

[0140] S1: Dissolve 3.9 g, 14 mmol, 1 equiv. of benzoxylphosphine in 50 mL of dichloromethane and add 2.4 mL, 14 mmol, 1 equiv. of 18% wt hydrochloric acid aqueous solution and stir for 20 min.

[0141] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphonocation, abbreviated as phosphate P7, with the following structure:

[0142]

[0143] Example 21: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0144] S1: Dissolve 8.7 g, 14 mmol, 1 equiv. of dihexadecanyl(phenyl)phosphine in 50 mL of dichloromethane and add 2.4 mL, 14 mmol, 1 equiv. of 18% wt hydrochloric acid aqueous solution and stir for 20 min.

[0145] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphorus cation, abbreviated as phosphate P8, with the following structure:

[0146]

[0147] Example 22: The preparation method of phosphorus cation-based phosphate in this example is as follows:

[0148] S1: Dissolve di-tert-butyl(phenyl)phosphine (3.35 mL, 14 mmol, 1 equiv.) in dichloromethane (50 mL), and add 18% wt hydrochloric acid aqueous solution (2.4 mL, 14 mmol, 1 equiv.), and stir for 20 min;

[0149] S2: Subsequently, hexafluorophosphate (0.4 mL, 14 mmol, 1 equiv., 70 vol%) was added and the mixture was stirred at 25 °C for 20 min. The organic phase was separated, and the organic solvent was removed by rotary evaporation to obtain a phosphate based on the phosphonate, abbreviated as phosphate P9, with the following structure:

[0150]

[0151] Catalytic polymerization of conjugated dienes and bio-based terpenes

[0152] Examples 23-28 investigate the effects of different borate or phosphate systems on the polymerization of conjugated dienes and bio-based terpenes.

[0153] Example 23:

[0154] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0155] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0156] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 23, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0157] Example 24:

[0158] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0159] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B4 (3.7 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0160] Preparation of vulcanized rubber: 100 parts by weight of the elastomer polymer of Example 24, 53 parts of N330, 1.5 parts of vulcanizing agent NOBS, 1.2 parts of sulfur, 5 parts of stearic acid, and 5 parts of zinc oxide were weighed and mixed and vulcanized to obtain vulcanized rubber.

[0161] Example 25:

[0162] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0163] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B7 (6.7 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0164] Preparation of vulcanized rubber: 100 parts by weight of the elastomer polymer of Example 25, 53 parts of N330, 1.5 parts of vulcanizing agent NOBS, 1.2 parts of sulfur, 5 parts of stearic acid and 5 parts of zinc oxide were weighed and mixed and vulcanized to obtain vulcanized rubber.

[0165] Example 26:

[0166] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0167] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B11 (5.5 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0168] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 26, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0169] Example 27:

[0170] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0171] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and phosphate P1 (4.3 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0172] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 27, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0173] Example 28:

[0174] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0175] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and phosphate P4 (3.5 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0176] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 28, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0177] Examples 23 and 29-30 investigate the effects of different iron catalysts on the polymerization of conjugated dienes and bio-based terpenes.

[0178] Example 29:

[0179] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0180] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-7 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0181] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 29, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0182] Example 30:

[0183] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0184] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-9 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0185] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 30, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0186] Examples 23 and 31-32 investigate the effect of monomer addition on polymerization.

[0187] Example 31:

[0188] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0189] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 1000 equiv.), triisobutylaluminum (793 mg, 4 mmol, 40 equiv.), iron catalyst Fe-8 (10 mL, 100 μmol, 1 equiv.), and borate B1 (31 mg, 100 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0190] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 31, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0191] Example 32:

[0192] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0193] Under an argon atmosphere, anhydrous cyclohexane (250 mL), isoprene (25 mL, 250 mmol, 25000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 1000 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0194] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 32, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0195] Examples 23 and 33-34 investigate the effects of different reaction temperatures on the polymerization of isoprene and bio-based terpenes.

[0196] Example 33:

[0197] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0198] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 0 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0199] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 33, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0200] Example 34:

[0201] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0202] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 50 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0203] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 34, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0204] Examples 23, 35-45 investigate the effects of different polymerizing monomers on the polymerization of isoprene and bio-based terpenes.

[0205] Example 35:

[0206] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0207] Under an argon atmosphere, anhydrous cyclohexane (89 mL), butadiene (8.9 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0208] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 35, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0209] Example 36:

[0210] Under an argon atmosphere, anhydrous cyclohexane (173 mL), β-myrcene (17.3 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 500 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0211] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 36, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0212] Example 37:

[0213] Under an argon atmosphere, anhydrous cyclohexane (275 mL), β-farnesene (27.5 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 500 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0214] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 37, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0215] Example 38:

[0216] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0217] Under an argon atmosphere, anhydrous cyclohexane (93 mL), isoprene (7 mL, 70 mmol, 7000 equiv.), butadiene (2.7 mL, 30 mmol, 3000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0218] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 38, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0219] Example 39:

[0220] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0221] Under an argon atmosphere, anhydrous cyclohexane (120 mL), isoprene (7 mL, 70 mmol, 7000 equiv.), β-myrcene (5.2 mL, 30 mmol, 3000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0222] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 39, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0223] Example 40:

[0224] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0225] Under an argon atmosphere, anhydrous cyclohexane (120 mL), isoprene (9 mL, 90 mmol, 9000 equiv.), β-farnesene (2.8 mL, 10 mmol, 1000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0226] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 40, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0227] Example 41:

[0228] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0229] Under an argon atmosphere, anhydrous cyclohexane (120 mL), butadiene (6.2 mL, 70 mmol, 7000 equiv.), β-myrcene (5.2 mL, 30 mmol, 3000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0230] Preparation of vulcanized rubber: 100 parts by mass of the elastomer polymer of Example 41, 53 parts of N330, 1.5 parts of vulcanizing agent NOBS, 1.2 parts of sulfur, 5 parts of stearic acid, and 5 parts of zinc oxide were weighed and mixed and vulcanized to obtain vulcanized rubber.

[0231] Example 42:

[0232] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0233] Under an argon atmosphere, anhydrous cyclohexane (150 mL), butadiene (8 mL, 90 mmol, 9000 equiv.), β-farnesene (2.8 mL, 10 mmol, 1000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0234] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 42, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0235] Example 43:

[0236] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0237] Under an argon atmosphere, anhydrous cyclohexane (150 mL), isoprene (7 mL, 70 mmol, 7000 equiv.), β-myrcene (2.6 mL, 15 mmol, 1500 equiv.), β-farnesene (4.2 mL, 15 mmol, 1500 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0238] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 43, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0239] Example 44:

[0240] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0241] Under an argon atmosphere, anhydrous cyclohexane (150 mL), butadiene (6.2 mL, 70 mmol, 7000 equiv.), β-myrcene (2.6 mL, 15 mmol, 1500 equiv.), β-farnesene (4.2 mL, 15 mmol, 1500 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0242] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 44, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0243] Example 45:

[0244] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0245] Under an argon atmosphere, anhydrous cyclohexane (150 mL), isoprene (3.5 mL, 35 mmol, 3500 equiv.), butadiene (3.1 mL, 35 mmol, 3500 equiv.), β-myrcene (2.6 mL, 15 mmol, 1500 equiv.), β-farnesene (4.2 mL, 15 mmol, 1500 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (3.1 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0246] Preparation of vulcanized rubber: 100 parts by weight of the elastomer polymer of Example 45, 53 parts of N330, 1.5 parts of vulcanizing accelerator NOBS, 1.2 parts of sulfur, 5 parts of stearic acid, and 5 parts of zinc oxide were weighed and mixed and vulcanized to obtain vulcanized rubber.

[0247] Examples 23 and 46 investigate the effects of different boron salt addition amounts on the polymerization of conjugated dienes and bio-based terpenes.

[0248] Example 46:

[0249] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0250] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (0.3 mg, 1 μmol, 0.1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0251] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 46, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0252] Examples 23 and 47 investigate the effects of different solvent addition amounts on the polymerization of conjugated dienes and bio-based terpenes.

[0253] Example 47:

[0254] The industrial production method for catalytic conjugated diene and bio-based terpene polymerization in this embodiment follows the steps below:

[0255] Under an argon atmosphere, anhydrous cyclohexane (30 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B1 (31 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0256] Preparation of vulcanized rubber: Weigh 100 parts by weight of the elastomer polymer of Example 47, 53 parts by weight of N330, 1.5 parts by weight of the vulcanizing agent NOBS, 1.2 parts by weight of sulfur, 5 parts by weight of stearic acid, and 5 parts by weight of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0257] Comparative Example 1:

[0258] The difference between this comparative example and Examples 23-28 is that the boron salt system used is different. The boron salt structure used is as follows, while other parameters are the same as those in Examples 23-28.

[0259] The polymerization steps in this comparative example are as follows:

[0260] Under an argon atmosphere, anhydrous cyclohexane (100 mL), isoprene (10 mL, 100 mmol, 10000 equiv.), triisobutylaluminum (79.3 mg, 0.4 mmol, 40 equiv.), iron catalyst Fe-8 (1 mL, 10 μmol, 1 equiv.), and borate B (9.2 mg, 10 μmol, 1 equiv.) were added sequentially to a 250 mL Schlenk tube. Polymerization was carried out at 30 °C for 120 min. The reaction was then terminated with 25 mL of a mixed solution of methanol and hydrochloric acid (MeOH / HCl volume ratio = 50 / 1) and 1 mL of an antioxidant. After discarding the supernatant, the polymer was washed three times with ethanol. The resulting polymer was then vacuum dried at 40 °C to constant weight to obtain the elastomer polymer.

[0261] Preparation of vulcanized rubber: Weigh 100 parts by mass of the elastomer polymer of Comparative Example 1, 53 parts by mass of N330, 1.5 parts by mass of the vulcanizing agent NOBS, 1.2 parts by mass of sulfur, 5 parts by mass of stearic acid, and 5 parts by mass of zinc oxide, and obtain vulcanized rubber by mixing and vulcanization.

[0262] The chemical formula of the borate used in the comparative example is as follows:

[0263]

[0264] Table 1 Test data of conjugated diene homopolymer elastomer

[0265]

[0266]

[0267] Table 2 Test data of conjugated diene homopolymer elastomers

[0268]

[0269] Table 3 Test data for conjugated diene homopolymer elastomers

[0270]

[0271] Table 4 Test data of conjugated diene homopolymer elastomer

[0272]

[0273] Table 5. Test data for conjugated diene random copolymer elastomers

[0274]

[0275] Table 6 Test data for conjugated diene random copolymer elastomers

[0276]

[0277] Table 7 Test data for conjugated diene random copolymer elastomers

[0278]

[0279] Table 8 Test data for conjugated diene random copolymer elastomers

[0280]

[0281] Table 9 Test data for conjugated diene random copolymer elastomers

[0282]

[0283] Table 10 Test data for conjugated diene random copolymer elastomers

[0284]

[0285] Table 11 Test data of conjugated diene random copolymer elastomer

[0286]

[0287] Table 12 Test data for conjugated diene random copolymer elastomers

[0288]

[0289]

[0290] Note: In Tables 1-12, IP represents isoprene, BD represents butadiene, MY represents myrcene, and FA represents farnesene.

[0291] Table 13 Performance test data of homopolymers and random copolymers of conjugated dienes and bio-based terpenes

[0292]

[0293]

[0294] 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. A phosphate / borate based on phosphocations, characterized in that, The general structural formula is: In the formula, X is F, Cl or Br, and R1, R2, R3, R4, R5 and R6 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 of R1, R2, R3 or R4, R5 and R6 is ≥10.

2. The borate / phosphate according to claim 1, characterized in that, Phosphocation-based borates are selected from one of formulas B1 to B13: Phosphophosphates based on phosphonates are selected from one of formulas P1 to P9:

3. The method for preparing borate / phosphate according to claim 1 or 2, characterized in that, The method described: S1: Dissolve the corresponding organophosphorus compound in a suitable organic solvent, add an equimolar amount of hydrochloric acid aqueous solution, and stir for a certain period of time; S2: Subsequently, an equimolar amount of aqueous haloborate or hexafluorophosphate solution was added and stirred for a certain period of time. The organic phase was then separated, and the organic solvent was removed by rotary evaporation to obtain borate / phosphate based on phosphocation.

4. The method according to claim 3, characterized in that, The general structural formula of the organophosphorus compound is: In the formula, R1, R2, R3, R4, R5, and R6 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, R3 or R4, R5, and R6 is ≥10; the haloborate is one or more of tetrafluoroboric acid, sodium tetrafluoroborate, tetrachloroboric acid, sodium tetrachloroborate, tetrabromoboric acid, or sodium tetrabromoborate; the organic solvent is one or more of n-hexane, cyclohexane, dichloromethane, diethyl ether, toluene, ethylbenzene, and THF; the molar ratio of organophosphorus compound to hydrochloric acid is (1-3):1; the molar ratio of haloborate or hexafluorophosphate to organophosphorus compound is (1-3):1; the stirring time after adding hydrochloric acid in step S1 is >10 min; the reaction temperature in step S2 is 0-50℃; and the reaction time is >10 min.

5. The application of the borate / phosphate as described in claim 1 or 2 as a third component in the polymerization of conjugated dienes catalyzed by activated iron catalysts, characterized in that... The polymerization method steps are as follows: Under anhydrous and oxygen-free conditions, solvent, conjugated diene monomer, alkyl aluminum, iron catalyst, and the above-mentioned phosphate-based borate / phosphate were added to the reactor. The polymerization reaction was carried out by stirring at 0–100 °C for 10–120 min. After the reaction was completed, quenching agent and anti-aging agent were added. After washing, the mixture was vacuum dried to constant weight to obtain the conjugated diene polymer.

6. The application according to claim 5, characterized in that, The conjugated diene is selected from one or more petroleum-based conjugated dienes and bio-based terpenes; The general structural formula of iron catalysts is: Wherein, R7 and R8 are alkyl, alkoxy, nitrogen-containing or sulfur-containing substituents, and X is EHA-, NDA- or acac-, wherein EHA- is NDA - for acac- for n is 2 or 3; Alkyl aluminum is one or more of the following: diethylaluminum monochloro, diethylaluminum dichloro, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, triisopropylaluminum, and diisobutylaluminum hydride.

7. The application according to claim 6, characterized in that, The petroleum-based conjugated diene is at least one of 1,3-butadiene and isoprene; the bio-based terpene is one or more of α-myrcene, β-myrcene, α-farnesene, and β-farnesene; the iron catalyst has one of the following structures:

8. The application according to claim 5, characterized in that, The volume ratio of solvent to monomer is (1-15):1, the molar ratio of monomer to iron in iron catalyst is (100-50000):1, the molar ratio of boron or phosphorus in phosphate-based borate / phosphate to iron in iron catalyst is (0.1-20):1, the molar ratio of aluminum in alkylaluminum to iron in iron catalyst is (10-100):1, the reaction temperature is 0-50℃, and the reaction time is 30-120 min.

9. The application according to claim 8, characterized in that, The volume ratio of solvent to monomer is (3-10):1, the molar ratio of monomer to iron in iron catalyst is (1000-25000):1, the molar ratio of boron or phosphorus in phosphate-based borate / phosphate to iron in iron catalyst is (0.1-5):1, and the molar ratio of aluminum in alkylaluminum to iron in iron catalyst is (20-40):

1.

10. The conjugated diene polymer obtained by the application according to any one of claims 5-9, characterized in that, The conjugated diene polymer has a number-average molecular weight of 200,000 to 700,000 g / mol, a molecular weight distribution of 1.5 to 5.0, a molar content of 3,4-structure in the petroleum-based conjugated diene polymer unit of 50 to 90% and / or a molar content of 1,2-structure of 50 to 70%, a molar content of 3,4-structure in the bio-based terpene polymer unit of 40 to 70%, and a glass transition temperature range of -80℃ to 10℃.

11. The vulcanization method of the conjugated diene polymer according to claim 10, characterized in that, The vulcanization method: Weigh out 100 parts of conjugated diene polymer, 1-60 parts of carbon black, 10-100 parts of silica, 1-3 parts of vulcanizing accelerator, 0.1-12 parts of vulcanizing agent, 1-10 parts of stearic acid and 1-10 parts of zinc oxide by mass, mix and knead.

12. The method according to claim 11, characterized in that, The carbon black is one or more of N110, N234, N324, and N330, the vulcanizing accelerator is one or more of NS, NOBS, and TT, and the vulcanizing agent is sulfur.

13. The vulcanized rubber obtained by the method of claim 11 or 12, characterized in that, The vulcanized rubber has a tensile strength >17MPa, an elongation at break >300%, a stress at 300% constant elongation >6MPa, a resilience of 20-35%, and DMA test results: when tanδ>0.3, the damping temperature range is above 30℃.

14. The application of the vulcanized rubber of claim 13 in tire manufacturing, noise reduction, damping, and shock absorption.

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