Polar functionalized conjugated diene polymer and preparation method thereof

Abstract

The invention relates to a polar functionalized conjugated diene polymer and a preparation method thereof. The polymer has a chemical structure as shown in a formula I or a formula II. In the formula 1, R1 is hydrogen or methyl, and R2 is methyl, ethyl, isopropyl, n-butyl or isobutyl; a is an integer between 0 and 10; b is an integer between 0 and 10; c is an integer between 0 and 10; x, y, z, m and n are integers and n is not equal to 0; the preparation method comprises the following step: carrying out coordination copolymerization reaction on one of butadiene and isoprene and a polar conjugated diene monomer under the action of a late transition metal catalyst with strong polarity tolerance to prepare the polar functionalized conjugated diene polymer. The preparation method is simple, the production cost is reduced, the synthesis route is simplified, and the prepared product is high in molecular weight, narrow in molecular weight distribution and controllable in polar functional group content.

Description

Technical Field

[0001] The invention belongs to the technical field of high-performance polyolefins and relates to a polar functionalized conjugated diene polymer and a preparation method thereof. Background Art

[0002] Polybutadiene and polyisoprene materials are widely used in the preparation of various synthetic rubber products, such as gloves, seals, tires, etc., due to their excellent elasticity, wear resistance, low rolling resistance and good anti-slip performance. However, the traditional polybutadiene and polyisoprene molecular chains are composed only of carbon and hydrogen elements and exhibit non-polar characteristics, which makes this type of material poorly compatible with other polar additives such as inorganic fillers and dyes during processing, resulting in defects in the prepared products and reduced performance. Therefore, it is usually necessary to perform polar functional modification on polybutadiene and polyisoprene.

[0003] Polar functional groups are introduced into the polymer molecular chains in the form of covalent bonds by chemical reaction methods. The polar groups in the prepared polar functionalized polymers are firmly bonded to the molecular chains and are evenly dispersed, which solves the problem of poor compatibility between polar groups and non-polar matrices. Therefore, it is an effective means. The chemical reaction method includes post-functionalization of polymers, reactive group functionalization, and direct copolymerization. Among them, the direct coordination copolymerization of conjugated dienes and polar monomers catalyzed by transition metals can not only effectively avoid side reactions such as cross-linking and chain scission, but also eliminate the tedious polymer post-processing process. Therefore, it is the simplest, most effective and feasible method for preparing polar functionalized conjugated diene polymers.

[0004] However, in the direct copolymerization of conjugated dienes and polar monomers, since the electron-rich polar functional groups are easy to form stable chelate products with positively charged metal centers and produce strong poisoning effects, the currently used transition metal catalysts are easily deactivated or show very low catalytic activity, and the molecular weight of the polymerized product is significantly reduced. Therefore, one of the commonly used means in the prior art is to use active metal aluminum compounds to protect polar functional groups to weaken their poisoning effects on catalysts, such as document 1 (Polym.Chem., 2020, 11, 2034) and document 2 (Polym.Chem., 2021, 12, 1653), firstly, active trimethylaluminum or diethylaluminum chloride is used to react with hydroxyl groups in polar monomers at low temperatures, and then used for direct copolymerization with other conjugated dienes, but the use of additional protective agents at low temperatures increases the complexity of anhydrous and oxygen-free polymerization operations and increases costs. Therefore, it is necessary to develop a catalyst with strong polar tolerance so that copolymerization reactions can be directly catalyzed without the need for protective agents, thereby greatly simplifying polymerization operations and reducing costs.

[0005] In addition, due to the difference in polymerization mechanism, transition metals cannot catalyze the copolymerization of conjugated diene monomers with commonly used commercial monoolefin monomers containing polar functional groups. It is necessary to use conjugated diene monomers containing polar functional groups, which requires the selection of reasonable structural design of polar conjugated diene monomers. When introducing polar groups in the prior art, the polar group ends usually also have large steric hindrances. Although the polarity is improved, the activity will be negatively affected. For example, reference 3 (ACS MacroLett. 2016, 5, 777), reference 4 (Macromolecules 2017, 50, 8464) and reference 5 (J. Am. Chem. S ℃. 2017, 139, 6823) use nickel catalysts to catalyze isoprene and polar monomers containing large steric hindrance groups such as aromatic rings at the ends to directly copolymerize and introduce polar functional groups on the polymer molecular chain. However, the large steric hindrance contained at the ends of the polar monomers not only reduces the polymerization rate, but also has limited improvement on the polarity of the polymer due to the embedding of polar heteroatoms by large steric hindrance groups. In addition, patents CN 114805685 A and CN 114736235A synthesize polar conjugated diene monomers containing tert-butyl siloxane at the end based on myrcene monomer design, and use iron catalysts of structures such as pyridine imine to prepare polar functionalized polymers, but the synthesis of the polar monomer is complex, requiring five-step reaction and column chromatography purification process to complete, and the polar monomer structure prepared from myrcene is relatively limited, that is, the distance between the polar functional group and the olefin double bond is fixed, and cannot be flexibly regulated (determined by the myrcene raw material structure). Therefore, it is also urgently needed to scientifically and rationally design the structure of the polar conjugated diene to promote the copolymerization process of transition metal-catalyzed conjugated diene and polar monomer.

[0006] Therefore, it is of great significance to study a polar functionalized conjugated diene polymer and a preparation method thereof to solve the problems existing in the prior art. Summary of the invention

[0007] The purpose of the present invention is to solve the problems existing in the prior art and provide a polar functionalized conjugated diene polymer and a preparation method thereof.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A polar functionalized conjugated diene polymer having a chemical structure as shown in Formula I or Formula II;

[0010]

[0011]

[0012] Wherein, R1 is hydrogen or methyl, R2 is methyl, ethyl, isopropyl, n-butyl or isobutyl; a is an integer between 0 and 10; b is an integer between 0 and 10; c is an integer between 0 and 10; x, y, z, m and n are integers and n≠0; the * on the benzene ring indicates that the position of the substitution is the ortho, meta or para position of another substituent on the benzene ring.

[0013] As the preferred technical solution:

[0014] The polar functionalized conjugated diene polymer as described above has a number average molecular weight of 1.5×10 4 ~60.0×10 4 g / mol, molecular weight distribution is 1.20~2.20, glass transition temperature (T g ) is -90~100℃, and the polar functional group content is 0.16~15.8mol%.

[0015] The present invention also provides a method for preparing a polar functionalized conjugated diene polymer as described above, wherein one of butadiene and isoprene and a polar conjugated diene monomer are subjected to coordination copolymerization reaction under the action of a late transition metal catalyst with strong polarity tolerance to obtain a polar functionalized conjugated diene polymer, and the polymerization activity is 1×10 5 ~5×10 6 g·mol -1 ·h -1 ;

[0016] The chemical structures of butadiene and isoprene are shown in formula A, and the chemical structure of the polar conjugated diene monomer is shown in formula B1 or B2;

[0017]

[0018] Wherein, R2 is methyl, ethyl, isopropyl, n-butyl or isobutyl; a is an integer between 0 and 10; b is an integer between 0 and 10; c is an integer between 0 and 10;

[0019] The chemical structure of the late transition metal catalyst with strong polarity tolerance is any one of formulas C1 to C12;

[0020]

[0021] Among them, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18, R 19 , R 20 and R 21 Each is independently selected from an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group; M is iron or cobalt; and Y is chlorine, bromine or iodine.

[0022] As the preferred technical solution:

[0023] The method for preparing a polar functionalized conjugated diene polymer as described above comprises the following steps of preparing a polar conjugated diene monomer: adding 2-chloro-1,3-butadiene to a tetrahydrofuran solution of magnesium chips in an anhydrous and oxygen-free nitrogen atmosphere, then adding 1,2-dibromoethane and zinc dichloride as catalysts, reflux the mixture after the reaction at 66-80° C. for 4-24 hours to obtain a green turbid liquid, adding a halide (bromide or iodide) and dilithium tetrachlorocuprate at -10-0° C., and reacting at 20-40° C. for 24-48 hours to obtain a polar conjugated diene monomer;

[0024] The reaction equation is as follows:

[0025]

[0026] wherein X is Br or I.

[0027] According to the method for preparing a polar functionalized conjugated diene polymer, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:1.2-5; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 200-500 mL:1 mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.02-0.1:0.02-0.1:1; and the ratio of the amount of halogenated substance, lithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.1-0.5:1.

[0028] The preparation method of the polar functionalized conjugated diene polymer as described above, the preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0029] (1) reacting a primary amine with an imidazoline chloride or an imidazolidinyl chloride, and using an acid-binding agent (triethylamine, sodium carbonate or diisopropylethylamine) to capture the generated hydrogen chloride to generate an imidazoline-2-imine derivative or an imidazolidinyl-2-imine derivative; or reacting a bromine-containing primary amine with an imidazoline chloride or an imidazolidinyl chloride, and using an acid-binding agent to capture the generated hydrogen chloride to generate a bromide of imidazoline-2-imine or a bromide of imidazolidinyl-2-imine;

[0030] (2) reacting a non-primary amine-containing bromine-containing amine compound, a bromide of imidazoline-2-imine, or a bromide of imidazolidin-2-imine with n-butyl lithium (n-BuLi) at -80 to -70°C for 0.5 to 2 hours, and then adding a chlorophosphine derivative to react for 1 to 24 hours to generate a phosphine-containing amine compound, an imidazoline-2-imine phosphine compound, or an imidazolidin-2-imine phosphine compound;

[0031] (3) reacting an imidazoline-2-imine derivative, an imidazolidin-2-imine derivative, a phosphine-containing amine compound, an imidazoline-2-imine phosphine compound or an imidazolidin-2-imine phosphine compound with a dihalide (MY2) to obtain a late transition metal catalyst with strong polarity tolerance.

[0032] The reaction equations for preparing formulas C1 to C8 are as follows, wherein the acid-binding agent is triethylamine NEt3 as an example, but is not limited to NEt3:

[0033]

[0034] The reaction equations for preparing formulas C9 to C10 are as follows:

[0035]

[0036] The reaction equations for preparing formulas C11 to C12 are as follows:

[0037]

[0038] The method for preparing a polar functionalized conjugated diene polymer as described above, wherein the primary amine in step (1) is o-phenylenediamine, ethylenediamine, 8-aminoquinoline, 2-picolylamine, 1,8-naphthalenediamine, propylenediamine, 2-(iminomethyl)aniline or 2-(imino)ethylamine, and the bromine-containing primary amine is 2-bromoaniline or 2-bromoethylamine; the molar ratio of the primary amine to the imidazoline chloride or imidazolidine chloride is 1:1-2.5, and the molar ratio of the primary amine to the acid binding agent is 1:2-4; the molar ratio of the bromine-containing primary amine to the imidazoline chloride or imidazolidine chloride is 1:1-1.5, and the molar ratio of the bromine-containing primary amine to the acid binding agent is 1:2-4;

[0039] The imidazoline-2-imine derivative or imidazolidin-2-imine derivative is N,N'-(1,2-phenylene)bis(1,3-diphenylimidazoline-2-imine), N,N'-(ethane-1,2-diyl)bis(1,3-dimethyl-1,3-dihydro-2H-imidazoline-2-imine), N-(1,3-dimethylimidazoline-2-imino)quinolin-8-amine, N-(1,3-dimethylimidazoline-2-imino)-2-pyridinemethylamine, N 1 ,N 8-Bis(1,3-dimethylimidazoline-2-imide)-1,8-naphthalenediamine, N 1 ,N 3 -bis(1,3-dimethylimidazolin-2-imide)-1,3-propylenediamine, 1,3-dimethyl-N-(2-((methylimino)methyl)phenyl)-1,3-dihydro-2H-imidazole-2-imide or 1,3-dimethyl-N-(3-(methylimino)butan-2-yl)-1,3-dihydro-2H-imidazole-2-imide;

[0040] The bromide of imidazoline-2-imine or the bromide of imidazolidin-2-imine is N-(2-bromophenyl)-1,3-dimethylimidazol-2-imine or N-(2-bromoethyl)-1,3-dimethylimidazol-2-imine;

[0041] In step (2), the non-primary amine-containing bromine-containing amine compound is 2-bromo-N,N-dimethylaniline or 2-bromo-N,N-dimethylethylamine, the imidazoline-2-imide phosphine compound or imidazolidine-2-imide phosphine compound is N-(1,3-dimethyl-1H-imidazole-2(3H)-imine)-2-(diphenylphosphine)ethylamine or N-(2-(diphenylphosphino)phenyl)-1,3-dimethylimidazole-2-imine; the imidazoline-2-imine The molar ratio of the bromide or the bromide of imidazolidin-2-imine to n-butyl lithium is 1:1-1.5, and the molar ratio of the bromide of imidazolidin-2-imine or the bromide of imidazolidin-2-imine to the chlorophosphine derivative is 1:1-1.5; the molar ratio of the bromide-containing amine compound of non-primary amine to n-butyl lithium is 1:1-1.5, and the molar ratio of the bromide-containing amine compound of non-primary amine to the chlorophosphine derivative is 1:1-1.5;

[0042] In step (3), the molar ratio of the imidazoline-2-imine derivative or the imidazolidin-2-imine derivative to the dihalide is 1:1 to 1.5, the molar ratio of the imidazoline-2-imine phosphine compound or the imidazolidin-2-imine phosphine compound to the dihalide is 1:1 to 1.5; and the molar ratio of the phosphine-containing amine compound to the dihalide is 1:1 to 1.5.

[0043] In the method for preparing a polar functionalized conjugated diene polymer as described above, a co-catalyst is also added to the reaction, and the co-catalyst is EADC (ethylaluminum dichloride), DEAC (diethylaluminum chloride), EASC (sesquiethylaluminum chloride), MAO (methylaluminoxane) or MMAO (modified methylaluminoxane), and the molar ratio of the aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 10 to 700:1.

[0044] The method for preparing a polar functionalized conjugated diene polymer as described above is carried out in a solution state, the solvent is one or two of toluene, dichloromethane, xylene, benzene, cyclohexane, n-hexane, petroleum ether, n-pentane, n-heptane, n-octane and decahydronaphthalene, the reaction temperature is 0-80°C, and the reaction time is 7min-4h.

[0045] In the method for preparing a polar functionalized conjugated diene polymer as described above, the ratio of one of butadiene and isoprene, the polar conjugated diene monomer and the late transition metal catalyst substance with strong polarity tolerance is 500-30000:1-5000:1. Principle of the invention:

[0046] The present invention aims at the problem that the direct coordination copolymerization method of conjugated dienes and polar monomers catalyzed by transition metals in the prior art needs to protect the polar functional groups of the polar monomers before polymerization to prevent the polar functional groups from poisoning the metal centers during the polymerization process. In order to avoid adding unnecessary steps and costs due to such pre-protection measures, a solution strategy of dual design of the transition metal catalyst structure and the polar conjugated diene monomer structure is adopted.

[0047] On the one hand, in terms of catalyst structure design, the present invention ingeniously uses structures with strong electron-donating properties such as imidazoline diimide and imidazoline diimide phosphine as ligands, which can significantly weaken the Lewis acidity of the central metal iron or cobalt. In the polymerization reaction, this design forms an unstable chelation reaction between the polar group and the catalyst metal center, thereby avoiding the catalyst from being poisoned by the polar group. Therefore, this type of catalyst can directly and efficiently catalyze the copolymerization reaction of conjugated olefins and polar monomers without the aid of protective reagents, and exhibits high stability and high activity, and can produce high molecular weight polymers.

[0048] On the other hand, in the design of the polar conjugated diene monomer structure, the present invention introduces a new polar group containing an ester group (-COOR, where R is other non-hydrogen groups, R is methyl, ethyl, isopropyl, n-butyl or isobutyl), and the distance between the ester group and the olefin double bond can be flexibly adjusted as needed, thereby greatly enriching the types of monomers. In addition, in the preparation process of polar monomers, cheap chloroprene (also known as 2-chloro-1,3-butadiene) is used as a raw material, and a high-purity polar conjugated diene monomer can be efficiently synthesized through a simple two-step reaction, which reduces production costs and simplifies the synthesis path.

[0049] Beneficial effects:

[0050] (1) A polar functionalized conjugated diene polymer of the present invention has good catalyst stability, high activity, "active polymerization characteristics", strong polarity tolerance (no need to add protective reagents during the polymerization process), strong copolymerization ability (reactive to a variety of monomers); the polymer has a high molecular weight (can reach an ultra-high molecular weight range of more than one million), a narrow molecular weight distribution, and the polar functional group content can be adjusted.

[0051] (2) The polar functionalized conjugated diene polymer of the present invention contains polar functional groups, which can enhance the interaction with polar compound additives such as dyes and reinforcing agents.

[0052] (3) The method for preparing a polar functionalized conjugated diene polymer of the present invention adopts a solution strategy of dual design of the transition metal catalyst structure and the polar conjugated diene monomer structure, which effectively solves the problem that the polar functional groups of the polar monomers need to be protected before polymerization in the prior art of direct coordination copolymerization of conjugated dienes and polar monomers catalyzed by transition metals to prevent the polar functional groups from poisoning the metal centers during the polymerization process. In addition, the method uses cheap chloroprene as a raw material and can efficiently synthesize high-purity polar conjugated diene monomers through a simple two-step reaction, thereby reducing production costs and simplifying the synthesis path. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 The polar conjugated diene monomer of Example 1 1 H NMR (CDCl3, 600MHz);

[0054] Figure 2 This is a single crystal test image of the late transition metal catalyst with strong polarity tolerance of Example 1;

[0055] Figure 3 The polar functionalized conjugated diene polymer of Example 1 1 H NMR (CDCl3, 600MHz);

[0056] Figure 4 is the GPC curve of the polar functionalized conjugated diene polymer of Example 1;

[0057] Figure 5 This is the DSC curve of the polar functionalized conjugated diene polymer of Example 1. DETAILED DESCRIPTION

[0058] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0059] The test methods involved in the performance indicators of the present invention are as follows:

[0060] Molecular weight and molecular weight distribution: Use high temperature gel chromatography (PL GPC-220) for testing, use 1,2,4-trichlorobenzene as the mobile phase, and use polystyrene with narrow molecular weight distribution provided by PL as the standard sample for calibration. Take 10 mg of sample and 10 mL of solvent trichlorobenzene, heat at 150°C until fully dissolved, filter with molecular sieves and place in GPC test vials for testing. The flow rate of the mobile phase during the test is 1.0 mL / min. Finally, use molecular weight analysis software to analyze the test data.

[0061] Catalytic activity: The copolymerization catalytic activity is the ratio of the total mass of the copolymer obtained to the amount of catalyst substance and the polymerization time, and the unit is g·mol -1 ·h -1 .

[0062] Polar monomer insertion rate, i.e., the content of each structural unit in the structure of Formula I and Formula II in the molecular chain: tested using German Bruker Ascend-600, 5 mg of sample was weighed into a nuclear magnetic resonance tube at room temperature, deuterated tetrachloroethane was added to dissolve the sample, and then placed in the nuclear magnetic resonance instrument, and parameters were set to select hydrogen spectrum scanning to obtain data; the data can be analyzed by MestReNova software, and the monomer insertion rate can be calculated based on the proportion of the integrated area of ​​the characteristic peak on the quantitative hydrogen spectrum.

[0063] Polymer thermal properties test: using differential scanning calorimetry (TA DSC Q2000), the sample was tested in a nitrogen atmosphere (flow rate 50mL / min), 5mg of sample was taken, the sample was placed in an aluminum crucible, and placed in a sample cell for testing. The test temperature range was -90 to 150°C. In order to eliminate the thermal history, the secondary heating mode was adopted, and the heating rate was 10°C / min. The results were all taken from the second heating curve, and the DSC software was used to analyze the thermal properties of the sample such as the glass transition temperature.

[0064] Example 1

[0065] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0066] (1) Preparation of polar conjugated diene monomers;

[0067] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 66°C for 24 hours to obtain a green turbid liquid. Methyl 4-iodobutyrate and dilithium tetrachlorocuprate were added at -10°C, and the reaction was carried out at 20°C for 48 hours to obtain a polar conjugated diene monomer; the structural formula is as follows:

[0068] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:1.2; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 200mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.02:0.02:1; the ratio of methyl 4-iodobutyrate, lithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.1:1;

[0069] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0070] (2.1) reacting o-phenylenediamine with 2-chloro-1,3-dimethylimidazolium chloride, and using triethylamine to capture the generated hydrogen chloride to generate N1,N2-bis(1,3-dimethylimidazolidine-2-imide)-1,2-phenylenediamine;

[0071] The molar ratio of o-phenylenediamine to 2-chloro-1,3-dimethylimidazolium chloride is 1:2.5, and the molar ratio of o-phenylenediamine to triethylamine is 1:2.

[0072] (2.2) The N1,N2-bis(1,3-dimethylimidazolidine-2-imide)-1,2-phenylenediamine produced in step (2.1) is reacted with cobalt dichloride to obtain a late transition metal catalyst with strong polarity tolerance, the structural formula of which is as follows:

[0073] Wherein, the molar ratio of N1,N2-bis(1,3-dimethylimidazolidine-2-imide)-1,2-phenylenediamine to cobalt dichloride is 1:1;

[0074] (3) under nitrogen protection, isoprene and the polar conjugated diene monomer obtained in step (1) are added to toluene, and a coordination copolymerization reaction is carried out at 20° C. for 30 min under the action of a late transition metal catalyst with strong polar tolerance and a DEAC co-catalyst, and a 10 wt % methanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0075] The molar ratio of isoprene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 2000:200:1; the molar ratio of polar conjugated diene monomer and toluene is 1:50; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 100:1;

[0076] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0077] The catalytic activity of the polymerization system is 1×10 5 g·mol -1 ·h -1 .

[0078] like Figure 1 The polar conjugated diene monomer prepared in Example 1 is shown. 1 H NMR characterization diagram proves that the polar conjugated diene monomer was successfully prepared;

[0079] like Figure 2 The figure shows the crystal structure of the late transition metal catalyst prepared in Example 1 characterized by single crystal diffraction, which proves that the catalyst was successfully prepared;

[0080] like Figure 3 The polar functionalized conjugated diene polymer of Example 1 is shown. 1 H NMR showed that the polar functionalized conjugated diene polymer was successfully prepared; the content of cis-1,4 units in the polymer was 44.43 mol%, the content of 3,4 units was 55.57 mol%, and the content of polar conjugated diene chain structural units was 5.49 mol%.

[0081] like Figure 4 The GPC curve of the polar functionalized conjugated diene polymer of Example 1 is shown. The number average molecular weight of the polar functionalized conjugated diene polymer is 2.64×10 5 , the weight average molecular weight is 4.53×10 5 , the molecular weight distribution is 1.7.

[0082] like Figure 5 The DSC curve of the polar functionalized conjugated diene polymer of Example 1 is shown. The glass transition temperature of the polar functionalized conjugated diene polymer is -17.566°C.

[0083] Example 2

[0084] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0085] (1) Preparation of polar conjugated diene monomers;

[0086] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 70°C for 16 hours to obtain a green turbid liquid. Phenyl bromoacetate and dilithium tetrachlorocuprate were added at -8°C, and the reaction was carried out at 25°C for 42 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0087] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:1.4; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 220mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.1:0.02:1; the ratio of phenyl bromoacetate, lithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.1:1;

[0088] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0089] (2.1) reacting 8-aminoquinoline with 2-chloro-1,3-dimethylimidazolium chloride, and capturing the generated hydrogen chloride with sodium carbonate to generate N-(1,3-dimethylimidazolidine-2-imide)-8-quinolinamine;

[0090] The molar ratio of 8-aminoquinoline to 2-chloro-1,3-dimethylimidazolium chloride is 1:1, and the molar ratio of 8-aminoquinoline to sodium carbonate is 1:2;

[0091] (2.2) The N-(1,3-dimethylimidazolidine-2-imide)-8-quinolinamine generated in step (2.1) is reacted with ferrous chloride to obtain a late transition metal catalyst with strong polarity tolerance, the structural formula of which is as follows:

[0092] Wherein, the molar ratio of N-(1,3-dimethylimidazolidine-2-imide)-8-quinolinamine to ferrous chloride is 1:1.2;

[0093] (3) under nitrogen protection, butadiene and the polar conjugated diene monomer prepared in step (1) are added to a mixed solvent of dichloromethane and xylene in a volume ratio of 1:1, and a coordination copolymerization reaction is carried out at 0° C. for 4 hours under the action of a late transition metal catalyst with strong polarity tolerance and an EADC co-catalyst, and a 5 wt % methanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0094] The molar ratio of butadiene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 4000:200:1; the molar ratio of polar conjugated diene monomer and mixed solvent of dichloromethane and xylene with a volume ratio of 1:1 is 1:100; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 10:1;

[0095] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0096] The content of cis-1,4-unit is 10 mol%, the content of 3,4-unit is 90 mol%, and the content of polar conjugated diene chain structural unit is 2.53 mol%; the catalytic activity of the polymerization system is 2×10 5 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 40×10 4 g / mol, molecular weight distribution is 1.3, and glass transition temperature is -44°C.

[0097] Example 3

[0098] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0099] (1) Preparation of polar conjugated diene monomers;

[0100] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 74°C for 10 hours to obtain a green turbid liquid. 2-bromoacetate and dilithium tetrachlorocuprate were added at -5°C, and the reaction was carried out at 30°C for 36 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0101] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:1.5; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 300mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.021:0.02:1; the ratio of the amount of 2-bromoacetate, dilithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.2:1;

[0102] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0103] (2.1) reacting 1,8-naphthalenediamine with 2-chloro-1,3-dimethylimidazolinium chloride, and capturing the generated hydrogen chloride with diisopropylethylamine to generate N1,N8-bis(1,3-dihydro-1,3-dimethyl-2H-imidazolin-2-imide)-1,8-naphthalenediamine;

[0104] The molar ratio of 1,8-naphthalenediamine to 2-chloro-1,3-dimethylimidazoline chloride is 1:2.3, and the molar ratio of 1,8-naphthalenediamine to diisopropylethylamine is 1:3.

[0105] (2.2) The N1,N8-bis(1,3-dihydro-1,3-dimethyl-2H-imidazoline-2-imide)-1,8-naphthalenediamine produced in step (2.1) is reacted with cobalt iodide to obtain a late transition metal catalyst with strong polarity tolerance, the structural formula of which is as follows:

[0106]

[0107] Wherein, the molar ratio of N1,N8-bis(1,3-dihydro-1,3-dimethyl-2H-imidazoline-2-imide)-1,8-naphthalenediamine to cobalt iodide is 1:1.3;

[0108] (3) under nitrogen protection, isoprene and the polar conjugated diene monomer prepared in step (1) are added to a mixed solvent of cyclohexane and n-hexane in a volume ratio of 1:1, and a coordination copolymerization reaction is carried out at 80° C. for 7 min under the action of a late transition metal catalyst with strong polarity tolerance and an EASC co-catalyst, and a 10 wt % ethanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0109] The molar ratio of isoprene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 2000:100:1; the molar ratio of polar conjugated diene monomer and mixed solvent of cyclohexane and n-hexane with a volume ratio of 1:1 is 1:200; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 200:1;

[0110] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0111] The content of cis-1,4-unit is 20 mol%, the content of 3,4-unit is 80 mol%, and the content of polar conjugated diene chain structural unit is 10.10 mol%; the catalytic activity of the polymerization system is 5×10 6 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 10×104 g / mol, molecular weight distribution is 2, and glass transition temperature is 20℃.

[0112] Example 4

[0113] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0114] (1) Preparation of polar conjugated diene monomers;

[0115] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 78°C for 6 hours to obtain a green turbid liquid. 4-iodophenyl acetate and dilithium tetrachlorocuprate were added at -2°C, and the reaction was carried out at 35°C for 30 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0116] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:2; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 300mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.1:0.1:1; the ratio of the amount of 4-iodophenyl acetate, tetrachlorocuprate dilithium and 2-chloro-1,3-butadiene is 1:0.2:1;

[0117] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0118] (2.1) Propylenediamine is reacted with 2-chloro-1,3-dimethylimidazolium chloride, and the generated hydrogen chloride is captured by triethylamine to generate N1,N3-bis(1,3-dimethylimidazolidine-2-imide)-1,3-propylenediamine;

[0119] Wherein, the molar ratio of propylenediamine to 2-chloro-1,3-dimethylimidazolium chloride is 1:2.4, and the molar ratio of propylenediamine to triethylamine is 1:4;

[0120] (2.2) The N1,N3-bis(1,3-dimethylimidazolidine-2-imide)-1,3-propylenediamine generated in step (2.1) is reacted with ferric diiodide to obtain a late transition metal catalyst with strong polarity tolerance, the structural formula of which is as follows:

[0121] Wherein, the molar ratio of N1,N3-bis(1,3-dimethylimidazolidine-2-imide)-1,3-propylenediamine to ferric diiodide is 1:1.5;

[0122] (3) under nitrogen protection, butadiene and the polar conjugated diene monomer prepared in step (1) are added to a mixed solvent of petroleum ether and n-pentane in a volume ratio of 1:1, and a coordination copolymerization reaction is carried out at 40° C. for 2 h under the action of a late transition metal catalyst with strong polarity tolerance and an MAO co-catalyst, and a 5 wt % methanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0123] The molar ratio of butadiene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 30000:5000:1; the molar ratio of polar conjugated diene monomer and mixed solvent of petroleum ether and n-pentane with a volume ratio of 1:1 is 1:300; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 300:1;

[0124] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0125] The content of cis-1,4-unit is 34.5mol%, the content of 3,4-unit is 65.5mol%, and the content of polar conjugated diene chain structural unit is 11.12mol%. The catalytic activity of the polymerization system is 3×10 5 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 1.5×10 4 g / mol, molecular weight distribution is 2.2, and glass transition temperature is 100℃.

[0126] Example 5

[0127] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0128] (1) Preparation of polar conjugated diene monomers;

[0129] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 80°C for 4 hours to obtain a green turbid liquid. 3-iodoacetate and dilithium tetrachlorocuprate were added at 0°C, and the reaction was carried out at 40°C for 24 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0130] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:3.5; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 400mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.1:0.1:1; the ratio of the amount of 3-iodoacetate, dilithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.3:1;

[0131] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0132] (2.1) 2-Bromo-N,N-dimethylaniline was reacted with n-butyl lithium at -80°C for 2 h, and then diphenylphosphine chloride was added and reacted for 24 h to generate 2-(diphenylphosphino)-N,N-dimethylaniline;

[0133] Wherein, the molar ratio of 2-bromo-N,N-dimethylaniline to n-butyllithium is 1:1, and the molar ratio of 2-bromo-N,N-dimethylaniline to diphenylphosphine chloride is 1:1;

[0134] (2.2) The 2-(diphenylphosphino)-N,N-dimethylaniline produced in step (2.1) is reacted with cobalt bromide to obtain a late transition metal catalyst having strong polarity tolerance, the structural formula of which is as follows:

[0135] wherein the molar ratio of 2-(diphenylphosphino)-N,N-dimethylaniline to cobalt bromide is 1:1;

[0136] (3) under nitrogen protection, isoprene and the polar conjugated diene monomer prepared in step (1) are added to a mixed solvent of n-octane and decahydronaphthalene in a volume ratio of 1:1, and a coordination copolymerization reaction is carried out at 60° C. for 1 h in the presence of a late transition metal catalyst with strong polarity tolerance and an MMAO co-catalyst, and a 7 wt % methanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0137] The molar ratio of isoprene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 500:1:1; the molar ratio of polar conjugated diene monomer and mixed solvent of n-octane and decalin with a volume ratio of 1:1 is 1:400; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 400:1;

[0138] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0139] The content of cis-1,4-unit is 50.5mol%, the content of 3,4-unit is 49.5mol%, and the content of polar conjugated diene chain structural unit is 0.16mol%. The catalytic activity of the polymerization system is 6×10 5 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 60×10 4 g / mol, molecular weight distribution is 1.2, and glass transition temperature is -90℃.

[0140] Example 6

[0141] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0142] (1) Preparation of polar conjugated diene monomers;

[0143] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 66°C for 24 hours to obtain a green turbid liquid. 2-iodophenyl acetate and dilithium tetrachlorocuprate were added at -5°C, and the reaction was carried out at 20°C for 48 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0144] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:4; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 500mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.1:0.1:1; the ratio of the amount of 2-iodophenyl acetate, tetrachlorocuprate dilithium and 2-chloro-1,3-butadiene is 1:0.4:1;

[0145] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0146] (2.1) 2-Bromo-N,N-dimethylethylamine was reacted with n-butyl lithium at -70°C for 0.5 h, and then diphenylphosphine chloride was added and reacted for 2 h to generate 2-(diphenylphosphino)-N,N-dimethylethylamine;

[0147] Wherein, the molar ratio of 2-bromo-N,N-dimethylethylamine to n-butyl lithium is 1:1.5, and the molar ratio of 2-bromo-N,N-dimethylethylamine to diphenylphosphine chloride is 1:1.5;

[0148] (2.2) The 2-(diphenylphosphino)-N,N-dimethylethylamine produced in step (2.1) is reacted with ferrous bromide to obtain a late transition metal catalyst having strong polarity tolerance, the structural formula of which is as follows:

[0149] Wherein, the molar ratio of 2-(diphenylphosphino)-N,N-dimethylethylamine to ferrous bromide is 1:1.5;

[0150] (3) under nitrogen protection, butadiene and the polar conjugated diene monomer obtained in step (1) are added to a mixed solvent of n-heptane and n-octane in a volume ratio of 1:1, and a coordination copolymerization reaction is carried out at 10° C. for 3.5 hours under the action of a late transition metal catalyst with strong polarity tolerance and a DEAC co-catalyst, and a 7 wt % ethanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0151] The molar ratio of butadiene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 3000:200:1; the molar ratio of polar conjugated diene monomer and mixed solvent of n-heptane and n-octane with a volume ratio of 1:1 is 1:500; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 500:1;

[0152] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0153] The content of cis-1,4-unit is 64 mol%, the content of 3,4-unit is 36 mol%, and the content of polar conjugated diene chain structural unit is 3.20 mol%; the catalytic activity of the polymerization system is 8×10 5 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 37×10 4 g / mol, molecular weight distribution is 1.4, and glass transition temperature is -30℃.

[0154] Example 7

[0155] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0156] (1) Preparation of polar conjugated diene monomers;

[0157] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 75°C for 9 hours to obtain a green turbid liquid. Methyl 2-iodobenzoate and dilithium tetrachlorocuprate were added at -8°C, and the reaction was carried out at 30°C for 36 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0158] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:4.5; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 500mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.08:0.02:1; the ratio of the amount of methyl 2-iodobenzoate, lithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.5:1;

[0159] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0160] (2.1) 2-bromoaniline is reacted with 2-chloro-1,3-dimethylimidazolium chloride, and the generated hydrogen chloride is captured by sodium carbonate to generate N-(2-bromophenyl)-1,3-dimethylimidazolidine-2-imine;

[0161] The molar ratio of 2-bromoaniline to 2-chloro-1,3-dimethylimidazolium chloride is 1:1, and the molar ratio of 2-bromoaniline to sodium carbonate is 1:2;

[0162] (2.2) reacting the N-(2-bromophenyl)-1,3-dimethylimidazolidine-2-imine obtained in step (2.1) with n-butyl lithium at -76°C for 1.5 h, then adding diphenylphosphine chloride and reacting for 8 h to generate N-(2-(diphenylphosphino)phenyl)-1,3-dimethylimidazolidine-2-imine;

[0163] Wherein, the molar ratio of N-(2-bromophenyl)-1,3-dimethylimidazolidin-2-imine to n-butyl lithium is 1:1.5, and the molar ratio of N-(2-bromophenyl)-1,3-dimethylimidazolidin-2-imine to diphenylphosphine chloride is 1:1.2;

[0164] (2.3) The N-(2-(diphenylphosphino)phenyl)-1,3-dimethylimidazole-2-imine produced in step (2.2) is reacted with cobalt dichloride to obtain a late transition metal catalyst with strong polarity tolerance, the structural formula of which is as follows:

[0165]

[0166] wherein the molar ratio of N-(2-(diphenylphosphino)phenyl)-1,3-dimethylimidazol-2-imide to cobalt dichloride is 1:1.5;

[0167] (3) under nitrogen protection, isoprene and the polar conjugated diene monomer prepared in step (1) are added to decalin, and a coordination copolymerization reaction is carried out at 30° C. for 0.75 h in the presence of a late transition metal catalyst with strong polarity tolerance and an EADC co-catalyst, and a 4 wt % methanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0168] The molar ratio of isoprene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 3500:200:1; the molar ratio of polar conjugated diene monomer and decalin is 1:300; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 600:1;

[0169] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0170] The content of cis-1,4-unit is 85 mol%, the content of 3,4-unit is 15 mol%, and the content of polar conjugated diene chain structural unit is 3.45 mol%; the catalytic activity of the polymerization system is 4.6×10 5 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 32×10 4 g / mol, molecular weight distribution is 1.5, and glass transition temperature is -70℃.

[0171] Example 8

[0172] A method for preparing a polar functionalized conjugated diene polymer, the specific steps are as follows:

[0173] (1) Preparation of polar conjugated diene monomers;

[0174] In an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene was added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride were added as catalysts. The mixture after the reaction was refluxed at 80°C for 4 hours to obtain a green turbid liquid. Methyl 3-iodobenzoate and dilithium tetrachlorocuprate were added at -10°C, and the reaction was carried out at 40°C for 24 hours to obtain a polar conjugated diene monomer; the structural formula is shown below:

[0175] Among them, the ratio of the amount of 2-chloro-1,3-butadiene to magnesium chips is 1:5; the ratio of the volume of tetrahydrofuran to the amount of 2-chloro-1,3-butadiene is 500mL:1mol; the ratio of the amount of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.08:0.02:1; the ratio of the amount of methyl 3-iodobenzoate, lithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.5:1;

[0176] (2) The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows:

[0177] (2.1) reacting 2-bromoethylamine with 2-chloro-1,3-dimethylimidazolium chloride, and capturing the generated hydrogen chloride with diisopropylethylamine to generate N-(2-bromoethyl)-1,3-dimethylimidazolidine-2-imine;

[0178] Wherein, the molar ratio of 2-bromoethylamine to 2-chloro-1,3-dimethylimidazolium chloride is 1:1.5, and the molar ratio of 2-bromoethylamine to diisopropylethylamine is 1:4;

[0179] (2.2) reacting the N-(2-bromoethyl)-1,3-dimethylimidazolidine-2-imine obtained in step (2.1) with n-butyl lithium at -78°C for 1.75 h, then adding diphenylphosphine chloride and reacting for 16 h to generate N-(2-(diphenylphosphino)ethyl)-1,3-dimethylimidazolidine-2-imine;

[0180] Wherein, the molar ratio of N-(2-bromoethyl)-1,3-dimethylimidazolidine-2-imine to n-butyl lithium is 1:1.5, and the molar ratio of the bromide of imidazolidine-2-imine to diphenylphosphine chloride is 1:1.5;

[0181] (2.3) The N-(2-(diphenylphosphino)ethyl)-1,3-dimethylimidazolidine-2-imine produced in step (2.2) is reacted with cobalt dichloride to obtain a late transition metal catalyst with strong polarity tolerance, the structural formula of which is as follows:

[0182]

[0183] wherein the molar ratio of N-(2-(diphenylphosphino)ethyl)-1,3-dimethylimidazolidine-2-imine to cobalt dichloride is 1:1.5;

[0184] (3) under nitrogen protection, butadiene and the polar conjugated diene monomer obtained in step (1) are added to dichloromethane, and a coordination copolymerization reaction is carried out at 50° C. for 0.5 h under the action of a late transition metal catalyst with strong polar tolerance and an EASC co-catalyst, and a 4 wt % methanol solution is added to terminate the reaction to prepare a polar functionalized conjugated diene polymer;

[0185] The molar ratio of butadiene, polar conjugated diene monomer and late transition metal catalyst with strong polarity tolerance is 3800:200:1; the molar ratio of polar conjugated diene monomer and dichloromethane is 1:300; the molar ratio of aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polarity tolerance is 700:1;

[0186] The polar functionalized conjugated diene polymer finally obtained has the chemical structure shown below:

[0187] The content of cis-1,4-unit is 90 mol%, the content of 3,4-unit is 10 mol%, and the content of polar conjugated diene chain structural unit is 4.26 mol%; the catalytic activity of the polymerization system is 7.6×10 5 g·mol -1 ·h -1 ; The number average molecular weight of the polar functionalized conjugated diene polymer is 15×10 4 g / mol, molecular weight distribution is 1.8, and glass transition temperature is -50℃.

Claims

1. A polar functionalized conjugated diene polymer, characterized in that: Having a chemical structure as shown in Formula I or Formula II; Wherein, R1 is hydrogen or methyl, R2 is methyl, ethyl, isopropyl, n-butyl or isobutyl; a is an integer between 0 and 10; b is an integer between 0 and 10; c is an integer between 0 and 10; x, y, z, m and n are integers and n≠0; The * on the benzene ring indicates that the substitution is located at the ortho, meta or para position to another substituent on the benzene ring.

2. The polar functionalized conjugated diene polymer according to claim 1, characterized in that: The number average molecular weight of the polar functionalized conjugated diene polymer is 1.5×10 4 ~60.0×10 4 g / mol, the molecular weight distribution is 1.20-2.20, the glass transition temperature is -90-100°C, and the polar functional group content is 0.16-15.8 mol%.

3. A method for preparing a polar functionalized conjugated diene polymer as claimed in claim 1 or 2, characterized in that: A polar functionalized conjugated diene polymer was prepared by coordination copolymerization of one of butadiene and isoprene with a polar conjugated diene monomer in the presence of a late transition metal catalyst with strong polarity tolerance. The polymerization activity was 1×10 5 ~5×10 6 g·mol -1 ·h -1 ; The chemical structure of the polar conjugated diene monomer is shown in Formula B1 or B2; Wherein, R2 is methyl, ethyl, isopropyl, n-butyl or isobutyl; a is an integer between 0 and 10; b is an integer between 0 and 10; c is an integer between 0 and 10; The chemical structure of the late transition metal catalyst with strong polarity tolerance is any one of formulas C1 to C12; Among them, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 Each is independently selected from an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group; M is iron or cobalt; and Y is chlorine, bromine or iodine.

4. The method for preparing a polar functionalized conjugated diene polymer according to claim 3, characterized in that: The preparation process of the polar conjugated diene monomer is as follows: in an anhydrous and oxygen-free nitrogen atmosphere, 2-chloro-1,3-butadiene is added to a tetrahydrofuran solution of magnesium chips, and then 1,2-dibromoethane and zinc dichloride are added as catalysts. The mixture after the reaction is refluxed at 66 to 80° C. for 4 to 24 hours to obtain a green turbid liquid, and a halide and dilithium tetrachlorocuprate are added at -10 to 0° C., and the reaction is carried out at 20 to 40° C. for 24 to 48 hours to obtain a polar conjugated diene monomer.

5. The method for preparing a polar functionalized conjugated diene polymer according to claim 4, characterized in that: The molar ratio of 2-chloro-1,3-butadiene to magnesium chips is 1:1.2-5; the volume ratio of tetrahydrofuran to the molar ratio of 2-chloro-1,3-butadiene is 200-500 mL:1 mol; the molar ratio of 1,2-dibromoethane, zinc dichloride and 2-chloro-1,3-butadiene is 0.02-0.1:0.02-0.1:1; the molar ratio of halogenated compound, dilithium tetrachlorocuprate and 2-chloro-1,3-butadiene is 1:0.1-0.5:

1.

6. The method for preparing a polar functionalized conjugated diene polymer according to claim 3, characterized in that: The preparation steps of the late transition metal catalyst with strong polarity tolerance are as follows: (1) reacting a primary amine with an imidazoline chloride or an imidazolidinyl chloride, and capturing the generated hydrogen chloride with an acid-binding agent to generate an imidazoline-2-imine derivative or an imidazolidinyl-2-imine derivative; or reacting a bromine-containing primary amine with an imidazoline chloride or an imidazolidinyl chloride, and capturing the generated hydrogen chloride with an acid-binding agent to generate a bromide of imidazoline-2-imine or a bromide of imidazolidinyl-2-imine; (2) reacting a non-primary amine-containing bromine-containing amine compound, a bromide of imidazoline-2-imine, or a bromide of imidazolidin-2-imine with n-butyl lithium at -80 to -70°C for 0.5 to 2 hours, and then adding a chlorophosphine derivative to react for 1 to 24 hours to generate a phosphine-containing amine compound, an imidazoline-2-imine phosphine compound, or an imidazolidin-2-imine phosphine compound; (3) reacting an imidazoline-2-imine derivative, an imidazolidin-2-imine derivative, a phosphine-containing amine compound, an imidazoline-2-imine phosphine compound or an imidazolidin-2-imine phosphine compound with a dihalide to obtain a late transition metal catalyst having strong polarity tolerance.

7. The method for preparing a polar functionalized conjugated diene polymer according to claim 6, characterized in that: In step (1), the primary amine is o-phenylenediamine, ethylenediamine, 8-aminoquinoline, 2-picolylamine, 1,8-naphthalenediamine, propylenediamine, N-[(2-aminophenyl)methylene]aniline or 2-(imino)ethylamine, and the bromine-containing primary amine is 2-bromoaniline or 2-bromoethylamine; the molar ratio of the primary amine to imidazoline chloride or imidazolidine chloride is 1:1-2.5, and the molar ratio of the primary amine to the acid binding agent is 1:2-4; the molar ratio of the bromine-containing primary amine to imidazoline chloride or imidazolidine chloride is 1:1-1.5, and the molar ratio of the bromine-containing primary amine to the acid binding agent is 1:2-4; In step (2), the bromine-containing amine compound of the non-primary amine is 2-bromo-N,N-dimethylaniline or 2-bromo-N,N-dimethylethylamine; the molar ratio of the bromide of imidazoline-2-imine or the bromide of imidazolidin-2-imine to n-butyllithium is 1:1-1.5, and the molar ratio of the bromide of imidazoline-2-imine or the bromide of imidazolidin-2-imine to the chlorophosphine derivative is 1:1-1.5; the molar ratio of the bromine-containing amine compound of the non-primary amine to n-butyllithium is 1:1-1.5, and the molar ratio of the bromine-containing amine compound of the non-primary amine to the chlorophosphine derivative is 1:1-1.5; In step (3), the molar ratio of the imidazoline-2-imine derivative or the imidazolidin-2-imine derivative to the dihalide is 1:1 to 1.5, the molar ratio of the imidazoline-2-imine phosphine compound or the imidazolidin-2-imine phosphine compound to the dihalide is 1:1 to 1.5; and the molar ratio of the phosphine-containing amine compound to the dihalide is 1:1 to 1.

5.

8. The method for preparing a polar functionalized conjugated diene polymer according to claim 3, characterized in that: A co-catalyst is also added to the reaction, and the co-catalyst is EADC, DEAC, EASC, MAO or MMAO, and the molar ratio of the aluminum element in the co-catalyst to the metal element in the late transition metal catalyst with strong polar tolerance is 10-700:

1.

9. The method for preparing a polar functionalized conjugated diene polymer according to claim 3, characterized in that: The reaction is carried out in a solution state, the solvent is one or two of toluene, dichloromethane, xylene, benzene, cyclohexane, n-hexane, petroleum ether, n-pentane, n-heptane, n-octane and decahydronaphthalene, the reaction temperature is 0-80°C, and the reaction time is 7min-4h.

10. The method for preparing a polar functionalized conjugated diene polymer according to claim 9, characterized in that: The amount ratio of one of butadiene and isoprene, the polar conjugated diene monomer and the late transition metal catalyst substance with strong polarity tolerance is 500-30000:1-5000:1.

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