Nitrogen-containing functionalized star-shaped polymer as well as preparation method and application thereof

Abstract

The invention discloses a nitrogen-containing functionalized star-shaped polymer and a preparation method and application thereof, the nitrogen-containing functionalized star-shaped polymer is of a core-shell structure composed of a shell composed of a nitrogen-containing functionalized linear elastomer polymer and a core composed of a polyvinyl arene compound, and the structural formula of the nitrogen-containing functionalized star-shaped polymer is as follows: # imgabs0 #, the # imgabs 1 # represents a nitrogen-containing functionalized linear elastomer polymer, the number of the # imgabs 2 # is 8-12, and the # imgabs 3 # is a polyvinyl aromatic hydrocarbon compound. The nitrogen-containing functionalized star-shaped polymer provided by the invention can improve the rolling resistance, tensile property and / or wet skid resistance and other properties of a rubber product.

Description

Technical Field

[0001] The invention belongs to the technical field of high-performance synthetic rubber and relates to a nitrogen-containing functionalized star polymer and a preparation method and application thereof. Background Art

[0002] In recent years, a new type of polymer nanoparticles: star polymers (also known as hair nanoparticles) have attracted widespread attention due to their unique structure (composed of an inorganic or polymer core and a flexible polymer shell). Combining nanoparticles with rubber matrix polymers usually brings different physical properties from the matrix. Currently, hair nanoparticles with hard cores made of organic materials, such as copolymers of polystyrene and polydivinylbenzene, have been studied.

[0003] Compared with traditional fiber or particle reinforced rubber materials, nanoscale reinforcing fillers embedded in the rubber matrix can provide excellent physical properties due to their high surface-to-volume ratio. Star-shaped polymer nanoparticles with a hairy shell and a solid core structure may provide excellent physical properties in rubber applications. They have controllable particle size, chemical composition and structure, and are particularly suitable for certain applications: such as tire rubber, scratch-resistant coatings, precursors of nanoporous polymers, nanocarriers for drugs, gene delivery, etc. It is of great significance to fill this new type of star polymer into rubber elastomers. The addition of such polymer nanoparticles will affect the physical properties of the rubber system. Filled rubber is widely used, the most important of which is the production of automobile tires. Its performance characteristics are greatly affected by the filling properties, especially the thermodynamic properties, such as the change in the glass transition temperature, which will directly affect the use of rubber. In recent years, some studies have also shown that the thermodynamic properties of the prepared nanoparticles used to reinforce rubber materials can be increased by functionalizing them. This also provides us with a way to prepare new functionalized nanoparticle polymers.

[0004] Existing patents have few descriptions of functionalized star-shaped polymer particles, and have not explored the effects of the introduction of different types or contents of functional groups on the performance of star-shaped polymer particles, a structural reinforcement rubber material. Therefore, it is important to develop a new type of nitrogen-containing functionalized star-shaped polymer particles, which have controllable molecular weight and strong functional group designability, and prepare nitrogen-containing functionalized star-shaped polymer particles as a reinforcing agent for use in rubber materials, in the rubber tire industry, to prepare high-performance rubber and improve tire performance.

[0005] US Patent No. 8,057,899 discloses a method for synthesizing "hair polymer nanoparticles" and their application in the rubber industry. The nanoparticles are synthesized by anionic polymerization, the core is composed of benzene olefin polymer, the surface layer is composed of conjugated diene or olefin polymer, and the average diameter is 100nm. However, due to its large particle diameter, the dispersion effect is poor when added to the elastomer, and the material softens at a higher use temperature, thereby reducing its effectiveness as a reinforcing filler.

[0006] U.S. Patent No. 6,977,286 discloses a rubber formulation comprising a crosslinked polymer particle as a key component and a non-crosslinked rubber component. This rubber component can be used to obtain vulcanized rubber. The purpose of using this crosslinked polymer particle is to make the rubber polymer have good processing properties and enhanced tensile strength and anti-slip performance after vulcanization, but the contribution to reducing the rolling resistance of the material is not great.

[0007] Chinese patent CN107828032A discloses a hyperbranched star-shaped polyionic liquid and a preparation method thereof. The preparation method firstly synthesizes a macromolecular chain transfer reagent HPG-CTA by a DCC condensation method using hyperbranched polyglycidol (HPG) and a chain transfer reagent 2-(butyl trithiocarbonate)-2-methylpropionic acid, then uses the macromolecular chain transfer reagent HPG-CTA to initiate RAFT polymerization of a chloromethylstyrene (CMS) monomer to synthesize a hyperbranched star-shaped copolymer HPG-PCMS, and finally reacts the hyperbranched star-shaped copolymer HPG-PCMS with an N-methylimidazole compound to synthesize a hyperbranched star-shaped polyionic liquid HPG-PVBMM+Cl-. The star-shaped polymer is obtained by condensation and then a group containing anions and cations is grafted onto the star-shaped polymer to obtain a polyionic liquid. The polymerization reaction is a RAFT reaction, and the reaction mechanism is similar to the ATRP reaction. The preparation method is completely different from the technical route of the present invention.

[0008] Chinese patent CN110144032A discloses a four-arm star polymer and a preparation method thereof, wherein a four-arm star compound containing Cl or Br and N-isopropylacrylamide are reacted in an inert system of anisole as solvent by using CuCl / dNbpy / CuCl 2 The catalytic system catalyzes the ATRP reaction to obtain a four-arm star polymer with a hydrophobic inner layer and a hydrophilic outer layer, which is used as a drug release carrier or a catalyst carrier. However, the four-arm star polymer has not been shown to be used in the field of rubber technology and to improve the physical properties of rubber; in addition, the preparation method performs an ATRP reaction, and the molecular weight distribution of the polymer obtained by chain transfer polymerization in the ATRP reaction is relatively wide, which cannot achieve the purpose of precise control. Summary of the invention

[0009] The object of the present invention is to provide a nitrogen-containing functionalized star polymer and a preparation method and application thereof, so as to improve the rolling resistance, tensile properties and / or anti-slip properties of rubber products.

[0010] To achieve the above object, the present invention provides a nitrogen-containing functionalized star polymer, which is a core-shell structure composed of a shell composed of a nitrogen-containing functionalized linear elastomeric polymer and a core composed of a polyvinyl aromatic compound, and its structural formula is as follows:

[0011]

[0012] in, represents a nitrogen-functionalized linear elastomeric polymer and ● is a polyvinylarene compound.

[0013] However, it should be noted that the structural formula of the nitrogen-containing functionalized star polymer shown above is only for the convenience of those skilled in the art to understand the structure of the nitrogen-containing functionalized star polymer of the present invention. The number is not intended to limit the present invention. In some embodiments, The number of is preferably 8 to 12, but the present invention is not limited thereto.

[0014] Furthermore, the nitrogen-containing functionalized linear elastomeric polymer is a chain-end functionalized elastomeric polymer or a multifunctional elastomeric polymer in the chain, and its specific structure is as follows:

[0015]

[0016] Furthermore, the molecular weight of the nitrogen-containing functionalized star polymer is 3,000-10,000,000.

[0017] Furthermore, the molecular weight of the nitrogen-functionalized linear elastomeric polymer is 1,000-100,000, preferably 1,000-40,000.

[0018] The present invention also provides a method for preparing a nitrogen-containing functionalized star polymer, the preparation method comprising the following steps:

[0019] A nitrogen-functionalized linear elastomeric polymer is added to a reaction container, an initiator is added to the reaction container, and then a vinyl-substituted aromatic hydrocarbon and a cross-linking agent are added to carry out an anionic polymerization reaction. After the polymerization reaction is completely completed, the reaction container is cooled, and a terminator mixed with an antioxidant is added. The obtained reaction product is subjected to negative pressure to remove volatiles to obtain a nitrogen-functionalized star polymer.

[0020] Furthermore, the preparation method of the nitrogen-containing functionalized linear elastomeric polymer is selected from any one of the following:

[0021] (a) placing an organic solvent in a reaction vessel, adding a conjugated olefin monomer and then a nitrogen-containing functionalized initiator, and carrying out a polymerization reaction under the protection of an inert gas without water or oxygen to obtain a chain-end functionalized elastomeric polymer with a single active center; or

[0022] (b) placing an organic solvent in a reaction vessel, adding a nitrogen-containing functional monomer and a conjugated olefin monomer, and then adding an initiator, and performing an anionic polymerization reaction under the protection of an inert gas without water or oxygen to obtain a mid-chain multifunctional elastomeric polymer; or

[0023] (c) placing an organic solvent in a reaction vessel, adding a nitrogen-containing functionalized monomer, and then adding an initiator, and carrying out a polymerization reaction under the protection of an inert gas without water or oxygen. After the nitrogen-containing functionalized monomer is completely converted, a conjugated olefin monomer is added to the system to continue the reaction, thereby obtaining a chain-end functionalized elastomeric polymer with multiple active centers.

[0024] Furthermore, the inert gas is nitrogen or argon; and the organic solvent is at least one of n-hexane, pentane, cyclopentane, cyclohexane, toluene and tetrahydrofuran.

[0025] Furthermore, in (a), (b) or (c), the structural formula of the conjugated olefin monomer is as follows:

[0026]

[0027] Wherein, R is a straight chain or branched chain alkyl or aromatic group having 1 to 4 carbon atoms.

[0028] Further, the initiator is one of alkyl lithium, alkyl aluminum, alkali metal amide and sodium naphthalene;

[0029] The alkyl lithium is at least one of n-butyl lithium, sec-butyl lithium, tert-butyl lithium and isobutyl lithium;

[0030] The alkyl aluminum is at least one of triisobutyl aluminum and tert-butyl aluminum, and the alkali metal amide is at least one of sodium amide and lithium amide.

[0031] Further, in (a), the nitrogen-containing functionalized initiator is an amine lithium initiator formed by the reaction of a secondary amine compound and an alkyl lithium initiator; the secondary amine compound is selected from at least one of the following compounds:

[0032]

[0033] Among them, R 1 is a straight or branched alkyl or aromatic group having 1 to 4 carbon atoms;

[0034] R 2 , R 3 The same or different, each independently selected from hydrogen, or a linear or branched alkyl or cycloalkyl or aromatic group having 1 to 4 carbon atoms;

[0035] Y is one of nitrogen, oxygen, sulfur or silicon;

[0036] a, b, and n are the same or different and are independently selected from an integer of 2 to 10;

[0037] Preferably, a and b are the same or different and are each independently selected from 2 or 3.

[0038] Furthermore, in (b) or (c), the nitrogen-containing functionalized monomer is obtained by coupling reaction of a styrene derivative of a halogenated alkyl group with a secondary amine compound.

[0039] Furthermore, the structural formula of the halogenated alkyl styrene derivative is as follows:

[0040]

[0041] Wherein, m is an integer of 1-4, and X is a halogen element. Preferably, m is 1 or 2, and X is chlorine or bromine.

[0042] Furthermore, the structure of the secondary amine compound is selected from at least one of the following compounds:

[0043]

[0044]

[0045] Among them, R 1 is a straight chain, branched chain or cyclic alkyl or aromatic group having 1 to 4 carbon atoms;

[0046] R 2 , R 5 are the same or different and are independently selected from hydrogen, or a linear or branched alkyl, cycloalkyl, aromatic or allyl group containing 1 to 10 carbon atoms;

[0047] R 3 , R 4 are the same or different and are independently selected from hydrogen, or a linear or branched alkyl or cycloalkyl or aromatic hydrocarbon group containing 1 to 4 carbon atoms;

[0048] R 6 is hydrogen, or a straight or branched chain alkyl, aryl, allyl or alkoxy group containing 1 to 10 carbon atoms;

[0049] Y is one of nitrogen, sulfur or silicon;

[0050] a, b, and n are the same or different and are each independently selected from an integer of 2-10.

[0051] Preferably, R 4 The alkyl group in is preferably methyl or ethyl; 1 , R 2 , R 3 , R 5 are the same or different and are each independently preferably selected from methyl or hydrogen; the aromatic group is preferably phenyl; n is preferably 4, 5 or 6; a and b are the same or different and are each independently preferably selected from 2 or 3.

[0052] Furthermore, the vinyl-substituted aromatic hydrocarbon is at least one selected from styrene, α-methylstyrene, α-ethylstyrene, vinyltoluene, methoxystyrene, tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methylvinylnaphthalene, divinyl-substituted aromatic hydrocarbons and trivinyl-substituted aromatic hydrocarbons. Preferably, it is styrene.

[0053] Furthermore, the crosslinking agent is a vinyl-substituted aromatic hydrocarbon, but at least a divinyl-substituted aromatic hydrocarbon, such as at least one of divinylbenzene, trivinylbenzene and divinylnaphthalene. Preferably, it is divinylbenzene (DVB).

[0054] Furthermore, the terminator is carbon dioxide, organic acid, water, isopropanol, siloxane, SiCl 4 and SnCl 4 Preferably, it is isopropanol.

[0055] Further, the amount of the antioxidant is 0.5-5% of the mass amount of the polymerized monomer, and the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol, 2,6 di-tert-butylphenol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 4,6-bis(octylthiomethyl)-o-cresol and tris(2,4-di-tert-butyl)phenyl phosphite. The polymerized monomer refers to the sum of the nitrogen-containing functionalized initiator or the nitrogen-containing functionalized monomer and the conjugated diene monomer.

[0056] Furthermore, in (b) or (c), the molar ratio of the nitrogen-containing functionalized monomer to the conjugated olefin monomer is 0.1-20:100, preferably 0.5-8:100.

[0057] Furthermore, the molar ratio of the vinyl-substituted aromatic hydrocarbon to the cross-linking agent is 1-10:1, preferably, 2-6:1; the total mass ratio of the vinyl-substituted aromatic hydrocarbon and the cross-linking agent to the total mass ratio of the monomers used in the nitrogen-functionalized linear elastomeric polymer is 1:0.1-10, preferably, 1:0.8-1.5.

[0058] Further, the reaction temperature is 20-90°C, and the reaction time is 30-500 min. Preferably, the reaction temperature is 40-70°C, and the reaction time is 100-200 min. The reaction refers to any one of the preparation of nitrogen-containing functionalized initiators, the preparation of nitrogen-containing functionalized monomers, the preparation of nitrogen-containing functionalized linear elastomeric polymers, or the preparation of nitrogen-containing functionalized star polymers.

[0059] The present invention further provides an application of the nitrogen-containing functionalized star polymer in rubber materials.

[0060] Furthermore, the nitrogen-containing functionalized star polymer is used as an additive in the preparation of a rubber material, and the rubber material is a natural rubber / carbon black system (or white carbon black), a styrene-butadiene rubber / carbon black system (or white carbon black), a cis-1,4-butadiene rubber / carbon black system (or white carbon black), an isoprene rubber / carbon black system (or white carbon black), a chloroprene rubber / carbon black system (or white carbon black), a butyl rubber / carbon black system (or white carbon black), and an ethylene-propylene rubber / carbon black system (or white carbon black); or the nitrogen-containing functionalized star polymer is used as a reinforcing filler and prepared with natural rubber, styrene-butadiene rubber, cis-1,4-butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, and ethylene-propylene rubber to obtain a composite rubber material.

[0061] The nitrogen-containing functionalized star polymer of the present invention is composed of a shell composed of a functionalized linear polymer and a core composed of a polyvinyl aromatic compound to form a core-shell structure, also known as a star-shaped branched structure, and the nitrogen-containing functionalized star polymer is mainly used for rubber reinforcement. The nitrogen-containing functionalized star polymer is mixed with rubber, or the nitrogen-containing functionalized star polymer is added as an additive to the mixed rubber formula, which can enhance the mechanical properties and wear resistance of the rubber, and can also better solve the problems of low rolling resistance and dynamic modulus of tires.

[0062] The hair molecules of the shell of the nitrogen-containing functionalized star polymer of the present invention can be connected to the rigidly reinforced particle core at one end and to the flexible polymer body at the other end like elastic bonds. After vulcanization, all shell molecules can be covalently bonded to the rubber, thereby significantly enhancing the mechanical properties of the rubber. From the principle of reinforcement, it is feasible to use nanoparticles with hard cores and hairs for rubber reinforcement. At the same time, the presence of nitrogen-containing functional groups can increase the interaction between fillers and rubber, improve the dispersibility of fillers in the rubber matrix, and improve the rolling resistance or anti-slip performance of rubber products. The nitrogen-containing functionalized star polymer of the present invention can reduce the tanδ (60°C) of rubber materials by about 8%.

[0063] The nitrogen-containing functionalized star polymer of the present invention has a simple preparation process, controllable molecular weight, and is very suitable for industrial production. Different from the prior art, the preparation method of the nitrogen-containing functionalized star polymer of the present invention adopts a one-time addition mode of monomers, which reduces the process steps, simplifies the device design in the industrial process, and makes the process control more precise and stable. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 The GPC elution curve of the nitrogen-containing functionalized star polymer obtained in Example 1. THF was selected as the solvent, and the chromatographic column was calibrated with polystyrene standards, and the average molecular weight of the sample was estimated based on these standard samples and the universal calibration curve.

[0065] Figure 2 The nitrogen-containing functionalized star polymer obtained in Example 2 1 H NMR spectrum. Deuterated chloroform (containing 1.0% TMS) was selected as the solvent.

[0066] Figure 3 This is the AFM spectrum of the nitrogen-containing functionalized star polymer obtained in Example 4. The sample was diluted with THF and then prepared by a rotary sprayer. After the solvent evaporated, the graphite sheet with the polymer sample was placed in the AFM for testing. DETAILED DESCRIPTION

[0067] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0068] In the following embodiments, the treatment of monomers, solvents and cross-linking agents: The pretreatment of monomers and solvents uses molecular sieves and alumina to remove impurities, calcium hydride to remove water, and nitrogen bubbling to remove oxygen. First, put the required molecular sieves and calcium oxide into a glass bottle and put it into a vacuum oven for drying. Nitrogen protection is required when taking out, and the cap is immediately sealed with waterproof tape. After opening the cap of the positive pressure bottle, molecular sieves, alumina (both treated) and calcium hydride are placed in sequence. After adding the reagent (monomer or solvent) with a funnel, the bottle mouth is sealed with a rubber pad and a metal cap, and nitrogen is bubbled for 8 to 12 hours. After pretreatment, the solvent is placed at room temperature, and the monomer needs to be frozen.

[0069] For the pretreatment of styrene: first prepare a solution of a certain ratio with n-hexane, and place it in a large pressure bottle filled with alumina, molecular sieve and calcium hydride, and bubbling nitrogen for 8 to 12 hours before placing it in a refrigerator. The treatment method of DVB is generally to place it in a small pressure bottle filled with alumina, molecular sieve and calcium hydride, and bubbling nitrogen for 8 to 12 hours before placing it in a refrigerator.

[0070] Pretreatment of secondary amine reagents: Prepare the solution with n-hexane as solvent and use calcium hydride to remove water.

[0071] Isopropanol terminator: a certain amount of antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) is prepared into an isopropanol solution containing 3% BHT and then subjected to a deoxygenation operation by nitrogen bubbling.

[0072] 0.80 mol / L n-butyl lithium: dilute the purchased 2.5 mol / L n-butyl lithium reagent dissolved in n-hexane to a concentration of 0.80 mol / L with n-hexane from which water and oxygen have been removed.

[0073] The syringes used in the experiment were handled by removing air by sucking and pumping nitrogen.

[0074] The rest of the raw materials or processing techniques, unless otherwise specified, are conventional commercially available raw materials or conventional processing reagents in the art.

[0075] Evaluation method:

[0076] Molecular weight and molecular weight distribution: With reference to the industry standard SH / T 1759-2007, the molecular weight and distribution of all polymer matrices with different compositions were tested using a volumetric discharge chromatograph (1515 HPLC pump, 2414 differential refractometer) from Waters, USA.

[0077] Tensile mechanical properties: With reference to GB / T 528-1998 national standard, the tensile properties of rubber materials were tested using the 5567A material testing machine from Instron, USA.

[0078] Embodiment 1:

[0079] (1) Synthesis of nitrogen-containing functionalized initiators

[0080] Use a 20mL syringe to extract 18.2mL of pretreated n-hexane into a 210mL pressure bottle, then use a 2mL syringe to extract 1.8mL of cyclohexylamine treated with calcium hydride into the bottle to prepare a cyclohexylamine / n-hexane solution with a concentration of about 0.8mol / L. Then use a 30mL syringe to extract 20mL of n-butyl lithium solution (0.8M) and slowly add it to the pressure bottle containing 10mL (1mol / L) of cyclohexylamine solution to react. In order to promote the rapid progress of the reaction, the reaction bottle is placed in a constant temperature water bath shaker at 60°C for reaction. The reaction time is 2h to obtain an amine lithium initiator.

[0081] (2) Synthesis of chain-end functionalized elastomeric polymers

[0082] Use a double-ended needle to introduce 100 mL of solvent from a large pressure bottle containing pretreated n-hexane into a 210 mL small pressure bottle; use a 20 mL syringe to extract 10 mL of pretreated isoprene from the large pressure bottle, and use a 1 mL syringe to inject 0.45 mL of the amine lithium initiator obtained in step (1) into the reaction bottle. After all the reagents are added, a certain amount of nitrogen is injected into the reagent bottle to ensure positive pressure in the bottle and strictly ensure anhydrous and oxygen-free reaction conditions. Then transfer the reaction bottle to a constant temperature water bath shaker at 60°C for reaction. After 2 hours, the monomer conversion is complete, and the reaction bottle is removed from the shaker and cooled to room temperature.

[0083] (3) Synthesis of nitrogen-functionalized star polymers

[0084] After the reaction bottle of step (2) is cooled to room temperature, first use a 1mL syringe to inject 0.32mL of butyl lithium into the reaction bottle, then use a 20mL syringe to add 19mL of styrene / n-hexane solution (styrene volume fraction is 27%) into the reaction bottle, and then use a 5mL syringe to add 1.9mL of DVB into the reaction bottle. It is worth noting that after all the reagents are added, a certain amount of nitrogen is injected into the reagent bottle. Then transfer the reaction bottle to a constant temperature water bath shaker at 60°C for reaction. After 2h, the monomer conversion is complete, the reaction bottle is removed from the shaker and cooled to room temperature. Finally, use a syringe to inject 1mL of terminator (isopropanol containing 3% antioxidant BHT by mass) into the reaction bottle. Then the product is devolatilized and vacuum dried to obtain a nitrogen-containing functionalized star polymer.

[0085] Embodiment 2:

[0086] (1) Synthesis of nitrogen-containing functionalized monomers

[0087] Use a 60mL syringe to extract 40mL of pretreated solvent n-hexane in a 210mL pressure bottle, and then add 20mL of pretreated chloromethylstyrene (VBC) reagent to the pressure bottle. Finally, in an ice-water bath, use a double-ended needle to introduce the secondary amine reagent cyclohexylimide into the pressure bottle. The amount of the secondary amine reagent is a molar ratio of 2:1 to the actual amount of VBC, and the introduction process should be as slow as possible. After the secondary amine reagent is added, remove the ice-water bath and stir at room temperature for 12 to 24 hours. After the reaction is completed, place the pressure bottle in a refrigerator to stand and freeze it. "VBC-cyclohexylimide", "VBC-4-methylpiperidine" and "VBC-pyrrolidine" are prepared.

[0088] (2) Synthesis of multifunctional elastomeric polymers in the chain

[0089] Prepare a 200mL pressure bottle, use a double-ended needle to introduce 100mL of n-hexane solvent from a large pressure bottle containing pretreated n-hexane into the 200mL pressure bottle in sequence, use a syringe to extract 10mL of isoprene and add it to the pressure bottle, use a syringe to extract VBC-cyclohexylimine from the pressure bottle containing VBC-cyclohexylimine, and the amount of VBC-cyclohexylimine extracted accounts for 4% of the mass of 10mL of isoprene. Use a syringe to add 0.6mL of n-butyl lithium initiator to the pressure bottle (the initiator is slightly excessive to remove impurities contained in the functionalized monomer). After all the reagents are added, inject a certain amount of nitrogen into the reagent bottle. Then transfer the reaction bottle to a constant temperature water bath shaker at 60°C for reaction. After 2h, the monomer conversion is complete, remove the reaction bottle from the shaker, and cool to room temperature.

[0090] (3) Synthesis of nitrogen-functionalized star polymers

[0091] After the reaction bottle of step (2) is cooled to room temperature, first use a 1mL syringe to inject 0.32mL of butyl lithium into the reaction bottle, then use a 20mL syringe to add 19mL of styrene / n-hexane solution (styrene volume fraction is 27%) into the reaction bottle, and then use a 5mL syringe to add 1.9mL of DVB into the reaction bottle. It is worth noting that after all the reagents are added, a certain amount of nitrogen is injected into the reagent bottle. Then transfer the reaction bottle to a constant temperature water bath shaker at 60°C for reaction. After 2h, the monomer conversion is complete, the reaction bottle is removed from the shaker and cooled to room temperature. Finally, use a syringe to inject 1mL of terminator (isopropanol containing 3% antioxidant BHT by mass) into the reaction bottle. Then the product is devolatilized and vacuum dried to obtain a nitrogen-containing functionalized star polymer.

[0092] Embodiment 3:

[0093] (1) Synthesis of nitrogen-containing functionalized monomers

[0094] The difference from Example 2 is that the "secondary amine reagent cyclohexyl imine" is replaced by "secondary amine reagent 4-methylpiperidine" to prepare "VBC-4-methylpiperidine". The rest is the same as Example 2.

[0095] (2) Synthesis of multifunctional elastomeric polymers in the chain

[0096] The difference from Example 2 is that "using a syringe to extract VBC-cyclohexylimine from a pressure bottle containing VBC-cyclohexylimine, the amount of VBC-cyclohexylimine extracted accounts for 4% of the mass of 10 mL of isoprene" is replaced by "using a syringe to extract VBC-4-methylpiperidine from a pressure bottle containing VBC-4-methylpiperidine, the amount of VBC-4-methylpiperidine extracted accounts for 4% of the mass of 10 mL of isoprene". Other procedures are the same as Example 2.

[0097] (3) Synthesis of nitrogen-functionalized star polymers

[0098] Same as Example 2.

[0099] Embodiment 4:

[0100] (1) Synthesis of nitrogen-containing functionalized monomers

[0101] The difference from Example 2 is that the "secondary amine reagent cyclohexylimide" is replaced by "secondary amine reagent pyrrolidine" to prepare "VBC-pyrrolidine". The rest is the same as Example 2.

[0102] (2) Synthesis of multifunctional elastomeric polymers in the chain

[0103] The difference from Example 2 is that "using a syringe to extract VBC-cyclohexylimine from a pressure bottle containing VBC-cyclohexylimine, the amount of VBC-cyclohexylimine extracted accounts for 4% of the mass of 10 mL of isoprene" is replaced by "using a syringe to extract VBC-pyrrolidine from a pressure bottle containing VBC-pyrrolidine, the amount of VBC-pyrrolidine extracted accounts for 4% of the mass of 10 mL of isoprene". Other procedures are the same as Example 2.

[0104] (3) Synthesis of nitrogen-functionalized star polymers

[0105] Same as Example 2.

[0106] The reaction mechanism of above-mentioned embodiment 2~4 is as follows:

[0107]

[0108] Embodiment 5:

[0109] (1) Synthesis of nitrogen-containing functionalized monomers

[0110] Same as Example 4.

[0111] (2) Synthesis of multifunctional elastomeric polymers in the chain

[0112] Prepare a 200mL pressure bottle, use a syringe to extract 100mL of n-hexane solvent and add it to the bottle, then extract 10mL of isoprene and add it to the pressure bottle, use a syringe to extract VBC-pyrrolidine from the pressure bottle containing VBC-pyrrolidine, and the amount of VBC-pyrrolidine extracted accounts for 2% of the mass of 10mL of isoprene. Use a syringe to add 0.6mL of n-butyl lithium initiator to the pressure bottle (the initiator is slightly excessive to remove impurities contained in the functionalized monomer). After all the reagents are added, inject a certain amount of nitrogen into the reagent bottle. Then transfer the reaction bottle to a constant temperature water bath shaker at 60°C for reaction. After 2h, the monomer conversion is complete, remove the reaction bottle from the shaker, and cool to room temperature.

[0113] (3) Synthesis of nitrogen-functionalized star polymers

[0114] After the reaction bottle of step (2) is cooled to room temperature, first use a 1mL syringe to inject 0.32mL of butyl lithium into the reaction bottle, then use a 20mL syringe to add 19mL of styrene / n-hexane solution (styrene volume fraction is 27%) into the reaction bottle, and then use a 5mL syringe to add 1.9mL of DVB into the reaction bottle. It is worth noting that after all the reagents are added, a certain amount of nitrogen is injected into the reagent bottle. Then transfer the reaction bottle to a constant temperature water bath shaker at 60°C for reaction. After 2h, the monomer conversion is complete, the reaction bottle is removed from the shaker and cooled to room temperature. Finally, use a syringe to inject 1mL of terminator (isopropanol containing 3% antioxidant BHT by mass) into the reaction bottle. Then the product is devolatilized and vacuum dried to obtain a nitrogen-containing functionalized star polymer.

[0115] Embodiment 6:

[0116] (1) Synthesis of nitrogen-containing functionalized monomers

[0117] Same as Example 5.

[0118] (2) Synthesis of multifunctional elastomeric polymers in the chain

[0119] The difference from Example 5 is that "the amount of VBC-pyrrolidine extracted accounts for 2% of the mass of 10 mL of isoprene" is replaced by "the amount of VBC-pyrrolidine extracted accounts for 6% of the mass of 10 mL of isoprene". The rest is the same as Example 5.

[0120] (3) Synthesis of nitrogen-functionalized star polymers

[0121] Same as Example 5.

[0122] Embodiment 7:

[0123] (1) Synthesis of nitrogen-containing functionalized monomers

[0124] Same as Example 5.

[0125] (2) Synthesis of multifunctional elastomeric polymers in the chain

[0126] The difference from Example 5 is that "the amount of VBC-pyrrolidine extracted accounts for 2% of the mass of 10 mL of isoprene" is replaced by "the amount of VBC-pyrrolidine extracted accounts for 8% of the mass of 10 mL of isoprene". The rest is the same as Example 5.

[0127] (3) Synthesis of nitrogen-functionalized star polymers

[0128] Same as Example 5.

[0129] Comparative Example 1:

[0130] The preparation of the star polymer without functional groups is different from that in Example 1 in that the synthesis of the nitrogen-containing functionalized initiator is not performed, and the synthesis of the chain-end functionalized elastomeric polymer does not add the nitrogen-containing functionalized initiator (i.e., amide lithium initiator) but adds n-butyl lithium initiator. The specific preparation process is as follows:

[0131] (1) Synthesis of elastomeric polymers

[0132] Use a double-ended needle to introduce 100 mL of solvent from a large pressure bottle containing pretreated n-hexane into a 210 mL small pressure bottle; use a 20 mL syringe to extract 10 mL of pretreated isoprene from the large pressure bottle, and use a 1 mL syringe to inject 0.45 mL of n-butyl lithium initiator into the reaction bottle. After all the reagents are added, a certain amount of nitrogen is injected into the reagent bottle to ensure positive pressure in the bottle and strictly ensure anhydrous and oxygen-free reaction conditions. Then transfer the reaction bottle to a constant temperature water bath shaker at 60 ° C for reaction. After 2 hours, the monomer conversion is complete, remove the reaction bottle from the shaker, and cool to room temperature.

[0133] (2) Synthesis of star polymers

[0134] After the reaction bottle of step (1) is cooled to room temperature, 0.32 mL of butyl lithium is first injected into the reaction bottle with a 1 mL syringe, and then 19 mL of styrene / n-hexane solution (styrene volume fraction is 27%) is added to the reaction bottle using a 20 mL syringe, and then 1.9 mL of DVB is added to the reaction bottle using a 5 mL syringe. It is worth noting that after all the reagents are added, a certain amount of nitrogen is injected into the reagent bottle. Then the reaction bottle is transferred to a constant temperature water bath shaker at 60°C for reaction. After 2 hours, the monomer conversion is complete, the reaction bottle is removed from the shaker and cooled to room temperature. Finally, 1 mL of terminator (isopropanol containing 3% antioxidant BHT by mass) is injected into the reaction bottle using a syringe. The product is then devolatilized and vacuum dried to obtain a star polymer.

[0135] Table 1 Molecular weight and molecular weight distribution of star polymers prepared in Examples 1 to 7 and Comparative Examples

[0136]

[0137]

[0138] Embodiments 8 to 14:

[0139] The star polymers prepared in Examples 1 to 7 and Comparative Example 1 were added to the natural rubber mixture with carbon black as the reinforcement system as reinforcing agents for the rubber material. The formula of the rubber mixture is shown in Table 2, and the blank control is shown in Comparative Example 2 in Table 2. The star polymer prepared in Comparative Example 1 was added to the rubber mixture of Comparative Example 3 as a set of internal standards. The nitrogen-containing functionalized star polymer prepared in Example 1 was added to the rubber mixture of Example 8, the nitrogen-containing functionalized star polymer prepared in Example 2 was added to the rubber mixture of Example 9, and the nitrogen-containing functionalized star polymer prepared in Example 3 was added to the rubber mixture of Example 10. The nitrogen-containing functionalized star polymer prepared in Example 4 was added to the rubber mixture of Example 11. The nitrogen-containing functionalized star polymer prepared in Example 5 was added to the rubber mixture of Example 12. The nitrogen-containing functionalized star polymer prepared in Example 6 was added to the rubber mixture of Example 13. The nitrogen-containing functionalized star polymer prepared in Example 7 was added to the rubber mixture of Example 14.

[0140] Table 2 Comparative Examples 2-3, Examples 8-14 Mixing Formula

[0141]

[0142]

[0143] The rubber samples prepared in Comparative Examples 2 to 3 and Examples 8 to 14 were subjected to a cured sample rubber ring tensile test, a dynamic mechanical property test and a wet skid test. The test data are shown in Tables 3 and 4. The test results show that the rubber samples added with Examples 1 to 7 have better tensile properties and reduced rolling resistance than the comparative example 3 added with comparative example 1 and the blank control sample of comparative example 2, and the wet skid resistance of some samples is also improved.

[0144] Table 3 Rheological test data of rubber samples of Comparative Examples 2-3 and Examples 8-14

[0145]

[0146] Table 4 Tensile test data of rubber samples of Comparative Examples 2 to 3 and Examples 8 to 14

[0147]

[0148]

[0149] The experimental data in Table 3 show that, with the addition of the nitrogen-containing functionalized star polymer of the present invention, the △G' value of the rubber material is reduced compared with the blank sample comparative example 2 and the control sample comparative example 3, which indicates that the nitrogen-containing functionalized star polymer prepared by the present invention has a certain weakening of the Payne effect of the NR / CB rubber sample, and at the same time, the tanδ value of the sample at 60°C has a certain decrease, indicating that the nitrogen-containing functionalized star polymer prepared by the present invention has a certain improvement in the rolling resistance of the NR / CB rubber material. Similarly, if the rolling resistance (60°C tanδ value) and the anti-wet skid performance (0°C tanδ value) of the rubber are comprehensively analyzed and compared, it can be seen that the nitrogen-containing functionalized star polymer of the present invention can well balance the two properties of anti-wet skid and rolling resistance. The experimental data in Table 4 show that, with the addition of the nitrogen-containing functionalized star polymer of the present invention, the Tb and Eb values ​​of the rubber material are improved compared with the blank sample comparative example 2 and the control sample comparative example 3, which indicates that the application of the nitrogen-containing functionalized star polymer of the present invention improves the tensile properties of the rubber product. The tensile test was carried out according to the standard ASTM-D412, and the ambient temperature during the test was 25°C. The test sample was annular, with an inner diameter of 14.0 mm, an outer diameter of 16.0 mm, and a height of 2.80 mm. Anton Paar EC302 rheometer was used to determine the dynamic mechanical properties of the cured samples. The dynamic mechanical properties test sample was also annular, with the same size as the tensile test sample. The test conditions were: strain sweep from 0.001% to 15% at 0°C and a frequency of 0.5 Hz.

[0150] Embodiment 15:

[0151] The only difference from Example 1 is that "cyclohexylimide" is replaced by "pyrrolidine" in the synthesis of (1) nitrogen-containing functionalized initiator.

[0152] Embodiment 16:

[0153] The only difference from Example 1 is that "cyclohexyl imine" is replaced by "1-methylpiperazine" in the synthesis of (1) nitrogen-containing functionalized initiator.

[0154] Embodiment 17:

[0155] The only difference from Example 1 is that in (1) the synthesis of the nitrogen-containing functionalized initiator, "cyclohexylimide" is replaced by "thiomorpholine".

[0156] Embodiment 18:

[0157] The only difference from Example 1 is that "cyclohexylimine" in the synthesis of (1) nitrogen-containing functionalized initiator is replaced by "4-cyclopentylpiperidine".

[0158] Embodiment 19:

[0159] The only difference from Example 1 is that "cyclohexyl imine" in the synthesis of (1) nitrogen-containing functionalized initiator is replaced by "4-cyclohexylpiperidine".

[0160] Embodiment 20:

[0161] The difference from Example 2 is that "isoprene" is replaced by "butadiene" in the synthesis of the multifunctional elastomeric polymer in the chain (2).

[0162] Embodiment 21:

[0163] The difference from Example 3 is that "isoprene" is replaced by "butadiene" in the synthesis of the multifunctional elastomeric polymer in the chain (2).

[0164] Embodiment 22:

[0165] The difference from Example 4 is that "isoprene" is replaced by "butadiene" in the synthesis of the multifunctional elastomeric polymer in the chain (2).

[0166] Embodiment 23:

[0167] The difference from Example 15 is that in (2) the synthesis of the chain-end multifunctional elastomeric polymer, "isoprene" is replaced by "butadiene".

[0168] Embodiment 24:

[0169] The difference from Example 16 is that "isoprene" is replaced by "butadiene" in (2) the synthesis of the chain-end multifunctional elastomeric polymer.

[0170] Embodiment 25:

[0171] The difference from Example 17 is that "isoprene" is replaced by "butadiene" in (2) the synthesis of the chain-end multifunctional elastomeric polymer.

[0172] Embodiment 26:

[0173] The difference from Example 18 is that "isoprene" is replaced by "butadiene" in (2) the synthesis of the chain-end multifunctional elastomeric polymer.

[0174] Embodiment 27:

[0175] The difference from Example 19 is that "isoprene" is replaced by "butadiene" in (2) the synthesis of the chain-end multifunctional elastomeric polymer.

[0176] Embodiment 28:

[0177] The only difference from Example 2 is that in the synthesis of (2) chain-end functionalized elastomeric polymer, "use a syringe to draw 10 mL of isoprene and add it to the pressure bottle, use a syringe to draw VBC-cyclohexylimine from the pressure bottle containing VBC-cyclohexylimine, and the amount of VBC-cyclohexylimine drawn accounts for 4% of the mass of 10 mL of isoprene. Use a syringe to add 0.6 mL of n-butyllithium initiator to the pressure bottle" is replaced by "use a syringe to draw VBC-cyclohexylimine from the pressure bottle containing VBC-cyclohexylimine, and the amount of VBC-cyclohexylimine drawn accounts for 10 mL. Use a syringe to add 0.6 mL of n-butyllithium initiator to the pressure bottle. After the reaction is completed, use a syringe to draw 10 mL of isoprene and add it to the pressure bottle to continue the reaction", to obtain a chain-end functionalized elastomeric polymer with multiple active centers.

[0178] Embodiment 29:

[0179] The only difference from Example 28 is that in the synthesis of (2) the chain-end functionalized elastomeric polymer, "VBC-cyclohexylimide" is replaced by "VBC-4-methylpiperidine" to obtain a chain-end functionalized elastomeric polymer with multiple active centers.

[0180] Embodiment 30:

[0181] The only difference from Example 28 is that in the synthesis of (2) the chain-end functionalized elastomeric polymer, "VBC-cyclohexylimide" is replaced by "VBC-pyrrolidine" to obtain a chain-end functionalized elastomeric polymer with multiple active centers.

[0182] Embodiment 31:

[0183] The only difference from Example 28 is that in the synthesis of (2) the chain-end functionalized elastomeric polymer, "isoprene" is replaced by "butadiene" to obtain a chain-end functionalized elastomeric polymer with multiple active centers.

[0184] Embodiment 32:

[0185] The only difference from Example 29 is that in the synthesis of (2) the chain-end functionalized elastomeric polymer, "isoprene" is replaced by "butadiene" to obtain a chain-end functionalized elastomeric polymer with multiple active centers.

[0186] Embodiment 33:

[0187] The only difference from Example 30 is that in the synthesis of (2) the chain-end functionalized elastomeric polymer, "isoprene" is replaced by "butadiene" to obtain a chain-end functionalized elastomeric polymer with multiple active centers.

[0188] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A nitrogen-containing functionalized star polymer, It is characterized in that The nitrogen-containing functionalized star polymer is a core-shell structure composed of a shell composed of a nitrogen-containing functionalized linear elastomeric polymer and a core composed of a polyvinyl aromatic compound, and its structural formula is as follows: in, represents a nitrogen-functionalized linear elastomeric polymer, The number of is 8 to 12, and ● is a polyvinyl aromatic compound.

2. The nitrogen-containing functionalized star polymer according to claim 1, It is characterized in that The nitrogen-containing functionalized linear elastomeric polymer is a chain-end functionalized elastomeric polymer or a multifunctional elastomeric polymer in the chain, and its specific structure is as follows:

3. The nitrogen-containing functionalized star polymer according to claim 1, It is characterized in that The molecular weight of the nitrogen-containing functionalized star polymer is 3,000-10,000,000.

4. The nitrogen-containing functionalized star polymer according to claim 1, It is characterized in that The nitrogen-functionalized linear elastomeric polymer has a molecular weight of 1,000-100,000.

5. A method for preparing a nitrogen-containing functionalized star polymer, It is characterized in that The following steps are involved: A nitrogen-functionalized linear elastomeric polymer is added to a reaction container, an initiator is added to the reaction container, and then a vinyl-substituted aromatic hydrocarbon and a cross-linking agent are added to carry out an anionic polymerization reaction. After the polymerization reaction is completely completed, the reaction container is cooled, and a terminator mixed with an antioxidant is added. The obtained reaction product is subjected to negative pressure to remove volatiles to obtain a nitrogen-functionalized star polymer.

6. The preparation method according to claim 5, It is characterized in that The preparation method of the nitrogen-functionalized linear elastomeric polymer is selected from any one of the following: (a) placing an organic solvent in a reaction vessel, adding a conjugated olefin monomer and then a nitrogen-containing functionalized initiator, and carrying out a polymerization reaction under the protection of an inert gas without water or oxygen to obtain a chain-end functionalized elastomeric polymer with a single active center; or (b) placing an organic solvent in a reaction vessel, adding a nitrogen-containing functional monomer and a conjugated olefin monomer, and then adding an initiator, and performing an anionic polymerization reaction under the protection of an inert gas without water or oxygen to obtain a mid-chain multifunctional elastomeric polymer; or (c) placing an organic solvent in a reaction vessel, adding a nitrogen-containing functionalized monomer, and then adding an initiator, and carrying out a polymerization reaction under the protection of an inert gas without water or oxygen. After the nitrogen-containing functionalized monomer is completely converted, a conjugated olefin monomer is added to the system to continue the reaction, thereby obtaining a chain-end functionalized elastomeric polymer with multiple active centers.

7. The preparation method according to claim 6, It is characterized in that The inert gas is nitrogen or argon; the organic solvent is at least one of n-hexane, pentane, cyclopentane, cyclohexane, toluene and tetrahydrofuran.

8. The preparation method according to claim 6, It is characterized in that In (a), (b) or (c), the structural formula of the conjugated olefin monomer is as follows: Wherein, R is a straight chain or branched chain alkyl or aromatic group having 1 to 4 carbon atoms.

9. The preparation method according to claim 5 or 6, It is characterized in that The initiator is one of alkyl lithium, alkyl aluminum, alkali metal amide and sodium naphthalene; The alkyl lithium is at least one of n-butyl lithium, sec-butyl lithium, tert-butyl lithium and isobutyl lithium; The alkyl aluminum is at least one of triisobutyl aluminum and tert-butyl aluminum, and the alkali metal amide is at least one of sodium amide and lithium amide.

10. The preparation method according to claim 6, It is characterized in that In (a), the nitrogen-containing functionalized initiator is an amine lithium initiator formed by the reaction of a secondary amine compound and an alkyl lithium initiator; the secondary amine compound is selected from at least one of the following compounds: Among them, R 1 is a straight or branched alkyl or aromatic group having 1 to 4 carbon atoms; R 2 , R 3 The same or different, each independently selected from hydrogen, or a linear or branched alkyl or cycloalkyl or aromatic group having 1 to 4 carbon atoms; Y is one of nitrogen, oxygen, sulfur or silicon; a, b, and n are the same or different and are each independently selected from an integer of 2-10.

11. The preparation method according to claim 6, It is characterized in that In (b) or (c), the nitrogen-containing functionalized monomer is obtained by coupling reaction of a styrene derivative of a halogenated alkyl group with a secondary amine compound.

12. The preparation method according to claim 11, It is characterized in that The structural formula of the styrene derivative of the halogenated alkane group is as follows: Wherein, m is an integer of 1-4, and X is a halogen element.

13. The preparation method according to claim 11, It is characterized in that The structure of the secondary amine compound is selected from at least one of the following compounds: Among them, R 1 is a straight chain, branched chain or cyclic alkyl or aromatic group having 1 to 4 carbon atoms; R 2 , R 5 are the same or different, each independently selected from hydrogen, or a linear or branched alkyl, cycloalkyl, aromatic or allyl group containing 1 to 10 carbon atoms; R 3 , R 4 are the same or different and are independently selected from hydrogen, or a linear or branched alkyl or cycloalkyl or aromatic hydrocarbon group containing 1 to 4 carbon atoms; R 6 is hydrogen, or a straight or branched chain alkyl, aryl, allyl or alkoxy group containing 1 to 10 carbon atoms; Y is one of nitrogen, sulfur or silicon; a, b, and n are the same or different and are each independently selected from an integer of 2-10.

14. The preparation method according to claim 13, It is characterized in that R 4 The alkyl group in is methyl or ethyl; 1 , R 2 , R 3 , R 5 are the same or different and are independently selected from methyl or hydrogen; the aromatic group is phenyl; n is 4, 5 or 6; a and b are the same or different and are independently selected from 2 or 3.

15. The preparation method according to claim 5, It is characterized in that The vinyl-substituted aromatic hydrocarbon is selected from at least one of styrene, α-methylstyrene, α-ethylstyrene, vinyltoluene, methoxystyrene, tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methylvinylnaphthalene, divinyl-substituted aromatic hydrocarbons and trivinyl-substituted aromatic hydrocarbons.

16. The preparation method according to claim 5, It is characterized in that The crosslinking agent is a vinyl-substituted aromatic hydrocarbon, and is at least divinyl-substituted.

17. The preparation method according to claim 16, It is characterized in that The cross-linking agent is at least one of divinylbenzene, trivinylbenzene and divinylnaphthalene.

18. The preparation method according to claim 5, It is characterized in that The terminator is carbon dioxide, organic acid, water, isopropanol, siloxane, SiCl 4 and SnCl 4 One of them.

19. The preparation method according to claim 5, It is characterized in that The antioxidant is used in an amount of 0.5-5% of the mass of the polymerized monomer, and the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 4,6-bis(octylthiomethyl)-o-cresol and tris(2,4-di-tert-butyl)phenyl phosphite.

20. The preparation method according to claim 6, It is characterized in that In (b) or (c), the molar ratio of the nitrogen-containing functional monomer to the conjugated olefin monomer is 0.1-20:

100.

21. The preparation method according to claim 5, It is characterized in that The molar ratio of the vinyl-substituted aromatic hydrocarbon to the crosslinking agent is 1-10:1; the total mass ratio of the vinyl-substituted aromatic hydrocarbon and the crosslinking agent to the total mass ratio of the monomers used in the nitrogen-containing functionalized linear elastomeric polymer is 1:0.1-10.

22. The preparation method according to claim 5 or 6 or 10 or 11, It is characterized in that The reaction temperature is 20-90°C, and the reaction time for each reaction is 30-500 minutes.

23. Use of the nitrogen-containing functionalized star polymer according to any one of claims 1 to 4 in rubber materials.

24. The use according to claim 23, It is characterized in that The nitrogen-containing functionalized star polymer is used as an additive for preparing a rubber material, and the rubber material is a natural rubber / carbon black system (or white carbon black), a styrene-butadiene rubber / carbon black system (or white carbon black), a cis-1,4-butadiene rubber / carbon black system (or white carbon black), an isoprene rubber / carbon black system (or white carbon black), a chloroprene rubber / carbon black system (or white carbon black), a butyl rubber / carbon black system (or white carbon black), and an ethylene-propylene rubber / carbon black system (or white carbon black); or the nitrogen-containing functionalized star polymer is used as a reinforcing filler and prepared with natural rubber, styrene-butadiene rubber, cis-1,4-butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, and ethylene-propylene rubber to obtain a composite rubber material.

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