Star-shaped functionalized branching agent as well as preparation and application thereof

Abstract

The invention discloses a star-shaped functionalized branching agent, the branching agent is a star-shaped butadiene polymer, the structure of the branching agent is A-Y-(Bd) n, A is alkyl with functional groups such as an imino group, a phenyleneimino group or an epoxy group; y is Si or Sn; bd is a polybutadiene homopolymer; and n is the number of arms of the polymer and is 3-6. The invention also discloses a preparation method and application thereof. The star-shaped functionalized branching agent is used for modifying the rare earth butadiene rubber, branching not only can reduce the viscosity of a rubber solution in the polymerization process, but also can bring quantitative functional groups into a molecular chain, and the functional groups can enhance the dispersion of a reinforcing filler, especially white carbon black, in a rubber matrix, so that the mechanical properties of the rubber matrix are improved. The strength, the compression fatigue temperature rise performance, the heat generation performance and the like of the butadiene rubber are improved, and the synthesized butadiene rubber is suitable for being used as a high-performance tire sidewall and tread combined rubber.

Description

Technical Field

[0001] The invention relates to a star-shaped functionalized branching agent and the preparation and application thereof. Background Art

[0002] Butadiene rubber is widely used in tire, tape, hose, rubber shoes and other manufacturing industries due to its advantages of high elasticity, low heat generation, low temperature resistance, low rolling resistance, flex resistance, wear resistance, water resistance, etc., easy polymerization process, and cheap and easy-to-obtain raw materials. Rare earth (neodymium) butadiene rubber (NdBR) molecular chain has a highly stereoregular structure and is prone to strain crystallization, thus giving it more excellent tensile / tear resistance, wear resistance, flex resistance, low heat generation, low rolling resistance, etc., which can reduce tire hysteresis loss and internal heat generation, reduce rolling resistance, reduce fuel consumption, improve tire wear resistance, durability and high-speed performance, and its comprehensive performance is better than traditional butadiene rubber such as nickel, titanium and cobalt, meeting the needs of green tires. On the other hand, the higher linear structure of rare earth butadiene rubber makes its solution viscosity greater than that of other types of butadiene rubber with the same Mooney. The high viscosity of the rubber increases the difficulty of engineering production, brings difficulties to polymer transportation and drying, and also makes the processing performance worse. Compared with linear rare earth rubber materials, branched rare earth rubber materials, due to their unique physical and chemical properties and branched structure, have the ability to obtain high molecular weight polymers while maintaining low melt and solution viscosities, thus achieving the unity of their physical and mechanical properties and processing properties at a lower viscosity of the rubber solution.

[0003] From the perspective of molecular structure optimization design, long-chain branched rare earth butadiene rubber can greatly reduce the viscosity of the rubber while maintaining the regularity of the molecular chain and not increasing the molecular chain ends, and at the same time improve the processing performance, which is undoubtedly the most important development direction of butadiene rubber. At the same time, compared with the corresponding linear rare earth butadiene rubber, long-chain branched rare earth butadiene rubber has the following advantages: (1) reducing the viscosity of the rubber during the polymerization process and reducing the difficulty of engineering in industrial production; (2) improving the cold flow resistance of the raw rubber; (3) improving the tensile strength, reducing the hysteresis loss, and reducing the heat generation, which is conducive to energy saving and consumption reduction and improving safety, and achieving a comprehensive balance of rolling resistance, anti-slip and wear resistance.

[0004] Carbon black / white carbon black is the most widely used reinforcing filler in rubber. There is no polar group in the molecular chain of butadiene rubber, and its compatibility with carbon black / white carbon black is poor during processing. The Payne effect is significant, and the mechanical properties are significantly reduced. Introducing star structures and functional groups in branching agents can enhance the polarity of the molecular chain of butadiene rubber, improve the compatibility of butadiene rubber and reinforcing fillers, and also improve product performance. Summary of the invention

[0005] The inventors found that the existing rare earth butadiene rubber polymer solution has high viscosity and the interaction between polar rubber and carbon black / white carbon black is poor, resulting in the rubber product's tensile strength and compression fatigue temperature rise performance failing to meet expectations. After further research and development, the present invention was made.

[0006] As one aspect of the present invention, it relates to a star-functionalized branching agent, wherein the branching agent is a star-functionalized butadiene polymer, and its structure is shown in formula (I):

[0007] AY-(Bd) n

[0008] (I)

[0009] Wherein, A is an alkyl group with imine, phenylimine or epoxy functional groups; Y is Si or Sn; Bd is a polybutadiene polymer; n is the number of arms of the polymer, n = 3 to 6. The number average molecular weight of the polymer is 2000-50000, and the molecular weight distribution is 1.2-2.0.

[0010] As another aspect of the present invention, it relates to a method for preparing the above-mentioned star-shaped functionalized branching agent, comprising: mixing butadiene, a solvent (such as hexane, cyclohexane, cyclopentane, etc.) and a structure regulator (such as tetrahydrofuran, diethylene glycol dimethyl ether, etc.), using an alkyl lithium (such as n-butyl lithium) as an initiator, polymerizing, and after the polymerization conversion rate reaches 100%, adding an alkoxy silicon / tin compound coupling agent AY-(OCH3)3 containing an epoxy group, an aniline group or an imine group, A and Y are as described above, the butadiene active chain segment and the alkoxy group in AY-(OCH3)3 undergo coupling reaction, and the alkoxy group is removed to obtain a branching agent with a star-shaped functional group. The structure regulator can increase the content of vinyl in the butadiene unit.

[0011] As another aspect of the present invention, it relates to the use of the star-shaped functionalized branching agent in the preparation of long-chain branched rare earth butadiene rubber.

[0012] As another aspect of the present invention, it relates to a long-chain branched rare earth butadiene rubber, the structural formula of which is shown in formula (II):

[0013]

[0014] (II)

[0015] Wherein, Bd1 is a polybutadiene rubber branch chain (in a specific embodiment, the number average molecular weight is 10000-20000); m is the number of branches, selected from a natural number of 20-40; AY-(Bd) nis the main chain (in a specific embodiment, the number average molecular weight is 2000-50000), wherein A is an alkyl group with an imine group, a phenylimine group or an epoxy group functional group; Y is Si or Sn; Bd is a polybutadiene polymer; n is the number of arms of the polymer, n=3-6.

[0016] As another aspect of the present invention, butadiene is subjected to a branched rare earth catalyst to prepare a long-chain branched rare earth butadiene rubber through coordination polymerization, wherein the branched rare earth catalyst contains the star-shaped functionalized branching agent. The rare earth catalyst is prepared by sequentially adding neodymium carboxylate, alkyl aluminum, alkyl aluminum hydride, the star-shaped functionalized branching agent, and alkyl aluminum halide to a solvent and aging. The molar ratio of the rare earth neodymium carboxylate, alkyl aluminum, alkyl aluminum hydride, alkyl aluminum halide, and branching agent is 1:3-20:2-20:1-6:1-10.

[0017] As another aspect of the present invention, it relates to the use of the long-chain branched rare earth butadiene rubber in the preparation of tires.

[0018] As another aspect of the present invention, it relates to a tire, comprising the long-chain branched rare earth butadiene rubber.

[0019] In the present invention, firstly, alkyl lithium is used as an initiator, hydrocarbons are used as solvents, organic matter with a certain polarity is used as a structure regulator, and butadiene is used as a monomer to synthesize a butadiene polymer, and then a star coupling agent AY-(OCH3)3 is used for coupling reaction to obtain a star-shaped branching agent, AY-(Bd) n , wherein A is an alkyl group with functional groups such as imine, phenylimine or epoxy; Y is Si or Sn; Bd is a polybutadiene polymer; n is the number of arms of the polymer, n=3-6. The number average molecular weight of the polymer is 2000-50000, and the molecular weight distribution is 1.2-2.0. The long-chain branched rare earth cis-butadiene rubber is prepared by coordination polymerization using the branching agent and butadiene under the action of a rare earth catalyst. The invention not only reduces the viscosity of the polymerized rubber during the polymerization process, but also increases the interaction between the polar butadiene rubber and the carbon black / white carbon black, thereby ensuring the butadiene rubber has the properties of high strength, flex resistance, low heat generation and the like.

[0020] The percentages described in the present invention all refer to mass percentages.

[0021] In a specific embodiment, the preparation method of the functionalized rare earth butadiene rubber branching agent may include the following steps: the preparation of the branching agent, based on 100% of the total mass of the reaction monomers, firstly, in a stainless steel reactor with a jacket, argon is replaced 2 to 4 times, 300% to 800% of the solvent, butadiene monomer and 0.01% to 0.5% of the polarity regulator are added to the reactor in sequence, and an alkyl lithium initiator is added, the reaction temperature is 50°C to 90°C, and the reaction pressure is 0.1MPa to 0. 25MPa, reaction time is 50min~80min; after the conversion rate reaches 100%, coupling agent AY-(OCH3)3 is added for coupling reaction to form: AY-(Bd)n, A is an alkyl group with functional groups such as epoxy, imine, and phenylimine, and n=3~6; the molar ratio of the star coupling agent to the alkyl lithium is 0.1~1.0, the coupling temperature is 60℃~90℃, the time is 20min~80min, and after the reaction is completed, a star-shaped branching agent with functional groups is obtained.

[0022] In a specific embodiment, the preparation method of the long-chain branched butadiene rubber may include the following steps: based on 100% of the total mass of the reaction monomers, first, in a stainless steel reactor with a jacket, argon is replaced 2 to 4 times, 200% to 800% of the solvent and butadiene monomer are added to the reactor, and the aged rare earth catalyst and the branching agent are added to the reactor to initiate the polymerization reaction. The reaction temperature is 50°C to 80°C, the reaction pressure is 0.2MPa to 0.4MPa, and the reaction time is 120min to 300min. After the reaction is complete, an alcohol terminator and an antioxidant are added, and the long-chain branched rare earth butadiene rubber product is obtained by condensation and drying.

[0023] The polymerization reaction for preparing the branching agent of the present invention is carried out in an oxygen-free, water-free, preferably in an inert gas environment. The polymerization process is completed in a hydrocarbon solvent, and preferred hydrocarbon solvents include straight-chain alkanes, cycloalkanes and aromatic hydrocarbons, such as hexane, octane, heptane, cyclohexane, benzene, toluene, ethylbenzene and mixtures thereof, preferably hexane. The amount added is not particularly limited, and the amount required for the usual polymerization reaction can be used, such as 300 to 800 wt% of the total weight of the monomers.

[0024] The initiator used in the preparation of the branching agent of the present invention is preferably an organic monolithium compound, and a hydrocarbon monolithium compound is commonly used, i.e., RLi, wherein R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or a composite group of the above groups containing 1 to 20 carbon atoms. Such organic lithium compounds include n-butyl lithium, sec-butyl lithium, methyl butyl lithium, phenyl butyl lithium, naphthalene lithium, cyclohexyl lithium, dodecyl lithium, etc. The most commonly used are n-butyl lithium and sec-butyl lithium. The amount of organic lithium added is determined by the molecular weight of the designed polymer.

[0025] In the polymerization system for preparing the branching agent of the present invention, 0.01% to 0.5% of a polar organic compound is added as a structural regulator to cause the alkyl lithium initiator to produce a polarization or solvation effect, reduce its association degree, and increase the initiation reaction speed of a positive initiator such as n-butyl lithium. At the same time, the regulator can increase the content of vinyl in the butadiene unit. Such polar organic compounds include diethylene glycol dimethyl ether (2G), tetrahydrofuran (THF), ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, hexamethylphosphonic triamide, etc., preferably diethylene glycol dimethyl ether and tetrahydrofuran.

[0026] The star coupling agent used in the preparation of the branching agent of the present invention is an alkoxy silicon or tin compound containing one or more epoxy groups, aniline or imine groups, and its general formula is: AY-(OR2)3, wherein A is an alkyl or cycloalkyl group containing epoxy groups, aniline or imine groups, and the functional groups can be R2 is an alkyl group containing 1-4 carbon atoms; Y is a silicon atom or a tin atom. The coupling agent is a silicon or tin compound containing multiple active centers. The coupling agent containing the above functional groups reacts with the active chain P to introduce functional groups such as epoxy, imine, and phenylimine into the polymer, thereby obtaining a polymer containing functional groups. The amount of the above multi-active center coupling agent depends on the amount of the initiator. Generally, the molar ratio of the coupling agent to the organic lithium is 0.1 to 1.0.

[0027] The method for preparing the branched rare earth catalyst of the present invention can be, for example, adding rare earth carboxylate, alkyl aluminum, alkyl aluminum hydride, branching agent and halogen compound into a solvent, mixing evenly, and aging at room temperature for 0.2h to 2h to obtain the branched rare earth catalyst. The molar ratio of the branching agent to the rare earth catalyst can be 1:1 to 10:1.

[0028] The amount of rare earth catalyst added in the polymerization process of long-chain branched polybutadiene is measured by the molar ratio of rare earth carboxylate to butadiene monomer, which is 2×10 -5 ~2×10 -4 :1.

[0029] In the process of preparing the rare earth catalyst, the branching agent is aged together with the rare earth carboxylate neodymium, alkyl aluminum and the like which play a catalytic role. Compared with adding the branching agent to the system after the rare earth catalyst is added to the polymerization system to polymerize into a macromolecule, the technical effect achieved is better. On the one hand, the branching agent can be used as a large sterically hindered ligand. The large volume of steric hindrance destroys the association of the rare earth neodymium and avoids the catalyst from forming heterogeneous particle precipitation. In industrial production, the heterogeneous catalyst is easy to block the pipeline due to precipitation, resulting in polymerization instability and affecting long-term production. On the other hand, it can avoid the introduction of trace impurities when the branching agent is added in the late stage of polymerization. The introduction of impurities will reduce the branching coefficient and affect the branching effect.

[0030] By using the preparation method of branched rare earth butadiene rubber disclosed in the present invention, a polymer with a cis-1,4-structure content greater than 98%, an adjustable weight-average molecular weight within the range of 200,000 to 1,000,000, a branching coefficient of 2.0 to 3.5, and a solution viscosity (η) of 1.2 dL / g to 3.0 dL / g can be synthesized.

[0031] A rare earth butadiene rubber star-shaped functionalized branching agent (referred to as star-shaped branching agent in this application) is used to modify the rare earth butadiene rubber. The star-shaped branching can significantly reduce the solution viscosity of the polymer, bringing convenience to the processes of heat transfer, transportation, glue spraying and coagulation in production. At the same time, the functional group can increase the polarity of the rubber, improve the compatibility of non-polar rubber with carbon black / white carbon black, and bring good processing performance and excellent tensile strength, flex resistance, low heat generation and other properties. DETAILED DESCRIPTION

[0032] The inventors referred to CN1342718A and added a 3d group transition metal organic compound (such as nickel neodecanoate) during the catalyst preparation process, and the intrinsic viscosity of the polymer was reduced from 7.5 dL / g to 5.3 dL / g. However, this operation caused the cis-1,4-structure content of the polyisoprene structural unit to drop from 98.9% to 97.6%.

[0033] The inventors refer to CN202110838519.7 and CN202210011239.3, and use a rare earth catalyst system two-step method to obtain a star-shaped branched rare earth rubber with a rare earth core and a branched chain structure. The synthesized rubber is a star-shaped structure, which does not belong to the long-chain branched type, and the catalyst used is a cyclopentadienyl rare earth complex as the main catalyst, and an organic boron reagent is used. The catalyst synthesis is cumbersome and the price is relatively expensive.

[0034] The inventors prepared branched rare earth isoprene rubber with reference to CN201310165531.1. The branching agent used is liquid rubber, does not contain functional groups, and has no interaction with rubber / filler dispersion.

[0035] The inventors conducted relevant experiments with reference to CN102115509A and US20040102589A1, but since they did not contain functional groups, the results were not as expected by the inventors.

[0036] In view of the fact that the existing technologies cannot meet the expectations of the inventors, the present invention was made after further research and development.

[0037] The raw materials used in the examples of the present invention are all industrial polymer grade and used after purification, without other special requirements. The results of the examples and comparative examples are listed in Table 1. The branching coefficient test method is g=ML 1+4 100℃ *10 / SV,ML 1+4 100℃ is the Mooney viscosity of the sample, SV is the dynamic viscosity of the sample, in mPa·S. The intrinsic viscosity of the polymerized glue was measured using an Ubbelohde viscometer at 25°C, with toluene as the solvent, and the calculation formula is [η] = [2(η sp -lnη r )] 1 / 2 / c, where η r =t / t0,η sp =η r -1, t is the flow time of the polymer toluene solution with a concentration of c, and t0 is the flow time of toluene.

[0038] In the following examples, the catalyst without a branching agent is referred to as a rare earth catalyst, and the catalyst containing a branching agent is referred to as a branched rare earth catalyst.

[0039] Embodiment 1:

[0040] (1) Preparation of branching agent: In a 1L reactor with a jacket, argon was introduced to replace the system three times. 240 g of hexane, 0.2 g of tetrahydrofuran, 60 g of butadiene, and 30 mmol of n-butyl lithium were added to the reactor, the temperature was raised to 60°C, and polymerization was carried out for 50 min. After the monomers were completely converted, 10 mmol of The coupling agent CH2CH2-Si-(OCH3)3 was used for coupling reaction at a temperature of 60°C and a reaction time of 80 min. After the coupling reaction was completed, the reaction was terminated and set aside.

[0041] The prepared branching agent is a polymer represented by formula (I), wherein A is CH2CH2, Y is Si, Bd is a butadiene polymerization unit, n=3, and the polymer molecular weight is 2000.

[0042] (2) Preparation of long-chain branched rare earth butadiene rubber: Under argon protection, 50 mL of hexane was added to a dry catalyst preparation bottle, and then 0.03 mmol of neodymium isooctanoate, 0.75 mmol of triisobutylaluminum, 0.15 mmol of diethylaluminum hydride, 0.09 mmol of diethylaluminum chloride, and 0.2 mmol of the branching agent prepared in step 1 were mixed in the order of hexane + neodymium + aluminum + aluminum hydride + branching agent + aluminum chloride, and aged at room temperature for 1 hour to obtain a branched rare earth catalyst for use.

[0043] Under argon protection, 3200 g of hexane and 800 g of butadiene were added to a 10 L stainless steel reactor with a jacket, and then the prepared catalyst was added according to the molar ratio of butadiene to neodymium isooctanoate, the molar ratio of neodymium isooctanoate to butadiene was 1×10 -4 , polymerize at 60-70°C for 3 hours, and add 1wt% 2,6-di-tert-butyl-p-methylphenol ethanol solution to terminate the reaction. The rubber solution is wet coagulated and dried to obtain a long-chain branched rare earth butadiene rubber as shown in formula (II), wherein (Bd1)n is a polybutadiene branch chain with a number average molecular weight of 10,000 and a branch number m of 20; CH2CH2-Si-(Bd)3 is the main chain, the number average molecular weight is 2000, and Bd is the butadiene polymerization unit.

[0044] Comparative Example 1:

[0045] The other process conditions and the amount of raw materials added are the same as those in Example 1, except that no branching agent is added during the polymerization process to obtain a universal rare earth butadiene rubber product.

[0046] Embodiment 2:

[0047] (1) Preparation of branching agent: In a 1L reactor with a jacket, argon was introduced to replace the system three times. 420 g of hexane, 0.02 g of pentamethyldiethylenetriamine, 60 g of butadiene, and 15 mmol of n-butyllithium were added to the reactor, the temperature was raised to 70°C, and polymerization was carried out for 60 min. After the monomers were completely converted, 5 mmol of The coupling agent CH2CH2-Si-(OCH3)3 was used for coupling reaction, the coupling temperature was 70°C, and the reaction time was 70 min. After the coupling reaction was completed, the reaction was terminated and set aside.

[0048] The prepared branching agent is a polymer represented by formula (I), wherein A is CH2CH2, Y is Si, Bd is a butadiene polymerization unit, n=3, and the polymer molecular weight is 4000.

[0049] (2) Preparation of long-chain branched rare earth butadiene rubber: Under argon protection, add 50 mL of hexane to a dry catalyst preparation bottle, then add 0.04 mmol of neodymium nonanoate, 0.6 mmol of triisobutylaluminum, 0.4 mmol of dibutylaluminum hydride, 0.16 mmol of diisobutylaluminum chloride, and 0.3 mmol of the branching agent prepared in step 1, mix them evenly in a certain order, and age them at 50° C. for 30 min to obtain a branched rare earth catalyst for use.

[0050] Under argon protection, 4000 g of hexane and 800 g of butadiene were added to a 10 L stainless steel reactor with a jacket, and then the prepared catalyst solution was added. The molar ratio of neodymium nonanoate to butadiene was 5×10 -5 , polymerized at 60°C for 4 hours, and 1 wt% of an antioxidant 1076 [3,5-di-tert-butyl-4-hydroxyphenylpropionic acid octadecyl] in ethanol solution was added to terminate the reaction. The rubber solution was wet coagulated and dried to obtain a long-chain branched rare earth butadiene rubber as shown in formula (II), wherein (Bd1)n is a polybutadiene branch chain with a number average molecular weight of 14,000 and a branch number m of 25; CH2CH2-Si-(Bd)3 is the main chain, the number average molecular weight is 4000, and Bd is the butadiene polymerization unit.

[0051] Comparative Example 2:

[0052] Other process conditions and raw material addition amounts are the same as those in Example 2, except that: the branching agent uses a non-functionalized butadiene polymer, that is, no star coupling agent is added in the branching agent preparation step, and a linear butadiene polymer is obtained.

[0053] Embodiment 3:

[0054] (1) Preparation of branching agent: In a 1L reactor with a jacket, argon was introduced to replace the system three times. 560 g of cyclohexane, 0.15 g of diethylene glycol dimethyl ether, 70 g of butadiene, and 7 mmol of n-butyl lithium were added to the reactor. The temperature was raised to 80°C and the polymerization was carried out for 50 min. After the monomers were completely converted, 2.33 mmol of The coupling agent CH2CH2-Sn-(OCH3)3 was used for coupling reaction, the coupling temperature was 80°C, and the reaction time was 30 min. After the coupling reaction was completed, the reaction was terminated and set aside.

[0055] The prepared branching agent is a polymer represented by formula (I), wherein A is CH2CH2, Y is Sn, Bd is a butadiene polymerization unit, n=3, and the polymer molecular weight is 10000.

[0056] (2) Preparation of long-chain branched rare earth butadiene rubber: Under argon protection, add 95 mL of hexane to a dry catalyst preparation bottle, then add 0.02 mmol of neodymium neodecanoate, 0.8 mmol of diisobutylaluminum hydride, 0.04 mmol of sesquiethylaluminum chloride, and 0.18 mmol of the branching agent prepared in step 1. After mixing well, age at room temperature for 1 hour to obtain a branched rare earth catalyst for use.

[0057] Under argon protection, 3600 g of cyclohexane and 600 g of butadiene were added to a 10 L stainless steel reactor with a jacket, and then the prepared catalyst solution was added. The molar ratio of neodymium neodecanoate to butadiene was 2×10 -5 , polymerized at 70°C for 3 hours, and 1 wt% of an antioxidant 1076 [3,5-di-tert-butyl-4-hydroxyphenylpropionic acid octadecyl] in ethanol solution was added to terminate the reaction. The rubber solution was wet coagulated and dried to obtain a long-chain branched rare earth butadiene rubber as shown in formula (II), wherein (Bd1)n is a polybutadiene branch chain with a number average molecular weight of 16,000 and a branch number m of 30; CH2CH 2 -Sn-(Bd)3 is the main chain, the number average molecular weight is 10000, and Bd is the butadiene polymerization unit.

[0058] Comparative Example 3:

[0059] The other process conditions and the amount of raw materials added are the same as those in Example 3, except that the branching agent is epoxidized liquid polybutadiene rubber, and the epoxidized functional groups account for 20%-40% of the moles of double bonds.

[0060] Embodiment 4:

[0061] (1) Preparation of branching agent: In a 1L reactor with a jacket, argon was passed through the system to replace it three times. 280g of cyclopentane, 0.09g of tetrahydrofurfuryl ether, 70g of butadiene, and 8mmol of n-butyl lithium were added to the reactor, and the temperature was raised to 80°C and polymerized for 50min. After the monomers were completely converted, 1.6mmol of NH(CH2-Si-(OCH3)3)2 coupling agent was added at once for coupling reaction. The coupling temperature was 90°C and the reaction time was 20min. After the coupling reaction was completed, the reaction was terminated and set aside.

[0062] The prepared branching agent is a polymer represented by formula (I), wherein A is NH(CH2)2, Y is Si, Bd is a butadiene polymerization unit, n=6, and the polymer molecular weight is 20,000.

[0063] (2) Preparation of long-chain branched rare earth butadiene rubber: Under argon protection, add 50 mL of hexane to a dry catalyst preparation bottle, then add 0.05 mmol of neodymium decanoate, 0.25 mmol of tributylaluminum, 1.5 mmol of diethylaluminum hydride, 0.15 mmol of dibutylaluminum chloride, and 0.4 mmol of the branching agent prepared in step 1, mix well, and age at room temperature for 1 h to obtain a branched rare earth catalyst for use.

[0064] Under argon protection, 4000 g of cyclopentane and 800 g of butadiene were added to a 10 L stainless steel reactor with a jacket, and then the catalyst solution prepared above was added. The molar ratio of neodymium decanoate to butadiene was 2×10 -4 , polymerized at 90°C for 2 hours, and 1wt% antioxidant 2,6-di-tert-butyl-p-methylphenol ethanol solution was added to terminate the reaction. The rubber solution was wet coagulated and dried to obtain long-chain branched rare earth butadiene rubber as shown in formula (II), wherein (Bd1)n is a polybutadiene branch chain with a number average molecular weight of 20,000 and a branch number m of 35; NH(CH2-Si-)2(Bd)6 is the main chain with a number average molecular weight of 20,000, and Bd is a butadiene polymerization unit.

[0065] Comparative Example 4:

[0066] The other process conditions and the order of adding raw materials are the same as those in Example 4, except that the branching agent is not aged together with the catalyst, the branching agent is added after the polymerization is completed, and the branching agent is prepared in step (1) of Example 4.

[0067] Embodiment 5:

[0068] (1) Preparation of branching agent: In a 1L reactor with a jacket, argon was introduced to replace the system three times. 480 g of hexane, 0.35 g of tetrahydrofuran, 80 g of butadiene, and 2.3 mmol of n-butyl lithium were added to the reactor, the temperature was raised to 90°C, and polymerization was carried out for 50 min. After the monomers were completely converted, 0.8 mmol of The coupling agent CH2CH2-Sn-(OCH3)3 was used for coupling reaction, the coupling temperature was 80°C, and the reaction time was 30 min. After the coupling reaction was completed, the reaction was terminated and set aside.

[0069] The prepared branching agent is a polymer represented by formula (I), wherein A is CH2CH2, Y is Sn, Bd is butadiene polymerization unit, n=3, and the polymer molecular weight is 35000.

[0070] (2) Preparation of long-chain branched rare earth butadiene rubber: Under argon protection, add 70 mL of cyclohexane to a dry catalyst preparation bottle, then add 0.01 mmol of neodymium isooctanoate, 0.05 mmol of triethylaluminum, 0.05 mmol of dibutylaluminum hydride, 0.04 mmol of diisobutylaluminum chloride, and 0.08 mmol of the branching agent prepared in step 1, mix well, and age at room temperature for 0.5 h to obtain a branched rare earth catalyst for standby use.

[0071] Under argon protection, 3200 g of hexane and 800 g of butadiene were added to a 10 L stainless steel reactor with a jacket, and then the prepared catalyst solution was added. The molar ratio of neodymium isooctanoate to butadiene was 1×10 -4 , polymerize at 80°C for 3 hours, and add 1wt% antioxidant 2,6-di-tert-butyl-p-methylphenol ethanol solution to terminate the reaction. The rubber solution is wet coagulated and dried to obtain long-chain branched rare earth butadiene rubber as shown in formula (II), wherein (Bd1)n is a polybutadiene branch chain with a number average molecular weight of 15000 and a branch number m of 40; CH2CH 2- Sn-(Bd)3 is the main chain, the number average molecular weight is 35000, and Bd is the butadiene polymerization unit.

[0072] Comparative Example 5:

[0073] The other process conditions and the order of adding raw materials are the same as those in Example 5, except that the branching agent is not aged together with the catalyst, the branching agent is added after the polymerization is completed, and the type of the branching agent is dialkyldiolefin silane disclosed in the patent.

[0074] Embodiment 6:

[0075] (1) Preparation of branching agent: In a 1L reactor with a jacket, argon was introduced to replace the system three times. 420 g of cyclohexane, 0.24 g of tetrahydrofuran, 70 g of butadiene, and 1.4 mmol of n-butyl lithium were added to the reactor, the temperature was raised to 80°C, and polymerization was carried out for 50 min. After the monomers were completely converted, 0.56 mmol of The coupling agent CH2CH2-Si-(OCH3)3 was used for coupling reaction, the coupling temperature was 60°C, and the reaction time was 70 min. After the coupling reaction was completed, the reaction was terminated and set aside.

[0076] The prepared branching agent is a polymer represented by formula (I), wherein A is CH2CH2, Y is Si, Bd is a butadiene polymerization unit, n=3, and the polymer molecular weight is 50,000.

[0077] (2) Preparation of long-chain branched rare earth butadiene rubber: Under argon protection, add 80 mL of hexane to a dry catalyst preparation bottle, then add 0.04 mmol of neodymium decanoate, 0.20 mmol of tributylaluminum, 1.0 mmol of diethylaluminum hydride, 0.12 mmol of dibutylaluminum chloride, and 0.28 mmol of the branching agent prepared in step 1, mix well, and age at room temperature for 0.6 h to obtain a branched rare earth catalyst for use.

[0078] Under argon protection, 3000g of cyclohexane and 800g of butadiene were added to a 10L stainless steel reactor with a jacket, and then the above prepared catalyst solution was added, the molar ratio of neodymium decanoate to butadiene was 5×10-4, and the polymerization was carried out at 70°C for 3.5 hours, and 1wt% of the antioxidant TNPP ethanol solution was added to terminate the reaction. The rubber solution was wet coagulated and dried to obtain a long-chain branched rare earth butadiene rubber as shown in formula (II), wherein (Bd1)n is a polybutadiene branch chain with a number average molecular weight of 18000 and a branch number m of 30; CH2CH2-Si-(Bd)3 is the main chain, the number average molecular weight is 50,000, and Bd is the butadiene polymerization unit.

[0079] Comparative Example 6:

[0080] The other process conditions and the order of adding raw materials are the same as those in Example 6, except that the branching agent is not aged together with the catalyst, the branching agent is added after the polymerization is completed, and the type of the branching agent is the liquid isoprene rubber disclosed in the patent.

[0081] Table 1 Physical properties and dynamic mechanical properties of the embodiments and comparative examples

[0082]

[0083] The results in Table 1 show that the content of cis-1,4 structure of the long-chain branched rare earth butadiene rubber synthesized by the present invention is above 98%, the branching coefficient is between 2.48-3.12 (a high branching coefficient indicates a good branching effect), and the viscosity of the rubber is significantly lower than that of the unbranched and different branched cases in the comparative example. Since the branching also carries functional groups, the tensile strength and compression fatigue temperature rise (which can represent heat generation, the lower the more beneficial) are significantly better than the unbranched and branched cases disclosed in the comparative example. It can be seen from the embodiment and the comparative example 1 that the viscosity of the rubber after branching is reduced from 5.67dL / g to 2.35dL / g, which is beneficial to solving the transportation and post-processing of the polymerization process. At the same time, the tensile strength is increased from 16.5MPa to 18.6MPa, and the compression fatigue temperature rise is reduced from 27.6℃ to 23.2℃, indicating that the material has low fatigue heat generation. From Example 2-3 and Comparative Example 2-3, it can be seen that in the presence of branching, the amine functional group containing the functional group can promote the dispersion of carbon black / white carbon black in the rubber, so the tensile strength is improved, the compression fatigue temperature rise is significantly reduced, and the tensile strength is improved, which is extremely beneficial to improving the stiffness and low heat generation of the tire sidewall material. From Example 4-6 and Comparative Example 4-6, it can be seen that compared with adding the branching agent to the polymerization system after aging with the catalyst and adding the branching agent to the system at the end of the polymerization, the branching coefficient of the embodiment is higher, the viscosity of the rubber is lower, and the rolling resistance performance is better.

[0084] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A star-shaped functionalized branching agent, characterized in that: The branching agent is a star-shaped functionalized butadiene polymer, as shown in formula (I), AY-(Bd) n (I)， Wherein, A is an alkyl group with an imine group, a phenylimine group or an epoxy group functional group; Y is Si or Sn; Bd is a polybutadiene polymer; and n is the number of arms of the polymer, n=3-6.

2. The star-shaped functionalized branching agent according to claim 1, characterized in that: The number average molecular weight of the polymer is 2000-50000, and the molecular weight distribution is 1.2-2.

0.

3. A method for preparing the star-shaped functionalized branching agent according to any one of claims 1 or 2, characterized in that: include: Butadiene, solvent and structure regulator are mixed, alkyl lithium is used as initiator, polymerization is carried out, and after the polymerization is completed, a star coupling agent is added to carry out coupling reaction.

4. The method according to claim 3, characterized in that The structure regulator is tetrahydrofuran or diethylene glycol dimethyl ether; the alkyl lithium is n-butyl lithium; and the star coupling agent is an alkoxy silicon or tin compound containing one or more epoxy groups, aniline groups or imine groups.

5. Use of the star-shaped functionalized branching agent according to any one of claims 1 or 2 in the preparation of long-chain branched rare earth butadiene rubber.

6. A long-chain branched rare earth butadiene rubber, characterized in that: The long-chain branched rare earth butadiene rubber is as shown in formula (II), Wherein, Bd1 is a polybutadiene rubber branch chain; m is the number of branches, selected from a natural number of 20-40; AY-(Bd) n is the main chain, wherein A is an alkyl group with an imine group, a phenylimine group or an epoxy group functional group; Y is Si or Sn; Bd is a polybutadiene polymer; n is the number of arms of the polymer, n=3-6.

7. The long-chain branched rare earth butadiene rubber according to claim 6, characterized in that: Bd1 is a polybutadiene rubber branched chain with a number average molecular weight of 10000-20000; AY-(Bd) n It is the main chain and has a number average molecular weight of 2000-50000.

8. A method for preparing the long-chain branched rare earth butadiene rubber according to any one of claims 6 or 7, characterized in that: include: Long-chain branched rare earth cis-1,1-butadiene is prepared by coordination polymerization under the action of a branched rare earth catalyst, wherein the branched rare earth catalyst contains the star-shaped functionalized branching agent described in any one of claims 1 or 2.

9. The method of claim 8, characterized in that The branched rare earth catalyst is prepared by sequentially adding neodymium carboxylate, alkyl aluminum, alkyl aluminum hydride, the star-shaped functionalized branching agent according to any one of claims 1 or 2, and alkyl aluminum halide into a solvent and aging.

10. The method according to claim 9, characterized in that The molar ratio of the neodymium carboxylate, alkyl aluminum, alkyl aluminum hydride, alkyl aluminum halide and branching agent is 1:3-20:2-20:1-6:1-10.

11. Use of the long-chain branched rare earth butadiene rubber according to any one of claims 6 or 7 in the preparation of tires.

12. A tire, characterized in that: Comprising the long-chain branched rare earth butadiene rubber as described in any one of claims 6 or 7.

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