Tertiary amine functionalized multi-element integrated rubber, preparation method and application thereof, rubber composition and application thereof, vulcanized rubber and application thereof

Abstract

The invention provides tertiary amine functionalization-containing multi-element integrated rubber and a preparation method and application thereof, a rubber composition and application thereof, and vulcanized rubber and application thereof, and relates to the technical field of functional polymers. The main skeleton of the multi-element integrated rubber containing tertiary amine functionalization provided by the invention is provided by the styrene monomer and the diene monomer, and a tertiary amine polar functional group is introduced, so that the polarity of the multi-element integrated rubber and the dispersity and compatibility of filler particles such as carbon black and the like are greatly improved. Moreover, the multi-element integrated rubber has an adjustable cis / trans-1, 4-structure proportion, can realize functionalization at any position in a chain, and can fully utilize the wear resistance of trans-rubber and the high elasticity of cis-rubber. Moreover, the multi-element integrated rubber containing the tertiary amine functionalization provided by the invention can realize accurate regulation and control of polymer molecular weight and distribution thereof, a microscopic sequence structure and quantification and positioning of the tertiary amine functionalization, and the comprehensive performance of the multi-element integrated rubber containing the tertiary amine functionalization is excellent.

Description

Technical Field

[0001] The invention relates to the technical field of functional polymers, and in particular to a multi-component integrated rubber containing tertiary amine functionalization, a preparation method and application thereof, a rubber composition and application thereof, and a vulcanized rubber and application thereof. Background Art

[0002] Integral Rubber is a new technology product in the field of synthetic rubber and a cutting-edge topic in the field of macromolecular design. It belongs to the category of "tailor-made" in polymer synthetic chemistry. Integrated rubber synthesized by anionic polymerization is mostly prepared by polymerization of styrene and various conjugated dienes initiated by alkyl lithium. Since the synthesized integrated rubber products have the characteristics of high and low temperature resistance, low rolling resistance, good wear resistance, and excellent anti-slip performance, they have important application value in the fields of high-performance tires, high-impact resins, shock-absorbing devices, and viscosity index improvers. However, when the existing integrated rubber is used to prepare vulcanized rubber, it has poor compatibility with fillers such as carbon black. Summary of the invention

[0003] In view of this, the object of the present invention is to provide a multi-component integrated rubber containing tertiary amine functionalization and a preparation method and application thereof, a rubber composition and an application thereof, a vulcanized rubber and an application thereof. The multi-component integrated rubber containing tertiary amine functionalization provided by the present invention has excellent mechanical properties, dynamic damping performance and good compatibility.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a multi-component integrated rubber containing tertiary amine functionalization, wherein the structural units include styrene structural units, diene structural units and tertiary amine functionalized structural units; the molar percentage of the tertiary amine functionalized structural units in the multi-component integrated rubber containing tertiary amine functionalization is 0.1-25%, and the molar percentage of the styrene structural units is ≤25%;

[0006] The styrene structural unit has a structure shown in Formula 1;

[0007] The diene structural unit has one or more structures shown in formulas 2 to 4;

[0008] The tertiary amine functionalized structural unit has one or more structures shown in Formula 5 to Formula 6;

[0009]

[0010] Among them, R 1 Including -H or C1~C4 alkyl; R 2 and R 3 independently include -H or methyl; R 4and R 5 independently include C1-C10 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic groups; the wavy line represents the bond to the main chain;

[0011] The dotted lines in Formula 5 and Formula 6 represent ring formation or non-ring formation.

[0012] Preferably, the arrangement of the styrene structural units, diene structural units and tertiary amine functional structural units includes one or more of a block sequence, a random sequence, an alternating sequence and a tapered block sequence.

[0013] Preferably, the number average molecular weight of the tertiary amine-functionalized multi-component integrated rubber is 1-1000 kg / mol, and the molecular weight distribution is 1.02-4.

[0014] The present invention also provides a method for preparing the multi-component integrated rubber containing tertiary amine functionalization according to the above technical solution, comprising the following steps:

[0015] In anhydrous, oxygen-free and protective atmosphere, styrene monomers, diene monomers, tertiary amine functionalized monomers, alkyl lithium and organic solvents are mixed and in-situ copolymerized to obtain the multi-component integrated rubber containing tertiary amine functionalization;

[0016] The structural formula of the styrene monomer is as follows:

[0017] The structural formula of the diene monomer is as follows:

[0018] The structural formula of the tertiary amine functional monomer is as follows: and / or

[0019] Preferably, a polarity regulator is also added during the mixing process, and the polarity regulator includes one or more of potassium alcoholate, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane and N,N-dialkyltetrahydrofurfurylamine;

[0020] The molar ratio of the polarity regulator to the styrene monomer is 0 to 100:1;

[0021] The molar ratio of the styrene monomer to the alkyl lithium is 1:0.0001-1;

[0022] The organic solvent includes one or more of cyclohexane, cyclopentane, benzene, toluene, hexane, pentane, cyclopentyl methyl ether and tetrahydrofuran;

[0023] The temperature of the in-situ copolymerization reaction is 0-100° C., and the time is 0.5-6 hours.

[0024] The present invention also provides a rubber composition, comprising a tertiary amine functionalized multi-component integrated rubber and an additive, wherein the tertiary amine functionalized multi-component integrated rubber is the tertiary amine functionalized multi-component integrated rubber described in the above technical scheme or the tertiary amine functionalized multi-component integrated rubber prepared by the preparation method described in the above technical scheme.

[0025] Preferably, the auxiliary agents include reinforcing agents, vulcanizing agents, vulcanization activators, vulcanization accelerators and antioxidants.

[0026] Preferably, the raw materials for preparing the rubber composition include, by weight percentage: 100 parts of tertiary amine functionalized multi-component integrated rubber, 30-50 parts of reinforcing agent, 0.5-2 parts of vulcanizing agent, 0.2-2 parts of vulcanization activator, 1-1.6 parts of vulcanization accelerator and 0.5-4 parts of antioxidant.

[0027] The present invention also provides a vulcanized rubber, which is obtained by mixing and vulcanizing the rubber composition described in the above technical solution.

[0028] The present invention also provides the use of the multi-component integrated rubber containing tertiary amine functionalization described in the above technical solution, the multi-component integrated rubber containing tertiary amine functionalization prepared by the preparation method described in the above technical solution, the rubber composition described in the above technical solution or the vulcanized rubber described in the above technical solution in tread rubber.

[0029] The tertiary amine functionalized multi-component integrated rubber provided by the present invention introduces a tertiary amine polar functional group, which greatly improves the polarity of the multi-component integrated rubber and the dispersibility and compatibility with filler particles such as carbon black.

[0030] The main skeleton of the multi-component integrated rubber containing tertiary amine functionalization provided by the present invention is provided by styrene structural units and diene structural units, and the tertiary amine functional group is provided by a tertiary amine-substituted styrene structural unit or an isoprene structural unit, so that the multi-component integrated rubber has an adjustable cis / trans 1,4-structure ratio, and can achieve functionalization at any position in the chain, can make full use of the wear resistance of trans rubber and the high elasticity of cis rubber, and can be used to prepare vulcanized rubber with excellent comprehensive performance. Moreover, the multi-component integrated rubber containing tertiary amine functionalization provided by the present invention can achieve precise regulation of polymer molecular weight and its distribution, microscopic sequence structure, and quantitative and localized tertiary amine functionalization, and the multi-component integrated rubber containing tertiary amine functionalization has excellent comprehensive performance.

[0031] The present invention adopts an in-situ copolymerization method to prepare a multi-component integrated rubber containing tertiary amine functionalization, which can not only realize simple regulation of the ratio of cis-1,4-structure and trans-1,4-structure, but also can introduce tertiary amine functional groups into the polymer chain to greatly improve the polarity and compatibility of the product.

[0032] The present invention uses tertiary amine functionalized monomers to achieve integrated rubber functionalization through in-situ copolymerization, overcoming the problems of complex process, low efficiency, high cost and poor repeatability of traditional functionalization strategies. Moreover, the preparation method provided by the present invention has the advantages of simple operation, high efficiency, low cost, high functionalization and complete controllability, and is suitable for industrial promotion and application.

[0033] The preparation raw materials used in the invention include isopentylene monomers that can provide high trans 1,4-structures. The monomers are derived from abundant C5 byproducts, are cheap and are suitable for being used as key monomers for anionic polymerization.

[0034] The present invention also provides a rubber composition and a vulcanized rubber. Since the carbon black has high dispersibility in the multi-component integrated rubber containing tertiary amine functionalization provided by the present invention, the problem of poor dispersion of carbon black particles in traditional non-functionalized integrated rubber is overcome, and the filler in the rubber composition and the vulcanized rubber thereof has good dispersibility in the polymer matrix, has high wear resistance, low rolling resistance and high anti-wet skid characteristics, and is suitable for use as a new green energy-saving tread rubber. DETAILED DESCRIPTION

[0035] The present invention provides a multi-component integrated rubber containing tertiary amine functionalization, wherein the structural units include styrene structural units, diene structural units and tertiary amine functionalized structural units; the molar percentage of the tertiary amine functionalized structural units in the multi-component integrated rubber containing tertiary amine functionalization is 0.1-25%, and the molar percentage of the styrene structural units is ≤25%;

[0036] The styrene structural unit has a structure shown in Formula 1;

[0037] The diene structural unit has one or more structures shown in formulas 2 to 4;

[0038] The tertiary amine functionalized structural unit has one or more structures shown in Formula 5 to Formula 6;

[0039]

[0040] Among them, R 1 Including -H or C1~C4 alkyl; R 2 and R 3 independently include -H or methyl; R 4 and R 5 independently include C1-C10 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic groups; the wavy line represents the bond to the main chain;

[0041] The dotted lines in Formula 5 and Formula 6 represent ring formation or non-ring formation.

[0042] In the present invention, the C1-C4 alkyl group preferably includes methyl, ethyl, C3 alkyl or C4 alkyl; the C3 alkyl group preferably includes n-propyl or isopropyl; the C4 alkyl group preferably includes n-butyl, isobutyl or tert-butyl. 1 The substitution sites include ortho, meta or para.

[0043] In the present invention, the C1~C10 alkyl group preferably includes C1~C10 straight-chain alkyl group or C3~C10 branched alkyl group; the C1~C10 alkyl group preferably includes methyl group, ethyl group, C3~C10 alkyl group; the C3~C10 alkyl group preferably includes C3 alkyl group, C4 alkyl group, C5 alkyl group, C6 alkyl group, C7 alkyl group, C8 alkyl group, C9 alkyl group or C10 alkyl group.

[0044] In the present invention, the C4-C10 cycloalkyl group preferably includes a C4 cycloalkyl group, a C5 cycloalkyl group, a C6 cycloalkyl group, a C7 cycloalkyl group, a C8 cycloalkyl group, a C9 cycloalkyl group or a C10 cycloalkyl group.

[0045] In the present invention, the C6-C10 aromatic group preferably includes phenyl, C7 aromatic, C8 aromatic, C9 aromatic or C10 aromatic; the C7 aromatic group preferably includes methyl styrene, and the substitution site of the methyl in the methyl styrene preferably includes ortho, meta or para; the C8 aromatic group preferably includes ethyl styrene and dimethyl styrene, and the substitution site of the ethyl in the ethyl styrene preferably includes ortho, meta or para, and the substitution site of the methyl in the dimethyl styrene preferably includes one or two of ortho, meta and para; the C9 aromatic group preferably includes propyl styrene or methyl-ethyl styrene; the substitution site of the propyl in the propyl styrene preferably includes ortho, meta or para. The propyl group preferably includes n-propyl or isopropyl; the substitution sites of the methyl and ethyl groups in the methyl-ethylstyrene preferably include one or two of the ortho, meta and para positions; the C10 aromatic group preferably includes butylstyrene, methyl-propylstyrene or diethylstyrene; the substitution site of the butyl group in the butylstyrene preferably includes the ortho, meta or para positions, and the butyl group preferably includes n-butyl, isobutyl or tert-butyl iso; the substitution sites of the methyl and propyl groups in the methyl-propylstyrene preferably include one or two of the ortho, meta and para positions, and the propyl group preferably includes n-propyl or isopropyl; the substitution site of the ethyl group in the diethylstyrene preferably includes one or two of the ortho, meta and para positions.

[0046] In the present invention, the R 1 Preferably -H, methyl, ethyl, isopropyl or tert-butyl; said R 4 and R 5 Independently, preferably include C1-C4 straight chain alkyl, C3-C6 branched chain alkyl, C5-C7 cycloalkyl or C6-C7 aromatic group.

[0047] In the present invention, the molar percentage of tertiary amine functionalized structural units in the tertiary amine functionalized multi-component integrated rubber is 0.1-25%, more preferably 1-15%; in a specific embodiment, it can be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%.

[0048] In the present invention, the total molar content of styrene structural units and diene structural units in the tertiary amine-functionalized multi-component integrated rubber is preferably 75-99.9%, more preferably 85-99%. In a specific embodiment, it can be 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or 99.9%.

[0049] In the present invention, the molar percentage of styrene structural units in the tertiary amine-functionalized multi-component integrated rubber is preferably ≤25%, more preferably ≤20%; in a specific embodiment, it can be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 8%, 9%, 10%, 11%, 11.6%, 11.9%, 12%, 12.5%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%.

[0050] In the present invention, based on the molar amount of the diene structural unit as 100%, the diene structural unit preferably includes: 0-95% of the structure shown in Formula 2, 0-93% of the structure shown in Formula 3, and the balance of the structure shown in Formula 4; in a specific embodiment, the content of the structure shown in Formula 2 can be 0%, 1%, 2%, 3%, 4%, 5%, 10%, 12%, 15%, 20%, 25%, 28%, 30%, 32%, 35%, 40%, 45%, 50%. , 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%; in a specific embodiment, the content of the structure shown in Formula 3 can be 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 36%, 40%, 45%, 50%, 52%, 54%, 55%, 60%, 65%, 70%, 75%, 80%, 84%, 85%, 86%, 88%, 89%, 90% or 93%.

[0051] In the present invention, the arrangement of the styrene structural units, diene structural units and tertiary amine functional structural units preferably includes one or more of block sequence, random sequence, alternating sequence and tapered block sequence, more preferably a random sequence or tapered block sequence.

[0052] In the present invention, the number average molecular weight of the multi-component integrated rubber containing tertiary amine functionalization is preferably 1 to 1000 kg / mol, and in a specific embodiment can be 1 kg / mol, 50 kg / mol, 100 kg / mol, 150 kg / mol, 170.9 kg / mol, 189 kg / mol, 200.4 kg / mol, 204 kg / mol, 207.2 kg / mol, 208 kg / mol, 210.9 kg / mol, 218 kg / mol, 218.9 kg / mol, 222 kg / mol, 223.9 kg / mol, 228 kg / mol, 228.5 kg / mol, 229 kg / mol 1, 232kg / mol, 250kg / mol, 300kg / mol, 400kg / mol, 500kg / mol, 600kg / mol, 678.2kg / mol, 700kg / mol, 800kg / mol, 900kg / mol or 1000kg / mol; the molecular weight distribution of the multi-component integrated rubber containing tertiary amine functionalization is preferably 1.02-4, and in a specific embodiment can be 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.15, 1.2, 1.5, 2, 2.5, 2.59, 3, 3.5 or 4.

[0053] The tertiary amine functionalized multi-component integrated rubber provided by the present invention introduces a tertiary amine polar functional group, which greatly improves the polarity of the multi-component integrated rubber and the dispersibility and compatibility with filler particles such as carbon black.

[0054] The main skeleton of the multi-component integrated rubber containing tertiary amine functionalization provided by the present invention is provided by styrene structural units and diene structural units, and the tertiary amine functional group is provided by a tertiary amine-substituted styrene structural unit or an isoprene-derived hanging functionalized structural unit, so that the multi-component integrated rubber has an adjustable cis / trans 1,4-structure ratio, and can achieve functionalization at any position in the chain, can make full use of the wear resistance of trans rubber and the high elasticity of cis rubber, and can be used to prepare vulcanized rubber with excellent comprehensive performance. Moreover, the multi-component integrated rubber containing tertiary amine functionalization provided by the present invention can achieve precise control of polymer molecular weight and its distribution, microscopic sequence structure, and quantitative and localized tertiary amine functionalization, and the multi-component integrated rubber containing tertiary amine functionalization has excellent comprehensive performance.

[0055] The present invention provides a method for preparing the multi-component integrated rubber containing tertiary amine functionalization according to the above technical solution, comprising the following steps:

[0056] In anhydrous, oxygen-free and protective atmosphere, styrene monomers, diene monomers, tertiary amine functionalized monomers and organic solvents are mixed, and alkyl lithium is added to carry out in-situ copolymerization to obtain the multi-component integrated rubber containing tertiary amine functionalization;

[0057] The structural formula of the styrene monomer is as follows:

[0058] The structural formula of the diene monomer is as follows:

[0059] The structural formula of the tertiary amine functional monomer is as follows: and / or

[0060] Among them, R 1 The definition of R in Formula 1 is the same as 1 Same; R 2 and R 3 The definition of R in Formulas 2 to 4 is the same as 2 and R 3 Same; R 4 and R 5 The definition of R in Formulas 5 to 6 is the same as 4 and R 5 same.

[0061] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0062] In the present invention, the water content of the anhydrous state is preferably less than 5 ppm, and the oxygen content of the anaerobic state is preferably less than 5 ppm.

[0063] In the present invention, the protective atmosphere preferably includes nitrogen, argon or helium.

[0064] In the present invention, the molar ratio of the styrene monomer, diene monomer and tertiary amine functionalized monomer is based on the molar percentage of the styrene structural unit, diene structural unit and tertiary amine functionalized structural unit in the multi-component integrated rubber containing tertiary amine functionalization.

[0065] In the present invention, the styrene-based monomers preferably include one or more of styrene, methyl-styrene, ethyl-styrene, propyl-styrene, isopropyl-styrene, n-butyl-styrene, isobutyl-styrene and tert-butyl-styrene; the substitution position of the substituent on styrene in the styrene-based monomers includes one or more of ortho, meta and para positions.

[0066] In the present invention, the diene monomer preferably includes butadiene, piperylene, isoprene, myrcene or farnesene, and more preferably includes trans-1,4-piperylene, trans-1,4-butadiene, cis-1,4-isoprene, cis-1,4-myrcene or cis-1,4-farnesene. The preparation raw materials used in the present invention include piperylene monomers that can provide high trans-1,4-structures, which are derived from abundant C5 byproducts, are cheap and suitable for use as key monomers for anionic polymerization.

[0067] In the present invention, the tertiary amine functionalized monomer preferably includes a tertiary amine substituted isoprene monomer and / or a tertiary amine substituted methyl styrene monomer, and more preferably includes one or more of the following structures:

[0068]

[0069] In the present invention, a polarity regulator is preferably added during the mixing process, and the polarity regulator preferably includes one or more of potassium alcoholate, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane and N,N-dialkyltetrahydrofurfurylamine; the potassium alcoholate preferably includes potassium tert-butoxide and / or potassium tert-amyl alcoholate. In the present invention, the molar ratio of the polarity regulator to the styrene monomer is preferably 0 to 100:1, and in a specific embodiment can be 0:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1.

[0070] In the present invention, the organic solvent preferably includes one or more of cyclohexane, cyclopentane, benzene, toluene, hexane, pentane, cyclopentyl methyl ether and tetrahydrofuran, and more preferably cyclohexane, cyclopentane, toluene or cyclopentyl methyl ether. In the present invention, the ratio of the mass of the tertiary amine functionalized monomer to the volume of the organic solvent is preferably 1g:25-500mL, and in a specific embodiment, it can be 1g:25mL, 1g:50mL, 1g:100mL, 1g:150mL, 1g:200mL, 1g:250mL, 1g:300mL, 1g:350mL, 1g:400mL, 1g:450mL or 1g:500mL.

[0071] In the present invention, the alkyl lithium preferably includes at least one of alkyl monolithium, alkyl dilithium and alkyl polylithium, and more preferably includes one or more of n-butyl lithium, sec-butyl lithium, tert-butyl lithium, N,N-diisopropylamine lithium, cyclopentyl imine lithium, cyclohexyl imine lithium and naphthalene lithium. In the present invention, the molar ratio of the styrene monomer to the alkyl lithium is preferably 1:0.0001-1, and in a specific embodiment, it can be 1:0.0001, 1:0.0005, 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1.

[0072] In the present invention, the mixing may be: adding styrene monomers, diene monomers, tertiary amine functionalized monomers and polarity regulators into an organic solvent at one time or in sequence, and adding alkyl lithium at 0 to 100°C; in a specific embodiment, the temperature for adding the alkyl lithium system may be 0°C, 10°C, 20°C, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C.

[0073] In the present invention, the mixing may also be: adding a polarity regulator, alkyl lithium and an initiator into an organic solvent, stirring and mixing, and adding the styrene monomer, the diene monomer and the amine functionalized monomer at once or sequentially.

[0074] In the present invention, the temperature of the in situ copolymerization reaction is preferably 0-100°C, and in a specific embodiment it can be 0°C, 10°C, 20°C, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C; the time of the in situ copolymerization reaction is preferably 0.5-6h, and in a specific embodiment it can be 0.5h, 1h, 2h, 3h, 4h, 5h or 6h.

[0075] After the in-situ copolymerization reaction is completed, the present invention preferably further comprises: adding methanol or terminating the reaction or adding a coupling agent to terminate the coupling, then adding an antioxidant solution, washing and precipitating the polymer, and drying to obtain the multi-component integrated rubber containing tertiary amine functionalization.

[0076] In the present invention, the precipitant used for washing and precipitating the polymer preferably includes methanol and / or ethanol. In the present invention, the volume ratio of the antioxidant solution to ethanol is preferably 1:20-80, and in a specific embodiment can be 1:20, 1:30, 1:40, 1:50, 1:60, 1:70 or 1:80.

[0077] In the present invention, the coupling agent preferably includes one or more selected from dihaloalkanes, polychlorosilanes, polyalkoxysilanes, polyvinyl aromatics and polyepoxidized compounds, and more preferably includes one or more selected from dibromoethane, trichlorosilane, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, divinylbenzene, divinylbiphenyl, soybean oil and epoxy polybutadiene oligomers. In the present invention, the molar ratio of the styrene monomer to the coupling agent is preferably 1:0.00001-1, and in a specific embodiment can be 1:0.00001, 1:0.0001, 1:0.0005, 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1.

[0078] In the present invention, the antioxidant in the antioxidant solution preferably includes one or more of 2,6-di-tert-butyl-4-methylphenol, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), dilauryl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite, and the solvent preferably includes cyclohexane; the concentration of the antioxidant solution is preferably 0.01 to 1.0 mol / L, and in a specific embodiment it can be 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L or 1 mol / L. In the present invention, the molar ratio of the styrene monomer to the antioxidant is preferably 1:0.01-100, and in specific embodiments can be 1:0.01, 1:0.05, 1:0.1, 1:1, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100.

[0079] In the present invention, the drying preferably includes vacuum drying, and the drying temperature is preferably 20-60°C, and in a specific embodiment can be 20°C, 30°C, 40°C, 50°C or 60°C; the present invention has no special limitation on the drying time, and drying to constant weight is sufficient.

[0080] The present invention adopts an in-situ copolymerization method to prepare a multi-component integrated rubber containing tertiary amine functionalization, which can not only realize simple regulation of the ratio of cis-1,4-structure and trans-1,4-structure, but also can introduce tertiary amine functional groups into the polymer chain to greatly improve the polarity and compatibility of the product.

[0081] The present invention uses tertiary amine functionalized monomers to achieve integrated rubber functionalization through in-situ copolymerization, overcoming the problems of complex process, low efficiency, high cost and poor repeatability of traditional functionalization strategies. Moreover, the preparation method provided by the present invention has the advantages of simple operation, high efficiency, low cost, high functionalization and complete controllability, and is suitable for industrial promotion and application.

[0082] The present invention also provides a rubber composition, comprising a tertiary amine functionalized multi-component integrated rubber and an additive, wherein the tertiary amine functionalized multi-component integrated rubber is the tertiary amine functionalized multi-component integrated rubber described in the above technical scheme or the tertiary amine functionalized multi-component integrated rubber prepared by the preparation method described in the above technical scheme.

[0083] In the present invention, the auxiliary agent preferably includes a reinforcing agent, a vulcanizing agent, a vulcanization activator, a vulcanization accelerator and an antioxidant. In the present invention, the reinforcing agent preferably includes one or more of carbon black, white carbon black and silicon dioxide. In the present invention, the vulcanizing agent preferably includes one or more of sulfur, polysulfide-containing compounds and organic peroxide compounds. In the present invention, the vulcanization activator preferably includes one or more of zinc oxide, magnesium oxide and stearic acid. In the present invention, the vulcanization accelerator preferably includes one or more of accelerator DM (dithiothiazoles), accelerator D (guanidines), dithiocarbamates, thiurams and thioureas. In the present invention, the antioxidant preferably includes one or more of antioxidant RD, antioxidant 124 and antioxidant DNP.

[0084] The present invention does not specifically limit the types of the vulcanizing agent, vulcanization activator, vulcanization accelerator and antioxidant, and any vulcanizing agent, vulcanization activator, vulcanization accelerator and antioxidant known to those skilled in the art may be used.

[0085] In the present invention, the raw materials for preparing the rubber composition include, by weight percentage: 100 parts of a multi-component integrated rubber functionalized with a tertiary amine; 30 to 50 parts of a reinforcing agent, which may be 30 parts, 35 parts, 40 parts, 45 parts or 50 parts in a specific embodiment; 0.5 to 2 parts of a vulcanizing agent, which may be 0.5 parts, 1 parts, 1.5 parts or 2 parts in a specific embodiment; 0.2 to 2 parts of a vulcanization activator, which may be 0.2 parts, 0.5 parts, 1 parts, 1.5 parts or 2 parts in a specific embodiment; 1 to 1.6 parts of a vulcanization accelerator, which may be 1 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts or 1.6 parts in a specific embodiment; and 0.5 to 4 parts of an antioxidant, which may be 0.5 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts in a specific embodiment.

[0086] Since carbon black has high dispersibility in the tertiary amine-functionalized multi-component integrated rubber provided by the present invention, the problem of poor dispersion of carbon black particles in traditional non-functionalized integrated rubber is overcome, the filler in the rubber composition has good dispersion in the polymer matrix, and has high wear resistance, low rolling resistance and high anti-skid properties, and is suitable for use as a new green and energy-saving tread rubber.

[0087] The present invention also provides a vulcanized rubber, which is obtained by mixing and vulcanizing the rubber composition described in the above technical solution.

[0088] In the present invention, the preparation method of the vulcanized rubber comprises the following steps: plasticizing the multi-component integrated rubber containing tertiary amine functionalization, adding a reinforcing agent for mixing, adding a vulcanization activator for start-kneading to obtain a start-kneaded rubber; and cutting, triangular packing and thin-passing the start-kneaded rubber, a vulcanization accelerator, a vulcanizing agent and an antioxidant in sequence to obtain a vulcanized rubber.

[0089] In the present invention, the plasticizing temperature is preferably 80-120°C, and in a specific embodiment it can be 80°C, 90°C, 100°C, 110°C or 120°C; the plasticizing roller distance is preferably 0.7-0.9mm, and in a specific embodiment it can be 0.7mm, 0.8mm or 0.9mm; the plasticizing time is preferably 0.5-1.5min, and in a specific embodiment it can be 0.5min, 1min or 1.5min.

[0090] In the present invention, the mixing temperature is preferably 80-120°C, and in a specific embodiment it can be 80°C, 90°C, 100°C, 110°C or 120°C; the mixing roller distance is preferably 0.7-0.9mm, and in a specific embodiment it can be 0.7mm, 0.8mm or 0.9mm; the mixing time is preferably 1-2min, and in a specific embodiment it can be 1min, 1.5min or 2min.

[0091] In the present invention, the temperature of the mixing process is preferably 120-160°C, and in a specific embodiment it can be 120°C, 130°C, 140°C, 145°C, 150°C or 160°C; the roller spacing of the mixing process is preferably 0.7-0.9 mm, and in a specific embodiment it can be 0.7 mm, 0.8 mm or 0.9 mm; the mixing time is preferably 1.5-2.5 min, and in a specific embodiment it can be 1.5 min, 2 min or 2.5 min.

[0092] In the present invention, the lower piece is preferably further included after the opening training.

[0093] In the present invention, the step of placing the rubber material obtained by kneading on a sheet is preferably included before the step of placing the rubber material on a sheet. In the present invention, the step of placing the rubber material on a sheet is preferably at room temperature, and the step of placing the rubber material on a sheet is preferably 7 to 9 hours, and in a specific embodiment, it may be 7 hours, 8 hours, or 9 hours.

[0094] In the present invention, the cutting operation is preferably 2 / 3 to 4 / 5 (in a specific embodiment, it can be 2 / 3, 3 / 4 or 4 / 5) cutting 2 to 5 times (in a specific embodiment, it can be 2 times, 3 times, 4 times or 5 times); taking the 3 / 4 cutting 3 times for example, that is, 3 / 4 width of the rubber is cut from the left and right sides of the roller, respectively, and then folded and put back into the roller, and repeated 3 times. In the present invention, the roller spacing of the cutting operation is preferably 0.4 to 0.6 mm, and in a specific embodiment, it can be 0.4 mm, 0.5 mm or 0.6 mm.

[0095] In the present invention, the number of times of making triangular packages is preferably 4 to 8 times, and in a specific embodiment it can be 4 times, 5 times, 6 times, 7 times or 8 times; the roller distance of making triangular packages is preferably 0.1 to 0.3 mm, and in a specific embodiment it can be 0.1 mm, 0.2 mm or 0.3 mm.

[0096] In the present invention, the number of thin passes is preferably 2 to 8 times, and in a specific embodiment can be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times or 8 times; the roller spacing of the thin pass is preferably 0.1 to 0.3 mm, and in a specific embodiment can be 0.1 mm, 0.2 mm or 0.3 mm.

[0097] In the present invention, the thin-passing preferably further comprises a lower sheet to obtain vulcanized rubber. In the present invention, the roller distance during the lower sheet is preferably 1 to 1.5 mm, and in a specific embodiment can be 1 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm or 1.5 mm.

[0098] In the present invention, the preparation of the vulcanized rubber is preferably carried out in an open mill, and the rotation speed of the open mill is preferably 20 to 40 r / min, and in a specific embodiment can be 20 r / min, 30 r / min or 40 r / min.

[0099] The present invention has no particular limitation on the preparation conditions of the vulcanized rubber, and the preparation conditions well known to those skilled in the art may be used.

[0100] Since carbon black has high dispersibility in the tertiary amine-functionalized multi-component integrated rubber provided by the present invention, the problem of poor dispersion of carbon black particles in traditional non-functionalized integrated rubber is overcome, and the filler in the vulcanized rubber has good dispersion in the polymer matrix, and has high wear resistance, low rolling resistance and high anti-skid properties, and is suitable for use as a new green and energy-saving tread rubber.

[0101] The present invention also provides the use of the multi-component integrated rubber containing tertiary amine functionalization described in the above technical solution, the multi-component integrated rubber containing tertiary amine functionalization prepared by the preparation method described in the above technical solution, the rubber composition described in the above technical solution or the vulcanized rubber described in the above technical solution in tread rubber.

[0102] Integrated rubber materials with high content of trans-1,4-polydiene have excellent dynamic properties, wear resistance and good flexural resistance, and are potential materials for new high-performance green tires, but too high trans structures (such as eucommia gum) can easily lead to crystallization and show plastic properties. Integrated rubbers with high content of cis-1,4-polyconjugated olefins have excellent elasticity and low-temperature resistance, but they also have poor tear resistance, poor anti-skid performance, poor processing performance, and the raw rubber has a certain cold flow tendency, and the adhesion is not as good as styrene-butadiene rubber. Integrated rubbers with high content of 1,2-structured polydiene have unique advantages in low rolling resistance and anti-skid properties, and are particularly suitable for manufacturing high-performance tires, but they are deficient in physical and mechanical properties. The multi-component integrated rubber functionalized with tertiary amines provided by the present invention contains adjustable cis-trans 1,4-structures, which provides a simple formula for regulating the comprehensive performance of the multi-component integrated rubber. At the same time, the polar tertiary amine functional group can significantly improve the dispersibility of filler particles such as carbon black.

[0103] In order to further illustrate the present invention, the tertiary amine-functionalized multi-component integrated rubber and its preparation method and application, rubber composition and its application, vulcanized rubber and its application provided by the present invention are described in detail below in combination with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0104] In the following examples, the cis-trans 1,4-structure microstructure of the diene, the ratio of the styrene-based structural unit and the tertiary amine functionalized structural unit were determined by NMR; the molecular weight and its distribution were determined by GPC; the glass transition temperature was determined by DMA; the comprehensive mechanical properties of rubber were tested using a universal tensile testing machine; and the carbon black dispersibility was determined by TEM.

[0105] Comparative Example 1: SBIR-THF

[0106] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 2.5 mL of 0.5 M THF (cyclohexane dilution) regulator and 5 mL of 0.5 M n-butyl lithium cyclohexane solution were added in sequence, stirred at 50°C for 5 min, and then 220 g of butadiene, 60 g of styrene and 220 g of isoprene were added continuously, and the polymerization reaction was carried out at 60-70°C for 1 h, and 2 mL of methanol was added to terminate the reaction. The above SIB integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate the polymer, and the obtained polymer was dried in a vacuum drying oven at 40°C to constant weight to obtain a polymer with a yield of 100%. The molar content of polystyrene PS structural units is 11.8%, the molar content of polybutadiene PB structural units is 44.5%, and the rest are polyisoprene PI structural units; wherein, the molar content of cis / trans 1,4-PB structures in the polybutadiene PB structural units is 34% / 56%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structures in the polyisoprene PI structural units is 91% / 2%, and the rest are trans 1,4-PI structures, the molecular weight is 218kg / mol, the molecular weight distribution is 1.05, and the product has double glass transition temperature characteristics (Tg=-63°C and 76°C).

[0107] Comparative Example 2: SBIR-K

[0108] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M potassium tert-butoxide (diluted with toluene) regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 220 g of butadiene, 60 g of styrene and 220 g of isoprene were added continuously, and the polymerization reaction was carried out at 60-70°C for 2 h, and 2 mL of methanol was added to terminate the reaction. The above SIB integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 11.6%, the molar content of polybutadiene PB structural units is 44.9%, and the rest are polyisoprene PI structural units; among them, the molar content of cis / trans 1,4-PB structure in polybutadiene PB structural units is 32% / 54%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in polyisoprene PI structural units is 90% / 2%, and the rest are trans 1,4-PI structures; the molecular weight is 232kg / mol, the molecular weight distribution is 1.09, and the product has a single glass transition temperature characteristic (Tg=-45°C).

[0109] Example 1: SBIR-KN-A1

[0110] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M potassium tert-butoxide (diluted with toluene) regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 220 g of butadiene, 35 g of styrene and 220 g of isoprene, and 25 g of N-A1 monomer were added continuously, and the polymerization reaction was carried out at 60-70°C for 1.5 h, and 2 mL of methanol was added to terminate the reaction. The above SIB integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with methanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural unit is 6.8%, the molar content of polybutadiene PB structural unit is 44.7%, the molar content of poly N-A1 structural unit is 5.1%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PB structure in polybutadiene PB structural unit is 30% / 55%, and the rest are 1,2-structure; the molar content of cis / trans 1,4-PI structure in polyisoprene PI structural unit is 88% / 2%, and the rest are trans 1,4-PI structure; the molecular weight is 228kg / mol, the molecular weight distribution is 1.09, and the product has a single glass transition temperature characteristic. (Tg=-49°C).

[0111] Example 2: SPIR-THF-N-A3

[0112] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclopentane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 220 g of isoprene, 35 g of styrene, 25 g of N-A3 monomer and 220 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 3 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 6.9%, the molar content of polyisoprene PPD structural units is 44.5%, the molar content of polyN-A3 structural units is 5.0%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 3% / 89%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 82% / 4%, and the rest are trans 1,4-PI structures; the molecular weight is 200.4 kg / mol, the molecular weight distribution is 1.08, and the product has a single glass transition temperature characteristic (Tg=-54°C).

[0113] Example 3: SPIR-THF-N-A5

[0114] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of hexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 110 g of isoprene, 35 g of styrene, 25 g of N-A5 monomer and 330 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 3 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 7.1%, the molar content of polyisoprene PPD structural units is 21.5%, the molar content of polyN-A5 structural units is 5.1%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 5% / 85%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 81% / 5%, and the rest are trans 1,4-PI structures, the molecular weight is 170.9 kg / mol, the molecular weight distribution is 1.08, and the product has a single glass transition temperature characteristic (Tg=-59°C).

[0115] Example 4: SPIR-THF-N-A7

[0116] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of hexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) sec-butyl lithium initiator were added thereto in sequence, stirred at 50°C for 5 min, and then 330 g of isoprene, 35 g of styrene, 25 g of N-A7 monomer and 110 g of isoprene were added continuously, and the polymerization reaction was carried out at 85-90°C for 4 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed and precipitated with ethanol, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 7.2%, the molar content of polyisoprene PPD structural units is 66.5%, the molar content of polyN-A7 structural units is 5.2%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 5% / 84%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 80% / 6%, and the rest are trans 1,4-PI structures; the molecular weight is 218.9 kg / mol, the molecular weight distribution is 1.12, and the product has a single glass transition temperature characteristic (Tg=-40°C).

[0117] Example 5: SBIR-KN-B1

[0118] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M potassium tert-amyl alcohol (diluted with toluene) regulator and 5 mL of 0.5 M (diluted with cyclohexane) tert-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 220 g of butadiene, 35 g of styrene and 220 g of isoprene, and 25 g of N-B1 monomer were added continuously, and the polymerization reaction was carried out at 60-70°C for 2 h, and 2 mL of methanol was added to terminate the reaction. The above SIB integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with methanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural unit is 6.9%, the molar content of polybutadiene PB structural unit is 44.9%, the molar content of poly N-B1 structural unit is 5.2%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PB structure in polybutadiene PB structural unit is 28% / 52%, and the rest are 1,2-structure; the molar content of cis / trans 1,4-PI structure in polyisoprene PI structural unit is 80% / 4%, and the rest are trans 1,4-PI structure; the molecular weight is 208kg / mol, the molecular weight distribution is 1.11, and the product has a single glass transition temperature characteristic. (Tg=-43°C).

[0119] Example 6: SPIR-THF-N-B3

[0120] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 220 g of isoprene, 35 g of styrene, 25 g of N-B3 monomer and 220 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 3 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 6.8%, the molar content of polyisoprene PPD structural units is 44.4%, the molar content of polyN-B4 structural units is 5.1%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 5% / 85%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 85% / 3%, and the rest are trans 1,4-PI structures; the molecular weight is 228.5 kg / mol, the molecular weight distribution is 1.08, and the product has a single glass transition temperature characteristic (Tg=-46°C).

[0121] Example 7: SPIR-THF-N-B6

[0122] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of hexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 110 g of isoprene, 35 g of styrene, 25 g of N-B6 monomer and 330 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 2 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with methanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 7.0%, the molar content of polyisoprene PPD structural units is 21.3%, the molar content of polyN-B6 structural units is 5.1%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 4% / 84%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 81% / 4%, and the rest are trans 1,4-PI structures; the molecular weight is 210.9 kg / mol, the molecular weight distribution is 1.08, and the product has a single glass transition temperature characteristic (Tg=-44°C).

[0123] Example 8: SPIR-THF-N-B7

[0124] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of hexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) sec-butyl lithium initiator were added thereto in sequence, stirred at 50°C for 5 min, and then 330 g of isoprene, 35 g of styrene, 25 g of N-B7 monomer and 110 g of isoprene were added continuously, and the polymerization reaction was carried out at 85-90°C for 4 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polystyrene PS structural units is 7.1%, the molar content of polyisoprene PPD structural units is 66.9%, the molar content of poly N-B7 structural units is 5.0%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 3% / 86%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 85% / 3%, and the rest are trans 1,4-PI structures; the molecular weight is 223.9 kg / mol, the molecular weight distribution is 1.11, and the product has a single glass transition temperature characteristic (Tg=-39°C).

[0125] Example 9: MSPIR-THF-N-B6

[0126] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) sec-butyl lithium initiator were added thereto in sequence, stirred at 50°C for 5 min, and then 150 g of isoprene, 100 g of methyl styrene, 100 g of N-B6 monomer and 150 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 1 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of polymethylstyrene PS structural unit is 19.6%, the molar content of polyisoprene PPD structural unit is 29.5%, the molar content of polyN-B6 structural unit is 20.3%, and the rest are polyisoprene PI structural units, among which the molar content of cis / trans 1,4-PPD structure in the polyisoprene PPD structural unit is 2% / 90%, and the rest are 1,2-structure; the molar content of cis / trans 1,4-PI structure in the polyisoprene PI structural unit is 85% / 5%, and the rest are trans 1,4-PI structure; the molecular weight is 204kg / mol, the molecular weight distribution is 1.10, and the product has a single glass transition temperature characteristic (Tg=-38°C).

[0127] Example 10: BSPIR-THF-N-B6

[0128] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 150 g of isoprene, 100 g of p-tert-butylstyrene, 100 g of N-B6 monomer and 150 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 1 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of poly (p-tert-butylstyrene) PS structural units is 19.5%, the molar content of poly (isoprene) PPD structural units is 29.8%, the molar content of poly (N-B6) structural units is 20.5%, and the rest are poly (isoprene) PI structural units, wherein the molar content of cis / trans 1,4-PPD structure in the poly (isoprene) PPD structural units is 3% / 90%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PI structure in the poly (isoprene) PI structural units is 90% / 2%, and the rest are trans 1,4-PI structures; the molecular weight is 222 kg / mol, the molecular weight distribution is 1.09, and the product has a single glass transition temperature characteristic (Tg=-37°C).

[0129] Example 11: BSPMR-THF-N-A6

[0130] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 150 g of isopentadiene, 100 g of p-tert-butylstyrene, 100 g of N-A6 monomer and 150 g of myrcene were added continuously, and the polymerization reaction was carried out at 75-80°C for 1 h, and 2 mL of methanol was added to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of poly (p-tert-butylstyrene) PS structural units is 19.9%, the molar content of poly (isopentylene) PPD structural units is 29.9%, the molar content of poly (N-A6) structural units is 20.3%, and the rest are poly (myrcene) PMY structural units, wherein the molar content of cis / trans 1,4-PPD structure in the poly (isopentylene) PPD structural units is 4% / 89%, and the rest are 1,2-structures; the molar content of cis / trans 1,4-PMY structure in the poly (myrcene) PMY structural units is 89% / 2%, and the rest are trans 1,4-PMY structures; the molecular weight is 207.2 kg / mol, the molecular weight distribution is 1.12, and the product has a single glass transition temperature characteristic (Tg=-57°C).

[0131] Example 12: BSPIR-THF-Si

[0132] High-purity nitrogen was filled into an anhydrous and oxygen-free reactor, and 3000 mL of cyclohexane, 5 mL of 0.5 M (diluted with cyclohexane) THF regulator and 5 mL of 0.5 M (diluted with cyclohexane) n-butyl lithium initiator were added in sequence, stirred at 50°C for 5 min, and then 150 g of isoprene, 100 g of p-tert-butylstyrene, 100 g of N-B6 monomer and 150 g of isoprene were added continuously, and the polymerization reaction was carried out at 75-80°C for 1 h, and 1.25 mL of 0.5 M (diluted with cyclohexane) silicon tetrachloride coupling agent was added, and the reaction was continued for 0.5 h to terminate the reaction. The above SPI integrated rubber solution was mixed with 50 mL of cyclohexane solution of 0.5 wt% 2,6-di-tert-butyl-4-methylphenol, and then poured into 3 L of ethanol, and the polymer was repeatedly washed with ethanol to precipitate, and dried in a vacuum drying oven at 40°C to constant weight to obtain a multi-component integrated rubber with a yield of 100%. The molar content of poly (p-tert-butylstyrene) PS structural unit is 19.4%, the molar content of poly (isoprene) PPD structural unit is 29.8%, the molar content of poly (N-B6) structural unit is 20.3%, and the rest are poly (isoprene) PI structural units, wherein the molar content of cis / trans 1,4-PPD structure in the poly (isoprene) PPD structural unit is 3% / 90%, and the rest are 1,2-structure; the molar content of cis / trans 1,4-PI structure in the poly (isoprene) PI structural unit is 90% / 1%, and the rest are trans 1,4-PI structure; the molecular weight is 678.2 kg / mol, the molecular weight distribution is 2.59, and the product has a single glass transition temperature characteristic (Tg=-42°C) and a GPC multi-peak characteristic.

[0133] Example 13

[0134] Raw materials for preparing vulcanized rubber: 100 parts of multi-component integrated rubber, 50 parts of carbon black, 2 parts of stearic acid, 4 parts of zinc oxide, 1.2 parts of accelerator DM, 0.4 parts of accelerator D, 1.2 parts of antioxidant RD and 1.7 parts of sulfur. The multi-component integrated rubber is any one of the multi-component integrated rubbers prepared in Comparative Examples 1 to 3 and Examples 1 to 12.

[0135] The preparation process of vulcanized rubber is as follows: the multi-component integrated rubber is plasticized for 1 minute at 100°C, 30r / min, and the roll gap of the open mill is 0.8mm, carbon black is added and mixed for 1.5 minutes under the above conditions, stearic acid and zinc oxide are added in sequence, and the open mill is milled for 2 minutes at 145°C, 30r / min, and the roll gap is 0.8mm, the sheet is removed, and the sheet is left to stand for 8 hours to obtain the open mill rubber. The roll gap is adjusted to 0.5mm, the open mill rubber, accelerator DM, accelerator D, antioxidant RD and sulfur are added, the left and right 3 / 4 cutters are used 3 times each, the roll gap is adjusted to 0.2mm, the triangle package is made 6 times, the thin pass is made 5 times, the roll gap is adjusted to 1.2mm, the sheet is removed, and the vulcanized rubber is obtained.

[0136] Test Example 1

[0137] The mechanical properties and dynamic mechanical properties of the 14 vulcanized rubbers prepared in Example 13 were tested. The results are shown in Table 1, wherein the tensile strength test method refers to GB / T 528-2009.

[0138] The test method for elongation at break refers to GB / T 528-2009.

[0139] The test method for 300% tensile strength refers to GB / T 528-2009.

[0140] The permanent deformation test method refers to GB / T 7759-2015.

[0141] The tear strength test method refers to GB / T 529-2008.

[0142] The Shore hardness test method refers to GB / T 531.1-2008.

[0143] Tanδ(0℃) test method refers to GB / T9870.1-2006.

[0144] Tanδ(60℃) test method refers to GB / T9870.1-2006.

[0145] Table 1 Mechanical properties and dynamic mechanical properties test results of vulcanized rubber

[0146]

[0147] As shown in Table 1, the copolymerization properties introduced by tertiary amine monomers have a significant improvement in the tear strength and dynamic damping properties of the product (improvement in anti-slip properties and reduction in rolling resistance), and the sample prepared by replacing butadiene with isoprene (such as Example 1) has certain advantages in mechanical strength and dynamic damping properties. The synergistic effect of isoprene and tertiary amine monomers is conducive to further improving the comprehensive properties of the copolymer, such as Examples 2 to 12.

[0148] In summary, the multi-component integrated rubber functionalized with tertiary amines of the present invention has excellent comprehensive mechanical properties, the multi-component integrated rubber with a high ratio of trans-1,4-polyisoprene exhibits higher mechanical strength and wear resistance, the multi-component integrated rubber with a high ratio of cis-1,4-polyisoprene or polymyrcene exhibits more excellent elasticity, all multi-component integrated rubbers functionalized with tertiary amines have more excellent rolling resistance and anti-slip properties, and the multi-component integrated rubber containing isoprene structural units has more excellent wear resistance and hardness.

[0149] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A multi-component integrated rubber containing tertiary amine functionalization, wherein the structural units include styrene structural units, diene structural units and tertiary amine functionalized structural units; the molar percentage of the tertiary amine functionalized structural units in the multi-component integrated rubber containing tertiary amine functionalization is 0.1 to 25%, and the molar percentage of the styrene structural units is ≤25%; The styrene structural unit has a structure shown in Formula 1; The diene structural unit has one or more structures shown in formulas 2 to 4; The tertiary amine functionalized structural unit has one or more structures shown in Formula 5 to Formula 6; in, R1 includes -H or C1-C4 alkyl; R2 and R3 independently include -H or methyl; R4 and R5 independently include C1-C10 alkyl, C4-C10 cycloalkyl or C6-C10 aromatic; the wavy line represents the bond to the main chain; The dotted lines in Formula 5 and Formula 6 represent ring formation or non-ring formation.

2. The multi-component integrated rubber containing tertiary amine functionalization according to claim 1, characterized in that: The arrangement of the styrene structural units, diene structural units and tertiary amine functional structural units includes one or more of a block sequence, a random sequence, an alternating sequence and a tapered block sequence.

3. The multi-component integrated rubber containing tertiary amine functionalization according to claim 1 or 2, characterized in that: The number average molecular weight of the multi-component integrated rubber containing tertiary amine functionalization is 1-1000 kg / mol, and the molecular weight distribution is 1.02-4.

4. The method for preparing the multi-component integrated rubber containing tertiary amine functionalization according to any one of claims 1 to 3, comprising the following steps: In anhydrous, oxygen-free and protective atmosphere, styrene monomers, diene monomers, tertiary amine functionalized monomers, alkyl lithium and organic solvents are mixed and in-situ copolymerized to obtain the multi-component integrated rubber containing tertiary amine functionalization; The structural formula of the styrene monomer is as follows: The structural formula of the diene monomer is as follows: The structural formula of the tertiary amine functional monomer is as follows:

5. The preparation method according to claim 4, characterized in that: A polarity regulator is also added during the mixing process, and the polarity regulator includes one or more of potassium alcoholate, tetrahydrofuran, N,N,N',N'-tetramethylethylenediamine, tetrahydrofuran alkyl ether, ditetrahydrofurfuryl propane and N,N-dialkyltetrahydrofurfurylamine; The molar ratio of the polarity regulator to the styrene monomer is 0 to 100:1; The molar ratio of the styrene monomer to the alkyl lithium is 1:0.0001-1; The organic solvent includes one or more of cyclohexane, cyclopentane, benzene, toluene, hexane, pentane, cyclopentyl methyl ether and tetrahydrofuran; The temperature of the in-situ copolymerization reaction is 0-100° C., and the time is 0.5-6 hours.

6. A rubber composition comprising a tertiary amine functionalized multi-component integrated rubber and an additive, wherein the tertiary amine functionalized multi-component integrated rubber is the tertiary amine functionalized multi-component integrated rubber as described in any one of claims 1 to 3 or the tertiary amine functionalized multi-component integrated rubber prepared by the preparation method as described in any one of claims 4 to 5.

7. The rubber composition according to claim 6, characterized in that The auxiliary agents include reinforcing agents, vulcanizing agents, vulcanization activators, vulcanization accelerators and antioxidants.

8. The rubber composition according to claim 6 or 7, characterized in that: Calculated by weight percentage, the raw materials for preparing the rubber composition include: 100 parts of tertiary amine functionalized multi-component integrated rubber, 30-50 parts of reinforcing agent, 0.5-2 parts of vulcanizing agent, 0.2-2 parts of vulcanization activator, 1-1.6 parts of vulcanization accelerator and 0.5-4 parts of antioxidant.

9. A vulcanized rubber obtained by mixing and vulcanizing the rubber composition according to any one of claims 6 to 8.

10. Use of the multi-component integrated rubber containing tertiary amine functionalization as described in any one of claims 1 to 3, the multi-component integrated rubber containing tertiary amine functionalization obtained by the preparation method as described in any one of claims 4 to 5, the rubber composition as described in any one of claims 6 to 8 or the vulcanized rubber as described in claim 9 in tread rubber.

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