Preparation and application of amido-functionalized polyisoprene rubber with high ethylene side groups

Abstract

The invention relates to preparation and application of amido functionalized polyisoprene rubber with high ethylene side groups. The preparation method comprises the following steps: initiating isoprene polymerization in an inert organic hydrocarbon solvent by virtue of a novel bicyclic amine regulator / lithium alkylide through a classical anion polymerization reaction, and simultaneously introducing an amido-functionalized monomer to prepare amido-functionalized polyisoprene rubber with high ethylene side groups through in-situ copolymerization. The highest content of vinyl side groups in the rubber is in the range of 90-95%, the 1, 2 structure of polyisoprene is adjustable in the range of 20-30%, the 3, 4-structure of polyisoprene is adjustable in the range of 60-75%, and the rest is the 1, 4-structure. In addition, the amino functionalization degree can be adjusted in the range of 0%-50%, the molecular weight of the product is controllable, and the molecular weight distribution is narrow (1.03-1.20). Compared with the prior art, the regulator designed by the invention has the characteristics of stronger structure regulation capability and temperature insensitivity to the 1, 2-structure, abundant types of amido functionalized monomers, mild reaction conditions and simplicity and convenience in operation.

Description

Technical Field

[0001] The invention relates to the field of diene rubber synthesis, in particular to an amine-functionalized polyisoprene rubber with high vinyl side groups. Background Art

[0002] Compared with monoolefins, products prepared from dienes by various active / controlled polymerization methods are widely used as rubber tires, adhesives, key materials for high-frequency and low-loss communications, high-end damping materials, and polymer modified materials, etc., due to their many isomer types and diversified performance characteristics. Taking polyisoprene as an example, for example, high cis-1,4-polyisoprene has excellent elasticity of natural rubber and is used as rubber tire material, high trans-1,4-polyisoprene has excellent crystallization properties similar to natural eucommia gum and is used as golf ball shell material, and high vinyl side-group polyisoprene is often synthesized through curing process to synthesize high-end seals or damping materials due to its rich vinyl side chains (including 1,2-structure and 3,4-structure, due to steric hindrance, the reaction activity of 1,2-structure is higher than that of 3,4-structure) and highly saturated main chain structure. Therefore, the design and regulation of diene microstructures have important research significance.

[0003] Classic living anionic polymerization (LAP) has great advantages in regulating the microstructure of dienes. It can achieve refined design and regulation of the microstructure without changing the controllable characteristics of polymerization activity with the help of a variety of process additives and process conditions. Despite this, LAP also has a key problem in the design and synthesis of high-ethylene side-group polyisoprene: how to improve the more active 1,2-structure in the polyisoprene chain? It is well known that Lewis base polar regulators are commonly used to regulate the microstructure of dienes in LAP research. The regulator system currently commonly used includes chelated ether regulators (such as ditetrahydrofurfuryl propane DTHFP), chelated amine ether regulators (such as N,N-dimethyltetrahydrofurfurylamine THFP) and chelated amine regulators (such as N,N,N',N'-tetramethylethylenediamine TMEDA). In his master's thesis "Synthesis and Application of High-efficiency Asymmetric Tetrahydrofuranyl Ether / Amine Regulators", Xie Fengli of Hunan University of Technology examined in detail the regulation effect of high-efficiency amine ether regulators on the vinyl content of dienes, and found that the limit of most regulators for polybutadiene 1,2-structure is 90%. Although the total ethylene structure content of isoprene can reach 90%, the regulation ability of isoprene 1,2-structure is very limited (no more than 20%). Among the types of regulators reported so far, only N,N-dipiperidineethane can achieve 99% controllable synthesis of 1,2-polybutadiene under low temperature conditions (0-30°C), which is attributed to the unique spatial configuration restriction of this type of regulator (Chem. Sci., 2024, 15, 20493-20502). However, when DPE was used in isoprene polymerization, it was found that the unique steric hindrance effect was conducive to the formation of 3,4-structure, and the 1,2-structure content was less than 20%. However, in theory, this unique spatial restriction can be used to introduce unique substituent groups into the DPE matrix to increase the steric hindrance effect and the coordination with the alkyl lithium atom. Therefore, this patent uses the unique electron-pushing alkyl substitution and heteroatom synergistic coordination to design and synthesize a series of high-vinyl side-group polyisoprene rubbers for the synthesis of higher 1,2-structures.

[0004] In addition, we found that polyisoprene rubber is limited by its own non-polar properties. When used to modify tires or other polymer materials, there are compatibility problems and dispersion problems with inorganic fillers. Therefore, it needs to be polarized. At present, the polarization modification strategies include in-situ introduction and post-amine functionalization modification. The in-situ modification has the characteristics of simple process, simple post-processing process and low post-processing cost. Market research has found that functionalized polydiene rubber has important application value in various industries such as high-frequency 6G communications / epoxy resin toughening / sealing devices. At present, there are no reports on patents for amine-functionalized polyisoprene rubber with high 1,2-structure content. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a preparation and application of high vinyl side group amine functionalized polyisoprene rubber. The preparation method provided by the present invention uses a new bicyclic amine compound as a key regulator and an amine functionalized monomer as a comonomer to provide a method for preparing high vinyl side group amine functionalized polyisoprene rubber by a native copolymerization anionic polymerization process.

[0006] In order to achieve the above-mentioned invention object, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing an amine-functionalized polyisoprene rubber having a high vinyl side group, comprising the following steps:

[0008] In an anhydrous and oxygen-free inert gas atmosphere, an inert organic hydrocarbon solvent, a novel bicyclic amine structure regulator, an alkyl lithium initiator, isoprene and an amine functionalized monomer are mixed for anionic copolymerization to obtain a high 1,2-structured high vinyl side group amine functionalized polyisoprene rubber.

[0009] Preferably, the novel bicyclic amine structure regulator described is any one or more of the structural compounds shown in NN-1 to 12, more preferably NN-1, NN-2, NN-5, NN-6, NN-7, NN-8, NN-9, NN-11 and NN-12.

[0010]

[0011] Preferably, the molar ratio of the novel regulator to the alkyl lithium is (0.1-10):1, more preferably (0.25-5):1.

[0012] Preferably, the amine functionalized monomer described is any one or more of the structural compounds shown in VB-1 to 14.

[0013]

[0014] Preferably, the amine functional monomers described account for 0-50% by weight of the monomers.

[0015] Preferably, the polymerization reaction is carried out at a temperature of -10-80°C and a time of 0.05-24h.

[0016] The amino functionalized polyisoprene rubber obtained by the preparation method provided by the invention has a 1,2-structure content of 20-30% and a 3,4-structure content of 60-75%.

[0017] Preferably, the number average molecular weight of the amine-functionalized polyisoprene rubber is 1000-200000 g / mol.

[0018] Preferably, the molecular weight distribution of the amine-functionalized polyisoprene rubber is 1.03-1.20.

[0019] The invention discloses an amine-functionalized polyisoprene rubber with high vinyl side groups prepared by anionic polymerization, using a novel bicyclic amine compound as a key regulator and an amine-functionalized monomer as a comonomer. The obtained polyisoprene rubber has a higher 1,2-structure, a controllable molecular weight, a very narrow molecular weight distribution, a controllable degree of amine functionalization, a wide range of amine-functionalized groups to be selected, and the preparation method provided by the invention has mild polymerization conditions, low cost, and is suitable for industrial operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the effect of different ratios of NN-10 / Li on the microstructure of isoprene rubber;

[0021] Figure 2 The H-NMR spectrum of high vinyl side group polyisoprene rubber functionalized with 0-25% tertiary amine;

[0022] Figure 3 The DSC spectrum of polyisoprene rubber with high vinyl side groups functionalized with 0-25% tertiary amine. DETAILED DESCRIPTION

[0023] The present invention provides a method for preparing an amine-functionalized polyisoprene rubber having a high vinyl side group, comprising the following steps:

[0024] In an anhydrous and oxygen-free inert gas atmosphere, an inert organic hydrocarbon solvent, a novel structure regulator, an alkyl lithium initiator, isoprene and an amine-functionalized monomer are mixed for anionic copolymerization to obtain an amine-functionalized polyisoprene rubber with a high 1,2-structure and a high vinyl side group.

[0025] In the present invention, the organic solvent preferably includes one or more of cyclohexane, cyclopentane, toluene, benzene, hexane, and heptane. The present invention has no particular limitation on the amount of the organic solvent, and any amount that can evenly mix the raw materials will meet the requirement.

[0026] In the present invention, the novel regulator described is any one or more of the structural compounds shown in NN-1 to 12.

[0027]

[0028] In the present invention, the mechanism of action of the novel regulator is as follows:

[0029]

[0030] In the present invention, the novel regulator can be synthesized by organic synthesis methods well known to those skilled in the art.

[0031] In the present invention, the molar ratio of the novel regulator to the alkyl lithium is preferably (0.1-10):1, and the preferred ratio is 0.25-5.0.

[0032] In the present invention, the amino functional monomer is any one or more of the compounds with structures shown in VB-1 to 14.

[0033]

[0034] In the present invention, the amino functional monomer accounts for 0-50% of the monomer mass fraction.

[0035] In the present invention, the order of adding the inert organic hydrocarbon solvent, the novel regulator, the alkyl lithium initiator, the isoprene monomer and the amine functionalized monomer is preferably:

[0036] Inert organic hydrocarbons, novel regulators, and alkyl lithium initiators are added into a reaction kettle, and then isoprene and amine functionalized monomers are continuously added as mixed monomers; or

[0037] Inert organic hydrocarbons, novel regulator, isoprene and amine functionalized monomers are mixed and added into a reaction kettle, and then alkyl lithium initiator is added;

[0038] In the present invention, the polymerization reaction temperature is preferably room temperature, no additional heat source or cooling source is required, and the reaction time is 0.05-24h.

[0039] In the present invention, all raw materials need to be treated in anhydrous and oxygen-free conditions, and the polymerization reaction is carried out in an inert gas atmosphere.

[0040] In the present invention, after the polymerization reaction, preferably, a terminator and an antioxidant are added, and alcohol substances are precipitated or high-temperature steam is used to wash the rubber to obtain the above-mentioned polyisoprene rubber.

[0041] The amino functionalized polyisoprene rubber obtained by the preparation method provided by the invention has a 1,2-structure content in the range of 20-30% and a 3,4-structure content in the range of 60-75%.

[0042] In the present invention, the number average molecular weight of the amine-functionalized polyisoprene rubber is 1000-200000 g / mol, preferably 2000-100000 g / mol.

[0043] In the present invention, the molecular weight distribution of the amine-functionalized polyisoprene rubber is 1.03-1.20, preferably 1.03-1.10.

[0044] The present invention also provides the use of the amino-functionalized polyisoprene rubber described in the above scheme in a green tire anti-slip rubber modifier, epoxy resin toughened modified rubber or high-frequency communication copper-clad laminate bonding curing resin.

[0045] To further illustrate the present invention, the amino-functionalized polyisoprene rubber provided by the present invention and its preparation method and application are described in detail below in conjunction with examples, but they should not be construed as limiting the scope of protection of the present invention.

[0046] Comparative Example 1:

[0047] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 10mL of 2.5M THF regulator and 10mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 500g of isoprene was slowly added dropwise. The polymerization reaction was carried out at room temperature for 1h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The polyisoprene rubber solution was poured into 2L ethanol containing 40mL of antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. The polymer was then repeatedly washed with acidic deionized water and ethanol. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer had 1,2-structure 0%, 3,4-structure 31.5%, molecular weight 21500g / mol, and molecular weight distribution 1.04.

[0048] Comparative Example 2:

[0049] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 10mL of 2.5M THF regulator and 10mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 monomer were slowly added dropwise at the same time. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The polyisoprene rubber solution was poured into 40mL of antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol) in 2L ethanol to precipitate the polymer, and then washed repeatedly with acidic deionized water and ethanol. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 99%. The polymer had 0% 1,2-structure, 39.3% 3,4-structure, 5% VB-1 mass fraction, molecular weight of 22300g / mol, and molecular weight distribution of 1.07.

[0050] Comparative Example 3:

[0051] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 10mL of 2.5M NN-2 regulator and 10mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 10min, and then 450g of isoprene and 50g of VB-1 monomer were slowly added dropwise at the same time. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The polyisoprene rubber solution was poured into 2L ethanol containing 40mL of antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was repeatedly washed with acidic deionized water and ethanol. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure accounted for 18.5%, 3,4-structure accounted for 60.4%, VB-1 mass fraction accounted for 4.9%, molecular weight was 20800g / mol, and molecular weight distribution was 1.08.

[0052] Embodiment 1:

[0053] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 50mL of 0.5M NN-1 regulator and 10mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 3min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure is 15.8%, 3,4-structure is 61.8%, VB-1 functional monomer accounts for 5.1%, molecular weight is 22500g / mol, and molecular weight distribution is 1.07.

[0054] Embodiment 2:

[0055] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclopentane, 50mL of 0.5M NN-2 regulator and 10mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 18%, 3,4-structure 61.1%, VB-1 functional monomer accounted for 4.9%, molecular weight 19500g / mol, and molecular weight distribution 1.03.

[0056] Embodiment 3:

[0057] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-3 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-1 amine functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 1h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure is 10.8%, 3,4-structure is 57.3%, VB-1 amine functional monomer accounts for 5.1%, molecular weight is 43500g / mol, and molecular weight distribution is 1.09.

[0058] Embodiment 4:

[0059] A 5L reactor was filled with high-purity nitrogen, and 2500mL of n-heptane, 25mL of 0.5M NN-4 regulator and 5mL of 2.5M sec-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 amine functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 2.8%, 3,4-structure 45.0%, VB-1 amine functional monomer accounted for 4.7%, molecular weight 42200g / mol, and molecular weight distribution 1.04.

[0060] Embodiment 5:

[0061] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 50mL of 0.5M NN-5 regulator and 10mL of 2.5M tert-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2L ethanol of 40mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure is 16.8%, 3,4-structure is 60.5%, VB-1 amine functional monomer accounts for 4.8%, molecular weight is 24200g / mol, and molecular weight distribution is 1.09.

[0062] Embodiment 6:

[0063] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 12.5mL of 0.5M NN-6 regulator and 2.5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure is 16.2%, 3,4-structure is 55.5%, VB-1 functional monomer accounts for 4.8%, molecular weight is 81500g / mol, and molecular weight distribution is 1.12.

[0064] Embodiment 7:

[0065] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 12.5mL of 0.5M NN-7 regulator and 2.5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 amine functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer had 1,2-structure 26.2%, 3,4-structure 67.5%, VB-1 amine functional monomer accounted for 4.9%, molecular weight 90600g / mol, and molecular weight distribution 1.10.

[0066] Embodiment 8:

[0067] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 12.5mL of 0.5M NN-8 regulator and 2.5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at 0°C for 4h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer had 1,2-structure 29.2%, 3,4-structure 64.5%, VB-1 functional monomer accounted for 5.0%, molecular weight 78800g / mol, and molecular weight distribution 1.11.

[0068] Embodiment 9:

[0069] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-9 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at 10°C for 1h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, the polymer was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer had a 1,2-structure of 27.9%, a 3,4-structure of 65.0%, a VB-1 functional monomer of 4.9%, a molecular weight of 41200g / mol, and a molecular weight distribution of 1.05.

[0070] Embodiment 10:

[0071] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-10 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 1h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 4.9%, 3,4-structure 54.5%, VB-1 functional monomer accounted for 5.1%, molecular weight 40300g / mol, and molecular weight distribution 1.12.

[0072] Embodiment 11:

[0073] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-11 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 450g of isoprene and 50g of VB-1 amine functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 1h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, the polymer was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer had 1,2-structure 26.9%, 3,4-structure 56.5%, VB-1 functional monomer accounted for 5.0%, molecular weight 39500g / mol, and molecular weight distribution 1.19.

[0074] Embodiment 12:

[0075] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-12 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-1 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 26.1%, 3,4-structure 55.9%, VB-1 functional monomer accounted for 5.1%, molecular weight 41600g / mol, and molecular weight distribution 1.09.

[0076] Embodiment 13:

[0077] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-7 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-5 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 25.1%, 3,4-structure 57.9%, VB-5 functional monomer accounted for 4.7%, molecular weight 38000g / mol, and molecular weight distribution 1.09.

[0078] Embodiment 14:

[0079] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-9 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-7 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 27.1%, 3,4-structure 56.5%, VB-7 functional monomer accounted for 4.9%, molecular weight 40100g / mol, and molecular weight distribution 1.06.

[0080] Embodiment 15:

[0081] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-11 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-9 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 25.1%, 3,4-structure 57.0%, VB-9 silicon-containing functional monomer accounted for 5.2%, molecular weight 42000g / mol, and molecular weight distribution 1.09.

[0082] Embodiment 16:

[0083] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-12 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-12 monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer had 1,2-structure 27.1%, 3,4-structure 55.0%, VB-12 functional monomer accounted for 5.1%, molecular weight 45200g / mol, and molecular weight distribution 1.07.

[0084] Embodiment 17:

[0085] A 5L reactor was filled with high-purity nitrogen, and 2500mL of cyclohexane, 25mL of 0.5M NN-8 regulator and 5mL of 2.5M n-butyl lithium initiator were added in sequence. The mixed solution was stirred at room temperature for 5min, and then 475g of isoprene and 25g of VB-14 functional monomer were slowly added. The polymerization reaction was carried out at room temperature for 2h, and 1M hydrochloric acid methanol solution was added to terminate the reaction. The amino-functionalized polyisoprene rubber solution was poured into 2.5L ethanol of 50mL antioxidant (ethanol solution of 2,6-di-tert-butyl-4-methylphenol), and the polymer was precipitated. Then, it was washed with acidic deionized water and ethanol in turn. The obtained polymer was dried in a vacuum drying oven to obtain a polymer with a yield of 100%. The polymer 1,2-structure 28.1%, 3,4-structure 54.0%, VB-12 functional monomer accounted for 5.0%, molecular weight 42900g / mol, and molecular weight distribution 1.05.

[0086] Finally, it should be noted that the above embodiments are only used to illustrate the implementation process and features of the present invention, rather than to limit the technical methods of the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field should understand that the present invention can still be modified or replaced by equivalents, and any modification or partial replacement that does not depart from the spirit and scope of the present invention should be covered by the protection scope of the present invention.

Claims

1. A method for preparing an amine-functionalized polyisoprene rubber having a high vinyl side group, characterized in that: The following steps are involved: In an anhydrous and oxygen-free inert gas atmosphere, an inert organic hydrocarbon solvent, a novel bicyclic amine structure regulator, an alkyl lithium initiator, isoprene and an amine functionalized monomer are mixed for anionic polymerization to obtain an amine functionalized polyisoprene rubber with high 1,2-structure and 3,4-structure.

2. The preparation method according to claim 1, characterized in that: The novel bicyclic amine modulator described is any one of the structural compounds shown in NN-1 to 12:

3. According to the preparation method described in claim 1, the molar ratio of the novel bicyclic amine regulator to the alkyl lithium is (0.1-10):

1.

4. The preparation method according to claim 1, characterized in that: The described amine functional monomer is any one of the structural compounds shown in VB-1 to 14:

5. The preparation method according to claim 1, characterized in that: The described amine functional monomer accounts for 0-50% of the monomer mass fraction.

6. The preparation method according to claim 1, characterized in that: The polymerization reaction temperature is described as -10-80°C and the time is 0.05-24h.

7. The amine-functionalized polyisoprene rubber with high vinyl side groups obtained by the preparation method described in claims 1-6, wherein the 1,2-structure content is 20-30%, and the 3,4-structure content is 60-75%.

8. The amino-functionalized polyisoprene rubber with high vinyl side groups according to claim 7, characterized in that: The number average molecular weight of the amine functionalized polyisoprene rubber is 1000-200000 g / mol.

9. The amine-functionalized polyisoprene rubber according to claim 7, characterized in that: The molecular weight distribution of the amino-functionalized polyisoprene rubber is 1.03-1.

20.

10. The amino-functionalized polyisoprene rubber according to any one of claims 7 to 9 can be used as a green tire anti-skid rubber modifier, epoxy resin toughened modified rubber or high-frequency communication copper-clad laminate bonding curing resin.

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