CN115960319A - Syndiotactic 1,2-polybutadiene reinforced nickel-based butadiene rubber alloy and its preparation method and application - Google Patents

Abstract

A syndiotactic 1, 2-polybutadiene reinforced nickel series butadiene rubber alloy and a preparation method and application thereof belong to the field of synthetic rubber. The preparation method of the syndiotactic 1, 2-polybutadiene reinforced nickel series butadiene rubber alloy comprises the following steps: s1: preparing nickel-based butadiene rubber glue solution; s2: preparing sPB in situ in the Ni-series butadiene rubber glue solution; s3: and (4) coagulating and drying the polymerization glue solution. The method can lead the syndiotactic 1, 2-polybutadiene (sPB) to be uniformly dispersed in the nickel-based butadiene rubber matrix by in-situ preparation of the nickel-based butadiene rubber alloy, can generate co-vulcanization with the nickel-based butadiene rubber matrix during vulcanization, and can be used as a filler to enhance the interaction between the sPB and the nickel-based butadiene rubber matrix by in-situ preparation, thereby improving the reinforcing effect and reducing the internal consumption of the tire.

Description

Syndiotactic 1,2-polybutadiene reinforced nickel-based butadiene rubber alloy and its preparation method and application

technical field

The invention relates to the field of synthetic rubber, in particular to a syndiotactic 1,2-polybutadiene reinforced nickel-based butadiene rubber alloy and a preparation method and application thereof.

Background technique

Butadiene rubber is widely used in tires, rubber hoses, tapes and other fields due to its excellent properties such as high elasticity, low rolling resistance, high wear resistance, low heat generation, and fatigue resistance. However, since its main chain structure is dominated by cis-1,4-units, it must be reinforced to meet service requirements when some high-modulus, high-strength components are used. For example, in tire sidewall rubber, the proportion of nickel-based butadiene rubber is as high as 40%. When the car is running at high speed and turning, the sidewall is subjected to large mechanical deformation, which is the main pressure and heating part, which determines that the sidewall rubber must have a higher modulus and better dynamic fatigue resistance. , to ensure the safety of the car's handling. Moreover, in recent years, with the development of lightweight (meaning more fuel-efficient) high-performance tires, sidewalls have become increasingly "thin and stronger", posing higher challenges to their modulus and strength.

For the sidewall of the tire, the traditional technology mostly uses methods of adding inorganic fillers or increasing the degree of cross-linking to increase its modulus. However, since the main chain of butadiene rubber is composed of non-polar carbon and hydrogen atoms, the interfacial interaction force between the butadiene rubber and the polar filler is small, and the compatibility is poor, which will lead to high internal friction of the sidewall rubber during the driving process of the car. High heat affects its dynamic fatigue performance and aging performance. In contrast, crystalline polymers added to the sidewall as fillers can also have a reinforcing effect, and at the same time, their lower density can meet the requirements of tire lightweight development. Syndiotactic 1,2-polybutadiene (sPB) is a crystalline polymer prepared by a coordination polymerization catalyst system such as cobalt and iron. Microscopically, sPB presents a short fiber structure and shows great potential in reinforcing butadiene rubber (J.Appl.Polym.Sci, 2019, 136(33), 47934). At the same time, the main chain of sPB is rich in suspended double bonds, which can co-vulcanize with the butadiene rubber matrix during vulcanization, which can significantly improve the interaction between the matrix and the filler, reduce the internal friction and heat generation of the tire sidewall during driving, and ensure safe driving .

Direct mechanical blending of nickel-based butadiene rubber and sPB (such as kneading, banburying, etc.), the shear force generated is difficult to destroy the original aggregate state of sPB, reduce its size, and finally cause sPB to be in the butadiene rubber matrix Inhomogeneous dispersion in the medium can not achieve the ideal reinforcing effect.

Contents of the invention

The invention provides a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy, a preparation method and application thereof. By in-situ preparation of syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy, the sPB can be uniformly dispersed in the nickel-based butadiene rubber matrix, and can be mixed with the nickel-based butadiene rubber matrix during vulcanization Co-vulcanization occurs, and as a filler, the in-situ preparation enhances the interaction between the sPB and the nickel-based butadiene rubber matrix, improves the reinforcing effect, and reduces the internal friction of the tire.

The preparation method of the syndiotactic 1,2-polybutadiene reinforced nickel-based butadiene rubber alloy involved in the present invention comprises the following steps:

S1: Preparation of nickel-based butadiene rubber glue;

S2: In situ preparation of sPB in nickel-based butadiene rubber glue;

S3: coagulation and drying of the polymer gel;

Preparation of nickel-based butadiene rubber glue in step S1 of the present invention is selected from one of the following two methods: (1) obtain nickel-based butadiene rubber solution by polymerization; (2) dry nickel-based butadiene rubber The gel is soluble in the solvent;

In the step S1 of the present invention, a nickel-based butadiene rubber solution is obtained by polymerization, wherein the polymerization step is: after mixing the nickel compound, aluminum alkyl, fluorine-containing compound, and butadiene monomer solution, the polymerization is initiated;

In the step S1 of the present invention, the nickel compound is preferably an organic nickel compound, and more specifically, the organic nickel compound is an organic acid nickel containing 1 to 20 carbon atoms. More preferred are nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, nickel neodecanoate, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicylate, nickel bis(cyclopentadiene) , one or more of double (π-allyl) nickel and nickel tetracarbonyl, more preferably one or more of nickel naphthenate, nickel neodecanoate and nickel octoate.

In the step S1 of the present invention, the alkylaluminum is one of trialkylaluminum, dialkylaluminum hydride or methylaluminoxane, and the structural formula is (R ₁ ) ₃ Al or (R ₂ ) ₂ AlH, R ₁ , _R2 is independently represented as an aliphatic group with carbon 1-20, preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum One or more of aluminum hydride and methylaluminoxane, more preferably one or more of triethylaluminum, triisobutylaluminum and trioctylaluminum.

The fluorine-containing compound in step S1 of the present invention is hydrogen fluoride or boron trifluoride and corresponding coordination compounds, preferably boron trifluoride ether compounds, boron trifluoride alcohol compounds, boron trifluoride ketones Compounds, one or more of boron trifluoride ester compounds, more preferably boron trifluoride etherate complexes.

In the step S1 of the present invention, the molar ratio among nickel compound, aluminum alkyl, fluorine-containing compound and butadiene monomer is 1:(2-100):(0.5-10):(1000-100000).

The polymerization temperature of the step S1 in the present invention is 20-150°C.

After the nickel-based butadiene rubber solution is obtained by polymerization in step S1 of the present invention, in order to reduce the influence of aluminum, fluorine, etc. on the later-stage iron-based catalyst, a heteroatom compound can be selectively added for treatment, and the heteroatom compound of the heteroatom compound It is at least one of oxygen, nitrogen, and phosphine, and the preferred heteroatom compound is one of alcohols, phenols, and amines.

Dissolving nickel-based butadiene rubber dry glue in a solvent in step S1 of the present invention is to dissolve solid nickel-based butadiene rubber in a solvent. The solvent is an aliphatic hydrocarbon and/or an aromatic hydrocarbon, and the aliphatic hydrocarbon is preferably hexane, Cyclohexane, carbon 6 oil, one or more of hydrogenated gasoline, aromatic hydrocarbons are preferably one or more of benzene, toluene, xylene, and solvents are preferably hexane, cyclohexane, hydrogenated One of gasoline and toluene.

In the step S2 of the present invention, the in-situ preparation of sPB in nickel-based butadiene rubber glue is to use the system catalyst system to initiate butadiene polymerization in-situ preparation of sPB, wherein the polymerization step is to prepare iron compound, phosphine-containing compound, alkyl Aluminum co-catalyst, butadiene monomer solution, and nickel-based butadiene rubber glue are mixed to initiate polymerization in situ.

The iron compound described in step S2 of the present invention is preferably an organic iron compound, more specifically an organic acid iron containing 1 to 20 carbon atoms, preferably iron benzoate, iron acetate, naphthene One or more of ferric acid, iron caprylate, iron neodecanoate, iron palmitate, iron stearate, iron acetylacetonate, iron salicylate, more preferably iron naphthenate, iron octanoate, acetylacetone A kind of iron.

The phosphine-containing compound described in step S2 of the present invention is a phosphine-containing electron donor, preferably a phosphite compound or a phosphate compound, more preferably dimethyl phosphite, diethyl phosphite, phosphite One or more of dibutyl phosphate, diisooctyl phosphite, diphenyl phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, and triphenylphosphine, More preferably, it is one of diethyl phosphite, diisooctyl phosphite, and triphenyl phosphate;

In the step S2 of the present invention, the alkylaluminum cocatalyst is one of trialkylaluminum or methylaluminoxane, and the alkyl group in the alkylaluminum is preferably an aliphatic group with carbon 1-20, and the alkylaluminum The cocatalyst is preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, more preferably triethylaluminum, triisobutylaluminum.

In the step S2 of the present invention, the molar ratio between the iron compound, the phosphine-containing compound, the alkylaluminum cocatalyst, and the butadiene monomer is 1: (0.1-50): (5-200): (200-50000) , The polymerization temperature is 20-150°C.

In the step S3 of the present invention, the specific step is to obtain the sPB reinforced nickel-based butadiene rubber alloy through coagulation and drying after the polymerization system is terminated.

The syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy of the present invention is prepared by the above-mentioned preparation method, and the sPB is uniformly dispersed in the nickel-based butadiene rubber.

In the prepared sPB-reinforced nickel-based butadiene rubber alloy, the mass percentage of sPB in the sPB-reinforced nickel-based butadiene rubber alloy is between 5% and 50%, preferably between 10% and 30%.

The prepared syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy, in the nickel-based butadiene rubber part, has a number average molecular weight (Mn) of 5-100×10 ⁴ , and a molecular weight distribution (Mw /Mn) is 1.50-5.50.

The syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy of the present invention has great application potential in tire treads, sidewalls, rubber shoes and adhesive tapes.

Compared with the prior art, the beneficial effects of the present invention are:

The present invention directly adds the required catalyst system (preferably iron series) in the preparation of sPB in the nickel-based butadiene rubber glue, because the active center of the catalyst is evenly dispersed, the sPB polymer chains produced by in-situ polymerization can be well dispersed in the Nickel-based butadiene rubber, with uniform size and adjustable ratio, can achieve the expected reinforcing effect.

Description of drawings

Figure 1, the DSC spectrum of a nickel-based butadiene rubber alloy reinforced with syndiotactic 1,2-polybutadiene (sPB) (Example 4).

Figure 2, the FTIR spectrum of a nickel-based butadiene rubber alloy reinforced with syndiotactic 1,2-polybutadiene (sPB) (Example 4).

Figure 3. The apparent difference between the rubber obtained in Example 4 (left side) and Comparative Example 1 (right side).

Detailed ways

The present invention is further illustrated by the following examples, but does not constitute a limitation to the protection scope and implementation of the present invention.

The microstructure of the syndiotactic 1,2-polybutadiene (sPB) reinforced rare earth butadiene rubber alloy provided by the invention is calculated by FTIR spectrum.

The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of the syndiotactic 1,2-polybutadiene (sPB) reinforced rare earth butadiene rubber alloy provided by the present invention are passed through gel permeation chromatography (GPC) assay.

The glass transition temperature and melting point of the alloy material of syndiotactic 1,2-polybutadiene (sPB) reinforced rare earth butadiene rubber provided by the present invention are measured by TA-Q200.

The Mooney viscosity of the alloy material of syndiotactic 1,2-polybutadiene (sPB) reinforced rare earth butadiene rubber provided by the invention is measured by an American ALPHA MV 2000 Mooney viscometer.

Example 1:

Under a nitrogen atmosphere, 10 g of nickel-based butadiene rubber (Mn=11.2×10 ⁴ , PDI=3.5, Mooney 44) was dissolved in 150 ml of hexane to obtain a hexane solution of nickel butadiene rubber. Then add 10ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 1g), hexane solution of iron isooctanoate (addition: 1.85×10 ^-5 mol), diethyl phosphite Esters (added in an amount of 3.7×10 ^-5 mol), triisobutylaluminum in hexane (added in an amount of 5.55×10 ^-4 mol), stirred evenly, and reacted at 50°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel butadiene rubber alloy. The total yield of the polymer was 95.2%, and the mass percentage of sPB was 6.9%.

Example 2: Under a nitrogen atmosphere, 10 g of nickel-based butadiene rubber (Mn=11.2×10 ⁴ , PDI=3.5, Mooney 44) was dissolved in 150 ml of hexane to obtain a hexane solution of nickel butadiene rubber. Then add 10ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 3.7×10 ^-5 mol), diisophosphorous acid Octyl ester (6.4×10 ^-5 mol added), triisobutylaluminum hexane solution (1.11×10 ^-3 mol added), stirred evenly, and reacted at 50°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel butadiene rubber alloy. The total yield of the polymer was 90.2%, and the mass percentage of sPB was 15.7%.

Example 3:

Under a nitrogen atmosphere, 10 g of nickel-based butadiene rubber (Mn=11.2×10 ⁴ , PDI=3.5, Mooney 44) was dissolved in 150 ml of hexane to obtain a hexane solution of nickel butadiene rubber. Then add 10ml of butadiene hexane solution (concentration is 0.1g/ml, butadiene addition is 4g), hexane solution of iron naphthenate and toluene solution of iron acetylacetonate (addition amount is 7.4×10 ^-5 mol), diethyl phosphite (the addition amount is 1.3×10 ^-4 mol), the hexane solution of triisobutylaluminum (the addition amount is 3.75×10 ^-3 mol), after stirring evenly, react at 50°C for 4 Hour. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel butadiene rubber alloy. The total yield of the polymer was 83.7%, and the mass percentage of sPB was 33.5%.

Example 4:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 3.7×10 ^-5 mol), diethyl phosphite Esters (added in an amount of 7.4×10 ^-5 mol), triisobutylaluminum in hexane (added in an amount of 11.11×10 ^-4 mol), stirred evenly, and continued to react at 50°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 85.8%, and the mass percentage of sPB was 15.6% (see Figure 2). Mn=18.0×10 ⁴ , PDI=3.1. T _g =-103.0°C, T _m =161.4°C (see Figure 1). Mooney viscosity 60.

Example 5:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 3.7×10 ^-5 mol), diethyl phosphite Esters (added in an amount of 7.4×10 ^-5 mol), triisobutylaluminum in hexane (added in an amount of 11.11×10 ^-4 mol), stirred evenly, and continued to react at 80°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 96.4%, and the mass percentage of sPB was 17.5%. Mn=20.8×10 ⁴ , PDI=3.6. _Tg = -104.2°C, _Tm = 166.8°C. Mooney viscosity 62.

Embodiment 6:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add the toluene solution of pyridine (the ratio of pyridine to nickel naphthenate is 10:1), and stir evenly. Then add 20ml butadiene hexane solution (concentration is 0.1g/ml, butadiene addition is 2g), toluene solution of iron acetylacetonate (addition amount is 3.7×10 ^-5 mol), triphenyl phosphate ( The addition amount is 7.4×10 ^-5 mol), the hexane solution of triisobutylaluminum (the addition amount is 11.11×10 ^-4 mol), after stirring evenly, the reaction is continued at 80°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 93.8%, and the mass percentage of sPB was 16.4%. Mn=18.9×10 ⁴ , PDI=3.4. _Tg = -103.4°C, _Tm = 161.2°C. Mooney viscosity 60.

Embodiment 7:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel acetylacetonate, triisobutylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=50, B/Ni=3), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 3.7×10 ^-5 mol), diisophosphorous acid Octyl ester (7.4×10 ^-5 mol added), triisobutylaluminum hexane solution (11.11×10 ^-4 mol added) ^, stirred evenly, and continued to react at 100°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 82.3%, and the mass percentage of sPB was 15.5%. _Tg = -101.2°C, _Tm = 154.2°C. Mooney viscosity 54.

Embodiment 8:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triisobutylaluminum, boron trifluoride etherate complex (catalyst The amount used is Bd/Ni=2000, Al/Ni=10, B/Ni=2), and then polymerized at 40°C for 6h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 7.4×10 ^-6 mol), diethyl phosphite Esters (added in an amount of 7.4×10 ^-5 mol), triethylaluminum in hexane (added in an amount of 7.4×10 ^-4 mol), stirred evenly, and continued to react at 50°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 78.9%, and the mass percentage of sPB was 0.2%. _Tg = -95.2°C, _Tm = 151.2°C. Mooney viscosity 42.

Embodiment 9:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 40ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 4g), hexane solution of iron isooctanoate (addition: 7.4×10 ^-5 mol), diethyl phosphite Esters (added in an amount of 1.5×10 ^-4 mol), trioctylaluminum in hexane (added in an amount of 2.2×10 ^-3 mol), stirred evenly, and continued to react at 80°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 90.1%, and the mass percentage of sPB was 25.7%. _Tg = -101.4°C, _Tm = 155.8°C. Mooney viscosity 58.

Example 10:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel acetylacetonate, triisobutylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=50, B/Ni=3), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml butadiene toluene solution (concentration is 0.1g/ml, butadiene addition is 2g), toluene solution of iron acetylacetonate (addition amount is 3.7×10 ^-5 mol), diisooctyl phosphite (the addition amount is 7.4×10 ^-5 mol), triisobutylaluminum in hexane solution (the addition amount is 11.11× ^{10 -4} mol), after stirring evenly, the reaction is continued at 60°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 88.5%, and the mass percentage of sPB was 16.4%. _Tg = -102.8°C, _Tm = 150.1°C. Mooney viscosity 54.

Example 11:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron naphthenate (addition: 3.7×10 ^-5 mol), diphosphite Butyl ester (7.4×10 ^-5 mol added), diisobutylaluminum hydrogen hexane solution (11.11×10 ^-4 mol added), stirred evenly, and continued to react at 60°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 93.1%, and the mass percentage of sPB was 7.4%. _Tg = -105.2°C. Mooney viscosity 48.

Example 12:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 3.7×10 ^-5 mol), diethyl phosphite Esters (added in an amount of 5.6×10 ^-5 mol), trioctylaluminum in hexane (added in an amount of 22.22×10 ^-4 mol), stirred evenly, and continued to react at 60°C for 4 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 94.5%, and the mass percentage of sPB was 13.2%. _Tg = -103.8°C, _Tm = 161.5°C. Mooney viscosity 59.

Example 13:

Under nitrogen protection, in dry 500ml reaction bottle, add butadiene monomer solution 200ml (concentration is 0.1g/ml), nickel naphthenate, triethylaluminum, boron trifluoride etherate complex (catalyst dosage) Bd/Ni=10000, Al/Ni=10, B/Ni=2), and then polymerized at 50°C for 4h. Then add the toluene solution of 2,6-di-tert-butyl-p-cresol (the ratio of 2,6-di-tert-butyl-p-cresol to nickel naphthenate is 10:1), and stir evenly. Then add 20ml of butadiene hexane solution (concentration: 0.1g/ml, butadiene addition: 2g), hexane solution of iron isooctanoate (addition: 3.7×10 ^-6 mol), diethyl phosphite Esters (added in an amount of 5.6×10 ^-6 mol), MAO in toluene (added in an amount of 1.85×10 ^-3 mol), stirred evenly, and continued to react at 60°C for 10 hours. After that, it is terminated with an ethanol solution containing 1% anti-aging agent 264, and coagulated with ethanol to obtain a syndiotactic 1,2-polybutadiene (sPB) reinforced nickel-based butadiene rubber alloy. The total yield of the polymer was 83.2%, and the mass percentage of sPB was 7.6%. _Tg = -104.9°C. Mooney viscosity 50.

Comparative example 1

Dissolve nickel-based butadiene rubber and sPB directly in hexane, stir evenly, find that sPB is suspended in hexane, and then dry to obtain a mixture of sPB and nickel-based butadiene rubber, compared to Example 1 and Example 4 , it can be clearly seen that sPB aggregates obviously in butadiene rubber, and the dispersion is poor (see Figure 3).

Claims (10)

1. A method for preparing syndiotactic 1, 2-polybutadiene reinforced nickel series butadiene rubber alloy is characterized by comprising the following steps:

s1: preparing nickel-based butadiene rubber glue solution;

s2: preparing syndiotactic 1, 2-polybutadiene in situ in the nickel-series butadiene rubber glue solution;

s3: and (4) coagulating and drying the polymerization glue solution.

2. The method for preparing syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy according to claim 1, wherein in step S1, the nickel-based cis-butadiene rubber solution is prepared by one of the following two methods: (1) obtaining a nickel-based butadiene rubber solution through polymerization; and (2) dissolving the nickel-based butadiene rubber dry glue in a solvent.

3. The method for producing syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy as defined in claim 2, wherein the nickel-based cis-butadiene rubber solution is obtained by polymerization, wherein the polymerization step is: the nickel compound, the alkyl aluminum, the fluorine-containing compound and the butadiene monomer solution are mixed to initiate polymerization.

4. The process for producing a syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy as defined in claim 3, wherein the nickel compound is an organic nickel compound, more specifically an organic acid nickel having 1 to 20 carbon atoms; preferably one or more of nickel benzoate, nickel acetate, nickel naphthenate, nickel octoate, nickel neodecanoate, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicylate, nickel bis (cyclopentadienyl), nickel bis (pi-allyl) and nickel tetracarbonyl;

and/or the alkyl aluminum is one of trialkyl aluminum, dialkyl aluminum hydride or methyl aluminoxane, and the structural formula is (R) ₁ ) ₃ Al or (R) ₂ ) ₂ AlH，R ₁ ，R ₂ Independently represent aliphatic group of carbon 1-20, preferably one or more of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride and methyl aluminoxane;

and/or the fluorine-containing compound is hydrogen fluoride or boron trifluoride and a corresponding coordination compound, preferably one or more of a boron trifluoride ether compound, a boron trifluoride alcohol compound, a boron trifluoride ketone compound and a boron trifluoride ester compound;

and/or the molar ratio of the nickel compound, the alkyl aluminum, the fluorine-containing compound and the butadiene monomer is 1 (2-100), 0.5-10 and 1000-100000;

and/or the polymerization temperature is 20-150 ℃.

5. The method for preparing syndiotactic 1, 2-polybutadiene reinforced nickel-based butadiene rubber alloy according to claim 2, wherein the step of dissolving the nickel-based butadiene rubber dry rubber in the solvent is to dissolve solid nickel-based butadiene rubber in the solvent, the solvent is aliphatic hydrocarbon and/or aromatic hydrocarbon, the aliphatic hydrocarbon is preferably one or more of hexane, cyclohexane and C6 oil, and hydrogenated gasoline, and the aromatic hydrocarbon is preferably one or more of benzene, toluene and xylene.

6. The method for preparing syndiotactic 1, 2-polybutadiene reinforced nickel-based butadiene rubber alloy according to claim 1, wherein after the nickel-based butadiene rubber solution is obtained by polymerization in step S1, a heteroatom compound is added for impurity removal, wherein the heteroatom of the heteroatom compound is at least one of oxygen, nitrogen and phosphine, and preferably the heteroatom compound is one of alcohols, phenols and amines.

7. The method for preparing syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy according to claim 1, wherein in step S2, sPB is prepared in situ in the nickel-based cis-butadiene rubber cement, and sPB is prepared in situ for initiating butadiene polymerization by using a system catalyst system, wherein the polymerization steps are as follows: mixing an iron compound, a phosphine-containing compound, an alkyl aluminum cocatalyst, a butadiene monomer solution and a nickel-based butadiene rubber glue solution, and carrying out in-situ initiation polymerization.

8. The method for preparing syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy according to claim 7, wherein said iron compound is preferably an organic iron compound, more specifically an organic iron compound containing 1 to 20 carbon atoms, preferably one or more of iron benzoate, iron acetate, iron naphthenate, iron caprylate, iron neodecanoate, iron palmitate, iron stearate, iron acetylacetonate and iron salicylate;

and/or the phosphine-containing compound is an electron donor containing phosphine, preferably a phosphite ester compound or a phosphate ester compound, more preferably one or more of dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diisooctyl phosphite, diphenyl phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate and triphenyl phosphate;

and/or the alkyl aluminum cocatalyst is one of trialkyl aluminum or methyl aluminoxane, the alkyl in the alkyl aluminum is preferably an aliphatic group with 1-20 carbon atoms, and the alkyl aluminum cocatalyst is preferably trimethyl aluminum, triethyl aluminum, triisobutyl aluminum or trioctyl aluminum;

and/or the molar ratio of the iron compound, the phosphine-containing compound, the alkyl aluminum cocatalyst and the butadiene monomer is 1 (0.1-50) (5-200) (200-50000), and the polymerization temperature is 20-150 ℃.

9. A syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy, characterized in that it is obtained by the production method as claimed in any one of claims 1 to 8, wherein the syndiotactic 1, 2-polybutadiene is uniformly dispersed in the nickel-based cis-butadiene rubber; the mass percentage of the syndiotactic 1, 2-polybutadiene to the syndiotactic 1, 2-polybutadiene reinforced nickel series butadiene rubber alloy is between 5 and 50 percent.

10. The syndiotactic 1, 2-polybutadiene reinforced nickel-based cis-butadiene rubber alloy as defined in claim 9, for use in a tread, sidewall, rubber shoe, tape of a tire.

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