Bio-based itaconate rubber, preparation method thereof and bio-based itaconate rubber product

Abstract

The invention relates to the technical field of rubber materials, in particular to bio-based itaconate rubber, a preparation method of the bio-based itaconate rubber and a bio-based itaconate rubber product. According to the preparation method provided by the invention, a small amount of styrene monomer, emulsifier, reducing agent, initiator and chain transfer agent are supplemented in the second-stage polymerization reaction, so that the content of residual itaconate in the finally obtained rubber is reduced to be less than 500 ppm; the problems that in the prior art, the conversion rate of itaconate is low, a large number of unreacted monomers are left, and resources are wasted are effectively solved, operation is easy, and the reaction period is short. And the added styrene is more inclined to monomer addition instead of chain transfer, so that the crosslinking risk is remarkably reduced. Due to the fact that the content of the residual itaconate in the latex is extremely low, the content of the itaconate entering waste water and waste gas is basically zero in the follow-up flocculation and washing process, the treatment cost is reduced, and environmental pollution is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber materials, in particular to bio-based itaconate rubber, a preparation method thereof, and bio-based itaconate rubber products. Background Art

[0002] Given the shortage of natural rubber resources, the unsustainable development of the synthetic rubber industry, and the pressure of the "dual carbon" era, the development of high-performance, low-cost, and low-carbon-emission bio-based rubber has become an inevitable trend in the future development of rubber materials. Bio-based itaconate rubber, as a new type of green and environmentally friendly rubber material, is prepared using an emulsion polymerization process and has excellent comprehensive properties. The "green carbon reduction concept" and excellent performance of bio-based itaconate rubber give it huge application potential in areas such as tires, footwear, conveyor belts, and damping. However, during the polymerization process of bio-based itaconate rubber, the unreacted itaconate monomers remaining in the latex cannot be effectively recycled, resulting in a waste of resources. Secondly, during the post-treatment processes of bio-based itaconate rubber, such as flocculation, washing, and drying, the unreacted monomers will enter the wastewater and exhaust gas, increasing the treatment costs of the wastewater and exhaust gas and causing certain pollution to the environment.

[0003] To address these issues, patent CN116217809A discloses a method for preparing bio-based rubber. This involves emulsion polymerization of itaconate monomers and conjugated diene monomers. By repeatedly adding one or more of a molecular weight regulator, a conjugated diene monomer, and an emulsifier, the itaconate monomer conversion rate can reach over 99%, eliminating the need for high-boiling-point monomer removal, resulting in energy conservation and environmental protection. However, this patent still suffers from the problem of complex operation due to the multiple subsequent additions of conjugated diene and emulsifier.

[0004] Furthermore, dynamic mechanical analysis is an important method for studying polymer structure and properties. A higher loss factor (tan δ) at 0°C indicates better wet-slip resistance and greater safety for products made from that material. However, the wet-slip resistance of existing bio-based itaconate rubbers still needs to be improved. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide bio-based itaconate rubber, a preparation method thereof and bio-based itaconate rubber products. The preparation method provided by the present invention can prepare bio-based itaconate rubber from itaconate with an extremely high conversion rate, and the obtained bio-based itaconate rubber has excellent strength, wear resistance and anti-slip properties after being made into rubber products.

[0006] The present invention provides a method for preparing bio-based itaconate rubber, comprising the following steps:

[0007] S1) conducting a first stage polymerization reaction of itaconate, conjugated diene, desalted water, an emulsifier, an electrolyte, an activator, a reducing agent, an oxygen scavenger, and a chain transfer agent in the presence of an initiator;

[0008] S2) subjecting styrene, an emulsifier, a reducing agent, a chain transfer agent, and the polymer product obtained in step S1) to a second polymerization reaction in the presence of an initiator, adding a terminator after the reaction is completed, and stripping, flocculating, washing, and drying the obtained latex to obtain bio-based itaconate rubber;

[0009] In some embodiments of the present invention, the raw materials for preparing the bio-based itaconate rubber include, based on 100 parts by weight of the total weight of itaconate and conjugated diene, 10-90 parts by weight of itaconate, 200-400 parts by weight of desalted water, 2-6 parts by weight of an emulsifier, 0.2-1 parts by weight of an electrolyte, 0.1-0.3 parts by weight of an activator, 0.04-0.15 parts by weight of a reducing agent, 0.01-0.1 parts by weight of an oxygen scavenger, 0.1-0.4 parts by weight of a chain transfer agent, 0.05-0.2 parts by weight of an initiator, 2-10 parts by weight of styrene, and 0.05-1 parts by weight of a terminator. The amount of styrene added must be carefully controlled, otherwise it will affect the properties of the final product.

[0010] The itaconate ester of the present invention is selected from at least one of dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dihexyl itaconate, diheptyl itaconate, dioctyl itaconate, dinonyl itaconate and didecyl itaconate; the conjugated diene is selected from at least one of butadiene, isoprene and myrcene; the emulsifier is selected from at least one of potassium oleate, sodium oleate, disproportionated rosin acid potassium soap, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium laurate, sodium palmitate, sodium stearate and sodium fatty acid; the electrolyte is selected from sodium carbonate, potassium chloride, sodium hydrogen phosphate, potassium phosphate, sodium phosphate and acetic acid The activator is selected from at least one of sodium ethylenediaminetetraacetic acid ferric sodium salt and ferrous sulfate-ethylenediaminetetraacetic acid disodium salt; the reducing agent is sodium formaldehyde sulfoxylate (commonly known as Rongbai powder or Diaobai block); the scavenger is sodium dithionite; the chain transfer agent is selected from at least one of alkyl mercaptans and polythiothiol compounds, preferably at least one of tert-dodecyl mercaptan, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate, and isooctyl 3-mercaptopropionate; the initiator is selected from at least one of p-menthane hydroperoxide, tert-butyl hydroperoxide, and isopropylbenzene hydroperoxide. The terminator is one or more of sodium polysulfide, hydroxylamine compounds, and sodium dimethyldithiocarbamate.

[0011] The bio-based itaconate rubber provided by the present invention is prepared by two-stage polymerization reactions of itaconate, conjugated diene, desalted water, emulsifier, electrolyte, activator, reducing agent, scavenger, chain transfer agent and styrene, step S1) and step S2), wherein the styrene is only added in the second stage polymerization reaction, the emulsifier, chain transfer agent, reducing agent and initiator need to be added in both the first stage polymerization reaction and the second stage polymerization reaction, and the remaining components are only added in the first stage polymerization reaction. Preferably, in step S2), the amount of the emulsifier used accounts for 3 wt% to 10 wt% of the total amount of the emulsifier used in steps S1) and S2); the amount of the chain transfer agent used accounts for 10 wt% to 30 wt% of the total amount of the chain transfer agent used in steps S1) and S2); the amount of the reducing agent used accounts for 5 wt% to 20 wt% of the total amount of the reducing agent used in steps S1) and S2); and the amount of the initiator used accounts for 5 wt% to 20 wt% of the total amount of the initiator used in steps S1) and S2). In the present invention, the addition of the emulsifier, reducing agent, and initiator in the second-stage polymerization reaction primarily serves to ensure material dispersion and reaction rate in the second-stage polymerization.

[0012] The present invention first conducts a first-stage polymerization reaction of itaconate, a conjugated diene, desalted water, an emulsifier, an electrolyte, an activator, a reducing agent, an oxygen scavenger, and a chain transfer agent in the presence of an initiator. The temperature of the first-stage polymerization reaction of the present invention is 4°C to 10°C, and the time of the first-stage polymerization reaction is 6 hours to 10 hours. In one embodiment of the present invention, the temperature of the first-stage polymerization reaction is 5°C to 6°C, and the time of the first-stage polymerization reaction is 6 hours. In another embodiment of the present invention, the temperature of the first-stage polymerization reaction is 6°C to 7°C, and the time of the first-stage polymerization reaction is 6 hours. In another embodiment of the present invention, the temperature of the first-stage polymerization reaction is 8°C to 10°C, and the time of the first-stage polymerization reaction is 8 hours.

[0013] Prior to carrying out the first stage polymerization reaction, the present invention further includes pre-emulsifying the itaconate, conjugated diene, desalted water, emulsifier, electrolyte, activator, reducing agent, scavenger, and chain transfer agent, and then carrying out the first stage polymerization reaction in the presence of an initiator. The pre-emulsification temperature of the present invention is 4°C to 10°C, and the pre-emulsification time is 1 hour to 4 hours.

[0014] After the first stage polymerization reaction, the present invention conducts a second stage polymerization reaction with styrene, an emulsifier, a chain transfer agent, a reducing agent, and the polymerization product obtained in step S1) in the presence of an initiator to produce bio-based itaconate rubber. Specifically, after the first stage polymerization reaction, styrene and the remaining emulsifier, chain transfer agent, reducing agent, and initiator are directly added to the reaction system to proceed with the second stage polymerization reaction. After the second stage polymerization reaction, the present invention further includes adding a terminator and subjecting the latex obtained after the second stage polymerization reaction to steam stripping, flocculation, water washing, and drying to produce bio-based itaconate rubber. The temperature of the second stage polymerization reaction is 6°C to 15°C, and the reaction time is 3 to 5 hours. In one embodiment of the present invention, the temperature of the second stage polymerization reaction is 6°C to 15°C, and the reaction time is 4 hours. In another embodiment of the present invention, the temperature of the second stage polymerization reaction is 6°C to 15°C, and the reaction time is 3 hours. In another embodiment of the present invention, the temperature of the second stage polymerization reaction is 10° C. to 15° C.; and the time of the second stage polymerization reaction is 4 h.

[0015] The present invention provides a bio-based itaconate rubber obtained by the preparation method described in any of the above technical solutions. The bio-based itaconate rubber obtained by the preparation method provided by the present invention has a residual itaconate content of less than 0.05% (mass content, equivalent to less than 500 ppm), an itaconate monomer conversion rate of greater than 99.8%, and incorporates styrene structural units into the molecular chain of the bio-based itaconate rubber, resulting in excellent strength and anti-slip properties.

[0016] The present invention provides a bio-based itaconate rubber product, which is prepared from an additive and a bio-based itaconate rubber obtained by the preparation method described in any of the above technical solutions. Preferably, the bio-based itaconate rubber product provided by the present invention is prepared from the following components: 90-110 parts by weight of bio-based itaconate rubber; 40-50 parts by weight of white carbon black; 1-2 parts by weight of Si69; 4-6 parts by weight of zinc oxide; 2-3 parts by weight of stearic acid; 0.5-1.5 parts by weight of paraffin wax; 3-5 parts by weight of PEG4000; 1-3 parts by weight of an antioxidant; 1-3 parts by weight of an accelerator; and 1-3 parts by weight of sulfur. More preferably, the bio-based itaconate rubber product provided by the present invention is made from the following components: 90-110 parts by weight of bio-based itaconate rubber; 40-50 parts by weight of white carbon black; 1-2 parts by weight of Si69; 4-6 parts by weight of zinc oxide; 2-3 parts by weight of stearic acid; 0.5-1.5 parts by weight of paraffin wax; 3-5 parts by weight of PEG4000; 1-3 parts by weight of antioxidant 1010; 0.5-1.5 parts by weight of accelerator ACT-70; 0.5-1.5 parts by weight of accelerator DM; and 1-3 parts by weight of sulfur. The bio-based itaconate rubber product provided by the present invention has significantly improved strength and wet-slip resistance compared to existing similar products.

[0017] The present invention also provides a preparation method for the above-mentioned bio-based itaconate rubber product, comprising the following steps: after plasticizing the bio-based itaconate rubber of the present invention, adding white carbon black and Si69 for heat treatment, and then adding zinc oxide, stearic acid, paraffin, PEG4000, antioxidant, accelerator and sulfur for mixing to obtain the bio-based itaconate rubber product; wherein the plasticizing time is 1 min~2 min; the heat treatment temperature is 140℃~160℃, the heat treatment time is 4 min~6 min; and the mixing time is 8 min~10 min.

[0018] The application provides a bio-based itaconate rubber, a preparation method thereof and a bio-based itaconate rubber product. The preparation method provided by the application reduces the content of residual itaconate monomer in the final obtained bio-based itaconate rubber to below 500 ppm by adding a small amount of styrene monomer, an emulsifier, an initiator, a chain transfer agent and a reducing agent in a two-stage polymerization reaction, effectively solving the problem of low conversion rate of itaconate monomer and resource waste caused by a large amount of residual unreacted monomer in the prior art, and the method is simple to operate and has a short reaction period. In addition, the added styrene tends to be monomer addition rather than chain transfer, which significantly reduces the crosslinking risk. In addition, due to the extremely low content of residual itaconate monomer in the bio-based itaconate rubber emulsion, the content of itaconate in the waste water and waste gas during the subsequent flocculation and washing process is basically zero, thereby reducing the treatment cost of waste water and waste gas and reducing environmental pollution. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 H-NMR spectrum of the bio-based itaconate rubber prepared in Example 1. DETAILED DESCRIPTION

[0020] The application discloses a bio-based itaconate rubber, a preparation method thereof and a bio-based itaconate rubber product. Those skilled in the art can refer to the content herein and appropriately improve the process parameters for implementation. It should be particularly pointed out that all similar replacements and changes are obvious to those skilled in the art, and they are all regarded as included in the application. The method and application of the application have been described by means of preferred embodiments, and relevant personnel can obviously make changes or appropriate changes and combinations to the method and application herein without departing from the content, spirit and scope of the application, to realize and apply the technical content of the application.

[0021] The bio-based itaconate rubber latex in the embodiments of the application is self-made in a laboratory.

[0022] The application will be further described below in combination with examples:

[0023] Example 1

[0024] In a 2L polymerization reactor, 870 g of desalted water, 12 g of sodium fatty acid / potassium disproportionate rosin acid composite emulsifier, 1.2 g of potassium chloride, 0.26 g of ferrous sulfate-ethylenediaminetetraacetic acid disodium salt, 0.20 g of sodium formaldehyde sulfoxylate, 0.09 g of sodium dithionite, 176 g of diethyl itaconate, 0.29 g of n-dodecyl mercaptan, 114 g of butadiene, and 0.23 g of p-menthane hydroperoxide were added. After reacting at 5-6°C for 6 h, the polymerization conversion rate was tested to be 83.5%. 14.5 g of styrene monomer, 0.8 g of sodium fatty acid / potassium disproportionate rosin acid composite emulsifier, 0.06 g of n-dodecyl mercaptan, 0.04 g of sodium formaldehyde sulfoxylate, and 0.04 g of p-menthane hydroperoxide were added to the reactor. The reaction was carried out at 8-10°C for 4 h. The residual diethyl itaconate in the latex was tested to be 220 ppm, terminate the polymerization reaction to obtain bio-based itaconate rubber latex. The latex is stripped with 0.5 wt% calcium chloride solution, flocculated, washed with water, and dried to obtain bio-based itaconate rubber. Figure 1 As shown, Figure 1 This is the H-NMR spectrum of the bio-based itaconate rubber prepared in Example 1.

[0025] Example 2

[0026] In a polymerization kettle, 870 g of desalted water, 10.5 g of a potassium oleate / sodium dodecylbenzene sulfonate composite emulsifier, 1.2 g of sodium phosphate, 0.3 g of EDTA-sodium iron salt, 0.20 g of sodium formaldehyde sulfoxylate, 0.1 g of sodium dithionite, 176 g of dibutyl itaconate, 0.25 g of tert-dodecyl mercaptan, 114 g of butadiene, and 0.30 g of cumene hydroperoxide were added. After reacting at 6–7°C for 5 h, the polymerization conversion was 85%. 8.7 g of styrene monomer, 1.0 g of a potassium oleate / sodium dodecylbenzene sulfonate composite emulsifier, 0.1 g of n-dodecyl mercaptan, 0.04 g of sodium formaldehyde sulfoxylate, and 0.05 g of cumene hydroperoxide were added to the reactor. The reaction was continued at 10–15°C for 3 h. The residual dibutyl itaconate in the latex was 280 ppm, and the polymerization was terminated to obtain a bio-based itaconate rubber latex. The latex was stripped with 0.5 wt% calcium chloride solution, flocculated, washed with water, and dried to obtain bio-based itaconate rubber.

[0027] Example 3

[0028] A polymerization kettle was charged with 600 g of desalted water, 10 g of a sodium stearate / potassium disproportionate rosin acid composite emulsifier, 2.0 g of sodium carbonate, 0.28 g of EDTA-sodium iron salt, 0.20 g of sodium formaldehyde sulfoxylate, 0.2 g of sodium dithionite, 174 g of diethyl itaconate, 0.3 g of n-dodecyl mercaptan, 114 g of butadiene, and 0.25 g of p-menthane hydroperoxide. After reacting at 8–10°C for 8 h, the polymerization conversion was 76%. The reactor was then supplemented with 35 g of styrene monomer, 1 g of a sodium stearate / potassium disproportionate rosin acid composite emulsifier, 0.12 g of n-dodecyl mercaptan, 0.03 g of sodium formaldehyde sulfoxylate, and 0.03 g of p-menthane hydroperoxide. The reaction was continued at 10–15°C for 5 h. The residual dimethyl itaconate in the latex was 380 ppm, and the polymerization was terminated to obtain a bio-based itaconate rubber latex. The latex was stripped with 0.5 wt% calcium chloride solution, flocculated, washed with water, and dried to obtain bio-based itaconate rubber.

[0029] Comparative Example 1

[0030] Corresponding to Example 1, the polymerization conversion rate was improved by adding chain transfer agent, conjugated diene, initiator, and emulsifier in batches, as follows:

[0031] In a polymerization kettle, 870 g of deionized water, 12 g of potassium oleate / disproportionated rosin acid potassium soap composite emulsifier, 1.2 g of sodium phosphate, 0.3 g of EDTA-sodium iron salt, 0.20 g of sodium formaldehyde sulfoxylate, 0.1 g of sodium dithionite, 176 g of diethyl itaconate, 0.25 g of tert-dodecyl mercaptan, 114 g of butadiene, and 0.20 g of p-menthane hydroperoxide were added. The reaction was carried out at 6 ° C and 0.5 MPa pressure for 4 h. When the polymerization conversion rate was 65.3%, 0.06 g of n-dodecyl mercaptan was added; when the polymerization conversion rate was 70.3%, 0.6 g of potassium oleate and 8 g of butadiene were added; when the polymerization conversion rate was 78.6%, 0.35 g of potassium oleate and 6 g of butadiene were added; when the polymerization conversion rate was 92.5%, 0.35 g of potassium oleate and 6 g of butadiene were added. g; the DEI content was tested to be 820 ppm, and the polymerization reaction was terminated to obtain a bio-based rubber latex. The latex was stripped with a 0.5 wt% calcium chloride solution, flocculated, washed with water, and dried to obtain a bio-based itaconate rubber.

[0032] Comparative Example 2

[0033] Corresponding to Example 2, the polymerization conversion rate was improved by adding chain transfer agent, conjugated diene, initiator, and emulsifier in batches, as follows:

[0034] In a polymerization kettle, 870 g of desalted water, 12 g of potassium oleate / sodium dodecylbenzenesulfonate composite emulsifier, 1.2 g of sodium phosphate, 0.3 g of EDTA-sodium iron salt, 0.20 g of sodium formaldehyde sulfoxylate, 0.1 g of sodium dithionite, 176 g of dibutyl itaconate, 0.25 g of tert-dodecyl mercaptan, 114 g of butadiene, and 0.25 g of p-menthane hydroperoxide were added. The reaction was carried out at 6 ° C and 0.5 MPa pressure for 4 h. When the polymerization conversion rate was 68.83%, 0.06 g of n-dodecyl mercaptan was added; when the polymerization conversion rate was 75.2%, 0.6 g of potassium oleate and 8 g of butadiene were added; when the polymerization conversion rate was 80.5%, 0.35 g of potassium oleate and 6 g of butadiene were added; when the polymerization conversion rate was 90.5%, 0.35 g of potassium oleate and 6 g of butadiene were added; the DEI content was 820 The polymerization reaction was terminated at 0.5 wt% ppm to obtain a bio-based rubber latex. The latex was stripped with 0.5 wt% calcium chloride solution, flocculated, washed with water, and dried to obtain a bio-based itaconate rubber.

[0035] The test samples were prepared according to the formula shown in Table 1 (calculated in parts by weight):

[0036] Table 1

[0037]

[0038] The raw rubber was mixed in an internal mixer for 1 minute. Silica and Si69 were added in batches and heat-treated at 150°C for 5 minutes. After cooling to room temperature, zinc oxide, stearic acid, and paraffin were added and mixed for 2 minutes. PEG4000 and an antioxidant were added and mixed for 2 minutes. Finally, an accelerator and sulfur were added and mixed for 5 minutes to obtain the final rubber mix. Test samples were prepared by hot-press vulcanization at 150°C in a flat-plate vulcanizer. The tensile strength, DIN abrasion resistance, and dynamic mechanical properties of the samples were measured. The test results are listed in Table 2.

[0039] Table 2

[0040]

[0041] As can be seen from Table 2, the bio-based itaconate rubber prepared in the present invention not only has a high conversion rate, but also has excellent strength, wear resistance and anti-slip properties.

[0042] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing bio-based itaconate rubber, characterized in that: The following steps are involved: S1) conducting a first stage polymerization reaction of itaconate, conjugated diene, desalted water, an emulsifier, an electrolyte, an activator, a reducing agent, an oxygen scavenger and a chain transfer agent in the presence of an initiator; S2) subjecting styrene, an emulsifier, a chain transfer agent, a reducing agent and the product obtained in step S1) to a second stage polymerization reaction under the action of an initiator, adding a terminator after the reaction is completed, and subjecting the obtained latex to steam stripping, flocculation, water washing and drying to obtain bio-based itaconate rubber.

2. The preparation method according to claim 1, characterized in that Based on 100 parts by total weight of itaconate and conjugated diene, the raw materials for preparing the bio-based itaconate rubber include: 10-90 parts of itaconate, 10-90 parts of conjugated diene, 200-400 parts of desalted water, 2-6 parts of emulsifier, 0.2-1 part of electrolyte, 0.1-0.3 part of activator, 0.04-0.15 part of reducing agent, 0.01-0.1 part of deoxidizer, 0.1-0.4 part of chain transfer agent, 0.05-0.2 part of initiator, 2-10 parts of styrene and 0.05-1 part of terminator.

3. The preparation method according to claim 1, characterized in that In step S2), the amount of the emulsifier used accounts for 3 wt% to 10 wt% of the total amount of the emulsifier used in steps S1) and S2); The amount of the chain transfer agent used accounts for 10 wt% to 30 wt% of the total amount of the chain transfer agent used in step S1) and step S2); The amount of the reducing agent used accounts for 5 wt% to 20 wt% of the total amount of the reducing agent used in step S1) and step S2); The amount of the initiator used accounts for 5 wt% to 20 wt% of the total amount of the initiator used in step S1) and step S2).

4. The preparation method according to claim 1, characterized in that In step S1), the temperature of the first stage polymerization reaction is 4° C. to 10° C., and the time of the first stage polymerization reaction is 6 h to 10 h.

5. The preparation method according to claim 1, characterized in that In step S2), the temperature of the second stage polymerization reaction is 6° C. to 15° C., and the time of the second stage polymerization reaction is 2 h to 5 h.

6. The preparation method according to claim 1, characterized in that The itaconate ester is selected from at least one of dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dihexyl itaconate, diheptyl itaconate, dioctyl itaconate, dinonyl itaconate and didecyl itaconate; The conjugated diene is selected from at least one of butadiene, isoprene and myrcene; The emulsifier is at least one selected from oleate, linoleate, disproportionated rosin salt, alkyl sulfonate, alkyl sulfate, laurate and fatty acid salt; The electrolyte is selected from at least one of sodium carbonate, potassium chloride, sodium hydrogen phosphate, potassium phosphate, sodium phosphate and sodium acetate; The activator is selected from at least one of ethylenediaminetetraacetic acid sodium iron salt and ferrous sulfate-ethylenediaminetetraacetic acid sodium salt; The reducing agent is sodium formaldehyde sulfoxylate; The deoxidizer is sodium dithionite; The chain transfer agent is selected from at least one of alkyl mercaptan and polythiol mercaptan compounds; The initiator is selected from at least one of p-menthane hydroperoxide, tert-butyl hydroperoxide and cumene hydroperoxide; The terminator is one or more of sodium polysulfide, hydroxylamine compounds and sodium dimethyldithiocarbamate.

7. The preparation method according to claim 1, characterized in that Step S1) is specifically as follows: Pre-emulsifying itaconate, conjugated diene, desalted water, emulsifier, electrolyte, activator, reducing agent, scavenger and chain transfer agent, and subjecting the pre-emulsified materials to a first stage polymerization reaction in the presence of an initiator; The pre-emulsification temperature is 4° C. to 10° C., and the pre-emulsification time is 1 h to 4 h.

8. Bio-based itaconate rubber obtained by the preparation method according to any one of claims 1 to 7.

9. Bio-based itaconate rubber product, characterized in that: The invention is prepared from additives and bio-based itaconate rubber obtained by the preparation method according to any one of claims 1 to 7.

10. The bio-based itaconate rubber product according to claim 9, characterized in that: Made from the following components: 90-110 parts by weight of bio-based itaconic acid rubber; 40-50 parts by weight of white carbon black; 1-2 parts by weight of Si69; 4-6 parts by weight of zinc oxide; 1-3 parts by weight of stearic acid; 0.5-1.5 parts by weight of paraffin wax; 3-5 parts by weight of PEG4000; 1-3 parts by weight of antioxidant 1010; 1-3 parts by weight of accelerator; and 1-3 parts by weight of sulfur.

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