Myrene / conjugated diene copolymer type bio-based low-temperature-resistant rubber as well as preparation method and application thereof

Abstract

The invention discloses myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber and a preparation method and application thereof, and belongs to the technical field of chemical synthetic rubbers, raw materials comprise a myrcene monomer and a conjugated diene monomer, and the myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber is prepared by adopting a low-temperature redox emulsion polymerization method. According to the myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber as well as the preparation method and the application thereof, a low-temperature oxidation-reduction emulsion polymerization method is low in production cost, simple in process, environmentally friendly and suitable for industrial production; the prepared myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber has better low-temperature resistance, and has huge application potential in the field of winter tire tread rubber.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of chemical synthetic rubber, in particular to a myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber and a preparation method and application thereof. BACKGROUND

[0002] Due to the influence of various restriction factors such as geographical location, climate condition and pest and disease, the growth and rubber yield of natural rubber are affected, so that the self-production of natural rubber in China is seriously insufficient and the dependence on import is high. The rapid development of synthetic rubber solves the problem of insufficient self-production of natural rubber, but the existing synthetic rubber takes fossil resources such as petroleum as raw materials. Today, energy, resources and environment are all under severe challenge, and the modern synthetic rubber industry which consumes a large amount of non-renewable energy and resources at the cost is facing severe challenges. Therefore, the development of bio-based synthetic elastomer, especially the development of engineering application, is very important and urgent. In recent years, various types of bio-based synthetic elastomers have been developed, including bio-based isoprene rubber, bio-based ethylene-propylene rubber and bio-based polyester elastomer. The preparation process of the bio-based polyester rubber is to first convert biomass into traditional monomers, and then polymerize by using traditional means, which is high in cost, and the bio-based polyester rubber obtained by condensation polymerization still has relatively low molecular weight.

[0003] At present, various polymerization methods have been used to prepare bio-based elastomers. Although the development of these polymerization methods is meaningful in terms of sustainability, there is still a lack of green environmental protection and low energy consumption. SUMMARY

[0004] The purpose of the application is to provide a myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber and a preparation method and application thereof. The low-temperature redox emulsion polymerization method is low in production cost, simple in process and environmentally friendly, and is suitable for industrialized production. The prepared myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber has good low-temperature resistance and has great application potential in the field of winter tire tread rubber.

[0005] To achieve the above purpose, the application provides a preparation method of a myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber, which is prepared by using a low-temperature redox emulsion polymerization method and comprises the following steps: S1, mixing a water-soluble component and an oil-soluble component, and then adding a conjugated diene monomer for pre-emulsification; S2, after the pre-emulsification is completed, an initiator is added for polymerization reaction to obtain a myrcene / conjugated diene copolymer latex; S3, after the polymerization reaction is completed, a flocculating agent is added for demulsification, drying is performed, and a myrcene / conjugated diene copolymer type bio-based low-temperature-resistant rubber is obtained.

[0006] Preferably, in S1, the water-soluble component includes deionized water, emulsifier, electrolyte, activator, and sodium hydrosulfite; the oil-soluble component includes myrcene monomer and chain transfer agent; and the conjugated diene monomer includes butadiene or isoprene. In S2, the initiator includes at least one of p-menthol peroxide, azobisisobutyronitrile, tert-butyl hydroperoxide, and cumene hydroperoxide. In S3, the flocculant includes at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyandiamine formaldehyde condensate, epoxide amine compounds, and dilute sulfuric acid.

[0007] Furthermore, the mass ratio of myrcene monomer to conjugated diene monomer is 1:0.1-9, the mass ratio of the total mass of myrcene monomer to conjugated diene monomer to deionized water, emulsifier, electrolyte, activator and sodium hydrosulfite is 100:100-300:0.5-15:0.1-3:0.01-0.5:0.01-0.05, and the mass ratio of the total mass of myrcene monomer to conjugated diene monomer to chain transfer agent is 100:0.01-0.4.

[0008] Furthermore, the emulsifier includes at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, potassium disproportionate, sodium fatty acid, and alkylphenol polyoxyethylene ether; the electrolyte includes at least one of potassium phosphate, potassium chloride, and sodium bicarbonate; the activator includes at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, sodium ferric ethylenediaminetetraacetate, and tetrasodium ethylenediaminetetraacetate; the sodium dithionite includes sodium dithionite; and the chain transfer agent includes at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, carbon tetrabromide, and isooctyl 3-mercaptopropionate.

[0009] Preferably, in S1, the mass ratio of water-soluble component to oil-soluble component is 835:0.01-400, the pre-emulsification time is 1-5 hours, and the pre-emulsification temperature is 0-30℃.

[0010] Preferably, in S2, the total mass ratio of myrcene monomer and conjugated diene monomer to initiator is 100:0.01-5, the polymerization reaction time is 3-20 h, and the polymerization reaction temperature is 0-30 °C.

[0011] Preferably, the mass of the flocculant in S3 is 20-60 wt% of the mass of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber.

[0012] Preferably, the structural formula of the myrcene / butadiene copolymer type bio-based low-temperature resistant rubber is: , Where m = 1~99%, n = 1~99%, x = 1~50%, y = 1~80%, z = 1~40%.

[0013] The present invention also provides a myrcene / conjugated diene copolymer type vulcanizate, which is prepared by mixing the myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber prepared by the above-mentioned preparation method with rubber additives and then molding and vulcanizing it.

[0014] Preferably, the rubber additives include at least one of rubber vulcanization aids, rubber protective aids, rubber adhesive aids, process operation aids, and reinforcing filler aids, and the mass ratio of myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber to rubber additives is 100:10-120, and the compression molding vulcanization temperature is 120-180℃.

[0015] Furthermore, the rubber vulcanizing aids include zinc oxide, stearic acid, accelerator CZ, accelerator NS and sulfur, the rubber protective aids include antioxidant 4020 and antioxidant RD, the reinforcing and filling aids include at least two of silica, carbon black and silane coupling agent Si69, and the mass ratio of myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber to rubber aids is 100:30-80.

[0016] The present invention also provides an application of a myrcene / conjugated diene copolymer type vulcanizate, wherein the above-mentioned myrcene / conjugated diene copolymer type vulcanizate is applied to a winter tire tread compound.

[0017] Therefore, the present invention employs the above-mentioned myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber, its preparation method, and its application, which have the following beneficial effects: (1) This invention employs a low-temperature redox emulsion polymerization method. The core principle of this method is that the polymerization reaction occurs within a large number of latex particles suspended in the aqueous phase, essentially belonging to a dispersed small-scale bulk polymerization system. This characteristic gives it two significant advantages: firstly, a faster polymerization rate, and secondly, the ability to efficiently synthesize high molecular weight polymers. From the perspective of the free radical reaction mechanism, the lifetime of free radicals under normal conditions is usually only 0.1s; however, in the emulsion polymerization system, due to the isolation and embedding effect of latex particles on free radicals, their lifetime can be extended to 10-100s, providing sufficient time for polymer chain growth, which is one of the key factors for achieving high molecular weight synthesis. In addition, to address the problem of strong steric hindrance effect of myrcene monomers during free radical polymerization, this invention further improves the molecular weight of the polymer by introducing conjugated dienes with weaker steric hindrance effect into the polymerization system for copolymerization modification. At the same time, the conjugated diene segments themselves have better flexibility, and this structural characteristic can also effectively reduce the glass transition temperature of myrcene polymers, taking into account both the requirements of increasing molecular weight and material flexibility.

[0018] (2) The low-temperature redox emulsion polymerization method used in this invention uses water as a medium to replace the toxic organic solvent required for coordination polymerization, and uses a low-toxicity redox initiator to react at low temperature, which is energy-efficient, safer, and simple in process, suitable for industrial production.

[0019] (3) The myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber prepared by the present invention has a molecular weight between 100,000 and 300,000 and a molecular weight distribution between 2.5 and 4.6. It has excellent mechanical properties, low temperature resistance and good processing performance, and is suitable for industrial applications.

[0020] (4) The myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber of the present invention is mixed with rubber additives and molded and vulcanized to obtain myrcene / conjugated diene copolymer type vulcanizate with excellent mechanical properties, wide and adjustable glass transition temperature range, which can meet engineering applications; compared with traditional tread rubber materials, it is not easy to crystallize at low temperature, and has great application potential in the field of winter tire tread rubber.

[0021] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0022] Figure 1 This refers to the raw rubber state of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber prepared in Examples 1-9 of this invention; Figure 2 This is the 1H NMR spectrum of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber prepared in Example 6 of this invention; Figure 3 It is the glass transition temperature of the myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber prepared in Examples 1-9 of this invention; Figure 4 The loss factor-temperature curves of the myrcene / conjugated diene copolymer type vulcanizates prepared in Examples 1-9 of this invention are shown. Detailed Implementation

[0023] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0024] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0025] In this invention, unless otherwise specified, the test materials and instruments are all conventional test materials in the field and can be purchased through commercial channels.

[0026] Example 1 This invention provides a method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber, comprising the following steps: S1. Add 800g deionized water, 30g sodium dodecyl sulfate, 4g potassium chloride, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 0.1g sodium dithionite, 0.6g tert-dodecyl mercaptan, and 40g myrcene to the reactor. Seal the reactor and replace it with a nitrogen atmosphere (nitrogen is evacuated 3 times to remove oxygen). Add 360g butadiene and pre-emulsify at 20℃ for 1 hour. S2. After pre-emulsification, 0.6g of hydrogen peroxide was added to initiate the polymerization reaction of montanane. The reaction was carried out at 20°C for 5 hours to obtain myrcene / conjugated diene copolymer latex. S3. Remove the remaining butadiene under reduced pressure, add 500g of ethanol for demulsification, and dry under vacuum in an oven to constant weight to obtain myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber, denoted as PMyBd10.

[0027] Calculations showed a conversion rate of 95%, and the number-average molecular weight M of PMyBd10 was [missing value]. n =8.6×10 4 The molecular weight distribution is M w / M n =2.41.

[0028] Example 2 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 80g, and the mass of butadiene added is 320g; In S3, the product obtained is denoted as PMyBd20.

[0029] The conversion rate was calculated to be 94%, M n =12.4×10 4 M w / M n =1.43.

[0030] Example 3 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 120g, and the mass of butadiene added is 280g; In S3, the product obtained is denoted as PMyBd30.

[0031] The conversion rate is calculated to be 90%, M n =14.7×10 4 M w / M n =3.99.

[0032] Example 4 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 160g, and the mass of butadiene added is 240g; In S3, the product obtained is denoted as PMyBd40.

[0033] The conversion rate was calculated to be 87%, M n =11.4×10 4 M w / M n =3.15.

[0034] Example 5 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 200g, and the mass of butadiene added is 200g; In S3, the product obtained is denoted as PMyBd50.

[0035] The conversion rate is calculated to be 90%, M n =13.2×10 4 M w / M n =4.40.

[0036] Example 6 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 240g, and the mass of butadiene added is 160g; In S3, the product obtained is denoted as PMyBd60.

[0037] The conversion rate is calculated to be 90%, M n =14.5×10 4 M w / M n =3.91.

[0038] Example 7 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 280g, and the mass of butadiene added is 120g; In S3, the product obtained is denoted as PMyBd70.

[0039] The conversion rate was calculated to be 86%, M n =16.5×10 4 M w / M n =4.60.

[0040] Example 8 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 320g, and the mass of butadiene added is 80g; In S3, the product obtained is denoted as PMyBd80.

[0041] The conversion rate was calculated to be 79%, M n =12.4×10 4 M w / M n =4.60.

[0042] Example 9 This embodiment operates the same as Embodiment 1, except that: In S1, the mass of myrcene added is 360g, and the mass of butadiene added is 40g; In S3, the product obtained is denoted as PMyBd90.

[0043] The conversion rate was calculated to be 77%, M n =17.4×10 4 M w / M n =4.88.

[0044] Application Example 1 This invention also provides a myrcene / conjugated diene copolymer type vulcanizate, which is prepared by mixing the myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber prepared above with additives and silane coupling agents, and then molding and vulcanizing it. Specifically, it includes the following steps: Take 100.0g of PMyBd10 prepared in Example 1, and mix it evenly with 5.0g of zinc oxide, 2.0g of stearic acid, 1.0g of antioxidant 4020, 1.0g of antioxidant RD, 1.0g of accelerator CZ, 1.2g of accelerator NS, 1.5g of sulfur, 60.0g of silica VN3, and 6.0g of Si69 on a two-roll mill to obtain a compound. The compound is then molded and vulcanized at 150°C to obtain a myrcene / conjugated diene copolymer vulcanizate, denoted as PMyBd10 / silica.

[0045] Application Example 2 This application example is operated in the same way as application example 1, except that 100g of PMyBd20 prepared in example 2 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd20 / silica.

[0046] Application Example 3 This application example is operated in the same way as application example 1, except that 100g of PMyBd30 prepared in example 3 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd30 / silica.

[0047] Application Example 4 This application example is operated in the same way as application example 1, except that 100g of PMyBd40 prepared in example 4 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd40 / silica.

[0048] Application Example 5 This application example is operated in the same way as application example 1, except that 100g of PMyBd50 prepared in example 5 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd50 / silica.

[0049] Application Example 6 This application example is operated in the same way as application example 1, except that 100g of PMyBd60 prepared in example 6 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd60 / silica.

[0050] Application Example 7 This application example is operated in the same way as application example 1, except that 100g of PMyBd70 prepared in example 7 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd70 / silica.

[0051] Application Example 8 This application example is operated in the same way as application example 1, except that 100g of PMyBd80 prepared in example 8 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd80 / silica.

[0052] Application Example 9 This application example is operated in the same way as application example 1, except that 100g of PMyBd90 prepared in example 9 is added to obtain a myrcene / conjugated diene copolymer type vulcanizate, which is denoted as PMyBd90 / silica.

[0053] Comparative Example 1 The operation of this comparative example is the same as that of application example 1, except that 100.0g of solution-polymerized styrene-butadiene rubber is added to obtain solution-polymerized styrene-butadiene vulcanizate.

[0054] The raw rubber state of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber prepared in Examples 1-9 is as follows: Figure 1 As shown, from Figure 1As can be seen, with the increase of myrcene content, the raw rubber state of the obtained myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber gradually changes from milky white rubber particles to translucent rubber blocks.

[0055] The microstructure of PMyBd60 prepared in Example 6 was characterized by proton nuclear magnetic resonance spectroscopy at a frequency of 600 MHz using CDCl3 as the solvent. The results are as follows. Figure 2 As shown, from Figure 2 As can be seen, the chemical hydrogen shifts at 5.34 and 5.41 ppm belong to the cis-1,4 and trans-1,4 configurations of the butadiene unit, respectively. The chemical hydrogen shift at 4.94 ppm corresponds to the 1,2- configuration of the butadiene unit. The chemical shift at 5.09 ppm is the proton on the carbon-carbon double bond of myrcene, whose structural unit is mainly the 1,4- configuration.

[0056] The low-temperature resistance of rubber mainly depends on its glass transition temperature (T). g Whether the rubber crystallizes at low temperatures is determined by testing the rubber's Tg. g Its low-temperature performance can be determined. The thermal properties of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubbers prepared in Examples 1-9 were characterized using differential scanning calorimetry, and the results are as follows: Figure 3 As shown, from Figure 3 As can be seen from this, the T of the myrcene / conjugated diene copolymer type of bio-based low-temperature resistant rubber is... g All temperatures were below -67°C, and no crystallization peaks were observed between -90°C and 40°C, further indicating that the prepared myrcene / conjugated diene copolymer bio-based low-temperature resistant rubbers were amorphous. This is mainly because the bio-based monomer myrcene can lower the glass transition temperature of the polymer and inhibit polymer crystallization, while the steric hindrance effect of butadiene helps to increase the molecular weight of the copolymer, and its compliant segments can further lower the glass transition temperature of the myrcene polymer. Therefore, the amorphous structure and low Tg of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber are characteristic of this process. g This gives it the potential to be used in low-temperature environments and makes it a promising candidate for application in the field of low-temperature resistant elastomers.

[0057] The loss factor (tanδ) of the myrcene / conjugated diene copolymer vulcanizates prepared in Examples 1-9 was tested using dynamic viscoelastic spectrometry as a function of temperature. The test conditions were: 10 Hz, 0.3% strain, and heating from -100℃ to 100℃ at a rate of 3°C / min. The results are as follows: Figure 4 As shown, from Figure 4 As can be seen from this, the T of the myrcene / conjugated diene copolymer type vulcanizate is... gThe temperature rises from -64℃ to -46℃ with increasing myrcene content. In the tire industry, it is generally believed that a higher tanδ value at 0℃ indicates better wet skid resistance, while a lower tanδ value at 60℃ indicates lower rolling resistance. With increasing myrcene content, the tanδ value of the myrcene / conjugated diene copolymer vulcanizate at 60℃ shows an upward trend, indicating that the rolling resistance of the myrcene / conjugated diene copolymer vulcanizate gradually worsens, but remains less than 0.1, demonstrating good low rolling resistance characteristics. The tanδ value at 0℃ also increases, indicating improved wet skid resistance of the myrcene / conjugated diene copolymer vulcanizate.

[0058] The mechanical and dynamic mechanical properties of the myrcene / conjugated diene copolymer vulcanizates prepared according to examples 1-9 were analyzed. Tensile tests were conducted according to ASTM D412 standard (dumbbell-shaped specimens), and the relationship between the loss factor (tanδ) and strain was tested using a rubber processing analyzer (RPA). The results are shown in Table 1.

[0059] Table 1 Performance test results of samples from Application Examples 1-9 and Comparative Example 1

[0060] As shown in Table 1, the mechanical and dynamic mechanical properties of the myrcene / conjugated diene copolymer-type bio-based low-temperature resistant rubber of the present invention, obtained by compounding and molding with rubber additives, can be controlled by the monomer feed ratio. In this application, the properties of the myrcene / conjugated diene copolymer-type vulcanizate and solution-polymerized styrene-butadiene vulcanizate were systematically studied. The mechanical properties of the myrcene / conjugated diene copolymer-type vulcanizate prepared in Application Example 6 are generally better than those of the solution-polymerized styrene-butadiene vulcanizate, and their glass transition temperatures are all lower than those of the solution-polymerized styrene-butadiene vulcanizate. The dynamic viscoelasticity shows a regular change with the change of the myrcene feed ratio. The preferred myrcene monomer feed ratio is 40-80%. Combined with its mechanical properties, it was found that both can meet the requirements of engineering applications. Application Example 9 has the best anti-icing performance, and its tanδ value at -20℃ is higher than that of the solution-polymerized styrene-butadiene vulcanizate. This shows that the myrcene / conjugated diene copolymer-type vulcanizate has the application potential of green tread rubber. The vulcanized rubber products of the present invention have mechanical properties that meet engineering applications, excellent dynamic viscoelasticity, and good low-temperature resistance, and have great application potential in the field of winter tire tread rubber.

[0061] Therefore, this invention employs the above-mentioned myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber, its preparation method, and its application. The low-temperature oxidation-reduction emulsion polymerization method has low production cost, simple process, and environmentally friendly characteristics, making it suitable for industrial production. The prepared myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber has good low-temperature resistance and has great application potential in the field of winter tire tread rubber.

[0062] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber, characterized in that: Myrcene / conjugated diene copolymer-type bio-based low-temperature resistant rubber is prepared by low-temperature redox emulsion polymerization, including the following steps: S1. Mix the water-soluble and oil-soluble components, and then add the conjugated diene monomer for pre-emulsification; S2. After pre-emulsification, an initiator is added to carry out a polymerization reaction to obtain myrcene / conjugated diene copolymer latex. S3. After the polymerization reaction is completed, a flocculant is added for demulsification and drying to obtain myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber.

2. The method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber according to claim 1, characterized in that: In S1, the water-soluble components include deionized water, emulsifier, electrolyte, activator, and sodium hydrosulfite; the oil-soluble components include myrcene monomer and chain transfer agent; and the conjugated diene monomer includes butadiene or isoprene. In S2, the initiator includes at least one of p-menthol peroxide, azobisisobutyronitrile, tert-butyl hydroperoxide, and cumene hydroperoxide. In S3, the flocculant includes at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyandiamine formaldehyde condensate, epoxide amine compounds, and dilute sulfuric acid.

3. The method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber according to claim 1, characterized in that: In S1, the mass ratio of water-soluble components to oil-soluble components is 835:0.01-400, the pre-emulsification time is 1-5 hours, and the pre-emulsification temperature is 0-30℃.

4. The method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber according to claim 2, characterized in that: The mass ratio of myrcene monomer to conjugated diene monomer is 1:0.1-9; the mass ratio of the total mass of myrcene monomer to conjugated diene monomer to deionized water, emulsifier, electrolyte, activator and sodium hydrosulfite is 100:100-300:0.5-15:0.1-3:0.01-0.5:0.01-0.05; and the mass ratio of the total mass of myrcene monomer to conjugated diene monomer to chain transfer agent is 100:0.01-0.

4.

5. The method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber according to claim 2, characterized in that: The emulsifier includes at least one of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, potassium disproportionate, sodium fatty acid, and alkylphenol polyoxyethylene ether; the electrolyte includes at least one of potassium phosphate, potassium chloride, and sodium bicarbonate; the activator includes at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, sodium ferric ethylenediaminetetraacetate, and tetrasodium ethylenediaminetetraacetate; the sodium dithionite includes sodium dithionite; and the chain transfer agent includes at least one of n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, carbon tetrabromide, and isooctyl 3-mercaptopropionate.

6. The method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber according to claim 1, characterized in that: In S2, the total mass ratio of myrcene monomer and conjugated diene monomer to initiator is 100:0.01-5, the polymerization time is 3-20 h, and the polymerization temperature is 0-30℃.

7. The method for preparing a myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber according to claim 1, characterized in that: The mass of the flocculant in S3 is 20-60 wt% of the mass of the myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber.

8. A myrcene / conjugated diene copolymer type vulcanizate, characterized in that: The myrcene / conjugated diene copolymer bio-based low-temperature resistant rubber prepared by the method described in any one of claims 1-7 is mixed with rubber additives and then molded and vulcanized.

9. The myrcene / conjugated diene copolymer type vulcanizate according to claim 8, characterized in that: Rubber additives include at least one of rubber vulcanization additives, rubber protective additives, rubber adhesive additives, process operation additives, and reinforcing filler additives. The mass ratio of myrcene / conjugated diene copolymer type bio-based low-temperature resistant rubber to rubber additives is 100:10-120, and the compression molding vulcanization temperature is 120-180℃.

10. An application of a myrcene / conjugated diene copolymer type vulcanizate, characterized in that: The myrcene / conjugated diene copolymer type vulcanizate according to claim 8 is used in winter tire tread compound.

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