An integrated functionalized itaconate / butadiene / isoprene bio-based rubber and vulcanizates thereof and methods of making

Abstract

The application discloses an integrated functionalized itaconate / butadiene / isoprene bio-based rubber and a vulcanized rubber and a preparation method thereof, relates to the technical field of rubber synthesis, and the number average molecular weight of the bio-based rubber is 50-100 million, preferably 100-800 million; the molecular weight distribution is 1.5-10.0, preferably 2.0-5.0. The application prepares high-performance bio-based rubber by copolymerization of itaconate monomers, butadiene monomers, isoprene monomers and functionalized monomers, significantly improves the wet skid resistance of the material while not losing the rolling resistance, provides an effective idea for the preparation of green tires, and exhibits excellent comprehensive performance in tire application. Through reasonable structure design, the integrated functionalized itaconate / butadiene / isoprene bio-based rubber can be comparable to functionalized solution styrene-butadiene rubber (SSBR) in comprehensive performance, and such bio-based integrated rubber has not been reported before.

Description

Technical Field

[0001] This invention relates to the field of rubber synthesis technology, and more specifically, to an integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber, its vulcanizate, and its preparation method. Background Technology

[0002] The applicant disclosed high molecular weight isoprene-based itaconic acid ester rubber in "A method for preparing itaconic acid ester / isoprene copolymer type bioengineering rubber raw rubber by low temperature emulsion polymerization" (CN102558437A); and disclosed butadiene-based itaconic acid ester rubber with better comprehensive performance in "An itaconic acid ester / butadiene copolymer type bio-based engineering rubber and its preparation method" (CN104945817A).

[0003] With the implementation of the dual-carbon strategy, the importance of developing bio-based rubber is self-evident. However, the bio-based production of rubber raw materials is only the beginning; the final material performance is also indispensable. Dynamic mechanical analysis (DMA) is a key test in the tire industry for evaluating the dynamic performance of materials. It can obtain the relationship between the material's loss factor (tanδ) and the test temperature. For rubber composites used in treads, a larger tanδ value at 0℃ indicates better wet skid resistance and better driving and braking safety in tires made from this material; a smaller tanδ value at 60℃ indicates lower rolling resistance and better fuel economy in tires made from this material. However, balancing these two factors simultaneously has long been a challenge for the tire industry. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides an integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber, its vulcanizate, and a preparation method thereof. This invention prepares a high-performance bio-based rubber through copolymerization of itaconic acid ester monomers, butadiene monomers, isoprene monomers, and functionalized monomers. This significantly improves the material's wet skid resistance without sacrificing rolling resistance, providing an effective approach for the preparation of green tires and demonstrating excellent overall performance in tire applications.

[0005] One objective of this invention is to provide an integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber, wherein the bio-based rubber has the following structural formula:

[0006]

[0007] R1 and R2 are hydrogen atoms or C atoms. 1～20 The alkyl group, where X1 is a hydrogen atom or a methyl group, and X2 is a functional group containing at least one of an epoxy group, a carboxyl group, a hydroxyl group, and an amide group, where a+b = 1~95%, n = 1~99%, x+y+z = 1~95%, and p = 1~30%, wherein R1 and R2 can be the same or different;

[0008] Preferably, R1 is hydrogen or C. 1-10 Alkyl group; R2 is hydrogen or C 1-10 Alkyl groups, a+b = 5–90%, n = 10–90%, x+y+z = 5–90%, p = 1–20%.

[0009] In a preferred embodiment of the above technical solution, the integrated epoxidized itaconic acid ester / butadiene / isoprene bio-based rubber has the following structure:

[0010]

[0011] In the bio-based rubber, the structural units derived from itaconic acid esters account for 1-99% by mass in the copolymer, preferably 10-90%.

[0012] Preferably, the number-average molecular weight (Mn) of the bio-based rubber is 50,000 to 1,000,000, more preferably 100,000 to 800,000; and the molecular weight distribution (Mw / Mn) is 1.5 to 10.0, more preferably 2.0 to 5.0.

[0013] Preferably, the bio-based rubber is obtained by copolymerizing raw materials comprising the following components:

[0014] Each component, by weight:

[0015] Based on a total mass of itaconic acid ester monomer, butadiene, isoprene, and functionalized monomers, in 100 parts by weight:

[0016] The mass ratio of itaconic acid ester monomer, butadiene, isoprene, and functionalized monomer is (0.5-90):(0.25-90):(0.25-90):1;

[0017] 100-400 parts by weight of deionized water;

[0018] Emulsifier 0.05-20 parts by weight;

[0019] Electrolyte 0.05-3 parts by weight;

[0020] Activator: 0.01-0.2 parts by weight;

[0021] Chain transfer agent 0.01-0.4 parts by weight;

[0022] Initiator 0.01-5 parts by weight;

[0023] The amount of flocculant used is 20-60 wt% of the total mass of the copolymer latex after emulsion polymerization.

[0024] Preferably, the components are expressed in parts by weight as follows:

[0025] Based on a total mass of itaconic acid ester monomer, butadiene, isoprene, and functionalized monomers, in 100 parts by weight:

[0026] The mass ratio of itaconic acid ester monomer, butadiene, isoprene and functionalized monomer is (1-80):(0.5-80):(0.5-80):1;

[0027] 150-300 parts by weight of deionized water;

[0028] Emulsifier 2-15 parts by weight;

[0029] Electrolyte 0.1-2.0 parts by weight;

[0030] Activator: 0.02-0.1 parts by weight;

[0031] Chain transfer agent 0.03-0.25 parts by weight;

[0032] Initiator 0.02-2 parts by weight;

[0033] The amount of flocculant used is 30-50 wt% of the total mass of the copolymer latex after emulsion polymerization.

[0034] Preferably, the itaconic acid ester monomer is at least one selected from the following: dimethyl itaconic acid, monomethyl itaconic acid, diethyl itaconic acid, monoethyl itaconic acid, dipropyl itaconic acid, monopropyl itaconic acid, dibutyl itaconic acid, monobutyl itaconic acid, dipentyl itaconic acid, monopentyl itaconic acid, dihexyl itaconic acid, diheptyl itaconic acid, monoheptyl itaconic acid, dioctyl itaconic acid, dinonyl itaconic acid, monononyl itaconic acid, didecyl itaconic acid, and monodecyl itaconic acid; and / or,

[0035] The functionalized monomer is at least one selected from glycidyl methacrylate, allyl glycidyl ether, limonene oxide, vinylsiloxane, methacrylic acid, hydroxyethyl methacrylate, and acrylamide. The functionalized monomer is a monomer with reactive functional groups. This monomer unit is intended to further enhance the interfacial interaction of the filler, improve filler dispersion, and thus optimize the dynamic mechanical properties of the material; and / or,

[0036] The emulsifier can be a commonly used emulsifier in the rubber industry, preferably at least one of sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfonate (SDS), potassium disproportionated rosinate, sodium fatty acid, and alkylphenol polyoxyethylene ether (OP-10), preferably a mixture of potassium disproportionated rosinate and sodium fatty acid; and / or,

[0037] The electrolyte can be a commonly used electrolyte in the rubber industry, preferably at least one of potassium phosphate, potassium chloride, and sodium bicarbonate, with potassium chloride being the most preferred; and / or,

[0038] The activator can be a commonly used activator in the rubber industry, preferably at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, ferric sodium ethylenediaminetetraacetate, and tetrasodium ethylenediaminetetraacetate, and more preferably at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, and tetrasodium ethylenediaminetetraacetate; and / or,

[0039] The chain transfer agent is at least one selected from n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, carbon tetrabromide, and isooctyl 3-mercaptopropionate. By adding a special chain transfer agent with a large chain transfer constant, the molecular weight of the rubber product can be adjusted. The chain transfer agent becomes a free radical through a chain transfer reaction, which can initiate the reaction and act as an active center. Ultimately, it can be bound to the polymer and consumed. A small amount can effectively interfere with excessive growth and branching of macromolecular chains, reducing gelation; and / or,

[0040] The initiator can be a commonly used initiator in the rubber industry, preferably at least one of p-menthol peroxide, azobisisobutyronitrile, tert-butyl hydroperoxide, and cumene hydroperoxide, more preferably at least one of p-menthol peroxide or cumene hydroperoxide; and / or,

[0041] The flocculant can be a commonly used flocculant in the rubber industry, preferably at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyandiamine formaldehyde condensate, epoxide amine compounds, and dilute sulfuric acid, preferably at least one of ethanol or epoxide amine compounds.

[0042] A second objective of this invention is to provide a method for preparing an integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber, the method comprising:

[0043] The bio-based rubber is prepared by mixing water-soluble and oil-soluble components, adding butadiene for pre-emulsification, adding an initiator for emulsion polymerization, and then demulsifying and drying with a flocculant.

[0044] The water-soluble components include deionized water, emulsifier, electrolyte, and activator;

[0045] The oil-soluble components include itaconic acid ester monomers, isoprene, functionalized monomers, and chain transfer agents.

[0046] Preferably, the pre-emulsification time is 0.1-5h, more preferably 0.5-3h.

[0047] The emulsion polymerization temperature is 0-85℃, preferably 2-80℃, and the emulsion polymerization time is 1-72h, preferably 2-48h.

[0048] The following solutions can be adopted:

[0049] First, water-soluble components are added to the polymerization reactor, followed by oil-soluble components and mixing. Then, butadiene is added for pre-emulsification, and finally, an initiator is added for polymerization. The bio-based rubber is obtained by demulsification with a flocculant and drying.

[0050] The water-soluble components include deionized water, emulsifiers, electrolytes, and activators.

[0051] Oil-soluble components include itaconic acid ester monomers, isoprene, functionalized monomers, and chain transfer agents.

[0052] A third objective of this invention is to provide a vulcanizate made from an integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber, wherein the vulcanizate is obtained by mixing and vulcanizing raw materials comprising the following components:

[0053] Bio-based rubber, fillers and additives.

[0054] Preferably, the filler is 10-100 parts by weight per 100 parts by weight of rubber, and the filler includes silica, carbon black, lignin, cellulose, etc.

[0055] The fourth objective of this invention is to provide a method for preparing a vulcanizate made from an integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber, the method comprising:

[0056] The components are mixed and then vulcanized to obtain the vulcanized rubber.

[0057] Preferably, the vulcanization is compression molding vulcanization, and the compression molding vulcanization temperature is 120-180℃.

[0058] The following solutions can be adopted:

[0059] The bio-based rubber is blended with additives and then subjected to compression molding and vulcanization at 120-180°C to obtain the vulcanized rubber.

[0060] Preferably, the additives are commonly used additives in the rubber industry, such as zinc oxide, stearic acid, antioxidant 4020, antioxidant RD, accelerator CZ, accelerator NS, sulfur, etc.

[0061] Preferably, the mass ratio of the bio-based rubber to the additives is 100:(8-15).

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] The itaconic acid ester monomer used in this invention is derived from the bulk bio-based chemical itaconic acid. An integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber is prepared using redox emulsion polymerization technology, which is environmentally friendly and has low energy consumption. The resulting polymer has a molecular weight between 100,000 and 800,000, with a molecular weight distribution between 2.0 and 5.0, demonstrating potential for engineering applications. Compared to itaconic acid ester / butadiene copolymer-type bio-based engineering rubbers, the integrated bio-based rubber prepared in this invention can improve the rubber's anti-slip properties while maintaining its rolling resistance with minimal loss. It achieves excellent and balanced dynamic mechanical properties, namely a high tanδ value at 0°C and a low tanδ value at 60°C. Furthermore, the presence of functionalized monomers in the molecular chain can further enhance the interfacial interaction between the filler and the rubber, reduce disordered chain segment movement, and lower rolling resistance. Through reasonable structural design, the comprehensive performance of the integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber is comparable to that of functionalized solution-polymerized styrene-butadiene rubber (SSBR). This type of bio-based integrated rubber has not been previously reported. Attached Figure Description

[0064] Figure 1 The 1H NMR spectrum of the bio-based rubber prepared in Example 1;

[0065] In the figure, the chemical shift at 5.5 ppm is the single hydrogen atom bonded to a carbon atom in -CH=CH2, labeled q; the chemical shifts at 5.4–5.3 ppm are the hydrogen atom shifts of the cis-trans 1,4 double bond in butadiene, labeled h, i, l, m; the chemical shifts at 5.1–5.0 ppm are the hydrogen atom shifts of the cis-trans 1,4 double bond in isoprene, labeled b', g'; the chemical shift at 4.9 ppm is the hydrogen atom shift of the double bond in 1,2-butadiene, labeled r; the chemical shifts at 4.1–4.0 ppm are the hydrogen atom shifts of the hydrogen atom bonded to the ester group in dibutyl itaconic acid, labeled c; and the chemical shifts at 4.4 and 3.8 ppm are the hydrogen atom shifts of the hydrogen atom bonded to the ester group in glycidyl methacrylate, labeled u. The 1H NMR spectrum confirms the successful copolymerization of each monomer unit. Detailed Implementation

[0066] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0067] All raw materials used in the embodiments of this invention are commercially available products, and the specific information is shown in Table 1 below.

[0068] Table 1

[0069] Raw materials and reagents Product Description dibutyl itaconic acid Analytical grade, Sigma-Aldrich Dimethyl itaconic acid Analytical grade, Alfa Aesar diethyl itaconic acid Analytical purity, TCI Corporation dipropyl itaconic acid Analytical purity, TCI Corporation Dihexyl itaconic acid Analytical purity, TCI Corporation Itaconic acid didecyl ester Analytical purity, TCI Corporation Isoprene Analytical grade, Alfa Aesar butadiene Analytical grade, Sigma-Aldrich glycidyl methacrylate Analytical grade, Sigma-Aldrich Vinylsiloxane Analytical grade, Sigma-Aldrich methacrylic acid Analytical grade, Sigma-Aldrich Hydroxyethyl methacrylate Analytical grade, Sigma-Aldrich Acrylamide Analytical grade, Sigma-Aldrich Potassium disproportionate 50% aqueous solution, Beijing Leiberhes Biotechnology Co., Ltd. Sodium fatty acids Beijing Leiberhes Biotechnology Co., Ltd. Ferrous sulfate Analytical grade, Sigma-Aldrich Sodium formaldehyde bisulfite Analytical grade, Sigma-Aldrich Tetrasodium ethylenediaminetetraacetate Analytical grade, Sigma-Aldrich tert-dodecyl mercaptan Analytical grade, Alfa Aesar Hydrogen peroxide for monane Analytical grade, Sigma-Aldrich Potassium chloride Analytical grade, Sigma-Aldrich Deionized water Analytical grade, Beijing Chemical Plant ethanol Analytical grade, Beijing Chemical Plant

[0070] Example 1

[0071] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 40g isoprene to the reactor for sealing. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 120g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain the copolymer. The emulsion was demulsified under reduced pressure to remove butadiene, and then demulsified with 500g of ethanol. After drying in a vacuum oven to constant weight, a bio-based rubber of itaconic acid dibutyl ester / butadiene / isoprene / glycidyl methacrylate (structural formula as follows) was obtained. According to the characteristic peak area ratio calculation analysis in the NMR spectrum, itaconic acid dibutyl ester (n) accounts for 58.3wt%, butadiene (x+y+z) accounts for 30.6wt%, isoprene (a+b) accounts for 8.8wt%, and glycidyl methacrylate (p) accounts for 2.3wt%. Its molecular weight is 402,000 and its dispersion index is 2.6.

[0072]

[0073] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0074] Example 2

[0075] In a reaction vessel, add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 80g isoprene to seal the vessel. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structural formula as follows) of itaconic acid dibutyl ester / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: itaconic acid dibutyl ester (n) accounted for 57.2wt%, butadiene (x+y+z) accounted for 22.5wt%, isoprene (a+b) accounted for 17.6wt%, and glycidyl methacrylate (p) accounted for 2.7wt%. Its molecular weight was 368,000, and its dispersion index was 2.7.

[0076]

[0077] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0078] Example 3

[0079] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 120g isoprene to the reactor for sealing. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 40g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain the copolymer. The emulsion was demulsified under reduced pressure to remove butadiene, and then demulsified with 500g of ethanol. After drying in a vacuum oven to constant weight, a bio-based rubber of itaconic acid dibutyl ester / butadiene / isoprene / glycidyl methacrylate (structural formula as follows) was obtained. According to the characteristic peak area ratio calculation analysis in the NMR spectrum, itaconic acid dibutyl ester (n) accounts for 56.3wt%, butadiene (x+y+z) accounts for 10.8wt%, isoprene (a+b) accounts for 30.2wt%, and glycidyl methacrylate (p) accounts for 2.7wt%. Its molecular weight is 325,000 and its dispersion index is 2.8.

[0080]

[0081] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0082] Example 4

[0083] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dimethyl itaconic acid, and 80g isoprene to a reaction vessel for sealing. Seal the vessel with 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain a copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structural formula as follows) of itaconic acid dimethyl ester / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: itaconic acid dimethyl ester (n) accounted for 58.1wt%, butadiene (x+y+z) accounted for 20.9wt%, isoprene (a+b) accounted for 18.5wt%, and glycidyl methacrylate (p) accounted for 2.5wt%. Its molecular weight was 374,000, and its dispersion index was 2.5.

[0084]

[0085] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0086] Example 5

[0087] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g diethyl itaconic acid, and 80g isoprene to a reaction vessel to seal the vessel. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structure shown below) of diethyl itaconic acid / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: diethyl itaconic acid (n) accounted for 58.7wt%, butadiene (x+y+z) accounted for 19.0wt%, isoprene (a+b) accounted for 19.4wt%, and glycidyl methacrylate (p) accounted for 2.9wt%. Its molecular weight was 452,000, and its dispersion index was 2.6.

[0088]

[0089] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0090] Example 6

[0091] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dipropyl itaconic acid, and 80g isoprene to a reaction vessel for sealing. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structure shown below) of itaconic acid dipropyl ester / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: itaconic acid dipropyl ester (n) accounted for 58.5wt%, butadiene (x+y+z) accounted for 19.9wt%, isoprene (a+b) accounted for 18.5wt%, and glycidyl methacrylate (p) accounted for 3.1wt%. Its molecular weight was 398,000, and its dispersion index was 2.4.

[0092]

[0093] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0094] Example 7

[0095] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dihexyl itaconic acid, and 80g isoprene to a reaction vessel to seal the vessel. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structural formula as follows) of itaconic acid dihexyl ester / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that itaconic acid dihexyl ester (n) accounted for 56.8 wt%, butadiene (x+y+z) accounted for 22.2 wt%, isoprene (a+b) accounted for 18.0 wt%, and glycidyl methacrylate (p) accounted for 3.0 wt%. Its molecular weight was 267,000, and its dispersion index was 3.6.

[0096]

[0097] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0098] Example 8

[0099] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g itaconic acid didecyl ester, and 80g isoprene to a reaction vessel for sealing. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structural formula as follows) of itaconic acid didecyl ester / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: itaconic acid didecyl ester (n) accounted for 58.5wt%, butadiene (x+y+z) accounted for 21.9wt%, isoprene (a+b) accounted for 16.5wt%, and glycidyl methacrylate (p) accounted for 3.1wt%. Its molecular weight was 189,000, and its dispersion index was 4.2.

[0100]

[0101] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0102] Example 9

[0103] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 80g isoprene to the reactor for sealing. Add 12g methacrylic acid and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer. The latex was subjected to depressurization to remove butadiene, followed by demulsification with 500g of ethanol, and then dried in a vacuum oven to constant weight to obtain a bio-based rubber (structural formula as follows) of itaconic acid dibutyl ester / butadiene / isoprene / methacrylic acid. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: itaconic acid dibutyl ester (n) accounted for 57.5wt%, butadiene (x+y+z) accounted for 30.8wt%, isoprene (a+b) accounted for 9.3wt%, and methacrylic acid (p) accounted for 2.4wt%. Its molecular weight was 335,000, and its dispersion index was 3.0.

[0104]

[0105] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0106] Example 10

[0107] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 80g isoprene to a reaction vessel to seal the vessel. Add 12g vinylsiloxane and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-mentholane to initiate polymerization and react at 10°C for 8 hours to obtain the copolymer. The latex was subjected to depressurization to remove butadiene, followed by demulsification with 500g of ethanol, and then dried in a vacuum oven to constant weight to obtain a bio-based rubber (structural formula as follows). Analysis of the characteristic peak area ratios in the NMR spectrum showed that: dibutyl itaconic acid (n) accounted for 57.3wt%, butadiene (x+y+z) accounted for 30.7wt%, isoprene (a+b) accounted for 9.4wt%, and vinylsiloxane (p) accounted for 2.6wt%. Its molecular weight was 448,000, and its dispersion index was 3.6.

[0108]

[0109] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0110] Example 11

[0111] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 80g isoprene to a reaction vessel to seal the vessel. Add 12g hydroxyethyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain the copolymer. Latex was subjected to depressurization to remove butadiene, followed by demulsification with 500g of ethanol and drying in a vacuum oven to constant weight, yielding a bio-based rubber (structural formula below) of itaconic acid dibutyl ester / butadiene / isoprene / hydroxyethyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum revealed that: itaconic acid dibutyl ester (n) accounted for 57.4 wt%, butadiene (x+y+z) accounted for 30.9 wt%, isoprene (a+b) accounted for 9.5 wt%, and hydroxyethyl methacrylate (p) accounted for 2.2 wt%. Its molecular weight was 308,000, and its dispersion index was 2.6.

[0112]

[0113] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0114] Example 12

[0115] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 80g isoprene to a reaction vessel to seal the vessel. Add 12g acrylamide and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain the co-polymer. Polymer latex was demulsified by removing butadiene under reduced pressure, and then demulsified with 500g of ethanol. After drying to constant weight in a vacuum oven, itaconic acid dibutyl ester / butadiene / isoprene / acrylamide bio-based rubber (structural formula as follows) was obtained. According to the characteristic peak area ratio calculation analysis in the NMR spectrum, itaconic acid dibutyl ester (n) accounts for 57.1wt%, butadiene (x+y+z) accounts for 31.5wt%, isoprene (a+b) accounts for 9.3wt%, and acrylamide (p) accounts for 2.1wt%. Its molecular weight is 344,000 and its dispersion index is 2.9.

[0116]

[0117] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0118] Example 13

[0119] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 80g dibutyl itaconic acid, and 240g isoprene to the reactor for sealing. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain copolymer latex. Butadiene was removed under reduced pressure, and the mixture was demulsified with 500g of ethanol and dried to constant weight in a vacuum oven to obtain a bio-based rubber (structural formula as follows) of itaconic acid dibutyl ester / butadiene / isoprene / glycidyl methacrylate. Analysis of the characteristic peak area ratios in the NMR spectrum showed that: itaconic acid dibutyl ester (n) accounted for 18.5wt%, butadiene (x+y+z) accounted for 20.6wt%, isoprene (a+b) accounted for 58.2wt%, and glycidyl methacrylate (p) accounted for 2.7wt%. Its molecular weight was 291,000, and its dispersion index was 2.2.

[0120]

[0121] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0122] Example 14

[0123] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 20g dibutyl itaconic acid, and 300g isoprene to the reactor for sealing. Add 12g glycidyl methacrylate and replace the atmosphere with nitrogen (nitrogen evacuation three times to remove oxygen). Add 80g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain the copolymer. The emulsion was demulsified under reduced pressure to remove butadiene, and then demulsified with 500g of ethanol. After drying in a vacuum oven to constant weight, a bio-based rubber of itaconic acid dibutyl ester / butadiene / isoprene / glycidyl methacrylate (structural formula as follows) was obtained. According to the characteristic peak area ratio calculation analysis in the NMR spectrum, itaconic acid dibutyl ester (n) accounts for 3.8wt%, butadiene (x+y+z) accounts for 18.9wt%, isoprene (a+b) accounts for 74.4wt%, and glycidyl methacrylate (p) accounts for 2.9wt%. Its molecular weight is 351,000 and its dispersion index is 3.3.

[0124]

[0125] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0126] Comparative Example 1

[0127] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, and 240g dibutyl itaconic acid to a reactor. Seal the reactor and replace the atmosphere with nitrogen. Add 160g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization. The copolymer latex was obtained by reacting at 10℃ for 8 hours. Butadiene was removed under reduced pressure, and the latex was demulsified with 500g of ethanol. The latex was then dried in a vacuum oven to constant weight to obtain dibutyl itaconic acid / butadiene bio-based rubber (structural formula as follows). According to the characteristic peak area ratio calculation analysis in the NMR spectrum, dibutyl itaconic acid (n) accounts for 61wt%, butadiene (x+y+z) accounts for 39wt%, its molecular weight is 248,000, and its dispersion index is 2.6.

[0128]

[0129] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0130] Comparative Example 2

[0131] Add 30g potassium disproportionated rosinate, 10g sodium fatty acid, 800g deionized water, 0.1g ferrous sulfate, 0.3g sodium formaldehyde sulfoxylate, 0.5g tetrasodium ethylenediaminetetraacetate, 4g potassium chloride, 0.6g tert-dodecyl mercaptan, 240g dibutyl itaconic acid, and 12g glycidyl methacrylate to a reaction vessel. Seal the vessel and replace the atmosphere with nitrogen. Add 160g butadiene and pre-emulsify at 25°C for 1 hour. Add 0.6g hydrogen peroxide to p-menthol to initiate polymerization and react at 10°C for 8 hours to obtain... The copolymer latex was subjected to depressurization to remove butadiene, demulsified with 500g of ethanol, and dried in a vacuum oven to constant weight to obtain a dibutyl itaconic acid / butadiene / glycidyl methacrylate bio-based rubber (structural formula as follows). Analysis of the characteristic peak area ratio in the NMR spectrum showed that: dibutyl itaconic acid (n) accounted for 59wt%, butadiene (x+y+z) accounted for 38.2wt%, and glycidyl methacrylate (p) accounted for 2.8wt%. Its molecular weight was 326,000 and its dispersion index was 2.7.

[0132]

[0133] 100.0g of the above-mentioned bio-based rubber, 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150°C to prepare a vulcanized rubber.

[0134] Comparative Example 3

[0135] 100.0g of NR (smoked sheet rubber), 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 1165, and 6.0g of Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150℃ to prepare NR / silica vulcanizate.

[0136] Comparative Example 4

[0137] 100.0g ESBR (smoked sheet rubber), 5.0g zinc oxide, 2.0g stearic acid, 1.0g antioxidant 4020, 1.0g antioxidant RD, 1.0g accelerator CZ, 1.2g accelerator NS, 1.5g sulfur, 60.0g silica 1165, and 6.0g Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150℃ to prepare NR / silica vulcanizate.

[0138] Comparative Example 5

[0139] 100.0g SSBR (smoked sheet rubber), 5.0g zinc oxide, 2.0g stearic acid, 1.0g antioxidant 4020, 1.0g antioxidant RD, 1.0g accelerator CZ, 1.2g accelerator NS, 1.5g sulfur, 60.0g silica 1165, and 6.0g Si69 were mixed evenly on a two-roll mill to obtain a compound. The compound was then molded and vulcanized at 150℃ to prepare NR / silica vulcanizate.

[0140] The samples prepared in the above embodiments and comparative examples were subjected to performance tests. The tensile strength, stress at a constant elongation (300%), and elongation at break were tested in accordance with the GB / T 528-2009 standard.

[0141] According to the reference Composites Part B: Engineering, 2023, 248, 110383, the relationship between the loss factor (tanδ) and temperature was tested using a dynamic viscoelastic spectrometer. The mode was tensile, and the test conditions were: 10 Hz, 0.3% strain, and a temperature rise of 3℃ / min from -80℃ to 100℃.

[0142] The specific test results are shown in Table 2 below:

[0143] Table 2

[0144]

[0145] Note: Since the elongation at break of Comparative Example 5 did not reach 300%, the corresponding data for its 300% constant elongation strength in the table were not measured.

[0146] For rubber composites used in tire treads, a larger tanδ value at 0℃ indicates better wet skid resistance and improved braking safety in tires made from this material; a smaller tanδ value at 60℃ indicates lower rolling resistance and better fuel economy in tires made from this material. Table 2 shows that the dynamic mechanical properties of the integrated functionalized itaconic acid ester / butadiene / isoprene bio-based rubber composite prepared in this invention can be controlled by adjusting the itaconic acid ester side group length and the ratio of butadiene and isoprene monomers. Specifically, the introduction of isoprene units significantly improves wet skid resistance while maintaining relatively stable rolling resistance; as the itaconic acid ester side group length decreases, wet skid resistance improves, but rolling resistance increases. Based on this control relationship, selecting appropriate side group lengths and isoprene dosages can regulate the dynamic mechanical properties of the composite material.

[0147] Compared with Comparative Examples 1 and 2, the bio-based rubber of this invention exhibits significantly improved wet skid resistance and rolling resistance. When compared with NR and ESBR, its wet skid resistance is significantly superior, and its overall performance is comparable to functionalized solution styrene-butadiene rubber (SSBR). This demonstrates that the integrated functionalized bio-based rubber structure provided in this study can possess both high wet skid resistance and low rolling resistance, offering insights for the design of next-generation novel bio-based rubbers for tire treads.

[0148] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Other variations and modifications are possible without departing from the technical solutions described in the claims.

Claims

1. An integrated functionalized itaconate / butadiene / isoprene bio-based rubber, characterized in that The structure of the bio-based rubber is: R1, R2 are hydrogen atoms or C 1~20 alkyl groups, X1 is a hydrogen atom or a methyl group, X2 is a functional group containing at least one of an epoxy group, a carboxyl group, a hydroxyl group, an amide group, a+b = 1 to 95%, n = 1 to 99%, x+y+z = 1 to 95%, p = 1 to 30%, wherein R1, R2 can be the same or different; The number average molecular weight of the bio-based rubber is 500,000-1,000,000; and the molecular weight distribution is 1.5-10.

0.

2. The itaconate / butadiene / isoprene bio-based rubber according to claim 1, wherein: R1is hydrogen or C 1-10 alkyl; R2is hydrogen or C 1-10 alkyl, a+b=5~90%, n=10~90%, x+y+z=5~90%, p=1~20%.

3. The itaconate / butadiene / isoprene bio-based rubber according to claim 1, wherein: The number average molecular weight of the bio-based rubber is 1,000,000-8,000,000; and the molecular weight distribution is 2.0-5.

0.

4. Itaconate / butadiene / isoprene bio-based rubber according to claim 1, characterized in that The bio-based rubber is prepared by copolymerization of raw materials comprising: The components are in parts by weight: The total mass of the itaconate monomer, butadiene, isoprene and functional monomer is 100 parts by weight; The mass ratio of the itaconate monomer, butadiene, isoprene and functional monomer is (0.5-90):(0.25-90):(0.25-90):1; Deionized water 100-400 parts by weight; Emulsifier 0.05-20 parts by weight; Electrolyte 0.05-3 parts by weight; Activator 0.01-0.2 parts by weight; Chain transfer agent 0.01-0.4 parts by weight; Initiator 0.01-5 parts by weight; The amount of the flocculating agent is 20-60 wt% of the total mass of the copolymer latex after emulsion polymerization.

5. The integrated functional itaconate / butadiene / isoprene bio-based rubber according to claim 4, wherein: The components are in parts by weight: The total mass of the itaconate monomer, butadiene, isoprene and functional monomer is 100 parts by weight; The mass ratio of the itaconate monomer, butadiene, isoprene and functional monomer is (1-80):(0.5-80):(0.5-80):1; Deionized water 150-300 parts by weight; Emulsifier 2-15 parts by weight; Electrolyte 0.1-2.0 parts by weight; Activator 0.02-0.1 parts by weight; Chain transfer agent 0.03-0.25 parts by weight; Initiator 0.02-2 parts by weight; The amount of the flocculating agent is 30-50 wt% of the total mass of the copolymer latex after emulsion polymerization.

6. The integrated functional itaconate / butadiene / isoprene bio-based rubber according to claim 4, wherein: The itaconate monomer is at least one of dimethyl itaconate, monomethyl itaconate, diethyl itaconate, monoethyl itaconate, dipropyl itaconate, monopropyl itaconate, dibutyl itaconate, monobutyl itaconate, dipentyl itaconate, monopentyl itaconate, dihexyl itaconate, monohexyl itaconate, diheptyl itaconate, monohexyl itaconate, dioctyl itaconate, monooctyl itaconate, dinonyl itaconate, monononyl itaconate, didecyl itaconate, monodecyl itaconate; and / or, The functional monomer is at least one of glycidyl methacrylate, allyl alcohol glycidyl ether, limonene epoxide, vinyl siloxane, methacrylic acid, hydroxyethyl methacrylate, acrylamide; and / or, The emulsifier is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, potassium disulfated rosin acid, sodium fatty acid, alkyl phenol polyoxyethylene ether; and / or, The electrolyte is at least one of potassium phosphate, potassium chloride, sodium bicarbonate; and / or, The activator is at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, iron sodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate; and / or, The chain transfer agent is at least one of n-dodecanethiol, tert-dodecanethiol, mercaptoethanol, carbon tetrabromide, 3-mercaptoisooctyl propionate; and / or, The initiator is at least one of p-menthane hydroperoxide, azobisisobutyronitrile, tert-butyl hydroperoxide, cumene hydroperoxide; and / or, The flocculating agent is at least one of methanol, ethanol, calcium chloride, sodium chloride, dicyandiamide formaldehyde condensate, epoxy amine compound, dilute sulfuric acid.

7. The integrated functionalized itaconate / butadiene / isoprene bio-based rubber according to claim 6, characterized in that: The emulsifier is a mixture of potassium disulfide rosin acid and sodium fatty acid; and / or, The electrolyte is potassium chloride; and / or, The activator is at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, tetrasodium ethylenediaminetetraacetate; and / or, The initiator is at least one of p-menthane hydroperoxide or dicumene hydroperoxide; and / or, The flocculating agent is at least one of ethanol or epoxy amine compound.

8. A process for the preparation of an integrated functionalized itaconate / butadiene / isoprene bio-based rubber according to any one of claims 1 to 7, characterized in that The method comprises: After mixing the water-soluble component and the oil-soluble component, adding butadiene for pre-emulsification, and finally adding an initiator for emulsion polymerization, the bio-based rubber is obtained after breaking the emulsion with a flocculating agent and drying. The water-soluble component includes deionized water, an emulsifier, an electrolyte, and an activator. The oil-soluble component includes itaconate monomer, isoprene, functionalized monomer, and chain transfer agent.

9. The preparation method of the integrated functionalized itaconate / butadiene / isoprene bio-based rubber according to claim 8, characterized in that: The pre-emulsification time is 0.1-5 h; The emulsion polymerization temperature is 0-85℃, and the emulsion polymerization time is 1-72 h.

10. The preparation method of the integrated functionalized itaconate / butadiene / isoprene bio-based rubber according to claim 9, characterized in that: The pre-emulsification time is 0.5-3 h; The emulsion polymerization temperature is 2-80℃, and the emulsion polymerization time is 2-48 h.

11. A vulcanizate made from the integrated functionalized itaconate / butadiene / isoprene bio-based rubber of any of claims 1-7, characterized in that The vulcanized rubber is prepared by mixing and vulcanizing raw materials including: Bio-based rubber, filler, and auxiliary agent.

12. A process for the preparation of a vulcanizate made of the integrated functionalized itaconate / butadiene / isoprene bio-based rubber according to claim 11, characterized in that The method comprises: The component is mixed and vulcanized to prepare the vulcanized rubber.

13. The preparation method of the vulcanized rubber prepared from the integrated functionalized itaconate / butadiene / isoprene bio-based rubber according to claim 12, characterized in that: The vulcanization is compression molding vulcanization, and the compression molding vulcanization temperature is 120-180℃.

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