Low-temperature-resistant diene composite material and preparation method thereof
By combining modified styrene-butadiene rubber, silica, and additives to form a dynamic cross-linked network, the problem of brittle fracture of styrene-butadiene rubber at low temperatures is solved, and the low-temperature toughness and low-temperature resistance of the material are improved.
Patent Information
- Application Number
- CN202511889562.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-15
- Publication Date
- 2026-01-20
AI Technical Summary
Styrene-butadiene rubber is prone to brittle fracture at low temperatures, which limits its application in extremely cold regions and low-temperature environments.
By combining modified styrene-butadiene rubber, modified silica, and modified additives, and utilizing the design of dynamic crosslinking networks and polysiloxane segments, reversible bond breaking and recombination are formed, thereby enhancing the low-temperature toughness of the material.
It significantly reduces the glass transition temperature of the material, improves its toughness at low temperatures, and prevents the initiation and propagation of cracks.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of diene material preparation, and particularly relates to a low-temperature-resistant diene composite material and a preparation method thereof. BACKGROUND
[0002] Styrene butadiene rubber is a widely used synthetic rubber, which is obtained by copolymerization of two monomers, butadiene and styrene. Butadiene provides high elasticity and wear resistance of the rubber, while styrene endows the material with good processing performance and mechanical strength. Due to its excellent comprehensive performance, styrene butadiene rubber is widely used in the fields of automobiles, tires, soles, wires and cables, etc. However, the asymmetry of the styrene segment and the butadiene segment in the molecular chain of the styrene butadiene rubber leads to relatively high glass transition temperature and brittle temperature (usually in the range of -50℃ to -60℃), and the low-temperature resistance is far from that of natural rubber or cis-butadiene rubber. This seriously limits its application in cold regions (such as high latitude regions, aerospace, polar exploration) and related low-temperature environments. SUMMARY
[0003] The present application relates to the technical field of diene material preparation, and particularly relates to a low-temperature-resistant diene composite material and a preparation method thereof.
[0004] The object of the present application can be achieved by the following technical solutions. A preparation method of a low-temperature-resistant diene composite material, specifically comprising the following steps: Step A1: Dissolve the styrene butadiene rubber in cyclohexane, add 2,2-dimethoxy-2-phenylacetophenone and furfuryl mercaptan, and protect with nitrogen. Under the conditions of a rotation speed of 150-200 r / min and a temperature of 20-25℃, irradiate with 365 nm ultraviolet light for 1-1.5 h to prepare modified styrene butadiene rubber; Step A2: Disperse the white carbon black in ethanol, and under the conditions of a rotation speed of 200-300 r / min and a temperature of 70-75℃, stir and add gamma-aminopropyl triethoxysilane and deionized water, and react for 4-6 h to prepare pretreated white carbon black; Step A3: Mix the pretreated white carbon black, stearaldehyde and toluene, and under the conditions of a rotation speed of 150-200 r / min and a temperature of 70-80℃, stir and add glacial acetic acid, and react for 3-5 h to prepare modified white carbon black; Step A4: Weigh the following raw materials: modified styrene butadiene rubber 80-100 parts, modified additive 5-8 parts and modified white carbon black 20-30 parts, and add the raw materials into a banbury mixer, and under the conditions of a rotation speed of 60-80 r / min and a temperature of 150-155℃, mix and process for 6-8 min to prepare a low-temperature-resistant diene composite material.
[0005] Further, the molar ratio of the double bond on the styrene butadiene rubber and furfuryl mercaptan in step A1 is 10:1, the amount of 2,2-dimethoxy-2-phenylacetophenone is 0.5% of the mass of furfuryl mercaptan, and the type of the styrene butadiene rubber is 2466.
[0006] Further, the amount of γ-aminopropyl triethoxysilane in step A2 is 3% of the mass of the white carbon black.
[0007] Further, the molar ratio of the amino group on the pretreated white carbon black and stearaldehyde in step A3 is 1:1, and the amount of glacial acetic acid is 1% of the mass of stearaldehyde.
[0008] Further, the modified additive is prepared by the following steps: Step B1: 4-maleimide phenol, tetrabutylammonium bromide, hydroquinone and toluene are mixed, nitrogen is introduced for protection, stirring is performed at a rotation speed of 200-300 r / min and a temperature of 60-70℃, potassium carbonate and epichlorohydrin are added, reaction is performed for 4-6 h, sodium hydroxide solution is added, and reaction is continued for 1-1.5 h to prepare intermediate 1; intermediate 1, 1,6-hexanediamine, triethylamine and toluene are mixed, reaction is performed at a rotation speed of 150-200 r / min and a temperature of 80-90℃ for 3-5 h to prepare intermediate 2; Step B2: lithium trimethylsilanolate and tetrahydrofuran are mixed, stirring is performed at a rotation speed of 150-200 r / min and a temperature of 0-3℃, hexamethylcyclotrisiloxane is added, the temperature is raised to 25-30℃, reaction is performed for 7-9 h, then trichlorosilane is added, and reaction is continued for 1-1.5 h to prepare branched polysiloxane; the branched polysiloxane, acrylic acid, Karstedt catalyst and DMF are mixed, nitrogen is introduced for protection, stirring is performed at a rotation speed of 200-300 r / min and a temperature of 80-85℃, and reaction is performed for 6-8 h to prepare carboxylated polysiloxane; Step B3: intermediate 2, carboxylated polysiloxane, p-toluenesulfonic acid and dimethylbenzene are uniformly mixed, reaction is performed at a rotation speed of 200-300 r / min and a temperature of 110-120℃ for 3-5 h to prepare the modified additive.
[0009] Further, the amount ratio of 4-maleimide phenol, potassium carbonate, epichlorohydrin and sodium hydroxide solution in step B1 is 0.3 mol:0.32 mol:0.3 mol:35 mL, the amount of tetrabutylammonium bromide is 1% of the mass of 4-maleimide phenol, the amount of hydroquinone is 0.1% of the mass of 4-maleimide phenol, the mass fraction of sodium hydroxide solution is 25%, the molar ratio of intermediate 1 and 1,6-hexanediamine is 4:1, and the amount of triethylamine is 0.5% of the amount of intermediate 1.
[0010] Further, the molar ratio of lithium trimethylsilanolate, hexamethylcyclotrisiloxane and Si-Cl bond on trichlorosilane in step B2 is 1:5:1, the molar ratio of branched polysiloxane and acrylic acid is 1:1, and the amount of cast catalyst is 0.01% of the mass of acrylic acid.
[0011] Further, the molar ratio of intermediate 2 and carboxylated polysiloxane in step B3 is 1:4, and the amount of p-toluenesulfonic acid is 2% of the mass of carboxylated polysiloxane.
[0012] The low-temperature-resistant diene composite material disclosed by the application comprises the following raw materials: modified butadiene styrene rubber, modified additive, and modified white carbon black. The modified butadiene styrene rubber is prepared by treating butadiene styrene rubber with furfuryl mercaptan so that the double bond on the butadiene styrene rubber molecular chain segment reacts with the mercapto group on the furfuryl mercaptan. The modified white carbon black is prepared by treating white carbon black with γ-aminopropyl triethoxysilane so that the surface of the white carbon black is grafted with amino groups. The modified white carbon black is prepared by reacting the pretreated white carbon black with stearyl aldehyde so that the amino group on the surface of the pretreated white carbon black reacts with the aldehyde group on the stearyl aldehyde.
[0013] The modified additive is prepared by using 4-maleimide phenol and epichlorohydrin as raw materials, making the phenolic hydroxyl group on the 4-maleimide phenol react with the epoxy group on the epichlorohydrin, and then closing the ring to form a new epoxy group under the action of sodium hydroxide solution to obtain intermediate 1. The intermediate 1 is reacted with 1,6-hexanediamine to make the epoxy group on the intermediate 1 react with the amino group on the 1,6-hexanediamine to obtain intermediate 2. Lithium trimethylsilanol is used as an initiator, and hexamethylcyclotrisiloxane is used as a polymerization monomer to form polysiloxane with one end being lithium silanol. Then, trichlorosilane is added to make the Si-Cl bond on the trichlorosilane react with the lithium silanol to obtain branched polysiloxane. The branched polysiloxane is reacted with acrylic acid to make the Si-H bond on the branched polysiloxane react with the double bond on the acrylic acid to obtain carboxylated polysiloxane. The intermediate 2 is reacted with the carboxylated polysiloxane to make the hydroxyl group on the intermediate 2 esterify with the carboxyl group on the carboxylated polysiloxane to obtain the modified additive.
[0014] During the raw material mixing process, the maleimide group in the modified additive molecule reacts with the furan group on the side chain of the modified butadiene styrene rubber to form a D-A bond, and then a dynamic crosslinking network is formed. Under the action of stress, the dynamic crosslinking network can dissipate energy through reversible bond breaking and recombination, avoiding the continuous accumulation of stress, thereby delaying or preventing the initiation and expansion of cracks, improving the low-temperature toughness of the material, and increasing the spacing between butadiene styrene rubber molecular chains by the polysiloxane chain segment on the side chain and the long-chain alkyl group on the modified white carbon black, thereby weakening the interaction force between the molecular chains and creating more free volume for the movement of the chain segments at low temperatures, thereby significantly reducing the overall glass transition temperature of the modified rubber. DETAILED DESCRIPTION
[0015] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.
[0016] Embodiment 1, a preparation method of a low-temperature-resistant diene composite material, specifically comprising the following steps: Step A1: dissolving styrene-butadiene rubber in cyclohexane, adding 2,2-dimethoxy-2-phenylacetophenone and furfuryl mercaptan, and performing reaction under the condition of nitrogen protection, a rotation speed of 150 r / min, a temperature of 20℃ and 365 nm ultraviolet light irradiation for 1 h to prepare modified styrene-butadiene rubber; Step A2: dispersing white carbon black in ethanol, stirring under the condition of a rotation speed of 200 r / min and a temperature of 70℃, and adding γ-aminopropyl triethoxysilane and deionized water to perform reaction for 4 h to prepare pretreated white carbon black; Step A3: mixing pretreated white carbon black, stearaldehyde and toluene, stirring under the condition of a rotation speed of 150 r / min and a temperature of 70℃, and adding glacial acetic acid to perform reaction for 3 h to prepare modified white carbon black; Step A4: weighing the following raw materials: 80 parts of modified styrene-butadiene rubber, 5 parts of modified additive and 20 parts of modified white carbon black, and adding the raw materials into a mixer to perform mixing treatment for 6 min under the condition of a rotation speed of 60 r / min and a temperature of 150℃ to prepare a low-temperature-resistant diene composite material.
[0017] The molar ratio of the double bond on the styrene-butadiene rubber in Step A1 to furfuryl mercaptan is 10:1, the amount of 2,2-dimethoxy-2-phenylacetophenone is 0.5% of the mass of furfuryl mercaptan, and the type of the styrene-butadiene rubber is 2466.
[0018] The amount of γ-aminopropyl triethoxysilane in Step A2 is 3% of the mass of white carbon black.
[0019] The molar ratio of the amino group on the pretreated white carbon black in Step A3 to stearaldehyde is 1:1, and the amount of glacial acetic acid is 1% of the mass of stearaldehyde.
[0020] The modified additive is prepared by the following steps: Step B1: 4-maleimide phenol, tetrabutylammonium bromide, hydroquinone and toluene were mixed, protected by nitrogen, stirred at 200 r / min and 60℃, and then potassium carbonate and epichlorohydrin were added and reacted for 4 h. Sodium hydroxide solution was added and reacted for another 1 h to obtain intermediate 1. Intermediate 1, 1,6-hexanediamine, triethylamine and toluene were mixed, reacted at 150 r / min and 80℃ for 3 h to obtain intermediate 2. Step B2: lithium trimethylsilanolate and tetrahydrofuran were mixed, stirred at 150 r / min and 0℃, and then hexamethylcyclotrisiloxane was added. The temperature was raised to 25℃, reacted for 7 h, and then trichlorosilane was added and reacted for another 1 h to obtain branched polysiloxane. The branched polysiloxane, acrylic acid, Karstedt catalyst and DMF were mixed, protected by nitrogen, reacted at 200 r / min and 80℃ for 6 h to obtain carboxylated polysiloxane. Step B3: intermediate 2, carboxylated polysiloxane, p-toluenesulfonic acid and xylene were uniformly mixed, reacted at 200 r / min and 110℃ for 3 h to obtain the modified additive.
[0021] The amount ratio of 4-maleimide phenol, potassium carbonate, epichlorohydrin and sodium hydroxide solution in step B1 was 0.3 mol:0.32 mol:0.3 mol:35 mL. The amount of tetrabutylammonium bromide was 1% of the mass of 4-maleimide phenol. The amount of hydroquinone was 0.1% of the mass of 4-maleimide phenol. The mass fraction of sodium hydroxide solution was 25%. The molar ratio of intermediate 1 and 1,6-hexanediamine was 4:1. The amount of triethylamine was 0.5 mol% of the amount of intermediate 1.
[0022] The molar ratio of lithium trimethylsilanolate, hexamethylcyclotrisiloxane and Si-Cl bond on trichlorosilane in step B2 was 1:5:1. The molar ratio of branched polysiloxane and acrylic acid was 1:1. The amount of Karstedt catalyst was 0.01% of the mass of acrylic acid.
[0023] The molar ratio of intermediate 2 and carboxylated polysiloxane in step B3 was 1:4. The amount of p-toluenesulfonic acid was 2% of the mass of carboxylated polysiloxane.
[0024] Example 2, a method for preparing a low-temperature-resistant diene composite, specifically comprising the following steps: Step A1: butadiene styrene rubber was dissolved in cyclohexane, 2,2-dimethoxy-2-phenylacetophenone and furfuryl mercaptan were added, protected by nitrogen, and then irradiated with 365 nm ultraviolet light at 150 r / min and 25℃ for 1.5 h to obtain modified butadiene styrene rubber. Step A2: dispersing the white carbon black in ethanol, stirring and adding γ-aminopropyl triethoxysilane and deionized water at a rotation speed of 200 r / min and a temperature of 75℃, and reacting for 5 h to obtain pretreated white carbon black; Step A3: mixing the pretreated white carbon black, stearaldehyde and toluene, stirring and adding glacial acetic acid at a rotation speed of 150 r / min and a temperature of 75℃, and reacting for 4 h to obtain modified white carbon black; Step A4: weighing the raw materials in the following proportions: 90 parts of modified butadiene styrene rubber, 6.5 parts of modified additive and 25 parts of modified white carbon black, and mixing the raw materials in an internal mixer at a rotation speed of 60 r / min and a temperature of 155℃ for 7 min to obtain a low-temperature-resistant diene composite material.
[0025] The molar ratio of the double bond on the butadiene styrene rubber in Step A1 to furfuryl mercaptan is 10:1, the amount of 2,2-dimethoxy-2-phenylacetophenone is 0.5% of the mass of furfuryl mercaptan, and the type of butadiene styrene rubber is 2466.
[0026] The amount of γ-aminopropyl triethoxysilane in Step A2 is 3% of the mass of white carbon black.
[0027] The molar ratio of the amino group on the pretreated white carbon black in Step A3 to stearaldehyde is 1:1, and the amount of glacial acetic acid is 1% of the mass of stearaldehyde.
[0028] The modified additive is prepared by the following steps: Step B1: mixing 4-maleimide phenol, tetrabutylammonium bromide, hydroquinone and toluene, protecting with nitrogen, stirring and adding potassium carbonate and epichlorohydrin at a rotation speed of 200 r / min and a temperature of 65℃, and reacting for 5 h, then adding sodium hydroxide solution and continuing to react for 1.3 h to obtain intermediate 1, mixing intermediate 1, 1,6-hexanediamine, triethylamine and toluene at a rotation speed of 150 r / min and a temperature of 85℃, and reacting for 4 h to obtain intermediate 2; Step B2: mixing lithium trimethylsilanolate and tetrahydrofuran at a rotation speed of 150 r / min and a temperature of 3℃, stirring and adding hexamethylcyclotrisiloxane, warming to 25℃, and reacting for 8 h, then adding trichlorosilane and continuing to react for 1.3 h to obtain branched polysiloxane, mixing the branched polysiloxane, acrylic acid, Karstedt catalyst and DMF, protecting with nitrogen, and reacting at a rotation speed of 200 r / min and a temperature of 85℃ for 7 h to obtain carboxylated polysiloxane; Step B3: Intermediate 2, carboxylated polysiloxane, p-toluenesulfonic acid and xylene were mixed uniformly, and reacted for 4 h at 200 r / min and 115℃ to obtain the modified additive.
[0029] The use amount ratio of 4-maleimide phenol, potassium carbonate, epichlorohydrin and sodium hydroxide solution in step B1 was 0.3 mol:0.32 mol:0.3 mol:35 mL, the use amount of tetrabutylammonium bromide was 1% of the mass of 4-maleimide phenol, the use amount of hydroquinone was 0.1% of the mass of 4-maleimide phenol, the mass fraction of sodium hydroxide solution was 25%, the molar ratio of intermediate 1 and 1,6-hexanediamine was 4:1, and the use amount of triethylamine was 0.5% of the use amount of intermediate 1.
[0030] The molar ratio of lithium trimethylsilanolate, hexamethylcyclotrisiloxane and Si-Cl bond on trichlorosilane in step B2 was 1:5:1, the molar ratio of branched polysiloxane and acrylic acid was 1:1, and the use amount of Karstedt catalyst was 0.01% of the mass of acrylic acid.
[0031] The molar ratio of intermediate 2 and carboxylated polysiloxane in step B3 was 1:4, and the use amount of p-toluenesulfonic acid was 2% of the mass of carboxylated polysiloxane.
[0032] Embodiment 3, a preparation method of a low-temperature-resistant diene composite material, specifically comprising the following steps: Step A1: Butadiene styrene rubber was dissolved in cyclohexane, 2,2-dimethoxy-2-phenylacetophenone and furfuryl mercaptan were added, nitrogen was introduced for protection, and the mixture was irradiated with 365 nm ultraviolet light at a rotation speed of 200 r / min and a temperature of 25℃ for 1.5 h to obtain modified butadiene styrene rubber. Step A2: White carbon black was dispersed in ethanol, stirred at a rotation speed of 300 r / min and a temperature of 75℃, and then γ-aminopropyltriethoxysilane and deionized water were added and reacted for 6 h to obtain pretreated white carbon black. Step A3: The pretreated white carbon black, stearaldehyde and toluene were mixed, stirred at a rotation speed of 200 r / min and a temperature of 80℃, and then glacial acetic acid was added and reacted for 5 h to obtain modified white carbon black. Step A4: The following raw materials were weighed: 100 parts of modified butadiene styrene rubber, 8 parts of modified additive and 30 parts of modified white carbon black, and the raw materials were added to a banbury mixer, mixed and treated at a rotation speed of 80 r / min and a temperature of 155℃ for 8 min to obtain a low-temperature-resistant diene composite material.
[0033] The molar ratio of the double bond on the butadiene styrene rubber and furfuryl mercaptan is 10:1, the amount of 2,2-dimethoxy-2-phenylacetophenone is 0.5% of the mass of furfuryl mercaptan, and the type of butadiene styrene rubber is 2466.
[0034] The amount of γ-aminopropyl triethoxysilane is 3% of the mass of white carbon black.
[0035] The molar ratio of the amino group on the pretreated white carbon black and stearaldehyde is 1:1, and the amount of glacial acetic acid is 1% of the mass of stearaldehyde.
[0036] The modified additive is prepared by the following steps: Step B1: 4-maleimide phenol, tetrabutylammonium bromide, hydroquinone and toluene are mixed, nitrogen is introduced, stirring is carried out at a rotation speed of 300 r / min and a temperature of 70℃, potassium carbonate and epichlorohydrin are added, and reaction is carried out for 6h, sodium hydroxide solution is added, and reaction is continued for 1.5h to prepare intermediate 1, intermediate 1, 1,6-hexanediamine, triethylamine and toluene are mixed, reaction is carried out at a rotation speed of 200 r / min and a temperature of 90℃ for 5h to prepare intermediate 2; Step B2: lithium trimethylsilanolate and tetrahydrofuran are mixed, stirring is carried out at a rotation speed of 200 r / min and a temperature of 3℃, hexamethylcyclotrisiloxane is added, the temperature is raised to 30℃, reaction is carried out for 9h, then trichlorosilane is added, and reaction is continued for 1.5h to prepare branched polysiloxane, the branched polysiloxane, acrylic acid, Karstedt catalyst and DMF are mixed, nitrogen is introduced, stirring is carried out at a rotation speed of 300 r / min and a temperature of 85℃, and reaction is carried out for 8h to prepare carboxylated polysiloxane; Step B3: intermediate 2, carboxylated polysiloxane, p-toluenesulfonic acid and dimethylbenzene are uniformly mixed, reaction is carried out at a rotation speed of 300 r / min and a temperature of 120℃ for 5h to prepare the modified additive.
[0037] The amount ratio of 4-maleimide phenol, potassium carbonate, epichlorohydrin and sodium hydroxide solution in step B1 is 0.3mol:0.32mol:0.3mol:35mL, the amount of tetrabutylammonium bromide is 1% of the mass of 4-maleimide phenol, the amount of hydroquinone is 0.1% of the mass of 4-maleimide phenol, the mass fraction of sodium hydroxide solution is 25%, the molar ratio of intermediate 1 and 1,6-hexanediamine is 4:1, and the amount of triethylamine is 0.5% of the amount of intermediate 1.
[0038] The molar ratio of lithium trimethylsilanolate, hexamethylcyclotrisiloxane and Si-Cl bond on trichlorosilane in step B2 is 1:5:1, the molar ratio of branched polysiloxane and acrylic acid is 1:1, and the amount of cast catalyst is 0.01% of the mass of acrylic acid.
[0039] The molar ratio of intermediate 2 and carboxylated polysiloxane in step B3 is 1:4, and the amount of p-toluenesulfonic acid is 2% of the mass of carboxylated polysiloxane.
[0040] Comparative Example 1, this comparative example uses pre-treated white carbon black instead of modified white carbon black compared with Example 1, and the rest of the steps are the same.
[0041] Comparative Example 2, this comparative example uses intermediate 2 instead of modified additive compared with Example 1, and the rest of the steps are the same.
[0042] Comparative Example 3, this comparative example uses butadiene styrene rubber instead of modified butadiene styrene rubber compared with Example 1, and the rest of the steps are the same.
[0043] The brittle temperature of the composite material prepared in Examples 1-3 and Comparative Examples 1-3 was measured according to the standard of GB / T15256-2014 when using Procedure A, and the compression set value of the composite material was measured under the conditions of -30℃, 72h and compression rate of 25% according to the standard of GB / T7759.2-2014, and the test results are shown in Table 1.
[0044] Table 1
[0045] From Table 1, it can be seen that the present application has good low temperature resistance effect.
[0046] The above content is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the concept of the invention or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.
Claims
1. A method of making a low temperature resistant diene composite material, characterized in that: Specifically comprising the following steps: Step A1: dissolving styrene butadiene rubber in cyclohexane, adding 2,2-dimethoxy-2-phenylacetophenone and furfuryl mercaptan, protecting with nitrogen, and reacting to obtain modified styrene butadiene rubber; Step A2: dispersing white carbon black in ethanol, stirring, adding γ-aminopropyl triethoxysilane and deionized water, and reacting to obtain pretreated white carbon black; Step A3: mixing pretreated white carbon black, stearaldehyde and toluene, stirring, adding glacial acetic acid, and reacting to obtain modified white carbon black; Step A4: weighing the following raw materials: 80-100 parts of modified styrene butadiene rubber, 5-8 parts of modified additive, and 20-30 parts of modified white carbon black, adding the raw materials into a mixer, and mixing to obtain low-temperature-resistant diene composite material.
2. The method of claim 1, wherein: The molar ratio of the double bond on the styrene butadiene rubber in step A1 to furfuryl mercaptan is 10:
1.
3. The method of claim 1, wherein: The amount of γ-aminopropyl triethoxysilane in step A2 is 3% of the mass of white carbon black.
4. The method of claim 1, wherein: The molar ratio of the amino group on the pretreated white carbon black in step A3 to stearaldehyde is 1:
1.
5. The method of claim 1, wherein: The modified additive is prepared by the following steps: Step B1: mixing 4-maleimide phenol, tetrabutylammonium bromide, hydroquinone and toluene, protecting with nitrogen, stirring, adding potassium carbonate and epichlorohydrin, and reacting, adding sodium hydroxide solution, and continuing to react to obtain intermediate 1, mixing intermediate 1, 1,6-hexanediamine, triethylamine and toluene, and reacting to obtain intermediate 2; Step B2: mixing lithium trimethylsilanolate and tetrahydrofuran, stirring, adding hexamethylcyclotrisiloxane, and reacting after heating, adding trichlorosilane, and continuing to react to obtain branched polysiloxane, mixing branched polysiloxane, acrylic acid, Karstedt catalyst and DMF, protecting with nitrogen, and reacting to obtain carboxylated polysiloxane; Step B3: mixing intermediate 2, carboxylated polysiloxane, p-toluenesulfonic acid and xylene, and reacting to obtain modified additive.
6. The method of claim 5, wherein: The amount ratio of 4-maleimide phenol, potassium carbonate, epichlorohydrin and sodium hydroxide solution in step B1 is 0.3 mol:0.32 mol:0.3 mol:35 mL, and the molar ratio of intermediate 1 to 1,6-hexanediamine is 4:
1.
7. The method of claim 5, wherein the method further comprises: The molar ratio of Si-Cl bond on lithium trimethylsilanolate, hexamethylcyclotrisiloxane and trichlorosilane in step B2 is 1:5:1, and the molar ratio of branched polysiloxane to acrylic acid is 1:
1.
8. The method of claim 5, wherein: The molar ratio of intermediate 2 to carboxylated polysiloxane in step B3 is 1:
4.
9. A low temperature resistant diene composite, characterized in that: Prepared according to the preparation method of any one of claims 1-8. Prepared according to the preparation method of any one of claims 1-8.