Controllable crosslinking hydrogenated aromatic conjugated diene polymer and preparation method thereof

Abstract

The invention discloses a controllable crosslinking hydrogenated aromatic conjugated diene polymer and a preparation method thereof, and a vulcanized rubber sheet and a preparation method thereof. The polymer comprises a hydrogenated styrene structural unit I and a hydrogenated farnesene or myrcene structural unit IV. The polymer is introduced into the vulcanized rubber sheet, and the obtained vulcanized rubber has excellent heat resistance, ageing resistance and good mechanical strength and can be used for preparing automobile door and window sealing strips, building waterproof sheets, electric wires and cables and medical sealing materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of styrene-based thermoplastic elastomer synthesis, and relates to a controllably cross-linkable hydrogenated aromatic conjugated diene polymer and a preparation method thereof, as well as a vulcanized film and a preparation method thereof. Background Art

[0002] Hydrogenated styrene thermoplastic elastomers, such as hydrogenated styrene / butadiene block polymer SEBS, hydrogenated styrene / isoprene block polymer SEPS, and hydrogenated styrene / isoprene and butadiene block polymer SEEPS, have the advantages of low modulus, high strength, good resilience, and excellent aging resistance. Therefore, they are widely used in various consumer electronics, automobiles, building materials, tools, daily necessities and other fields.

[0003] However, the PS segment glass transition temperature T g Due to the influence of the temperature (approximately 80°C), the glass transition temperature of this type of elastomer is low. Once the glass transition temperature is exceeded, the performance of the elastomer will be affected. In addition, the compression set of this type of elastomer at 70°C and 100°C is much greater than that of thermoplastic vulcanizate (TPV) (50%), which limits its application areas.

[0004] Therefore, by designing the structure of hydrogenated styrene thermoplastic elastomers and selecting appropriate processing technology, a hydrogenated aromatic conjugated diene polymer with controllable cross-linking is prepared, thereby improving the heat resistance temperature and reducing the permanent deformation of compression. This is the key to expanding the application of hydrogenated styrene thermoplastic elastomers in medical seals, automotive door and window sealing strips, building waterproof sheets, wires and cables, automotive parts and other fields. Summary of the Invention

[0005] To address the shortcomings of existing thermoplastic elastomer materials, the first objective of the present invention is to provide a hydrogenated aromatic conjugated diene polymer. The aromatic ring structure, pendant groups attached to the aromatic rings, and hydrogen bonds in this polymer provide high thermal stability. The long carbon chain structural units significantly enhance the flexibility of the molecular chain. Furthermore, the crosslinking degree of this polymer can be controlled by adjusting the content of hydrogenated styrene structural units.

[0006] The second object of the present invention is to provide a method for preparing a hydrogenated aromatic conjugated diene polymer, which has simple operation, mild conditions and low production cost.

[0007] A third object of the present invention is to provide a vulcanized rubber sheet that, by introducing a hydrogenated aromatic conjugated diene polymer, can improve the performance of the vulcanized rubber, particularly in terms of heat resistance and compression set. The vulcanized rubber sheet has a high heat resistance temperature, good stability in high-temperature environments, and excellent rebound resilience and deformation recovery. The vulcanized rubber sheet is suitable for use in the preparation of automotive door and window sealing strips, building waterproof sheets, wires and cables, and medical sealing materials, particularly medical sealing materials.

[0008] A fourth object of the present invention is to provide a method for preparing a vulcanized rubber sheet, which has a simple process, no reversion during the process, no frosting on the product, and has the potential for industrial production.

[0009] In order to achieve the above technical objectives, the present invention provides a controllably cross-linkable hydrogenated aromatic conjugated diene polymer comprising a hydrogenated styrene structural unit I and a hydrogenated farnesene or hydrogenated myrcene structural unit IV;

[0010] The structural unit I is One of the following;

[0011] The structural unit IV is

[0012] Wherein, R is one of methyl, ethyl, tert-butyl, and isobutyl;

[0013] When R1 is -CH3, R2 is

[0014] R1 is When R2 is H;

[0015] Based on the total amount of the copolymer, the content of the structural unit I is 10-40 wt%; the content of the z1+z2 is 10-30 wt%, wherein the content of the structural unit corresponding to z2 is 5-20%.

[0016] The hydrogenated aromatic conjugated diene polymer provided by the present invention comprises hydrogenated styrene structural units. The aromatic ring structure, the side groups attached to the aromatic rings, and the hydrogen bonds provide high thermal stability. Furthermore, the polymer comprises hydrogenated farnesene or hydrogenated myrcene structural units, which have relatively long carbon chains, improving the flexibility of the molecular chain and the heat resistance of the polymer. Consequently, the hydrogenated and cross-linked polymer exhibits excellent heat resistance and low compression set. Furthermore, the cross-linking degree of the polymer can be controlled during application by controlling the content of hydrogenated styrene structural units I and the cross-linking agent, thereby enhancing the adjustability of the polymer during application.

[0017] As a preferred solution, based on the total amount of the copolymer, the content of the structural unit I is 15-25 wt%; and the content of the z1+z2 is 10-20 wt%.

[0018] As a preferred solution, the hydrogenated aromatic conjugated diene polymer further comprises hydrogenated butadiene structural unit II and / or hydrogenated isoprene structural unit III;

[0019] The structural unit II is

[0020] The structural unit III is

[0021] Based on the total amount of structural unit II, structural unit III and structural unit IV, the content of x1+x2 is 0-70wt%, wherein the structural unit corresponding to x2 accounts for 8-40% of the content of x1+x2; the content of y1+y2 is 0-40wt%, wherein the content of the structural unit corresponding to y2 is 7-30%.

[0022] In the present invention, the thermal stability and flexibility of the polymer can be further increased by introducing long-chain carbon hydrogenated butadiene structural unit II and / or hydrogenated isoprene structural unit III. At the same time, by controlling the content of structural unit II, structural unit III and structural unit IV, the molecular weight of the polymer and the mechanical properties of the resulting film can be comprehensively controlled.

[0023] As a preferred solution, based on the total amount of structural unit II, structural unit III and structural unit IV, the content of x1+x2 is 30-50 wt%; the content of y1+y2 is 20-35 wt%.

[0024] As a preferred embodiment, the molecular weight of the hydrogenated aromatic conjugated diene polymer is 50,000 to 200,000, more preferably 80,000 to 150,000.

[0025] As a preferred solution, the hydrogenation degree of the hydrogenated aromatic conjugated diene polymer is 95-100%. The polymer of the present invention has a high hydrogenation degree because the presence of unsaturated bonds affects the heat resistance, weather resistance and aging resistance of the polymer, and is more preferably 98-100%.

[0026] The present invention also provides a method for preparing a hydrogenated aromatic conjugated diene polymer capable of controllable crosslinking, which comprises dropwise adding a mixed monomer comprising a hydrogenated styrene structural unit I and a hydrogenated farnesene or hydrogenated myrcene structural unit IV into an anionic polymerization reaction solution system comprising a regulator and an initiator to carry out a polymerization reaction to obtain an aromatic conjugated diene random copolymer; and the aromatic conjugated diene random copolymer is subjected to a hydrogenation reaction under the catalysis of a nickel-based catalyst to obtain the obtained product.

[0027] As a preferred solution, the polymerization reaction is terminated by adding a terminator. The terminator used in the present invention is at least one of 2,4,6-tri-tert-butylphenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine.

[0028] The present invention uses cyclohexane as a polymerization reaction solvent to provide an environment for the polymerization reaction. By varying the amounts of monomers and initiators and the polymerization reaction conditions, the structural unit type and the molecular weight of the polymer can be controlled, thereby controlling the performance of the final product. The regulator of the present invention can adjust the microstructure of the polymer, thereby affecting the polymer performance. The amount of the regulator used relative to the amount of the solvent is 30 to 100 mg / kg.

[0029] As a preferred solution, the mixed monomer accounts for 5 to 15 wt % in the polymerization solvent.

[0030] As a preferred solution, the polymerization reaction conditions are: temperature of 60-70° C., pressure of 0.1-0.5 MPa, and time of 30-40 min.

[0031] As a preferred solution, the conditions for the hydrogenation reaction are: temperature of 80-90°C, pressure of 1.6-1.8 MPa, and reaction time of 2-3 h.

[0032] As a preferred embodiment, the initiator is n-butyl lithium; the modifier is at least one of ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol ethyl ether, and 1,2-dimethoxypropane. The amount of initiator used is determined by the desired molecular weight; a higher amount of initiator results in a lower molecular weight of the polymer. The amount of initiator used relative to the amount of solvent is 0.5 to 2 mmol / L.

[0033] The present invention also provides a vulcanized rubber sheet comprising the following raw materials in parts by mass: 90 to 110 parts of hydrogenated aromatic conjugated diene polymer, 20 to 50 parts of carbon black, 20 to 80 parts of calcium carbonate, 10 to 40 parts of paraffin oil, 0 to 3 parts of polyethylene glycol, 1 to 5 parts of stearic acid, 3 to 8 parts of zinc oxide, 1 to 3 parts of an antioxidant, and 1 to 2 parts of a vulcanizing agent.

[0034] The vulcanized rubber sheet of the present invention incorporates a hydrogenated aromatic conjugated diene polymer containing hydrogenated styrene structural units, which can improve the heat resistance, oxygen resistance, aging resistance, and weather resistance of the vulcanized rubber while reducing compression set. The aromatic ring structures and hydrogen bonds in the hydrogenated styrene structural units provide high thermal stability. The presence of these structural units in the vulcanized rubber can hinder the thermal motion of molecules and reduce intermolecular kinetic energy, thereby enhancing the heat resistance of the vulcanized rubber. The hydrogenated styrene structural units have good aggregation ability and can interact with the cross-linked structures in the raw materials during mixing and vulcanization. After the vulcanized rubber undergoes compression or deformation, the hydrogenated styrene structural units can provide strong elastic force, prompting the vulcanized rubber molecular chains to return to their original conformation and shape, thereby reducing the compression set of the vulcanized rubber. The hydrogenated aromatic conjugated diene polymer also comprises hydrogenated butadiene structural units and / or hydrogenated isoprene structural units, as well as hydrogenated farnesene / myrcene structural units. These structures have relatively long carbon chains, which further enhance the elasticity and flexibility of the vulcanized rubber. The presence of these structural units can increase the torsion and activity of the vulcanized rubber molecular chain, imparting excellent recovery ability to the vulcanized rubber after being subjected to stress. Due to the presence of these flexible chain segments, the vulcanized rubber can absorb external stress and restore its shape after the stress subsides, thereby alleviating the stress concentration effect of the vulcanized rubber, avoiding or reducing cracking and fatigue damage in the vulcanized rubber, and enhancing tensile properties and resistance to permanent compression set.

[0035] As a preferred solution, the carbon black is one of fast extrusion furnace black FEF, high wear-resistant furnace black HAF and white carbon black; the antioxidant is at least one of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 2,6-di-tert-butyl-4-methylphenol, 2,2-methylene-bis(4-methyl-6-tert-butylphenol) and 4,4-bis(2,2-dimethylbenzyl)diphenylamine.

[0036] As a preferred embodiment, the vulcanizing agent is one of dicumyl peroxide (DCP), dibenzoyl peroxide, di-tert-butyl peroxide, and 1,3-di-tert-butyl peroxide. The vulcanizing agents used in the present invention are all peroxides, which can cross-link the molecular chains with the side groups on the benzene rings of the polymer, thereby forming a polymer network structure.

[0037] The present invention also provides a method for preparing a vulcanized film, comprising mixing a hydrogenated aromatic conjugated diene polymer, carbon black, calcium carbonate, paraffin oil, polyethylene glycol, stearic acid, zinc oxide and an antioxidant, performing mixing and sheeting operations, and then adding a vulcanizing agent for vulcanization treatment.

[0038] Compared with the sulfur vulcanization process, the preparation method of the present invention has a relatively simple formula for the peroxide cross-linking process, and a higher cross-linking temperature can be used to improve the cross-linking efficiency. The rubber material after peroxide cross-linking has good resistance to compression deformation at high temperature, good heat resistance, good extraction resistance, no reversion phenomenon during the process, and basically no frosting problem on the surface of the product.

[0039] As a preferred solution, the mixing process is: mixing the hydrogenated aromatic conjugated diene polymer, carbon black, calcium carbonate, paraffin oil, polyethylene glycol and stearic acid, and mixing them at a temperature of 100-120° C. and a rotation speed of 50-90 rpm for 3-5 minutes, then adding zinc oxide and an antioxidant and mixing them at a temperature of 120-140° C. and a rotation speed of 50-90 rpm for 4-6 minutes.

[0040] As a preferred solution, the conditions for the sheet unloading operation are: a roller distance of 0.6 to 0.9 mm, and a standing time of 4 to 6 hours.

[0041] As a preferred solution, the conditions for the vulcanization treatment are: temperature of 160-180° C., pressure of 8-12 MPa, and time of 8-10 min.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] The present invention provides a hydrogenated aromatic conjugated diene polymer, which is applied to the preparation of vulcanized rubber. Due to the specific structural units contained in the polymer structure, the vulcanized rubber prepared has excellent heat resistance, aging resistance and good mechanical strength. The enhanced performance of the vulcanized rubber is mainly due to the addition of the hydrogenated aromatic conjugated diene polymer. The hydrogenated styrene structural units and hydrogenated farnesene or myrcene structural units in the polymer increase the flexibility and elasticity of the molecular chain, thereby greatly improving the durability of the vulcanized rubber. At the same time, the weather resistance and chemical resistance of the vulcanized rubber are also enhanced, making it better able to adapt to complex and changing application environments. In addition, the optimized cross-linked network ensures that the vulcanized rubber can effectively return to its original state after compression or stretching, showing a small compression set. These characteristics give the vulcanized rubber a wide range of application prospects in the fields of automotive door and window sealing strips, building waterproof sheets, wires and cables, medical sealing materials, and high-demand industrial components. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The aromatic conjugated diene copolymer in Example 1 1 H NMR spectrum.

[0045] Figure 2 is the hydrogenated aromatic conjugated diene polymer in Example 1 1 H NMR spectrum.

[0046] Figure 3 This is the GPC chart of the hydrogenated aromatic conjugated diene polymer in Example 1. Peak 1 in the chart represents macromolecular impurities generated by partial molecular chain coupling due to incomplete polymerization termination before hydrogenation of the aromatic conjugated diene polymer. Peak 2 corresponds to the molecular weight of the hydrogenated aromatic conjugated diene polymer.

[0047] Figure 4 This is the vulcanization curve of the cross-linked hydrogenated aromatic conjugated diene polymer in Example 1. DETAILED DESCRIPTION

[0048] The present invention is further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments. Obviously, the embodiments described below are only a part of the embodiments, and all other embodiments obtained by professionals in this field without making creative efforts are still within the scope of protection of the present invention.

[0049] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0050] Example 1

[0051] 1) Synthesis of hydrogenated aromatic conjugated diene polymers

[0052] 2500 mL of cyclohexane was added to a polymerization kettle replaced with dry nitrogen, and stirring was started. The temperature in the polymerization kettle was maintained at 65° C. and the pressure was 0.3 MPa. Ditetrahydrofurfuryl propane (configured into a 0.5 mol / L cyclohexane solution, the amount was equivalent to 80 mg / kg solvent) and n-butyl lithium (concentration was 0.21 mol / L, the amount was equivalent to 2.5 mmol), and then a mixed monomer of 50 g of p-methylstyrene, 112.5 g of butadiene, 50 g of isoprene and 37.5 g of farnesene was slowly added. The addition time was 30 min. After the addition was completed, the reaction was carried out for 40 min. Finally, a terminator 2,4,6-tri-tert-butylphenol (configured into a 10 g / 100 mL cyclohexane solution, the amount was equivalent to 0.66 g) was added to obtain an aromatic conjugated diene copolymer glue.

[0053] After the polymerization reaction is completed, the rubber liquid is transferred to the matching hydrogenation kettle by pressure difference. The temperature of the hydrogenation kettle is controlled at 85°C, and the main hydrogenation catalyst (nickel isooctanoate / triisobutylaluminum) is added in an amount equivalent to 9 mmol / kg of dry rubber). Then hydrogen is introduced for replacement twice, and the hydrogen pressure is maintained at 1.7 MPa for hydrogenation reaction. The reaction time is 2h. The co-catalyst (isooctanol) is added 3 times in the middle, each time with an amount of 2 mL. Finally, the rubber liquid is condensed by water vapor to remove the solvent and then dried to obtain the hydrogenated aromatic conjugated diene polymer.

[0054] 2) Preparation of vulcanized rubber

[0055] Take 100 parts of hydrogenated aromatic conjugated diene polymer, 50 parts of carbon black, 40 parts of calcium carbonate, 40 parts of paraffin oil, 1 part of polyethylene glycol, and 2 parts of stearic acid, add them into an internal mixer in sequence, mix at 110°C and 70 rpm for 3 minutes, then set the roller spacing on the open mixer to 0.8 mm, put the sheet down, and let it stand for 4 hours.

[0056] The above-mentioned mixed rubber, 5 parts of zinc oxide and 2 parts of antioxidant were added to the internal mixer in sequence, mixed at 130°C and 70 rpm for 5 minutes, and then the roller distance on the open mixer was set to 0.8 mm, the sheet was removed and allowed to stand for 2 hours.

[0057] The temperature of the open mill is 140℃, the roller gap is set to 0.5mm, and the obtained mixed rubber is added to form a smooth and gapless roller rubber. Then 1.5 parts of dicumyl peroxide DCP are added, and the roller gap is adjusted to 0.2mm. Triangle wrap is made 6 times, thin pass is made 10 times, and finally the roller gap is adjusted to 1mm and the sheet is unrolled.

[0058] The final mixed rubber sheet was placed in a preheated mold and vulcanized on a flat vulcanizer at 170°C, with a pressure of 10 MPa and a time of 8 minutes to obtain a vulcanized rubber sheet.

[0059] Example 2

[0060] The method of Example 1 was followed, except that the amount of n-butyl lithium used in this example was 3.1 mmol.

[0061] Example 3

[0062] The method of Example 1 was followed, except that the amount of n-butyl lithium used in this example was 1.7 mmol.

[0063] Example 4

[0064] According to the method of Example 1, the difference is that the consumption of ditetrahydrofurfuryl propane in this embodiment is equivalent to 50 mg / kg solvent.

[0065] Example 5

[0066] The method according to Example 1 was carried out except that the amount of ditetrahydrofurfuryl propane used in the present embodiment was equivalent to 100 mg / kg solvent.

[0067] Example 6

[0068] The method of Example 1 was followed, except that the composition of the mixed monomers in this example was 37.5 g of p-methylstyrene, 125 g of butadiene, 50 g of isoprene and 37.5 g of farnesene.

[0069] Example 7

[0070] The method of Example 1 was followed, except that the composition of the mixed monomers in this example was 62.5 g of p-methylstyrene, 100 g of butadiene, 50 g of isoprene and 37.5 g of farnesene.

[0071] Comparative Example 1

[0072] The method of Example 1 was followed, except that the composition of the mixed monomers in this comparative example was 12.5 g of p-methylstyrene, 112.5 g of butadiene, 87.5 g of isoprene and 37.5 g of farnesene.

[0073] The results show that when the content of p-methylstyrene in the polymer is reduced, that is, the content of structural unit I is reduced, the degree of crosslinking between the polymer and the crosslinker is reduced, resulting in a significant decrease in the tensile strength and hardness of the prepared vulcanized film, and a decrease in the compression permanent set performance.

[0074] Comparative Example 2

[0075] The method of Example 1 was followed, except that the composition of the mixed monomers in this comparative example was 50 g of p-methylstyrene, 112.5 g of butadiene, 87.5 g of isoprene and 0 g of farnesene.

[0076] The results show that when the farnesene monomer is not added to the polymer, that is, when the structural unit IV is not included, the flexibility of the molecular chain is reduced, resulting in a significant decrease in the elongation at break of the prepared vulcanized film.

[0077] The microstructure and composition of the polymers obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were characterized, wherein the microstructure was characterized by nuclear magnetic resonance spectroscopy (NMR), the molecular weight was tested by gel permeation chromatography (GPC), and the degree of hydrogenation was determined by NMR or iodine titration.

[0078] The vulcanized rubber sheets obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were tested for tensile properties, hardness, and compression set, respectively. The tensile properties were measured in accordance with GB / T528-2009, the hardness was measured in accordance with GB / T531.1-2008, and the compression set was measured in accordance with GB / T7759-1996 at 70° C. for 22 h and a strain rate of 25%.

[0079] Table 1 Structure and composition of hydrogenated aromatic conjugated diene polymers obtained in Examples 1 to 7 and Comparative Examples 1 to 2

[0080]

[0081] Note: In the table, p-MS / Bu / Ip / Fa represent the contents of hydrogenated styrene structural unit I, hydrogenated butadiene structural unit II, hydrogenated isoprene structural unit III and hydrogenated farnesene structural unit IV, respectively, based on the total amount of the copolymer; x2 / y2 / z2 represent the contents of x2, y2 and z2 in the corresponding structural units, respectively.

[0082] Table 2 Test results of properties of vulcanized sheets obtained in Examples 1 to 7 and Comparative Examples 1 to 2

[0083]

[0084]

Claims

1. A controllably crosslinkable hydrogenated aromatic conjugated diene polymer, characterized in that: Comprising a hydrogenated styrene structural unit I and a hydrogenated farnesene or hydrogenated myrcene structural unit IV; The structural unit I is One of the following; The structural unit IV is Wherein, R is one of methyl, ethyl, tert-butyl, and isobutyl; When R1 is -CH3, R2 is R1 is When R2 is H; Based on the total amount of the copolymer, the content of structural unit I is 10 to 40 wt%; The content of z1+z2 is 10-30 wt%, wherein the content of the structural unit corresponding to z2 is 5-20%.

2. The controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 1, wherein: Based on the total amount of the copolymer, the content of the structural unit I is 15-25 wt%; the content of the z1+z2 is 10-20 wt%.

3. The controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 1 or 2, characterized in that: Also includes hydrogenated butadiene structural unit II and / or hydrogenated isoprene structural unit III; The structural unit II is The structural unit III is Based on the total amount of structural unit II, structural unit III and structural unit IV, the content of x1+x2 is 0-70wt%, wherein the structural unit corresponding to x2 accounts for 8-40% of the content of x1+x2; the content of y1+y2 is 0-40wt%, wherein the content of the structural unit corresponding to y2 is 7-30%.

4. The controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 3, wherein: Based on the total amount of structural unit II, structural unit III and structural unit IV, the content of x1+x2 is 30-50 wt%; the content of y1+y2 is 20-35 wt%.

5. The controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 4, wherein: The molecular weight of the hydrogenated aromatic conjugated diene polymer is 50,000 to 200,000.

6. The controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 5, wherein: The hydrogenation degree of the hydrogenated aromatic conjugated diene polymer is 95-100%.

7. The method for preparing a controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to any one of claims 1 to 6, characterized in that: A mixed monomer comprising hydrogenated styrene structural unit I and hydrogenated farnesene or hydrogenated myrcene structural unit IV is added dropwise to an anionic polymerization reaction solution system comprising a regulator and an initiator to carry out a polymerization reaction to obtain an aromatic conjugated diene random copolymer; and the aromatic conjugated diene random copolymer is subjected to a hydrogenation reaction under the catalysis of a nickel-based catalyst to obtain the obtained product.

8. The method for preparing a controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 7, wherein: The polymerization reaction conditions are: temperature of 60-70° C., pressure of 0.1-0.5 MPa, and reaction time of 30-40 min; the hydrogenation reaction conditions are: temperature of 80-90° C., pressure of 1.6-1.8 MPa, and reaction time of 2-3 h.

9. The method for preparing a controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 7, wherein: The initiator is n-butyl lithium; The regulator is at least one of ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol ethyl ether and 1,2-dimethoxypropane.

10. A vulcanized film, characterized in that: The invention comprises the following raw materials in parts by mass: 90 to 110 parts of the hydrogenated aromatic conjugated diene polymer according to any one of claims 1 to 6, 20 to 50 parts of carbon black, 20 to 80 parts of calcium carbonate, 10 to 40 parts of paraffin oil, 0 to 3 parts of polyethylene glycol, 1 to 5 parts of stearic acid, 3 to 8 parts of zinc oxide, 1 to 3 parts of an antioxidant, and 1 to 2 parts of a vulcanizing agent.

11. A vulcanized rubber sheet according to claim 10, characterized in that: The carbon black is one of fast extrusion furnace black FEF, high wear resistant furnace black HAF and white carbon black; The antioxidant is at least one of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 2,6-di-tert-butyl-4-methylphenol, 2,2-methylene-bis(4-methyl-6-tert-butylphenol) and 4,4-bis(2,2-dimethylbenzyl)diphenylamine; The vulcanizing agent is one of dicumyl peroxide DCP, dibenzoyl peroxide, di-tert-butyl peroxide and 1,3-di-tert-butyl peroxide.

12. The method for preparing a vulcanized rubber sheet according to claim 10 or 11, characterized in that: The hydrogenated aromatic conjugated diene polymer, carbon black, calcium carbonate, paraffin oil, polyethylene glycol, stearic acid, zinc oxide and an antioxidant are mixed and kneaded, and then a vulcanizing agent is added to carry out vulcanization treatment.

13. The use of a controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 10, characterized in that: The mixing process comprises: mixing a hydrogenated aromatic conjugated diene polymer, carbon black, calcium carbonate, paraffin oil, polyethylene glycol and stearic acid, and then mixing the mixture for 3 to 5 minutes at a temperature of 100 to 120° C. and a rotation speed of 50 to 90 rpm; then adding zinc oxide and an antioxidant, and mixing the mixture for 4 to 6 minutes at a temperature of 120 to 140° C. and a rotation speed of 50 to 90 rpm.

14. The use of a controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 13, characterized in that: The conditions for the sheet unloading operation are: a roller distance of 0.6 to 0.9 mm and a standing time of 4 to 6 hours.

15. The use of a controllably cross-linkable hydrogenated aromatic conjugated diene polymer according to claim 13, characterized in that: The conditions of the vulcanization treatment are: temperature of 160-180° C., pressure of 8-12 MPa, and time of 8-10 minutes.

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