Application of perhydrogenated cyclic olefin polymer and solid tire rubber material

Abstract

The invention discloses application of a perhydrogenated cyclic olefin polymer and a solid tire rubber material. Wherein the fully-hydrogenated cyclic olefin polymer comprises a hydrogenated aromatic ethylene block and a hydrogenated conjugated diene block, and the solid tire rubber material comprises the following components in parts by mass: 35-60 parts of the fully-hydrogenated cyclic olefin polymer; 15 to 25 parts of polypropylene; 10 to 20 parts of polyethylene; 1-5 parts of a wear-resistant agent; 0.1 to 1 part of an antioxidant; and 0.05 to 0.5 part of an anti-ultraviolet absorbent. The solid tire rubber material adopting the fully-hydrogenated cyclic olefin polymer is good in processing fluidity and excellent in thermo-oxidative aging resistance, and a prepared solid tire has excellent wear resistance, good rebound resilience, high weather resistance, explosion-proof performance and puncture-proof performance; and the performance requirements of manufacturing artificial intelligence equipment tires such as meal delivery robots and remote control cars can be met.

Description

Technical Field

[0001] This invention relates to the application of a fully hydrogenated cyclic olefin polymer, specifically to its application in solid tire compounds, and also to solid tire compounds, belonging to the field of novel functional polymer material development. Background Technology

[0002] With the rapid development of technology, artificial intelligence has entered people's lives, affecting all aspects of daily life, including clothing, food, housing, and transportation. Examples include fun and technologically advanced food delivery robots and remote-controlled shopping carts with real-time conversational capabilities. Tires, as a crucial component, play a vital role in supporting the entire weight of the vehicle, transmitting traction and braking torque, ensuring traction between the wheels and the road surface, and reducing and absorbing vibrations and impacts during operation, thus ensuring driving safety, handling stability, comfort, and energy efficiency. Solid tires, with their solid carcass, do not require an inner tube or airtight layer and are commonly used in low-speed, high-load vehicles or machinery. Solid tires are generally used under high loads, requiring the rubber compound to have sufficiently high tensile stress, high hardness, low permanent deformation, and good wear and scratch resistance. However, existing solid tires have poor wear resistance and scratch resistance, which not only reduces their lifespan but also their performance, increasing the risk of accidents.

[0003] Currently, solid tire materials fall into two main categories: polyurethane elastomers and hydrogenated styrene elastomers. Patents for polyurethane elastomers used in tires include CN104693401A, CN105330811A, and CN104497252A. These elastomers exhibit high tear strength and load-bearing capacity. However, their processing is complex, requiring numerous additives, and they suffer from drawbacks such as easy hardening and loss of elasticity, poor heat dissipation, high rolling resistance, softening at high temperatures, susceptibility to tire slippage, poor scratch resistance, and poor wear resistance. On the other hand, patents for hydrogenated styrene elastomers used in tires include CN108997701B, CN109810454A, and CN109503913A. These elastomers offer good resilience, can be directly molded, have a simple process, and are recyclable. However, they are heavy, costly, prone to bursting, prone to deformation, have poor elasticity and fatigue resistance, high rolling resistance, poor weather resistance and wear resistance, and rapid aging.

[0004] Therefore, developing a solid tire material with high tear strength, good wear resistance, good resilience, and better explosion-proof and puncture-proof properties to improve tire safety performance is of great significance. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the first objective of this invention is to provide an application of a fully hydrogenated cyclic olefin polymer. This fully hydrogenated cyclic olefin polymer, when used in the preparation of solid tire compounds, can improve the processing fluidity and heat and oxygen aging resistance of the compounds.

[0006] The second objective of this invention is to provide a solid tire compound. This tire compound exhibits high strength, good toughness, heat aging resistance, and excellent processing flow properties. Furthermore, this tire compound can be used to manufacture solid tires through various molding processes such as extrusion, injection molding, and blow molding. The resulting solid tires possess excellent wear resistance, good resilience, high weather resistance, and puncture and explosion-proof properties.

[0007] To achieve the above-mentioned technical objectives, this invention provides an application of a fully hydrogenated cyclic olefin polymer for preparing solid tire compounds; wherein the fully hydrogenated cyclic olefin polymer comprises hydrogenated aromatic ethylene blocks and hydrogenated conjugated diene blocks, the hydrogenated aromatic ethylene blocks comprising hydrogenated aromatic ethylene structural units as shown in Formula 1, and the hydrogenated conjugated diene blocks comprising hydrogenated conjugated diene structural unit I as shown in Formula 2 and hydrogenated conjugated diene structural unit II as shown in Formula 3.

[0008]

[0009] Among them, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are all H or C1-C3 alkyl groups, R 10 R 11 R 12 R 13 and R 14 All are H or C1-C4 alkyl groups.

[0010] The fully hydrogenated cyclic olefin polymer of this invention exhibits the good resilience of rubber at room temperature and the high fluidity of resin at high temperatures, with very few unsaturated double bonds. Compared to conventional SEBS, its heat resistance and aging resistance are significantly improved. While improving the compatibility of elastomers with plastics and inorganic fillers and the processing performance of blends, it can reduce dynamic internal friction, increase the service temperature of blends, and also has good resilience and strength. Therefore, its use in the preparation of solid tire compounds can greatly improve the toughness, strength, and wear resistance of tire compounds.

[0011] As a preferred embodiment, in the fully hydrogenated cyclic olefin polymer, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, R9 is H or methyl, and R... 10 R 11 R 13 and R 14 All of them are one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0012] As a preferred embodiment, in the fully hydrogenated cyclic olefin polymer, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, R9 is H or methyl, and R... 10 R 11 R 13 and R 14 Both are H, R 12 It is a C1-C4 alkyl group.

[0013] As a preferred embodiment, the mass content of the hydrogenated aromatic ethylene block is 15-55%, and the mass content of the hydrogenated conjugated diene block is 45-85%.

[0014] As a preferred embodiment, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 in the hydrogenated conjugated diene block is 8-60%, more preferably 10-50%, and most preferably 12-45%.

[0015] As a preferred embodiment, the degree of hydrogenation of the fully hydrogenated cyclic olefin polymer is 85-100%, more preferably 95-100%.

[0016] As a preferred embodiment, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 40,000 to 250,000.

[0017] As a preferred embodiment, the fully hydrogenated cyclic olefin polymer has a tensile strength of 8–45 MPa, a hardness (Shore A) of 70–85, and a melt flow index (MFR) of 0.1–10 g / 10 min (230 °C, 5 kg).

[0018] As a preferred embodiment, the preparation process of the fully hydrogenated cyclic olefin polymer is as follows: mixing aromatic ethylene monomer, conjugated diene monomer, solvent, initiator and activator for polymerization reaction, adding a terminator after the reaction is completed to obtain a polymer base solution, and then subjecting the polymer base solution to a hydrogenation reaction to obtain the fully hydrogenated cyclic olefin polymer.

[0019] As a preferred embodiment, the initiator is a C1-C4 alkyllithium.

[0020] As a preferred embodiment, the activator includes at least one of tetrahydrofuran, diethyl ether, anisole, tetrahydrofurfural ethyl ether, bis(tetrahydrofurfural)propane, triethylamine, tetramethylethylenediamine, and N-methylmorpholine.

[0021] As a preferred embodiment, the terminator includes at least one of alcohol terminators, phenol terminators, and silane terminators.

[0022] As a preferred embodiment, the mass percentage of the aromatic ethylene monomer and the conjugated diene monomer is 15%–55%: 45%–85%.

[0023] As a preferred embodiment, the total concentration of the aromatic ethylene monomer and the conjugated diene monomer in the polymerization reaction system is 3-15 wt%, more preferably 5-10 wt%.

[0024] As a preferred embodiment, the amount of initiator added relative to the solvent is 0.5 to 5 mmol / kg.

[0025] As a preferred embodiment, the amount of activator added relative to the solvent is 30-200 mg / kg, more preferably 40-180 mg / kg.

[0026] As a preferred embodiment, the molar amount of the terminator is 1.0 to 1.5 times that of the initiator.

[0027] As a preferred embodiment, the hydrogenation reaction uses a heterogeneous supported metal catalyst, wherein the metal includes at least one selected from platinum, palladium, rhodium, ruthenium, iron, nickel, cobalt, and other Group VIII metals. More preferably, the metal includes at least one selected from nickel, cobalt, and ruthenium.

[0028] As a preferred embodiment, the catalyst support includes at least one of silica, alumina, diatomaceous earth, silica gel, and activated carbon, and is more preferably silica and / or alumina.

[0029] As a preferred embodiment, the particle size of the catalyst is 5–50 μm, more preferably 10–20 μm.

[0030] As a preferred embodiment, the amount of catalyst added is 0.01 to 10% of the dry mass of the polymer base adhesive, more preferably 0.05 to 5%.

[0031] As a preferred embodiment, the conditions for the hydrogenation reaction are: temperature of 80–250°C, more preferably 150–230°C; pressure of 2–8 MPa, 4–7 MPa; and time of 0.5–20 h, more preferably 0.5–6 h.

[0032] As a preferred embodiment, the raw materials used in the preparation of solid tire compound include the following components by weight:

[0033] 35-60 parts of the above-mentioned fully hydrogenated cyclic olefin polymer;

[0034] 15-25 parts of polypropylene;

[0035] 10-20 parts of polyethylene;

[0036] 1-5 parts of wear-resistant agent;

[0037] Antioxidant 0.1 to 1 part;

[0038] 0.05–0.5 parts of UV absorber;

[0039] The raw materials are mixed and then melt-granulated to obtain solid tire rubber compound.

[0040] As a preferred embodiment, the polypropylene is homopolymer polypropylene and / or copolymer polypropylene.

[0041] As a preferred embodiment, the density of the polyethylene is 0.912–0.935 g / cm³. 3 .

[0042] As a preferred embodiment, the wear-resistant agent includes at least one of silicates, titanates, and silicones.

[0043] As a preferred embodiment, the antioxidant comprises at least one of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, tris(2,4-di-tert-butylphenyl)phosphite, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0044] As a preferred embodiment, the UV absorber includes at least one of 2-hydroxy-4-n-octyloxybenzophenone, (2-hydroxy-4-methoxyphenyl)phenyl ketone, and n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0045] As a preferred embodiment, the conditions for melt granulation are: the main screw speed is 40-50 r / s, the feeding screw speed is 30-40 r / s, and the extrusion temperature is 180-255℃.

[0046] The present invention also provides a solid tire compound, which comprises the following components in parts by weight:

[0047] 35–60 parts of fully hydrogenated cyclic olefin polymer;

[0048] 15-25 parts of polypropylene;

[0049] 10-20 parts of polyethylene;

[0050] 1-5 parts of wear-resistant agent;

[0051] Antioxidant 0.1 to 1 part;

[0052] 0.05 to 0.5 parts of UV absorber.

[0053] The fully hydrogenated cyclic olefin polymer mentioned above refers to the fully hydrogenated cyclic olefin polymer involved in the aforementioned scheme (including the preferred scheme).

[0054] This invention requires controlling the components of the solid tire compound within specific ranges to ensure the material's superior performance. Specifically, excessively low levels of fully hydrogenated cyclic olefin polymers significantly reduce the tear strength and elongation of the tire compound, while excessively high levels of fully hydrogenated cyclic olefin polymers, resulting in relatively low polyolefin resin content, decrease the compound's abrasion resistance. Solid tires prepared using this compound exhibit excellent abrasion resistance, good resilience, high weather resistance, and puncture and explosion-proof properties.

[0055] As a preferred embodiment, the polypropylene is homopolymer polypropylene and / or copolymer polypropylene. The melt index of the polypropylene is 8-12 g / 10 min (test conditions: 200℃, 2.16 kg yards).

[0056] As a preferred embodiment, the density of the polyethylene is 0.912–0.935 g / cm³. 3 The melt index of the polyethylene is 6–50 g / 10 min at 190°C and a load of 2.16 kg.

[0057] As a preferred embodiment, the wear-resistant agent includes at least one of silicates, titanates, and silicones.

[0058] As a preferred embodiment, the antioxidant comprises at least one of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (antioxidant 1076), tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010).

[0059] As a preferred embodiment, the UV absorber includes at least one selected from 2-hydroxy-4-n-octyloxybenzophenone (UV531), (2-hydroxy-4-methoxyphenyl)phenyl ketone (UV9), and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate (UV2908). A further preferred UV absorber is UV531.

[0060] The preparation process of a solid tire compound according to the present invention is as follows: after mixing a fully hydrogenated cyclic olefin polymer, polypropylene, polyethylene, abrasion resistant agent, antioxidant and UV resistant agent, the mixture is melt-granulated to obtain the final product.

[0061] As a preferred embodiment, the conditions for melt granulation are: the main screw speed is 40-50 r / s, the feeding screw speed is 30-40 r / s, and the extrusion temperature is 180-255℃.

[0062] As a preferred embodiment, the extrusion temperature is 185±5℃ for the first stage, 190±5℃ for the second stage, 205±5℃ for the third stage, 225±5℃ for the fourth stage, 245±5℃ for the fifth stage, 255±5℃ for the sixth stage, 220±5℃ for the die head, and 240±5℃ for the melt temperature.

[0063] The solid tire compound of this invention can be used to manufacture solid tires for food delivery robots, remote-controlled cars, electric vehicles, and small rickshaws. The solid tire compound can be injection molded to obtain robot tires.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] (1) Using fully hydrogenated cyclic olefin polymers as the base material for solid tires, since fully hydrogenated cyclic olefin polymers have very few unsaturated double bonds, the strength, toughness, heat aging resistance and processing fluidity of the tire compound are greatly improved.

[0066] (2) By using a specific ratio of raw materials, the wear resistance, resilience, weather resistance, explosion-proof and puncture-proof properties of solid tire rubber are improved, resulting in excellent performance and good appearance of the tire rubber, which can meet the performance requirements of tires for artificial intelligence equipment such as food delivery robots and remote control vehicles.

[0067] (3) The preparation method is simple, and it can be directly processed and shaped without vulcanization. Its scraps can be recycled and waste materials can be reused. It is environmentally friendly and low-cost, and suitable for industrial production. Attached Figure Description

[0068] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0069] Figure 1 The image shows the 1H NMR spectrum of the fully hydrogenated cyclic olefin polymer obtained in Example 1 of this invention. Detailed Implementation

[0070] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0071] In the synthesis of the fully hydrogenated cyclic olefin polymer of this invention, the catalyst ruthenium / alumina product model 11103-72-3 was purchased from Nanxing Chemical (Jiangsu) Co., Ltd.

[0072] The polypropylene product used in this invention is PP K7760, which was purchased from Sinopec Yanshan Petrochemical Company.

[0073] The polyethylene product used in this invention is LDPE2420H, which was purchased from Nanjing Yangzi BASF Co., Ltd.

[0074] The wear-resistant agent used in this invention is silicone MB50-002, which was purchased from Dow Corning Incorporated, USA.

[0075] The antioxidant 1010 and UV absorber UV-531 used in this invention were both purchased from BASF.

[0076] In this invention, the content of styrene structural units, vinyl content, and degree of hydrogenation can all be determined by nuclear magnetic resonance (NMR) spectroscopy (H NMR). 1 The H-NMR method was calculated using the formula described in Synthetic Rubber Industry, 2012-09-15, 53(5): 332-335.

[0077] Unless otherwise stated, all molecular weights are number-average molecular weights determined by gel permeation chromatography (GPC). Polymer tensile strength and hardness (Shore A) were measured according to GB / T 528-2009, and melt flow index (MFR) was measured according to GB / T 3682-2018. Tear strength of the special material was determined using an INSTRON 5565 tensile testing machine. Abrasion of the special material was determined using a Gibitre DIN roller abrasion tester.

[0078] Example 1

[0079] Step 1: Synthesis of fully hydrogenated cyclic olefin polymers

[0080] In a 5-liter polymerization reactor purged with high-purity nitrogen, 3000 mL of pure cyclohexane and bis(tetrahydrofurfuryl) propane (equivalent to 40 mg / kg solvent) were added. Stirring was initiated, and the temperature was raised to 60°C. In the first stage, 45 g of styrene monomer and 1.5 mmol of n-butyllithium were added, and the polymerization reaction was allowed to proceed for 40 minutes. In the second stage, 210 g of butadiene monomer was added, and the reaction temperature was controlled below 80°C using a jacketed water-cooling system. After reacting for 30 minutes, 45 g of styrene monomer was added, and the reaction was allowed to proceed at 65°C for 40 minutes. 1.5 mmol of methanol was added as a terminator to terminate the active chain segment. The pressure inside the reactor was maintained at 0.5 MPa throughout the polymerization process. After the polymerization reaction was complete, the polymer solution was introduced into a 5-liter hydrogenation reactor, and 3 g of supported ruthenium catalyst was added. The temperature was raised to 230°C, and hydrogen gas was introduced. The hydrogenation pressure was controlled at 5.5 MPa, and the hydrogenation reaction was allowed to proceed for two hours. The hydrogenated polymer solution was then collected, centrifuged, and dried to obtain a fully hydrogenated cyclic olefin polymer.

[0081] The number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 180,000, the mass content of the aromatic ethylene block is 30%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 in the hydrogenated conjugated diene block is 35.2%, and the degree of hydrogenation of the polymer aromatic ring is 99.5%.

[0082] Step 2: Mix the components evenly in a high-speed mixer according to the formula in Table 1, and then extrude and granulate them on a twin-screw extruder. The process parameters are shown in Table 2.

[0083] Table 1. Solid Tire Rubber Compound Formulation (Unit: g)

[0084]

[0085] Table 2 Extrusion process parameters

[0086] interval 1 section 2 segments 3 segments 4 segments 5 segments 6 segments machine head melt temperature 180 190 205 225 245 255 220 240

[0087] Example 2

[0088] The polymer was synthesized according to the method of Example 1, except that the monomer mass ratio of the polymer styrene / butadiene was 15 / 85.

[0089] The specific steps are as follows: 3000 mL of pure cyclohexane and bis(tetrahydrofurfuryl) propane (equivalent to 40 mg / kg solvent) were added to a 5 L polymerization reactor purged with high-purity nitrogen. Stirring was started, and the temperature was raised to 60 °C. In the first stage, 22.5 g of styrene monomer and 1.5 mmol of n-butyllithium were added, and the polymerization reaction was allowed to proceed for 40 minutes. In the second stage, 255 g of butadiene monomer was added, and the reaction temperature was controlled below 80 °C using a jacketed water-cooling system. After reacting for 30 minutes, 22.5 g of styrene monomer was added, and the reaction was allowed to proceed for another 40 minutes at 60 °C. The polymerization was terminated by adding 1.5 mmol of methanol as a terminator. Throughout the polymerization process, the pressure inside the reactor was maintained at 0.2 MPa. After the polymerization reaction was completed, the polymer solution was introduced into a 5 L hydrogenation reactor, and 3 g of supported ruthenium catalyst was added. The temperature was raised to 230 °C, and hydrogen gas was introduced. The hydrogenation pressure was controlled at 5.0 MPa, and the hydrogenation reaction was allowed to proceed for two hours. The hydrogenated polymer solution was then collected, centrifuged, and dried to obtain a fully hydrogenated cyclic olefin polymer.

[0090] In this embodiment, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 182,000, the mass content of the aromatic ethylene block is 15%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 36%, and the degree of hydrogenation of the polymer aromatic ring is 99.6%.

[0091] Example 3

[0092] The polymer was synthesized according to the method of Example 1, except that the monomer mass ratio of the polymer styrene / butadiene was 55 / 45.

[0093] The specific steps are as follows: 3000 mL of pure cyclohexane and bis(tetrahydrofurfuryl) propane (equivalent to 40 mg / kg solvent) were added to a 5 L polymerization reactor purged with high-purity nitrogen. Stirring was started, and the temperature was raised to 60 °C. In the first stage, 82.5 g of styrene monomer and 1.5 mmol of n-butyllithium were added, and the polymerization reaction was allowed to proceed for 40 minutes. In the second stage, 135 g of butadiene monomer was added, and the reaction temperature was controlled below 80 °C using a jacketed water-cooling system. After reacting for 30 minutes, 82.5 g of styrene monomer was added, and the reaction was allowed to proceed for another 40 minutes at 60 °C. The polymerization was terminated by adding 1.5 mmol of methanol as a terminator. Throughout the polymerization process, the pressure inside the reactor was maintained at 0.1 MPa. After the polymerization reaction was completed, the polymer solution was introduced into a 5 L hydrogenation reactor, and 3 g of supported ruthenium catalyst was added. The temperature was raised to 230 °C, and hydrogen gas was introduced. The hydrogenation pressure was controlled at 5.5 MPa, and the hydrogenation reaction was allowed to proceed for two hours. The hydrogenated polymer solution was then collected, centrifuged, and dried to obtain a fully hydrogenated cyclic olefin polymer.

[0094] In this embodiment, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 183,000, the mass content of the aromatic ethylene block is 55%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 34.5%, and the degree of hydrogenation of the polymer aromatic ring is 99.5%.

[0095] Example 4

[0096] The polymer was synthesized according to the method of Example 1, except that the amount of butyllithium added to the polymer was 1.0 mmol, and the number-average molecular weight of the obtained polymer was 241,000.

[0097] In this embodiment, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 241,000, the mass content of the aromatic ethylene block is 30%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 35.5%, and the degree of hydrogenation of the polymer aromatic ring is 99.7%.

[0098] Example 5

[0099] The polymer was synthesized according to the method of Example 1, except that the amount of butyllithium added to the polymer was 3.5 mmol, and the number-average molecular weight of the obtained polymer was 72,000.

[0100] In this embodiment, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 72,000, the mass content of the aromatic ethylene block is 30%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 35.6%, and the degree of hydrogenation of the polymer aromatic ring is 99.4%.

[0101] Example 6

[0102] The polymer was synthesized according to the method of Example 1, except that the amount of tetrahydrofuran in the polymer composite regulating system was 180 mg / kg and the amount of tetrahydrofurfural ethyl ether was 40 mg / kg. The obtained polymer had a vinyl content (hydrogenated conjugated diene structural unit II shown in Formula 3) of 45%.

[0103] The specific steps are as follows: In a 5-liter polymerization reactor purged with high-purity nitrogen, add 3000 mL of pure cyclohexane, the amount equivalent to 180 mg / kg of tetrahydrofuran solvent, and the amount equivalent to 40 mg / kg of tetrahydrofurfural ethyl ether solvent. Start stirring and heat to 60°C. Add 45 g of styrene monomer and 1.5 mmol of n-butyllithium in the first stage, and polymerize for 40 minutes. Add 210 g of butadiene monomer in the second stage, and control the reaction temperature below 80°C using a jacketed water cooling system. After reacting for 30 minutes, add 45 g of styrene monomer and react at 65°C for 40 minutes. Finally, add 1.5 mmol of methanol as a terminator to terminate the polymerization. Maintain the reactor pressure at 0.5 MPa throughout the entire polymerization process. After the polymerization is complete, introduce the polymer solution into a 5-liter hydrogenation reactor, add 3 g of supported ruthenium catalyst, heat to 230°C, and introduce hydrogen gas. Control the hydrogenation pressure at 5.5 MPa and hydrogenate for two hours. Collect the hydrogenated polymer solution, centrifuge, and dry to obtain a fully hydrogenated cyclic olefin polymer.

[0104] In this embodiment, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 183,000, the mass content of the aromatic ethylene block is 30%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 45%, and the degree of hydrogenation of the polymer aromatic ring is 99.7%.

[0105] Example 7

[0106] The polymer was synthesized according to the method of Example 1, except that the degree of hydrogenation of the aromatic ring of the polymer was controlled to be 85%.

[0107] The specific process is as follows: After the polymerization reaction is completed, the gel solution is introduced into a 5L hydrogenation reactor, 1g of supported nickel catalyst is added, the temperature is raised to 230℃, hydrogen gas is introduced, the hydrogenation pressure is controlled at 5.5MPa, the hydrogenation reaction is carried out for two hours, the hydrogenated gel solution is taken, centrifuged and dried to obtain a fully hydrogenated cyclic olefin polymer.

[0108] In this embodiment, the number average molecular weight of the fully hydrogenated cyclic olefin polymer is 185,000, the mass content of the aromatic ethylene block is 30%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 35.5%, and the degree of hydrogenation of the polymer aromatic ring is 85%.

[0109] Comparative Example 1

[0110] The polymer was synthesized according to the method of Example 1, except that the degree of hydrogenation of the aromatic ring of the polymer was controlled to be 65%.

[0111] The specific process is as follows: After the polymerization reaction is completed, the gel solution is introduced into a 5L hydrogenation reactor, 0.5g of supported nickel catalyst is added, the temperature is raised to 230℃, hydrogen gas is introduced, the hydrogenation pressure is controlled at 5.5MPa, the hydrogenation reaction is carried out for two hours, the hydrogenated gel solution is taken, centrifuged and dried to obtain a fully hydrogenated cyclic olefin polymer.

[0112] In this comparative example, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 184,000, the mass content of the aromatic ethylene block is 30%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 35.8%, and the degree of hydrogenation of the polymer's aromatic ring is 65%.

[0113] Comparative Example 2

[0114] The polymer was synthesized according to the method of Example 1, except that the monomer mass ratio of the polymer styrene / butadiene was 70 / 30.

[0115] In this comparative example, the number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 186,000, the mass content of the aromatic ethylene block is 70%, the mass content of the hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 is 32.5%, and the degree of hydrogenation of the polymer's aromatic ring is 99.5%.

[0116] Comparative Example 3

[0117] The main component was SEBS YH503 (produced by Sinopec Hunan Petrochemical Co., Ltd.), a commercially available, conventional non-fully hydrogenated product. Its number-average molecular weight was 178,000, the mass content of aromatic ethylene blocks was 33%, the mass content of hydrogenated conjugated diene structural unit II (vinyl structure) shown in Formula 3 was 36.2%, and the degree of hydrogenation of the polymer aromatic ring was 0%. The components were mixed uniformly in a high-speed mixer according to the formulation in Table 3, and then extruded and granulated on a twin-screw extruder. The process parameters are shown in Table 4.

[0118] Table 3 Solid Tire Rubber Compound Formulation

[0119]

[0120] Table 4 Extrusion Process Parameters

[0121]

[0122]

[0123] Comparative Example 4

[0124] Solid tire compound was prepared according to Example 1, except that: 30 parts by weight of fully hydrogenated cyclic olefin polymer, 25 parts of polypropylene, 20 parts of polyethylene, 3 parts of abrasion resistant agent, 0.5 parts of antioxidant, and 0.1 parts of UV absorber.

[0125] Comparative Example 5

[0126] Solid tire compound was prepared according to Example 1, except that: the fully hydrogenated cyclic olefin polymer was 65 parts by weight, polypropylene was 20 parts, polyethylene was 15 parts, abrasion resistant agent was 3 parts, antioxidant was 0.5 parts, and UV absorber was 0.1 parts.

[0127] Table 5 shows the structural and property test results of the fully hydrogenated cyclic olefin polymers obtained in Examples 1-7 and Comparative Examples 1-3.

[0128] Table 5. Results of polymer structure and physical property tests

[0129]

[0130] Note: The degree of hydrogenation of the conjugated diene of the above polymers is ≥99%, and the melt flow index (MFR) test conditions are 5 kg load and 230 °C.

[0131] As shown in Table 5, Examples 1-3 and Comparative Example 2 can adjust the hardness and elasticity of the polymer by controlling the mass ratio of styrene to butadiene. The higher the styrene content, the greater the hardness and the worse the elasticity. Examples 4-5 can adjust the processing fluidity of the polymer by controlling the molecular weight. The larger the molecular weight, the smaller the melt index and the worse the processing performance. Examples 7 and Comparative Examples 1 and 3 can regulate the strength and fluidity of the polymer by controlling the degree of hydrogenation of the aromatic ring. The higher the degree of hydrogenation of the benzene ring, the higher the polymer strength. When the degree of hydrogenation of the benzene ring is 0, the processing fluidity is poor.

[0132] Table 6 shows the physical property test results of the tire rubber compounds prepared in Examples 1-7 and Comparative Examples 1-5.

[0133] Table 6. Test Results of Tire Rubber Compound Properties

[0134]

[0135] Note: The melt flow index (MFR) test conditions are a load of 5 kg and a temperature of 230 °C.

[0136] As shown in Table 6, the tire compounds prepared in Examples 1-7 all meet the application and processing requirements of solid tires, exhibiting high tear strength, low abrasion, and excellent overall performance. In contrast, Comparative Example 1 shows high abrasion, Comparative Example 2 shows low elongation and poor elasticity, and Comparative Example 3, made from commercially available conventional non-fully hydrogenated SEBS, has lower strength and higher abrasion. The data from Comparative Example 4 indicates that a low content of fully hydrogenated cyclic olefin polymer significantly reduces the tear strength and elongation of the special compound. The data from Comparative Example 5 indicates that a high content of fully hydrogenated cyclic olefin polymer and a relatively low content of polyolefin resin lead to increased abrasion in the special compound.

[0137] Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An application of a fully hydrogenated cyclic olefin polymer, characterized in that: A fully hydrogenated cyclic olefin polymer is used to prepare solid tire rubber compounds; the fully hydrogenated cyclic olefin polymer comprises hydrogenated aromatic ethylene blocks and hydrogenated conjugated diene blocks, wherein the hydrogenated aromatic ethylene blocks comprise hydrogenated aromatic ethylene structural units as shown in Formula 1, and the hydrogenated conjugated diene blocks comprise hydrogenated conjugated diene structural unit I as shown in Formula 2 and hydrogenated conjugated diene structural unit II as shown in Formula 3. Among them, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are all H or C1-C3 alkyl groups, R 10 R 11 R 12 R 13 and R 14 All are H or C1-C4 alkyl groups.

2. The application of the fully hydrogenated cyclic olefin polymer according to claim 1, characterized in that: In the fully hydrogenated cyclic olefin polymer, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, R9 is H or methyl, and R... 10 R 11 R 13 and R 14 All of them are one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Alternatively, in the fully hydrogenated cyclic olefin polymer, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, R9 is H or methyl, and R... 10 R 11 R 13 and R 14 Both are H, R 12 It is a C1-C4 alkyl group.

3. The application of a fully hydrogenated cyclic olefin polymer according to claim 1 or 2, characterized in that: The hydrogenated aromatic ethylene block has a mass content of 15-55%, and the hydrogenated conjugated diene block has a mass content of 45-85%.

4. The application of the fully hydrogenated cyclic olefin polymer according to claim 1, characterized in that: The mass content of the hydrogenated conjugated diene structural unit II in the hydrogenated conjugated diene block is 8-60%; The degree of hydrogenation of the fully hydrogenated cyclic olefin polymer is 85-100%.

5. The application of the fully hydrogenated cyclic olefin polymer according to claim 1, characterized in that: The number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 40,000 to 250,000.

6. The application of the fully hydrogenated cyclic olefin polymer according to claim 1, characterized in that: The preparation process of the fully hydrogenated cyclic olefin polymer is as follows: aromatic ethylene monomer, conjugated diene monomer, solvent, initiator and activator are mixed and polymerized. After the reaction is completed, a terminator is added to obtain a polymer base solution. Then, the polymer base solution is subjected to a hydrogenation reaction to obtain the fully hydrogenated cyclic olefin polymer.

7. The application of the fully hydrogenated cyclic olefin polymer according to claim 6, characterized in that: The initiator is a C1-C4 alkyl lithium; The activator includes at least one of tetrahydrofuran, diethyl ether, anisole, tetrahydrofurfural ethyl ether, bis(tetrahydrofurfural propane), triethylamine, tetramethylethylenediamine, and N-methylmorpholine; The terminator includes at least one of alcohol terminators, phenol terminators, and silane terminators; The mass percentage of the aromatic ethylene monomer and the conjugated diene monomer is 15%–55%: 45%–85%; The total concentration of the aromatic ethylene monomer and the conjugated diene monomer in the polymerization reaction system is 3-15 wt%. The amount of the initiator added relative to the solvent is 0.5–5 mmol / kg; The amount of activator added relative to the solvent is 30-200 mg / kg; The molar amount of the terminator is 1.0 to 1.5 times that of the initiator.

8. The application of the fully hydrogenated cyclic olefin polymer according to claim 6, characterized in that: The catalyst used in the hydrogenation reaction is a heterogeneous supported metal catalyst, wherein the metal includes at least one of platinum, palladium, rhodium, ruthenium, iron, nickel, cobalt, and other group VIII metals; the catalyst support includes at least one of silica, alumina, diatomaceous earth, silica gel, and activated carbon.

9. The application of a fully hydrogenated cyclic olefin polymer according to claim 6, 7 or 8, characterized in that: The conditions for the hydrogenation reaction are: temperature 80–250℃, pressure 2–8 MPa, and time 0.5–20 h.

10. The application of the fully hydrogenated cyclic olefin polymer according to claim 1, characterized in that: In the preparation of solid tire rubber compound, the raw materials include the following components by weight: The fully hydrogenated cyclic olefin polymer is 35-60 parts; 15-25 parts of polypropylene; 10-20 parts of polyethylene; 1-5 parts of wear-resistant agent; Antioxidant 0.1 to 1 part; 0.05–0.5 parts of UV absorber; The raw materials are mixed and then melt-granulated to obtain solid tire rubber compound.

11. The application of the fully hydrogenated cyclic olefin polymer according to claim 10, characterized in that: The polypropylene is homopolymer polypropylene and / or copolymer polypropylene; The density of the polyethylene is 0.912–0.935 g / cm³. 3 .

12. The application of the fully hydrogenated cyclic olefin polymer according to claim 10, characterized in that: The wear-resistant agent includes at least one of silicates, titanates, and silicones; The antioxidant includes at least one of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, tris(2,4-di-tert-butylphenyl)phosphite, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The UV absorber includes at least one of 2-hydroxy-4-n-octyloxybenzophenone, (2-hydroxy-4-methoxyphenyl)phenyl ketone, and 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester.

13. The application of a fully hydrogenated cyclic olefin polymer according to any one of claims 10 to 12, characterized in that: The conditions for melt granulation are as follows: the main screw speed is 40-50 r / s, the feeding screw speed is 30-40 r / s, and the extrusion temperature is 180-255℃.

14. A solid tire compound, characterized in that: Includes the following components by weight: 35–60 parts of fully hydrogenated cyclic olefin polymer; 15-25 parts of polypropylene; 10-20 parts of polyethylene; 1-5 parts of wear-resistant agent; Antioxidant 0.1 to 1 part; 0.05–0.5 parts of UV absorber; The fully hydrogenated cyclic olefin polymer comprises hydrogenated aromatic ethylene blocks and hydrogenated conjugated diene blocks. The hydrogenated aromatic ethylene blocks comprise hydrogenated aromatic ethylene structural units as shown in Formula 1, and the hydrogenated conjugated diene blocks comprise hydrogenated conjugated diene structural unit I as shown in Formula 2 and hydrogenated conjugated diene structural unit II as shown in Formula 3. Among them, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are all H or C1-C3 alkyl groups, R 10 R 11 R 12 R 13 and R 14 All are H or C1-C4 alkyl groups.

15. A solid tire compound according to claim 14, characterized in that: In the fully hydrogenated cyclic olefin polymer, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, R9 is H or methyl, and R... 10 R 11 R 13 and R 14 All of them are one of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Alternatively, in the fully hydrogenated cyclic olefin polymer, R1, R2, R3, R4, R5, R6, R7, and R8 are all H, R9 is H or methyl, and R... 10 R 11 R 13 and R 14 Both are H, R 12 It is a C1-C4 alkyl group.

16. A solid tire compound according to claim 14, characterized in that: The hydrogenated aromatic ethylene block has a mass content of 15-55%, and the hydrogenated conjugated diene block has a mass content of 45-85%.

17. A solid tire compound according to claim 14, characterized in that: The mass content of the hydrogenated conjugated diene structural unit II in the hydrogenated conjugated diene block is 8-60%; The degree of hydrogenation of the fully hydrogenated cyclic olefin polymer is 85-100%.

18. A solid tire compound according to any one of claims 14 to 17, characterized in that: The number-average molecular weight of the fully hydrogenated cyclic olefin polymer is 40,000 to 250,000.

19. A solid tire compound according to claim 14, characterized in that: The wear-resistant agent includes at least one of silicates, titanates, and silicones; The antioxidant includes at least one of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, tris(2,4-di-tert-butylphenyl)phosphite, and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The UV absorber includes at least one of 2-hydroxy-4-n-octyloxybenzophenone, (2-hydroxy-4-methoxyphenyl)phenyl ketone, and 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester.

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