Recycled vegetable oil-modified tire rubber and preparation method thereof

Abstract

The invention discloses a tire rubber modified by recycled vegetable oil, which is made of the following raw materials in parts by weight: 70-80 parts of block random solution-polymerized styrene-butadiene rubber, 8-12 parts of nitrile rubber, 10-15 parts of recycled vegetable oil, 15-20 parts of modified polyurethane elastomer, 1.2-1.7 parts of sulfur, 1-1.2 parts of vulcanization accelerator, 2-4 parts of nano zinc oxide, and 1-2 parts of stearic acid. The invention makes the recycled vegetable oil-modified tire rubber have high tear strength and excellent tear resistance by combining appropriate addition amounts of various component raw materials and corresponding preparation processes; high tensile strength and elongation at break, good mechanical properties; good wear resistance, low brittle temperature, and good low temperature resistance.

Description

Technical Field

[0001] The invention relates to the technical field of sustainable development tire materials, and in particular to a tire rubber modified by recycled vegetable oil and a preparation method thereof. Background Art

[0002] Styrene butadiene rubber (SBR), also known as polystyrene butadiene copolymer, has physical properties, processing properties and product performance close to natural rubber. It is widely used in tire production and is the largest general-purpose synthetic rubber variety. It is also one of the earliest rubber varieties to achieve industrial production.

[0003] With the progress of the times, more sustainable tires made of a higher proportion of bio-based materials and recyclable materials have become a new direction leading the tire material revolution. Sustainable material tires are mainly composed of recyclable and biomass materials.

[0004] However, the styrene-butadiene rubber used for tires currently still has the following problems:

[0005] 1. The rubber oil used in existing tires is petroleum-based oil, which is a non-renewable resource, not in line with the direction of sustainable development and not conducive to the realization of carbon peak and carbon neutrality;

[0006] 2. The tear strength is low, and the mechanical properties such as tensile strength and elongation at break are poor, which cannot meet the requirements of high-performance use;

[0007] 3. The wear resistance is poor and needs to be further improved;

[0008] 4. The low-temperature resistance is poor. Due to the use environment of the tire, it is easy to become brittle and damaged during alternating high and low temperature use.

[0009] Based on the above situation, the present invention proposes a tire rubber modified with recycled vegetable oil and a preparation method thereof, which can effectively solve the above problems. Summary of the invention

[0010] The purpose of the present invention is to provide a tire rubber modified by recycled vegetable oil and a preparation method thereof. The tire rubber modified by recycled vegetable oil of the present invention is combined with each other by appropriately adding various component raw materials and combining corresponding preparation processes, so that the prepared tire rubber modified by recycled vegetable oil has high tear strength and excellent tear resistance; high tensile strength and elongation at break, good mechanical properties; good wear resistance, low brittle temperature, and good low temperature resistance.

[0011] In order to solve the above technical problems, the technical solution provided by the present invention is:

[0012] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0013] 70-80 parts of random block solution-polymerized styrene-butadiene rubber,

[0014] 8-12 parts of nitrile rubber,

[0015] 10-15 parts of recycled vegetable oil,

[0016] 15-20 parts of modified polyurethane elastomer,

[0017] Sulfur 1.2-1.7 parts,

[0018] 1 to 1.2 parts of vulcanization accelerator,

[0019] 2-4 parts of nano zinc oxide,

[0020] 1 to 2 parts of stearic acid.

[0021] The recycled vegetable oil-modified tire rubber of the present invention has high tear strength and excellent tear resistance through the mutual coordination of various component raw materials by adding appropriate amounts and combining corresponding preparation processes; high tensile strength and elongation at break, good mechanical properties; good wear resistance, low brittle temperature and good low temperature resistance.

[0022] Preferably, the recycled vegetable oil-modified tire rubber is made of the following raw materials in parts by weight:

[0023] 75 parts of random block solution-polymerized styrene-butadiene rubber,

[0024] 10 parts of nitrile rubber,

[0025] 12.5 parts of recycled vegetable oil,

[0026] 17.5 parts of modified polyurethane elastomer,

[0027] 1.45 parts of sulfur,

[0028] 1.1 parts of vulcanization accelerator,

[0029] 3 parts of nano zinc oxide,

[0030] 1.5 parts of stearic acid.

[0031] Preferably, the preparation process of the regenerated vegetable oil comprises the following steps:

[0032] S1. The recovered "gutter oil (vegetable oil content greater than 90wt%)" is filtered through a filter press to separate the solid and liquid, and then the liquid is passed through filters of different mesh sizes to remove impurities;

[0033] S2. 100 to 120 parts by weight of the oil filtered in step S1 is poured into a stirring tank, and then 1 to 2 parts by weight of dioxygenase is added, stirred for 10 to 20 minutes, and allowed to stand for 1 to 2 hours, and then 1 to 2 parts by weight of laccase and 0.5 to 1 part by weight of manganese peroxidase are added, stirred for 10 to 15 minutes, and allowed to stand for 2 to 3 hours;

[0034] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 6 to 8;

[0035] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0036] S5. Add 0.2 to 0.5 parts by weight of decolorizing agent (activated carbon) to the upper layer of oil separated in step S4 and pour it into the reactor, the mixing speed is 30 to 60 rpm, the heating temperature is 100 to 130 ° C, and the stirring time is 30 to 60 min;

[0037] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0038] S7. After heating the oil in step S6 to 60-90° C., add it to a deodorizer for deodorization to remove substances that affect the temperature and color, lower the temperature to below 40° C. and fill it to obtain the regenerated vegetable oil.

[0039] A comparative test was conducted on the tire rubber modified with the recycled vegetable oil in the preparation process of Examples 2 to 4 of the present invention. It was found that the Mooney viscosity (100°C*4min) of the recycled vegetable oil in the tire rubber raw material composition modified with the recycled vegetable oil of the present invention decreased by 6% to 8%; the scorch time (127°C*60min) increased by 3% to 5%; the vulcanization time decreased by 8% to 11%; and the glass transition temperature decreased by 10 to 15°C; thus, it can be seen that after the waste edible oil is purified, it reaches the industrial index range, and a large amount of "gutter oil" discarded in the catering industry and other industries is consumed, which has broad market prospects.

[0040] In addition, petroleum-based oil is used in existing tires. Petroleum-based oil is a non-renewable resource, which is not in line with the direction of sustainable development and is not conducive to the realization of carbon peak and carbon neutrality. It also contains toxic and harmful substances such as PAH, which pollutes the environment. As a major tire producer, if my country can use waste cooking oil in tires, it can not only consume a large amount of "gutter oil" and reduce the risk of it returning to the table, but also avoid using expensive imported environmentally friendly rubber oil, which is conducive to reducing the cost and improving the quality of tires.

[0041] The regenerated vegetable oil in the tire rubber modified with the regenerated vegetable oil in the present invention can significantly reduce the glass transition temperature Tg of the tire compared with petroleum-based oil, has favorable processability, and improves low-temperature resistance; at the same time, basic properties such as tensile strength remain at the same level as petroleum-based oil.

[0042] Preferably, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 22-26%.

[0043] The block random solution polymerized styrene butadiene rubber selected in the present invention is used as the main raw material to give the tire tread rubber low rolling resistance and high anti-slip performance, and is further modified by using recycled vegetable oil and modified polyurethane elastomer.

[0044] Preferably, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0045] 100-125 parts of polycaprolactone diol,

[0046] 50-65 parts of polypropylene glycol,

[0047] 4-6 parts of trisilanolphenyl-cage polysilsesquioxane,

[0048] 2.5 to 3.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0049] 16-22 parts of hexamethylene diisocyanate,

[0050] 50-100 parts of ethyl acetate,

[0051] Short glass fiber 75-95 parts.

[0052] Preferably, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0053] Preferably, the length of the short glass fiber is 3 to 5 mm, and the diameter of the single fiber is 9 to 13 um.

[0054] The short glass fibers selected in the present invention can be well distributed evenly in the matrix of the present invention, have excellent wet dispersion fluidity, and are easily impregnated with polyurethane and other tree species.

[0055] Preferably, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0056] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0057] B. Then add trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane [trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane cooperate with each other to play a good synergistic enhancement role, and at the same time it is conducive to the formation of a sea island structure (trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane are connected with macromolecular polyols through chemical reaction to form an organic-inorganic hybrid island structure), which has a better dispersing effect than the addition of white carbon black, and the comprehensive performance of the tire rubber modified by the regenerated vegetable oil of the present invention is more significantly improved] continue to stir and disperse evenly, and gradually heat up to 60-70° C., and keep the temperature for reaction for 20-30 minutes;

[0058] C. Then add the pre-mixed and uniformly dispersed polycaprolactone diol, polypropylene glycol [the use of polypropylene glycol further improves the molecular chain flexibility of the tire rubber modified by the regenerated vegetable oil of the present invention, thereby improving the elasticity, low temperature resistance, tear resistance and other properties] and short glass fiber mixture, continue stirring, then add the remaining 1 / 2 of hexamethylene diisocyanate diluted with the remaining 2 / 3 of ethyl acetate, cool to 55-60° C., and keep warm for reaction for 20-30 minutes;

[0059] D. After the reaction is completed, the solvent ethyl acetate is removed, and the solid is chopped into solid particles with a diameter of less than 1 cm to obtain the modified polyurethane elastomer.

[0060] The present invention obtains a special modified polyurethane elastomer through the raw material composition and preparation method of the modified polyurethane elastomer described above, wherein trisilanol phenyl-cage polysilsesquioxane has a large number of benzene ring rigid structures and high steric hindrance, and has three active hydroxyl groups. The present invention selects flexible hexamethylene diisocyanate to react with it first, so that three hexamethylene diisocyanates are grafted on a trisilanol phenyl-cage polysilsesquioxane (and one isocyanate group is unreacted), and then reacts with polycaprolactone diol and polypropylene glycol and continues to extend the chain, thereby forming a special sea-island structure (trisilanol phenyl-cage polysilsesquioxane is an island, and other flexible chains such as polycaprolactone diol and polypropylene glycol constitute a sea), which is very helpful for improving the tear resistance, tensile strength, wear resistance and brittle temperature of the tire rubber modified by the regenerated vegetable oil of the present invention;

[0061] The short glass fibers added in the present invention are coated by the formed polyurethane elastomer, which not only ensures its good reinforcing effect, but also greatly improves the tear resistance, elongation at break, wear resistance and brittle temperature of the recycled vegetable oil-modified tire rubber of the present invention.

[0062] Preferably, the vulcanization accelerator is vulcanization accelerator DCBS.

[0063] The present invention also provides a method for preparing the regenerated vegetable oil-modified tire rubber, which is characterized by comprising the following steps:

[0064] ① The block random solution polymerized styrene butadiene rubber and nitrile butadiene rubber are firstly plasticized on an open mill at 90-95°C for 30-40 minutes, and recycled vegetable oil is added during plasticization;

[0065] ② Then mix the two together on an internal mixer at 120-140°C for 8-12 minutes to obtain a mixed rubber material;

[0066] ③ Then add the modified polyurethane elastomer and continue kneading for 8 to 12 minutes, then cool to 80 to 90° C., add the remaining materials and knead and mix evenly, and then calender and vulcanize to obtain the recycled vegetable oil modified tire rubber in the form of a plate or sheet.

[0067] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0068] The recycled vegetable oil-modified tire rubber of the present invention has high tear strength and excellent tear resistance through the mutual coordination of various component raw materials by adding appropriate amounts and combining corresponding preparation processes; high tensile strength and elongation at break, good mechanical properties; good wear resistance, low brittle temperature and good low temperature resistance.

[0069] The preparation method of the invention has simple process and convenient operation, and ensures the comprehensive performance of the tire rubber modified by the regenerated vegetable oil of the invention. DETAILED DESCRIPTION

[0070] In order to enable those skilled in the art to better understand the technical solution of the present invention, the preferred implementation scheme of the present invention is described below in conjunction with specific examples, but it should not be understood as a limitation of this patent.

[0071] The experimental methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials are obtained from conventional commercial channels or prepared by conventional methods unless otherwise specified.

[0072] Embodiment 1:

[0073] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0074] 70-80 parts of random block solution-polymerized styrene-butadiene rubber,

[0075] 8-12 parts of nitrile rubber,

[0076] 10-15 parts of recycled vegetable oil,

[0077] 15-20 parts of modified polyurethane elastomer,

[0078] Sulfur 1.2-1.7 parts,

[0079] 1 to 1.2 parts of vulcanization accelerator,

[0080] 2-4 parts of nano zinc oxide,

[0081] 1 to 2 parts of stearic acid.

[0082] Preferably, the recycled vegetable oil-modified tire rubber is made of the following raw materials in parts by weight:

[0083] 75 parts of random block solution-polymerized styrene-butadiene rubber,

[0084] 10 parts of nitrile rubber,

[0085] 12.5 parts of recycled vegetable oil,

[0086] 17.5 parts of modified polyurethane elastomer,

[0087] 1.45 parts of sulfur,

[0088] 1.1 parts of vulcanization accelerator,

[0089] 3 parts of nano zinc oxide,

[0090] 1.5 parts of stearic acid.

[0091] Preferably, the preparation process of the regenerated vegetable oil comprises the following steps:

[0092] S1. The recovered "gutter oil (vegetable oil content greater than 90wt%)" is filtered through a filter press to separate the solid and liquid, and then the liquid is passed through filters of different mesh sizes to remove impurities;

[0093] S2. 100 to 120 parts by weight of the oil filtered in step S1 is poured into a stirring tank, and then 1 to 2 parts by weight of dioxygenase is added, stirred for 10 to 20 minutes, and allowed to stand for 1 to 2 hours, and then 1 to 2 parts by weight of laccase and 0.5 to 1 part by weight of manganese peroxidase are added, stirred for 10 to 15 minutes, and allowed to stand for 2 to 3 hours;

[0094] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 6 to 8;

[0095] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0096] S5. Add 0.2 to 0.5 parts by weight of decolorizing agent (activated carbon) to the upper layer of oil separated in step S4 and pour it into the reactor, the mixing speed is 30 to 60 rpm, the heating temperature is 100 to 130 ° C, and the stirring time is 30 to 60 min;

[0097] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0098] S7. After heating the oil in step S6 to 60-90° C., add it to a deodorizer for deodorization to remove substances that affect the temperature and color, lower the temperature to below 40° C. and fill it to obtain the regenerated vegetable oil.

[0099] Preferably, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 22-26%.

[0100] Preferably, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0101] 100-125 parts of polycaprolactone diol,

[0102] 50-65 parts of polypropylene glycol,

[0103] 4-6 parts of trisilanolphenyl-cage polysilsesquioxane,

[0104] 2.5 to 3.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0105] 16-22 parts of hexamethylene diisocyanate,

[0106] 50-100 parts of ethyl acetate,

[0107] Short glass fiber 75-95 parts.

[0108] Preferably, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0109] Preferably, the length of the short glass fiber is 3 to 5 mm, and the diameter of the single fiber is 9 to 13 um.

[0110] Preferably, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0111] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0112] B. Then add trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane and continue to stir and disperse evenly, and gradually increase the temperature to 60-70°C, and keep the temperature for reaction for 20-30 minutes;

[0113] C. Then add the pre-mixed and evenly dispersed mixture of polycaprolactone diol, polypropylene glycol and short glass fibers, continue stirring, and then add the remaining 1 / 2 of hexamethylene diisocyanate diluted with the remaining 2 / 3 of ethyl acetate, cool to 55-60°C, and keep warm for reaction for 20-30 minutes;

[0114] D. After the reaction is completed, the solvent ethyl acetate is removed, and the solid is chopped into solid particles with a diameter of less than 1 cm to obtain the modified polyurethane elastomer.

[0115] Preferably, the vulcanization accelerator is vulcanization accelerator DCBS.

[0116] The present invention also provides a method for preparing the recycled vegetable oil-modified tire rubber, comprising the following steps:

[0117] ① The block random solution polymerized styrene butadiene rubber and nitrile butadiene rubber are firstly plasticized on an open mill at 90-95°C for 30-40 minutes, and recycled vegetable oil is added during plasticization;

[0118] ② Then mix the two together on an internal mixer at 120-140°C for 8-12 minutes to obtain a mixed rubber material;

[0119] ③ Then add the modified polyurethane elastomer and continue kneading for 8 to 12 minutes, then cool to 80 to 90° C., add the remaining materials and knead and mix evenly, and then calender and vulcanize to obtain the recycled vegetable oil modified tire rubber in the form of a plate or sheet.

[0120] Embodiment 2:

[0121] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0122] 70 parts of random block solution-polymerized styrene-butadiene rubber,

[0123] 8 parts of nitrile rubber,

[0124] 10 parts of recycled vegetable oil,

[0125] 15 parts of modified polyurethane elastomer,

[0126] 1.2 parts of sulfur,

[0127] 1 part of vulcanization accelerator,

[0128] 2 parts of nano zinc oxide,

[0129] 1 part of stearic acid.

[0130] In this embodiment, the preparation process of the regenerated vegetable oil comprises the following steps:

[0131] S1. The recovered "gutter oil (vegetable oil content greater than 90wt%)" is filtered through a filter press to separate the solid and liquid, and then the liquid is passed through filters of different mesh sizes to remove impurities;

[0132] S2. 100 parts by weight of the oil filtered in step S1 was poured into a stirring tank, and then 1 part by weight of dioxygenase was added, stirred for 10 minutes, allowed to stand for 1 hour, and then 1 part by weight of laccase and 0.5 parts by weight of manganese peroxidase were added, stirred for 10 minutes, and allowed to stand for 2 hours;

[0133] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 6;

[0134] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0135] S5. Add 0.2 parts by weight of decolorizing agent (activated carbon) to the upper layer of oil separated in step S4 and pour into the reactor, the mixing speed is 30 rpm, the heating temperature is 100 ° C, and the stirring time is 60 min;

[0136] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0137] S7. After heating the oil in step S6 to 60° C., add it to a deodorizer for deodorization to remove substances that affect the temperature and color, lower the temperature to below 40° C. and fill it to obtain the regenerated vegetable oil.

[0138] In this embodiment, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 22%.

[0139] In this embodiment, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0140] 100 parts of polycaprolactone diol,

[0141] 50 parts of polypropylene glycol,

[0142] 4 parts of trisilanol phenyl-cage polysilsesquioxane,

[0143] 2.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0144] 16 parts of hexamethylene diisocyanate,

[0145] 50 parts of ethyl acetate,

[0146] 75 parts of short glass fiber.

[0147] In this embodiment, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0148] In this embodiment, the length of the short glass fiber is 3-5 mm, and the diameter of the single fiber is 9-13 um.

[0149] In this embodiment, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0150] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0151] B. Then add trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane and continue to stir and disperse evenly, and gradually increase the temperature to 60°C and keep the temperature for reaction for 30 minutes;

[0152] C. Then add the pre-mixed and evenly dispersed mixture of polycaprolactone diol, polypropylene glycol and short glass fibers, continue stirring, and then add the remaining 1 / 2 of hexamethylene diisocyanate diluted with the remaining 2 / 3 of ethyl acetate, cool to 55°C, and keep warm for reaction for 30 minutes;

[0153] D. After the reaction is completed, the solvent ethyl acetate is removed, and the solid is chopped into solid particles with a diameter of less than 1 cm to obtain the modified polyurethane elastomer.

[0154] In this embodiment, the vulcanization accelerator is vulcanization accelerator DCBS.

[0155] In this embodiment, the method for preparing the tire rubber modified by recycled vegetable oil comprises the following steps:

[0156] ① The block random solution polymerized styrene butadiene rubber and nitrile butadiene rubber were firstly plasticized on an open mill at 90°C for 40 min, and recycled vegetable oil was added during plasticization;

[0157] ② Then mix the two together on an internal mixer at 120°C for 12 minutes to obtain a mixed rubber material;

[0158] ③ Then add the modified polyurethane elastomer and continue kneading for 12 minutes, then cool to 80°C, add the remaining materials and knead and mix evenly, and then calender and vulcanize to obtain the recycled vegetable oil modified tire rubber in the form of a plate or sheet.

[0159] Embodiment 3:

[0160] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0161] 80 parts of random block solution-polymerized styrene-butadiene rubber,

[0162] 12 parts of nitrile rubber,

[0163] 15 parts of recycled vegetable oil,

[0164] 20 parts of modified polyurethane elastomer,

[0165] Sulfur 1.7 parts,

[0166] 1.2 parts of vulcanization accelerator,

[0167] 4 parts of nano zinc oxide,

[0168] 2 parts of stearic acid.

[0169] In this embodiment, the preparation process of the regenerated vegetable oil comprises the following steps:

[0170] S1. The recovered "gutter oil (vegetable oil content greater than 90wt%)" is filtered through a filter press to separate the solid and liquid, and then the liquid is passed through filters of different mesh sizes to remove impurities;

[0171] S2. 120 parts by weight of the oil filtered in step S1 was poured into a stirring tank, and then 2 parts by weight of dioxygenase was added, stirred for 20 minutes, and allowed to stand for 2 hours, and then 2 parts by weight of laccase and 1 part by weight of manganese peroxidase were added, stirred for 15 minutes, and allowed to stand for 3 hours;

[0172] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 8;

[0173] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0174] S5. Add 0.5 parts by weight of decolorizing agent (activated carbon) to the upper layer of oil separated in step S4 and pour into the reactor, the mixing speed is 60 rpm, the heating temperature is 130 ° C, and the stirring time is 60 min;

[0175] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0176] S7. After heating the oil in step S6 to 90° C., add it to a deodorizer for deodorization to remove substances that affect the temperature and color, lower the temperature to below 40° C. and fill it to obtain the regenerated vegetable oil.

[0177] In this embodiment, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 26%.

[0178] In this embodiment, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0179] 125 parts of polycaprolactone diol,

[0180] 65 parts of polypropylene glycol,

[0181] 6 parts of trisilanol phenyl-cage polysilsesquioxane,

[0182] 3.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0183] 22 parts of hexamethylene diisocyanate,

[0184] 100 parts of ethyl acetate,

[0185] 95 parts of short glass fiber.

[0186] In this embodiment, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0187] In this embodiment, the length of the short glass fiber is 3-5 mm, and the diameter of the single fiber is 9-13 um.

[0188] In this embodiment, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0189] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0190] B. Then add trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane and continue to stir and disperse evenly, and gradually increase the temperature to 70°C and keep the temperature for reaction for 20 minutes;

[0191] C. Then add the pre-mixed and evenly dispersed mixture of polycaprolactone diol, polypropylene glycol and short glass fibers, continue stirring, and then add the remaining 1 / 2 of hexamethylene diisocyanate diluted with the remaining 2 / 3 of ethyl acetate, cool to 60°C, and keep warm for 20 minutes;

[0192] D. After the reaction is completed, the solvent ethyl acetate is removed, and the solid is chopped into solid particles with a diameter of less than 1 cm to obtain the modified polyurethane elastomer.

[0193] In this embodiment, the vulcanization accelerator is vulcanization accelerator DCBS.

[0194] In this embodiment, the method for preparing the tire rubber modified by recycled vegetable oil comprises the following steps:

[0195] ① The block random solution polymerized styrene butadiene rubber and nitrile butadiene rubber were firstly plasticized on an open mill at 95°C for 30 min, and recycled vegetable oil was added during plasticization;

[0196] ② Then the two were mixed together in an internal mixer at 140°C for 8 minutes to obtain a mixed rubber material;

[0197] ③ Then add the modified polyurethane elastomer and continue kneading for 8 minutes, then cool to 90°C, add the remaining materials and knead and mix evenly, and then calender and vulcanize to obtain the recycled vegetable oil modified tire rubber in the form of a plate or sheet.

[0198] Embodiment 4:

[0199] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0200] 75 parts of random block solution-polymerized styrene-butadiene rubber,

[0201] 10 parts of nitrile rubber,

[0202] 12.5 parts of recycled vegetable oil,

[0203] 17.5 parts of modified polyurethane elastomer,

[0204] 1.45 parts of sulfur,

[0205] 1.1 parts of vulcanization accelerator,

[0206] 3 parts of nano zinc oxide,

[0207] 1.5 parts of stearic acid.

[0208] In this embodiment, the preparation process of the regenerated vegetable oil comprises the following steps:

[0209] S1. The recovered "gutter oil (vegetable oil content greater than 90wt%)" is filtered through a filter press to separate the solid and liquid, and then the liquid is passed through filters of different mesh sizes to remove impurities;

[0210] S2. 110 parts by weight of the oil filtered in step S1 was poured into a stirring tank, and then 1.5 parts by weight of dioxygenase was added, stirred for 15 minutes, allowed to stand for 1.5 hours, and then 1.5 parts by weight of laccase and 0.75 parts by weight of manganese peroxidase were added, stirred for 12.5 minutes, and allowed to stand for 2.5 hours;

[0211] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 7;

[0212] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0213] S5. Add 0.35 parts by weight of decolorizing agent (activated carbon) to the upper layer of oil separated in step S4 and pour into the reactor, the mixing speed is 40 rpm, the heating temperature is 115 ° C, and the stirring time is 40 min;

[0214] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0215] S7. After heating the oil in step S6 to 75°C, add it to a deodorizer for deodorization to remove substances that affect the temperature and color, lower the temperature to below 40°C and fill it to obtain the regenerated vegetable oil.

[0216] In this embodiment, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 24%.

[0217] In this embodiment, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0218] 113 parts of polycaprolactone diol,

[0219] 57.5 parts of polypropylene glycol,

[0220] 5 parts of trisilanol phenyl-cage polysilsesquioxane,

[0221] 3 parts of aminopropylheptyl-cage polysilsesquioxane,

[0222] 19 parts of hexamethylene diisocyanate,

[0223] 75 parts of ethyl acetate,

[0224] 85 parts of short glass fiber.

[0225] In this embodiment, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0226] In this embodiment, the length of the short glass fiber is 3-5 mm, and the diameter of the single fiber is 9-13 um.

[0227] In this embodiment, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0228] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0229] B. Then add trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane and continue to stir and disperse evenly, and gradually increase the temperature to 65°C and keep the temperature for reaction for 25 minutes;

[0230] C. Then add the pre-mixed and evenly dispersed mixture of polycaprolactone diol, polypropylene glycol and short glass fibers, continue stirring, and then add the remaining 1 / 2 of hexamethylene diisocyanate diluted with the remaining 2 / 3 of ethyl acetate, cool to 57.5°C, and keep warm for 25 minutes;

[0231] D. After the reaction is completed, the solvent ethyl acetate is removed, and the solid is chopped into solid particles with a diameter of less than 1 cm to obtain the modified polyurethane elastomer.

[0232] In this embodiment, the vulcanization accelerator is vulcanization accelerator DCBS.

[0233] In this embodiment, the method for preparing the tire rubber modified by recycled vegetable oil comprises the following steps:

[0234] ① The block random solution polymerized styrene butadiene rubber and nitrile butadiene rubber were firstly plasticized on an open mill at 92°C for 35 min, and recycled vegetable oil was added during plasticization;

[0235] ② Then the two were mixed together in an internal mixer at 130°C for 10 minutes to obtain a mixed rubber material;

[0236] ③ Then add the modified polyurethane elastomer and continue kneading for 10 minutes, then cool to 85°C, add the remaining materials and knead and mix evenly, and then calender and vulcanize to obtain the recycled vegetable oil modified tire rubber in the form of a plate or sheet.

[0237] Comparative Example 1:

[0238] The difference from Example 4 is that the regenerated vegetable oil is replaced by paraffin oil KP200#, and the rest is the same as Example 4.

[0239] Comparative Example 2:

[0240] The difference from Example 4 is that the regenerated vegetable oil is replaced by the "waste oil" (with a vegetable oil content of more than 90 wt%) in step S1., and the rest is the same as Example 4.

[0241] Comparative Example 3:

[0242] The difference from Example 4 is that no modified polyurethane elastomer is used, and the other aspects are the same as Example 4.

[0243] Comparative Example 4:

[0244] The difference from Example 4 is that the modified polyurethane elastomer does not contain trisilanol phenyl-cage polysilsesquioxane, and trisilanol phenyl-cage polysilsesquioxane is replaced by aminopropylheptyl-cage polysilsesquioxane. The rest is the same as Example 4.

[0245] Comparative Example 5:

[0246] The difference from Example 4 is that there is no short glass fiber in the modified polyurethane elastomer, and the corresponding mass proportion of short glass fiber is added together with the remaining materials in step ③ of the preparation method of the recycled vegetable oil-modified tire rubber, and the rest is the same as Example 4.

[0247] The performance tests are performed on the tire rubber modified with the recycled vegetable oil obtained in Examples 2 to 4 of the present invention and Comparative Examples 1 to 8. The test results are shown in Table 1:

[0248] During the test, tear strength: refer to GB / T 529-2008 "Determination of tear strength of vulcanized rubber or thermoplastic rubber" for testing;

[0249] Tensile strength and elongation at break: Tested in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber";

[0250] Wear resistance: Tested in accordance with GB / T 9867-2008 "Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrasion machine method)"

[0251] Brittle temperature: Refer to GB / T 1682-2014 "Determination of low-temperature brittleness of vulcanized rubber" and conduct brittle temperature test using the single specimen method.

[0252] Table 1

[0253]

[0254]

[0255] In addition, a comparative test was conducted on the tire rubber modified with the recycled vegetable oil in the preparation process of Examples 2 to 4 of the present invention. It was found that the Mooney viscosity (100°C*4min) of the recycled vegetable oil in the tire rubber raw material composition modified with the recycled vegetable oil of the present invention decreased by 6% to 8%; the scorch time (127°C*60min) increased by 3% to 5%; the vulcanization time decreased by 8% to 11%; and the glass transition temperature decreased by 10 to 15°C. It can be seen that after the waste edible oil is purified, it reaches the industrial index range, and a large amount of "gutter oil" discarded in the catering industry and other industries is consumed, which has broad market prospects.

[0256] The above are only preferred embodiments of the present invention. It should be noted that the above preferred embodiments should not be regarded as limiting the present invention, and the protection scope of the present invention should be based on the scope defined by the claims. For ordinary technicians in this technical field, several improvements and modifications can be made without departing from the spirit and scope of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A tire rubber modified with recycled vegetable oil, characterized in that: Made from the following raw materials in parts by weight: 70-80 parts of random block solution-polymerized styrene-butadiene rubber, 8-12 parts of nitrile rubber, 10-15 parts of recycled vegetable oil, 15-20 parts of modified polyurethane elastomer, Sulfur 1.2-1.7 parts, 1 to 1.2 parts of vulcanization accelerator, 2-4 parts of nano zinc oxide, 1-2 parts of stearic acid; The modified polyurethane elastomer is made from the following raw materials in parts by weight: 100-125 parts of polycaprolactone diol, 50-65 parts of polypropylene glycol, 4-6 parts of trisilanolphenyl-cage polysilsesquioxane, 2.5 to 3.5 parts of aminopropylheptyl-cage polysilsesquioxane, 16-22 parts of hexamethylene diisocyanate, 50-100 parts of ethyl acetate, Short glass fiber 75-95 parts.

2. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The regenerated vegetable oil-modified tire rubber is made of the following raw materials in parts by weight: 75 parts of random block solution-polymerized styrene-butadiene rubber, 10 parts of nitrile rubber, 12.5 parts of recycled vegetable oil, 17.5 parts of modified polyurethane elastomer, 1.45 parts of sulfur, 1.1 parts of vulcanization accelerator, 3 parts of nano zinc oxide, 1.5 parts of stearic acid.

3. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The preparation process of the regenerated vegetable oil comprises the following steps: S1. The recovered "gutter oil" is filtered through a filter press to separate the solid and liquid, and then the liquid is passed through filters of different mesh sizes to remove impurities; S2. 100 to 120 parts by weight of the oil filtered in step S1 is poured into a stirring tank, and then 1 to 2 parts by weight of dioxygenase is added, stirred for 10 to 20 minutes, and allowed to stand for 1 to 2 hours, and then 1 to 2 parts by weight of laccase and 0.5 to 1 part by weight of manganese peroxidase are added, stirred for 10 to 15 minutes, and allowed to stand for 2 to 3 hours; S3. Add alkali solution to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 6 to 8; S4. Add water to step S3, wash with water, and separate the upper layer of oil; S5. Add 0.2 to 0.5 parts by weight of decolorizing agent to the upper layer of oil separated in step S4 and pour into the reactor, the mixing speed is 30 to 60 rpm, the heating temperature is 100 to 130 ° C, and the stirring time is 30 to 60 min; S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize; S7. After heating the oil in step S6 to 60-90° C., add it to a deodorizer for deodorization to remove substances that affect the temperature and color, lower the temperature to below 40° C. and fill it to obtain the regenerated vegetable oil.

4. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The content of styrene monomer units in the block random solution-polymerized styrene-butadiene rubber is 22-26%.

5. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

6. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The length of the short glass fiber is 3-5 mm, and the diameter of the single fiber is 9-13 um.

7. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The preparation method of the modified polyurethane elastomer comprises the following steps: A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute; B. Then add trisilanol phenyl-cage polysilsesquioxane and aminopropylheptyl-cage polysilsesquioxane and continue to stir and disperse evenly, and gradually increase the temperature to 60-70°C, and keep the temperature for reaction for 20-30 minutes; C. Then add the pre-mixed and evenly dispersed mixture of polycaprolactone diol, polypropylene glycol and short glass fibers, continue stirring, and then add the remaining 1 / 2 of hexamethylene diisocyanate diluted with the remaining 2 / 3 of ethyl acetate, cool to 55-60°C, and keep warm for reaction for 20-30 minutes; D. After the reaction is completed, the solvent ethyl acetate is removed, and the solid is chopped into solid particles with a diameter of less than 1 cm to obtain the modified polyurethane elastomer.

8. The tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The vulcanization accelerator is vulcanization accelerator DCBS.

9. A method for preparing tire rubber modified with recycled vegetable oil according to any one of claims 1 or 8, characterized in that: The following steps are involved: ① The block random solution polymerized styrene butadiene rubber and nitrile butadiene rubber are firstly plasticized on an open mill at 90-95°C for 30-40 minutes, and recycled vegetable oil is added during plasticization; ② Then mix the two together on an internal mixer at 120-140°C for 8-12 minutes to obtain a mixed rubber material; ③ Then add the modified polyurethane elastomer and continue kneading for 8 to 12 minutes, then cool to 80 to 90° C., add the remaining materials and knead and mix evenly, and then calender and vulcanize to obtain the recycled vegetable oil modified tire rubber in the form of a plate or sheet.

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