A process and equipment for producing tire rubber modified by recycled vegetable oil

Abstract

The invention relates to a production process of tire rubber modified by recycled vegetable oil, comprising the following steps: 1) preparing recycled vegetable oil; 2) preparing modified polyurethane elastomer; 3) preparing tire rubber modified by recycled vegetable oil. The invention overcomes the shortcomings of the prior art and has a reasonable design. After the waste edible oil is purified, it reaches the range of industrial indicators to obtain renewable bio-based oil that meets the requirements of tire use, and can consume a large amount of "gutter oil" discarded in the catering industry and other industries. At the same time, the obtained 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.

Description

Technical Field

[0001] The invention relates to the technical field of sustainable development tire material production, and in particular to a production process and equipment for tire rubber modified with recycled vegetable oil. 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] Waste cooking oil, commonly known as "gutter oil", is collected by illegal vendors and simply processed before returning to the dining table, seriously harming people's lives and health. The "gutter oil" problem has become a serious food safety issue that has attracted widespread concern.

[0005] However, the currently used styrene-butadiene rubber for tires and its production and processing still have the following problems:

[0006] 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;

[0007] 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;

[0008] 3. The wear resistance is poor and needs to be further improved;

[0009] 4. Poor low temperature resistance. Due to the use environment of the tire, it is easy to become brittle and damaged during the alternating use of high and low temperatures;

[0010] 5. The production equipment of recycled vegetable oil modified rubber for tires includes the following parts: raw material preparation (filtering equipment is required, but the existing filtering equipment still has problems such as inconvenient replacement of filter cloth and low filtering production efficiency), rubber plasticizing, mixing, pressing, vulcanization, and post-processing. At present, petroleum-based oil is widely used in tire manufacturing. This resource is not only non-renewable, but also contains harmful substances such as PAH, which pollutes the environment. As a major tire producer, using "gutter oil" to manufacture bio-based oil and create sustainable development tires has become a new direction leading the tire material revolution. To this end, we propose a production process and equipment for recycled vegetable oil modified rubber for tires. Summary of the invention

[0011] The purpose of the present invention is to provide a process and equipment for producing rubber for tires modified by recycled vegetable oil, which can solve the problems raised in the background technology. The rubber for tires modified by recycled vegetable oil of the present invention cooperates with each other through appropriate addition of various component raw materials, and is combined with the corresponding preparation process, so that the rubber for tires modified by recycled vegetable oil has high tear strength and excellent tear resistance; and high tensile strength and elongation at break, good mechanical properties; good wear resistance, low brittle temperature, and good low temperature resistance; In addition, the production equipment for rubber for tires modified by recycled vegetable oil of the present invention includes a filter press for preparing recycled vegetable oil, and an open mill, internal mixer, calendering equipment and vulcanization equipment for rubber production; the filter press removes the positioning piece, rotates the roller mechanism below, and rolls up the used filter cloth. After the old filter cloth is rolled up, the positioning piece is inserted for fixing, and there is no need to remove the old filter cloth, so the replacement speed is fast and the efficiency is high.

[0012] In order to solve the above technical problems, the technical solution provided by the present invention is:

[0013] A process for producing tire rubber modified with recycled vegetable oil, comprising the following steps:

[0014] 1) Preparation of recycled vegetable oil

[0015] 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;

[0016] 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;

[0017] 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;

[0018] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0019] 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;

[0020] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0021] S7. After heating the oil in step S6 to 60-90°C, adding it to a deodorizer for deodorization to remove substances that affect the temperature and color, lowering the temperature to below 40°C for filling to obtain the regenerated vegetable oil;

[0022] 2) Preparation of modified polyurethane elastomer

[0023] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0024] 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;

[0025] 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;

[0026] 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;

[0027] 3) Preparation of tire rubber modified with recycled vegetable oil

[0028] 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;

[0029] ② Then mix the two together on an internal mixer at 120-140°C for 8-12 minutes to obtain a mixed rubber material;

[0030] 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 plate-shaped or flaky tire rubber modified with the recycled vegetable oil;

[0031] There is no particular order for steps 1) to 2).

[0032] Preferably, the filter mesh number is 50-200, and at least two filters are arranged in descending order of mesh number.

[0033] Preferably, the decolorizing agent is one of activated clay or activated carbon.

[0034] Preferably, the recycled vegetable oil-modified tire rubber is made of the following raw materials in parts by weight:

[0035] 70-80 parts of random block solution-polymerized styrene-butadiene rubber,

[0036] 8-12 parts of nitrile rubber,

[0037] 10-15 parts of recycled vegetable oil,

[0038] 15-20 parts of modified polyurethane elastomer,

[0039] Sulfur 1.2-1.7 parts,

[0040] 1 to 1.2 parts of vulcanization accelerator,

[0041] 2-4 parts of nano zinc oxide,

[0042] 1 to 2 parts of stearic acid.

[0043] Preferably, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0044] 100-125 parts of polycaprolactone diol,

[0045] 50-65 parts of polypropylene glycol,

[0046] 4-6 parts of trisilanolphenyl-cage polysilsesquioxane,

[0047] 2.5 to 3.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0048] 16-22 parts of hexamethylene diisocyanate,

[0049] 50-100 parts of ethyl acetate,

[0050] Short glass fiber 75-95 parts.

[0051] Preferably, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0052] 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.

[0053] Preferably, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 22-26%.

[0054] Preferably, the vulcanization accelerator is vulcanization accelerator DCBS.

[0055] The present invention also provides a regenerated vegetable oil-modified tire rubber production equipment, which is suitable for the regenerated vegetable oil-modified tire rubber production process. The regenerated vegetable oil-modified tire rubber production equipment comprises a filter press for preparing regenerated vegetable oil, and an open mixer, an internal mixer, a calendering device and a vulcanizing device for rubber production; the filter press (i.e., the filter press in step S1.) comprises a filter press body and a plurality of filter plates arranged thereon, support plates are arranged at the four corners of the filter plate, roller mechanisms are arranged on the upper and lower sides of the filter plate, and both sides of the roller mechanism are installed on the support plate. A supporting rod is inserted in the support plate on one side for supporting the roller mechanism, and a rotating positioning piece is provided on the support plate on the other side for limiting the rotation of the roller mechanism; a filter cloth cylinder is installed on the roller mechanism on the upper side, and one end of the filter cloth is pulled downward and fixed to the roller mechanism on the lower side. When the filter cloth between the filter plates needs to be replaced, the rotating positioning pieces on the upper and lower sides are removed, and the roller mechanism on the lower side is rotated at this time so that the roller mechanism on the lower side rewinds the filter cloth. At this time, the used filter cloth between the filter plates will be wound around the next roller mechanism, and there is no need to remove the old filter cloth, so the replacement speed is fast and the efficiency is high.

[0056] Preferably, the roller mechanism includes a roller cylinder, a support rod and a limit block, both sides of the roller cylinder are connected to the limit blocks via support rods, the support rods are detachable and inserted into the roller cylinder and rotate with the roller cylinder, the limit block is movably mounted on the support plate, the limit block and the support plate on one side are supported by a support plug rod, and the rotation of the limit block and the support plate on the other side is restricted by a rotating positioning piece; the support plug rod and the rotating positioning piece are pulled out, at this time the limit block can be removed from the support plate, and the roller mechanism can be further removed, which is convenient for replacing a new filter cloth cylinder, and the rotating positioning piece is removed separately, at this time the limit block can rotate relative to the support plate, that is, the roller mechanism can rotate relative to the support plate, which is convenient for the roller mechanism on the lower side to rewind the used filter cloth.

[0057] Preferably, the cross section of the support rod is a polygonal structure, and cavities matching the shape of the support rod are provided inside both sides of the roller shaft tube, so that the support rod can drive the roller shaft tube to rotate.

[0058] Preferably, the rotating positioning member comprises a handle, a positioning rod and a connecting rope, wherein the positioning rod is symmetrically mounted on both sides of the handle and passes through the limit block and the support plate to limit the limit block from rotating relative to the support plate, and the handle is connected to the support plate via a connecting rope;

[0059] The handle is connected to the support plate by a connecting rope. When the handle is pulled, the positioning rod is pulled out from the limit block and the support plate. At this time, the limit block can rotate relative to the support plate. When the handle is released, the handle will not fall to the ground under the pulling of the connecting rope;

[0060] Among them, a plurality of insertion holes cooperating with the positioning rod are evenly opened on the limit block, and a rotation limit hole cooperating with the positioning rod is opened on the support plate. The positioning rod passes through the insertion holes and the rotation limit hole in sequence to limit the limit block relative to the support plate. When the handle is pulled, the positioning rod is pulled out of the insertion holes and the rotation limit hole, and at this time the limit block can rotate relative to the support plate.

[0061] Preferably, the support plate is provided with a support groove for matching the limit block, and one side of the support groove is open. When the support rod is pulled out, the rod portion of the support rod is pulled out from the opening of the support groove. At this time, the rod portion of the support rod does not support and limit the limit block in the support groove, which is convenient for removing the limit block from the support plate, that is, it is convenient to remove the roller mechanism and install a new filter cloth cylinder; a support limit hole matching the support rod is penetrated through the side surface of the support plate, and the support rod passes through the support limit holes on multiple support plates in turn, and the side wall of the support rod abuts against the side wall of the limit block, so that the support rod supports the limit block; one support rod is used to pass through all the support plates on the same side. When the support rod is pulled out, the limit blocks on all the support plates on the same side are no longer abutted by the support rod, which is convenient for the overall rapid replacement of a new filter cloth cylinder.

[0062] Preferably, both the upper and lower sides of the filter plate are provided with a shaking mechanism, the shaking mechanism includes a shaking rod rotating on the filter plate, one side of the shaking rod is rotatably connected to a rolling body, one side of the shaking rod is connected to the filter plate by a spring, and the other side is connected to a pull ring by a pull rope; at this time, the pull rope drives the shaking rod to move intermittently, and under the action of the spring, the shaking rod can intermittently reciprocate, and further enables the shaking rod to drive the rolling body to intermittent reciprocating deflection movement, and at this time, the rolling body reciprocates and deflects to contact and push the filter cloth between the filter plates to move. The filter cloth itself is elastic, and will shake and stretch under the push of the rolling body, so as to shake off impurities on the filter cloth, which is easy to clean and efficient.

[0063] Preferably, the angle between the shaking rod and the pull rope is an obtuse angle. When the shaking rod is deflected, the rolling body is driven to deflect, so that the rolling body can intermittently contact and push the filter cloth to move, that is, the filter cloth is shaken and the material falls off; the two sides of the rolling body are connected to the shaking rod through a ball; the rolling body has a larger rotation space, and at this time, the side of the rolling body will not touch the filter cloth after deflection, thereby avoiding scratching the filter cloth.

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

[0065] 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.

[0066] The regenerated vegetable oil modified tire rubber production equipment of the present invention comprises a filter press for preparing the regenerated vegetable oil, and an open mixer, internal mixer, calendering equipment and vulcanization equipment for rubber production; the advantages of the filter press are as follows:

[0067] 1. After the waste cooking oil is purified, it can meet the industrial index range and obtain renewable bio-based oil that can be used for tires. It can consume a large amount of "gutter oil" discarded from the catering industry and other industries. At the same time, as a green material, it has broad market prospects.

[0068] 2. Remove the positioning piece, turn the roller mechanism below, and roll up the used filter cloth. After rolling up the old filter cloth, insert the positioning piece to fix it. There is no need to remove the old filter cloth, which makes the replacement fast and efficient.

[0069] 3. Pull the pull ring intermittently. Under the action of the spring, the shaking rod will intermittently reciprocate and deflect. At this time, the rolling body will intermittently push the filter cloth, causing the filter cloth to shake and shake off the impurities on the surface, making cleaning easy and efficient.

[0070] 4. Remove the rotating positioning piece and the supporting rod, separate the roller mechanism from the supporting plate, put the new cloth cylinder on the roller cylinder, and then put the roller mechanism on the supporting plate. Pull the filter cloth downward and fix it to the roller mechanism on the lower side of the filter plate, and then insert the rotating positioning piece and the supporting rod. At this time, the installation of the roller mechanism is completed, which is convenient for replacing and installing the new filter cloth cylinder. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 It is a three-dimensional schematic diagram of the overall structure of the filter press of the present invention.

[0072] Figure 2 It is a three-dimensional schematic diagram of the roller mechanism structure of the filter press of the present invention.

[0073] Figure 3 It is a three-dimensional schematic diagram of the support plate structure of the filter press described in the present invention.

[0074] Figure 4 It is a three-dimensional schematic diagram of the material shaking mechanism structure of the filter press described in the present invention.

[0075] Figure 5 For the present invention Figure 1 A magnified schematic diagram of the structure in the middle.

[0076] Figure 6 For the present invention Figure 1 A magnified schematic diagram of structure B in the middle.

[0077] Figure 7 For the present invention Figure 2 Enlarged schematic diagram of the C structure in the middle.

[0078] Figure 8 For the present invention Figure 2 A magnified schematic diagram of the D structure.

[0079] In the figure: filter press body 1; filter plate 2; support plate 3; support groove 31; support limit hole 32; rotation limit hole 33; roller cylinder 34; support rod 42; limit block 43; plug hole 44; support plug rod 5; handle 61; positioning rod 62; connecting rope 63; material shaking rod 71; rolling body 72; spring 73; pull rope 74; pull ring 75. DETAILED DESCRIPTION

[0080] In order to enable those skilled in the art to better understand the scheme of the present invention, the technical scheme in the embodiment of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiment of the present invention. Obviously, the described embodiment is only a part of the embodiment of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0081] 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.

[0082] In the description of the present invention, it is necessary to understand that the terms "upper", "lower", "front", "back", "left", "right", "top", "bottom", "inside" and "outside" etc., indicating directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific direction, be constructed and operated in a specific direction, and therefore cannot be understood as a limitation on the present invention.

[0083] Example 1

[0084] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0085] 70-80 parts of random block solution-polymerized styrene-butadiene rubber,

[0086] 8-12 parts of nitrile rubber,

[0087] 10-15 parts of recycled vegetable oil,

[0088] 15-20 parts of modified polyurethane elastomer,

[0089] Sulfur 1.2-1.7 parts,

[0090] 1 to 1.2 parts of vulcanization accelerator,

[0091] 2-4 parts of nano zinc oxide,

[0092] 1 to 2 parts of stearic acid.

[0093] 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.

[0094] Preferably, the recycled vegetable oil-modified tire rubber is made of the following raw materials in parts by weight:

[0095] 75 parts of random block solution-polymerized styrene-butadiene rubber,

[0096] 10 parts of nitrile rubber,

[0097] 12.5 parts of recycled vegetable oil,

[0098] 17.5 parts of modified polyurethane elastomer,

[0099] 1.45 parts of sulfur,

[0100] 1.1 parts of vulcanization accelerator,

[0101] 3 parts of nano zinc oxide,

[0102] 1.5 parts of stearic acid.

[0103] Preferably, the preparation process of the regenerated vegetable oil comprises the following steps:

[0104] 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;

[0105] 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;

[0106] 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;

[0107] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0108] 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;

[0109] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] Preferably, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 22-26%.

[0115] 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.

[0116] Preferably, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0117] 100-125 parts of polycaprolactone diol,

[0118] 50-65 parts of polypropylene glycol,

[0119] 4-6 parts of trisilanolphenyl-cage polysilsesquioxane,

[0120] 2.5 to 3.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0121] 16-22 parts of hexamethylene diisocyanate,

[0122] 50-100 parts of ethyl acetate,

[0123] Short glass fiber 75-95 parts.

[0124] Preferably, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0125] 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.

[0126] 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.

[0127] Preferably, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0128] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0129] 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;

[0130] 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;

[0131] 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.

[0132] 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;

[0133] 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.

[0134] Preferably, the vulcanization accelerator is vulcanization accelerator DCBS.

[0135] The present invention also provides a method for preparing the regenerated vegetable oil-modified tire rubber, which is characterized by comprising the following steps:

[0136] 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;

[0137] ② Then mix the two together on an internal mixer at 120-140°C for 8-12 minutes to obtain a mixed rubber material;

[0138] 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.

[0139] The production equipment applicable to the process for producing tire rubber modified by regenerated vegetable oil of the present invention comprises a filter press for preparing regenerated vegetable oil, and an open mixer, internal mixer, calendering equipment and vulcanizing equipment for rubber production; the filter press is described in detail in the attached drawings. Figure 1-8 , including a filter press body 1 and a plurality of filter plates 2 arranged thereon, support plates 3 are provided at the four corners of the filter plate 2, roller mechanisms are provided on the upper and lower sides of the filter plate 2, and both sides of the roller mechanisms are installed on the support plates 3, a support plug 5 is inserted in the support plate 3 on one side for supporting the roller mechanism, and a rotating positioning piece is provided on the support plate 3 on the other side for limiting the rotation of the roller mechanism, a filter cloth drum is installed on the roller mechanism on the upper side, one end of the filter cloth is pulled downward and fixed to the roller mechanism on the lower side, when the filter cloth between the filter plates 2 needs to be replaced, the rotating positioning pieces on the upper and lower sides are removed, and the roller mechanism on the lower side is rotated at this time, so that the roller mechanism on the lower side rewinds the filter cloth, and the used filter cloth between the filter plates 2 will be wound around the next roller mechanism, and there is no need to remove the old filter cloth, so the replacement speed is fast and the efficiency is high.

[0140] To ensure the stability of winding, support rods 5 are inserted into the support plates 3 at both ends of the lower side of the filter plate 2, and the lower support rods 5 are against the bottom of the roller mechanism to support it and prevent the roller mechanism from falling.

[0141] In order to ensure the cleanliness of the filter cloth on the filter cloth cylinder, a protective shell is provided on the filter plate 2, and the protective shell covers the roller mechanism to prevent dust from contaminating the filter cloth on the filter cloth cylinder.

[0142] The roller mechanism includes a roller cylinder 41, a support rod 42 and a limit block 43. Both sides of the roller cylinder 41 are connected to the limit block 43 through the support rod 42. The support rod 42 is detachable and inserted into the roller cylinder 41, which is convenient for replacing a new filter cloth cylinder. The support rod 42 rotates with the roller cylinder 41, and the limit block 43 is movably installed on the support plate 3. The limit block 43 on one side is supported by the support plug rod 5 and the rotation of the limit block 43 on the other side is limited by the support plate 3. The support plug rod 5 and the rotation positioning member are pulled out. At this time, the limit block 43 can be removed from the support plate 3, and the roller mechanism can be further removed, which is convenient for replacing a new filter cloth cylinder. The rotation positioning member is removed separately. At this time, the limit block 43 can rotate relative to the support plate 3, that is, the roller mechanism can rotate relative to the support plate 3, which is convenient for the roller mechanism on the lower side to reel in the used filter cloth.

[0143] The cross section of the support rod 42 is a polygonal structure, and cavities matching the shape of the support rod 42 are provided inside both sides of the roller tube 41 to facilitate the support rod 42 to drive the roller tube 41 to rotate.

[0144] The rotating positioning member includes a handle 61, a positioning rod 62 and a connecting rope 63. The positioning rod 62 is symmetrically installed on both sides of the handle 61 and passes through the limit block 43 and the support plate 3, and is used to limit the rotation of the limit block 43 relative to the support plate 3. The handle 61 is connected to the support plate 3 through the connecting rope 63. When the handle 61 is pulled, the positioning rod 62 is pulled out from the limit block 43 and the support plate 3. At this time, the limit block 43 can rotate relative to the support plate 3. When the handle 61 is released, the handle 61 will not fall to the ground under the pulling of the connecting rope 63.

[0145] Among them, a plurality of insertion holes 44 cooperating with the positioning rod 62 are evenly opened on the limit block 43, and a rotation limit hole 33 cooperating with the positioning rod 62 is opened on the support plate 3. The positioning rod 62 passes through the insertion hole 44 and the rotation limit hole 33 in sequence, and is used to limit the limit block 43 relative to the support plate 3. When the handle 61 is pulled, the positioning rod 62 is pulled out from the insertion hole 44 and the rotation limit hole 33, and at this time, the limit block 43 can rotate relative to the support plate 3.

[0146] Furthermore, in order to facilitate the rotation of the roller mechanism, a protruding column is provided on the limit block 43 .

[0147] A support groove 31 is provided on the support plate 3 to cooperate with the limit block 43. One side of the support groove 31 is open. When the support rod 5 is pulled out, the rod portion of the support rod 5 is pulled out from the opening of the support groove 31. At this time, the rod portion of the support rod 5 does not support and limit the limit block 43 in the support groove 31, which makes it easy to remove the limit block 43 from the support plate 3, that is, to remove the roller mechanism and install a new filter cloth cylinder.

[0148] A support limit hole 32 matching the support rod 5 is penetrated through the side of the support plate 3. The support rod 5 passes through the support limit holes 32 on multiple support plates 3 in sequence, and the side wall of the support rod 5 abuts against the side wall of the limit block 43, so that the support rod 5 can support the limit block 43.

[0149] Furthermore, a support rod 5 is used to pass through all the support plates 3 on the same side. When the support rod 5 is extracted, the limit blocks 43 on all the support plates 3 on the same side are no longer abutted by the support rod 5, which facilitates the overall rapid replacement of a new filter cloth cylinder.

[0150] The filter plate 2 is provided with a shaking mechanism on the upper and lower sides, and the shaking mechanism includes a shaking rod 71 rotating on the filter plate 2. One side of the shaking rod 71 is rotatably connected to a rolling body 72. One side of the shaking rod 71 is connected to the filter plate 2 by a spring 73, and the other side is connected to a pull ring 75 by a pull rope 74. The pull ring 75 is pulled intermittently, and at this time the pull rope 74 drives the shaking rod 71 to move intermittently. Under the action of the spring 73, the shaking rod 71 can reciprocate intermittently, and further enables the shaking rod 71 to drive the rolling body 72 to intermittently reciprocate and deflect. At this time, the rolling body 72 reciprocates and deflects to contact and push the filter cloth between the filter plates 2 to move. The filter cloth itself is elastic, and will shake and stretch under the push of the rolling body 72, so as to shake off impurities on the filter cloth, making cleaning convenient and efficient.

[0151] The angle between the shaking rod 71 and the pull rope 74 is an obtuse angle. When the shaking rod 71 deflects, it drives the rolling body 72 to deflect, so that the rolling body 72 can intermittently contact and push the filter cloth to move, that is, the filter cloth is shaken and the material falls off.

[0152] The two sides of the rolling body 72 are connected to the material shaking rod 71 through a ball, so that the rolling body 72 has a larger rotation space. At this time, the side of the rolling body 72 will not contact the filter cloth after deflection, thereby avoiding scratching the filter cloth.

[0153] Working principle: Install the filter cloth cylinder on the roller mechanism on the upper side of the filter plate 2, then pull the filter cloth downward and fix it to the roller mechanism on the lower side of the filter plate 2, where the rolling body 72 will support the side of the filter cloth to prevent the filter cloth from hanging on the side of the filter plate 2, then pick up the handle 61, insert the positioning rod 62 into the socket 44 and the rotation limit hole 33, so that the upper and lower roller mechanisms are fixed relative to the support plate 3.

[0154] When cleaning impurities on the surface of the filter cloth, the adjacent filter plates 2 are separated and the pull ring 75 is pulled intermittently. At this time, the pull rope 74 intermittently drives the shaking rod 71 to move. Under the action of the spring 73, the shaking rod 71 will intermittently reciprocate and deflect. At this time, the rolling body 72 will intermittently push the filter cloth. At this time, the filter cloth will shake to shake off the surface impurities, which is convenient to clean and efficient.

[0155] Remove the positioning piece and rotate the roller mechanism under the filter plate 2. At this time, the roller mechanism below will roll up the used filter cloth. After the old filter cloth is rolled up, the positioning piece is inserted to fix it. There is no need to remove the old filter cloth. The replacement speed is fast and the efficiency is high.

[0156] Remove the rotating positioning piece and the supporting plug rod 5, separate the roller mechanism from the supporting plate 3, separate the supporting rod 42 from the roller cylinder 41, remove the cloth cylinder that has been used on the upper side and the cloth cylinder after the next use, then put the new cloth cylinder on the roller cylinder 41, and then insert the supporting rod 42 into the roller cylinder 41, place the roller mechanism on the supporting plate 3, pull the filter cloth downward and fix it to the roller mechanism on the lower side of the filter plate 2, and then insert the rotating positioning piece and the supporting plug rod 5. At this time, the installation of the roller mechanism is completed, which is convenient for replacing and installing a new filter cloth cylinder.

[0157] Embodiment 2:

[0158] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0159] 70 parts of random block solution-polymerized styrene-butadiene rubber,

[0160] 8 parts of nitrile rubber,

[0161] 10 parts of recycled vegetable oil,

[0162] 15 parts of modified polyurethane elastomer,

[0163] 1.2 parts of sulfur,

[0164] 1 part of vulcanization accelerator,

[0165] 2 parts of nano zinc oxide,

[0166] 1 part of stearic acid.

[0167] In this embodiment, the preparation process of the regenerated vegetable oil comprises the following steps:

[0168] 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;

[0169] 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;

[0170] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 6;

[0171] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0172] 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;

[0173] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0174] 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.

[0175] In this embodiment, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 22%.

[0176] In this embodiment, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0177] 100 parts of polycaprolactone diol,

[0178] 50 parts of polypropylene glycol,

[0179] 4 parts of trisilanol phenyl-cage polysilsesquioxane,

[0180] 2.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0181] 16 parts of hexamethylene diisocyanate,

[0182] 50 parts of ethyl acetate,

[0183] 75 parts of short glass fiber.

[0184] In this embodiment, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0185] 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.

[0186] In this embodiment, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0187] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0188] 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;

[0189] 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;

[0190] 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.

[0191] In this embodiment, the vulcanization accelerator is vulcanization accelerator DCBS.

[0192] In this embodiment, the method for preparing the tire rubber modified by recycled vegetable oil comprises the following steps:

[0193] 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;

[0194] ② Then mix the two together on an internal mixer at 120°C for 12 minutes to obtain a mixed rubber material;

[0195] 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.

[0196] Embodiment 3:

[0197] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0198] 80 parts of random block solution-polymerized styrene-butadiene rubber,

[0199] 12 parts of nitrile rubber,

[0200] 15 parts of recycled vegetable oil,

[0201] 20 parts of modified polyurethane elastomer,

[0202] Sulfur 1.7 parts,

[0203] 1.2 parts of vulcanization accelerator,

[0204] 4 parts of nano zinc oxide,

[0205] 2 parts of stearic acid.

[0206] In this embodiment, the preparation process of the regenerated vegetable oil comprises the following steps:

[0207] 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;

[0208] 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;

[0209] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 8;

[0210] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0211] 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;

[0212] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0213] 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.

[0214] In this embodiment, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 26%.

[0215] In this embodiment, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0216] 125 parts of polycaprolactone diol,

[0217] 65 parts of polypropylene glycol,

[0218] 6 parts of trisilanol phenyl-cage polysilsesquioxane,

[0219] 3.5 parts of aminopropylheptyl-cage polysilsesquioxane,

[0220] 22 parts of hexamethylene diisocyanate,

[0221] 100 parts of ethyl acetate,

[0222] 95 parts of short glass fiber.

[0223] In this embodiment, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0224] 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.

[0225] In this embodiment, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0226] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0227] 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 20 minutes;

[0228] 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;

[0229] 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.

[0230] In this embodiment, the vulcanization accelerator is vulcanization accelerator DCBS.

[0231] In this embodiment, the method for preparing the tire rubber modified by recycled vegetable oil comprises the following steps:

[0232] 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;

[0233] ② Then the two were mixed together in an internal mixer at 140°C for 8 minutes to obtain a mixed rubber material;

[0234] 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.

[0235] Embodiment 4:

[0236] A recycled vegetable oil-modified tire rubber is prepared from the following raw materials in parts by weight:

[0237] 75 parts of random block solution-polymerized styrene-butadiene rubber,

[0238] 10 parts of nitrile rubber,

[0239] 12.5 parts of recycled vegetable oil,

[0240] 17.5 parts of modified polyurethane elastomer,

[0241] 1.45 parts of sulfur,

[0242] 1.1 parts of vulcanization accelerator,

[0243] 3 parts of nano zinc oxide,

[0244] 1.5 parts of stearic acid.

[0245] In this embodiment, the preparation process of the regenerated vegetable oil comprises the following steps:

[0246] 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;

[0247] 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;

[0248] S3. Add alkali solution (hydroxide solution) to step S2 for alkali washing, stir well, and adjust the pH value of the solution to 7;

[0249] S4. Add water to step S3, wash with water, and separate the upper layer of oil;

[0250] 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;

[0251] S6. Pour the mixture from step S5 into a filter bottle, filter and vacuumize;

[0252] 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.

[0253] In this embodiment, the content of styrene monomer units in the block random solution polymerized styrene butadiene rubber is 24%.

[0254] In this embodiment, the modified polyurethane elastomer is made of the following raw materials in parts by weight:

[0255] 113 parts of polycaprolactone diol,

[0256] 57.5 parts of polypropylene glycol,

[0257] 5 parts of trisilanol phenyl-cage polysilsesquioxane,

[0258] 3 parts of aminopropylheptyl-cage polysilsesquioxane,

[0259] 19 parts of hexamethylene diisocyanate,

[0260] 75 parts of ethyl acetate,

[0261] 85 parts of short glass fiber.

[0262] In this embodiment, the molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000.

[0263] 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.

[0264] In this embodiment, the preparation method of the modified polyurethane elastomer comprises the following steps:

[0265] A. Add 1 / 3 of ethyl acetate into a sealed reaction vessel, and then add 1 / 2 of hexamethylene diisocyanate, and stir to dilute;

[0266] 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;

[0267] 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 the temperature for reaction for 25 minutes;

[0268] 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.

[0269] In this embodiment, the vulcanization accelerator is vulcanization accelerator DCBS.

[0270] In this embodiment, the method for preparing the tire rubber modified by recycled vegetable oil comprises the following steps:

[0271] 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;

[0272] ② Then the two were mixed together in an internal mixer at 130°C for 10 minutes to obtain a mixed rubber material;

[0273] 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.

[0274] Comparative Example 1:

[0275] 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.

[0276] Comparative Example 2:

[0277] 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.

[0278] Comparative Example 3:

[0279] The difference from Example 4 is that no modified polyurethane elastomer is used, and the other aspects are the same as Example 4.

[0280] Comparative Example 4:

[0281] 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.

[0282] Comparative Example 5:

[0283] 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.

[0284] 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:

[0285] During the test, tear strength: refer to GB / T 529-2008 "Determination of tear strength of vulcanized rubber or thermoplastic rubber" for testing;

[0286] 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";

[0287] 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)"

[0288] 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.

[0289] Table 1

[0290]

[0291]

[0292] 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.

[0293] Embodiments 2-4 of the present invention can also use the production equipment of a regenerated vegetable oil-modified tire rubber production process suitable for the present invention in Embodiment 1, including a filter press for preparing regenerated vegetable oil, and an open mixer, internal mixer, calendering equipment and vulcanization equipment for rubber production.

[0294] 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 process for producing tire rubber modified with recycled vegetable oil, characterized in that: The following steps are involved: 1) Preparation of regenerated vegetable oil 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, adding it to a deodorizer for deodorization to remove substances that affect the temperature and color, lowering the temperature to below 40°C for filling to obtain the regenerated vegetable oil; 2) Preparation of modified polyurethane elastomer 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 raise 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; 3) Preparation of tire rubber modified with recycled vegetable oil 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 plate-shaped or flaky tire rubber modified with the recycled vegetable oil; There is no particular order for steps 1) to 2).

2. The process for producing tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The mesh number of the filter is 50 to 200, and at least two filters are arranged in descending order of mesh number.

3. The process for producing tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: The decolorizing agent is one of activated clay and activated carbon.

4. The process for producing 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: 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 to 2 parts of stearic acid.

5. The process for producing tire rubber modified with recycled vegetable oil according to claim 1, characterized in that: 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.

6. The process for producing tire rubber modified with recycled vegetable oil according to claim 5, characterized in that: The molecular weight of the polycaprolactone diol is 2000, and the molecular weight of the polypropylene glycol is 1000; The length of the short glass fiber is 3-5 mm, and the diameter of the single fiber is 9-13 um.

7. The process for producing tire rubber modified with recycled vegetable oil according to claim 4, characterized in that: The block random solution polymerized styrene butadiene rubber has a styrene monomer unit content of 22-26%. The vulcanization accelerator is vulcanization accelerator DCBS.

Images