High-performance functionalized rubber nano composite material as well as preparation method and application thereof

Abstract

The invention provides a high-performance functionalized rubber nano composite material as well as a preparation method and application thereof. The high-performance functionalized rubber nano composite material is prepared from the following raw materials: functionalized rubber, a side reaction inhibitor, a filler, an activator, a vulcanizing agent, an accelerant, an anti-aging agent and a softening agent. The side reaction inhibitor is added in the preparation process of the functionalized rubber nano composite material for shearing and blending, side reaction generated in the processing process is inhibited, the high-performance functionalized rubber composite material is obtained, the scorching time is prolonged, the processing performance is improved, the filler is uniformly dispersed, the filler-rubber interaction is good, and the service life of the rubber nano composite material is prolonged. Good dynamic mechanical properties and physical and mechanical properties are realized. When applied to a tire, the high-wear-resistance and heat-generation-resistant rubber composition shows relatively low rolling resistance and relatively high wet skid resistance, wear resistance and heat generation performance are improved, fuel oil consumption can be reduced, and safety and durability of the tire are improved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber materials, and more particularly to a high-performance functionalized rubber nanocomposite material and a preparation method and application thereof. Background Art

[0002] Fillers have a good reinforcing effect in rubber, but due to the presence of a large number of hydroxyl groups on the filler surface, the compatibility between polar fillers and non-polar rubber is poor, resulting in agglomeration of fillers in the rubber matrix, affecting the various properties of rubber nanocomposites and limiting their application in the rubber field. In order to improve the dispersion of fillers in rubber, it is necessary to modify the fillers or functionalize the rubber.

[0003] Among the silane coupling agents, bifunctional silane bis(3-triethoxysilylpropyl) tetrasulfide (Si69) is widely used in filler modification. Through the reaction of siloxane with the silanol groups on the filler surface, it is grafted onto the filler surface, weakening its polarity, thereby reducing the agglomeration of the filler in the rubber matrix. In addition, the polysulfide group of Si69 further constructs the interface between the filler and the rubber molecular chain by reacting with the double bonds in the rubber.

[0004] Another way is rubber functionalization, which can be divided into chain-end functionalization and mid-chain functionalization. Chain-end functionalization can introduce a small amount of polar groups at the end of the rubber molecule chain to reduce the free end of the chain. Compared with chain-end functionalization, mid-chain functionalization can introduce more polar groups, improve the interaction with the filler, and thus improve the performance of the rubber. The thiol-ene click reaction is to introduce polar groups such as hydroxyl, amino, carboxyl, siloxane and other groups through the reaction of thiol and double bonds. However, in the thiol-ene click chemistry reaction, with the increase of click temperature and the increase of thiol reagent content, more side reactions such as carbon-carbon cross-linking will occur in the functionalized rubber, the dispersion of fillers in the rubber will deteriorate, and the bound rubber content of the functionalized rubber composite will decrease. (Wang L, Lu Y, Xie X, et al. In situ grafting onto solution polymerized styrene butadiene rubbers (SSBR) filled with silica via solid state method [J]. Journal of Applied Polymer Science, 2018, 135 (34): 46653.) In order to inhibit the occurrence of side reactions and improve the comprehensive performance of rubber, Romani F et al. used initiators to graft thioglycolic acid and its fatty acid esters onto styrene butadiene rubber, and optimized the degree of functionalization by changing experimental conditions such as reaction temperature, initiator type, and solvent to minimize the formation of insoluble cross-linked polymers (Romani F, Passaglia E, Aglietto M, et al. Functionalization of SBR copolymer by free radical addition of thiols [J]. Macromolecular Chemistry and Physics, 1999, 200 (3): 524-530.).

[0005] In the prior art, the preparation of functionalized rubber by thiol clicking requires the generation of thiol free radicals first, which then react with the double bonds in the rubber molecular chain to graft the functional groups into the rubber. When the thiol clicks the double bonds, carbon free radicals will be generated. The carbon free radicals have a certain stability and will continue to react during the rubber processing to produce side reactions such as carbon-carbon crosslinking. In addition, the thiol reagents in the clicking process will remain and continue to trigger the generation of side reactions, which will have an adverse effect on scorch and seriously affect the processing performance of the composite material. Therefore, it is necessary to study a method that can inhibit side reactions to obtain high-performance functionalized rubber nanocomposites. Summary of the invention

[0006] In order to solve the technical problems existing in the prior art, the present invention provides a high-performance functionalized rubber nanocomposite material and a preparation method and application thereof.

[0007] The invention provides an efficient and simple method for preparing a high-performance functionalized rubber nanocomposite material, which is easy to operate. In the process of preparing the functionalized rubber nanocomposite material, a side reaction inhibitor is added to perform shear blending to inhibit side reactions occurring during the processing, and finally a high-performance functionalized rubber composite material is obtained through vulcanization.

[0008] The present invention adds a multifunctional thiol reagent during the processing process, thereby avoiding the use of a large amount of solvent and the waste liquid treatment problem in the solution click method. Because the temperature in the solution method is generally controlled at a relatively low level, the click efficiency is low, while the solid phase click solves the problem of temperature limiting the solution click, reduces costs and improves efficiency.

[0009] The high-performance functionalized rubber composite material prepared by the present invention has a prolonged scorch time, improved processing performance, uniform filler dispersion, good filler-rubber interaction, and good dynamic mechanical properties and physical mechanical properties. When the composite material is used in a tire, it exhibits lower rolling resistance, higher anti-wet skid capability, and improved wear resistance and heat generation performance.

[0010] One of the purposes of the present invention is to provide a high-performance functionalized rubber nanocomposite material, which is prepared from raw materials including functionalized rubber, a side reaction inhibitor, a filler, an activator, a vulcanizing agent, an accelerator, an antioxidant and a softener.

[0011] In a preferred embodiment of the present invention,

[0012] Based on 100 parts by weight of the functionalized rubber, it includes:

[0013]

[0014] In a preferred embodiment of the present invention,

[0015] The functionalized rubber is prepared by mixing raw materials including rubber and a multifunctional thiol reagent uniformly by heat treatment; preferably,

[0016] The molar ratio of the multifunctional thiol reagent to the rubber double bond is (0.01-0.9):1, more preferably (0.02-0.06):1; and / or,

[0017] The rubber is a rubber having double bonds in the main chain or the side chain; more preferably at least one of styrene-butadiene rubber, nitrile rubber, EPDM rubber, silicone rubber, natural rubber, isoprene rubber, butadiene rubber, butyl rubber, butadiene rubber, and chloroprene rubber;

[0018] The multifunctional mercapto reagent has at least one of a siloxane group, an amine group, a carboxyl group, an ester group, and a hydroxyl functional group and a mercapto functional group; more preferably at least one of 3-mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, ethyl mercaptoacetate, methyl mercaptoacetate, mercaptoethanol, 3-mercaptopropanol, 3-mercaptopropionic acid, mercaptoundecanoic acid, mercaptosuccinic acid, and mercaptoethylamine;

[0019] The heat treatment temperature is 10 to 160°C; more preferably 80 to 140°C;

[0020] The heat treatment time is 0.1 to 30 minutes; more preferably 1 to 20 minutes, more preferably 5 to 15 minutes;

[0021] The mixing method is mixing through an open mixer, an internal mixer, a single screw extruder, a twin screw extruder, a planetary screw extruder or a kneader.

[0022] In a preferred embodiment of the present invention,

[0023] The side reaction inhibitor is a substance that can inhibit or eliminate side reactions occurring during the thiol click reaction, preferably at least one of 5,5-dimethyl-1-pyrroline-N-oxide, 2,2,6,6-tetramethylpiperidinoxide, tea polyphenols, gallic acid, dopamine, butylated hydroxytoluene, 1,1-diphenylethylene, 2,2-diphenyl-1-trinitrophenylhydrazine, p-benzoquinone, tetramethylbenzoquinone, p-aminobenzoic acid, iodine, ascorbic acid, α-tocopherol, hydroquinone, β-carotene, gentisic acid, and N-tert-butyl-α-phenylimine;

[0024] The filler is a filler containing hydroxyl groups on the surface, preferably at least one of white carbon black, montmorillonite, talc, carbon black, graphene oxide, and carbon nanotubes;

[0025] The activator is at least one of stearic acid, lead oxide, fatty acid zinc, zinc oxide, amines, and magnesium oxide;

[0026] The vulcanizing agent is at least one of sulfur, dithiomorpholine, peroxide, co-crosslinking agent, and sulfur-containing compounds;

[0027] The accelerator is at least one of thiazoles, sulfonamides, thiurams, thioformates, and guanidines, preferably at least one of N-cyclohexyl-2-benzothiazole sulfonamide and diphenylguanidine;

[0028] The antioxidant is at least one of phenol, organic sulfide and p-phenylenediamine antioxidants;

[0029] The softener is at least one of paraffin, naphthenic oil, pine tar, coumarone resin, machine oil and esters.

[0030] The second object of the present invention is to provide a method for preparing a high-performance functionalized rubber nanocomposite material, comprising the following steps:

[0031] (1) mixing components including a functionalized rubber, a side reaction inhibitor, a filler, an activator, a softener, and an antioxidant to obtain a rubber compound;

[0032] (2) heat-treating the rubber mixture obtained in step (1), then adding a vulcanizing agent and an accelerator, mixing and vulcanizing after uniform mixing to obtain the high-performance functionalized rubber nanocomposite material.

[0033] In a preferred embodiment of the present invention,

[0034] Step (1),

[0035] The mixing temperature is 20 to 120° C., preferably 35 to 100° C.; and / or,

[0036] The mixing time is 5 to 30 minutes, preferably 5 to 15 minutes; and / or,

[0037] The mixing method is mixing by an open mixer, an internal mixer, a single screw extruder, a twin screw extruder, a planetary screw extruder or a kneader.

[0038] In a preferred embodiment of the present invention,

[0039] Step (2),

[0040] The temperature of the heat treatment is 130 to 180° C., preferably 130 to 160° C.; and / or,

[0041] The heat treatment time is 2 to 15 minutes, preferably 3 to 10 minutes; and / or,

[0042] The mixed rubber is left standing before vulcanization, the standing time being 6 to 24 hours, preferably 8 to 15 hours; and / or,

[0043] After adding the vulcanizing agent and accelerator, mix until uniform;

[0044] The vulcanization temperature is 120 to 180°C, preferably 140 to 160°C; and / or,

[0045] The vulcanization pressure is 10 to 20 MPa, preferably 12 to 15 MPa.

[0046] The third object of the present invention is to provide a high-performance functionalized rubber nanocomposite material obtained by the above preparation method.

[0047] A fourth object of the present invention is to provide a high-performance functionalized rubber nanocomposite material for use in rubber products, preferably in tires.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] In the prior art, when functionalization is performed, carbon free radicals generated when the thiol group clicks on the double bond will cause side reactions such as carbon-carbon crosslinking in the rubber matrix, and the thiol reagent will remain during the clicking process, continuing to trigger the generation of side reactions, which will have an adverse effect on scorch and seriously affect the processing performance of the composite material.

[0050] The present invention prepares a functionalized rubber, and a multifunctional thiol reagent is added during the processing, thereby avoiding the use of a large amount of solvent and the waste liquid treatment problem in the solution click method. Because the temperature in the solution method is generally controlled at a relatively low level, the click efficiency is low, while the solid phase click solves the problem of temperature limiting the solution click, reduces the cost and improves the efficiency.

[0051] The present invention adds a side reaction inhibitor during the preparation of the functionalized rubber nanocomposite material for shear blending, inhibits the side reactions occurring during the processing, and obtains a high-performance functionalized rubber composite material, which prolongs the scorch time, improves the processing performance, has uniform filler dispersion, and has good filler-rubber interaction, and has good dynamic mechanical properties and physical mechanical properties. When the composite material is used in a tire, it exhibits lower rolling resistance, higher anti-wet skid capability, improved wear resistance and heat rise performance, can reduce fuel consumption, and improve tire safety and durability. DETAILED DESCRIPTION

[0052] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0053] The raw materials used in the examples are all conventional commercially available raw materials, among which the functionalized rubber is prepared in the laboratory;

[0054] Table 1 Raw materials and suppliers

[0055]

[0056]

[0057] Test method:

[0058] The Payne effect of rubber was tested by RPA2000 rubber process analyzer (RPA2000, Alpha Corporation, USA). For the blend, the strain scan at 1 Hz and 60°C was 0.28%-200%; for the vulcanizate, the strain range at 10 Hz and 60°C was 0.28-42%.

[0059] The dynamic mechanical properties were characterized by a VA3000 dynamic mechanical thermal analysis (DMTA) system (Metravib, France), and the test conditions were set at 3°C / min and 10 Hz, and the tensile strain was 0.1%.

[0060] Abrasion test: The wear resistance of vulcanized rubber was tested using an MZ-4061 Arkon abrasion tester (Jiangsu Mingzhu Testing Machine Co., Ltd.) according to GB / T1689-201451 standard.

[0061] Vulcanization performance test: The vulcanization performance of the composite material was studied at 150°C using an MR-C3 rotorless rheometer that complies with ASTM D5289 standard.

[0062] Compression fatigue temperature rise test: The test was carried out by a RH-2000N compression heat rise tester (Gotech Testing Machine Co., Ltd.) at a temperature of 55°C in accordance with ISO 4666-3:2010 standard in pure compression mode at 30Hz. The static pressure during measurement was 10% and the pre-compression was 4.45mm.

[0063] The parts in the following examples and comparative examples are all parts by weight.

[0064] Example 1

[0065] 137.5 parts of solution polymerized styrene butadiene rubber (each 137.5 g contains 100 g of rubber and 37.5 g of oil, wherein the molar number of vinyl per 100 g of rubber is 0.79 mol) and 3.77 parts of 3-mercaptopropyltriethoxysilane (the molar ratio of 3-mercaptopropyltriethoxysilane to vinyl in solution polymerized styrene butadiene rubber is 0.02:1) are added into an internal mixer for mixing at 80°C for 5 min to obtain functionalized solution polymerized styrene butadiene rubber after uniform mixing.

[0066] 100 parts of the obtained functionalized solution-polymerized styrene-butadiene rubber were added to an internal mixer, and 1 part of 2,2,6,6-tetramethylpiperidinoxide, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black, 2 parts of antioxidant 4010NA, and 1.5 parts of paraffin were added to the functionalized solution-polymerized styrene-butadiene rubber in sequence, and the mixing temperature was 90°C for 15 minutes. Then, heat treatment was performed at 150°C for 5 minutes in an internal mixer, and after cooling, 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur were added to an open mixer to prepare a rubber mixture, which was left at room temperature for 12 hours. The rubber mixture was vulcanized at 150°C and 15MPa to obtain a high-performance functionalized rubber nanocomposite material.

[0067] Example 2

[0068] The difference from Example 1 is that the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0069] Except for the above differences, other conditions in Example 2 are the same as those in Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0070] Example 3

[0071] The difference from Example 1 is that the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 5 parts;

[0072] Except for the above differences, other conditions of Example 3 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0073] Example 4

[0074] The difference from Example 1 is that the amount of 3-mercaptopropyltriethoxysilane is 7.53 parts, and the molar ratio of 3-mercaptopropyltriethoxysilane to vinyl in solution-polymerized styrene-butadiene rubber is 0.04:1; the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0075] Except for the above differences, other conditions of Example 4 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0076] Example 5

[0077] The difference from Example 1 is that: the amount of 3-mercaptopropyltriethoxysilane is 10.36 parts, and the molar ratio of 3-mercaptopropyltriethoxysilane to vinyl in solution-polymerized styrene-butadiene rubber is 0.055:1; the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0078] Except for the above differences, other conditions of Example 5 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0079] Example 6

[0080] The difference from Example 1 is that the heat treatment time for preparing the functionalized solution-polymerized styrene-butadiene rubber is 10 min; the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0081] Except for the above differences, other conditions of Example 6 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0082] Example 7

[0083] The difference from Example 1 is that the heat treatment time for preparing the functionalized solution-polymerized styrene-butadiene rubber is 15 min; the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0084] Except for the above differences, other conditions of Example 7 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0085] Example 8

[0086] The difference from Example 1 is that the heat treatment temperature for preparing the functionalized solution-polymerized styrene-butadiene rubber is 110° C.; the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0087] Except for the above differences, other conditions of Example 8 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0088] Example 9

[0089] The difference from Example 1 is that the heat treatment temperature for preparing the functionalized solution-polymerized styrene-butadiene rubber is 140° C.; the amount of 2,2,6,6-tetramethylpiperidinyl oxide is 2.47 parts;

[0090] Except for the above differences, other conditions of Example 9 are the same as those of Example 1, and a high-performance functionalized rubber nanocomposite material is obtained.

[0091] Example 10

[0092] The difference from Example 1 is that the side reaction inhibitor is replaced by butylated hydroxytoluene from 2,2,6,6-tetramethylpiperidinoxide, and the amount used is 3.48 parts;

[0093] Except for the above differences, other conditions of Example 10 are the same as those of Example 1 to obtain a high-performance functionalized rubber nanocomposite material.

[0094] Embodiment 11

[0095] 100 parts of cis-1,4-dibutyl rubber and 1.19 parts of 3-mercaptopropionic acid were added into an internal mixer for mixing. The molar ratio of 3-mercaptopropionic acid to vinyl in cis-1,4-dibutyl rubber was 0.02:1. The temperature was 80°C and the mixing time was 5 minutes. After uniform mixing, functionalized cis-1,4-dibutyl rubber was obtained.

[0096] 100 parts of the obtained functionalized butadiene rubber were added to the internal mixer, and 2.47 parts of 2,2,6,6-tetramethylpiperidinoxide, 1 part of zinc oxide, 1 part of stearic acid, 50 parts of white carbon black, 4 parts of antioxidant 4010NA, and 3 parts of paraffin were added to the functionalized butadiene rubber in sequence, and the mixing temperature was 35°C for 15 minutes. Then, heat treatment was performed at 160°C for 3 minutes in the internal mixer, and after cooling, 3 parts of accelerator CZ, 4 parts of accelerator D, and 1.5 parts of sulfur were added to the open mixer to prepare a rubber mixture, which was left at room temperature for 8 hours. The rubber mixture was vulcanized at 140°C and 15MPa to obtain a high-performance functionalized rubber nanocomposite material.

[0097] Example 12

[0098] 137.5 parts of solution polymerized styrene butadiene rubber and 3.77 parts of 3-mercaptopropyltriethoxysilane (the molar ratio of 3-mercaptopropyltriethoxysilane to the double bonds in the solution polymerized styrene butadiene rubber is 0.02:1) are added into an internal mixer for mixing at a temperature of 80°C for 5 minutes. After mixing evenly, functionalized solution polymerized styrene butadiene rubber is obtained.

[0099] 100 parts of the obtained functionalized solution-polymerized styrene-butadiene rubber were added to an internal mixer, and 2.47 parts of 2,2,6,6-tetramethylpiperidinoxide, 3 parts of zinc oxide, 2 parts of stearic acid, 80 parts of white carbon black, 2 parts of antioxidant 4010NA, and 1.5 parts of paraffin were added to the functionalized solution-polymerized styrene-butadiene rubber in sequence, and the mixing temperature was 100°C for 5 minutes. Then, heat treatment was performed at 130°C for 10 minutes in an internal mixer, and after cooling, 2 parts of accelerator CZ, 2 parts of accelerator D, and 1.5 parts of sulfur were added to an open mixer to prepare a rubber mixture, which was left at room temperature for 15 hours. The rubber mixture was vulcanized at 160°C and 12MPa to obtain a high-performance functionalized rubber nanocomposite material.

[0100] Comparative Example 1

[0101] The difference from Example 2 is that: 2,2,6,6-tetramethylpiperidinoxide is not added to the high-performance functionalized rubber nanocomposite material;

[0102] Except for the above differences, other conditions of Comparative Example 1 are the same as those of Example 2 to obtain a functionalized rubber nanocomposite material.

[0103] Table 2 Performance test of functionalized rubber nanocomposites prepared in Examples 1 to 12 and Comparative Example 1

[0104]

[0105] Table 2 shows the performance test of the functionalized rubber nanocomposites prepared in Examples 1 to 12 and Comparative Example 1. It can be seen from Table 2 that:

[0106] Compared with comparative example 1, examples 1 to 3 show that after adding the side reaction inhibitor, the scorch time is significantly prolonged, the rolling resistance, compression fatigue temperature rise and wear are significantly reduced, and the anti-skid performance is also greatly improved. The above results show that the side reaction inhibitor has a good effect of promoting thiol click and reducing cross-linking side reactions.

[0107] Examples 1 to 3 studied the effect of the amount of side reaction inhibitor added on the performance of functionalized solution-polymerized styrene-butadiene rubber nanocomposites, and found that increasing the amount of side reaction inhibitor added would improve the performance of the rubber in terms of scorch time, rolling resistance, wet skid resistance, compression fatigue temperature rise, etc. The more the amount of side reaction inhibitor added, the more thiol free radicals that promote the generation of thiol groups, and the greater the probability of addition reaction with double bonds. The present invention selects a more optimal amount of side reaction inhibitor through experiments.

[0108] Examples 2, 4, and 5 studied the effect of the amount of thiol reagent added on the functionalized solution-polymerized styrene-butadiene rubber nanocomposite material, and found that appropriately increasing the amount of thiol added was more conducive to improving the comprehensive properties of the rubber. The more thiol reagent was used, the more thiol free radicals generated by the reaction were, and the greater the probability of addition reaction with double bonds. However, if the amount of thiol reagent was too much, the probability of double radical termination between thiol free radicals would be greater, and the reaction between carbon free radicals in the rubber would be more, that is, more side reactions would occur. The present invention selected a more optimal amount of thiol reagent through experiments.

[0109] Examples 2, 6, and 7 studied the effect of reaction time on functionalized solution-polymerized styrene-butadiene rubber nanocomposites. Extending the click reaction time can greatly improve the scorch time, rolling resistance, Payne effect, anti-slip performance, compression fatigue temperature rise, etc. of the rubber nanocomposites. It shows that the longer the click reaction time, the higher the click rate. Properly increasing the reaction time is conducive to improving the click rate. However, if the reaction time is too long, more side reactions will occur. Therefore, the present invention selects a better reaction time through experiments.

[0110] Examples 2, 8, and 9 studied the effect of reaction temperature on functionalized solution-polymerized styrene-butadiene rubber nanocomposites. Increasing the click temperature can improve the performance of the rubber nanocomposites in terms of rolling resistance, anti-slip, and compression fatigue temperature rise. It shows that as the click temperature increases, the thiol reagent is more likely to generate thiol free radicals, and the probability of reacting with the vinyl double bond is greatly increased, which is beneficial to improving the click rate. However, when the temperature is too high, more cross-linking side reactions will occur, so the present invention selects a more optimal click temperature through experiments.

[0111] Examples 2 and 10 studied the effects of different side reaction inhibitors on functionalized solution-polymerized styrene-butadiene rubber nanocomposites. Compared with Comparative Example 1, different side reaction inhibitors were added, and it was found that the performance of the rubber nanocomposites in terms of rolling resistance, anti-skid, compression fatigue temperature rise, etc. were improved to varying degrees, indicating that different side reaction inhibitors can inhibit the occurrence of side reactions during the rubber functionalization process.

[0112] In the process of functionalized rubber processing, a side reaction inhibitor is added to inhibit the cross-linking side reaction. The functionalized rubber nanocomposites modified with the side reaction inhibitor prepared in Examples 1 to 12 have better anti-slip performance, wear resistance, lower dynamic compression heat rise, lower rolling resistance, and better filler dispersion than the functionalized rubber nanocomposites without the side reaction inhibitor. It is proved that adding a side reaction inhibitor during the preparation of the functionalized rubber nanocomposites is beneficial to reducing the carbon-carbon cross-linking side reaction and promoting the click of the thiol reagent, thereby obtaining a functionalized rubber nanocomposite with good comprehensive performance. The functionalized rubber nanocomposite modified with the side reaction inhibitor is a rubber composite material for tread rubber with better performance, has good application prospects in the field of "green tires", and is more suitable for passenger car tires.

Claims

1. A high-performance functionalized rubber nanocomposite material prepared from raw materials including functionalized rubber, a side reaction inhibitor, a filler, an activator, a vulcanizing agent, an accelerator, an antioxidant and a softener.

2. The high performance functionalized rubber nanocomposite material according to claim 1, Features: Based on 100 parts by weight of the functionalized rubber, it includes:

3. The high performance functionalized rubber nanocomposite material according to claim 2, Features: Based on 100 parts by weight of the functionalized rubber, it includes:

4. The high performance functionalized rubber nanocomposite material according to any one of claims 1 to 3, Features: The functionalized rubber is prepared by mixing raw materials including rubber and a multifunctional thiol reagent uniformly by heat treatment; preferably, The molar ratio of the multifunctional thiol reagent to the rubber double bond is (0.01-0.9):1, more preferably (0.02-0.06):1; and / or, The rubber is a rubber containing double bonds in the main chain or the side chain; more preferably at least one of styrene-butadiene rubber, nitrile rubber, EPDM rubber, silicone rubber, natural rubber, isoprene rubber, butadiene rubber, butyl rubber, butadiene rubber, and chloroprene rubber; and / or, The multifunctional mercapto reagent has at least one of siloxane, amine, carboxyl, ester, and hydroxyl functional groups and a mercapto functional group; more preferably at least one of 3-mercaptopropyltriethoxysilane, mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, ethyl mercaptoacetate, methyl mercaptoacetate, mercaptoethanol, 3-mercaptopropanol, 3-mercaptopropionic acid, mercaptoundecanoic acid, mercaptosuccinic acid, and mercaptoethylamine; and / or, The heat treatment temperature is 10 to 160° C.; preferably 80 to 140° C.; and / or, The heat treatment time is 0.1 to 30 min; preferably 1 to 20 min, more preferably 5 to 15 min; and / or, The mixing method is mixing through an open mixer, an internal mixer, a single screw extruder, a twin screw extruder, a planetary screw extruder or a kneader.

5. The high performance functionalized rubber nanocomposite material according to any one of claims 1 to 3, Features: The side reaction inhibitor is at least one of 5,5-dimethyl-1-pyrroline-N-oxide, 2,2,6,6-tetramethylpiperidinoxide, tea polyphenols, gallic acid, dopamine, butylated hydroxytoluene, 1,1-diphenylethylene, 2,2-diphenyl-1-trinitrophenylhydrazine, p-benzoquinone, tetramethylbenzoquinone, p-aminobenzoic acid, iodine, ascorbic acid, α-tocopherol, hydroquinone, β-carotene, gentisic acid, and N-tert-butyl-α-phenylimine; and / or, The filler is a filler containing hydroxyl groups on the surface, preferably at least one of white carbon black, montmorillonite, talc, carbon black, graphene oxide, and carbon nanotubes; and / or, The activator is at least one of stearic acid, lead oxide, fatty acid zinc, zinc oxide, amines, and magnesium oxide; and / or, The vulcanizing agent is at least one of sulfur, dithiomorpholine, peroxide, co-crosslinking agent, and sulfur-containing compounds; and / or, The accelerator is at least one of thiazoles, sulfonamides, thiurams, thioformates, and guanidines, preferably at least one of N-cyclohexyl-2-benzothiazole sulfonamide and diphenylguanidine; and / or, The antioxidant is at least one of phenol, organic sulfide and p-phenylenediamine antioxidants; and / or, The softener is at least one of paraffin, naphthenic oil, pine tar, coumarone resin, machine oil and esters.

6. A method for preparing a high-performance functionalized rubber nanocomposite material as claimed in any one of claims 1 to 5, The following steps are involved: (1) mixing components including a functionalized rubber, a side reaction inhibitor, a filler, an activator, a softener, and an antioxidant to obtain a rubber compound; (2) heat-treating the rubber mixture obtained in step (1), then adding a vulcanizing agent and an accelerator, mixing and vulcanizing after uniform mixing to obtain the high-performance functionalized rubber nanocomposite material.

7. The method for preparing the high performance functionalized rubber nanocomposite material according to claim 6, Features: Step (1), The mixing temperature is 20 to 120° C., preferably 35 to 100° C.; and / or, The mixing time is 5 to 30 minutes, preferably 5 to 15 minutes; and / or, The mixing method is mixing by an open mixer, an internal mixer, a single screw extruder, a twin screw extruder, a planetary screw extruder or a kneader.

8. The method for preparing the high performance functionalized rubber nanocomposite material according to claim 6, Features: Step (2), The temperature of the heat treatment is 130 to 180° C., preferably 130 to 160° C.; and / or, The heat treatment time is 2 to 15 minutes, preferably 3 to 10 minutes; and / or, The mixed rubber is left standing before vulcanization, the standing time being 6 to 24 hours, preferably 8 to 15 hours; and / or, The vulcanization temperature is 120 to 180°C, preferably 140 to 160°C; and / or, The vulcanization pressure is 10 to 20 MPa, preferably 12 to 15 MPa.

9. A high-performance functionalized rubber nanocomposite material obtained by the preparation method according to any one of claims 6 to 8.

10. Use of the high-performance functionalized rubber nanocomposite material according to any one of claims 1 to 5 and 9 in rubber products, preferably in tires.

Images