A high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material and preparation method thereof

Abstract

The invention discloses a high isoprene monomer content iron-based catalyzed butyl-pentene rubber tire tread composite material and a preparation method thereof, and belongs to the technical field of rubber materials and their preparation. The composite material of the invention is prepared from olefin rubber, reinforcing filler, silane coupling agent, zinc oxide, stearic acid, sulfur, antioxidant and accelerator, wherein the olefin rubber is mixed with natural rubber, solution-polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butyl-pentene rubber. The purpose of the invention is to increase the isoprene monomer content of the synthetic iron-based catalyzed butyl-pentene rubber, and then increase the propylene side group content of the iron-based catalyzed butyl-pentene rubber, thereby providing a new type of composite rubber with high anti-slip properties and a preparation method while maintaining low rolling resistance and high wear resistance.

Description

Technical Field

[0001] The invention relates to a high-isoprene monomer content iron-based catalyzed N-butylene-pentane rubber tire tread composite material and a preparation method thereof, belonging to the technical field of rubber materials and preparation thereof. Background Art

[0002] With the rapid development of the automobile industry, people have higher and higher requirements for the performance of passenger cars, including comfort, safety and fuel economy. Wet skid resistance is an important indicator to measure the safety of tire driving, especially the safety of driving in rainy days. For passenger cars, due to their high driving speed, the wet skid resistance of tires is even more important. The new European regulatory label was enforced in 2012. The main content is the three basic properties of passenger car tire treads, including rolling resistance, wet skid resistance and noise as hard limit indicators for passenger car tire replacement tires. As one of the mandatory requirements, wet skid resistance is related to the safety of the vehicle during driving, so the improvement of wet skid resistance is of great significance. Summary of the invention

[0003] The purpose of the present invention is to increase the isoprene monomer content of the synthetic iron-catalyzed butadiene-pentadiene rubber, thereby increasing the propylene side group content of the iron-catalyzed butadiene-pentadiene rubber, and provide a new type of composite rubber with high anti-slip properties and a preparation method while maintaining low rolling resistance and high wear resistance, thereby providing a new choice for the development of high-performance green tires.

[0004] The technical solution of the present invention:

[0005] One of the purposes of the present invention is to provide a high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material, the composite material is composed of the following raw materials in parts by weight:

[0006] 100 parts of olefin rubber;

[0007] 10 to 100 parts of reinforcing filler;

[0008] 1 to 9 parts of silane coupling agent;

[0009] 10-50 parts of plasticizer;

[0010] 1-10 parts of zinc oxide;

[0011] 0.5-10 parts of stearic acid;

[0012] 1-5 parts of sulfur;

[0013] 1 to 10 parts of accelerator;

[0014] 1 to 10 parts of antioxidant;

[0015] Among them, the olefin rubber is mixed by mass with 0-20 parts of natural rubber, 0-60 parts of solution-polymerized styrene-butadiene rubber, 0-30 parts of butadiene rubber and 5-80 parts of iron-based catalyzed butadiene-elastomer rubber, and the parts of natural rubber, solution-polymerized styrene-butadiene rubber and butadiene-elastomer rubber are not 0 at the same time; the iron-based catalyzed butadiene-elastomer rubber is prepared by coordination polymerization of monomer isoprene and monomer butadiene using an iron-based catalyst, and the molar ratio of monomer isoprene to butadiene in the preparation process is 9:(1-6), and the molecular weight is 20w-40w.

[0016] It is further defined that the composite material is composed of the following raw materials in parts by weight:

[0017] 100 parts of olefin rubber; 10-100 parts of reinforcing filler; 1-9 parts of silane coupling agent; 10-50 parts of plasticizer; 1-5 parts of zinc oxide; 0.5-3 parts of stearic acid; 1-3 parts of sulfur; 1-5 parts of accelerator; 1-5 parts of antioxidant.

[0018] It is further defined that the Tg of the iron-based catalyzed butadiene-pentadiene rubber is -30°C to -10°C, the side group content is 50% to 70%, and the side groups are vinyl and propylene.

[0019] It is further defined that the iron-based catalyzed NBR is composed of 3,4-polyisoprene, 1,4-polyisoprene, 1,2-polybutadiene and 1,4-polybutadiene structural units.

[0020] It is further defined that the molar content of 3,4-isoprene is 50% to 70%, the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 30% to 50%; the molar content of 1,2-butadiene is 20% to 60%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 40% to 80%.

[0021] It is further defined that the reinforcing filler is one or a mixture of carbon black, white carbon black, kaolin, talcum powder, ceramic powder, and calcium carbonate.

[0022] It is further defined that the plasticizer is one or a mixture of cycloparaffin-based rubber plasticizer, aromatic-based rubber plasticizer, and cycloalkyl rubber plasticizer.

[0023] It is further defined that the accelerator is one or a mixture of thiazoles, thiurams, sulfenamides, guanidines, and disulfide carbamates.

[0024] It is further defined that the sulfenamide accelerator is one or a mixture of N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydi(1,2-ethylene)-2-benzothiazole sulfenamide, N,N-dicyclohexyl-2-benzothiazole sulfenamide, and N-tert-butyl-2-benzothiazole sulfenamide.

[0025] It is further defined that the silane coupling agent is one or a mixture of sulfur-containing silane coupling agents, amino silane coupling agents, and epoxy silane coupling agents.

[0026] It is further defined that the antioxidant is one or a mixture of ketoamine antioxidants, diaryl secondary amine antioxidants, p-phenylenediamine antioxidants, and phenol antioxidants.

[0027] The second object of the present invention is to provide a method for preparing a high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material, the method comprising the following steps:

[0028] Step 1, raw rubber plasticizing: in an internal mixer, the filling coefficient is 0.6-0.8, natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butadiene-pentadiene rubber are added for plasticizing, the plasticizing temperature is 120°C-135°C, the plasticizing time is 180s-240s, and the plasticizing is completed to obtain plasticized rubber;

[0029] Step 2, masterbatch mixing: in an internal mixer, the filling factor is 0.6-0.8, the plasticized rubber, reinforcing filler and processing aid (including silane coupling agent, plasticizer, zinc oxide and stearic acid) parked for more than 4 hours are put into the internal mixer for mixing, the mixing temperature is 135°C-150°C, the mixing time is 240s-300s, and the mixing is completed to obtain the mixed masterbatch;

[0030] Step 3, final refining and sulfur addition: adjust the roller distance of the mixing mill to 1mm, put the mixed masterbatch into the mixing mill for thinning twice, unload the material, adjust the roller distance of the mixing mill to 1.5mm, add accelerator and sulfur, make triangle bags 3 times, unload the material, adjust the roller distance to 5.0mm, cut the rubber 3 / 4 twice, and unload the sheet.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The molecular weight of the iron-based catalyzed butyl-pentane rubber used in the present invention is between 20W and 40W, and has a low Mooney viscosity, which enhances the dispersibility of the filler, reduces the proportion of retained rubber, increases the volume of effective rubber molecules that can move freely, increases the loss factor, and greatly improves the value of tanδ at 0°C, thereby improving the anti-skid performance of the tire.

[0033] (2) The iron-based catalyzed N-butyl rubber used in the present invention has a high side group content. When the prepared rubber composite material is deformed by force, the contact area between the small and large rubber chain side groups and the filler increases, thereby generating greater internal friction, so that when the N-butyl rubber contacts a slippery road surface, the grip of the rubber composite material and the road surface is improved, and at the same time, the contribution of the propylene side group to improving the grip ability is higher than that of the vinyl side group. Therefore, the N-butyl rubber with a high side group isoprene content significantly improves the anti-slip performance of the rubber composite material.

[0034] (3) The iron-based catalytic butyl rubber used in the present invention is composed of a large number of 3,4-isoprene structural units. The 3,4-isoprene side group is large in size, and -CH3 has electron-donating ability, which makes the double bond in the propylene group easier to break the chain to form C - Ions are conducive to reacting with the surface groups of the filler and promoting the dispersion of the filler in the rubber matrix. On the other hand, the propylene side groups can better reduce the reactivity of the double bonds of the main chain compared to the vinyl side groups, and the cross-linking density is relatively low, thereby improving the anti-skid performance of the rubber material.

[0035] (4) The iron-based catalyzed butyl-ethylene rubber used in the present invention also contains a certain amount of 1,2-butadiene, 1,4-butadiene and 1,4-isoprene structural units, which have a high structural similarity with natural rubber, styrene-butadiene rubber and cis-1,4-butadiene rubber, and can be better blended to improve the anti-skid performance while ensuring its high wear resistance and low rolling resistance. DETAILED DESCRIPTION

[0036] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0037] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained through commercial channels by those skilled in the art.

[0038] The formulations and compositions of the rubber composite materials in all the embodiments of the present invention are listed in Table 1, and the main properties of the rubber composite materials are listed in Table 2.

[0039] Embodiment 1:

[0040] The raw material formula of the high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material of this embodiment is shown in the data corresponding to Example 1 in Table 1;

[0041] The molecular weight of the butadiene-vinyl rubber is 38.5w, and the side group content is 65%; the butadiene-vinyl rubber is prepared by coordination polymerization using an iron-based catalyst, and the molar ratio of monomers butadiene to isoprene is 9:1 during the preparation process; the iron-based butadiene-vinyl rubber consists of 3,4-isoprene, 1,4-isoprene, 1,2-butadiene and 1,4-butadiene structural units; the molar content of 1,2-butadiene is 40%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 60%; the molar content of 3,4-isoprene is 68%, and the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 32%.

[0042] The method for preparing the high isoprene monomer content iron-based catalyzed N-butyl rubber tire tread composite material of Example 1 is carried out by the following steps:

[0043] Step 1, plasticizing of raw rubber: in an internal mixer, the filling factor is 0.7±0.02, natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butadiene-pentadiene rubber are added for plasticizing, the plasticizing temperature is 130±5°C, the plasticizing time is 180s, and the plasticizing is completed to obtain plasticized rubber;

[0044] Step 2, masterbatch mixing: in an internal mixer, the filling factor is 0.7±0.02, the plasticized rubber, reinforcing filler and processing aids (including silane coupling agent, plasticizer, zinc oxide and stearic acid) parked for more than 4 hours are put into the internal mixer for mixing, the mixing temperature is 145±5°C, the mixing time is 240s, and the mixing is completed to obtain a mixed masterbatch;

[0045] Step 3, final refining and sulfur addition: adjust the roller distance of the mixing mill to 1mm, put the mixed masterbatch into the mixing mill for thinning twice, unload the material, adjust the roller distance of the mixing mill to 1.5mm, add accelerator and sulfur, make triangle bags 3 times, unload the material, adjust the roller distance to 5.0mm, cut the rubber 3 / 4 twice, and unload the sheet.

[0046] Embodiment 2:

[0047] The raw material formula of the high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material of this embodiment is shown in the data corresponding to Example 2 in Table 1;

[0048] The molecular weight of the butadiene-vinyl rubber is 28.3w, and the side group content is 61%; the butadiene-vinyl rubber is prepared by coordination polymerization using an iron-based catalyst, and the molar ratio of monomers butadiene to isoprene is 8:2 during the preparation process; the iron-based butadiene-vinyl rubber consists of 3,4-isoprene, 1,4-isoprene, 1,2-butadiene and 1,4-butadiene structural units; the molar content of 1,2-butadiene is 34%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 66%; the molar content of 3,4-isoprene is 68%, and the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 32%.

[0049] The method for preparing the high isoprene monomer content iron-based catalyzed N-butyl rubber tire tread composite material of Example 2 is carried out by the following steps:

[0050] Step 1, plasticizing of raw rubber: in an internal mixer, the filling factor is 0.7±0.02, natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butadiene-pentadiene rubber are added for plasticizing, the plasticizing temperature is 130±5°C, the plasticizing time is 180s, and the plasticizing is completed to obtain plasticized rubber;

[0051] Step 2, masterbatch mixing: in an internal mixer, the filling factor is 0.7±0.02, the plasticized rubber, reinforcing filler and processing aids (including silane coupling agent, plasticizer, zinc oxide and stearic acid) parked for more than 4 hours are put into the internal mixer for mixing, the mixing temperature is 145±5°C, the mixing time is 240s, and the mixing is completed to obtain a mixed masterbatch;

[0052] Step 3, final refining and sulfur addition: adjust the roller distance of the mixing mill to 1mm, put the mixed masterbatch into the mixing mill for thinning twice, unload the material, adjust the roller distance of the mixing mill to 1.5mm, add accelerator and sulfur, make triangle bags 3 times, unload the material, adjust the roller distance to 5.0mm, cut the rubber 3 / 4 twice, and unload the sheet.

[0053] Embodiment 3:

[0054] The raw material ratio of the high isoprene monomer content iron-based catalyzed N-butyl rubber tire tread composite material of this embodiment is shown in the data corresponding to Example 3 in Table 1;

[0055] The molecular weight of the butadiene-vinyl rubber is 32.4w, and the side group content is 55.4%; the butadiene-vinyl rubber is prepared by coordination polymerization using an iron-based catalyst, and the molar ratio of monomers butadiene to isoprene is 7:3 during the preparation process; the iron-based butadiene-vinyl rubber consists of 3,4-isoprene, 1,4-isoprene, 1,2-butadiene and 1,4-butadiene structural units; the molar content of 1,2-butadiene is 40%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 60%; the molar content of 3,4-isoprene is 62%, and the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 38%.

[0056] The method for preparing the high isoprene monomer content iron-based catalyzed N-butyl rubber tire tread composite material of Example 3 is carried out by the following steps:

[0057] Step 1, plasticizing of raw rubber: in an internal mixer, the filling factor is 0.7±0.02, natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butadiene-pentadiene rubber are added for plasticizing, the plasticizing temperature is 130±5°C, the plasticizing time is 180s, and the plasticizing is completed to obtain plasticized rubber;

[0058] Step 2, masterbatch mixing: in an internal mixer, the filling factor is 0.7±0.02, the plasticized rubber, reinforcing filler and processing aids (including silane coupling agent, plasticizer, zinc oxide and stearic acid) parked for more than 4 hours are put into the internal mixer for mixing, the mixing temperature is 145±5°C, the mixing time is 240s, and the mixing is completed to obtain a mixed masterbatch;

[0059] Step 3, final refining and sulfur addition: adjust the roller distance of the mixing mill to 1mm, put the mixed masterbatch into the mixing mill for thinning twice, unload the material, adjust the roller distance of the mixing mill to 1.5mm, add accelerator and sulfur, make triangle bags 3 times, unload the material, adjust the roller distance to 5.0mm, cut the rubber 3 / 4 twice, and unload the sheet.

[0060] Embodiment 4:

[0061] The raw material ratio of the high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material of this embodiment is shown in the data corresponding to Example 4 in Table 1;

[0062] The molecular weight of the butadiene-vinyl rubber is 33.5w, and the side group content is 57.6%; the butadiene-vinyl rubber is prepared by coordination polymerization using an iron-based catalyst, and the molar ratio of monomers butadiene to isoprene is 6:4 during the preparation process; the iron-based butadiene-vinyl rubber consists of 3,4-isoprene, 1,4-isoprene, 1,2-butadiene and 1,4-butadiene structural units; the molar content of 1,2-butadiene is 42%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 58%; the molar content of 3,4-isoprene is 68%, and the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 32%.

[0063] The method for preparing the high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material of Example 4 is carried out by the following steps:

[0064] Step 1, plasticizing of raw rubber: in an internal mixer, the filling factor is 0.7±0.02, natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butadiene-pentadiene rubber are added for plasticizing, the plasticizing temperature is 130±5°C, the plasticizing time is 180s, and the plasticizing is completed to obtain plasticized rubber;

[0065] Step 2, masterbatch mixing: in an internal mixer, the filling factor is 0.7±0.02, the plasticized rubber, reinforcing filler and processing aids (including silane coupling agent, plasticizer, zinc oxide and stearic acid) parked for more than 4 hours are put into the internal mixer for mixing, the mixing temperature is 145±5°C, the mixing time is 240s, and the mixing is completed to obtain a mixed masterbatch;

[0066] Step 3, final refining and sulfur addition: adjust the roller distance of the mixing mill to 1mm, put the mixed masterbatch into the mixing mill for thinning twice, unload the material, adjust the roller distance of the mixing mill to 1.5mm, add accelerator and sulfur, make triangle bags 3 times, unload the material, adjust the roller distance to 5.0mm, cut the rubber 3 / 4 twice, and unload the sheet.

[0067] Comparative Example 1:

[0068] The raw material ratio of the high isoprene monomer content iron-based catalyzed butyl-pentene rubber tire tread composite material of this comparative example is shown in the data corresponding to comparative example 1 in Table 1; its raw material types and preparation method are the same as those of Example 1.

[0069] Comparative Example 2:

[0070] The raw material ratio of the high isoprene monomer content iron-based catalyzed butyl-pentene rubber tire tread composite material of this comparative example is shown in the data corresponding to comparative example 2 in Table 1;

[0071] The molecular weight of the butadiene-vinyl rubber is 35.5w, and the side group content is 58%; the butadiene-vinyl rubber is prepared by coordination polymerization using an iron-based catalyst, and the molar ratio of monomers butadiene to isoprene is 6:4 during the preparation process; the iron-based butadiene-vinyl rubber consists of 3,4-isoprene, 1,4-isoprene, 1,2-butadiene and 1,4-butadiene structural units; the molar content of 1,2-butadiene is 42%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 58%; the molar content of 3,4-isoprene is 69%, and the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 31%.

[0072] The method for preparing the high isoprene monomer content iron-based catalyzed butyl-pentene rubber tire tread composite material of Comparative Example 2 is carried out by the following steps:

[0073] Step 1, plasticizing of raw rubber: in an internal mixer, the filling factor is 0.7±0.02, natural rubber, solution polymerized styrene-butadiene rubber, butadiene rubber and iron-based catalyzed butadiene-pentadiene rubber are added for plasticizing, the plasticizing temperature is 130±5°C, the plasticizing time is 180s, and the plasticizing is completed to obtain plasticized rubber;

[0074] Step 2, masterbatch mixing: in an internal mixer, the filling factor is 0.7±0.02, the plasticized rubber, reinforcing filler and processing aids (including silane coupling agent, plasticizer, zinc oxide and stearic acid) parked for more than 4 hours are put into the internal mixer for mixing, the mixing temperature is 145±5°C, the mixing time is 240s, and the mixing is completed to obtain a mixed masterbatch;

[0075] Step 3, final refining and sulfur addition: adjust the roller distance of the mixing mill to 1mm, put the mixed masterbatch into the mixing mill for thinning twice, unload the material, adjust the roller distance of the mixing mill to 1.5mm, add accelerator and sulfur, make triangle bags 3 times, unload the material, adjust the roller distance to 5.0mm, cut the rubber 3 / 4 twice, and unload the sheet.

[0076] Table 1 Composition of rubber composite materials

[0077] Components Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Natural rubber STR20 10.0 10.0 10.0 10.0 10.0 5.0 Solution Polystyrene Butadiene NS626 0.0 20.0 40.0 60.0 80.0 10.0 Butadiene rubber BR9000 10.0 10.0 10.0 10.0 10.0 10.0 Iron-based catalytic NBR 80.0 60.0 40.0 20.0 0.0 85.0 Aromatic oil 10.0 10.0 10.0 10.0 10.0 10.0 White Carbon Black 7000GR 30.0 30.0 30.0 30.0 30.0 30.0 Carbon Black N330 40.0 40.0 40.0 40.0 40.0 40.0 Silane coupling agent Si-69 3.0 3.0 3.0 3.0 3.0 3.0 Oxidized ZnO 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid SA 1.8 1.8 1.8 1.8 1.8 1.8 Antioxidant 4020 2.0 2.0 2.0 2.0 2.0 2.0 Antioxidant RD 1.0 1.0 1.0 1.0 1.0 1.0 sulfur 2.0 2.0 2.0 2.0 2.0 2.0 Accelerator CZ 1.2 1.2 1.2 1.2 1.2 1.2 Accelerator DETU 0.6 0.6 0.6 0.6 0.6 0.6

[0078] Table 2 Main properties of rubber composite materials

[0079] Performance parameters Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Tensile Strength 24.52 24.55 24.47 24.33 21.32 22.31 100% tensile stress, MPa 3.35 3.23 3.12 3.01 2.31 2.52 300% tensile stress, MPa 14.49 14.22 14.13 14.23 11.34 12.21 Elongation at break, % 540.01 538.64 536.45 528.64 501.3 510.5 Shore Hardness 57 58 58 59 60 60 Tear strength, KN / m 23.7 23.5 23.9 23.3 19.1 18.8 Tanδ,0℃ 0.6321 0.6145 0.5387 0.4334 0.2190 0.3098 Tanδ,60℃ 0.1734 0.1754 0.1774 0.1788 0.1853 0.1800 <![CDATA[DIN wear, mm 3 / 40m]]> 0.1899 0.1909 0.1910 0.1989 0.2197 0.2012

[0080] As shown in Table 2, the addition of iron-based catalytic butyl-pentene rubber has obvious advantages, whether it is partially or completely dissolved in styrene-butadiene rubber. The DMA test results of the comparative example and the comparative example show that as the amount of iron-based catalytic butyl-pentene rubber added increases from 5 parts to 80 parts, the Tanδ value of the rubber composite material at 0°C continues to increase, and can be increased to 3 times that of the comparative example. This is mainly due to the high side group (propylene group) content of iron-based catalytic butyl-pentene rubber, which greatly increases the rigidity of the molecular chain. At lower temperatures, the 3,4-isoprene segment has strong rigidity, which enables it to cut through the water film and maintain good anti-skid performance. As the temperature rises, the 3,4-isoprene segment begins to move, the system has a large viscosity, and the friction resistance is enhanced, thereby improving the anti-skid ability of the tire. The iron-based catalytic butyl rubber used is composed of a large number of 3,4-isoprene structural units. 3,4-isoprene is large in size. Because -CH3 has electron-donating ability, the double bond in the propylene group is easier to break than the double bond in the vinyl group, and it is easier to form C - Ions react with the surface groups of the fillers, promote the dispersion of the fillers in the rubber matrix, reduce the crosslinking density, and thus reduce the storage modulus, thereby improving the anti-slip performance of the rubber material. However, due to the high glass transition temperature of iron-catalyzed butyl ethylene rubber, excessive addition will increase the glass transition temperature of the composite material as a whole and affect the low-temperature performance of the rubber composite material. Therefore, the addition amount should not exceed 80 parts.

[0081] In addition, the addition of iron-based catalyzed butyl-elastomer rubber also improves other properties of the composite material to a certain extent. It can be seen from the DMA data that the Tanδ value at 60°C is slightly lower than that of the control group, indicating that the rolling resistance of the composite material is low. And the tensile strength, elongation at break and wear resistance of the composite material have been significantly improved compared with the control group. This is because there are still a certain amount of 1,2-butadiene, 1,4-butadiene and 1,4-isoprene structural units in the iron-based catalyzed butyl-elastomer rubber in the composite material, which can be better blended with the polyisoprene structural unit in natural rubber, the polybutadiene structural unit in styrene-butadiene rubber, and the polybutadiene structural unit in butadiene rubber during the vulcanization process, enhancing the synergistic effect and maximizing the advantages of various rubbers.

[0082] Although the present invention has been disclosed as above in the preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A high isoprene monomer content iron-based catalyzed N-butyl rubber tire tread composite material, characterized in that: It is composed of the following raw materials in parts by weight: 100 parts of olefin rubber; 10 to 100 parts of reinforcing filler; 1 to 9 parts of silane coupling agent; 10-50 parts of plasticizer; 1-10 parts of zinc oxide; 0.5-10 parts of stearic acid; 1-5 parts of sulfur; 1 to 10 parts of accelerator; 1 to 10 parts of antioxidant; Among them, the olefin rubber is mixed by mass with 0-20 parts of natural rubber, 0-60 parts of solution-polymerized styrene-butadiene rubber, 0-30 parts of butadiene rubber and 20-80 parts of iron-based catalyzed butadiene-elastomer rubber, and the parts of natural rubber, solution-polymerized styrene-butadiene rubber and butadiene-elastomer rubber are not 0 at the same time; the iron-based catalyzed butadiene-elastomer rubber is prepared by coordination polymerization of monomer isoprene and monomer butadiene using an iron-based catalyst, and the molar ratio of monomer isoprene to butadiene in the preparation process is 9:(1-6), and the molecular weight is 20w-40w.

2. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The Tg of the iron-based catalyzed butadiene-pentadiene rubber is -30°C to -10°C, the side group content is 50% to 70%, and the side groups are vinyl and propylene.

3. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: Iron-based catalyzed butylene-vinyl rubber is composed of 3,4-polyisoprene, 1,4-polyisoprene, 1,2-polybutadiene and 1,4-polybutadiene structural units.

4. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The molar content of 3,4-isoprene is 50% to 70%, and the total molar content of cis-1,4-isoprene and trans-1,4-isoprene is 30% to 50%; the molar content of 1,2-butadiene is 20% to 60%, and the total molar content of cis-1,4-butadiene and trans-1,4-butadiene is 40% to 80%.

5. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The reinforcing filler is one or a mixture of carbon black, white carbon black, kaolin, talcum powder, ceramic powder and calcium carbonate.

6. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The plasticizer is one or a mixture of cycloparaffin-based rubber plasticizer, aromatic-based rubber plasticizer and cycloalkyl rubber plasticizer.

7. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The accelerator is one or a mixture of thiazoles, thiurams, sulfenamides, guanidines and disulfide carbamates.

8. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The silane coupling agent is one or a mixture of sulfur-containing silane coupling agents, amino silane coupling agents, and epoxy silane coupling agents.

9. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The antioxidant is one of ketoamine antioxidants, diaryl secondary amine antioxidants, p-phenylenediamine antioxidants, and phenol antioxidants, or a mixture of several of them.

10. The high isoprene monomer content iron-based catalyzed N-butylene rubber tire tread composite material according to claim 1, characterized in that: The preparation is carried out by mixing in stages.