Rubber with high performance, low rolling resistance and thermo-oxidative aging resistance and preparation method thereof

Abstract

The invention discloses rubber with high performance, low rolling resistance and thermo-oxidative aging resistance and a preparation method thereof.The rubber comprises, by weight, 100 parts of raw rubber, (0, 100) parts of carbon black and 0.5-2 parts of an interface modifier, and the interface modifier is a sulfydryl amino compound; the preparation method comprises the following steps: mixing the raw rubber, the carbon black and the interface modifier in parts by weight by adopting a double-roller open milling mode, then adding the vulcanizing agent and the vulcanization accelerator for mixing, and finally performing high-temperature vulcanization to obtain the rubber. The use amount of the vulcanizing agent is 0.3-10 parts, and the use amount of the vulcanization accelerator is 0.3-5 parts. According to the invention, the dispersion state of the carbon black can be improved, the interface interaction between the carbon black and the rubber can be enhanced, and the rubber with high performance, low rolling resistance and thermo-oxidative aging resistance can be prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber, and particularly relates to a rubber with high performance, low rolling resistance and resistance to thermal-oxidative aging, and a preparation method thereof. Background Art

[0002] Vulcanized rubber is widely used in various fields due to its high strength and high elasticity, especially in the tire industry. In practical applications, vulcanized rubber must be blended with nano-fillers such as carbon black (CB), carbon nanotubes (CNT), silica, boron nitride (BN), graphene oxide and nano-clay to provide sufficient mechanical reinforcement for the rubber matrix. CB can comprehensively improve the ultimate strength, wear resistance and service life of rubber products, and still plays an irreplaceable role in rubber reinforcement. Since 1904, CB has been the main filler used in the rubber industry due to its unparalleled low-cost and high-performance advantages. More than 92% of the CB production is used in the rubber industry.

[0003] However, due to the strong van der Waals force between particles, CB particles are easily formed into large aggregates in the rubber matrix. Under dynamic loading, the rupture and recombination of these aggregates will lead to additional energy dissipation, thereby increasing the hysteresis loss of the composite material and inevitably increasing energy and resource consumption. Therefore, improving the dispersion state of CB and the interfacial adhesion between CB and rubber is crucial for the preparation of high-energy-efficiency rubber products.

[0004] Adding an interfacial modifier to the rubber carbon black composite is the simplest and most effective way, but the reported industrial interfacial modifiers currently do not comprehensively improve the performance. The interfacial modifiers with excellent performance synthesized in the laboratory face the dilemmas of too high cost and difficult industrial production. Summary of the Invention

[0005] Aiming at the above problems, the present invention aims to provide a rubber with high performance, low rolling resistance and resistance to thermal-oxidative aging, and a preparation method thereof.

[0006] The technical solution of the present invention is as follows:

[0007] On the one hand, there is provided a rubber with high performance, low rolling resistance and resistance to thermal-oxidative aging, which comprises, by weight parts, 100 parts of raw rubber, (0, 100] parts of carbon black and 0.5 - 2 parts of an interfacial modifier, and the interfacial modifier is a mercaptoamino compound.

[0008] Preferably, the raw rubber is any one or more of ethylene propylene diene monomer rubber, natural rubber, styrene butadiene rubber, cis-1,4-polybutadiene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, styrene / butadiene block copolymer, polyisoprene rubber, polynorbornene, unsaturated polyester rubber, epoxidized butadiene rubber, epoxidized isoprene rubber, epoxidized styrene / butadiene block copolymer, and epoxidized styrene / isoprene block copolymer.

[0009] Preferably, the interfacial modifier is any one or more of the following mercaptoamino compounds:

[0010]

[0011] Preferably, the interfacial modifier is any one or more of 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, and 2-aminothioanisole.

[0012] Preferably, it further includes additives, and the additives are any one or more of zinc oxide, stearic acid, antioxidant, and antiozonant.

[0013] Preferably, by weight, the amount of zinc oxide is 3 - 8 parts, the amount of stearic acid is 1 - 4 parts, the amount of antioxidant is 1 - 3 parts, and the amount of antiozonant is 1 - 3 parts.

[0014] Preferably, the antioxidant is N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, and the antiozonant is poly(1,2-dihydro-2,2,4-trimethylquinoline).

[0015] On the other hand, a preparation method of the rubber with high performance, low rolling resistance, and resistance to heat and oxygen aging described in any one of the above is also provided, including the following steps: mixing the raw rubber, carbon black, and interfacial modifier by weight using a two-roll mill, then adding a vulcanizing agent and a vulcanization accelerator for mixing, and finally obtaining the rubber by high-temperature vulcanization; the amount of the vulcanizing agent is 0.3 - 10 parts, and the amount of the vulcanization accelerator is 0.3 - 5 parts.

[0016] Preferably, the vulcanizing agent is any one or more of sulfur, potassium polysulfide, liquid polysulfide rubber, insoluble sulfur, trisodium thiocyanurate, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, bis(tert-butylperoxyisopropyl)benzene, 3,3,5,7,7-pentamethyl-1,2,4-triepoxyhexane, cumene hydroperoxide, zinc oxide, magnesium oxide, p-tert-butylphenol formaldehyde resin, brominated p-tert-octylphenol formaldehyde resin, tetramethylthiuram disulfide, and tetraethylthiuram disulfide;

[0017] The vulcanization accelerator is any one or more of N-cyclohexyl-2-benzothiazolesulfonamide, tetramethylthiuram disulfide, pentamethylenethiuram tetrasulfide, tetraethylthiuram disulfide, 4-(2-benzothiazolyldithio)morpholine, tetramethylthiuram tetrasulfide, 4,4'-dithiodimorpholine, N,N-polythiobis(dimethylamine), N,N'-polythiobis(diethylamine), 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazolesulfenamide, dibenzothiazole disulfide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N-dicyclohexyl-2-benzothiazolesulfenamide, zinc dimethyldithiocarbamate, and zinc diethyldithiocarbamate.

[0018] Preferably, the temperature for high-temperature vulcanization is 120 - 190 °C, the pressure is 7 - 20 MPa, and the time is 15 - 120 min.

[0019] The beneficial effects of the present invention are:

[0020] By introducing a bifunctional interfacial modifier, the present invention can react with both CB and rubber chains simultaneously and establish a covalent connection at the interface, thereby improving the compatibility between CB and the rubber matrix, improving the dispersion state of CB, and enhancing the interfacial interaction, so as to prepare a rubber with high performance, low rolling resistance, and resistance to thermal oxygen aging. Moreover, the preparation method of the present invention is simple, very suitable for industrial application and promotion, and has excellent cost advantages. Description of the Drawings

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0022] Figure 1 Schematic diagram of the vulcanization curves of rubbers prepared with different interfacial modifiers;

[0023] Figure 2 Schematic diagram of the test results of the polysulfide and disulfide contents in the vulcanization networks of PIP, ABT-0.5, ABT-1, and ABT-2;

[0024] Figure 3 Infrared spectra of the reactions of different interfacial modifiers with zinc oxide and carbon black respectively;

[0025] Figure 4Transmission electron microscope spectra of different rubbers; among them, (a) is PIP, (b) is ABT-0.5, (c) is ABT-1, (d) is ABT-2, (e) is MBT-0.5, and (f) is OTD-0.5;

[0026] Figure 5 Rheological strain sweep curves of rubbers prepared with different interfacial modifiers; among them, (a), (b), and (c) are the sample curves in the unvulcanized state, and (d), (e), and (f) are the sample curves after vulcanization;

[0027] Figure 6 DSC cyclohexane freezing point depression curves of rubbers prepared with different interfacial modifiers;

[0028] Figure 7 Tensile curves of rubbers prepared with different interfacial modifiers;

[0029] Figure 8 Crystallization curves of rubbers prepared with different interfacial modifiers;

[0030] Figure 9 Performance test curves of the rubbers in Examples 6-9; among them, (a) is the vulcanization curve at 143 °C, (b) is the rheological strain sweep curve of the unvulcanized sample, (c) is the rheological strain sweep curve of the vulcanized sample, (d) is the DSC cyclohexane freezing point depression curve, (e) is the rubber tensile curve, and (f) is the rubber crystallization curve;

[0031] Figure 10 DMA temperature sweep tanδ curves of rubbers prepared with different interfacial modifiers;

[0032] Figure 11 Tensile strength and tensile strain retention rate curves of the rubber samples added with ABT interfacial modifier after aging;

[0033] Figure 12 Tensile curves of rubber samples aged for different times;

[0034] Figure 13 Vulcanization curves of natural rubber, cis-butadiene rubber, and styrene-butadiene rubber added with ABT interfacial modifier;

[0035] Figure 14 Tensile curves of natural rubber, cis-butadiene rubber, and styrene-butadiene rubber added with ABT interfacial modifier. Detailed implementation manners

[0036] The present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be noted that, without conflict, the embodiments in the present application and the technical features in the embodiments can be combined with each other. It should be pointed out that unless otherwise specified, all technical and scientific terms used in the present application have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present application belongs. The term "including" or "comprising" and the like used in the disclosure of the present invention mean that the elements or objects appearing before this term cover the elements or objects listed after this term and their equivalents, without excluding other elements or objects.

[0037] On the one hand, the present invention provides a rubber with high performance, low rolling resistance and resistance to thermal-oxidative aging. Calculated by weight parts, it includes 100 parts of raw rubber, (0, 100] parts of carbon black, and 0.5 - 2 parts of an interface modifier, and the interface modifier is a mercaptoamino compound.

[0038] In the present invention, the interface modifier adopts a bifunctional mercaptoamino compound. The mercapto group therein can not only react with the rubber main chain, establish a covalent bond between the carbon black and the rubber main chain, improve the compatibility between the carbon black and the rubber matrix, improve the dispersion state of the carbon black and enhance the interfacial interaction, but also regulate the ratio of disulfide bonds and polysulfide bonds in the vulcanization network, significantly increasing the polysulfide bonds in the vulcanization network. The bond energy of polysulfide bonds is relatively low and can preferentially break and dissipate energy during the stretching process, thereby enhancing and toughening the rubber; at the same time, polysulfide bonds have better ductility and exchangeability, can endow the rubber with higher strain-induced crystallization ability, and thus significantly improve the mechanical properties of the rubber sample.

[0039] In a specific embodiment, the raw rubber is any one or more of ethylene-propylene-diene monomer rubber, natural rubber, styrene-butadiene rubber, cis-1,4-polybutadiene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, styrene / butadiene block copolymer, polyisoprene rubber, polynorbornene, unsaturated polyester rubber, epoxidized butadiene rubber, epoxidized isoprene rubber, epoxidized styrene / butadiene block copolymer, epoxidized styrene / isoprene block copolymer. Optionally, the raw rubber is polyisoprene rubber.

[0040] In a specific embodiment, the interface modifier is any one or more of the following mercaptoamino compounds:

[0041]

[0042] In a specific embodiment, the interface modifier is any one or more of 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, 2-aminophenyl methyl sulfide. Optionally, the interface modifier is 2-aminothiophenol.

[0043] In a specific embodiment, the high-performance, low rolling resistance, and thermo-oxidative aging-resistant rubber of the present invention further comprises an additive, and the additive is any one or more of zinc oxide, stearic acid, antioxidant, and anti-aging agent.

[0044] In a specific embodiment, by weight, the dosage of the zinc oxide is 3 - 8 parts, the dosage of the stearic acid is 1 - 4 parts, the dosage of the antioxidant is 1 - 3 parts, and the dosage of the anti-aging agent is 1 - 3 parts.

[0045] In a specific embodiment, the antioxidant is N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, and the anti-aging agent is poly(1,2-dihydro-2,2,4-trimethylquinoline).

[0046] On the other hand, there is also provided a method for preparing the high-performance, low rolling resistance, and thermo-oxidative aging-resistant rubber according to any one of the above, comprising the following steps: mixing the raw rubber, carbon black, and the interfacial modifier by weight using a two-roll open mill, then adding a vulcanizing agent and a vulcanization accelerator for mixing, and finally obtaining the rubber through high-temperature vulcanization; the dosage of the vulcanizing agent is 0.3 - 10 parts, and the dosage of the vulcanization accelerator is 0.3 - 5 parts.

[0047] In a specific embodiment, the preparation method comprises the following steps:

[0048] (1) Using a two-roll open mill, thin the raw rubber 3 - 6 times, add zinc oxide and stearic acid and thin them 3 - 6 times, and then add the anti-aging agent and antioxidant and knead them 3 - 5 times;

[0049] (2) Add the interfacial modifier and thin it 3 - 6 times, add carbon black and thin it 5 - 10 times, and then add the vulcanizing agent and vulcanization accelerator and thin them 3 - 6 times;

[0050] (3) Scrape down the two-roll drugs, thin them 5 - 8 times with the minimum roll gap, and then use a flat vulcanizer for high-temperature vulcanization, and the hot press vulcanization time is determined according to T90.

[0051] In a specific embodiment, the vulcanizing agent is any one or more of sulfur, potassium polysulfide, liquid polysulfide rubber, insoluble sulfur, trisodium thiocyanurate, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, bis(tert-butylperoxyisopropyl)benzene, 3,3,5,7,7-pentamethyl-1,2,4-triepoxyhexane, cumene hydroperoxide, zinc oxide, magnesium oxide, p-tert-butylphenol formaldehyde resin, brominated p-tert-octylphenol formaldehyde resin, tetramethylthiuram disulfide, tetraethylthiuram disulfide;

[0052] The vulcanization accelerator is any one or more of N-cyclohexyl-2-benzothiazolesulfonamide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, tetraethylthiuram disulfide, 4-(2-benzothiazolyldithio)morpholine, tetramethylthiuram tetrasulfide, 4,4'-dithiodimorpholine, N,N-polythiobis(dimethylamine), N,N'-polythiobis(diethylamine), 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazolesulfenamide, dibenzothiazyl disulfide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N-dicyclohexyl-2-benzothiazolesulfenamide, zinc dimethyldithiocarbamate, and zinc diethyldithiocarbamate.

[0053] In a specific embodiment, the temperature of the high-temperature vulcanization is 120 - 190 °C, the pressure is 7 - 20 MPa, and the time is 15 - 120 min.

[0054] Example 1

[0055] A rubber with high performance, low rolling resistance, and resistance to heat-oxygen aging is prepared by the following steps:

[0056] (1) Using a two-roll open mill, the raw rubber (polyisoprene rubber (PIP), grade IR70) of 100 parts by weight is thin-sliced 5 times, 5 parts by weight of zinc oxide and 2 parts by weight of stearic acid are added and thin-sliced 5 times, then 1 part by weight of antioxidant (poly(1,2-dihydro-2,2,4-trimethylquinoline)) and 1 part by weight of antioxidant (N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine) are added and kneaded 5 times;

[0057] (2) 0.5 part by weight of interfacial modifier (2-aminobenzenethiol (ABT)) is added and thin-sliced 5 times, 40 parts by weight of carbon black (carbon black 330 purchased from Cabot Chemical) is added and thin-sliced 10 times, then 2 parts by weight of vulcanizing agent (sulfur) and 1 part by weight of vulcanization accelerator (N-cyclohexyl-2-benzothiazolesulfonamide) are added and thin-sliced 5 times;

[0058] (3) The two-roll medicine is scraped off, thin-sliced 5 times with the minimum roll gap, then using a flat vulcanizer, high-temperature vulcanization is carried out at 143 °C and 10 MPa, and the hot-press vulcanization time is determined according to T90, and the obtained product is denoted as ABT-0.5.

[0059] Example 2

[0060] Differing from Example 1, in step (2) of this example, the dosages of the interfacial modifier are 1 part by weight and 2 parts by weight respectively, and the obtained products are denoted as ABT-1 and ABT-2.

[0061] Example 3

[0062] Different from Example 1, in step (1) of this example, the raw rubbers are natural rubber, cis-1,4-polybutadiene rubber and styrene-butadiene rubber respectively, and the obtained products are denoted as NR-0.5, BR-0.5 and SBR-0.5.

[0063] Example 4

[0064] Different from Example 3, in step (2) of this example, the dosages of the interfacial modifier are 1 part by weight respectively, and the obtained products are denoted as NR-1, BR-1 and SBR-1.

[0065] Example 5

[0066] Different from Example 1, in step (2) of this example, the interfacial modifier is 4-aminothiophenol (AMP), and the dosages are 0.5, 1, 2 parts by weight respectively, and the obtained products are denoted as AMP-0.5, AMP-1, AMP-2.

[0067] Example 6

[0068] Different from Example 1, in step (2) of this example, the interfacial modifier is 3-aminothiophenol (ATP), and the dosages are 0.5, 1, 2 parts by weight respectively, and the obtained products are denoted as ATP-0.5, ATP-1, ATP-2.

[0069] Example 7

[0070] Different from Example 1, in step (2) of this example, the interfacial modifier is 2-aminothioanisole (AMTH), and the dosages are 0.5, 1, 2 parts by weight respectively, and the obtained products are denoted as AMTH-0.5, AMTH-1, AMTH-2.

[0071] Example 8

[0072] Different from Example 1, in step (2) of this example, the dosage of the interfacial modifier is 1 part by weight, the dosage of the vulcanizing agent is 2.5 parts by weight, and the dosage of the vulcanization accelerator is 1.25 parts by weight, and the obtained product is denoted as ABT-1-S2.5.

[0073] Example 9

[0074] Different from Example 8, in step (2) of this example, the dosage of the vulcanizing agent is 2.75 parts by weight, and the dosage of the vulcanization accelerator is 1.375 parts by weight, and the obtained product is denoted as ABT-1-S2.75.

[0075] Example 10

[0076] Different from Example 1, in step (2) of this example, the dosage of the interfacial modifier is 2 parts by weight, the dosage of the vulcanizing agent is 2.5 parts by weight, and the dosage of the vulcanization accelerator is 1.25 parts by weight. The obtained product is denoted as ABT-2-S2.5.

[0077] Example 11

[0078] Different from Example 10, in step (2) of this example, the dosage of the vulcanizing agent is 2.75 parts by weight, and the dosage of the vulcanization accelerator is 1.375 parts by weight. The obtained product is denoted as ABT-2-S2.75.

[0079] Comparative Example 1

[0080] Different from Example 1, in this comparative example, the interfacial modifier in step (2) is monofunctional o-toluidine (OTD), and the dosages are 0.5, 1, and 2 parts by weight respectively. The obtained products are denoted as OTD-0.5, OTD-1, and OTD-2.

[0081] Comparative Example 2

[0082] Different from Example 1, in this comparative example, the interfacial modifier in step (2) is monofunctional o-thiocresol (MBT), and the dosages are 0.5, 1, and 2 parts by weight respectively. The obtained products are denoted as MBT-0.5, MBT-1, and MBT-2.

[0083] Test Example 1

[0084] The vulcanization curves of each example and each comparative example were tested using an RPA8000 rubber processing analyzer, and the results are as Figure 1 shown. It can be seen from Figure 1 that the addition of the interfacial modifier can increase the vulcanization rate. However, since the reaction between the interfacial modifier and the rubber main chain is a competitive reaction with the sulfur cross-linking of the rubber main chain, the cross-linking density will decrease and the torque will drop.

[0085] Test Example 2

[0086] The content of disulfide and polysulfide in the vulcanization network of the rubber samples of each example was tested. The test results of Example 1 and Example 2 are as Figure 2 shown. It can be seen from Figure 2 that compared with the pure PIP rubber sample, the addition of the ABT interfacial modifier significantly increased the content of polysulfide bonds in the vulcanization network. This increase in the content of polysulfide bonds can endow the ABT-modified rubber sample with excellent mechanical properties.

[0087] Test Example 3

[0088] The infrared spectra of different interfacial modifiers after reacting with zinc oxide and carbon black were measured in the ATR-IR mode on Nicoleti S10. Some of the results are asFigure 3 as shown. From Figure 3 It can be seen that the bifunctional ABT interfacial modifier can react with both zinc oxide and carbon black simultaneously, thereby improving the dispersion of the filler. However, the monofunctional MBT and OTD can only react with carbon black and zinc oxide respectively, and have little effect on improving the filler dispersion.

[0089] Test Example 4

[0090] The morphologies of the rubber materials of each example and each comparative example were observed on a G2F20S-TWIN transmission electron microscope (TEM) with an accelerating voltage of 100 KV. Some of the results are as Figure 4 shown. From Figure 4 It can be seen that the dispersion states of carbon black and zinc oxide in the PIP sample are very poor, with large aggregates existing. However, the addition of the ABT interfacial modifier significantly improves the dispersion of carbon black and zinc oxide. This is because ABT can form covalent bonds between the filler and the rubber chain, significantly enhancing the interaction force between the filler and the rubber matrix, and greatly improving the filler dispersion. However, the addition of the monofunctional OTD and MBT interfacial modifiers does not enhance the interfacial interaction between the filler and the rubber matrix and does not improve the filler dispersion.

[0091] Test Example 5

[0092] The dynamic rheological behaviors of the rubbers of each example and each comparative example were measured using a HAAKE PXR800 rheometer. The strain amplitude of the unvulcanized material was 0.1 - 200% (60 °C, 1 Hz), and the strain amplitude of the vulcanized material was 0.1 - 40% (60 °C, 10 Hz). The filler dispersion state was evaluated through the "Payne effect", and the "Payne effect" was represented by the difference (ΔG') in storage modulus (G') between small strain and large strain. The smaller ΔG' is, the better the filler dispersion state. The test results are as Figure 5 shown. From Figure 5 It can be seen that as the strain amplitude increases, the G' of all samples shows a non-linear decrease, which is caused by the collapse of the filler aggregates. At the same filler content, the "Payne effect" of the ABT / rubber composite is weaker than that of PIP, indicating that the dispersion state of the filler is better after adding the ABT interfacial modifier. However, the "Payne effect" of the MBT and OTD composites is almost the same as that of PIP, indicating a weak interfacial interaction, which is also consistent with the TEM results.

[0093] Test Example 6

[0094] A DCS (Q200, TA) was used to observe the exothermic chemical reaction during the heating process of the sample (the interfacial interaction was further evaluated by measuring the freezing point of cyclohexane in the expanded rubber composite). The heating rate was 3 °C / min, an aluminum crucible was used, and the sample mass was 5 - 7 mg. The test results are asFigure 6 As shown. From Figure 6 It can be seen that two exothermic peaks can be observed in the solidification curve. The peak at 6 °C is the crystallization of free cyclohexane, while the other peak at a lower temperature is the crystallization of the encapsulated cyclohexane in the expanded rubber composite. The temperature difference (ΔT) between these two crystallization peaks can qualitatively describe the dispersion state of the filler. Here, the ΔT of the ABT rubber composite is higher than that of PIP and continues to increase with the increase in ABT content. This is because the enhanced interfacial interaction restricts the mobility of the network chains, thereby reducing the size of the solvent cage for the nucleation of the encapsulated cyclohexane. Compared with the ABT rubber composite, the ΔT of the MBT and OTD rubber composites is smaller, indicating that the interfacial interaction of these rubber composites is weaker. Therefore, the good dispersion state and strong interfacial interaction between the filler and the rubber are very important for high-performance rubber products after adding the ABT interfacial modifier.

[0095] Test Example 7

[0096] Tensile experiments were carried out using INSTRON68TM-10 in the United States at a tensile rate of 100 mm / min, and the test results are as Figure 7 shown. From Figure 7 It can be seen that the addition of bifunctional interfacial modifiers (e.g., AMP, ATP, ABT, AMTH) can significantly improve the mechanical properties of the rubber composite. However, the addition of monofunctional OTD and MBT interfacial modifiers has little effect on the performance improvement.

[0097] Test Example 8

[0098] The crystallization curves of the rubber samples in Test Examples 8 - 11, and the test results are as Figure 8 shown. From Figure 8 It can be seen that compared with PIP, the addition of the ABT interfacial modifier can significantly improve the initial strain and the highest crystallinity of SIC. This is because the enhanced interfacial interaction promotes the chain orientation, thereby reducing the initial strain of SIC. However, the SIC behavior of the OTD rubber composite is almost the same as that of PIP, which is also consistent with the tensile results. Although the mechanical properties of the MBT rubber composite are poor, its SIC performance is excellent due to the highest polysulfide bond content. Therefore, ABT can be used as an efficient interfacial modifier for CB-filled rubber composites and has great potential in the development of high-performance engineering rubbers.

[0099] Test Example 9

[0100] The vulcanization curves, rheological strain sweep curves, DSC cyclohexane freezing point depression curves, rubber tensile curves, and rubber crystallization curves of the rubber samples in Test Examples 8 - 11, and the results are as Figure 9 shown. From Figure 9It can be seen that after adding sulfur accelerators, the vulcanization rate and modulus of the rubber samples are significantly improved. Rheological tests and DSC tests also prove that the modified samples still have good filler dispersion and interfacial strength. Therefore, the tensile properties of the modified samples are significantly enhanced, and the crystallization properties are also significantly improved.

[0101] Test Example 10

[0102] Dynamic mechanical analysis (DMA) was performed using a Q800 (TA Instruments). For the rolling resistance test, the sample was heated from -20 °C to 90 °C in the tensile mode at a heating rate of 3 °C / min, a frequency of 10 Hz, and a strain maintained at 5%, and the results are as Figure 10 shown. Rolling resistance is one of the most important properties of tread rubber. The low rolling resistance of tread rubber can reduce the fuel consumption and heat generation of the tire. From Figure 10 it can be seen that the tanδ values of the ABT-0.5 and ABT-x-Sy rubber composites at 60 °C are much lower than those of PIP. For example, compared with PIP, the tanδ value of the ABT-1-S2.5 composite at 60 °C is reduced by 22%. However, the tanδ values of the MBT and OTD rubber composites at 60 °C are almost the same as those of PIP, which is consistent with the previous test results. Therefore, using ABT as an interfacial modifier has significant advantages in reducing rolling resistance. The addition of the ABT interfacial modifier can improve the dispersion state of the filler and the interfacial interaction between the filler and the rubber matrix, thereby reducing the internal friction between CB particles and between CB and rubber chains under dynamic deformation, and significantly reducing the rolling resistance of the rubber composite. The higher mechanical properties and lower rolling resistance of the ABT composite indicate that it has great application potential in saving fuel consumption and improving tire safety.

[0103] Test Example 11

[0104] A self-made tensile machine was used to stretch rectangular samples, and strain-induced crystallization during stretching was studied. Synchrotron radiation wide-angle X-ray diffraction (WAXD) was tested at the BL16B1 beamline of the Shanghai Synchrotron Radiation Facility (SSRF). The wavelength of the X-ray was 0.124 nm. The air background was deducted from the samples during processing. The stretching rate was 12.5 mm / min, and a MARCCD detector was used to continuously collect in-situ signals with an exposure time of 5 s. The distance from the sample to the detector was calibrated using CeO 2 and the result was 187.5 mm. The tensile test results are as Figure 11 and Figure 12 shown.

[0105] From Figure 11It can be seen that the retention rates of the tensile strength and elongation at break of the ABT rubber composite are much higher than those of PIP, indicating that the ABT interfacial modifier has excellent heat-resistant oxidative aging ability. This is because the aromatic amine structure of the ABT interfacial modifier can capture macromolecular free radicals. At the same time, the thiol groups in the ABT interfacial modifier increase the content of polysulfide bonds in the vulcanization network, and these polysulfide bonds can be rapidly exchanged and rearranged during the aging process, thereby partially repairing the defects generated during the aging process. Their synergistic effect greatly improves the heat-resistant oxidative aging performance of the rubber composite. Compared with PIP, the ABT-1-S2.5 and ABT-2-S2.5 samples also exhibit good heat-resistant oxidative aging properties. However, adding excessive sulfur and accelerators will reduce the heat-oxidative aging performance of ABT-1-S2.75 and ABT-2-S2.7.

[0106] From Figure 12 It can be seen that at the same aging time, the retention rates of the tensile strength and elongation at break of the ABT rubber composite are much higher than those of PIP, indicating that the ABT interfacial modifier has excellent heat-resistant oxidative aging ability.

[0107] Test Example 12

[0108] The vulcanization curves of the rubber samples in Examples 3-4 were tested using an RPA8000 rubber processing analyzer, and the results are as Figure 13 shown. From Figure 13 It can be seen that the addition of the interfacial modifier can increase the vulcanization rate, but since the reaction of the interfacial modifier with the rubber main chain is a competitive reaction with the sulfur cross-linking of the rubber main chain, the cross-linking density will decrease and the torque will slightly decrease.

[0109] Test Example 13

[0110] The rubber samples in Examples 3-4 were tested for tensile experiments using an American INSTRON68TM-10 at a tensile rate of 100 mm / min, and the test results are as Figure 14 shown. From Figure 14 It can be seen that even when using different rubber varieties (natural rubber, cis-butadiene rubber, and styrene-butadiene rubber), the addition of the ABT interfacial modifier can still significantly improve the mechanical properties of the rubber composite.

[0111] In summary, the present invention can provide a rubber with high performance, low rolling resistance, and heat-oxidation resistance using a bifunctional interfacial modifier. Compared with the prior art, the present invention has made significant progress.

[0112] As described above, these are only representative embodiments of the present invention and do not impose any formal limitations on the present invention. Any person skilled in the relevant art, without departing from the scope of the technical solution of the present invention, using the technical content disclosed above to make some modifications or improvements to the embodiments is an equivalent embodiment of the present invention. However, any simple modifications, equivalent changes and improvements made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A high-performance, low rolling resistance and thermal-oxidative-aging resistant rubber, characterized in that: The invention comprises, by weight, 100 parts of raw rubber, (0,100] parts of carbon black and 0.5-2 parts of an interface modifier, wherein the interface modifier is a thiolamino compound.

2. The high performance, low rolling resistance and thermal oxidative aging resistant rubber according to claim 1, characterized in that: The raw rubber is any one or more of EPDM rubber, natural rubber, styrene-butadiene rubber, butadiene rubber, polybutadiene rubber, butyl rubber, nitrile rubber, styrene / butadiene block copolymer, polyisoprene rubber, polynorbornene, unsaturated polyester rubber, epoxidized butadiene rubber, epoxidized isoprene rubber, epoxidized styrene / butadiene block copolymer, and epoxidized styrene / isoprene block copolymer.

3. The high performance, low rolling resistance and thermal oxidative aging resistant rubber according to claim 1, characterized in that: The interfacial modifier is any one or more of the following thiolamino compounds:

4. The high performance, low rolling resistance and thermal oxidative aging resistant rubber according to claim 3, characterized in that: The interface modifier is any one or more of 4-aminothiophenol, 3-aminothiophenol, 2-aminothiophenol, and 2-aminothioanisole.

5. The high performance, low rolling resistance and heat-oxidative aging resistant rubber according to any one of claims 1 to 4, characterized in that: The invention also comprises auxiliary agents, which are any one or more of zinc oxide, stearic acid, antioxidants and anti-aging agents.

6. The high performance, low rolling resistance and thermal oxidative aging resistant rubber according to claim 5, characterized in that: In parts by weight, the amount of zinc oxide is 3-8 parts, the amount of stearic acid is 1-4 parts, the amount of antioxidant is 1-3 parts, and the amount of antioxidant is 1-3 parts.

7. The high performance, low rolling resistance and thermal oxidative aging resistant rubber according to claim 5, characterized in that: The antioxidant is N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, and the antioxidant is poly(1,2-dihydro-2,2,4-trimethylquinoline).

8. The method for preparing a rubber having high performance, low rolling resistance and resistance to thermal oxidation aging as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: The raw rubber, carbon black and interfacial modifier are mixed by weight by a double-roll open mill, and then a vulcanizing agent and a vulcanization accelerator are added and mixed, and finally the rubber is vulcanized at high temperature; the amount of the vulcanizing agent is 0.3-10 parts, and the amount of the vulcanization accelerator is 0.3-5 parts.

9. The method for preparing the rubber with high performance, low rolling resistance and resistance to thermal oxidation aging according to claim 8, characterized in that: The vulcanizing agent is any one or more of sulfur, potassium polysulfide, liquid polysulfide rubber, insoluble sulfur, trisodium thiocyanate, diisopropylbenzene peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxyisopropylbenzene, 3,3,5,7,7-pentamethyl-1,2,4-triepoxyhexane, cumyl hydroperoxide, zinc oxide, magnesium oxide, p-tert-butylphenol formaldehyde resin, brominated p-tert-octylphenol formaldehyde resin, tetramethylthiuram disulfide, and tetraethylthiuram disulfide; The vulcanization accelerator is any one or more of N-cyclohexyl-2-benzothiazole sulfonamide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, tetraethylthiuram disulfide, 4-(2-benzothiazolyl dithio)morpholine, tetramethylthiuram tetrasulfide, 4,4'-dimorpholine disulfide, N,N-polysulfobis(dimethylamine), N,N'-polysulfobis(diethylamine), 2-mercaptobenzothiazole, N-tert-butyl-2-benzothiazole sulfenamide, dibenzothiazole disulfide, N-oxydiethylene-2-benzothiazole sulfenamide, N,N-dicyclohexyl-2-benzothiazole sulfenamide, zinc dimethyldithiocarbamate, and zinc diethyldithiocarbamate.

10. The method for preparing the rubber with high performance, low rolling resistance and resistance to thermal oxidation aging according to claim 8 or 9, characterized in that: The temperature of high temperature vulcanization is 120-190°C, the pressure is 7-20MPa, and the time is 15-120min.

Images