Environment-friendly rubber auxiliary as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly rubber auxiliary as well as a preparation method and application thereof, and belongs to the technical field of silane coupling agents. The preparation method comprises the following steps: putting polysulfide silane and a polyether oligomer into a reaction container; heating and stirring; performing constant-temperature reaction for a period of time to obtain a reaction material; adding a certain amount of carbon black, pouring the reaction materials into a barrel of a high-speed stirring dispersion machine, and stirring and mixing for a period of time; and taking out the mixed material, and granulating to obtain the environment-friendly rubber additive product. According to the invention, organic chains with relatively long molecular chains are adopted to replace ethyoxyl groups at two ends of TESPT. During silanization reaction, less low-molecular-weight organic matters are generated, and emission of VOC (Volatile Organic Compounds) is reduced; the modification efficiency of the white carbon black can be improved, and the dispersity of the white carbon black is improved; and thirdly, redundant hydroxyl groups on the surface of the white carbon black can be shielded by a relatively long organic chain, so that the affinity of the white carbon black and rubber is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber additives, and in particular relates to an environmentally friendly rubber additive and a preparation method and application thereof. Background Art

[0002] In 1990, the world-renowned Michelin used a silane coupling agent to perform in-situ modification of silica, replacing carbon black as a reinforcing filler in tire treads. This significantly reduced rolling resistance while maintaining wet-skid resistance. This marked the world's first introduction of the "Green Tire" concept. Current standards for low-rolling-resistance tires require: continuous improvements in wet-skid, wear, and noise performance, a 30% reduction in rolling resistance, and fuel savings exceeding 6%. The product must capture over 50% of the domestic market share, further reducing tire rolling resistance and energy consumption while also minimizing VOC emissions during the silanization reaction to protect the environment.

[0003] Currently, the rubber industry primarily uses Si69 and Si75 as silane coupling agents. However, the silanization process produces large amounts of volatile organic compounds (VOCs) and volatile lower alcohols, which are released into the atmosphere through photochemical reactions and damage the atmosphere. Furthermore, these lower alcohols can cause headaches and dizziness in workers during industrial production. To further improve silica modification, Momentive has developed a new coupling agent, NXT. However, it has few reactive functional groups, requires high dosage, and is expensive. Degussa has developed a new silane, Si-363, but its high molecular weight requires increased dosage, and its mercapto group can easily cause premature scorching. Furthermore, it is expensive. Summary of the Invention

[0004] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for preparing an environmentally friendly rubber additive, comprising the following steps: S1. Weigh a certain amount of polysulfide silane and polyether oligomer and put them into a reaction container; S2, a stirring device is installed in the reaction vessel, the reaction vessel is heated to a certain temperature, and then the stirring device starts to stir the interior of the reaction vessel; S3, the reaction container is kept at a constant temperature for a period of time to obtain a reaction material; S4. Add a certain amount of carbon black into the cylinder of the high-speed stirring disperser, pour the above reaction materials into the cylinder of the high-speed stirring disperser, cover the cylinder cover and start the high-speed stirring disperser to stir the materials in the cylinder for a period of time; S5. Take out the mixed materials and transfer them to a granulator for granulation to obtain an environmentally friendly rubber additive product.

[0005] As a preferred embodiment of the above technical solution, the polysulfide silane is any one or more of bis-(3-(triethoxysilane)propyl)-disulfide, bis-(3-(triethoxysilane)propyl)-tetrasulfide, and bis-(3-(triethoxysilane)propyl)-trisulfide; the polyether oligomer is any one or more of polyoxypropylene glycol, polytetramethylene glycol, polyethylene glycol, polyoxypropylene triol, and fatty alcohol polyoxyethylene ether.

[0006] As a preferred embodiment of the above technical solution, the weight ratio of polysulfide silane to polyether oligomer in S1 is 2:0.5-1.5, and the weight ratio of reaction material to carbon black in S4 is 1:0.8-1.5.

[0007] As a preferred embodiment of the above technical solution, the reaction container in S2 is heated in an oil bath at a temperature of 130-135°C; the reaction container in S3 is kept at a constant temperature of 130-135°C for reaction for 0.8-1.5h; the stirring speed of the high-speed stirring disperser in S4 is 750-800rpm, the stirring and mixing time is 5-10min, and the temperature during stirring and mixing is 25-35°C; the temperature during granulation in S5 is 25-35°C.

[0008] The environmentally friendly rubber additive is prepared by the above preparation method.

[0009] The application of the environmentally friendly rubber additive is to use the environmentally friendly rubber additive (silane coupling agent) as a raw material for the production of vulcanized rubber with inorganic fillers as reinforcing agents.

[0010] The vulcanized rubber is used to produce tires: The beneficial effects of the present invention are as follows: the present invention replaces the ethoxy groups at both ends of TESPT with organic chains with longer molecular chains. Environmentally friendly rubber additives have three advantages: first, they can reduce the generation of low-molecular organic matter during the silanization reaction, thereby reducing VOC emissions; second, they can improve the modification efficiency of silica and enhance the dispersibility of silica; and third, the longer organic chains can shield excess hydroxyl groups on the surface of silica, thereby increasing the affinity between silica and rubber. Compared with traditional Si69 and Si75 coupling agents, they can effectively improve the dispersibility of fillers, enhance the interfacial interaction between rubber and inorganic fillers, reduce heat generation, reduce rolling resistance, and reduce VOC emissions during rubber processing by more than 1 / 3. The IMLV series coupling agents can extend the Mooney scorch time of rubber products, indicating that the use of IMLV coupling agents is safer and can further improve the processing stability and safety of rubber compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1Schematic diagram of the organic chain replacing the ethoxy groups at both ends of TESPT in the present invention; Figure 2 TEM images of the rubber product in Example 2 and the rubber product in Comparative Example 1. DETAILED DESCRIPTION

[0012] The technical solutions of the present invention are described clearly and completely below with reference to the accompanying drawings. It should be understood that the embodiments described herein are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are intended to fall within the scope of protection of the present invention.

[0013] Example 1 S1, weighing 240g bis-(3-(triethoxysilane) propyl group)-disulfide and 120g polytetrahydrofuran diol are packed in reaction vessel; S2. A stirring device is installed in the reaction vessel, the reaction vessel is heated to 135° C., and then the stirring device starts to stir the interior of the reaction vessel; S3, the reaction container is kept at a constant temperature of 135° C. for 1 hour to obtain a reaction mass; S4, add 320g of carbon black into the cylinder of the high-speed stirring disperser, pour the above reaction materials into the cylinder of the high-speed stirring disperser, cover the cylinder cover and start the high-speed stirring disperser to stir, control the speed between 750-800rpm, control the temperature at about 30°C, and stir and mix for 10 minutes; S5. Take out the mixed materials and transfer them to a granulator for granulation. The temperature is controlled at about 30°C to obtain an environmentally friendly rubber additive product.

[0014] The above-mentioned environmentally friendly rubber additive is used as a raw material for the production of vulcanized rubber with an inorganic filler as a reinforcing agent; the above-mentioned silane coupling agent is used as a raw material for the production of vulcanized rubber with an inorganic filler as a reinforcing agent: 10 parts of environmentally friendly rubber additive product, 100 parts of styrene-butadiene rubber, 70 parts of SiO2 inorganic filler, 20 parts of softener, 5 parts of accelerator, etc., are obtained through processes such as mixing, calendering, molding, and vulcanization to obtain rubber products for tire production.

[0015] Example 2 S1. Weigh 240 g of bis-(3-(triethoxysilane)propyl)-trisulfide and 100 g of polyoxypropylene triol into a reaction vessel; S2. A stirring device is installed in the reaction vessel, the reaction vessel is heated to 135° C., and then the stirring device starts to stir the interior of the reaction vessel; S3, the reaction container is kept at a constant temperature of 135° C. for 1 hour to obtain a reaction mass; S4, add 300g of carbon black into the cylinder of the high-speed stirring disperser, pour the above reaction materials into the cylinder of the high-speed stirring disperser, cover the cylinder cover and start the high-speed stirring disperser to stir, control the speed between 750-800rpm, control the temperature at about 30°C, and stir and mix for 10 minutes; S5. Take out the mixed materials and transfer them to a granulator for granulation. The temperature is controlled at about 30°C to obtain an environmentally friendly rubber additive product.

[0016] The above-mentioned environmentally friendly rubber additive is used as a raw material for the production of vulcanized rubber with inorganic fillers as reinforcing agents: 10 parts of environmentally friendly rubber additive product, 100 parts of styrene-butadiene rubber, 70 parts of SiO2 inorganic filler, 20 parts of softener, 5 parts of accelerator, etc., and rubber products for tire production are obtained through processes such as mixing, calendering, molding, and vulcanization.

[0017] Example 3 S1. Weigh 240 g of bis-(3-(triethoxysilane)propyl)-disulfide and 120 g of fatty alcohol polyoxyethylene ether into a reaction vessel; S2. A stirring device is installed in the reaction vessel, the reaction vessel is heated to 135° C., and then the stirring device starts to stir the interior of the reaction vessel; S3, the reaction container is kept at a constant temperature of 135° C. for 1 hour to obtain a reaction mass; S4, add 320g of carbon black into the cylinder of the high-speed stirring disperser, pour the above reaction materials into the cylinder of the high-speed stirring disperser, cover the cylinder cover and start the high-speed stirring disperser to stir, control the speed between 750-800rpm, control the temperature at about 30°C, and stir and mix for 10 minutes; S5. Take out the mixed materials and transfer them to a granulator for granulation. The temperature is controlled at about 30°C to obtain an environmentally friendly rubber additive product.

[0018] The above-mentioned environmentally friendly rubber additive is used as a raw material for the production of vulcanized rubber with inorganic fillers as reinforcing agents: 10 parts of environmentally friendly rubber additive product, 100 parts of styrene-butadiene rubber, 70 parts of SiO2 inorganic filler, 20 parts of softener, 5 parts of accelerator, etc., and rubber products for tire production are obtained through processes such as mixing, calendering, molding, and vulcanization.

[0019] Comparative Example 1 Commercially available Si69 silane coupling agent is used as the raw material for the production of vulcanized rubber with inorganic fillers as reinforcing agents: 10 parts of silane coupling agent product, 100 parts of styrene-butadiene rubber, 70 parts of SiO2 inorganic filler, 20 parts of softener, 5 parts of accelerator, etc., and rubber products for tire production are obtained through processes such as mixing, calendering, molding, and vulcanization.

[0020] The tire samples prepared in the above examples and comparative examples were subjected to performance tests using TEM and DMA dynamic performance tests. Figure 2 As shown, the rubber product containing silica in Comparative Example 1 exhibited significant agglomeration, while the rubber product in Example 2 exhibited less agglomeration and better dispersion. DMA dynamic performance testing revealed that the rubber product in Comparative Example 1 had a rolling resistance coefficient of 9.1, the rubber product in Comparative Example 2 had a rolling resistance coefficient of 8.8, and the rubber product in Comparative Example 1 had a rolling resistance coefficient of 9.4. This demonstrates that the environmentally friendly rubber additive of the present invention can effectively reduce the rolling resistance of rubber products.

[0021] It is worth mentioning that the technical features such as the granulator and high-speed stirring disperser involved in the patent application of this invention should be regarded as prior art. The specific structure, working principle and possible control method and spatial layout method of these technical features can be selected by conventional means in the field and should not be regarded as the inventive point of this patent. This patent will not be further elaborated.

[0022] The above describes in detail the preferred specific embodiments of the present invention. It should be understood that ordinary technicians in this field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solutions that can be obtained by technicians in this technical field through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of existing technologies should be within the scope of protection determined by the claims.

Claims

1. A method for preparing an environmentally friendly rubber additive, characterized in that: The following steps are included: S1. Weigh a certain amount of polysulfide silane and polyether oligomer and put them into a reaction container; S2, a stirring device is installed in the reaction vessel, the reaction vessel is heated to a certain temperature, and then the stirring device starts to stir the interior of the reaction vessel; S3, the reaction container is kept at a constant temperature for a period of time to obtain a reaction material; S4. Add a certain amount of carbon black into the cylinder of the high-speed stirring disperser, pour the above reaction materials into the cylinder of the high-speed stirring disperser, cover the cylinder cover and start the high-speed stirring disperser to stir the materials in the cylinder for a period of time; S5. Take out the mixed materials and transfer them to a granulator for granulation to obtain an environmentally friendly rubber additive product.

2. The method for preparing the environmentally friendly rubber additive according to claim 1, wherein: The polysulfide silane is any one or more of bis-(3-(triethoxysilane)propyl)-disulfide, bis-(3-(triethoxysilane)propyl)-tetrasulfide, and bis-(3-(triethoxysilane)propyl)-trisulfide; the polyether oligomer is any one or more of polyoxypropylene glycol, polytetramethylene glycol, polyethylene glycol, polyoxypropylene triol, and fatty alcohol polyoxyethylene ether.

3. The method for preparing the environmentally friendly rubber additive according to claim 2, wherein: The weight ratio of the polysulfide silane to the polyether oligomer in the S1 is 2:0.5-1.5, and the weight ratio of the reaction material to the carbon black in the S4 is 1:0.8-1.

5.

4. The method for preparing the environmentally friendly rubber additive according to claim 3, wherein: The reaction vessel in S2 is heated in an oil bath at a temperature of 130-135°C; the reaction vessel in S3 is kept at a constant temperature of 130-135°C for reaction for 0.8-1.5h; the stirring speed of the high-speed stirring disperser in S4 is 750-800rpm, the stirring and mixing time is 5-10min, and the temperature during stirring and mixing is 25-35°C; the temperature during granulation in S5 is 25-35°C.

5. Environmentally friendly rubber additive, characterized in that: Prepared by the preparation method according to any one of claims 1 to 4.

6. The use of the environmentally friendly rubber additive according to claim 5, characterized in that: The environmentally friendly rubber additive is used as a raw material for producing vulcanized rubber with an inorganic filler as a reinforcing agent.

7. The use of the environmentally friendly rubber additive according to claim 6, characterized in that: The vulcanized rubber is used to produce tires.

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