Bio-based white carbon black dispersing agent as well as preparation method and application thereof

Abstract

The invention discloses a bio-based white carbon black dispersing agent as well as a preparation method and application thereof. The dispersing agent is prepared by heating and mixing a bio-based raw material and petroleum resin, the bio-based raw material is one or more of rhamnolipid, sophorolipid and trehalose lipid, and the petroleum resin is one or more of C5 aliphatic petroleum resin, C9 aromatic petroleum resin, DCPD cycloaliphatic diene petroleum resin and alpha-methylstyrene petroleum resin. The preparation method comprises the following steps: heating and stirring the bio-based raw materials until the raw materials are molten, adding the petroleum resin, continuously stirring and uniformly mixing in a heating state, and cooling to room temperature. The bio-based white carbon black dispersing agent has the characteristics of simple preparation process, mild conditions and good compatibility with raw rubber, and can significantly improve the dispersibility of white carbon black, reduce the heat generation of a rubber material and improve the quality of a rubber product.

Description

Technical Field

[0001] The invention relates to the technical field of rubber production, and in particular to a bio-based white carbon black dispersant and a preparation method and application thereof. Background Art

[0002] In the rubber industry, the application of white carbon black is becoming more and more extensive. Using white carbon black to partially replace carbon black in tire rubber can reduce tire heat generation, rolling resistance and fuel consumption, and at the same time improve the puncture resistance, chipping resistance and wet skid resistance of the tread rubber. At present, the requirements for tire rubber are to have both good physical properties and good processing properties. Although the rubber compound with white carbon black has good physical properties, the strong polarity of white carbon black will lead to its poor compatibility with hydrocarbon rubber molecules, making it difficult to disperse in the rubber compound and having poor processing properties, so its application is greatly limited.

[0003] Traditional silica dispersants are mainly silane coupling agents. The main dispersing principle is to improve the compatibility of silica with rubber by reacting with silica at high temperature in an internal mixer, thereby improving the dispersibility of silica. This method requires a long time and high temperature to fully react. When the mixing temperature is higher than 160°C, the polysulfide bonds will break and participate in the vulcanization reaction, which can easily cause the rubber to burn. Therefore, the order of adding silane coupling agents and other compounding agents must be considered, and the discharge temperature must be strictly controlled below 140°C. In addition, ethanol will be produced during the silanization reaction, resulting in the emission of volatile organic compounds (VOCs). Summary of the invention

[0004] The purpose of the present invention is to provide a bio-based silica dispersant to address the problems in the prior art that traditional silane coupling agent-based silica dispersants have high temperature requirements and difficult to control production conditions. The bio-based silica dispersant can play a bridging role and improve the dispersibility of silica in the rubber compound in an internal mixer and an open mixer, thereby reducing the heat generation of the rubber compound and reducing rolling resistance.

[0005] The technical solution of the present invention is described in detail as follows: In a first aspect, the present invention provides a bio-based white carbon black dispersant, which is prepared by heating and mixing a bio-based raw material and a petroleum resin; The bio-based raw materials are one or more of rhamnolipids, sophorolipids, and trehalolipids; The petroleum resin is one or more of C5 aliphatic petroleum resin, C9 aromatic petroleum resin, DCPD cycloaliphatic diene petroleum resin (ie dicyclopentadiene resin), and α-methylstyrene petroleum resin.

[0006] Optionally or preferably, in the above-mentioned bio-based silica dispersant, the molecular weight of the petroleum resin is 100-5000 g / mol; more preferably 300-3000 g / mol.

[0007] Optionally or preferably, in the above-mentioned bio-based silica dispersant, the ratio of the bio-based raw material to the petroleum resin is 60~80:40~20 by mass; more preferably 70~75:30~25.

[0008] In a second aspect, the present invention provides a method for preparing any of the above-mentioned bio-based silica dispersants, which comprises heating and stirring the bio-based raw materials until they are melted, adding petroleum resin, continuously stirring and mixing while maintaining the heating state, and cooling to room temperature.

[0009] Optionally or preferably, in the above preparation method, the heating temperature is 80°C to 150°C; more preferably 100°C to 130°C.

[0010] Optionally or preferably, in the above preparation method, the stirring rate is 70 r / min to 120 r / min; more preferably 80 r / min to 100 r / min.

[0011] Optionally or preferably, in the above preparation method, the stirring time during the preparation process is 0.5h~2h; more preferably 1h~1.5h.

[0012] In a third aspect, the present invention provides use of any of the above-mentioned bio-based silica dispersants in the preparation of rubber products.

[0013] In a fourth aspect, the present invention provides a rubber product, wherein any of the above-mentioned bio-based silica dispersants is added to the raw materials, and the added amount is 5phr~15phr; more preferably, the added amount is 6phr~10phr.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The bio-based silica dispersant of the present invention is simple to prepare, has mild conditions, and has no other by-products. It plays a bridging role between silica and rubber through the interaction between the polar groups of the bio-based raw materials and silica, and can well disperse silica, avoid the problem of strict temperature requirements of traditional dispersants, and reduce production energy consumption. The bio-based silica dispersant of the present invention can also avoid scorching, reduce heat generation of rubber, and effectively improve product quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is an electron microscope photograph of the white carbon black dispersion effect of comparative example 1.

[0016] Figure 2 This is an electron microscope photograph of the white carbon black dispersion effect of Example 1.

[0017] Figure 3 This is an electron microscope photograph of the white carbon black dispersion effect of Example 2. DETAILED DESCRIPTION

[0018] In order to make the technical personnel in this field better understand the present application scheme, the present application will be clearly and completely described below in conjunction with the embodiments and drawings. Obviously, the described embodiments are only embodiments of a part of the present application, rather than all embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work should belong to the scope of protection of this application. The instruments and reagents used in the embodiments are all derived from commercial channels unless otherwise specified.

[0019] Example 1 (1) Add 70 g of rhamnolipid into a reaction flask, heat it to 125°C with a heating mantle, and stir until the rhamnolipid is in a molten state; (2) Add 30 g of C5 aliphatic petroleum resin (i.e., petroleum resin C5), maintain a stirring speed of 100 r / min under heating, and continue stirring for 1 hour; (3) After being fully mixed, cool down and filter out the material (basically without filter residue, which is mainly raw material that has not been fully melted).

[0020] Example 2 (1) Add 75 g of rhamnolipid into a reaction flask, heat it to 125°C with a heating mantle, and stir to melt the rhamnolipid until it is molten; (2) Add 25g of petroleum resin C5, maintain a stirring speed of 100r / min under heating, and continue stirring for 1h; (3) After fully mixing, cool down and filter the material.

[0021] Comparative Example 1 White carbon black dispersant Si69 (coupling agent Si-69) sold on the market.

[0022] Different white carbon black dispersants of Examples 1, 2 and Comparative Example 1 were added to the rubber raw material formula, and rubber products were prepared by conventional preparation methods. The rubber raw material formula and addition amount are shown in Table 1 below: Table 1 Rubber raw material formula and dosage (weight kg) The carbon black dispersion tester was used to analyze the white carbon black dispersion of the three groups of rubber products. The results are as follows: Figure 1-3 As shown, Figure 1-3 The white carbon black dispersion effects of Comparative Example 1, Examples 1 and 2 are shown respectively. It can be seen from the electron microscope that the agglomeration phenomenon of Comparative Example 1 is still quite obvious, while Examples 1 and 2 can both disperse white carbon black very well, indicating that the white carbon black dispersant of the present invention has a relatively ideal dispersion effect on white carbon black.

[0023] The three groups of rubber products were tested for performance, and the results are shown in Table 2 below.

[0024] Table 2 Performance test results of rubber products prepared by adding different silica dispersants As can be seen from Table 2, the addition of bio-based white carbon black dispersant in the formulations of Example 1 and Example 2 can give the vulcanized rubber a stronger tensile strength and elongation at break, and the 60°C rolling resistance Tanδ can be reduced by 13.28% and 6.6% relative to Comparative Example 1. The rolling resistance is proportional to the heat generation performance of the rubber. When the rolling resistance is low, the heat generation of the rubber will also decrease.

[0025] The vulcanization data is tested by RPA instrument (Rubber Processing Analyzer), see the table below for details: Table 3 RPA vulcanization properties of rubber products prepared by adding different silica dispersants It can be seen from the above table that the scorch time TS2 in Example 1 and Example 2 is longer than that in Comparative Example 1, indicating that a longer safe operation time can be retained in actual production to avoid the phenomenon of early vulcanization and thus avoid scorch.

[0026] The role of the white carbon black dispersant is to improve the dispersibility of white carbon black, thereby reducing rolling resistance. It can be seen from the above table that the bio-based white carbon black dispersants of Implementation 1 and Implementation 2 can both reduce rolling resistance, further illustrating the dispersibility of white carbon black.

[0027] The invention concept is described in detail using specific examples herein, and the description of the above embodiments is only used to help understand the core idea of ​​the invention. It should be pointed out that any obvious modification, equivalent substitution or other improvement made by a person of ordinary skill in the art without departing from the invention concept should be included in the protection scope of the present invention.

Claims

1. A bio-based silica dispersant, characterized in that: Made by heating and mixing bio-based raw materials and petroleum resin; The bio-based raw materials are one or more of rhamnolipids, sophorolipids, and trehalolipids; The petroleum resin is one or more of C5 aliphatic petroleum resin, C9 aromatic petroleum resin, DCPD cycloaliphatic diene petroleum resin, and α-methylstyrene petroleum resin.

2. The bio-based silica dispersant according to claim 1, characterized in that: The molecular weight of the petroleum resin is 100-5000 g / mol.

3. The bio-based silica dispersant according to claim 1, characterized in that: The ratio of the bio-based raw material to the petroleum resin is 60-80:40-20 by mass.

4. The method for preparing the bio-based silica dispersant according to any one of claims 1 to 3, characterized in that: Heat and stir the bio-based raw materials until they are melted, then add the petroleum resin, continue stirring to mix thoroughly while keeping the heat on, and cool to room temperature.

5. The preparation method according to claim 4, characterized in that: The heating temperature is 80℃-150℃.

6. The preparation method according to claim 4, characterized in that: The stirring rate is 70 r / min to 120 r / min.

7. The preparation method according to claim 4, characterized in that: The stirring time during the preparation process is 0.5h~2h.

8. Use of the bio-based silica dispersant according to any one of claims 1 to 3 in the preparation of rubber products.

9. A rubber product, characterized in that: The bio-based silica dispersant according to claims 1 to 3 is added to the raw materials in an amount of 5 phr to 15 phr.

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