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CN-122011011-A - Quaternary ammonium salt type silane coupling agent, preparation method and application thereof

CN122011011ACN 122011011 ACN122011011 ACN 122011011ACN-122011011-A

Abstract

The application provides a quaternary ammonium salt type silane coupling agent, a preparation method and application thereof. The quaternary ammonium salt type silane coupling agent consists of cations and anions and has a chemical structure shown in a formula (I), wherein n 1 、n 2 、n 3 and n 4 are respectively and independently selected from 0 or 1, at least two of n 1 、n 2 、n 3 and n 4 are 1;R 1 、R 2 、R 3 and R 4 are respectively and independently selected from-R 5 -Si(OR 6 ) 3 ;R 5 is selected from alkylene of C 1 ～C 6 , R 6 is selected from alkyl of C 1 ～C 4 , and X ‑ is halogen ion. The quaternary ammonium salt type silane coupling agent with the specific chemical structure can effectively improve the dispersibility of the white carbon black in a rubber matrix, improve the processing performance of sizing materials, simultaneously can remarkably reduce the emission of harmful gases in the vulcanization process, and provides a new solution for innovation and popularization of green tire formulas. (I)

Inventors

  • SUN MEI
  • WANG SHINING
  • ZHENG SHANSHAN

Assignees

  • 赛轮集团股份有限公司

Dates

Publication Date
20260512
Application Date
20260204

Claims (10)

  1. 1. The quaternary ammonium salt type silane coupling agent is characterized by comprising cations and anions, and has a chemical structure shown in a formula (I): (I); Wherein n 1 、n 2 、n 3 and n 4 are each independently selected from 0 or 1, and at least two of said n 1 , said n 2 , said n 3 , and said n 4 are 1; R 1 、R 2 、R 3 and R 4 are each independently selected from the group consisting of-R 5 -Si(OR 6 ) 3 ;R 5 is selected from the group consisting of C 1 ～C 6 alkylene groups, R 6 is selected from the group consisting of C 1 ～C 4 alkyl groups; x - is a halogen ion.
  2. 2. The quaternary ammonium salt silane coupling agent according to claim 1, wherein R 5 is selected from alkylene of C 1 ～C 4 , R 6 is selected from linear or branched alkyl of C 2 ～C 4 , and X - is chloride or bromide; Preferably, R 5 is propylene and R 6 is ethyl.
  3. 3. The quaternary ammonium salt type silane coupling agent according to claim 1 or 2, characterized in that the quaternary ammonium salt type silane coupling agent is selected from one or more of compounds 1 to 6: 、 、 、 、 、 。
  4. 4. a method for producing the quaternary ammonium salt type silane coupling agent according to any one of claims 1 to 3, characterized by comprising: Step S1, carrying out substitution reaction on hexamethylenetetramine and a reaction raw material in a polar solvent in a protective gas atmosphere to obtain a product system, wherein the reaction raw material has a chemical structure shown in a formula (II), Q-R 5 -Si(OR 6 ) 3 (II), wherein Q is selected from halogen, R 5 is selected from alkylene of C 1 ～C 6 , R 6 is selected from alkyl of C 1 ～C 4 , and the molar ratio of the hexamethylenetetramine to the reaction raw material is 1 (2.1-4.5); And S2, drying the product system to obtain the quaternary ammonium salt type silane coupling agent, wherein the charge number of cations in the quaternary ammonium salt type silane coupling agent is any integer from 2 to 4.
  5. 5. The method for producing a quaternary ammonium salt type silane coupling agent according to claim 4, wherein the quaternary ammonium salt type silane coupling agent has a charge number of 2 cations, a molar ratio of hexamethylenetetramine to the reaction raw material is 1 (2.1 to 2.6), and/or, The charge number of cations in the quaternary ammonium salt type silane coupling agent is 3, the mol ratio of the hexamethylenetetramine to the reaction raw material is 1 (3-3.6), and/or, The charge number of cations in the quaternary ammonium salt type silane coupling agent is 4, and the molar ratio of the hexamethylenetetramine to the reaction raw material is 1 (4-4.5).
  6. 6. The process for producing a quaternary ammonium salt type silane coupling agent according to claim 4 or 5, wherein in the formula (II), Q is selected from chlorine or bromine, R 5 is selected from alkylene of C 1 ～C 4 , R 6 is selected from linear or branched alkyl of C 2 ～C 4 ; Preferably, the reaction raw material is selected from bromopropyl triethoxysilane and/or chloropropyl triethoxysilane.
  7. 7. The method for preparing a quaternary ammonium salt type silane coupling agent according to claim 6, wherein in the step S1, the temperature of the substitution reaction is 25-82 ℃ and the time is 4-36 hours; Preferably, the Q in the reaction raw material is chlorine, the temperature of the substitution reaction is 45-82 ℃ and the time is 8-36 h, or the Q in the reaction raw material is bromine, the temperature of the substitution reaction is 25-55 ℃ and the time is 4-24 h; preferably, in the step S2, the drying temperature is 50-60 ℃ and the drying time is 12-24 hours.
  8. 8. The method for producing a quaternary ammonium salt type silane coupling agent according to any one of claims 4 to 7, wherein step S1 comprises mixing the hexamethylenetetramine with a part of the polar solvent in the protective gas atmosphere to obtain a first mixed solution, mixing the reaction raw material with the rest of the polar solvent to obtain a second mixed solution, adding the second mixed solution dropwise to the first mixed solution to carry out the substitution reaction, and distilling under reduced pressure after the completion of the reaction to obtain the product system.
  9. 9. The method for producing a quaternary ammonium salt type silane coupling agent according to any one of claims 8, wherein in the dropping process, the temperatures of the first mixed liquid and the second mixed liquid are controlled to be 25-65 ℃ independently, and the dropping rate is 0.4-0.5 ml/min; preferably, in the first mixed solution, the mass concentration of the hexamethylenetetramine is 0.05-0.1 g/mL; preferably, in the second mixed solution, the mass concentration of the reaction raw materials is 0.5-1.5 g/mL; Preferably, the polar solvent is selected from one or more of acetonitrile, propionitrile, butyronitrile and N, N-dimethylformamide; Preferably, the shielding gas is selected from nitrogen and/or an inert gas.
  10. 10. The rubber composition is characterized by comprising, by weight, 90-100 parts of a rubber substrate, 85-95 parts of white carbon black, 7-13 parts of a silane coupling agent, 2-3 parts of an activating agent, 1-3 parts of an anti-aging agent, 1-1.5 parts of a vulcanization accelerator and 1-2 parts of a vulcanizing agent, wherein the silane coupling agent is selected from the quaternary ammonium salt type silane coupling agents according to any one of claims 1-3.

Description

Quaternary ammonium salt type silane coupling agent, preparation method and application thereof Technical Field The application relates to the technical field of rubber formula materials, in particular to a quaternary ammonium salt type silane coupling agent, a preparation method and application thereof. Background With the increasing demands of global energy conservation, emission reduction and low carbon travel, the tire industry gradually develops toward green and high performance. For tires, rolling resistance, wet grip, and wear life are core performance indicators that determine tire performance and user experience. How to obtain more ideal balance among the three performance indexes is the key of tyre material research and formulation innovation. Although the traditional reinforcing filler carbon black has low price and mature process, the traditional reinforcing filler carbon black has limited potential in the aspects of reducing the rolling resistance of tires, improving the grip of wet lands and the like. In recent years, more and more research and industry practice has turned to the use of precipitated silica, white carbon black, as the primary reinforcing material for green tires. The white carbon black has higher specific surface area and active surface property, and can effectively improve the dynamic performance of the tire. The white carbon black can obviously reduce rolling resistance, reduce fuel consumption of an automobile or prolong the endurance mileage of a new energy automobile, and on a wet road surface, the white carbon black is favorable for improving friction performance and enhancing grip force, so that driving safety is improved. Meanwhile, as an inorganic mineral material, the white carbon black has rich sources and accords with the trend of environmental protection and sustainable development. However, the use of white carbon black in rubber substrates remains a significant challenge. Because of the large number of silanol groups on the surface of the white carbon black, the white carbon black is extremely easy to form strong aggregates through hydrogen bond interaction. The characteristic not only ensures that the white carbon black is unevenly dispersed in the rubber matrix, but also generally improves the Mooney viscosity of the rubber material in the mixing process, thereby increasing the energy consumption. In addition, the aggregation of the white carbon black can also lead to uneven performance of the vulcanized rubber material, and the mechanical property and the wear resistance are influenced, so that the application of the white carbon black in the high-performance tire is limited. In order to improve the dispersibility and interface bonding effect of the white carbon black in the rubber matrix, a silane coupling agent is generally adopted in the industry to modify the white carbon black. At present, silane coupling agents used for reinforcing systems of white carbon black mainly include polysulfide type and mercapto type. Polysulfide type silane coupling agent can participate in vulcanization reaction to promote formation of denser crosslinked network, but can release sulfur dioxide, methyl mercaptan and other irritant gases in the vulcanization process, so that environmental burden is increased, and higher requirements on equipment and field management are required. The mercapto silane coupling agent has strong reactivity, can quickly weaken the network strength of the filler and inhibit the agglomeration of white carbon black, but easily initiates the early vulcanization of rubber, has lower process fault tolerance and increases the production difficulty. In order to reduce the emission of irritant gases and Volatile Organic Compounds (VOCs), a strategy of blocking or blocking mercapto groups is often adopted in industrial production, and the reactivity of the mercapto groups in the mercapto coupling agent is temporarily inhibited by chemical means, but this method needs to make a compromise between cost control and the component cooperativity of rubber raw materials and the like, and is difficult to achieve an ideal reinforcing effect. The silane coupling agents commonly used at present also comprise silane coupling agents containing amino or epoxy functional groups, however, the reinforcing effect of the two silane coupling agents in a tread rubber system is not as good as that of the sulfur-containing silane coupling agents in the aspect of cooperative improvement of three performance indexes. Therefore, there is still room for improvement in the existing coupling agent systems in terms of improving the dispersibility of white carbon black and environmental friendliness. In summary, a quaternary ammonium salt type silane coupling agent with low emission of volatile organic compounds and multi-point reaction capability and a preparation method thereof are researched and developed to improve the dispersibility of white carbon black in a rubber matrix and reduce