Search

CN-122011636-A - High-toughness rubber composition, preparation method and application thereof to semiconductor sealing ring

CN122011636ACN 122011636 ACN122011636 ACN 122011636ACN-122011636-A

Abstract

The invention belongs to the technical field of polymer composite materials, and particularly relates to a high-toughness rubber composition, a preparation method and application thereof on a semiconductor sealing ring. The preparation method comprises the steps of using gamma- (2, 3-glycidoxy) propyl trimethoxy silane to carry out end-capping modification on carboxyl-terminated liquid fluororubber to obtain modified liquid fluororubber solution, using the modified liquid fluororubber solution to modify aramid fiber to obtain modified aramid fiber, using gamma- (2, 3-glycidoxy) propyl trimethoxy silane to carry out epoxy functionalization modification on fumed silica, and compounding the modified aramid fiber, the epoxy modified fumed silica with the carboxyl-terminated liquid fluororubber, an acid absorber, a processing aid, a vulcanizing agent and a crosslinking aid to obtain the high-toughness fluororubber composition. The composition remarkably improves toughness, tear resistance and processing stability while maintaining excellent heat and chemical resistance of fluororubber, and can be applied to preparing semiconductor sealing rings.

Inventors

  • ZHAO GANG
  • QIN LILU

Assignees

  • 北京海岚科技有限公司

Dates

Publication Date
20260512
Application Date
20260309

Claims (10)

  1. 1. A preparation method of a high-toughness rubber composition is characterized by comprising the following steps: Step one, reacting carboxyl-terminated liquid fluororubber with gamma- (2, 3-glycidoxy) propyl trimethoxy silane to obtain a modified liquid fluororubber solution; immersing the surface modified aramid fiber in a modified liquid fluororubber solution, and reacting to obtain the modified aramid fiber; Step three, mixing and stirring the carboxyl-terminated liquid fluororubber, the reinforcing filler, the acid absorber and the processing aid, adding the modified aramid fiber, and continuing mixing and stirring to obtain a composite sizing material; and step four, adding a vulcanizing agent and a crosslinking auxiliary agent into the composite sizing material, and stirring to obtain the high-toughness fluororubber composition.
  2. 2. The method for preparing a high-toughness rubber composition according to claim 1, wherein the first step specifically comprises: Adding the carboxyl-terminated liquid fluororubber into acetone, and stirring and mixing to obtain a mixed solution A; Adding gamma- (2, 3-glycidoxy) propyl trimethoxy silane and triethylamine into acetone, and stirring and mixing to obtain a mixed solution B; And heating the mixed solution B to a set temperature, dropwise adding the mixed solution A in a nitrogen atmosphere, reacting after the dropwise adding is finished, and cooling after the reaction is finished to obtain the modified liquid fluororubber solution.
  3. 3. The preparation method of the high-toughness rubber composition according to claim 2, wherein the mass ratio of the carboxyl-terminated liquid fluororubber in the mixed solution A to the gamma- (2, 3-glycidoxy) propyl trimethoxysilane in the mixed solution B to the triethylamine in the mixed solution B is 1 (0.4-0.6): 0.01-0.012), and the reaction condition is that the reaction is carried out for 6-10 hours under the set temperature in nitrogen atmosphere; The set temperature is 95-100 ℃.
  4. 4. The method for preparing a high-toughness rubber composition according to claim 1, wherein the second step specifically comprises: adding the surface modified aramid fiber into the modified liquid fluororubber solution, adding a catalyst, stirring for reaction, leaching out after the reaction is finished, washing, and drying to obtain the modified aramid fiber; Wherein the mass ratio of the surface modified aramid fiber to the modified liquid fluororubber solution to the catalyst is 10 (400-600) (3-5), and the stirring reaction condition is that the reaction is carried out for 1.5-2.5 hours at 50-60 ℃ under the stirring speed of 200-400 r/min; the catalyst is prepared from deionized water and ethanol according to the volume ratio of 1 (3-5).
  5. 5. The method for preparing a high-toughness rubber composition according to claim 4, wherein the surface modified aramid fiber comprises the following steps: firstly, carrying out cleaning treatment on the aramid fiber, and then carrying out plasma treatment on the aramid fiber after drying to obtain the surface modified aramid fiber; Wherein the plasma treatment condition is that the treatment time is 3-5min under 50-100W power in air atmosphere.
  6. 6. The method for preparing the high-toughness rubber composition according to claim 1, wherein in the third step, the mass ratio of the carboxyl-terminated liquid fluororubber to the modified aramid fiber to the reinforcing filler to the acid absorber to the processing aid is 100 (15-25): (4-8): (1.5-3): (2-4), the condition of stirring and mixing is that the mixture is mixed for 8-12min at a stirring speed of 200-400r/min, and the condition of continuing the mixing and stirring is that the mixture is mixed for 25-35min at a stirring speed of 200-400 r/min; The acid absorber comprises magnesium oxide; the processing aid comprises zinc stearate; the reinforcing filler comprises epoxy modified fumed silica.
  7. 7. The method for preparing a high-toughness rubber composition according to claim 6, wherein the epoxy modified fumed silica comprises the steps of: Adding the fumed silica after the drying treatment into ethanol, and performing ultrasonic dispersion to obtain a silica suspension; adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into deionized water, stirring and hydrolyzing to obtain a silane coupling agent solution; Mixing the silicon dioxide suspension with a silane coupling agent solution, reacting, centrifuging, washing and drying after the reaction is finished to obtain the epoxy modified fumed silica; wherein the mass ratio of the fumed silica in the silica suspension to the gamma- (2, 3-glycidoxy) propyl trimethoxy silane in the silane coupling agent solution is 1 (4-6), and the reaction condition is that stirring reaction is carried out for 2-4h at the temperature of 60-80 ℃.
  8. 8. The method for preparing a high-toughness rubber composition according to claim 1, wherein in the fourth step, the adding amount of the vulcanizing agent is 1.5-2.5% of the mass of the composite rubber material, the adding amount of the crosslinking auxiliary agent is 1-2% of the mass of the composite rubber material, and the stirring condition is that stirring is carried out for 15-25min at a speed of 200-300r/min under a vacuum condition; the vulcanizing agent comprises 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; The crosslinking aid includes triallyl isocyanurate.
  9. 9. A high-toughness rubber composition produced by the process for producing a high-toughness rubber composition according to any one of claims 1 to 8.
  10. 10. Use of the high-toughness rubber composition according to claim 9 on a semiconductor sealing ring.

Description

High-toughness rubber composition, preparation method and application thereof to semiconductor sealing ring Technical Field The invention belongs to the technical field of polymer composite materials, and particularly relates to a high-toughness rubber composition, a preparation method and application thereof on a semiconductor sealing ring. Background In the field of semiconductor manufacturing and packaging, core equipment and piping systems are required to maintain extremely high seal integrity under severe conditions. Fluororubber exhibits excellent high temperature resistance, chemical corrosion resistance and low permeability by virtue of the high bond energy of C-F bonds in the molecular chain, so that fluororubber is widely applied to the manufacture of sealing rings of key parts such as cavity seals, valve gaskets, pipeline connectors and the like. The stability of the performance is directly related to the cleanliness, process repeatability and equipment operation reliability of semiconductor production, and is one of the basic materials for ensuring the smooth proceeding of the prior process. At present, in order to continuously upgrade the requirements of a semiconductor process on longer-acting and more reliable sealing materials, the modification research of fluororubber in the industry mainly focuses on several directions, namely, optimizing low-temperature resistance or medium resistance by adjusting monomer composition (such as copolymerization proportion of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene) of a polymer main chain, adopting different types of reinforcing filler systems such as nano carbon black, modified white carbon black or inorganic nano particles to improve mechanical strength and wear resistance, and optimizing a vulcanization system (such as bisphenol AF/accelerator BPP or peroxide system) to construct a more stable three-dimensional network structure and improve heat aging resistance. However, these conventional technology paths tend to raise certain performance, either causing new problems or sacrificing other critical performance. For example, the addition of a large amount of reinforcing filler to increase hardness and compression set often results in increased mooney viscosity and deteriorated flowability of the compound, making compression molding of the complex cross-section seal ring difficult and possibly damaging elastic recovery ability, while the design of a tightly crosslinked network intended to increase heat resistance tends to result in increased brittleness of the material, decreased toughness, tear resistance and fatigue durability, and easy initiation of cracks in frequent temperature and pressure cycles, eventually leading to abrupt seal failure. In addition, conventional fillers and adjuvants may introduce precipitable metal ions or low molecular weight substances, which pose a pollution risk to the semiconductor process environment, and complex formulation and process adjustments also increase production costs and quality control difficulties. Therefore, development of a novel fluororubber composition is needed in the industry, and the fluororubber composition aims to break through the bottleneck of performance imbalance in the prior art, so that toughness, tear resistance and processing stability can be remarkably improved while inheriting the essence of excellent heat resistance and chemical resistance, and the increasing demands of semiconductor manufacturing on high-reliability sealing materials are met. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a high-toughness rubber composition, and aims to solve the technical problems that the processing fluidity is deteriorated and the elasticity is damaged due to the fact that a large amount of fillers are added for improving the mechanical strength of fluororubber sealing materials in the prior art, the high toughness and the heat aging stability are difficult to be compatible when a tight crosslinked network is constructed for improving the heat resistance, and the multi-component composite material is weak in interface bonding and easy to cause performance unbalance and reliability reduction. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: A preparation method of a high-toughness rubber composition comprises the following steps: step one, reacting carboxyl-terminated liquid fluororubber with gamma- (2, 3-glycidoxy) propyl trimethoxy silane (silane coupling agent KH 560) to obtain a modified liquid fluororubber solution; immersing the surface modified aramid fiber in a modified liquid fluororubber solution, and reacting to obtain the modified aramid fiber; Step three, mixing and stirring the carboxyl-terminated liquid fluororubber, the reinforcing filler, the acid absorber and the processing aid, adding the modified aramid fiber, and continuing mixing and stirring to obtain a composite sizi