Search

CN-122011508-A - Amino-functionalized cubic mesoporous silica composite filler and modified fluororubber

CN122011508ACN 122011508 ACN122011508 ACN 122011508ACN-122011508-A

Abstract

The invention provides an amino-functionalized cubic mesoporous silica composite filler and modified fluororubber, which adopt an improved sol-gel method assisted by normal hexane to controllably synthesize mesoporous silica with highly ordered cubic morphology, and the microstructure endows a material with extremely high specific surface area, uniform mesoporous aperture and regular cubic topological structure. The modified filler can greatly improve the tensile strength (about 233.3 percent) of the material, and simultaneously effectively improve the thermal stability and the thermal conduction rate of the material.

Inventors

  • JIN HUILE
  • LI HAO
  • WU YADONG
  • LI JUN
  • Peng Xuqiang
  • WANG SHUN

Assignees

  • 温州大学新材料与产业技术研究院
  • 温州大学

Dates

Publication Date
20260512
Application Date
20260209

Claims (10)

  1. 1. The amino functionalized cubic mesoporous silica composite filler is characterized by comprising the following steps of: S1, adding ammonia water into a surfactant solution, stirring until the solution is clarified, sequentially adding n-hexane and ethyl orthosilicate, stirring and reacting for 10-14 hours at 30-50 ℃ to obtain a colloid suspension, centrifugally washing and drying to obtain solid powder, and calcining the solid powder at 550-650 ℃ for 5-7 hours to obtain cubic mesoporous silica powder; S2, uniformly dispersing the cubic mesoporous silica powder in a solvent, adding an aminosilane coupling agent under a protective atmosphere, heating to 100-120 ℃ for reacting for 22-26 hours, centrifuging, filtering, washing and drying to obtain the amino-functionalized cubic mesoporous silica composite filler.
  2. 2. The amino-functionalized cubic mesoporous silica composite filler according to claim 1, wherein in the step S1, the concentration of the surfactant solution is 5-8 g/L, the concentration of the ammonia water is 20-35 wt%, and the volume ratio of the surfactant solution to the ammonia water is (20-25): 1.
  3. 3. The amino-functionalized cubic mesoporous silica composite filler according to claim 2, wherein the volume ratio of the surfactant solution to the n-hexane in the step S1 is (7-9): 1.
  4. 4. The amino-functionalized cubic mesoporous silica composite filler according to claim 2, wherein in the step S1, the volume ratio of the surfactant solution to the tetraethoxysilane is (30-35): 1.
  5. 5. The amino-functionalized cubic mesoporous silica composite filler according to claim 1, wherein in the step S1, the surfactant is cetyltrimethylammonium bromide.
  6. 6. The amino-functionalized cubic mesoporous silica composite filler according to claim 1, wherein in the step S2, the aminosilane coupling agent is KH550.
  7. 7. The amino-functionalized cubic mesoporous silica composite filler according to claim 1, wherein in the step S2, the mass-volume ratio of the cubic mesoporous silica powder to the aminosilane coupling agent is 0.8-1.2 g/mL.
  8. 8. A modified fluororubber is characterized in that the modified fluororubber is obtained by compounding the amino-functionalized cubic mesoporous silica composite filler in any one of claims 1-7 in fluororubber.
  9. 9. The modified fluororubber according to claim 8, wherein the mass ratio of the amino-functionalized cubic mesoporous silica composite filler to fluororubber is (5-12.5) 100.
  10. 10. The modified fluororubber as claimed in claim 8, wherein the preparation method comprises the steps of: (A) Fully mixing fluororubber and amino functionalized cubic mesoporous silica composite filler at 40-60 ℃, sequentially adding TAIC and Bifide-Pentah, and uniformly mixing to obtain a mixture; (B) Vulcanizing the mixture at the temperature of 150-190 ℃ for 5-15min to obtain vulcanized fluororubber; (C) Vulcanizing vulcanized fluororubber for 10-14 hours at 180-220 ℃ to obtain modified fluororubber; wherein the parts ratio of fluororubber to amino functionalized cubic mesoporous silica composite filler to TAIC to Bifive is 100 (5-12.5) (1-3) (0.5-2).

Description

Amino-functionalized cubic mesoporous silica composite filler and modified fluororubber Technical Field The invention relates to the technical field of fluororubber, in particular to an amino-functionalized cubic mesoporous silica composite filler and modified fluororubber. Background Fluororubbers (FKM) are special synthetic polymer elastomers containing fluorine atoms in the main chain or side chain carbon atoms. Thanks to the extremely high bond energy C-F bond (about 485 kJ/mol) in the molecular structure, FKM shows excellent high temperature resistance, excellent chemical stability and ageing resistance, and is a key sealing material which cannot be replaced in the tip fields of national defense and military industry, aerospace, semiconductors, petrochemical industry and the like. However, the interaction force between the pure fluororubber molecular chains is weak, so that the mechanical strength is low, the wear resistance is poor, and the actual engineering application value is hardly increased under the condition of not filling the reinforcing agent. Therefore, reinforcing fillers must be introduced to meet the mechanical properties requirements in severe service environments. Compared to traditional carbon black fillers, which are limited in color and non-insulation, nano-silica (SiO 2) has been of great interest for its good insulation, rich surface chemistry and adjustable transparency. However, the existing commercial gas phase or precipitation process white carbon black is mostly spherical or spheroidal particles. This spherical geometry results in a mostly point contact with the polymer matrix, a limited interfacial contact area and a weak mechanical interlock. In addition, the extremely high specific surface energy of the nano particles can cause the nano particles to be extremely easy to generate self-agglomeration in a viscous fluororubber matrix to form microscopic defects, so that the further improvement of the reinforcing efficiency is severely limited. The contradiction between filler agglomeration and weak interface bonding is difficult to thoroughly solve by the traditional physical blending or simple surface modification. In order to overcome the limitations of conventional spherical fillers, it is highly desirable to develop a filler with anisotropic morphology as an effective solution. Disclosure of Invention The invention aims to overcome the defects and shortcomings in the prior art and provide an amino-functionalized cubic mesoporous silica composite filler and modified fluororubber. The invention adopts the technical scheme that the first aspect of the invention provides an amino-functionalized cubic mesoporous silica composite filler, and the preparation method comprises the following steps: S1, adding ammonia water into a surfactant solution, stirring until the solution is clarified, sequentially adding n-hexane and ethyl orthosilicate, stirring and reacting for 10-14 hours at 30-50 ℃ to obtain a colloid suspension, centrifugally washing and drying to obtain solid powder, and calcining the solid powder at 550-650 ℃ for 5-7 hours to obtain cubic mesoporous silica powder; S2, uniformly dispersing the cubic mesoporous silica powder in a solvent, adding an aminosilane coupling agent under a protective atmosphere, heating to 100-120 ℃ for reacting for 22-26 hours, centrifuging, filtering, washing and drying to obtain the amino-functionalized cubic mesoporous silica composite filler. Preferably, in the step S1, the concentration of the surfactant solution is 5-8 g/L, the concentration of the ammonia water is 20-35 wt%, and the volume ratio of the surfactant solution to the ammonia water is (20-25): 1. Preferably, in step S1, the volume ratio of the surfactant solution to n-hexane is (7-9): 1. Preferably, in step S1, the volume ratio of the surfactant solution to the ethyl orthosilicate is (30-35): 1. Preferably, in step S1, the surfactant is cetyltrimethylammonium bromide. Preferably, in step S2, the aminosilane coupling agent is KH550. Preferably, in the step S2, the mass-volume ratio of the cubic mesoporous silica powder to the aminosilane coupling agent is 0.8-1.2 g/mL. The second aspect of the invention provides a modified fluororubber, which is obtained by compounding the amino-functionalized cubic mesoporous silica composite filler as described above into fluororubber. Preferably, the mass part ratio of the amino functionalized cubic mesoporous silica composite filler to the fluororubber is (5-12.5): 100. Preferably, the preparation method comprises the following steps: (A) Fully mixing fluororubber and amino functionalized cubic mesoporous silica composite filler at 40-60 ℃, sequentially adding TAIC and Bifide-Pentah, and uniformly mixing to obtain a mixture; (B) Vulcanizing the mixture at the temperature of 150-190 ℃ for 5-15min to obtain vulcanized fluororubber; (C) Vulcanizing vulcanized fluororubber for 10-14 hours at 180-220 ℃ to obtain modified fluororubber; wherein t