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CN-121975110-A - Guanidino-pyridine bridged porous organic polymer composite gas generating agent and preparation method thereof

CN121975110ACN 121975110 ACN121975110 ACN 121975110ACN-121975110-A

Abstract

The invention provides a guanidino-pyridine bridged porous organic polymer composite gas generating agent and a preparation method thereof, comprising the following steps of mixing a guanidino derivative monomer, a pyridyl monomer and a first organic solvent, adding an organic base, and carrying out degassing treatment; the preparation method comprises the steps of carrying out reaction at 120-150 ℃ after degassing to obtain a guanidyl-pyridine bridged porous organic polymer, dispersing the guanidyl-pyridine bridged porous organic polymer in a second organic solvent, adding basic copper nitrate, stirring and carrying out ultrasonic treatment, removing the second organic solvent to obtain powder, and carrying out tabletting and granulation to obtain the guanidyl-pyridine bridged porous organic polymer composite gas generating agent. According to the invention, the guanidyl functional group and the pyridine group are combined through covalent bonds to construct the porous organic polymer, so that the integrated integration of the fuel function and the coordination function is realized, the effective compounding of GBPOP and CuBN is realized by combining a solvent-pre-coordination strategy, and the prepared compound gas generating agent has high energy density and excellent combustion stability.

Inventors

  • Yin Zixi
  • FU ZHEN
  • ZHANG LIULIU
  • WANG SONG

Assignees

  • 湖北文理学院

Dates

Publication Date
20260505
Application Date
20260205

Claims (10)

  1. 1. The preparation method of the guanidino-pyridine bridged porous organic polymer composite gas generating agent is characterized by comprising the following steps of: s1, mixing a guanidino derivative monomer, a pyridyl monomer and a first organic solvent to obtain a mixed solution; s2, adding organic alkali into the mixed solution, and carrying out degassing treatment; S3, reacting the degassed mixed solution at 120-150 ℃, collecting a solid product, washing and drying to obtain the guanidino-pyridine bridged porous organic polymer; S4, dispersing the guanidino-pyridine bridged porous organic polymer in a second organic solvent, adding basic copper nitrate, stirring and carrying out ultrasonic treatment; s5, removing the second organic solvent to obtain powder, and tabletting and granulating to obtain the guanidyl-pyridine bridged porous organic polymer composite gas generating agent.
  2. 2. The method for preparing the guanidino-pyridine bridged porous organic polymer composite gas generating agent according to claim 1, wherein in the step S1, the guanidino derivative monomer comprises cyanoguanidine or 1, 1-diaminoguanidine, and the pyridyl monomer comprises 2,4, 6-tris (4-pyridyl) -1,3, 5-triazine; And/or the molar ratio of the guanidyl derivative monomer to the pyridyl monomer is 1 (1-1.2).
  3. 3. The method for preparing the guanidino-pyridine bridged porous organic polymer composite gas generator according to claim 1, wherein in the step S1, the first organic solvent comprises a polar aprotic solvent and an inert solvent, wherein the polar aprotic solvent comprises N, N-dimethylformamide, and the inert solvent comprises at least one of mesitylene and 1,3, 5-trimethylbenzene; And/or the mass volume ratio of the guanidyl derivative monomer to the first organic solvent is 1g (30-60) mL.
  4. 4. The method for preparing the guanidyl-pyridine bridged porous organic polymer composite gas generating agent according to claim 1, wherein in the step S2, the organic base comprises at least one of triethylamine, N-diisopropylethylamine, tributylamine, and 4-dimethylaminopyridine; and/or the molar ratio of the organic base to the guanidyl derivative monomer is (2-5): 1.
  5. 5. The method for preparing a guanidyl-pyridine bridged porous organic polymer composite gas generating agent according to claim 1, wherein in step S2, the degassing treatment is specifically performed by freeze-pump-defrost cycles, and the cycle number is 3-5.
  6. 6. The method for preparing the guanidino-pyridine bridged porous organic polymer composite gas generating agent according to claim 1, wherein in the step S3, the reaction time is 72-96 h; And/or the washing mode is that DMF, methanol and tetrahydrofuran are sequentially used for continuously extracting the solid product in a Soxhlet extractor for 24-48 hours; and/or the drying temperature is 100-120 ℃, and the drying time is 12-24 hours.
  7. 7. The method for preparing the guanidino-pyridine bridged porous organic polymer composite gas generator according to claim 1, wherein in the step S4, the guanidino-pyridine bridged porous organic polymer accounts for 25% -45% of the total mass of the guanidino-pyridine bridged porous organic polymer and the basic copper nitrate.
  8. 8. The method for preparing a guanidino-pyridine bridged porous organic polymer composite gas generator according to claim 1, wherein in said step S4, said second organic solvent comprises acetonitrile; And/or the mass-volume ratio of the guanidyl-pyridine bridged porous organic polymer to the second organic solvent is 1g (15-25) mL.
  9. 9. The method for preparing the guanidino-pyridine bridged porous organic polymer composite gas generating agent according to claim 1, wherein in the step S4, the stirring time is 1-3 hours, and the ultrasonic treatment time is 20-40 minutes.
  10. 10. The guanidino-pyridine bridged porous organic polymer composite gas generating agent is characterized by being prepared by the preparation method of the guanidino-pyridine bridged porous organic polymer composite gas generating agent according to any one of claims 1-9.

Description

Guanidino-pyridine bridged porous organic polymer composite gas generating agent and preparation method thereof Technical Field The invention relates to the technical field of gas generating agents, in particular to a guanidino-pyridine bridged porous organic polymer composite gas generating agent and a preparation method thereof. Background Automotive airbag systems are a standard safety configuration for modern passenger vehicles and have the core function of rapidly deploying an airbag in the event of a collision, providing cushioning protection for the occupants. The function of the system is achieved extremely depending on the gas generating agent inside. The gas generant is a special energetic material capable of producing a large quantity of gas for inflating the airbag in a controlled combustion reaction in milliseconds. With the increase of environmental protection requirements, nontoxic and harmless environmental protection gas generating agents based on basic copper nitrate gradually replace early toxic azide systems, and become the main technical direction in the field. Such a generating agent is usually used in combination with a fuel rich in nitrogen element, such as guanidine nitrate or aminoguanidine nitrate, and the like, and a target gas such as nitrogen gas is generated through oxidation-reduction reaction. However, the conventional small molecule fuel represented by guanidine nitrate faces a fundamental technical problem in practical application that uniform mixing of fuel and oxidant is difficult to achieve. At present, the industry mainly adopts physical mixing methods such as mechanical ball milling and the like, and the method can only reach the mixing scale of micron or millimeter level. This macro-mixing inhomogeneity results in a large number of "fuel rich zones" and "oxidant rich zones" being present at the microscopic level. When ignition occurs, combustion waves propagate among areas with uneven chemical components, and the speed and stability of the combustion waves continuously fluctuate, and the combustion waves are characterized in that 1) the combustion stability is poor, uncontrollable pressure peaks and oscillations are easy to generate, smoothness of airbag deployment is affected, potential risks are formed for safety of passengers, and 2) the combustion speed controllability is low, the combustion performance is too sensitive to changes of working pressure and environment temperature, namely, the sensitivity coefficient of pressure index and combustion speed temperature is higher, so that uncertainty exists in the deployment performance of the airbag under extreme environments (such as severe cold or summer heat). To address the uniformity and stability issues described above, researchers have attempted to incorporate porous materials, such as metal organic frameworks or porous organic polymers, into gas generant systems. However, these prior solutions have significant limitations, firstly, such studies have focused on high energy ligands such as triazoles, tetrazoles, etc., which have complex synthetic routes, high costs, and high mechanical sensitivity of parts of the materials, which are disadvantageous for safe production, and secondly, more importantly, in application, the prior art generally adds these porous materials to the formulation only as a single fuel or physically doped catalyst by simple mechanical mixing. The addition of the 'rough' type does not fully utilize the structural characteristics of the porous material, and the problems of uniform dispersion and close contact of the fuel and the oxidant in the nanometer scale cannot be essentially solved. The existing solution has limited effect of improving combustion stability and combustion speed, and cannot fundamentally break through the current technical bottleneck. Therefore, a new material design and application strategy is still sought. Disclosure of Invention In view of the technical problems in the background art, the invention provides a guanidyl-pyridine bridged porous organic polymer composite gas generating agent and a preparation method thereof, and aims to solve the technical problems of poor mixing uniformity and poor combustion stability of fuel and oxidant in the traditional gas generating agent. In a first aspect, the invention provides a method for preparing a guanidino-pyridine bridged porous organic polymer composite gas generating agent, comprising the following steps: s1, mixing a guanidino derivative monomer, a pyridyl monomer and a first organic solvent to obtain a mixed solution; s2, adding organic alkali into the mixed solution, and performing degassing treatment; S3, reacting the degassed mixed solution at 120-150 ℃, collecting a solid product, washing and drying to obtain the guanidino-pyridine bridged porous organic polymer; S4, dispersing the guanidyl-pyridine bridged porous organic polymer in a second organic solvent, adding basic copper nitrate, and stirring and carrying o