CN114478145B - Gas generating agent with excellent water repellency and preparation method thereof - Google Patents
Gas generating agent with excellent water repellency and preparation method thereof Download PDFInfo
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- CN114478145B CN114478145B CN202111509065.5A CN202111509065A CN114478145B CN 114478145 B CN114478145 B CN 114478145B CN 202111509065 A CN202111509065 A CN 202111509065A CN 114478145 B CN114478145 B CN 114478145B
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- generating agent
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- water repellency
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 18
- 239000005871 repellent Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 230000002940 repellent Effects 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000003826 tablet Substances 0.000 claims description 28
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 14
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 6
- 229920000126 latex Polymers 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 238000005550 wet granulation Methods 0.000 claims description 6
- 229920002396 Polyurea Polymers 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 238000007908 dry granulation Methods 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 108010073771 Soybean Proteins Proteins 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 239000007891 compressed tablet Substances 0.000 claims description 2
- 238000007907 direct compression Methods 0.000 claims description 2
- XRPZVNIXPWZPCA-UHFFFAOYSA-N ethenyl acetate;styrene Chemical compound CC(=O)OC=C.C=CC1=CC=CC=C1 XRPZVNIXPWZPCA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- 235000019710 soybean protein Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000013053 water resistant agent Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 51
- 238000001035 drying Methods 0.000 description 18
- 238000011049 filling Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000013350 formula milk Nutrition 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 235000020610 powder formula Nutrition 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
- C06B31/12—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate with a nitrated organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/10—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of solids with liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Air Bags (AREA)
Abstract
The invention provides a gas generating agent with excellent water repellency and a preparation method thereof, wherein the gas generating agent comprises the following components in parts by mass: 25% -60% of organic fuel; 37% -59% of an oxidant; 1 to 10 percent of adhesive added with water repellent agent, the total mass percent of all the components is 100 percent, and the dosage is calculated by the solid content of the effective components. The improved gas generating agent is added with the polymer adhesive with the water-resistant agent, so that the water repellency of the gas generating agent is enhanced, the environmental adaptability is improved, the bonding of particles due to moisture absorption is prevented, the particle fluidity can be increased, the tabletting consistency is ensured, and the tabletting speed is increased.
Description
Technical Field
The invention belongs to the technical field of pyrotechnic gas generants for automobile safety airbags, and particularly relates to a gas generant with excellent water repellency and a preparation method thereof.
Background
At present, the technology relating to the protection of motor vehicle occupants has been greatly developed, the latest generation of motor vehicles incorporate several safety systems of the airbag type in the passenger compartment, the combustion gases of pyrotechnic gas generants ensure the operation of the safety systems; among the airbag type systems, there are a front airbag (for a driver or a passenger) and a side airbag (curtain, chest protection).
The main disadvantages of the gas generating agent prepared from an oxidizing agent represented by Basic Copper Nitrate (BCN) and an organic fuel represented by Guanidine Nitrate (GN) are that the raw materials and the pressed materials have high hygroscopicity, the requirement on the assembly environment is high, and the assembly in a low-humidity environment is required. The gas generating agent is inevitably affected by the humidity of the environment when used for a long period of time. The process is slow, but the service life of the automobile is long and accumulated, particularly the service life of the automobile is easy to exceed 10 years, after the gas generating agent absorbs certain moisture, the combustion performance is affected, ignition delay is caused, and the gas generating agent even completely fails in severe cases, so that the expected gas output curve cannot be reached.
The prior art adopts helium filling to check the sealing performance or adds some molecular sieves as moisture absorbents in the gas generating agent to solve the problems, but the effect is not obvious and the production cost of the generating agent is high. Therefore, how to effectively solve the problem of low cost and hygroscopicity of the gas generating agent is an urgent need.
Disclosure of Invention
The present inventors have made intensive studies in order to overcome the drawbacks of the prior art, and have provided a gas generating agent excellent in water repellency and a method for producing the same, which are capable of effectively preventing and retarding the permeation of water in the gas generating agent by adjusting the components thereof, thereby enhancing the moisture resistance of the gas generating agent and ensuring the stability of the output performance of the gas generating agent for a long period of time, thereby completing the present invention.
The technical scheme provided by the invention is as follows:
in a first aspect, a gas generating agent with excellent water repellency comprises the following components in parts by mass: 25% -60% of organic fuel; 37% -59% of an oxidant; 1 to 10 percent of adhesive added with water repellent agent, the total mass percent of each component is 100 percent, and the dosage is calculated by the solid content of the effective component.
In a second aspect, a method for producing a gas generating agent excellent in water repellency, comprising the steps of:
step 1, weighing organic fuel and oxidant according to the designed component proportion;
step 2, weighing the adhesive added with the water repellent agent according to the designed component proportion, and uniformly mixing the adhesive with the organic fuel and the oxidant;
and 3, adopting wet granulation, dry granulation or spray granulation to press the mixture into tablets.
According to the gas generating agent with excellent water repellency and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
(1) According to the gas generating agent with excellent water repellency and the preparation method thereof, the improved gas generating agent component is added with the adhesive mixed with the water repellent agent, so that the moisture resistance of the gas generating agent is improved, and the risks of combustion and output uncertainty caused by moisture absorption of the gas generating agent in a high-humidity environment are reduced;
(2) According to the gas generating agent with excellent water repellency and the preparation method thereof, the improved gas generating agent component is added with the adhesive mixed with the water repellent agent, so that the particle fluidity can be increased, the tabletting consistency is ensured, and the tabletting speed is increased;
(3) The improved preparation method of the gas generating agent has the advantages of simple process, low cost and the like;
(4) The improved gas generating agent is used in a gas generator of a passive airbag system of an automobile and is suitable for inflating various airbags such as front, passenger side, side airbags, curtain airbags and the like.
(5) The water repellent formula provided by the invention is not limited to a gas generating agent, and can also be used for a propellant formula and an automatic ignition powder formula.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
According to a first aspect of the present invention, there is provided a gas generating agent excellent in water repellency, comprising the following components in parts by mass:
25 to 60 percent of organic fuel, preferably 35 to 45 percent;
37 to 59 percent of oxidant, preferably 40 to 56 percent;
1 to 10 percent of adhesive added with water repellent agent, preferably 3 to 6 percent;
the total mass percent of all the components is 100 percent, and the dosage is calculated by the solid content of the effective components.
In a preferred embodiment, the organic fuel is selected from at least one of 5-aminotetrazole, guanidine nitrate or nitroguanidine and derivatives thereof.
In a preferred embodiment, the oxidizing agent comprises a primary oxidizing agent, which is basic copper nitrate and strontium nitrate. The oxidizer may further include 0 to 5% of a secondary oxidizer selected from at least one of metal oxides, perchlorates, hypochlorites or nitrates to improve the combustion rate and gas composition. The metal oxides include, but are not limited to, iron oxide, copper oxide; the perchlorate salts include, but are not limited to, ammonium Perchlorate (AP) or potassium perchlorate; the nitrate salts include, but are not limited to, potassium nitrate or sodium nitrate; such hypochlorites include, but are not limited to, potassium hypochlorite, sodium hypochlorite.
In a preferred embodiment, the binder is selected from at least one of cellulose derivatives and salts such as cellulose, hemicellulose, methyl cellulose salts, cellulose acetate and the like, polyvinyl alcohol, guar gum, starch, modified starch, vinyl acetate styrene white latex, styrene butadiene latex, butyronitrile latex, soy protein, acrylic emulsion and styrene acrylic copolymer emulsion, various emulsion modified by copolymerization with acrylic acid, various emulsion modified by copolymerization with styrene and the like, and preferably cellulose.
The adding mode of the adhesive can be determined according to the property and the process of the formula materials, the adhesive can be directly weighed into the formula in the form of dry powder or liquid, or can be prepared into an aqueous solution and then added with water, and the solid content is generally 10-60 percent, preferably 50 percent.
In a preferred embodiment, the water repellent agent is at least one selected from urea formaldehyde resin, melamine formaldehyde resin, polyamide polyurea resin or polyamide polyamine epichlorohydrin resin, and is used in an amount of 1% to 8% (based on the solid content) of the binder, preferably in an amount of 3% to 6%.
In order to optimize the process performance and combustion performance of the improved gas generating agent formula, various combustion rate catalysts, process aids, low-temperature slag bonding agents and the like can be added into the formula, and the components can also influence the calculation of oxygen balance and the formation of residues; the content of the organic fuel, the oxidant and the binder added with the water repellent agent in the improved gas generating agent is more than 90 percent of the total mass. Because of differences in the gas generant forming process, generant design and transfer charge, the oxygen balance of the formulation is affected when the binder containing organic materials is added, and it is considered in the formulation calculation, the oxygen balance is controlled to be 3% to-5%, preferably-1.5% to-3.5% in the present invention. The composition of the modified gas generant formulation may be appropriately adjusted depending on the residue morphology and gas composition. When used for other purposes, the oxygen balance may not be considered.
The improved preparation method of the gas generating agent adopts wet granulation, dry granulation, tabletting after spray granulation or direct dry powder compression; the compressed improved gas generant tablets are mesoporous or solid and the diameter and thickness of the tablets may be adjusted depending on the properties of the generant.
The inventor finds that after the current organic fuel and oxidant or conventional burning rate catalyst, process auxiliary agent, low-temperature slagging agent and the like are added to form a formula in long-term production practice, the fluidity of particles in the material is poor, the tabletting consistency is difficult to ensure, and the yield is low. After a large number of researches, the water repellent agent is selected to be urea-formaldehyde resin, melamine formaldehyde resin, polyamide polyurea resin or polyamide polyamine epoxy chloropropane resin, so that the particle fluidity can be effectively improved, and the problem caused by tabletting of a product is solved.
According to a second aspect of the present invention, there is provided a method for producing a gas generating agent excellent in water repellency, comprising the steps of:
step 1, weighing organic fuel and oxidant according to the designed component proportion;
step 2, weighing the adhesive added with the water repellent agent according to the designed component proportion, and uniformly mixing the adhesive with the organic fuel and the oxidant;
and 3, adopting wet granulation, dry granulation or spray granulation and then pressing into tablets, or directly pressing dry powder.
In a preferred embodiment, in steps 1 and 2, the selection of the components and the ratio is the same as in the first aspect, and will not be described herein again.
In a preferred embodiment, in step 3, the process parameters for compression into tablets using Feite P2020 are as follows:
for wet granulation followed by compression into tablets, the process parameters included: the rotating speed is 65-70 r/min, and the pressure is 6.0-6.5 kN;
for dry granulated and compressed tablets, the process parameters included: the rotating speed is 65-70 r/min, and the pressure is 6.0-6.5 kN;
for spray granulation followed by compression into tablets, the process parameters included: the rotating speed is 70-75 r/min, and the pressure is 6.0-6.5 kN;
for direct dry powder direct compression, the process parameters included: the rotating speed is 55-60 r/min, and the pressure is 6.0-6.5 kN.
Examples
Example 1
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of sodium carboxymethylcellulose solution with the solid content of 50 percent and 30g of melamine formaldehyde resin, mixing, adding into 10kg of water with the temperature of 40 ℃, uniformly stirring, carrying out spray granulation and drying to obtain granules with good fluidity, pressing into circular tablets with the diameter of 5mm and the thickness of 2mm by using a rotary tablet press at the rotating speed of 70r/min, the filling capacity of 5mm and the pressure of 6.0kN, and drying for 4 hours in an oven at the temperature of 110 ℃, wherein the water content of the improved gas generant is controlled to be less than or equal to 0.3 percent, and the actual measurement value is 0.19 percent.
Example 2
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of sodium carboxymethylcellulose solution with the solid content of 50 percent and 30g of polyamide polyurea resin, mixing, adding into 10kg of water with the temperature of 40 ℃, uniformly stirring, carrying out spray granulation and drying to obtain granules with good fluidity, pressing into round tablets with the diameter of 5mm and the thickness of 2mm by using a rotary tablet press at the rotating speed of 70r/min, the filling capacity of 5mm and the pressure of 6.0kN, and drying for 4 hours in an oven at the temperature of 110 ℃, wherein the water content of the improved gas generating agent is controlled to be less than or equal to 0.3 percent, and the actual measurement value is 0.24 percent.
Example 3
Respectively weighing 4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate; weighing 1kg of sodium carboxymethylcellulose solution with the solid content of 50 percent and 30g of polyamide polyamine epichlorohydrin resin, mixing, adding into 10kg of water with the temperature of 40 ℃, uniformly stirring, carrying out spray granulation and drying to obtain particles with good fluidity, mechanically pressing into circular tablets with the diameter of 5mm and the thickness of 2mm by using a rotary tablet press at the rotating speed of 70r/min, the filling amount of 5mm and the pressure of 6.0kN, and drying for 4 hours in an oven at the temperature of 110 ℃, wherein the water content of the improved gas generating agent is controlled to be less than or equal to 0.3 percent, and the actual measurement value is 0.20 percent.
Example 4
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of starch solution with the solid content of 50 percent and 30g of melamine formaldehyde resin, mixing, adding the mixture into 10kg of water with the temperature of 40 ℃, uniformly stirring, carrying out spray granulation and drying to obtain particles with good fluidity, pressing into circular tablets with the diameter of 5mm and the thickness of 2mm by using a rotary tablet press under the conditions of the rotating speed of 70r/min, the filling capacity of 5mm and the pressure of 6.0kN, and drying for 4 hours in a drying oven at the temperature of 110 ℃, wherein the moisture content of the improved gas generating agent is controlled to be less than or equal to 0.3 percent, and the actual measurement value is 0.18 percent.
Example 5
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of starch solution with the solid content of 50 percent and 30g of polyamide polyurea resin, mixing, adding into 10kg of water with the temperature of 40 ℃, uniformly stirring, carrying out spray granulation and drying to obtain particles with good fluidity, pressing into round tablets with the diameter of 5mm and the thickness of 2mm by using a rotary tablet press under the conditions of the rotating speed of 70r/min, the filling capacity of 5mm and the pressure of 6.0kN, and drying for 4 hours in a drying oven at the temperature of 110 ℃, wherein the moisture content of the improved gas generating agent is controlled to be less than or equal to 0.3 percent, and the actual measurement value is 0.25 percent.
Example 6
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of starch solution with the solid content of 50 percent and 30g of polyamide polyamine epichlorohydrin resin, mixing, adding into 10kg of water with the temperature of 40 ℃, uniformly stirring, carrying out spray granulation and drying to obtain particles with good fluidity, mechanically pressing into circular tablets with the diameter of 5mm and the thickness of 2mm by using a rotary tablet press under the conditions of the rotating speed of 70r/min, the filling capacity of 5mm and the pressure of 6.0kN, and drying for 4 hours in an oven at the temperature of 110 ℃, wherein the water content of the improved gas generating agent is controlled to be less than or equal to 0.3 percent, and the actual measurement value is 0.23 percent.
Comparative example 1
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of sodium carboxymethylcellulose solution with solid content of 50%, mixing, adding into 10kg of water with temperature of 40 ℃, stirring uniformly, performing spray granulation and drying to obtain granules with good fluidity, pressing into round tablets with diameter of 5mm and thickness of 2mm by using a rotary tablet press at the rotating speed of 50r/min, the filling amount of 5.5mm and the pressure of 6.0kN, and drying in an oven at 110 ℃ for 4 hours, wherein the water content of the improved gas generant is controlled to be less than or equal to 0.3%, and the actual measurement value is 0.23%.
Comparative example 2
4.0kg of guanidine nitrate, 5.2kg of basic copper nitrate and 300g of strontium nitrate are respectively weighed; weighing 1kg of starch solution with solid content of 50%, mixing, adding into 10kg of water with temperature of 40 ℃, stirring uniformly, carrying out spray granulation and drying to obtain granules with good fluidity, pressing into round tablets with diameter of 5mm and thickness of 2mm by using a rotary tablet press at the rotating speed of 50r/min, filling capacity of 5.5mm and pressure of 6.0kN, and drying in an oven at 110 ℃ for 4 hours, wherein the water content of the improved gas generating agent is controlled to be less than or equal to 0.3%, and the actual measurement value is 0.19%.
100g of the gas generants of examples 1 to 6 and comparative examples 1 to 2 were weighed, respectively, laid flat in a pan, placed in a high humidity cabinet at a temperature of 23 ℃ plus or minus 2 ℃ and a relative humidity of 70% plus or minus 5%, left for 12 hours, and subjected to moisture test using a rapid moisture meter, respectively. See table 1.
TABLE 1 moisture content data after moisture absorption of tablets
| Examples | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Water content% | 2.3 | 1.9 | 2.5 | 4.8 |
| Examples | Example 4 | Example 5 | Example 6 | Comparative example 2 |
| Water content% | 2.7 | 2.3 | 2.6 | 5.2 |
As can be seen from the above tablet data after completion of the moisture absorption test, for the formulation with the binder added, the water repellency of the gas generant was greatly improved after the addition of the corresponding curing agent, with moisture absorption of about 50% of the comparative example. The principle of improving the hygroscopicity is that the polymer binder forms a water-repellent polymer network on the outer surface and the inner part of the gas generating agent. The gas generating agent with strong water repellency can improve the environmental adaptability of the gas generating agent, keep the performance not to be reduced in the long-term use process, and also can reduce the cost for controlling the production environment.
TABLE 2 tabletting Condition and yield data
| Examples | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Tabletting condition and yield | Good, 99.9% | Good, 99.9% | Good, 99.9% | General, 96.9% |
| Examples | Example 4 | Example 5 | Example 6 | Comparative example 2 |
| Tabletting condition and yield | Good, 99.9% | Good, 99.9% | Good, 99.9% | General, 93.6% |
According to the tabletting condition and the finished product rate data, for the formula added with the adhesive, the tabletting finished product rate is obviously improved after the corresponding curing agent is added, and the improvement of the production efficiency is facilitated.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (5)
1. The gas generating agent with excellent water repellency is characterized by comprising the following components in parts by mass: 25% -60% of organic fuel; 37% -59% of an oxidant; 1-10% of adhesive added with water repellent agent, wherein the water repellent agent accounts for 1-8 wt% of the adhesive in terms of solid content;
the water repellent agent is selected from at least one of polyamide polyurea resin and polyamide polyamine epichlorohydrin resin;
the organic fuel is at least one of 5-aminotetrazole, guanidine nitrate or nitroguanidine;
the adhesive is selected from at least one of cellulose, hemicellulose, methyl cellulose salt, cellulose acetate, polyvinyl alcohol, guar gum, starch, modified starch, vinyl acetate styrene white latex, styrene butadiene latex, butyronitrile latex, soybean protein, acrylic emulsion and styrene acrylic copolymer emulsion;
the total mass percent of all the components is 100 percent, and the dosage is calculated by the solid content of the effective components.
2. The gas generating agent excellent in water repellency according to claim 1, characterized in that the oxidizing agent comprises a main oxidizing agent, and the main oxidizing agent is basic copper nitrate and strontium nitrate.
3. The gas generating agent with excellent water repellency according to claim 1, wherein the oxidizing agent further comprises 0 to 5 mass% of a secondary oxidizing agent selected from at least one of a metal oxide, a perchlorate, a hypochlorite and a nitrate.
4. A method for producing a gas generating agent excellent in water repellency according to any one of claims 1 to 3, characterized by comprising the steps of:
step 1, weighing organic fuel and oxidant according to the designed component proportion;
step 2, weighing the adhesive added with the water repellent agent according to the designed component proportion, and uniformly mixing the adhesive with the organic fuel and the oxidant;
and 3, adopting wet granulation, dry granulation or spray granulation and then pressing into tablets, or directly pressing dry powder.
5. The process for producing a gas generating agent excellent in water repellency according to claim 4, characterized in that,
for wet granulation followed by compression into tablets, the process parameters included: the rotating speed is 65 to 70r/min, and the pressure is 6.0 to 6.5kN;
for dry granulated and compressed tablets, the process parameters included: the rotating speed is 65 to 70r/min, and the pressure is 6.0 to 6.5kN;
for spray granulation followed by compression into tablets, the process parameters included: the rotating speed is 70 to 75r/min, and the pressure is 6.0 to 6.5kN;
for direct dry powder direct compression, the process parameters include: the rotation speed is 55 to 60r/min, and the pressure is 6.0 to 6.5kN.
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