CN109206290A - Without sulphur without chlorine pyrotechnics drug composition - Google Patents
Without sulphur without chlorine pyrotechnics drug composition Download PDFInfo
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- CN109206290A CN109206290A CN201811322844.2A CN201811322844A CN109206290A CN 109206290 A CN109206290 A CN 109206290A CN 201811322844 A CN201811322844 A CN 201811322844A CN 109206290 A CN109206290 A CN 109206290A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B41/00—Compositions containing a nitrated metallo-organic compound
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- 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
- C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/36—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing both an organic explosive or thermic component and an inorganic explosive or thermic component
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Abstract
The invention discloses a kind of no sulphur without chlorine pyrotechnics drug composition, including following components: oxidant, catalyst, priming, incendiary agent, and oxidant is nitrate, and catalyst is metallocene and its derivative, and priming is high energy nickel coordination compound, and incendiary agent is charcoal.Of the invention is highly-safe without chlorine pyrotechnics drug composition without sulphur, environment friendly and pollution-free, easy to maintain, flammability is good, thrust is strong, has excellent performance.
Description
Technical field
The present invention relates to a kind of pyrotechnics drug composition, especially a kind of no sulphur is without chlorine pyrotechnics drug composition.
Background technique
Main power source of the black powder as various fireworks pyrotechnic products almost becomes the fire of all fireworks indispensabilities
Medicine.Its main component is chlorate, sulphur, charcoal, however the ingredient sensitivity of the sulphur in existing black powder is higher, is not special
Stablize, occur often with unexpected in the preparation of the production process of fireworks, caused by casualties and economic loss
It is inestimable, lead to serious consequence, and the sulfur dioxide gas discharged after element sulphur burning is extremely pungent and toxic, often
The release of fireworks results in the pollution of environment.Since potassium chlorate sensitivity is very high, current country prohibites quick-fried in fireworks
Bamboo production in use potassium chlorate, potassium hyperchlorate as potassium chlorate substitution drug stabilisation it is preferable, mechanical sensitivity is lower, energy of oxidation
Power is strong, but still has higher sensitivity, and perchlorate is the persistent pollutant with high diffusion, inhibits human body pair
The absorption of iodine influences the normal function of human thyroglobulin, upsets the metabolism of human normal, influences in fetus and baby's nerve
The normal growth of pivot and development can be to the mucous membranes, eye for placing oneself in the midst of people under this state if perchlorate such as occurs with dust form
Eyeball and skin generate stimulation, the ill symptoms such as respiratory disorder and cough occur, if long-term work is in the environment, it may appear that
Liver, kidney injury and erythrocyte such as destroy at the symptoms, while it may also be to gene expression level there are potential impact and to exempting from
Epidemic disease system has an impact, therefore is badly in need of the oxidant and its formula of research environment-friendly high-efficiency.In addition, black powder is asked due to setting off burn rate
Topic, is unable to full combustion, generates a large amount of flue dust.
Tang Guilin of Beijing Institute of Technology etc. after study, using hydrocarbon oxygen compound, hydrocarbon nitrogen compound, nitro compound
Element sulphur in object and aqueous hydrocarbon oxygen compound substitution black powder.By measuring, produced after four kinds of new black powder burnings
Raw gas is nontoxic, and smoke greatly reduces, and solid residue significantly reduces after burning, and mechanical sensitivity and friction sensitivity are substantially
Degree reduces.
American scientist develops a kind of golden gunpowder, its ingredient is KNO used in black powder3And ascorbic acid,
And sulphur and charcoal are not added.Its energy effect is 1.25 times of black powder or so, and residue has lacked much after combustion.
But since ascorbic acid easily makes moist, and cost is excessively much higher compared to charcoal sulphur, fails to be widely used later.Moral
The country such as state and France also attempts to utilize KNO3Proportion is carried out with rubber polymer, special black powder is made, and deliver thus specially
Benefit, but set off performance and the ignition performance of this gunpowder are not able to satisfy the various needs as transmitting medicament.
The sulphurless powder that present factory generallys use is that metal powder is added in potassium nitrate and charcoal (generally to add hundred
/ mono- aluminium powder), the type sulphurless powder can satisfy requirement in performance, but metal powder is easy to oxidize,
This just brings difficulty to gunpowder in preservation.
Chinese invention patent CN106316725B discloses a kind of no sulphur propellant powder and preparation method, this contains without sulphur propellant powder
Have: potassium hyperchlorate, filler, adhesive, calcium stearate and Potassium Hydrogen Phthalate, this is without sulphur propellant powder friction sensitivity and shock
Sensitivity is low, hydroscopicity is small, thrust reduces by force the pollution to environment simultaneously.
Chinese invention patent CN104761417B discloses a kind of no sulphur propellant for fireworks and crackers, by the original of following parts by weight
Material is prepared: 20~25 parts of terephthalic acid (TPA), 15~20 parts of phthalic anhydride, 20~30 parts of potassium hydroxide, 3.5~4.5 parts of camphor powder,
15~17 parts of waste of flax powder, 8~9 parts of face powder, 12~13 parts of graphite powder, 30-40 parts of potassium hyperchlorate, 0.3~0.5 part of strong agent powder and
10.5~11.5 parts of water.The propellant powder usage amount is few, and product not sulfur-bearing, arsenic, lead, mercury and the sulfide to burn, significantly
Reduce atmosphere pollution.
Chinese invention patent CN102924193B provides a kind of fireworks safe and environment-friendly, porous structure micro- cigarette propellant powder,
The weight fraction ratio of each component are as follows: 30-50 parts of high energy oxidizers, 1-5 parts of catalyst, 10-80 parts of single original washing powders, 1-5 parts of stabilization agents,
1-5 parts of adhesives, 10-30 parts of primings, 10-20 parts of stomata foaming agents, 1-5 parts of burn rate modifying agents；The high energy oxidizer
For any one in perchloric acid nitryl, ammonium perchlorate, potassium permanganate；The catalyst is ammonium dichromate or ferrocene；Institute
The stabilization agent stated is amylalcohol or diphenylamines；The adhesive is end hydroxy butadiene；The priming be nitroguanidine or
Nickel hydrazine nitrate；The stomata foaming agent is carbon black or nitrate；The burn rate modifying agent is Manganese perchlorate or cupric perchlorate.
The propellant powder impact sensitivity 40% or so, without burning or explode in 5% or so, 12 meter of fall-down test by friction sensitivity, and hydroscopicity≤
0.8%, 75 DEG C of stability test results are " stable ".
But product provided by above-mentioned patent uses perchlorate oxidizing agents, although perchlorate is compared with chlorate fusing point
Height, reactivity are lower, the far super chlorate of safety in friction sensitivity, but still have very high impact sensitivity, generally 80-
90%, and environmental pollution is serious, can not adapt to the public demand to safety and environmental protection fireworks.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of no sulphur without chlorine pyrotechnics
Drug composition, it is highly-safe, it is environment friendly and pollution-free, easy to maintain, thrust is strong, there is excellent performance.
The purpose of the present invention can be achieved through the following technical solutions:
One aspect of the present invention provides no sulphur without chlorine pyrotechnics drug composition, including following components: oxidant, catalyst, priming,
Incendiary agent.
The oxidant is nitrate, and the catalyst is metallocene and its derivative, and the priming is matched for high-energy nickel
Position compound, the incendiary agent are charcoal.
Any one of the oxidant in potassium nitrate, barium nitrate, ammonium nitrate, sodium nitrate, strontium nitrate；Catalyst choosing
From any one in ferrocene, biferrocene, cobaltocene, dicyclopentadienyl nickel；Priming is selected from nickel hydrazine nitrate, hydrazine nitrate cobalt, folds
Any one in nitrogen hydrazine nickel；Charcoal selection black wood charcoal, brown charcoal, any one in chestnut charcoal.
Therefore, according to a preferred embodiment, the main composition of composition of the invention is: the oxidant
For potassium nitrate, catalyst is ferrocene, and priming is nickel hydrazine nitrate.
The charcoal is poplar charcoal.
The priming has carried out coating modification processing.The coating modification processing is the coating modification of demulsification method or mutually separates
Method coating modification.
About the proportion of each ingredient, advantageous combination is as follows:
The parts by weight of each component are as follows: 70-80 parts of oxidants, 3-10 parts of catalyst, 3-10 parts of primings, 10-20 parts of combustions
Burn agent.As preferred embodiment, the parts by weight of each component are as follows: 75 parts of oxidants, 5 parts of catalyst, 5 parts of detonations
Medicine, 15 parts of incendiary agents.
Further, the no sulphur further includes adhesive, the preferred EVA hot-melt adhesive of adhesive without chlorine pyrotechnics drug composition.
Another aspect of the present invention provides preparation method of no sulphur without chlorine pyrotechnics drug composition, and specific preparation process is as follows:
1) above-mentioned oxidant is ground, ground oxidant powder is by 120 meshes then in drying box with 80 DEG C
The dry 1h of temperature after it is cooling after pack be put into it is spare in drier；For above-mentioned catalyst by grinding and crossing 120 meshes, 40 DEG C dry
Dry 2h is spare；Above-mentioned priming is spare with 50 DEG C of dry 2h in drying box；Above-mentioned incendiary agent is ground and cross after 120 meshes
Pack with the dry 1h of 80 DEG C of temperature that be put into drier spare in drying box after cooling.
2) above-mentioned raw materials are successively poured into mortar according to said ratio to grind, milling time is greater than 30min, is mixed
Object is closed up to no sulphur without chlorine pyrotechnics drug composition.
Further, as an improvement, further including step 3)
3) above-mentioned adhesive is added in the mixture of step 2 acquisition and is mixed, then be twisted into small medicine with the mesh screen of 8 mesh or 10 mesh
Then item swings circle with treucher or aluminium dish, swings light to get no sulphur without chlorine pyrotechnics drug composition.
Due to containing chlorine using more oxidant in the prior art, in order to overcome the defect of the formula containing chlorine, the present invention
Using nitrate as oxidant, nitrate is most common oxidant, oxygen-containing more, good security, and fusing point is low (334 DEG C)
Easily light, it is cheap, but need to make with other additive compatibilities such as suitable reducing agent (generally sulphur) and incendiary agents
Standby qualified propellant powder, therefore focus of the invention is that using nitrate be oxidant without sulphur launching fireworks medicine composition.
Further, for using potassium nitrate as oxidant, the heated decomposition reaction of potassium nitrate is as follows:
Step 1: 2KNO3→2KNO2+O2
Step 2: 2KNO2→K2O+NO2+NO
Step 3: 2NO2→2NO+O2
Step 4: 2NO → N2+O2
The Δ H value that potassium nitrate decomposes is+75.5kcal/mol, this is the reaction of strong endothermic, wherein four-step reaction is very slow, one
As need to export high metal powder with energy and be used together, just can be carried out, final potassium nitrate be decomposed at high temperature potassium oxide,
Nitrogen and oxygen, both environmental protection also can get bulk gas, but metal powder is easy to oxidize, and potassium nitrate moisture absorption, and metal powder holds
Vigorous reaction easily occurs with moisture and explodes, the pyrotechnic composition of this formula is not easy to maintain, and stability is poor.
If the decomposition product of potassium nitrate is potassium nitrite and oxygen under low-temperature condition, gas production is substantially reduced, if not
Using the high reducing agent of other gas production (such as sulphur) and incendiary agent, then the requirement of propellant powder is unable to reach.
The present invention is free of sulphur, thus creative selection metallocene, and if ferrocene is as catalyst, ferrocene is a kind of
Organo-transition metal compound, chemical formula C10H10Fe, scientific name dicyclopentadieny iron are a kind of oranges with camphor taste
Yellow needles.Fusing point is 172 DEG C -174 DEG C, and boiling point is 249 DEG C, and 10 DEG C or more distil, and ferrocene heat with higher is steady
Qualitative and chemical stability is heated to 470 DEG C and does not also decompose, and 18 electronic structures in luxuriant molecule not only contribute to the chemistry of molecule
Stability and thermal stability are more conducive to the transfer of electronics, form activated intermediate and Effect of Nitric Oxide, accelerate NO reaction
Nitrogen and oxygen are generated, and ferrocene carbohydrate content is high, can be improved the combustion heat.
In order to solve the sucting wet problem of potassium nitrate, EVA hot-melt adhesive adhesive is introduced in formula, EVA hot-melt adhesive is a kind of
Be not required to solvent, moisture-free, 100% solid meltability polymer, therefore hydrophobic performance and bond properties are all more excellent,
Burn free from extraneous odour, nontoxic, and being attached to potassium nitrate surface can be reduced with the contact probability of the reduction potassium nitrate and water of high degree
The hydroscopicity of pyrotechnic composition.
Nickel hydrazine nitrate is a kind of coordination energetic material of function admirable, and the mechanical sensitivity of nickel hydrazine nitrate is lower, flame sensitivity
Higher, hygroscopicity is low, and bursting point is easily ignited at 212 DEG C or so, is a kind of outstanding priming, nickel hydrazine nitrate completely burned
Product is nitrogen, water and nickel oxide, and product is nontoxic and pollution-free, and is generated without cigarette, substitutes sulphur with it, reduces harmful gas
The generation of body, while energy content, combustibility and gas production are better than sulphur, and mechanical sensitivity is lower, so that the peace of pyrotechnic composition
Full property can be promoted.
The burn rate of traditional black powder is generally 7-10 mm.s-1, potassium nitrate and charcoal are only used without sulfureted pyrotechnic composition
Burn rate is slower, and the addition of catalyst ferrocene and nickel hydrazine nitrate substantially increases burn rate, is allowed to suitable with black powder, meets hair
Penetrate the requirement of medicine.
It is also the endothermic reaction that oxygen reaction is put in the decomposition of nitrate oxidizer, and therefore, it is also less sensitive to mechanism, is changed
It is also relatively good to learn stability, ferrocene stable chemical performance, the friction sensitivity of nickel hydrazine nitrate is 22% or so relatively low, therefore should
It is formulated whole good security.But for the production of fireworks, transport, storage, sensitivity is still excessively high, and therefore, the present invention couple
Scheme is improved, and is carried out coating modification to nickel hydrazine nitrate and is further processed: (1) weighing a certain amount of aqueous polyurethane cream
Liquid is added at normal temperature in the single-necked flask for filling 50mL distilled water, and 60 DEG C of constant temperature stirrings are uniformly mixed the two；
(2) after a certain period of time, proper amount of surfactant is added, continues constant temperature and stirs 30min；
(3) it is cooled to demulsification temperature, nickel hydrazine nitrate is added, being sufficiently stirred makes to be uniformly mixed；
(4) alum solution is weighed, alum solution is added dropwise into flask with 1 drop/s rate, constant temperature stirs at a temperature of 40 DEG C
15min is precipitated aqueous polyurethane from lotion and is coated on the surface of nickel hydrazine nitrate；
(5) cool down, filter, wash 2~3 times, polyurethane is obtained after drying and coats nickel hydrazine nitrate.
The invention has the advantages that:
1) no sulphur provided by the invention is free of perchlorate, sulphur without chlorine pyrotechnics drug composition, and joined metallocene and its spread out
Biology and high energy nickel coordination compound are substituted, and friction sensitivity and impact sensitivity are zero, and ignition point actual measurement is 436-469 DEG C,
Good security, burn rate are fast compared with black powder.
2) binder is provided simultaneously with very strong hydrophobic ability, solves using traditional nitrate as oxidant knot easy to moisture absorption
The problem of block, hydroscopicity will not agglomerate less than 0.4% and be easy to save.
3) sulphur is free of in composition, will not be generated the toxic gases such as sulfur dioxide, hydrogen sulfide and be endangered environment.
4) perchlorate is free of in composition, will not be generated perchlorate contaminated environment, be met increasingly strict environmental requirement.
5) the more traditional black fire of burn rate is fast, is free of metal powder, will not generate a large amount of flue dust, reduces the row of the dust such as PM2.5
It puts.
6) using traditional nitrate as oxidant, non-environmental-pollution is low in cost, at the same in catalyst metallocene and its
Under the action of derivative, oxygen release reaction is suitably accelerated, ensure that combustibility and gas production.
7) nitrogen that the excellent energy content of nickel hydrazine nitrate, combustibility and gas production and nitrate generate, compensates for scarce
The problem of few sulphur bring gas production is reduced, can be used as propellant powder.
Specific embodiment
Combined with specific embodiments below, the application is described in detail.
The embodiment recorded herein is specific specific embodiment of the invention, for illustrating design of the invention,
Be it is explanatory and illustrative, should not be construed as the limitation to embodiment of the present invention and the scope of the invention.Except what is recorded herein
Outside embodiment, those skilled in the art can also based on the claim of this application book and specification disclosure of that using aobvious and
The other technical solutions being clear to, these technical solutions include using any obvious to making for the embodiment recorded herein
The technical solution of substitutions and modifications.
A kind of no sulphur of the invention is free of perchlorate, sulphur, including following components without chlorine pyrotechnics drug composition: oxidation
Agent, catalyst, priming, incendiary agent, the oxidant be nitrate, the catalyst be metallocene and its derivative, it is described
Priming be high energy nickel coordination compound, the incendiary agent be charcoal, the oxidant be selected from potassium nitrate, barium nitrate, ammonium nitrate,
Any one in sodium nitrate, strontium nitrate；Catalyst is any one in ferrocene, biferrocene, cobaltocene, dicyclopentadienyl nickel
Kind；Any one of priming in nickel hydrazine nitrate, hydrazine nitrate cobalt, nickel hydrazine azide；The charcoal selects black wood charcoal, brown charcoal, chestnut
Any one in charcoal, the parts by weight of each component are as follows: 70-80 parts of oxidants, 3-10 parts of catalyst, 3-10 parts of primings, 10-
20 parts of incendiary agents
The no sulphur further includes adhesive, the preferred EVA hot-melt adhesive of adhesive without chlorine pyrotechnics drug composition.
Above-mentioned preparation method of the no sulphur without chlorine pyrotechnics drug composition, specific preparation process is as follows:
1) above-mentioned oxidant is ground, ground oxidant powder by 100-120 mesh then in drying box with
Pack is put into spare in drier after cooling down after the dry 1-2h of 70-80 DEG C of temperature；Above-mentioned catalyst is by grinding and crossing 100-
120 meshes, 40-50 DEG C of dry 2-3h are spare；Above-mentioned priming is spare with 50-60 DEG C of dry 2-3h in drying box；It will be above-mentioned
Incendiary agent is ground and crosses to be packed after cooling in drying box with the dry 1-2h of 70-80 DEG C of temperature after 100-120 mesh and is put into
Drier is spare.
2) above-mentioned raw materials are successively poured into mortar according to said ratio to grind, milling time is greater than 30min, acquisition
Mixture is up to no sulphur without chlorine pyrotechnics drug composition.
Above-mentioned adhesive is added to as a preferred technical solution, in the mixture of step 2 acquisition and is mixed, then with 8 mesh
Or 10 the mesh screen of mesh be twisted into small medicinal strip, then swing circle with treucher or aluminium dish, swing light to get no sulphur without chlorine pyrotechnics drug composition.
Priming nickel hydrazine nitrate the preparation method comprises the following steps: by concentration be 5-10wt% hydrazine hydrate aqueous solution be placed in beaker in tall form
In, it is heated to 65-75 DEG C or so in water bath with thermostatic control, while starting blender, adjusts voltage to medium mixing speed, lead to
The method for crossing titration, is slowly added dropwise 10-50 wt% nickel nitrate aqueous solution, and 65-75 DEG C of constant temperature stirs 10-20min after charging,
Continue stirring and is gradually cooling to 35 DEG C hereinafter, suspension obtained is filtered with vacuum filtration machine, by the powder-like of acquisition
Product are washed with distilled water 3 times, which is placed in drying basin, is put into thermostatic drying chamber, 55-60 DEG C of dry 6-8h,
Obtain nickel hydrazine nitrate.
The priming can also carry out coating modification processing.The coating modification processing is the coating modification of demulsification method, side
Method are as follows: (1) weigh the aqueous polyurethane emulsion of 6-24 parts by weight, be added to the single port for filling 50 parts by weight distilled water at normal temperature
In flask, 50-60 DEG C of constant temperature stirring is uniformly mixed the two；
(2) after a certain period of time, proper amount of surfactant is added, continues constant temperature and stirs 30-40min；
(3) it is cooled to demulsification temperature, the nickel hydrazine nitrate of 100 parts by weight is added, being sufficiently stirred makes to be uniformly mixed；
(4) 18-72 parts by weight alum solution is weighed, alum solution is added dropwise into flask with 1-2 drop/s rate, at 40-50 DEG C
At a temperature of constant temperature stir 15-20min, aqueous polyurethane is precipitated from lotion and is coated on the surface of nickel hydrazine nitrate；
(5) cool down, filter, wash 2~3 times, polyurethane is obtained after drying and coats nickel hydrazine nitrate.So make pyrotechnics obtained
Medicine sensitivity further decreases.
Embodiment 1
The preparation of nickel hydrazine nitrate
The hydrazine hydrate aqueous solution that concentration is 5wt% is placed in beaker in tall form, 65 DEG C or so are heated in water bath with thermostatic control,
Blender is started simultaneously, adjusts voltage to medium mixing speed and it is water-soluble to be slowly added dropwise by the method for titration for 10 wt% nickel nitrates
Liquid, 65 DEG C of constant temperature stir 10min after charging, continue stirring and are gradually cooling to 35 DEG C hereinafter, by suspension obtained with very
Empty pump filter is filtered, and the powder sample of acquisition is washed with distilled water 3 times, which is placed in drying basin, is put
Enter in thermostatic drying chamber, 55 DEG C of dry 6h, obtain nickel hydrazine nitrate, under above-mentioned process conditions, nickel hydrazine nitrate yield is 96%, granularity
It is 8.35 μm, free-running property is good, and product is rose.
Embodiment 2
1 nickel hydrazine nitrate of embodiment carries out demulsification method coating modification, and steps are as follows
(1) aqueous polyurethane emulsion of 24g is weighed, is added in the single-necked flask for filling 50mL distilled water at normal temperature, 60 DEG C
Constant temperature stirring is uniformly mixed the two；
(2) after a certain period of time, proper amount of surfactant is added, continues constant temperature and stirs 30min；
(3) it is cooled to demulsification temperature, the nickel hydrazine nitrate of 100g is added, being sufficiently stirred makes to be uniformly mixed；
(4) 72g alum solution is weighed, alum solution is added dropwise into flask with 1 drop/s rate, constant temperature stirs at a temperature of 40 DEG C
15min is precipitated aqueous polyurethane from lotion and is coated on the surface of nickel hydrazine nitrate；
(5) cool down, filter, wash 2~3 times, polyurethane is obtained after drying and coats nickel hydrazine nitrate.
Being detected polyurethane cladding nickel hydrazine nitrate Initiation Pressure value is 383MPa, and 50% is under fire distance for 1.98cm.
Embodiment 3
A kind of no sulphur of the invention is without chlorine pyrotechnics drug composition, including following components: 80g potassium nitrate, 10g ferrocene, 10g nitric acid
Hydrazine nickel, 10g charcoal.
Wherein potassium nitrate is purchased to Xilong Chemical Co., Ltd, and ferrocene, which is purchased to Tianjin, recovers fine chemistry industry research institute,
Nickel hydrazine nitrate is nickel hydrazine nitrate prepared by embodiment 1.
The present embodiment sulphur is without chlorine pyrotechnics drug composition the preparation method comprises the following steps: 1) grinding potassium nitrate, ground oxygen
Then agent powder is put by 120 meshes in drying box with pack after cooling after the dry 1h of 80 DEG C of temperature standby in drier
With；For above-mentioned ferrocene by grinding and crossing 120 mesh, 40 DEG C of dry 2h are spare；Above-mentioned nickel hydrazine nitrate is dry with 50 DEG C in drying box
Dry 2h is spare；Charcoal is ground and crosses to pack after cooling in drying box with the dry 1h of 80 DEG C of temperature after 120 meshes and is put into
Drier is spare.
2) above-mentioned raw materials are successively poured into mortar according to said ratio to grind, milling time is greater than 30min, obtains nothing
Sulphur is without chlorine pyrotechnics drug composition.
Embodiment 4
A kind of no sulphur of the invention is without chlorine pyrotechnics drug composition, including following components: 80g potassium nitrate, 10g ferrocene, the poly- ammonia of 10g
Ester coats nickel hydrazine nitrate, 10g charcoal.
Wherein potassium nitrate is purchased to Xilong Chemical Co., Ltd, and ferrocene, which is purchased to Tianjin, recovers fine chemistry industry research institute,
It is prepared by embodiment 2 that polyurethane, which coats nickel hydrazine nitrate,.
The present embodiment sulphur is without chlorine pyrotechnics drug composition the preparation method comprises the following steps: 1) grinding potassium nitrate, ground oxygen
Then agent powder is put by 120 meshes in drying box with pack after cooling after the dry 1h of 80 DEG C of temperature standby in drier
With；For above-mentioned ferrocene by grinding and crossing 120 mesh, 40 DEG C of dry 2h are spare；Above-mentioned polyurethane cladding nickel hydrazine nitrate is in drying box
In it is spare with 50 DEG C of dry 2h；Charcoal is ground and is crossed to be cooled with the dry 1h of 80 DEG C of temperature in drying box after 120 meshes
It is spare to be put into drier for pack afterwards.
2) above-mentioned raw materials are successively poured into mortar according to said ratio to grind, milling time is greater than 30min, obtains nothing
Sulphur is without chlorine pyrotechnics drug composition.
Embodiment 5
5gEVA hot melt adhesive is increased in the composition of embodiment 3 as adhesive.
Preparation method are as follows: 1) grind potassium nitrate, ground oxidant powder is by 120 meshes then dry
It is put into dry case with pack after cooling after the dry 1h of 80 DEG C of temperature spare in drier；Above-mentioned ferrocene is by grinding and mistake
120 mesh, 40 DEG C of dry 2h are spare；Above-mentioned nickel hydrazine nitrate is spare with 50 DEG C of dry 2h in drying box；Charcoal is ground and crosses 120
Pack with the dry 1h of 80 DEG C of temperature that be put into drier spare after mesh after cooling in drying box.
2) above-mentioned raw materials are successively poured into mortar according to said ratio to grind, milling time is greater than 30min, is mixed
Close object.
3) 5gEVA hot melt adhesive is added in the mixture of step 2 acquisition and is mixed, then be twisted into the mesh screen of 8 mesh or 10 mesh
Then small medicinal strip swings circle with treucher or aluminium dish, swings light to get no sulphur without chlorine pyrotechnics drug composition.
Embodiment 6
Difference with embodiment 5 is that the polyurethane prepared by embodiment 2 coats nickel hydrazine nitrate and replaces nickel hydrazine nitrate.
Embodiment 7
Difference with embodiment 3 is, composition of raw materials are as follows: 75g potassium nitrate, 5g ferrocene, 5g nickel hydrazine nitrate, 15g charcoal.
Embodiment 8
Difference with embodiment 4 is, composition of raw materials are as follows: 75g potassium nitrate, 5g ferrocene, 5g polyurethane cladding nickel hydrazine nitrate,
15g charcoal.
Embodiment 9
Difference with embodiment 5 is, composition of raw materials are as follows: 75g potassium nitrate, 5g ferrocene, 5g nickel hydrazine nitrate, 15g charcoal,
5gEVA hot melt adhesive.
Embodiment 10
Difference with embodiment 6 is, composition of raw materials are as follows: 75g potassium nitrate, 5g ferrocene, 5g polyurethane cladding nickel hydrazine nitrate,
15g charcoal, 5gEVA hot melt adhesive.
Embodiment 11
Difference with embodiment 9 is, composition of raw materials are as follows: 75g barium nitrate, 5g biferrocene, 5g hydrazine nitrate cobalt, 15g charcoal,
5gEVA hot melt adhesive.
Embodiment 12
Difference with embodiment 9 is, composition of raw materials are as follows: 75g ammonium nitrate, 5g cobaltocene, 5g nickel hydrazine azide, 15g charcoal,
5gEVA hot melt adhesive.
Embodiment 13
Difference with embodiment 9 is, composition of raw materials are as follows: 75g sodium nitrate, 5g dicyclopentadienyl nickel, 5g nickel hydrazine nitrate, 15g charcoal,
5gEVA hot melt adhesive.
Embodiment 14
Difference with embodiment 9 is, composition of raw materials are as follows: 75g strontium nitrate, 5g ferrocene, 5g nickel hydrazine nitrate, 15g charcoal,
5gEVA hot melt adhesive.
Comparative example 1
Without high energy nickel coordination compounds such as nickel hydrazine nitrates in the comparative example, it is formulated as 80g KNO3,10g ferrocene, 10g wood
Raw material crushed 120 meshes by charcoal, then carry out uniformly being prepared by mixing into no sulphur without chlorine pyrotechnics drug composition.
Comparative example 2
Without high energy nickel coordination compounds such as nickel hydrazine nitrates in the comparative example, it is formulated as 75g KNO3,10g ferrocene, 15g wood
Raw material crushed 120 meshes by charcoal, then carry out uniformly being prepared by mixing into no sulphur without chlorine pyrotechnics drug composition.
Comparative example 3
Without the high energy nickel coordination compound such as nickel hydrazine nitrate in the comparative example, it is formulated as 80g KNO3,5g ferrocene, 15g charcoal,
Raw material be crushed into 120 meshes, then carry out uniformly being prepared by mixing into no sulphur without chlorine pyrotechnics drug composition.
Comparative example 4
Traditional black powder (military project nitre), composition of raw materials are 75g potassium nitrate, 15g charcoal, 10g sulphur.
According to the test method that GB10631-2013 and GJB5384.6-2005 gives, to above-described embodiment and comparative example system
Standby is tested without sulphur without chlorine pyrotechnics drug composition, and index of correlation see the table below:
| Burn rate mm.s-1 | Impact sensitivity % | Friction sensitivity % | Ignition point DEG C | Hydroscopicity % | |
| Embodiment 3 | 9.8 | 0 | 0 | 436 | 3.1 |
| Embodiment 4 | 10.1 | 0 | 0 | 457 | 2.8 |
| Embodiment 5 | 10.7 | 0 | 0 | 459 | 0.2 |
| Embodiment 6 | 9.1 | 0 | 0 | 461 | 0.3 |
| Embodiment 7 | 11.5 | 0 | 0 | 463 | 4.0 |
| Embodiment 8 | 13.2 | 0 | 0 | 467 | 3.3 |
| Embodiment 9 | 12.4 | 0 | 0 | 465 | 0.3 |
| Embodiment 10 | 12.9 | 0 | 0 | 469 | 0.4 |
| Embodiment 11 | 10.5 | 0 | 0 | 453 | 0.2 |
| Embodiment 12 | 11.6 | 0 | 0 | 460 | 0.3 |
| Embodiment 13 | 11.9 | 0 | 0 | 455 | 0.4 |
| Embodiment 14 | 9.3 | 0 | 0 | 462 | 0.3 |
| Comparative example 1 | 2.9 | 23 | 21 | 388 | 5.7 |
| Comparative example 2 | 3.5 | 18 | 16 | 393 | 3.9 |
| Comparative example 3 | 3.3 | 19 | 17 | 397 | 4.6 |
| Comparative example 4 | 8.6 | 62 | 30 | 390 | 7.1 |
The present invention is not limited to the above-described embodiments, anyone can obtain other various forms of productions under the inspiration of the present invention
Product, however, make any variation in its shape or structure, it is all with technical solution identical or similar to the present application,
It falls within the scope and spirit of the invention.
Claims (7)
1. without sulphur without chlorine pyrotechnics drug composition, which is characterized in that including following components:
70-80 parts of oxidant
3-10 parts of catalyst
3-10 parts of priming
10-20 parts of incendiary agent
0-10 parts of adhesive.
2. no sulphur according to claim 1 is without chlorine pyrotechnics drug composition, which is characterized in that the parts by weight of each component
Are as follows:
75 parts of oxidant
5 parts of catalyst
5 parts of priming
15 parts of incendiary agent
5 parts of adhesive.
3. no sulphur according to claim 1 is without chlorine pyrotechnics drug composition, which is characterized in that the oxidant is nitrate,
The catalyst is metallocene and its derivative, and the priming is high energy nickel coordination compound, and the incendiary agent is charcoal, institute
Stating adhesive is EVA hot-melt adhesive.
4. no sulphur according to any one of the preceding claims is without chlorine pyrotechnics drug composition, which is characterized in that the oxidant choosing
From any one in potassium nitrate, barium nitrate, ammonium nitrate, sodium nitrate, strontium nitrate；Catalyst be selected from ferrocene, biferrocene,
Any one in cobaltocene, dicyclopentadienyl nickel；Any one of priming in nickel hydrazine nitrate, hydrazine nitrate cobalt, nickel hydrazine azide；Institute
Stating incendiary agent is poplar charcoal.
5. no sulphur according to any one of the preceding claims is without chlorine pyrotechnics drug composition, which is characterized in that the oxidant is
Potassium nitrate, catalyst are ferrocene, and priming is nickel hydrazine nitrate.
6. no sulphur according to any one of the preceding claims has carried out coating modification without chlorine pyrotechnics drug composition, the priming
Processing.
7. no sulphur according to claim 5 is without chlorine pyrotechnics drug composition, which is characterized in that the coating modification processing is broken
Newborn method coating modification or phase separation method coating modification.
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| CN115108872A (en) * | 2022-06-29 | 2022-09-27 | 湖南明义烟花集团有限公司 | Ignition medicine composition of firework fuming bright bead |
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