CN112357895A - Preparation method and device of sulfur-nitrogen polymer - Google Patents
Preparation method and device of sulfur-nitrogen polymer Download PDFInfo
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Abstract
The invention discloses a preparation method and a device of a sulfur-nitrogen polymer. The preparation device comprises S4N4Decomposed structure and S2N2A polymeric structure; s4N4The decomposing structure comprises a first container, the lower part of which is S4N4A heating sublimation area, wherein the middle part is a pyrolysis area, and the upper part is a cooling crystallization area; s2N2The polymerization structure comprises a second container, a polymerization area of the second container is communicated with the cooling crystallization area through a gas guide pipe, and a valve is arranged on the gas guide pipe; the polymerization zone can be cooled by a cooling structure; the second container is connected with a vacuum pump through a pipeline; the first container and the second container are both closed containers. In the preparation method of the sulfur-nitrogen compound, dimer is sublimated and catalytically decomposed into monomer, the monomer is cooled and crystallized, the monomer is gradually sublimated to a crystallization polymerization area in the whole process, and the monomer is heated in two different areas and cooled in two different areas, the heating and cooling can keep complete independence and stop switching freely, so that the nitrogen-sulfur polymer can be safely, efficiently and freely switchedWhile also ensuring high purity of the polymer.
Description
Technical Field
The invention relates to a preparation method and a device of a sulfur-nitrogen polymer, belonging to the technical field of synthesis of sulfur-nitrogen polymers.
Background
As early as 1910, chemists discovered a polymer for sulfur and nitrogen only (hereinafter referred to as sulfur polyazonitride) with "metallic" luster. Until 1975, IBM corporation of america discovered that this polymer could become a superconducting material at low temperatures. Most of the known polymers have very high resistivity at room temperature, the resistivity is further increased along with the reduction of the temperature, the nitrogen-sulfur polymer crystals show high anisotropic metal characteristics, the resistivity is reduced along the polymer chain along with the reduction of the temperature, and finally disappears at the superconducting transition temperature of about 0.3K, which is the first report of the superconductivity of the polymers. Therefore, research into the physicochemical properties of such materials can help to gain insight into the design of other polymeric metals and superconductors that may have higher transition temperatures.
The polymer of sulfur and nitrogen has high anisotropy and metallicity, and the crystal of the polymer is composed of chains with S, N atoms alternated. In the direction parallel to the S-N chain, the metal has good conductivity; in the vertical direction, the conductivity is much worse. The horizontal axis polarization of light also indicates that it is metallic, the crystal appears bluish black, and has a metallic luster. In 1973, the nobel prize winner of chemistry, mckdimed, began the Study of (SN) x, namely, sulfur nitride, a polymer with metallic conductivity. His best known research effort was to discover and study conductive polymers, i.e., conductive plastics, and, by virtue of its pioneering contribution in this field, he won the 2000-year nobel prize of chemistry with the allen black, white-english tree.
The synthesis of the nitrogen sulfur polymers is carried out by various routes as shown in Table 1. By monomers (S)2N2) Polymerization can occur at a temperature, which is the most classical synthetic route and is the primary method of preparing high purity polymers. Due to monomer (S)2N2) Is extremely explosive at very low temperature or slight friction, and passes through dimer (S)4N4) Decomposition into monomers (S)2N2) Is polymerized simultaneously, avoiding the monomer (S)2N2) Separating out the unsafe factors.
Monomer (S)2N2) The thermal instability of the polymer leads to the formation of nitrogen-sulfur polymers under the condition of slightly increased temperature, and impurities contained in monomers generated by sublimation in the polymerization process easily dope polymer crystals with impurities, and the corresponding performance and stability of the polymer are also influenced. Thus, only the dimer (S) of high purity is obtained4N4) Can ensure the purity of the nitrogen-sulfur polymer and the dimer (S)4N4) The preparation method can be realized by the following reactions:
1)
S4N3Cl→S4N4
2)
S3N2Cl2→S4N4
3)
S3N3Cl3→S4N4
4)
5)
in the above synthesis method, 1), 2) and 3) use hydrochloride containing only nitrogen and sulfur as starting material, and the hydrochlorideThe acid salt is particularly sensitive to moisture and is decomposed to form elemental sulfur solid, and the moisture is strictly controlled in the experimental operation process. The resulting dimer (S)4N4) Repeated recrystallization with dioxane is required, and the dimer (S) is purified by sublimation4N4) Finally, the purity can be proved to meet the requirement when the melting point is measured at 189 ℃. In the above-mentioned synthesis methods, disulfide dichloride used in 4) and 5) as a starting material also has a problem of forming elemental sulfur after absorbing moisture, and subsequent purification also undergoes a particularly complicated process.
TABLE 1 Synthesis of Nitrogen-sulfur polymers
Disclosure of Invention
The invention aims to provide a method and a device for preparing a sulfur-nitrogen polymer, which can efficiently prepare high-purity dimer (S)4N4) And then the high-purity sulfur-nitrogen polymer is generated from the dimer through a reasonable reaction process and a reaction device.
The preparation of the high-purity sulfur-nitrogen polymer is realized by controlling the following key points: 1) dimer (S)4N4) Can fully decompose, 2) the monomer can stay in a certain stage, 3) the monomer which is sublimated can complete effective polymerization in a proper space.
The preparation device of the sulfur-nitrogen polymer provided by the invention comprises S4N4Decomposed structure and S2N2A polymeric structure;
said S4N4The decomposing structure comprises a first container, the lower part of which is S4N4A heating sublimation area, wherein the middle part is a pyrolysis area, and the upper part is a cooling crystallization area;
said S2N2The polymerization structure comprises a second container, a polymerization area of the second container is communicated with the cooling crystallization area through a gas guide pipe, and a valve is arranged on the gas guide pipe; the polymerization zone can be cooledCooling the structure;
the second container is connected with a vacuum pump through a pipeline;
the first container and the second container are both closed containers.
In the above-mentioned manufacturing apparatus, an oil bath heating device is fitted to the lower part of the first container;
the middle part of the first container is coated with an electric heating sleeve;
an annular cavity is formed at the upper part of the first container, and a cavity defined by the inner wall of the annular cavity is internally provided with a coolant I;
the coolant i is preferably liquid nitrogen.
In the above-mentioned production apparatus, a crystalline polymer network is provided in the polymerization zone;
a cavity defined by the polymerization area is internally provided with a coolant II to form the cooling structure;
the coolant II is preferably brine ice;
and the cooling structure is provided with a coolant inlet pipeline and a coolant outlet pipeline.
By utilizing the preparation device, the dimer (S) can be completed in the same closed system4N4) Heating to sublimate and then decomposing monomer (S)2N2) Deep low temperature crystallization of the resulting product, monomer (S)2N2) After gradually raising the temperature, the mixture is sublimated to be efficiently crystallized to a polymerization area.
The device is connected with the vacuum pump, so that the dynamic vacuum state is always kept, the temperature required by sublimation is reduced, and the product can be kept to flow in one direction in the sublimation process of steam.
When the preparation device is used for preparing the sulfur-nitrogen polymer, the preparation method can be carried out according to the following steps:
s1, reacting sulfur, silver nitrate and hexamethyldisilazane in an inert atmosphere, and recrystallizing to obtain S4N4；
S2, mixing the S4N4And the S of the first container in which silver fibers are respectively placed in the preparation device4N4Heating ofThe valve is opened in the sublimation area and the pyrolysis area, and the vacuum pump is started to pump vacuum;
s3, keeping a vacuum condition, heating the pyrolysis zone, and adding the coolant I into the cooling crystallization zone after the temperature is stable; starting to heat the heating sublimation area to enable the S4N4Sublimating to give S4N4Steam of said S4N4The steam reacts with the silver fiber in the pyrolysis zone to obtain Ag2S; in the Ag2Under the catalysis of S, the S4N4Decomposition of the vapor to give S2N2Steam; said S2N2Cooling and crystallizing the vapor in the cooling and crystallizing area to obtain S2N2A crystal;
s4, keeping the vacuum condition, and opening the cooling structure to cool the polymerization area; stopping cooling the cooling crystallization area, wherein in the process of natural temperature rise of the cooling crystallization area, S2N2After the crystals are sublimated, the crystals enter the polymerization area through the air guide pipe and are cooled and crystallized; and closing the valve, continuously cooling the polymerization area for 24-36 h, closing the cooling structure, naturally heating the system, and carrying out polymerization reaction to obtain the sulfur-nitrogen polymer.
In the above-mentioned production method, in step S1, the dimer (S)4N4) The reaction equation of the synthesis reaction of (1) is as follows:
the reaction temperature is 125-130 ℃, and the reaction time is 1.5-2 h;
recrystallizing with dioxane;
carrying out suction filtration after recrystallization to obtain a solid, washing by adopting dioxane, and directly refrigerating;
in step S1, by adjusting the ratio of the raw materials, Hexamethyldisilazane (HMDS) can be used as an accelerator to significantly increase the dimer (S) during the reaction4N4) In a yield of (2), while the dimer(S4N4) The Hexamethyldisilazane (HMDS) liquid can be crystallized and easily separated, and the dimer with high purity is obtained through recrystallization and purification; due to the dimer (S)4N4) And has certain explosion risk, so the process of post-drying the solvent needs to be well controlled and safe. Can be used in the device of the invention in the dimer (S)4N4) Residual solvent was removed in vacuo prior to sublimation decomposition.
In the above-mentioned production method, in step S3, the dimer (S)4N4) The reaction equation of the decomposition reaction of (2) is as follows:
Ag+S4N4→Ag2S+N2
dimer (S)4N4) Silver sulfide generated by reaction with silver is taken as a catalyst for decomposition reaction, so that the reaction speed is accelerated;
the silver fiber and the dimer (S)4N4) The mass ratio of (A) to (B) is 1-1.5: 2;
heating the heating sublimation area to 75-80 ℃;
heating the pyrolysis zone to 320-340 ℃;
when said S is4N4And after the decomposition is completed, continuously heating the heating sublimation area and the pyrolysis area for 15-20 min.
In this step, the dimer (S) is heated under vacuum4N4) The sublimation temperature is much lower than the normal pressure, the degradation caused by overhigh heating temperature is reduced, and the temperature is controlled by using an electric heating belt due to the change of the temperature when steam enters the silver fiber area for decomposition. The amount of silver fiber used at this time affects whether the dimer is sufficiently decomposed, and if the decomposition is insufficient, the dimer is crystallized together with the monomer in the crystallization region. Due to monomer (S)2N2) Is particularly poor, via dimer (S)4N4) Must be extremely low after decompositionStored at temperature, thus using liquid nitrogen for deep cooling. The liquid nitrogen is refrigerated in a designated area through a system, and the liquid nitrogen can be conveniently removed for natural temperature rise after the dimer is decomposed.
In the above-mentioned production method, in step S4, the monomer (S)2N2) The reaction equation of the polymerization reaction of (1) is as follows:
monomer (S)2N2) Has certain stability at very low temperature, gradually polymerizes after being kept at about 0 ℃, and then fully polymerizes after being heated to room temperature.
When the S in the cooling crystallization zone2N2Closing the valve after 3-3.5 hours after the crystal is completely sublimated;
heating the system to room temperature and reacting for 6.5-7 days;
in this step, monomer (S)2N2) Slowly raising the temperature to room temperature after cryogenic crystallization, and keeping the system in a vacuum state in the process to obtain the monomer (S)2N2) Slowly sublimating. Cooling the polymerization net region with ice salt water, allowing the monomer vapor to completely enter the crystallization net via the conduit, slowly crystallizing and polymerizing, and allowing the monomer (S) to react2N2) After complete sublimation, the vapor conduit front end was closed. The area is designed into a net structure and can be fully cooled, so that the crystalline monomer is effectively absorbed, and the crystalline monomer is prevented from being taken out of the system by a vacuum pump. After a certain low-temperature polymerization, the temperature is returned to normal temperature for sufficient polymerization. The cooling liquid of the ice brine cools the reticular crystallization area from the system, and the refrigeration can be conveniently stopped after the refrigeration stage is finished.
In the preparation method, the next flow can be freely switched after the flow of each step is finished, the system is kept not to be in contact with the external environment, and the water and other impurities are prevented from entering, so that the purity of the polymer is influenced; in the monomer (S)2N2) The sublimated liquid can be efficiently crystallized in a polymerization area, so that the sublimated liquid is not taken out by vacuumLoss is formed outside the system; in the whole process, the heating and low-temperature conditions of all the processes are carried out in the system, and the equipment does not need to be disassembled and reassembled. In the process of the invention, the dimer (S)4N4) The sublimation and catalytic decomposition are carried out by means of a heating device arranged outside the apparatus, such as a glass apparatus, the monomer (S)2N2) The cooling crystallization is carried out by external liquid nitrogen and ice salt water.
The invention provides a preparation method of a sulfur nitrogen compound and a dimer (S)4N4) After sublimation, catalytically decomposing into monomer (S)2N2) The monomer is cooled and crystallized, and the monomer is gradually sublimated to the whole crystallization polymerization area, and is heated in two different areas and cooled in two different areas, and the heating and cooling can keep complete independence and stop switching freely. The four areas are connected and communicated according to a specified flow sequence, so that the system is in a uniform vacuum state, and the sublimation vapor can be transferred according to the flow direction by dynamic vacuum. The integrated design of decomposition, sublimation and polymerization ensures the safe and efficient production of the nitrogen-sulfur polymer and the high purity of the polymer.
Drawings
FIG. 1 is a schematic view of the structure of an apparatus for producing a sulfur-nitrogen polymer according to the present invention.
The respective symbols in the figure are as follows:
1. heating in oil bath; 2. s4N4Heating the sublimation zone; 3. a pyrolysis zone; 4. an electrical heating belt; 5. a liquid nitrogen coolant; 6. 7, 9 and 12 valves, 8, a cooling liquid inlet pipeline, 10 and a cooling liquid outlet pipeline; 11. a pipeline; 13. crystallizing the polymeric network; 14. and cooling the liquid by using brine ice.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
As shown in fig. 1, the schematic structural diagram of the apparatus for preparing a polymer of sulfur and nitrogen provided by the present invention includes a first closed container and a second closed container.Wherein the lower part of the first container is S4N4Heating the sublimation zone 2 for placing the dimer (S)4N4) Which is matched with an oil bath heating 1 for heating S4N4(ii) a The middle part is a pyrolysis zone 3 for placing silver fiber, and an electric heating belt 4 is matched outside the pyrolysis zone for heating silver fiber and heating sublimed dimer (S)4N4) Where the decomposition is carried out; the upper part is a cooling crystallization area which forms an annular cavity, and liquid nitrogen coolant 5 is placed in a cavity defined by the inner wall of the annular cavity and used for cooling the cooling crystallization area. The polymerization zone of second container is through an air duct and cooling crystallization zone intercommunication, is equipped with valve 6 on the air duct, is provided with ice brine cooling liquid 14 in the cavity that the polymerization zone encloses for cool off the polymerization zone, input the coolant liquid through coolant liquid inlet tube 8, export the coolant liquid through coolant liquid outlet pipe 10, distribute on coolant liquid inlet tube 8 and the coolant liquid outlet pipe 10 and be equipped with valve 7 and 9. A crystalline polymer network 13 is provided in the polymerization zone to efficiently absorb the crystalline monomer. The cooled polymerization zone is connected to a vacuum pump via a line 11, which line 11 is provided with a valve 12.
By utilizing the preparation device, the dimer (S) can be completed in the same closed system4N4) Heating to sublimate and then decomposing monomer (S)2N2) Deep low temperature crystallization of the resulting product, monomer (S)2N2) After gradually raising the temperature, the mixture is sublimated to be efficiently crystallized to a polymerization area.
The following describes in detail the process for preparing a polymer of sulfur and nitrogen by means of the apparatus of the invention:
1. dimer (S)4N4) Synthesis of (2)
Adding AgNO into a double-mouth round-bottom flask3(4g, 23.6mmol) and sulfur (1.28g, 40.1mmol), the flask was purged of air with nitrogen, and HMDS (25ml, 119.4mmol, 99.9%) was added with stirring under nitrogen. Heating in oil bath to reflux with internal temperature of 127 deg.C, allowing black precipitate to appear after 10 min, heating for 1 hr, standing for 10 min, pressing the supernatant into another dry round bottom flask with nitrogen, standing at about 100 deg.C for about 0.5 hr to obtain crystal.
And cooling step by step, and keeping the temperature for 0.5h every time when the temperature is reduced by 5 ℃ until the final temperature is 50 ℃ and standing for 5 h. The liquid was slowly decanted, 10ml of dioxane was added to wash the solids and the solution was decanted, 10ml of dioxane was added again and heated to dissolve and clarify. Standing at room temperature to precipitate solid for 2h, and refrigerating in refrigerator overnight. After suction filtration, the solid was washed with a little cold dioxane and directly stored in a plastic bag in a refrigerator (note: the solvent could not be dried).
2. Preparation of nitrogen-sulfur polymers
(1) Adding raw materials, assembling equipment
At S4N4Heating the sublimation area 2, adding the dimer (S) containing a little dioxane prepared in the step 14N4) Silver fibers are carefully placed in the pyrolysis zone 3, ice is kept from contacting the bottom of the cooling crystallization zone, and the amount of silver fibers used is half the mass of the dimer. After all the joints are sealed, the valve 6 is in an open state, after the piston 12 is opened, the vacuum pump is used for vacuumizing for half an hour through the pipeline 11 at room temperature (cold hydrazine equipment is added in front of the vacuum pump to prevent the solvent from entering the pump body), the residual solvent is removed as much as possible, and the vacuumizing state is kept all the time.
(2) Dimer (S)4N4) Sublimating and decomposing into monomer (S)2N2) Crystallization of
And (3) keeping the system under vacuum pumping, heating the electric heating belt 4 to 330-335 ℃, adding a liquid nitrogen coolant 5 into the cooling crystallization area after the temperature is stable, starting oil bath heating 1, and gradually increasing the temperature to 78 ℃. At this time, the dimer (S)4N4) The sublimation begins, the vapor rises to a high-temperature decomposition area 3 to contact silver fiber and then generates Ag2S, followed by catalytic decomposition of the dimer to form the monomer (S)2N2) The steam is subjected to cryogenic crystallization on the inner wall of the cooling crystallization area. When all dimers (S)4N4) After the disappearance, the oil bath heating 1 and the electric heating belt 4 are kept in the heating state for 15min, and then the heating is stopped.
(3) Monomer (S)2N2) Recrystallization and polymerization after sublimation
Keeping the system under vacuum, opening valves 7 and 9, and introducing ice salt water for 15min to crystallize the polymer network 13, fully cooling. The liquid nitrogen coolant 5 outside the cooling crystallization zone was carefully removed and allowed to warm to room temperature naturally, at which point the monomer (S)2N2) The sublimation begins slowly and the crystals are cooled down in the crystallizing polymer network 13. Cooling the inner wall solids of the crystallization zone for 3 hours after the solid matter had almost disappeared to allow the monomer (S)2N2) Crystallization is complete as far as possible at the crystallization polymer network 13, the valve 6 being closed. And continuously keeping the introduction of the ice brine for 1 day, stopping introducing the ice brine, gradually returning the whole system to the room temperature, keeping the room temperature for 7 days, and completely polymerizing to obtain the sulfur-nitrogen polymer.
The molecular weight of the polymer of sulfur and nitrogen prepared in this example is 1100, wherein, S%: 68.5%, N%: 28.1 percent.
Claims (10)
1. A preparation device of a sulfur-nitrogen polymer comprises S4N4Decomposed structure and S2N2A polymeric structure;
said S4N4The decomposing structure comprises a first container, the lower part of which is S4N4A heating sublimation area, wherein the middle part is a pyrolysis area, and the upper part is a cooling crystallization area;
said S2N2The polymerization structure comprises a second container, a polymerization area of the second container is communicated with the cooling crystallization area through a gas guide pipe, and a valve is arranged on the gas guide pipe; the polymerization zone being capable of being cooled by a cooling structure;
the second container is connected with a vacuum pump through a pipeline;
the first container and the second container are both closed containers.
2. The manufacturing apparatus according to claim 1, characterized in that: an oil bath heating device is matched at the lower part of the first container;
the middle part of the first container is coated with an electric heating sleeve;
an annular cavity is formed at the upper part of the first container, and a cavity enclosed by the inner wall of the annular cavity is internally provided with a coolant I.
3. The manufacturing apparatus according to claim 2, characterized in that: the coolant I is liquid nitrogen.
4. The manufacturing apparatus according to any one of claims 1 to 3, wherein: a crystalline polymer network is arranged in the polymerization area;
and a cavity surrounded by the polymerization area is internally provided with a coolant II to form the cooling structure.
5. The manufacturing apparatus according to claim 4, wherein: the coolant II is ice brine;
and the cooling structure is provided with a coolant inlet pipeline and a coolant outlet pipeline.
6. Use of the production apparatus according to any one of claims 1 to 5 for producing a polymer of sulfur and nitrogen.
7. A preparation method of a sulfur-nitrogen polymer comprises the following steps:
s1, reacting sulfur, silver nitrate and hexamethyldisilazane in an inert atmosphere, and recrystallizing to obtain S4N4；
S2, mixing the S4N4And silver fibers are respectively placed in the S of the first container in the production apparatus of any one of claims 1 to 54N4Heating the sublimation area and the pyrolysis area, opening the valve, and opening the vacuum pump to extract vacuum;
s3, keeping a vacuum condition, heating the pyrolysis zone, and adding the coolant I into the cooling crystallization zone after the temperature is stable; starting to heat the heating sublimation area to enable the S4N4Sublimating to give S4N4Steam of said S4N4The steam reacts with the silver fiber in the pyrolysis zone to obtain Ag2S; in the Ag2Under the catalysis of S, the S4N4Decomposition of the vapor to give S2N2Steam; the above-mentionedS2N2Cooling and crystallizing the vapor in the cooling and crystallizing area to obtain S2N2A crystal;
s4, keeping the vacuum condition, and opening the cooling structure to cool the polymerization area; stopping cooling the cooling crystallization area, wherein in the process of natural temperature rise of the cooling crystallization area, S2N2After the crystals are sublimated, the crystals enter the polymerization area through the air guide pipe and are cooled and crystallized; and closing the valve, continuously cooling the polymerization area for 24-36 h, closing the cooling structure, naturally heating the system, and carrying out polymerization reaction to obtain the sulfur-nitrogen polymer.
8. The method of claim 7, wherein: in the step S1, the reaction temperature is 125-130 ℃, and the reaction time is 1.5-2 h;
recrystallizing with dioxane;
and (4) carrying out suction filtration after recrystallization to obtain a solid, and directly refrigerating after washing by adopting dioxane.
9. The production method according to claim 7 or 8, characterized in that: in the step S3, heating the heating sublimation area to 75-80 ℃;
heating the pyrolysis zone to 320-340 ℃;
when said S is4N4And after the decomposition is completed, continuously heating the high-temperature decomposition area and the heating sublimation area for 15-20 min.
10. The production method according to any one of claims 7 to 9, characterized in that: in step S4, when S in the cooling crystallization zone2N2Closing the valve after 3-3.5 hours after the crystal is completely sublimated;
and the system is heated to room temperature and then reacts for 6.5-7 days.
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| CN112315460A (en) * | 2020-11-04 | 2021-02-05 | 公安部物证鉴定中心 | Application of sulfur-nitrogen polymer in fingerprint display |
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| DE2943160A1 (en) * | 1978-10-26 | 1980-05-08 | Nat Res Dev | Sulphur nitride cpds. and polymer prodn. - by reducing nitrate or halide, the polymers being useful as semiconductors |
| GB2038297A (en) * | 1978-10-26 | 1980-07-23 | Nat Res Dev | Producing sulphur-nitrogen groups |
| JPS5924725A (en) * | 1982-07-31 | 1984-02-08 | Agency Of Ind Science & Technol | Production of polythiazyl |
| CN110402235A (en) * | 2017-03-14 | 2019-11-01 | 英国国防部 | Prepare the method for the metal halide adduct of S4N4 and by the mark visualization method and equipment on object |
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2020
- 2020-11-04 CN CN202011219676.1A patent/CN112357895A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2943160A1 (en) * | 1978-10-26 | 1980-05-08 | Nat Res Dev | Sulphur nitride cpds. and polymer prodn. - by reducing nitrate or halide, the polymers being useful as semiconductors |
| GB2038297A (en) * | 1978-10-26 | 1980-07-23 | Nat Res Dev | Producing sulphur-nitrogen groups |
| JPS5924725A (en) * | 1982-07-31 | 1984-02-08 | Agency Of Ind Science & Technol | Production of polythiazyl |
| CN110402235A (en) * | 2017-03-14 | 2019-11-01 | 英国国防部 | Prepare the method for the metal halide adduct of S4N4 and by the mark visualization method and equipment on object |
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| Title |
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| BASKARAN GANESH KUMAR ET AL.: "S4N4 as an intermediate in Ag2S nanoparticle synthesis", 《RSC ADVANCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112315460A (en) * | 2020-11-04 | 2021-02-05 | 公安部物证鉴定中心 | Application of sulfur-nitrogen polymer in fingerprint display |
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Application publication date: 20210212 |