CN115028829A - 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, and synthesis method and application thereof - Google Patents
1,2, 3-triazole-4-methylene nitrate modified azide adhesive, and synthesis method and application thereof Download PDFInfo
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- CN115028829A CN115028829A CN202210707623.7A CN202210707623A CN115028829A CN 115028829 A CN115028829 A CN 115028829A CN 202210707623 A CN202210707623 A CN 202210707623A CN 115028829 A CN115028829 A CN 115028829A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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Abstract
The invention provides a 1,2, 3-triazole-4-methylene nitrate modified azide adhesive which is characterized by having a structural formula as follows:
Description
Technical Field
The invention belongs to the technical field of adhesive preparation, relates to a burning rate catalyst, and particularly relates to a 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, a synthesis method and application.
Background
The azide adhesive has the advantages of positive heat generation, quick combustion, high energy, clean fuel gas, good thermal stability, low mechanical sensitivity and the like, and is an ideal adhesive for high-energy low-characteristic signal propellants, fuel gas generators and high-solid-content propellant. The azide binder is typically represented by polyaziridine glycidyl ether (GAP), such as by Pont Edimer et al in "preliminary studies of mechanical properties of GAP propellants" solid rocket technology, 1995, 18 (2): 31-34, discloses the molecular structure characteristics of a typical GAP adhesive and the mechanical properties of a polyurethane elastomer film formed after curing, wherein the molecular structure of the GAP is simply as follows:
due to the existence of azido in the GAP side chain, the intermolecular interaction is poor, GAP is used as an adhesive, N-100 is used as a curing agent, and when the R value is 1.2, the prepared polyurethane elastomer film has the maximum tensile strength of 0.53MPa at room temperature, the elongation at break of 56.5 percent and low mechanical property.
Therefore, it is urgent to actively develop an adhesive capable of imparting high mechanical properties to polyurethane elastomers to replace the application of GAP adhesives in propellants.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, a synthesis method and application, and solve the technical problem that a polyurethane elastomer film prepared in the prior art is poor in mechanical property.
In order to solve the technical problems, the invention adopts the following technical scheme to realize:
the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive has a structural formula shown as follows:
wherein x is an integer of 6 to 10, and y is an integer of 24 to 40.
The invention also has the following technical characteristics:
the invention also provides a synthetic method of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, which comprises the following synthetic route:
wherein x is an integer of 6 to 10, y is an integer of 24 to 40, and n is x + y.
Further, the method comprises the steps of:
adding polyazide glycidyl ether and 1, 2-dichloroethane, adding propiolic alcohol nitrate under the stirring condition, stirring until the mixture is completely dissolved, heating for reaction, and carrying out reduced pressure distillation after the reaction to obtain the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive.
Specifically, the molar ratio of the polyaziridine glycidyl ether to the propargyl alcohol nitrate is 1 (6-10).
Furthermore, the temperature rise reaction is carried out for 6-12 h when the temperature rises to 60-70 ℃.
Further, the reduced pressure distillation comprises concentration at 40-70 deg.C under vacuum degree of 5-20 mmHg.
The invention also protects the application of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive for a high-energy low-characteristic signal propellant; or the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive prepared by the synthesis method of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is applied to high-energy low-characteristic signal propellants.
Preferably, the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is added in an amount of 8.3 wt.% in the high energy, low characteristic signal propellant.
Compared with the prior art, the invention has the following technical effects:
the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive contains a rigid group triazole ring and a nitrate group with strong intermolecular action, and a polyurethane elastomer prepared by using the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive as a raw material has the maximum tensile strength of 0.62MPa and the elongation at break of 210 percent, so that the mechanical property of the polyurethane elastomer is greatly improved; the synthesis method is simple, the synthesis condition is mild, and the yield is high.
The present invention will be explained in further detail with reference to examples.
Detailed Description
It is to be noted that all the raw materials in the present invention, unless otherwise specified, may be those known in the art.
The conception of the invention is as follows: the reason why the mechanical properties of the polyurethane elastomer film formed after the GAP adhesive is cured is that the mechanical properties are low because the acting force between molecular chains is weakened by azide groups in side chains of GAP molecules. In order to improve the mechanical property of the elastomer, the invention synthesizes the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive with partial azide groups replaced, on one hand, propiolic alcohol and partial azide of GAP generate triazole ring through 1, 3-dipolar cyclization reaction, and the triazole ring is used as a rigid group, thus being beneficial to improving the mechanical property of the elastomer; on the other hand, nitrate groups have stronger intermolecular interaction, which is beneficial to the aggregation of elastomer hard chain segments and promotes the microphase separation of the elastomer, thereby improving the mechanical property of the elastomer.
In the invention, the following test equipment is adopted:
the infrared spectrum was measured using a Nexus 870 Fourier transform Infrared spectrometer from Nicolet, USA;
nuclear magnetism is tested by AVANCE AV500 type nuclear magnetic resonance instrument of Bruker company in Germany;
the number average molecular weight was measured by GPC-50 gel permeation chromatography of PL corporation, UK;
the mechanical properties of the elastomers were measured using an Instron model 4505 Universal Material testing machine, Instron, USA.
High energy low signature propellant: the propellant is high-energy propellant with low characteristic signals generated during combustion so as to achieve the purposes of effectively hiding and ensuring survival of a weapon system. At present, the azide polyether propellant can be developed into a high-energy, insensitive and low-characteristic signal propellant, and a GAP/nitrate/HMX (RDX)/AP/Al system low-characteristic signal propellant is already applied.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
this example provides a 1,2, 3-triazole-4-methylene nitrate modified azide adhesive characterized by the following structural formula:
wherein x is an integer of 6 to 10, and y is an integer of 24 to 40.
This example also shows the synthesis of 1,2, 3-triazole-4-methylene nitrate modified azide adhesive as described above, which is as follows:
wherein x is an integer of 6 to 10, y is an integer of 24 to 40, and n is x + y.
The method comprises the following steps:
adding polyazide glycidyl ether (with the number average molecular weight of 4000, 10g and 2.5mmol) and 1, 2-dichloroethane (50mL) into a three-necked bottle provided with a mechanical stirring device and a thermometer, uniformly stirring, adding propargyl alcohol nitrate (1.5g and 15mmol) for four times, stirring until all the materials are dissolved after the materials are added, heating to 70 ℃, reacting for 6h, and finally carrying out reduced pressure distillation at 50 ℃/10mmHg to remove 1, 2-dichloroethane, thus obtaining yellow viscous liquid.
And (3) structural identification:
1 H NMR(CDCl 3 ，500MHz)：1.61，2.62，3.32～3.73，4.56，5.64。
IR，ν max (cm -1 )：3445(-OH)，2939、2885(C-H)，2102(-N 3 )，1720(C＝C)，1638(-ONO 2 )，1078(C-O-C)。
number average molecular weight was 4120 and hydroxyl number was 25.19mg KOH/g.
The above data confirm that the synthesized compound is the target compound of the invention, namely, the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive.
The 1,2, 3-triazole-4-methylene nitrate modified azide adhesives of this example were used in high energy, low signature signal propellants.
Preferably, the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is added in an amount of only 8.3 wt.%.
Preferably, the high energy, low signature propellant comprises an azido polyether propellant.
Example 2:
this example shows a 1,2, 3-triazole-4-methylene nitrate modified azide adhesive having the same structural formula as in example 1.
This example also shows a method for synthesizing a 1,2, 3-triazole-4-methylenenitrate modified azide adhesive as described above, comprising the steps of:
adding poly-azido glycidyl ether (with the number average molecular weight of 4000, 10g and 2.5mmol) and 1, 2-dichloroethane (50mL) into a three-mouth bottle provided with a mechanical stirring device and a thermometer, uniformly stirring, adding propynol nitrate (2.0g and 20mmol) for four times, stirring until the mixture is completely dissolved after the addition is finished, heating to 65 ℃, reacting for 8 hours, and finally distilling under reduced pressure at 55 ℃/10mmHg to remove 1, 2-dichloroethane to obtain yellow viscous liquid.
Number average molecular weight 4483 and hydroxyl number 23.15mg KOH/g.
The structure identification data and results of this example are the same as those of example 1.
The 1,2, 3-triazole-4-methylene nitrate modified azide adhesives of this example were used in high energy, low signature signal propellants.
Preferably, the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is added in an amount of only 8.3 wt.%.
Preferably, the high energy low signature signal propellant comprises an azide polyether propellant.
Example 3:
this example shows a 1,2, 3-triazole-4-methylene nitrate modified azide adhesive having the same structural formula as in example 1.
This example also shows a method for synthesizing a 1,2, 3-triazole-4-methylenenitrate modified azide adhesive as described above, comprising the steps of:
adding polyazide glycidyl ether (with the number average molecular weight of 4000, 10g and 2.5mmol) and 1, 2-dichloroethane (50mL) into a three-necked bottle provided with a mechanical stirring device and a thermometer, uniformly stirring, adding propargyl alcohol nitrate (2.5g and 25mmol) for four times, stirring until all the materials are dissolved after the materials are added, heating to 60 ℃, reacting for 12 hours, and finally carrying out reduced pressure distillation at 60 ℃/10mmHg to remove 1, 2-dichloroethane to obtain yellow viscous liquid.
Number average molecular weight 4673, hydroxyl number 22.21mg KOH/g.
The structure identification data and results of this example are the same as those of example 1.
The 1,2, 3-triazole-4-methylene nitrate modified azide adhesive of this example was used in a high energy, low characteristic signal propellant.
Preferably, the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is added in an amount of only 8.3 wt.%.
Preferably, the high energy low signature signal propellant comprises an azide polyether propellant.
As can be seen from the comparison among the examples 1,2 and 3, the preparation method of the invention has good stability in the production process and is suitable for industrial large-scale popularization.
Evaluation of application Performance:
(1) evaluation of miscibility with isocyanate curing agent
The miscibility and reactivity of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive and the curing agent were examined using N-100 as the curing agent.
The 1,2, 3-triazole-4-methylene nitrate modified azide adhesive has good miscibility with an N-100 curing agent, the mixed solution is clear and transparent, and the formed mixed solution can be stably subjected to curing reaction at the temperature of 60-70 ℃.
(2) Mechanical properties of elastomers
The 1,2, 3-triazole-4-methylene nitrate modified azide adhesive with the number average molecular weight of 4120 is used as a raw material and is mixed with a curing agent N-100 for heating and curing, and when the R value is 1.2, the prepared polyurethane elastomer has the following mechanical properties: the maximum tensile strength was 0.62MPa, and the elongation at break was 210%.
From the above results, it can be seen that the mechanical properties of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive synthesized by the method of the present invention are significantly improved compared with the prior art which discloses that when the R value is 1.2 by using GAP as an adhesive and N-100 as a curing agent, the maximum tensile strength of the prepared polyurethane elastomer film at room temperature is 0.53MPa, and the elongation at break is 56.5%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. The 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is characterized in that the structural formula is as follows:
wherein x is an integer of 6 to 10, and y is an integer of 24 to 40.
2. A method for synthesizing the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive as defined in claim 1, wherein the synthetic route of the method is as follows:
wherein x is an integer of 6 to 10, y is an integer of 24 to 40, and n is x + y.
3. The method of synthesizing the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive of claim 2 comprising the steps of: adding polyazide glycidyl ether and 1, 2-dichloroethane, adding propiolic alcohol nitrate under the stirring condition, stirring until the mixture is completely dissolved, heating for reaction, and carrying out reduced pressure distillation after the reaction to obtain the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive.
4. The synthesis method of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive as claimed in claim 3, wherein the molar ratio of the polyazidyl glycidyl ether to the propargyl alcohol nitrate is 1 (6-10).
5. The synthesis method of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive as defined in claim 3, wherein the temperature rise reaction comprises raising the temperature to 60-70 ℃ and reacting for 6-12 hours.
6. The method for synthesizing the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive according to claim 3, wherein the reduced pressure distillation includes concentration at a temperature of 40-70 ℃ and a vacuum degree of 5-20 mmHg.
7. Use of the 1,2, 3-triazole-4-methylene nitrate modified azide adhesives of claim 1 for high energy, low signature signal propellants; or the 1,2, 3-triazole-4-methylene nitrate modified azide adhesives prepared by the method for synthesizing the 1,2, 3-triazole-4-methylene nitrate modified azide adhesives as described in any one of claims 2 to 6 for use as high energy low signature propellants.
8. The use of claim 7, wherein the 1,2, 3-triazole-4-methylene nitrate modified azide adhesive is added to the high energy, low signature propellant at 8.3 wt.%.
9. The use of claim 7, wherein said high energy low signature signal propellant comprises an azide polyether propellant.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2285624A (en) * | 1988-02-01 | 1995-07-19 | Rockwell International Corp | Glycidyl azide polymer azide |
| CN105669493A (en) * | 2016-03-14 | 2016-06-15 | 西安近代化学研究所 | Azide nitric acid ester oligomer and preparing method thereof |
| CN110511372A (en) * | 2019-08-28 | 2019-11-29 | 西安近代化学研究所 | One kind terminal isocyanate group curing agent containing energy and its synthetic method |
| CN111574705A (en) * | 2020-05-21 | 2020-08-25 | 西安近代化学研究所 | Dual-curing nitrate polyether and synthetic method thereof |
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- 2022-06-21 CN CN202210707623.7A patent/CN115028829B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2285624A (en) * | 1988-02-01 | 1995-07-19 | Rockwell International Corp | Glycidyl azide polymer azide |
| CN105669493A (en) * | 2016-03-14 | 2016-06-15 | 西安近代化学研究所 | Azide nitric acid ester oligomer and preparing method thereof |
| CN110511372A (en) * | 2019-08-28 | 2019-11-29 | 西安近代化学研究所 | One kind terminal isocyanate group curing agent containing energy and its synthetic method |
| CN111574705A (en) * | 2020-05-21 | 2020-08-25 | 西安近代化学研究所 | Dual-curing nitrate polyether and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 梁磊;妮;耿孝恒;蔺少婷;: "聚叠氮缩水甘油醚GAP的合成及性能研究", 中北大学学报(自然科学版) * |
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