Claw-type polyene polyamine bonding agent, its preparation method and application in composite solid propellant
By introducing flexible polyether chains and multifunctional groups into polyene-polyamine bonding agents, the problem of insufficient activity of existing bonding agents is solved, and the mechanical and combustion properties of composite solid propellants are improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUBEI SANJIANG AEROSPACE JIANGHE CHEM TECH
- Filing Date
- 2023-12-08
- Publication Date
- 2026-07-03
AI Technical Summary
Existing polyene-polyamine bonding agents have a limited number of active functional groups, resulting in poor bonding effects. Their short molecular chains cannot form effective entanglement with the macromolecules in the bonding system, thus affecting the mechanical and combustion performance of composite solid propellants.
A claw-shaped polyene-polyamine bonding agent is used. This agent is prepared by introducing a flexible polyether chain into the molecular chain and introducing multiple active groups such as hydroxyl and cyano groups at both ends. The preparation method includes reacting polyether diglycidyl ether with polyethylene polyamine, followed by the addition of hydroxyethyl acrylate, acrylonitrile and modified glycidyl ether, to form a bonding agent with multifunctional groups.
It significantly improves the entanglement between the bonding agent and the adhesive, enhances the mechanical and combustion properties of the composite solid propellant, and strengthens the bonding effect.
Smart Images
Figure CN117659383B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis and composite solid propellant technology, specifically relating to a claw-shaped polyene-polyamine bonding agent, its preparation method, and its application in composite solid propellants. Background Technology
[0002] Common oxidizer fillers in composite solid propellants, such as ammonium nitrate (RDX, HMX) and ammonium perchlorate (AP), are non-reinforcing fillers. Their use easily leads to delamination, or "wetting," at the interface between the filler and the binder, adversely affecting the mechanical, combustion, and storage properties of the propellant. Therefore, bonding agents need to be added to the propellant to enhance the interaction between the binder and the filler and improve the "wetting" phenomenon. Polyene-polyamine compounds have long been reported as effective bonding agents for composite solid propellants, with representative compounds including triethylenetetramine, tetraethylenepentamine, TEPAN, and TEPANOL.
[0003] The inventors discovered the following problems with this type of bonding agent during application: First, the limited number of active functional groups results in an unsatisfactory bonding effect; second, the short molecular chain, small molecular weight, and numerous active secondary amine groups prevent it from forming entanglement with the macromolecules of the adhesive system and, to some extent, act as a crosslinking agent, which is detrimental to improving the elongation at break of the propellant. Therefore, there is an urgent need to develop new polyene-polyamine bonding agents to solve these problems. Summary of the Invention
[0004] This invention provides a claw-shaped polyene-polyamine bonding agent, its preparation method, and its application in composite solid propellants. The bonding agent has flexible chain groups and double claw multifunctional groups, which enable it to have a better bonding effect.
[0005] To achieve the above objectives, the present invention adopts the following technical solution: a claw-shaped polyene polyamine bonding agent, the structural formula of which is as follows:
[0006] ;
[0007] Where n = 0~1, R 1 For polyethylene glycol chains, polypropylene glycol chains, or chains, R 2 It is one of -OH, -OCH2CH=CH2, or -OCH2CH2CH2Si(OCH3)3.
[0008] Furthermore, R 1 The molecular weight is 400~1200.
[0009] This invention also relates to a method for preparing the claw-shaped polyene-polyamine bonding agent, comprising the following steps:
[0010] S1. Using polyether diglycidyl ether as raw material, add polyethylene polyamine, heat to 30~50℃ and react for 3~5 hours, then cool.
[0011] S2. Add hydroxyethyl acrylate to the material obtained in S1, heat to 50~90℃ and react for 1~3 hours, then cool.
[0012] S3. Add acrylonitrile to the material obtained in S2, heat to 50~90℃ and react for 1~3 hours, then cool.
[0013] S4. Add modified glycidyl ether to the material obtained in S3, heat to 30~50℃ and react for 3~5 hours; then distill to remove unreacted small molecule compounds to obtain claw-type polyene polyamine bonding agent.
[0014] Furthermore, the polyether diglycidyl ether in S1 includes, but is not limited to, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetrahydrofuran glycol diglycidyl ether, and the polyethylene polyamine is triethylenetetramine or tetraethylenepentamine.
[0015] Furthermore, the molar ratio of polyether diglycidyl ether to polyethylene polyamine is 1:2 to 2.1; the polyethylene polyamine is added dropwise at a rate of 0.5 mL / min to 1.0 mL / min.
[0016] Furthermore, the molar ratio of polyethylenepolyamine to hydroxyethyl acrylate is 1:1 to 1.05. Hydroxyethyl acrylate is added dropwise at a rate of 0.5 mL / min to 1.0 mL / min.
[0017] Furthermore, the molar ratio of polyethylenepolyamine to acrylonitrile is 1:1 to 1.05. Acrylonitrile is added dropwise at a rate of 0.5 mL / min to 1.0 mL / min.
[0018] Furthermore, the molar ratio of polyethylene polyamine to modified glycidyl ether is 1:1 to 1.05; the modified glycidyl ether includes, but is not limited to, glycidol, allyl glycidyl ether, and γ-glycidyl etheroxypropyltrimethoxysilane; the modified glycidyl ether is added dropwise at a rate of 0.5 mL / min to 1.0 mL / min.
[0019] Furthermore, the distillation in S4 is vacuum distillation at a temperature of 70~90℃.
[0020] This invention also relates to the application of the claw-shaped polyene-polyamine bonding agent in the preparation of composite solid propellants.
[0021] The present invention has the following beneficial effects:
[0022] This invention introduces a flexible polyether chain in the middle of the claw-shaped polyene polyamine bonding agent molecular chain, which can entangle with the polymer of the adhesive system; the claw-shaped polyene polyamine derivatives at both ends contain multiple hydroxyl groups, cyano groups and other active groups, which are beneficial to their participation in the curing of the adhesive system and adsorption of ammonium nitrate or perchloric acid amine, thereby significantly improving the bonding effect. Attached Figure Description
[0023] Figure 1 The image shows the infrared spectrum of the compound synthesized in Example 1. Detailed Implementation
[0024] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be regarded as limiting the scope of the present invention.
[0025] Example 1
[0026] (1) Weigh 0.5 mol of polyethylene glycol diglycidyl ether-600 and add it to a three-necked reaction flask. Slowly add 1.03 mol of tetraethylenepentamine through a dropping funnel. After the addition is complete, control the reaction temperature of the system to 40℃. After the reaction is carried out for 4 hours, cool to room temperature.
[0027] (2) Slowly add 1.04 mol of hydroxyethyl acrylate to the product of step 1. After the addition is complete, raise the temperature to 80°C and react for 3 hours, then cool to room temperature.
[0028] (3) Continue to add 1.04 mol of acrylonitrile to the product in step 2. After the addition is complete, continue to heat the system to 80°C and react for 3 hours. Then cool to room temperature.
[0029] (4) Slowly add 1.05 mol of allyl glycidyl ether dropwise to the product from step 3. After the addition is complete, continue heating the system to 40°C and react for 4 hours. Remove unreacted small molecule compounds by vacuum distillation at 80°C, and cool to room temperature to obtain the target light yellow viscous liquid product. Its infrared spectrum is shown in [reference needed]. Figure 1 3300cm -1 The absorption peaks are for alcohol hydroxyl groups, at 2925 and 2835 cm⁻¹. -1 The peak for the CH stretching vibration of the methylene group is 2226 cm⁻¹. -1 The absorption peak for cyano is 1450 cm⁻¹. -1 This is the CN bond stretching vibration peak, 1101 cm⁻¹. -1 The peak represents the stretching vibration of the CO bond, and the infrared spectrum indicates that the synthesized compound is the target compound.
[0030] Example 2
[0031] (1) Weigh 0.5 mol of polypropylene glycol diglycidyl ether-400 and add it to a three-necked reaction flask. Slowly add 1.02 mol of triethylenetetramine through a dropping funnel. After the addition is complete, control the reaction temperature of the system to 40℃. After the reaction is carried out for 5 hours, cool to room temperature.
[0032] (2) Slowly add 1.02 mol of hydroxyethyl acrylate to the product of step 1. After the addition is complete, raise the temperature to 70°C and react for 3 hours, then cool to room temperature.
[0033] (3) Continue to add 1.02 mol of acrylonitrile to the product in step 2. After the addition is complete, continue to heat the system to 70°C and react for 3 hours. Then cool to room temperature.
[0034] (4) Slowly add 1.03 mol of glycidol to the product of step 3. After the addition is complete, continue to heat the system to 50°C. After reacting for 4 hours, remove the unreacted small molecule compounds by vacuum distillation at 80°C. Cool to room temperature to obtain the target yellow viscous liquid product.
[0035] Example 3
[0036] (1) Weigh 0.5 mol of polytetrahydrofurandiol diglycidyl ether-1000, add it to a three-necked reaction flask and slowly add 1.02 mol of tetraethylenepentamine through a dropping funnel. After the addition is complete, control the reaction temperature of the system to 30℃. After the reaction is carried out for 4 hours, cool to room temperature.
[0037] (2) Slowly add 1.04 mol of hydroxyethyl acrylate to the product of step 1. After the addition is complete, raise the temperature to 90°C and react for 3 hours, then cool to room temperature.
[0038] (3) Continue to add 1.04 mol of acrylonitrile to the product in step 2. After the addition is complete, continue to heat the system to 90°C and react for 3 hours. Then cool to room temperature.
[0039] (4) Slowly add 1.03 mol of γ-glycidoxypropyltrimethoxysilane to the product of step 3. After the addition is complete, continue to heat the system to 40°C and react for 4 hours. Remove unreacted small molecule compounds by vacuum distillation at 80°C. Cool to room temperature to obtain the target light yellow viscous liquid product.
[0040] Comparative Example 1: Triethylenetetramine was used as a bonding agent.
[0041] The products obtained in the above examples and comparative examples were used as bonding agents in the preparation of composite solid propellants. The specific formulation of the composite solid propellant is 56.5 parts AP, 18 parts Al powder, 13 parts RDX, and 12.5 parts hydroxyl-butyl rubber and other additives (solid content 87.5%).
[0042] The mechanical properties of the propellant were tested according to "GJB 770B—2005 Test Methods for Gunpowder". The test temperature was 23℃ and the tensile speed was 100mm / min. The specific properties are shown in Table 1 below.
[0043] Table 1
[0044]
[0045] As can be seen from Table 1 above, the butylated hydroxyl tetrapropellant prepared with the claw-type polyene polyamine bonding agent of the present invention has good mechanical properties.
[0046] The above embodiments describe preferred embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other way. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention. Therefore, the protection scope of this patent should be determined by the appended claims.
Claims
1. A claw-shaped polyene-polyamine bonding agent, characterized in that, Its structural formula is as follows: ； Where n=1 or 2, R 1 R is one of polyethylene glycol chain, polypropylene glycol chain, or polytetrahydrofuran chain. 2 It is one of -OH, -OCH2CH=CH2, or -OCH2CH2CH2Si(OCH3)3; Its preparation includes the following steps: S1. Using polyether diglycidyl ether as raw material, add polyethylene polyamine, heat to 30~50℃ and react for 3~5 hours, then cool; the polyether diglycidyl ether is polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether or polytetrahydrofuran glycol diglycidyl ether; the polyethylene polyamine is triethylenetetramine or tetraethylenepentamine; S2. Add hydroxyethyl acrylate to the material obtained in S1, heat to 50~90℃ and react for 1~3 hours, then cool. S3. Add acrylonitrile to the material obtained in S2, heat to 50~90℃ and react for 1~3 hours, then cool. S4. Add modified glycidyl ether to the material obtained in S3, and heat to 30~50℃ and react for 3~5 hours; the modified glycidyl ether is glycidol, allyl glycidyl ether, or γ-glycidyl etheroxypropyltrimethoxysilane; then distill to remove unreacted small molecule compounds to obtain claw-type polyene polyamine bonding agent.
2. The claw-shaped polyene-polyamine bonding agent according to claim 1, characterized in that: R 1 The molecular weight is 400~1200.
3. The claw-shaped polyene-polyamine bonding agent according to claim 1, characterized in that: The molar ratio of polyether diglycidyl ether to polyethylene polyamine is 1:2~2.
1.
4. The claw-shaped polyene-polyamine bonding agent according to claim 1, characterized in that: The molar ratio of polyethylene polyamine to hydroxyethyl acrylate is 1:1 to 1.
05.
5. The claw-shaped polyene-polyamine bonding agent according to claim 1, characterized in that: The molar ratio of polyethylene polyamine to acrylonitrile is 1:1 to 1.
05.
6. The claw-shaped polyene-polyamine bonding agent according to claim 1, characterized in that: The molar ratio of polyethylene polyamine to modified glycidyl ether is 1:1 to 1.
05.
7. The claw-shaped polyene-polyamine bonding agent according to any one of claims 1-6, characterized in that: Distillation in S4 is vacuum distillation at a temperature of 70-90℃.