Polyether amine type hydantoin bonding agent as well as preparation method and application thereof
By developing polyetheramine-type hein bonding agent and introducing hein functional groups using amineene addition reaction, the problem of weakening of bonding cooperation of hein bonding agents at high temperatures is solved, and the high-temperature mechanical properties of solid propellants are significantly improved, and the stable combustion and efficient energy output requirements of high-performance engines are met.
Patent Information
- Application Number
- CN202510216544.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-26
- Publication Date
- 2025-05-30
AI Technical Summary
The bonding effect of existing Hein-like bonding agents is weakened under high temperature environments, resulting in a significant decrease in the mechanical properties of solid propellants, which cannot meet the requirements of high-performance engines for stable combustion and efficient energy output of propellants.
A polyetheramine-type hein bonding agent was developed, and the hein functional groups were introduced through amineene addition reaction, so that it could chemically adsorb AP, and was suitable for large-scale industrial production through a simple preparation method.
It significantly improves the high-temperature mechanical properties of solid propellants, improves the interface performance of propellants, and meets the requirements of high-performance engines for stable combustion and efficient energy output of propellants.
Smart Images
Figure CN120059162A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of solid propellants, and in particular to a polyetheramine type hydantoin bonding agent, a preparation method and application thereof. Background Art
[0002] As the power source of missile weapons, solid propellant plays an important role in the development of missile weapons, and its performance level determines the performance level of solid engines. The diversification of the application environment and functions of tactical missile weapons has put forward the requirements of high energy, overload resistance and wide temperature range adaptability for solid rocket engines, which requires the propellant to have good mechanical properties in high temperature environments.
[0003] Hydantoin-type bonding agents are a class of compounds containing a five-membered nitrogen heterocyclic structure of hydantoin in their molecular structure. By selecting the group connected to the N atom in the nitrogen heterocyclic ring, the bonding agent can have different physical and chemical properties, thereby making this type of bonding agent have strong structural designability. However, despite the significant structural advantages of hydantoin-type bonding agents, they still face some challenges in practical applications. In particular, when this type of bonding agent is physically adsorbed onto the surface of solid particles such as AP (oxidants such as ammonium perchlorate) and nitramine explosives, although it can provide effective bonding at room temperature and enhance the mechanical strength and combustion performance of the propellant, this physical adsorption effect is often weakened or even ineffective in high temperature environments. This leads to a significant decrease in the mechanical properties of the propellant at high temperatures, which cannot meet the strict requirements of high-performance engines for stable combustion and efficient energy output of the propellant.
[0004] Therefore, the development of new hydantoin-based bonding agents that not only maintain the advantage of their structural designability but also overcome the defect of weakened bonding at high temperatures has become a key issue that needs to be urgently addressed in the current field of propellant technology. Summary of the invention
[0005] In view of the above problems, the first object of the present invention is to provide a polyetheramine type hydantoin bonding agent, which has both secondary amine functional groups and hydantoin functional groups, has bonding effects on AP and nitramine explosives, and the secondary amine group can also form chemical adsorption with AP.
[0006] The second object of the present invention is to provide a method for preparing a polyetheramine type hydantoin bonding agent. The polyetheramine type hydantoin bonding agent is prepared by an amine-ene addition reaction.
[0007] The third object of the present invention is to provide an application of a polyetheramine type hydantoin bonding agent, which can improve the interface properties of solid propellants and significantly improve the high temperature mechanical properties of propellants.
[0008] To achieve the first object, the first technical solution of the present invention is: a polyetheramine type hydantoin bonding agent, the basic structural unit of which is:
[0009]
[0010] Among them, R 1 and R 2 and R 3 and R 4 include at least one ether bond and one amino group, and also include hydrogen atoms, aliphatic linear alkanes or branched alkanes containing 1 to 20 carbon atoms;
[0011] W, X, Y, and Z are hydroxyl groups, hydantoin functional groups, hydrogen, or methyl groups, and at least one hydroxyl group and one hydantoin functional group are included among W, X, Y, and Z;
[0012] The degree of polymerization is 800 to 10,000.
[0013] To achieve the second object, the second technical solution of the present invention is: a preparation method of a polyetheramine-based hydantoin bonding agent, including: preparing a first product and a second product;
[0014] The preparation method of the first product is: under the condition of the first temperature, subjecting polyetheramine and glycidol with a molar ratio of 1:1 to 2 to a ring-opening reaction to obtain the first product;
[0015] The preparation method of the second product is: under the condition of ethanol reflux, reacting a hydantoin compound, a strong base, and an olefin halide with a molar ratio of 1:1 to 1.5:1 to 1.5 to obtain the second product;
[0016] Under the condition of the second temperature, reacting the first product and the second product with a molar ratio of 1:1 to 2 to obtain the polyetheramine-based hydantoin bonding agent.
[0017] Preferably, the polyetheramine is one or more of bifunctional, trifunctional, or tetrafunctional terminal amine-based polyethers, and the molecular weight is 400 to 9500.
[0018] Preferably, the hydantoin compound is one or more of hydantoin, 5,5-dimethylhydantoin, 5-ethylhydantoin, or 5-isopropylhydantoin.
[0019] Preferably, the strong base is one or more of sodium hydroxide, potassium hydroxide, sodium tert-butoxide, or potassium tert-butoxide.
[0020] Preferably, the olefin halide is a monosubstituted halogen element of ethylene to decene, and the halogen element includes one of chlorine, bromine, and iodine.
[0021] Preferably, the first temperature is 30°C to 45°C, and the second temperature is 40°C to 70°C.
[0022] Preferably, the concentration of the ethanol is 50% to 90%.
[0023] To achieve the third objective, the third technical solution of the present invention is: an application of a polyetheramine-based hydantoin bonding agent, which is applied in HTPB propellants, GAP propellants, PET propellants, and PEG propellants.
[0024] Preferably, the dosage of the polyetheramine-based hydantoin bonding agent is 0.05% - 0.50% of the total mass of the solid propellant.
[0025] Advantages of the above technical solution:
[0026] Compared with the existing hydantoin bonding agents, the polyetheramine-based hydantoin bonding agent provided by the present invention introduces hydantoin functional groups into the polyetheramine molecular chain through a simple amine-alkene addition reaction, enabling the new bonding agent to form a chemical adsorption effect on AP. The preparation method of the polyetheramine-based hydantoin bonding agent provided by the present invention is simple, with fewer by-products, suitable for large-scale industrial production, and has broad application prospects in solid propellants.
[0027] The polyetheramine-based hydantoin bonding agent provided by the present invention can be simultaneously applied to HTPB and NEPE systems, effectively improving the interfacial properties between nitramine explosives and polyurethane binder matrices, and enhancing the high-temperature mechanical properties of the propellants. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] To more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.
[0029] Figure 1 It is the infrared spectrum diagram of the polyetheramine-based hydantoin bonding agent provided by an embodiment 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0030] The following will further describe the embodiments of the present application in detail. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than an exhaustive list of all embodiments. It should be noted that, without conflict, the embodiments and features in the embodiments of the present application can be combined with each other.
[0031] The terms "first", "second", etc. (if any) in the specification and claims are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged under appropriate circumstances so that the embodiments described herein can be implemented in an order other than that illustrated or described herein. In addition, the terms "comprising" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that comprises a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products, or devices.
[0032] It should be understood that the term "and / or" used herein is merely a relationship describing associated objects, indicating that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " herein generally represents an "or" relationship between the associated objects before and after.
[0033] The polyetheramine-based hydantoin bonding agent provided by the present invention has a preparation method including: preparing a first product and a second product;
[0034] The preparation method of the first product is: under the condition of 30°C to 45°C, subject polyetheramine and glycidol with a molar ratio of 1:1 to 2 to a ring-opening reaction to obtain the first product;
[0035] The preparation method of the second product is: under the condition of refluxing with ethanol at a concentration of 50% to 90%, react a hydantoin compound, a strong base, and an olefin halide with a molar ratio of 1:1 to 1.5:1 to 1.5 to obtain the second product;
[0036] Under the condition of 40°C to 70°C, react the first product and the second product with a molar ratio of 1:1 to 2 to obtain the polyetheramine-based hydantoin bonding agent.
[0037] The polyetheramine is one or more of bifunctional, trifunctional, or tetrafunctional terminal amine group polyethers, and the molecular weight is 400 to 9500.
[0038] The hydantoin compound is one or more of hydantoin, 5,5-dimethylhydantoin, 5-ethylhydantoin, or 5-isopropylhydantoin.
[0039] The strong base is one or more of sodium hydroxide, potassium hydroxide, sodium tert-butoxide, or potassium tert-butoxide.
[0040] The olefin halide is a monosubstituted product of halogen elements of ethylene to decene, and the halogen elements include chlorine, bromine, and iodine.
[0041] Example 1
[0042] This example provides a polyetheramine-based hydantoin bonding agent, denoted as BAG-1, and the preparation method is as follows:
[0043] First, at a temperature of 30 °C to 45 °C, 1 mol of trifunctional polyetheramine with a molecular weight of about 2000 and 1 mol of epoxyethanol are added to a three-necked flask equipped with a thermometer and a condenser, and stirred and mixed for 30 min to 45 min to complete the ring-opening reaction to obtain 1 mol of hydroxyl-terminated polyetheramine; then, 2 mol of 5,5-dimethylhydantoin, 2.4 mol of sodium hydroxide, and 2.4 mol of allyl chloride are mixed evenly, and stirred and reacted for 3 h under ethanol reflux conditions to obtain 2 mol of allyl 5,5-dimethylhydantoin; 1 mol of hydroxyl-terminated polyetheramine and 2 mol of allyl 5,5-dimethylhydantoin are reacted at 50 °C for 4 h to obtain BAG-1 (where x + y + z = 5.3). The infrared spectrum is shown in Figure 1 , and the structural formula is as follows.
[0044]
[0045] Example 2
[0046] This example provides a polyetheramine-based hydantoin bonding agent, denoted as BAG-2. The difference in the preparation method from Example 1 is only that the molar ratio of the polyetheramine to glycidol used is 1:2, and the molar ratio of the obtained hydroxyl-terminated polyether to allyl 5,5-dimethylhydantoin is 1:1. The structural formula is as follows.
[0047]
[0048] Comparative Example 1
[0049] 1 mol of 5,5-dimethylhydantoin, 1.2 mol of sodium hydroxide, and 1.2 mol of allyl chloride are mixed evenly, stirred and reacted for 3 h under ethanol reflux conditions, cooled and allowed to stand, filtered, and the filtrate is rotary evaporated to obtain BAG-3 (allyl 5,5-dimethylhydantoin).
[0050] Application of polyetheramine-based hydantoin bonding agent in solid propellants
[0051] The polyetheramine-based hydantoin bonding agent provided by the present invention is applied to different types of solid propellants, and performance evaluation is carried out. The specific applications and performances are as follows.
[0052] (1) Application in HTPB propellant
[0053] In the HTPB propellant formulation shown in Table 1, the bonding agents provided in Example 1 and Comparative Example 1 are added to obtain a solid propellant. Among them, the bonding agent accounts for 0.30% of the total mass of the solid propellant.
[0054] Table 1 HTPB Propellant Formulation
[0055]
[0056] The test results of the mechanical properties of the solid propellant billets are shown in Table 2, where the blank is the HTPB propellant formulation shown in Table 1.
[0057] Table 2 Mechanical Property Parameters of Solid Propellants with Different Bonding Agents
[0058]
[0059] The above results show that when the polyetheramine-based hydantoin bonding agent provided by the present invention is applied in HTPB propellants, its use effect is better than that of small-molecule hydantoin bonding agents. Among them, the HTPB propellant corresponding to BAG-1 with more hydantoin groups has a greater high-temperature elongation, and the HTPB propellant corresponding to BAG-2 with more hydroxyl groups has a higher high-temperature strength.
[0060] (2) Application in GAP Propellants
[0061] In the GAP propellant formulation shown in Table 3, the bonding agents provided in Example 1 and Comparative Example 1 were added to obtain solid propellants. Among them, the bonding agent accounts for 0.30% of the total mass of the solid propellant.
[0062] Table 3 GAP Propellant Formulation
[0063]
[0064] The test results of the mechanical properties of the solid propellant billets are shown in Table 4, where the blank is the GAP propellant formulation shown in Table 3.
[0065] Table 4 Mechanical Property Parameters of Solid Propellants with Different Bonding Agents
[0066]
[0067] The above results show that in GAP propellants, the use effect of the polyetheramine-based hydantoin bonding agent provided by the present invention is better than that of small-molecule hydantoin bonding agents. Among them, the GAP propellant corresponding to BAG-1 with more hydantoin groups has a greater high-temperature elongation, and the GAP propellant corresponding to BAG-2 with more hydroxyl groups has a higher high-temperature strength.
[0068] (3) Application in PET Propellants
[0069] In the PET propellant formulation shown in Table 5, the bonding agents provided in Example 1 and Comparative Example 1 were added to obtain solid propellants. Among them, the bonding agent accounts for 0.30% of the total mass of the solid propellant.
[0070] Table 5 PET Propellant Formulation
[0071]
[0072] The test results of the mechanical properties of the solid propellant billets are shown in Table 6, where the blank is the PET propellant formulation shown in Table 5.
[0073] Table 6 Mechanical property parameters of solid propellants with different bonding agents
[0074]
[0075] The above results show that in the PET propellant, the use effect of the polyetheramine-based hydantoin bonding agent provided by the present invention is better than that of the small molecule hydantoin bonding agent. Among them, the PET propellant corresponding to BAG-1 with more hydantoin groups has a larger high-temperature elongation rate, and the PET propellant corresponding to BAG-2 with more hydroxyl groups has a higher high-temperature strength.
[0076] (IV) Application in PEG propellants
[0077] In the PEG propellant formulation shown in Table 7, the bonding agents provided in Example 1 and Comparative Example 1 were added to obtain a solid propellant. Among them, the bonding agent accounts for 0.30% of the total mass of the solid propellant.
[0078] Table 7 PEG propellant formulation
[0079]
[0080] The test results of the mechanical properties of the solid propellant billets are shown in Table 8, where the blank is the PEG propellant formulation shown in Table 7.
[0081] Table 8 Mechanical property parameters of new solid propellants with different bonding agent contents
[0082]
[0083] The above results show that when the polyetheramine-based hydantoin bonding agent provided by the present invention is applied in the PEG propellant, its use effect is better than that of the small molecule hydantoin bonding agent. Among them, the PEG propellant corresponding to BAG-1 with more hydantoin groups has a larger high-temperature elongation rate, and the PEG propellant corresponding to BAG-2 with more hydroxyl groups has a higher high-temperature strength.
[0084] In summary, the polyetheramine-based hydantoin bonding agent provided by the present invention is applied in different types of solid propellants. From the test results of the mechanical property parameters of different types of solid propellants, it can be seen that the propellant corresponding to BAG-1 with more hydantoin groups has a larger high-temperature elongation rate, and the propellant corresponding to BAG-2 with more hydroxyl groups has a higher high-temperature strength. It can be seen that the use effect of the polyetheramine-based hydantoin bonding agent provided by the present invention is better than that of the small molecule hydantoin bonding agent, effectively improving the high-temperature mechanical properties of the propellant and can be widely used in solid propellants.
[0085] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.
Claims
1. A polyetheramine type hydantoin bonding agent, characterized in that: The basic structural units are: Wherein, R1, R2, R3, and R4 include at least one ether bond and one amine group, and also include hydrogen atoms, aliphatic linear alkanes or branched alkanes containing 1 to 20 carbon atoms, and; W, X, Y, and Z are hydroxyl, hydantoin functional group, hydrogen or methyl, and W, X, Y, and Z include at least one hydroxyl and one hydantoin functional group; The degree of polymerization is 800-10000.
2. A method for preparing the polyetheramine type hydantoin bonding agent as claimed in claim 1, characterized in that: include: preparing a first product and a second product; The preparation method of the first product is: under a first temperature condition, a polyetheramine and glycidol in a molar ratio of 1:1-2 are subjected to a ring-opening reaction to obtain the first product; The preparation method of the second product is: under ethanol reflux conditions, reacting a hydantoin compound, a strong base and an olefin halide in a molar ratio of 1:1 to 1.5:1 to 1.5 to obtain the second product; Under the second temperature condition, the first product and the second product in a molar ratio of 1:1-2 are reacted to prepare a polyetheramine type hydantoin bonding agent.
3. The method for preparing the polyetheramine type hydantoin bonding agent according to claim 2, characterized in that: The polyetheramine is one or more of difunctional, trifunctional or tetrafunctional terminal amine polyethers, and has a molecular weight of 400-9500.
4. The method for preparing the polyetheramine type hydantoin bonding agent according to claim 2, characterized in that: The hydantoin compound is one or more of hydantoin, 5,5-dimethylhydantoin, 5-ethylhydantoin or 5-isopropylhydantoin.
5. The method for preparing the polyetheramine type hydantoin bonding agent according to claim 2, characterized in that: The strong base is one or more of sodium hydroxide, potassium hydroxide, sodium tert-butoxide or potassium tert-butoxide.
6. The method for preparing the polyetheramine type hydantoin bonding agent according to claim 2, characterized in that: The olefin halide is a halogen element monosubstituted product of ethylene to decene, and the halogen element includes one of chlorine, bromine and iodine.
7. The method for preparing the polyetheramine type hydantoin bonding agent according to claim 2, characterized in that: The first temperature is 30°C to 45°C, and the second temperature is 40°C to 70°C.
8. The method for preparing the polyetheramine type hydantoin bonding agent according to claim 2, characterized in that: The concentration of the ethanol is 50% to 90%.
9. An application of the polyetheramine type hydantoin bonding agent as claimed in claim 1, characterized in that: Used in HTPB propellants, GAP propellants, PET propellants and PEG propellants.
10. The use of the polyetheramine type hydantoin bonding agent according to claim 9, characterized in that: The usage of the polyetheramine type hydantoin bonding agent is 0.05% to 0.50% of the total mass of the solid propellant.