Novel alcohol amine bonding agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of polymer synthesis, and particularly discloses a novel alcohol amine bonding agent and a preparation method and application thereof.The preparation method comprises the steps that an alkanolamine compound and a reaction solvent are weighed and placed in a reaction device, weighed perchloric acid is dropwise added into the reaction device, after the perchloric acid is dropwise added, heating and reacting are conducted, and a reaction product is obtained; and carrying out reduced pressure distillation to obtain the novel alcohol amine bonding agent. Molecules of the novel alcohol amine bonding agent only contain tertiary amine groups and do not contain primary amine and secondary amine, the bonding agent is weak in alkalinity, meanwhile, the reaction activity of the tertiary amine groups and AP is low, and the situation that curing of a propellant is affected due to the fact that the ammonia gas release rate is too high is avoided.

Description

Technical Field

[0001] The invention relates to the technical field of solid propellants, and in particular to a novel alcoholamine bonding agent and a preparation method and application thereof. Background Art

[0002] During the mixing and curing process of solid propellants, the network structure of the binder matrix (continuous phase) "wets" the solid filler particles (dispersed phase) through physical and chemical effects, forming additional cross-linking points to enhance the mechanical properties of the composite solid propellant. However, this interaction force is generally small. When the composite solid propellant is subjected to an external load, tiny holes or cracks will appear between the solid filler and the binder matrix, eventually leading to the complete separation of the binder and the solid particles, that is, "dewetting". The occurrence of dewetting will reduce the additional cross-linking points and cause the volume expansion and mechanical properties of the composite solid propellant. Therefore, studying the interfacial interaction between the binder matrix and the filler particles is of great significance for regulating and improving the mechanical properties of composite solid propellants.

[0003] The application of bonding agents in solid propellants began with Oberth's research findings that bonding agents can prevent "dewetting" of the propellant interface and are an important method to improve the mechanical properties of solid propellants. With the development of higher energy, high performance, low fragility, and green propellants, various new materials have been introduced into propellants, bringing new "dewetting" problems at the interface of propellant fillers and matrices. The existing bonding agents can no longer meet the mechanical performance requirements of composite solid propellants, so new and efficient bonding agents must be developed to meet the high index requirements of propellant mechanical properties.

[0004] Design corresponding bonding agent systems for different adhesive / solid filler formula systems to improve the performance of the interface between the continuous phase and the dispersed phase of the composite solid propellant. In terms of improving the network structure, alkanolamines and their derivatives are widely used in composite solid propellants, and they play a significant role in improving the interface performance and network structure of composite solid propellants; however, the active hydrogen functionality in the current alcohol amine bonding agent molecules is relatively high, and can form hydrogen bonds with the filler and the adhesive at the same time, which will increase the viscosity of the propellant slurry to a certain extent; and the bonding agent itself is highly alkaline, which has a certain catalytic effect on the matrix curing reaction, which will shorten the applicability period of the slurry. The combined effect of the two makes the process performance of the propellant containing the new bonding agent average. Summary of the invention

[0005] In view of the above problems, the first object of the present invention is to provide a new type of alcoholamine bonding agent, which has only tertiary amine groups in its molecules, no primary amines and secondary amines, and the bonding agent itself has weak alkalinity. At the same time, the tertiary amine groups have low reaction activity with AP, and the ammonia release rate is not too fast to affect the curing of the propellant.

[0006] The second object of the present invention is to provide a method for preparing the above-mentioned novel alcoholamine bonding agent.

[0007] The third object of the present invention is to provide the application of the above-mentioned novel alcohol amine bonding agent.

[0008] The first technical solution adopted by the present invention is: a new type of alcohol amine bonding agent, the structural formula of the new type of alcohol amine bonding agent is:

[0009]

[0010] The second technical solution adopted by the present invention is: a method for preparing the novel alcoholamine bonding agent as described in the first technical solution, comprising the following steps:

[0011] The alkanolamine compound and the reaction solvent are weighed in a reaction device, and the weighed perchloric acid is added dropwise into the reaction device. After the perchloric acid is added dropwise, the temperature is increased and reacted, and a novel alcoholamine bonding agent is obtained by vacuum distillation.

[0012] Preferably, the alkanolamine compound includes one or more of diethanolamine, triethanolamine, and N-(2-cyanoethyl)diethanolamine.

[0013] Preferably, the molar ratio of the perchloric acid to the alkanolamine compound is 0.25-0.66:1.

[0014] Preferably, the reaction solvent is one or more of deionized water, ethanol and acetone.

[0015] Preferably, the amount of the reaction solvent is 80-150 mL.

[0016] Preferably, the preparation method of the novel alcoholamine bonding agent comprises:

[0017] Weigh the alkanolamine compound and the reaction solvent in a reaction bottle with a water removal device, add the weighed perchloric acid into the dropping funnel, open the dropping funnel without water bath heating, and drop the perchloric acid into the reaction bottle. After the addition of the perchloric acid is completed, raise the water bath temperature to 75-80°C, react for 6-8h, and distill under reduced pressure for 7 hours to obtain a new alcoholamine bonding agent.

[0018] The third technical solution adopted by the present invention is: an application of the novel alcohol amine bonding agent as described in the first technical solution in the preparation of solid propellant.

[0019] Preferably, the use of the novel alcoholamine bonding agent in the preparation of a solid propellant comprises: adding the novel alcoholamine bonding agent to a solid propellant premix slurry and mixing them uniformly to obtain a solid propellant containing the novel alcoholamine bonding agent;

[0020] The solid propellant containing a novel alcoholamine bonding agent includes a NEPE system propellant, a HTPB system propellant, a PET propellant, a PEG propellant or a GAP propellant containing a novel alcoholamine bonding agent.

[0021] Preferably, the mass ratio of the novel alcohol amine bonding agent to the solid propellant is 0.2% to 2.0%.

[0022] Beneficial effects of the above technical solution:

[0023] (1) The active hydrogen functionality in the current alcohol amine bonding agent molecules is relatively high, and can form hydrogen bonds with fillers and adhesives at the same time, which will increase the viscosity of the propellant slurry to a certain extent; and the bonding agent itself has strong alkalinity, which has a certain catalytic effect on the matrix curing reaction and shortens the applicable period of the slurry. The combined effect of the two makes the process performance of the propellant containing the new bonding agent average. The new alcohol amine bonding agent molecules disclosed in the present invention only have tertiary amine groups, no primary amines and secondary amines, the bonding agent itself has weak alkalinity, and the tertiary amine group has low reactivity with AP, so the ammonia release rate is not too fast to affect the curing of the propellant.

[0024] (2) Aiming at the characteristics of the composite solid propellant formula having a large variety of solid fillers and a high content, the present invention designs an alkanolamine bonding agent for the AP / adhesive interface to prevent the composite solid propellant from "dehumidifying", and uses alkanolamine and its derivatives to improve the network structure of the propellant. The novel alkanolamine bonding agent disclosed in the present invention is a triethanolamine derivative, which can significantly improve the interfacial bonding performance between the ammonium perchlorate oxidizer (AP) and the solid propellant adhesive matrix, and significantly improve the mechanical performance level of the composite solid propellant; the novel alkanolamine bonding agent has a wide application prospect in high-energy propellants, and can also be applied to other composite solid propellants.

[0025] (3) The novel alcohol amine bonding agent disclosed in the present invention is a compound used to strengthen the interface between AP particles and adhesive matrix. The nitrogen atom in its structure has an unshared electron pair, which can form a coordination bond with the hydrogen atom in AP to form strong chemical and physical adsorption. The hydroxyl group in the alcohol amine can react with the isocyanate curing agent to make it enter the elastomer network structure, thereby forming a strong interface layer between AP and the adhesive matrix.

[0026] (4) Through a large number of experiments, the optimal mass percentage of the new alcohol amine bonding agent in the propellant is given as 0.2% to 2%. Under this ratio, the new alcohol amine bonding agent and propellant obtained have the best quality and performance.

[0027] (5) The novel alcohol amine bonding agent of the present invention can adjust the network structure, thereby improving the mechanical properties of the composite solid propellant and meeting the requirements for the mechanical properties of the composite solid propellant. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 A schematic flow chart of a method for preparing a novel alcoholamine bonding agent provided in one embodiment of the present invention. DETAILED DESCRIPTION

[0029] The present invention is further described below through specific embodiments. It should be pointed out that, for ordinary technicians in this field, several modifications and improvements can be made without departing from the principle of the present invention, and these should also be regarded as belonging to the protection scope of the present invention.

[0030] The contents not described in detail in the specification of the present invention belong to the common knowledge of the professionals in this field.

[0031] The invention discloses a novel alcoholamine bonding agent, which is an alcoholamine bonding agent and has the structural formula:

[0032]

[0033] The present invention discloses a method for preparing a novel alcoholamine bonding agent, comprising:

[0034] Weigh the alkanolamine compound and the reaction solvent in a reaction bottle with a water removal device, add the weighed perchloric acid (HClO4) into the dropping funnel, open the dropping funnel without water bath heating, and slowly drop HClO4 into the reaction bottle. After the addition of HClO4 is completed, raise the water bath temperature to 75-80°C, preferably 75°C, react for 6-8h, and distill under reduced pressure for 7 hours to distill off the solvent and unreacted raw materials to obtain a brown-yellow viscous liquid product, i.e., a novel alcoholamine bonding agent.

[0035] Wherein, the molar ratio of the perchloric acid to the alkanolamine compound is 0.25-0.66:1, and the amount of the reaction solvent is 80-150 mL;

[0036] The alkanolamine compound includes one or more of diethanolamine, triethanolamine, and N-(2-cyanoethyl)diethanolamine.

[0037] The reaction solvent is one or more of deionized water, ethanol and acetone.

[0038] The present invention also discloses an application of a novel alcoholamine bonding agent in preparing a solid propellant, comprising adding the novel alcoholamine bonding agent into a solid propellant premix slurry and mixing the mixture evenly to obtain the solid propellant; for example, a NEPE system propellant (i.e. a propellant containing a polyether adhesive), a HTPB system propellant (i.e. a hydroxybutyl propellant), a PET propellant, a PEG propellant or a GAP propellant is prepared based on the novel alcoholamine bonding agent.

[0039] Among them, the propellant of the NEPE system includes, for example, a new alcohol amine bonding agent, an adhesive, an oxidant, a fuel, a curing agent and other functional components; wherein the mass ratio of the new alcohol amine bonding agent to the propellant is 0.2% to 2.0%; the adhesive is, for example, polyazide glycidyl ether (GAP); the oxidant mainly includes, for example, ammonium perchlorate (AP) and octogen (HMX); the fuel is, for example, aluminum powder (Al); the curing agent is, for example, isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 1,6-hexamethylene diisocyanate (HDI), etc.; other functional components are, for example, a burning rate catalyst, a curing catalyst, etc.

[0040] Example 1

[0041] Perchloric acid, 100 ml of deionized water and triethanolamine were added to a reaction bottle, and the molar ratio of perchloric acid to triethanolamine was 0.25:1; the reaction temperature was controlled between 75-80°C, and the vacuum distillation device was replaced to vacuum distill off the solvent and unreacted raw materials to obtain a brown-yellow viscous liquid product, i.e., a new alcoholamine bonding agent BAG-25A; infrared analysis identified that the new alcoholamine bonding agent BAG-25A contained amino, hydroxyl and perchlorate groups, of which 3355 cm -1 is the absorption peak of hydroxyl group, 1636cm -1 It is the absorption peak of amine group, 1094cm -1 It is the absorption peak of the perchlorate group.

[0042] Example 2

[0043] Perchloric acid, 100 ml of deionized water and triethanolamine are added into a reaction bottle, wherein the molar ratio of perchloric acid to triethanolamine is 0.5:1; the reaction temperature is controlled between 75-80°C, a vacuum distillation device is replaced, and the solvent and unreacted raw materials are distilled off under reduced pressure to obtain a brown-yellow viscous liquid product, i.e., a new alcoholamine bonding agent BAG-25B; infrared analysis shows that the new alcoholamine bonding agent BAG-25B contains an amino group, a hydroxyl group and a perchlorate group.

[0044] Example 3

[0045] Perchloric acid, 100 ml of deionized water and triethanolamine are added to a reaction bottle, and the molar ratio of perchloric acid to triethanolamine is 0.66:1; the reaction temperature is controlled between 75-80°C, and the vacuum distillation device is replaced to distill off the solvent and unreacted raw materials under reduced pressure to obtain a brown-yellow viscous liquid product, i.e., a new alcoholamine bonding agent BAG-25C; infrared analysis shows that the new alcoholamine bonding agent BAG-25C contains amino, hydroxyl and perchlorate groups.

[0046] Example 4

[0047] Perchloric acid, 100 ml of ethanol and diethanolamine were added into a reaction bottle, and the molar ratio of perchloric acid to diethanolamine was 0.5:1; the reaction temperature was controlled at 75°C, and the vacuum distillation device was replaced to distill off the solvent and unreacted raw materials under reduced pressure to obtain a brown-yellow viscous liquid product, i.e., a new alcoholamine bonding agent BAG-25D; infrared analysis showed that the new alcoholamine bonding agent BAG-25D contained amino, hydroxyl and perchlorate groups.

[0048] Example 5

[0049] Perchloric acid, 100 ml of acetone, triethanolamine and N-(2-cyanoethyl)diethanolamine are added into a reaction bottle, wherein the molar ratio of perchloric acid to the total amount of triethanolamine and N-(2-cyanoethyl)diethanolamine is 0.5:1; the reaction temperature is controlled at 80° C., a vacuum distillation device is replaced, and the solvent and unreacted raw materials are distilled off under reduced pressure to obtain a brown-yellow viscous liquid product, i.e., a novel alcoholamine bonding agent BAG-25E; infrared analysis shows that the novel alcoholamine bonding agent BAG-25E contains an amino group, a hydroxyl group and a perchlorate group.

[0050] Example 6

[0051] The application of three different new alcohol amine bonding agents (BAG-25A, BAG-25B, BAG-25C) in the PET propellant formulation is shown in Table 1. The tensile strength σ of the propellant is determined by the uniaxial tensile method according to 413.1 maximum tensile strength, breaking strength, maximum elongation and breaking elongation of GJB 770B-2005 "Test Methods for Propellants". m , elongation ε m The measurement results are shown in Table 2.

[0052] Table 1 PET propellant formulation composition

[0053]

[0054]

[0055] Table 2 Performance of bonding agents in PET propellants

[0056]

[0057] From the propellant performance data in Table 2, it can be seen that the new alcohol amine bonding agent can greatly improve the normal, high and low temperature mechanical properties of PET propellant, especially BAG-25B synthesized with a molar ratio of perchloric acid to triethanolamine of 0.5:1 has the best comprehensive performance.

[0058] Example 7

[0059] The application of three different bonding agents (BAG-25A, BAG-25B, BAG-25C) in the PEG propellant formulation is shown in Table 3. The tensile strength σ of the propellant was determined by the uniaxial tensile method according to 413.1 maximum tensile strength, breaking strength, maximum elongation and breaking elongation of GJB 770B-2005 "Test Methods for Propellants". m , elongation ε m The measurement results are shown in Table 4.

[0060] Table 3 PEG propellant formulation composition

[0061]

[0062] Table 4 Bonding agent performance results

[0063]

[0064] Judging from the propellant performance data, the new alcohol amine bonding agent can greatly improve the normal, high and low temperature mechanical properties of PEG propellant, especially BAG-25C synthesized with a molar ratio of perchloric acid to triethanolamine of 0.66:1 has the best comprehensive performance.

[0065] Example 8

[0066] The application of three different bonding agents (BAG-25A, BAG-25B, BAG-25C) in the GAP propellant formula. The composition of the GAP propellant formula is shown in Table 5. The tensile strength σ of the propellant is determined by the uniaxial tensile method according to 413.1 Maximum tensile strength, breaking strength, maximum elongation and breaking elongation of GJB 770B-2005 "Test Methods for Propellants". m , elongation ε m The measurement results are shown in Table 6.

[0067] Table 5 GAP propellant formula composition

[0068]

[0069] Table 6 Performance results

[0070]

[0071]

[0072] Judging from the propellant performance data, the new alcohol amine bonding agent can greatly improve the normal, high and low temperature mechanical properties of GAP propellant, especially BAG-25C synthesized with a molar ratio of perchloric acid to triethanolamine of 0.66:1 has the best comprehensive performance.

[0073] Example 9

[0074] The application of three different bonding agents (BAG-25A, BAG-25B, BAG-25C) in the HTPB propellant formulations. The HTPB propellant formulation composition is shown in Table 7. The tensile strength σ of the propellant was determined by the uniaxial tensile method according to 413.1 Maximum tensile strength, breaking strength, maximum elongation and breaking elongation of GJB 770B-2005 "Test Methods for Propellants". m , elongation ε m The measurement results are shown in Table 8.

[0075] Table 7 Composition of HTPB propellant formula

[0076]

[0077] Table 8 Performance results

[0078]

[0079] Judging from the propellant performance data, the new alcohol amine bonding agent can greatly improve the normal, high and low temperature mechanical properties of HTPB propellant, especially BAG-25A synthesized with a molar ratio of perchloric acid to triethanolamine of 0.25:1 has the best comprehensive performance.

[0080] Comparative Example 1

[0081] Boron trifluoride triethanolamine was added to the hydroxybutyl propellant formula shown in Table 7, and the tensile strength σ of the propellant was measured by the uniaxial tensile method according to 413.1 Maximum tensile strength, breaking strength, maximum elongation and breaking elongation of GJB 770B-2005 "Test Methods for Propellants" m , elongation ε m The measurement results are shown in Table 9.

[0082] Table 9 Performance results of the new alcohol amine bonding agent and boron trifluoride triethanolamine

[0083]

[0084] The novel alcoholamine bonding agent prepared by the present invention has the advantages of simple synthesis process, wide source of raw materials, less toxicity, etc. compared with the triethanolamine bonding agent in the prior art, and lower ammonia release amount when reacting with ammonium perchlorate; and from the data in Table 9, it can be seen that compared with boron trifluoride triethanolamine, the novel alcoholamine bonding agent disclosed in the present invention can significantly improve the mechanical properties of the composite solid propellant, and meet the requirements of the mechanical properties of the composite solid propellant.

Claims

1. A novel alcoholamine bonding agent, characterized in that: The structural formula of the novel alcohol amine bonding agent is:

2. A method for preparing the novel alcoholamine bonding agent as claimed in claim 1, characterized in that: The following steps are involved: The alkanolamine compound and the reaction solvent are weighed in a reaction device, and the weighed perchloric acid is added dropwise into the reaction device. After the perchloric acid is added dropwise, the temperature is increased and reacted, and a novel alcoholamine bonding agent is obtained by vacuum distillation.

3. The method for preparing the novel alcoholamine bonding agent according to claim 2, characterized in that: The alkanolamine compound includes one or more of diethanolamine, triethanolamine, and N-(2-cyanoethyl)diethanolamine.

4. The method for preparing the novel alcoholamine bonding agent according to claim 3, characterized in that: The molar ratio of the perchloric acid to the alkanolamine compound is 0.25-0.66:

1.

5. The method for preparing the novel alcoholamine bonding agent according to claim 2, characterized in that: The reaction solvent is one or more of deionized water, ethanol and acetone.

6. The method for preparing the novel alcoholamine bonding agent according to claim 5, characterized in that: The amount of the reaction solvent used is 80-150 mL.

7. The method for preparing the novel alcoholamine bonding agent according to claim 2, characterized in that: include: Weigh the alkanolamine compound and the reaction solvent in a reaction bottle with a water removal device, add the weighed perchloric acid into the dropping funnel, open the dropping funnel without water bath heating, and drop the perchloric acid into the reaction bottle. After the addition of the perchloric acid is completed, raise the water bath temperature to 75-80°C, react for 6-8h, and distill under reduced pressure for 7 hours to obtain a new alcoholamine bonding agent.

8. Use of the novel alcoholamine bonding agent as claimed in claim 1 in the preparation of solid propellants.

9. The use of the novel alcoholamine bonding agent according to claim 8 in the preparation of solid propellants, characterized in that: include: Adding the novel alcoholamine bonding agent into the solid propellant premix slurry and mixing them evenly to obtain a solid propellant containing the novel alcoholamine bonding agent; The solid propellant containing a novel alcoholamine bonding agent includes a NEPE system propellant, a HTPB system propellant, a PET propellant, a PEG propellant or a GAP propellant containing a novel alcoholamine bonding agent.

10. The use of the novel alcoholamine bonding agent according to claim 8 in the preparation of solid propellants, characterized in that: The mass ratio of the novel alcohol amine bonding agent to the solid propellant is 0.2% to 2.0%.

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