CN114956921B - A kind of magneto-deformable solid rocket hybrid gel propellant and preparation method thereof - Google Patents

Abstract

The invention discloses a magnetically deformable solid rocket hybrid gel propellant and a preparation method thereof. The propellant is composed of an oil phase and a water phase, and the oil phase includes an organic solvent and an oil phase gel polymer monomer, oil phase cross-linking agent, oil phase initiator, magnetic particles; the water phase includes water, oxidant, reducing agent, burning rate regulator, cooling agent, and water phase gel polymer. The hybrid gel propellant of the present invention is prepared by mixing the water phase and the oil phase gel. The water phase gel is the oxidizing agent, reducing agent and other components of the propellant. The power of deformation is provided by introducing magnetic particles into the oil phase gel. The propellant is endowed with the ability to be greatly deformed, and the shape of the burning surface can be quickly changed according to the demand, thereby rapidly changing the performance of the engine. The magnetic field response rate of the hybrid gel propellant of the present invention is ≥10mm/s, and the elongation rate is ≥50%.

Description

A kind of magneto-deformable solid rocket hybrid gel propellant and preparation method thereof

technical field

The invention relates to a gel propellant and a preparation method thereof, in particular to an oil/water phase mixed gel rocket solid propellant through magnetic deformation and a preparation method thereof.

Background technique

Gel propellant is a new type of propellant that is safer than liquid propellant and more flexible to control thrust than solid propellant. It has broad prospects for development and can be used in anti-missile weapons and space vehicles. In civilian use, it can be used for oil extraction. Its specific impulse is much higher than that of solid propellants, and its other comprehensive properties are good. It is expected to gradually replace part of liquid propellants and solid propellants.

Gel propellants use gel as a carrier, and load oxidizing agents and reducing agents in the gel to form a propellant with a certain structure and specific properties. Gel propellants are mainly divided into three parts: oxidizing agent, reducing agent and gel carrier. The unique flexibility of the gel carrier can endow the propellant with deformable characteristics while serving as a fuel to provide the propellant with combustible elements. At present, it is known that most of the gel propellants have a pre-designed combustion surface shape, and the adaptability is poor.

CN110950728B discloses a deformable solid propellant and its preparation method. Although it uses shape memory polymer material as a binder, it can provide a change in the shape of the propellant, but its deformation rate is slow, and the shape of the propellant cannot be greatly changed. , and the degree of deformation often needs to be set in advance, and it is difficult to freely adjust it once set.

Contents of the invention

In order to overcome the problems of single gel propellant such as poor adaptability, need for presetting, slow response speed, and small deformation range, and better adapt to flight conditions, the present invention provides a magnetically deformable solid rocket hybrid gel propellant and its preparation method.

The purpose of the present invention is achieved through the following technical solutions:

A magnetically deformable solid rocket hybrid gel propellant, which consists of two parts, an oil phase and a water phase, wherein:

The mass ratio of the oil phase and the water phase is 1:1~20;

The oil phase includes organic solvent, oil phase gel polymer monomer, oil phase crosslinking agent, oil phase initiator, magnetic particles, organic solvent, oil phase gel polymer monomer, oil phase crosslinking agent, oil phase initiator The mass ratio of agent to magnetic particles is 30~80:1~50:0.0001~10:0.0001~10:1~80;

Described aqueous phase comprises water, oxidizing agent, reductant, burning rate regulating agent, cooling agent, aqueous phase gel polymer, the quality of water, oxidizing agent, reducing agent, burning rate regulating agent, cooling agent, aqueous phase gel polymer The ratio is 10~90: 20~50: 10~25, 0~10, 0~10: 1~60;

Described organic solvent is liquid paraffin or glycerin;

The oil-phase gel polymer monomer is one or more of hydroxyethyl acrylate (HEA), methyl methacrylate (MMA), tripropylene glycol diacrylate (TPGDA), acrylate, and styrene. kind;

The oil phase initiator is one of dibenzoyl peroxide (BPO) and azobisisobutylimidazoline hydrochloride (VA-044);

The magnetic particles are one or more magnetic particles such as ferric oxide, iron, cobalt, nickel, neodymium iron boron, etc.;

The aqueous gel polymer is one or more of polyacrylamide, polyvinyl alcohol, sodium carboxymethylcellulose, poly(N-isopropylacrylamide), polydopamine, and polyacrylamide;

The water-phase gel polymer can be replaced by water-phase initiator and water-phase gel polymer monomer, water, oxidant, reductant, burning rate regulator, cooling agent, water-phase initiator and water-phase gel polymerization The mass ratio of monomers is 10~70: 20~50: 10~25, 0~10, 0~10: 0.0001~10: 1~60;

The aqueous gel polymer monomer is one or more of kaolin, nanoclay, diatomaceous earth, acrylamide (AM), methylenebisacrylamide (MBAA), and hydroxyethyl acrylate;

The water phase initiator is 2,2-azobis(2-methylpropylimidium) dihydrochloride (VA-056);

The oxidant is one or more of energetic materials such as ammonium perchlorate, ammonium dinitramide, ammonium perchlorate, ammonium nitrate, and octogold;

The reducing agent is one or more of aluminum powder, magnesium powder, aluminum hydride, etc.;

The burning rate regulator is one or more of chromium trioxide, chromium oxide, tert-butylferrocene, carborane, etc.;

The cooling agent is one or more of pentaerythritol, ammonium sulfate and the like.

A method for preparing the above-mentioned magnetically deformable solid rocket hybrid gel propellant includes the following two technical solutions:

Technical scheme 1, one-pot blending method

Mix the water phase and the oil phase, disperse at 100-20000 rpm for 5-20 min, and then heat at 20-150 °C for 1-5 h to obtain a magnetically deformable solid rocket hybrid gel propellant.

Technical scheme two, step-by-step preparation method

Step 1, preparation of aqueous phase gel

(1) Preparation of hydrogel precursor solution: Assemble the condensing reflux stirring device, add the aqueous phase gel polymer and water, or the aqueous phase gel polymer monomer, the aqueous phase initiator and water into the three-necked flask, and heat to 20~150℃, control the stirring speed at 100~20000 rpm, condense and reflux for 1~5 h until it is completely dissolved, stop heating and continue stirring to cool down to room temperature, then take it out for later use; add oxidizing agent, reducing agent, burning rate regulator, cooling agent to get Hydrogel precursor;

(2) Gelation: Centrifuge the hydrogel precursor solution to remove air bubbles, control the speed at 100-20000rpm, and take it out for 1-30 minutes, then pour it into the mold; use the freeze-thaw method to gel, and it will be filled The syringe of the hydrogel precursor solution was frozen in a refrigerator at -18°C for 12-30 hours, and then thawed in an oven at 10-50°C for 0.5-5 hours. Take out the bag and set aside;

(2) Surface modification of hydrogels

The hydrogel is firstly soaked in acetone for 1-30 min, then taken out to dry; then a stirring device with nitrogen gas is assembled, and the two drugs are taken out according to the volume ratio of acryloyl chloride:dichloromethane=0.06:1, according to the volume ratio of acryloyl chloride: Add dichloromethane=1:7 into the constant pressure funnel and mix evenly, add the remaining dichloromethane into the four-necked flask, add the dried hydrogel, and control the volume ratio of hydrogel to acryloyl chloride to 1:0.8 ~1, use an ice-water bath to control the temperature near 0°C, and then introduce nitrogen gas into the solution to stir evenly and stably for 1-30 min; turn off the nitrogen gas, seal the environment, open the constant pressure funnel, and drop the mixed solution at a rate of 2 s/drop into the In the four-necked flask, keep constant stirring and 0°C environment during the process, add 0.1~5 ml triethylamine every 20 minutes and pass nitrogen for 3~5 minutes; after the dropwise addition, continue the ice water bath for 30 minutes, then remove , continue to stir and react at room temperature for 1-20 h, then stop the reaction, take out the surface-modified hydrogel, wash with ultrapure water for 2-4 times, immerse in 1-10% Na ₂ CO ₃ solution, stir and wash for 5 ~30 min, then wash with ultra-pure water for 10 min, repeat this operation 2-3 times until the pH of the cleaning solution is neutral, take it out and dry it quickly with high-purity nitrogen, and pack it in a nitrogen environment for later use;

(3) Preparation of Magnetic Responsive Organogel Precursor

First, mix the oil-phase gel polymer monomer with an organic solvent, add an oil-phase initiator and an oil-phase cross-linking agent, dissolve and mix it uniformly into a solution, take nano-magnetic particles into the solution, and mix them uniformly with ultrasound to obtain a magnetic response organic gel precursor;

(4) Combination of magnetically responsive organic-hydrogels

First put the modified hydrogel into the mold, then absorb the magnetic response organogel precursor to cover the modified hydrogel, put it in an oven at 20-100°C for 0.1-10 h, and take out the magnetic field after the gel is completed. Responsive organo-hydrogels, pouches.

In the present invention, the composition of the mixed gel propellant is shown in Figure 1, and the deformed burning surface of the mixed gel propellant is shown in Figure 2. In Figure 2, from the left of the figure to the right of the figure, the combustion surface becomes larger, the engine thrust increases, and the rocket speed becomes faster; from the right of the figure to the left of the figure, the combustion surface decreases, the engine thrust decreases, and the rocket speed decreases. Both situations can effectively change the maneuverability of the missile. Using the ferrofluid in the mixed gel propellant, the rapid conversion between left → right or right → left can be achieved by applying a magnetic field and closing the magnetic field, and even by changing the magnetic field to produce more complex deformations.

Compared with the prior art, the present invention has the following advantages:

1. The mixed gel propellant of the present invention is prepared by mixing the water phase and the oil phase gel. The water phase gel is the oxidizing agent, reducing agent and other components of the propellant, and the magnetic particles are introduced into the oil phase gel to provide deformation Power, which endows the propellant with the ability to be greatly deformed, and realizes rapid changes in the shape of the combustion surface according to requirements, thereby rapidly changing the performance of the engine.

2. The magnetic field response rate of the hybrid gel propellant of the present invention is ≥10 mm/s.

3. The elongation rate of the mixed gel propellant of the present invention is ≥50%.

Description of drawings

Figure 1 is a schematic diagram of the composition of the hybrid gel propellant;

Fig. 2 is a schematic diagram of the deformed combustion surface of the hybrid gel propellant.

Detailed ways

The technical solution of the present invention will be further described below in conjunction with the examples, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention within the scope of protection.

Example 1:

Oil phase: 40g of liquid paraffin, 12g of methyl methacrylate (MMA), 0.5g of tripropylene glycol diacrylate (TPGDA), 0.015g of BPO, 20g of iron oxide particles.

Water phase: 36.8g ultrapure water, 3.2g kaolin, 40g acrylamide (AM), 0.4g methylenebisacrylamide (MBAA), 2,2-azobis(2-methylpropylimidium) disalt Salt (VA-056) 0.04g, ammonium perchlorate 20g, aluminum powder 5g, pentaerythritol 0.1g.

After mixing according to the above ratio, use a homogenizer to disperse at 10,000 rpm for 5 minutes, and then heat at 65°C for 30 minutes to obtain a mixed gel propellant. The magnetic field response rate and elongation rate are shown in Table 1.

Example 2:

Oil phase: glycerin 50g, methyl methacrylate (MMA) 13g, tripropylene glycol diacrylate (TPGDA) 0.6g, BPO 0.015g, NdFeB particles 25g.

Water phase: 40g of ultrapure water, 50g of polyacrylamide, 21g of ammonium dinitramide, 6g of magnesium powder, and 0.2g of pentaerythritol.

After mixing according to the above ratio, use a homogenizer to disperse at 5000 rpm for 10 minutes, and then heat at 60°C for 40 minutes to obtain a mixed gel propellant. The magnetic field response rate and elongation rate are shown in Table 1.

Example 3:

1. Preparation of PVA (polyvinyl alcohol) hydrogel

(1) Preparation of PVA hydrogel precursor solution: assemble the condensing reflux stirring device, add 15g PVA and 85g ultrapure water into a three-necked flask, heat to 90°C, control the stirring speed to 400r/min, and condense and reflux for 4 hours until the PVA is completely Dissolve, stop heating and continue stirring to cool down to room temperature and take it out for later use. Add 20 g of ammonium dinitramide as an oxidizing agent and 10 g of magnesium powder as a reducing agent.

(2) Gelation: Centrifuge the PVA hydrogel precursor solution to remove air bubbles, control the speed at 5000r/min, and pour it into the mold for 10 minutes; use the freeze-thaw method to gel, and then fill it with PVA hydrogel The syringe of the gel precursor was frozen in a refrigerator at -18°C for 22 hours, and then thawed in an oven at 30°C for 2 hours.

2. Surface modification of PVA hydrogel

PVA hydrogel was soaked and dehydrated in acetone for 10 min, taken out to dry, and its mass was called xg, and the volume of acryloyl chloride used was calculated to be 0.84x ml; secondly, a stirring device with nitrogen gas was assembled, and the volume ratio of acryloyl chloride:dichloromethane =0.06:1Take out the two medicines, add acryloyl chloride:dichloromethane=1:7 into the constant pressure funnel and mix evenly, add the remaining dichloromethane into the four-necked flask, add the dried PVA hydrogel Glue, using an ice-water bath to control the temperature at around 0°C, and then uniformly and stably magnetically stir for 10 minutes after introducing nitrogen gas; turn off the nitrogen gas, seal the environment, open the constant pressure funnel, and drop the mixed solution into the four-necked flask at a rate of 2 s/drop During this process, keep constant stirring and 0°C environment, add 1 ml of triethylamine every 20 min and pass nitrogen gas for 5 min; The reaction was stopped after h, and the surface-modified PVA hydrogel was taken out, washed three times with ultrapure water, immersed in 5% Na ₂ CO ₃ solution, stirred and cleaned for 10 min, and then washed with ultrapure water for 10 min, and the process was repeated. Operate 3 times until the pH of the cleaning solution is neutral, take it out and dry it quickly with high-purity nitrogen, and pack it in a nitrogen environment for later use.

3. Preparation of PHEA (polyhydroxyethyl acrylate) magnetic response organogel precursor

Mix 6g hydroxyethyl acrylate (HEA) and 4g glycerin, add 0.15g initiator VA-044, crosslinking agent 0.42 gMBAA, ultrasonically dissolve and mix to form a solution, take 0.5g nano Fe ₃ O ₄ into the solution, Ultrasonic mixing was performed to obtain the PHEA magnetic response hydrogel precursor.

4. Magnetically responsive organic-hydrogel combination

First put the modified PVA hydrogel into the mold, then absorb the PHEA magnetic response hydrogel precursor to cover the modified PVA hydrogel, put it in a 55°C oven and heat it for 2 hours, and take out the magnetic response after the gel is completed. The organo-hydrogel is packed into a bag, and its magnetic field response rate and elongation rate are shown in Table 1.

Example 4

1. Preparation of PAM (polyacrylamide) hydrogel

Ultrapure water 74g, nanoclay 6.4g, acrylamide (AM) 80g, methylenebisacrylamide (MBAA) 0.8g, 2,2-azobis(2-methylpropylimidium) dihydrochloride ( VA-056) 0.08g, ammonium perchlorate 40g, aluminum powder 10g, pentaerythritol 0.2g.

2. Surface modification of PAM hydrogel

PAM hydrogel was soaked and dehydrated in acetone for 10 min, taken out to dry, and its mass was called xg, and the volume of acryloyl chloride used was calculated to be 0.84x ml; secondly, a stirring device with nitrogen gas was assembled, and the volume ratio of acryloyl chloride: dichloromethane =0.06:1 Take out the two medicines, add acryloyl chloride:dichloromethane=1:7 into the constant pressure funnel and mix evenly, add the remaining dichloromethane into the four-necked flask, add the dried PAM hydrogel Glue, using an ice-water bath to control the temperature at around 0°C, and then uniformly and stably magnetically stir for 10 minutes after introducing nitrogen gas; turn off the nitrogen gas, seal the environment, open the constant pressure funnel, and drop the mixed solution into the four-necked flask at a rate of 2 s/drop During this process, keep constant stirring and 0°C environment, add 1 ml of triethylamine every 20 min and pass nitrogen gas for 5 min; The reaction was stopped after h, and the surface-modified PAM hydrogel was taken out, washed three times with ultrapure water, immersed in 5% Na ₂ CO ₃ solution, stirred and cleaned for 10 min, and then washed with ultrapure water for 10 min, and the process was repeated. Operate 3 times until the pH of the cleaning solution is neutral, take it out and dry it quickly with high-purity nitrogen, and pack it in a nitrogen environment for later use.

3. Preparation of PMMA (polymethyl methacrylate) magnetically responsive organogel precursor

Liquid paraffin 4g, methyl methacrylate (MMA) 1.2g, tripropylene glycol diacrylate (TPGDA) 0.05g, BPO 0.002g, iron ferric oxide particles 2g.

4. Magnetically responsive organic-hydrogel combination

First put the modified PAM hydrogel into the mold, then absorb the PMMA magnetic response hydrogel precursor to cover the modified PAM hydrogel, put it in a 60°C oven and heat it for 1.5h, and take out the magnetic response after the gel is completed. The organo-hydrogel is packed into a bag, and its magnetic field response rate and elongation rate are shown in Table 1.

Table 1

Claims (6)

1. A magnetically deformable solid rocket propellant gel mixture, characterized in that the propellant is composed of an oil phase and a water phase, wherein:

the mass ratio of the oil phase to the water phase is 1:1 to 20;

the oil phase comprises an organic solvent, an oil phase gel polymer monomer, an oil phase cross-linking agent, an oil phase initiator and magnetic particles, wherein the mass ratio of the organic solvent, the oil phase gel polymer monomer, the oil phase cross-linking agent, the oil phase initiator and the magnetic particles is 30-80: 1 to 50:0.0001 to 10:0.0001 to 10:1 to 80;

the oil phase gel polymer monomer is one or more of hydroxyethyl acrylate, methyl methacrylate, tripropylene glycol diacrylate, acrylate and styrene, the oil phase initiator is one of dibenzoyl peroxide and azobisisobutyrimidazoline hydrochloride, and the magnetic particles are one or more of ferroferric oxide, iron, cobalt, nickel and neodymium iron boron;

the water phase comprises water, an oxidant, a reducing agent, a combustion speed regulator, a temperature reducing agent and a water-phase gel polymer, wherein the mass ratio of the water, the oxidant, the reducing agent, the combustion speed regulator, the temperature reducing agent to the water-phase gel polymer is 10 to 90:20 to 50:10 to 25, 0 to 10, and 0 to 10:1 to 60;

the aqueous phase gel polymer is one or more of polyacrylamide, polyvinyl alcohol, sodium carboxymethylcellulose, poly (N-isopropylacrylamide) and polydopamine, the oxidant is one or more of ammonium perchlorate, ammonium dinitramide, ammonium perchlorate, ammonium nitrate and octogen, and the reducing agent is one or more of aluminum powder, magnesium powder and aluminum hydride.

2. The magnetically deformable solid-rocket hybrid gel propellant according to claim 1, wherein the aqueous gel polymer is replaced by an aqueous phase initiator and an aqueous gel polymer monomer, and the mass ratio of water, oxidant, reductant, combustion speed regulator, temperature reducer, aqueous phase initiator and aqueous gel polymer monomer is 10 to 70:20 to 50:10 to 25, 0 to 10, and 0 to 10:0.0001 to 10:1 to 60, the water phase gel polymer monomer is one or more of acrylamide, methylene bisacrylamide and hydroxyethyl acrylate, and the water phase initiator is 2,2-azobis (2-methylpropylamidine) dihydrochloride.

3. The magnetically deformable solid-rocket propellant system of claim 1 wherein said organic solvent is liquid paraffin or glycerol.

4. A magnetically deformable solid-rocket hybrid gel propellant according to claim 1 or 2, wherein said fire rate modifier is one or more of chromium oxide, t-butyl ferrocene, carborane, and temperature reducing agent is one or more of pentaerythritol, ammonium sulfate.

5. A method of making a magnetically deformable solid rocket propellant gel hybrid according to any one of claims 1 to 4, characterized in that said method comprises the steps of:

mixing the water phase and the oil phase, dispersing for 5 to 20 min at the rotating speed of 100 to 20000 rpm, and then heating for 1 to 5h at the temperature of 20 to 150 ℃ to obtain the solid rocket mixed gel propellant capable of being magnetically deformed.

6. A method of making a magnetically deformable solid rocket propellant system as claimed in any one of claims 1 to 4, said method comprising the steps of:

step one, preparation of aqueous phase gel

(1) Preparing a hydrogel precursor solution: assembling a condensation reflux stirring device, adding a water-phase gel polymer and water, or a water-phase gel polymer monomer, a water-phase initiator and water into a three-neck flask, heating to 20-150 ℃, controlling the stirring speed to be 100-20000 rpm, carrying out condensation reflux for 1-5 h until the water-phase gel polymer and the water are completely dissolved, stopping heating, continuing stirring, cooling to room temperature, and taking out for later use; adding an oxidant, a reducing agent, a combustion speed regulator and a cooling agent to obtain hydrogel precursor liquid;

(2) And (3) gelation: removing air bubbles from the hydrogel precursor by adopting a centrifugal method, controlling the rotating speed to be 100 to 20000 rpm and the time to be 1 to 30min, taking out and pouring into a mould; adopting a freeze-thaw method for gelation, namely putting an injector filled with hydrogel precursor liquid into a refrigerator at the temperature of-18 ℃ for freezing for 12 to 30h, then unfreezing for 0.5 to 5h in an oven at the temperature of 10 to 50 ℃, wherein the cycle is one, and the hydrogel is taken out and packaged for later use after the freeze-thaw cycle is 1~5 times;

step two, surface modification of hydrogel

Firstly, soaking the hydrogel in acetone for dehydration for 1 to 30min, taking out and airing; then assembling a stirring device for introducing nitrogen, wherein the nitrogen is introduced into the stirring device according to the volume ratio of acryloyl chloride: dichloromethane =0.06:1, taking out two medicines, namely acryloyl chloride according to the volume ratio: dichloromethane =1:7, adding the mixture into a constant-pressure funnel, uniformly mixing, adding the rest dichloromethane into a four-neck flask, adding the dried hydrogel, controlling the volume ratio of the hydrogel to the acryloyl chloride to be 1Controlling the temperature of the water bath to be about 0 ℃, introducing nitrogen, and uniformly and stably stirring for 1 to 30min by magnetic force; closing nitrogen, sealing the environment, opening a constant-pressure funnel, dropwise adding the mixed solution into a four-neck flask at the speed of 2 s/droplet, keeping constant stirring and the environment at 0 ℃ in the process, adding 0.1-5 ml of triethylamine every 20 min, and introducing nitrogen for 3-5 min; after the dropwise addition, continuing the ice water bath for 30min, removing the ice water bath, continuing stirring at room temperature for reaction for 1-20 h, stopping the reaction, taking out the surface-modified hydrogel, cleaning with ultrapure water for 2~4 times, and immersing in 1-10% Na ₂ CO ₃ Stirring and cleaning the solution for 5 to 30min, cleaning the solution for 10min by using ultrapure water, repeating the operation for 2~3 times until the pH value of the cleaning solution is neutral, taking out the solution, quickly drying the solution by using high-purity nitrogen, and bagging the solution in a nitrogen environment for later use;

step three, preparation of magnetic response organic gel precursor liquid

Firstly, mixing an oil phase gel polymer monomer and an organic solvent, adding an oil phase initiator and an oil phase cross-linking agent, ultrasonically dissolving and uniformly mixing to obtain a solution, adding nano magnetic particles into the solution, and ultrasonically mixing uniformly to obtain a magnetic response organogel precursor solution;

step four, combining the magnetic response organic-hydrogel

Firstly, putting the modified hydrogel into a mold, then absorbing the precursor liquid of the magnetic response organic gel to coat the modified hydrogel, putting the modified hydrogel into an oven with the temperature of 20-100 ℃, heating for 0.1-10 h, taking out the magnetic response organic-hydrogel after the gelation is finished, and bagging.

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