JP3081027B2 - Polyether and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyether used as a fuel binder for a composite solid propellant for a rocket motor and a method for producing the same. More specifically, the present invention relates to a polyether used as a fuel binder as a main component of the binder in a composite solid propellant comprising an oxidizing agent, a binder, an auxiliary agent, a combustion catalyst and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years,
Attention has been paid to a method of using a polyether having an azide group as a fuel binder in order to improve the combustion characteristics of a composite solid propellant. This kind of polyether is represented by the general formula (II)

[0003]

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(Wherein n represents a positive number) A polyether having an azidomethyl group in its side chain (US Pat.
No. 4,268,450) and the general formula (III)

[0005]

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A polyether comprising a copolymer of BAMO and tetrahydrofuran (THF) represented by the formula (where n and m represent positive numbers) has been proposed (JP-A-2-239178). In general, it is known that the greater the amount of azide group in the polyether, the greater the improvement in combustion characteristics when used as a propellant, especially the specific thrust. Therefore, polyethers containing more azide groups than conventional polyethers are expected to have improved combustion characteristics when used as propellants.

Hitherto, polyethers composed of BAMO and AMMO have been studied mainly as propellant binders (JP-A-2-14216). However, since this polyether has high crystallinity, it has a high melting point and high viscosity. However, since the range of viscosity that can be handled in the production of propellant is limited, when a high-viscosity polyether is used as a fuel binder, the amount of addition of components such as a solid oxidizing agent is limited. Is a big problem. In addition, polyethers having a high melting point, which are solid at the working temperature of propellant production, have a fatal drawback that they cannot be used as fuel binders. Due to these problems, BAMO can be used as a fuel binder in propellants
A polyether consisting of a copolymer of PEG and AMMO has not been developed so far.

[0008]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies on a polyether comprising BAMO and AMMO and having low crystallinity. It has been found that a low-melting point, low-viscosity, low-crystalline polyether having a low melting point and a low viscosity can be obtained in a specific AMMO content and a specific molecular weight range by adopting a solution polymerization using a compound of formula (I). That is, the present invention provides a compound represented by the general formula (I):

[0009]

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(Wherein, m and n are natural numbers), which is a polyether comprising a copolymer of a BAMO component and an AMMO component, wherein the number of moles of BAMO is n and the number of moles of AMMO is m The value of the ratio n / m is 0.05 to 9.5, and the number average molecular weight is 500 to 600.
0, and the viscosity at 60 ° C. measured by a B-type viscometer is 100
In a polyether and a halogenated hydrocarbon, which are not more than poise, BAMO, AMMO, BF ₃ O (C ₂ H ₅ ) ₂ as a reaction initiator and a diol component as a molecular weight regulator are collectively charged. It is intended to provide a method for producing a polyether represented by the general formula (I), which is characterized by reacting.

In the general formula (I), the value of n / m is 0.05
9.5, preferably 0.1 to 9.0.
If the value of n / m is less than 0.05, the combustion characteristics of the propellant decrease, and if it exceeds 9.5, the crystallinity of the polyether increases, and the production of the propellant becomes difficult. The polyether has a number average molecular weight of 500 to 6000, particularly 1000 to 50.
It is preferably in the range of 00. When the number average molecular weight is less than 500, the mechanical strength of the propellant decreases, and when the number average molecular weight exceeds 6,000, the viscosity becomes extremely high. Furthermore, it is desirable that substantially all of the terminals of the polyether of the present invention are hydroxyl groups.

The polyether of the present invention contains BAMO, AMMO, and BF ₃ O (C ₂ H ₅ ) ₂ as a reaction initiator in a halogenated hydrocarbon.
And the diol component as a molecular weight regulator is charged at once,
It is obtained by reacting. The reaction temperature is 0 to 50 ° C,
It is particularly preferable that the temperature be in the range of 15 to 35 ° C. When the reaction temperature is lower than 0 ° C., the reaction hardly proceeds, so that it is not practical. On the other hand, when the reaction temperature exceeds 50 ° C., the reaction rate increases, and an abnormal reaction occurs due to reaction heat.

The halogenated hydrocarbon used in the present invention includes dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, carbon tetrachloride and the like. Dichloromethane and carbon tetrachloride are preferred. Although the amount of the halogenated hydrocarbon is not particularly limited, it is 1.0 to 10 with respect to the reaction raw material.
It is preferable to use it by weight. According to the present invention, by using a halogenated hydrocarbon as a reaction solvent, since the polarity of the entire reaction system is changed, the blocking property of BAMO and AMMO is reduced, and as a result, the crystallinity of polyether is reduced. Presumed.

The diol component used as the molecular weight regulator is not particularly limited, but includes 1,2-ethanediol and 1,1-ethanediol.
2-propanediol, 1,3-propanediol, 1,2
-Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4- Pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol, etc., and especially 1,2-ethanediol ,
1,3-propanediol, 1,4-butanediol, 1,5
-Pentanediol is preferred. By changing the molar ratio between these molecular weight regulators and BAMO or AMMO, a polyether having an arbitrary molecular weight can be obtained.

Further, the halogenated hydrocarbon used in the production of the polyether of the present invention, a reaction initiator (BF ₃ O (C
_{2 H 5) 2), BAMO} , AMMO and molecular weight regulator (diol component)
Is preferably 1000 ppm or less, particularly preferably 500 ppm or less. BF used as a reaction initiator
The addition amount of ₃ O (C ₂ H ₅ ) ₂ is preferably 0.1 to 2 times, more preferably 0.3 to 0.9 times the mol of the molecular weight regulator. If the amount of addition is less than 0.1 times the molar amount of the molecular weight modifier, the reaction rate is reduced, so that it is not practical. On the other hand, if the molar ratio is more than 2 times, a side reaction occurs and the molecular weight distribution of the obtained polyether is undesirably widened.

[0016]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 <Synthesis of BAMO> 3,3-bischloromethyloxetane 200
g was placed in a glass separable flask having a nitrogen blowing tube, 670.5 g of dimethylformamide and 183.8 g of sodium azide were added, and mixed well at room temperature. Next, the mixture was slowly heated to 90 ° C. in an oil bath. The temperature was continuously maintained at 90 ° C., and the reaction was carried out for 2 hours with stirring to synthesize BAMO. After completion of the reaction, the temperature of the mixture was lowered to room temperature, 1.5 liter of methylene chloride and 1.5 liter of water were added, and the mixture was separated with a separating funnel. After liquid separation, the lower layer liquid (methylene chloride solution) was separated. Further, using a separatory funnel, the separated methylene chloride solution was mixed with 1.5 liters of water for 2 to 2 minutes.
After washing three times with water, the water dissolved in the lower layer liquid collected at the end was dehydrated by adding anhydrous sodium sulfate. Thereafter, this solution was filtered, and methylene chloride was removed with a rotary evaporator. Furthermore, pressure 3mmHg, temperature 120-140
Purified by distillation at ℃, colorless and transparent or pale yellowish white BAMO
I got As a result of measuring the purity by GC (gas chromatography), it was 99.9% or more. The water content was measured by the Karl Fischer method and found to be 60 ppm or less.

<Synthesis of AMMO> 200 g of 3-chloromethyl-3-methyloxetane was placed in a glass separable flask having a nitrogen blowing tube, and dimethylformamide 43 was added.
1 g and 118.1 g of sodium azide were added and mixed well at room temperature. Next, slowly mix the above mixture in an oil bath at 90 ° C.
Was heated. The reaction was continued for 2 hours while maintaining the temperature at 90 ° C. with stirring to synthesize AMMO. After the reaction,
The temperature of the mixture was lowered to room temperature, 0.6 liter of methylene chloride and 3.6 liters of water were added, and the mixture was sufficiently mixed. The mixture was separated with a separating funnel, and a lower layer solution (methylene chloride solution) was separated. Further, the methylene chloride solution collected using a separating funnel was washed with water (3.6 liters) two to three times, and finally the water dissolved in the separated lower layer solution was dehydrated by adding anhydrous sodium sulfate. Thereafter, this solution was filtered, and methylene chloride was removed with a rotary evaporator. Further, it was purified by distillation under the conditions of a pressure of 3 mmHg and a temperature of 70 to 90 ° C. to obtain a colorless and transparent AMMO. As a result of measuring the purity by GC (gas chromatography), it was 99.9% or more. The water content was measured by the Karl Fischer method and found to be 70 ppm or less.

<Production of polyether> 0.1248 mol of 1,4-butanediol dehydrated and purified according to a conventional method, carbon tetrachloride
517 g, 0.808 mol of BAMO and 0.808 mol of AMMO were placed in a flask which had been previously purged with nitrogen, and mixed well. Further, at room temperature, 0.0624 mol of BF ₃ O (C ₂ H ₅ ) ₂
−0.5 times the molar amount of butanediol) and raise the temperature.
The reaction was continued for 5 days while maintaining the temperature at 25 ° C. Thereafter, the reaction solution was diluted with 500 ml of methylene chloride, the reaction was stopped by adding distilled water, and saturated aqueous sodium hydrogen carbonate was added to add BF ₃ O (C ₂ H
₅ ) ₂ was neutralized. Further, 3 liters of distilled water was added and mixed well, and then separated using a separating funnel to separate a lower layer solution (a mixed solution of carbon tetrachloride and methylene chloride). Further, using a separating funnel, the mixed solution of carbon tetrachloride and methylene chloride was washed with 3 liters of water two to three times to sufficiently remove the reaction initiator. Thereafter, carbon tetrachloride and methylene chloride were removed with a rotary evaporator, and the mixture was further heated under reduced pressure to remove residual solvents, residual moisture, and the like, to obtain polyether. This was a colorless viscous liquid, and as a result of analysis using ¹ H-NMR, the molar ratio n / m between BAMO and AMMO was 1.0, the number average molecular weight determined from the hydroxyl value was 2000, and B The viscosity at 60 ° C. measured by a mold viscometer was 15 poise. Further, the melting point was lower than room temperature and the number of functional groups was 2.0, so that it could be sufficiently used as a fuel binder.

Example 2 BAMO and AMMO prepared in the same manner as in <Synthesis of BAMO> and <Synthesis of AMMO> in Example 1 were charged at 1.07 mol and 0.460 mol, respectively. Preparation of Ether> Polyether was obtained in the same manner as in the above. This is ¹ H−
As a result of analysis using NMR, the molar ratio between BAMO and AMMO was n /
The value of m was 2.33, and the number average molecular weight determined from the hydroxyl value was 200.
0, and the viscosity at 60 ° C. measured with a B-type viscometer is 20
poise. Further, the number of functional groups was 2.0, and it could be sufficiently used as a fuel binder.

Example 3 The number of moles of BAMO and AMMO obtained in the same manner as in <Synthesis of BAMO> and <Synthesis of AMMO> in Example 1 was 0.513, respectively.
Mol, 1.20 mol, and a polyether was obtained in the same manner as in <Production of polyether> of Example 1. This is ¹ H−
As a result of analysis using NMR, the molar ratio between BAMO and AMMO was n /
The value of m was 0.43, and the number average molecular weight determined from the hydroxyl value was 200.
0, and the viscosity at 60 ° C. measured with a B-type viscometer is 12
poise. Further, the number of functional groups was 2.0, and it could be sufficiently used as a fuel binder.

Example 4 BAMO and AMMO prepared in the same manner as in <Synthesis of BAMO> and <Synthesis of AMMO> in Example 1 were charged at 2.50 mol and 2.50 mol, respectively. Production of ether>
A polyether was obtained in the same manner as described above. This is ¹ H-NM
As a result of analysis using R, the molar ratio between BAMO and AMMO was n / m.
Is 1.0, the number average molecular weight determined from the hydroxyl value is 6000,
Further, the viscosity at 60 ° C. measured with a B-type viscometer is 90 poi.
was se. Further, the number of functional groups was 2.0, and it could be sufficiently used as a fuel binder.

Example 5 1,2-Ethanediol 0.0083 purified by dehydration according to a conventional method.
3 mol, 95 g of methylene chloride, and BAMO 0.100 obtained in the same manner as in <Synthesis of BAMO> and <Synthesis of AMMO> of Example 1.
6 mol and 0.235 mol of AMMO were placed in a flask which had been previously purged with nitrogen, and mixed well. In addition, it is a reaction initiator at 0 ° C.
_{BF 3 O (C 2 H 5} ) 2 and 0.00833 moles - added (1,2 equimolar to ethanediol) was continued for 5 days the reaction while maintaining the temperature at 0 ° C.. Then, after the reaction was stopped by adding distilled water to the reaction solution, saturated aqueous sodium bicarbonate was added to add BF ₃ O (C ₂ H ₅ ) ₂
Was neutralized. Further, 1 liter of distilled water was added, and the mixture was sufficiently mixed. Then, the mixture was separated with a separating funnel, and a lower layer liquid (methylene chloride solution) was separated. Further, using a separating funnel, the separated methylene chloride solution was washed with 1 liter of water two to three times to sufficiently remove the reaction initiator. Thereafter, methylene chloride was removed with a rotary evaporator, and the mixture was further heated under reduced pressure to remove residual solvents, residual moisture, and the like, to obtain polyether. This was a colorless viscous liquid, and as a result of analysis using ¹ H-NMR, the value of the molar ratio n / m between BAMO and AMMO was 0.1.
43. The number average molecular weight determined from the hydroxyl value was 5,700, and the viscosity at 60 ° C. measured by a B-type viscometer was 75 poise. Further, the number of functional groups was 2.0, and it could be sufficiently used as a fuel binder.

Comparative Example 1 The number of moles of BAMO and AMMO prepared in the same manner as in <Synthesis of BAMO> and <Synthesis of AMMO> in Example 1 was 0.421, respectively.
Mol and 0.421 mol, and a polyether was obtained in the same manner as in Example 5. The product was analyzed using ¹ H-NMR. As a result, the molar ratio n / m between BAMO and AMMO was 1.0, the number average molecular weight determined from the hydroxyl value was 15,000, and the value was measured with a B-type viscometer. The viscosity at ° C was greater than 100 poise.
Although the number of functional groups was 2.0, it could not be used as a fuel binder because of its high viscosity.

Comparative Example 2 The moles of BAMO and AMMO prepared in the same manner as in <Synthesis of BAMO> and <Synthesis of AMMO> in Example 1 were 0.745, respectively.
Mol and 0.319 mol, and a polyether was obtained in the same manner as in Example 5. The product was analyzed using ¹ H-NMR. As a result, the molar ratio n / m between BAMO and AMMO was 2.33, the number average molecular weight determined from the hydroxyl value was 20,000, and the viscosity was 60%. Could not be measured. Although the number of functional groups was 2.0, it had a high melting point and was solid at 60 ° C., so that it could not be used as a fuel binder.

Comparative Example 3 A polymerization reaction was carried out in the same manner as in Example 2 except that the reaction temperature was lowered to -10 ° C. without adding carbon tetrachloride, thereby producing a polyether. The viscosity at 60 ° C measured with a B-type viscometer is
It was larger than 100 poise and could not be used as a fuel binder.

Continuation of the front page (56) References JP-A-4-39328 (JP, A) JP-A-2-14216 (JP, A) UK Patent Application No. 2222440 (GB, A)

Claims (3)

(57) [Claims] 1. A compound of the general formula (I) (Where, m and n indicate natural numbers).
Bisazidemethyloxetane (abbreviated as BAMO) component and 3-
A polyether comprising a copolymer with an azidomethyl-3-methyloxetane (abbreviated as AMMO) component, comprising BAMO
The ratio n / m of the number of moles n of n to the number of moles m of AMMO is 0.05 to
9.5. A polyether having a number average molecular weight of 500 to 6000 and a viscosity at 60 ° C. measured by a B-type viscometer of 100 poise or less. 2. The polyether according to claim 1, wherein the value of n / m is 0.1 to 9.0 and the number average molecular weight is 1,000 to 5,000. 3. In a halogenated hydrocarbon, 3,3-bisazidomethyloxetane, 3-azidomethyl-3-methyloxetane, BF ₃ O (C ₂ H ₅ ) ₂ as a reaction initiator and diol as a molecular weight regulator The method for producing a polyether according to claim 1 or 2, wherein the components are charged at once and reacted.