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WO2011149166A1 - Composition de propulseur solide thermodurcissable comprenant une amine tertiaire non volatile et procédé de maîtrise de la vitesse de durcissement de la composition - Google Patents

Composition de propulseur solide thermodurcissable comprenant une amine tertiaire non volatile et procédé de maîtrise de la vitesse de durcissement de la composition Download PDF

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Publication number
WO2011149166A1
WO2011149166A1 PCT/KR2010/008582 KR2010008582W WO2011149166A1 WO 2011149166 A1 WO2011149166 A1 WO 2011149166A1 KR 2010008582 W KR2010008582 W KR 2010008582W WO 2011149166 A1 WO2011149166 A1 WO 2011149166A1
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WO
WIPO (PCT)
Prior art keywords
composition
propellant
weight
tertiary amine
nonvolatile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2010/008582
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English (en)
Inventor
Yoo Jin Yim
Young Chul Park
Ji Chang Yoo
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Agency for Defence Development
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Agency for Defence Development
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Priority to US13/698,751 priority Critical patent/US20130056117A1/en
Publication of WO2011149166A1 publication Critical patent/WO2011149166A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/36—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing both an organic explosive or thermic component and an inorganic explosive or thermic component
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a thermosetting solid propellant composition comprising a nonvolatile tertiary amine, and a method for controlling a cure rate of the composition.
  • Solid propellant is produced by homogenously mixing its all ingredients, casting in a preset frame during the time, for which the fluidity of the propellant is maintained to allow the casting process (hereinafter, referred to as "pot life", and curing at the temperature of 50 to 60°C for 7 to 10 days.
  • a nitramine oxidizing agent for example, 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), 2,4,6,7,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW) or the like, is used, and thus, its variation exponent of a combustion rate depending on a pressure change (i.e., pressure exponent) is very high, namely, at least 0.6. Accordingly, in order to reduce the pressure exponent, a ballistic modifier, such as lead or bismuth compounds, has been used in propellant formulation.
  • RDX 1,3,5-trinitroperhydro-1,3,5-triazine
  • HMX 1,3,5,7-tetranitro-1,3,5,7-tetrazocane
  • HNIW 2,4,6,7,10,12-hexanitro-2,4,6,
  • the curing reaction rate depends on temperature as well as a cure catalyst.
  • the mixing and casting processes of the propellant should be conducted at a lower temperature, such as below 15°C, which is lower than the typical processing temperature of 50°C in order to reduce the curing reaction rate.
  • a refrigerating equipment is required, thereby increasing a preparation cost, which is a problem to be necessarily solved.
  • an object of the present invention is to provide a method for increasing the time, for which the fluidity of a propellant is maintained, by controlling a viscosity buildup of a nitrate ester polyether (NEPE)-based solid propellant composition.
  • NEPE nitrate ester polyether
  • Another object of the present invention is to provide a method for preparing a nitrate ester polyether (NEPE)-based solid propellant composition, enabling to carry out mixing and casting processes at room temperature, at which cooling with tap water is possible without any separate refrigerating system.
  • NEPE nitrate ester polyether
  • a nitrate ester polyether-based thermosetting sold propellant composition comprising 1 to 4% by weight of bismuth subsalicylate as a ballistic modifier, and 0.005 to 0.03% by weight of a nonvolatile tertiary amine as a cure rate modifier, with respect to the total weight of the composition.
  • a method for controlling a viscosity buildup of a nitrate ester polyether-based thermosetting sold propellant composition comprising bismuth subsalicylate as a ballistic modifier, characterized by adding to the composition 0.005 to 0.03% by weight of a nonvolatile tertiary amine selected from the group consisting of 1.4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene and any combination thereof.
  • the nonvolatile tertiary amine is used as a cure rate modifier, thereby preventing from drastic viscosity buildup, which is caused due to a bismuth compound used as a ballistic modifier acting as a curing reaction catalyst, which makes it possible to maintain the viscosity as low as enabling to carry out mixing and casting processes of the propellant at room temperature.
  • mixing and casting processes of the propellant can be conducted at room temperature, and the temperature can be maintained at room temperature using tap water as a coolant, whereby any separate refrigerating system is not required.
  • FIG. 1 shows viscosity buildup curves for a propellant depending on temperature (a: 15°C, b: 25°C, c: 50°C);
  • FIG. 2 shows viscosity buildup curves for propellants with or without addition of DABCO at 25°C (a: with DABCO, b: without DABCO);
  • FIG. 3 shows viscosity buildup curves for propellants depending on the kinds of tertiary amine at 25°C (a: addition of 0.013% by weight of DABCO, b: addition of 0.015% by weight of DBU, c: addition of 0.02% by weight of DBN); and
  • FIG. 4 shows viscosity buildup curves for propellants depending on the content of DABCO at 25°C (a: addition of 0.003% by weight, b: addition of 0.013% by weight, c: addition of 0.02% by weight).
  • the present invention relates to a nitrate ester polyether (NEPE)-based thermosetting solid propellant composition
  • NEPE nitrate ester polyether
  • thermosetting solid propellant composition is influenced mainly by temperature, a cure catalyst and acidity.
  • a lead or bismuth compound is used as a ballistic modifier.
  • bismuth subsalicylate unlike lead compounds, is environmentally friendly and is very superior in improving combustion characteristics.
  • bismuth subsalicylate has been well known to have a very strong catalytic function in a urethane curing reaction and to promote the urethane curing reaction in an acidic condition.
  • Bismuth subsalicylate causes generation of acids when it is mixed with a nitrate ester plasticizer and a polar polymer.
  • the propellant composition is mixed at 50°C which is a typical processing temperature, it is cured so fast to lead to a drastic increase of viscosity, which results in shortening of the pot life.
  • the present invention was completed based on the recognition that the cure rate of the propellant can be controlled if acids generated during the propellant mixing process are neutralized with an appropriate base, and in this case, the mixing and casting processes can be carried out at a higher temperature than that in the conventional art.
  • an inorganic base or a primary or secondary organic amine cannot be used because they may cause a urethane reaction or aging of the propellant.
  • a volatile base also cannot be used because the propellant mixing process is conducted under a vacuum condition. Therefore, in the present invention, a nonvolatile tertiary amine, which does not cause any urethane reaction or aging of the propellant, and is nonvolatile under a vacuum condition, is used as a base for neutralizing acids generated during the mixing process of the propellant composition.
  • the nonvolatile tertiary amine is selected from the group consisting of 1.4-diazabicyclo[2.2.2]octane (hereinafter, referred to as "DABCO", 1,5-diazabicyclo[4.3.0]non-5-ene (hereinafter, referred to as "DBN”, 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter, referred to as "DBU”, and any combination thereof, and the content of the nonvolatile tertiary amine is preferable to have 0.005 to 0.03% by weight with respect to the total weight of the thermosetting solid propellant composition. If the amount of the tertiary amine is less than 0.005% by weight, an appropriate pot life is not secured, and if the amount of the tertiary amine exceeds 0.03% by weight, a curing reaction is not normally proceeded.
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • thermosetting solid propellant composition according to the present invention may have the same composition as a typical NEPE-based minimum smoke propellant composition, except for comprising a ballistic modifier and further comprising a nonvolatile tertiary amine as a cure rate modifier. Therefore, in addition to the nonvolatile tertiary amine, the propellant composition of the present invention may comprise 20 to 30% by weight of a nitrate ester plasticizer, 55 to 62% by weight of a nitramine oxidizing agent, 1 to 1.5% by weight of a combustion stabilizer, 1 to 4.0% by weight of a ballistic modifier, 0.5 to 2.0% by weight of a stabilizer, and polymers (prepolymers and curing agent) composing the rest.
  • the nitrate ester plasticizer may be selected from the group consisting of nitroglycerin, butanetriol trinitrate, trimethylolethane trinitrate, triethylene glycol dinitrate, diethylene glycol dinitrate, n-butyl nitratoethylnitramine, and any combination thereof, and the polymer may be selected from the group consisting of polyethylene glycol, glycidyl azide polymer, polydiethylene glycol adipate, ORP-2, poly caprolactone, and any combination thereof.
  • the ballistic modifier is bismuth subsalicylate.
  • the addition of a small amount of the nonvolatile tertiary amine allows neutralization of acids generated during the mixing process of the NEPE-based minimum smoke propellant, by which the curing reaction rate of the propellant is controlled, thereby enabling to sufficiently extend the time of maintaining the pot life of the propellant composition even at room temperature, i.e., at the temperature range of 20 to 25°C. Since the present invention enables to carry out the mixing and casting processes of the propellant at room temperature, tap water can be used as a coolant.
  • the present invention relates to a method for controlling a viscosity buildup of a nitrate ester polyether (NEPE)-based thermosetting solid propellant composition comprising bismuth subsalicylate as ballistic modifier, by addition of a nonvolatile tertiary amine to the composition.
  • NEPE nitrate ester polyether
  • the present invention also relates to a method for preparing a nitrate ester polyether (NEPE)-based thermosetting solid propellant composition, characterized by adding a nonvolatile tertiary amine during a mixing process for preparing the propellant composition, and conducting mixing and casting processes at room temperature.
  • NEPE nitrate ester polyether
  • the viscosity of the propellant should be below about 20 kilopoise.
  • Line a in FIG. 1 shows that the viscosity of the propellant composition of the comparative example is maintained below 10 kilopoise at 15°C for at least 6 hours
  • line b in FIG. 1 shows that the viscosity of the propellant composition of the comparative example exceeds 20 kilopoise at 25°C in 2 hours
  • line c in FIG. 1 shows that the fluidity of the propellant composition of the comparative example disappeared to the extent that casting become impossible at 50°C in 10 minutes. Therefore, it was concluded that the composition of the comparative example allows casting of the propellant at 15°C but not at a temperature higher than 15°C.
  • Example 2 The same propellant composition as that in Example 1 was prepared, except that 27% by weight of HMX were used as a nitramine oxidizing agent instead of 30% by weight of HNIW, and 3% by weight of polymers was additionally used. The viscosity change depending on time at 25°C was observed. The similar viscosity buildup pattern to line a in FIG. 2 was observed.
  • a refrigerating system In order to maintain the processing temperature for preparing the propellant at 15°C, a refrigerating system is required to maintain the temperature of a coolant below 15°C, whereas the temperature of 25°C can be maintained only using tap water as a coolant.
  • FIG. 3 shows the comparison of the viscosity buildup of the compositions at 25°C according to examples of the present invention.
  • Line a in FIG. 3 shows results when 0.013% by weight of DABCO was added
  • line b in FIG. 3 shows results when 0.015% by weight of DBU was added
  • line c in FIG. 3 shows results when 0.02% by weight of DBN was added.
  • FIG. 3 shows that the addition of each of the three tertiary amines results in a similar viscosity buildup pattern to one another.
  • FIG. 4 shows the variation of the propellant viscosity depending on the contents of DABCO and time.
  • Line a in FIG. 4 shows results when 0.003% by weight of DABCO was added
  • line b in FIG. 4 show results when 0.013% by weight of DABCO was added
  • line c in FIG. 4 shows results when 0.02% by weight of DABCO was added.
  • Line a in Fig. 4 shows a drastic viscosity buildup after four hours
  • line c in FIG. 4 shows that almost no viscosity change was observed for up to 8 hours.
  • the hardness of the propellant was lower than that in a or b in FIG. 4, which is inferred because the curing reaction was not normally proceeded. Therefore, it was concluded that the optimum content of DABCO is 0.013% by weight of the total composition.
  • the nonvolatile tertiary amine has no volatility and reactivity, it has no effect on other characteristics of the propellant. Therefore, it was found that the nonvolatile tertiary amine is a useful additive when preparing a propellant composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une composition de propulseur solide thermodurcissable à base de polyéther d'ester de nitrate comprenant une amine tertiaire non volatile, ainsi qu'un procédé de maîtrise de l'augmentation de la viscosité de la composition de propulseur solide thermodurcissable à base de polyéther d'ester de nitrate, caractérisé par l'ajout d'une amine tertiaire non volatile.
PCT/KR2010/008582 2010-05-24 2010-12-02 Composition de propulseur solide thermodurcissable comprenant une amine tertiaire non volatile et procédé de maîtrise de la vitesse de durcissement de la composition Ceased WO2011149166A1 (fr)

Priority Applications (1)

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US13/698,751 US20130056117A1 (en) 2010-05-24 2010-12-02 Thermosetting solid propellant composition comprising nonvolatile tertiary amine and method for controlling cure rate of the composition

Applications Claiming Priority (2)

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KR20100048243 2010-05-24
KR10-2010-0048243 2010-05-24

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WO2011149166A1 true WO2011149166A1 (fr) 2011-12-01

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KR101508630B1 (ko) * 2013-05-14 2015-04-07 국방과학연구소 비스무스계 화합물을 포함하는 무연 추진제 조성물 및 그 제조 방법
KR101559905B1 (ko) 2015-07-27 2015-10-14 국방과학연구소 이온성 액체 추진제의 점화지연시간 단축을 위한 이온성 액체 혼합물 제조방법 및 이에 의해 제조된 이온성 액체 혼합물

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020007886A1 (en) * 1999-08-09 2002-01-24 Jamie B. Neidert Gas generator for expelling halon replacements
US20060046068A1 (en) * 2004-09-02 2006-03-02 Barancyk Steven V Multi-component coatings that include polyurea coating layers
US20060217489A1 (en) * 2003-04-04 2006-09-28 Yakayuki Yako Building sealant composition

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Publication number Priority date Publication date Assignee Title
US4047988A (en) 1967-06-29 1977-09-13 The United States Of America As Represented By The Secretary Of The Navy Liquid monopropellant compositions
FR2210590B1 (fr) * 1972-12-19 1977-04-22 Poudres & Explosifs Ste Nale
US6293201B1 (en) * 1999-11-18 2001-09-25 The United States Of America As Represented By The Secretary Of The Navy Chemically reactive fragmentation warhead

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020007886A1 (en) * 1999-08-09 2002-01-24 Jamie B. Neidert Gas generator for expelling halon replacements
US20060217489A1 (en) * 2003-04-04 2006-09-28 Yakayuki Yako Building sealant composition
US20060046068A1 (en) * 2004-09-02 2006-03-02 Barancyk Steven V Multi-component coatings that include polyurea coating layers

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KR101213410B1 (ko) 2013-01-09
KR20110128736A (ko) 2011-11-30

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