US3897283A - Plastic bonded explosive composition - Google Patents

Plastic bonded explosive composition Download PDF

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Publication number
US3897283A
US3897283A US642651A US64265167A US3897283A US 3897283 A US3897283 A US 3897283A US 642651 A US642651 A US 642651A US 64265167 A US64265167 A US 64265167A US 3897283 A US3897283 A US 3897283A
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explosive
binder
mixture
composition
diallyl phthalate
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US642651A
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Ethyl F Wiebke
Charles W Falterman
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US Department of Navy
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Us Of Amercia As Represented B
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
    • 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
    • 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
    • C06B45/20—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component
    • C06B45/22—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component the coating containing an organic compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds

Definitions

  • ABSTRACT An explosive composition which will withstand temperature exposure and temperature shock at supersonic speeds and upon environment exposure. It consists essentially of a high explosive pre-coated with a polyester resin consisting of the polyester portion of Laminac 4116 and 4134 admixed with vinyl toluene, alpha-methyl styrene and diallyl phthalate.
  • the invention relates to an improved castable plastic bonded explosive composition and its preparation capable of withstanding temperature exposure and temperature shock at supersonic speeds and upon environmental exposure.
  • Castable plastic-bonded explosive formulations developed up to the present time have shown energy characteristics similar to those of Composition B, a British developed composition during the period between World Wars I and II and which was standardized by the United States early in World War II.
  • Composition B is a TNT-based composition and it has been considered a desirable and worthwhile goal to attempt to improve the explosive potential of the plastic-bonded types to exceed that of the best TNT-based formulations and still retain the desirable physical properties of the former.
  • the present invention provides a formulation superior to the aforementioned conventional TNT- based explosives not only in respect to their resistance to melting at high temperatures but also in regard to physical properties and ease of processing.
  • the general purpose of this invention is to provide an explosive composition for a missile warehead which can withstand the environment at the supersonic speeds to which the warhead will be subjected.
  • An object of this invention is to provide an explosive composition which can be used in applications involving aerodynamic heating.
  • Another object of this invention is to provide an explosive composition which has a reduced exotherm, is less brittle than other plastic bonded explosives, and resists cracking.
  • Yet another object of this invention is to provide an explosive composition which has the economic advantages of savings in time and materials used.
  • the invention contemplates incorporating a polyester resin-coated explosive selected from the group consisting of cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX), diaminotrinitrobenzene (DATB) and others with a binder composition consisting essentially of vinyl toluene, alpha-methyl styrene and diallyl phthalate.
  • RDX cyclotrimethylenetrinitramine
  • HMX cyclotetramethylenetetranitramine
  • DATB diaminotrinitrobenzene
  • the explosive is pre-coated with a mixture of unsaturated polyester resin sold under the tradename Laminac EPX 147-1 by American Cyanamid Company.
  • the liquids consisting of vinyl toluene, alpha-methyl styrene and diallyl phthalate were added to a mixing kettle then the resin-coated explosive was added and the mixture stirred until the resin dissolved and the explosive dispersed. Vacuum is usually applied to the kettle during the last portion of the mixing operation to remove entrapped air. When thoroughly mixed the batch was catalyzed.
  • the catalyst-accelerator combination used consisted of methyl ethyl ketone peroxide in the form of 60% solution in dimethyl phthalate and cobalt naphthenate solution (6% cobalt as metal). The amounts of catalystaccelerator may be adjusted to produce the desired pot life of the composition. Acceptable results have been obtained using 0. 1% cobalt naphthenate solution and 0.5% methyl ethyl ketone peroxide solution (based on binder weight of the batch).
  • the explosive composition should have as high an explosive content as possible, being limited by the practical consideration of processability and explosive sensitivity.
  • the following formulation has a detonation velocity of 8060 m/sec in 1 /8 inch-diameter and an impact sensitivity of 36 cm (as compared to Composition Bs 33 cm).
  • the binder content may be increased.
  • diallyl phthalate may range from 20 to 25 percent of the binder composition. Above 25% the product is too weak and below 20% it is not sufficiently flexible. When omitted from the binder, the solutility characteristics of the binder are altered to the point where phase separation occurs.
  • the vinyl toluene contributes to reducing the shrinkage of the cross-linked polyester, but produces a vigorous exotherm. In combination with alpha-methyl styrene, the polymerization is controlled and a negligible exotherm results.
  • the alpha methyl styrene content may vary between 25%, the 2% level being adequate without slowing down the reaction excessively.
  • the percentage binder is important to the viscosity and processability of the composition. A total binder content of 17% produced a better detonation velocity than Composition B. Less binder than this would make it too difficult to process on a large scale and more binder would decrease its energetic properties.
  • the combination of vinyl toluene, alpha-methyl styrene and diallyl phthalate as a binder for unsaturated, styrene free polyester resin coated high explosives is new and the composition produced has superior physical properties.
  • the Laminac unsaturated polyester resin EPX 147-1 which is used to pre-coat the high explosive before mixing with the liquid binder in the formulations described herein is manufactured by American Cyanamid. It is a monomer free polyester resin consisting of a blend of the reaction products of adipic acid, maleic acid with diethylene glycol and phthalic acid, maleic acid with propylene glycol.
  • the method of preparing the reaction products is fully described in U.S. Pat. No. 2,255,313, issued Sept. 9, 1941, which discloses preparation by reacting an alpha, beta-ethylenically unsaturated dicarboxylic acid and a glycol with or without a dicarboxylic acid free of non-benzenoid unsaturation.
  • the binder consisting essentially of unsaturated polyester resin, vinyl toluene, alpha-methyl styrene and diallyl phthalate is potentially useful for propellants and pyrotechnics formulations.
  • the plastic bonded explosive composition consisting essentially of Ingredients Percent by weight A high explosive Binder said explosive being a member selected from the group consisting of cyclotetramethylenetetranitramine, cyclotrimethylenetrinitramine, and diaminotrinitrobenzene;
  • said binder consisting of 42.4% of a blend of the reaction products of adipic acid, maleic acid with diethylene glycol and phthalic acid, maleic acid with propylene glycol; 33.1% vinyl toluene; 2% alphamethyl styrene; and 22.5% diallyl phthalate.
  • composition of claim 1 which comprises a. pre-coating said high explosive with a blend of the reaction products of adipic acid and maleic acid with diethylene glycol, and phthalic acid and maleic acid with propylene glycol;
  • a binder formulation consisting essentially of the following:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

An explosive composition which will withstand temperature exposure and temperature shock at supersonic speeds and upon environment exposure. It consists essentially of a high explosive pre-coated with a polyester resin consisting of the polyester portion of Laminac 4116 and 4134 admixed with vinyl toluene, alpha-methyl styrene and diallyl phthalate.

Description

United States Ratent Wiebke et a1.
PLASTIC BONDED EXPLOSIVE COMPOSITION Inventors: Ethyl F. Wiebke; Charles W.
Falter-man, both of China Lake, Calif.
The United States of Amercia as represented by the Secretary of the Navy, Washington, DC.
Filed: May 19, 1967 Appl. No.: 642,651
Assignee:
11.8. C1. 149/19.5; 149/11; 149/19.91; 149/19.93; 149/92; 149/105; 260/78.4 UA; 264/3 R Int. Cl. C06B 45/10 Field of Search 149/19, 92, 11, 19.91, 149/19.5, 19.93, 105; 264/3, 3 R; 260/291, 260/78.4 UA
Primary Examiner-Leland A. Sebastian Attorney, Agent, or FirmR. S. Sciascia; Roy Miller [57] ABSTRACT An explosive composition which will withstand temperature exposure and temperature shock at supersonic speeds and upon environment exposure. It consists essentially of a high explosive pre-coated with a polyester resin consisting of the polyester portion of Laminac 4116 and 4134 admixed with vinyl toluene, alpha-methyl styrene and diallyl phthalate.
3 Claims, N0 Drawings PLASTIC BONDED EXPLOSIVE COMPOSKTION The invention herein described may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
The invention relates to an improved castable plastic bonded explosive composition and its preparation capable of withstanding temperature exposure and temperature shock at supersonic speeds and upon environmental exposure.
Castable plastic-bonded explosive formulations developed up to the present time have shown energy characteristics similar to those of Composition B, a British developed composition during the period between World Wars I and II and which was standardized by the United States early in World War II. Composition B is a TNT-based composition and it has been considered a desirable and worthwhile goal to attempt to improve the explosive potential of the plastic-bonded types to exceed that of the best TNT-based formulations and still retain the desirable physical properties of the former. The present invention provides a formulation superior to the aforementioned conventional TNT- based explosives not only in respect to their resistance to melting at high temperatures but also in regard to physical properties and ease of processing.
The general purpose of this invention, therefore, is to provide an explosive composition for a missile warehead which can withstand the environment at the supersonic speeds to which the warhead will be subjected.
An object of this invention is to provide an explosive composition which can be used in applications involving aerodynamic heating.
Another object of this invention is to provide an explosive composition which has a reduced exotherm, is less brittle than other plastic bonded explosives, and resists cracking.
Yet another object of this invention is to provide an explosive composition which has the economic advantages of savings in time and materials used.
Other objects and the attendant advantages of this invention will be readily appreciated as the same become better understood by reference to the following detailed description.
The invention contemplates incorporating a polyester resin-coated explosive selected from the group consisting of cyclotrimethylenetrinitramine (RDX), cyclotetramethylenetetranitramine (HMX), diaminotrinitrobenzene (DATB) and others with a binder composition consisting essentially of vinyl toluene, alpha-methyl styrene and diallyl phthalate. The explosive is pre-coated with a mixture of unsaturated polyester resin sold under the tradename Laminac EPX 147-1 by American Cyanamid Company.
In preparing the formulation the liquids consisting of vinyl toluene, alpha-methyl styrene and diallyl phthalate were added to a mixing kettle then the resin-coated explosive was added and the mixture stirred until the resin dissolved and the explosive dispersed. Vacuum is usually applied to the kettle during the last portion of the mixing operation to remove entrapped air. When thoroughly mixed the batch was catalyzed. The catalyst-accelerator combination used consisted of methyl ethyl ketone peroxide in the form of 60% solution in dimethyl phthalate and cobalt naphthenate solution (6% cobalt as metal). The amounts of catalystaccelerator may be adjusted to produce the desired pot life of the composition. Acceptable results have been obtained using 0. 1% cobalt naphthenate solution and 0.5% methyl ethyl ketone peroxide solution (based on binder weight of the batch).
It is important to use this particular catalyst combination, since the use of other catalyst systems in particular, t-butyl perbenzoate, will cause the diallyl phthalate to enter into the polymerization reaction rather than acting as a plasticizer and the resulting product will lack flexibility and low shrinkage characteristics. After the catalyst has been mixed in, the material is cast into preforms or molds and allowed to stand at room temperature until gelled and cured. Heat may be applied to accelerate curing, the temperature being limited by the nature of the explosive filler.
The explosive composition should have as high an explosive content as possible, being limited by the practical consideration of processability and explosive sensitivity.
The following formulation has a detonation velocity of 8060 m/sec in 1 /8 inch-diameter and an impact sensitivity of 36 cm (as compared to Composition Bs 33 cm).
For applications where a lower detonation velocity is acceptable or desired, the binder content may be increased.
In preparing the binder, diallyl phthalate may range from 20 to 25 percent of the binder composition. Above 25% the product is too weak and below 20% it is not sufficiently flexible. When omitted from the binder, the solutility characteristics of the binder are altered to the point where phase separation occurs. The vinyl toluene contributes to reducing the shrinkage of the cross-linked polyester, but produces a vigorous exotherm. In combination with alpha-methyl styrene, the polymerization is controlled and a negligible exotherm results. The alpha methyl styrene content may vary between 25%, the 2% level being adequate without slowing down the reaction excessively.
Small samples of the explosive composition were prepared using 17, 20, 25 and 22.5% diallyl phthalate. The sample using 22.5% diallyl phthalate in the binder showed minimum cracking.
The percentage binder is important to the viscosity and processability of the composition. A total binder content of 17% produced a better detonation velocity than Composition B. Less binder than this would make it too difficult to process on a large scale and more binder would decrease its energetic properties.
Two pound samples of the present formulation and several similar formulations were cured nearly adiabatically and their temperature rises were recorded. The formulation set out above exhibited an exotherm of approximately 5 F. While the other plastic-bonded explosives showed as much as 100 F. rise.
The combination of vinyl toluene, alpha-methyl styrene and diallyl phthalate as a binder for unsaturated, styrene free polyester resin coated high explosives is new and the composition produced has superior physical properties. The diallyl phthalate, a potentially reactive monomer, acts as a solubilizing agent and plasticer.
The Laminac unsaturated polyester resin EPX 147-1 which is used to pre-coat the high explosive before mixing with the liquid binder in the formulations described herein is manufactured by American Cyanamid. It is a monomer free polyester resin consisting of a blend of the reaction products of adipic acid, maleic acid with diethylene glycol and phthalic acid, maleic acid with propylene glycol. The method of preparing the reaction products is fully described in U.S. Pat. No. 2,255,313, issued Sept. 9, 1941, which discloses preparation by reacting an alpha, beta-ethylenically unsaturated dicarboxylic acid and a glycol with or without a dicarboxylic acid free of non-benzenoid unsaturation.
The binder consisting essentially of unsaturated polyester resin, vinyl toluene, alpha-methyl styrene and diallyl phthalate is potentially useful for propellants and pyrotechnics formulations.
Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.
What is claimed is:
1. The plastic bonded explosive composition consisting essentially of Ingredients Percent by weight A high explosive Binder said explosive being a member selected from the group consisting of cyclotetramethylenetetranitramine, cyclotrimethylenetrinitramine, and diaminotrinitrobenzene;
said binder consisting of 42.4% of a blend of the reaction products of adipic acid, maleic acid with diethylene glycol and phthalic acid, maleic acid with propylene glycol; 33.1% vinyl toluene; 2% alphamethyl styrene; and 22.5% diallyl phthalate.
2. The process for the preparation of the composition of claim 1 which comprises a. pre-coating said high explosive with a blend of the reaction products of adipic acid and maleic acid with diethylene glycol, and phthalic acid and maleic acid with propylene glycol;
b. mixing together vinyl toluene, alpha-methyl styrene and diallyl phthalate to form a homogeneous liquid binder;
c. stirring said pre-coated explosive into said binder until the resin is dissolved and the explosive is dispersed thereby forming a mixture;
d. catalyzing said mixture with a solution of cobalt naphthenate and methyl ethyl ketone peroxide;
e. casting said catalyzed mixture into molds; and
f. curing said mixture at room temperature until a solid product forms.
3. A binder formulation consisting essentially of the following:

Claims (3)

1. THE PLASTIC BONDED EXPLOSIVE COMPOSITION CONSISTING ESSENTIALLY OF
2. The process for the preparation of the composition of claim 1 which comprises a. pre-coating said high explosive with a blend of the reaction products of adipic acid and maleic acid with diethylene glycol, and phthalic acid and maleic acid with propylene glycol; b. mixing together vinyl toluene, alpha-methyl styrene and diallyl phthalate to form a homogeneous liquid binder; c. stirring said pre-coated explosive into said binder until the resin is dissolved and the explosive is dispersed thereby forming a mixture; d. catalyzing said mixture with a solution of cobalt naphthenate and methyl ethyl ketone peroxide; e. casting said catalyzed mixture into molds; and f. curing said mixture at room temperature until a solid product forms.
3. A binder formulation consisting essentially of the following:
US642651A 1967-05-19 1967-05-19 Plastic bonded explosive composition Expired - Lifetime US3897283A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3968723A (en) * 1975-03-03 1976-07-13 The United States Of America As Represented By The Secretary Of The Navy Method for reclaiming and recycling plastic bonded energetic material
US4640947A (en) * 1984-06-01 1987-02-03 Diehl Gmbh & Co. Adhesive medium for the bonding of surfaces in the ammunition containing explosive charges

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3116186A (en) * 1955-10-20 1963-12-31 Jr James T Paul Explosive composition and process for fabricating weapon cases
US3269880A (en) * 1965-01-13 1966-08-30 Visnov Martin Heat resistant butadiene-acrylonitrile propellants
US3296041A (en) * 1964-07-08 1967-01-03 Eastman Kodak Co Granulated crystalline plastic bonded explosives
US3348986A (en) * 1955-02-04 1967-10-24 Charles W Sauer Process of preparing plastic coated high explosive particles and articles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3348986A (en) * 1955-02-04 1967-10-24 Charles W Sauer Process of preparing plastic coated high explosive particles and articles
US3116186A (en) * 1955-10-20 1963-12-31 Jr James T Paul Explosive composition and process for fabricating weapon cases
US3296041A (en) * 1964-07-08 1967-01-03 Eastman Kodak Co Granulated crystalline plastic bonded explosives
US3269880A (en) * 1965-01-13 1966-08-30 Visnov Martin Heat resistant butadiene-acrylonitrile propellants

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3968723A (en) * 1975-03-03 1976-07-13 The United States Of America As Represented By The Secretary Of The Navy Method for reclaiming and recycling plastic bonded energetic material
US4640947A (en) * 1984-06-01 1987-02-03 Diehl Gmbh & Co. Adhesive medium for the bonding of surfaces in the ammunition containing explosive charges

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