CA1341570C

CA1341570C - Explosive compositions

Info

Publication number: CA1341570C
Application number: CA000599369A
Authority: CA
Inventors: Deirdre Hallam; Ronald Edward Hollands
Original assignee: BAE Systems PLC
Current assignee: BAE Systems PLC
Priority date: 1988-05-11
Filing date: 1989-05-11
Publication date: 2008-03-25
Anticipated expiration: 2025-03-25
Also published as: GB2365420B; SE529845C2; FR2893614A1; SE8901693D0; GB2365420A; AU784682B1; SE8901693L; FR2893614B1; GB8811127D0

Abstract

A plastic mouldable explosive composition comprises a gelled binder and a particulate explosive filler contained in the binder, wherein the binder comprises a blend of polyethylene wax polymer together with a tackifying resin comprising a polyisobutene polymer. Desirably, the amount of the polyethylene wax polymer in the composition is in the range 2 to 35 per cent by weight, the polyethylene polymer having a molecular weight in the inclusive range 3,000 to 15,000. Desirably, the polyisobutene polymer comprises a liquid polyisobutene having a molecular weight of from 500 to 7,000.

Description

134-15r 01 -leL-EXPLOSIVE COMPOSITIONS

The present invention relates to explosive compositions, particularly plastic mouldable explosive compositions.
A known explosive composition manufactured by the present Applicants, which composition has been in service use by the UK Ministry of Defence for many years comprises RDX, a particulate high explosive filler, incorporated in a binder which comprises liquid paraffin gelled to form a grease together with other minor additives. This composition is detonator sensitive (ie does not require a booster initiation) and is a plastic material which may be moulded like putty under light pressure by the user into a desired shape eg to fill a cavity or to line an edge between mating surfaces.
This known composition suffers from the problems that the low molecular weight liquid components of the binder tend to migrate causing the composition to become brittle during its service life, the low temperature (-20 C) mouldability of the material is poor and binder ingredients tend to exude at elevw.ted temperatures.

13415~

It is the purpose of the present invention to provide a novel plastic mouldable explosive composition in which the aforementioned problems are reduced or eliminated.

According to the present invention there is provided a plastic mouldable explosive composition comprising: a binder and a particulate explosive filler contained in the binder, wherein the binder comprises a gelled blend of a polyethylene wax polymer having a molecular weight in the inclusive range 3000 to 15000 and comprising polymerised ethylene groups forming at least 50 per cent by weight of the polymer together with a tackifying resin comprising a polyisobutene polymer having a molecular weight in the inclusive range 5000 to 7000 and comprising polymerised isobutene groups forming at least 50 per cent by weight of the polymer.

By a "polyethylene polymer" is meant a polymer comprising ethylene optionally copolymerised with one or more than other compounds, the ethylene content forming desirably at least 90 per cent by weight of the polymer.

By a "polyisobutene polymer" is meant polyisobutene optionally copolymerised with one or more other compounds, the isobutene content forming desirably at least 90 per cent by weight of the polymer.

The relative proportions of the components of the binder depend upon the grades of the components employed in the blend. The most suitable amount of the polyethylene wax polymer in the blend will in many cases be in the range 2 to 35 per cent by weight especially when the polyethylene polymer has a molecular weight in the inclusive range 3,000 to 15,000.
However, the amount of the polyethylene wax polymer may be present in an amount of up to 90 per cent by weight of the blend with the tackifying resin when the polyethylene polymer has a low molecular weight, eg. in the range 3,000 to 7,000.
lwu ls, 2a Any liquid polyisobutene having a molecular weight of from 500 to 7,000, preferably from 500 to 5,000 may be used in or as the tackifying resin.

-AM

-3- 134 15i0 Preferred compositions comprise binders including polyisobutene having a molecular weight of from 500 to 5000 Ond a polyethylene having a molecular weight of from 3000 to 13000, polyisobutene forming 85 per cent by weight or more of the polyisobutene/polyethylene blend.
Optional additives to the binder blend in the explosive composition according to the present invention comprise:
(a) micrystalline wax forming up to 10 per cent by weight of the binder;
(b) a plasticiser having a viscosity of less than 50 cst preferably less than 2 cst at 20 C and having a melting point less than 0 C, the plasticiser forming up to 20 per cent by weight of the binder;
(c) an anti-oxidant forming up to 1 per cent by weight of the binder.
For example, a suitable plasticiser comprising a quantity of material selected from one or more known energetic plasticisers such as GAP (glycidyl azide polymer), BDNPA/F(bis-2,2-dinitropylacetal/formal), bis-(2,2-dinitropropyl)formal, bis (2,2,2-trinitroethyl)formal bis(2-fluoro-2,2 dinitroethyle)formal, diethylene glycol dinitrate, glycerol trinitrate, glycol trinitrate, triethylene glycol dinitrate, trimethylolethane trinitrate, butanetriol trinitrate, or 1,2,4-butanetriol trinitrate may be added to form the binder.
Alternatively, or in addition the binder may incorporate one or more known non-energetic plasticisers such as one or more esters of phthalic, adipic or sebacic acid. For example the optional plasticiser may comprise a dialkyl phthalate eg, dibutyl phthalate or diethyl phthalate or may be selected from triacetin, 13 4 1 5 7~

tricresyl phosphate, polyalkylene glycols and their alkyl ether derivatives, eg. polyethylene glycol, polypropylene glycol, diethylene glycol butylether and dioctyl sebacate.
As suitable optional anti-oxidant compounds polymerised trimethyl dihydroquinone; or 2,2'-methylene-bis (4-methyl-6-butylphenol); or peritaerythrityl-tetrakis(3,3,5-ditertbutyl-4-hydroxyp henyl)propionate may be incorporated in the binder in an extent of up to 1 per cent, eg. about 0.5 per cent, by weight of the binder.
Preferably at least 75% desirably at least 88%
by weight of the explosive filler in the composition according to the present invention is constituted by one or more heteroalicyclic nitramine compounds. Nitramine compounds are those containing at least one N-NO2 group.
Heteroalicyclic nitramines bear a rina containing N-NO2 groups. Such ring or rings may contain for example from two to ten carbon atoms and from two to ten ring nitrogen atoms. Examples of preferred heteroalicyclic nitramines are RDX(cyclo-1,3,5-trimethylene-2,4,6-trinitramine, hexagen), HMX
(cyclo-1,3,5,7-tetramethylene-2,4,6,8-tetranitramine, octogen and mixtures thereof. The filler may alternatively be selected from TATND
(tetranitro-tetraminodecalin, HNS
(hexanitrostilbene) NTO(3-nitro-1,2,4-thiazol-5one), and TATB 30 (triaminotrinitrobenzene).
Preferably, the explosive filler comprises from 50% to 100% by weight of RDX.
Other highly energetic filler materials may be used in place of or in addition to the compounds specified above. Examples of other suitable known highly energetic materials include picrite (nitroguanidine), aromatic nitramines such as ;7 3 4 1 5 7~1 tetryl, ethylene dinitramine, and nitrate esters such as nitroglycerine (glycerol trinitrate), butane triol trinitrate or pentaerythritol tetranitrate, trinitrotoluene (TNT), inorganic oxidisers such as ammonium salts, eg. ammonium nitrate or ammonium perchlorate, and energetic alkali metal and alkaline earth metal salts.
Known metallic fuels such as aluminium powder may be added to form part of the energetic solids filler, eg. forming 1 to 50 per cent, eg. up to 30 per cent by weight of the total composition.
Alternative metal fuels include magnesium, magnesium/aluminiujm alloy. Metallic fuel is preferably included together with RDX or with RDX
and ammonium perchlorate.
The amount of explosive filler incorporated in the binder in the composition according to the present invention depends upon the amount of the filler required to convert the binder from a gel into a plastic mouldable mass but the explosive filler content is conveniently in the range 50 to 95 per cent by weight, desirably 85 to 90 per cent by weight, of the explosive composition.
In the case where the explosive is RDX and the metallic fuel comprises aluminium, the metallic fuel preferably comprises up to 30 per cent by weight of the total composition, being up to 52 per cent by weight of the energetic filler in compositions having up to 88 per cent by weight solids loading.
The compositions according to the present invention may be made by adding the polyethylene to the polyisobutene and other optional ingredients at a temperature above the melting point of the polyethylene and then mixing the two together until a homogeneous liquid is produced. The explosive 1~4'5 70 filler is then added as a powder optionally in a water wet condition and optionally with a suitable single organic solvent added to the binder to facilitate processing. Following further stirring to give a further homogeneous mass the product is cast, pressed, extruded or rolled as appropriate into suitable shapes which are allowed to cool to room temperature (25 C).
A compatible coupling agent, in an extent of up to 2 per cent by weight of the overall composition, may be added during mixture of the filler with the binder to improve adhesion between the two.
Examples of suitable coupling agents are:
(1) silane coupling agents eg (i) 1,2-ethane-diamine, N-(ethynylphenylmethyl)-- N-(3-trimethoxysilyl)propylmonohydrochloride or (ii) CH2:CHSi(OCH2CH2OCH3)3 (2) organotitanate coupling agents eg isopropyltri (dioctylphosphate)titanate.
A compatible surfactant in an extent of up to 2 per cent by weight of the overall composition may be added to improve workability. Examples of suitable surfactants include eg. (i) lecithin, (ii) polyoxyethylene(20)sorbitan esters, eg monolaurate, monopalmitate or mono-oleate; or (iii) dioctyl ester of sodium sulphonic acid or (iv) pentaerythritoldioleate (PEDO).
A compatible dye, in an extent of up to 0.5%
by weight of the overall composition, may be added during mixture of the filler with the binder as an aid to concealment.
Explosive compositions embodying to the present invention show useful moulding properties similar to those shown by the known material mentioned above, but advantageously show reduced migration of liquid binder components (and hence brittleness) with ageing, reduced exudation at elevated temperatures and improved low temperature mouldability.
in addition, the hydrophobic nature of the binder imparts greater stability, adhesion and workability when the explosive compositions are used underwater.
Examples of the preparation and properties of compositions embodying the present invention will now be described by way of example as follows.
Various suitable materials (the 'gelled binder" specified above) were first prepared by the following method, Method A
Method A
Polyisobutene (PIB), and other optional ingredients such as plasticisers and antioxidants but not the polyethylene were added to a mixing vessel at room temperature (20 C). The vessel was heated to a temperature of 1400 C, slow stirring being applied at temperatures above 80 C.
When the temperature reached 115-120 C
polyethylene was added in increments to form a homogenous fluid.
The composition formed was cast into moulds or storage vessels and allowed to cool Explosive compositions were prepared from the resulting binder materials produced by Method A
according to either of the alternative Method B, Method C or Method D as follows.
An incorporator was heated to a temperature of 95-100 C:
Method B
The binder material was dissolved in an equal mass of solvent by heating at 60-80 C with stirring to form a suitable lacquer.

-s- 13 4 5 7 0 The explosive filler eg RDX, including any optional additives such as coupling agent but not metallic fuel, was provided in a water wet condition in a mixer which was heated to a suitable elevated temperature, eg. 80-95 C for RDX.
Binder lacquer was then added carefully followed by stirring with heating then cooling and drying.
After removal of water and solvent, any required metallic fuel, eg powdered aluminium, was added.
Method C
An incorporator was preheated at a temperature of 85 to 950 C. Increments of the solid explosive filler in water wet form and the binder were added at intervals followed by mixing of the ingredients after each addition. Water was removed optionally under vacuum and the mixture stirred until homogeneous. The mixture was cooled optionally under vacuum to room temperature stirring being continued during cooling, and then stored in a container for use.
Method D
About one half of the binder ingredients were added to an incorporation preheated to a temperature of 95-100 C.
A first increment of wetted nitramine was added and mixed for about 15 minutes at atmospheric pressure, allowing water to evaporate.
Further increments of wetted nitramine were added each being allowed to incorporate for 10-15 minutes before addition of the next. Loose powder of unmixed composition between additions was scraped down.
When all explosive has been added aluminium was put in if required, allowing each increment to incorporate for approximately 10 minutes with scraping down between additions.

-9- 1 34 1 57 n The remaining presoftened binder was poured and then incorporated for approximately 1 hour with scraping down every 15-20 minutes. A vacuum was applied if required to ensure complete removal of water.
The material was removed from the mixer either whilst hot, or after first cooling to the desired temperature whilst mixing.
If curing ingredients were to be included the material was cooled to 60-80 C, curing ingredients were added and the resultant material mixed for 15-20 minutes before removal from the incorporator.
Examples of binders made by Method A are given in Tables 1 and 2 as follows.

-10- ~ 3 4 1 570 GELLED-POLYETHYLENE BINDER SYSTEMS

TABLE 1: COMPOSITION
INGREDIENTS
Example Polyethylene Polyisobutene Antioxidant Number Type (%w/w) Type (%w/w) ($w/w) Bi P2 7.5 PIB1 92.0 0.5 B2 P2 7.5 PIB2 92.0 0.5 B3 P2 7.5 PIB2 92.0 0.5 B4 P2 20.0 PIB3 92.0 0.5 B5 P2 22.0 PIB3 77.5 0.5 B6 P2 25.0 PIB3 74.5 0.5 B7 P2 27.0 PIB3 72.5 0.5 B8 P2 30.0 PIB3 69.5 0.5 B9 P2 35.0 PIB3 64.5 0.5 B10 P3 89.5 PIB1 10.0 0.5 B11 P3 89.5 PIB2 10.0 0.5 B12 P3 89.5 PIB3 10.0 0.5 B13 P1 59.5 PIB1 40.0 0.5 B14 Pi 59.5 PIB2 40.0 0.5 B15 P1 59.5 PIB3 40.0 0.5 GELLED-POLYETHYLENE BINDER SYSTEMS (Continued) TABLE 1: COMPOSITION (Continued) INGREDIENTS

Example Polyethylene Polyisobutene Antioxidant DOS
Number Type (%w/w) Type (%w/w) (%w/w) B16 P2 22.0 PIB4 77.5 0.5 -B17 P2 22.0 PIB3 77.5 0.5 -B18 P1 22.0 P185 77.5 0.5 -B19 P1 22.0 PIB4 77.5 0.5 -B20 Pl 22.0 PIB3 77.5 0.5 -B21 P3 22.0 PIB5 77.5 0.5 -B22 P3 7.5 PIB3 92.0 0.5 -B23 P1 7.5 PIB3 92.0 0.5 -B24 P2 7.5 PIB1 92.0 0.5 -B25 P3 7.5 PIBl 92.0 0.5 -B26 P2 5.0 PIB1 94.5 0.5 -B27 P2 7.5 PIB3 87.0 0.5 5 B28 P2 7.5 PIB1 87.0 0.5 5 B29 P2 7.5 PIB2 92.0 0.5 -13 'F70 GELLED-POLYETHYLENE/POLYISOBUTENE BINDER SYSTEMS
TABLE 2: PROPERTIES

Example Softening Number TMD Point Penetration (g/cm3) ( C) (mm x 10-1) B1 0.906 21 273 B2 0.911 23 -B3 0.916 28 253 B4 0.915 34 218 B5 0.915 35 228 B6 0.915 94 223 B7 0.915 94 213 B8 0.915 98 200 B9 0.915 9R 178 B10 0.907 100 8 B11 0.907 101 6 B12 0.908 98 5 B13 0.906 96 11 B14 0.908 96 11 B15 0.910 101 10 1 3 4 1 57'0 GELLED-POLYETHYLENE/POLYISOBUTENE BINDER SYSTEMS (Continued) TABLE 2: PROPERTIES (Continued) Example Softening Number Point Penetration ( C) (mm x 10-1) B21 87 25 ) B29 92 22 ) In Table 1 the Antioxidant is 2,2'-methylene-bis-(4-methyl-6-butylphenol).
In Table 1 the polyethylene is as follows:
Type P1: Molecular weight n8000.
Type P2: Molecular weight n12000 Type P3: Molecular weight n4000 In Table 1 the polyisobutene type is as follows:
Type PIBl: molecular weight n1300 Type P1B2: molecular weight n2100 13 41 5 7 ~

Type PIB3: molecular weight n2400 Type PIB4: molecular weight n3800 Type PIB5: molecular weight n5800.
Type PIB6: molecular weight n780 Type PIB7: molecular weight n1000 In Table 1 DOS is the plasticiser dioctyl sebacate.
In Table 2 TMD is theoretical maximum density.
In Table 2 the softening point is measured according to the known standard ASTM D36-8 (British Standard BS4692:1972) In Table 2 the penetration is measured according to the known standard ASTM-2884-82 using a 100g weight and a 20s drop at 25 C.
Examples of explosive compositions made by Method B or C using binder materials listed in Table 1 are listed in Tables 3 and 4 as follows.

i~ 41 1 57'fl PLASTIC EXPLOSIVE COMPOSITIONS EMPLOYING
GELLED-POLYETHYLENE/POLYISOBUTENE BINDERS
TABLE 3: COMPOSITION

Explosive Binder Solids Loading Composition Example $w/w $v/v Example Number Number El B2 88.0 78.8 E2 B1 88.0 78.7 E3 B5 88.0 78.8 E4 B9 88.0 78.8 E5 B16 88.0 78.8 E6 B17 88.0 78.7 E7 B18 88.0 78.8 E8 B22 88.0 78.6 E9 B23 88.0 78.6 E10 B24 88.0 78.6 E11 B26 88.0 78.6 E12 B25 88.0 78.6 E13 B27 88.0 78.7 E14 B28 88.0 78.6 E15 B28 88.0 78.6 E16 B5 88.0 78.8 ~3 PLASTIC EXPLOSIVE COMPOSITIONS EMPLOYING
GELLED-POLYETHYLENE/POLYISOBUTENE BINDERS
TABLE 4: PROPERTIES

TMD Penetration Weight Loss (g/cm3) (mm x 10-1) on Ageing El 1.613 16 2.5 E2 1.612 30 2.1 E3 1.615 11 .18 E4 1.615 - .27 E5 1.614 - 0.46 E6 1.612 8 0.00 E7 1.614 11 -E8 1.611 10 - ) E9 1.611 22 E10 1.610 28 E11 1.610 35 E12 1.610 27 ) E13 1.612 24 E14 1.610 31 1.10 ) E15 1.610 87 ) E16 1.615 - - ) In Table 3 the solids loading comprises particulate RDX
the remainder of the explosive composition being the binder material (eg. Bl, B2 etc).
In Table 4 penetration is measured to the known standard ASTM-2284-82 using a 100g weight and a 20s drop at 25 C.

13 ~ 1 5 7 0 dxn Table 4 ageing comprises 3 months at a temperature of 60oC.
~ .,.
-At a- t1)_t tF' prn= ar*.a. a c n f ~as1-~Ytm at 250Q _ _ Examples of hazard data for Examples E14 and E15 are as follows:
E14 figure of insensitiveness: 110 (RDX = 80) Mallet Friction (steel on steel) 0%
These tests are specified in Sensitiveness Collaboration Committee (SCC) Manual No 3.

Claims

CLAIMS:

1. A plastic mouldable explosive composition comprising:
a binder and a particulate explosive filler contained in the binder, wherein the binder comprises a gelled blend of a polyethylene wax polymer having a molecular weight in the inclusive range 3000 to 15000 and comprising polymerised ethylene groups forming at least 50 per cent by weight of the polymer together with a tackifying resin comprising a polyisobutene polymer having a molecular weight in the inclusive range 5000 to 7000 and comprising polymerised isobutene groups forming at least 50 per cent by weight of the polymer.

2. A plastic mouldable explosive composition as claimed in claim 1 and wherein the polyethylene polymer comprises ethylene groups forming at least 90 per cent by weight of the polymer.

3. A plastic mouldable explosive composition as claimed in claim 1 or claim 2 and wherein the polyisobutene polymer comprises isobutene groups forming at least 90 per cent by weight of the polymer.

4. A plastic mouldable explosive composition as claimed in claim 1 and wherein the amount of the polyethylene wax polymer in the binder is in the range 2 to 35 per cent by weight.

5. A plastic mouldable explosive composition as claimed in claim 1 and wherein the polyethylene polymer has a molecular weight in the inclusive range 3,000 to 7,000 and the amount of polyethylene wax polymer in the binder is less than 90%.

6. A plastic mouldable explosive composition as claimed in claim 1 and wherein the polyisobutene wax polymer comprises a liquid polyisobutene having a molecular weight of from 500 to 5,000.

7. A plastic mouldable explosive composition as claimed in claim 1 and wherein said polyisobutene has a molecular weight of from 500 to 5000 and said polyisobutene forming 85 per cent by weight or more of the binder.

8. A plastic mouldable explosive composition as claimed in claim 1 and wherein the composition comprises as an additive to the binder one or more of the following:

(a) microcrystalline wax forming up to 10 per cent by weight of the binder;

(b) a plasticiser having a viscosity of less than 50 cst at 20°C, the plasticiser forming up to 20 per cent by weight of the binder;

(c) an anti-oxidant forming up to 1 per cent by weight of the binder.

9. A plastic mouldable explosive composition as claimed in claim 1 and wherein at least 75% by weight of the explosive filler in the composition is constituted by one or more heteroalicyclic nitramine compounds.

10. A plastic mouldable explosive composition as claimed in claim 9 and wherein the explosive filler comprises from 50%
to 100% by weight of hexahydro-1,3,5-trinitro-1,3,5-triazine based on the total weight of filler.

11. A plastic mouldable explosive composition as claimed in claim 1 and wherein the explosive filler forms from 85 to 90 per cent by weight of the explosive composition.

12. A plastic mouldable explosive composition as claimed in claim 1 and wherein the filler comprises from 1 to 52 per cent by weight of a metallic fuel based on the total weight of filler.

13. A plastic mouldable explosive composition as claimed in claim 12 and wherein the filler comprises hexahydro-1,3,5-trinitro-1,3,5-triazine as explosive and aluminium as metallic fuel, the aluminium comprising up to 52 per cent by weight of the energetic filler.

14. A plastic mouldable explosive composition as claimed in claim 1 and which comprises an explosive-to-binder compatible coupling agent in an extent of up to 2 per cent by weight of the overall composition.

15. A plastic mouldable explosive composition as claimed in claim 1 and which includes a compatible surfactant in an extent of up to 2 per cent by weight of the overall composition.

16. A plastic mouldable explosive composition as claimed in claim 1 and including a compatible dye, in an extent of up to 0.5 per cent by weight of the overall composition.