PT89763B

PT89763B - PROCESS FOR THE PREPARATION OF NEW EXPLOSIVE COMPOSITIONS IN EMULSION

Info

Publication number: PT89763B
Application number: PT8976389A
Authority: PT
Inventors: Agustin Gonzalez Ocejo; Jose Ramon Quintana Angulo
Original assignee: Union Explosivos Rio Tinto
Priority date: 1988-07-27
Filing date: 1989-02-20
Publication date: 1995-01-31
Also published as: EP0352396B1; EP0352396A1; PT89763A; ES2037870T3; DE3876798T2; DE3876798D1

Abstract

The invention provides a novel explosive composition in emulsion, comprising an oxidizing agent, a fuel, an emulsifying agent and a polymer structure which envelopes the discontinuous oxidizing phase, supplementing the interfacial structure of the emulsifying system -- used. The invention also provides a method for their preparation consisting in forming an aqueous solution of oxidizing salts and of one or more low molecular-weight organic monomers capable of polymerizing by - - addition. The aqueous solution is emulsified in a fuel in the presence of the emulsifying agent so as subsequently to bring about polymerization, straight-chain or cross linking polymerization of the monomers. Polymerization occurs basically at the interface and adjacent areas, producing an enveloping macrostructure - - which increases the stability of the emulsion.

Description

MEMÓRIA DESCRITIVADESCRIPTIVE MEMORY

A presente invenção refere-se a um processo pa ra a preparaçao de composiçoes explosivas em emulsão do tipo água em óleo, assim como às próprias composiçoes que se obtêm. As referidas composiçoes compreendem como fase contínua um combustível orgânico, e como fase descontínua uma solução aquosa que contêm, entre outros componentes, sais oxidantes.The present invention relates to a process for the preparation of explosive water-in-oil emulsion compositions, as well as the compositions that are obtained. Said compositions comprise an organic fuel as a continuous phase and an aqueous solution as a discontinuous phase containing, among other components, oxidizing salts.

As composiçoes explosivas do tipo emulsão água em óleo têm vindo a ser empregues profusamente, graças ao facto de combinarem bons resultados com uma grande seguran ça na sua utilização.Explosive compositions of the water-in-oil emulsion type have been used extensively, thanks to the fact that they combine good results with great safety in their use.

No entanto, e devido principalmente ao facto de se basearem na dispersão de um volume relativamente grande de fase aquosa numa fase contínua oleosa, apresentam—se muito frequantemente problemas de estabilidade que têm sido resolviHowever, and mainly due to the fact that they are based on the dispersion of a relatively large volume of aqueous phase in a continuous oily phase, stability problems that have been solved very often arise.

BAD ORIGINAL dos à custa da perda de eficêcia noutros aspectos.ORIGINAL BAD at the expense of loss of efficiency in other respects.

Assim, em diversos casos, recorreu—se ao uso de polímeros de natureza diferente como componentes da fase oleosa, melhorando a estabilidade da emulsão e das bolhas de ar oclusas na mesma quando este foi o processo utilizado para a sua sensibilização, através do efeito dos referidos polímeros nas propriedades reolfigicas da fase continua. Como invenções com esta finalidade podemos destacar!Thus, in several cases, the use of polymers of different nature was used as components of the oil phase, improving the stability of the emulsion and the air bubbles occluded in it when this was the process used for its sensitization, through the effect of said polymers in the reolfigic properties of the continuous phase. As inventions for this purpose we can highlight!

Patente americana 4 548 660. Nesta patente con templa—se a adiçao à fase oleosa de um polímero do grupo formado por resinas epoxi, resinas de poliéster insaturado, poli buteno, poliisobutileno, resina de petróleo, resina de buta— dieno e copolímeros etileno—acetato de vinilo.American patent 4,548,660. This patent includes the addition to the oil phase of a polymer of the group formed by epoxy resins, unsaturated polyester resins, poly butene, polyisobutylene, petroleum resin, buta resin - diene and ethylene copolymers— vinyl acetate.

Patente americana 4 470 855· Nesta patente re vela—se a incorporação ao componente oleoso principal ( cera de parafina) de um polímero que contêm etilo como modificador da reologia.US patent 4 470 855 · In this patent, the incorporation into the main oil component (paraffin wax) of a polymer containing ethyl as a rheology modifier.

Patente americana 4 486 505· Com a mesma fina lidade que no caso anterior esta Patente apresenta a incorporação na fase oleosa de copolímeros de acrilato e metacrilato e copolímeros olefínicos.American patent 4 486 505 · With the same finesse as in the previous case, this patent presents the incorporation in the oil phase of acrylate and methacrylate copolymers and olefinic copolymers.

Patente britânica 2 098 976. Neste caso a fase oleosa ê constituída por copolímeros acrilonitrilo—acrilato de butilo ou acetato de vinilo—etilo, ou ainda por uma mis tura de ambos, conjuntamente com combustíveis tradicionais.British patent 2,098,976. In this case, the oil phase consists of acrylonitrile copolymers — butyl acrylate or vinyl acetate — ethyl, or even a mixture of both, together with traditional fuels.

Patente americana 4 343 668. Neste caso a fase combustível contínua ê formada por um polímero que pode re ticular—se para dar uma resina termoestávei.American patent 4,343,668. In this case, the continuous fuel phase is formed by a polymer that can be reticulated to give a thermostable resin.

Patente americana 4 525 225- Nesta Patente, e no seguimento do anteriormente descrito, a fase oleosa empre—US Patent 4,525,225- In this patent, and in line with the foregoing, the oil phase employed

BAD ORIGINALORIGINAL BAD

gue ê uma mistura de poliéster e estireno.which is a mixture of polyester and styrene.

Em todos os casos o aumento da estabilidade do sistema que se consegue ê sempre acompanhado por uma variaÇao drástica nas propriedades reoiógicas, o que limita o âmbito de aplicaÇao das composiçoes obtidas.In all cases the increase in the stability of the system that is achieved is always accompanied by a drastic variation in the rheological properties, which limits the scope of application of the obtained compositions.

Com a finalidade de estabilizar directamente as próprias gotas da fase aquosa dispersa foi já descrita (Pa tente americana 4 602 970) a polimerizaçao do emulsionante de modo que pudessem reunir—se assim as moléculas de emulsionan— te adjacentes na interface. No entanto os resultados práticos que se obtêm nao representam uma grande melhoria com respeito ao que já ê conhecido, visto que se utilizaram emulsões tradi cionalmente empregues que cumprem esta condição, resultam inapropriadas para a polimerizaçao. Com efeito estes emulsionan tes sao derivados dos ácidos oleico, linoleico e linoiênico e apresentam as duplas ligações a meio das moléculas, que constam de 18 átomos de carbono. Como se sabe, a reactividade da dupla ligaÇao diminui ao diminuir o carácter polar da molécula e ao distanciar—se a dupla ligaçao dos extremos da molécula- Por esse motivo tirna—se muito difícil a polimerizaçao dos emulsionantes convencionalmente empregues em emulsões explosi vas até ao ponto de formarem uma macroestrutura que estabilize as gotas dispersas de modo eficaz, pelo que a melhoria do comportamento conseguidas sao muito pouco importantes.In order to directly stabilize the droplets of the dispersed aqueous phase directly, it has already been described (American patent 4 602 970) the polymerization of the emulsifier so that the adjacent emulsifying molecules at the interface could be combined. However, the practical results obtained do not represent a great improvement with respect to what is already known, since emulsions traditionally used that fulfill this condition have been used, are inappropriate for polymerization. In fact, these emulsifiers are derived from oleic, linoleic and lininoic acids and have double bonds in the middle of the molecules, which consist of 18 carbon atoms. As is known, the reactivity of the double bond decreases by decreasing the polar character of the molecule and by distancing itself - by double bonding the ends of the molecule- For this reason it becomes very difficult to polymerize the emulsifiers conventionally used in explosive emulsions up to point of forming a macrostructure that effectively stabilizes the dispersed droplets, so the improvement in behavior achieved is very minor.

objectivo da presente invenção ê uma nova composição explosiva em emulsão que apresenta uma estabilidade superior âs emulsões explosivas existentes sem necessidade de variar consideravelmente as suas condiçoes reoiógicas nem os métodos de fabricaçao. Esta nova composição explosiva em emulsão apresenta uma macroestrutura polimérica hidratada que envolve a fase oxidante aquosa e que está localizada nas proximidades da camada interfacial criada pelo sistema de emulsionante. A criaÇao desta macroestrutura compreende um novo método para a formaÇao d_a composição explosiva final. Este méThe object of the present invention is a new explosive emulsion composition that has a stability superior to the existing explosive emulsions without the need to vary considerably their rheological conditions or the manufacturing methods. This new explosive emulsion composition features a hydrated polymeric macrostructure that surrounds the aqueous oxidizing phase and is located in the vicinity of the interfacial layer created by the emulsifier system. The creation of this macrostructure comprises a new method for the formation of _the final explosive composition. This method

BAD ORIGINAL ³ L......ORIGINAL BAD ³ L ......

todo consiste em adicionar à solução aquosa um ou mais compos tos orgânicos de baixo peso molecular, susceptíveis de poiime rizar por adiçao, e que denominaremos monômeros. Estes monóme ros polimerizam-se in situ uma vez formada a emulsão. A poli— merizaçao tem lugar predominantemente na região interfacial da emulsão e zonas próximas do interior das gotas» visto que sen do os monómeros produtos orgânicos, têm uma certa afinidade para a fase orgânica continua. Estes monómeros apresentam ligações duplas nos extremos da molécula que os tornam suscepti veis de polimerizar via radical. A iniciaÇao da polimerização faz—se de preferência por meio de um iniciador químico, embora sejam possíveis outros tipos de iniciaÇao, como a térmica ou a fotoquímica·the whole consists of adding to the aqueous solution one or more organic compounds of low molecular weight, susceptible to polymerize by addition, which we will call monomers. These monomers polymerize in situ once the emulsion is formed. Polymerization takes place predominantly in the interfacial region of the emulsion and in areas close to the interior of the droplets »since monomers organic products, have a certain affinity for the continuous organic phase. These monomers have double bonds at the ends of the molecule that make them susceptible to radical polymerization. The initiation of polymerization is preferably done by means of a chemical initiator, although other types of initiation are possible, such as thermal or photochemical ·

Devido â natureza orgânica dos monómeros a po limerizaÇao tem lugar fundamentalmente na interface e zonas próximas, originando uma macroestrutura envolvente de certa espessura que aumenta a estabilidade da emulsão sem influir apenas na sua viscosidade. A estabilidade desta macroestrutu— ra pode ser aumentada mediante a utilizaÇao de monómeros com mais do que uma dupla ligaÇao ou com grupos funcionais adequa dos que permitam uma reticulaÇao química.Due to the organic nature of the monomers, the limerization takes place fundamentally at the interface and nearby areas, creating an enveloping macrostructure of a certain thickness that increases the stability of the emulsion without affecting only its viscosity. The stability of this macrostructure can be increased through the use of monomers with more than one double bond or with suitable functional groups that allow chemical crosslinking.

A adiçao de monómeros à fase aquosa, em vez de polímeros, apresenta adicionalmente outras vantagens devido ao pequeno peso molecular do monómero face ao do polímero. As emulsões tendem a formar—se com menor tamanho de gotas, dado que a fase aquosa contendo o monómero apresenta uma viscosida de muito menor do que a que apresentaria se se tivesse adicio nado o polímero já formado. A presença do monómero favorece inclusivamenxe a formaçao de gotas de menor tamanho, visto que sendo solúvel tanto em água como num grande número de compostos orgânicos, aumenta em certa extensão a compatibilidade da fase aquosa-e oleosa, ajudando desta forma à forfliaÇao da emul sao ·The addition of monomers to the aqueous phase, instead of polymers, has additional advantages due to the small molecular weight of the monomer compared to that of the polymer. Emulsions tend to form with a smaller droplet size, since the aqueous phase containing the monomer has a much lower viscoside than it would have if the already formed polymer had been added. The presence of the monomer even favors the formation of smaller droplets, since being soluble in water as well as in a large number of organic compounds, it increases to a certain extent the compatibility of the aqueous-and oily phase, thus helping to emulate the emulsion. ·

As composiçoes explosivas em emulsão do tipo água em óleo da presente invenção podem apresentar um amploThe water-in-oil emulsion explosive compositions of the present invention can have a wide range of

- 4 - BAD OR/Gímal intervalo de viscosidade e podem ser usadas a granel ou embaladas em cartuxos de diâmetros de 25 mm ou superior, e apresentando sensibilidade ao multiplicador e ao detonador num e noutro caso, respectivamente.- 4 - BAD OR / Gímal viscosity range and can be used in bulk or packaged in cartridges with diameters of 25 mm or greater, and presenting sensitivity to the multiplier and detonator in both cases, respectively.

A emulsão ê constituida por uma fase continua cujos componentes sao um ou vérios combustíveis de hidrocarbo netos, e uma fase descontinua constituida por uma solução so— bressaturada de sais inorgânicos oxidantes e uma macroestrutu ra polimérica que ê criada uma vez formada a emulsão, mediante a polimerizaçao dos monómeros, parcial ou totalmente soló veis em égua, que tenham sido adicionados à solução aquosa an tes de formar—se a emulsão. A emulsão ê originada por meio de um sistema emulsionante e posteriormente adicionam—se agentes sensibilizantes.The emulsion consists of a continuous phase whose components are one or more hydrocarbon fuels, and a discontinuous phase consisting of a saturated solution of oxidizing inorganic salts and a polymeric macrostructure that is created once the emulsion is formed, by means of the emulsion. polymerization of monomers, partially or totally soluble in water, which have been added to the aqueous solution before the emulsion is formed. The emulsion is originated by means of an emulsifying system and afterwards sensitizing agents are added.

Os sais oxidantes inorgânicos utilizados nesta invenção sao do tipo de nitratos, cloratos e percloratos de amónio, de metais alcalinos e alcalinoterrosos. Estes sais podem ser utilizados isoladamente ou misturando 2 ou mais deThe inorganic oxidizing salts used in this invention are of the type of ammonium nitrates, chlorates and perchlorates, of alkali and alkaline earth metals. These salts can be used alone or by mixing 2 or more

Λ *** entre eles. Os sais inorgânicos representativos sao o nitrato de amónio, o nitrato de sódio, o nitrato de potéssio, o nitra to de célcio, o nitrato de magnésio, perclorato de amónio, per clorato de sódio, perclorato de potéssio, perclorato de magné sio ou outros conhecidos na técnica aqui descrita. A quantida de segundo a qual estes sais formam parte de emulsão esté com preendida entre 30 θ 90% em peso da da composição.Entre *** among them. Representative inorganic salts are ammonium nitrate, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, ammonium perchlorate, sodium chlorate, potassium perchlorate, magnesium perchlorate or others known in the art described herein. The amount of seconds by which these salts form part of the emulsion is between 30 θ 90% by weight of that of the composition.

Preferivelmente utiliza—se uma mistura de nitrato de amónio, numa percentagem de pelo menos 50% em peso da composição total, e nitrato de sódio que faz parte da emulsão com uma percentagem que varia entre 5 e 30% e preferivelmente 10 e 20%.Preferably, a mixture of ammonium nitrate is used, in a percentage of at least 50% by weight of the total composition, and sodium nitrate that forms part of the emulsion with a percentage ranging between 5 and 30% and preferably 10 and 20%.

A quantidade de égua na fase descontínua da emulsão pode ser escolhida de acordo com a utilização que se queira dar à emulsão e pode variar entre aproximadamente 0 eThe amount of water in the discontinuous phase of the emulsion can be chosen according to the intended use of the emulsion and can vary between approximately 0 and

- 5 sad original- 5 sad original

30% em peso da composição total. Está de preferencia compreen dida entre 10 e 20%.30% by weight of the total composition. It is preferably comprised between 10 and 20%.

De acordo com a invenção adicionam—se à solução salina um ou mais produtos orgânicos que apresentam pelo menos uma dupla ligaÇao e que sao por conseguinte susceptíveis de polimerizar por adiçao. Estes produtos sao parcial ou totalmente solúveis em água e fazem parte do grupo constituido por aldeído acrílico, acrilamida, ácido acrílico, ácido meta— crllico, ácido itacônico, acrilonitrilo, alilamina, álcool ali lico, anidrido maleico, ácido crotônico, os seus corresponden tes derivados e outros de natureza química semelhante.According to the invention, one or more organic products are added to the saline solution which have at least a double bond and which are therefore susceptible to polymerization by addition. These products are partially or totally soluble in water and are part of the group consisting of acrylic aldehyde, acrylamide, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, allylamine, alcohol, maleic anhydride, crotonic acid, their corresponding derivatives and others of a similar chemical nature.

Estes produtos tomam parte na composição numa proporção que varia entre 0,1 e 10% em peso da composição total, de preferência entre 0,2 e 4%.These products take part in the composition in a proportion that varies between 0.1 and 10% by weight of the total composition, preferably between 0.2 and 4%.

Entre os monómeros solúveis totalmente em água utilizam—se de preferência aqueles que apresentam um maior po der de penetraÇao na fase oleosa.Among the monomers that are totally soluble in water, preferably those that have a higher penetration power in the oil phase are preferable.

Embora a iniciaçao da polimerizaçao possa ser realizada por meio de qualquer dos métodos existentes em poli merizaÇao via radical, ê preferível a originada por meio de iniciadores químicos que submetidos ao calor, radiações electromagnéticas ou reacçao química, experimentam uma homolítica cisão, em radicais de maior reactividade que os radicais mono méricos. Como sistemas de reacçao para produzir radicais podem empregar—se os seguintes:Although the initiation of polymerization can be carried out by means of any of the existing methods in radical polymerization, it is preferable to that originated by chemical initiators that submitted to heat, electromagnetic radiation or chemical reaction, experience a homolytic fission, in radicals of greater reactivity than monomeric radicals. As reaction systems to produce radicals the following can be used:

— Decomposição térmica, que se aplica geralmente a compostos orgânicos peróxidos ou azo, por exemplo: peróxido de benzoilo, peróxido de dicumilo, peróxido de metiietilceto na , ,</—azobisisobutironitrilo. Esta decomposição pode ser acelerada por meio dos catalisadores apropriados.- Thermal decomposition, which generally applies to organic peroxide or azo compounds, for example: benzoyl peroxide, dicumyl peroxide, methyl ethyl peroxide na,, </ - azobisisobutyronitrile. This decomposition can be accelerated by means of the appropriate catalysts.

— Decomposição fotolítica, que ê aplicável a iodetos e al— quilos de metais, e compostos azo como o azobisisobutiro—- Photolytic decomposition, which is applicable to iodides and alkalis of metals, and azo compounds such as azobisisobutyr—

- 6 dad original nitrilo — Reacções redox, como por exemplo a reacçao entre o iao fer roso e o peróxido de hidrogénio. Os peróxidos de alquilo podem ser utilizados em vez do peróxido de hidrogénio.- 6 original nitrile dad - Redox reactions, such as the reaction between ferrous ion and hydrogen peroxide. Alkyl peroxides can be used instead of hydrogen peroxide.

— PersulfatoS) que se decompoem em fase aquosa, por exemplo persulfato de potássio e persulfato de amónio.- PersulfateS) that decompose in an aqueous phase, for example potassium persulfate and ammonium persulfate.

A polimerização pode iniciar-se tanto a partir da fase aquosa como a partir da fase oleosa. No primeiro caso utilizam—se geralrnente as reacções redox e persulfatos. No caso da iniciaçao na fase continua oleosa utiliza—se geral mente a decomposição térmica ou fotolítica dos iniciadores qui micos, de preferência a térmica.Polymerization can begin either from the aqueous phase or from the oil phase. In the first case, redox and persulfate reactions are generally used. In the case of initiation in the continuous oily phase, thermal or photolytic decomposition of chemical initiators is generally used, preferably thermal.

A emulsão deve ser formada antes que a polime rizaÇao se tenha iniciado.The emulsion must be formed before polymerization has started.

Se se iniciar a partir da fase oleosa o iniciador pode ser adicionado sem qualquer restrição em qualquer momento depois da formaçao da emulsão. Esta forma de iniciação permite—nos restringir de forma simples a polimerização á região interfacial. No caso de o iniciador ser adicionado à fa se aquosa a concentração de monómero e iniciador devem ser· tais que a emulsão se forme antes que o processo de polimeri— zaÇao adquira um progresso importante. Por meio de uma escolha apropriada da concentração de monómero , concentração do iniciador, temperatura e concentraÇao do catalisador, é possi vel para qualquer especialista conseguir que a polimerizaÇao se dê essencialmente num intervalo razoavelmente curto de tem po de formaçao da emulsão.If starting from the oil phase, the initiator can be added without any restrictions at any time after the formation of the emulsion. This form of initiation allows us to simply restrict polymerization to the interfacial region. In the event that the initiator is added to the aqueous phase the concentration of monomer and initiator must be such that the emulsion is formed before the polymerization process makes significant progress. Through an appropriate choice of monomer concentration, initiator concentration, temperature and catalyst concentration, it is possible for any specialist to achieve that the polymerization takes place essentially within a reasonably short interval of time for the emulsion to form.

A macroestrutura polimêrica que se origina na polimerização confere uma grande estabilidade mecânica à gota, uma vez que inibe o crescimento de cristais inorgânicos, aumentando portanto a vida da emulsão. Embora a macroestrutura se encontre localizada na zona interfacial ou zonas próximas do interior, mantêm—se dentro da gota, pelo que a sua presen—The polymeric macrostructure that originates in the polymerization gives a great mechanical stability to the drop, since it inhibits the growth of inorganic crystals, therefore increasing the life of the emulsion. Although the macrostructure is located in the interfacial zone or in areas close to the interior, they remain within the drop, so that its presence—

- 7 - BAD ORIGINAL- 7 - ORIGINAL BAD

ça nao influi nas condiçoes reolôgicas da emulsão. Por esse mo tivo um caso de especial interesse sao as emulsões às quais se exige capacidade de Vazamento, ou, o que é o mesmo,-baixa vis cosidade e/ou que sejam susceptíveis de produção por meio de técnicas que implicam baixos esforços de cisaihamento.does not affect the rheological conditions of the emulsion. For this reason, a case of special interest are the emulsions that are required for pouring capacity, or, which is the same, - low viscosity and / or that are susceptible to production through techniques that involve low shearing efforts. .

Àparte a localizaçao específica do polímero na zona periférica da gota, a adiçao do monómero à fase aquosa para o polimerizar uma vez formada a emulsão, apresenta ou tra vantagem face a adiçao inicial do polxmero a fase aquosa. Tendo em conta o grande aumento da viscosidade da fase aquosa devido à dissolução de um polímero na mesma, a substituição deste por um monómero antes de formar—se a emulsão faz aumen tar a relaçao de viscosidade fase oleosa/fase aquosa, o que origina uma diminuição no tamanho de gotas da emulsão para um mesmo esforço de cizalhamento. Isto implica uma maior estabilidade e simplicidade da emulsão ao aumentar a superfície de contacto oxidante — combustível.Apart from the specific location of the polymer in the peripheral zone of the droplet, the addition of the monomer to the aqueous phase to polymerize it once the emulsion is formed, presents or has an advantage over the initial addition of the polymer to the aqueous phase. Taking into account the great increase in viscosity of the aqueous phase due to the dissolution of a polymer in it, replacing it with a monomer before forming the emulsion increases the viscosity ratio of oil phase / aqueous phase, which results in a decrease in the emulsion droplet size for the same shearing effort. This implies greater stability and simplicity of the emulsion by increasing the oxidizing - fuel contact surface.

De acordo com a presente invenção, o emulsio— nante pode ser qualquer dos tipos normalmente utilizados nesta ciasse de emulsões e pode ser utilizado isoladamente ou em combinação. Estes emulsionantes podem incluir por exemplo ésteres de ácidos gordos de sorbitano, tais como sesquioleato de sorbitano, monooleato de sorbitano, monopalmitato de sorbi tano, monoestearato de sorbitano, trioieato de sorbitano, e triestearato de sorbitano. Também se inclui polioxietileno— -sorbitano, ésteres alquílicos de ácidos gordos de lanolina, ésteres de polialquilenos, oxazolinas substituídas, ésteres fosfato de álcoois gordos, amidas de aicanois gordos, éteres gordos etoxilados, lecitina de soja, derivados de lanolina, mono e diglicêridos de ácidos gordos, sais de ácidos gordose aminas gordas, entre outros.According to the present invention, the emulsifier can be any of the types normally used in this emulsion class and can be used alone or in combination. These emulsifiers may include, for example, sorbitan fatty acid esters, such as sorbitan sesquioleate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioieate, and sorbitan tristearate. Also included are polyoxyethylene sorbitan, alkyl esters of lanolin fatty acids, polyalkylene esters, substituted oxazolines, fatty alcohol phosphate esters, fatty amide amides, ethoxylated fatty ethers, soy lecithin, lanolin derivatives, mono and diglycerides fatty acids, salts of fatty acids, fatty amines, among others.

Nos casos em que o emulsionante apresenta du— pias ligações na sua molécula este pode entrar tomando parte na macroestrutura originada na polimerização, Geralmente obtém _o BAD ORIGINAL ~ ⁸ . __________à —se uma emulsificaçao aceitável quando o emuisionante constitui 0,1 a 6% e de preferência 0,2 a 4%, e particularmente pre ferível de 0,5 a 3% em peso da composição explosiva total.In cases where the emulsifier has du- sinks bonds in its molecule this may enter caused taking part in the macrostructure in the polymerization, usually obtained BAD ORIGINAL ~ ^8. __________ à —is an acceptable emulsification when the emulsifier constitutes 0.1 to 6% and preferably 0.2 to 4%, and particularly preferable from 0.5 to 3% by weight of the total explosive composition.

Para os fins da presente invenção a fase contínua orgânica hidrófoba da emulsão ”água em óleo, consiste normalmente num hidrocarboneto ou combustível de carbono de origem mineral, animal ou vegetal, liquido ou sólido à temperatura ambiente (sendo neste caso um liquido nas condiçoes de formaçao da emulsão).For the purposes of the present invention, the continuous hydrophobic organic phase of the water-in-oil emulsion normally consists of a hydrocarbon or carbon fuel of mineral, animal or vegetable origin, liquid or solid at room temperature (in this case being a liquid under formation conditions) emulsion).

Entre os compostos orgânicos apropriados incluem—se hidrocarbonetos aromáticos e alifáticos saturados e insaturados e os seus derivados, bem como misturas de qualqua quer destes. Entre os compostos preferidos incluem—se óleos minerais, óleos diesel, óleo e cera de parafina, destilados do petróleo, benzeno, tolueno, xilenos, óleo de soja epoxida— do, dinitrotolueno e misturas dos mesmos. Tambám com a finali dade de controlar a reologia do sistema podem adicionar—se ce ras à fase orgânica continua. Em geral a fase orgânica continua total corresponde a valores entre 1 e 20%, de preferência entre 2 e 10% em peso, da composição explosiva total.Suitable organic compounds include saturated and unsaturated aromatic and aliphatic hydrocarbons and their derivatives, as well as mixtures of any of these. Preferred compounds include mineral oils, diesel oils, paraffin oil and wax, petroleum distillates, benzene, toluene, xylenes, epoxy soybean oil, dinitrotoluene and mixtures thereof. Also, for the purpose of controlling the rheology of the system, they can be added to the continuous organic phase. In general the organic phase remains total corresponds to values between 1 and 20%, preferably between 2 and 10% by weight, of the total explosive composition.

As composiçoes da presente invenção podem incluir tambám combustíveis auxiliares ou suplementares. Entre estes incluem—se os que se podem adicionar à fase aquosa como sejam! glucose, sacarose, fructose, maltose, melaços, glicois formamida, ureia, hexametileno—tetramida, nitrato de metilami na, nitrato de hexametileno—tetramina e outros nitratos orgânicos. Também como combustíveis suplementares se incluem materiais sólidos em forma de partículas como carvao , grafite, enxofre, alumínio, magnésio e percloratos.The compositions of the present invention can also include auxiliary or supplementary fuels. These include those that can be added to the water phase as they are! glucose, sucrose, fructose, maltose, molasses, glycosyl formamide, urea, hexamethylene — tetramide, methylamine nitrate, hexamethylene nitrate — tetramine and other organic nitrates. Also as supplementary fuels, solid particulate materials such as coal, graphite, sulfur, aluminum, magnesium and perchlorates are included.

As quantidades de combustível suplementar podem variar de acordo com as características que se queiram dar à emulsão explosiva finai, mas em geral está compreendida entre 0 e 20%, de preferência entre 0,5 e 10% em peso da com- 9 SAD ORIGINAL posição explosiva totalThe quantities of supplementary fuel may vary according to the characteristics that you want to give to the final explosive emulsion, but in general it is comprised between 0 and 20%, preferably between 0.5 and 10% by weight of the com- 9 SAD ORIGINAL position total explosive

De acordo com a presente invenção a composição explosiva também compreende um componente gasoso descontí nuo com a finalidade de aumentar a sua sensibilidade e ao mes mo tempo diminuir a sua densidade até valores compreendidos preferivelmente entre 0,7 e 1,4 g/cm^. As bolhas de ar ou gás podem ser incorporadas na composição explosiva por meio de mis tura de partículas ocas tais como microesferas de vidro,micro esferas de resina, partículas porosas tais como perlite e tam bêm por meio de agitaçao mecânica, injecção ou o borbulhar de gás através da composição, ou por meio da produção química de gás in situ com auxílio de produtos tais como peróxido de hidrogénio, nitrito de sódio, carbonato de sódio, N,N’-dinitro— so-pentametilenotetramina, ácido nitroso ou os seus sais que se decompoes em soluçoes ácidas e agentes espumantes orgânicos, tais como compostos dinitrosos e diisocianatos. 0 componente gasoso é normaimente adicionado à emulsão durante o arrefecimento e faz parte da emulsão numa proporção que varia entre 0,01 e 60% em volume da composição explosiva final.According to the present invention the explosive composition also comprises a gaseous batch component in order to increase its sensitivity and at the same time decrease its density to values preferably between 0.7 and 1.4 g / cm3. Air or gas bubbles can be incorporated into the explosive composition by mixing hollow particles such as glass microspheres, resin microspheres, porous particles such as perlite and also by mechanical agitation, injection or bubbling. gas through composition, or through chemical production of gas in situ with the aid of products such as hydrogen peroxide, sodium nitrite, sodium carbonate, N, N'-dinitro— so-pentamethylenetetramine, nitrous acid or its salts that decompose in acidic solutions and organic foaming agents, such as dinitrous compounds and diisocyanates. The gaseous component is usually added to the emulsion during cooling and forms part of the emulsion in a proportion ranging from 0.01 to 60% by volume of the final explosive composition.

As composiçoes explosivas da presente invenção podem utilizar—se tanto a granel como encartuxadas em diâ metros de 25 mm ou superiores, consoante a viscosidade e os componentes apropriados adicionados.The explosive compositions of the present invention can be used both in bulk and packaged in diameters of 25 mm or greater, depending on the viscosity and the appropriate components added.

A invenção ê elucidada pelos exemplos que se seguem, que de modo algum sao limitativos, e nos quais as per centagens estão expressas em peso.The invention is elucidated by the following examples, which are by no means limiting, and in which the percentages are expressed by weight.

EXEMPLO 1EXAMPLE 1

Com a finalidade de demonstrar as vantagens que apresentam as composiçoes explosivas em emulsão água em óleo da presente invenção face às emulsões explosivas a granei conhecidas, prepararam—se e ensaiaram—se 10 composiçoes diferentes (quadro 1).In order to demonstrate the advantages of the explosive water-in-oil emulsion compositions of the present invention over the known bulk explosive emulsions, 10 different compositions were prepared and tested (Table 1).

BAD ORIGINALORIGINAL BAD

A composição 1 corresponde a uma emulsão explosiva convencional e foi preparada e ensaiada de acordo com o seguinte esquema operativo:Composition 1 corresponds to a conventional explosive emulsion and was prepared and tested according to the following operating scheme:

Uma mistura de nitrato de amónio (59,70 partes), nitrato de sódio (l8,35 partes) e água (Ι3,θθ partes) foi aquecida a 70°C, agitando—se vigorosamente atê se formar uma solução aquosa. Esta solução aquosa foi adicionada à refe rida temperatura, com agitaçao rápida» a uma solução de - mono— oleato de sorbitano (1,40 partes) em óleo de parafina (5,25 partes). Prolongou—se a agitaçao atê se obter uma emulsão uni forme. Posteriormente adicionaram—se microesferas de vidro (1,50 partes) e misturaram—se atê obter uma mistura homogénea. A densidade da mistura final a 25°C era de 1,25 g/cm^ e a vis cosidade era de 653 Ρ· A velocidade de detonaÇao a 5°C, confi nada em ferro com um diâmetro de 50 ^mm e iniciada com um multiplicador de 17 g de pentrite foi de 4700 m/s. A emulsão foi armazenada a 10°C e periodicamente foi submetida ao ensaio descrito. A emulsão falhou depois de 5 semanas.A mixture of ammonium nitrate (59.70 parts), sodium nitrate (1.88 parts) and water (Ι3, θθ parts) was heated to 70 ° C, stirring vigorously until an aqueous solution was formed. This aqueous solution was added at said temperature, with rapid stirring, to a solution of sorbitan mono-oleate (1.40 parts) in paraffin oil (5.25 parts). Stirring was continued until a uniform emulsion was obtained. Subsequently, glass microspheres (1.50 parts) were added and mixed until a homogeneous mixture was obtained. The density of the final mixture at 25 ° C was 1.25 g / cm2 and the viscosity was 653 Ρ · The detonation speed at 5 ° C, relied on iron with a diameter of 50 ^mm and started with a multiplier of 17 g of pentrite was 4700 m / s. The emulsion was stored at 10 ° C and periodically subjected to the described test. The emulsion failed after 5 weeks.

A composição 2 corresponde a uma emulsão explosiva preparada de acordo com o método descrito na Patente americana n2 4 602 970.'Composition 2 corresponds to an explosive emulsion prepared according to the method described in U.S. Patent No. 4,602,970.

Repetiu—se o processo da composição 1, com ex cepçao de que a solução oleosa era composta por 1,40 partes de monooleato de sorbitano, 5,24 partes de óleo de parafina e 0,01 partes de CGít-azobisisobutironitrilo. A emulsão foi mantida a 80°C durante 1 hora. A densidade final da emulsão a 25° C era de 1,24 g/cm^ e a sua viscosidade era de 674 Ρ. A velocidade de detonaÇao, segundo o ensaio descrito no caso anterior, foi de 4600 m/s. A emulsão foi armazenada a 10°C e periodicamente foi submetida ao ensaio descrito. A emulsão falhou depois de 7 semanas.The process of composition 1 was repeated, except that the oily solution was composed of 1.40 parts of sorbitan monooleate, 5.24 parts of paraffin oil and 0.01 parts of CGit-azobisisobutyronitrile. The emulsion was maintained at 80 ° C for 1 hour. The final density of the emulsion at 25 ° C was 1.24 g / cm 2 and its viscosity was 674 Ρ. The detonation speed, according to the test described in the previous case, was 4600 m / s. The emulsion was stored at 10 ° C and periodically subjected to the described test. The emulsion failed after 7 weeks.

A composição 3 corresponde a uma emulsão explosiva na qual se provocou a polimerizaÇao da acrilamida na fase aquosa anteriormente à formaçao da emulsão:Composition 3 corresponds to an explosive emulsion in which the polymerization of acrylamide was caused in the aqueous phase prior to the formation of the emulsion:

BAD ORIGINALORIGINAL BAD

Uma mistura de nitrato de amónio (59,70 partes) nitrato de sódio (l8,34 partes) e água (13,30 partes) foi aquecida a 70°C agitando—se vigorosamente atê formar uma solu çao aquosa. Posteriormente adicionaram—se 1,50 partes de acri lamida e 0,01 partes de persuifato de amónio. A poiimerizaçao foi realizada com conversão total, fixando—se o fim da polime rizaçao no momento em que a viscosidade da solução aquosa se manteve constante. O valor final desta viscosidade a 70°C foi de 4 P. Esta solução aquosa quente foi adicionada mediante agitaÇao rêpida a uma solução de monooleato de sorbitano (1,40 partes) em óleo de parafina (4,35 partes). Prolongou-se a agi taÇao atê se obter uma emulsão uniforme. Posteriormente adicionaram—se microesferas de vidro (1,50 partes) e misturaram— —se atê obter—se uma mistura homogénea. A densidade da emulsão final a 25°C era de 1,24 g/cm3 e a sua viscosidade era de 601 Ρ. A velocidade de detonaçao de acordo com o ensaio já des crito foi de 4400 m/s. A emulsão foi guardada a 10°C e periodicamente foi submetida a ensaios de velocidade de detonaçao. A emulsão falhou passadas 5 semanas.A mixture of ammonium nitrate (59.70 parts) sodium nitrate (1.88 parts) and water (13.30 parts) was heated to 70 ° C while stirring vigorously until an aqueous solution was formed. Subsequently, 1.50 parts of acrylamide and 0.01 parts of ammonium persuifate were added. The polymerization was carried out with total conversion, fixing the end of polymerization at the moment when the viscosity of the aqueous solution remained constant. The final value of this viscosity at 70 ° C was 4 P. This hot aqueous solution was added by rapid stirring to a solution of sorbitan monooleate (1.40 parts) in paraffin oil (4.35 parts). Stirring was continued until a uniform emulsion was obtained. Subsequently, glass microspheres (1.50 parts) were added and mixed until a homogeneous mixture was obtained. The density of the final emulsion at 25 ° C was 1.24 g / cm3 and its viscosity was 601 Ρ. The detonation speed according to the test already described was 4400 m / s. The emulsion was stored at 10 ° C and periodically subjected to detonation speed tests. The emulsion failed after 5 weeks.

As composiçoes 4 a 10 foram preparadas deacor do com o processo da presente invenção, embora mantendo—se com ponentes semelhantes na medida do possível:Compositions 4 to 10 were prepared according to the process of the present invention, while maintaining similar components as far as possible:

Composição 4:Composition 4:

Uma mistura de nitrato de amónio (59,70 partes), nitrato de sódio (i8,35 partes) ecrilamida (i,50 partes) e água (13,30 partes) foi aquecida a 80°C agitando-se vigorosamente atê se formar uma solução aquosa. Esta solução aquosa foi adicionada à mesma temperatura, com agitaçao rápida, a uma solução oleosa constituída por 1,40 partes de monooleato de sorbitano, 4,24 partes de óleo de parafina e 0,01 partes de Λ , (fv azobisisobutironitrilo. A emulsão foi mantida a 80°C durante i hora. Posteriormente adicionaram—se à emulsão 1,50 partes de microesferas de vidro. A densidade final da emulsão a 25°C era de 1,25 g/cm^ e a sua viscosidade era de 735 Ρ· A bad originalA mixture of ammonium nitrate (59.70 parts), sodium nitrate (i8.35 parts) ecrilamide (i, 50 parts) and water (13.30 parts) was heated to 80 ° C while stirring vigorously until it formed an aqueous solution. This aqueous solution was added at the same temperature, with rapid stirring, to an oily solution consisting of 1.40 parts of sorbitan monooleate, 4.24 parts of paraffin oil and 0.01 parts of Λ, (fv azobisisobutyronitrile. The emulsion it was kept at 80 ° C for 1 hour, then 1.50 parts of glass microspheres were added to the emulsion, the final density of the emulsion at 25 ° C was 1.25 g / cm2 and its viscosity was 735 Ρ · A bad original

ensaio já descrito era de a 10°C e periodicamente foi de detonaçao descrito.A emui 30 semanas.assay already described was at 10 ° C and periodically described was detonation.A in 30 weeks.

velocidade de detonaçao segundo o 5500 m)s. A emulsão foi armazenada submetida ao ensaio de velocidade sao continuou a detonar depois dedetonation speed according to 5500 m) s. The emulsion was stored subjected to the sound velocity test and continued to detonate after

Composição 5^: Composition 5 ^:

Uma mistura de nitrato de amónio (59»70 partes) nitrato de sódio (18,35 partes) e água (Ι3»3θ partes) foi aquecida a 70°C agitando-se vigorosamente atê se formar uma solução aquosa· Posteriormente adicionaram—se 1»5θ partes de acrilamida e 0,01 partes de persulfato de amónio e adicionou— —se imediatamente esta solução aquosa final à mesma temperatu ra e com agitaÇao rápida, a uma solução oleosa constituída por 1,40 partes de monooleato de sorbitano e 4,25 partes de óleo de parafina, Deste modo a polimerização teve lugar depois de formada já a emulsão. Esta foi mantida 1 hora a 70°C. A visco sidade da solução aquosa formada por nitrato de amónio, nitra to de sódio, acrilamida e água a 70°C era menor do que 1 Ρ. A viscosidade da emulsão final a 25°C era de 714 P e a sua densidade era de 1,24 g/cm^. A velocidade de detonaçao segundo o ensaio já descrito era de 51θθ m/s. A emulsão foi armazenada a 10°C e periodicamente procedeu—se à medição da sua velocidade de detonaçao. A emuisao continuou a detonar depois de 26 sema na s.A mixture of ammonium nitrate (59 »70 parts) sodium nitrate (18.35 parts) and water (Ι3» 3θ parts) was heated to 70 ° C, stirring vigorously until an aqueous solution was formed · Subsequently, 1 »5θ parts of acrylamide and 0.01 parts of ammonium persulfate and immediately added this final aqueous solution at the same temperature and with rapid stirring, to an oily solution consisting of 1.40 parts of sorbitan monooleate and 4 , 25 parts of paraffin oil. Thus, the polymerization took place after the emulsion was formed. This was maintained for 1 hour at 70 ° C. The viscosity of the aqueous solution formed by ammonium nitrate, sodium nitrate, acrylamide and water at 70 ° C was less than 1 Ρ. The viscosity of the final emulsion at 25 ° C was 714 P and its density was 1.24 g / cm2. The detonation speed according to the test already described was 51θθ m / s. The emulsion was stored at 10 ° C and its detonation speed was periodically measured. Emission continued to detonate after 26 weeks in the week.

Composição 6:Composition 6:

Repetiu—se o esquema operatório da composição 5 com excepção de que em vez de acrilamida se utilizou N—hi— droximetilacrilamida. A densidade da emuisao final a 25°C era de 1,25 g/cm^ _{e a} sua viscosidade era de 7θ9 Ρ· A velocidade de detonaçao de acordo com o ensaio já descrito era de 5000 m/s. A emuisao foi armazenada a 10°C e mediu—se periodicamente a sua velocidade de acordo com o mesmo ensaio. A emuisao continuou a detonar depois de 28 semanas.The operative scheme of composition 5 was repeated with the exception that instead of acrylamide, N -hydroxymethylacrylamide was used. The density of the final emission at 25 ° C was 1.25 g / cm2 _and its viscosity was 7θ9 Ρ · The detonation speed according to the test already described was 5000 m / s. The emission was stored at 10 ° C and its speed was measured periodically according to the same test. The emission continued to detonate after 28 weeks.

Composição 7· ^{D QRIGINAL}jComposition 7 · ^{D QRIGINAL} j

II

Repetiu—se o esquema operatório da composição 4 com a diferença de que em vez de 1,50 partes de acrilamida se empregaram 1,00 partes de acrilamida e 0,50 partes de N,N— —bismetilenoacrilamida· A viscosidade da emulsão final a 25°C era de 731 P e a sua densidade era de 1,24 g/cm^. A velocidade de detonaÇao de acordo com o ensaio já descrito era de 53θθ m/s. A emulsão foi armazenada a 10° C e periodicamente mediu—se a sua velocidade de detonaçao segundo o mesmo ensaio. Depois de 35 semanas a emulsão ainda detonava.The procedure for composition 4 was repeated with the difference that instead of 1.50 parts of acrylamide, 1.00 parts of acrylamide and 0.50 parts of N, N— —bismethylene acrylamide were used · The viscosity of the final emulsion 25 ° C was 731 P and its density was 1.24 g / cm2. The detonation speed according to the test already described was 53θθ m / s. The emulsion was stored at 10 ° C and its detonation speed was periodically measured according to the same test. After 35 weeks the emulsion still detonated.

Composição δ:Composition δ:

Uma mistura de nitrato de amónio (59,70 partes) nitrato de sódio (ΐδ,35 partes) e égua (13,3θ partes) foi aquecida a 70°C agitando—se vigorosamente. Posteriormente adi cionaram—se 1,00 partes de acrilamida e 0,50 partes de N,N'—bismetilenoacrilamida. Logo que os monómeros se dissolveram a solução aquosa quente foi adicionada, mediante agitaçao rápida, a uma solução de monooleato de sorbitano (l,40 partes)e peróxido de benzoilo (0,005 partes) em óleo de parafina (4,24 partes). Continuou—se a agitaçao atê se obter uma emulsão uni forme. Depois do arrefecimento da emulsão a 40°C adicionaram— —se microesferas de vidro (1,50 partes) e dimetilparatoluidi— na (0,005 partes) e mi sturaram—se atê se obter uma mistura ho mogênea. A densidade da emulsão final a 25°C era de 1,24 g/cm3 e a sua viscosidade era de 756 Ρ. A velocidade de detonaçao de acordo com o ensaio já descrito era de 56OO m/segundo. A emul sao foi armazenada a 10°C e submeteu—se periodicamente ao mes mo ensaio de velocidade de detonaçao. A emulsão detonava ainda passadas 37 semanas.A mixture of ammonium nitrate (59.70 parts) sodium nitrate (ΐδ, 35 parts) and mare (13.3θ parts) was heated to 70 ° C while stirring vigorously. Subsequently, 1.00 parts of acrylamide and 0.50 parts of N, N'— bismethylene acrylamide were added. As soon as the monomers had dissolved, the hot aqueous solution was added, with rapid stirring, to a solution of sorbitan monooleate (1.40 parts) and benzoyl peroxide (0.005 parts) in paraffin oil (4.24 parts). Stirring was continued until a uniform emulsion was obtained. After cooling the emulsion to 40 ° C, glass microspheres (1.50 parts) and dimethylparatoluine (0.005 parts) were added and mixed until a homogeneous mixture was obtained. The density of the final emulsion at 25 ° C was 1.24 g / cm3 and its viscosity was 756 Ρ. The detonation speed according to the test already described was 5600 m / second. The emulation was stored at 10 ° C and periodically subjected to the same detonation speed test. The emulsion detonated after 37 weeks.

Composição 9^: Composition 9 ^:

Repetiu—se o esquema de trabalho da composição 5 com a diferença de em vez de acrilamida utilizou—se áci do acrílico, e como iniciador empregaram-se 0,01 partes de per sulfato de amónio e 0,01 partes de metabissulfito de sódio. A • densidade da emulsão final a 25 C era de 1,25 g/cm-⁵ e a suaThe working procedure for composition 5 was repeated with the difference that instead of acrylamide, acrylic acid was used, and 0.01 parts of ammonium per sulfate and 0.01 parts of sodium metabisulfite were used as the initiator. The density of the final emulsion at 25 C was 1.25 g / cm- ⁵ and its

GA D ORIGINALGA D ORIGINAL

viscosidade era de 7^1 Ρ. A velocidade de detonaçao segundo o ensaio já descrito foi de 5^00 m/segundo. A emulsão foi guardada a 10°C e mediu-se periodicamente a sua velocidade de acor do com o mesmo ensaio. A emulsão continuou a detonar passadas 28 semanas.viscosity was 7 ^ 1 Ρ. The detonation speed according to the test already described was 5 ^ 00 m / second. The emulsion was stored at 10 ° C and its speed according to the same test was periodically measured. The emulsion continued to detonate after 28 weeks.

Composição 10:Composition 10:

Repetiu—se o modo operatório da composição 9 com excepção que se empregaram 13»53 partes de água em vez de 13»2O e substituíram-se as 1,5θ partes de ãcido acrílico por 1,27 partes de anidrido maleico. A densidade da emulsão final a 25°C era de 1,25 g/cm^ e a sua viscosidade era de 713 Ρ· A velocidade de detonaçao segundo o ensaio já descrito foi de 53OO m/segundo. A emulsão foi armazenada a 10°C e mediu—se pe riodicamente a sua velocidade de acordo com o mesmo ensaio. A emulsão continuou a detonar passadas 28 semanas.The procedure for composition 9 was repeated except that 13.53 parts of water were used instead of 13.2% and the 1.5% parts of acrylic acid were replaced by 1.27 parts of maleic anhydride. The density of the final emulsion at 25 ° C was 1.25 g / cm2 and its viscosity was 713 Ρ · The detonation speed according to the test already described was 5300 m / second. The emulsion was stored at 10 ° C and its speed was measured periodically according to the same test. The emulsion continued to detonate after 28 weeks.

Como se pode ver no quadro 1 as composiçoes de acordo com a presente invenção mostram uma estabilidade con sideravelmente superior a das convencionais sem que sejam afe ctadas de modo sensível outras propriedades.As can be seen in Table 1, the compositions according to the present invention show considerably greater stability than conventional ones without any other properties being significantly affected.

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EXEMPLO 2EXAMPLE 2

De modo análogo ao exemplo 1, prepararam-se e ensaiaram—se diferentes composiçoes de emulsões embaladas em cartuxos de vários calibres (quadro 2).Similar to example 1, different emulsion compositions packaged in cartridges of various calibers were prepared and tested (Table 2).

A composição 11 corresponde a uma emulsão explosiva convencional e foi preparada de acordo com o seguinte esquema operatótio:Composition 11 corresponds to a conventional explosive emulsion and was prepared according to the following operative scheme:

Uma mistura de nitrato de amónio (59,10 partes) nitrato de só dio (18,20 partes) e água (13,60 partes) foi aquecida a 70°C, agitando—se vigorosamente atê se formar uma solução aquosa.Es ta solução aquosa foi adicionada à mesma temperatura e median te agitaçao rápida, a uma mistura-de monooleato de sorbitano (2<7θ partes) óleo de parafina (0,70 partes) cera parafínica (1,50 partes) e cera microcristalina (l,90 partes) aquecida a Ó5°C. Prolongou—se a agitaçao atê se obter uma emulsão unifor me. Posteriormente adicionaram—se microesferas de vidro (2,30 partes) e misturaram—se atê se obter uma mistura homogénea· A densidade da mistura final a 25°C cra de l,l6 g/cm^. A mistura final foi embalada em cartuxos de papel com um diâmetro de 32 mm. A velocidade de detonaçao da emulsão iniciada com um detonador n2 8 foi de 4700 m/s. A emulsão foi armazenada a 10° C e periodicamente foi submetida a esta iniciaÇao. A emulsão falhou depois de 22 semanas.A mixture of ammonium nitrate (59.10 parts) sodium nitrate (18.20 parts) and water (13.60 parts) was heated to 70 ° C, stirring vigorously until an aqueous solution was formed. Aqueous solution was added at the same temperature and with rapid stirring, to a mixture of sorbitan monooleate (2 <7θ parts) paraffin oil (0.70 parts) paraffin wax (1.50 parts) and microcrystalline wax (l, 90 parts) heated to 5 ° C. Stirring was continued until a uniform emulsion was obtained. Subsequently, glass microspheres (2.30 parts) were added and mixed until a homogeneous mixture was obtained · The density of the final mixture at 25 ° C, with a value of 1.6 g / cm2. The final mixture was packed in paper cartridges with a diameter of 32 mm. The detonation speed of the emulsion initiated with a # 8 detonator was 4700 m / s. The emulsion was stored at 10 ° C and periodically subjected to this initiation. The emulsion failed after 22 weeks.

As composiçoes 12 a l6 foram preparadas de acordo com o processo da presente invenção:Compositions 12 to 16 were prepared according to the process of the present invention:

Composição 12:Composition 12:

Uma mistura de nitrato de amónio (59,10 partes) nitrato de sódio (18,20 partes) e água (13,10 partes) foi aquecida a 80°C, agitando—se vigorosamente atê se formar uma solução aquosa. Posteriormente adicionaram—se 1,50 partes de acrilamida. A solução final foi adicionada à mesma temperatura e mediante agitaçao rápida a uma mistura·de monooleato deA mixture of ammonium nitrate (59.10 parts) sodium nitrate (18.20 parts) and water (13.10 parts) was heated to 80 ° C, stirring vigorously until an aqueous solution was formed. Subsequently, 1.50 parts of acrylamide were added. The final solution was added at the same temperature and with rapid stirring to a mixture of monooleate of

BAD ORIGINALORIGINAL BAD

sorbitano (2,70 partes) óleo parafínico (0,69 partes) cera pa rafínica (1,17 partes) cera microcristalina (1,67 partes) e azobiisobutironitrilo (0,01 partes) aquecida a 80°C. Manteve—se a emulsão a 80°C durante 1 hora· Posteriormente adicionaram—se microesferas de vidro (2,30 partes) e misturaram -se atê se obter uma mistura homogénea. A densidade da mistura final a 25 C foi de 1,16 g/cm . A mistura final foi embala da em cartuxos de papel com um diâmetro de 32 mm. A velocidade de detonaÇao da emulsão iniciada com um detonador nC 8 foi de 5000 m/s. A emulsão foi armazenada a 10 C e periodicamente foi submetida a esta iniciaçao. A emulsão continuou a deto nar depois de 5θ semanas.sorbitan (2.70 parts) paraffin oil (0.69 parts) paraffin wax (1.17 parts) microcrystalline wax (1.67 parts) and azobiisobutyronitrile (0.01 parts) heated to 80 ° C. The emulsion was maintained at 80 ° C for 1 hour. Subsequently, glass microspheres (2.30 parts) were added and mixed until a homogeneous mixture was obtained. The density of the final mixture at 25 ° C was 1.16 g / cm. The final mixture was packed in paper cartridges with a diameter of 32 mm. The detonation speed of the emulsion initiated with a nC 8 detonator was 5000 m / s. The emulsion was stored at 10 ° C and periodically subjected to this initiation. The emulsion continued to detect after 5θ weeks.

Composição 13^: Composition 13 ^:

Uma mistura de nitrato de amónio (59»10 partes) nitrato de sódio (l8,l8 partes) e água (134,10 partes) foi aquecida a 70°C, agitando—se vigorosamente atê se formar uma solução aquosa· Posteriormente adicionaram—se 1,50 partes de ácido acrílico, 0,01 partes de sulfato de amónio e 0,01 par tes de metabissulfito de sódio^ Esta solução final foi adicio nada imediatamente, mediante agitaçao rápida, a uma mistura de monooleato de sorbitano (2,70 partes) óleo de parafina (0^70 partes) cera parafínica (1,17 partes) e cera microcristalina (1,67 partes) aquecida a 65°C. Manteve-se a agitaçao até se obter uma emulsão uniforme. Posteriormente adicionaram—se microesferas de vidro (2,3θ partes) e misturou—se atê se obter uma mistura homogénea.A mixture of ammonium nitrate (59 »10 parts) sodium nitrate (18, 18 parts) and water (134.10 parts) was heated to 70 ° C, stirring vigorously until an aqueous solution was formed. if 1.50 parts of acrylic acid, 0.01 parts of ammonium sulphate and 0.01 parts of sodium metabisulfite ^ This final solution was added immediately, by rapid stirring, to a mixture of sorbitan monooleate (2, 70 parts) paraffin oil (0 ^ 70 parts) paraffin wax (1.17 parts) and microcrystalline wax (1.67 parts) heated to 65 ° C. Stirring was continued until a uniform emulsion was obtained. Subsequently, glass microspheres (2.3θ parts) were added and mixed until a homogeneous mixture was obtained.

A densidade da mistura final a 25°C era de 3The density of the final mixture at 25 ° C was 3

1,17 g/cm . A mistura final foi embalada em cartuxos de papel com um diâmetro de 32 mm. A velocidade de detonaÇao da emulsão iniciada com um detonador nS 8 foi de 4900 m/s. A emulsão foi armazenada a 10°C e periodicamente foi submetida a esta iniciaçao. Depois de 63 semanas a emulsão ainda detonava.1.17 g / cm. The final mixture was packed in paper cartridges with a diameter of 32 mm. The detonation speed of the emulsion initiated with an # 8 detonator was 4900 m / s. The emulsion was stored at 10 ° C and periodically subjected to this initiation. After 63 weeks, the emulsion still detonated.

Composição l4:Composition l4:

ORIGINALJORIGINALJ

Repetiu-se o modo operatório da composição 13 com a diferença de em vez de ácido acrílico utilizou—se N—hi— droximetilacrilamida e empregou—se como iniciador unicamente persulfato de amónio. A densidade da emulsão final a 25°C era de l,l6 g/cm . A emulsão foi embalada em cartuxos de papel comThe procedure for composition 13 was repeated with the difference that instead of acrylic acid, N —hydroxymethylacrylamide was used and the ammonium persulfate was used as the initiator only. The density of the final emulsion at 25 ° C was 1.6 g / cm. The emulsion was packed in paper cartridges with

A ** ** um diâmetro de 32 mm. A velocidade de detonaçao da emulsão iniciada com um detonador nfi 8 foi de 53θθ m/s. A emulsão foi armazenada a 10°C e periodicamente foi submetida a esta ini— ciaÇao. A emulsão continuou a detonar depois de 7θ semanas.A ** ** a diameter of 32 mm. The detonation speed of the emulsion initiated with an # 8 detonator was 53θθ m / s. The emulsion was stored at 10 ° C and periodically subjected to this initiation. The emulsion continued to detonate after 7θ weeks.

Composição 15·Composition 15 ·

Repetiu—se o esquema operatório da composição 12 com a excepção de se empregarem 13>33 partes de água em vez de 13>10 e ter-se substituido as 1,5θ partes de acrilamida por 1,27 partes de anidrido maleico. A densidade da emulsão final a 25°C era de 1,16 g/cm^. A emulsão foi embalada em cartuxosThe operating procedure for composition 12 was repeated with the exception that 13> 33 parts of water were used instead of 13> 10 and the 1.5θ parts of acrylamide were replaced by 1.27 parts of maleic anhydride. The density of the final emulsion at 25 ° C was 1.16 g / cm2. The emulsion was packaged in cartridges

A ** de papel com um diâmetro de 32 mm. A velocidade de detonaÇao da emulsão iniciada com um detonador nfi 8 foi de 51θθ m/s. A emulsão foi armazenada a 10°C e foi periodicamente submetida a esta iniciaçao. Ao fim de 67 semanas a emulsão continuava a detonar.A ** of paper with a diameter of 32 mm. The detonation speed of the emulsion initiated with a nfi 8 detonator was 51θθ m / s. The emulsion was stored at 10 ° C and was periodically subjected to this initiation. After 67 weeks, the emulsion continued to detonate.

Composição l6:Composition l6:

Uma mistura de nitrato de amónio (59,10 partes) nitrato de sódio (18,20 partes) e água (13,10 partes)foi aquecida a 70°C, agitando—se vigorosamente. Po steriormente adi cionaram—se 1,00 partes de acrilamida e 0,50 partes de N,N— -bismetilenoacrilamida. Quando os monómeros se dissolveram, a solução aquosa quente foi adicionada mediante agitaçao rápida a uma mistura quente (Ó5°C) de monooleato de sorbitano (2,70 partes) óleo de parafina (0,69 partes) cera de parafina (l,17 partes) cera microcristalina (1,67 partes) e peróxido de benzoilo (0,005 partes). Prolongou—se a agitaçao ató se obter uma emulsão uniforme. Seguidamente adicionaram—se microesferas de vidro (2,30 partes) e ·, · . . _η. (0,005 partes) e mistu— ^r dimetilanilmaA mixture of ammonium nitrate (59.10 parts) sodium nitrate (18.20 parts) and water (13.10 parts) was heated to 70 ° C, stirring vigorously. Thereafter, 1.00 parts of acrylamide and 0.50 parts of N, N-bismethylene acrylamide were added. When the monomers dissolved, the hot aqueous solution was added by rapid stirring to a hot mixture (Ó5 ° C) of sorbitan monooleate (2.70 parts) paraffin oil (0.69 parts) paraffin wax (1.17 parts) microcrystalline wax (1.67 parts) and benzoyl peroxide (0.005 parts). Stirring was continued until a uniform emulsion was obtained. Then glass microspheres (2.30 parts) and ·, · were added. . _η . (0.005 parts) and ^r mistu- dimetilanilma

BAD ORIGINAL rou—se até se obter uma mistura homogénea· A densidade da emul sao final a 25°C era de 1,17 g/cm^. A emulsão foi embalada em cartuxos de papel com um diâmetro de 32 mm. A velocidade de detonaÇao da emulsão iniciada com um detonador ηΩ 8 era de 5100 m/s. A emulsão foi armazenada a 10° C e periodicamente foi submetida a esta iniciaçao. A emulsão continuou a detonar ao fim de 75 semanas.ORIGINAL BAD was continued until a homogeneous mixture was obtained · The density of the final emulsion at 25 ° C was 1.17 g / cm2. The emulsion was packed in paper cartridges with a diameter of 32 mm. The detonation speed of the emulsion initiated with a ηΩ 8 detonator was 5100 m / s. The emulsion was stored at 10 ° C and periodically subjected to this initiation. The emulsion continued to detonate after 75 weeks.

Como se pode ver no quadro 2 o processo da pre sente invenção permite obter composiçoes com propriedades de estabilidade nitidamente melhoradas em emulsões embaladas em cartuxos de baixos calibres.As can be seen in Table 2, the process of the present invention allows to obtain compositions with markedly improved stability properties in emulsions packaged in low-caliber cartridges.

BAD ORIGINALORIGINAL BAD

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Claims

- lô Process for the preparation of new explosive emulsion compositions containing a continuous fuel phase and a discontinuous aqueous phase dispersed therein, containing oxidizing salts and a macromolecular structure, characterized by the fact that it comprises the phases

a) the preparation of an aqueous solution containing essentially oxidizing inorganic salts and at least one polymerizable organic monomer;

b) the preparation of an oily and immiscible mixture with the aqueous solution, containing essentially hydrocarbon fuels and one or more emulsifying agents;

c) the formation of an emulsion of the type "water in oil" from the mixtures prepared in the previous phases;

d) the polymerization, after the formation of the emulsion, of the monomer or monomers contained in the aqueous dispersed phase.

2. A process according to claim 1, characterized in that the monomer or monomers included in the aqueous phase have at least a double bond in their molecule.

- 3 Process according ^to claims 1 and 2,

ORIGINAL BAD characterized by the fact that the monomer or monomers are preferably chosen from the group formed by acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic anhydride, acrylamide, acrylamide, allylamine, allylamine, acrylonitrile and the its derivatives.

4. Process according to claims 1 and 3, characterized in that the monomer or monomers are incorporated in a proportion ranging from 0.01 to 20% by weight of the final composition.

5. ^A process according to claim i, characterized in that the monomer, or at least one of them if there are several, has more than one double bond.

6. A process according to claims 1 and 2, characterized in that the monomer, or at least one of them if there are several, has a reactive functional group.

Process according to claim 6, ca23 BAD ORIGINAL characterized by the fact that at least one monomer has as reactive functional groups hydroxyl groups, amines, acids or methoxymethyls.

8. Process according to claims 6 and 7, characterized in that an organic compound capable of reacting with the functional groups of the existing monomer or monomers forming a crosslinking is added.

- Process according to claim 8, characterized in that the organic compound that is added belongs to the group consisting of melamine resins, is maldehydes, benzoguanamines, dianhydrides -diepoxides, phenolic, tetralkylthitenates, diisocyanates, dimethoxymethylurea, methylated trimethylamine. , butylated trimethylimelamine, butylated methyl-olbenzoguanatnine, bismetoxymethylureas, bisetoxymethylene urea and similar amino resins, polyols and polymers derived from n-methylol acrylamides.

- Process according to claim ±, characterized in that the polymerization is initiated by means of a chemical initiator.

- read _

- 24 - ORIGINAL BAD ^!

Process according to claim 10, characterized in that the initiator is added to the aqueous solution immediately before the emulsion is formed, so that the polymerization of the monomers before said formation is negligible.

12. A process according to claim 10, characterized in that the initiator is added to the oil phase.

Process according to claims 10 to 12, characterized in that the polymerization is initiated by means of redox type initiators.

- 14 to _

Process according to claims 10 to 12, characterized in that the chemical initiation is carried out by means of the thermal decomposition of an azo compound, peroxide, peracetate or hydroperoxide.

- Process according to claim i4, characterized in that the thermal decomposition of the initiator

25 BAD ORIGINAL be catalyzed so that said decomposition takes place at temperatures below 80 ° C.

Process according to claim 1, characterized in that the polymerization is initiated by means of electromagnetic radiation.

17. A process according to claim 1, characterized in that in addition to the monomers, a transfer agent is added to the aqueous solution.

- 18th _

Process according to claim 1, characterized in that the oxidizing inorganic salts are chosen from ammonium nitrates, chlorates or perchlorates and from alkali or alkaline earth metals.

19. ^A process according to claims 1 and 18, characterized in that the amount of inorganic oxygen salts used is between 20 and 90% by weight of the final composition.

26 ORIGINALJ

20th

Process according to claim 1, characterized in that the water insoluble hydrocarbon fuels can be aliphatic, alicyclic and / or aromatic and can be saturated and / or unsaturated.

21 & Process according to claim 20, characterized in that the hydrocarbon fuel is chosen from the group of fuel oil, diesel oil, distilled oils, petroleum, heavy oils, paraffin oils and waxes, microcrystalline waxes, benzene, toluene, xylenes, asphalt materials, polymeric oils and waxes, animal oils and waxes, they are tomeres, vegetable oils and waxes, such as epoxidized soybean oil, and mixtures thereof.

- 22β Process according to claims i,

20 and 21, characterized by the fact that hydrocarbon fuels are incorporated in quantities between 2 and 3θ% by weight of the final composition ·

- 23rd _

Process according to claim 1, characterized in that the emulsifying agents incorporated in the oil phase are chosen from the group formed by é—

ORIGINAL BAD sorbitan esters, pentaerythritol esters, fatty acid glycerides, alkoxylated alcohols, alkoxylated phenols, alkoxy fatty amines, polyoxyalkylene sorbitan esters, glycol and polyoxyalkylene esters, acid amides, fatty amines, alkaline oxides, alkaline amines , imidazolines, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl phosphates, alkenyl phosphate, phosphate esters, lecithin, lanolin derivatives, polyoxyalkylene glycol copolymers and 12-hydroxystearic lipid.

Process according to claims 1 and 23, characterized in that the emulsifying agents are incorporated in amounts between 0.2 and 7% of the final composition

- 25 ^to process according to claim I, characterized in that the composition sensibiiizaÇao be accomplished by incorporating a discontinuous gaseous phase in order to achieve a density of 0.7

O is 1.4 g / cm.

- 26â _

Process according to claim 25, characterized in that the discontinuous gas phase can be incorporated by direct injection of air, occlusion, addition

28 ORlGlNAt-j of gas generators and addition of hollow particles, such as glass microspheres, polymeric microspheres, volcanic microspheres, perlite and volatile ash.

- 27 ^to process according to claim 1, ca- 'rf racterizado in that they can be incorporated into the composition auxiliary fuel such as aluminum, magnesium, aluminum alloys, magnesium, aluminum-silicon alloys, ferrosilicon, carbohydrates, amines, amides, sulfur and coal.

Process according to claim 275, characterized in that the auxiliary fuels are incorporated in quantities of less than 25% by weight of the final composition.

29. Process according to claim 1, characterized in that the sensitization of the composition can be increased by the addition of auxiliary sensitizers, such as nitrated amines, nitrotoluenes, PETN, PDX, HMX, nitrocellulose or mixtures thereof.

- 30 ^to process according to Claim 29 »Ca

29 ORIGINAL BAD characterized by the fact that auxiliary sensitizing agents are added in amounts less than 30% and ^{K1 by} weight of the final composition.